ASSIGNMENT-1

PETROLEUM AND PETROCHEMICALS

(UCH-850)

Submitted to
RAKESH KUMAR GUPTA

Submitted by
ARPIT THUKRAL
Roll No. 101601010
Group - CHE-1

DEPARTMENT OF CHEMICAL ENGINEERING

THAPAR INSTITUTE OF ENGINEERING & TECHNOLOGY,
(Deemed to be University) PATIALA,
147004, PUNJAB, INDIA
 Task 1

• Describe the differences between catalytic alkylation and catalytic

polymerization process used in petroleum industry in terms of their
applications, type of feed required, products, process, engineering
challenges etc.?
Solution: Catalytic alkylation: Catalytic alkylation is a conversion process used in petroleum
refineries to upgrade light olefins and iso-butane into a highly branched Paraffins. It is a process in
which addition of alkyl group takes place on any compound with the presence of a catalyst. It is
used to covert low molecular weight alkenes like iso-butene into alkylate, which is used as blending
components for making gasoline. For example:- One mole of olefin reacts with one mole of iso-
butane to form an iso-paraffin exactly 4 carbon numbers heavier.
Step 1: Addition of proton H+ supplid by sulfuric acid which acts as a catalyst.

Step 2: Addition of ion to olefin to form long chain.

Catalytic polymerization:
Catalytic polymerization is a process in which light olefins like propylene are induced to combine,
or polymerize into molecules of two or three times their original molecular weight. The products
coming from catalytic polymerization is also used as gasoline blending stocks. The catalysts used
consist of phosphoric acid on pellets of kieselguhr, a porous sedimentary rocks. For special
purposes only purified feeds of propylene or iso-butylene only are majorly used.
 PROCESS ALKYLATION POLYMERIZATION
1. Application Produces a high octane gasoline by reacting Polymerize propene and butenes
light olefins with light iso-paraffins. to form a high octane gasoline.
2. Feed Generally a mixture of ethylene, propylene Light olefins propylene and
and butylene with iso-butane. butylene are used as feed in the
process.
3. Operating Temperature:- 21-40oC Temperature:- 175-230oC
Conditions Pressure:- 1-10 atm Pressure:- 27-25 atm
4. Catalyst used Sulfuric acid and hydro-flouric acid Phosphates are mainly used. The
commercially used catalyst are
phosphoric acid.
5. Products LPG grade propane, Normal butane liquid, Liquefied petroleum gas, High
obtained C5 + alkylate octane naphtha, Petrochemical
feedstock.
6. Process flow
diagram

Isobutan
e Make Fractionato
up r
Olefin Reacto
feed r

Fresh
Acid Spent Alkylat
Acid e
product

Task 2

• Completely discuss any finishing process which is much used currently in

petroleum refining industry.
Solution: The refining process in petroleum industry has 3 basic steps to be followed: separation,
conversion, finishing. Before petroleum products can be marketed, impurities like hydrogen
sulfide(H2S), mercaptans (RSH), nitrogen compounds must be removed. There are various finishing
methods like Hydrodesulphurization, hydrodenitrogenation, hydro treatment etc. which are used in
the petroleum refinery.
Hydrotreating:
Catalytic HDT is a fundamental refining process for the upgrading of a wide variety of streams,
ranging from straight-run naphtha to vacuum residue (VR) or even heavy and extra-heavy crude
oils. The HDT process is commonly employed for reducing the contents of hydrocarbon impurities
such as sulfur, nitrogen, oxygen, and aromatics by the so-called hydrogen addition route. The
process has gained significant relevance in the industry due to the growing demand for
transportation fuels and the strict environmental legislations. From a practical standpoint, HDT is a
process in which the hydrogen/carbon ratio of the feed is increased in the presence of a catalyst in a
hydrogen-rich atmosphere. The typical configuration of an HDT unit is presented in Figure below.
The sequence of operations begins with the preparation of the feedstock. The hydrogen recycle
stream is mixed with the feed oil, and afterward the mixture is heated to the required reaction
temperature in the feed heater. The gas–liquid mixture is subjected to HDT conditions in a single
reactor or a series of reactors, typically operating in down flow fixed-bed mode. Depending on the
amount of heat release, the reactor can have multiple beds separated by quench zones in order to
inject cold hydrogen streams, typically from the recycle stream. The reactor effluent is sent to a
high-pressure separator (HPS) where the liquid products are recovered from the gases. The liquid
hydrocarbon stream from the HPS passes through a stripping unit in order to remove the remaining
dissolved hydrogen sulfide and ammonia. The gas stream is scrubbed with diethylamine (DEA) in
order to remove the excess of hydrogen sulfide and ammonia generated by chemical reaction. The
resulting high-purity hydrogen stream is recompressed and recycled to the reaction system.
Depending on the extent of HCR, the hydrotreated product can be fractionated into various distillate
products. The HDT catalyst is typically a CoMo/NiMo alumina supported catalyst, the composition
and textural properties of which vary according to the different purposes. The severity of the
operating conditions depends on the feed type and the final product quality. In general, the process
is carried out at high pressures and temperatures; typical industrial units operate at pressures of 2–
20 MPa, temperatures of 320–440 C, H2/oil ratios of 350–1800 Nm3 /m3 , and liquid hourly space
velocities (LHSVs) between 0.2 and 8.
Concerning reactor technology, there are currently four main kinds of HDT reactors that can be
classified according to the type of catalytic bed: FBR, MBR, EBR, and slurry-phase reactor (SPR)..
FBRs are the most widely used technology for all types of HDT operations due to their relative
simplicity, flexibility, and ease of operation. MBRs and EBRs, on the other hand, are designed for
the upgrading of heaviest feeds. Initially, FBRs were employed for processing light feeds (naphtha
and gas oil), but eventually they were adapted for tougher feeds such as vacuum gas oil (VGO) and
residues. Their main disadvantage for upgrading heavy feeds is the drastically reduced length of run
owing to the rapid catalyst deactivation caused by metals accumulation and coking. Layered
catalyst systems were introduced to make better use of the catalyst inventory in order to extend
significantly the length of run. The main feature of this technology is the front-end HDM
macroporous catalyst that allows the disaggregation of asphaltene molecules for metal removal, so
that the downstream HDS/HCR catalysts can operate with low metal and coke precursor content
hydrocarbons. MBRs and EBRs overcome the catalyst cycle life limitations of FBRs. Such
technologies allow for replacing spent catalyst without interrupting operation; therefore, they are
the best option for handling the most problematic feeds with high contents of metals and
asphaltenes. The application of these reactors is specifically in front-end de-metallization to protect
subsequent FBRs for HDS and HCR. EBRs constitute the most advanced hydroprocessing
technology, specifically designed for upgrading extra-heavy feeds directly, without any kind of
pretreatment. The continuous catalyst replacement feature allows the use of conventional high-
activity HDS/HCR catalysts. The operation is very flexible, conversion is very efficient (up to 90
vol%), and products have low levels of sulfur, metals, and nitrogen. Nevertheless, ebullated-bed
technologies suffer from considerable sediment formation and high catalyst consumption.

Figure: Flow diagram of a hydrotreating unit