GASIFICATION,COMBUSTION, PYROLYSIS

BIOMASS
Biomass includes a) Solid biomass (organic, non-fossil material of biological origins) b) Biogas (principally methane and carbon dioxide produced by anaerobic digestion of biomass and combusted to produce heat and/or power) c) Liquid bio fuels (bio-based liquid fuel from biomass transformation, mainly used in transportation applications) d) Municipal waste (wastes produced by the residential, commercial and public services sectors and incinerated in specific installations to produce heat and/or power).

WHY BIOMASS?
Renewable energy source Carbon Neutral Suitable for rural/decentralized generation of energy Potential for using existing infrastructure Biomass provides already 15% of the worlds primary energy production Huge availability and relatively cheap resource The combustion of biomass produces less ash than coal combustion and the ash produced can be used as a soil additive on farms

WAYS TO PRODUCE ENERGY

Gasification Combustion Pyrolysis Fermentation Anaerobic digestion

Gasification
The production of generator gas (producer gas) called gasification, is partial combustion of solid fuel (biomass) and takes place at temperatures of about 1000C. The reactor is called a gasifier. The combustion products from complete combustion of biomass generally contain nitrogen, water vapor, carbon dioxide and surplus of oxygen. However in gasification where there is a surplus of solid fuel (incomplete combustion) the products of combustion are combustible gases like Carbon monoxide (CO), Hydrogen (H2) and traces of Methane and nonuseful products like tar and dust

Gasification
Thus the key to gasifier design is to create conditions such that a) biomass is reduced to charcoal and, b) charcoal is converted at suitable temperature to produce CO and H2.

Gasification
The oxidising medium is normally air, oxygen or steam. Inorganic residues and an oil-tar fraction are also produced in the process. The product gas generally has a heating value between one tenth and half that of natural gas, depending on the composition of the biomass input and the gasification process employed

GASIFICATION
The gasification process convert any carbon containing material into synthesis gas composed primarily of carbon monoxide and hydrogen. Syngas can be used as a fuel to generate electricity or stream or used as a basic chemical building block for a large number of uses in the petrochemical and refining industries. Gasification adds value to low- to negative- value feed stocks by converting them to marketable fuels and products.

GASIFICATION CHEMISTRY

COAL GASIFICATION

GASIFICATION-BASED ENERGY CONVERSION SYSTEM

GASIFIER CONFIGURATIONS

SYNGAS PROCESSING
Reducing syngas temperature - Extract valuable energy - Permit use of more conventional materials - Use conventional/commercial processes Removal of chemical species that - Foul, corrode, or erode system components - Poison or deactivate chemical processing agents - Environmentally unacceptable for release Target Syngas purity - H2S and COS concentration - CO2 concentration Adjustment of H2/CO ratio

SYNGAS COOLING

ACID GAS REMOVAL (AGR)

GASIFICATION PROCESS SCHEMATIC

SYN GAS UTILIZATION OPTIONS

ADVANCED GASIFICATION (IGCC)

The Integrated Gasification Combined Cycle (IGCC) combining a synthesis gas fired turbine with a steam

turbine - represents the most efficient and cleanest way to

turn carbonaceous feedstocks (especially coal and resids) into electricity, hydrogen, transportation fuels, and other chemicals.

Replacing Natural Gas with Syn Gas

INTEGRATED GASIFICATION COMBINED CYCLE (IGCC)

GASIFICATION POTENTIAL

HYDROGEN PRODUCTION
Key Processes in Hydrogen production are: - Syn Gas Generation - Water Gas Shift - Desulphurization - Hydrogen Purification - CO2 Removal - Final Polishing

CHALLENGES WITH GASIFICATION

WATER GAS SHIFT REACTIONS

Water Gas Shift - Hydrogen Separation Membrane Reactor

CO + H2O
catalyst

CO2 + H2

H2

Membrane Tube

Reactor Shell

Removal of hydrogen drives reaction to completion Carbon dioxide stream at high pressure, ready for sequestration Hydrogen available as a clean energy source

GAS TO LIQUID TECHNOLOGIES

Gas-to-liquid (GTL) technologies are capable of converting gas to clean, useful liquid hydrocarbons

and thus suitable for

addressing problems of remote gas utilization (not readily transported), increase in crude oil price, depletion of fossil fuel and environmental pollution.

