RESEARCH PROPOSAL ON BIODESULFURIZATIO N OF HIGH SPEED DIESEL

By

Engr. Nadeem Hussain

For Admission to MS Petroleum Engineering at Univesiti Teknologi Petronas, Malaysia

Biodesulfurization of diesel to produce clean diesel Abstract: Oil refineries are facing many challenges, including heavier crude oils, increased fuel quality standards, and a need to reduce air pollution emissions. Global society is stepping on the road to zero-sulfur fuel, with only differences in the starting point of sulfur level and rate reduction of sulfur content between different countries. Hydrodesulfurization (HDS) is the most common technology used by refineries to remove sulfur from intermediate streams. However, HDS has several disadvantages, in that it is energy intensive, costly to install and to operate, and does not work well on refractory organosulfur compounds. Recent research has therefore focused on improving HDS catalysts and processes and also on the development of alternative technologies. Among the new technologies one possible approach is biocatalytic desulfurization (BDS). The advantage of BDS is that it can be operated in conditions that require less energy and hydrogen. BDS operates at ambient temperature and pressure with high selectivity, resulting in decreased energy costs, low emission, and no generation of undesirable side products. Over the last two decades several research groups have attempted to isolate bacteria capable of efficient desulfurization of oil fractions. This review examines the developments in our knowledge of the application of bacteria in BDS processes, assesses the technical viability of this technology and examines its future challenges. The nature of the problem The main problem with fossil fuels is that their combustion products are the cause of pollution on Earth. Carbon dioxide is responsible for causing global warming. Nitrogen oxides and sulfur oxides emissions are the main cause of acid rain which dissolves buildings, kills forests and poisons lakes. Governments throughout the world have recognized the problems associated with these emissions and moved to reduce them through rules and regulations The restriction of greenhouse gas emissions (particularly Carbon dioxide) is currently subject of fierce debate. For the past decade, almost everyone has agreed that restricting sulfur emissions is a good idea; the battle now is to fight over the level of emissions to allow. The easiest way to limit the amount of Sulfur dioxide emitted into the air is to limit the amount of sulfur in fuel. Another (but less practical) way would be to make more efficient scrubbers on stationary emitters and install them on mobile emitters (such as trains, planes and automobiles). Government agencies worldwide have selected to control the concentration of sulfur in fuels. For this purpose they have targeted gasoline and diesel. Straight run diesel, which is taken directly from the crude distillation tower, can

have sulfur ranging from less than 500 ppm to more than 5000 ppm, depending on which type of crude oil is used and whether or not it is already desulphurized in refineries. Conventional Desulfurization Technique Overview:Conventional HDS is a high-pressure (150200 psig) and high-temperature (200450 0C) catalytic process that converts organic sulfur to hydrogen sulfide gas by reacting crude oil fractions with hydrogen in the presence of an efficient inorganic catalyst. The reactivity of organosulfur compounds varies widely depending on their structure and the local sulfur atom environment. The conditions depend upon the level of desulfurization required (Gupta et al., 2005).HDS of diesel feedstock for a low-sulfur product requires a larger reactor volume, longer processing times, and substantial hydrogen and energy inputs. Deep HDS technology results in various problems in the process, which limit its usefulness: (i) the application of extreme conditions to desulphurized refractory compounds results in the deposition of carbonaceous coke on the catalysts; (ii) exposure of crude oil fractions to severe conditions including temperatures above about 360 0C decreases the fuel value of treated product; (iii) deep HDS processes need large new capital investments and/or have higher operating costs; (iv) the H2S that is generated poisons the catalysts and shortens their useful life; (v) deep HDS is affected by components in the reaction mixture such as organic heterocompounds and polyaromatic hydrocarbons Biodesulfurization BDS is often considered as a potential alternative to the conventional deep HDS processes used in refineries. In this process, bacteria remove organosulfur from petroleum fractions without degrading the carbon skeleton of the organosulfur compounds. During a BDS process, alkylated dibenzothiophenes (Cx-DBTs) are converted to non-sulfur compounds, for example 2-hydroxybiphenyl (2-HBP), and sulfate. BDS offers mild processing conditions and reduces the need for hydrogen. Both these features would lead to high energy savings in the refinery. Further, significant reductions in greenhouse gas emissions have also been predicted if BDS is used (Linguist & Pacheco, 1999 Disadvantages of HDS:1. This process has high cost. 2. This technique does not work well with polyaromatic sulfur heterocycles found in heavier fractions. 3. Dibenzothiophene (DBT) and DBTs bearing alkyl substitutions that are considered as model compounds for the organic sulfur components of fossil fuels are difficult to remove using HDS. 4. This technique results in the release of large amounts of Carbon dioxide. 5. This process works at high temperature and pressure.

