Foam Fractionation of Surfactant using a semi-batch Foam-bed Reactor

Balraj Singh Meena, Amit A. Gaikwad and Ashok N. Bhaskarwar Department of Chemical Engineering Indian Institute of Technology, Delhi Hauz Khas, New Delhi 110 016 INDIA The purpose of this study was to investigate the use of foam fractionation to recover surfactant from aqueous reacting solution. A semi-batch foam-bed reactor was used for the first time to study the foam fractionation in the presence of a chemical reaction. In all the foam fractionation studies reported so far, only physical processes occurred. Here, we attempted to study foam fractionation of a surfactant in the presence of a chemical reaction. The system chosen for this study was the carbonation of hydrated lime using pure carbon dioxide gas. Effect of various parameters like foam height, gasflow rate, initial surfactant concentration in the storage section, volume of slurry in the storage section, concentration of calcium hydroxide in the slurry, and type of surfactant on enrichment ratio were studied. Experimental results showed that enrichment increased with increase in the foam height, increase in concentration of calcium hydroxide in the slurry, decrease in surfactant concentration, and decrease in volume of slurry. Maximum enrichment was observed at a gas-flow rate of 8.5 lpm, above and below which the enrichment decreased. Two surfactants were used for the foam fractionation study, namely, cetylepyridinium tetrachloro zincate and sodium lauryl sulfate. The enrichment initially was similar for both the surfactants, but during the later stages of reaction (after 150s of operation), the enrichment for sodium lauryl sulfate was higher than that for cetylepyridinium tetrachloro zincate. Enrichment ratio as high as 7 was obtained during some experiments. The experimental results were in decent agreement (20% error margin) with the modified single-stage model of a foam-bed reactor (Gaikwad and Bhaskarwar, 2006).

1. Introduction
Surfactants can be present in low concentrations in effluent wastewater from various industrial operations. The increasing use of surfactant-based separation processes has resulted in the presence of surfactants in water generated by these processes. The surfactant concentration must be reduced to a permissible limit in order to meet environmental standards in discharging these wastewater streams to the environment. Also, in some cases, recovery of the surfactant for reuse is sometimes economical and desirable.

Foam fractionation has been shown to be an effective method of removing anionic or cationic surfactants from effluent streams. The purpose of this study was to investigate the use of foam fractionation to recover surfactant from aqueous reacting solution. A semi-batch foam-bed reactor was used for the first time to study the foam fractionation in the presence of a chemical reaction. In all the foam fractionation studies reported so far, only physical processes occurred. Here, we attempted to study foam fractionation of a surfactant in the presence of a chemical reaction. The system chosen for this study was the carbonation of hydrated lime using pure carbon dioxide gas.

2. Experimental
2.1 Experimental Set-up A schematic representation of experimental set-up is shown in figure 1. It consisted of glass column 0.79 m tall and 0.093 m in diameter. A glass cone was attached at the bottom of this column with the help of flanged joint. A distributor made of 0.003 m thick Perspex plate was placed between the flanges. An inclined manometer was attached to the manometer port of the reactor (not shown in the figure), which was located at a height of 0.16 m from the distributor plate. Two infrared lamps were used to heat the regulator of gas cylinder (not shown in the figure) to prevent formation of dry ice and to obtain a steady flow of carbon dioxide gas from the cylinder.

Figure 1 Experimental set-up for foam fractionation of surfactants 2.2 Experimental Procedure Slurry of known concentration of calcium hydroxide was prepared in distilled water. A known amount of surfactant was added to the slurry and mixed thoroughly. Carbon dioxide gas from the cylinder was metered by a rotameter and then fed into the column at the desired flow rate. When the flow rate of carbon dioxide became steady, the wellstirred slurry of calcium hydroxide was carefully poured into the column and a stopwatch was started immediately to measure the run time. The foam breaker sieve plate coated with n-butanol was then suspended from the top at the desired height to maintain the foam height and immediately. Foam was collected from foam section at various time intervals and at various foam heights. The concentration of the surfactant in the collected foam samples was measured (Vogel, 1989).

Effect of various parameters like foam height, gas-flow rate, initial surfactant concentration in the storage section, volume of slurry in the storage section, concentration of calcium hydroxide in the slurry, and type of surfactant on enrichment ratio were studied. In the graphs, the markers represent the experimental data while the lines represent the model predictions.

3. Results and discussion

The experiments were repeated two-to-three times to ensure reproducibility of results. While analyzing the effect of one parameter, efforts were made to keep rest of the parameters constant. The results were interpreted in terms of enrichment ratio of surfactant which is defined as the ratio of concentration of surfactant in the foamate to that in the initial slurry. 3.1 Effect of Foam Height The foam height was varied from 0.4 m to 0.6 m keeping all other parameters constant. As seen from figure 2, enrichment increased with time for any foam height. It also increased with increase in foam height. The increase in enrichment with time took place because the surfactant molecules got adsorbed on calcium carbonate and also at the gasliquid interface. Enrichment increased with increase in foam height because liquid-hold up decreased with the increase in foam height. Hence, at higher foam heights, where liquid hold-up was lesser, the surfactant concentration was higher as compared to that at lower foam heights. The slight reduction in enrichment after 240s might be because of the fact that some surfactant molecules adsorb on the foam breaker plate. Also, most of the surfactant had already been removed from the slurry during sample collection; hence the overall concentration was reduced. The experimental results were in decent agreement (20% error margin) with the modified single-stage model of a foam-bed reactor (Gaikwad and Bhaskarwar, 2006).

