Adsorption Batch Study and Kinetics

A) AIM:
To observe and understand the process of dehumidification of air. To plot the breakthrough curve for adsorption of water vapour on Silica gel.

B) INTRODUCTION:
Definition:
Adsorption is the adhesion of atoms, ions, bio-molecules or molecules of gas, liquid, or dissolved solids to a surface. This process creates a film of the adsorbate (the molecules or atoms being accumulated) on the surface of the adsorbent. It differs from absorption, in which a fluid permeates or is dissolved by a liquid or solid. It is a surface phenomenon. Adsorption is of two types, physisorption and chemisorption. The reverse process of adsorption is known as desorption.

Introduction to the adsorbent used in the experiment:

The present experiment is adsorption of moisture on Silica gel. Silica is used for drying of process air (e.g. oxygen, natural gas) and adsorption of heavy (polar) hydrocarbons from natural gas. Silica gel is a matrix of hydrated silicon dioxide. It is a chemically inert, nontoxic, polar and dimensionally stable (< 400 C or 750 F) amorphous form of SiO2. It is prepared by the reaction between sodium silicate and acetic acid, which is followed by a series of aftertreatment processes such as aging, pickling, etc. These after treatment methods results in various pore size distributions.

Factors affecting adsorption: 1. Surface area of adsorbent - Greater surface area implies a greater adsorption capacity.
2. Particle size of adsorbent - Smaller particle sizes reduce internal diffusion and mass transfer limitation to the penetration of the adsorbate inside the adsorbent (i.e., equilibrium is more easily achieved and nearly full adsorption capability can be attained). 3. Contact time or residence time - The longer the time the more complete the adsorption will be. However, the equipment will be larger. 4. Solubility of solute (adsorbate) in liquid - Substances slightly soluble in liquid will be more easily removed from liquid (i.e., adsorbed) than substances with high solubility. 5. Size of the molecule with respect to size of the pores- Large molecules may be too large to enter small pores. This may reduce adsorption independently of other causes.

Some applications of adsorption using silica gel:

1. Through the inclusion of silica gel packets, electronics can be preserved longer. 2. It is used to keep the relative humidity (RH) inside a high frequency radio or satellite transmission system waveguide as low as possible. 3. It is used to dry the air in industrial compressed air systems. 4. In chemistry, silica gel is used in chromatography as a stationary phase.

C) BRIEF THEORY:
In principle adsorption can occur at any solid-fluid interface. In any adsorption process the material being adsorbed (e.g., a pollutant) is simply but effectively removed from one phase (e.g., wastewater) and transferred to another phase (e.g., activated carbon). This means that adsorption is a physical separation process in which the adsorbed material is not chemically altered. This implies that the activated carbon now contains the adsorbed material. Therefore, appropriate actions must then be taken to treat the spent activated carbon at the end of a cycle. The carbon can be regenerated, disposed or destroyed. Some of the common adsorbents are activated carbon, silica gel etc. The driving force for adsorption is the reduction in interfacial (surface) tension between the fluid and the solid adsorbent as a result of the adsorption of the adsorbate on the surface of the solid.

Adsorption equilibrium:
Upon contacting an amount of adsorbent with a solution containing an absorbable substance adsorption will take place. Adsorption will continue until equilibrium will be established between the substance in solution and the same substance in the adsorbed state. At equilibrium a relationship exists between the concentration of the species in solution and the concentration of the same species in the adsorbed state (i.e., the amount of species adsorbed per unit mass of adsorbent).

Breakthrough point and curve:

When the air containing moisture is made to flow over the silica gel, the moisture present in the air gets adsorbed on the gel. The ratio of outlet concentration of moisture in air C and the inlet concentration Co is plotted with the time on other axis. The obtained curve is called breakthrough curve. The shape of this curve is generally S shape. The characteristic shape of this curve will depend on the equilibrium between the solid and liquid phase, and is based on the kinetic adsorption process which is divided into four phenomena: 1. Diffusion in the bulk fluid 2. External mass transfer 3. Intra-particular mass transfer 4. Micro-pore adsorption The steepness of the breakthrough curve determines the extent to which the capacity of an adsorbent bed can be utilized. Thus, the shape of the curve is very important in determining the length of the adsorption bed. In this experiment a fluid mixture is passed through a stationary bed of adsorbent. As the increasing amounts of fluids are passed through such a bed, the solid adsorbs increasing amounts of solute, and an unsteady state prevails. This technique is very widely used and finds applications in: 1. Recovery of valuable solvent vapors from gases 2. Purifying air through gas masks

3. Dehydration of gases and liquids 4. Decolorizing mineral and vegetable oils In the present experiment air is passed through a bed of silica gel and the properties of the output gas are studied. The idealized adsorption curve is shown below.

