Selected Waste Plastics Degradation Via Catalytic Cracking: Light Crude Oil Production and Characterization Jhonfil T.

Huesca and Engr. Myrna S. Ceniza Department of Chemistry College of Arts and Sciences Mindanao University of Science and Technology Cagayan de Oro City, Philippines

Abstract

The study was made to produce light crude oils from different solid waste plastics, such as, high density polyethylene (HDPE), low density polyethylene (LDPE), and polyethylene terephthalate (PET). The production of light crude oil used the concept of catalytic cracking. The catalysts: copper(II) oxide and sodium silicate; additives: ammonium nitrate, sodium nitrate, and calcium sulfate; kerosene; and conical-glass reactor powered by double-walled heating element with the conditions: maximum temperature (290-330C) and atmospheric pressure under presence of nitrogen were crucial in the conversion of solid to liquid polymers. The light crude oils were characterized by their color, odor intensity, density, specific gravity and infrared spectroscopy (IR).

In the production of light crude oils, LDPE had the highest recovery of 74.76% followed by PET with 66.80% and the HDPE with 55.49%. The results of the characterization of each oil were; color: HDPE has a light orange crude oil, LDPE has a dark orange crude oil, and PET has a yellow orange crude oil; odor intensity: PET < HDPE < LDPE; density: HDPE < PET < LDPE; and specific gravity: HDPE < PET < LDPE. A single factor ANOVA and T-test were used as the statistical tool in the evaluation of data including IR of the three crude oils. This study was able to recover light crude oils with more than 50% oil conversion using the parameters and conditions set by the researcher. Keywords: catalytic cracking, light crude oil production, characterization

Introduction

One of the common problems that humanity is facing is the management of waste. Waste is unwanted or useless materials. Even unwanted substances that are expelled in the body like toxins, urine, sweat and stool are considered as waste; and these show that man was accompanied with waste. According to Barbalace (1995), the emergence of the problem of waste did not occur at 20 th century. Even before, many incidents that were done by man really produced enormous waste and this can be seen in the timeline that the researcher provided.

Today, many landfills and dumpsites were opened to accommodate the waste of the increasing human population. Because land disposal method is no longer enough to sustain the increasing waste, integrated methods were developed: incineration (a process which uses the concept of cracking, gasification, and pyrolysis), recycling, biological reprocessing (digestion process using the microbes), and energy recovery (uses the concept of gasification, pyrolysis, and hydrolysis) (Al-Salem, 2009). In the said methods, recycling and biological reprocessing are practiced in the Philippines.

The Philippine Brown Environment Quality, a movement which concerned with the air, water pollution and solid waste management, found out that an average Filipino generates 0.3 and 0.5 kg. of garbage daily at urban and rural areas, respectively (Senate Economic Planning Office of the Philippines, 2005). Most of the wastes are solids and 15% of these are plastics. Majority of these plastics were plastic bags and water bottles; and most are made from High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), and Polyethylene Terephthalate (PET). Aside from the problem on wastes, the demand, consumption, and price of petroleum fuels are rising.

Based on these difficulties, the researcher formulated a study which may contribute solution to the problem. The study was built to liquefy the selected waste plastics.

Methodology

The preliminaries for the development of the heating medium as well as the solvent and the collection of physico-chemical data from the production and characterization of light crude oils take almost a year.

Sampling and Plastic Characterization. The plastics were checked and verified if the given recyclable labels were present in the different garbage cans, dumpsites, and landfills within the boundary of Cagayan de Oro city and the selection of plastics was based on their basic appearance. The samples were cleaned and cut into smaller pieces.

Figure 1. Recyclable labels for the plastics.

Developments of Heating Element for the Reactor and Solvent. Different insulators for the heating element were tested to determine its capacity and efficiency in accordance with the conditions set in the study. In the same time, different solvents were investigated in order to produce the desired product.

The reactor that was used is a conical glass with three-neck adapter for the thermometer, condenser, and nitrogen supply. A fine, dried sand was used as the heating medium because it could achieve the desired temperature rather than oil and water. A tin can was used as the container, its insulation was improved by a double-walled tin can enclosed with teflon tapes on top and bottom for effective conduction of heat.

Figure 2. The reactor and the heating element.

Catalytic Cracking Process. The catalysts, the additive agents, solvent, and the plastic samples were added in the reactor. Then, the reactor was purge with nitrogen and was left for 5 minutes (15 psig N2 supply was applied, in order to prevent the buildup of pressure in the reactor), this was done to remove the air in the reactor. The cracking process was divided into two major stages: the reflux and the recovery. In refluxing, it allows the gas to evolve and condense, until such time that the mixture is no longer viscous, then, refluxing will be ended.

