Lecture 9

Material Balance around CDU

 For a given feed flow rate in barrels per calendar day (BPCD), and given the specific
gravity of the feed, the mass flow rate of the feed can be calculated.
 The mass flow rate of the vacuum residue is calculated as the difference between the feed
mass flow rate and the total mass flow rate of all products lighter than the vacuum
residue.
 Similarly from the mass flow rate of the residue and its gravity, its volumetric flow rate
can be calculated.
o The sum of the volumetric flow rates of the products may become higher than the
feed. This is expected, since the volume change of mixing is negative for
petroleum fractions.
o When the fractions are mixed, the total volume of the mixture is less than the sum
of the volumes of the fractions. Following problem will illustrate the material
balance calculations.

Problem 4.4:

For Kuwait export crude (API = 31.5) given in the Prob. 4.2, perform amaterial balance CDU calculations for
a feed rate of 100,000 BPCD.

Table Prob.4.2 Volumetric yield of cuts and their properties

Solution:

The volumetric product yield is converted to mass flow rates. Mass flow rate of feed is 573,844 kg/h.
 Table: Crude unit material balance

Sulphur Material Balance

For crude oil containing significant amounts of sulphur, it is necessary tomake a sulphur balance
around the crude unit.

The sulphur content of thecrude oil should be given. The sulphur content of the products
should also beknown. If these data are not available the estimation of the sulphur content of
petroleum fractions can be calculated using the following equations of Riaziet al., 1999.

For fractions with M <200

Eq. 1

And for fractions with M ≥200

Eq. 2

where SG is the specific gravity, Riis the refractivity intercept defined as

wheren and d are the refractive index and density of liquid hydrocarbon at68 oF (20oC) in g/cm3.
The parameter "m" is defined as

Eq. 3
After calculating the wt% S in each product except the vacuum residue, theamount of sulphur is
calculated by multiplying this percentage by the massrate of each product.

The sulphur in the vacuum residue is calculated fromthe difference of the total sulphur in
the crude feed and the total sulphur inthe products.

Problem 4.5

Perform a sulphur balance on the crude unit of Prob. 4.4 (given below), knowing that thesulphur
content of Kuwait export is 2.52 wt%.

Table: Crude unit material balance

Solution:

The wt% S in each product except the vacuum residue is calculated using Eq. 1 and 2, the
following table is obtained.

Table: Calculation of sulphur content of the products

The Sulphur material balance is shown in following

Table: Sulphur Material Balance

 Chapter No: 5

Catalytic Reforming and Isomerization

Catalytic reforming of heavy naphtha (C7-C10) and isomerization of light naphtha (C5-C6)
constitute a very important source of products having high octane numbers which are key
components in the production of gasoline.
Environmental regulations limit on the benzene content in gasoline. If benzeneis present
in the final gasoline it produces carcinogenic material on combustion.Elimination of benzene
forming hydrocarbons, such as, hexane will prevent the formation of benzene. These light
paraffinic hydrocarbons can be used in an isomerization unit to produce high octane number
isomers.

Catalytic Reforming

 Catalytic reforming is the process of transforming C7–C10 hydrocarbons with low octane
numbers to aromatics and iso-paraffins which have high octane numbers.
 It is a highly endothermic process requiring large amounts of energy.
 A schematic presentation of the feedstock, products and process condition is shown in
Figure 5.1. The process can be operated in two modes: a high severity mode to produce
mainly aromatics (80–90 vol%) and a middle severity mode to produce high octane
gasoline (70 vol% aromatics content).

Figure 5.1 Catalytic reforming process

Reformer Feed Characterization

 Feeds are characterized by the Watson characterization factor (K), naphthenes (N) vol%
and aromatics (A) vol% in which (N + 2A) must be defined.
 Inaddition, initial boiling points (IBP) and end points (EP) for feeds must be
characterized. Feeds can be also characterized by the hydrocarbon family and their
number of carbon atoms.
 Naphthenic feeds give a much higher yield than paraffinic feeds.

Figure 5.2 Role of Reformer in the Refinery

Reforming Reactions

1. Naphthene Dehydrogenation of Cyclohexanes

2. Paraffin Dehydrogenation

3. Dehydrocyclization

All the above reactions are highly endothermic.

4. Isomerization

Isomerization is a mildly exothermic reaction and leads to the increase of an octane number.

5. Hydrocracking Reactions

Hydrocracking reactions are the main sources of C4- hydrocarbons (C1, C2, C3 and C4). The
reactions are highly exothermic and consume high amounts of hydrogen. Cracking results in the
loss of the reformate yield.

