International Journal of Advances in Engineering & Technology, Mar. 2013.

IJAET ISSN: 2231-1963

CHARACTERIZATION OF INCINERATED MEDICAL WASTE RESIDUES USING BATCH LEACHING

N. Nagendra Gandhi1, P. Arunraj2, and R. Thirumalai Kumar3
Professor and Head, 2 Department of Chemical Engineering, A.C. Tech., Anna University, Chennai, India 3 Department of Oil and Gas Engineering, All Nations University College, Koforidua-Ghana, West Africa
1

ABSTRACT
The hospital wastes produced during the course of health-care activities pose a threat to public health and environment than any other type of wastes. In the present paper physiochemical properties of the incinerated solid waste sample such as sampling, batch test operation, sequential extraction and chemical speciation have been studied. The results show that the concentration of heavy metals decreases with increase in L/S ratio. Batch test analyse shows the static view of leachate produced by the ash and sequential extraction shows the potential mobility of heavy metals. Chemical speciation and distribution of heavy metals varied greatly this trend was due to the higher ion exchange capacity of the extractants and formation of anionic metal species, leading to more metal species leaching out of each chemical fraction.

KEYWORDS: Medical Waste, Batch Leaching, Waste Residue, Incineration

I.

INTRODUCTION

Hospital is one of the complex institutions, which is frequented by people from every walk of life in the society. Waste is always a sensitive topic for public, health-care waste is especially so. The medical wastes are increasing in its amount and type over a period of time due to increased inhabitants and advances in science and technology. In pursuing their aims of reducing health problems and eliminating potential risks to peoples health, health care services inevitably create waste that may itself be hazardous to health. Technically solid waste is any waste which is not discharged into the air and hence the term can be applied to liquids. Solid waste comprises the largest percentage of hospital generated waste and includes such waste types as general office trash, food service waste and even the fastest growing waste type, recyclable waste. The impact of rare earth elements from medical waste incinerated ash residues. Crust normalized patterns indicated medical wastes were enriched with Ce and La. DTPA and EDTA extraction tests revealed rare earth elements were generally low in bioavailability. Sequential extraction studies revealed that the leaching of heavy metals depends upon composition of calcium evaluated the leaching characteristics of heavy metals in municipal solid waste incinerator fly ash. The potential release of Pb, Zn, Cr, and Cu in municipal solid waste incinerator (MSWI) fly ash was investigated by batch leaching experiments using sodium acetate solution as the extractant. The concentrations of heavy metals decreased against the increase of liquid-to-solid (L/S) ratio with the exception of Zn. The slag obtained from incinerated hospital waste. The sources of health care waste can be classified as major or minor according to the quantities produced. The major sources are listed below: university hospital, general hospital, district hospital. Other health cares establishments like emergency medical care services, health care centres dispensaries, obstetric and maternity clinics, outpatient clinics, first-aid and sick bays, long term health care establishments and hospices, transfusion

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centers and military medical services. Thirdly related laboratories and research centre, medical and biomedical laboratories biotechnology laboratories and institutions, medical research centre. Finally blood banks, blood collection services and nursing home the elderly.

II.

MATERIALS AND METHODS

2.1. Sampling
The residual ash samples are obtained from the Common Bio-Medical Waste Treatment Facility (CBMWTF) located near Padappai (Chennakuppam)-Chennai. This facility has a treatment capacity of 15,000 beds. At present, 157 healthcare units have registered with this facility to supply wastes of only 2400-3100 beds per day. This unit is located 60 km away from the city, 3 km away from the habitats. Incineration and autoclaving are the main processes in these facilities. The residual ashes were first identified and an adequate sampling period (two months) was presumed for collection of samples due to temporal variability in the ash. The point of generation was determined, as for bottom ash the collection was at grate siftings and combustion chamber. The increments are obtained by falling stream and stationary stream which are likely to produce representative samples. Primarily about 12 increments of 5kg increments were collected from the stream. They are sub sampled to obtain a 2 kg lot from which about 0.5 kg was obtained for analysis. The spacing of the increments was varied, as the sampling was collected at different discharge. The sampling devices used are shovel and bucket.