GTL OPTIONS
GTL options include not only the well-known production of liquids fuels but also the production

of oxygen containing fuels, fuel additives and

chemicals, such as methanol and DME.

Methane rich gases are converted into liquid

synthetic fuels either via direct conversion or via

Syn gas as an intermediate, for example, using

the Fischer Tropsch or Mobil processes.

DIRECT CONVERSION
The direct conversion of methane eliminates the cost of producing synthesis gas but involves a high

activation energy of C-H bond of methane to

establish C-C bond for C2+ hydrocarbons and is

difficult to control.
Several direct conversion processes have been

developed but none have been commercialized being

economically unattractive.

DIRECT CONVERSION PROCESSES

Two methods are considered for activating the C-H bond : Thermal coupling requires high temperatures for the formation of free radicals which will recombine to form liquid aromatic hydrocarbons. Oxidative coupling operates at lower temperatures bur requires the presence of oxygen and a catalyst.

THERMAL COUPLING
Thermal coupling requires high temperatures (>1000 0C) and very short residence time, but the formation of coke is the main problem. Acetylene can be produced by pyrolysis in an electric arc which will be viable only when low-cost electricity is available. Another process requires the presence of hydrogen to promote the production of C2+ hydrocarbons. To obtain sufficient conversion yield (30%) and good selectivity (85% of C2+), it is necessary to operate at 1200 0C. This process uses a ceramic reactor to withstand the temperature required and obtain a very short residence time by providing a very high heat flux. A mixture containing acetylene, ethylene and benzene is obtained, which, after selective hydrogenation and polymerization, is transformed into gasoline.

THERMAL COUPLING
The conversion of C2+ hydrocarbons can be favored by the presence of Cl2. the C-Cl bond is less stable as compared to CH bond and is easier to activate. The reaction of methane with chlorine at about 10000C, produces HCl, H2 and C2+ hydrocarbons.

In principle, this makes it possible to obtain high hydrocarbon

selectivity (73%) at lower temperatures. The problems connected with Cl2 recycling (special equipment resisting to corrosion required) make it difficult to apply this process commercially.

OXIDATIVE COUPLING
The conversion of methane to C2+ hydrocarbons in the presence of oxygen and catalysts (Li/MgO) takes place

in the temperature range of 700 to 800 0C.

The oxidative coupling reaction is exothermic and this

reaction can be combined with the steam cracking of

ethane which is endothermic, so as to maximize the ethylene production.

OXIDATIVE COUPLING
Another method is to use a Redox type system, employing a metallic oxide catalyst. In the first step,

methane is oxidized by the catalyst and in the second

step, the catalyst is reoxidized by air. The anticipated selectivity is relatively high but at a high catalyst circulation rate. The combined use of chlorine and oxygen and the use of organometallic catalyst can be considered as an option for obtaining C2+ compounds from methane.

INDIRECT CONVERSION PROCESSES

FISCHER TROPSCH PROCESS

Methane is partially oxidized to CO, CO2, H2 and H2O. The CO to H2 ratio is adjusted by using the water-gas shift reaction and the excess CO2 is removed by aqueous solutions of alkanolamine (or physical solvents) yielding syn gas that is chemically reacted over an iron or cobalt catalyst

to produce liquid hydrocarbons and other

byproducts.

