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2OOO

PUSRI- IIB PROJECT


MTPDAMMONIA& 2750 MTPDUREA trg
PRODUCTBROCHUREHYDROTREATER
CATALYST(101.D)

CLARIANT=

PT.CLARIANTKUJANGCATALYSTS

OWNER PT. PUPUKSRIWDJAJAPALEMBANG


CONTRACTOR CONSORTIUM .
OF PT.REKAYASAINDUSTRI
TOYOENGINEERING
CORPORATION

PROJECTTITLE PUSRI- IIB PROJECT

LOCATION PALEMBANG,
SOUTHSUMATERAINDONESIA

JOB NO. 12-1812I 8A1066

ITEMNO 101-D

PO NO P2B-10-00-PO-02/LR

EQUIPMENT
NAME. HydrotreaterCatalyst

DOCUMENTNO. 101D.01-KSC
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1 3 Oct.2014 lssuedfor lnJormation IKH


0 21 April 2014 lssuedfor lnformation IKH RH
REV.NO. DATE DESCRIPTION PREPD CHKD APPVD
Sheet 1 of I

JOBNO.: l2-1812/ BAl006 REV


PRODUCTBROCHUREHYDROTREATER
CATALYST
DOC. NO- : 101D-01-KSC
V
(101-D) DATE BY CHKD
3 ocl.2014 IKH RH

REVISION
HISTOR]CAL
SHEET

Rev.No. Date Description

0 21 Aptil 2014 lssuedfor lnformation

1 3 Oct.2014 lssuedfor lnformation


Product Bulletin

Issue, April 2014


PUBLISHER
PT. CLARIANT KUJANG CATALYSTS
CONTACT
For further information or
support, please contact
sales@clariant-kujang.com

Catalyst for
HYDRODESULPHURIZATION
Catalyst for
Hydrodesulphurization
HDMax@ 200

CONTENT

General ............................................................................................................................. 1

Product features................................................................................................................ 1

Applications ...................................................................................................................... 2

Poisons ............................................................................................................................. 4

Technical services ............................................................................................................. 4

Guarantees ....................................................................................................................... 5

Shipping information ........................................................................................................ 5

What is precious to you?


GENERAL
The hydrogenation catalyst is a cobalt molybde-
num or nickel molybdenum catalysts, which are
commonly referred to as CoMo and NiMo
catalysts, respectively. The hydrogenation
catalysts used in hydrogenation services in the
pretreatment systems of syngas plants as well as
widely used in refinery operations.

The CoMo catalysts exist in several formulations


with respect to the cobalt and molybdenum
content. The CoMo catalyst as presented in this
brochure, has been particularly developed and
utilized in the hydrodesulphurization and olefin
saturation of hydrocarbon feeds to steam
reforming units.

The Clariant Group (fomerly: Süd-Chemie) has


been supplying CoMo hydrogenation catalysts to
industry since the 1950´s. This operating
experience makes our company uniquely qualified
to provide the best products available. HDMax@
200 is one of CoMo catalyst produced by Clariant.
The original name is C49-1. Replacing product
name was done in line with Clariant’s simplifying
product nomenclature in order for the customer to
more easily recognize the products and their
usage.

PRODUCT FEATURES
The HDMax@ 200 catalyst contains cobalt and
molybdenum oxides as active component. It is
used to react hydrogenete organic sulfur such as
mercaptan, sulfide, disulfide and carbonyl sulfide.

HDMax@ 200 has blue appearance, no odor,


insoluble in water and the melting point is more
than 800oC. It is negligible fire and explosion
hazards when exposed to heat or flame by
reaction with incompatible substances. The
catalyst is formed in CDS extrusion form with size
of 1.5 and 3.2 mm diameter. The selection of the
size depends on the particular application. The
higher activity of the smaller dimension and
possible smaller bed size has to be considered
against the relatively higher pressure drop.

PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group 1


HDMax @ 200 visualization The chemistry of sulfur removal by zinc oxide is
basically carried under equilibrium reactions as
follows:

ZnO(s) + H2S ===== ZnS(s) + H2O


ZnO(s) + COS ===== ZnS(s) + CO2

The ActiSorb S 2 either used alone, or in


combination with other desulphurization systems,
such as after ydrodesulphurization unit. It is
mainly used to remove sulfur from hydrocarbon
feedstock to steam hydrocarbon reforming units
beside sulfur removal in synthesis gas; raw
natural gas; CO2, N2, helium and argon streams;
and coal gasification streams, etc.

FEED RANGE

It is necessary for correct function of the


The HDMax@ 200 catalyst is manufactured to give downstream hydrocarbon steam reforming
an optimum combination of low bulk density which catalysts (nickel) that the feed is clean of sulfur
is equal to a high surface area and high crush and that the hydrocarbon is fully saturated to
strength to ensure maximum activity and life. avoid carbon formation. All the sulfur compounds
Physical integrity is particularly important with the in the feed are converted to H2S over the CoMo
catalyst as it can be regenerated (in situ or catalyst and the H2S is removed by adsorption in
externally) several times during its service life. The a downstream zinc oxide system before the feed
HDMax@ 200 catalyst can have a service life of over passes to the steam reformer. The feed to the
10 years when operating on natural gas feeds. reforming unit may consist of any of the following
hydrocarbons:
▪ Natural gas
Typical properties of HDMax® 200 ▪ LPG
▪ Off gases
▪ Naphtha

Nominal Content, wt% HDMax® 200

The HDMax@ 200 catalyst can be applied in


CoO 3-5 purification of all above feeds.

MoO3 9 - 11 Organic sulphur compound - In this service,


HDMax@ 200 catalyst is placed upstream of a zinc
Aluminate Balance
oxide system, where the sulfur removal is
Bulk density, kg/liter 0.45 completed by the adsorption of the H2S by the
zinc oxide. Typical reactions involved are:
Shape CDS Extrusion

Size, mm 1.5, 3.2 R-SH + H2 ----------- -H + H2S


R-S-R´ + 2H2 --------- -H + R´-H + H2S
R-S-S-R´ + 3H2 -------- -H + R´-H + 2H2S
COS + H2 --------- 2S
CS2 + 4H2 --------- 4 + 2H2S
C4H4S + 4H2 ---------- 4H10 + H2S
APPLICATION
Sulfur compounds are poisons of most of the Saturation of olefines - this application is also
catalysts used in ammonia, hydrogen, and particularly referenced to steam reforming units,
methanol plants, or of those used to process where the hydrocarbon feed like LPG or off gases
refinery streams. Sulfur compounds also must be may contain small levels of unsaturated
removed from commercial streams such as carbon hydrocarbons. It is necessary to avoid passage
dioxide, nitrogen, helium and argon, coal
gasification streams, or from high sulfur natural of these olefins to the steam reformer as they
gas streams before putting the natural gas into will generate undesirable carbon deposition
distribution lines. on the reforming catalyst. The olefin

PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group 2


saturation reaction over the HDMax@ 200 The hydrogen is normally supplied by recycle from
catalyst is as follows: the methanator outlet in the steam reforming
plant and, in case of ammonia plants, can also be
recycled from the first stage syngas compressor or
R-C=C-R´ + H2 ---------- -CH-CH-R´ purge gas recycle. The hydrogen levels given here
can be considered minimum but normally an
A specific CoMo hydrogenation system may be a adequate requirement for efficient hydrode-
combination of the above two applications sulfurization in a stable operation. If, however,
depending on the nature of the feed stream. there is a possibility of occasional peaks of
thiophenes in the feed, it may be prudent to use a
higher hydrogen content to ensure full hydro-
Oxygen removal – the HDMax@ 200 catalyst may
desulfurization.
also be used for hydrogenation of oxygen according
to reaction as follows:

