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Of Chemical Engineering University of New Brunswick PO Box 4400, Fredericton NB, E3B 5A3 Nov 13th, 2013 Dear Dr. Felipe Chibante & Ms.Linda Bulmer, We have enclosed Milestone 3 which presents a general overview of our project as well as the results of a literature review. Background information is provided for the company Enovex as well as the gas adsorbing materials they produce. Design and project scope are outlined providing a frame work for future work moving forward. Results of research and comparison of three of the most prominent MOF production processes are included as well as the results of research into the economic viability of this project. Proceeding the literature research and process selection, a base case design is introduced with a block flow diagram explaining the main components of the process. Also innovative additions are implemented along with major safety and environmental considerations. We believe you will find this report in line with your expectations, however if you have any questions regarding this report, please do not hesitate to contact us directly at (506) 447- 0159.
Best Regards, Group 9. Sarbjyot Bains (Team Leader) Omar El-kadri Yousef Aloufi
Leroy Rodrigues
ChE 4225: Chemical Engineering Plant Design Milestone 3 Production of Metal Organic Frameworks (MOFs)- Enovex
Submitted to: Ms. Linda Bulmer Prof. Felipe Chibante Due Date: 11/13/2013
Abstract
The objective of the following report is to cast an overview of the process and specifications of the projected plant for the manufacturing of Metal Organic Frameworks (MOFs) and to present the results of a literature review designed to determine which production system is the most desirable. The main function of MOFs is the efficient separation of gases such as nitrogen and oxygen. The MOFs under study are to demonstrate 2-3 times better separation in comparison to current technologies available. General client needs include an overall design process that constitutes environmental, economic and risk assessment studies. These assessments should enable group 9 to build a green pilot size process plant that produces an approximation of 100kg/day of plant operation that also complies with all safety and environmental regulations. Also a description of the feedstock and production rates are mentioned as well as anticipated purity and yield will be discussed within. Further research will also be performed on plant location and downstream environmental concerns regarding possible waste water, and/or disposal of hazardous waste. Along with all the process steps, there are many constraints to be addressed, such as economic indicators, environmental regulations, and health and safety issues. The following report will highlight several key points that outline a responsible and sustainable operation. Research was done into the economic viability of this project and the findings were encouraging. There is significant market demand for materials of this type. Though a scale up of the process is unproven, which could be seen as a liability, it is this same characteristic which gives this project
the potential for tremendous opportunity. Maximum potential profit was determined by comparing the product market value and the costs of the precursor chemicals. The results of an extensive literature review are presented detailing comparisons made between three of the most prominent MOF production methods. The 3 processes examined were the Electrochemical, Microwave Assisted and Solvothermal. Advantages and disadvantages of these production methods were detailed and careful consideration was given in order to select the process that will most suit Enovexs needs. It was determined that the solvothermol process had significant overall advantage when compared to the other methods. Further proceeding the literature review and process selection, a base case design is introduced demonstrating the main components of the design via a block flow diagram. Also explanation in detail is presented for each section of the proposed BFD. Also innovative additions are suggested, such as an overall control system that monitors and controls the process along with recycling streams that recycle the expensive solvents needed for the process.
Contents
1. Project Definition ...................................................................................................................................... 3 1.1 Introduction ........................................................................................................................................ 3 1.2 Design Scope ....................................................................................................................................... 4 1.2.1 General Client Needs ................................................................................................................... 4 1.2.2 Feedstock ..................................................................................................................................... 6 1.2.3 Plant Location and Environment.................................................................................................. 7 1.2.4 Decision Criteria/ Constraints ...................................................................................................... 9 1.3 Project Scheduling ............................................................................................................................ 11 2.0 Literature review................................................................................................................................... 12 2.1 Overview of Product Markets ........................................................................................................... 12 2.1.1 Product End Uses ....................................................................................................................... 12 2.1.2 Product Specifications................................................................................................................ 14 2.1.3 Product Pricing........................................................................................................................... 15 2.1.4 Product Supply and Existing Producers ..................................................................................... 15 2.1.5 Product Demand ........................................................................................................................ 16 2.2 Assessment of Alternative Process Technologies ......................................................................... 16 2.2.1 Electrochemical Synthesis Process ............................................................................................ 16 2.2.2 1.2.3 Microwave Assisted Synthesis ............................................................................................ 19 Solvo/Hydro Thermal Synthesis Process ............................................................................. 22
2.5 Competitive Cost Considerations...................................................................................................... 24 2.6 Recommended Process Technologies............................................................................................... 25 2.7 Maximum Potential Profit................................................................................................................. 29 3.0 3.1 Base Case Design............................................................................................................................. 30 Pre-activation process................................................................................................................. 32
3.1.1 Reactor process and chemistry .................................................................................................. 32 3.1.2 Filtration ..................................................................................................................................... 33 3.1.3 Drying ......................................................................................................................................... 33 3.1.4 Soaking ....................................................................................................................................... 33 3.1.5 Filtration ..................................................................................................................................... 34 3.1.6 Recycle Streams ......................................................................................................................... 34 1
