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FCC MANUAL 5.

FCC CATALYST ANALYSES

SUMMARY

To monitor the quality of fresh catalyst deliveries to our customers, an extensive


analysis program is carried out. Test certificates are issued for each fresh catalyst
batch leaving Albemarle Catalysts’ production sites. Equilibrium catalyst analyses
are also carried out on a frequent basis, in order to monitor catalyst performance in
commercial operation and to optimize product yields and qualities.

The most important catalyst analyses are discussed in this section.

CONTENTS
1. Activity and selectivity
2. Metals analyses
3. Carbon on catalyst
4. Physical properties
5. Fresh catalyst analyses
6. Equilibrium services

1. ACTIVITY AND SELECTIVITY

A procedure to determine the activity of equilibrium or laboratory deactivated FCC


catalysts by means of a Micro Activity Test (MAT) has been developed and
standardized by the ASTM (ASTM D-3907). In the MAT test a sample of catalyst is
contacted with gas oil in a fixed bed reactor. Gas chromatographic analyses of gas
and liquid products are used to determine the yield structure (figure 1 shows an
Albemarle modified version of MAT testing, called MST).

Albemarle have adapted the MAT conditions of contact time and riser temperature to
simulate commercial results more accurately. The reactor has also been changed from
downflow fixed bed to a fluid bed reactor (figure 2). The modified Fluid-Bed
Simulation Test (FST) is widely used for customer service and performance
predictions. Since the official ASTM feed is no longer available, the FST uses
Kuwait VGO as a standard feed. Other companies using different feedstocks and
operating conditions in their catalyst activity testing units will likely report different
activity numbers and yields.

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Figure 1: Flowsheet of the Micro Simulation Test

Pump

Feed

Injection valve
Stripping
Nitrogen Sample

Feed line
Stripping line

Main water
Reactor supply

Furnace Gas
Collection
Balance
Product receiver

Figure 2: Current FST reactor configuration

The equilibrium catalyst (E-cat) samples are tested after burning off residual coke, by
calcination in air at 600 ºC, to avoid effects of varying amounts of remaining carbon.
Fresh catalysts are usually deactivated by steaming before activity is measured; a
typical procedure is 4 or 5 hours at 788 ºC in 100% steam. Other deactivation

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procedures have also been developed, to better simulate commercial deactivation.
Conversion, hydrogen and coke factors are reported on the E-cat analysis sheets,
though full FST yield distributions are available upon request.

MAT/FST Conversion (wt%)

The FST conversion, the indication of catalyst activity, is calculated from the mass
balance as:

% conversion = 100 – LCO – slurry = coke + gas + LPG + gasoline

The E-cat activity is measured at standard conditions of cat/oil ratio, contact time,
reactor temperature, and so on. It can be related to the commercial unit performance,
allowing the refiner to distinguish between catalyst activity effects and process or feed
quality influences. A detailed study of unit performance is needed to find the
optimum catalyst activity.

In general, a higher catalyst activity results in:

• improved conversions
• higher regenerator temperatures
• lower cat/oil ratios

Hydrogen Factor (HF)

The hydrogen factor is a relative number, proportional to the specific hydrogen yield.
Specific hydrogen is defined as:

Specific H2 = H2 yield x (function of FST conversion)

The hydrogen factor depends on the catalyst quality and is affected by the nickel (and
other metals to a lesser extent) deposited on E-cat. Only the trend of HF is important,
and it can be correlated with the H2/CH4 ratio in the FCC unit.

Coke Factor (CF)

The coke factor is also relative, proportional to specific coke, defined as:

Specific coke = coke yield x (100 – conversion) / conversion

Like the hydrogen factor, CF is affected by metals on the E-cat. The trend indicates
the contribution of the E-cat quality to the delta coke (coke on spent – coke on
regenerated catalyst) in the commercial unit. However, delta coke depends mostly on
the feed quality and catalyst activity. It can also be calculated from unit data as:

Delta coke = coke yield (wt% on feed) / cat/oil ratio

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2. METAL ANALYSES

Usually X-ray fluorescence spectrometry is applied to determine the metals content of


the catalyst. This includes the metals used in manufacturing the catalyst as well as
those deposited from the feed. Over 20 different metals are detected (standard is 21,
analysis for 23 metals is in development), although only the major metals affecting
performance are usually reported on the E-cat sheets. If needed, other metals can be
measured such as platinum, which is used to track amount of CO combustion
promoter.

