Chemical Engineering Study Project 4

Chemical Engineering Study Project 4 (U04634)

Membrane Separations for CO2 Capture: Dual Stage Process simulations Paul Connaghan

S0820010

Abstract: The separation of CO2 from the flue gas of a 600 MWe Coal fired power station was investigated with the aim of achieving 90% recovery of CO2 and a permeate purity of 90% CO2. The separation was to be performed using a dual stage membrane process. A range of variables were investigated including membrane area, membrane configurations, sweep flowrates and pressure ratios. The dual stage process was able to achieve up to 89.57% recovery and 85.87% purity at a substantial energy cost. The dual stage process was deemed to be able to achieve the targets but not within acceptable limits.

Paul Connaghan s0820010 Submission December 2011 University of Edinburgh, School of Engineering (and Electronics)

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Table of Contents 1 2 Introduction ........................................................................................................................ 3 Literature Review ............................................................................................................... 4 2.1 2.2 Current Technologies .................................................................................................. 4 Theory of membrane separation units ......................................................................... 6 Membrane types ................................................................................................... 7 Models used ......................................................................................................... 8 Membrane parameters ........................................................................................ 11

2.2.1 2.2.2 2.2.3 2.3 3

Conclusion................................................................................................................. 13

Modelling Process ............................................................................................................ 14 3.1 3.2 Aims .......................................................................................................................... 14 Simulator Modelling Strategy ................................................................................... 14 Manipulated Variables ....................................................................................... 14 Monitored Variables .......................................................................................... 16 Key Performance Parameters ............................................................................. 17 Simulator Interface............................................................................................. 18

3.2.1 3.2.2 3.2.3 3.2.4 3.3 3.4 3.5 4

Results ....................................................................................................................... 19 Critical Review .......................................................................................................... 27 Conclusion................................................................................................................. 32

Appendices ....................................................................................................................... 33

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1 Introduction
A substantial amount of CO2 is produced through anthropogenic activities; In particular the amount produced through power generation. Power generation is estimated to account for up to 80% of worldwide greenhouse gas production[1]. Furthermore up to 25% of the energy supply and 40% of the emissions produced are generated by coal fired power stations and the rest largely through gas and oil [2]. With power demands increasing, especially within developing countries which have a plentiful supply of coal: the emissions from coal fired energy are set to increase by around 350% from 2000 to 2050 [3]. This represents an increase from 40% to 55% of total global power emissions [4]. The effects of CO2 on the mechanisms of global warming has not been understood fully as of yet but many climate models have shown that the continued increasing trends of CO2 atmospheric concentration will have a dramatic effect on the earths climate by 2100[5]. More and more governments and industries are looking for ways to reduce and limit their CO2 emissions due to increasing numbers of directives and protocols. As a result of these issues there is mounting pressure to find a way to sequester CO2 at an affordable rate. This report looks into sequestration of coal fired emissions and how to achieve a satisfactory degree of separation through membrane technologies. There are a number of options available for capturing the CO2 produced by coal fired power plants. The three main options as outlined by DOE [6] and the IEA [7] are: 1- Post-combustion CO2 capture from the flue gas produced 2- Pre-combustion CO2 capture from gasified coal synthesis gas 3- Oxy-combustion Fuel is burnt with almost pure oxygen to produce a high purity CO2 effluent Both pre-combustion and oxy-combustion can capture 90% of CO2 produced with a high purity [8] but are unable to sequester the CO2 produced by a direct fired coal power plant without further modifications [9]: pre-combustion requires gasified coal syngas to be prepared; oxy-combustion requires special equipment for N2 separation[10]; both require a turbine system for combustion. The vast majority of coal fired power plants are directly fired air combustion coal burning and this type will be continued to be constructed for the foreseeable future. With this in mind researching possible sequestration techniques for these

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standard air fired combustion systems is an important area if we are to try to reduce our CO 2 emissions. A number of techniques are available for post combustion CO2 sequestration which must deal with two main considerations: 1- Large flowrates of flue gas [4, 11] 2- The low partial pressures of CO2 in the flue gas The main sequestration method that is promising is the use of amine absorption. This is a proven technology which has been used for many years for industrial applications; however, when used for power plant sequestrations it will be costly and energy intensive. Use of this technology could result in a rise in cost of energy anywhere between 50-90% which is undesirable[4]. Membranes are a developing area with respect to CO2 separations. They are a promising candidate for this process due to a number of advantages: the ability to deal with large flows; lack of moving parts means lower maintenance costs; a very small footprint. There is much doubt as to whether membranes can be used to achieve the separation realistically. Although they have many advantages, the use of a single membrane unit is insufficient for achieving the necessary separation and we must look to dual stage processes for the feasibility of achieving DOE targets [12]. There are a number of key factors that can affect a dual stage process and all of these must be investigated if the process is to be competitive.

2 Literature Review
2.1 Current Technologies
There is a lot of effort being put into developing gas separation techniques as these are used in so many different industries and processes. Furthermore to this, a lot of effort is being put towards developing techniques for the separation of CO2 due to increasing pressure on industries and the apparent criticality of the CO2 emissions. As mentioned before the increasing pressure on reducing CO2 emissions to the atmosphere has bolstered the research performed in the area of CO2 separation. The three main options for reducing CO2 emissions as produced through power generation are as follows[8]:

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Reduction of energy intensity Reduction of carbon intensity Enhancing CO2 sequestration

As power generation from fossil fuels is a mature technology there is little in the way of substantial improvements that can be made in the efficiency of existing power stations and therefore we must look to points two and three for improvements[8]. Reduction in carbon intensity is not feasible for fossil fuel schemes; however, improvements could be made through partial or complete use of renewable sources such as biofuels or wind energy. Again this has little potential when looking into existing power stations as it would require costly modifications to existing plants[9]. In order to have a sizeable impact on current CO2 emissions, sequestration needs to be investigated. There are a number of technologies currently being researched for post combustion CO2 sequestration. The most mature is chemical absorption and the most extensively studied within chemical absorption is monoethanolamine (MEA) absorption[8], which has been used for many years in industries for a range of separations including CO2 recovery and natural gas sweetening [9]. Amine absorption has been a prime candidate for CO2 sequestration for some time. Some of the advantages associated are that it is a well developed technology which is highly selective and can produce high purity CO2. However, it carries numerous disadvantages such as large energy penalties, large plant footprint, degradation of material and equipment and a low CO2 loading capacity [8]. The energy penalty and running costs incurred through amine absorption is severe and questions the overall feasibility of the process. Membranes themselves are a somewhat mature area of technology with 20 years of commercial experience and 50 years of development [13]. Loeb and Sourirajan first created high flux anisotropic membranes with large surface area capabilities in 1960 which attracted considerable interest due to applications to reverse osmosis[13]. Permea adapted the Loeb Sourirajan membrane to produce the worlds first commercially available membrane, Prism, in 1980. This was successfully applied to H2 recovery processes and showed the potential of membranes for performing low cost separations. There has been substantial research into membranes over the past 10-15 years as the market share has grown rapidly to an estimated 2-3 billion per year[14]. The majority of the research has been focused on advancing the Page | 5

