Effect of Temperature and Carbon Dioxide Concentration on the Adsorption of Carbon Dioxide on Activated Carbon Department of Chemical and

Biological Engineering Tufts University Brian Rohr, Brian Fink, Joshua Zannoni December 10, 2012

Abstract Adsorption has many important industrial applications. For this reason the amount of carbon dioxide adsorbed in an activated carbon packed column was examined at different concentrations of carbon dioxide as well as at different temperatures. The results show that the maximum amount of carbon dioxide is adsorbed at low temperatures and high concentrations of carbon dioxide. The best condition for adsorption that was tested was at 30C and five percent carbon dioxide. The reason for lower temperature being more favorable is that it favors the higher entropy adsorbed state. The reason higher concentration is more favorable is that more collisions between the packing and the carbon dioxide occur resulting in more occupied sites. It is hypothesized that if flow rate is decreased that the bed would behave more ideally since the packing and gas flow would have more time to equilibrate.

Introduction Adsorbers operate by flowing a fluid of two or more components over a solid that captures one of the species from the mixture by adsorption. A species is adsorbed once it binds to an available site on the surface of the solid. The entering concentration of the species in the mixture is greater than the exiting concentration since some is adsorbed as it passes through the adsorption column. After all of the available sites are occupied the exiting concentration is the same as the entering concentration. In industry adsorption is an invaluable process that may be used for a variety of purposes: purification of proteins and polymers, point source carbon capture, manufacturing of paint, softening of hard water, the Haber-Bosch process, and clarification of sugar. Breakthrough curves are one way to study adsorption, a graphical analysis of exiting concentration vs. time. Real breakthrough curves differ from the ideal for a variety of reasons. Axial diffusion and dispersion due to packing are two causes that lead to the observed ramping between the time of breakthrough and time of equilibration. Furthermore, reaction kinetics and non-ideal isotherms also contribute to the non-ideal behavior. In both the real and ideal case exiting concentration began at zero and eventually reached the feed concentration. The effects of temperature and feed concentration on breakthrough times were analyzed. By optimizing the temperature and feed concentration it is possible to operate an adsorber more effectively. Materials and Methods An Armfield fixed bed adsorption unit was used to analyze the effects of varying temperature and concentration on breakthrough curves. The Armfield unit has a one-foot column packed with activated carbon. Activated carbon works well to adsorb nonpolar carbon dioxide molecules. The data was measured and recorded on a laptop using the included Armfield software. A schematic of the adsorber can be seen below.

In order to set up the adsorber close V1, V2, V6, and open V5 and the white plastic valve. The column was then set to bypass mode (V3 and V4 ). The tiny plastic cap was removed from the exhaust port for the IR detector. The pressure of the CO2 and He from the compressed cylinder was set to 30 psi and 45 psi respectively. The valves on the wall were then opened to allow the gas to reach the adsorber. Next, the Armfield software was opened and the adsorber was turned on. Trials were conducted at three temperatures: 30, 40, and 50 degrees Celsius, and four concentrations of CO2: 2.5%, 3.5%, 4.5%, and 5%. This resulted in 12 unique trials and one repeat. The temperature was set to the desired value on the adsorber and the heat pump was turned on. After the temperature stabilized the system was ready. To begin the trial V1 (Helium) was opened and set to a flow rate of 3.5 SLPM. The flow rate through the IR detector was set to no more than 1.0 SLPM via V6 and the plastic valve. Next, the desired concentration of CO2 was set using V2 (CO2). Once set the adsorber was switch out of bypass mode and data was recorded every second. Once the outlet stream reached the initial set concentration, the CO2 flow was set to 0 SLPM and the column was desorbed. Data was continued to be sampled every second through the desorption process. Once fully desorbed sampling was stopped, the adsorber was set to bypass mode and prepared for the next trial. Results The isotherms clearly show the trend that the quantity of carbon dioxide adsorbed increases with increasing bulk carbon dioxide concentration. Also, the plot show that the quantity of carbon dioxide adsorbed decreases with increasing temperature.

