Clean fuels Introduction Clean fuels are fuels that contain very few of components that may harm

the environment, like sulphur, nitrogen, and organometallic compounds. Benzene can also be included along with polycyclic aromatic hydrocarbons (PAH). In the olden days human beings use to use fuels in its crude form for their livelihood but in the past few decades we have caused serious damage to our environment due to unregulated use of non-clean fuels which lead to many hazards, recognizing the need for protection of our environment governments in world have raised the issue of producing clean fuels. This motivated the search for producing clean fuels by different processes. New technology and better design of refinery equipment are also being developed in order to produce clean and less expense fuels. Fuels obtained from crude oil do not meet specifications given by the government, a list of specification are given below, so we must clean the products obtained from crude oil in order to meet specifications, make clean fuels, get maximum benefits from the fuels with minimum effect to our environment, many process are involved to fulfill these tasks, following are the list of processes involved in making clean fuels and all these process come under common name petroleum refining process in case of petroleum products, other sources of clean are from natural gas, coal, and in the recent times focus is on bio-fuels, so in this presentation we shell look into different ways and means to produce clean fuels . Petrol and Diesel as clean fuels

Petroleum Refining Processes for producing clean petrol and diesel 1 Physical Separation Processes Desalting, distillation, Solvent Deasphalting, solvent extraction, crystallization, adsorption, Solvent Dewaxing.

2 Chemical Catalytic Conversion Processes Reforming hydrotreating, hydrocracking (H-addition), isomersization, dimerizatoin. 3 Thermal Chemical Conversion Processes Delayed coking, flexi coking, visbreaking(c-rejection)

FCC(C-rejection),

alkylation,

1 Physical Separation processes Crude oils are first desalted and then introduced with steam to an atmospheric distillation column. The atmospheric residue is then introduced to a vacuum distillation tower operating at about 50 mmHg, where heavier products are obtained. a) Desalting When the crude oil enters the unit, it carries with it some brine in the form of very fine water droplets emulsified in the crude oil. The salt content of the crude measured in pounds per thousand barrels (PTB) can be as high as 2000. Desalting of crude oil is an essential part of the refinery operation. b) Fractional Distillation by Atmospheric distillation unit (ADU) and ( VDU)

List of products from crude distillation unit

C) Solvent Deasphalting This is the only physical process where carbon is rejected from heavy petroleum fraction such as vacuum residue. Propane in liquid form (at moderate pressure) is usually used to dissolve the whole oil, leaving asphaltene to precipitate. The deasphalted oil (DAO) has low sulphur and metal contents since these are removed with asphaltene. This oil is also called Bright Stock and is used as feedstock for lube oil plant. The DAO can also be sent to cracking units to increase light oil production. 2 Chemical Catalytic Conversion Processes a) Catalytic reforming Catalytic reforming is the process of transforming C7C10 hydrocarbons with low octane numbers to aromatics(A) and iso-paraffins which have high octane numbers. It is a highly endothermic process requiring large amounts of energy. A schematic presentation of the feedstock, products and process condition is shown below, The process can be operated in two modes: a high severity mode to produce mainly aromatics (8090 vol%) and a middle severity mode to produce high octane gasoline (70% aromatics content).

Reforming reactions

Catalytic system - bifunctional Pt-M/Alumina-Cl M= Re, Ir, Sn. The catalyst used for reforming is a bifunctional catalyst composed of platinum metal on chlorinated alumina. Platinum acts as the centre for the dehydrogenation reaction, and chlorinated alumina acts as

an acidic site to promote structure changes, such as cyclization of paraffins and isomerization of the naphthenes, promoting agents like Iridium (Ir) is added to boost activity, Rhenium (Re) is added to operate at lower pressures and Tin (Sn) is added to improve yield at low pressures. b) Hydrotreating The term hydrotreating is used to describe the process of the removal of sulphur, nitrogen and metal impurities in the feedstock by hydrogen in the presence of a catalyst. Hydrotreating exhibit following functions: 1. Removing impurities, such as sulphur, nitrogen and oxygen for the control of a final product specification or for the preparation of feed for further processing (naphtha reformer feed and FCC feed) 2. Removal of metals, usually in a separate guard catalytic reactor when the organo-metallic compounds are hydrogenated and decomposed, resulting in metal deposition on the catalyst pores (e.g. atmospheric residue desulphurization (ARDS) guard reactor) 3. Saturation of olefins and their unstable compounds. 4. Hydrotreating units are needed in the refinery to clean streams from material such as sulphur, nitrogen or metals harmful to the catalysts. That is why they are located before the reformer, hydrocracker and FCC.

