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Lec.14 & 15 Exercise

This document discusses hydrotreating in petroleum refining. Hydrotreating removes impurities like sulfur, nitrogen, and oxygen from petroleum streams. It also removes metals and saturates olefins. Hydrotreating units are located before processes like reforming, hydrocracking, and fluid catalytic cracking to clean feedstocks. The main roles of hydrotreating are to meet product specifications and prepare feeds for downstream units. Common hydrotreating reactions remove sulfur compounds and saturate aromatics and naphthenes. Hydrotreating uses catalysts containing metals like cobalt, nickel, molybdenum and tungsten. Key operating conditions include pressure, temperature, and hydrogen

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190 views7 pages

Lec.14 & 15 Exercise

This document discusses hydrotreating in petroleum refining. Hydrotreating removes impurities like sulfur, nitrogen, and oxygen from petroleum streams. It also removes metals and saturates olefins. Hydrotreating units are located before processes like reforming, hydrocracking, and fluid catalytic cracking to clean feedstocks. The main roles of hydrotreating are to meet product specifications and prepare feeds for downstream units. Common hydrotreating reactions remove sulfur compounds and saturate aromatics and naphthenes. Hydrotreating uses catalysts containing metals like cobalt, nickel, molybdenum and tungsten. Key operating conditions include pressure, temperature, and hydrogen

Uploaded by

malak
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Petroleum Refining Fourth Year Dr.Aysar T.

Jarullah

Hydrotreating
Hydrotreating achieves the following objectives:
 Removing impurities, such as sulphur, nitrogen and oxygen for the control of a final
product specification or for the preparation of feed for further processing (naphtha
reformer feed and FCC feed);
 Removal of metals, usually in a separate guard catalytic reactor when the organo-
metallic compounds are hydrogenated and decomposed, resulting in metal deposition
on the catalyst pores (e.g. atmospheric residue desulphurization (ARDS) guard
reactor); and,
 Saturation of olefins and their unstable compounds.

Role of Hydrotreating
Hydrotreating units are needed in the refinery to clean streams from material such as
sulphur, nitrogen or metals harmful to the catalysts. That is why they are located before the
reformer, hydrocracker and FCC as shown in Figure below.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

They are also needed to adjust the final product specification for various streams, such as
light naphtha, kerosene and low sulphur fuel oils (LSFOs).
Hence, the main role of hydrotreating can be summarized as follows:

1. Meeting finished product specification.


 Kerosene, gas oil and lube oil desulphurization.
 Olefin saturation for stability improvement.
 Nitrogen removal.
 De-aromatization for kerosene to improve cetane number, which is the percentage
of pure cetane in a blend of cetane and alpha-methyl-naphthalene. The
latter matches the ignition quality of kerosene sample.

2. Feed preparation for downstream units:


 Naphtha is hydrotreated for removal of metal and sulphur.
 Sulphur, metal, polyaromatics and Conradson carbon removal from vacuum gas oil
(VGO) to be used as FCC feed.
 Pretreatment of hydrocracking feed to reduce sulphur, nitrogen and aromatics.

Hydrotreating reactions
1. Desulphurization
a. Mercaptanes:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Hydrotreating Catalysts
The hydrotreating catalyst is a porous alumina matrix impregnated with combinations of
cobalt (Co), nickel (Ni), molybdenum (Mo) and tungsten (W). The reactivities of each
catalyst are given in Table below:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Hydrotreating Processes
Hydrotreating processes are similar in common elements and in general can be represented as
shown in Figure below. The liquid feed is mixed with hydrogen and fed into a heater and the
mixture is brought to the reaction temperature in a furnace and then fed into a fixed bed
catalytic reactor. The effluent is cooled and hydrogen-rich gas is separated using a high
pressure separator. Before the hydrogen is recycled, hydrogen sulphide can be removed using
an amine scrubber. Some of the recycle gas is also purged to prevent the accumulation of
light hydrocarbons (C1 – C4) and to control hydrogen partial pressure. The liquid effluent for
the reactor is introduced to a fractionator for product separation.

Make-up Hydrogen
A certain hydrogen partial pressure should be maintained in the reactors by recycling un-
reacted hydrogen and adding a make-up hydrogen to compensate for the amount consumed.
The make-up hydrogen can be calculated by the following expression:

Make-up hydrogen = hydrogen in feed - hydrogen consumed for chemical requirement


- hydrogen purged - amount of hydrogen dissolved in product

Hydrogen purge is the amount of hydrogen lost with the purging of light hydrocarbons (C1-
C4) and hydrogen sulphide (if not removed by amine treatment). This hydrogen can be
predicted using flash calculation, or using the purge gas ratio. The purge ratio is defined as:

Operating Conditions
The operating conditions of the hydrotreating processes include pressure, temperature,
catalyst loading, feed flow rate and hydrogen partial pressure. The hydrogen partial pressure
must be greater than the hydrocarbon partial pressure. Increasing hydrogen partial pressure
improves the removal of sulphur and nitrogen compounds and reduces coke formation.
Higher temperatures will increase the reaction rate constant and improve the kinetics.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

However, excessive temperatures will lead to thermal cracking and coke formation. The
space velocity is the reverse of reactor residence time. High space velocity results in low
conversion, low hydrogen consumption and low coke formation. The range of operating
conditions for hydrotreating of different feed fractions is given in Table below.

Naphtha and Gas Oil Hydrotreating Correlations


The standard cubic foot of hydrogen per barrel of feed (SCFB) required for complete sulphur
removal is calculated as:

Where Sf is the sulphur wt% in feed.


The increase in the API gravity of a product is calculated as:

Where p and f refer to product and feed, respectively. In some cases, if it is required to
saturate aromatics and naphthenes to the corresponding paraffin, a set of correlations for PNA
analysis is required to predict the naphtha composition. These are:

Where Kf is the feed Watson characterization factor.

Example:
It is required to hydrotreate naphtha which has 1 wt% S and API = 50. Find: a) How much
hydrogen is required to remove all the sulphur in the feed by empirical correlations? b) How
much of this H2 is used for chemical requirements. c) If the mean average boiling point of
this naphtha is 135 F and assuming that the naphthene and aromatic present in the naphtha are
cyclohexane and benzene, respectively. Find the volume of hydrogen (SCFB) to convert all
cyclohexane and benzene into hexane.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Thus the following Table can be constructed for the calculation of the volume of H2 required
to convert cyclohexane and benzene to hexane.
The final amount of H 2 required can be summed up as:

It can be seen that the amount of hydrogen for naphthenes and aromatics saturation is much
higher than that needed for other requirements such as sulphur removal.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Middle Distillate Hydrotreating Correlations


The amount of hydrogen required can be calculated as:

Where Sf is the wt% sulphur in the feed and HDS% is the percent of hydrodesulphurization
required (degree of severity). The increase in product API is calculated as:

This equation is used for feed sulphur content of 0.5–6.0 wt%.

Example:
Gas oil has an API of 30, and a sulphur content of 1.5 wt% is fed into a hydrotreater. It is
required to carry out HDS at a severity of 90%. Calculate the hydrogen required and the
product API.

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