Converting Waste plastic To Gasoline-like Fuel at low temperature

Nagi Insura, Jude Onwudili and Paul T. Williams, Energy and Resource Research Institute, School of Process, Materials, Environmental Engineering, University of Leeds 1. Introduction
Growing amounts of solid waste and the need for its disposal is currently generating worldwide concern regarding the environmental, health and economic issues. Waste plastics represent a large fraction of municipal solid waste. In the UK, the quantity of plastic waste produced yearly is almost 3 million tonnes. European legislations require reducing the amount of organic waste sent to landfills and encourage recycling and energy recovery .In addition to environmental and economic benefits, it greatly improves the recycling of waste. Consequently recycling of waste plastics is carried out in many ways. According to a 2001 UK Environment Agency report, 80% of plastic waste was sent to landfill, 8 % to incinerator and the amount recycled was about 7-10 % . Recently, there have been promising developments in recycling plastic waste by thermal treatment techniques. Besides avoiding the risk outcomes from landfills and incinerators, thermo chemical recycling produces cheap resources of energy & chemical feedstock.

3. Experimental procedures
3.1 Materials: Real plastic waste, German source 3.2 experimental reactor: The reactor used here is
batch pump reactor, Fig 1. It is characterised by allowing Pyrolysis under high pressure and long residence time so secondary reaction can be performed. The following schematic diagram of the reactor used for thermal and catalytic pyrolysis of plastic waste. It was heated by a mantle Type Furnace covers the reactor sides.
Air purging and sampling valves

Pressure gauge

Heat controller

2. Objectives
The main objective of this study is to convert waste plastic into valuable hydrocarbon fuel and raw chemical feed stock by investigating the effects of a zeolite catalyst, temperature and residence to ascertain the optimum conditions necessary for the desired proportions of products.

3.3 procedures
Sample heated under nitrogen gas at specific temperature ( 400, 425, 450 and 500C) for 0-1 hour. CaO used here to scrub CO2 from gas product.
Fig 1 . Diagram of pyrolysis pump reactor

Reaction vessel Sample

3.3.1 product analysis

Pyrolysis product s were mainly characterised by GCs and FTIR. For gas product, hydrocarbon gas were analyzed on a Varian C-3380 gas chromatograph with a Flame Ionization Detector. Permanent gases were analyzed on a Varian CP-3380 gas chromatograph fitted with a thermal conductivity detector. Oil product was analysed mainly by GC/FID and extra analyses with GC/MS and IR spectrometry to characterize and confirm oil composition.

4.3 Influences on the composition or distribution of oil product

60 50 40 yie ld, w t % 30 20 no catalyst 2 g zeolite

Inert atmosphere + 425 C 30 min

Mixed real waste plastic

HZMS-5 with CaO

Gasoline like oil

Fig 6. shows oil samples of oil product from thermal pyrolysis (1&2) and sample from catalytic pyrolysis with zeolite catalyst (3).

4. Results
4.1 Yield of pyrolysis products
Table 1. shows product yield at 425 C in presence and absence of catalyst product yield, wt % Thermal Pyrolysis Catalytic Pyrolysis with Zeolite (No catalyst) Oil Gas Solid Residual (char & CaO ) 76.7 1.2 7.3 0.50 16 1.2 81.4 0.96 9.6 0.81 9 0.4

10 0 cycloalkanes alkanes alkenes aromatics

5. Discussion
5.1 The influence of a catalyst:
With thermal cracking of mixed plastic waste at 425 C, 60 min, oil components were distributed from C4-C38 aliphatics with low yield of aromatics and naphthenes. 40 wt % of its structure was distributed in the gasoline range. However in presence of HZMS-5 zeolite catalyst, plastic waste was conversed to lighter fractions at 425 C, even at lower reaction time, 30 min. It improved oil and gas yields while char yield reduced. It increased the yield of alkanes by increasing propane gas ratio to nearly 50 % gas yield as well as butane yield while other gases yield reduced such as alkenes, hydrogen and carbon mono oxide as shown in table 1 and Fig 2. At this low temperature, 425 C, even at 30 min oil product distributed within gasoline range boiling points. As it is showed in the fig 6 oil is clear and has light color. It is dominated by aromatics, nearly 60 wt %, in addition to aliphatics, 30 % and around 6 % of cycloalkanes as it is seen in Fig 3. There were only seven main components including ethyl benzene, toluene, benzene, xylenes as in Fig 4. The mixture contained other compounds such as C5-C15 aliphatics, alkyl benzene, alkyl toluene, naphthalene and alkyl naphthalenes furthermore, 99 wt % of its structure was within gasoline range. Those compounds have a high octane rating number and therefore would raise the total octane number of oil product. The oil composition was in the light range and could be said to be gasoline-like. 100 % of oil components with boiling point less than 240 C according to simulated curve in Fig 5 moreover, it had high calorific value, 48 MJ/kg, made it an excellent fuel. The results showed that HZMS-5 catalyst is highly active in the liquefaction of mixed plastic waste to give high yields of very light gasoline-like oil with high aromatic content. The high activity may be attributed to high acidity strength, high pore size and high surface area. The high pore size permits even larger molecule hydrocarbons to go inside the pore, adsorbed and experienced catalytic reactions such as dehydrogenation, cyclization and aromatization, thus increasing the content of single ring aromatics and other light hydrocarbons in the derived oil. Besides it has strong acidity make it active catalyst in romatization.

-Catalyst presence enhanced the yield of both gas and oil products, whereas it reduced the yield char product.

4.2 Distribution of gas product.

Fig. 4 the effects of zeolite catalyst in enhancing of the yield of aromatics in pyrolysis oil product.

Fig 2. Shows gas product distribution at 425 C in presence and absence of zeolite catalyst Propane and butane ratios are highly enhanced. Propane gas dominated gas product 46 wt % followed by butane , 22 %. Consequently the total alkane yield increased to 83.7 wt %. Increasing the saturated gases in gas product is definitely will increase its calorific value since alkanes have higher values than unsaturated ones. Gas product could be used as heating or energy source either for the same process or others.

Fig.5 shows simulated distillation curves of oil products comparing to gas fuel oil

Fig. 3 pyrolysis oil produced at 425C in presence and absence of zeolite catalyst

6. Conclusion
Real commingled plastic waste has been pyrolysed in a autoclave reactor at 425 for 30 or 60 min in presence and absence of HZMS-5 catalyst. Calcium oxide was used to remove acidic gases such as hydrogen halides and carbon dioxide from gas product. HZSM-5 zeolite catalyst is very active to perform the pyrolysis under low levels of temperature and residence time. In presence of catalyst, oil and gas yields improved in favor of reduction of char product yield. The gas product is dominated by propane and butane gases compared to that in absence of catalyst. The influence of catalysts noticeably increased the yield of single ring aromatic compounds in the derived oil. The derived oil structure changed to a light structure where concentration of aliphatic fraction is decreased. In addition; carbon number distribution is shifted to lower values creating very light oil with distribution similar to that in gasoline fuel. Oil components distributed within boiling point range up to 240 C. The main aromatic hydrocarbons in the oils were toluene, ethylbenzene, xylenes, propylbenzene, butyl benzene, benzene in addition to short chain aliphatics and cycloalkanes dominated by C6 and C7. The activity and selectivity of ZSM-5 catalyst enhanced the aromatization mechanism in catalytic pyrolysis of real mixed plastic waste.