Role of hydrotreating 1. Meeting finished product specification. Kerosene, gas oil and lube oil desulphurization. Olefin saturation for stability improvement. Nitrogen removal. De-aromatization for kerosene to improve cetane number

2. Feed preparation for downstream units: Naphtha is hydrotreated for removal of metal and sulphur. Sulphur, metal, polyaromatics and Conradson carbon removal from vacuum gas oil (VGO) to be used as FCC feed. Pretreatment of hydrocracking feed to reduce sulphur, nitrogen and aromatics.

Chemistry of hydrotreating 1. Desulphurization a. Mercaptanes: RSH + H2 RH + H2S

Hydrotreating Catalysts The hydrotreating catalyst is a porous alumina matrix impregnated with combinations of cobalt (Co), nickel (Ni), molybdenum (Mo) and tungsten (W). The catalysts mainly have pores with a surface area of (200300 m2/g). CoMo catalysts are the most popular for desulphurization of straight run petroleum fractions. NiMo catalysts are chosen when higher activity is required for the saturation of polynuclear aromatic compounds or for the removal of nitrogen and refractory sulphur compounds, while NiW catalysts are chosen only when very high activity aromatic saturation is required . The pore size of a catalyst should be chosen carefully because a smaller size will favor hydrodesulphurization (HDS) on the expense of hydrodemetallization (HDM).

Naphtha Hydrotreating Heavy naphtha hydrotreating is usually used to remove the impurities so that the hydrotreated naphtha can be introduced to the catalytic reformer. The expensive platinum based catalyst used in the reformer is sensitive to poisoning by such impurities. Middle Distillates Hydrotreating Middle distillate is mainly composed of saturated paraffins and also some aromatics which include simple compounds with up to three aromatic rings. Kerosene, jet fuel oil and diesel fuel are all derived from middle distillate fractions.

c) Hydrocracking (H-addition), Hydrocracking is a catalytic hydrogenation process in which high molecular weight feedstocks are converted and hydrogenated to lower molecular weight products. The catalyst used in hydrocracking is a bifunctional one. It is composed of a metallic part, which promotes hydrogenation, and an acid part, which promotes cracking. Hydrogenation removes impurities in the feed such as sulphur, nitrogen and metals. Cracking will break bonds, and the resulting unsaturated products are consequently hydrogenated into stable compounds. Functions It is mainly used to produce middle distillates of low sulphur content such as kerosene and diesel. If mild hydrocracking is used, a LSFO can be produced. More recently, it has been used to remove wax by catalytic dewaxing and for aromatic removal by hydrogen saturation. This has

been applied to the lube oil plants and is gradually replacing the old solvent dewaxing and aromatic solvent extraction.

Hydrocracking chemistry

Hydrocracking catalyst Hydrocracking catalysts have a cracking function and a hydrogenationdehydrogenation function. The cracking function is provided by an acidic support, whereas the hydrogenation

dehydrogenation function is provided by active metals. The acidic support can be (a) amorphous oxides (e.g. silicaalumina), (b) a crystalline zeolite (mostly modified Y zeolite) plus binder (e.g. alumina) or (c) a mixture of crystalline zeolite and amorphous oxides. Cracking and isomerization reactions take place on the acidic support. The metals providing the hydrogenationdehydrogenation function can be noble metals (palladium, platinum) or nonnoble metal sulphides from Group VI.A (molybdenum, tungsten) and group VIII.A (cobalt, nickel). These metals catalyze the hydrogenation of the feedstock, making it more reactive for cracking and heteroatom removal and reducing the coking rate. They also initiate the cracking by forming a reactive olefin intermediate via dehydrogenation. The ratio between the catalysts cracking function and hydrogenation function can be adjusted to optimize activity and selectivity.

d) FCC(C-rejection)

The fluidised catalytic cracking (FCC) unit is the heart of the refinery and is where heavy lowvalue petroleum stream such as vacuum gas oil (VGO) is upgraded into higher value products, mainly gasoline and C3/C4 olefins, which can be used in the alkylation unit for production of ultraclean gasoline (C7C8 alkylates). The role of the FCC is to take heavy desulphurised feedstock and crack it into lighter, mainly high octane gasoline. In a typical refinery, a FCC is installed mainly to produce gasoline. The FCC also produces olefins (C5and C4) and LPG. Olefins can be utilised for alkylation and MTBE production. In fact, some FCC units can be dedicated for the production of petrochemicals, as in the UOP petro-FCC process.

FCC Reactions The main reaction in the FCC is the catalytic cracking of paraffin, olefins, naphthenes and side chains in aromatics.. The VGO undergoes the desired primary cracking into gasoline and LCO. A secondary reaction also occurs, which must be limited, such as a hydrogen transfer reaction which lowers the gasoline yield and causes the cycloaddition reaction. The latter could lead to coke formation (needed to provide heat for catalyst.