Figure 3. The refluxing (left) and recovery (right) stages.

After the refluxing, the condenser is changed with a shorter condenser for recovery. In this part, the gas that will produce will be condensed in the condenser and the liquid will be collected into a receiver (125 mL erlenmeyer flask). The recovery process will be ended if there is no more evolution of gas. The crude oil recovered is the combination of the solvent and the plastics.

Production Yield. For light crude oil, it was calculated using ratio of the weight of the oil to the sample, catalysts, additive agents and solvent weight, expressed in percentage, and likewise for residue. The calculation was established due to the appearance of products and the result in the infrared spectra of crude oils.

Light Crude Oil Characterization. The crude oil was examined using direct observation of the color and odor intensity, density and specific gravity determination, and infrared spectrophotometer.

Results and Discussion

Preliminary for the Efficiency of the Insulators. The basis for selection was focused on the system that could raise the highest temperature at most less time.

350 300 Temperature, C 250 200 150 100 50 0 0

Trends of Insulators
Tin can Aluminum foil Plaster of paris Doublewalled

50

100 150 Time, minutes

200

Figure 4. The efficacy of different insulator designs using oil as the subject matter in the test.

Table 1 Remarks of the Efficiency of Insulators

Type Insulators

Results

Aluminum foil Plaster of paris Double-walled

Not operative Not operative in the long run Operative

As we can see in the figure, tin can alone cannot reach the desired temperature. To elevate the temperature aside from using another hotplate, the researcher used the concept of an insulator. The first insulator was the aluminum foil, in the diagram above aluminum shows lesser increased of temperature in the starting part of the test than as the tin can, this mainly due to the higher heat capacity of the aluminum. As an insulator, some of the heat is also absorbed by the aluminum, but as the developments proceed, the aluminum was able to isolate the heat and able to surpass the temperature that the tin can could only provide and likewise with the preferred temperature. But this design was not used as for the reason that the aluminum would deteriorate if it is further used.

Plaster of paris was also employed as the insulator; this design was remarked as not operative because the insulator would collide as it is further used. Primarily, the reason of this is due to the liberation of water during heating, which lessens the insulators strength. The product of interaction between plaster of paris (CaSO4.1/2H2O) and water produced a dihydrate form of CaSO4 (CaSO4.2H2O or gypsum). The crystal lattice of gypsum is held with hydrogen bonding which is the reason for its rigidity, and when temperature is applied, the water of crystallization is easily remove and makes the structure collide, but in terms of its effectiveness as an insulator, it able to reach the desired temperature.

The double-walled insulator was selected among the insulators because of its fastest rate of increase in temperature at less time to reach the desired temperature. This is due to high conduction of heat which is supplied to the heating medium (sand).

Preliminary for the Efficiency and Characteristics of the Solvents. Instead of using toluene as solvent for the cracking process, diesel and kerosene fuels which are less expensive were tried.

350 300 250 Temperature, C 200 150 100 50 0 0 200

Efficiency of Solvents

Diesel Kerosene

400

600 800 Time, minutes

1000

1200

Figure 5. The efficiency of the solvents in the crude oil production using HDPE as the sample.

In the figure above, the diesel needed much higher time and temperature due to its viscosity, the viscosity is a vital aspect in the recovery because it shows if the sample is totally dissolved and mixed with the reagent. When the sample is not dissolved, then, there is a possibility that in the recovery part lesser amount of polymer will be carried out of the reactor; polymer alone needs higher temperature and pressure to convert it into gaseous phase as shown in the related studies. In addition to viscosity, viscosity shows how close the molecules are (Elert, 2011) so when further temperature (thermal energy) is applied, it is now easier to convert the mixture into its gaseous form. While in the other solvent, kerosene took a little, both in time and temperature, in viscosity aspect. In terms of

boiling point, the diesel boils faster than kerosene (68 vs. 100C) but otherwise in time (21.37 vs. 20.11 min.).

In the recovery part, diesel took a very long time because of the viscosity even though higher temperature was employed in the refluxing stage. Evolution of gas was minute which provides slow rate in the collection of the distillate. Unlike the diesel, the kerosene produced more viscous mixture which makes the refluxing and recovery part fast as well to its amount of distillate produced.

Figure 6. Diesel wax and distillate (left) and kerosene wax and distillate (left).

Table 2 Characteristics and Yield of Crude Products from HDPE using the Solvents Solvents Distillate Color Wax Color % Distillate % Residue

Diesel Kerosene

Yellow Light orange

Dark brown Grey

5.88 54.28

76.84 26.91

Diesel has a golden yellow color, while the kerosene is colorless. The deviation of the colors shows that the HDPE plastic has been depolymerized and was added in the solvents making the colors slightly darker form the original color of the solvents.