3.2 Activation Process ............................................................................................................................. 34 3.3 Innovation ......................................................................................................................................... 35 3.3.1 Process control and data analysis .............................................................................................. 35 3.3.2 Solvent Recycling ....................................................................................................................... 36 3.4 Health, Safety and Environmental Considerations ........................................................................... 37 3.4.1 Health and safety ....................................................................................................................... 37 3.4.2 Environmental ............................................................................................................................ 38 4.0 References ............................................................................................................................................ 39 5.0 Appendix ............................................................................................................................................... 41
1. Project Definition
1.1 Introduction
Enovex is a leading technology startup company based in Atlantic Canada specializing in advanced materials for improved separation capacities for portable and industrial O2/N2 production. Refined O2 and N2 are both high demand products used for many purposes both industrially and commercially. The oxygen for example is supplied to hospitals, steel and metal processing industries among others. One of the largest users of refined nitrogen are the food industries whose main uses are for freezing applications. There are many other uses of these products making this a multimillion dollar industry. Enovex has designed a unique porous material, which separates 2 to 3 times as much gas as the existing materials available and result in a 50% drop in energy usage in the production of industrial nitrogen. This material has the potential to reduce gas plant size by up to 66%. These high performance materials called Metal Organic Frameworks or MOFs are a new class of porous polymer materials which combine metals with organic ligands. They are highly tunable and favorable for industrial gas processes (Walton, 2013). The existing technology for non-cryogenic N2 production , carbon molecular sieves (CMS), are inefficient and have a number of operational problems including; slow mass transfer due to kinetic based separation, long mass transfer zones, low product recovery, limited volumetric uptake and low material tune-ability. To address these problems Enovex has invented a metal organic framework or MOF which exhibits equilibrium O2 selectivity, high O2 capacity and a linear isothermal shape. Other desirable attributes include; functionalized pores for high O2 selectivity,
a mix of meso and micro pores providing favorable kinetics and material also provides reversible O2 adsorption (Walton, 2013). Enovex plans to scale up the existing lab scale production processes to a commercialized pilot enabling the contracted manufacture of the MOF material. Distribution will be accomplished by using the supply channels of a large gas company. To date the Enovex team has raised $2.5M in cash and $2M in capital equipment investments as well as hired multiple leading material scientists including a consultant who is a premier scientists in the field. Enovexs assets include a laboratory in India with advanced equipment and have also built a PSA lab in Canada for commercial testing. It is our teams intention to fulfill the clients expressed need to advance the conceptualization, design and specification of a MOF production facility capable of producing kilogram sized batches of Enovexs product (Walton, 2013).
Enovex has requested group 9 to design a commercialized sized pilot plant for the production of MOFs that have the function of separating oxygen gas from nitrogen gas via absorption. Currently there is no existing plant for the projected design, hence the client requirements include every
single aspect of the process design from utilities, feedstock used, to final product, pelletizing and packaging (Walton, 2013). The process design requirements include: The selection of plant location based on financial aspects determined by comparing the proximity of the plant to both the supplier of the raw materials and the buyer of the product (Walton, 2013). The building of the plant with all the process components from reactors, boilers, stream lines and utility feeds to the pelletizing, packaging and storage of the product (Walton, 2013). Abiding by all safety and design regulation set by provincial laws that govern such processes. Building and performing tasks based on green plant design strategies. Further safety systems such as fire suppression systems and other non-process related designs will be contracted to firms specialized in these fields (Walton, 2013). Continuous monitoring of the process and input is also required. Certain indicators need to be collected during the process to ensure input and process integrity. An overall economic assessment for the feasibility of the plant and profitability of the product is also a task that group 9 is required to perform with special attention for payback period and other financial aspects of the design. A deadline for the plant design limited at a maximum range of three years must be met (Walton, 2013).
1.2.2 Feedstock
The feedstock is a set of raw materials required for the entire process of manufacturing MOFs. The main industrial function for MOFs is to replace existing technologies for non-cryogenic N2 production such as carbon molecular sieves (CMS). The raw materials to be processed in the plant include metal salts (Zinc Nitrate), solvents/co-solvents (N,N-dimethylformamide), ligands/coligands (Terephthalic acid) along with supplementary additives. The projected plant size is limited to a small pilot plant that will produce approximately 100kg/day. The production rate can be estimated conservatively to project feedstock rate in the case of having a specific production rate requirement from Enovex. In this project case the production rate is a variable in determining the optimal feed for the optimal product. Hence precise feedstock volumes will be determined based on experimental trials that would find the optimal feed rates for the highest quality and yield of product. Based on client requirements, the anticipated purity should be 95% or greater and will be tested using a powder x-ray diffraction device. Further tests can be performed via FTIR and physisorption to determine optimal surface area and pore volume. The process will start with an approximation for feedstock quantities and then results of experimental trials will determine optimal feedstock rates. Tests that are required to determine the pore size and optimal structure are beyond the process scope, and are the responsibility of Enovex (Walton, 2013). MOFs can be generally described as a class of porous polymeric materials, consisting of metal ions linked together by organic bridging ligands. The raw materials used are not the actual
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materials to be processed, where Enovex will keep this information confidential for patenting purposes. Group 9 will be using analogous materials that will allow proper design of the process (Walton, 2013). 1.2.3 Plant Location and Environment
The following section will discuss the variables that affect plant location as well as environmental concerns that relate to the best location.
