06/03/2013

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Something can burn

Gaseous Fuels
Natural gas
Refinery gas Why hydrocarbons?
Many are liquids - high density, easy to transport
Liquid Fuels Lots of it located at Middle East, Saudi Arabia,
Kerosene Iran, Iraq
Relatively non-toxic fuel & combustion products
Gasoline, diesel
Relatively low explosion hazard
Alcohol (Ethanol)
Oil
Solid Fuels
Coal (Anthracite, bituminous, subbituminous, lignite)
Wood

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Covalent Bonds and Radicals

Chemical bonds result from a mutual sharing of electrons between atoms,

the shared electrons are in the outermost shell, known as valence electrons

Lewis notation:

Hydrogen Atomic # 1 1 valence electron H

Carbon Atomic # 6 4 valence electrons C

Oxygen Atomic # 8 6 valence electrons
O

Atoms like to have electron configuration like noble gas, usually eight valence
electrons, an octet.
H
H2 H H CH4 H C H
H
Atoms and molecules with unpaired valence electrons are called radicals
e.g. O, H, OH, N, C

Most common hydrocarbon fuels are Alkyl Compounds and are

grouped as:
Paraffins (alkanes): single-bonded, open-chain, saturated (no more
hydrogen can be added)

CnH2n+2 n= 1 CH4 methane n= 4 C4H10 butane

n= 2 C2H6 ethane n= 8 C8H18 n-octane and
n= 3 C3H8 propane isooctane

H H H H H H H H H H H H

H C H H C C C H H C C C C C C C C H

H H H H H H H H H H H H

methane propane n-octane

For alcohols one hydroxyl (OH) group is substituted for one hydrogen
e.g. methane becomes methyl alcohol (CH3OH) also known as methanol
ethane becomes ethyl alcohol (C2H5OH) also known as ethanol

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Olefins (alkenes): open-chain containing one double-bond,

unsaturated (break bond more hydrogen can be added)
H H
H propene
CnH2n n=2 C2H4 ethene
C C C H
n=3 C3H6 propene
H
H
Note: n=1 yields CH2 is an unstable molecule
H H

Napthenes Alkanes with cyclo structure C Cyclopropane

(not very stable -lots of strain in C-C bonds)
H-C-C-H
H H
H
|
C
Aromatics - contains one or H H
more six-sided ring structures C C
Benzene
(benzene structure)
C C
H H
C
|
H

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Olefins (alkenes): open-chain containing one double-bond,

unsaturated (break bond more hydrogen can be added)
H H
H
CnH2n n=2 C2H4 ethene
C C C H
n=3 C3H6 propene
H propene
H

Note: n=1 yields CH2 is an unstable molecule

Acetylenes (alkynes): open-chain containing one C-C triple-bond

unsaturated H C C H

CnH2n-2 n=2 C2H2 acetylene acetylene

n=3 C3H4 propyne

More Fuels : hydrogen, carbon monoxide, ammonia

Alkana C - C

Aliphatic Alkena C = C

Alkuna C C

Hydrocarbon Alicyclic Cyclo-alkana

Cyclo-propana Cyclo-butana

Aromatic

Benzene Toluene

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COAL (others : wood, coke)

Macro-organism Bituminous Semi-anthracite

Peat (gambut) Sub-bituminous Anthracite

Brown coal Lignite Meta Anthracite Grapite

Anthracite (hard)
Bituminous (soft)
Mixture of C, H2, S, O2, N2, water and non-combustibles
(e.g. Ash)

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Elemental Composition
C 65-95%
Inhomogeneous organic fuel formed
H 2-7% mainly from decomposed plant
matter.
O <25%
Over 1200 coals have been
S <10% classified.

N 1-2% Coalification forms different coal

types:
Proximate Analysis

Char 20-70% (Peat)

Ash 5-15% Lignite
Bituminous coal
H2O 2-20% Anthracite
(Graphite) Time, Temperature
VM 20-45% Coal Rank

Coal

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Anthracite
Highest grade; over 85%
carbon.
Most efficient to burn.
Lowest sulfur content; the least
Carbon content (%) polluting.
0 20 40 60 80 100
The most exploited and most
rapidly depleted coal resource
Energy in many areas.
Lighite Carbon
Bituminous
Medium grade coal, about 50-
75% carbon content.
Higher sulfur content and is
Bituminous
less fuel-efficient.
Most abundant coal found in
the USA.
Anthracite
Lignite
Lowest grade of coal, with
about 40% carbon content.
0 500 1000 1500 2000 Low energy content.
Burned energy (1,000 calories per kg) Most sulfurous and most
polluting.

Carbon Volatile matter Moisture Ash Heating value

(%) (%) (%) (%) (106 J kg-1)
Anthracite (PA) 77.1 3.8 5.4 13.7 27.8
Bituminous (PA) 70.0 20.5 3.3 6.2 33.3
Subbituminous (CO) 45.9 30.5 19.6 4.0 23.6
Lignite (ND) 30.8 28.2 34.8 6.2 16.8

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Main Processes in Coal

Combustion
homogeneous
combustion CO2, H2O,
coal particle volatiles
p-coal, d=30-
70m
heterogeneous
combustion
char CO2, H2O,

devolatilization

tdevolatile=1-5ms tvolatiles=50-100ms tchar=1-2sec

Coke :
adalah batu bara yang
dihilangkan moisture dan volatile
matter. Prosesnya disebut
karbonisasi pirolisa.