Figure 1. The idealized adsorption curve

D) EXPERIMENTAL DIAGRAM:

Apparatus required:
1. Air pump which pumps atmospheric air containing moisture 2. Glass rod filled with silica gel 3. Sensors that detect temperature and humidity 4. Weighing machine to measure the initial and final weight of silica gel. 5. Stop watch (mobile) 6. Bubble flow meter, for measuring the volumetric flow rate of the air.

E) EXPERIMENTAL PROCEDURE:
1. Before beginning the experiment, measure the weight of the adsorbent trap. Also make a note of the outlet relative humidity, dry bulb temperature and wet bulb temperature. 2. Set up the apparatus as shown in the figure above. Connect one end of the glass rod to the hygrometer and the other to the aquarium pump. 3. Note the values of relative humidity and temperature from the RH meter once every five minutes and weight of silica gel tube once every ten minutes. 4. Note the value till the relative humidity reaches 90% of its initial value. After this is finished, disconnect the glass rod and measure the weight of silica gel after the experiment. 5. Now measure the flow rate of the feed using the given soap bubble flow apparatus.

F) PRECAUTIONS:
1. The tubes should be tight, and there should be no blockages. 2. The adsorbent trap should not be moved since the area of contact between the bed and the feed might change. 3. While measuring the flow rate with the bubble flow meter, the fluid should not enter the bottom of the glass tube. 4. The silica gel is poisonous to health so care is to be taken while handling it. It should not be inhaled. 5. All the glass ware used should be handled carefully, especially the bubble flow meter. 6. During the experiment, flow rate is to be measured three or four times and an average value should be taken. 7. The apparatus should not be disturbed during the experiment as it may alter the flow rates. 8. The color of the silica gel gives an indication of how much humidity has been adsorbed, hence it should be observed to determine how close the gel is to saturation.

G) EXPERIMENTAL DATA:
Initial observation data:
Initial humidity = 68.9% Initial temperature = 27.3 degrees Celsius Length of silica gel = 3.6 cm Initial weight of the silica gel + tube + cotton = 5.6628 gm. Final weight of the silica gel + tube + cotton = 5.822 gm. Accumulated weight of water vapor approximately is = 0.1592 gm. Average density of air (kg/m^3) = 1.163 Initial weight of silica gel = 0.9908 gm. Weight of Glass and Cotton = 4.672 gm Two sand tubes were kept downstream to reduce the flow rate of air. The masses of both the sand tubes were measured before and after the experiment. They remained same, hence allowing us to conclude that the sand did not adsorb/absorb any water. Weight of sand packings before the experiment= 7.22 gm Weight of sand packings before the experiment= 7.22 gm

The tabulation of the variation of RH, Dry bulb temperature and Wet bulb temperature with time is given below: Time (minutes) 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 Dry bulb Wet bulb Temperature Temperature (degrees Celsius) (degrees Celsius) 27.3 23 27.3 10.6 27.4 10.3 27.6 14 27.6 16 27.9 18.7 27.9 19.7 28.2 20.6 28 20.7 28 21.1 27.9 21.2 28 22 28 21.7 28.1 22.1 28 21.9 27.8 21.5 27.8 21.7 28 22.4 28 22.2 28 22.3 27.8 22

Relative humidity (%) 68.9 6.3 4.8 19.6 29.2 41.8 46.8 50.4 51.8 54.1 55.1 59.5 58 59.2 58.7 57.7 58.5 61.5 60.5 61.4 60.3

The variation of the weight of the trap along with time is given below: Time (minutes) Trap weight (gm) 0 5.67 10 5.71 20 5.74 30 5.77 40 5.78 50 5.79 60 5.8 70 5.81 80 5.82 90 5.83 100 5.83

Once the experiment was performed, the flow rate of air was measured. This was done by using a setup in which a soap bubble was made to traverse a known volume and the time was measured using a stopwatch. This was repeated many times to get a more accurate estimate of the flow rate. Time Flow rate (seconds) Travel(ml) (ml/minute) 12.19 20 98.44135 13.82 25 108.5384 13.75 25 109.0909 13.66 25 109.8097 14.24 25 105.3371 This averages out to 109 ml/minute as the flow rate of air. Moving Front of the Silica Gel:

Front after 2 minutes

Front after 4 minutes

Front after 5 minutes: Near breakthrough region

H) SAMPLE CALCULATIONS:
At each point the weight of the silica gel was measured, the gel was in equilibrium with the exiting concentration of water-vapor in air. The breakthrough happened very fast, and this took place in just over eight minutes. Please refer to the photographs in the experimental data section. The sample calculation done here is at t=30 minutes. Since we know both the dry and wet bulb temperatures, we use it to find the absolute humidity of the air which is exiting the silica gel.