1.2.3.1 Plant Location Selection
The three locations that are currently being considered for the plant are: Saint John, NB Canada, where it is in proximity to the clients headquarters and port of Saint John. Land costs are low but production costs very high. India, where it is in proximity to Enovexs Research and Development Centre and has numerous ports for quick shipping of the product. Europe, where it is in close proximity to most of the major clients of Enovex. It is centrally located on the map and this makes it the best location for transportation throughout the world.
Product distribution: Site should be in proximity to clients (air separation plants). Feedstock availability: Site should be in proximity to required feedstock. Relevant climatic conditions: Site should have controllable humidity as the end product is sensitive to humidity. Site meteorology and weather conditions should be assessed.
Property costs: The property prices and property taxes should be low to match Enovexs budget.
Labor Costs and Expertise Availability: Skilled labor should be available at affordable cost. Direct labor costs include wages plus payroll, benefits and related taxes.
Regulatory environment: The local, state and federal laws and regulations should be taken into consideration for site selection.
Geotechnical conditions: Borings must be obtained early in the process to attain the cost and schedule implications foundation designs, structural fill, soil compaction, surcharging and piling.
Availability of Public Sector Funding: Grants will help in reducing land costs and taxes. Potential for expansion: The site should be large enough to expand the pilot plant into a commercial plant.
A critical concern in the design of a chemical plant is its impact on the environment.
Disposal of hazardous waste: The hazardous waste would be the unconsumed reagents in the effluent. The non-recyclable waste material will go through an incinerator and the residue will be landfilled. Moreover, under the reaction conditions used there is no appreciable decomposition into other materials. Rejected finished product is also a non-recyclable source of waste to be addressed.
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Proper operating and disposal procedures will be formed to prevent potential impacts on the environment. A list of critical environmental permits and plans would be developed for the chosen location by an environmental consulting company. Proper level of safety would be provided to prevent exposure to hazardous conditions. 1.2.4 Decision Criteria/ Constraints
Flushing out and evaluating a number of process constraints will prove to be of great importance in the process of decision-making and selecting the process design and its components. Most of these constraints directly affect the quality and performance of the final product. Constraints include economic feasibility, environmental risks, safety risks, technological feasibility and regulatory issues.
1.2.4.1 Environmental aspects
Since this particular process deals with chemicals that are harmful to the environment or/and human life, a number of safety measures will be necessary. Most of the raw materials that will be used in the process processes flammable properties and produce hazardous vapors, therefore measures will be needed to be taken in order to prevent any harmful effects to the environment. Another aspect that needs to be taken into consideration is the handling of the hazardous waste. These constrains will play an important role in finalizing the location of the plant (Wilkins, 2012).
1.2.4.2 Health and Safety
A number of measures need to be taken in order to minimize health hazards. This particular product deals with toxic vapors, therefore the employees will need to follow proper safety protocols in order to ensure their safety. Also safety measures will be needed to be taken in order to prevent
the escape of these harmful vapors to the surroundings. Some of the feeds (raw materials) processes highly flammable properties, therefore safety precautions will be needed in order to prevent any associated injury or damage (Walton, 2013). The raw materials and products of this process havent been tested on a pilot scale, therefore more lab scale testing needs to be conducted to ensure smooth pilot scale operation.
1.2.4.3 Economic Feasibility
A critical constraint that most industries face is financial. Since this plant is dealing with a new product a fixed budget has not yet been set by the client, but a predicted healthy cash flow will be essential to maintain investor interest and sustain long term operational viability.
1.2.4.4 Technological Risks
Since this project is currently at laboratory stage, proper equipment selection will be of primary importance. One of the key criteria for this project is the purity and yield of the product, therefore if economically feasible, control systems can be implemented throughout the process to ensure optimum product results. An important aspect with regards to the selection of the technologies is the cost of the equipment and facilities.
1.2.4.5 Production Reliability
An important operational constraint is a reliable power supply. The design should include some form of power redundancy in order to ensure smooth operation of the plant.
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Since this particular plant deals with hazardous materials it is essential to abide by associated codes and regulations in with its hosted location. The codes will focus on all the minor and major aspects of the plant design, these include the handling of waste and quality of air. These codes will ensure the safety of the workforce and surrounding areas. This factor could play an important role in selecting the location for the plant.
