RESEARCH OF DISPOSAL TREATMENT OF HAZARDOUS HYDROCARBON SLUDGE GENERATED FROM THE REFINING OIL PROCESS AND REGENERATION OF USED OILS.

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1 RESEARCH OF DISPOSAL TREATMENT OF HAZARDOUS HYDROCARBON SLUDGE GENERATED FROM THE REFINING OIL PROCESS AND REGENERATION OF USED OILS Nebojsa Knezevic Civil Engineering Institute IG LLC Banja Luka, Kralja Petra I Karađorđevića 92-98, Banjaluka, Republic of Srpska, BaH, izg@blic.net

2 INTRODUCTION Contamination of petroleum derivatives is one of the most serious environmental problems in the world today. The more numerous reservoirs of oil fuel and other petroleum derivatives that have been buried in the ground are the increasing danger for the purity of the land and ground waters. The tests have shown that in the most cases these reservoirs leak its contents into the environment. Pollution of the environment with waste oils is a very actual problem. In the process of treatment and regeneration of used motor oil there are different tailings and residues, and as such they represent a waste that can not be used for further technological processing.

3 INTRODUCTION The sludge is a mixture of oil residues, tar, and sulfuric acid with admixture of heavy metals and polyhalogenic hydrocarbons. Acid sludge is a black gelatinous mass with following basic structure: % of humidity, % of ashes, % of carbon, 8-9,5% of hydrogen, % of combustible sulfure and % N+O. The upper calorie power of this waste is from kj/kg, and the lower calorie power is from kj/kg. Heavy metals that appears in this waste are: lead (Pb), cadmium (Cd), nickel (Ni), tin (Sn), zinc (Zn), arsenic (As), copper (Cu), and other.

4 INTRODUCTION

5 MATERIAL AND METHODS OF WORK In order to obtain relevant indicators of composition of this waste and to estimate quantity, it was necessary to conduct extensive research works in site of this landfill that included: drilling and sampling the sludge and soil, physical and chemical analysis of the same, geophysics and geodetic researches and recording of the landfill, and all as foundation and starting point for selection of appropriate procedure for final disposal of this hazardous waste. For the selection of the appropriate procedure for the waste disposal different methods and various solutions of final waste disposal are analysed, economic analysis of all variant has been done, and for each variant advantages and disadvantages have been analysed. Volume of available options of the treatment of this waste is very wide.

6 MATERIAL AND METHODS OF WORK Various solutions of final disposal of the hazardous acid sludge that are analysed in this paper are: Recycle of waste; Neutralization and solidification of waste; Export and disposal abroad; Waste deposition; Use as fuel in power plants and in the process of production of cement clinker in cement factories; Pyrolisys of waste; Processing of waste with plasma technology; Heat treatment of waste (insineration) and Thermal desorption.

7 MATERIAL AND METHODS OF WORK Arrangement of measured points of geoelectric soundings and positions for an exploratory well

8 MATERIAL AND METHODS OF WORK For the need of the identification of disposed waste and contaminated soil from the vicinity of the sludge landfill was performed sampling on the landfill of this waste which is placed in the oil rafinery in Bosanski Brod. These drillings have been done with special geomechanic drilling tools with accessory equipment which can drill through the waste body. Eight wells have been drilled (five at the landfill and three in the vicinity of the landfill). Forty samples have been taken for analysis (25 samples of acid sludge and 15 samples of contaminated soil in the vicinity of the landfill). Sampled waste is subjected to thorough laboratory analysis in the laboratory Chemica s.r.l. Società di Servizi Analisi Chimiche e Ambientali Viale Cadorna, Busto Arsizio (VA).

9 RESULTS AND DISCUSSION Results of the researches on the field showed that the analysed landfill of the sludge waste is the landfill with hazardous waste under the code 05 01, the waste from refining oil process, and now in the mentioned landfill around ,00 tons of this waste is dumped. Geologic research works, beside basic purpose to do appropriate sampling of this waste, found certain profiles of the sludge waste in depth and the degree of contamination of surrounding soil. Results of the researches showed that this waste on the analysed landfill is in certain layers, and certain breach has been done in depth and width in the surrounding soil around the landfill.

10 RESULTS AND DISCUSSION Sludge waste from sludge pit Količina (m 3 ) Sludge waste from the vicinity of the sludge pit TOTAL SLUDGE 550 Contaminated soil from the vicinity of sludge pit Contaminated soil from the slope of the sludge pit TOTAL SOIL Sludge waste from sludge pit TOTAL FOR TREATMENT

11 RESULTS AND DISCUSSION Geologic and later laboratory testing showed that there is around ,00 tons of contaminated soil in the vicinity of the landfill that should be disposed in an appropriate way. Results of geophysics researches confirmed this testing and found out in the measured geoelectric sounds and prognostic 3 D depth model. Based on the value of specific electric resistance, the following lithological environments are separated: environment 1 - mound, sandy clay, waste; environment 2 - hydrocarbon layer (sludge); environment 3 - brown clay; environment 4 - sandy gray clay; environment 5 - sand with water.

12 RESULTS AND DISCUSSION

13 RESULTS AND DISCUSSION

14 RESULTS AND DISCUSSION Quantitative interpretation of geo-electric measuring points of sounding is based on determination of the specific electrical resistance and the thickness of registered lithological - geoelectric areas. Interpretation of results of geo-electric sounding is performed by a computer programs IPI 2win and Res 2dinv and graphic - analytic method with help of album ORELIANA - MOONEY for double- and triple- layer theoretic cases. Thereby are determined parameters ρ (specific electric resistance) and h (thickness) for each recorded lithological - geolectric area.