2.2. Graduation Analysis

The sieve analysis test is used to determine the size distribution of the aggregates and is a suitable method for bottom ash. The grain size distribution gives the percentage by weight of different sizes of the particles, which are used to assess other physical properties such as shear strength, bearing capacity, permeability. The grain sizes were determined using varying sieves. The following mesh sizes 10, 30, 60, 100, 200 are used to obtain the residues at various fractions.

2.3. Loss of Ignition (LOI)

Loss of ignition (LOI) has been used to provide an indication of the degree of burnout achieved during combustion or the combustion efficiency. LOI is determined by the weight loss of the residual ash samples, previously dried for 24 hours at 105C after exposure to 550C in a muffle furnace for sufficient time to achieve a constant weight. Typically the results are expressed as a percentage of the dried sample weight. LOI was calculated using the equation (1). LOI =

100. (1)

where; WDA = weight of ash dried at 105C in grams, WMA = weight of ash muffled at 550C in grams.

2.4. Experimental Methodology for Batch Test

Two different types of batch tests were developed to characterize the leaching potential associated with the incinerated residues: contact time tests and sequential extraction tests. The contact time test provides an estimate of the time necessary to mobilize minerals from solid wastes. This test also provides insight into the sequence of dissolution, allowing for the identification of readily soluble species, thus providing a static view of the interaction between the leachant and the waste material. The sequential extraction test provides a dynamic view of the materials behavior as it encounters fresh leachant at regular time intervals. This test allows for simulation of the sequential changes in leaching mechanisms that occur as fresh water interacts with the waste material. 2.4.1. Batch Test Optimization Preliminary batch tests were conducted to optimize the liquid to solid (L/S) mass ratios of distilled water to ash and the duration of the contact intervals. The first study focused on determining the contact time intervals necessary for diffusion to occur, while providing adequate volume to conduct leachate characterization tests. The leachates from the preliminary batch tests were characterized and the data

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from these initial tests was used to develop a final protocol for the testing of the incinerated residue samples. 2.4.2. Preliminary Contact Time Tests The preliminary batch tests, designed to determine the contact time requirements of the ash and the leachant were conducted using an L/S ratio of 10. This ratio L/S = 10, the waste can be considered 100% solid and any residual water in the material can be disregarded in the calculation of leachant waste relationships. The ash samples were placed in individual bottles and distilled water was added until an L/S ratio of 10 was reached based on an average density of 1 g/mL for distilled water. The contact times ranged from 24 to 48 hours. At the end of the assigned time interval, the leachate was removed and tested for pH. 2.4.3. Preliminary Sequential Extraction Tests The second set of this test is used to assess difference in leaching based on the L/S ratio. As before, the removed leachate was tested for a limited number of parameters. However, upon removing the leachate at the end of 48 hours, an equal amount of distilled water was used to replenish the leachant, thus maintaining a constant L/S ratio in the bottle but increasing the total L/S ratio over time. The L/S of 2, 4 and 6 did not provide sufficient leachate for analysis. Based on this information, the actual batch tests were based on an L/S value of either 8 or 10. The results from the preliminary batch tests were used to set basic parameters for the contact time and sequential extraction batch tests. The establishment of equilibrium at approximately 48 hours influenced the time intervals used in both types of batch tests. The L/S =10 was determined to be the best option since sufficient leachate was produced for analysis and the solid required no pre-treatment. 2.4.4. Contact Time Tests The contact time batch test was designed to yield a static view of the interaction between the waste material and the leachant. The initial set-up for all batch tests was identical; 125 mL HDPE bottles were pre-cleaned by soaking in an acid bath of 1% nitric acid for 24 hours. The bottles were then rinsed five times with distilled water and allowed to air dry for two to three days. Once completely dried, the bottles were placed on an analytical balance, tarred, and approximately 10grams of ash were added to each bottle. The exact mass was recorded and sufficient distilled water was added to achieve an L/S = 10. The volume added was usually slightly more than 10 ml, which completely fills the bottle, eliminating headspace. At the end of each time interval, the three bottles were removed from the incubator and the leachate was removed by filtration. The leachate was divided into three volumes, one for immediate testing and the other two were preserved for chemical characterization.