Sources of Syngas
Initial sources Coal, Natural Gas, Biomass, Methane and other hydrocarbons Methane and other hydrocarbons can be partially combusted to create syngas
CH 4 1 2O2 2 H 2 CO Coal, Natural Gas, and Biomass are processed through Gasification or steam reforming into SynGas

SYNGAS TO LIQUID HYDROCARBON

The key variable is the hydrogen to carbon monoxide ratio with a 2:1 ratio recommended for F-T synthesis. Conversion of the syngas to liquid hydrocarbon is a chain growth reaction of carbon monoxide and hydrogen on the surface of a heterogeneous catalyst. The catalyst is either iron- or cobalt-based and the reaction is highly exothermic. The temperature, pressure and catalyst determine whether a light or heavy syncrude is produced. For example at 3300C mostly gasoline and olefins are produced whereas at 180 to 2500C mostly diesel and waxes are produced.

FT CHEMISTRY

FT REACTORS
There are mainly two types of F-T reactors: The vertical fixed tube type has the catalyst in tubes that are cooled externally by pressurized boiling water. For a large plant, several reactors in parallel may be used presenting energy savings. The other process is uses a slurry reactor in which preheated synthesis gas is fed to the bottom of the reactor and distributed into the slurry consisting of liquid wax and catalyst particles. As the gas bubbles upwards through the slurry, it is diffused and converted into more wax by the F-T reaction. The heat generated is removed through the reactor's cooling coils where steam is generated for use in the process.

FT REACTORS

FISCHER TROPSCH PROCESS

ADVANTAGES OF FT SYNTHESIS

Fischer-Tropsch vs. Crude oil

Fischer-Tropsch Today
There are multiple FT plants throughout the world Plant in Malaysia produces low-sulfur diesels South Africa uses both coal and natural gas There have been proposed facilities in the US to turn coal and waste-coal into FT fuels

MOBIL PROCESS
An alternative path starts by conversion of the natural gas to syngas, conversion of the syngas to methanol which is subsequently polymerized into alkanes over a Zeolite catalyst. It was developed by Mobil in early 1970s. Methanol is made from natural gas in a series of three reactions: Steam reforming: CH4 + H2O CO + 3 H2 rH = +206 kJ mol-1 Water shift reaction CO + H2O CO2 + H2 rH = +206 kJ mol-1 Synthesis 2 H2 + CO CH3OH rH = -92 kJ mol-1

MOBIL PROCESS
The methanol thus formed may be converted to gasoline by the Mobil process. First methanol is dehydrated to give Dimethyl ether: 2 CH3OH CH3OCH3 + H2O This is then further dehydrated over a zeolite catalyst, ZSM-5, to give a gasoline with 80% (by weight based on the organics in the product stream) C5+ hydrocarbon products. ZSM-5 is deactivated by a carbon build-up ("coking") over time in converting methanol to gasoline. The catalyst can be re-activated by burning off the coke in a stream of hot (500C) air; however, the number of reactivation cycles is limited.

MOBIL PROCESS
In the first part, methanol is converted to an equilibrium mixture of methanol, dimethylether, and water . This step releases 15-20% of the overall heat of reaction and is controlled by chemical equilibrium. As such, it is inherently stable. In the second step, the equilibrium mixture is mixed with recycle gas and passed over specially designed ZSM-5 catalyst to produce hydrocarbons and water. Most of the hydrocarbon products are in the gasoline range.

MOBIL PROCESS
Most of the gas is recycled to the ZSM-5 reactor. The water phase contains 0.1-0.2 wt% oxygenates which can be treated by conventional biological means. The conversion reactor inlet temperatures are controlled individually by adjusting the flow of reactor effluent to the recycle gas / reactor effluent heat exchangers and by adjusting the temperature difference across exchangers. Reactor effluent is also used to preheat, vaporize and superheat the methanol feed to the DME reactor.

Dimethyl Ether (DME)

AMMONIA PRODUCTION FROM GASIFICATION

 The Fisher-Tropsch process produces a broad spectrum of straight-chain paraffinic hydrocarbons that requires upgrading to produce commercial quality gasoline, jet fuel and diesel. In contrast, MTG selectively converts methanol to one liquid product: a very low sulfur, low benzene regular octane gasoline

COAL TO LIQUID (CTL)

Converting coal to a liquid fuel a process referred to as coal liquefaction allows coal to be utilized as an alternative to oil. The primary objective of any coal-liquefaction process is to increase the hydrogen-to-carbon ratio and remove sulfur, nitrogen, oxygen, and ash.

