ICONICE-2007

REVIEW ON BIODIESEL EXHAUST EMISSIONS: BASICS, STANDARDS AND CONTROL MEASURES

Abstract: This paper is a compilation of a review of the basics of biodiesel emissions, worldwide regulations on emissions and control measures. Introduction: The diesel engine is used more than any other type of engine for transportation, thermal power generation and many other industrial and agricultural applications [2]. Combustion is the major process of energy generation. At present, more than 90 percent of the energy used is obtained from the combustion of fossil fuels. Combustion generated pollutants of concern include, particulate matter such as soot, unburnt and partially burned hydrocarbons such as aldehydes, oxides of Nitrogen, NOx and oxides of carbon. This paper presents the detailed literature review on various emission control methods in a diesel engine working on straight vegetable oils and their blends with diesel as an alternate fuel [3]. There is a need to search and find ways of using alternative fuels, which are preferably renewable and also emit low levels of gaseous and particulate pollutants in internal combustion engines. In case of agricultural applications, fuels that can be produced in rural areas in a decentralized manner, near the consumption points will be favored. The permissible emission levels can also be different in rural areas as compared to urban areas on account of the large differences in the number density of engines. Fuels like vegetable oils (both edible and nonedible oils) and biodiesel are being investigated by researchers for engine applications as an alternate fuel for diesel [4]. Biodiesel: Bio-diesel is a renewable fuel made by a chemical reaction of alcohol and vegetable or animal oils, fats, or greases, through a refinery process called transesterification. Properties of Biodiesel [11]: Low content free glycerin (<0.02 better <0.002) High degree of tranesterification (>99.8%) Low acid Number (<0.5 better <0.2%) No polymers, very clean Benefits of Biodiesel [9]: Greatest reduction in emission. Higher lubricity. Biodegradable- 95% degradation in 28 days, where as diesel fuel degrades 40% in 28 days. Non-toxicity. Decreased Global warming. Positive impact on agriculture. Engine Operation, Performance and Durability: The energy content of neat bio-diesel fuel is about eleven percent (11%) lower than that of petroleum-based diesel fuel (on a per gallon basis), which results in a power loss in engine operation. The viscosity range of bio-diesel fuel, however, is higher than that of petroleum-based diesel fuel (1.9 6.0 centistokes versus 1.3 5.8 centistokes), which tends to reduce barrel/plunger leakage and thereby slightly improve injector efficiency. The net effect of using B100, then, is a loss of approximately five to seven percent (5-7%) in maximum power output. The actual percentage power loss will vary depending on the percentage of biodiesel blended in the fuel. Any adjustment to the engine in service to compensate for such power loss may result in a violation of EPAs anti-tampering provisions. To avoid such illegal tampering, as well as

