Refinery Operations Naphtha Characterization Syn Gas Production needs Characterization methodology GBHE VULCAN software Impurities in crude HDS Report HDS Design method HDS Design guide

1. By Gerard B. Hawkins
Managing Director, CEO

2.  Refinery Operations
 Naphtha Characterization
 Syn Gas Production needs
 Characterization methodology
 GBHE VULCAN software
 Impurities in crude
 HDS Report
 HDS Design method
 HDS Design guide

3.  Crude Oil and Petroleum Products can
characterized two ways
 Physical
 Chemical

4.  Don’t need to know exact chemical composition
 Products largely go into fuel industry
 Need to know how easily it can be handled
◦ Viscosity, density
 How much heating or energy value it has
◦ Calorific Value

5.  Cut points are
approximate
 Distillation defines
quality of crude
◦ Hence quality of
fractions
 Quality = Octane #
 = Profit
0
100
200
300
400
500
600
0% 20% 40% 60% 80% 100%
% vol distilled
BoilingTemperaturedegC
Heavy Gas Oil
Light Gas Oil
Kerosene
Heavy Naphtha
Light Naphtha
Light Ends

6. 0
50
100
150
200
250
300
350
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
% vol distilled
BoilingTemperaturedegC
Light Naphtha Heavy Naphtha Kerosene

7.  Boiling Range
 Density (Specific Gravity)
 Viscosity
 Refractive Index
 Calorific Value

8.  Only Physical
characteristics
 Summary
Report is
approximate
 Target is octane
value of
feedstock as
inferred by
Gasoline,
Naphtha and
Gas Oil content

9.  Crude Oil and Petroleum Products contain
multitude of chemical species
 Typically categorised as hydrocarbons i.e.
compounds solely comprised of carbon &
hydrogen atoms
Can be
◦ simple e.g. Propane C3H8
◦ complex e.g. ‘chicken wire’ compounds
.. multiple ring stuctures

10.  Chemical composition
◦ PONA
 Paraffins
 Olefins
 Naphthenes
 Aromatics
 Average Molecular Weight
 Carbon: Hydrogen ratio

11.  Sulfur species
 Chloride species
 Nitrogenous species
 Arsenic
 Heavy Metals
◦ Mercury, Nickel, Vanadium, Copper
 Salt

12.  Its in the feed, where does it end up?
 Depends on boiling point
 B Pt depends on species
 Need to understand speciation!
 So looking at sulfur compounds…………

13. Boiling Point at
atm Pressure
Thermal decomposition
temperature
degC degC
Methyl mercaptan CH3SH 6 150
Ethyl mercaptan C2H5SH 35 150
Propyl mercaptan C3H7SH 67 150
n-butyl mercaptan C4H9SH 99 150
i-butyl mercaptan C4H9SH 89 225-250
phenyl mercaptan C6H5SH 169 200
cyclohexyl mercaptan C6H11SH 159 200
phenyl benzyl sulphide C6H5SC6H4CH3 197 300
diethyl sulphide C2H5SC2H5 92 400
diphenyl sulphide C6H5SC6H5 296 450
dimethyl disulfide CH3SSCH3 110 ~150
2,5-dimethylthiophene (CH3)2C4H2S 137 475
benzothiophene C6H5C4H2S 221 800
dibenzothiophene C6H5C4SC6H5 332 800
thiophene C4H4S 84 900
tetrahydrothiophene C4H8S 121

14. Boiling
Point at atm
Pressure
Thermal
decomposition
temperature
degC degC
thiophene C4H4S 84 900
diethyl sulphide C2H5SC2H5 92 400
dimethyl disulphide CH3SSCH3 110 ~150
tetrahydrothiophene C4H8S 121 640
phenyl mercaptan C6H5SH 169 200

15. Straight run Naphtha
0.0
50.0
100.0
150.0
200.0
250.0
0% 20% 40% 60% 80% 100%
Cumulative Boiling Fraction
BPtdegC
Boiling Curve
Thiophene
Diethyl Sulfide
Dimethyl Disulfide
Tetrahydrothiophene
Phenyl Mercaptan
PONA Analysis (w/w)
Paraffins = 84.3%
Olefins = 2.3%
Naphthenes = 11.4%
Aromatics = 2.0%

16.  Space Velocity
◦ SV is defined as Liquid Hourly Space Velocity, LHSV
◦ LHSV because
 Naphtha is a liquid as supplied to plant battery limits
 Naphtha pumped into plant
 Flow measurement easier as liquid rather than vapor

17.  Naphtha Flow (1)
◦ Vapor flow calculated from mass flow and Naphtha
average M Wt
◦ Vapor flow = 22.414 * Naphtha mass flow / M Wt
Nm3/hr kg/hr
 Naphtha Flow (2)
◦ Volumetric liquid flow calculated from liquid density
◦ Liquid flow = Naphtha mass flow / Liquid density
m3/hr kg/hr kg/m3
 LHSV = Liquid flow / Catalyst Volume

18. GBHE Mediterranean Client - Naphtha/LPG feed VULCAN DSMAKE Ver 2.0
NAPHTHA RATE 342.8 kgmol/hr
NAPHTHA MOLECULAR WEIGHT 56.8
NAPHTHA DENSITY 600.0 kg/m3
HYDROGEN RECYCLE MOLAR RATIO 0.270
TEMPERATURE 360.0 C
PRESSURE 33.3 atma = 33.4 kg/cm2g
INLET H2S 1.0 ppm w/w = 1 ppm w/w S
INLET disulphides(DMDS) 0.0 ppm w/w
INLET mercaptans (Phenyl mercaptan) 151.3 ppm w/w = 44 ppm w/w S
INLET sulphides (DES) 0.0 ppm w/w
INLET tetrahydrothiophene 14.2 ppm w/w = 5 ppm w/w S
INLET thiophene 0.0 ppm w/w
EXIT NON-REACTED SULPHUR 0.2 ppm w/w S
CATALYST DENSITY 710.0 kg/m3
Reduced thiophene rates used, see CFR 127662
NUMBER OF BEDS OF ZNO 2.0
LIFE REQUIRED PER BED 200.0 days
CATALYST VHT-S101/VHT-N101 VOLUME 4.85 m3
LIQUID HOURLY SPACE VELOCITY 6.695 /hr – should be max 2.0 /hr
Therefore increase volume to 4.85 * 6.695 / 2 = 16.25 m3

19.  How does it work?
 Calculates catalyst volume for each species based
on kinetics
 Allows for equilibrium effects of H2S
 Has inbuilt catalyst activity factor based on
VHT-S101 and VHT-N101
 Adds volumes together to give answer.