Technical Bulletin

FCC OFF-GAS
PROCESSING
Issue 1, January 2013

FOR CLARIANT CUSTOMER USE ONLY

PUBLISHER
CLARIANT INTERNATIONAL LTD
CATALYSTS

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4132 Muttenz
Switzerland
COPYRIGHT ©
CLARIANT INTERNATIONAL LTD

2013

CONTACT
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support, please contact
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 Technical Bulletin
FCC Off-Gas Processing

OLEMAX® SERIES CATALYSTS FOR OFF-GAS PURIFICATION

TABLE OF CONTENTS
Introduction ............................................................................. 3
Contaminant Removal Chemistry ....................................... 3
Process Configuration ............................................................. 8
OleMax Catalysts for FCC Off-Gas Purification ................... 10
History ................................................................................. 11
OleMax 100 Series Catalysts...............................................12
Operating Conditions for OleMax 100 Series Catalysts ........12
Operating Rate: GHSV ........................................................12
Temperature versus Sulfur Content ...................................12
Operating Pressure .............................................................13
H2 Concentration ................................................................13
Carbon Monoxide Concentration .......................................14
Nickel Carbonyl ...................................................................14
Metals ..................................................................................14
Operating Instructions for OleMax 100 Series Catalysts ...... 15
Loading Requirements ....................................................... 15
Reduction and Sulfiding ..................................................... 15
Start-Up .............................................................................. 18
Normal Operation .............................................................. 18
Bed Swapping ..................................................................... 20
Catalyst Regeneration ........................................................ 20
Vessel Entry .........................................................................21
Catalyst Disposal ................................................................ 22

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INTRODUCTION
OleMax 100 series catalysts offer a new, alternative method of economically
recovering light olefins such as ethylene and propylene from refinery off-gases . Fluid
catalytic cracking (FCC) off-gas processing converts hydrocarbon fractions of
petroleum crude oils to gasoline, olefinic gases, and other products. This new process
can be integrated into an existing olefin plant (that has FCC unit [FCCU] off-gas
available), where the recovered ethylene and propylene are then mixed with the
cracked gas in the compression train and separated using conventional distillation.

OleMax 100 series catalysts have been used successfully since the late 1950s to
selectively hydrogenate acetylene and other diolefins from raw gas ethylene feeds. The
selection of the correct OleMax 100 series catalyst to treat FCCU off-gas and other
refinery off-gases depends on the feed composition and available pressure. The
OleMax 100 series catalysts are sulfided nickel catalysts that are quite flexible and
can handle variations in both feedstock and poison levels.

A typical FCCU off-gas stream can contain several components: 5-15% ethylene, 5-
10% propylene, 5-20% hydrogen, 35-55% methane + ethane, up to 100 ppmw of
acetylene, up to 0.1% 1,3-butadiene, 500-2000 ppmw oxygen, 1-10 ppmw, and 1- 5%
nitrogen. Other impurities, such as H2S, COS, NH3, HCN, arsine, phosphine, stibine,
and mercury, are present in varying levels.

OleMax 100 catalysts remove nearly all of the poisons, via adsorption, to very low
levels. Acetylene is selectively hydrogenated to less than 1 ppm, and NOX and O2 are
removed. Since the feed already contains sufficient H2, no additional H2 is required
for reaction.

CONTAMINANT REMOVAL CHEMISTRY

In the production of high purity olefins from FCC off-gas, three purification steps are
required:

1. Complete removal of acetylene and a significant reduction of butadiene and

MAPD with high selectivity (i.e., low olefin loss).
2. Removal of NOX and O2 that are fouling precursors in the cryogenic (cold box)
section of an ethylene plant.
3. Absorption of trace levels of contaminants typically found in FCCU off-gas such as
arsine, phosphine, stibine, and mercury that permanently deactivate precious
metal catalysts in downstream processes.

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Selective Hydrogenation
Selective hydrogenation is the most commonly used process for the elimination of
acetylene during the production of ethylene.

CH ≡ CH + H2 → CH2 = CH2
∆H = −422 kcal/mol (1)
acetylene hydrogen ethylene

Selective hydrogenation is highly exothermic resulting in a temperature rise of

typically 33°C (91˚F) per 1% acetylene converted, depending on the feed composition
and temperature. The rate of reaction is directly related to the temperature and the
concentration of hydrogen. The reaction is suppressed by CO, sulfur, and other
contaminants in the feed.

In addition to acetylene, there may be methyl acetylene, propadiene, and butadiene in

the feed. These highly unsaturated compounds will also be selectively hydrogenated to
the corresponding olefin.

