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Submitted by: Hardik Patel 09BCH152 Guided by: Dr. R.K. Mewada Associate Professor


The conversion of used lubricating oil to transport fuel by cracking is a suitable way to dispose of waste oil. By cracking of used lubricating oil changes its classification from a waste produce to a liquid fuel as a new alternative for the replacement of petroleum fuels. We can also produce diesel - like fuel from waste engine oil by pyrolitic distillation. In recent years, diminishing of fossil fuel sources, growing of demand and cost of petroleum based fuels, and environmental hazards as a result of burning of them have encouraged researchers to investigate possibility of using alternative fuels instead of fossil fuels.

Keywords: cracking, pyroliytic distillation, used lubricating oil


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1 2 3 4 Introduction

Catalytic cracking reaction of used lubricating oil Catalytic cracking reaction of used lubricating oil References

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Alternative energy resources are becoming more imperative because there is an increasing demand for clean transport fuels. Many researchers are concentrating on developing alternative and renewable sources of liquid fuels, which are new energy resources to replace commercial petroleum products for the future. Large and increasing volumes of used lubricating oil are produced each year that, after use, are considered hazardous wastes. This is so because waste oils typically consist of a mixture of undegraded base oil and additives which high concentrations of metals, varnish, gums, and other asphaltic compounds coming from overlay on bearing surface sand degradation of the fresh lubricant component The used oil is disposed in many ways including incineration, landspreading, and dumping on the ground and into water. All used oil eventually creates environmental hazards. However, combustion and incineration of wastes is often difficult and cleaning of flue gases is complex and expensive because they contain important quantities of contaminants. As a solution to this problem of disposal, waste lubricating oil could be collected and processed via a re-refining process to become re-refined lubricating oil with an equivalent quality to new lubricating oil or via direct upgrade from thermal cracking or catalytic cracking. In thermal cracking, hydrocarbons with higher molecular weight in lubricating oils can be transformed to lighter hydrocarbon products by thermolysis at higher temperature, which is accompanied with the formation of coke; large amounts of gas and naphtha with lower quality are produced due to over cracking. reported a higher yield in volatile gases when the temperature was increased (3560% from 873K to 973K). Methane, light olefins, and benzene, toluene, and xylene (BTX) were the most abundant byproducts studied batch low temperature pyrolysis of waste oils (693-713K) with a high holding time of the residue (5-50min), in order to elucidate the cracking reaction kinetics of the paraffins at low temperature to obtain naphtha investigated the pyrolysis of a mixture of waste ship lubricating oil (WSLO) and waste fishing rope (WFR) in the temperature range of 573-723K; the fraction of light hydrocarbons below C15 in the pyrolyzed oil of the WSLO/WFR mixture was higher than that of the WSLO or WFR alone. These lubricating oils are longchain hydrocarbon molecules, which can be converted to light hydrocarbons, by using many types of catalysts. HZSM-5 was determined to be most efficient in the oil cracking

processes of organic liquid fuel production that give mainly aromatic hydrocarbons. In addition, sulfated zirconia, as a member of the sulfated metal oxide as a solid super acid catalyst for the isomerization of n-butane at room temperature. It has also been shown to be active in several other reactions, including cracking, alkylation, and esterification. Sulfated zirconia uses a stronger acid catalyst and is more reactive as a cracking catalyst for long-chain hydrocarbons, under mill conditions. It has been termed as a strong solid acid and is effective for hydro-isomerization and hydrocracking of long-chain paraffins The higher acidity of sulfated zirconia shows an increase in the frequency of hydride abstractions, which can be derived from the cracking mechanism this study, sulfated zirconia was applied to the catalytic cracking of used lubricating oil to become liquid fuel, and the effects of temperature, initial pressure, reaction time, and kinetic model were investigated.

Production of diesel-like fuel from waste oils such as industrial and engine waste oils, wood pyrolysis oils, fresh and waste fats and vegetable oils is an excellent way for producing alternative fuel sources. Industrial and engine waste oils , wood pyrolysis oils , fresh and waste fats and vegetable oils have been proposed as pyrolysis raw material to produce gasoline and diesel-like fuels. There is plenty of the waste engine oil in the world. Abundant amounts of used engine lubricating oils are produced worldwide every year . Annually, about 40 million metric tones are produced, and around 60% of the production becomes waste . Less than 45% of available waste oil was collected worldwide in1995, and the remaining 55% was either misused or discarded by the end user in the environment. It should be collected and re-used in order to decrease detrimental effects on environment, and underground and surface waters, since it pollutes the atmospheric air as a result of burning, and has negative effects on living organisms, underground and surface waters when it is discharged into soil or water. Conversion of the waste engine oils into diesel like fuel by using pyrolitic distillation, and by utilization of the product as a diesel fuel has positive effects on environment and atmospheric air, and also has economical value.