Alumina (Al2O3, wt%)

Alumina is present in several components of the catalyst, such as zeolite, clay (kaolin)
and active matrices. The total alumina content is the result of the contributions of
each component. The alumina content of E-cat can often be used to calculate the
extent of replacement when switching to a catalyst with different alumina content.

Rare Earth (RE2O3, wt%)

The rare earth content of the zeolite indicates its hydrogen transfer activity. Higher
rare earth on zeolite enhances hydrogen transfer, reducing product olefinicity and
research octane of the gasoline. Cracking reactions are terminated by hydrogen
transfer, thus reducing overcracking from gasoline to LPG. Hydrogen transfer also
increases aromatization and coking. The RE content measured depends on zeolite
content in the catalyst. Specific activity (per m2/g surface area) generally increases
with the zeolite rare earth content.

Sodium (Na, wt%)

Small amounts of sodium (0.1-0.5wt%) are present in the fresh catalyst, from the
manufacturing process. Sodium can also be introduced by the feed, especially if resid
is processed. In case of high sodium levels on E-cat the feed quality should be
checked. Malfunctioning crude oil desalters, or processing of imported feeds
contaminated with seawater are the typical causes of high sodium levels.

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Deposited sodium is a catalyst poison with neutralizes acid sites and destroys zeolite.
Approximately 6 points of MAT activity are lost per wt% Na originating from the
FCC feed. At high levels the catalyst is also more sensitive to high regenerator
temperature, due to increased rates of sintering and surface area destruction (figure 3).
Eventually, plugging of cyclone diplegs may occur due to formation of low melting
point eutectics (with vanadium). High fresh catalyst addition rates are required to
recover from sodium poisoning.

Figure 3: Effect of sodium poisoning on E-cat surface area

Vanadium (V, ppm)

Vanadium enters with the feed and deposits on the E-cat. Under regenerator
conditions, vanadium is mobile and is able to enter the catalyst and destroy zeolite.
As a consequence, catalyst activity and conversion suffer. For conventional catalyst,
a rule of thumb is that two points of activity are lost per 1000 ppm V at constant unit
conditions. The deactivation rate depends strongly on temperature, and oxygen and
water vapor partial pressures in the regenerator, which enhance its mobility.

Nickel (Ni, ppm)

Like vanadium, Ni enters with feed and deposits on E-cat. Nickel is not mobile
however, and its primary effect is acting as a dehydrogenation catalyst. In the FCC,
nickel enhances non-selective cracking reactions that produce more hydrogen and
coke.

Antimony (Sb, ppm) or Bismuth (Bi, ppm)

Antimony is only present on E-cat if used as a passivator to reduce nickel


dehydrogenation activity. It is typically added at about 30 to 50% of the nickel
content to reduce hydrogen make. Excess addition will reduce platinum combustion
promoter activity as well. Bismuth is an alternative to antimony, somewhat less
effective on aged nickel, but equally as effective on freshly deposited Ni.

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Miscellaneous

Other metals may also affect catalyst performance. For example, iron and copper also
increase hydrogen make, while calcium and magnesium (found with sodium as salts
in seawater) affect catalyst activity and stability. Usually these metals are not present
in such concentrations that a significant impact on performance is noted. However,
iron is found to deposit preferentially on the catalyst surface rather than in pores, and
at higher concentrations will plug pore mouths and limit diffusion of hydrocarbons
into and out of the catalyst. Testing of such diffusion limitations is discussed under
section 4 below on physical properties.

The E-cat may also contain minor amounts non-metallic oxides, e.g., sulfur (S),
phosphorus (P), and elements like titanium (Ti), originating from the kaolin,
additives, or metal traps. The balance is usually silica.

3. CARBON ON CATALYST

In order to monitor the regenerator efficiency of an FCC unit, the residual carbon on
the regenerated catalyst is measured. In addition, the carbon on the catalyst flowing
from the reactor stripper to the regenerator (spent catalyst) can be measured, which
permits calculation of delta carbon, proportional to the delta coke level.