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potential engine problems that may occur if the engine is later operated with petroleum-based diesel fuel, EMA recommends that users not make such adjustments. Neat bio-diesel and higher percentage bio-diesel blends can cause a variety of engine performance problems, including filter plugging, injector coking, piston ring sticking and breaking, elastomer seal swelling and hardening/cracking and severe engine lubricant degradation [3]. At low ambient temperatures, bio-diesel is thicker than conventional diesel fuel, which would limit its use in certain geographic areas. In addition, elastomer compatibility with bio-diesel remains unclear; therefore, when biodiesel fuels are used, the condition of seals, hoses, gaskets, and wire coatings should be monitored regularly. There is limited information on the effect of neat bio-diesel and bio-diesel blends on engine durability during various environmental conditions. More information is needed to assess the viability of using these fuels over the mileage and operating periods typical of heavyduty engines [5]. Emissions associated with Biodiesel: The exhaust emissions are classified as unburnt fuel, carbon monoxide, nitrogen oxides, particulate matter and soot. Growing biodiesel market in India: India is stated to consume over 127 million tones of crude oil a year. Statistics point that India imports 70 percent of its needs. In addition diesel consumption is around 40 million tones per annum in India making it one of the biggest contributors in Petro-based products. In the area of Biofuels and enzymes, the dwindling reserves of fossil fuel, mounting oil prices, and increasing quantities of greenhouse gases have accelerated the focus on promoting the production and use of alternative fuels derived from renewable raw materials. Biodiesel can provide power similar to conventional diesel and thus can be used in diesel engines. Biodiesel is non-toxic and environment friendly as it produces substantially less carbon monoxide and the combustion gases contain no sulphur dioxide and unburnt hydrocarbons. India is stated to have consumed 9.3 million tons of petrol and 42.8 million tons of diesels in fiscal 2006-07. India is currently trying blends of ethanol extracted from sugarcane in petrol and blending diesel with non-edible oils like jatropha, pongamia, neem, and other non-edible oils. Considering Indias increasing vulnerability on the energy security front, Biofuels and industrial enzymes decidedly represent an area of opportunity for Indian Biotech. [8] India has great potential for production of bio-fuels like bio-ethanol and biodiesel from non-edible oil seeds. From about 100 varieties of oil seeds, only 10-12 varieties have been tapped so far. The annual estimated potential is about 20 million tones per annum. Wild crops cultivated in the waste land also form a source of biodiesel production in India and according to the Economic Survey of Government of India, out of the cultivated land area; about 175 million hectares are classified as waste and degraded land [2]. Thus, given a demand-based market, India can easily tap its potential and produce biodiesel in a large scale. Table-1 depicts the annual production of non-edible oil seeds in India. Annual Production of Non-edible Oil Seeds in India shown in Table -1 [7] Type Neem Karanja Kusum Pilu Ratanjot Jojoba Bhikal Thumba Wild Walnut Undi Production (MT) 500 200 80 50 100 04 Oil % 30 27-39 34 33 30-40 50 37 21 60-70 50-73

Effects of biodiesel emissions on Human health and Environment: All outdoor air pollution is estimated to pose 1% of cancer risk. Scientific research confirms that bio-diesel exhaust has a less harmful impact on human health than petroleum, diesel fuel. Bio-diesel emissions have roughly 45-90% lower toxic emission compared to diesel [1]. The health effect of diesel particulates, a complex mixture of solids and liquids, are still unclear. A growing number of

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epidemiological studies conclude that long term exposure to diesel exhaust may be associated with increase in the relative risk of lung cancer, mortality or both. As a result increasingly more health and government authorities worldwide classify diesel particulates as a human carcinogen. Increasingly tighter environmental regulations with regard to diesel particulate emissions will render the installation of particulate control device in diesel operated vehicles [2].

Emission Standards: Emission Standards [12] to be maintained are given in the Table -2: NOx (g/kWh) HC (g/kWh)

PM (mg/kWh)

Euro I (1992-93) 9.0 1.23 400 Euro II 1995-96) 7.0 1.1 150 Euro III (2000) 5.01 0.662 100/1603 Euro IV (2005/06) 3.51 0.462 20/303 Euro V (2008/09) 2.01 0.462 20/303 Emission Reduction Technologies [6]: Catalytic Converters: Diesel Oxidation Catalysts: In most applications, a diesel oxidation catalyst consists of a stainless steel canister that contains a honeycomb structure called a substrate or catalyst support. There are no moving parts, just large amounts of interior surface area. The interior surfaces are coated with catalytic metals such as platinum or palladium. It is called an oxidation catalyst because the device converts exhaust gas pollutants into harmless gases by means of chemical oxidation. In the case of diesel exhaust, the catalyst oxidizes CO, HCs, and the liquid hydrocarbons adsorbed on carbon particles. In the field of mobile source emission control, liquid hydrocarbons adsorbed on the carbon particles in engine exhaust are referred to as the soluble organic fraction (SOF) -- the soluble part of the particulate matter in the exhaust. Diesel oxidation catalysts are efficient at converting the soluble organic fraction of diesel particulate matter into carbon dioxide and water. Oxidation catalyst retrofits have proven effective at reducing particulate and smoke emissions on older vehicles. Under the U.S. EPA's urban bus rebuild/retrofit program, five manufacturers certified diesel oxidation catalysts as providing at least a 25 percent reduction in PM emissions for in-use urban buses. Certification data also indicates that oxidation catalysts achieve substantial reductions in CO and HC emissions. Currently, under the ARB and EPA retrofit technology verification processes, several technology manufacturers have verified diesel oxidation catalysts as providing at least a 25 percent reduction in PM emissions.