CH ≡ C − CH3 + H2 → CH2 = CH − CH3

∆H = −399 kcal/mol (2)
methyl acetylene hydrogen propylene

CH2 = C = CH2 + H2 → CH2 = CH − CH3

∆H = −414 kcal/mol (3)
propadiene hydrogen propylene

CH2 = CH − CH = CH2 + H2 → CH2 = CH − CH2 = CH3

∆H = −268 kcal/mol (4)
1,3-butadiene hydrogen 1-butene

Non-Selective Hydrogenation
Unfortunately, there are a number of side reactions which occur imultaneously with
acetylene hydrogenation. The most common is ethylene hydrogenation.

CH2 = CH2 + H2 → CH3 − CH3

∆H = −331 kcal/mol (5)
ethylene hydrogen ethane

This olefin hydrogenation reaction is also exothermic and typically results in a

temperature rise of 26°C (43˚F) per 1% ethylene converted, depending on the feed
composition and temperature. The rate of reaction is directly related to the

FCC OFF-GAS PROCESSING TECHNICAL BULLETIN | January 2013 Page 4 of 22

temperature and the concentration of hydrogen. The reaction is suppressed by low
concentrations of acetylene and CO. Other contaminants, like sulfur, also suppress the
reaction rate.

Other olefins (e.g., propylene and butylenes) may also be hydrogenated.

CH2 = CH − CH3 + H2 → CH3 − CH2 − CH3

∆H = −300 kcal/mol (6)
propylene hydrogen propane

CH2 = CH − CH2 = CH3 + H2 → CH3 − CH2 − CH2

∆H = −304 kcal/mol (7)
1-butene hydrogen n-butane

Oxide Reduction
Unlike steam crackers, FCC off-gas contains high concentrations of NOX and O2. The
concentration of these contaminants must be minimized for successful operation of
the cold box. Trace concentrations of nitric oxide and oxygen in the feed may lead to a
plugged cold box or the formation of explosive compounds.

Nitric oxide can be hydrogenated to ammonia over nickel catalyst at elevated

temperatures.

NO + H2 → NH3 + H2O
∆H = −54,300 BTU/mol (8)
nitric oxide hydrogen ammonia water

Oxygen is easily converted to water over nickel catalyst. This is a highly exothermic
reaction typically resulting in a temperature rise of 82°C (180˚F) per 1% O2 converted,
depending on the feed composition and temperature. This reaction accounts for most
of the temperature rise when processing FCC off-gas.

O2 + 2H2 → 2H2O
∆H = −192,000 BTU/mol (9)
oxygen hydrogen water

Non-Hydrogenation Reactions
Butadiene will dimerize and form green oil and polymers at elevated temperatures.

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m CH2 = CH − CH = CH2 → C4 − mH6m
(10)
1,3-butadiene oligomer

If heated to 315°C (600°F) or more, there are three different ways ethylene (and other
olefins) may react in the absence of hydrogen.

CH2 = CH2 → 2C + 2H2

∆H = −11 kcal/mol (11)
ethylene coke hydrogen

CH2 = CH2 → C + CH4

∆H = −30 kcal/mol (12)
ethylene coke methane

CH2 = CH2 → − CH2 − CH2

∆H = −33 kcal/mol (13)
ethylene polymer

The coke and polymer generated by these reactions will deactivate the catalyst. Coke
formed by ethylene decomposition cannot be completely removed by regeneration. In
extreme cases, these so-called “runaway” reactions can cause overheating of the
catalyst and the reactor vessel.

Ethylene Gain or Loss

Ethylene loss is defined as the amount of ethylene in the feed that is converted to
ethane. As a percentage, it is relative to the ethylene in the feed.

Ethylene Loss ≡ (14)

Calculation via this equation is not practical for operating plants because it is very
difficult to measure the difference in ethylene concentration between the inlet and
outlet of the catalyst bed. The small difference between the two ethylene
concentrations is statistically insignificant for spot readings.

Indirect Method: Concentration

A better method of determining selectivity is by measuring the change in the
concentration of acetylene and the reaction products between the inlet and outlet of
the catalyst beds.

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Ethylene Loss = (15)

This indirect method for calculating ethylene loss is very useful in a laboratory setting
because there is little or no ethane in the feed and the change in concentration can be
accurately determined. It is less useful on a commercial scale because the change in
the concentration of ethane between the inlet and outlet is small in comparison to the
absolute concentration. A similar method can be used for determining the selectivity
of the C3 and C4 selective hydrogenation reactions.