The carbon is burned to carbon dioxide, which is analyzed using an infrared detector.
Apart from measuring the carbon on regenerated catalyst (CRC), the carbon content
can be estimated by the refiner, by comparing the color of the E-cat with colors of
reference samples from the same unit.

High carbon levels on E-cat do not affect the measured activity, since samples are
tested after calcining. But a higher level does reduce the effective catalyst activity in
the unit, requiring higher C/O ratio to maintain conversion. At some level, yield
selectivities will also start to suffer.

4. PHYSICAL PROPERTIES

Surface Area (SA, m2/g)

FCC catalysts contain micropores smaller than 20 Ångstrom in diameter (2 nm) that
originate mostly from the zeolite, mesopores of 20-600 Å (2-60 nm), which provide
the surface area often referred to as matrix, and the macropores, which allow large
feed molecules to penetrate into the catalyst particle. The latter have negligible
amount of surface area.

Typical examples of nitrogen adsorption isotherms of FCC catalysts are illustrated in


figure 4, showing a so-called t-plot. This demonstrates the relationship between
volume of nitrogen adsorbed, and the average thickness of the adsorbed layer of
nitrogen (t) on the catalyst surface. From this plot, we obtain:

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• the intercept, which gives the micropore volume (PVmicro)
• the slope of the straight line, giving the mesopore surface (SAmeso)

Figure 4: Examples of nitrogen adsorption isotherms of FCC catalysts

These quantities are both reported, to allow identification of zeolite and matrix effects
in the E-cat data. The total SA of the catalyst is calculated with:

SA = 2178 x PVmicro + SAmeso

The surface area generally reflects the catalyst activity and has a strong effect on the
performance of the FCC unit (figure 5). However, when switching to a different
catalyst type, the surface area may not have the same proportionality to activity. High
surface area also increases adsorbed hydrocarbons, so more steam may be required in
the reactor stripper to compensate, and to keep delta coke and regenerator temperature
down.

Figure 5: Effect of equilibrium surface area on FCC performance

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Apparent Bulk Density (ABD, g/ml)

The apparent bulk density is determined by measuring the mass of a known volume of
catalyst, settled freely under its own weight. The apparent bulk density is important
for circulation and cyclone efficiency. A higher ABD generally means a higher
particle density, which would improve the separating efficiency of cyclones. The
effect on catalyst circulation is not clearcut, and depends on unit design and operation
as well as the particle size distribution.

Particle Size Distribution (PSD, wt%)

The particle size distribution is determined by laser light scattering, and is important
for monitoring the cyclone efficiency and catalyst circulation properties. If catalyst
losses and the average particle size (APS) of the e-cat are both increasing, a poorer
cyclone efficiency is indicated, and damaged (or plugged) cyclones are suspected.
This can be confirmed with PSD analyses of fines from the regenerator or reactor
cyclones showing increased amounts of material above 40 microns. Coarser E-cat is
also more difficult to circulate. If catalyst losses increase but APS is dropping, then
the cause may relate to:

• softer catalyst with poorer attrition resistance


• high velocities somewhere in the unit (hardware attrition source)
• increased fresh catalyst and/or fines addition

The PSD of fresh catalyst is important for fresh catalyst retention. The PSD of E-cat
is more affected by attrition factors and cyclone efficiency than by the fresh cat PSD.

Albemarle Accessibility Index (AAI)

FCC feeds have become heavier, while the time available for the heavier molecules to
diffuse into the catalyst, react, and products to diffuse back out has become less.
Diffusion of larger reactant molecules through the porous structure of the catalyst
particle to the reaction sites is now a more important factor in determination of the
overall reaction rate. In addition there must be sufficient time for the reaction
products to diffuse out of the catalyst particle, as efficiently as possible to prevent
overcracking to undesirable light products. The term accessibility is used to describe
this. Complicating this need for rapid diffusion into and out of the catalyst is
deposition of certain metals, especially iron, preferentially on the catalyst surface.
This will plug pore mouths and limit diffusion of hydrocarbons into and out of the
catalyst.

