IPTC 14454

Conversion of Olefins in LPG through Hydrogenation

Gurulakshmanan G, Balaji V, Ganesh D , Ramboll Oil and Gas-Doha Qatar

Copyright 2011, International Petroleum Technology Conference

This paper was prepared for presentation at the International Petroleum Technology Conference held in Bangkok, Thailand, 7–9 February 2012.

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Abstract
The objective is to remove undesirable components namely olefins present in the Liquefied petroleum gas (LPG) stream in order to match the
quality pertaining to environmental aspects and safet y requirements which are achieved by processing the unsaturated hydrocarbons to the
saturated hydrocarbon product. The principal reason for removing t he olefins is that it certainly produces significant smoke based on the mole
percent of olefin content when the fuel is burnt and that which is not desirable when it is being utilized b y the end users inorder to provide a
smoke free environment. Hence a detailed study and analysis which was carried out for hydrogenating the olefins to produce satu rates have
been discussed here. The complete analyses have been modelled and simulated using process modelling softw are hysys. The efficiency in
terms of the final achievable product with respect to the throughput plays a vital role in the qualit y of saturated LPG product. The results are
analyzed with respect to the feedstock composition of unsaturated LPG to the obtained satura ted LPG pr oduct composition. This g as
processing method of treating unsaturated LPG provides us a cleaner and safe environment by reducing the emission / smoke intensity levels
while burning the fuel.

Description of the model

In order to mitigate the olefins in the LPG and achieve desired specification, it is intended to go for a Hydrogenation facility to saturate olefins.
The feedstock comprises of known composition of the liquefied p etroleum gas with identified mole percent of the unsaturated hydrocarbons.
The complete model is carried out in the process modelling software, Hysys. Peng-robinson property package is used as the simulation basis.

Olefins in LPG entering into the feed vessel at a pressure of 26 bar and 40°C (Refer to Figu re 1 for the schematic representati on of the
hydrogenation facility), is then pumped via feed p ump to the equaliz er. Fresh hy drogen stream is mixed at the equalizer for hy drogenation
reaction to occu r in the Hydrogenation reactor. Mixer upstream of the r eactor ensures that p roper mixing t akes place for enha ncing the
reactivity of this two phase flo w. The reaction is input for 98% conversion of the base components which are fed as input with appropriate
stoichiometric coefficients. H ydrogenation reactor is loaded with specific metal based catal ysts which have ability to convert olefins to
saturated hydrocarbons. The exothermicity causes an increased temperature in the product. The flo w in the reactor to be taken c are to avoid
channelling effects for more efficient conversion. There a re two beds of reactor considered in t he reactor. Each reaction conti nues until the
specified conversion is attained or until a limiting reactant is depleted.
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Figure 1 Block diagram : Hydrogenation of olefins

The process operating conditions considered for each of the equipment considered is as shown in Table 1a-Process data of equipment

Table 1a – Process data of equipment in the block diagram

Process data
Service
Pressure (kPa) Temperature (°C)
Feed vessel 2330 40
Reactor feed 2450 85
Recycle stream 2700 38
Hydrogen regenerator overhead vapour 1800 20
LPG (saturated) product 1870 92

The specification at the column outlet to achieve t he LPG product specification are as below in Table 1b: Sieve ty pe of trays are used in the
model.

Table 1b – Specification data of the hydrogen regenerator

Parameters Specified Value
Reflux Ratio 0.64
Btms Prod Rate Kgmole/h 41.0
Butane fraction 0.35
Comp Fraction 0.50
No.of trays 10

It is observed from Table-1a that the temperature of the product is 92°C. The temperature of the liquid product nevertheless can be decreased
to attain desired end user temperature through the installation of a cooler before transporting the product.
The below table 1c, provides the heat and material balance for the simulated model.