Ethylene loss can also be calculated from the hydrogen balance. However, calculation
via hydrogen balance is also not practical for operating plants because it is very
difficult to measure the difference in hydrogen concentration between the inlet and
outlet of the catalyst bed. The small difference between the two values of hydrogen
concentration is statistically insignificant for spot readings.

Indirect Method:Temperature Rise

Ethylene loss can always be calculated from the temperature rise for adiabatic
systems.

∆ T * Cp − ∆ Ac * ∆ H − ∆ MA * ∆ H − ∆ PD * ∆ H − ∆ BD * ∆ H − ∆ O * ∆ H
⎛ ⎞
mix Ac MA PD BD 2 O2 =
Ethylene ⎜ − ∆ Ac ⎟ ∆ C2 in (16 a )
Loss =
⎝ ∆H− ⎠
C2

The temperature rise method is normally used in commercial plants because

selectivity can always be calculated using available readings. It is, however, prone to
error because small errors in temperature measurements can cause large errors in
estimating the ethylene loss. Using typical values for heat of reaction and heat
capacity, equation 16a can be restated as:

⎛ ∆ T − ∆ Ac * 33 − ∆ MA * 31 − ∆ PD * 32 − ∆ BD * 21 − ∆ O2 * 82 ⎞ =
Ethylene Loss = ⎜ − ∆ Ac ⎟ ∆ C2 (16 b − C)
⎝ 25 5 ⎠

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 ⎛ ∆ T − ∆ Ac * 59 − ∆ MA * 55 − ∆ PD * 57 − ∆ BD * 37 − ∆ O2 * 148 ⎞ =
Ethylene Loss = ⎜ − ∆ Ac ⎟ ∆ C2 (16 b − F)
⎝ 46 ⎠

where the change in concentration is expressed in mol %.

PROCESS CONFIGURATION

Figure 1: Typical FCC recovery train

The incondensable gasses from the main fractionator is compressed and

processed in the absorber-stripper towers. The absorber recovers essentially all of
the gasoline, over 90% of the C4, and approximately 80% of the C3 produced by the
FCCU. The stripper is designed to reject all of the C2 and lighter in order to meet
the light ends specification of the propylene product. The remaining off-gas
(hydrogen, methane, ethylene, ethane, propylene, etc.) is typically routed to the fuel
gas system, losing any petrochemical value.

Many refinery operators have chosen to recover the ethylene, propylene, and
C4 in the off-gas. Two configurations currently in operation are described
below.

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Figure 2: Typical process configuration with OleMax 100 series catalyst

The off-gas is compressed and then treated to remove carbon dioxide, nitrogen
dioxide, and most of the sulfurous compounds.

The gas is then heated and passes across the catalyst bed. The hydrogenation catalyst
is OleMax 100 series, a sulfided nickel-cobalt-chrome catalyst. Sulfur must be added
to the feed to control the activity and selectivity of the catalyst.

− The catalyst converts acetylene, methyl acetylene, propadiene, and butadiene to

the corresponding olefins.
− A small portion of the ethylene is converted to ethane.
− Nitric oxide is converted to ammonia and oxygen is converted to water.
− The heavy metals are adsorbed on the catalyst. Any sulfur in the feed is converted
to ethyl mercaptan.

The product then enters a dryer that removes trace moisture, oxygenates, and CO2
before entering the cold box and fractionation train. The treated gas is separated to
produce a hydrogen rich product, a methane rich fuel gas, ethylene, ethane, and LPG.
The LPG is then routed back to the FCC fractionation train to recover the propylene,
propane, C4, and gasoline.

FCC OFF-GAS PROCESSING TECHNICAL BULLETIN | January 2013 Page 9 of 22

Figure 3: Typical process configuration with OleMax 250 series catalyst

The off-gas is compressed and then treated to remove carbon dioxide and nitrogen
dioxide, and most of the sulfurous compounds. The feed then enters a dryer which
removes trace moisture, oxygenates, and CO2 before entering the first catalyst bed.

The first catalyst is a silver on alumina catalyst, ActiSorb® 200 series. Oxygen is
converted to water across the catalyst bed. The heavy metals are adsorbed on the
catalyst along with trace sulfur.

The second catalyst is palladium on an alumina catalyst, OleMax 250 series. The
catalyst converts acetylene, methyl acetylene, propadiene, and butadiene to the
corresponding olefins. A small portion of the ethylene is converted to ethane.
Nitrogen oxides are converted to ammonia or amines.