Catalytic cracking reaction can be used to produce liquid fuels from used lubricating oils. The catalyst used in this process is sulfated zirconia. The experiment, raw materials and chemicals, catalyst preparation and characterization and liquid product analysis has been discussed in the following section.

2.1 Raw materials and chemicals The oil is filtered to remove solid particle and then treated in a rotary evaporator at 333 K under vacuum (80 kPa) to eliminate water. Then, the contaminant agent which is suspended in waste lubricating oil was separated by solvent extraction technique Mixtures of used oil and 2propanol in weight proportion of 10/1 solvent/oil were poured into glass centrifugal tubes that were later introduced in the support of a centrifuge. After centrifugation at 500 rpm for 10min, a sludge phase (additive, impurities and carbonaceous particle) was segregated from the mixture of solvent and oil. The solvent was separated from the solvent/oil mixture by distillation in a rotary evaporator, and the recovered oil was obtained and used as starting material in all experimental runs. Used oil properties after this treatment. Hydrogen gas was used to trace the effect of the initial hydrogen gas pressure. A commercial-grade (minimum of 80% purification) 2- propanol was used without further purification.

2.2 Catalyst Preparation and Characterization Sulfated zirconia was prepared according to the method described by Zirconium oxynitrate (ZrO(NO3)2) was dissolved in a nitric acid solution, and aqueous ammonium was slowly added under stirring to precipitate zirconium hydroxide until pH 11 was attained. The obtained solid was washed with water and calcined to prepare zirconia at 573 K for 4 hour under atmospheric conditions. Sulfate was loaded by using an impregnation method, and 5 g of zirconia was suspended in aqueous solutions containing various amount of sulfuric acid with a constant volume of 100 cm3, followed by drying on a hotplate. After drying for 2 h, the obtained solid was calcined at 923K for 4 hour under atmospheric conditions. The N2 adsorptiondesorption isotherms were measured at 77 K under 30.39 kPa of nitrogen (P/P o =0.3) on a

Quantachrome Autosorb 1 instrument by using standard adsorption techniques. The surface area of 133m2/g was obtained by application of the BET procedures.

2.3. Apparatus and Procedure A quantity (20 g) of used lubricating oil was poured in a 316 SS stainless-steel cylindrical micro reactor that had a volume of 70 cm3. Sulfated zirconia (1 wt% based on weight of used oil) was added and hydrogen gas was supplied from a hydrogen tank to fill the reactor. The reactor was constructed to reaction unit specifications, with an injection heater and insulator. The reactor was heated from ambientroom temperature to the desired temperature and maintained at the desired temperature for any reaction times. The reaction was controlled by a programmable temperature controller with a K-type thermocouple used as a temperature detector. A control speed motor controlled the shaking of the micro-reactor. After the reaction was finished, the reactor was cooled down to room temperature. The liquid product was collected by vacuum filtration to separate the liquid oil products from solids. Liquid yield was calculated as (weight of oil)100/(weight of feed), while solid yield was defined as (weight of solid)100/(weight of feed). Gas yield was defined as (100-liquid yield-solid yield).

2.4. Liquid Product Analyses The boiling range distribution of oil products were analyzed by a Simulated Distillation Analyzer following the ASTM method D2887. The system consisted of Varian CP-3800 gas chromatograph equipped with an automatic sampler and a flame ionization detector (FID). Capillary column (15m0.25mm, i.d. 0.25 m film thickness) CPSIL 5CB was employed with a programmed temperature from 303 K to 593 K. The gas chromatography was calibrated by analyzing a mixture of normal paraffins with known boiling points and samples were injected in the CS2 solution. Naphtha, kerosene, light gas oil, gas oil and long residue fractions in product oils were referred to by boiling point in each fraction as follows: under 473 K (naphtha), 473523K (kerosene), 523-623K (light gas oil), 623-643K (gas oil) and over 643K (long residue). Information on molecular structures of oil products obtained was only available in terms of analyses in the GC-MS. A SHIMADZU GC-MS QP2010 equipped with DB-1 capillary column (30m0.25 mm, i.d. 0.25 m film thickness), and a 1 : 30 split ratio was used. The GC column

was ramped at 293Kmin1 from 313 K (hold 2min) to 593 K. Helium gas was used as the carrier gas with a flow rate 1.5 ml/min. Sample are injected into a CS2 solution.