Figure 1: Plots of moles of carbon dioxide adsorbed versus bulk carbon dioxide concentration at 30C, 40C, and 50 C. The values for moles of carbon dioxide adsorbed were found by finding average volumetric flow rate using Simpsons second order numerical integration approximation, and the ideal gas law was used to convert average volumetric flow rates to average mole flow rates. The results in Table 1 show that increasing temperature decreased the constant qmax and decreased the constant k. The physical significance of these findings are discussed below. Table 1: Constants for the Langmuir isotherm equations fit to the above data. The constants were found using the least squares error method. The equation is of the form: %CO2 molsadsorbed = qmax k + %CO2 . Temperature (C) qmax (mols) k (%) Initial slope (mol/%) 30 0.17 6.6 0.026 40 0.15 9.1 0.016 50 0.14 12.5 0.011 The results in table 2 indicate that bed efficiency is not dependent on temperature or on bulk carbon dioxide concentration. The efficiency of this bed at a flow rate of 3-4 SLPM is about 60 5% regardless of the temperature or bulk concentration. Other factors affecting bed efficiency are discussed below. Table 2: Bed Efficiency, , at different bulk CO2 concentrations at 30C, 40C, and 50C. Bed efficiency is defined as the moles of CO2 adsorbed at breakthrough divided by the moles of CO2 adsorbed at equilibrium. These quantities were found by integrating the breakthrough curves using Simpsons second order numerical integration approximation.

Concentration CO2 (%) (30C) (40C) (50C) 2.5 0.61 0.58 0.55 3.5 0.63 0.60 0.60

4.5 5

0.60 0.62

0.63 0.60

0.57 0.63

The temperatures change because energy is released when carbon dioxide is adsorbed onto the column, and energy is consumed when carbon dioxide desorbs from the column. This data is useful for determining the location of the carbon dioxide front during adsorption and the pure helium front during desorption. This data is also used for characterizing the degree to which the fronts are non-ideal.

Figure 2: Temperature versus time for each of the six thermocouples. The six thermocouples are evenly spaced along the adsorption column. Thermocouple T6 is located at the upstream end of the column, and thermocouple T1 is located at the downstream end of the column. In all trials, the front velocity was almost exactly constant. The R-squared value for the linear fit to the location versus time data was greater than 0.95 for all trials. For both adsorption and desorption, the data indicates that the front velocities increase with increasing temperature and with increasing bulk carbon dioxide concentration.

Figure 4: Carbon dioxide front velocity versus bulk carbon dioxide concentration at 30C, 40C, and 50C. The location of the carbon dioxide front during adsorption was determined by finding the maxima of the temperature versus time plots for each of the six thermocouples which are evenly

distributed along the adsorption column. The velocities plotted above are the slopes of these location versus time graphs. The desorption front velocities are very similar: see appendix for graph. Discussion The results in figure 1 clearly show that the more moles of carbon dioxide are adsorbed at higher bulk carbon dioxide concentrations. This result is supported by the theory of equilibrium: As predicted by LeChateliers principle, increasing the amount of carbon dioxide shifts the equilibrium to the right, causing more of the carbon dioxide to be adsorbed. The other clear trend shown in figure 1 is that fewer moles of carbon dioxide are adsorbed at higher temperatures. This result is supported by the theory of entropy. The equation for Gibbs Free Energy, , predicts that higher temperatures favor higher entropy systems. In this case, the more carbon dioxide adsorbed to the activated carbon, the lower the entropy of the system. Similarly, the more carbon dioxide that remains freely moving in the gaseous state, the higher entropy the system. The in Figure 1 strongly show this trend. The highest temperature yielded the highest entropy system (least adsorption), and the lowest temperature yielded the lowest entropy system (most adsorption). Furthermore, the reaction as written above is exothermic. Therefore, LeChateliers principle predicts that an increase in temperature would cause the equilibrium to shift left, which is exactly the result that was observed. As shown in figure 1, the equilibrium-based Langmuir model was fit to the data, giving isotherms that fit the data very well. The Langmuir model seems to be an excellent model for the data collected in the experiments. Table 1 shows the values of the constants for the Langmuir equation: qmax and k. Favorable isotherms give a large amount of adsorbed carbon dioxide at low bulk concentrations of carbon dioxide. Therefore, the most favorable isotherms have high initial slopes. The expression for initial slope can be derived from the Langmuir equation: q y q q 0 q = qmax = max - max 2 k+y y y = 0 k + 0 ( k + 0) q qmax q y q qmax - max 2 = = y k + y (k + y) k y y = 0 Using this formula, the initial slope of each of the isotherms was calculated. Clearly, the experiments run at low temperatures gave the greatest initial slope as well as the highest qmax (Table 1). Therefore, the most favorable isotherms were the low temperature isotherms. The bed efficiency of the adsorber is determined to be 60 5 %. This efficiency remains the same regardless of the bulk carbon dioxide concentration and temperature of column. Our results indicate that bed efficiency does not depend on either of those variables. In all of the trials run in the experiment, the total flow rate is 3.5 0.3 SLPM. Since flow rate is not varied in this set of experiments, the effect of flow rate on bed efficiency is not seen. However, the group hypothesizes that increasing flow rate would cause a decrease in bed efficiency. A perfect bed efficiency (=1) is observed in the extreme case of the ideal breakthrough curve. In an ideal breakthrough curve, the exit concentration of the adsorbate is zero until the bed is saturated, and the concentration of the adsorbate immediately jumps to the inlet concentration. If the carbon dioxide and helium mixture were sent through the adsorber at a very low flow rate, the adsorber would have ample time to equilibrate with the mixture, and the breakthrough curve would be nearly ideal. However, if the mixture were sent through the adsorber at a very high flow rate, there would be insufficient contact time between the

