Chemical Engineering 4L2, Membrane Gas Separation

CHEMICAL ENGINEERING 4L02

MEMBRANE GAS SEPARATION
I. Laboratory Relevance and Goals Membranes are widely used for a variety of industries. Monsanto developed the !PRISM Separator1 and overnight this technology revolutionized the chemical process industry (CPI) and also the ammonia industry. The separator was used to separate, recycle and recover Hydrogen gas from Ammonia. In our laboratory, we will be using the !-PRISM Separator. The apparatus unit is a laboratory bench scale unit that has just been recently converted into a portable experiment. In our study, the separator will split an incoming air stream into an oxygen rich (permeate stream) and oxygen deficient (retentate stream) air stream. The concentrations of the permeate and the retentate streams will be measured and these values will be compared to a computer simulation running in Excel. Geankoplis2 Chapter 13 can be used as reference in order to understand the concepts introduced in this laboratory. This laboratory has the following goals, which are in addition to the general goals presented in the course outline: Determine the permeability coefficients for pure oxygen and pure nitrogen. Determine the concentration (purities) and flow rates of the retentate and permeate streams. Measure the dependent variables (flux, selectivity, and recovery) as a function of changing independent operating variables of feed pressure, feed flow rate. Simulate the performance of the !-PRISM Gas Separator in terms of selectivity, purity of the product streams, and membrane productivity. Compare the experimental performance to the computer simulation. The apparatus can be run with either of two !-PRISM membrane separators or with both permeators connected in series. In addition either permeator can be run in cocurrent or countercurrent mode. The computer simulation can be used to compare to experimental results for three different flow configurations (cocurrent, countercurrent, perfect mixing). Specific Objectives will be given out stating which of the above configurations should be studied.

In order to evaluate the performance of the membrane separator, the basic concepts of material balances, mass transfer and membrane separations must be applied. These

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Chemical Engineering 4L2, Membrane Gas Separation concepts are presented in the following courses in the Chemical Engineering Curriculum: Chem Eng 2D4, Chem Eng 3M4, Chem Eng 4M3.

II.

Introduction and Background Theory

Mathematical modeling of the !-PRISM permeators requires that the pure gas permeability coefficients be known. Either you will measure the permeability of pure O2 and pure N2 or these data will be provided for you to analyze. A schematic of the device is presented in Figure 1.

Feed LI, xI

Feed Channel (outside membrane fibers)

Retentate LR, xR

Permeate Channel (inside membrane fibers)

Permeate VP, yP

Figure 1: Schematic diagram of a !-PRISM Gas Separation unit. Performing a total mass balance calculation and a component mass balance calculation on the permeator, gives the following two expressions: L I = LR + V P LI x I = LR x R + VP y P (1) (2)

When separation occurs, the !-PRISM modules employ the principle of selective permeation to separate the gases. As the gas flows through the module, the faster gas preferentially diffuses through a polymer membrane to create the permeate stream. In

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Chemical Engineering 4L2, Membrane Gas Separation this case, an oxygen rich stream (permeate stream) and an oxygen deficient stream (retentate stream) exit the module. 1.1 Membrane Performance In order to measure the performance of the membrane, 3 factors must be addressed. The selectivity factor is one indicator that determines the performance of the membrane. It can selectively separate components over a wide range of particle sizes and weights. It splits the feed into 2 streams: the permeate stream consisting of components small enough to pass through the pores and the retentate stream consisting of large molecules retained by the membrane.3 The composition of the membrane will also affect the selectivity of the membrane. Another important indicator that determines membrane performance is membrane productivity. This is a measure of the quantity of a component that permeates through the membrane. This is characterized by the transport flux through the membrane and the driving force behind this flux is the partial pressure differentials between the feed channel and the permeate channel. In general, Flux of component i partial pressure driving force (3)