SCR Systems: A Selective Catalytic Reduction (SCR) system uses a metallic or ceramic washcoated catalyzed substrate, or a homogeneously extruded catalyst and a chemical reductant to convert nitrogen oxides to molecular nitrogen and oxygen in oxygen-rich exhaust streams like those encountered with diesel engines. In mobile source applications, an aqueous urea solution is usually the preferred reductant. Upon thermal decomposition in the exhaust, urea decomposes to ammonia which serves as the reductant. In some cases ammonia has been used as the reductant in mobile source retrofit applications. As exhaust and reductant pass over the SCR catalyst, chemical reactions occur that reduce NOx emissions to nitrogen and water. SCR catalysts can be combined with a particulate filter for combined reductions of both PM and NOx. Open loop SCR systems can reduce NOx emissions by 75 to 90 percent. Closed loop systems on stationary engines can achieve NOx reductions of greater than 95 percent. SCR systems are also effective in reducing HC emissions up to 80 percent and PM emissions 20 to 30 percent. Like all catalystbased emission control technologies, SCR performance is enhanced by the use of low sulfur fuel. Lean NOx Catalysts: Controlling NOx emissions from a diesel engine is inherently difficult because diesel engines are designed to run lean. In the oxygen-rich environment of diesel exhaust,

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it is difficult to chemically reduce NOx to molecular nitrogen. The conversion of NOx to molecular nitrogen in the exhaust stream requires a reductant (HC, CO or H2) and under typical engine operating conditions, sufficient quantities of reductant are not present to facilitate the conversion of NOx to nitrogen.

Some lean NOx catalyst (LNC) systems inject a small amount of diesel fuel or other reductant into the exhaust upstream of the catalyst. The fuel or other hydrocarbon reductant serves as a reducing agent for the catalytic conversion of NOx to N2. Other systems operate passively without any added reductant at reduced NOx conversion rates. A lean NOx catalyst often includes a porous material made of zeolite (a micro-porous material with a highly ordered channel structure), along with either a precious metal or base metal catalyst. The zeolites provide microscopic sites that are fuel/hydrocarbon rich where reduction reactions can take place. Without the added fuel and catalyst, reduction reactions that convert NOx to N2 would not take place because of excess oxygen present in the exhaust. Currently, peak NOx conversion efficiencies typically are around 10 to 30 percent (at reasonable levels of diesel fuel reductant consumption). Lean NOx Traps: Another type of catalyst being developed for diesel engines are known as lean NOx traps (LNT) because they function by trapping the NOx in the form of a metal nitrate during lean operation of the engine. The most common compound used to capture NOx is Barium Hydroxide or Barium Carbonate. Under lean air to fuel operation, NOx reacts to form NO2 over a platinum catalyst followed by reaction with the Barium compound to form BaNO3. Following a certain amount of lean operation, the trapping function will become saturated and must be regenerated. This is commonly done by operating the engine in a fuel rich mode for a brief period of time to facilitate the conversion of the barium compound back to a hydrated or carbonated form and giving up NOx in the form of N2 or NH3. LNT catalyst can be combined with a zeolite based SCR catalyst to trap ammonia and further reduce NOx via a selective catalytic reduction reaction to nitrogen.

Particulate Filters Diesel particulate filters remove particulate matter found in diesel exhaust by filtering exhaust from the engine. Diesel particulate filters or (DPF) can come in a variety of types depending on the level of filtration required. The simplest form of particulate removal can be achieved using a DOC as discussed as part of the diesel catalyst section. Diesel particulate filters can be either partial, flow through devices or wall flow designs which achieve the highest filtration efficiency.