permeability and selectivity of membranes; two key properties for any separation. Advancement on this front has been limited with the exception of some membranes which are in early stages [15], and will most likely not be ready for commercialisation for some time. Some success has come from development of hybrid membranes which can combine optimal features from two or more membranes with impressive properties. It has been suggested that for significant improvement a deeper understanding of the transport on a molecular level should be sought after[16], which suggests that our current understanding and models of the transport within membranes is insufficient. As mentioned before, membranes are already in widespread use in industry; one of the greatest benefits from membranes is the process intensification scale that can be achieved due to their small footprint and efficiency. The use of membranes in water desalination can yield a process 10 times more energetically efficient than thermal options [16] and Baker [17] states that 5000-10000 N2 separation units are in operation worldwide and account for 1/3 of N2 production. The application of membranes in the sequestration of CO2 is a relatively undeveloped area compared to industrial applications. Much research has been done to try and ascertain the feasibility and optimum processes for it but little has been done in the way of larger scale investigations. A pilot plant was constructed in 2008 in Arizona, Cholla, to test a membrane separation process on the flue gas stream of a 995MW power plant [18]. The project is looking to investigate a 6 month operational period with emphasis on the cost efficient fabrication of a membrane skid and assessing the performance of the membrane. A map of cost reductions for feasibility will also be generated. The initial results are promising with respect to contaminants such as SOx within the process but the overall results are limited as of yet. Another pilot plant has been constructed and reported on in Australia but there is limited data as to the success of it [19]: CHEMECA [20] stated that it was producing purities in the range of 20-50% but with no specifications on the recovery achieved, it can be assumed that the process is achieving 90% recovery.

2.2 Theory of membrane separation units

Membranes have been used for many years to perform separations on a variety of fluids [21].As discussed in section 2.1 some processes are well defined and have been optimised over many years and some are emerging technologies which require much research. There is

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a substantial amount of theory surrounding membrane separation which must be understood if any process is to be correctly modelled.
2.2.1

Membrane types

The basis for all membrane separations is that there are two process streams divided by a permeable wall, or membrane. The structure of the membrane can vary greatly depending on what material it is constructed from but the membrane types largely fall into two categories: porous and dense. Porous membranes are those which have many pores permeating through the membrane, these are analogous to a conventional sieve or filter; it is by these pores that the membrane is able to separate different gases. Figure 1a shows a porous membrane; the separation takes place chiefly by physical size separation where smaller molecules will be able to pass through the pores and larger ones will be unable to fit through, the driving force is primarily the pressure gradient and molecular motion of the gaseous species. Due to the pore sizes used (20 - 1000+ [13]) these membranes are used for separation of large molecules such as colloidal mixtures or bio molecules such as proteins[22].

Figure 1 [13] - (a) porous membrane (b) dense membrane

Dense or polymeric membranes consist of a dense polymeric material which separates gaseous molecules by allowing certain species to preferentially adsorb and diffuse through the membrane; this can be seen in figure 1b. The separation will therefore not only work on the basis of size but will favour different molecules; this is advantageous when separating molecules of similar size such as in flue gases. The driving force for dense separations relies on the chemical potential gradient of the species in question. Dense membranes will be

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focussed on in this paper as these are the most promising membranes for a commercially viable gas separation process[21].
2.2.2

Models used

There have been a number of models used to describe the diffusion of species through membranes. The modelling process carried out in this simulator must be understood if an investigation is to be successfully carried out. The relationships used to model the process are laid out in this section. The models used to describe porous membrane transport are problematic; as of yet no unified theory has been accepted for widespread use[13]. This is largely due to the heterogeneous nature of porous membranes, as seen in figure 1a. Another difficulty is the lack of a satisfactory set of parameters that can be used to correctly characterise porous membranes. As discussed in 2.2.1 porous membranes are unable to separate gaseous mixtures due to the limiting size of the pores and as such will not be discussed any further. The model used to describe transport through polymeric membranes is known as the solutiondiffusion model. This has been developed through a series of improvements over a period of 20 years from 1960-1980 [13]. The transport of gaseous species through a polymeric film can be seen to happen in 3 main steps: 1- The molecule is absorbed into the membrane feed surface and dissolved into the polymer 2- The molecule diffuses through the polymeric membrane 3- The molecule is desorbed from the permeate side of the membrane The absorption and desorption of the molecule is relatively simple to model and can be represented by the conditions (Temperature, Pressure and Concentration) of the membrane feed and a characteristic known as the sorption coefficient. This will be covered in more detail later. The diffusion of a gaseous molecule through a polymeric membrane entails the molecule moving through the empty spaces created by the thermal movement of polymer chains, known as the free volume [13]. The relations used to describe the diffusion through a membrane start with the proposition that the driving force for the gaseous species is dependent on the chemical potential. The use of chemical potential effectively links the Page | 8

temperature, pressure, concentration and electrical potential together as can be seen in equation 2 and 3. By using the observation that the movement of a species from a high to low concentration is governed by Ficks law we obtain equation 1[13] to describe species flux across the system: (1) Where Ji is the flux of component i, Li is the coefficient of proportionality and i is the chemical potential of component i in the membrane, R is the molar gas constant, T the temperature and ni the number of moles of component i. It can be seen that an expression describing the component concentration gradient within the membrane is required to model the flux of species i. This is acquired using the chemical potential of the species throughout the membrane. The chemical potential of the species is equated at the membrane feed interface: the feed gas phase is taken as a compressible fluid; the membrane phase as an incompressible medium. The chemical potential of each phase can be seen in equations 2 and 3 [13]: Incompressible medium - (2) Compressible fluid - (3) Here, i represents the activity coefficient of component, vi the molar volume and p the pressure. A superscript o indicates a reference value and a subscripted o indicates the feed interface with subscripted m indicating the membrane phase. Equations 2 and 3 can be rearranged to provide an expression for the concentration of the species in the membrane as shown in equation 4 which is simplified due to the exponential term being very close to one: (4) By calculating the concentration of component i from equation 4 and combining the terms for the feed-membrane and membrane-permeate interfaces and then combining this with equation 1 we can arrive at equation 6 which fully describes the flux across the membrane. A sorption coefficient has been defined as in equation 5:

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(5)

(6) Here, m denotes the molar density of component i and Di the diffusion coefficient. l is the thickness of the membrane. The subscripted l indicates the permeate side of the membrane. In equation 6, KiGDi are combined to give the permeability coefficient of the gaseous species. Similarly, an expression can be derived describing the permeate-membrane interface. In order to model the flux across the membrane system a mass balance is used; a mass balance is constructed over both interfaces of the membrane. The mass balance for the feed side can be seen in equation 7, the mass balance for the permeate side has a positive flux as components are flowing into it. The system is treated as a 1D plug flow scenario; other assumptions taken are that the system is isothermal, isobaric, the gases behave ideally and that there is constant permeability. (7) In equation 7, the permeability coefficient and the thickness are combined in order to give the overall permeance of the membrane with respect to species i, ; the permeance is analogous to the permeability of a membrane. Furthermore, to allow consideration of other components the permeance of component i is taken as the key permeance and a dimensionless ratio known as the selectivity is defined, . This relates the permeance of each component relative to component i. A more thorough explanation of the modelling of membrane processes can be seen in [23]. The simulator uses the backwards finite difference method to solve the mass balance over the interval. This method uses two calculated points and a solution interval to solve to varying levels of accuracy. By calculating F at each point and taking the difference between these points the method can approximate the gradient of the function (in this case dF/dA). This is solved iteratively until the values are in close agreement. One step of the method can be seen in equation (8): (8)

