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Catalysts for

Olefin Processes
a world leader in catalyst
science and technology
Johnson Matthey
Johnson Matthey is a leading global supplier of high performance process catalysts and technology for
a diverse range of market applications. We have continued to develop our technology for almost 200
years, demonstrating the company's ability to maintain world leadership by adapting constantly to
rapidly changing customer needs. Today, Johnson Matthey remains synonymous with accuracy, reliability
and integrity.

Johnson Matthey Process Technologies division holds a Chemical Catalysts including PRICAT TM, PURASPECTM,
leading position across the petrochemical, syngas, oil HTCTM and KATALCOTM catalysts specifically designed for the
refining and gas processing industries as a supplier of olefins value chain.
catalysts, licensing technologies and other services.
Steam cracking of hydrocarbons is a primary source of
With our dynamic group of dedicated, skilled people and olefins. The yield of ethylene and its by-products -
unparalleled technical service, we meet the needs of our propylene, butylenes, butadiene and aromatics - are
customers worldwide, and develop and manufacture the dictated by the feedstock, plant configuration and cracking
catalysts that optimise chemical processes. severity. Chemical Catalysts offer catalysts and absorbents
suitable for every plant configuration in the olefins value
Our global resources, combined with our expertise in the chain to improve the product quality, reliability and cost
chemical market and our heritage in chemical processes, effectiveness of these essential operations.
has enabled us to develop and manufacture a family of

Olefins Value Chain 3


H2
Methanation Hydrogen

3 3 3
Feed Steam C2 Acetylene Monomer
LPG Ethylene
Purification Cracking Conversion Purification

3 3
C3
3 MAPD Monomer Propylene
Conversion Purification
Naphtha, Feed Steam
Condensate Purification Cracking 3
C4 C4 Acetylene Butadiene
Butadiene
Hydrogenation Extraction

3
Gas Oil Steam
Cracking C4 Selective
Butylene
Hydrogenation

3
3
Total Butane
Import Feed Saturation Pentane
Ethylene Purification
3
C5 Selective
Pentene
3 Hydrogenation

Import Feed 3
Propylene Purification C5+ Pyrolysis Hydro-
Aromatics
Gasoline Desulphurisation

3 denotes where Johnson Matthey offer catalysts in this process


Acetylene conversion
Acetylene levels can reach as high as 25 kg per MT of ethylene produced, however current requirements demand this to be
reduced to less than 1 ppm. We offer catalysts for selective hydrogenation, for both ethylene plant configurations: front-end
and tail-end.

Front-end configuration Front-end acetylene conversion catalysts


The front-end acetylene converter is located upstream of PRICAT PD PRICAT PD PRICAT PD
the cold box prior to the separation of hydrogen from the 308/2 308/6 308/7
olefins. In addition to acetylene and ethylene, the feed Active metal Pd Pd Pd
contains various amounts of hydrogen, carbon monoxide Promoted no yes yes
and heavier hydrocarbons, depending on the distillation Size (mm) 3x3 3x3 3x3
configuration. PRICAT PD 308 series catalysts are
Shape tablet tablet tablet
formulated to ensure complete acetylene removal whilst
Support alumina alumina alumina
avoiding significant ethylene hydrogenation. All versions of
Service
PRICAT PD 308 are designed to reduce the acetylene
concentration to less than 1 ppm. de-ethaniser yes yes
de-propaniser yes yes yes
raw gas

PRICAT PD 308/6 is suitable for low CO concentrations.

Tail-end configuration Tail-end acetylene conversion catalysts


The tail-end acetylene converter is located downstream of PRICAT PD PRICAT PD PRICAT PD
the cold box and de-ethaniser. The feed contains 408/5 408/7 608/1
acetylene, ethylene, ethane and only a trace of lighter and Active metal Pd Pd Pd
heavier compounds. A controlled amount of hydrogen is Promoted yes yes yes
added to effect the selective hydrogenation of acetylene.
Size (mm) 2-4 2-4 2-4
The PRICAT 408 series catalysts are for specific duties
Shape sphere sphere sphere
that require tailored activity or selectivity. The PRICAT 608
Support alumina alumina alumina
series has been formulated to achieve complete acetylene
Service
removal with significant gains over previous generations.
Carbon monoxide is not required for the operation of the lead bed yes yes yes
408 and 608 series but with it selectivity gains can be middle bed yes yes yes
made and green oil formation rates are minimised. clean-up bed yes yes
MAPD conversion
Selective hydrogenation can be used in the C3 (propylene)
cut from the steam cracking operation. Although a by-
product itself, propylene streams from cracking can carry up
to 2% methyl acetylene (MA) and 1.5% propadiene (PD). By
employing selective hydrogenation techniques we can convert
these impurities to chemical grade propylene. This route
offers considerable efficiencies compared to processes which
downgrade to propane instead. This selective hydrogenation
unit can be located on the distillate of the depropaniser or
the bottoms of the de-ethaniser, depending on the main
plant configuration. We offer catalysts for MAPD converters
configured as vapour phase or liquid phase reactors, to suit
the plant’s needs.

