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A Method for Adsorbing and Desorbing a CO2-Helium Binary Mixture using a Fixed Bed A. Tran, B. Choi, D.

Graziano

1. Introduction
Considering the pressing concerns surrounding climate change and the concentration of greenhouse gases steadily rising, it is becoming increasingly important to develop efficient methods of extracting CO . This is especially true for industrial process outlet streams containing CO that would otherwise end up straight into the atmosphere. One such method is gas adsorption through a carbon substrate. The adsorption of gases by carbon was first studied more than two centuries ago, when charcoal was found to decolorize solutions by a surface adsorption mechanism [1]. Since then, many processes of adsorption have been studied to increase the efficiency of the process. By using highly porous materials such as activated carbon with a large internal surface area, a significant amount of CO or various different adsorbents may be taken up by the solid. The adsorbed gas is attached to the surface of the adsorbent with a material that selectively attracts the gas by intermolecular interactions such as the Van der Waals forces [2]. Different variables such as temperature and partial pressure of the gases affected the adsorption and desorption rates of gases. Specifically, with increased CO partial pressure and decreased adsorber temperature, the amount of gas adsorbed would be expected to increase. In this study, the partial pressure of the CO was varied by using three different feed concentrations of CO . Temperature was also varied between 30C, 40C, 50C, making for a total of n=9 trial runs. A binary mixture of helium and carbon dioxide gases were adsorbed and desorbed in a fixed-bed adsorber reactor packed with activated carbon. Temperature data and CO volume fractions were recorded at six different positions through the column every second. With this data, concentrations and temperature front velocities were calculated, and isotherms were determined to be compared to an isotherm model.
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Figure 1 - Absorber/Desorber Diagram. Inlet streams of CO2 and He pass through V1 and V2, and their flowrates are measured by F1 and F2 respectively. The column was put into bypass mode by using V3. V6 controlled the rate of gas flow rate into the IR detector.

2. Experimental Methods
To collect the adsorption and desorption data, an Armfield Engineering Model-UOP15 Fixed Bed Adsorption unit was used, as seen in Figure 1. Source cylinders of CO and Helium were ensured to be at least 30 and 45 psi, respectively, before the experiment was run. First, the system was set to bypass the column for initial CO concentration calibration using valve V3. The heater and pump were then activated via two toggle switches on the front of the unit, and the temperature was set using the integrated PID controller. The operating temperatures tested in this experiment were 30 C 40 C and 50 C. After this, the helium flow-rate was set to 3-4 liters per minute through the bypass. The gas flow was then routed through the IR detector and regulated to a rate of less than 1 liter per minute. Throughout the duration of the experiment, the Armfield UOP15 software package was used to monitor flow-rates, temperatures, and CO concentration. After the monitoring software was configured, the CO flow was adjusted until it reached the desired concentration (3.5%, 4% and 4.5% respectively). This made for a total of nine trials consisting of three concentrations of CO being tested along with three different operating temperatures. After the desired concentration was attained, the system was switched from
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bypass mode and the gas feed stream began flowing into the column. Simultaneously, the data logger on the Armfield software was activated to take temperature readings from the thermocouples placed throughout the length of the column as well as the CO concentration readings output by the IR detector.
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(Eq. 2) With known parameters of C , as percentages of CO2, and the value of qe able to be calculated with equation 3:
e

The adsorption process was tracked by monitoring the temperature values at each point in the column. The adsorption of CO onto the activated carbon packing was an exothermic process, thus a temperature increase indicated the binding of the gas to the packing. When the temperature of each of the thermocouples returned to the starting steadystate values, and the CO concentration measured by the IR meter returned to the set point, the column was said to be fully adsorbed. At this point the CO stream was shut off to begin the desorption process. The desorption process was an endothermic reaction which was complementary to the exothermic adsorption reaction. As a result, this process was indicated by a drop in temperature at each respective thermocouple in the column. The desorption process was considered complete when the column temperature once again returned to the aforementioned set-point temperature.
2 2

(Eq.

3)

Values of K and beta were determined, and tabulated in Table 1 of the results section. m, the mass of the granular activated carbon (GAC) could be determined from the data given by the lab manual. By multiplying density of the GAC given as 820 kg/m , multiplied by the column volume, the mass was found to be 327 grams. [3]
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To find the concentration front velocity, the following equation was used: (Eq. 4) Where x was the length of the column known to be 325 mm, and t0.05 was the time elapsed for the IR meter to read CO2 concentrations. To measure the temperature front velocities peak temperature measurements for each thermocouple was taken and plotted against time. With this data we were able to use the following equation to find v:

A CO2 adsorption isotherm that relates equilibrium concentrations of the adsorbates and amount adsorbed onto the surface may be determined by the following model: (Eq. 1) With variables: q =amount adsorbed/mass adsorbent, C =equilibrium solution concentration (% CO ).
e e 2

(Eq. 5)

This isotherm model may be easily linearized to determine the parameters K and beta, which were empirical parameters. By method of linearization, we were able to get the following linearized equation:

Where x was the distance between the thermocouple, and ti was for when the temperature peak was read.