2.5. Sequential Extraction (SE)

2.5.1. Exchangeable fraction 40mL of 0.11molL acetic acid was added to 1.0 g of dry residues in a 50-mL polypropylene tube. The mixture was shaken for 16 hr then the extract was separated from the solid phase by centrifugation at 3800 rpm for 20 min. The supernatant liquid was decanted into a100-mL beaker and then covered with a watch-glass. The residue was washed by adding 20mL of double-distilled water, shaking for 15 min, and then centrifuging. The second supernatant liquid was discarded without any loss of residue. 2.5.2 Iron and Manganese oxides fraction Metals bound to iron and manganese oxides were extracted by adding 40ml of 0.1molL hydroxyl ammonium chloride (adjusted to pH2 with 2molL nitric acid) on to the residue from the rst step. After shaking the mixture for 16 h it was centrifuged for 15 min, and then decanted into a beaker. Using 20 mL of distilled water, the residue was washed, centrifuged, and the supernatant was preserved. 2.5.3 Organic Matter Fraction 10mL of 8.8molL hydrogen peroxide as carefully added in small aliquots to the residue in the centrifuge tube. The tube ingredients were digested at room temperature for 1h with occasional manual shaking. The procedure was continued for 1h and the volume reduced to a few millilitres by further heating in a

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water bath. A second aliquot of 10mL of hydrogen peroxide was added to the residue and the digestion procedure was repeated. The solution was heated to near dryness, and 50 mL of1.0molL ammonium acetate solution (adjusted to pH 2 with nitric acid) was added to the moist residue. The samples solution was shaken and centrifuged, and the extract was separated as described above. 2.5.4 Residual Fraction The analysis of the residue was performed using aqua regia for metals insoluble in the previous steps. For this purpose, 6 mL of distilled water and then aqua regia solution in a sequence of 15 and10mL were added to the remaining residue. After adding each aqua regia solution, the residue was evaporated to near dryness on a water bath. The extract was ltered through lter paper by adding 1 mol litre HNO3 solution in small amounts on the last residue in the centrifuge tube. The tube walls were carefully washed with the same acids solution and then collected in a beaker.

2.6 Chemical Speciation

A total of 1M sodium acetate was used as the leachant in these batch leaching experiments. Five L/S ratios, 5, 10, 15, 20, and 25, were chosen to determine the releasing behaviour of heavy metals from the bottom ash. Other batch leaching experiments were conducted with a series of solutions with a pH range from 2 to 12 when the L/S ratio was fixed at 10. For each leaching experiment, the first 10 g of bottom ash was placed in a bottle, and then the leaching solvent was added in the appropriate L/S ratio. Subsequently, the container was closed and then shaken in a horizontal shaker for 8 h at room temperature. The samples were allowed to settle for approximately 16 h. After pH values were measured, the solutions were filtered, and then analyzed. The raw sample was acid digested using (HNO3 + HCl) and the heavy metals concentration were determined. Three replicates were developed to identify the heavy metals concentration. The heavy metals were measured using Atomic Absorption spectrometer (AAS).

III.

RESULTS AND DISCUSSIONS

3.1 Gradation Analysis

The presence of glass, wood and unburned solid residues are separated to obtain uniform sized particles. These individual fractions are further utilized for physical and chemical characterization. These gradation analysis are helpful to segregate the particles (<1mm) by which the chemical speciation of metals are studied further.

Figure 1. Particle size distribution of bottom ash residues

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International Journal of Advances in Engineering & Technology, Mar. 2013. IJAET ISSN: 2231-1963 3.2 Loss of Ignition (LOI) of Bottom Ash

Figure 2. Bottom Ash LOI as function of particle size

From the figure 2 it can be seen, there is a maxima, at a larger particle size (mesh size #60 for sample 1 and mesh #30 for sample 2) which is uncombusted material. The other tends to be at very small particle sizes and reflects the fact that very fine materials in bottom ashes can be organic materials.