Partial or Flow through Filters: The first level of filtration can be achieved using a partial or flow through particulate filter. In this type of device, the filter element can be made up of a variety of materials and designs such as, sintered metal, metal mesh or wire, or a reticulated metal or ceramic foam structure. In this type of device the exhaust gasses and PM follow a tortuous path through a relatively open network. The partial filtration occurs as particles impinge on the rough surface of the mesh or wire network of the filter element. Partial filters can be catalyzed or uncatalyzed and are less prone to plugging than the more commonly used wall flow filters discussed below.

High Efficiency Wall Flow Filters: In order to meet the stringent particulate emissions that are required for diesel light duty vehicles starting with the 2007 model year, the highest efficiency particulate filter is required. These are commonly made from ceramic materials such as cordierite, aluminum titanate, mullite or silicon carbide. The basis for the design of wall flow filters is a honeycomb structure with alternate channels plugged at opposite ends. As the gasses passes into the open end of a channel, the plug at the opposite end forces the gasses through the porous wall of the honeycomb channel and out through the neighboring channel. The ultra fine porous structure of the channel walls results in greater than 85% percent collection efficiencies of these filters. Wall flow filters capture particulate matter by interception and impaction of the solid particles across the porous wall. The exhaust gas is allowed to pass through in order to maintain low pressure drop.

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Sensor Technologies Temperature Sensor: Temperature sensors are used for two purposes: The first is as a warning system, typically on obsolete oxidation-only catalytic converters. The function of the sensor is to warn of temperature excursions above the safe operating temperature of the catalytic converter. However, modern catalytic converters are not as susceptible to temperature damage. Many modern three-way Platinum-based converters are able to handle temperatures of 900 degrees C sustained, while many modern three-way Palladium-based converters are able to handle temperatures of 925 degrees C sustained. Temperature sensors are also used to monitor the temperature rise over the catalytic converter core.

Oxygen Sensor: Oxygen sensors are part of the closed loop fuel feedback control system, associated with modern three-way catalyst emission control systems on gasoline engines. The closed loop fuel feedback control system is responsible for controlling the air/fuel ratio of the catalytic converter feed gas. During the closed loop operation, the electronic control module (ECM) keeps the air/fuel ratio adjusted to around the ideal 14.7 to 1 ratio. Signal from the oxygen sensor is used to determine the exact concentration of oxygen in the exhaust stream. From this signal, the ECM determines whether the mixture is richer or leaner than the ideal 14.7 to 1 air/fuel ratio. If the air/fuel ratio deviates from its preprogrammed swings, catalyst efficiency decreases dramatically, especially for NOx reduction. The oxygen sensor informs the ECM of needed adjustments to injector duration based on exhaust conditions. After adjustments are made, the oxygen sensor monitors the correction accuracy and informs the ECM of additional adjustments. The oxygen sensor is also an integral part of the onboard diagnostic (OBD) system which monitors the proper functioning of the emission control system of the vehicle. If the sensor detects oxygen content of the exhaust that is outside the specified range of the engine calibration, it will trigger the engine light to come on in the instrument cluster. NOx Sensor: NOx sensors represent state of the art technology that can be applied to gasoline lean burn engines as part of a broader engine control or diagnostic system used to insure proper operation of the NOx emission control system. These sensors can be incorporated independent of the NOx emission control technology used on the vehicle and their function is primarily to monitor the NOx conversion efficiency of the catalyst. The sensors can work as part of a feedback loop to the control unit on the emissions system to make real time adjustments and optimize NOx conversion. The principle of operation of one type of NOx sensor is based on proven solid electrolyte technology developed for oxygen sensors. The dual chamber zirconia sensing element and electro-chemical pumps work in conjunction with precious metal catalyst electrodes to control the oxygen concentration within the sensor and convert the NOx to NO and nitrogen. The sensor sends output signals in volts that are directly proportional to ppm NOx concentration. The sensors can be incorporated upstream and downstream of the catalyst, for example, to provide a feedback control loop to the ECU of the emissions system. The ECU can than make adjustments to optimize NOx conversion performance. The ECU can than make adjustments to optimize NOx conversion performance. In the case of SCR technology, feedback can also be provided to the urea dosing system whereas in the case of lean NOx trap technology a feedback loop could signal the regeneration of the trap.

