Topic

Refinery

gases
Water gas
Carbureted gas

Refinery gases
Gases obtained during distillation,
cracking and other processing of
petroleum and its fractions which
contain paraffines(methane,
ethane,propane and butane),
olefins(ethylene,propene and
butane), H2 and H2S are called
refinery gases.

Cracking
Cracking,as the name suggests, is a
process in which large hydrocarbon
molecules are broken down into
smaller and more useful ones, for
example:

Crude Oil

Crude oil is a non-uniform material. The

composition depends on its location.

Flow scheme of a modern

refinery

Composition of refinery
gases

Propene + propane
Butene + butane
Ethylene + ethane
Methane
Hydrogen
Hydrogen sulphide
Calorific value, kcal/Nm3
(dry)
Specific gravity (air=1)

40-55%
Upto30%
8-12%
8-10%
6-8%
6-8%
20500
1.35

Yield of refinery gases in the

form of LPG
Chemical

processes

Thermal

Catalytic

Visbreaking
Delayed coking
Flexicoking

Hydrotreating
Catalytic reforming
Catalytic cracking
Hydrocracking
Catalytic dewaxing
Alkylation/Polymerization
Isomerization

Visbreaking

Visbreaking is a mild form of thermal cracking that lowers the

viscosity of heavy crude-oil residues without affecting the
boiling point range.
Residuum from the atmospheric distillation tower is heated
(425-510C) at atmospheric pressure and mildly cracked in a
heater.
Feed stock

Main products Yield of LPG

(wt % on feed

Residuum

Coke

5-10

Catalytic Reforming
Catalytic

reforming is an important process used to

convert low-octane naphthas into high-octane gasoline
blending components called reformates.
Reforming represents the total effect of numerous
reactions such as cracking, polymerization,
dehydrogenation, and isomerization taking place
simultaneously.
Depending on the properties of the naphtha feedstock
reformates can be produced with very high concentrations
of benzene, toluene, xylene, and other aromatics.
Hydrogen, a significant by-product, is separated from the
reformate for recycling and use in other processes.
Feed stock

Main products Yield of LPG

(wt % on feed

Light virgin
naphths

Aromatics,
gasolines
blendstocks

5-10

Alkylation
Alkylation

combines
low-molecular-weight
olefins (primarily a mixture of propylene and
butylene) with isobutene in the presence of a
catalyst, either sulfuric acid or hydrofluoric acid.
The product is called alkylate and is composed
of a mixture of high-octane, branched-chain
paraffinic hydrocarbons
Feed stock

Main products Yield of LPG

(wt % on feed

Butane
unsaturated
gases

Gasoline

10-15

Catalytic Cracking
Main

incentive for catalytic cracking is the need to

increase gasoline production.
Feedstock are typically gas oil.
Cracking is catalyzed by solid acids which promote the
rupture of C-C bonds. The crucial intermediates are
carbocations (+ve charged HC ions) formed by the
action of the acid sites on the catalyst.
Besides C-C cleavage many other reactions occur:
- isomerization
- protonation and deprotonation
- alkylation
- polymerization
- cyclization
and condensation.
Feed stock
Main products Yield of LPG
(wt % on feed
Gas oil

Ethylene,
proplylene(for
prtrochemical)

15-20

Uses
C3

and C4 hydrocarbons separated

by liquification such as (LPG)
H2 & higher hydrocarbons utilizeds
chemical, fertilizer, plastic.

Water gas
Water

gasis asynthesis gas

containingcarbon
monoxideandhydrogen.
Water gas called blue gas (bluish flame)
Flammability
Carbon monoxide poisoning
The gas is made by passingsteamover a
red-hot carbon fuel such ascoke.
Make 6L of water gas, 5L of air is
required.

Cylindrical steel vessel

Height 4-5m
Dia 2-3m

Manufacture of water gas

Water gas is produced by hard coke and anthracite
coke

Coke at 900-1000C
Water gas
grate
air

steam

Cylindrica
l steel
vessel
Height 45m
Dia 2-3m

Steam usually 4
min
Air blow 1-2min

ash

Reactions
C+H2O=CO+H2,
This

H=+28kcal/kmol

reaction is endothermic.

C+2H2O

CO2+2H2
H=+19000kcal/kmol
To avoid this reaction used air
C+O2

CO2
97000kcal/kmol
2C+02
2CO
29000kcal/kmol

H=H=-

Water gas composition

H2

48-51%

CO

40-42%

CH4

0.1-0.55%

CO2

3-5%

N2

3-6%

AIR

2-2.5Nm3/Nm3 gas

Uses
Fuel

in furnaces
It is enriched C.V
Ammonia synthesis
Semi water gas(mixture of H2 &
N2)

Carburetted water gas

Water

gas had a lowercalorific

valuethancoal gasso the calorific
value was often boosted by passing the
gas through a heatedretortinto which
oil was sprayed. The resulting mixed
gas was calledcarburetted water gas.
Mixture of water gas and oil gas
Oil gas:
A gaseous mixture derived from
mineral oils by destructive distillation.

Composition of
carburretted
CO2

5.6%

CmHn

7%

O2

0.4%

CO

30.5%

H2

37.0%

CH4

14%

N2

5.5%

GROSS C.V

4770 kcal/Nm3

AIR

4.27Nm3/Nm3 gas

Diagram
coke

reactor steam carbu

retor

superheater

air

oil

Waste heat
boiler

ash
dust

Flue gas
Carburetted
gas

Oil

is light petroleum fraction (B.p

200-300c)
Oil is sprayed water gas
Carburettor and super heater filled
chequered bricks.
Fuel gas used to WHB
Endothermic oil cracking process
Production of 1 Nm3 of carburetted
requires steam 0.65kg, coke
0.45kg, Oil 0.3kg , air is 1.5 Nm3

Uses
Ingredient

of town gas
Substitute of coal gas to meet peak
loads of gas supply

REFERENCES
Some great websites are:
http://lorien.ncl.ac.uk/ming/distil/
distil0.htm
http://science.howstuffworks.com/
oil-refining.htm
Elements of fuels, furnaces &
refractories