GBH ENTERPRISES, LTD

C2PT Catalyst Process Technology

VULCAN Chloride Guard Technology

By Gerard B Hawkins
Managing Director

Chloride removal
A number of fixed-bed adsorbents / absorbents
have been proposed by various suppliers:

Activated Aluminas
Promoted Activated Aluminas
Calcium Oxide, SodaLime, Molecular sieves
PURASPECTM
VULCAN Series Chloride Guards

MAKE GAS

OFF
GAS

RECYCLE

GAS
LPG

REFORMATE

NAPHTHA
FEED

VGP CRT-3000

Activated Aluminas
These are formed initially from aluminium tri-hydrate and are heated
to about 500oC in a flash calciner to form an amorphous type alumina.
The temperature activating step is used to form the special high surface
area necessary for chemisorption reactions to occur.
The surface area of the gamma type phase is about 300-350 m2/g . This
very high surface area makes it an ideal surface to promote adsorption
reactions. Unfortunately, these high surface area aluminas are acidic in
nature ( Lewis acid sites) and although the relative acidity of the sites are
considered to be of medium strength, the high surface area ensures that
the number and density of Lewis acid sites on the surface is very high.
It is the presence of the large number of Lewis Acid sites that promote the
unwanted side-reactions to occur.

Lewis Acid
OH Al

e
Al

Lewis Basic site

O-

Al

Al

Can accept an electron

OAl+
O

Al
O

Can donate an electron

H+ Cl- is a polar molecule and the chloride ion reacts

with the Lewis acid surface sites and liberates H2

 Incomplete removal of HCl leads to corrosion &

ammonium chloride fouling
Formation of organo-chloride gives
fouling/corrosion/poisoning in downstream units.
Green oil formation creates problems with pipes, valves
and flanges.
Short lives lead to frequent change-outs

Catalyst Poisoning
Downstream Corrosion
Ammonium Chloride Fouling
recycle compressors/export gas compressor
stabiliser column
heat exchangers

Product Specifications

Increased Maintenance Costs

washing stabilizer column
compressor maintenance
replacing corroded pipes & equipment

Loss of Hydrogen Source

Severe problems could take unit off line
Loss of production in downstream units

Poisoning of Downstream Catalysts

eg. Ni catalysts, Cu/Zn catalysts

1. Activated aluminas remove HCl by adsorption.

The HCl has a high dipole moment and is attracted to the polar sites on the alumina
surface where it is chemisorbed ( partially dissociated).There is some evidence to
suggest that some stronger bonds are actually formed.
2. Promoted activated aluminas contain a small quantity of basic metal oxide. The
promoter will chemically react with the HCl. This reaction is faster than adsorption and is
the dominant reaction until the promoter is exhausted. Once this stage is reached,
additional chloride removal is by chemisorption but this increases the acidity of the alumina
surface.
3. HCl Transformation occurs when the inlet HCl is transformed into organic chloride
species that are not retained by the bed and exit the reactor with the carrier stream. This
occurs over acidic aluminas and is accelerated in the presence of adsorbed HCl,
adsorbed H2O and unsaturated hydrocarbons. Evidence suggests that organo-chloride
formation occurs in the top layers.

(I)

Al2O3 + 6HCl

2AlCl3 + 3H2O

(ii)

2NaAlO4 + 2HCl

Al2O3 + 2NaCl + H20

Reactions (I) and (ii) are the principal mechanisms by which chloride is adsorbed
from the stream. It has been demonstrated that the presence of moisture
increases the chloride capacity although whether due to a capacity or merely a
rate effect is not clear.
For traditional aluminas the rate limiting step is likely to be some form of
solid state diffusion into the structure.

Unwanted Side Reactions Occurring Across Alumina

a)

Organic Chlorides
R = + HCI

b)

RCI

Green Oils
R1= + R2 =

H+

R1R2

Green Oil is formed by the reaction of organic chlorides with

aromatic compounds such as benzene and other unsaturated
hydrocarbons this reaction is well known in organic chemistry
(Freidel Crafts) and is catalysed by highly acidic surface sites on
alumina.
C6H6
+
C6H5R +

RCl
RCl

C6H5R + HCl
C6H5R-R + HCl

Hence long chain polymeric compounds are produced of such

high molecular weight that the precipitate out causing fouling and
blockage.

In the case of alumina adsorbents, various condensation and polymerisation reactions are
catalysed by anhydrous AlCl3.The high molecular weight polymers block pores and deposit
gums or green oil. The gums act to form lumps of agglomerated adsorbent which reduce
capacity due to channelling of gas flow. The formation of complex organic chlorides , some
of which are volatile, is also promoted byAlCl3, resulting in chloride loss from the adsorber
and corrosion or poisoning problems.
Aromatics + Anhydrous AlCl3
Naphthenes + Anhydrous AlCl3

dark red / orange complexes

polymeric tars
orange complexes and tar

Example: A sample of liquid drained from a vessel was tested and

found to be:
87% hydrocarbon boiling below 200 C and 13% polymeric naphthenes and aromatics
unable to be distilled as the material is pitch like, setting solid on cooling.

Addition of halogens to alkenes involves attack by positive

halogen to form an intermediate carbonium ion. The loosely held
pi electrons of an alkene make it more reactive.
The less reactive benzene molecule needs the assistance of a
Lewis acid . More reactive aromatic molecules ( those whose pi
electrons are more available, phenols, furans etc..) can react with
halogens in the absence of a Lewis acid.
Naphthenes are very prone to di & polyalkylation reactions
leading to polymeric long chain structures.