Thermal Management Strategies: The majority of emissions from today's gasoline and diesel engines occur during cold start before the catalyst can achieve optimum operating temperatures. Exhaust system manufacturers have been working together with catalyst companies to develop ways to heat up the catalyst as quickly as possible. The greatest impact came from the introduction of close coupled catalysts (CCC) to supplement the existing under floor systems in the mid-1990. This positioned a smaller catalytic converter close to the exhaust manifold to allow rapid oxidation of CO and hydrocarbons. The exothermic heat generated in the CCC by these reactions facilitates the rapid heat up of the down stream, larger, under floor, TWC. In later developments, the CCC was sometimes formulated to be a fully functional TWC with the under floor unit serving as a clean-up catalyst to convert the

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final 10-20% of the pollutants.

The beneficial impact on reducing cold start emissions via thermal management has led to numerous improvements to the exhaust system components up stream of the converter in order to retain as much heat as possible in the exhaust gases. Manufacturers have developed ways to insulate the exhaust manifold and exhaust pipe. Attaching the CCC to a double walled, stainless steel exhaust pipe containing an air gap within the tube walls is probably the most common thermal management strategy used today. To meet the tightest SULEV and PZEV regulations required attention to the temperature distribution at the face of the CCC. This led to new inlet cone designs and modification to the shape of the space in front of the close coupled substrate.

Evaporative Emission Controls: Evaporative emissions are generally classified into two broad categories: HC emissions associated with the release of vapors due to elevated ambient temperatures (diurnal losses) and HC emissions associated with the release of vapors during normal vehicle operation ("running losses"). Modern light-duty gasoline vehicles have implemented a variety of approaches and technologies to reduce evaporative emissions from these sources. In the early 1970s, carbon canisters were installed on vehicles to control gasoline vapor losses from fuel tanks. The canister systems include purge systems to release HCs absorbed on the carbon-based absorbent back into the combustion chamber once the engine is running. In addition to carbon canisters, other measures are being implemented on light-duty gasoline vehicles as tighter evaporative emission controls have been introduced as part of the EPA Tier 2 and ARB LEV II programs. New multi-layer polymer materials have been developed that have extremely low vapor permeation rates for use in gas tanks and, fuel line connectors and seals to reduce evaporative emissions. HC adsorber elements have been developed for use in air induction systems to reduce diurnal losses associated with fuel delivery components such as fuel injectors. These adsorber elements can be based on monolithic carbon honeycombs or metal substrates coated with zeolitic materials that have a high affinity for HC vapors.

Enhanced Combustion Technologies: Understanding and controlling the combustion process is the first step in reducing engine out emissions and reducing the burden on the emission control systems within the exhaust. Engine design is an important part of controlling and facilitating the combustion process. In diesel engines, controlling combustion is the key approach to reducing engine out particulate emissions by optimizing the mixing between the fuel and air. Some common ways to increase mixing is through combustion chamber modifications to facilitate turbulent flow as well as fuel injector design to modify the spray pattern. Variable geometry turbo charging (VGT), which delivers variable quantities of pressurized air based on driving conditions, has been effective in reducing PM emissions by maintaining lean combustion in the engine. Reducing compression ratios have been shown effective in reducing combustion temperatures and in turn NOx emissions. Some common approaches to enhance air turbulence and improve fuel distribution within the cylinders include improvements to the design of fuel injectors, combustion chambers and injection ports. Some engine manufacturers have been able to achieve improvements to the combustion during cold start by making modifications to the design of intake air control valves resulting in a 40-50% reduction in HC emissions and injection ports among others. Crankcase Emission Control Technologies: Today, in most turbocharged after cooled diesel engines, the crankcase breather is vented to the atmosphere often using a downward directed draft tube. While a rudimentary filter is often installed on the crankcase breather, substantial amount of particulate matter is released to the atmosphere. Emissions through the breather may exceed 0.7 g/bhp-hr during idle conditions on recent model year engines. For MY 1994 to 2006 heavy-duty diesel engines, crankcase PM emissions reductions provided by crankcase emission control technologies range from 0.01 g/bhp-hr to 0.04 g/bhp-hr or up to 25 percent of the tailpipe emission standards. One solution to this emissions problem is the use of a multi-stage filter designed to collect, coalesce, and return the emitted lube oil to the engine's sump. Filtered gases are returned to the intake system, balancing the differential pressures involved. Typical systems consist of filter housing, a pressure regulator, a pressure relief valve and an oil check valve. These systems greatly reduce crankcase emissions. Crankcase emission controls are available as a retrofit technology for existing diesel engines or as an original equipment component of a new diesel engine.