3.3 Batch Leaching Tests

3.3.1 pH and alkalinity Leachates from all ash samples had relatively high levels of pH regardless of source or leachate extraction method. The pH values for the leachate produced using the CT test ranged from pH = 10.3 to 12.0 are presented in Figure 3. Alkalinity is a measure of the buffering capacity of a solution, and the alkalinity results differ depending on the type of batch test used to produce the leachate and the source of the ash.
14 12 10

pH

8 6 4 2 0 0 20 40 60 Series1

L/S ratio

Figure 3. Contact time batch test pH results for Bottom ash

3.3.2 Solubility and release as function of L/S Ratio

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The concentrations of heavy metals decreased with an increase in the L/S ratio with the exception of Zn at L/S ratio of 20 in sample 2. When the L/S ratio was higher than 20, the amounts of heavy metals that leached out changed slightly. Because bottom ash contains large amounts of alkaline compounds, it has strong acid buffering capability so that the heavy metals in the samples could not be easily released into the leachate due to the low equilibrium concentrations. In the case of low L/S ratios, the concentrations of Pb and Zn were relatively high. But in high L/S ratios, the total amounts of Pb and Zn declined because of the dilution and neutralization processes that would result in the decrease of pH value and the re-precipitation of heavy metals that dissolved previously.
25 20 15 Pb 10 5 0 0 5 10 15 L/S ratio 20 25 30 Ni Zn

Concentration of metals (mg/L)

Concentration of metals (mg/L)

Figure 4. Concentration of metals with respect to L/S ratio (sample1)

18 16 14 12 10 8 6 4 2 0 0 5 10 15 L/S ratio 20 25 30 Pb Ni Zn

Figure 5. Concentration of metals with respect to L/S ratio (sample 2)

3.3.3 Solubility and release as function of pH The change of pH values would lead to different leaching patterns. The concentrations of heavy metals declined along with the increase of initial pH of leaching solvent. When the pH value was higher than 6, the concentrations of Pb remained at a low level. The relationship between initial pH of the leaching

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solvent and the leachate pH revealed that values greater than pH 6 shows gradual increase. This corresponds the fact that higher L/S ratio does not influence the amount of heavy metals dissolved. The concentration of lead declines with increase in pH. When the pH value is higher than 6, the concentrations of heavy metals remained at low level.
90 80 70 60 50 40 30 20 10 0
0 5 pH 10 15

Concentration of metals (mg/L)

Pb Ni Zn

Figure 6. Concentration of metals with respect to pH (sample1)

Concentration of metals (mg/L)

60 50 40 30 20 Pb Ni Zn

10 0
0 5 pH 10 15

Figure 7. Concentration of metals with respect to pH (sample2)

3.3.4 Sequential Extraction Chemical fraction distribution of each metal differed vastly as shown in Figure 6 and 7. About Pb was present in F1, and the contents of F2 and F3 were less. Zn exhibited a similar distribution in that the contents of F2. Ni concentrations were high in exchangeable fraction F1, whereas in F2 and F3 represented very less.

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18 16 14 12 10 8 6 4 2 0

Conc. of metal species (ppm)

Pb Ni Zn

Conc. of Ammonium acetate (M) Figure 8. Concentration of metals bound to exchangeable fraction (F1)

Con of metal species (ppm)

3 2.5 2 1.5 1 0.5 0 0 2 4 6 Pb Ni Zn

Conc of acetic acid (M)

Figure 9. Contcentration of metals bound to carbonate fraction (F2) 3.5

Con of metal species (ppm)

2.5
2 Pb 1.5 1 0.5 0 0 1 2 3 4 5 6 Conc. of NH2OH-HCl (M) Ni Zn

Figure 10. Contcentration of metals bound to Fe=Mn oxides (F3)

From the results it has been observed that Pb, Zn, are mainly present in the F1, Ni present almost in all the fraction F1, F2, F3, with equal amount. Hence the leachability could be well controlled in natural environment. But if there are sufficient amounts of reducing agents, heavy metals bound to Fe-Mn oxides (F3) would be gradually leached out, especially Pb and Zn. It is suggested that reducing conditions could accelerate the leaching process of bottom ash and a serious risk would be brought to

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the landll sites. Heavy metals bound to organic compounds (F2) could be transported to the environment slowly by reacting with complexing agents or oxidants, but they are not easily leached out under normal natural conditions. Heavy metals in residual condition are usually incorporated into the crystals, and thus the metals could not be dissolved even in destructive acidity conditions.

