First Waste Plastic Conversion into Liquid Fuel by Using Muffle Furnace through Reactor

The oil consumption in the United States and Canada is much higher per cap ita compared to rest of the world. Even though only 37.1 % of o il is used as a supply source for all the major demand sectors like, industrial t ransportation, residential and electric power, it is a limited natural resource that cannot be replaced. Many alternative sources such as, solar, hydro power, wind and some others are availab le in s mall numbers. In the current economic situation of the world, it is practically impossible to bring these high cost energy sources into mass numbers. A method to convert waste plastics into liquid fuel has been implemented and exercised in a closed muffle furnace and a stainless steel reactor unit. The process involves thermally breaking down the hydrocarbon bonds of polymers in a muffle furnace with temperature of 420°C to turn into liquid slurry and that slurry is then processed through a reactor with temperature of 380°C to convert into liquid fuel. The fuel obtained is of quality grade and has been tested to work with most conventional engines, generators and such. This technology main point is to reduce the amount of carbon footprint caused by abundant waste plastic. This present technology will remove waste plastics that are harmfu l to our environment and convert those harmful waste plastics in to valuable oil sources to full fill the energy crisis and strengthen the economy.


Introduction
Energy crisis and environmental degradation by polymer was tes h av e b een imp erat iv e to f in d an d p ro p o s e technologies for recovery of raw materials and energy from non-conventional sources like organic wastes, plastic wastes, scrap t ires , et c. A variety o f met hods and p rocesses conn ect ed with g lo bal o r nat ional po licies hav e been proposed worldwide. A new type of a tubular reactor with the molten metal bed is proposed for conversion of waste plastics to fuel like mixture of hydrocarbons. The results of the thermal degradation of polyolefins in the laboratory scale set-up based on this reactor are presented in the paper. The melt ing and cracking pro cesses were carried out at the temperatu re 300-420℃. Th e final p roduct cons isted of gaseous product 6% and liquid product 85% stream. Few amounts of residue products were produced that 6%. The light, ''gasoline" fraction of the liquid hydrocarbons mixtu re is (C 4 -C 11 ) made the liquid p roduct. It may by used for fuel production or electricity generation [1]. Since the continuous increase in po ly mer production and consumption leads to accumulat ion of large amounts of plastic wastes that pose serious environ mental p roblems , the conversion o f these wastes into a common fuel oil can be considered as their most promising recycling method. So me poly mer materials e.g., polystyrene (PS), can be deco mposed thermally in high yields to the monomers. However, this is not true for polyethylene (PE) or polypropylene (PP), which is among the most abundant polymeric waste materials, typically making up 60-70% of mun icipal solid waste. However, most studies have mainly concentrated on the catalytic degradation of pure polymers. It wou ld be desirable to convert these waste polyolefins into products of value other than the monomers, because they offset the collection and pyrolysis costs. It seems also that in the process of plastic pyrolysis, a particular kind of catalyst is effective for a particular kind of plastic. Un fortunately it can only be applied to pure plastics and is not recommended for mixed plastic wastes. A more d ifficult task is tertiary recycling of commingled post-consumer plastic waste since it consists of not only hydrocarbons but also nitrogen and sulphur containing mixed poly mers as well as so me mod ified materials. Study of the product distributions from the degradation of mixture of post-commercial poly mer waste (LDPE/HDPE/PP/PS) and to especially develop a suitable reaction model for ach ieving post use polymer is recycling [2]. In v iew of their versatility and relat ively low cost, the consumption of p lastic materials has been growing steadily, although the disposal of waste plastics constitutes a severe environmental problem due mainly to their chemical inertness. While a poly mer recycling is a requirement to mitigate their impact on the environ ment [3], various tertiary recycling processes are attractive, since they produce valuable chemicals or fuels [4,5]. Considering polyolefins, polyethylene and polypropylene have a massive production and consumption in a large nu mber of applicat ions. The tertiary recycling of polyolefins (particu larly polyethylene) has been attempted under different approaches. The most used laboratory technique with some variations, is that of contacting the plastic with the catalyst in a closed environment, heating them together until reaction temperature, and allowing for a certain reaction-time; products are then separated and analyzed (e.g. [6,7]). However the process we use doesn't require the use of any catalyst therefore the process is more cost effective and environmentally friendly co mpared to the ones that are studied in prev ious research. Thermal or catalytic cracking of waste plastics is one of the possible methods of their utilizat ion [3][4][5][6][7][8][9][10]. As a result of the cracking at 400 C or higher process temperature some quantities of hydrocarbon mixtu res in the form of gas, liquid products (gasoline and diesel fuel boiling range) as well as higher boiling liquid residue or solid can be obtained [3,8,10]. All these products can be used as fuels or fuel components. Especially liquid products of gasoline and diesel fuel boiling range can be applied as co mponents of engine fuels. It is however necessary to remember that products of cracking or pyrolysis of polyolefin's are highly unsaturated and therefore they have to be further submitted to hydrogenation and skeletal isomerization if they are to be applied as engine fuels. Application is cracking or hydro cracking catalyst and higher process. Temperature can enlarge conversion of waste plastics. The main goal of application of hydro cracking catalyst and hydrogen is hydro cracking of plastics and hydrogenation of olefins in process products. Taking into account these premises in these studies waste samples waste plastics were used as raw materials in thermal process by using muffle furnace through reactor [8][9][10][11][12][13][14][15].