The transport flux through the membrane can be mathematically represented as: (where i = O2, N2) Vi Q = ( i ) ( Pi p i ) A This equation follows a linear relationship with slope (4)

Qi and is a solution to Ficks First Law and for pure gases is determined by a plot of flux, Vi/A, versus the pressure driving force (Pi pi). Thus membrane productivity depends on the permeability of the membrane and the effective thickness of the membrane, . Qi and using Raoults Law (replacing the partial pressure with mole fraction times pressure) to give, For gas mixtures, such as air, equation (4) can be rearranged by substituting Qi ' = VP y = A Q1 ' ( P x p y ) for Oxygen (5) (6)

VP (1 y ) = A Q2 ' [ P (1 x) p (1 y )] for Nitrogen

Lastly, membrane stability is another indicator that determines membrane performance. For instance the membrane performance can be affected by chemical and/or mechanical process, such as acidic gases or high pressure. For the air separation application 2001/09 2001 McMaster University 3

Chemical Engineering 4L2, Membrane Gas Separation considered here, the membrane should be stable, however it is good to check for membrane changes by doing some repeat experiments. 1.2 Definition of Stage Cut Stage cut is one of two major independent variable in this apparatus and is defined as, = PermeateRate FeedRate (7)

which is basically the ratio of how much permeate you recover per unit feed to the membrane module or membrane system. Generally, like distillation, there is a trade-off between the purity and the quantity of the two outlet streams. A low stage cut means the highest purity of oxygen in the permeate and nitrogen in the retentate; but you only get a small amount of oxygen enriched permeate. As stage cut increases, more permeate is produced but at lower purity. Adjusting the needle valve in the retentate line varies the stage cut. When this valve is nearly closed very little retentate is produced and the stage cut is high. Conversely, opening the value gives a lower stage cut. However, opening the stage cut valve beyond a certain point makes no further difference in performance, as the stage cut approaches zero. III. Preparation Prior to the First Laboratory Session

Before the first laboratory session, an one EXCEL spreadsheet program will be supplied to facilitate the analysis of your data. This program checks the material balances around the unit and converts the raw data into SI units for further analysis. If the material balance does not close within 10%, then you are probably not yet at steady state; continue running until: Material Balance and Steady State The material balance is checked two ways. Firstly using the measured retentate and permeate flow rates and concentrations and using these values to calculate the feed flow rate and feed concentration; the feed concentration can then be compared to the known value of 21% oxygen for air. Secondly, the measure flow rates of retentate and permeate and concentration of the permeate, along with the known feed concentration of oxygen are used to calculate retentate concentration; this value is compared with the measured retentate concentration. One or the other of these methods should produce an error of less than 10%. You should wait at each new condition about 10 minutes to be certain that you are at steady state. When the material balance does not close that may mean you are not at steady state or the error in the measurements may just be relatively large.

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Chemical Engineering 4L2, Membrane Gas Separation The key ideas and concepts that you should know before entering the lab are: Understand the terms related to membrane performance (selectivity, productivity, purity). These terms can be found on other websites and in Geankopolis. Familiarize and sketch a simple schematic of the piping diagram related to the two membrane modules. Familiarize with the second Excel spreadsheet, GPCUT that simulates the membrane performance. You should be familiar with how this program can be used in theoretically calculating the retentate and permeate purities and flow rates, and the membrane area. Understand the setup of the 2 gas membrane modules and how they can be set up to perform different flow configurations.

The second spreadsheet, GPCUT, allows further analysis of your data and simulation of the performance of the gas separation permeators. These simulations can then be compared to the actual data of your experiment. The quality of the agreement between the model predictions and data is an indication of the accuracy of your data and of the validity of the assumptions made in the computer model. The program is fairly complex but the instructions on using the code are straightforward. Manuals and text for the gas separation theory can be obtained from the instructor.

IV.