7 6 5 enrichment (-) 4 H = 0.40 m 3 2 1 0 0 50 100 150 Time (s) 200 250 300 350 H = 0.40 m (model) H = 0.50 m H = 0.50 m (model) H = 0.60 m H = 0.60 m (model)

Figure 2 Effect of foam height on enrichment 3.2 Effect of gas-flow rate As shown in figure 3, when the flow rate was increased from 7.5 lpm to 8.5 lpm, enrichment increased but when the gas flow rate was further increased to 9.5 lpm, the enrichment decreased (experimental). At higher flow rates there was a decrease of enrichment ratio presumably due to increased hold-up which reduced the surfactant

concentration in the foamate and also due to increased bubble size which reduced the interfacial area available for adsorption of surfactant molecules. The model was not able to predict this decrease in enrichment at higher gas-flow rates.
8

enrichment (-)

4
Q = 7.5 lpm

Q = 7.5 lpm (model) Q = 8.5 lpm

Q = 8.5 lpm (model) Q = 9.5 lpm

1
Q = 9.5 lpm (model)

0 0 50 100 150 200 250 300 350

time (s)

Figure 3 Effect of gas-flow rate on enrichment 3.3 Effect of initial surfactant concentration in the storage section As shown in figure 4, when the surfactant concentration was increased from 1000 ppm to 4000 ppm, enrichment decreased presumably due to higher foam stability at higher surfactant concentration in the foam.
8 7 6 enrichment (-) 5 4
C = 1000 ppm

3 2 1 0 0 50 100 150 Time (s) 200 250

C = 1000 ppm (model) C = 2000 ppm C = 2000 ppm (model) C = 4000 ppm C = 4000 ppm (model)

300

350

Figure 4 Effect of initial surfactant concentration on enrichment 3.4 Effect of volume of slurry in the storage section The volume of slurry was varied from 200 ml to 300 ml and effect of the variation of volume of slurry on the surfactant concentration was observed as shown below in the figure 5. The enrichment decreased with the increase in the volume of slurry possibly because the liquid hold-up increased with volume. This might also be due to the fact that the initial surfactant concentration was same in all these experimental runs and the amount of surfactant removed was the same, hence the enrichment decreased for larger volumes.

5 enrichment (-)

3
V = 200 ml V = 200 ml (model)

V = 250 ml V = 250 ml (model)

V = 300 ml V = 300 ml (model)

0 0 50 100 150 Time (s) 200 250 300 350

Figure 5 Effect of volume of slurry in the storage section on enrichment 3.5 Effect of concentration of calcium hydroxide in the slurry The concentration of calcium hydroxide in the slurry was varied from 30 g/l to 50 g/l. As shown in figure 6, the enrichment increased with increase in concentration due to the fact that at higher concentrations, the number of molecules of calcium hydroxide available were higher leading to higher adsorption of surfactant molecules thereby increasing enrichment.
8 7 6 enrichment (-) 5 4 3 2 1 0 0 50 100 150 Time (s) 200 250 300 350

C = 30 g/l C = 30 g/l (model) C = 40 g/l C = 40 g/l (model) C = 50 g/l C = 50 g/l (model)

Figure 6 Effect of volume of slurry in the storage section on enrichment 3.6 Effect of nature of surfactant Effect of cetylepyridinium tetrachloro zincate (CPTZ) and sodium lauryl sulphate (SLS) were studied. As shown in figure 7, there was little difference in the enrichment ratio for both the surfactants initially but with the increase in time the difference in enrichment ratio increased. SLS has higher foam stability at higher concentrations than CPTZ one due to which the concentration of the SLS in the foam was higher leading to higher enrichment.

7 6 5 enrichment (-) 4 3 2 1 0 0 50 100 150 200 250 300 350 Time (s)

SLS SLS (model) CPTZ CPTZ (model)

Figure 7 Effect of nature of surfactant on enrichment

4. Results and discussion

A semi-batch foam-bed reactor was used for the first time to study the foam fractionation in the presence of a chemical reaction. In all the foam fractionation studies reported so far, only physical processes occurred. In this work, we attempted to study foam fractionation of a surfactant in the presence of a chemical reaction. Experimental results showed that enrichment increased with increase in the foam height, increase in concentration of calcium hydroxide in the slurry, decrease in surfactant concentration, and decrease in volume of slurry. Maximum enrichment was observed at a gas-flow rate of 8.5 lpm, above and below which the enrichment decreased. Two surfactants were used for the foam fractionation study, namely, cetylepyridinium tetrachloro zincate and sodium lauryl sulfate. The enrichment initially was similar for both the surfactants, but during the later stages of reaction (after 150 s of operation), the enrichment for sodium lauryl sulfate was higher than that for cetylepyridinium tetrachloro zincate. Enrichment ratio as high as 7 was obtained during some experiments. The experimental results were in decent agreement (20% error margin) with the modified single-stage model of a foam-bed reactor (Gaikwad and Bhaskarwar, 2006).

References
Gaikwad A.A. and Bhaskarwar A.N., 2006, Removal of carbon dioxide in a foam-bed reactor, International Conference on Environmental Science and Technology, Air Pollution and Air Quality Control, Waste Gas Control Techniques, August 19-22, Houston, Texas, USA. Vogel, A. I., 1989, Textbook of quantitative chemical analysis. Longman Scientific and Technical, England.