CTL is particularly suited to countries that rely heavily on oil imports and that have large domestic reserves of coal.

BENEFITS OF CTL
Coal to liquids has a number of benefits: Coal is affordable and available worldwide enabling countries to access domestic coal reserves and a wellsupplied international market - and decrease reliance on oil imports, improving energy security. Coal liquids can be used for transport, cooking, stationary power generation, and in the chemicals industry. Coal-derived fuels are sulphur-free, low in particulates, and low in nitrogen oxides. Liquid fuels from coal provide ultra-clean cooking fuels, alleviating health risks from indoor air pollution

COAL LIQUEFACTION PRODUCTS

An array of products can be made via these processes ultra-clean petroleum and diesel, as well as synthetic waxes, lubricants, chemical feedstocks and alternative liquid fuels such as methanol and dimethyl ether (DME). DME is non-carcinogenic and non-toxic to handle and generates less carbon monoxide and hydrocarbon air pollution than LPG. DME can also be used as an alternative to diesel for transport, as well as for on and off-grid power applications.

COAL LIQUEFACTION TECHNOLOGIES

There are two different methods for converting coal into liquid fuels:

Direct liquefaction works by dissolving the coal in a solvent at high temperature and pressure. This process is highly efficient, but the liquid products require further refining to achieve high grade fuel characteristics.
Indirect liquefaction gasifies the coal to form a syngas which is then condensed over a catalyst the Fischer-Tropsch process to produce high quality, ultra-clean products.

DIRECT COAL LIQUEFACTION

POLYGENERATION COAL TO LIQUID

CTL plant configured to produce electric power and liquid fuels can readily be modified to a Future Gen-type plant producing hydrogen.

GASIFIER DESIGN
The gasifier is the reactor in which the conversion of a feedstock into fuel gas takes place There are three fundamental types of gasifier 1. Fixed bed, 2. Fluidised bed 3. Indirect gasifier

Fixed bed reactors

Vertical fixed bed reactors (VFB) - the most Competitive fixed bed gasifiers. Updraft and downdraft gasifiers.

UPDRAFT GASIFIER
Counter-current gasifier, Feedstock is loaded from the top, whi le air is introduced from the bottom of the reactor. In the reactor the solid material is converted into combustible gas during its downward path. From the top: drying, pyrolysis, reduction and combustion greater than 1200 c. As a consequence of the updraft configuration,the tar coming from the pyrolysis zone is carried upward by the flowing hot gas: the result is the production of a gas with a high tar content. Typically, the sensible heat of gas is recovered by means of a direct Heat exchange with feedstock.

DOWNDRAFT GASIFIER
co-current the carbonaceous material is fed in from the top, the air is introduced at the sides above the grate while the combustible gas is withdrawn under the grate . As a consequence of the downdraft configuration, pyrolysis vapours allow an effective tar thermal cracking. However, the internal heat exchange is not as efficient as in the updraft gasifier

FIXED BED GASIFIERS

FLUIDISED BED GASIFIER

In fluidised bed gasifiers, biomass particles undergo drying, pyrolysis and gasification in a hot, fluidised mixture with inert bed material and air. The fluidised bed process enables good heat transfer between the gas and solid phases, and the high temperatures involved also provide some cracking of tars in the gas. Circulating fluidised bed gasifiers employ more turbulent mixing than bubbling fluidised bed systems, and use cyclones to separate solid particles from the gas stream before returning them to the bottom of the riser section. Fluidised bed gasifiers have higher throughput capacities than fixed bed gasifiers and have less stringent requirements for fuel type (they can process mixtures of woody and herbaceous fuels) or condition (they can process reasonably wet biomass).