Health and Safety Requirements

Before you begin performing the experiments, you need to understand the equipment and how to operate it safely. NOTE: Safety Glasses and eye protection is ESSENTIAL in the laboratory. Wear safety glasses at all times. Gas cylinders should be securely fastened to the tabletop to avoid any injury (ask your TA or instructor in order to move the gas cylinders). Do not allow the mass flow meters to exceed a value of 10 SLM. The MSDS sheets are located on the bench in front of the gas membrane apparatus. The students should read these sheets carefully to see how to handle the oxygen and nitrogen gas cylinders, the gas sensors and the !-PRISM membrane separation units safely.

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Chemical Engineering 4L2, Membrane Gas Separation V. Apparatus The experimental apparatus consists of 2 !-PRISM membrane modules, gas cylinders (oxygen, nitrogen and air), 2 mass flow meters, and 2 oxygen sensors. Each of the modules can be operated in cocurrent (permeate flows in the same direction as the feed gas) or countercurrent mode. It is also possible to operate both modules with the feed in series; in this case the permeates (cocurrent or countercurrent) are combined to form one permeate stream. Part I: Obtaining Pure Gas Permeability Coefficients of Oxygen and Nitrogen Pure gas coefficients for nitrogen and oxygen must be determined for each of the modules. The stage cut is irrelevant for pure gas and should be kept low to avoid wasting gas. Determine the permeation rate for the pure gas at various pressures and plot the permeate rate vs. average pressure difference (equation 4). This should produce a linear relationship through the origin with the slope related to the permeability coefficient. Part II: Separating a Pure Air Stream into Oxygen Rich and Nitrogen Rich Streams A pure air stream is fed into the !-PRISM membrane separator. Runs can be performed at varying stage cuts (at constant pressure). This can be repeated at various pressures. These experiments can be done for one or both modules separately or with the modules in series in cocurrent and/or countercurrent mode depending on the specific objectives given. A table on the front of the apparatus gives the valve setting appropriate for each the above options. For each experiment note the experimental configuration and record the feed, retentate, and permeate pressures, the retentate flow, permeate flow, permeate concentration, and retentate concentration. Remember to include some repeat experiments. The approximate range of possible stage cut values for each pressure is shown in Table 1. At higher pressures, the material balance is close to 10% error. However, at lower pressures it is very hard to get the material balances to within 10% error. Experimental Procedures

Table 1. Minimum and Maximum Range of Stage Cut Values for Varying Pressures Pressure Range, kPa (gauge) 200 300 400 500 600 700 Range of Stage Cuts Available for Desired Pressure Range 0.1954-0.9474 0.3037-0.8814 0.3297 0.8514 0.3678 0.9469 0.4638 0.9491 0.4863 0.7021

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Chemical Engineering 4L2, Membrane Gas Separation

Part III: Comparing Model GPCUT to Experimental Results The experimental results can be compared to a transport model for gas separation. Using the pure gas permeabilities, the inlet feed conditions and the flow configuration the computer simulation, GPCUT.M, can predict the module performance. You should use this simulation over a range of stage cuts and pressures to generate theoretical curves and then plot your actual data on the same figure (as points) to compare. General Procedure Notes Do not expose the oxygen probes to pure oxygen or pure nitrogen for a long period of time. Do not touch the sensor exposing the oxygen and nitrogen probes. Human contact with the probes can severely damage equipment operation. The membrane area for the counter-current mode in the program GPCUT is being predicted incorrectly. We are trying to fix this problem. Repeat experiments should be done for some of the operating conditions to check the reproducibility of the data. The stage cut valve is usually is set at low values; higher values only waste feed gas. Above 10 SLM for the flow meters the values are no longer accurate. Record the ambient temperature and pressure on each day, as this will affect the performance of the unit. It can be difficult to get the material balances to close within 10%, particularly at lower operating pressures. In some case you will have data with more than 10% error; just note the higher uncertainty in these data in your report.