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Where h is the step size and relates to the interval between j and j-1. The smaller the step size the greater the accuracy that is achieved.
2.2.3

Membrane parameters

It is obvious the flux of any species will depend heavily on many factors. Significant research has been done into the effect these parameters have on membrane separations. This section looks at reported trends and the reasons for any relationships present. Membrane - Arguably the most important feature of any membrane process is what membrane and therefore what selectivity and permeance is being used. If a process is to meet the targets set by the DOE then the optimal values for permeability and selectivity will need to be chosen. It has been shown that an increase in permeance will give an increase in recovery [4, 12]. This can be explained through equation 7 which shows the permeance being directly linked to the flux and therefore the recovery of CO2. Merkel also shows that an increase in permeance of 400% will lead to a lower capture cost by approximately 50% [4]. It can be seen that increasing the permeance will slightly lower the purity of the captured CO2 but to an almost negligible degree; conversely by altering the selectivity we can change the purity but with negligible effect on the recovery [12]. As discussed in 2.1 these values are set by the membrane used and are therefore relatively rigid with respect to membrane processes. Membrane Area - The area of the membrane used has been mainly used as a benchmark for the success of a process. This largely holds true for processes as the capital cost of membranes is prohibitive; the polaris membrane can cost upwards of $50/m2 [4], this can be very expensive when membrane areas reach into millions of m2. A well reported trend is that with an increase in area the recovery of the process will increase and the purity of the permeate will decrease [4, 12]. Membrane Configuration - One parameter with countless different options is the configuration of the membrane units along with the use of either compression or vacuum to drive the flow. Zhaos paper looks into the use of different configurations of compressors and vacuums used to achieve 70% recovery [24]. The variation of configuration leads to large differences between the energy and the area required for the (Area varying from 19m2 to 404m2, energy use varying from 113kWh/te to 312kWh/te): the key result being that there is a trade off between area and energy use. Using a vacuum pump is attractive as although vacuums are usually more energy intensive to produce the equipment will have to deal with a Page | 11

lower flowrate as it is being place on the permeate stream which should lead to lower energy consumption, however [14] shows that with vacuum suction a larger area will be required leading to another trade off between favourable values. A key area with less research done is the actual configurations and how they can be varied with respect to recycle streams and what effect this has on the efficiency of separation [25]. This is to be looked into in depth in this report and the results analysed.[12] shows that with a single membrane we cannot expect to achieve both high recovery and high permeate purity within an acceptable cost. This well researched finding has meant that more and more research is being done into dual and triple stage separations. With this a much higher separation can be achieved but with the key result of more energy being used as compressors and vacuums are needed for each stage. Sweep Configuration - The use of a sweep stream and the recycling of streams has had some investigation but the effect of differing compositions of sweep stream on the separation has not been fully researched yet. The typical sweep stream used is a set amount of the retentate stream. The flowrate of the sweep stream can also have an effect on the separation as this will directly affect the PPDF of the species and therefore warrants investigation. Temperature - The temperature and pressure of operation are also extremely important parameters as they can have significant effects on the results of the separation. The temperature can be seen to have a direct affect on the flux achieved through equation 7; this is closely linked to the idea of thermal motion and the fact that a higher temperature will lead to larger molecular motions. The actual operating temperature is fairly limited by the membrane being used; most membranes are not able to withstand elevated temperatures and could experience adverse performance if used out with close to ambient temperatures. Due to this, there has been very little work done on the effect of temperature on the separation achieved and it is unlikely that there is much to be done in this area. The development of new, more robust, membranes able to withstand higher temperatures whilst still possessing desirable permeance and selectivity would warrant further investigation into this area; inorganic membranes have been tested at temperatures as high as 600C while polymeric membranes area usually limited to around 200C [13, 16]. Pressure - The pressure operated at is a major factor for separations as this not only has a direct effect on the separation achieved but heavily influences the power consumed. Much Page | 12

work has been done into operation at different pressure ratios[4, 12]. The pressure ratio can be seen to limit the concentration enrichment attainable through equations 9 and 10[4]. These show that the concentration enrichment cannot exceed the pressure ratio between the feed and permeate. Merkel has shown that with an increase in pressure ratio the energy required to achieve 90% recovery increases but the area also decreases [4]; the optimum ratios were identified at values between 5 10. (9) (10)

2.3 Conclusion
As shown in this section, there has been a lot of work done in the area of CO2 sequestration with many different technologies being investigated. This creates a very competitive environment for achieving satisfactory separations. The options of pre and oxy combustion are becoming more attractive with respect to building a new power plant but the end of pipe techniques for post combustion should not be overlooked. The theory behind membrane transport has been heavily researched over 50 years and can describe membrane processes well but little knowledge is possessed of detailed molecular movements during separations. With the introduction of supercomputers this is being developed and may yet yield results which are able to be applied to new membranes. Membranes have been developed commercially over the past 30 years for separations of many kinds with some becoming industry preferred choices. The separation of CO2, however, is relatively undeveloped and although much work has been done in the area, still requires progress if it is to compete with the alternatives. The successful trial of pilot plants will demonstrate the actual effectiveness of membranes for separation of flue gases and will be key to determining whether further research could yield results. From the work done so far on membrane separations of CO2 from flue gases it seems unlikely that the targets required by the DOE will be able to be met by membranes within the near future; a significant breakthrough is required if membranes are to become competitive with other technologies.

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3 Modelling Process
3.1 Aims
The aim of this process was to model dual stage membrane separation simulations using the Unisim design R400 package. The separation was to be performed on the flue gas stream of a 600 MWe plant as specified by the DOE report [11]. The feasibility of achieving 90% recovery and 90% permeate purity of CO2 using two membrane units was investigated. The parameters investigated ranged from membrane configuration to pressure ratio and can be seen summarised in section 3.2.3. A number of key aspects of the process are to be monitored including CO2 recovery, permeate purity and energy use.