Advantages of Biodesulfurization:1. The BDS system is designed to operate at essentially ambient temperature and pressure, thereby removing the need for the expensive thick-walled reactors and other plant systems now required for Hydrodesulfurization. Additionally, BDS does not require the addition of hydrogen, the single most expensive component of the overall operating cost of Hydrodesulfurization. 2. Low emission, resulting in low amount of pollution. 3. No generation of undesirable side products. 4. Lower yield of sulfur in gasoline and diesel. 5. Capital cost of establishing its plant will be less than that of the current technology. 6. Whole microorganisms as well as their enzymes can use a wide range of compounds as substrates transforming them into specific products. Bio-Desulfurization Overview:Keeping in view the drawbacks of conventional desulfurization process, a new, more environmentally friendly process has been developed which is known as BioDesulfurization. This method promises to lower sulfur in gasoline and diesel, but at half the cost and without the huge increase in emissions inherent in current technology. Basically a microorganism has been identified that is naturally occurring in the soil that can be genetically enhanced to "eat" sulfur out of gasoline and diesel fuels. The organism can also be enhanced to "eat" sulfur out of coal and crude oil, which current Hydrodesulfurization technology cannot do. In biodesulfurization ("BDS") process, a genetically engineered variant of the Rhodococcus strain of bacteria is used with water and the fuel to be treated. The bacterium first incorporates the sulfur containing hydrocarbon molecule and then employs an enzymatic reaction to cleanly cut a sulfur-carbon bond in the molecule. The oxidized sulfur bearing molecule is then released by the bacterium into the water medium. When employed on large scale this bacterium can be used to effectively remove sulfur from fuels on a commercially viable scale. The relevant genes from the bacterium have been identified, sequenced, and successfully cloned. The Rhodococcus bacterium is a harmless species and poses no threat to humans, animals, or plant life in the event of an industrial accident. It is easily sustainable by means of an inexpensive nutrient solution and reproduces itself under process conditions. Moreover, the bacterium is able to process large quantities of fuel before its effectiveness begins to decline. Finally, it is easily killed by a simple application of heat and/or chemicals.

Bench Scale Bioreactor for BDS of Diesel

Explanation of Process The BDS reactors are operated at a 50:50 oil-to-water volumetric ratio, a biocatalyst concentration of 20 g/L (dry cell weight, combined phase basis) and a biocatalyst residence time of 50 hours. The majority of the water and biocatalyst supplied to the reaction section is provided by internal recycle. A portion of the biocatalyst inventory is, however, continuously purged from the system with an equivalent amount of fresh biocatalyst grown to maintain biocatalyst activity. The biocatalyst makeup is continuously grown on-site within the system The main processing sections of the BDS unit include a Feed Section, Reaction Section, and a Separation Section. The Feed Section consists of storage tanks and feed pumps

designed to provide all materials to the system. The feeds to the reactors include the raw diesel feed, air, water and the various substrates and nutrients necessary to sustain the activity of the biocatalyst. Also included in the feed system are unit operations to sterilize feed components as well as a fermentation system to grow fresh biocatalyst for makeup to the Reaction Section. The Reaction System consists of continuously stirred reactor in which the biodesulfurization reactions occur. The streams from the feed section are feed the reactor, and the emulsified water/oil/biocatalyst effluent from the reactor is pumped to the Decanter. The Decanter consists of two stages of gravity separation, the first to recover the desulfurized diesel product and the second to recover the bulk of the water and biocatalyst (plus some entrained oil) for recycle to the reactor. The concentrated oil streams are combined for a treatment in an electrostatic precipitator to produce a product diesel stream free from water and biocatalyst. A portion of the aqueous product is passed through a filter press to concentrate waste biocatalyst for disposal and water to wastewater treatment. The biocatalyst-containing sections are operated under aseptic conditions. Aseptic operation requires that all inputs to the system be treated to remove or destroy any foreign organisms. Foreign organisms, if introduced into the system, could inhibit the performance of the biodesulfurization organisms, possibly to the point of complete failure. Sterilization of the inputs to the system is accomplished either through removal of contaminants in cartridge filters or by deactivating (killing) the organisms through heating in continuous heat sterilizers. Where sterilization is by means of filtration, a prefilter is provided to remove relatively large suspended matter that could plug and thus shorten the life of the more expensive bio-filters. Where heat sterilization is employed, the sterilizers would be provided as a complete packaged system consisting of a heater, holding loop and cooler; heating would be provided by a separate circulating loop of steam-heated water. OBJECTIVE OF STUDY: Following are the points that need to be elaborated broadly in order to make this process commercialize. 1) Availability and cultivation of Microorganism 2) Enzyme selectivity 3) Better understanding of the reaction mechanism of microorganism and sulfur containing compounds 4) Development of biocatalyst having ability to desulfurize all sulfur containing compounds. Scope of study : Following areas will be my keen interest of study. 1) 2) 3) 4) 5) 6) Microbiology of Rhodococcus The Kinetics of Enzyme catalyzed Reaction Design and analysis of Biological reactor Transport Phenomena in bioprocess system Product recovery operation Instrumentation and process control