Materials
Waste plastic raw materials are collected fro m nearby groceries and supermarkets. After receiving the waste plastics they are separated out of all foreign materials such as food particle, paper, dust, cloth, glass, metal etc. The plastics are then washed with liquid soap (7 th generation company) and after washing they are dried for several hour in room temperature. After they are co mpletely dried the plastics are cut into small pieces with scissor to size 3-4 mm. During waste plastic washing period waste water was generated and waste water was kept into separate container for waste water treatment purpose. Waste water is treated with alkali and acidic method. Alkali is NaOH and acid ic solution is Potash Alum with different normality.

Raw Materi als Pre Analysis
Before liquefaction process the raw plastic are analyzed using Gas Chro matography and Mass Spectrometer (GC/MS) with Pyroprobe (CDS) gasification system and gasification system temperature was use 1200℃, FT-IR (Spectrum 100) ATR system, TGA (Pyris-1) and EA-2400. GC/M S is used to identify the co mpound structures of the plastics. This would g ive a clear idea of how the mo lecules of the poly mers will react in the temperature that will be used during the liquefaction p rocess FT-IR is used to identify the functional group of the plastics. TGA was used to find the onset temperature measurement telling what temperature range needs to be used to melt the plastic during the liquefaction process and finally the elemental analyzer (EA-2400) was used to identify the carbon, hydrogen, nitrogen percentage of the plastics. Waste plastic also per-analy zed by ICP (ASTM D1976) and found substantial metal content are percent such as Silver, Alu minu m, Boron, Bariu m, Calciu m, Chro miu m, Copper, Iron, Potassium, Lithiu m, Magnesium, Molybdenum, Sodiu m, Nickel, Phosphorus, Lead, Antimony, Silicon, Tin, Strontiu m, Titaniu m, Thalliu m, Vanadiu m and Zinc etc. all metal content present limit inside waste plastic ppm level. That metal content of the waste plastics act as a catalyst during the fuel production process. The metals are added to plastics during their production period to strengthen them as additive for co lor, hardness, softness and other good shape and additives was used 1-3%.