mixture and the adsorbent for equilibrium to be established. Therefore, the breakthrough time would be much earlier than the equilibrium time, yielding a very non-ideal breakthrough curve and a poor bed efficiency. Further experiments could be run at different flow rates to test this hypothesis. Figure 2 shows the temperature versus time plots for all six of the thermocouples in the bed. When carbon dioxide is adsorbed onto the activated carbon, heat is released. Since the constanttemperature water jacket is constantly removing the generated heat from the system, the temperature of the thermocouple minus the temperature of the water jacket is proportional to the rate of heat generation, and it is therefore also proportional to the rate of carbon dioxide adsorption. In other words, the temperature versus time plot is proportional to the derivative of the concentration versus time plot: the breakthrough curve (as shown below).
CO2 Exit Concentration vs. Time
Percent CO2 (%)

3.0
Area Under T vs t curve (au)

2950 1950

Integral of Temperature vs. Time for T1

2.0
1.0

950

0.0 0 1000
Time (s)

-50

2000

3000

Time (s)

2000

4000

Figure 5: a) A typical breakthrough curve. b) Integral of T vs. t where T is the deviation of temperature from the steady state value. They are similar in shape because T1 is very near the exit of the adsorber. The ideal temperature vs. time curve is therefore the derivative of the ideal breakthrough curve: a narrow, tall, sharp peak. As shown in figure 2, the curves become less and less ideal as the front moves down the column. This is due to dispersion, axial diffusion, and non-instantaneous kinetics. Imperfect packing of the activated carbon adsorbent is one of the causes of these non-idealities. Although the lower temperatures yielded the most favorable isotherms, the carbon dioxide front moved down the column more slowly in the lower temperature trials. This trend is clearly shown in figure 4. The carbon dioxide front speed increased with increasing carbon dioxide concentration. The best set of conditions for adsorbing the highest amount of carbon dioxide is therefore high bulk concentration and low temperature, but the best set of conditions for adsorbing carbon dioxide the fastest is high temperature and high bulk concentration. Conclusion The best circumstances to adsorb the highest amount of carbon dioxide is at a low temperature, 30C, and high concentration of carbon dioxide, five percent. While this is true, at low temperatures it takes more time to adsorb the carbon dioxide. In application it is not always possible to manipulate temperature and/or feed concentration. This can be true due to the feed stream being an exit stream from a process, cost of manipulating feed composition or temperature, as well as operation conditions. If neither of these variables can be controlled it is hypothesized that by decreasing flow rate the amount of occupied sites can be increased. Also increasing bed length may increase the amount of carbon dioxide absorbed since it is believed that unused bed length does not change with column length. It is always important to consider operating parameters and cost when deciding which variable to manipulate in order to achieve the desired amount of adsorption.