7) Bioprocess economics Methodology and experimental work: First part of the research involves reviewing the existing literature on Bio desulfurization of diesel to produce clean diesel. (Four months). Objectives mentioned earlier will be studied thoroughly in order to make this process most efficient. (Four months) An experimental procedure will be established for Formulation and process parameters analysis for Bio desulfurization of diesel to produce clean diesel.(Four months) Further study on literature will be carried out in order to establish compare/verify experimentation results (Four months). Project / Thesis will be shaped in final form for submission (Two months).

References: 1) John F Prescott, Rhodococcus equi: an Animal and Human Pathogen, Clinical Microbiology Reviews Bol.4, No. 1, Jan.1991, pp20-34. 2) Fuli Li, Ping Xu, Jinhui Feng,Ling Meng,Yuan Zheng, Lailong Luo, and Uiqing Ma, Microbial Desulfurization of Gasoline in a Mycobacterium goodiie X7B Immobilized-cell system, Applied and Environmental Microbiology,jan.2005pp276281. 3) Sylvia A.denome,Edwin S olson and Kevin D. Young, Identification and cloning of Genes Involved in Specific Desulfurization of Dibenzothiophene by Rhodococcus Sp. Strain IGTS8, Applied and Environmental Microbiology Vol.59,No.9 ,Sept.1993, pp 2837-2843. 4) B.R Folsom ,D.R Schieche,P .MD.Grazia, J.werner and S.Palmer, Microbial Desulfurization of Alkylated Dibenzothiophenes from a Hydrodesulfurized Middle Distillatte by Rhodococcus Erythropolis 1-19.Applied and Environmental Microbiology Vol.65,No.11 Nov.1991,pp 4967-4972. 5) Jonathan D.Van Hamme,Ajay Sing and Owen P.Ward, recent Advances in Petroleum Microbiology ,Microbiology and Molecular biology Reviews Vol.67No.4 Dec 2003,pp 503-549. 6) Enchira Biotechnology Corporation, The Woodlands XT Coordinating Research Council Alpharetta,GA.office of Industrial Technologies Energy Efficiency & Renewable Energy US Department of Energy Washington D.C.20585. 7) Biocatalytic desulfurization (BDS) of petrodiesel fuels Ghasemali Mohebali1 and Andrew S. Ball2, 1Department of Petroleum Biotechnology, Biotechnology Research Center, Research Institute of Petroleum Industry, Tehran, Iran, 2School of Biological Sciences, Flinders University of South Australia, Adelaide, SA 5001, Australia. 8) Wei Li, Miao-Dong Wang, Han Chen, Jian-Ming Chen and Yao Shi, Bio-Desulfurization of Di-Benzothiophene by growing cells of Gordonia sp. In batch cultures, Biotechnol Lett Vol.28,Jun.2006,pp1175-1179.

9) Nidhi Gupta, P.K. Roychoudhary, J.K Deb, Biotechnology of desulfurization of diesel prospect and chanlleges; Appl Microbial Biotechnol Vol.66 Nov, 2004. pp356-366. 10) S. Abbad-Andaloussi, M.Warzywoda and Monot, Microbial Desulfurization of Diesel oils by selected bacterial strains, Oil and Gas Science and technology Vol. 58, no.4,2003, pp505-513.