ChE 101

A. Fuels

2nd Sem AY 11-12

Fuels any source of heat or energy embracing the entire range of combustibles and including anything that burns. a. Gaseous Fuels Gaseous fuels are the most convenient requiring the least amount of handling and simplest and most maintenance free burner systems. Usually mixture of paraffins (alkanes), olefins (alkenes), sulfur, hydrogen and carbon monoxide. Types of Gaseous Fuels 1. Fuels Naturally Found in Nature Natural Gas Natural Gas are of two types fossil fuel gases and gases occurring naturally from some biological process. Associated with petroleum oil deposits, with coal seams or with the decay of organic matter. The quantities of the constituents vary but the principal component is methane. Other components include higher molecular weight hydrocarbons which can be separated out as a condensate. Sometimes it also contains hydrogen sulfide. Terms used to describe gases: i. dry or lean high methane content (less condensate) ii. wet high concentration of higher hydrocarbons (5-10 carbon long) iii. sour high concentration of H 2S iv. sweet low concentration of H2S v. residue gas gas remaining after the condensing process (removal of high molecular weight hydrocarbons) Typical Natural Gas Composition Gas Typical % vol CO2 33.6 CH4 63.8 H2 0.05 N2 2.4 Sulfur/CO/Alcohols Trace 2. Manufacture Gas or Synthetic Gas Gases may be manufactured from either a liquid or solid feedstock. The main commercial methods were developed for coal but the same technology applies to waste and biomass Examples of Manufacture Gas 1. From Wood by distillation or carbonization of wood (wood gas) Carbonization (or Pyrolysis) Heating of coal or organic feedstock to high temperature in the absence of oxygen to yield gas and tar. Distillation of wood Process in which wood is heated to form charcoal and methanol. 2. From Peat by distillation or carbonization of peat (Peat Gas) 3. From Coal by carbonization (Coal Gas) By gasification: i. Producer Gas The gas is produced by blowing air through an incandescent fuel bed (the process is self heating). The reaction with air is exothermic but insufficient air is added hence CO is produced. Producer gas has low heating value (amount of heat that can be produced). Typical Composition: Gas Typical % vol N2 50 CO 29 CO2 4 ii. Blue Gas or Water Gas This is produced in a similar manner to above but allows the production of fuel with higher heating value by simultaneously blasting the incandescent bed with air followed by steam such that the overall heat balance is maintained. The products of the air blast which contain nitrogen are discharged to the atmosphere since they have lower heating value. The products of the steam blast are kept since they have a higher heating value. Often used as synthesis gas in the chemical industry. Typical Composition Gas Typical % vol H2 49 CO 41 CO2 4.7 CH4 0.8 N2 4.5 iii. Carburetted Water Gas (Town Gas) Water gas has still low heating value for most purposes and this makes it unattractive to distribute. Carburetted water gas is the result the water gas and thermal cracking. Fuel oil is sprayed into a brick lined chamber during the blow period of the blue water gas plant with air. This heats the bricks to around 1000 oC. The air is then turned off and the oil is cracked to smaller hydrocarbons in the now heated chamber.

ChE 101
iv.

2nd Sem AY 11-12

Lurgi Gas the highest technology commercially used. Feed is gasified with an oxygen steam mix (1:8) at 900 oC and 30-35bar Typical Composition: Gas Typical % vol CO 28 CH4 17 H2 55

4.

From Petroleum and Oil Shale a. By cracking (Refinery Gas) Two types of Cracking i. Thermal Cracking - the process of dividing long chains of hydrocarbons (e.g. oil) to shorter chains (e.g. CH4) by using high temperature and high pressure. ii. Catalytic Cracking the same as thermal cracking but instead of using heat and high pressure chemical (catalyst) is used. b. By hydrogenation (oil gas) c. By water gas reaction (oil gas) d. By partial oxidation (oil gas) From Carbides with water Carbides a binary compound consisting of carbon and a more electropositive element Electrolysis of water (to produce H 2)

5. 6. b.