(i) Paraffin hydrocracking

(ii) Hydrocracking of aromatics

A summary of reformer reactions and interactions is shown by the reaction network shown
below.
Fig. 5.1: Network of reforming reaction

Thermodynamics of Reforming Reactions

 The dehydrogenation reactions are the main source of reformate product and are
considered to be the most important reactions in reforming.

 These are highly endothermic reactions and require a great amount of heat to keep the
reaction going. For this reason three reactors are usually used in the reforming process
with heating the product from each reactor before entering the other.

 The dehydrogenation reactions are reversible and equilibrium is established based on

temperature and pressure.
o It is usually important to calculate the equilibrium conversion for each reaction. In
reforming, a high temperature around 500oC (932oF) and a low hydrogen pressure
are required.
o The minimum partial pressure of hydrogen is determined by the amount of the
desired aromatics conversion.

Problem 5.1
Solution

Reforming Process Technology

There are several commercial processes available for reforming.
1. Platforming (UOP),
2. Powerforming (Exxon),
3. Magna forming (Engelhard),
4. Catalytic reforming (IFP),
5. Rheniforming (Chevron) and
6. Ultra forming (Amoco).

The old technologies are fixed bed configuration. Moving bed technology has also recently been
introduced.

Semi-regenerative Fixed Bed Process

The schematic flow diagram of this process is shown in Figure 5.2. The name semi-regenerative comes
from regeneration of the catalyst in the fixed bed reactors after shut down by burning off the carbon formed
on the catalyst surface.
 Reactions such as dehydrogenation of paraffins and naphthenes which are very rapid and highly
endothermic (Table 5.1) occur in the first reactor, with high temperature drop.
 Reactions that are considered rapid, such as paraffin isomerization and naphthens
dehydroisomerization, give moderate temperature decline in the second reactor.
 Furthermore, slow reactions such as dehydrocyclization and hydrocracking (Table 5.1) give low
temperature decline in the third reactor.
Figure 5.2Semi-regenerative (SR) fixed bed reforming process

 The temperature and concentration profile in each reactor is shown in Figure 5.3.

Figure 5.3(A) Furnace and reactor layout for fixed bed reformer. (B) Variation of temperature in the
reactors. (C) Variation in effluent compositions; P 0, initial Paraffins; N0, initialNapthenes andA0,
initialAromatics (Martino, 2001)

 To prevent catalyst coking, the hydrogen partial pressure is maintained at a level such that the
hydrogen-to-hydrocarbon ratio by weight (H2/HC) is greater than 25 for monometallic catalyst. This
is done by recycling some of the hydrogen produced (Figure 5.2).
 Some light hydrocarbons (C1–C4) are separated from the reformate in the stabilizer. At the top of
the stabilizer residual hydrogen and C1 to C4 are with-drawn as condenser products, which are
then sent to gas processing, and part of the liquid product (C3 and C4) is returned from the reflux
drum back to the stabilizer (Figure 5.2).
 The main product of the column is stabilized reformate, which is sent to the gasoline blending
plant.
 Reaction Kinetics and Catalysts

 The catalyst used for reforming is a bifunctional catalyst composed of platinum metal on
chlorinated alumina.
 Platinum acts as the centre for the dehydrogenation reaction, and chlorinated alumina acts
as an acidic site to promote structure changes, such as cyclization of paraffins and
isomerization of the naphthenes.
 Recently additional elements have been added to platinum to promote additional
properties for the catalyst.

1. Iridium (Ir) is added to boost activity,

2. Rhenium (Re) is added to operate at lower pressures and
3. Tin (Sn) is added to improve yield at low pressures.

The use of Pt/Re is now most common in semi-regenerative (SR) processes with Pt/Sn is used in
moving bed reactors.

The quantity of chlorine used is approximately 1 wt. % of the catalyst and the quantity of
platinum is from 0.2 to 0.6 wt. %.

Impurities that might cause deactivation or poisoning of the catalyst include: coke, sulphur,
nitrogen, metals and water. Because of these problems, the reformer feed has to be severely
hydrotreated to remove most of these impurities, and the reformer should be operated at high
temperature and low pressure to minimize coke deposition.

1. Paraffin and naphthene dehydrogenation reactions are very rapid and usually
occur in the first reactor.
2. The isomerization of paraffin and naphthenes is fast, whereas
3. Hydrocracking is slow and takes place in the last reactor.

The effect of operating conditions on reaction rate and other properties is shown in Table 5.1.