The product then enters the cold box and fractionation train. The treated gas is
separated to produce a hydrogen rich product, a methane rich fuel gas, ethylene,
ethane, and LPG. The LPG is then routed back to the FCC fractionation train to
recover the propylene, propane, C4, and gasoline.

OLEMAX CATALYSTS FOR FCC OFF-GAS PURIFICATION

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 OLEMAX LEGACY YEAR ACTIVE
CARRIER
DESIGNATION NAME INTRODUCED METALS
8 mm Al/Si
101 C36-1-02 1950s Ni
sphere
8 mm Al/Si
102 C36-2-02 1950s Ni
sphere
8 mm Al/Si
103 C36-3-02 1950s Ni
sphere
4 X 4 mm Al2O3
250 G-83A 1976 Pd
tablet

Table 1: FCC off-gas purification catalysts

HISTORY
OleMax 100 series catalysts have been used successfully since the late 1950s to
selectively hydrogenate acetylene and other diolefins from raw gas ethylene feed. In
1976, the OleMax 250 series was introduced to address the need for lower
concentrations of acetylene in the product and longer cycle lengths with no loss of
ethylene over the cycle.

Ethylene plant operators are always looking for a lower cost feedstock and
FCC off-gas is a good option. However, processing this stream presents
special safety and product purity issues due to the NOX and heavy metals in
the gas.

The OleMax 100 product series of sulfided nickel catalyst has been in commercial
operation for FCC off-gas processing years and for processing FCC off-gas in
combination with cracked gas feeds for fifteen years. .

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OLEMAX 100 SERIES CATALYSTS
Three versions of the OleMax 100 series catalyst are currently in operation for FCC
off-gas processing:

OLEMAX 101 OLEMAX 102 OLEMAX 103

SIZE & SHAPE 8 mm sphere 8 mm sphere 8 mm sphere

3
DENSITY (KG/M ) 1120 1120 1120
CARRIER SA low low low
NICKEL CONTENT 2.0% 1.0% 0.5%

Table 2: OleMax 100 series catalyst properties

OPERATING CONDITIONS FOR OLEMAX 100 SERIES CATALYSTS

OPERATING RATE: GHSV

The design overall GHSV is normally between 2000 and 3000 Nm3/hr/m3 (2100 and
3200 scfh/ft3), depending on the concentration of contaminants in the feed and other
design criteria.

The operable range, which is the GHSV where product specification can be achieved,
is much wider. Operation significantly outside the design GHSV may result in poor
selectivity, and continuous operation above the design GHSV will result in shorter
cycles. The process should be configured to ensure that the feed rate is at least 70% of
design.

TEMPERATURE VERSUS SULFUR CONTENT

Figure 4 shows the general relationship between temperature and sulfur with respect
to apparent activity.

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Figure 4: Relationship between activity, temperature, and sulfur content

(A)⎯Below this point, temperature (about 185˚C [365˚F] for hydrogen sulfide [H2S])
controls the activity; higher temperature gives more activity. Sulfur addition generally
has a small effect on the apparent activity and selectivity. In this range, large
quantities of sulfur can act as a poison, causing a sudden drop in activity.

(B)⎯ The middle range allows control by both temperature and sulfur addition and
therefore the best control of selectivity.

(C)⎯ Above this point, the sulfur effect is stronger and increasing temperature can
reduce activity. The process is controlled by using temperature to generate sufficient
activity for C2H2 removal and sulfur injection to maintain selectivity and minimize the
ΔT and ethylene loss.

Over time the feed temperature is normally increased during the run to accommodate
a slow activity reduction as the catalyst ages.

OPERATING PRESSURE
The normal operating pressure of FCC off-gas reactors is 10-20 bar (150-300 psi). The
operating pressure is directly related to the design GHSV of the catalyst bed, the
potential formation of nickel carbonyl, and indirectly the choice of catalysts.

H2 CONCENTRATION
The concentration of hydrogen in the feed has a direct effect on the activity. The
appropriate catalyst version is selected based on the hydrogen partial pressure.

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CARBON MONOXIDE CONCENTRATION
The most important impact of carbon monoxide (CO) concentration is the potential
formation of nickel carbonyl .

NICKEL CARBONYL
Nickel carbonyl (nickeltetracarbonyl, Ni(CO)4) is formed when nickel is exposed to
carbon monoxide. Formation is favored at lower temperatures, elevated pressure, and
elevated concentrations of carbon monoxide. The equilibrium concentration of nickel
carbonyl is lower over sulfided nickel than reduced nickel; however, OleMax 100
series catalysts are operated in a partially sulfided form.