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Figure 2 - Average Front Velocity with varying CO2 Concentrations and Temperature

3. Results
3.1 Concentration and Temperature Fronts As seen from Figure 2 the concentration front velocities were found to increase with temperature increases as well as feed CO2 concentration increases. For the 30oC and 50oC trials, a change in the feed concentration of CO2 resulted in a front velocity increase of approximately 0.2 cm/s. The average front velocity increase for the 40oC tests was slightly less at approximately 0.12cm/s. Additionally, as mentioned above, a correlation was found between temperature and concentration front velocity. An average increase of 0.44 cm/s was found between the fronts at 30oC and 40oC, and an increase of 0.31 cm/s was found between 40oC and 50oC. This positive correlation was corroborated by a relatively small standard deviation between measurements, as seen in Figure 2.

Table 1 - Beta and K Parameters of Freundlich Isotherm Equation

Temperature ( C) K

30 115

40 122

50 31.7 1.178

1.441 1.52

4. Discussion
The capacity of an adsorbent to uptake molecules decreased with increasing temperature. Raising the energy level of the adsorbed molecules allowed the adsorbed molecules to overcome the Van der Waals forces that were prevalent in the surface interactions. Providing this extra energy to the adsorbent allowed it to migrate back to the gas phase. Therefore, at higher temperatures the gases exited the column more quickly, but adsorbed less efficiently. The gas velocity was a determinant of contact or residence time between the gas stream and the adsorbent. The residence time of the gases was a direct indicator of gas contaminant (CO ) capture. Thus, the lower the gas velocity, the greater the probability of a molecule contacting the
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substrate site, which resulted in a higher capture efficiency. As could be seen in the Figure 3, with higher temperature of the adsorber, less efficient adsorption was observed. In Figure 2 we were able to see that the front velocities rise with both higher temperatures and increasing concentrations of O . The reason why front velocities increased with temperature was clear, since gases move more quickly with higher temperature.
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Figure 3 Carbon Dioxide Concentrations vs. Time at 40 degrees Celsius.

The average front velocities increased with higher CO concentration because with the higher concentrations, the substrate sites were filled more quickly with CO . Therefore, once the column was fully adsorbed, CO gases were able to move more freely, and showed higher front velocities. It should be noted that the temperature peaks at each point in the column were reached at varying time points. Namely, the time it took to reach a maximum temperature from thermocouple 1 to thermocouple 2 was often found to be longer than the time elapsed between 5 and 6. This could be a result of two factors: non-constant concentration front velocity in the column, and uneven spacing of thermocouples in the column. It was more than likely that the concentration gradient had a dynamic velocity due to varying packing densities and airflow mixing effects. Overall the variation in velocities was not extreme between thermocouple stages, but still noticeable. However, uneven spacing of the thermocouples within the column cannot be ruled out, as their placement along the column
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was not readily known. If the thermocouples were spaced unevenly in the column, it would also account for the slight discrepancies in the maximal value times on the chart. An adsorption isotherm forges a relationship between the equilibrium concentration of the adsorbate, which in this case was CO , and the amount adsorbed per mass of adsorbent substrate (granular activated carbon). This relationship, as the name isotherm implies, only holds for constant experiment temperatures, which the heater and circulation pump unit of the fixed bed column provided[4]. An isotherm provides a model of ideal adsorption dynamics to which experimental data can be compared to. Each isotherm was empirically determined and each have their own strengths and weaknesses. The Freundlich isotherm used in this lab, for instance, breaks down at high pressures, and extent of adsorption becomes independent of pressure [5]. This effect was not believed to be a problem at the pressures the column was run at, however. The experimental data ended up reasonably fitting the isotherm data in a mostly linear fashion (Figure 4). This implied that for the most part, the adsorption process occurred at close to ideal conditions, aside from some minor deviations.
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Freundlich Isotherm, 30C


Amount Adsorbed (g/kg)

2
1.5 1 0.5 0 0.0000%

2.0000%

4.0000%

6.0000%

Composition of Carbon Dioxide, v/v

Figure 4 Freundlich Isotherm with experimental 30 degree celcius data overlaid. A reasonable linear fit can be observed.

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5. Conclusion
The results of the experiment demonstrated that the granular activated carbon was an effective way to scrub CO from the binary mixture feed stream. Increasing the adsorber operation temperature increased both the average concentration and temperature front velocity. The adsorption proceeded with nearly ideal behavior, as indicated by a close fit of the experimental data to the Freundlich isotherm model. Thus, it can be concluded that the dilute mixtures of CO could effectively be captured and desorbed at various temperatures.
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6. References
[1] Knight, Andrew. "Gas Adsorption." Gas Adsorption. University of Florida, n.d. Web. 08 Nov. 2012. <http://www.chem.ufl.edu/~itl/4411L_f00/ ads/ads_1.html>. [2] Das, D., V. Gaur, and N. Verma. "Removal of Volatile Organic Compound by Activated Carbon Fiber." Carbon 42.14 (2004): 2949-962. Print. [3] Instruction Manual for UOP15, Fixed Bed Adsorption Column. N.p.: Armfield Limited, n.d. Print. [4] Makowski, Wacaw, and ukasz Ogorzaek. "Determination of the Adsorption Heat of N-hexane and N-heptane on Zeolites Beta, L, 5A, 13X, Y and ZSM-5 by Means of Quasi-equilibrated Temperatureprogrammed Desorption and Adsorption (QE-TPDA)." Thermochimica Acta 465.12 (2007): 30-39. Print. [5] "Freundlich Adsorption Isotherm | Chemistry Learning." Freundlich Adsorption Isotherm | Chemistry Learning. N.p., n.d. Web. 08 Nov. 2012. <http://www.chemistrylearning.com/freund lich-adsorption-isotherm>.