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Production of Gasoline From Naphtha

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Ahmad Ammar

on 29 December 2013

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Transcript of Production of Gasoline From Naphtha

Production of Gasoline From Naphtha
Presenting By:
Ahmad Ammar (BChE-FA10-010)
Ishtiaq Urehman (BChE-FA10-012)
Anis Shahid (BChE-FA10-039)
Mohsin Raza (BChE-FA10-041)
Hafiz Ali Amjad (BChE-FA10-048)

Oil Refineries in Pakistan
1) Pak-Arab Refinery Ltd., 100,000 bbl/d (16,000 m3/d)
2) National Refinery Ltd., 64,000 bbl/d (10,200 m3/d)
3) Attock Refinery Ltd., 46,000 bbl/d (7,300 m3/d)
4) Byco Petroleum Pakistan Ltd.,150,000 bbl/d (24,000 m3/d)
5) Pakistan Refinery Ltd., 50,000 bbl/d (7,900 m3/d)
6) Enar Petroleum Refinery 3,000 bbl/d (480 m3/d)
7) Indus Oil Refinery Ltd, 100,000 bbl/d (16,000 m3/d) (not yet operational)

Our Plant Capacity
15,000 barrels of naphtha PSD

What is Reforming?
It is a processing technique by which we convert straight chain hydrocarbons into branch chain hydrocarbons. The process is frequently applied to low-quality gasoline stocks to improve their combustion characteristics.

Types Of Reforming
Three Basic Types of reforming is used usually:
1) Thermal Reforming
2) Catalytic Reforming
3) Steam Reforming

THE AVAILABLE PROCESSES
1) CATFORMING PROCESS
2) HYPERFORMING PROCESS
3) REXFORMING PROCESS
4) CATALYTIC THERMOFORMING
5) PLATFORMING PROCESS
6) CCR PLATFORMING PROCESS

Platforming

Catalytic Reforming was developed by a chemist Vladimir Haensil in 1940s. He used Platinum as catalyst, that is why the process is named as platforming. Its name is extracted from PLATinum reFORMING.
JUSTIFICATION FOR SELECTION
1) Using modified Pt/Al catalyst which gives maximum conversion as compare to other catalysts.
2) Very high conversion of above 95%.
3) Operating pressure is low due to which the work of hydrogen compressor is less that makes the process more economical.
4) Efficient heat recovery by producing high pressure steam with effluent hot gases of Furnaces.
5) Continuous regeneration of catalyst that each catalyst particle in good condition which are most suitable for reaction.

Feed Composition
Feed naphtha to a Platforming Process Unit typically contains:
C6 to C11
Paraffins
Naphthenes
Aromatics


Reactions
The following reactions take place in the platforming Process

Dehydrogenation of Naphthenes
Isomerisation of Naphthenes and Paraffins 
Dehydrocyclization of Paraffins
Hydrocracking 
Demethylation 
Dealkylation of Aromatics

Dehydrogenation of Naphthenes:

ISOMERIZATION OF PARAFFINS:

Dehydrocyclization of paraffins:

Hydrocracking:

Demethylation:

Dealkylation of Aromatics:

Supervisor:
Engr. Ghulam Murtaza

History
1500 AD Chinese dig oil wells
1847 First “crude oil” refinery in England
1849 Canada distills kerosene from crude oil
1966 first well dug in Pakistan
1978 First oil refinery in Pakistan(ARL)


Consumption and Demand of Gasoline in Pakistan(in 2012)
Octane Number
octane number is the volumetric percentage of iso-octane in a mixture of iso-octane and n-heptane.

Feed Preparation
The feed must be properly hydrotreated to lower the sulfur and nitrogen contents to below 0.5 ppm. The heavy naphtha feed to the Platforming Process Unit is taken directly supplied from the Naphtha hydrotreating Process Unit (NHT). The feed is pumped and sent to the Combined Feed Exchanger.
Process Variables
Effect of Temperature
Effect of pressure
Effect of catalyst particle size
Effect of trace material in feed

Effect of Temperature

Temperature range in catalyst reforming is 450-550 Degree Celcius. Catalyst will deactivate if the temperature is lower then this range. If temperature exceed this limit, hydrocracking predominates.