Nickel carbonyl is highly toxic. The NIOSH recommended exposure limit (REL) and
OSHA permissible exposure limit (PEL) is 1 ppb, or 0.007 mg/m3 TWA (as Ni).

The equilibrium concentration of nickel carbonyl in the process gas is less than 1 ppb
if the concentration of CO in the gas is less than 0.5%, the operating pressure is less
than 20 bar (275 psig), and the temperature is greater than 200°C (390°F).

There are other toxins in the process gas. The NIOSH REL for carbon monoxide is
200 ppm. The NIOSH REL for hydrogen sulfide is 10 ppm (15 mg/m3). Engineering
controls, operational procedures, and personal protective equipment all help to
prevent exposure to toxins in the process gas. The measures taken to prevent
hazardous exposure to carbon monoxide and hydrogen sulfide will also reduce the
exposure to nickel carbonyl.

Please contact your Clariant representative for carbon monoxide limits at different
operating pressures and temperatures.

METALS
FCC off-gas contains many volatile metals such as arsine (AsH3), stibine (SbH3),
phosphine (PH3), and mercury (Hg). These compounds will adsorb on the catalyst and
may be partially removed during regeneration. The feed may also contain trace
amounts of sodium due to caustic carryover from the acid gas unit.

OleMax 100 series catalysts are highly effective at reducing the concentration of
metals in the process gas to less than 5 ppb. In some cases, additional adsorbent is
required for heavy metal or other contaminant removal to avoid overloading the
OleMax 100. The additional catalyst also helps to protect downstream catalyst and
equipment. When the catalyst is saturated with permanent poisons, replacement with

FCC OFF-GAS PROCESSING TECHNICAL BULLETIN | January 2013 Page 14 of 22

a fresh load of catalyst is required. Catalyst life is based on the concentration of metals
in the feed and the catalyst type. Your Clariant representative can assist in estimating
the catalyst life for your application.

OPERATING INSTRUCTIONS FOR OLEMAX 100 SERIES CATALYSTS

Safety
All personnel involved in the use of the catalyst must thoroughly review the catalyst
safety documentation and loading procedures prior to proceeding with catalyst
installation. Proper handling and special protection information as described in the
Material Safety Data Sheet must be followed at all times. In addition, personnel must
comply with current applicable occupational health and safety standards.

Storage
Clariant catalysts are typically shipped in plastic lined steel drums or big bags.

Catalysts must be stored in a clean and dry environment. Although it is preferable not
to subject the OleMax 100 series catalysts to freezing temperatures during storage,
neither the physical structure nor the activity will be impaired by freezing as long as it
is kept free of moisture. OleMax series catalysts have essentially an unlimited shelf life
in covered, dry storage (although the packaging may deteriorate over time).

Inside storage of the catalyst is recommended; however, if outside storage of the

catalyst is necessary, the steel drums must be supported off the ground on pallets and
a suitable cover provided to protect the catalyst against precipitation. If the catalyst
has been exposed to moisture or stored for long periods, a dry out procedure is
recommended prior to start-up. This can be achieved as part of the reduction
procedure.

Rolling of the drums should be strictly avoided so as to avoid the creation of dust.

LOADING REQUIREMENTS
Please consult the General Loading document for details.

REDUCTION AND SULFIDING

Proper reduction and sulfiding of the catalyst is essential for high selectivity and long
cycle length. The vessel must be purged with nitrogen or an inert gas to remove
oxygen before introducing any hydrocarbons or hydrogen-containing gases.

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Reduction
The gas used for reduction must contain at least 25% H2, preferably over 50% in
purity. It should not contain more than 0.5% olefins, but may contain as much as 2%
if suitable precautions are made. The balance of the carrier gas may contain hydrogen,
nitrogen, methane, ethane, other paraffin, or steam (if catalyst is above condensing
temperature). It must be sulfur free (less than 10 ppm). The oxygen content must be
less than 100 ppm. The pressure can be from near atmospheric to several hundred
pounds, the only limiting factor being the vessel design at the reduction temperature
of 370-400˚C (700-750˚F). If the carrier gas is nitrogen and the flowrates are near
the lower limit mentioned below, it is recommended to first heat the catalyst bed to
370˚C (600˚F) and then begin the introduction of hydrogen.