Vapour phase converter


The vapour C3 cut is superheated and a controlled amount
of hydrogen is added to effect the selective hydrogenation of
MAPD. PRICAT PD 308/5 is formulated to ensure complete
MAPD removal whilst avoiding significant propylene
hydrogenation.

Liquid phase converter


The liquid C3 cut is pressurised and a controlled amount of
hydrogen is added to effect the selective hydrogenation of
MAPD. PRICAT PD 309/3, PRICAT PD 468 and PRICAT
PD 469 are formulated to ensure complete MAPD removal
whilst avoiding significant propylene hydrogenation through
high selectivity operation.

MAPD conversion catalysts


PRICAT PD PRICAT PD PRICAT PD PRICAT PD
308/5 309/3 468 469
Active metal Pd Pd Pd Pd
Promoted yes no yes no
Size (mm) 2-4 2.5 2-4 2-4
Shape sphere trilobe extrudate sphere sphere
Support alumina alumina alumina alumina
Service vapour phase liquid phase liquid phase liquid phase
PRICAT PD 309/3 is suitable in high LHSV situations; high recycle rate lead beds.
PRICAT PD 468 is formulated to minimise propylene hydrogenation.
PRICAT PD 469 is a versatile palladium catalyst.
C4 acetylene C4 selective
hydrogenation hydrogenation
The production of butadiene from steam cracking varies from Over 180 kg of butylene per MT of ethylene can be
less than 30 kg per MT of ethylene produced to over 140 kg produced from liquids cracking depending upon cracking
per MT of ethylene produced, depending on cracking severity severity and feedstock. This butylene yield can be doubled by
and feedstock. The raw C4 cut from steam cracking contains selective hydrogenation of the co-produced acetylenes and
between 35% and 70% butadiene. This cut also contains up butadiene to butylene.
to 1.5% vinyl acetylene and 0.7% ethyl acetylene. The
After butadiene extraction, the butylene rich raffinate
modern specification for combined C4 acetylenes in
contains up to 1% butadiene which must be reduced to 100
butadiene product is less than 10 ppm. C4 acetylene can be
ppm or less via selective hydrogenation.
separated from butadiene as part of the extraction process,
however considerable efficiencies are available by converting A single, liquid phase adiabatic reactor is suitable for feed
vinyl acetylene to butadiene and ethyl acetylene to 1-butene containing up to 1% butadiene, with a trickle bed design for
instead of downgrading to fuel. higher feed concentration. Liquid recycle is added when the
feed concentration exceeds 4% butadiene.
This selective hydrogenation unit can be located
downstream of the debutaniser as part of the stream Our range of PRICAT PD catalysts cater for different
cracker complex or upstream of the first extractor in the applications and customer requirements, our technical
butadiene extraction unit. service team can discuss these with each customer and
advise on which of the range would be most suitable for the
PRICAT PD 468 is formulated to ensure high C4 acetylene
desired C4 duties. In addition to their use in olefin processes,
conversion whilst minimising butadiene hydrogenation.
our range of C4 catalysts can also be used in Refinery
applications, please contact us for more information.

C4 selective hydrogenation catalysts


PRICAT PD PRICAT PD PRICAT PD PRICAT PD
309/4 468 469 493
Active metal Pd Pd Pd Pd
Promoted no yes no no
Size (mm) 2.5 2-4 2-4 2-4
Shape trilobe extrudate sphere sphere sphere
Support alumina alumina alumina alumina
PRICAT PD 309/4 is formulated for operation in high LHSV situations.
PRICAT PD 468 is formulated to minimise butylene hydrogenation.
PRICAT PD 469 is a versatile palladium catalyst.
PRICAT PD 493 is formulated to maximise 2-butene formation.
C5 selective
hydrogenation Total saturation
Steam cracking can produce pentenes at over 130 kg per MT The yield of C4 and C5 unsaturates from ethane and
of ethylene produced from liquids cracking, depending upon propane is normally less than 100 kg per MT of ethylene
cracking severity and feedstock. After the first stage of produced. Many ethylene plant operators prefer to saturate
pyrolysis gasoline processing, the pentenes rich distillate may and recycle back to the cracker instead of shipping offsite for
contain up to 1% dienes which must be reduced to 100 ppm further processing.
or less via selective hydrogenation for most downstream
Cracker feeds should contain less than 5% unsaturates in
processes.
order to maximise ethylene yield and minimise heater coking.
Our range of PRICAT PD catalysts cater for different LPG products should contain less than 0.5% unsaturates.
applications and customer requirements, our technical
We support our customers in catalyst selection for total
service team discuss these with each customer and advise on
saturation duties by considering the feed composition and
which of the range would be most suitable for the desired
operating parameters, we then determine the optimal
C5 duties.
catalyst from the PRICAT PD or HTC ranges shown below