Hydrogen transfer plays a key role in the gas oil cracking process. It reduces the amount of olefins in the product, contributes to coke formation, and thereby influences the molecular weight distribution of the product. Through intermolecular (bimolecular) hydrogen transfer, highly reactive olefins are converted to more stable paraffins and aromatics as follows

Other primary cracking reactions in FCC :

Secondary reaction in FCC: Gasoline formed from primary cracking can undergo further secondary cracking, which is generally caused by hydrogen transfer mechanisms such as isomerisation, cyclisation and coke formation.

FCC Catalyst The main catalyst which is used in a FCC reactor is the zeolite type. It is in a powderform with an average particle size of 75 mm and an average surface area of 800 m2/g. It has a crystalline structure of aluminosilicates. A matrix is added to the zeolite which acts as a binder and filler. Active component The main active component in the catalyst is the Y-Zeolite. It is a crystalline structure of aluminosilicates which has the Y-faujasite structure. The highest pore size in the Y-faujasite

structure is 8 oA, which is called the super cage. It can allow some C18C25 mono-, di- and trinuclear aromatics present in the VGO to pass. In the cracking of long chain paraffins, another type of high silica zeolite is added. This zeolite is called ZSM-5 and is used to improve octane number. Matrix The matrix is added to the zeolite to increase the body of the catalyst and add some improved properties. Three types of substances constitute the matrix: 1. A binder is added as a glue which is then added to the catalyst to provide cohesion for zeolite particles. 2. A filler is added to make up the body of the catalyst. It is usually a clay (Kaoline). The function of the filler and binder is to provide physical integrity (density and attrition resistance). 3. Additives, such as a small amount (ppm) of metal, are added to the catalyst to promote the combustion of CO to CO2 in the regenerator. Metallic oxides are added to fix SOx on the catalyst. The sulphur is recovered as H2S in the reactor. An addition of 5% ZSM-5 zeolite will lead to an increase of one research octane number (RON). 3 The thermal Chemical Conversion Processes Thermal conversion is the cracking of heavy residues under severe thermal conditions. The liquid products of this process are highly olefinic, aromatic and have high sulphur content. They require hydrogen treatment to improve their properties. Coking is the process of carbon rejection from the heavy residues producing lighter components lower in sulphur, since most of the sulphur is retained in the coke. The thermal treatment of hydrocarbons follows a free radical mechanism where cracking reactions take place in the initiation step. The reactions in the final step result in the formation of heavy fractions and products like coke.

Thermal cracking processes

a) Visbreaking Visbreaking is a mild thermal cracking of vacuum or atmospheric residues to produce light products and 7585% cracked material of lower viscosity that can be used as fuel oil. Feed Sources The feed to visbreaker can be either Atmospheric residue (AR) Vacuum residue (VR)

Vacuum residue is the heaviest distillation product and it contains two fractions: heavy hydrocarbons and very heavy molecular weight molecules, such as asphaltene and resins. Visbreaking Reactions The main reaction in visbreaking is thermal cracking of heavy hydrocarbons. possible reactions in visbreaking are: Paraffinic side chain breaking which will also lower the pour point Cracking of naphthens rings at temperature above 482 oC (900o F) Coke formation by polymerization, condensation, dehydrogenation and dealkylation

b) Delayed Coking Delayed coking is a type of thermal cracking in which the heat required to complete the coking reactions is supplied by a furnace, while coking itself takes place in drums operating continuously on a 24 h filling and 24 h emptying cycles. The process minimizes residence time in the furnace, while sufficient time is allowed in the drums where coking takes place (hence the term delayed coking.) Coke is rejected in the drums, thus increasing the H/C ratio in the rest of the products. However, these products are still unstable and unsaturated, and require further hydrogenation. The feed to coker is usually vacuum residue which is high on asphaltenes, resins, aromatics, sulphur and metals. The deposited coke contains most of the asphaltenes, sulphur, and metals present in the feed, and the products are unsaturated gases (olefins) and highly aromatic liquids.

Clean fuels from natural gas and coal Natural gas (NG) is a major source of clean fuels. It can be used directly as a gaseous clean fuel or processed to produce liquid clean fuel with low aromatic and zero sulphur content. The technology that is used to convert natural gas into liquid hydrocarbon fuels is called gas-toliquid technology (GTL). The conversion of natural gas to hydrocarbons is currently one of the most promising topics in the energy industry. Coal or heavy residues can be used on sites where these are available at low costs. Coal and natural gas can be converted into synthesis gas, a mixture of predominantly CO and H2 , by either partial oxidation or steam reforming processes. Possible reactions of synthesis gas are shown below

Possible reactions of synthesis gas

Fischer and Tropsch (FT) process is used to convert synthesis gas to aliphatic hydrocarbons. The major reactions in FT process is carbon monoxide hydrogenation over metal catalyst (iron, cobalt or nickel) at 180-250 oC (356482oF) and atmospheric pressure.