The flow rate is normally over 500 GHSV, but must be over 200 Nm3/hr/m3 to avoid
channeling. Steam can be used with the reducing gas, if required, to increase the flow
to a minimum of 500 GHSV, but should not be added until temperatures are above
the dew point. Once flow of the reducing gas is established at the proper level, the
temperature can be raised at a rate of about 85˚C/h (150˚F/h). When the temperature
of any part of the bed reaches 315˚C (600˚F), temporarily stop raising the preheat
temperature of the reducing gas, but continue passage of the gas over the catalyst bed
for thirty minutes to one hour.

When it is observed that the reduction reaction is under control such that no point in
the catalyst bed exceeds 370˚C (700˚F), preheating may continue until the inlet bed
temperature reaches 315˚C (600˚F). Observe the catalyst bed temperatures as before.
Repeat at an inlet temperature of 340˚C (650˚F) or until it is observed that no
temperature rise due to reduction is occurring and then adjust the inlet temperature
of the reducing gas so the maximum temperature in the bed is about 370˚C (700˚F).
During the reduction, as the feed temperature is increased, a temperature rise will
pass through the bed at 15-30˚C (30-60˚F). The location of the thermocouples in the
catalyst bed sometimes limits the observance of the “heat wave”.

Sulfiding
The gas used for reduction should be used as the carrier gas for the sulfiding. Catalyst
temperature should be maintained at 370-400°C (700-750°F) and a gas hourly space
velocity of least 200 Nm3/hr/m3 (but preferably over 500). Add H2S or a sulfiding
agent like DMDS, TNPS, etc., for a concentration in the feed gas of 0.5-1 mol % sulfur.

To ensure complete sulfiding, pass a minimum of 115% of the theoretical sulfur

required. Table 3 shows the amount of sulfur as sulfur, H2S, and other popular

FCC OFF-GAS PROCESSING TECHNICAL BULLETIN | January 2013 Page 16 of 22

sulfiding agents. Continue sulfiding until the outlet concentration of sulfur is equal to
the inlet concentration.

OLEMAX 101 OLEMAX 102 OLEMAX 103

kg/m3 as S 14.1 7.0 3.5

H2S 94% 14.9 7.5 3.7

DMDS 68% 20.7 10.3 5.2

TBPS 55% 25.6 12.8 6.4

DMS 52% 27.3 13.6 6.8

EM 52% 26.8 13.4 6.7

Table 3: Sulfur Required (kg of sulfur per m3 of catalyst). To obtain values in lb of sulfur per ft3 of
3
catalyst, divide the value in kg of sulfur per m of catalyst by 16.0.

The time required to sulfide the catalyst depends on the sulfur addition rate, gas feed
rate, and the catalyst being sulfided. See Figure 6 for guidelines.

Figure 6 - Time required to sulfide the catalyst

After the desired quantity of sulfur has been added to the reducing gas at 370-400˚C
(700-750˚F), the catalyst can be cooled at a maximum rate of 80°C/h (150°F/h) with
H2 flow maintaining approximately 500 ppmv of H2S until maximum bed
temperature is approximately 300˚C (570˚F). Then, maintain 30-50 ppm H2S until

FCC OFF-GAS PROCESSING TECHNICAL BULLETIN | January 2013 Page 17 of 22

maximum temperature is 230°C (450°F). Sulfur must be maintained in the reducing
gas while cooling to operating temperature to ensure that sulfur is not stripped from
the catalyst. (Note: Steam/H2 flow can be used during the initial stages of cooling so
long as condensation is avoided by maintaining at least 30˚C (85˚F) above the dew
point. Then cooling should be continued with the H2 flow to a catalyst bed
temperature of 35-65°C (100-150°F) to ensure there is no condensation after the
reactor is blocked in.) Please check the metallurgy constraints of the vessel to
determine cooling rate.

START-UP
Note: Excessive catalyst temperatures during start-up will increase the time required
to reach on specification production and may cause damage to catalyst and
equipment.

The reactor is placed in operation by pressuring up with process gas and immediately
starting flow through the reactor at an inlet temperature of 200-210˚C (390-410˚F).
The method for introducing the feed varies based on equipment configuration,
therefore, general methods cannot be offered. Please contact Clariant Technical
Services for assistance.

NORMAL OPERATION
Catalysts change slowly over a period of weeks or months rather than hours. A sudden
change in C2H2 leakage or the ΔT is almost always due to an external change in feed
composition, sulfur levels, contaminants, temperature, pressure, etc. The difficult part
is identifying what has changed and returning to the previous values or adjusting the
operation to compensate. The basic controls are inlet temperature and the rate of
sulfur injection. The following measurements are needed to control the process.