O2 + 2H2 ---------- 2O
Hydrogenation of organic sulfur compounds,
liquid phase - liquid feeds such as naphtha often
contain high levels of sulfur, e.g. 100 ppm-wt, and
Liquid phase application - the majority of these it is therefore impracticable to handle such a feed
pretreatment systems are in the gaseous phase, but in a standard CoMo/ZnO system. The zinc oxide
the HDMax@ 200 catalyst may also be used in bed would have to be of very large proportions and
hydrodesulfurization of liquid hydrocarbon feeds. A have to be changed out frequently. In this case
liquid phase application normally implies relatively the desulfurization system contains an inter-
high sulfur levels in the feed and a multi stage mediate washing system and would be typically:
purification system may be required. • CoMo hydrodesulfurization - stage 1
• Washing system for bulk H2S removal
• CoMo hydrodesulfurization - stage 2
• ZnO for final H2S removal
OPERATING CONDITIONS

Typical design parameters for operation of HDMax@


200 catalyst applications are given as below. Typical operating conditions are:
However, recommendations should be requested • Temperature: 250 - 400°C
from our Technical Service Department for a • H2 partial pressure : 4 - 5 bar
specific application as optimization of the operation • LHSV - Stage 1: 6 - 10 m3/m3/h
will depend on: Stage 2: 2 - 4 m3/m3/h
▪ Feedstock composition
▪ Sulfur types For the hydrodesulfurization of the first stage, i.e.
▪ Unsaturates level etc. with high S-concentrations, we recommend to use
Clariant Group´s C20 series of CoMo catalysts.

Hydrogenation of organic sulfur compounds, gas


phase – typical operating conditions are: Saturation of olefins - It is important to note
here that hydrogenation of olefins is a highly
exothermic reaction. For example:
Feed Temperature, SV, Pressure, • Temperature rise per 1% olefin in natural
Type oC Nm3/m3/h bar gas is 10oC.
• Temperature rise per 1% olefin in propane
is 8oC.
NG 250 – 400 up to 5000 < 60
LPG 250 – 400 up to 5000 < 60
If the concentration of the olefins in the feed is
Naphtha 250 - 400 up to 4 < 60
such that it is calculated that a once through
operation would exceed the catalyst temperature
Hydrogen must be present in the feed stream at the limit of 400oC, then control of the exotherm
following levels of: should be carried out by recycle of hydrogenated
▪ Natural Gas : product to dilute the unsaturates in the base feed.
P < 10 bar, then p(H2) > 0.35 bar
P < 20 bar, then H2 > 5 vol. %
P > 20 bar, then H2 > 2 vol. % Typical operating conditions are:
▪ LPG: p (H2) = 1 - 3 bar • Temperature : 250 – 400oC
▪ Naphtha: p (H2) = 4 - 5 bar • Space Velocity: 6000 – 8000 Nm3/m3/h
• Pressure: up to 60 bar

Within the above operating parameters, organic


Within the operation parameters given above the
sulfur levels in the feed will be reduced below 0.05 olefins in the feed will be reduced to less than 10
ppm-v and the hydrocarbon can therefore be ppm-v which is acceptable for the downstream
passed to the downstream zinc oxide vessel for final
steam reformer operation.
sulfur removal.

PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group 3


Temperature limits - the maximum operating can be formed via the reversed water-gas shift
temperature of the CoMo catalyst is normally set to reaction as follows:
400oC. Higher temperatures are liable to promote
cracking, particularly with heavier hydrocarbon CO2 + H2 ---- 2O; ∆H = 41 kJ/mole
feeds, leading to carbon deposition on the catalyst.
This carbon deposition reduces catalyst activity by
blocking active sites and also increases pressure Subsequently CO can be methanated as described
drop. above.