The increased need for information about mass transfer impacts has led to
development of the Albemarle Accessibility Index test (AAI). This test is a rapid
method to screen catalysts based on liquid phase diffusion of large organic molecules
into the particle. No reaction is involved, and only initial diffusion characteristics of
the specific catalyst are determined. The relative amount of specific UV-absorbing
molecules are tracked, the amount removed from the liquid solution by catalyst is
monitored. The initial slope of the removal rate establishes the AAI; larger values
indicate higher rates of diffusion and lower mass transfer limitations.

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For each unit and specific feed, there is some value of minimum acceptable AAI.
Below this critical value, there will be a rapid deterioration of product selectivity.

Figure 6: Rapid performance deterioration below a critical AAI value (4 in example)

Unit Cell Size (UCS, Ångstrom)

The Y-type zeolite used in FCC catalysts is a crystalline material built up from unit
cells, having a characteristic size. This size can be determined using X-ray diffraction
according to ASTM method D-3492. During deactivation of catalyst in the unit, the
cell size shrinks. The unit cell size for E-cat varies between 24.20 and 24.40 Å (2.42-
2.44 nm), while fresh catalyst cell size ranges from 24.40-24.70 Å. The unit cell size
is affected by the zeolite rare earth content and the zeolite stability. A high rare earth
zeolite will usually equilibrate to a larger E-cat cell size. As a consequence, the unit
cell size of fresh catalyst after a standard steam deactivation is an indication of its
hydrogen transfer activity (larger cell size = higher hydrogen transfer) and gasoline
octane / olefins content (larger = lower RON and olefins content). Other zeolite
properties also affect the unit cell size, so UCS alone is not a good predictor of
catalyst quality.

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5. FRESH CATALYST ANALYSES

Analyses that are normally only performed on fresh catalyst samples are loss on
ignition and attrition.

Loss on Ignition (LOI, wt%)

The loss on ignition is determined by measuring weight loss (mainly water) upon
heating at 600 ºC for one hour. The measurement is required because catalyst is sold
on a dry basis. In general LOI has no influence on catalyst performance. The
chemical analyses are usually expressed in terms of dry weight, whereas physical
properties are often determined after one hour of calcination at about 600 ºC.

Attrition Index (AI, wt%)

A sample of fresh catalyst is fluidized by high velocity air jets. In the process, wear
of the particles occurs as they are blown against each other and the wall at high
velocity. The fines generated are removed from the attrition zone and weighed.

A lower attrition index indicates higher attrition resistance. Low catalyst losses can
be expected under normal unit conditions with attrition index levels up to 10 wt%.

Such a test can also be performed on E-cat, if its attrition resistance is suspect. An
alternative test, for fresh or E-cat, is the Hot Attrition Test (HAT). Conducted at
700ºC (1292ºF), catalyst ranking by this test is often markedly different from the
ranking obtained by similar testing at room temperature. More important, the trends
from HAT closely follow trends in mass loss from actual FCC units. Particularly for
E-cat, which has been processed already in the regenerator at high temperature, the
HAT results should tally better with actual refinery experience of attrition and losses.

6. EQUILIBRIUM SERVICES

Customers of Albemarle’s FCC catalysts receive pre-addressed sample envelopes and


sample bottles that are used to send E-cat to the Catalyst Laboratories (USA or
Holland). The standard set of analyses as described above is performed on these
samples immediately after receipt of the sample. The full program including sample
pretreatment is normally completed in 24 hours for the standard analyses, including
the reporting service. Sample transport time by mail/courier and analyses times are
monitored and reported back to the customer to ensure service is adequate. Special
analyses, such as AAI, attrition index (AI or HAT), UCS, or Pt, can take longer.

When all analyses are available, email or other electronic means are used to provide
the data to the refinery and other locations, to inform those concerned with the FCC
unit performance. Monthly printouts are also made of the database to cover the to-
date analyses of the E-cat samples. The Technical Service Staff evaluates the
equilibrium analyses on a regular basis and gives feedback on the E-cat performance.

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On special request, other methods of transferring the E-cat database are available.
The file is based on a spreadsheet, which can be pulled into other similar programs. If
required, full FST data including the product yield distribution can be provided along
with the standard E-cat analyses. The Technical Service Staff assists in handling and
interpreting these data. Especially when looking for specific catalyst selectivity
changes, these data can be helpful. However, the unit data will always be the final
word.

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