CHE 1014

PETROLEUM TECHNOLOGY

UNIT 1

CHARACTERISATION OF CRUDE
 EVALUATION OF PETROLEUM
Petroleum is divided into three congenial types (as per refinery terms) as
Paraffin base
Napthenic base and
Asphalt base
When key fraction 1 has
40 or more API - Paraffin base
Less than 33 API - Asphalt base
33 or more API - Napthenic base

When key fraction 2 has

30 or more API - Paraffin base
Less than 20 API - Asphalt base
20 to 30 API - Napthenic base
Value of K is
12.5 or more - Paraffin base
10 or less - Asphalt base
10 to 12.5 - Napthenic base
Distillation Characteristics CRUDE OIL ASSAY

It is essentially the chemical evaluation of

crude oil feedstocks by petroleum testing
laboratories.

Each crude oil type has unique

molecular, chemical characteristics.

No crude oil type is identical and there

are crucial differences in crude oil quality.

The results of crude oil assay testing

provide extensive detailed hydrocarbon
analysis data for refiners, oil traders and
producers.

Assay data help refineries determine if a

crude oil feedstock is compatible for a
particular petroleum refinery or if the
crude oil could cause yield, quality,
production, environmental and other
problems.
TRUE BOILING POINT

The composition of any crude oil sample is approximated

by a true boiling point (TBP).

The method used is basically a batch distillation operation,

using a large number of stages, usually greater than 60,

The temperature at any point on the temperature-

volumetric yield curve represents the true boiling
point of the hydrocarbon material present at the given
volume percent point distilled.
 CHE 1014
PETROLEUM TECHNOLOGY

UNIT 1

COMPOSITION OF PETROLEUM
 CHE 1014
P ETROLEUM T ECHNOLOGY

CHAPTER 2
DESULFURIZATION OF CRUDE OIL
 CHEMISTRY BEHIND HYDRO DESULFURISATION (HDS)
• Hydrodesulfurization is a Hydrogenolysis reaction (a type of
hydrogenation reaction).

• Hydrogenation is a class of chemical reactions in which the net result is

the addition of hydrogen (H).

• Hydrogenolysis results in the cleavage of the C-X chemical bond, where C

is a carbon atom and X is a sulfur.

• The net result of a hydrogenolysis reaction is the formation of C-H and H-

X chemical bonds.

• Using ethanethiol (C2H5SH), a sulfur compound present in some

petroleum products, as an example, the hydrodesulfurization reaction
can be simply expressed as

C2H5SH + H2 --- C2 H 6 + H2S

Ethanethiol + Hydrogen --- Ethane + Hydrogen sulfide
 Sulfur compounds in refinery feedstocks

• The refinery feedstocks (naphtha, kerosene, diesel oil, and heavier oils)
contain a wide range of organic sulfur compounds, including thiols,
thiophenes, organic sulfides, disulfides, and many others.

• These organic sulfur compounds are products of the degradation of sulfur

containing biological components, present during the natural formation
of the fossil fuel, petroleum crude oil.

• When the HDS process is used to desulfurize a refinery naphtha, it is

necessary to remove the total sulfur down to the parts per million range
or lower in order to prevent poisoning the noble metal catalysts in the
subsequent catalytic reforming of the naphtha.
 HYDRO DESULFURISATION (HDS)

• Catalytic chemical process widely used to remove sulfur (S) from natural gas and
from refined petroleum products such as gasoline or petrol, jet fuel, kerosene, diesel
fuel, and fuel oils.

• Technique of Impurity elimination.

• Resembles like removal of Sulfur, yet then impurities which can form hydrites are
taken off easily.

• Hydrogen over a catalyst is capable of reacting with Sulfur, Nitrogen, Halogens

and Oxygen from the respective compounds available in the fractions.

• S, N and Halogens escape from respective hydrates while Oxygen escapes as water
vapor.
• The purpose of removing the sulfur is to reduce
the sulfur dioxide (SO2) emissions that result
from using those fuels in automotive vehicles,
aircraft, railroad locomotives, ships, gas or oil
burning power plants, residential and industrial
furnaces, and other forms of fuel combustion.

• Another important reason for removing sulfur

from the naphtha streams within a petroleum
refinery is that sulfur, even in extremely low
concentrations, poisons the noble metal
catalysts (platinum and rhenium) in the
catalytic reforming units that are subsequently
used to upgrade the octane rating of the
naphtha streams.
 HDS
• The industrial hydrodesulfurization processes include facilities for the capture and
removal of the resulting hydrogen sulfide (H2S) gas.

• In petroleum refineries, the hydrogen sulfide gas is then subsequently converted

into byproduct elemental sulfur or sulfuric acid.

• The vast majority of the 64,000,000 metric tons of sulfur produced worldwide
till date was byproduct sulfur from refineries and other hydrocarbon processing
plants.

• An HDS unit in the petroleum refining industry is also often referred to as a

HYDROTREATER.
 CATALYSTS
• Popularly used Catalyst compositions are Nickel-Molybdenum and Cobalt-
Molybdenum on Alumina.

• Both are active, still some reservations are observed with reference to Ni-Co
compostions,

• These compositions are more active than Co-Mo catalysts, especially while
removing Nitrogen.

• Basically the structure, particle size and porosity of the catalyst are certain
parameters in judging the activity and life of catalyst.

• Sulfur in paraffins are easily removed, while aromatics are quite resistant.

• Co- Mo catalyst at 350 degree under a pressure of 100 atm can remove 90%
Nitrogen.

• Studies show Ni-Mo catalysts are effective for removal of Nitrogen, though
Hydrogen consumption with these catalysts are more.
CATALYSTS
 Catalytic Hydrodesulfurization Process
• Hydrotreating for sulfur removal is called hydrodesulfurization.

• In a typical catalytic hydrodesulfurization unit, the feedstock is deaerated

and mixed with hydrogen, preheated in a fired heater (315°-425° C) and
then charged under pressure (up to 70 bar) through a trickle-bed
catalytic reactor.

• In the reactor, the sulfur and nitrogen compounds in the feedstock are
converted into H2S and NH3.

• The reaction products leave the reactor and after cooling to a low
temperature enter a liquid/gas separator. The hydrogen-rich gas from
the high-pressure separation is recycled to combine with the feedstock,
and the low-pressure gas stream rich in H2S is sent to a gas treating unit
where H2S is removed.
 Catalytic Hydrodesulfurization Process

• The clean gas is then suitable as fuel for the refinery furnaces. The liquid
stream is the product from hydrotreating and is normally sent to a
stripping column for removal of H2S and other undesirable components.

• In cases where steam is used for stripping, the product is sent to a vacuum
drier for removal of water.

• Hydrodesulfurized products are blended or used as catalytic reforming

feedstock.
 Advantages of HDS

• Sulfur & nitrogen removal to less that 10 ppm

• Complete removal of metal compounds from feedstock
• Reduction of environmental pollutants
• Increase in catalysts age and reduction in poisoning of valuable metal
catalyst
• Reduction in corrosion of process equipment
• Easy treatment of waste water
• Simple operation to process
 OTHER USES OF HDS
• The hydrogenolysis reaction is also used to reduce the nitrogen content of
a petroleum stream in a process referred to as
HYDRODENITROGENATION (HDN).

• The process flow is the same as that for an HDS unit.

• Using pyridine (C5H5N), a nitrogen compound present in some

petroleum fractionation products.

• The overall hydrodenitrogenation reaction can be simply expressed as

mentioned

C5H5N + 5H2 --- C5H12 + NH3

Pyridine + Hydrogen --- Pentane + Ammonia
ADVANCES