The aim of this study is to obtain diesel-like fuel from waste lubrication engine oils by pyrolitic distillation method, which can be used in diesel engines. With this aim in mind, waste engine oil is collected in a tank, and it is purified from contaminants such as dust, heavy carbon soot, metal particles, gum-type materials and other impurities by filtering in the process prepared earlier. To investigate effects of additives known as sodium carbonate (NaCO3), zeolite and lime (CaO) on density, viscosity, flash point, sulfur content, heating value and distillation temperature, the purified oil samples are blended separately with additives having mass basis of 2%, 4%, 6%, 8% and 10%. The mixed samples are exposed to pyrolitic distillation process to produce fuels to be used in engines. Thermal and physical properties of the produced fuels such as density, flash point, viscosity, sulfur content, heating value and distillation temperatures are examined. From these results, the CaO with a ratio of 2% has the highest effect on decreasing of sulfur content of the waste engine oil and on acquiring the most suitable distillation temperatures close to values of a diesel fuel. Diesel-like fuel (DLF) is obtained as 60% of the waste lubrication engine oil.

3.1 Description of Fuel Production System A purifying and distillation system was designed and manufactured to purify waste lubricant oil from hazardous materials and reutilize the waste lubricating engine oil. For this purpose, control and measurement elements are installed on the system. The system was consisted of several components, which were named as waste oil storage tank, oil pump and filter, reactor, control panel, fuel storage tank, mixer and condenser. Main functions of the components will be explained briefly. The waste oil storage tank was used to collect waste engine oil or other contaminated oil. The oil pump and filter were used to transfer waste oil sample from the storage tank to the reactor, and then purify the oil from the contaminants. The other most impart part is the reactor, which is the heart of the system. Basically, the reactor of this system has a cylindrical shape with inner diameter and overall effective chamber length of about 30 and 40 cm, respectively. The reactor was designed and manufactured to heat the waste oil sample. Its capacity is enough for producing approximately

Fig.1 : Schematic diagram of purified and distillation system

25 l fuel. It proved to be adequate for testing the produced fuel characteristics, and engine performance. It includes an electrical heating unit which can be used to heat the waste oil mixture up to 600 C. The electrical heater has resistance heaters, and a voltage control which is used to adjust the heating rate. The heating control is performed by the control panel. The mixer is employed for blending the waste oil sample taken into the reactor to obtain uniform temperature in it. If the mixer were not used, then there would be a temperature layer within the reactor. This is a very important system component. Last component of the system is the condenser unit that is used to distillate the oil vaporized in the reactor. A water-cooled condenser was used to condense the fuel vapor vaporized at temperature ranges between 140 C and 400C. Temperature measurements were obtained by means of thermocouples placed in the locations where such measurements were needed; namely, in the middle of the reactor and oil vapor streams in the condenser.

3.2 Testing Procedure The waste lubricant oil is highly viscous and contains sulfur, carbon soot, small metal particles and some gum-type materials. It has high level of these materials. For example, it has plenty of sulfur with an amount of approximately 6000 ppm. This value is reasonably high. The contaminants originally exist in lubricating oils. Various additives are generally added in the lubricating oil to decrease sulfur amount. Three types of additives were used in this study. In order to purify and distillate the waste oil, several tests were carried out. The testing procedure can be summarized as follows. The waste oil collected iss taken from the storage tank and filtered using a qualitative filter of 20 lm to purify it from heavy metal particles, carbon soot, gum-type materials and other impurities. The purified waste oilleaving from the filter was taken into the reactor. Three additives known as Na2CO3, zeolite and lime (CaO) were added to the clean oil in the reactor and blended with mass basis of 2%, 4%, 6%, 8% and 10%, separately. Natural zeolite (NZ) was put in a water bath to regulate the temperature (298348 K). Adsorbed CO2 was removed by washing 1 N HCl solution. The converted zeolite samples were washed with deionized water, in order to wash the remaining gas, which may be found on the zeolite surface. This process was repeated continuously until no chlorine precipitated with 0.01 N AgNO3 in the wash water. SO2 was adsorbed by the NZ, adsorption fell to zero. The amount of powdered NZ sample was about 50 g. The new sample was mixed continuously and kept for 30 min at a room temperature of 25 C. Then, it was exposed to thermal and pyrolitic treatments. The thermal and pyrolitic treatments of the samples were performed in the presence of additives. Each sample mixed continuously was distillated and collected in a container. Characteristics of the produced fuel such as density, viscosity, flash and fire points, sulfur content, heat of combustion and distillation are examined.

1. Orhan Arpa, Recep Yumrutas, Ayhan Demirbas, " Production of diesel - like fuel from waste engine oil by pyrolitic distillation", Applied Energy 87 (2010), Pg 122 - 127. 2. Amnat Permsubscul, Tharapong Vitidsant and Somsak Damronglerd," Catalytic cracking reaction of used lubricating oil to liquid fuels catalysed by sulfated zirconia", Korean Journal of Chemical Engineering, 24(1), Pg 37 - 43