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The following table lists specific dates for project milestones and deadlines.
Table 1- Project Schedule.
North Americas developing interest in environmentally conscious processes and products, has stimulated a great deal of interest in the use of MOFs in non-cryogenic nitrogen production. Scientists at Enovex are trying to develop highly porous and tunable MOFs with favorable characteristics for industrial gas separation. Their huge surface area and pore volume makes them extremely useful for gas sequestration and as a catalyst. MOFs are an extremely useful product with multiple uses:
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Hydrogen Storage: Hydrogen is a clean energy carrier and potential replacement for petroleum products. Hydrogen storage is a critical enabling technology for the acceptance of hydrogen powered vehicles and MOFs play a great role in storing sufficient hydrogen at low temperatures and pressures (Yaghi, O'Keeffe, Cordova, & Furukawa, 2013).
CO2 sequestration: MOFs show substantial CO2 adsorption capacities at low and high pressures.
Catalysis: MOFs have a huge potential in numerous catalyst applications. Their high surface area, tunable porosity, diversity in metal and functional groups makes them highly suitable as catalysts (Seda & Seda, 2011).
Semiconductors: It has been proven through theoretical calculations that MOFs show properties of semiconductors and insulators with band gaps ranging between 1.0 eV and 5.5 eV.
Air Separation: MOFs have high selectivity for oxygen and the adsorption process is completely reversible.
Drug Delivery Vehicles: MOFs can be regarded as optimal drug delivery materials due to the possibility of adjusting their frameworks functional groups and tuning of their pore size. (Seda & Seda, 2011)
Potential Imaging Agents: A recent study demonstrated the potential use of nanoscale MOFs as multimodal imaging probes designed by incorporation of suitable metal ions and organic moieties using a microemulsion-based approach (Seda & Seda, 2011).
MOFs for Sensing: MOFs having luminescent properties together with size/shape selective sorption properties can be considered as potential sensing devices
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Currently, BASF is the only commercial producer of MOFs. The various grades available at BASF are shown below: (Aldrich, 2013).
Table 2:BASF Grades.
Hydrophilic Aluminum MOF BET surface area 1100-1500 m2/g Reactivation at 200oC Hydrophilic Copper MOF BET surface area 1100-2100 m2/g Reactivation at 200oC Organophilic Zinc, ZIF, Zeolitic Framework BET surface area 1300-1800 m2/g Reactivation at 100oC
BASOLITE C300(C18H6Cu3O12)
BASOLITE Z1200(C8H12N4Zn)
The product specification of the MOF produced by Enovex is: Product Name: MOF-5 or IRMOF (Isoreticular Metal Organic Framework)-1 Formula: Zn4O(C8H4O4)3 Appearance(Color): Orange Appearance (Form): Micro crystals Infrared spectrum: Conforms to Structure Purity (GC) > 99.5 %
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2.1.3 Product Pricing Price of MOFs is directly proportional to their surface area per gram and purity. The prices shown below are for lab samples and would vary for commercial applications (Aldrich, 2013).
Table 3: Product Pricing
From literature, it is found that MOFs have higher value in biomedical applications than in air separation applications. 2.1.4 Product Supply and Existing Producers
The MOFs sold by Sigma-Aldrich are manufactured in a BASF pilot plant in Ludwigshafen, Germany, in 100-kg-per-day batches. Only a portion of the plant's output is sold via Sigma-Aldrich and that BASF uses most of the material internally for various R&D projects. It is seen that industrial scientists in many companies are investigating framework compounds for use in purification, storage, and transportation of gases, among other applications. (Jacoby, 2008) The existing producers of MOFs include: 1. BASF: It is the only commercial producer of MOFs. 2. Sigma Aldrich: Supplier of customized MOFs on a lab scale. 3. Unknown Suppliers on Chemical Trading Websites: Supply reagent grade MOFs up to five grams per day.
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MOFs are currently at Research and Development stage and therefore most of the demand is coming from labs across the world for finding new applications of MOFs. However, in the near future, predicted demand for MOFs is in the following sectors: Automobile: For large scale hydrogen and methane storage. Gas Separation: Separating oxygen and nitrogen from the air. Reactors: As a catalyst with large surface area.
The following sections will discuss the main disadvantages and advantages of the three most favorable processes in the industry; electrochemical synthesis, microwave assisted synthesis and solvothermal synthesis. 2.2.1 Electrochemical Synthesis Process
Electrochemical synthesis is the synthesis of chemical compounds in an electrochemical cell. During the electrochemical synthesis process metal ions are continuously supplied through the anodic dissolution. It is an effective and versatile means of producing MOFs. The figure below provides a basic overview of an electrochemical synthesis process for the production of MOFs.