Liquid Fuels The main advantage of liquid fuels over gaseous fuels is its very high heating value per volume ratio. Liquid fuels may be divided into two main classes, based on how they will be used: Light Oils or Spirits and Heavy Oils. Types of Liquid Fuels a. Light oils or spirits from distillation and cracking of petroleum or from synthesis of hydrocarbons (e.g. low molecular weight alcohol, benzene). They are suitable for use with internal combustion engines and jet engines. It includes: i. The lighter more volatile fractions obtained by distilling or cracking natural petroleum oils and related natural deposits. ii. The light fractions obtained by the hydrogenation of coal, coal tar or heavy oil residues. iii. The light fractions obtained by the synthesis of hydrocarbons by the Fisher-Tropsch Process (synthesis of hydrocarbon from CO and H 2 in the presence of iron or cobalt) iv. Alcohols, particularly methyl and ethyl alcohol, obtained by synthesis or fermentation process v. Benzole, obtained by the distillation of coal tar or by extraction from coal gas. vi. Alcogas or Gasohol mixture of methyl or ethyl alcohol and gasoline. b. Furnace or Heavy Oils include the heaviest grades of natural petroleum oils and lubricating oils from which the more valuable lubricating oil and fractions have been removed by distillation. (e.g. Lubricating Oils, Bunker Oils)

c.

Solid Fuels generally contain appreciable percentages of mineral compounds (e.g. coals)

B. Combustion of Gaseous and Liquid Fuels Combustion a unit process in which oxidation reaction takes place. One of the most widely used but least understood chemical reactions since it is a free radical reaction. It is the rapid union of a substance (fuel: gaseous, liquid or solid) with oxygen accompanied by the emission of heat and light. It is used mostly for heat (to supply energy to the process industry) by chang ing the potential chemical energy of the fuel to thermal energy. It is also used as a means of destruction of unwanted materials. Products of burning are usually carbon dioxide and water, which are odorless and invisible. Problems occur because the process also produces other products, many of which are pollutants: carbon monoxide, oxides of sulfur, oxides of nitrogen, smoke, fly ash, etc. It was only recently that these by products were considered hazardous. Efficient a. b. c. combustion requires time to occur fully temperature to initiate and maintain turbulence to ensure that the reacting fuels and oxygen are in intimate contact

Types of Combustion 1. Complete combustion all combustible components are burned into forms which cannot be further oxidized. C + O2 CO2 H2 +

1 O2 H 2 O 2
3 O2 SO3 2

S + O2 SO2 sometimes S +

ChE 101

2nd Sem AY 11-12

2. Incomplete combustion partial oxidation of combustible components C+ Furnace

1 O2 CO 2
AIR (primary O2 source)

FEED (Fuel) usually composed of C and H sometimes contains S,O and N

Combustion Chamber (Furnace)

PRODUCT (flue gas, stack gas, exhaust gas)

Theoretical Oxygen amount of oxygen required to be brought into the process for complete combustion of a given amount of fuel

Example 1:

AIR

FEED (Fuel) = 200g 80% C, 10% H2, 10%S

Combustion Chamber (Furnace)

# of moles 160/12 = 13.33 20/2 = 10 20/32 = 0.625 Total =

Exhaust Gas

C H2 O

Mass 0.8x200g = 160g 0.1x200g = 20g 0.1x200g = 20g

MW 12 2 32

Mol O2 needed for complete combustion 13.33 10/2 = 5 0.625 18.955 mol or 606.56g

Theoretical air amount of air containing the theoretical oxygen Air composed mainly of Nitrogen and Oxygen (mol %: 79% N2 and 21% O2) * for simplicity, N2 accounts for other inert substances like He, Ar, etc. Weighted Average of Molecular Weight of Air, MWair = 0.79(MW N2) + 0.21(MW O2)

Example 2: Solution:

g g g = 0.79(28 ) + 0.21(32 ) = 28.84 mol mol mol

From Example 1 determine the mass of theoretical air. mol O2 in air = 21% mol of air

mol O2 in air 18.955mol 90.26mol of air 0.21 0.21 g mass of air = 90.26 mol of air x 28.84 = 2603.10 g air mol
mol of air = Excess Oxygen amount of oxygen in excess of the amount required for complete combustion moles excess O2 = moles O2 supplied moles theoretical O2 Percent Excess Oxygen = Percent excess air =

moles excess oxygen x100% moles theoretica l oxygen