Polyethylene from Ethanol/Manufacturing Instructions

=Ethanol production= Ethanol can be purchased or produced on-site

=Construction of fluid bed reactor= Instructions for construction of fluid bed reactor can be found on its own wikipage.

=Ethanol dehydration catalyst preparation protocol=

Gamma aluminium oxide doped with Ti02 has been reported to have 99%+ yields and selectivity and has been shown to be superior to other metals.

Protocol for preparation:

1. Combine 4 kg (approximately 1 l) g-Al2O3 with 5.0 l 0.5 mol/L Na2CO3 (264.9 g) solution in a three-necked rounded-bottomed ﬂask.

2. Calculate 10% wt content for TiO2 and solve for titanium sulfate addition(4 kg * .1 = 400 g/79.8 g/mol TiO2 = 5.01 mol = 5.01 mol * Ti(SO4)2 240 g/mol = 1202.37 g Ti(SO4)2). Add 26.4 l 0.19 mol/L Ti(SO4)2 aqueous solution and 26.4 l 0.5 mol/L Na2CO3 solution are added simultaneously with high agitation. Maintain the solution between pH 7-8.

3. The sulfate precipitate is washed at 4000 g over to remove the sulfate solution. The solution is then dried at 110 for 8 hr and then calcined at 500 C for 4 hr.

4. The calcined catalyst is crushed and sieved through 30-50 mesh.

=Dehydration reaction protocol= 1. The reaction zone is filled with catalyst, sealed, and connected to the subsystems.

2. A temperature of 420 - 440 C is established by the heat jacket and a light nitrogen flow is maintained.

3. Ethanol is loaded into the vaporization chamber and heated to 200 C with a Liquid Hourly Space Velocity of 50-100 v/v/hr.

4. Gas products flow through the three temperature phase liquid condenser and liquid water is removed and gaseous ethylene stored.

=Ethylene polymerization catalyst preparation= A simple Ziegler-Natta catalyst as reported by Goeke is proposed as a first generation polymerization catalyst that is economical and robust. Ti/Mg based catalysts are the foundation of much of the polymerization industry, and require an electron donating solvent (tetrahydrofuran THF), activator of triethylaluminium (TAE). Impregnation of catalyst on a silica base increases the interaction of the substrate and catalyst increasing activity of the catalyst

1. In a 5 liter flask combine anhydrous 41.8g (0.438 mol) MgCl2, in 2.5 l tetrahydrofuran (THF). Add 27.7 g (0.184 mol) TiCl4 in dropwise over 30 min with stir bar agitation. Add heat ~60 C for 30 min to completely dissolve TiCl4. THF 66 C boiling point

2. Dry 500 g silica at 800 C for 2 hr. Combine with 25 g triethylaluminum in 2 l THF at 60 C for 15 min. Dried activated silica at 65 C.

3. Impregnate support by combining 500 g porous silica with catalyst precursor mixture at 60 C. Dry the mixture at 60 C under N2 for 3-5 hr. Find method to control drying and ED content.

4. Prepare triethylaluminum in isopentane in 5-30% (v/v). Add to heated and loaded reactor.

=Polymerization reaction protocol= 1. The reactor is filled with the activated catalyst (~500 ml) on a silica support and an electron donating solvent such as tetrahydrofuran (THF).

2. A temperature of 95-100 C is established and the reactor pressurized to 150-350 psi.

3. Ethylene is added to the reactor in a mixture of nitrogen and hydrogen in a molar ratio of (5:3:2) with a gas flow of 2 m/s. TAE (5%) is added to the reactor in a molar ratio of 15-40 Al/Ti and 2-10% of the reaction mixture. A terminal alkene of C3-C8 is added to the mixture in the amount of 2-10% to control polymer density and acts to terminate chain lengthening. Controlling the density of the polymer is important to making products suitable for different applications, such as a low density polymer is suitable to being drawn into a film and a high density polymer is more suitable for injection molding.

4. Polythylene product is removed at the rate of formation as determined by the loss of ethylene in the recycle stream.