Product Acetylene
Optimum selectivity is obtained when the operation is adjusted so as to allow 1-4 ppm
acetylene to exit the converter. Operation with 0 ppm at the exit will usually result in
larger losses of ethylene.

Butadiene Conversion
Operating data suggests that when the butadiene conversion is 30-50% then the
selectivity is optimized, even when the acetylene concentration in the outlet is less
than 1 ppm.

FCC OFF-GAS PROCESSING TECHNICAL BULLETIN | January 2013 Page 18 of 22

Sulfur Concentration
For control of the activity and selectivity, the OleMax 100 catalyst must be in the form
of nickel sulfide. It is essential that plants have the ability to sulfide the catalyst in situ
and to control the addition of small concentrations of sulfur (2-35 ppm) to the process
feed for control. Typically, higher levels of sulfur are needed at the start of run and
lower levels required at the end of run. Measurement should be frequent enough to
show the variation that occurs in the feed. If possible, the type(s) of sulfur in the feed
should be identified since different types of sulfur compounds have different
effectiveness in controlling the catalyst activity and selectivity.

Feed Temperature
The control of selectivity (by limiting activity) is achieved through inlet temperature
as well as sulfur addition. Inlet temperature is typically controlled in the range of 200-
215˚C (390-420˚F) and is usually increased during the cycle. An outlet temperature
above 260˚C (500˚F) increases the risk of cracking and carbon or polymer laydown.

Increasing the temperature typically increases catalyst activity. However, since it also
increases the effectiveness of the sulfur present in the feed, at higher inlet
temperatures it is possible to cause a decrease in activity with a corresponding lower
ΔT (see Figure 4). The ΔT is a useful indicator of the overall hydrogenation activity
and will change with variation of feed composition. It can be used with analysis of O2,
C2H2, C4H6, and MAPD to calculate any C2H4 loss.

Catalyst Aging
During operation there is usually a gradual loss of activity as polymer forms on the
catalyst. This can be compensated for by adjustments in temperature and sulfur
injection with resulting increased ethylene losses. The end of the cycle is usually
determined by loss of activity (high C2H2 leakage), loss of selectivity (high ΔT and
C2H4 loss with C2H2 leakage), or excessive polymer buildup (high ΔP). Typical cycles
for FCC off-gas processing are two to three years, after which the catalyst is
regenerated or replaced.

The variables affecting OleMax 100 activity and selectivity include the following:

FCC OFF-GAS PROCESSING TECHNICAL BULLETIN | January 2013 Page 19 of 22

BASIC OPERATION
GHSV
Temperature versus sulfur content
H2 concentration
Operating pressure
Carbon monoxide concentration
CYCLE LENGTH
Fe, As, Sb, Hg, and other impurities deposited
Catalyst aging
Carbon or polymer laydown

Some of these variables are not only difficult to change but are also interdependent
with others. In general, any factor that increases the apparent activity will decrease
selectivity.

BED SWAPPING
FCC off-gas processing units are normally installed without spare reactors. In order to
replace the catalyst while the plant is operating, it is necessary to cool down, bypass,
and depressure the reactors. For systems with a spare reactor, it is possible to swap
reactors and maintain on specification production while making the transition. Your
Clariant representative can provide operating guidelines based on your exact catalyst
type and bed configuration.

CATALYST REGENERATION
Based on our laboratory investigations of regenerating promoted nickel selective
hydrogenation catalysts, the following procedure is the best method to ensure
optimum performance of regenerated OleMax 100 series catalyst.

Warm-up & Steam-Out

It is desirable to use a dry gas (e.g., nitrogen) to heat up the catalyst bed to
approximately 150°C (300°F) to avoid condensation on the catalyst upon introduction
of steam. If steam is used for heat-up, condensation on cold catalyst could result in
leaching metal salts from the unreduced catalyst.

The flow direction is typically downflow. The flow rate is normally 150-300 GHSV.
The limits are based on bed configuration. Please consult Clariant Technical Services
for assistance.

The catalyst can be heated with steam at a maximum rate of 80°C/h (150°F/h) to a
catalyst bed temperature of 370-400°C (700-750°F). Please check the metallurgy
constraints of the vessel to determine heating rate.

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Steam the catalyst at 370-400°C (700-750°F) to remove most of the green oil. This
typically takes 6 hours.

Oxidation
For optimum regeneration (coke burn), all the catalyst bed temperatures should be in
the range of 385-400°C (725-750°F) before introduction of air. Maintain a steady
steam rate between 150-300 GHSV.