Experi mental Process Description
A muffle furnace type F 6000 fro m Barnstead International Co mpany was initially used to convert the plastic samples into liquid slurry. The plastics were placed into a ceramic crucib le and covered. Ceramic crucible can tolerate temperature up to 1200 ℃ and mu ffle furnace temperature can go up to 1400℃. The experiment took place inside a vacuumed fu me hood. The crucible with 300 g m of plastics was placed inside the muffle furnace then the door was closed to start the experiment. The furnace program setup and muffle furnace temperature setup at 420℃. Muffle furnace start from roo m temperature and ramping rate at 20℃ per minute. Hold at final temperature for 30 minutes. Then the sample was left to cool down at 5℃ per minute. When temperature went down from 300 to 290℃ the muffle furnace door was open to transfer the liquid slurry into the reactor chamber for condensation process. During muffle furnace process some light gas escaped out and absorbed by fume hood filter. Muffle fu rnace experiment run was under in presence of o xygen. 1 st step muffle furnace liquid slurry transferred into a steel reactor and set up condensation unit with co llect ion flask unit. This 2 nd step process was then heated at temperature ranging from 300-420℃ to convert the liquid slurry into vapor, and then the vapor travels through a condenser unit with water cooling system and at the end collected liquid fuel or p lastic fuel (Shown fig.1, ١).
Optimu m temperature was for th is experiment 370℃ fro m start to end of the experiment. Water circu lator system was used and cooling water temperature range was 16-17℃.
During production period some light hydrocarbon gas was generated which was not condense because of minus boiling point range and gas was methane, ethane, propane and butane. This light gas passed through alkali solution wash for removing contamination fro m gas. It's called natural gas or light gas. Natural or light gas was storage into Teflon bag and this gas can be reuse for samp le heating sources or other purpose. For plastic to produced plastic fuel cleaning purpose a RCI fuel purification system was used to remove water particles and fuel sediments at the end collected final fuel. Produced fuel density is 0.78 g m/ ml. By using this process fuel yield percentage is 85%, residue (black coal) yield percentage is 6% and light gas yield percentage is 6%. During this process no catalyst or any extra chemical because waste plastic pre analysis result showed plastics already contains metal which stimulated the thermal degradation process reaction in which the long chain hydrocarbon break down into short chain hydrocarbon. For that reason this experiment did not use any kind of catalyst. During production period the metal co mpounds did not co me out with liquid fuel as they were leftover residue or black coal inside. Residue or black coal which was hard and color was black has a Btu value.  Perkin Elmer GC-MS pyroprobe analysis of non-coded raw solid waste plastics inside of pyroprobe raw solid waste plastics ( fig.2, ٢ and table 1, ١) turns into volatile gas with high temperature at 1200℃ and that volatile gas passed through the column to gas chromatography, heliu m (He) is used as a carrier gas and then sends the volatile gas to the mass spectroscopy and in mass co mpounds are detected according to the boiling point of indiv idual co mpound and among those only several co mpounds are introduced as well Non-Code waste plastic was analyzed by FT-IR ATR (Attenuated Total Reflectance) KRS -5 diamond p late. In according to the wave nu mber following types of functional groups are appeared in the analysis. According to the wave number 2916.05 cm -1 , functional group is CH 2 , wave number 2848.53 cm -1 , functional group is C-CH 3, wave number 1463.95 cm -1 , functional group is CH 3, as we as wave number 1376.92 cm -1 , functional group is also CH 3 and ultimately wave number 718.84 cm -1 , functional group is -CH=CH-(cis) respectively. For Each and every wave nu mber band energy was calculated accordingly. Energy, E=hcW, where h=Plan k's Constant, c= speed of light and W= wave number, such as wave number 2916.05 cm -1 (CH 2 ), energy, E=5.79x10 -20 J, then wave number 2848.53 cm -1 (C-CH 3 ) energy, E=5.65x10 -20 J, wave nu mber 1463.95 cm -1 CH 3 ) energy, E=2.90x10 -20 J, wave number 1376.92 cm -1 (CH 3 ) energy, E=2.75x10 -20 J and eventually wave nu mber 718.84 cm -1 (-CH=CH-(cis)) energy, E=1.42x10 -20 J.

Raw Sample Pre-anal ysis
EA-2400 analysis result showed fro m non-coded waste plastic materials carbon present 85.3 %, Hydrogen present 13.4% and Nitrogen present 0.35% and EA -2400 was analysis sample CHN mode and carrier has was Oxygen, Heliu m and Nit rogen. TGA (Pyris-1) was use for raw material onset temperature and inflect ion point temperature determination and analysis temperature setup was for TGA 50-800℃ and temperature increase rate was 15℃/ minute and sample was use for analysis 2.9 mg. Carrier gas was use heliu m at 20 ml/ min. Non-coded waste plastics was analysis by TGA and graph obtain results showed inflection point temperature 413.89℃ and onset temperature was 387.81℃. Fro m those temperatures was determined liquefaction temperature set up for waste plastic to liquid fuel production process. This analysis temperature was help ing us to raw materials fully volat ile percentage and leftover residue present after thermal degradation process.