3.2 Simulator Modelling Strategy

As shown in section 2.2.3 there are a number of key variables to be investigated in order to find the optimum configuration of a dual stage membrane process. The method of investigation of these variables is set out in this section. As many papers have investigated obtaining high recovery (70/90%) and economic energy use with little focus on the permeate purity this report will chiefly aim to achieve the DOE targets of 90% recovery and 90% permeate purity and then look into the power consumed. When using dual stage membrane processes it is important to note that one membrane will typically be deemed the high recovery membrane and one the high purity membrane. The high recovery membrane will be the membrane which has the retentate exiting the process; this membrane requires high recovery because as much CO2 needs to be removed as possible before discharging the retentate to the atmosphere. The high purity membrane is the membrane which has the permeate stream going to sequestration: high purity is required here if the DOE targets are to be met [11]. Examples of high purity and high recovery membranes can be seen in figure 2c; the membrane with streams 1 and 2 entering it is the high recovery membrane and the membrane with stream 5 entering is the high purity membrane.
3.2.1

Manipulated Variables

There are a number of variables that should be manipulated in order to ascertain their effect on the success of the separation process and find the optimal setup for a dual stage process.

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Membrane Configurations - The first area to be investigated was the use of different configurations for the membrane unit. As each unit has four streams associated with it this gives rise to a large number of possible configurations that could be used. Not all of these configurations will give useful or indeed meaningful benefits to the separation. A total of 5 configurations have been chosen for investigation as these have been specified as promising arrangements in Agrawals paper [25]. These can be seen in figure 2:

Figure 2 [25]- Membrane configurations

Investigating these configurations will allow the optimal arrangement to be determined with respect to the key performance parameters. Each configuration will have the sweep fraction, flowrate, membrane parameters and pressure ratio held constant and the areas varied until 90% recovery has been achieved. This should allow an effective comparison of the ability of each configuration to achieve the separation. For the first membrane unit in figure 2c stream 1 is the feed, stream 2 the sweep, stream 3 the retentate and stream 4 the permeate. Membrane Area As discussed in section 2.2.3 the area of the membrane used in the separation has a direct effect on the separation achieved. Membranes can generally achieve a high recovery through utilising a large area which is able to recover most of the CO2 passing over the membrane; a consequence of equation 7. The area of each membrane in the configuration will be altered from the lowest possible (some membrane areas are unstable and cannot be solved with this simulator, this is discussed further in section 3.4) to a sufficiently high value. The effect this has on both the recovery and permeate purity will be determined for both high purity and high recovery membranes.

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Sweep Flowrate Fraction The sweep flowrate fraction is an important variable. The fraction is as defined in equation (11) and directly affects the process. The sweep flowrate fraction is the molar flowrate percentage based on the feed. (11) Where n dot represents the molar flowrate of the stream. The effect on the process is derived from the PPDF governing the transport. By either changing the flowrate of the sweep gas or its composition we can directly affect the overall PPDF and therefore the flux through the membrane. By using a high sweep flowrate fraction (typically 10-20%) the recovery of a membrane can be increased. A lower sweep fraction is utilised in high purity membranes: typically 0-100 mol/s or less than 1% is used. These will be varied from 0-2% for the high purity membrane and 0-20% for the high recovery membrane. Pressure ratios The use of pressure ratios is an important aspect of membrane separations as this can greatly affect the requirements of the process. A larger pressure ratio will mean that a lower area is required for the same recovery. This is a direct result of the pressure ratio issue discussed in 2.2.3, equation 10. Using a larger pressure ratio will lead to increased running costs as the energy consumed by the compressors accounts for the majority of the overall energy use. The pressure ratio will be varied from 5 to 10 (corresponding to a change in inlet pressure from 110 kPa to 220 kPa where the outlet is kept constant at 22 kPa), this has been deemed as the suitable limit for pressure ratios with respect to power consumption[4]. Membrane Selectivity and Permeance The selectivity and Permeance of membranes are determined by which membrane is being used and as such the actual values feasible in reality are limited. The values used for the majority of the report are those of the Polaris Membrane which has a CO2/N2 selectivity of 50 and a CO2 permeance of 1000 GPU [4]. A theoretical membrane is also investigated which has a selectivity of 100 and a permeance of 12000 GPU, this has been named PIM + + and utilises the permeance of a membrane known as PIM [15] and the selectivity which has been deemed the optimal limit attainable.
3.2.2

Monitored Variables

In order to successfully analyse this simulation a number of variables need to be monitored and analysed to provide key performance parameters as discussed in section 3.2.

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The first and foremost variable to be monitored is the flowrates into and out of the membranes. The molar flowrate of each component should be recorded for the feed stream, sweep stream, permeate stream and retentate stream. By monitoring all of these flowrates we can determine the necessary key performance indicators. The simulator used had a built in spreadsheet function that allowed all molar flowrates to be measured and dynamically displayed. This ensured all variables could be recorded and key performance indicators calculated efficiently and swiftly. The power consumption of all units was monitored. All compressors were taken as a positive power consumption owing to the energy required to raise the pressure of components. The power consumption of turbo expanders was taken as negative owing to the energy released when a gases pressure is reduced.
3.2.3

Key Performance Parameters

Certain key performance parameters were to be calculated in order to ascertain the success and feasibility of the separation achieved. The key performance indicators for this process are defined as the recovery, the permeate purity, the retentate purity and the overall energy use. The recovery is defined how much of the CO2 entering the process is recovered in the outgoing permeate stream (stream 7 in figure 2c). The recovery was calculated as in equation (12): (12) The permeate and retentate purities were taken as the mole fractions of the corresponding streams with respect to CO2 (streams 3 and 7 respectively in figure 2c). This could be easily calculated using unisims spreadsheet function and equation (13): (13) The overall power consumption of the process was determined simply by measuring the power consumption of individual compressors and expanders and combining them as laid out in 3.2.2 and equation (14): (14)

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Another useful indicator for comparison between processes is the energy required to capture one mole of CO2, or the specific power consumption. This is easily worked out from the data gathered and is defined as in equation 15: (15)
Table 1 - Summary of Variables

Manipulated Variables Membrane area Membrane Configurations As seen in figure 2

Monitored Variables Molar Flowrates Feed Stream Sweep Stream Permeate Stream Retentate Stream

Key Performance indicators CO2 Recovery Permeate purity (CO2 content) Retentate purity (CO2 content) Overall power consumption Specific Power consumption

Sweep Flowrate Fraction Permeate and Feed side pressures Membrane Selectivity and Permeance 3.2.4

Power Consumption

Simulator Interface

The simulator used was an addition to the design program, Unisim Design R400. It was developed by the University of Edinburgh to model membrane separations with a focus on CO2 from flue gas streams. The interface consisted of 4 panels. The first panel allowed the user to connect feed, permeate, retentate and sweep streams to the unit operation. The second panel allowed the user to enter the parameters of the membrane: area, key permeance, selectivity of each component. The third panel allowed the user to set the number of grid points used int he solving mechanism. The fourth panel was the standard Unisim worksheet panel and allowed the user to monitor all streams entering and leaving the membrane. The interface of the membrane unit was well integrated into the Unisim environment and was able to be understood quickly with a basic knowledge of Unisim. The interface panels can be seen in appendix IIIa. As mentioned in 3.2.2 the spreadsheet function was used to aid data gathering. The spreadsheet layout can be seen in appendix IIIb. All relevant details are easily observed and key performance parameters are calculated automatically. Page | 18