C5 selective hydrogenation catalysts Total saturation catalysts


PRICAT PD HTC NI PRICAT PD PRICAT PD PRICAT PD HTC NI
309/5 400 RPS 469 309/4 469 500 RP
Active metal Pd Ni Pd Active metal Pd Pd Ni
Promoted no no no Promoted no no no
Size (mm) 2.5 2.5 2-4 Size (mm) 2.5 2-4 1.2
Shape trilobe trilobe sphere Shape trilobe sphere trilobe
extrudate extrudate extrudate extrudate
Support alumina alumina alumina Support alumina alumina alumina
PRICAT PD 309/5 is formulated for operation in high LHSV situations. PRICAT PD 309/4 is formulated for operation in high LHSV situations.
HTC NI 400 RPS is ideal for high sulphur and high contaminant feeds. PRICAT PD 469 is a versatile palladium catalyst.
PRICAT PD 469 is a versatile palladium catalyst. HTC NI 500 RP is ideal for high conversion applications where the
product must be sulphur free.
Pyrolysis gasoline
Gasoline can be a major by-product of steam cracking. The yield, which depends on cracking severity and feedstock, can be
over 690 kg per MT of ethylene produced from liquids cracking.

Raw pyrolysis gasoline contains a high level of unsaturated hydrocarbons (olefins and aromatics) making it an excellent source
of aromatics and high octane gasoline components, but it must be hydrotreated before further processing. Eliminating
acetylenes, dienes and aromatic olefins in this pyrolysis gasoline can produce a number of important benefits:

l improve the induction period and colour

l reduce gum content of gasoline blending components

l reduce fouling in the downstream hydrodesulphurisation unit

HTC NI 200 is the leading nickel catalyst for all designs of pyrolysis gasoline hydrogenation units. HTC NI 400 is a higher activity
product to handle higher feed rates, more stringent product specifications, higher contaminant levels and higher olefin
saturation.

PRICAT PD 309/6 is a palladium catalyst formulated for operation in high LHSV situations whereas PRICAT PD 469 is a
versatile palladium catalyst for this duty.

Nickel vs. palladium


Two-thirds of all pyrolysis gasoline units were designed to operate with palladium catalysts. PRICAT PD 309/6 and PRICAT PD
469 offer simple activation, high aromatic selectivity and high olefin selectivity. Lower olefin saturation results in lower hydrogen
consumption and higher octane C5 and C9+ cuts. Enhanced olefin saturation is available with PRICAT PD 309/6 by
formulating with higher palladium content or operating at elevated temperature.

Pyrolysis gasoline catalysts


HTC NI HTC NI HTC NI PRICAT PD PRICAT PD
200 400 500 309/6 469
Active metal Ni Ni Ni Pd Pd
Promoted no no no no no
Size (mm) 2.5 2.5 2.5 2.5 2-4
Shape trilobe extrudate trilobe extrudate trilobe extrudate trilobe extrudate sphere
Support alumina alumina alumina alumina alumina

HTC NI catalysts have an order of magnitude higher tolerance for heavy metals and sulphur in the feed than any palladium
based catalyst. There is no detectable aromatic loss with properly activated HTC NI catalysts.

HTC NI products come in four types to suit different activation situations. Once activated, all forms exhibit equally good
performance characteristics. RPS catalysts are activated within the normal operating temperature range of the unit without the
addition of sulphur.

Types of HTC NI catalyst


OX OXS RP RPS
Reduction temperature high moderate low lowest
Sulphur addition standard none standard none
Phenyl acetylene
selective
hydrogenation
Steam cracking can produce over 35 kg of styrene per MT of
ethylene produced from liquids cracking, depending upon
cracking severity and feedstock.

The crude C8 cut may contain up to 1% phenyl acetylene


which must be reduced to 300 ppm or less, via selective
hydrogenation, prior to extractive distillation.

We offer PGM based PRICAT PD and base metal HTC range


for phenyl acetylene hydrogenation, the choice of product
below is determined by our technical service team who will
take into account the feed quality and performance
requirements of our customers.