15 RESULTS AND DISCUSSION Based on determined parameters for ρ and h, it is shown interpreting 3D terrain model. The following can be concluded from the software analyses results: Environment with values of apparent specific resistance ρp < 30 0hmm, corresponding to the lithological complex made by clays. Environment with values of apparent specific resistance ρp from 30 0hmm up to 60 0hmm, lithologically corresponding to the clays and sandy clays. Environment with values of apparent specific resistance ρp from 60 0hmm up to 120 0hmm, lithologically corresponding to the sand. Environment with values of apparent specific resistance ρp over 150 0hmm, corresponding to the embankments, clayey-gravel and sandy layer and landfill waste material.

16 RESULTS AND DISCUSSION

17 RESULTS AND DISCUSSION The following can be concluded according to the analyses of obtained 3D model of sludge landfill: mound, sandy clay, waste, located in peripheral parts of investigated landfill. Thickness of this layer is variable and ranges from 1 m up to 3 meters; hydrocarbon layer (sludge), located in central parts of investigated landfill and its thickness ranges from 3 m up to 4 m; brown clay, located in all parts of investigated landfill. This section makes basis of hydrocarbon layer (sludge layer). Its thickness ranges from 1,5 m up to 3 m; sandy gray clay, represented in all parts of investigated landfill in deeper terrain layers. This section makes basis of hydrocarbon layer (sludge layer). Its thickness ranges from 5 up to 8 meters; sand with water, extends from gray sandy clay on the 5 meters depth in northwestern to 12 meters in southeastern parts of investigated landfill.

18 RESULTS AND DISCUSSION Physical and chemical analysis of the sludge waste from the analysed well (the well G2 which is placed in the centre of the landfill shows representative well for this landfill), show that the sludge has: low ph value (up to 1.7) large content of humidity (up to 20-40%), increased content of heavy metals (Cr, Pb, Ni, and other), which classify this waste as the waste with increased risk (hazardous waste) to the environment.

19 Average values of the results of sludge from the well Average values No Sulfuric parameter Unit 1. ph value Humidity content % Ash content % Cu mg/kg Cr mg/kg Tl mg/kg 0.1 Concentration of heavy metals Cd mg/kg 0.1 V mg/kg Pb mg/kg As mg/kg Sb mg/kg 0.1 Sn mg/kg Ni mg/kg Zn mg/kg PCB concentration mg/kg Cyanide concentration mg/kg Total content of sulfure, S+SO42- % Total content of sulfate, SO42- mg/kg Total content of nitrate, NO3- mg/kg Total content of nitrite, NO2- mg/kg Total content of chlorine mg/kg Total content of fluorine mg/kg Total content of bromine mg/kg Calorific value kcal/kg Total organic carbon, TOC % S.S The total hydrocarbons <12C mg/kg >12C % Determination of flash point 0C

20 RESULTS AND DISCUSSION On the basis of performed theoretical consideration for final disposal of hazardous sludge waste, performed waste analyses, waste categorization, economic analyses, the Thermal Desorption Method is selected as the best solution for processing of this type of waste. Analyzing all input waste parameters that should be processed and conditions that have to satisfy plant emissions (air quality, waste water quality and obtained ash and slug quality), and in cooperation with thermal desorption plant producer, it is made flow diagram of hazardous sludge waste thermal desorption process. All previously performed investigations and analyses, as well as thermal desorption flow diagram should serve as a basis for future system designing of hazardous sludge waste treatment made in the refining oil process and regeneration of used oils.

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23 CONCLUSION In the aim of the selection of appropriate technology for the disposal of the hazardous sludge waste from the refining oil process and regeneration of used oils, the appropriate research and laboratory works have been done on the landfill of the hazardous sludge waste and they included: drilling and sampling of the sludge waste and soil, geophysics and geoelectric researches, geodesy recording of the landfill and physical and chemical analyses of the waste. On the basis of the researches and laboratory analysis, clasification and categorization of the waste have been done in accordance with regulations of waste categories with catalogue. Also, the estimation of the waste quantity, that is on the landfill, has been done in the aim of the best technology selection from the point of technical and economic parameters and conditions of the environment protection. The waste is categorized as waste from the oil refining process with basic code (muds from the bottom of reservoir, acid base muds, acid tar, other tar, oils that contain acids, spent filter clays, waste that conclude sulfure from desulfurization of oil).

24 CONCLUSION In this sense, in this paper, the possibilities and alternative solutions of final disposal of industrial hazardous waste are analysed and the most acceptable technology of the waste disposal is suggested. In this paper, all advantages and disadvantages are shown for each analysed technology (method). For technology selection important condition was to find technologies which could be used on situ, on the spot, and which could be used relativly quickly.

25 CONCLUSION On the basis of all mentioned we can make conclusion that the most acceptable for the final disposal of the acid sludge waste is thermal methods of waste treatment, with the following advantages: Suggested technology can be relatively easy installed in site, on landfill of the waste, and large processing capacities of this waste can be done; This technology enables 99,9% of purification of waste emission gases from waste treatment facilities; Waste waters from waste processing are completely purified with this technology prior to discharge into the ultimate recipient; Construction of facilities for thermal desorption is simple, it doesn't need large infrastructure support and is easy to install; Cost of processing hazardous sludge waste with this technology is the cheapest of all analysed methods in this paper;

26 CONCLUSION There is no any preparation of the waste for application of this technology, therefore it is complete technology; The rest of the thermal desorption process is decontaminated soil which can be again returned to the site and use it for process of landfill reclamation; Obtained diagram shows that this technology represents a quite easily technological solution compared to other suggested technologies, and that for the same, there is no need for a large infrastructure investment. After reviewing the necessary approvals of the competent authorities for the implementation of this and other methods of final disposal of the waste and the needed financial investments, it shows that the use of this technology is the most simple, ecology the most acceptable and with minimum needed financial means.

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