Extraction of Polystyrene micro beads from EPS with Optimum Solvent Recovery

Purpose Of the Project

EPS- Expanded Polystyrene popularly known as Thermocol It consists mostly of voids filled with gas and are considered as Use-Throw materials Polystyrene micro beads are of more economic value This project is to obtain a more economic valued beads from Thermocol waste with an optimum solvent recovery

Stages Of Project
1) Extraction Of Micro beads
Dissolution of EPS in a solvent Phase Preparation Of Emulsion Separation Of Micro beads from Solvent Phase

2)Solvent Recovery Process

Need for most economical way with optimum recovery

Solvent Selection
D-Limonene is preferred as it is obtained from a renewable source (citrus oil) and is environment friendly solvent Initial stage of experiments are carried with toluene as solvent as it is cheaper than D-limonene and it readily dissolves poly styrene These results can be extended to d-limonene as solvent Solubility parameter values should be studied to select a suitable solvent for a dissolving polymer

Solubility Parameter
Dissolution of an amorphous polymer in a solvent is governed by the free energy of mixing Gm = Hm - TSm where Gm is the Gibbs free energy change on mixing, Hm is the enthalpy change on mixing, T is the absolute temperature, and Sm is the entropy change on mixing. The heat of mixing must be smaller than the entropic term for polymersolvent miscibility Gm < 0 The cohesive energy, CED; of a material is the increase in the internal energy per mole of the material if all of the intermolecular forces are eliminated Cohesive energy density = CED = (Hvap - RT)/V

Hildebrand Solubility parameters

Solubility Parameter is given by square root of CED d = (CED)1/2= ((Hvap - RT)/V)1/2 Hmix = Vmix[(E1/V1)1/2-(E2/V2)1/2]*(12) Hmix = Vmix[d1 - d2 ]*(12) 1 2 are mole fractions of solute and solvent Vmix is Volume of mixture E1 is energy of vaporization of specie 1 V1 is molar volume of specie 1 Therefore, [d1 - d2] should be small for dissolution.

Solubility Parameter Values

Solubility parameters for some common Solvents

Solubility parameters for some common polymers

Experiment

 Prepared samples of different wt% of EPS in toluene (1%, 2% and 4% of EPS in toluene). Solvents used are water, methanol, 1:1mixture of water and methanol. Take EPS- Toluene sample of known concentration in a test tube which forms the oil phase. To this sample (oil phase) add the solvent, drop by drop until the inversion phase occurs. Now shake the test tube to ensure proper and uniform dispersion and observe the formation of beads and observe their behaviour (i.e. stability, coagulation etc.).

Observations
For water as solvent, no beads are formed (irrespective of concentration of EPS-toluene sample), but the mixture sample is retained at the top surface of water. Shaking resulted in dispersion of EPS sample into polystyrene beads which immediately settled at the surface of water. For EPS-Toluene in methanol we got thread like structured fibers after immediate drying For EPS-toluene in 1:1 methanol/water emulsion, milky solution is formed, and slowly beads coalesce to form thread like structures.

Effect Of Concentration
These results are similar for 1%,2%,5% EPS in toluene So as far as concentration change is concerned no significant change is observed Also for all these concentrations, there was immediate separation of phases (oil phase at the top and water at the bottom) So in all the cases of experiments above, we stirred rigorously & within no time poured onto flat plate and dried it So we need to obtain stability of emulsion to prevent the separation of phases

Density effects
When tested with increased concentration of EPS in toluene(20%), the results ( Polystyrene Spheres Formation) were better with water than the remaining two solvents. This could be because of difference of densities of oil phase with that of solvent phase Increasing to 20% w/w of EPS (in toluene) will make the density of oil phase approximate to that of water Hence the possible dispersion occurs instead of immediate phase separation

Viscosity Effects
But increasing concentration increased the viscous nature of oil phase Difficult to separate the oil phase itself Also makes stirring difficult

Take away
Hence concentration of EPS in Toluene should be optimal considering the density and viscosity effects If possible a third component should be added to oil phase which doesnt increase viscosity but increases density Also for stability of emulsion, addition of emulsifier is must

What are Emulsifiers

When there is a problem of making an emulsion, emulsifying agent can be used to stabilize the emulsion