3.3 Results
Initially all 5 configurations were investigated to try and ascertain which was the most efficient at achieving 90% recovery of CO2. The permeate purity was to be investigated afterwards. The results of attaining 90% recovery can be seen summarised in table 2:
Table 2 - Configuration Investigation

Configuration

Area 1

Area 2

Total Area

Recovery

Permeate purity

Retentate Purity

Power consumption

Specific

Power

consumption

x105m2 x105m2 1 2 3 4 5 50 22 43 5.5 2.7 6.1 4.2 2.75 42 43

x105m2 % 56.1 26.2 45.75 47.5 45.7 83.53 90.76 90.12 90.17 90.09

% 51.95

% .5/8.39

x100MW .9714 0.62 1.335 1.264 1.295

kJ/mol CO2

39.62 20.41 50.45 47.76 48.9

33.57/9.236 1.75 63.76 63.28 63.69 1.128 1.142 1.221

It should be noted that the pressure ratio for each configuration was kept at 5 (inlet pressure of 110 kPa; outlet pressure of 22 kPa) unless stated otherwise. It can be seen from table 2 that configurations 3,4 and 5 are all promising configurations as they are able to achieve 90% recovery with a substantial permeate purity. Configuration 1 is by far the weakest. This required the largest area of all configurations, was unable to achieve 90% recovery (partially due to simulator stability issues discussed later) and gave a retentate stream with too high a CO2 content. Configuration 2 was promising with respect to achieving 90% recovery at a low energy cost and membrane area but was unable to produce a satisfactory permeate purity. Configurations 1 and 2 are unable to achieve satisfactory retentate or permeate streams due to the well known issue mentioned in Zhao [12] stating that 1 membrane unit is unable to provide both recovery and purity, showing that both a high recovery and high purity membrane area required. Configuration 1 can achieve a low retentate purity at first but is unable to recover much in the second membrane if purity is also desired here. Configuration 2 can recover a large amount in both but again but will not be able to provide high purity at the same time. Configurations 3, 4 and 5 are all comparable as the areas are similar and specific power consumption is also similar. Configuration 4 would seem to be the most attractive at this Page | 19

point due to the lower specific power consumption (~4% lower than 3 and 5) which would most likely be the deciding factor due to the overall similarity in membrane areas. All retentate purities are acceptable as they are below 2%. The permeate purities here appeared to reach a practical limit approaching 65% and surpassing this value seemed problematic. It should be noted that the pressure ratio issue discussed in equation 10 does not limit this process. Although the input concentration of CO2 is 14.1% which would suggest a limit of 70.5% at a pressure ratio of 5, the use of two membrane units and a recycle loop changes this as the feed to the high purity membrane will be significantly higher, around 40% in most cases, which theoretically allows the process to surpass 90% purity. From the results for achieving 90% recovery of CO2 with each configuration it can be seen that configurations 1 and 2 are not able to fulfil the DOE goals adequately due to the insufficient retentate or permeate purity issues as discussed above. From these results 3,4 and 5 are the most promising and these will be taken forward for further investigation. The next stage was to investigate the effect of changing the area of the membrane. Initially the area was varied and all relevant key performance indicators calculated. The results of varying the area can be seen in figures 3 a,b and c; it should be noted that the numbers next to each point correspond to the area of the membrane measured in 105m. All parameters were kept at the values in table 2 unless being altered. It should be noted that not all values recorded are included in this section and certain values have been omitted for the sake of clarity. All recorded values can be seen in appendix IV which is on a data CD. For more detailed information on the position of compressors and expanders appendix IIIc should be examined, this is also on the data CD.

Page | 20

72 Permeate purity (%CO2) 67 62 57 52 82

Figure 3 a - Configuration 3 area change

purity membrane area recovery membrane area

84

86

88 Recovery (%)

90

92

94

68 Permeate Purity (%CO2) 66 64 62 60 58 56 82 84

Figure 3 b - Configuration 4 area change

purity membrane area

recovery membrane area 86 88 Recovery (%) 90 92 94

66 65 64 63 62 61 60 59 58 57 56 82 84

Figure 3 c - Configuration 5 area change

purity membrane area

Permeate Purity (%CO2)

recovery membrane area 86 88 Recovery (%)

Figure 3 - (a)(b)(c) effect of changing membrane areas

90

92

94

The variables changed in figure 3 a,b and c were: The area of the purity membrane The area of the recovery membrane Page | 21

All 3 configurations can be seen to obey similar relationships; with an increase in the purity membrane area the recovery will increase but the permeate purity will decrease. This has been widely reported as a standard trend and can be linked to equation 7 [4, 12]. By increasing the area of the membrane, the flux of CO2 is increased leading to a higher recovery. However, by increasing the membrane area, the flux of other molecules (in this case H2O, N2 and O2) also increases, leading to a decrease in permeate purity as the CO2 concentration is diluted. The specific power consumption falls with an increase in the purity membrane area, this is due to the increased flux across the membrane. This will not only lead to more power recovered from the expander operating on the permeate stream but the larger amount of gases removed from the process will mean that less compressing power is required in other streams such as the recycle. The configurations can also be seen to increase in recovery and permeate purity if the area of the recovery membrane is increased. This is due to the fact that a larger area will allow a larger CO2 flux as shown above, again leading to an increase in recovery. This sends more CO2 to the high purity membrane and as the purity membrane area is constant causes the recycle stream and therefore the feed stream to be richer in CO2. The increased CO2 content passing over the high purity membrane causes an increase in CO2 purity in the permeate stream. This trend would most likely have been different if configurations 1 and 2 had been investigated. The lack of recycle would have caused the permeate purity to decrease slightly as the feed would not have been as rich in CO2. The expected result here would have been for the recovery to increase and the purity to decrease as has been shown in literature [4], this highlights the importance of the recycle stream. An increase in the size of the recovery membrane causes an increase in specific power consumption as the larger membrane flux creates a much larger recycle stream which needs to be recompressed before entering another membrane. The trends do not behave ideally as a straight line would be expected. This can largely be attributed to the simulation solver, equation 8 in particular, and is discussed further in 3.4 The next step was to investigate the effect that changing the flowrate of the sweep stream had on the separation process. The investigation into the sweep stream can be seen summarised in figure 4 a,b,c where the numbers on the graph correspond to the sweep flowrate fraction:

Page | 22

Figure 4 a - Configuration 3 Sweep change

67 66 65 64 63 62 61 60 59 58 57 56 76 78 80 82 84 86 Recovery (%) 88 90 92 Permeate purity (%CO2) recovery membrane sweep fraction

purity membrane sweep fraction

Figure 4 b - Configuration 4 Sweep change

68 Permeate purity (%CO2) 66 64 62 60 58 56 75 77 79 81 83 85 Recovery (%) 87 89 91 93 purity membrane sweep fraction recovery membrane sweep fraction

Figure 4 c - Configuration 5 Sweep change

68 Permeate purity (%CO2) 66 64 62 60 58 56 54 76 78 80 82 84 86 Recovery (%) 88 90 92 purity membrane sweep fraction recovery membrane sweep fraction