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2.2.1.1 Advantages
Some of the major advantages of an electrochemical synthesis process that makes it applicable in an industry are: Short Reaction Time: The reaction time for the implementation of an electrochemical synthesis process is much faster than the conventional methods of synthesis. It is also possible to have the system set in a continuous process. Controllability of the size of the crystals: The size of the crystals can be controlled by the manipulation of the voltage and concentration of metal ions. This can prove to be a key feature as the specifications of the product can be altered to fit the needs of the client. Elimination of the separation process of the anions from the synthesis solution and total utilization of the linker: The process uses metal ions instead of metal salts. This eliminates the reaction of the metal salts with the dissolved linker molecules that are present in the reaction medium. Therefore total utilization of the linker can be accomplished. Also there
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is no need to separate the anions from the synthesis solution, prior to the recycling of the solvent.
2.2.1.2 Disadvantages
The major disadvantages of an electrochemical synthesis process that makes it unsuitable for an industrial application are: Lower overall efficiency of the product: During the reaction some of the material that was used in the initial stage of the electrochemical process may get trapped inside the pores, resulting in pore blockage. This will decrease the overall efficiency of the product in terms of adsorption. Variation in the final product: Certain areas of the material that are electrically connected, are the only areas that are subject to the growth. Therefore there is less uniformity in the final product. Cost-intensive: An electrochemical process is an expensive process to conduct. Also the electrodes that are used during the course of the experiment, need to be changed continuously. This will increase the overall operating cost of the plant. Scalability of process: The electrochemical process for the manufacturing of MOFs has not yet been tested in an industrial application. Therefore the process may prove to be unreliable.
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Advantages Short Reaction Time Controllability of the size of the crystals Elimination of the separation process of the anions from the synthesis solution and total
Disadvantages Lower overall efficiency of the product Variation in the final product Cost-intensive Unreliability of process
In Microwave-Assisted Synthesis, an appropriate solvent which contains a substrate mixture is transferred to a vessel. After transferring the solvent to a vessel, the vessel is sealed and placed in the microwave oven. At the set temperature, the microwave oven will heat the content for the appropriate time. The permanent dipole moment of the molecule in the synthesis medium is coupled with an applied oscillating electric field inducing molecular rotations hence resulting in rapid heating of the liquid phase (Kerner, Palchik, & Gedanken, 2001).
Figure 3: Microwave-assisted solvothermal synthesis of MOF structures (Kerner, Palchik, & Gedanken, 2001).
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For the synthesis of microcrystals of Isoreticular Metal Organic Framework (IRMOF-1) dissolution of a mixture of an appropriate spacing ligand and a metal precursor in N,Ndiethylformamide (DEF) solvent. In order to create a homogenous seeding environment, the mixture is continuously stirred for about 15 minutes to get a clear solution (Jhung, et al., 2005).
H2BDC + Zn(NO3)24H2O
Zn4O(BDC)3(DEF)7
In a typical synthesis, an exact amount of benzenedicarboxylic acid (H2BDC) (0.033 g, 0.20 mmol) and Zn(NO3)24H2O (0.156 g, 0.60 mmol) is dissolved in 12 mL N,N-diethylformamide (DEF) resulting in a clear solution. The solution is heated in a microwave synthesizer for 25 seconds. After the microwave treatment a yellow suspension is formed. The product is centrifuged and redispersed in DEF by sonicating several times before analysis. The resulting suspended particles of IRMOF-1 are found to be micro-sized cubic crystals with an average size of 4 m (Kang, Park, & Wha-Seung, 1999).
2.2.2.3 Advantages
The advantages include: Fast crystallization and phase selectivity: microwave assisted synthesis has advantages in effectively saving reaction time, hastening the crystallization process, and producing phase-pure products of MOF materials in high yield and large scale. Narrow particle size distribution and facile morphology control. Controllable process: commercial microwave equipment provides adjustable power outputs and has a fiber optic temperature controller and pressure controller.
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The ability to produce new products: the growth process is not depending on nucleation on the walls or dust particles so it allows new types of MOFs to be discovered (Kang, Park, & Wha-Seung, 1999) (Jhung, Chang, Hwang, & Park, 2003).
2.2.2.4 Disadvantages
The disadvantages include: Limited reproducibility: hindering reproducibility is a main issue to be considered in microwave heating. The reaction conditions can by varied by controlling the temperature, reaction time, and irradiation power. Different instruments are unable to give the same conditions, ultimately hindering reproducibility (Kang, Park, & Wha-Seung, 1999). Dangerous process: microwave heating is dangerous. Heating a closed vessel containing volatile solvents and nitrates can cause an explosion. It creates hot spots that can accelerate the explosion. In particular the pressure in a vessel containing a volatile solvent can be much higher than with conventional synthesis (Jhung, Chang, Hwang, & Park, 2003). Not yet commercialized: High manufacturing risks and no commercial scale process yet seen light.
Table 5: Microwave Assisted Synthesis, advantages and disadvantages summary table.