Phenyl acetylene selective hydrogenation catalysts


HTC NI PRICAT PD
200 RPS 309/5
Active metal Ni Pd
Promoted no no
Size (mm) 2.5 2.5
Shape trilobe extrudate trilobe extrudate
Support alumina alumina
HTC NI 200 RPS is ideal for high sulphur and high contaminant feeds.
PRICAT PD 309/5 is formulated for higher selectivity in low sulphur feeds.
Feed purification
Feedstocks are being sought from alternate sources in order
to increase the profitability of plants. These feedstocks bring
with them new contaminant challenges.

Mercury is found in an ever-increasing number of


hydrocarbons worldwide. The level of mercury can vary
significantly depending on location. The situation is made
more complex in refineries and petrochemical plants, as
liquid feedstocks can contain elemental, organic and inorganic
species.

Complete removal of mercury is advisable to avoid


catastrophic failures in cryogenic equipment, to prevent
poisoning of process catalysts and for health and safety
reasons.

Crude olefin streams from refinery sources can bring elevated


levels of carbonyl sulphide, chloride and arsine which can
affect the performance of catalysts and equipment.

The new generation of PURASPEC absorbents have been


shown to give effective removal and long life without
impacting product quality.

PURASPEC series for olefin plant feed purification


Mercury COS Arsine Chloride H2S and COS
removal conversion removal removal removal
LPG feed PURASPEC PURASPEC PURASPEC PURASPEC
5158 5312 5110 5040
Naphtha, condensate PURASPEC
5158
Import ethylene PURASPEC PURASPEC
3110 3020
Import propylene PURASPEC PURASPEC PURASPEC PURASPEC
7312 7151 7110 7085
C3 and C4 fraction PURASPEC
7168

The above table contains a sample of materials available for purification duties. We will provide advice on which products are most suitable for
individual applications.
Methanation
Hydrogen produced as a by-product of ethylene production KATALCO 11-4 is the widely suitable replacement catalyst
contains 500 to 5,000 ppm carbon monoxide. The for all designs of methanators. KATALCO 11-4M provides
concentration of carbon monoxide must be reduced to less higher activity for higher GHSV operation with a slight
than 10 ppm prior to use in reactors containing palladium or increase in pressure drop.
platinum based catalysts. The most common method of
The pre-reduced catalysts KATALCO 11-4R and 11-4MR
carbon monoxide reduction is nickel catalyst based
have been reduced and stabilised with an oxide layer which
methanation. Purification using pressure swing adsorption,
makes the catalyst stable in air and prevents further re-
cryogenic ethane wash and low temperature ruthenium
oxidation. These catalysts require no activation stage and
catalysts are also used.
initiate methanation at maximum activity as soon as reaction
conditions are established.

Methanation catalysts
KATALCO KATALCO KATALCO KATALCO
11-4 11-4R 11-4M 11-4MR
Active metal Ni Ni Ni Ni
Promoted yes yes yes yes
Size (mm) 5.4 x 3.6 5.4 x 3.6 3.1 x 3.6 3.1 x 3.6
Shape tablet tablet tablet tablet
Support refractory oxides refractory oxides refractory oxides refractory oxides
Pre-reduced no yes no yes

Monomer purification
Several PURASPEC products have been developed to meet the most demanding purity requirements of polyethylene producers,
polypropylene producers and other users of high purity ethylene and propylene.

We can provide a full range of products to ensure an economic purification solution.

PURASPEC 3020 Hydrogen sulphide is reduced to less than 0.1 ppm

PURASPEC 3410 Acetylene is reduced to less than 0.5 ppm in a bed

A small amount of hydrogen is added to effect the reaction

PURASPEC 3450 Carbon monoxide is reduced to less than 0.1 ppm by operating in the oxide form

Oxygen is reduced to less than 0.1 ppm by operating in the reduced form

PURASPEC 7110 Hydrogen chloride is reduced to less than 0.1 ppmw

PURASPEC 7312 Carbonyl sulphide is converted to hydrogen sulphide to facilitate sulphur removal.

A small amount of water is added to the feed to effect this reaction

PURASPEC 7040 Hydrogen sulphide and carbonyl sulphide are reduced to less than 0.1 ppmw total sulphur

PURASPEC 7151 Arsine is reduced to less than 50 ppbw


For further information on Johnson Matthey Chemical Catalysts, contact your local
sales office or visit our website at www.jmprotech.com. HTC, KATALCO, PRICAT and
PURASPEC are trademarks of the Johnson Matthey Group of companies.
.
Headquarters: Other offices worldwide:
Hertfordshire, UK for contact details please visit
Tel +44 1763 253031 www.jmprotech.com/locations

chemcat@matthey.com
© Johnson Matthey Group
www.jmprotech.com 2014/JM/1014/1/olf