Introduce 1 mol % by volume air into the steam. A temperature rise of 60°C (110°F)
should be observed due to heat of reaction. Initial introduction of the air should take
place at a low rate to avoid uncontrolled heating in case the flow meters are inaccurate
or out of calibration. Note actual temperature rise versus expected.

As soon as the ΔT is noted and observed to be stable, increase the air concentration in
the steam in increments of ½% every 20 to 30 minutes, while carefully observing the
catalyst bed temperatures. Continue increasing air at the above defined rate until peak
bed temperatures exceed 450°C (850°F). The optimum peak bed temperature is 480-
500°C (900-925°F). If the peak bed temperature exceeds 510°C (950°F) then decrease
the air flow in ½% air-in-steam increments. If peak temperature exceeds 540°C
(1000°F), shut off air until all bed temperatures return to within 50°C (100°F) of the
steam temperature.

Maintain conditions and monitor bed temperatures, the temperature profile and the
effluent CO2 concentration. The catalyst bed TIs will fall slowly back to inlet steam
temperature starting at the top and progressing to the bottom. All bed temperatures
should return to within 5°C (10 °F) of the steam temperature and the measured CO2 in
the outlet should fall from ~0.4% to below 0.1%.

For a secondary burn, slowly raise the air flow to 100 GHSV. Monitor bed
temperatures and outlet CO2 for any signs of a burn. Slowly lower the steam flow
maintaining the steam-air mixture temperature to the reactor. Monitor bed
temperatures and outlet CO2 carefully, and reduce air flow if a burn is detected.

The oxidation is complete when the bed temperatures return to the inlet temperature
and no burn is detected.

VESSEL ENTRY
Note: The reactor vessel should be entered only after completion of the above
oxidation step. If vessel entry or catalyst removal is required, continue to cool catalyst

FCC OFF-GAS PROCESSING TECHNICAL BULLETIN | January 2013 Page 21 of 22

with N2 or air to 65˚C (150˚F) or as required by local rules and regulations.
Otherwise, proceed with reduction and sulfiding step as previously detailed.

CATALYST DISPOSAL
Used catalyst may have different hazards or properties than the original product.
Disposal of the catalyst must be done in compliance with current applicable
regulations. Also, there are reclaiming companies that recover metal components
from used catalyst. Please contact these companies regarding your particular
situation.

LIABILITY
The information contained herein does not constitute a guarantee. Because of technical manufacturing conditions,
deviations are possible.
This document is intended for use by persons having technical skill in accordance with their own independent
judgment and at their own discretion and responsibility. Although these instructions have been prepared by
experienced technicians and are based on the best available information derived from the laboratory, pilot-plant, and
commercial experience with this catalyst, these technicians do not have intimate knowledge of the customer’s plant
and operations. Therefore, Clariant, in issuing these instructions, cannot assume liability for any upsets to the
customer’s plant or personal injury or property damage. The customer is urged to review these instructions carefully,
to satisfy itself that their application will not be hazardous to his specific operations, and to assess whether or not or to
which extent to apply such instructions.
Furthermore, Clariant Technical Service representatives are present at plant start-ups in an advisory capacity only
and cannot be held responsible for hazardous conditions that might result from the application of instructions.

DISCLAIMER
This information corresponds to the present state of our knowledge and is intended as a general description of our
products and their possible applications. Clariant makes no warranties, express or implied, as to the information’s
accuracy, adequacy, sufficiency or freedom from defect and assumes no liability in connection with any use of this
information. Any user of this product is responsible for determining the suitability of Clariant's products for its particular
application.‫ ٭‬Nothing included in this information waives any of Clariant’s General Terms and Conditions of Sale,
which control unless it agrees otherwise in writing. Any existing intellectual/industrial property rights must be
observed. Due to possible changes in our products and applicable national and international regulations and laws, the
status of our products could change. Material Safety Data Sheets providing safety precautions, that should be
observed when handling or storing Clariant products, are available upon request and are provided in compliance with
applicable law. You should obtain and review the applicable Material Safety Data Sheet information before handling
any of these products. For additional information, please contact Clariant.

‫ ٭‬For sales to customers located within the United States and Canada the following applies in addition

NO EXPRESS OR IMPLIED WARRANTY IS MADE OF THE MERCHANTABILITY, SUITABILITY, FITNESS FOR A

PARTICULAR PURPOSE OR OTHERWISE OF ANY PRODUCT OR SERVICE.
®
Product and service marks protected by Clariant in many countries
© 2010 Clariant International Ltd, Rothausstrasse 61, 4132 Muttenz, Switzerland

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