Advantages Fast Crystallization Narrow particle size distribution Controllable process Producing new products
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In a sealed vessel, such as a bomb or autoclave, solvents can be brought to temperatures well above their boiling points by the increase in autogenously pressures resulting from heating. Performing a chemical reaction under such conditions is referred to as solvothermal processing or, in the case of water as solvent, hydrothermal processing (Yu, 2005). Solvents other than water can provide milder reaction conditions with lower energy requirements (Yang, 2006).
Stainless steel autoclave (1) Precursor solution (2) Teflon liner (3) Stainless steel lid (4) Spring (5)
MOFs, until now, have generally been prepared by either hydrothermal or solvothermal synthesis methods by electric heating in small scales. Solvothermal methods have a benefit of the sol-gel methods as well as a benefit of the hydrothermal methods. (Oliveira, Schnitzler, & Zarbin, 2003) Benefits are precise control over the size, shape distribution, and crystallinity of the nanostructures produced. Also, reaction temperature, reaction time, solvent type, metal salt and organic ligand precursors can all be varied in order to achieve the desired MOF specifications.
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2.2.3.1 Advantages
The advantages include: Proven technology in small scale: many different MOF types using different precursors and under different reaction conditions have been theorized and thoroughly tested in the lab. Leading technology: Opportunity to be a technological leader in this area. High Demand: Currently a demand for such a material that is currently not being met (Walton, 2013). Low energy consumption: the solvothermal method in particular requires low heat input to satisfy reaction temperature requirements (Yang, 2006). Milder reaction conditions: The solvothermal method generally requires milder reaction conditions, than hydrothermal, which allow the use of less costly equipment and lower capital cost (Yang, 2006). Precise specification control: MOF pore volume and structure can be more precisely controlled to obtain material best suited to the application it was designed for.
2.2.3.2 Disadvantages
The disadvantages include: Long reaction times: Reactions can take from hours to days to complete (Kang, Park, & Wha-Seung, 1999). Expensive equipment: Reaction pressures above atmospheric and nonstandard equipment increase capital costs.
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Unproven in large scale: Most MOF types have not been produced in more than gram scale quantities per batch (Kim, Hye-Young Cho, & Wha-Seung Ahn, 2012).
Advantages Proven technology Leading technology High Demand Milder reaction conditions Precise specification control
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A risk and value diagram also demonstrates the position of each process in terms of risk and value. The most favorable placement is for the upper right quadrant which designates lower risk and higher value.
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Electrochemical Synthesis
Micro-wave assisted synthesis Quick crystallization and selectivity Controllable process and process outputs Micro-wave heating produces dangerous fumes from volatile chemicals The use of microwaved processes require high caution and safety procedures. High manufacturing risks, no commercial scale process yet seen light High concern regarding hindered reproducibility caused by varying reaction conditions Not yet commercialized, financial indicators not available
Solvothermal synthesis
Faster than other conventional methods Less uniformity in final product Chemical treating procedures produce hazardous waste.
Long reaction times, can take up to few days Good control of product specifications Waste treatment is minimal.
Controllability of product
Environment
Safety risks
Commercialization
High cost, hence and obstacle for commercializing Regular replacement of main equipment components for this process Not yet commercialized, financial indicators not available
High demand product, several tech companies show interest At lab scale, reproducibility has been proven feasible
Economical profitability
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Table 8: Process Selection Matrix based on risk and value assessment according to aspect weight on process.
Selection Criteria Process Aspect (Risk Weight, Value Weight) Electrochemical Synthesis Risk Reaction Time (0.08,0.10) Specification Control (0.15,0.05) Environment (0.04,0.05) Safety (0.02,0.02) Scalability (0.2,0.15) Product Demand (0.14,0.3) Energy Usage (0.12,0.0.08) Proven (0.2,0.2) Capital Cost (0.05,0.05) Overall Score 4 4 Value 4 1 Microwave synthesis Solvothermal Synthesis
Risk 3 3
Value 3 3
Risk 2 4
Value 2 5
2 2 1 3
2 2 1 4
3 3 1 1
4 2 1 2
4 4 4 4
4 4 4 5
1 1 2.27
2 4 2.78
1 1 1.82
2 3 2.15
5 3 4.11
4 2 4.13
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High Value
Low
High
Risks
Low
Figure 5: Risk and Value four quadrant evaluation for the three processes.
Furthermore table 10 (see appendix) summarizes the grade point (out of 5) given by the five research team members based on thorough research summarized in the literature review section. The overall comparison of all three processes determined that the solvothermal synthesis process is the most favored due to the high controllability aspect of the product along with less environmental concerns regarding waste and by products. Also, financial indicators show that the solvothermal process can be a profitable one.