Probably the reason for the difference in the yield of the products is due to the solubility of the HDPE towards the solvents. The statement like dissolves like is a generalization that nonpolar substances dissolve in nonpolar solvents and otherwise with ionic and polar substances. This generalization is made up due to the examinations that substances with similar intermolecular

attractive forces tend to be soluble in one another (Brown, Lemay, Bursten, & Burdge, 2004). HPDE contains only london dispersion forces, for diesel it has london dispersion and dipole-dipole interaction due to its methyl ester (diesel contains 5% volume by volume biodiesel), while for kerosene (also known as paraffin oil) comprises also of London dispersion forces. Due to this, the HDPE is much soluble to the kerosene at higher temperature which is able to produce more distillate. One of the likely reasons is due to the viscosity of the solvents. In order for the reaction to occur, the reactants must come together (Brown et al., 2004). Solvent facilitates the mixing of the reactants; due to the diesel is more viscous (3.97 cSt) than kerosene (2.71 cSt) it does not provide more collisions for the molecules of the reactants to react. Due to the findings and data gathered, kerosene was employed as the solvent in the production of the crude oil.

Light Crude Oil Yield and their Characteristics. Table 3 presents the physico-chemical properties of the polymers which are the standard test for petroleum products especially for petrol and diesel.

Figure 7. Light crude oils of HDPE (left), LDPE (middle), and PET (right).

Table 3 Yield of the Light Crude Oils from the Selected Waste Samples and their Characteristics Polymer Color Odor % Light % Residue Density, Specific Samples intensity Crude Oil g/mL Gravity HDPE LDPE PET Light orange Dark orange Yellow orange Moderate Strong Mild 55.49 74.76 66.80 26.91 5.51 10.87 0.766079 0.912087 0.904337 0.770090 0.916692 0.909110

The difference in the yield and characteristics of the polymers show that due to the difference in orientation, arrangement, and composition of monomers which make up the structure and physical properties of polymers, the polymers can produce crude oils with different characteristics.

Conclusions and Recommendations

The researcher is able to degrade the waste plastics: HDPE, LDPE, and PET into light crude oils, by using the concept of catalytic cracking. The cracking is done in a conical-glass reactor powered by a double-walled heating element with the given set of conditions: nitrogen atmospheric pressure and 290-330C maximum temperature; with the catalysts: copper(II) oxide and sodium silicate; additive agents: ammonium nitrate, sodium nitrate, and calcium sulfate; and kerosene.

The light crude oils produced are 55.49 for HDPE, 74.76 for LDPE, and 66.80% for PET. HDPE has a light orange crude oil with moderate odor, while for LDPE has a dark orange crude oil with strong odor, and PET has yellow orange with mild odor crude oil. The densities of light crude oils are 0.766079, 0.912087, and 0.904337 g/mL, respectively for HDPE, LDPE, and PET. For specific gravity, HDPE has 0.770090, LDPE has 0.916692, and PET has 0.909110.

The IR spectra of polymers depict the IR spectra of kerosene except with the amine, silane, and C-O peak. The difference in color, odor intensity, density, specific gravity, and infrared spectra signifies that polyethylenes with different structures and physical properties can produce different light crude oils with different characteristics.

Based on the results of this study, certain recommendations were formulated in order to develop the study.

Optimization of the production must be done in order to improve the oil recovery. In the production, use more efficient heating medium like heating mantle, then use a vacuum pump in the recovery stage so that the heavy gas will be collected and this must be accompanied with more efficient condenser. In addition, separation/recovery of the solvent should be done in order to know the exact amount of crude oils that can be produced from the different waste plastics.

In the characterization, other physico-chemical tests for petroleum products should be done in order to classify the crude oils; if the crude oils would pass the entire test, then there could be a possibility that these crude oils can be used as alternative source of fuel. Most of all, in order to determine what kind of fuel can be produced from the polymers, characterization in the GC-MS could be the most efficient method. Regarding with the residues, characterization should be applied also in order to classify the residues and to know its possible importance and applications.