Figure 4 - (a)(b)(c) Effect of changing the sweep fraction

The variables changed in figure 4 a,b and c were: The sweep flowrate fraction of the purity membrane The sweep flowrate fraction of the recovery membrane Page | 23

Again all three configurations can be seen to obey similar relationships. When the sweep flowrate fraction of the recovery membrane is increased, the recovery and permeate purity can be seen to increase. This is due to the CO2 concentration being decreased in the permeate side due to the increased air flowrate; this causes a larger PPDF and increases the CO2 flux across the membrane leading to a higher recovery. The increased CO2 feed to the permeate membrane causes a higher CO2 flux relative to other components leading to a higher permeate purity. The increased CO2 content also passes on to the recycle leading to a higher feed content of CO2, these two effects act together to increase both the recovery and purity. The specific energy consumption of process rises with an increase in recovery membrane flowrate as this allows more gas into the system to be recompressed for the second membrane and also leads to a larger recycle stream. An increase in the sweep flowrate fraction of the purity membrane can be seen to cause a slight increase in recovery and a decrease in purity. The dilution of the CO2 concentration due to the increased air flowrate leads to a lower permeate purity and this causes a larger PPDF which allows a larger CO2 flux which causes the increase in recovery. This is compounded by the lower CO2 content in the recycle further leading to a decrease in permeate purity. The specific power consumption for an increase in purity membrane sweep flowrate fraction decreases as the larger flow exiting in the permeate stream allows more energy to be recovered from the turbo expander downstream. An interesting result in changing the recovery sweep fraction is that the recovery can be seen to decrease after a certain value (may not be completely clear here due to accuracy issues). This is most likely due to the fact that increasing the sweep flowrate will eventually lead to the PPDF being decreased due to the CO2 content in the air sweep stream. The trends observed here are largely the same when repeated at a pressure ratio of 10, however the point at which a configuration reaches a maximum with respect to recovery can be seen to change significantly (at a pressure ratio of 10 the maximum was 6.7% as compared to a maximum at 13% for a pressure ratio of 5). Configuration 4 would appear to be different in that the recovery does not tail off as it does with configurations 3 and 5. Configurations 3 and 5 can be seen to reach a limit of recovery at different sweep flowrate fractions (13% for configuration 3 and 17.7% for configuration 5) and therefore it can be assumed that the range of investigation was not large enough to allow the maximum to be reached for configuration 4. Page | 24

The key result from these investigations is the knock-on effect of the recycle and the fact that this can change reported trends. The next step was to investigate the effect that changing the pressure ratio had on the processes, this can be seen summarised in table 3:
Table 3 - Pressure ratio investigation

press area
Config.

Total Area
2 5 2

Recover y %

Permeate mol frac

%CO2

Retentate mol frac.

%CO2

energy use
x100MW

pressure in
kPa

pressure out
kPA

ure ratio 5 10 5 10 5 10

area 1
x10 m
5 2

2
x10 m
5

x10 m

3 3 4 4 5 5

43 13.5 5.5 1.25 2.7 1

2.75 1 42 16.5 43 15

45.75 14.5 47.5 17.75 45.7 16

90.02 90.22 90.7 89.99 90.09 90.82

63.76 76.6 63.39 78.15 63.69 75.55

1.128 1.198 1.147 1.146 1.221 0.8409

1.335 1.995 1.268 2.595 1.295 2

110 220 110 220 110 220

22 22 22 22 22 22

The area required for each configuration to achieve 90% can be seen to drop drastically; by around 65% for each configuration, this represents substantial capital cost savings in a membrane process. This is due to equation 7 and the PPDF increasing meaning that a smaller area is required to provide the same CO2 flux relating to 90% recovery. The downside to increasing the pressure ratio is the substantial increase in energy use due to the additional compression; an increase of 49%, 104% and 54% for configurations 3, 4 and 5 respectively. The permeate purity is increased which is most likely a result of the pressure ratio discussed in equation 10. By doubling the pressure ratio the concentration enrichment possible is effectively doubled as well which leads to a higher permeate purity. The retentate can be seen to remain relatively constant. A decrease in retentate purity is seen in configuration 5 and can be explained due to the increased recovery leaving a lower CO2 flow in the retentate. The effect of changing the sweep stream from an air stream to the recycled retentate stream was then investigated. This is effectively splitting stream 6 in figure 2c and recycling this to streams 2 and 8 to be used as the sweep. The results can be seen summarised in table 4:

Page | 25

Table 4 - Sweep composition investigation

Permeate Setup area 1 area 2

2

Retentate mol frac. %CO2 1.128

energy use x100MW 1.335

pressure ratio

Total Area
2

Recovery
2

mol frac %CO2 63.76

x10 m
C3 air sweep C3 double ret. sweep C3 double ret. sweep C4 air sweep C4 double ret. sweep C4 double ret. sweep C5 air sweep C5 double ret. sweep

x10 m

x10 m

% 90.02

43

2.75

45.75

40

43

90.16

62.41

1.419

1.263

13 5.5

1.05 42

14.05 47.5

90.17 90.7

75.75 63.39

1.349 1.147

1.939 1.268

10 5

38

44

90.38

59.5

1.281

1.285

1.15 2.7

18 43

19.15 45.7

90.7 90.09

79.35 63.69

1.162 1.221

2.967 1.295

10 5

2.85

41

43.85

90.02

62.48

1.447

1.247

The recycling of the retentate actually leads to an increase in the CO2 content of the sweep; this seems counterintuitive as by changing the sweep to the retentate the PPDF is decreased as the retentate has a higher CO2 content than the air being used. By recycling the otherwise discarded retentate stream it allows the process to capture some more CO2 from the stream and therefore increase the recovery (or allow a smaller area to provide the same recovery). The decrease in purity is a result of the lower PPDF allowing less CO2 to permeate. A small decrease in power is seen when the sweep stream is recycled, this can be attributed to the use of an already pressurised retentate stream being put through an expander to recover some energy. The air stream previously used was being expanded from 101.3 kPa to 22 kPa and the retentate stream is being expanded from 110 kPa to 22 kPa therefore allowing more energy to be recovered than before. With the major parameters investigated it can be seen that achieving 90% recovery and 90% permeate purity is unrealistic without consuming a significant amount of energy. As mentioned above, a theoretical membrane known as PIM + + was tested. This membrane is a hybrid between the PIM membrane[15] and a theoretical limit for membrane selectivity. PIM + + would have the selectivity of PIM and a selectivity of 100 which has been deemed as an

Page | 26

attainable limit for membranes. If this membrane can be produced commercially membrane processes stand a much better chance at achieving DOE targets.
Table 5 - Testing of PIM + + membrane

Permeate Total Area x10 m2 config. 3 config 3. ret. Recycle. PR 10 config. 4 config 4. ret. Recycle. PR 10 config. 5 config 5. ret. Recycle. PR 10 1.5525 89.87 85.87 1.56 3.98 83.89 89.33 79.24 69.38 1.406 3.7 89.28 83.9 84.9 72.67 3.76
5