VI. Major Laboratory Tasks and Schedule Guidance on the key tasks and when they should be completed is given in Table 2. The TA and instructor at the start of the laboratory will give specific objectives. Table 2. Guidance for a 4 Week Gas Separation Lab Timing Before 1st Session Ungraded activity Carefully read laboratory handout. Safety training. Equipment orientation. Graded Activity Tasks by Completion Lab Preparations Experimental plan Collect data to determine permeability coefficients. Draw plumbing and piping diagram of apparatus. 7

1st session

Lab data analysis

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Chemical Engineering 4L2, Membrane Gas Separation Between 1st and 2nd 2nd session 3rd session Mid lab review meeting. Define SDL task. Lab data analysis Calculate pure gas permeability coefficients Perform air separation at different operating conditions, as per specific objectives Continue with air separation experiments and the SDL Task. Complete air separation simulation by GPCUT computer program.

VII.

Discussion

Please include the answer to these questions in your discussion part of your report. The answers to these questions require more literature review / journal review. NOTE: These discussion questions should be incorporated into the discussion section of your report and should NOT encompass the entire discussion section. 1) Determine which is the best flow configuration (CO, CC, PM) for separating a pure air stream into nitrogen rich and oxygen rich streams? 2) Discuss the effect of using 2 membranes in series on membrane performance? (If the performance is better using 2 membranes in series, experimentally explain how much difference it will make when using 2 membranes instead of 1) 3) Compare the difference between the permeability coefficients of pure oxygen and pure nitrogen. (What does a lower permeability coefficient mean?) 4) Compare the difference between permeability coefficients of pure oxygen and pure nitrogen in module 1 and module 2? (How does the permeability coefficient differ when Module 1 and Module 2 are hooked up in series?) 5) How does the !-PRISM Membrane separation perform in terms of selectivity, membrane productivity and membrane stability? 6) How does the experimental data obtained from the experiment co-relate to the simulated data as produced by the GPCUT.m program? 7) What is the effect of the partial pressure on membrane flux and membrane productivity? 8) Determine the effect of increasing pressure differentials between the feed channel and the permeate channel on permeate concentration. Does a higher stage cut value produce a higher purity content in the permeate channel? VIII. Self- Directed Learning

In this section, you will define a knowledge-based learning goal that is related to this laboratory. By knowledge-based, we mean a goal directed to improving your understanding of gas separation and mass transfer.

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Chemical Engineering 4L2, Membrane Gas Separation

Your plan should include a program of investigation to achieve a certain goal. The program can include experimental, theoretical, and literature tasks; it must include some experimentation. Prepare a clear and concise explanation of your goal and the program for investigation. In your final laboratory report, briefly explain why you selected these goals and how you designed the program, as well as specific conclusions based on your investigations. In order to give you a general understanding of the membrane separation processes, . the following web sites shown in the references should be considered in order to have a fully defined self directed learning goal. Some potential problems to investigate: Different types of membrane separation processes (ultrafiltration, pervaporation, electrodialysis) and compare the areas of membrane application. Determine how membrane separation processes are used in chemical process industry (CPI) today and in water treatment plants. Provide recent experimental research done today on membrane research. Determine how membranes might be used in a biological context, or in an environmental context for pollution control.

IX. References 1) Prism Alpha, Prism Alpha Membrane Separators For Low Cost On-Site nitrogen. 2) Geankopolis C., Transport Processes and Unit Operations. Third Edition. Prentice-Hall, Inc. Englewood Cliffs, New Jersey, 1993. Related Websites 3) Pham, L., Guillermo, M., Nilseen., E. Essence Recovery by Pervaporation., Membrane Separation Group at UCSD. http://chemelab.ucsd.edu/pervap/ 4) An On-line resource for membrane research: http://www.membraneonline.com/ 5) An industrial site producing membranes: http://www.osmonics.com/ 6) Terminology for Membrane and Membrane Processes http://www.che.utexas.edu/nams/IUPAC/iupac.html

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