900 1200 C high temperatur coke

750 900 C medium temperatur coke
500 600 C low temperatur coke

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Coal Applications

Homes heat and cooking

Transportation steam engines
Industry metal works
Electricity power plants

A. Analisis PROXIMATE

Analisis yg paling sederhana, yaitu dgn memanaskan batu bara dgn cara2
tertentu, untuk memperoleh hasil analisa :
1. MOISTURE, M (water) : dipanaskan pada suhu 104 110oC dalam waktu
tertentu. Pengurangan berat dikalikan 100% = M
Surface moisture : moisture karena sumber luar, mis : percikan air,
hujan, kondensasi udara dll
Inherent moisture : moisture yg terikat dg batu bara dimana
menimbulkan kebasahan. Contoh : kadar IM 2 4 % u/ anthracite
& bitiminous

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2. VOLATILE MATTER , VM adl bahan yg mudah menguap : dipanaskan dalam ruang

tertutup pada 950oC selama 7 menit. VM terdiri dari Hidrogen, CO, CO2,
uap air
3. Kadar abu, A, (ash), caranya membakar sisa batu bara dalam dapur muffler pada
suhu 700 750oC.
4. FIXED CARBON, FC : dianggap sb kadar karbon tetap, ditentukan dg mengurangi
sisa M, VM dan A sehingga didapatkan :

FC = 100 ( M + VM + A )

Catatan : FC tsb bukan merupakan karbon murni, karena masih mengandung Si, Al, Fe,
Ti, Mg dll. Dan juga tidak mewakili total karbon dari batu bara krn ada C
dikeluarkan sebagai CO, CO2 dll

A. Analisis ULTIMATE

Analisi ultimate adalah analisa kandungan unsur kimia bahan bakar secara
kimia, terutama unsur-unsur karbon (C), hidrogen (H), oksigen (O) dan sulfur (S).
Dari kedua analisa diatas dapat dibuat suatu hubungan antara analisa ultimate
dengan analisa proximate seperti dibawah ini :

%C = 0,97 + 0,7 ( VM - 0,1A ) M ( 0,6 - 0,01M )

%H = 0,036 FC + 0,086 ( VM - 0,1A ) - 0,0035M2

%N2 = 2,10 0,020 VM

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O
8

Nilai kalor bahan bakar dapat dicari dengan :

1. Pengujian langsung dengan menggunakan CALORIMETER
- Padat & cair : bomb calorimeter
- Gas : gas calorimeter

2. Analisis dengan menggunakan rumus pendekatan yang dikembangkan oleh

DULONG PETIT :

HHV = 8080 C + 3446 ( H O / 8 + 2250 S ) ( kkal / kg bb )

Catatan : - diperlukan data analisa Ultimate

- Analisa tsb akan valid jika kadar karbon 76% dan kadar oksigen 10 %
- Jika kadar tsb memenuhi maka hasil yang didapat berbeda hanya 2% dari uji
laboratorium

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What is Petroleum?

Petroleum, also known as Crude Oil ,is

occurring brown to black flammable
liquid.
Mainly constituted of hydrocarbons mixed
with variable amount of sulfur, nitrogen,
oxygen and metal (such as V,Ni) compounds.
100,000 to 1,000,000 different compounds

Mainly properties of petroleum

API gravity 141.5

APIg rav ity 131.5

SG1 5 C
Most commonly crude oil in the rang 20~45
Higher API, more paraffine, higher yields of gasoline
Sulfur, wet %
Sour is S% > 1, Sweet is <0.5
Viscosity at 100F

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Skematik
Distilasi

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Technical features to make/improve fuels

Convert heavier products into lighter ones into gasoline, Such

as thermal cracking,coking, viscosity breaking, catalytic
cracking, and hydrocracking

C16H34 C8H16 + C5H10 + C3H8

Combining lighter products into heavier ones, such as butane

and propylene into alkylate , a high-octane gasoline
component,such as alkylation and polymerization

CH3 CH3 CH3

CH3
C CH2 + H C CH3 CH3 C CH2 C CH3
CH3 H CH3
CH3

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Rearranging the molecular structure to improve desirable

qualities,such as reforming low-octane gasoline into high octane,
such as catalytic reforming and isomerization
CH3

CH3 CH2 CH2 CH3 CH3 C H

CH3

Treating, to remove contaminants such as sulfur and nitrogen

A fuel designed for SIEs

Mixture of Hydrocarbon, (over 500)1, plus
additives.

1. 1 B. Hamilton, FAQ: Automotive Gasoline

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Coal tar distillates: Late 19th century.

Gasoline from Petroleum: Early 20th century.
Typical mid-1920s gasoline was 40 - 60 Octane.
1950s: compression ratio increase, requiring higher
octane fuels: Leaded was introduced.
1970s: leaded was prohibited.
1970-1990: slow changes in gasoline as lead was
phased-out.
1990 + : the US Clean Air Act started forcing major
compositional changes on gasoline.
These changes will continue into the 21st Century.

The sound of abnormal combustion.

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Natural Gas :
1. Low pressure Natural Gas : yang biasanya digunakan langsung untuk
memasak atau memanaskan rumah tangga. Umumnya disalurkan dalam pipa
dalam tanah.
2. CNG ( Compressed Natural Gas ) : adalah gas alam yang di compress
pada tekanan tinggi sehingga bisa di bawa dengan kendaraan misalnya
truck.
3. LNG ( Liquid Natural Gas ) : Gas alam yang di dinginkan sehingga
menjadi cair. LNG lebih padat dari CNG karena berbentuk cair sehingga
lebih mudah diangkut. LNG dibuat dengan proses refrigerasi 260 F.
Pendinginan tersebut akan menghilangkan uap air, butane, propane dan
beberapa gas lain, sehingga komponen utama LNG adalah 98 adalah
methane
LPG ( Liquid Petrolium Gas ) : Gas yang terutama terdiri dari propane
dan beberapa gas lain yang di compress dengan tekanan tinggi ( 200 psi)
sehingga mencair dan disimpan dalam tangki bertekanan.

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