FLUIDISED BED GASIFIER

INDIRECT GASIFIER
Indirect gasifiers are the reactors used for the steam indirect gasification and are grouped as char indirect gasifiers and gas indirect gasifiers depending on the type of internal energy source A char indirect gasifier consists of two separate reactors: a CFB steam gasifier that converts feedstock into produced gas and a CFB combustor that burns residual char to provide the necessary heat to gasify the feedstock Sand is circulated between the two reactors to transfer heat.

INDIRECT GASIFIER
Energy is provided by combustion of residual char, reserving all gaseous and condensable products for gas production This process is also called fast fluidised process because it has the highest throughputs and yields of gas. Gas indirect gasifiers use a steam fluidised bed gasifier within bed heat exchange tubes

 A fraction of combustible gas is burned with air in a pulse combustor and the hot combustion products provide heat to gasify the feed. Gas indirect gasification is extremely versatile with a wide range of feeds. The main advantage of indirect gasification is the high quality of the combustible gas produced in contrast with greater investment and maintenance cost of the reactor

COMBUSTION
Fire, or combustion of biomass, is arguably the oldest known and most widely used controllable energy source on earth Biomass can be converted into energy (heat or electricity) or energy carriers (charcoal, oil, or gas) using both thermochemical and biochemical conversion technologies Combustion is the most developed and most frequently applied process used for solid biomass fuels because of its low costs and high reliability.

COMBUSTION
During combustion, the biomass first loses its moisture at temperatures up to 100C, using heat from other particles that release their heat value. As the dried particle heats up, volatile gases containing hydrocarbons, CO, CH4 and other gaseous components are released. In a combustion process, these gases contribute about 70% of the heating value of the biomass. Finally, char oxidises and ash remains.

EMISSIONS CAUSED BY INCOMPLETE COMBUSTION

Poor mixing of combustion air and fuel in the combustion chamber, giving local fuel rich combustion zones An overall lack of available oxygen Combustion temperatures that are too low Residence times that are too short Radical concentrations that are too low

COMBUSTION SYSTEMS
Different biomass combustion systems are available for industrial purposes. Broadly, they can be defined as 1) Fixed-bed combustion, 2) Fluidised bed combustion, and 3) Dust combustion

DIRECT COMBUSTION TECHNOLOGIES

Biomass direct combustion is generally based on the Rankine cycle, where a steam turbine is employed to drive the generator. Most bioelectricity plants today are direct-fired In direct combustion, steam is generated in boilers burning solid biomass which has been suitably prepared (dried, baled, chipped, formed into pellets or briquettes or otherwise modified to suit the combustion technology) Direct combustion technologies may be divided into fixed bed, fluidized bed and dust combustion

DIRECT COMBUSTION TECHNOLOGIES

FIXED BED SYSTEMS

In fixed bed systems, the biomass fuel burns in a layer on a grate which moves to transport the fuel through the furnace towards ash removal. Fixed bed technologies are reliable and generally have relatively low investment costs compared with other direct combustion technologies. However, a given fixed bed boiler design can usually handle only a limited range of biomass fuel types. include grate furnaces and underfeed stokers. Primary air passes through a fixed bed, in which drying, gasification, and charcoal combustion takes place. The combustible gases produced are burned after secondary air addition has taken place, usually in a combustion zone separated from the fuel bed

FLUIDISED BED BOILERS

In fluidised bed boilers, the fuel burns in a constantly mixing suspension of hot, inert, granular bed material (usually silica sand or dolomite) into which combustion air enters from below. Because of the very effective mixing achieved, fluidised bed plants are very flexible in their ability to burn different biomass fuel types, although the fuel particle size must be relatively uniform. Fluidised bed systems have high investment and operating costs. Biomass fuel is burned in a self-mixing suspension of gas and bed material into which combustion air enters from below. Depending on the fluidisation velocity, bubbling fluidised bed and circulating fluidised bed combustion can be distinguished