Where, Tdry = Dry bulb temperature, Twet = Wet bulb temperature, w= Latent heat of water at wet bulb temperature Yw = wet bulb 100% humidity, Y = Absolute humidity

Using psychometric charts from Robert Treybal et al, the values were calculated. For example, at a wet bulb temperature of 19.7 C, the latent heat is 25,00,000 J/kg and YW = 0.0151. Substituting all the above terms into the formula, the actual absolute humidity is measure. This is obtained as Y = 0.011984 kg H2O/kg of dry air. The next step in the calculations was to convert this into concentration units. This was just done by assuming that dry air was an ideal gas. Hence for dry air, PV = nRT, and using this, the volume of 1 g of dry air was found as V of 1g of dry air = 0.0008497 m3 Similarly 18g of H2O, constitute a mole of water. Concentration of water was found as C = Y/(18*0.0008497)= 0.60649 mol/m3 Also, q was estimated as q = (Mass of adsorbate)/(Mass of adsorbent) q = (0.1/.9908) = 0.1009 These calculations were repeated for different time instants and the respective curves were plotted.

= 950

(Lewis Relation for air-water vapor systems)

The flow rates of air were calculated by dividing the volumes by the time taken. The average flow rate as obtained as: Q = 109.7481ml/min Mass Transfer Coefficient: Sh = 2.0 + 1.1*Re0.6*Sc0.33 for Re>3 This relation is from the Perrys handbook. Where, Re = Reynolds Number Sc = Schmidt Number = Porosity To find porosity: Mass of silica gel=0.9908g Density of silica gel (s) =2200kg/m3 => V=0.9908/2200000 = 4.5X10-7 m3 tube

Actual volume occupied = length of packing(L) * area of cross-section of = 3.5x10-2 X 3.14X0.42X 10-4

=1.75X10-6m3 = 0.25

Porosity() =

Reynolds number Re = Sc =

=(0.25*1.225*0.008*0.05869)/(1.86*10-5)=7.73

=0.76

Sh = 2+1.1*(5.875)0.6*(0.76)0.33 =5.42 = k= (5.42*2*10-5)/(0.008)= 0.0135 m/s

I) ERROR ANALYSIS:
1. Error in calculating porosity

2. Error in calculating Re = + Re=

3.142

+2

0.001 0.61

0.001 0.035

+2

0.01 0.4

= 0.08=8%

= 0.08+0.0125=0.0925=9.25 %

k = 2+1.1 0.6 0.33

3. Error in calculating k = 0.6

= 0.043 = 4.3%

J) RESULTS AND DISCUSSION:

The breakthrough curve is plotted below:

18 16 14 Mass of vapour per mass of dry air (g/kg) 12 10 8 6 4 2 0 0 20

Breakthrough curve

40

Time (min)

60

80

100

120

We can see that around 1 hour, the value of the Y axis does not change much with time. This is called the exhaust point of the curve.

At around 8-10 minutes, the Y axis is at a minimum value, which is the break point of the curve. This indicates that the silica gel is saturated with water vapor. The scatter plots the mass of adsorbed water/ mass of silica gel versus the absolute and relative humidity have also been plotted.
Weight of water absorbed/weight of silica gel 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0 0 5 10 15 20 Absolute humidity (g/m^3) 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0 0 10 20 30 40 50 60 70 Relative humidity (%)

From the calculation shown above, k is found to be approximately 0.0135 m/s.

1. Calcium hydroxide could be used instead of silica gel, as it is difficult to observe the wave front when the flow rates of air are high.

Weight of water absorbed/weight of silica gel

K) SUGGESTIONS:

2. Flow rate measuring equipment, such as a rotameter, can be improved. 3. Lower flow rates of air are required for this setup. 4. A program which records outlet humidity and temperatures at regular time intervals can be used for more accurate measurement. 5. Adsorption studies with varied flow rates of air can be done. 6. Disturbance of silica gel tube may show the deviation in result so make it steady.

L) CONCLUSIONS:

The breakthrough curve has been plotted.There is a discrepancy of around 0.0008 grams of water, when we compare the readings taken on the trap, which indicates a loss of 0.16 grams of water and the value that has been absorbed by the silica gel, which indicates a loss of 0.1592 grams of water. This small deficit has in reality, been absorbed by the glass casing of the trap.

M) REFERENCES:
1. Perrys Chemical engineering Handbook, 7th edition, McGraw-Hill publishers. 2. Mass Transfer Operations, Robert E. Treybal, 3rd Edition. 3. www.engineeringtoolbox.net 4. Conversion from Relative to Absolute humidity: http://www.humidity-calculator.com/index.php