Effect of pressure
Catalytic Reforming requires High temperature and pressure in range 500-700 Psi. The high pressure of hydrogen gas slow down the coke deposition on catalyst.
MATERIAL BALANCE
FEED:
°API Gravity = 65.0
Liquid Density = 720.0 kg/ m3
 
ASTM Distillation (°C):
IBP = 74.0
50% = 99.0
EP = 152.0

Composition (LV%):
Paraffins = 67 %
Napthenes = 21.2 %
Aromatics = 11.8 %
Mass Flowrate= 99356.25 kg/hr
Molar flow rate= 1077.733 kgmol/hr


Basis: 100kgmol / hr of Naphtha

Average Molecular Weight = 92.19 kg/kgmol
Molar Flow Rate = 99356.25 kg/hr


Kg mole hexane = 323.319 kg mol
Kg mol heptanes = 398.761 kg mol
Kg mol methyl cyclo hexane = 140.105 kg mol
Kg mol methyl cyclo pentane = 86.21kg mol
Kg mol benzene = 71.13 kg mol
Kg mol toluene = 56.04 kg mol

OVERALL MATERIAL BALANCE
Mass In:
Naphtha = 99356.25 kg/hr
 
Mass out:
Net H2 Gas = 7759.66 kg/hr
LPG = 8454.874 kg/hr
Reformate = 85909.754 kg/hr

Balance Around Reactor:
Feed consist of volume %

Paraffins = 67 %
Napthenes = 21.2 %
Aromatics = 11.8 %
Paraffins consist of hexane and heptanes.
Aromatics consist of toluene and benzene.
Napthenes consist of methyl cyclo hexane and methyl cyclo pentane.


Components Mol wt. Mol fraction
Hexane 86 0.3
Heptanes 100 0.37
Methyl cyclo hexane 98 0.13
Methyl cyclo pentane 84 0.08
Benzene 78 0.066
Toluene 92 0.052



Kg mole hexane = 323.319 kg mol
Kg mol heptanes = 398.761 kg mol
Kg mol methyl cyclo hexane = 140.105 kg mol
Kg mol methyl cyclo pentane = 86.21kg mol
Kg mol benzene = 71.13 kg mol
Kg mol toluene = 56.04 kg mol


Hydrogen inlet to reactor

Optimum recycle ratio of hydrogen to feed = 4
Molar flow rate of recycle hydrogen supply = 4310.93 kg mol/hr



Mol % Mol.wt. Moles kgs
H2 90 2 3879.83 7759.66
CH4 4 16 172.437 2758.992
C2H6 2.3 30 99.151 2974.53
C3H8 1.5 44 64.663 2845.172
C4H10 1.2 58 51.731 3000.398
C5H12 1 72 43.109 3103.848
Total 22442.6

References
www.pogeepakistan.com/OIL%20&%20GAS.pdf‎
http://en.wikipedia.org/wiki/List_of_oil_refineries#Pakistan
Elements of fuels, furnaces and refractories by O.P.Gupta
An Introduction to the study of fuel by J.C.Macrae
Petroleum Refining Engineering by Nelson
http://www.eia.gov/countries/

Effect of Catalyst particle size
The activity of catalyst increases as the particle size decreases. The interior portion of catalyst is ineffective because the reaction occurs before the reactant penetrate into the core.
Effect of trace materials in feed
Sulfur:
Higher the sulfur contents in the feed reduces the dehydrogenation of naphthenes and promotes the hydrocracking (which is unwanted reaction). It also deactivates the catalyst.

Nitrogen:
In presence of nitrogen the dehydrocyclization of paraffins is reduced.

Process Steps
Feed mixing with recycled hydrogen
Pre-heating of Feed
Reactor
Catalyst feeding
Catalyst Regeneration
Separator
Stabilizer

Components Mol wt Mol fraction
Hexane 86 0.3
Heptanes 100 0.37
Methyl cyclo hexane 98 0.13
Methyl cyclo pentane 84 0.08
Benzene 78 0.066
Toluene 92 0.052

So overall %ages are as mol %.
HexaneC6H14 = 30 %
heptanesC6H16 = 37 %
Methyl cyclo hexane CH3--C6H5 = 13 %
Methyl cyclo pentane CH3--C5H = 48 %
BenzeneC6H6 = 6.6 %
TolueneCH3--C6H5 = 5.2 %

Recycle Gas Composition
Reactions taking place in Reactors
(1) Hexane Reactions:

C6H14 isomerisation C6H14

C6H14 + 2H2 hydrocracking C3H8 + C2H6 + CH4

C6H14 dehydrocyclization C6H6 + 4H2
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