DUST COMBUSTION
In dust combustion, fuel in the form of small particles such as sawdust or fine wood shavings is injected along with air into the combustion chamber, and combustion takes place with the fuel in suspension. Is suitable for fuels available as small particles (average diameter smaller than 2 mm). A mixture of fuel and primary combustion air is injected into the combustion chamber. Combustion takes place while the fuel is in suspension, and gas burnout is achieved after secondary air addition. Variations of these technologies are available. Examples are combustion systems with spreader stokers and cyclone burners

 Fluidised bed systems are rapidly becoming the preferred technology for larger systems (>10MWe) because of their superior combustion characteristics. Biomass direct combustion plants are typically relatively small, usually less than 100MWe . With higher capital and operating costs than other direct combustion systems, fluidised bed systems are normally only considered for applications with capacity over about 20 MWth. Dust combustion systems are available for thermal capacities between 2 and 8 MW . The smaller scale of biomass direct combustion systems leads to generally higher unit costs and lower plant efficiencies compared with large-scale fossil fuel plants.

BIOMASS CO-FIRING
Biomass co-firing refers to the combustion of a mixture of fossil fuels such as coal and biomass fuels. Biomass proportions in co-firing range from a few percent up to approximately 40%, although most existing commercial projects are in the range of 3 to 5% by mass. Most biomass co-firing today is practiced on pulverised coal boilers, at power stations with capacities in the range 50-700MWe. Co-firing is a very attractive option for producing electricity from biomass because it takes advantage of the large investment, established power generation infrastructure and higher efficiencies of existing large-scale power plants while requiring comparatively low investment costs to include a fraction of biomass in the fuel. Because of the lower nitrogen and sulphur contents in biomass compared with coal, and the virtually CO2-neutral nature of biomass to- power production chains, biomass co-firing can be a very effective method forreduction of NOx, SOx and greenhouse gas emissions from fossil-fuelled power plants.

CO-FIRING
The options for implementing biomass co-combustion in pulverised coal power stations may be divided into three categories: 1. Direct co-firing 2. Indirect co-firing 3. Parallel co-firing

Direct co-firing
The appropriately prepared biomass is fed directly into the coal furnace. There are a number of ways in which this may be done. The simplest approach involves blending the biomass with coal on the fuel pile and providing the mixed fuel as input to the coal mills before supply to the boilers coal feeding system. This method is generally used at low biomass blend percentages. Alternatively, the biomass fuel preparation and feeding may be handled by a separate system which then feeds the prepared biomass to the coal burners or to separate, dedicated burners.

INDIRECT COFIRING
Involves separate gasification of the biomass to produce a low calorific value fuel gas which is then burnt in the coal-fired boiler furnace. The gasifier is usually of the air-blown, atmospheric pressure, circulating fluidised bed type. Indirect cofiring avoids risks to burner and boiler operation associated with direct combustion, but is more expensive than direct co-firing and is currently only available for wood fuels

PARALLEL CO-FIRING
Biomass is combusted in a separate boiler and the steam produced is fed to a coal-fired power station where it is upgraded to the higher temperature and pressure conditions of the large coal plant. The overall efficiency of conversion from energy in biomass to electrical energy is thereby increased. In an alternative form of parallel co-firing, the flue gases from combustion of biomass in a separate combustion chamber are fed into the boiler of the coal power plant . The need for a separate biomass combustion installation in parallel co-firing leads to higher costs.

Methods for co-firing biomass with pulverized coal. Clockwise from upper left: parallel cofiring with flue gases from biomass combustion fed to coal-fired boiler; direct co-firing with separate biomass combustion on grate; indirect co-firing; direct co-firing with separate biomass feed and burner

States with most potential for biomass production:

Andhra Pradesh (200 MW) Bihar (200 MW) Gujarat (200 MW) Karnataka (300 MW) Maharashtra (1,000 MW) Punjab (150 MW) Tamil Nadu (350 MW) Uttar Pradesh (1,000 MW)