Selection Of Emulsifier- The HLB System

There are hundreds of emulsifiers which are available in industry But only the appropriate emulsifiers can serve the purpose efficiently The selection of emulsifier can be done on the basis of HLB system HLB stands for Hydrophile-Lipophile Balance All emulsifiers consist of a molecule that combines both hydrophilic and lipophilic groups

HLB System
Hydrophile-Lipophile Balance is the balance of the size and strength of the hydrophilic (waterloving or polar) and the lipophilic (oil loving or non-polar) groups of the emulsifier. The HLB System enables you to assign a number to the ingredient or combination of ingredients you want to emulsify, and then to choose an emulsifier or blend of emulsifiers having this same number An emulsifier that is lipophilic in character is assigned a low HLB number (below 9.0), and one that is hydrophilic is assigned a high HLB number (above 11.0). Those in the range of 9-11 are intermediate.

Available emulsifiers in lab: SLS Tween 80 (HLB Value = 15) Span 80 (HLB Value = 4.3) The emulsifier we selected is Tween 80 Because the HLB number matches with that of ingredient Toluene

Experiment Ingredients
Solvent Conc of Eps in Toluene Emulsifier Concentration Stirring time Water 5% 5% of toluene 30 min Water 5% 10% of toluene 30 min Water 20% 5% of toluene 30 min Water 20% 10% of toluene 30 min

Solvent Conc of Eps in Toluene Emulsifier Concentration Stirring time

Methanol 5%

Methanol 5%

Methanol 20%

Methanol 20%

5% of toluene 30 min

10% of toluene 30 min

5% of toluene 30 min

10% of toluene 30 min

Solvent Conc of Eps in Toluene Emulsifier Concentration Stirring time

1:1 Met/Wat 5% 5% of toluene 30 min

1:1 Met/Wat 5% 10% of toluene 30 min

1:1 Met/Wat 20% 5% of toluene 30 min

1:1 Met/Wat 20% 10% of toluene 30 min

Taken Ingredients: Solvent: Water and Methanol Oil phase: Eps in Toluene of different concentrations Emulsifier: 4:1 blend of Tween 80 and Span 80 HLB Value of Blend of two emulsifiers: HLB Value of E1 = HLB1 HLB Value of E2 = HLB2 Volume fraction of E1 = x1 Volume fraction of E2 = x2 HLB Value of Blend = x1 * HLB1 + x2 * HLB2 For Tween 80 : Span 80 = 4:1 HLB Value of Blend = 0.8*15 + 0.2*4.3 = 12.86 Result No convincing change

Contd..
Emulsifier: Sodium Lauryl Sulphate Result: Addition of SLS to water phase: Mixed SLS in water and then added the oil phase drop by drop. After stirring and drying, we got fibrous structured polystyrene Addition of SLS to Oil phase: Taken SLS in oil phase and added water drop by drop to the oil phase We were able to get relatively good results in this case But after the stirring is done, in about 5-10 min and when the emulsion is poured in a flat plate we obtain small beads separated but after some time they coalesce

Take Away: In the first case i.e. addition of SLS to water, relatively amount of water taken is more, so the SLS concentration is less. So the SLS particles are less probable to interact with oil phase particles and hence unable to form emulsion but form the continuous fibrous structures. In the second case, i.e the addition of SLS in oil phase and adding water drop by drop to the oil phase, the SLS concentration is more in the initial oil phase taken and each water droplet is well dispersed due to parallel stirring so that SLS particles interact with the phases and hence forming clear emulsion. But immediately after adding large amount of water the sls concentration is decreased and as the time passed ,the emulsion poured in a flat plate initially, having the small beads well separated coalesced to form larger structures

Take Away: Actual HLB value of the oil phase has to be determined Because it is a mixture of Eps in Toluene not the pure toluene the HLB value may differ from 15 The procedure to determine HLB of system is Take the Eps in toluene solution Then prepare different ratios of Tween 80; Span 80 Now mix these samples(5% to 10% of weight of oil phase) with the emulsion and stir it Then find out the emulsion which have greater stability and it is the HLB value of the system of ingredients taken

Tween 80 1.0 0.9 0.8 0.7 0.6 0.5

Span 80 0 0.1 0.2 0.3 0.4 0.5

HLB 15

12.86

9.65