Li qui d Fuel Analysis
Fro m FT-IR analysis (Spectrum 100 Perkin Elmer) we found functional group (see fig.3, ٣ and table 2, ٢) and fro m functional g roup we found some band energy. FT-IR (Fourier Transform Infra-red Spectroscopy) analysis of Non-Code p lastic to fuel is noticed fo llo wing types of functional group appeared such as at wave number 3611.17 cm -1 , co mpound is Free OH, wave nu mber 3426.25 cm -1 , compound is intermo lecular H bonds, wave number 3077.64 cm -1 ,co mpound is H bonded NH, wave number 2857.17 cm -1 ,2730.97 cm -1 ,2671.63 cm -1 compound is C-CH 3 ,again appearing descending way wave number 1821.49 cm -1 ,1718.97 cm -1 co mpound is Non-Conjugated, wave number 1641.65 cm -1 ,compound is conjugated, wave number 1440.10 cm -1 and 1377.72 cm -1 co mpound is CH 3 , wave number 992.10 cm -1 compound is -CH=CH 2 ,wave number 965.32 cm -1 ,co mpound is -CH=CH-(trans),wave number 908.03 co mpound is -CH=CH 2 ,wave number 887.97 cm -1 , co mpound is C=CH 2 and ultimately wave number 721.79 cm -1 ,co mpound is -CH=CH-(cis) respectively. Energy value are calcu lated using energy formu la that is E=hcw, where E=energy, h =plank constant, ω=frequency number/wave number. Functional group C-CH 3 ,calculated energy value is 5.67x10 -20 J, functional group CH 3 ,energy value is 2.86x10 -20 J and ultimately functional group C=CH 2 , calculated energy value is 1.        fig.4, ٤ and table3, ٣. For GC/MS analysis purpose GC/MS (Perkin Elmer) Clarus 500 series with auto sampler process was used. Carrier gas heliu m (He) was used in GC/MS cap illary co lu mn. GC fuel injector port temperature is 300℃ for making volatile liquid fuel samp le to pass though GC colu mn. GC program was setup initial temperature is 40℃ because all mo isture such as water, carbon dioxide heliu m and nitrogen mass are not above 44 and MS mass detection level we setup 35 to 528. Init ial temperature set up to hold for 1 minute for volatile into injector port at 300℃. Setup final temperature at 350℃ and temperature ramp ing rate was 10℃ per minute and final temperature hold for 18 minutes. Total samp le run t ime was 50 minutes. Capillary colu mn (Perkin Elmer) specification elite-5MS 30 meter length, mmID 0.25, u m d f 0.

Conclusions
The thermal degradation of poly mer waste plastics was performed using muffle furnace through in a stainless steel reactor was shown to be a useful method for the production of potentially valuable hydrocarbons liquid fuel. The experiments discussed in this work show that the use of various ways improves the yield of hydrocarbon fuels and provide better selectivity in the product distributions. Overall, the light of the hydrocarbon products observed were in the gas phase with less than 10%. It is demonstrated that the conversion of post-consumer polymer non coded waste plastic to hydrocarbon fuels was more than 85% reactor used in this study. Moreover, the production of hydrocarbon as a chemical feedstock is potentially attractive and may offer greater pro fitability than production of saturated hydrocarbons and aromatics. Thermal degradation resulted in larger amounts of liquid hydrocarbons compared with the degradation over showed the lowest conversion light gas and generated a hydrocarbon product with the broadest carbon range. Greater product selectivity was observed thermal cracking with about liquid fuel 85% and light gas 9% was from 1 st step liquefaction process and 2 nd step condensation process and total conversion rate was 94% of the product in the C 3 -C 28 range studied. It is concluded that the use of appropriate reaction conditions without catalyst to a suitable way can give the ability to control product yield and distribution fro m non-coded waste polymer degradation, potentially leading to a cheaper process with more valuable products.

List of Abbreviations:
CDS: CDS Analytical, Inc. is a GC/MS Pyroprobe 5000 series manufacturer co mpany RCI: RCI is a manufacturer of fuel purification technology that is commercially available KRS-5: (FT-IR co mponent) Diamond plate for FT-IR liquid and solid analysis.
ATR: (FT-IR co mponent) (Attenuated Total Reflectance) is an universal ATR sampling accessory (for analyzing solid samples) TGA: (Thermogravemetric Analy zer) is an equip ment use to determine melt ing point DSC: (Differential Scanning Calorimeter) is an equipment use to determine boiling point, melting point and freezing point of liquid substances.
ICP: (Induced Couple Plasma) is an equip ment used for various metal content analyzing ASTM: A merican Standard and Testing Method is an organization that provides chemical characteristics and handling procedure.