R-Cl + AlCl3

AlCl4- + R +
H

R+ + C6H6

C6H5+

Slow

R
H
C6H5+

+ AlCl 4

C6H5R + HCl + AlCl3

Fast

C6H5R-R

Friedel-Crafts reaction is an electrophilic substitution with AlCl3 acting

as a Lewis acid.

Other chemical reactions may occur in the presence of AlCl3.The coupling

of two aromatic molecules by treatment with a Lewis Acid and a proton
acid is called the Scholl reaction.

H+

CH
AlCl3

This type of intramolecular reaction can also occur with

activated aluminas

In normal operation there will be trace amounts of unsaturated

hydrocarbons in reformer reactor product that will go into both the
offgas and reformate streams. For example, in hydrogen gas excatalytic reformers the concentration of unsaturates varies from 400
ppmv to 1000 ppmv.
These unsaturated hydrocarbons will react with HCl when promoted
by an acid catalyst . These organo-chlorides can therefore be formed
across activated aluminas. These organo-chloride species are not
removed by the alumina and exit the bed in the product stream. If the
off-gas stream supplies H2 to hydrotreating or hydrocracking units,
these organo-chlorides will be hydrogenated to HCl and initiate
corrosion problems and catalyst deactivation.

RCH2=CH

O-H

Cl
Al

RCH2CH2

O-H
Al

O-H

+
RCH2CH2Cl

Cl

Al
Alumina surface

unsaturated hydrocarbon reacts with surface hydroxyl ( acid) site

reactive carbonioum ion formed
Cl chemisorbed to alumina surface
carbonioum ion reacts instantly with Cl
R-Cl formed

Make gas and stabilizer feed from catalytic reformers contains a mixture of
olefins which should theoretically be present from equilibrium calculations:

Gas
Liquid

C2= to C4=
C4= to C8=

For typical reformate, C4= and above, the tertiary olefin is the major
component, broadly inline with equilibrium calculations. The level of
ethylene and propylene should only be about 15% of the total olefins.
The reaction to produce organic chlorides is most easily performed with
tertiary olefins due to the reactivity of the tertiary carbonium ion. Therefore,
for a mixture containing equal parts of primary, secondary and tertiary
butylene reacting with HCl, the major product is tertiary butyl chloride.

CH3CH2CH=CH2 + HCl
1-Butene

CH3CH3CHClCH3
Sec-butyl chloride

CHC=CH-CH3 + HCl
CH3
2-Methyl-2-Butene

CH3-C-CH2-CH3
tert-pentyl chloride
Cl

CH3-C=CH2 + HCl
CH3

CH3-C-CH3
CH3

Isobutylene
Cl
Tert-butyl chloride

Reactivity of alkenes with HCl

CH3
C=CH2 > CH3CH=CHCH3, CH3CH2CH=CH2,
CH3

CH3CH=CH2 >CH2=CH2

Stability of carbonium ions:

o

3 > 2 > 1 > CH3+

Leaching of components from the adsorbents can be a potential problem, leading

to both loss of chloride and contributing to fouling of the adsorbent mass.
Evidence for the mechanisms leading to leaching point to some form of
dissolution via:
AlCl3
AlCl3 + 3H2O
NaCl

Soluble in liquid water and organic solvent

Al(OH)3 + 3HCl
Soluble in liquid water only

Analysis of agglomerated lumps from one refinery application of their spent

activated aluminas has shown NaCl in the binding phase and unexpectedly high
LOI on the samples. This suggested that water must have been present.

- Enhanced chloride protection

- Proven track record in gaseous and liquid duties
- Reliable and safe operation
- Low capital cost
- Cost-effective operation
- Environmentally friendly
- No process losses
- Guaranteed solution to a problem

High Temperature
VGP CRT-3000

Low Temperature Gases

VGP CRT-2000

VULCAN Series Chloride Guards

Bi-metallic promoted

Low acidity / medium

surface area

Low side-reaction inducing

characteristics

A.B.D.
0.60-0.80 kg/l

Theoretical capacity
32% w/w

VULCAN Series Chloride Guards

New products are absorbents

HCl removed by chemical reaction
They have been manufactured with a reduced surface area to minimise aromatic
and hydrocarbon adsorption and its constituent components-( bi-metallic
promotion and highly porous support - do not have adsorption properties for HCl.

HCl does not exist freely or in an adsorbed or in a partially dissociated state

within the particle or on its surface.

The HCl is irreversibly chemically bound within the matrix.

VULCAN Series products are not acidic and minimises / retards organic
chloride synthesis or condensation and polymerisation reactions.

Chloride pick-up in excess of 30 % w/w in gas phase tests

HCl removal to < 0.1 ppmv

Chemisorption: Alumina
MO-

H+

...

CI-

H+

- Reversible
- Equilibrium loading function of T,
pHCI, pH2O
Chemical Reaction: VGP CRT 3000
Na2O + 2HCI => 2NaCI + H2O
2NaAIO4 + 2HCI => 2NaCI + H2O + AI2O3
- Irreversible
- Chloride loading constant

Chloride Guards - History & Development

Saturated Chloride capacity

Activated Alumina

( unpromoted)

Activated Alumina ) (5% calcium -promoted)

3-5%
5-8%

Activated Alumina ( 10% sodium promoted)

10-12 %

VGP CRT-3000 ( BIMETALLIC)

25-32%

Pick-up depends on temperature, pressure,

flowrate, feed composition, inlet chloride level
Different locations in a flow scheme will give
different expected lives
Lead-lag gives better absorbent usage and
continuous protection
Must change bed when chloride first breaks
through