Retentate mol frac. %CO2 1.615

energy use x100MW 1.405

pressure ratio

Recovery % 87.24

mol frac %CO2 71.6

1.409 2.12

2.558 1.358

10 5

2.77 1.242

4.146 1.354

10 5

1.14

2.739

10

From these results it can be seen that the increase in membrane parameters gives very promising results. The configurations running at a pressure ratio of 5 give good results, although still not achieving DOE targets. The configurations can come within 20% of the targets at a power consumption of around 22% of the plants output. The increase in energy consumption relative to the polaris membrane is due to the selectivity allowing less gas to permeate and causing a larger recycle which has to be compressed. By running at a pressure ratio of 10 the permeate purity can be increased significantly but at a great cost with respect to energy consumption. Configuration 5 can almost achieve the DOE targets when used with PIM + + and a pressure ratio of 10; at an energy use of 45.65% of the power plants output. The area required decreases massively with PIM + + but will also be much more expensive as this is not a physically constructed

3.4 Critical Review

This section looks into the simulation and assesses the viability of the modelling process and how accurate the results may be. Assumptions There are a number of assumptions made in this modelling process which could have a significant effect on the viability of the model produced. The membrane units are assumed to be isobaric and isothermal. In reality there will be a slight pressure and temperature drop over Page | 27

the membrane. The temperature drop is a largely safe assumption as with the proper design any possible drop could be minimised and rendered negligible. The assumption that the membrane is isobaric is justified as the membrane is a dense polymer and treating it as an incompressible medium is valid; again, a slight drop may be witnessed in reality but would be negligible with respect to effects on the process. The assumption of constant permeability can have more of an effect on the viability of the process compared to others. In reality the permeability of the membrane would change with numerous factors: pressure, temperature, time, concentration. For the purposes of the simulation this assumption is valid as including varying permeability would greatly complicate the model. Much research has been done into the variance of permeability in areas such as plasticisation or time dependence and if the simulation was to be carried out experimentally this could be accounted for. The Cholla pilot plant has reported that the membranes have been performing well with respect to contaminants which could degrade performance over time, this would seem to reinforce this assumption. The assumption of 1D plug flow allows the flux to be easily approximated. It is unlikely that the flow would be close to 1D plug flow in reality as there would be flow in multiple directions due to local pressure gradients that would most likely be present. The flux of the multidirectional flows can be assumed to be at least an order of magnitude smaller than the assumed flow direction. Also, as all CO2 is entering one plane and leaving the other parallel plane the overall flow can easily be modelled as 1D plug flow with respect to overall flow direction. Lastly, the permeate side flow was assumed to have perfect mixing. This allows the permeate side concentration to be approximated and easily calculated. In reality the concentration at the permeate interface would be significantly higher which would act to decrease the PPDF and lower the flux. Using a sweep flow will add to the mixing on the permeate side but a concentration gradient would still be present. The extent that this assumption has on the process cannot be properly determined and would warrant further investigation before designing any potential membrane processes. Modelling process The modelling process aimed to be carried out in the most efficient way which would allow all necessary variables to be calculated. By looking into the requirements of each Page | 28

configuration initially, the optimum configurations were able to be ascertained and these brought forward for further investigation, reducing the time required for simulations. The parameters investigated in this report seem to be sufficient to give a good understanding of the possibilities for a membrane separation process. Some additional areas of investigation which would have been advantageous but were unable to be carried out due to time constraints are: More than two pressure ratios could be investigated to determine any possible trending effects More than two membranes could be investigated so that a deeper understanding of the membrane parameters could be gained The investigations could be carried out with 80 grid points to provide greater accuracy and more distinct trends Carrying out an investigation into power consumption without any sweep streams may allow a better understanding of how parameters affect this An investigation into altering the sweep fraction with a recycled sweep stream could yield interesting results but would be time consuming due to the use of two recycle loops Investigation into the energy recoverable from heat sources such as compressed gases could yield considerable savings Carrying out these additional points would be very time consuming and as such only the main areas have been investigated this paper. As the energy consumption is such a key parameter in this process it would be advisable to carry out further investigation into this to determine the actual accuracy of the values observed. Unisim takes into account factors that would affect the power consumption of compressors and vacuums such as adiabatic and isentropic efficiencies and idealities. The power consumption in reality would likely be different to those calculated but cannot accurately be judged whether they would be higher or lower. The key performance indicators used are mostly adequate for analysis of the overall performance and only one additional performance indicator would be included if the simulation was repeated, the process selectivity. The process selectivity relates the permeate CO2/N2 ratio to that of the feed side and is used as a variable in [12]. Page | 29

Notes on the simulator The simulator was able to model the majority of the process with ease and performed well. The biggest issue would be the fact that the simulator experienced some stability issues with solving around certain values. This was first noticed when loading a previous simulation; the simulator was unable to solve if the area of each membrane was increased straight to the expected value initially. When trying to solve, the simulator experienced negative flowrates in some streams and would eventually reach an inconsistency which prevented it from being solved. Instead the area of each membrane had to be gradually increased until the required value was reached; this added some time to the simulations but was not overly time consuming. This was also experienced with the sweep flowrates. A useful method was to take note of the last values run in the simulation before the file was saved, if these were put into the simulation it would be able to run at the required values straight away and would save time. This stability issue was also observed when altering variables such as the flowrate and area. If a large change was made to the variable (eg. sweep flowrate of 3000 mol/s to 100 mol/s) the simulator would be unable to solve. Instead the values should be changed gradually (in steps of 250-500 mol/s for example) and the simulator would be able to solve successfully. The simulator solved to acceptable accuracy levels with respect to comparisons of runs and observing trends; if the process was to be carried out in real life it is unlikely that any higher accuracy would be desired or even needed. The accuracy is largely determined by the number of grid points used which relate to equation 8. 50 grid points were used for the majority of simulations as this gave an acceptable trade off between solving time and accuracy. For final results of individual runs such as the comparison between all 5 configurations or the pressure ratio investigation, 80 points were used in order to provide boosted accuracy allowing better comparisons between results. Even when 80 grid points were used some discrepancy was noticed when the same values were simulated twice; the discrepancy was less than with 50 grid points (~0.2% as opposed to ~0.8%). The simulation also seemed relatively sensitive to starting values. When changing variables the results would often be the same if the values were changed from 0 to the final value in steps but would change if the values were changed from the final value to 0. This is Page | 30

due to the fact that the simulator would have the flowrates and compositions from the last run and would solve iteratively using these as a starting point, leading to small differences in final values. Process viability/Results The main aim of this report was to determine the viability and effect of parameters on a dual stage membrane separation process. As discussed above, the results are relatively accurate and can be deemed accurate enough for the purposes of comparing technologies and determining the viability of the process. It can be seen from the results that a membrane process will be unable to attain a permeate purity of 90% at a pressure ratio of 5 within acceptable conditions. Achieving 90% recovery can be done relatively easy with a membrane area of around 4.5 million m2 and a power consumption of around 20% of the plant output. With a pressure ratio of 5 the permeate purity seems to reach a maximum at around 70% which is a high permeate purity but not high enough to meet the DOE targets. The investigations into the effect of the area and the sweep flowrate serve to highlight the importance of the recycle stream. The recycle stream not only allows more CO2 to be captured and therefore recovered but can have a knock-on effect which can further increase the permeate purity, or, in some cases decrease the permeate purity. Merkel states that to be competitive with current absorption the membrane process should use less than 30% of the power plants output[4]. This shows that it is unlikely that a pressure ratio of 5 will be able to be competitive with respects to overall purity at the same time as achieving 90% recovery. Increasing the pressure ratio must be done with attention to the power consumption as this increases the power consumption significantly. The final investigations show that in order to approach the 90% recovery and 90% purity mark we need increasingly difficult conditions such as high pressure ratios and experimental membranes. The results obtained seem to show that at the current level of technology it is possible, but not feasible, to obtain 90% recovery and 90% permeate purity from a dual stage membrane process.