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Type of Raw Material Metal Salt (Soluble Metal) Ligand (Linker/Spacer) Solvent (Reaction Medium)
A calculation is included in the appendix of a basic mass balance around the primary reactor. The reaction equation for MOF 5 is used and a specified percent conversion of 95%. Selling price per kilogram of product is subtracted from the sum of the industrial market values of all reactants used in the process. Through calculation it was determined that 100 kilograms of MOF product could yield a maximum potential profit of $1027.50.
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R-100 is the major reactor proposed for the MOF manufacturing plant. The reactor will run in batch mode and is similar to an autoclave. Solvents are brought to temperatures well above their boiling points by the increase in self-generated pressures resulting from heating. The resulting solvothermal process is proven and has precise control.
Stainless steel autoclave (1) Precursor solution (2) Teflon liner (3) Stainless steel lid (4) Spring (5)
For the synthesis of microcrystals of MOF-5, mixture of an appropriate spacing ligand and a metal precursor in N,N-diethylformamide (DEF) solvent are mixed. 3H2BDC + 4Zn(NO3)24H2O Zn4O(BDC)3(DEF)7 + 7H2O
In the synthesis, a measured amount of benzenedicarboxylic acid (H2BDC) and Zn(NO3)2.4H2O is dissolved in N,N-diethylformamide (DEF) resulting in a clear solution containing MOF-5, DEF solvent and water (Strachan, et al., 2010). The bound DEF of the post reaction product will be removed during the methanol soaking process to result in a chemical compound of the form: Zn4O(BDC)3.
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3.1.2 Filtration
The filtration process is a very important part of the overall process since our product is moist sensitive and it is critical to remove all the water coming from the product (See reaction equation in section above) (Heinsmann, 1990) (Adedibu & Isaac, 2012). The input to the filtration system includes unreacted raw material such as the hydrated salt and benzenedicarboxylic acid along with the diethyl formamide (DEF). During the filtration process the major components being removed are water and the solvent DEF. It is of utmost importance to control the pressure of the vacuum filtration in order to avoid any damage to the crystal structure of MOF-5. Also during this process the filtered product is washed with methanol to remove most of the DEF solvent. 3.1.3 Drying
The drying process involves further removal of water at low pressure vacuum suction using and industrial dryer. The pressure applied mustnt exceed levels that would damage the crystal structures of MOF-5 (Adedibu & Isaac, 2012) (Heinsmann, 1990). 3.1.4 Soaking
The resulting crystals from the drying process are to be soaked with methanol to dissolve the DEF from the crystals and prepare the MOF for the final step of drying (Walton, 2013) (Adedibu & Isaac, 2012).
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3.1.5 Filtration
After the soaking process further filtration following the same filtration mechanism in the previous section. In this filtration process lower vacuum pressure is required since MOF-5 is at the final stages to be tested for pore volume and stability of structure. (Heinsmann, 1990) 3.1.6 Recycle Streams
Due to the high price of solvents and washing materials (DEF and methanol), recycling streams were added to the process. This addition will ensure the reduction of waste, and also help reduce the cost of the solvent and washing material.
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trapped methanol will be removed in order to achieve a porous MOF material (Adedibu & Isaac, 2012) (Walton, 2013).
3.3 Innovation
3.3.1 Process control and data analysis
The ability to control a process is highly dependent on a detailed understanding of the system behavior. Advances in sensor technology such as high speed cameras and thermal imaging are providing new levels of information for process modeling in cost effective ways. We now have access to continuous and distributed data instead of single point measurements. Moreover, the rate of data generated and stored has exploded in the last few years. Extracting useful information from process data is not a trivial task and requires complex data analysis techniques.
Todays world is far from linear and far from simple. MIMO (Multiple-Input-Multiple-Output) systems are processes that have numerous components that can interact in complex ways. Traditional engineering approaches focus on linearization and decoupling of these complexities. The solution used in our process will rise to the challenge by integrating advanced sensor technology with state-of-the-art data analytics and proprietary control algorithms to achieve better levels of process performance.
The proposed software solution for our plant will be called Industrial Internet of Things. A patented multi-dimensional non-linear software algorithm that would leverage big data information from industrial equipment and then based on the algorithms optimization capability, it will provide
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control input into the key devices that operate the manufacturing process. The end result would be a more efficient manufacturing operation, with improved productivity, increased quality, and lower costs (Everett, Dubay, & McKillop, 2013).
A large proportion of DEF solvent is required as reaction medium since, even at the elevated temperatures used in the reactor, the BDC ligand has limited solubility. Solvent recovery is a necessity both from an economic and environmental perspective. Post reaction the DEF and water mixture can be largely separated from the MOF product before the methanol wash. It is proposed that the use of a drying agent be investigated to separate the DEF from the water of reaction. The Merck data tables list distillation as well as CaH2 and molecular sieves as suitable DEF drying methods. The methanol used for post reaction washing and the DEF can be kept from mixing, for the most part, by running the post reaction DEF/water filtrate into a separate receiver than will be used to hold the methanol wash filtrate. The primary objective of solvent recycling will be to remove the water of reaction. Separated and dried solvents will be stored in holding tanks, where they can then be feed back into the process feed streams as needed (Merck, 2005).