Presulfiding - thee standard application of


In service, it is good practice in order to increase HDMax@ 200 is the hydrogenation of natural gas
the life of the CoMo catalyst, to operate at the containing less than 20 ppm organic sulfur. In
lowest temperature consistent of course with this case no pretreatment of the catalyst is
satisfactory hydrogenation. As the service life of the required. When, however, natural gas with higher
catalyst extends, it will be necessary to raise the sulfur concentrations or heavy hydrocarbon
operating temperature. There will be no measurable feedstock is treated, it is strongly recommended to
temperature rise over the catalyst bed resulting presulfide the CoMo catalyst. The presulfiding
from the hydrodesulfurization reaction alone. operation transforms the cobalt and molybdenum
oxide to the metal sulfides. The advantages of the
sulfided catalyst are:
Low rate operation - at low feed rates there is a
possibility of hydrocarbon cracking on the walls of
the pre-heat coil before the CoMo catalyst reactor. • Maximum and immediate activity
This cracking can form unsaturated hydrocarbons • Reduced potential for cracking of higher
that will then be hydrogenated over the CoMo hydrocarbons or olefins
catalyst with consequent temperature rise over the Reduced tendency for methanation reaction.
catalyst bed. Plant personnel should be well aware •
of this possible condition and therefore immediately
take remedial reaction (i.e. increase flow rate or
reduce inlet temperature) to avoid bed
temperatures in excess of 400oC.
POISONS
The CoMo catalyst is normally the first catalyst in
the plant stream and therefore tends to filter out
Gases containing carbon oxides - the highly
any dust and solid particles in the feed in the top
exothermic methanation reaction can occur over
of the catalyst bed. This results in increased
CoMo catalyst with a feed containing levels of CO
pressure drop and to some extent also a loss in
and/or CO2 over about 5 vol. % each.
activity as the solids not only block the active
sites of the CoMo but also promote channeling.
CO+ 3H2 ---- 4+H2O; ∆H= -206 kJ/mole The pressure drop may become important enough
CO2+4H2 ---- 4+ 2H2O; ∆H= -165 kJ/mole that it will be necessary to take out the top layer
of catalyst and screen/replace with new catalyst.
Heavy metals in the hydrocarbon feed are virulent
The temperature increase is approx. 75oC per % CO
poisons for CoMo catalysts and will rapidly reduce
and 60% per % CO2 reacted. Besides the
activity for the hydrogenation reaction.
concentration of carbon oxides, the H2 partial
pressure is the most important parameter to
estimate possible methanation reaction. The
following table shows the fraction of reacting CO as
function of the H2 partial pressure:
TECHNICAL SERVICES
H2 partial pressure, bar % CO methanated Clariant Group firmly believes that even an
outstanding catalyst may not provide the best
performance without the appropriate level of
Less than 2 0 assistance during the phases of selection,
2-4 25 installation, start-up and operation. Within our
4-6 25 – 50 Technical Service Group, we have a wide range of
More than 7 More than 50 personnel with specific expertise in the areas of
catalyst characterization, research, catalyst
installation, start-up, plant operation, and
performance evaluations.
Below a H2 partial pressure of approx. 3 bar
normally no methanation reaction is observed. In
any case, however, the methanation is limited by This depth of knowledge allows us to provide the
the equilibrium conversion which is in the range of following services such as:
50% conversion under normal operating conditions.
In case of high CO2 and H2 partial pressures CO

PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group 4


▪ Review of reactor system design
▪ Selection of proper catalyst
▪ Technical reviews of start-up/shutdown
procedures
Technical assistance for loading, catalyst
▪ start-up and shutdown
Routine performance evaluations
▪ Trouble shooting
▪ Catalyst life projections
▪ Chemical and physical analyses of spent
catalyst

GUARANTEES
Clariant grants to the user process performance
guarantees covering the performance of its HDMax@
200 catalyst. Before granting such performance
guarantees, the design conditions and/or
anticipated operating conditions must be reviewed
and guarantees will be given based upon Clariant’s
design kinetic system.

SHIPPING INFORMATION
Shipments are made in steel drums with the
standard capacity of 200 and/or 208 liter per
drum.

PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group 5

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