Page | 31

3.5 Conclusion
The modelling process carried out here effectively shows the fact that there are a large number of factors which have a significant effect on the success of a membrane separation process. This report successfully investigated some of these factors and much research has been done on a multitude of other factors from different viewpoints. The sheer number of configurations, variables and performance indicators that can be changed and measured is prohibitively exhausting. This report has attempted to focus on the parameters largely relevant to achieving the DOE targets. The results obtained show that considerable levels of purity can be achieved at relatively low costs but the reality of achieving DOE targets at the current level of technology and within an acceptable cost are unlikely to be met. Achieving 90% recovery is relatively easy compared to 90% purity and can be done within acceptable energy use but at a substantial membrane area and therefore cost. Overall, membranes are a promising CO2 separation technology which requires key commercially available breakthroughs in order to compete with other developing technologies. Membranes with selectivities in excess of 100 would be beneficial as it appears that reaching 90% permeate purity is the limiting step for this process.

Page | 32

4 Appendices I.
1. 2. 3.

References
IEA, Emissions from Fuel Combustion 1971-2004, 2006a, International Energy Agency: Paris, France. Quadrelli, R. and S. Peterson, The energyclimate challenge: Recent trends in CO2 emissions from fuel combustion. Energy Policy, 2007. 35(11): p. 5938-5952. The Future of Coal Options for a Carbon Constrained World. MIT Interdisci-

plinary Study, 2007. 4. Merkel, T.C., et al., Power plant post-combustion carbon dioxide capture: An opportunity for membranes. Journal of Membrane Science, 2010. 359(1-2): p. 126139. J.T. Houghton, Y.D., D.J. Griggs, M. Noguer, P.J. van der Linden, X. Dai, K. and C.A.J. Maskell, Climate Change 2001: The Scientific Basis. Cambridge

5.

University Press, 2001. New York. 6. J.D. Figueroa, T.F., S. Plasynski, H. McIlvried, R.D. Srivastava Advances in CO2 capture technology the U.S. Department of Energys Carbon Sequestration

Program. International Journal of Greenhouse Gas Control 2008. 2: p. 920. 7. Adams, D., Davison, J., Capturing CO2, IEA Greenhouse Gas R&D Programme

Report. 2007. 8. 9. Yang, H., et al., Progress in carbon dioxide separation and capture: A review. Journal of Environmental Sciences, 2008. 20(1): p. 14-27. Wang, M., et al., Post-combustion CO2 capture with chemical absorption: A state-ofthe-art review. Chemical Engineering Research and Design, 2011. 89(9): p. 16091624. Scheffknecht, G., et al., Oxy-fuel coal combustionA review of the current state-ofthe-art. International Journal of Greenhouse Gas Control, 2011. 5: p. S16-S35. Cost and Performance Baseline for Fossil Energy Plants. Volume 1: Bituminous Coal and Natural Gas to Electricity, Aug 2007. DOE/NETL. Zhao, L., et al., A parametric study of CO2/N2 gas separation membrane processes for post-combustion capture. Journal of Membrane Science, 2008. 325(1): p. 284-294. Baker, R.W., Membrane Technology And Applications. 2004, Wiley: Membrane Technology and Research, Inc. Haiqing Lin, T.M., Richard Baker, The Membrane Solution to Global Warming, in Sixth Annual Conference on Carbon Capture & Sequestration2008, Membrane Technology and Research, Inc: Pittsburgh, Pennsylvania. Budd, P., et al., Gas permeation parameters and other physicochemical properties of a polymer of intrinsic microporosity: Polybenzodioxane PIM-1. Journal of Membrane Science, 2008. 325(2): p. 851-860. Page | 33

10. 11. 12. 13. 14.

15.

16. 17. 18. 19.

P. Bernardo, E.D., G. Golemme, Membrane Gas Separation: A Review/State of the Art. Industrial and Engineering Chemistry Reasearch, 2009. 48: p. 4638-4663. Baker, R.W., Future Directions of Membrane Gas Separation Technology. Industrial and Engineering Chemistry Reasearch, 2002. 41: p. 1393-1411. Jared P. Ciferno, J.D.F., Tim Merkel, Membrane Process to Capture CO2 from Power Plant Flue Gas, N.D. The energy lab, Editor 2008. C. Scholes, G.C., W. Tao, G. Stevens, S. Kentish, B. Hooper, A. Qader, Membrane based carbon capture pilot plant trials, in AMS-5: The fifth Conference of Aseanian Membrane Society, Kobe, Japan2009. Membrane Based Pilot Plant Trials of Carbon Dioxide Capture. 2011 [cited 2011 14/12/2011]; Conference proceedings of CHEMECA]. Available from: http://www.chemeca2011.com/abstract/244.asp. Kirk-Othmer, Membrane Technology, Kirk-Othmer Encyclopedia of Chemical Technology. 2004, Wiley. S. Ripperger, G.S., Wuppertal, Microporous membranes in biotechnical application. Bioprocess Engineering, 1986. 1: p. 43-49. K. Li, D.R.A.R.H., Mathematical Modelling of Multicomponent Membrane Parameters. Journal of Membrane Science, 1990. 52: p. 205-219. Zhao, L., et al., Multi-stage gas separation membrane processes used in postcombustion capture: Energetic and economic analyses. Journal of Membrane Science, 2010. 359(1-2): p. 160-172. Agrawal, R. and J.G. Xu, Gas-separation membrane cascades utilizing limited numbers of compressors. Aiche Journal, 1996. 42(8): p. 2141-2154.

20.

21. 22. 23. 24.

25.

Page | 34

II.

Nomenclature
Value Molar flux Coefficient of proportionality Chemical potential Gas constant Temperature number of moles distance activity coefficient molar volume pressure molar weight molar density Diffusion coefficient Key permeance Selectivity molar flowrate Units mol/m2s J/mol J/K mol K mol m mol-1 m3/mol Pa g/mol m3/mol m2/s GPU (10-6 cm3/cm2s cmHg) N/A mol/s

Variable Ji Li i R T ni x v P Mi Di

Page | 35

III.

Drawings

A Simulator Data Entry Screens

B Spreadsheet Data gathering function

C Please see attached data CD

IV.

Data

Please see attached CD Page | 36