References Al-Salem, S.M. (2009). Life Cycle Assessment (LCA) of Municipal Solid Waste Management in the State of Kuwait. Department of Engineering, Roberts Building, University College London (UCL), Torrington Place, London WC1E 7JE, UK. Retrieved from http://www.eurojournals.com/ejsr.htm Barbalace, R.C. (1995). The History of Waste: Do you want to be a Garbologist?. Retrieved from http://environmentalchemistry.com/yogi/environmental/wastehistory.html Brown T.E., Lemay, H.E., Bursten, B.E., & Burdge, J.R. (2004). Chemistry The Central Science.(9th edition). Person Education Inc., Upper Saddle River, New Jersey 07458

Deng, G.C., McClennen, W.H., Meuzelaar, H.L.C. (2010). Catalytic Degradation of High Density Polyethylene and Waste Plastic Below 200C. Microanalysis and Reaction Chemistry, University of Utah. Retrieved from http://www.anl.gov/PCS/.../42_4_LAS%20VEGAS_09-97_0987 .pdf Ding, W., Liang, J., & Anderson, L.L. (1996). Hydrocracking of Waste Plastics to Clean Liquid Fuels. Department of Chemistry and Fuels Engineering, University of Utah, Salt Lake City. Retrieved from http://www.anl.gov/PCS/acsfuel/.../42_4_LAS%20VEGAS_0-97_1008.pdf Elert, G. (2011). Viscosity. The Physics Hypertextbook. Retrieved from http://www.physics.info

Gaca, P., Drzewiecka, M., Kaleta, W., Kozubek, H., & Nowinska, K. (2007). Catalytic Degradation of Polyethylene Over Mesoporous Molecular Sieve MCM-41 Modified with Heteropoly Compound. Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-680 Poznan, Poland. Retrieved from http://www.pjoes.com/pdf/17.1/25-31.pdf Lee, K-H., Shin, D-H., & Suh, J-K. (2005). Catalytic Degradation of Waste High-Density Polyethylene Into Liquid Product. Fossil Energy & Environment Research Department and Applied & Engineering Chemistry Division, Korea Research Institute of Chemical Technology, Korea. Retrieved from http://www.ceric.net/wonmun3/ksee/04708872.pd McMurry, J. (2000). Organic Chemistry. (5th edition). Brooks/Cole, 511 Forest Lodge, Pacific Grove, CA 93950 USA. Mubarak, A., & Alsobaai, A. (2007). Development of Ni/W Zeolite Based Catalyst for Hydrocracking of Gas Oil: Synthesis, Characterization, Activity and Kinetic Studies. Universiti Sains Malaysia. Retrieved from http://eprints.usm.my/.../DEVELOPMENT_OF_NiW-ZEOLITE_BASED_ CATALYSTS _ FOR_ HYDROCRACKING _OF_GAS_OIL.pdf Pant, D. (2005). A New Role of Alumina in Polyethylene Degradation: A Step Towards Commercial Polyethylene Recycling. Journal of Scientific & Industrial Research. (Vol.64, pp.967-972). Department of Chemistry Kumaun University, Nainital. Retrieved from http://nopr.niscair.res.in/bitstream/123456789/.../JS R%206412)%20967-972.pdf Roy, P.K., Surekha, P., Rajagopal, C., & Choudhary, V. (2007). Thermal Degradation Studies of LDPE containing Cobalt Stearate as Pro-Oxidant. Centre for Fire, Explosive and Environment Safety and Centre for Polymer Science and Engineering, India. Retrieved from http://www.express polymlett.com/articles/EPL-0000133_article.pdf Silva, E.F.B., Ribiero, M.P., Galvao, L.P.F.C., Fernandes, V.J., & Araujo, A.S. (2010). Kinetic Study of Low Density Polyethylene Degradation on the Silicoaluminophosphate SAPO-11. Budapest Hungary. Retrieved from http://www.springerlink.com/index/J044 M972X48452L7.pdf Sutar, S. (2008). Depolymerization of Waste Rubber and Thermoplastics Including PVC or PET into Hydrocarbon Fuels. International Application Published Under the Patent Cooperation Treaty (PCT): World Intellectual Organization. Retrieved from http://www.sumobrain.com/.../Depolymerization ...wasterubberthermoplastics/WO208007384.html Venkatesh, K.R., Hu, J., Wang, W., Holder, G.D., Tierney, J.W., & Wender, I. (1996). Hydrocracking and Isomerization of Long-Chain Alkanes and Polyolefins over Metal-Promoted Anion-Modified Zirconium Oxides. Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pennsylvania. Retrieved from http://www.freepatentsonline.com/6184430.htm Xiao, X., Zmierczak, W., & Shabtai, J. (1994). Depolymerization Liquefaction of Plastics and Rubbers: Polypropylene, Polyethylene, and Polybutadidene. Department of Chemical and Fuels Engineering, University of Utah, Salt Lake City, Utah. Retrieved from http://www.anl.gov/PCS/ acsfuel/.../40_1_ANAHEIM_04-95_0004.pdf