Table 1c- Heat and material balance

Name Olefins (feed stream) Product (bottom outlet of regenerator)
Vapor fraction 0.0 0.0
Temperature (°C) 40 92
Pressure (Kpa) 2600 1870
Mass flow (Kg/h) 2500 2086
Heat Flow (kW) -1554 -1397
IPTC 14454 3

The Liquid prod uct which is obt ained from the bottom of the rea ctor is at a h igh temperature as compared with the inlet to the reactor. To
increase the efficiency , the liquid product can be depressurized to let of the lig ht gas, which can be rec ycled back to reactor for higher
conversion. In this case, the liquid product is controlled by a ratio controller which allows some portion of the inlet to the Hydrogen regenerator
throttled by the control valve to keep a constant pressure at the regenerator inlet. The remaining portion of the LPG saturated liquid stream is
the Recycle, pumped via the recy cle pump. To maintain the constant temperature at the inlet of reactor this liquid po rtion of the liquid product
is then allowed to pass the coole r (due to temper ature rise which has occurred during conversion reaction which is exothermic). Refer the
below graph, Figure 2: Temperature variation across each of the trays in the column.

Figure 2: Temperature variation across each of the trays in the column.

Finally the product obtained after stripping off the h ydrogen from saturated LPG is at the liquid bottom outlet from H 2 regenerator. It has to be
noted that the c onversion of olefins is main ly a f unction of the catalyst activity. Hence as the cataly st life deca ys, the conversion efficiency
decreases. This needs to be d ynamically studied for the optimu m performance between conversion efficiency versus life of cat alyst. In
practice, it can b e monitored by periodic testing of the LP G product for an y presence of olefins. The lower the conversion effi ciency of t he
catalyst, the more the unsaturated hydrocarbons in the LPG product stream.

In case of this hydrogenation facility being utilized as an intermittent operation, the throughput is of no concerns when loading of fresh catalyst
in the reactor bed is nece ssary. However, It is to be noted that in case of continuous service of fe ed stock supply of unsaturated LPG for
processing, bypass provision of this h ydrogenation facility is r equired while catalyst removal and loading with fresh catalyst. Alternatively, it
can be flared if it is adequate to handle the flow with peak rates till the loading of fresh catalyst can take place. Separate train of the complete
hydrogenation facility can be thought of for continuous processing of the feed stock if it is economically feasible.

The below graph (Figure 3) indicates the compo sitional variation (olefins and hydrogen) across each tray in the hydrogen regenator. It is
observed that the pressure drop across each tray is 4.3 Kpa. Pres sure drop requirement to be analyzed by throttling the control valve feeding
the liquid product to the hydrogen regenerator. The feed to this regenerator is controlled by ratio controller.

Figure 3: Compositional variation with respect to the trays.

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Analysis

After preparation of the model as descri bed above, simulation was carried out converting the unsaturated to saturate for obtaining the desired
LPG specification. The analysis was done comparative to the feedstock composition, results of which are shown in Table-1d.

Table 1d -Comparison between the feed (unsaturated LPG) and the product (saturated LPG):

Composition (mol %) (only unsaturates) Olefins (mol%) in feed stock Olefins (mol%) in saturated LPG
(throughput to the feed vessel) product (Liquid stream)

Propene 03.71 00.12

1-butene 10.18 00.09

i-butene 01.23 00.01

Tr2-butene 00.03 00.00

Total mol% of unsaturated hydrocarbons 15.15 0.22

Results
From the Table -1c, it is noticed t hat the olefins in feed st ock liquefied petroleum gas compos ition is around 15% and after th e process of
hydrogenation reaction and hydrogen regneration, the olefins present in the saturated LPG concentration decreased to 0.22 mol%. Hence this
model validates to provide us a cleaner fuel in terms of the reduced unsaturated hydrocarbon in the liquefied petroleum gas.

Nomeclature

LPG- Liquified Petroleum Gas

mol% - mole percentage
Kpa – Kilo pascal
KW- Kilo watt
°C- degree celcius