IV.

CONCLUSIONS

1) The physical characterization of the incinerated medical wastes reveals that the properties of the solid residues (bottom ash) depends upon composition of feed, type of incinerator used, and operating conditions and so on. 2) The batch test developed for this work fell into two categories: contact time and sequential extraction. The contact time test provided a static view of the leachate produced by the ash, since the leachant remained in contact with the same material long enough to establish equilibrium. The readily soluble materials leached out of the ash and become part of the leachate. 3) The sequential extraction test provided a dynamic view of the leaching properties of ash as fresh leachant encountered the material. 4) The concentration of heavy metals in the leachate was rather low and decreased against the rise of L/S ratio with the exception of Zn. In the case of low L/S ratios, the concentrations of Pb and Zn were relatively high. A change in pH values led to different leaching patterns. The concentrations of heavy metals declined along with the rise of initial pH of leaching solvent. When the pH value was greater than 6, the concentrations of heavy metals remained at a low level. The leaching characteristics of heavy metals could be well controlled through adjusting the pH in a desired range. 5) Chemical speciation and distribution of heavy metals varied greatly. Pb, Zn, and Ni were mainly present in the F1 and F2 so that their leachability could be well controlled in natural environment. On the whole, the extraction efficiency increased as the concentration of the extractant increased, but only for the third chemical fraction. This trend was due to the higher ion exchange capacity of the extractants and formation of anionic metal species, leading to more metal species leaching out of each chemical fraction.

V.

FUTURE WORK

In future work carried out by comparative study of leachate composition and solid waste nature plot using mat lab plots for the distribution analysis

REFERENCES
[1]. R.A. Rashid, G.C. Frantz, (1992) MSW incinerator ash as aggregate in concrete and masonry, J. Materials in Civil Engineering 4, 353368. [2]. C.S. Kirby, J.D. Rimstidt, (1993) Mineralogy and surface properties of municipal solid waste ash, Environmental Science and Technology 27, 652660. [3]. C.C.Wiles, (1996) Municipal solid waste combustion ash: state-of-the-knowledge, J. Hazardous Materials, 47 325344. [4]. Yang, G.C.C., Tsai, C.M., (1998) A study on heavy metal extractability and subsequent recovery by electrolysis for a municipal incinerator y ash. J. Hazard. Mater, 58, 103120. [5]. Hsien Wen Kuo, Shu-Lung Shu, Chin-Chung Wu and Jin-Shoung Lai, (1999) Characteristics of medical waste in Taiwan, J. Water, Air and Soil pollution, 114, 413-421. [6]. Kyung-Jin Hong, Shuzo Tokunga, Toshio Kajiuchi, (2000) Extraction of heavy metals from MSW incinerator fly ashes by chelating agents, J. Hazardous Materials, 75, 57-73. [7]. Abbas, Z., Moghaddam, A.P., Steenari, B.M. (2003), Release of Salts from Municipal Solid Waste Combustion Residues, Waste Management, 23, 291-305. [10]. James Thomson, (2005). A Report on Alternative Treatment and Non-Burn Disposal Practices Safe Management of Bio-medical Sharps Waste in India, Tata McGraw Hill, Chapter 4, pp. 64-