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3.4.2 Environmental
One of the major factors that influences the design of the process are the issues with regards to the environment. Since this particular process deals with chemicals that are harmful to the environment a number of safety measures will prove to be a necessity. Since this process deals with hazardous and flammable material, therefore measures will be needed to be taken to ensure the safe handling of the hazardous wastes. Some of the means to ensure the safe handling of the wastes include: The methanol waste can be treated and recycled back into the process to reduce the overall hazardous wastes. This will reduce the overall flammable properties of the waste. The hazardous waste can be treated to make it environmental friendly and then disposed in the environment. This process is known as land treatment.
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4.0 References
Adedibu , T. C., & Isaac, A. Y. (2012). Synthresis and Applications of Metal Organic Frameworks Materials: A Review. Acta Chimica & Pharmaceutica Indica, 75-81. Ahmed, I., Jeon, J., Khan, N. A., & Jhung, S. H. (2012). Synthesis of a MetalOrganic Framework, IronBenezenetricarboxylate, from Dry Gels in the Absence of Acid and Salt. Crystal Growth and Design. Aldrich, S. (2013, 10 19). BASF Pricing. USA. Everett, S., Dubay, R., & McKillop, J. (2013, 11 6). Intelligent Controls. Retrieved from Eigen Innovation: http://www.eigan.co/ Heinsmann, B. (1990). Heuristics in Chemical Engineering. Boston: Butterworth Heinsmann. Jacoby, M. (2008, August 25). Heading To Market With MOFs. Chemical and Engineering News. Jhung, S. H., Chang, J.-S., Hwang, J. S., & Park, S.-E. (2003). Selective formation of SAPO-5 and SAPO-34 molecular sieves with microwave irradiation and hydrothermal heating. Microporous and Mesoporous Materials. Jhung, S. H., Lee, J.-H., Yoon, J. W., Hwang, J.-S., Park, S.-E., & Chang, J.-S. (2005). Selective crystallization of CoAPO-34 and VAPO-5 molecular sieves under microwave irradiation in an alkaline or neutral condition. Microporous and Mesoporous Materials. Kang, K.-K., Park, C.-H., & Wha-Seung, A. (1999). Microwave preparation of a titanium-substituted mesoporous molecular sieve. Catalysis Letters. Kerner, R., Palchik, O., & Gedanken, A. (2001). Sonochemical and Microwave-Assisted Preparations of PbTe and PbSe. A Comparative Study. Chemistry of Materials. Kim, J., Hye-Young Cho, & Wha-Seung Ahn. (2012). Synthesis and Adsorption/Catalytic Properties of the Metal Organic Framework CuBTC. Catalysis Surveys from Asia. Merck. (2005, 08). Drying agents. Retrieved from Merck Data Tables: http://www.mercuryltd.co.il/admin/userfiles/image/Information/Drying%20Agents.pdf Oliveira, M. M., Schnitzler, D. C., & Zarbin, A. J. (2003). (Ti,Sn)O2 Mixed Oxides Nanoparticles Obtained by the SolGel Route. Chemistry of Materials. Seda , K., & Seda, K. (2011). Biomedical Applications of Metal Organic Frameworks. Industrial & Engineering Chemistry Research.
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Strachan, D., Chun, J., Henager, C., Matyas, J., Riley, B., Ryan, J., & Thallapally, P. (2010). Summary Report for the Development of Materials for Volatile Radionuclides . Washington : US. Department of Energy Waste Forms. Walton, M. S. (2013, 09 25). CEO. (A-consulting, Interviewer) Wilkins, D. F. (2012, 08 15). MSDS. Retrieved from PromoChemOnline: promochemonline.com Yaghi, O. M., O'Keeffe, M., Cordova, K. E., & Furukawa, H. (2013). The Chemistry and Applications of Metal-Organic Frameworks. California: Science Magazine. Yang, F. X. (2006). Inorganic Solvents. European Journal Inorganic Chemistry, 2229. Yu, C. J. (2005). Crystallization Growth. Solid State Chemistry, 178,321.
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5.0 Appendix
Table 10: Process aspect grading points.
Electrochemical synthesis
Solvothermal synthesis
Average
Average
Average
Reaction time Controllability of product Environment and safety Commercializatio n Reproducibility Economical profitability
4 2
5 3
3 1
3 2
4 3
3.8 2.2
5 3
4 4
5 3
5 3
4 4
4.6 3.4
2 3
3 5
2 4
2 5
3 5
2.4 4.4
2.4
2.0
3.4
1.8
1.4
4.0
2 1
3 2
4 1
2 1
3 2
2.8 1.8
1 2
1 1
1 1
2 1
1 2
1.2 1.4
4 3
3 4
5 4
3 3
3 3
3.6 3.4
Overall average
3.0
2.8
4.2
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