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Criteria - pollutants are reduced with biodiesel use:[10] Tests show the use of biodiesel in diesel engines results in substantial reductions of unburned hydrocarbons, carbon monoxide, and particulate matter. Emissions of nitrogen oxides stay the same or are slightly increased.

Carbon Monoxide -- The exhaust emissions of carbon monoxide (a poisonous gas) from biodiesel are on average 44 percent lower than carbon monoxide emissions from diesel. Particulate Matter -- Breathing particulate has been shown to be a human health hazard. The exhaust emissions of particulate matter from biodiesel are about 40 percent lower than overall particulate matter emissions from diesel. Hydrocarbons -- The exhaust emissions of total hydrocarbons (a contributing factor in the localized formation of smog and ozone) are on average 68 percent lower for biodiesel than diesel fuel. Nitrogen Oxides -- NOx emissions from biodiesel increase or decrease depending on the engine family and testing procedures. NOx emissions (a contributing factor in the localized formation of smog and ozone) from pure (100%) biodiesel increase on average by 6 percent. However, biodiesel's lack of sulfur allows the use of NOx control technologies that cannot be used with conventional diesel. So, biodiesel, NOx emissions can be effectively managed and efficiently eliminated as a concern of the fuel's use.

Future scope: Long-term performance and endurance test evaluate the durability of the engine with prolonged operation on blends. There is also scope for research on compatibility of elastomers and metals in engines using fuel blends to avoid the unforeseen problems in sealing gasket, O-rings and other metal components in the engine system due to corrosive effect of ethanol methanol on these components. Pilot projects and R&D work on biodiesel needs to be encouraged and supported to establish techno-economic viability of large-scale production. Specifications for biodiesel should be established along with test methods and should be independent of any specific feedstock. Energy education on biodiesel programme and storing information and database for wider information dissemination among the public at large should be taken up at a larger scale

References: 1. B.B.Belvins, Biodiesel as transportationfuel/CEC-600-2005-028-FS, June 2006 2. N.V. Deshpande and C. Konge, Development of diesel particulate filter (DPF) for diesel engine. 3. Omprakash.D.Hebbal, Experimental Investigations on the use of Vegetable oils and their esters in a single cylinder diesel engine, PhD Thesis, JNTU, June 2006. 4. G Lakshmi Narayana Rao, S Sampath, K Rajagopal, Experimental Studies on the Combustion and Emission Characteristics of a Diesel Engine Fuelled with Used Cooking Oil Methyl Ester and its Diesel Blends, International Journal Of Applied Science, Engineering And Technology Volume 4 Number 2 2007 ISSN 1307-4318.

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5. 6. 7. 8. 9. 10. 11. 12.

BIODIESEL AS AUTOMOBILE, Central pollution control board, 2007. Technology for clean air, MECA, 2002-2007. http://www.enginemanufacturers.org/admin/library/upload/297.pdf, TECHNICAL STATEMENT ON THE USE OF BIODIESEL FUEL IN COMPRESSION IGNITION ENGINES, Feb 2003 http://chemical.e-techherald.com/index.php. http://www.aumconsultancy.com/about-us.html http://www.veggiepower.org.uk/page940a.htm Babu A.K and Devardajane.G, Vegetable oils and their derivatives as Fuel for CI Engines- an Overview, SAE paper No. 2003-01-0767 http://www.dieselnet.com/standards/eu/ld.php

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