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67. [11]. Xiao Wan, Wei Wang, Tummin Ye, Yuwen Guo, Xingbao Gao,(2005) A study on the chemical and mineralogical characterization of MSWI fly ash using a sequential extraction procedure, J. Hazardous Materials, 137, 197-201. [12]. T. Jeremy and A. Honor( 2005) The Health Effects of Waste Incinerators, The 4th Report of The British Society for Ecological Medicine Moderators. [13]. S. V. Manyele, Toxic Acid Gas Absorber Design Con-siderations for Air Pollution Control in Process Indus-tries, Educational Research and Review, Vol. 3, No. 4, 2008, pp. 137-147. [14]. M.Y. Wey, K.Y. Liu, T.H. Tsai, J.T. Chou, (2006) Thermal treatment of the fly ash from municipal solid waste incinerator with rotary kiln, J. Hazard. Materials. B137, 981989. [15] Jean-Franois Viel, Marie-Caroline Clment, (2008) Dioxin Emissions from a Municipal Solid waste Incinerator and Risk of Invasive Breast Cancer: A Population-based Case-control Study with GIS-derived Exposure, International Journal of Health Geographics [16]. Kuen-ShengWanga, Kae-Long Linb, Ching-Hwa Lee (2009) Melting of municipal solid waste incinerator fly ash by waste-derived thermite reaction, Journal of Hazardous material (162) 338343. [17]. Jun Yao et.al, (2012) Heavy metals and PCDD/Fs in solid waste incinerator fly ash in Zhejiang province, China: chemical and bio-analytical characterization, Environmental Monitoring and Assessment , Volume 184, Issue 6, pp 3711-3720. [18]. Tobias Walser, Ludwing.K limbach et.al (2012) Persistance of engineered nano particles in municipal solid waste, Nature of Nanotechnology. [19]. Mingjiang Ni, Yingzhe Du, Shengyong Lu, Zheng Peng, Xiaodong Li,Jianhua Yan, Kefa Cen,(2012) Study of ashes from a medical waste incinerator in China: Physical and chemical characteristics on fly ash, ash deposits and bottom ash Environmental Progress & Sustainable Energy, DOI: 10.1002/ep.11649

AUTHORS
N. Nagendra Gandhi, Head and Professor in Chemical Engineering, A.C Tech Campus, Anna University Chennai, India. So far published 40 plus papers in national and international journals. He got several times best paper award. He is reviewer of many International Journals. He carried academic responsibilities like Controller of Examinations, Nodal-Officer, TEQIPACT, Placement and Training officer, Co-ordinator, Counselling Cell for Higher Studies, Coordinator, Distance Education, Co-ordinator, NBA accreditation, Chief- Superintendent, University Examinations, Co-ordinator, Entrance Exams for External Agencies, Anna University. He is invited keynote lecturer for Hydrotropy- A novel and cost effective method of liquid-liquid Extraction- Kyung Hee University-South Korea(2007), Computer Assisted Language Learning (CALL)-Kyung Hee University-SouthKorea(2007), Novel separation Techniques-Arunai Engineering collegeTiruvannamalai(2008), Higher studies opportunities for chemical Engineers in India and Abroad, Sriram Engineering College, Chennai(2010),Higher studies opportunities for Engineers and Technologists in India and Abroad ,Sri Venkateswara Engineering College (2001).He is guiding several Phd and M.Tech students.

P. Arunraj was born on 1st July 1985 at Neyveli, Tamil Nadu, India. He received B.Tech in Industrial Bio-Technology from Government College of Technology, Coimbatore in 2006. From July 2006 - May 2007 he worked as Junior Research Fellowship in Alagappa Tech Campus - Anna University Chennai. He graduated in M.Tech in Environmental Science & Technology during June 2007 - May 2009 from A.C Tech Campus - Anna University Chennai, Tamil Nadu. After that (May 2009 - Jan 2010) he worked as Freelancer Consultant in Carbon

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trading & Environmental Auditing. From 2010 to now he is working as Associate in Cognizant Technology Solutions, Coimbatore, Tamil Nadu, India. R. Thirumalai Kumar was born on 20th December 1982 at Shenkottai, (Mathalamparai-Home Town) TN, India. He received B.Tech in Chemical Engineering at Adhiyamaan College of Engineering, Hosur 2005. From July 2005 he has been worked as Senior Process engineer in Kwality Milk Foods Limited. In the year 2007 he was joined M. Tech in Petroleum Refining and PetroChemicals completed in the year 2009 from A.C Tech Campus-Anna University Chennai, TN. After that (2009) he has been worked as Process Engineer-Project in C2C Engineering, Chennai, India. From 2010 to till now he is working as Senior Lecturer in the Department of Oil and gas engineering at All Nations University College, Koforidua (E/R), Ghana. West Africa.

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