Possible products from FT synthesis

Bio fuels as clean fuels The term biofuel was known for the first time in the nineteenth century. Back then, ethanol was the only biofuel known. Due to crude oil discoveries. The field of biofuel technology and research declined. During the twentieth century, other fuels, mainly gasoline and diesel, were derived from crude oil. The reason for the dominance of fossil fuels in this sector is the large and cheap supply of its main feedstock, crude oil. Gasoline and diesel are still the most common fuels used in vehicles, but the (experimental) application of biofuels has been expanding due to European and international environmental policies. Biofuels have been used as additives to improve the quality of fuels applied in road vehicles. The increasing application of biofuels in transport has also been stimulated by environmental goals to reduce carbon dioxide (CO2) emissions that were set by national governments and international agreements, such as the Kyoto Protocol. biomass can produce different types of clean fuels that can be used directly by consumers. Bio-Diesel Vegetable oils are first produced by mechanical pressing or leaching oil seeds with a solvent such as hexane. The produced oil is highly viscous and has low cetane number (33-43). To improve its ignition quality, the vegetable oil is trans-esterified to change its structure from

branched structure of triglycerides into smaller straight chain methyl esters which are similar to fossil diesel. In this case, the trans-esterification reaction is carried out in the presence of catalyst (typically a strong acid or base).

The produced methyl ester is called Rapeseed Methyl Ester (RME). The reaction is carried at 1 mol% of H2 SO4 , alcohol/oil molar ratio of 30 to 1.0 at 65oC and 50 hours to reach complete conversion. The viscosity of RME is about twice the value of diesel fuel. Hence additive such as flow enhancers can be used to reduce viscosity. Since RME has similar fuel properties compared to diesel, it can be blended with fossil diesel in any proportion for application in conventional diesel engines. However, if 100% RME is to be used, a number of relatively minor changes in the engines are required. Material incompatibility with some engine components should be taken into account because RME shows a high chemical aggressiveness towards metallic materials, rubber seals, coatings and elastomers. Although RME can be mixed with fossil diesel in any ratio, car manufacturers often recommend not applying mixtures in their engines with a proportion of RME higher than 5%. A reason for this is that the certification level for the engine with regard to NOx emissions can be exceeded when a large proportion RME is used. Many diesel engine producers are working on an improved application of biodiesel. Some car manufacturers have produced private cars especially for the use of pure RME. In another application of bio-diesel, a mixture with ethanol, known as esterol, has been developed for regular diesel engines. Dimethylether (DME) has properties similar to LPG fuels. However, it has high cetane number (55) which makes it suitable to be used as a substitute for diesel. we find that diesel has 20times the viscosity of DME which might cause engine leak. The boiling point of DME can be utilized as spray injected to engine cylinder. The high oxygen content of DME ensures that it has high octane number (>55) which leads to good knocking properties. Ethanol and Methanol Ethanol has been used on a large scale as a transportation fuel, especially in Brazil. There, 60% of the produced ethanol is sold in a hydrated form (93 vol% ethanol and 7 vol% water), which completely replaces gasoline in vehicle engines. The remaining 40% ethanol is applied in waterfree form in a mixture with gasoline up to 24%. The predominant technology for converting biomass to ethanol is fermentation followed by distillation. Fermentation is a biochemical conversion process in which the biomass is decomposed using micro-organisms (bacteria or enzymes). This technology can be used for various types of biomass feedstocks (e.g. food crops, which are traditional feedstocks, and woody biomass, which is currently gaining a lot of attention). Like ethanol, methanol has also been used as a transportation fuel for quite a long

time, especially in the USA. Methanol can be produced from synthesis gas, which results from the gasification of biomass.

Bio-Fuel from Flash Pyrolysis Flash pyrolysis is the fast thermal decomposition of biomass in the absence of oxygen. The results of this pyrolysis are: gases, bio-fuels and char. Flash pyrolysis takes place at high temperatures between 700-1000oC (1292-1832 oF). The residence time in the reactor is below 1 second. This process is run to produce mainly liquid biofuels where the produced vapours are cooled and condensed. In this process very high heating rates of the biomass is followed by very rapid cooling of the produced vapours. The biomass is first dried and grinded, then it is fed to the reactor. Gasification Routes Biomass can be converted by means of a gasification process. Any type of biomass can be used as a feedstock, including lignocellulosic such as cellulosic materials from agricultural crops (straw, molasses) grasses and trees from forest plantations. Wet biomass, like municipal solid waste and agricultural residues can be used but with a lower efficiency. Gasification of biomass results in a mixture of combustible gases. This is called synthesis gas. A broad range of liquid biofuels can be produced by synthesis from this gas, depending on the process conditions.

Summary of different types of bio-fuels and fossil fuels which can be made into clean fuels

Assignment 1

Clean fuels
Submitted by V surya kumar Ca11m005 Ca11m005