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Effective October 7, 2004, Porocel has expanded into the catalyst services

market, representing three facilities previously owned by CRI International


(Louisiana-USA, Luxembourg and Singapore). Now, in addition to
offering our well established line of activated aluminas and inert bed
supports, we add the following services for our refining and petrochemical
industry customers:
State-of-the-art catalyst regeneration, featuring our groundbreaking
optiCATsm and revolutionary optiCAT Plussm processes
Unique ex situ catalyst presulfurizing, using our proprietary actiCAT
process
High quality regenerated catalyst resale
Advanced, patented length and density grading

The attached article (originally created by CRI) provides more detailed


information regarding our new products and capabilities. While the name
has changed, the commitment to technology, quality and value hasnt. With
three strategically located plants, were ideally positioned to service your
needs anywhere in the world.
Please visit our web site at www.porocel.com to learn more about our
Catalyst Services business and the other fine products and services that
Porocel offers.

REGENERATED
CATALYST PERFORMANCE
In an industry where cutting costs can make a competitive difference,
and environmental regulations are tightening, Patrick Gripka and Sal
Torrisi, CRI International, Inc., USA, consider the practical aspects
of reusing catalysts, in particular the effect of arsenic and
vanadium on regenerated catalyst performance.
riven by cost pressures and increasingly stringent
environmental legislation, refiners use of ex-situ catalyst regeneration continues to grow. Refiners continue to add hydroprocessing capacity to meet lower product sulfur specifications, while stricter regulations on the
disposal of spent catalyst are encouraging refiners to maximise reuse of catalyst.
With the increased use of regenerated catalyst, it is critical that refiners understand how the material will perform
relative to fresh catalyst, because the downside risk of poor
performance in a unit can quickly erase any benefits. CRI
does extensive testing of regenerated catalyst to ensure
that it will perform to expectations. This testing includes
measurement of catalyst physical and chemical properties
as well as directly measuring catalyst activity in a pilot
plant. CRI has fully equipped analytical laboratories at each
of its four plants worldwide, as well as automated four reactor Xytel pilot plants at research centres in Singapore and
The Woodlands, Texas, for evaluating catalyst performance.
Through this combination of analytical and performance
testing, CRI has been able to correlate the effect of two
common catalyst contaminants, arsenic and vanadium,
with regenerated catalyst performance.

on the catalyst surface. The rate and magnitude of coke


deposition is mainly affected by operating temperature,
hydrogen partial pressure and feed quality. Depending on
the feedstock and operating conditions, spent catalyst carbon concentrations can vary from <5 wt% to >30 wt%.

Catalyst deactivation
Hydroprocessing catalysts deactivate continuously
throughout an operating cycle. Reactor temperature is typically increased to compensate for the declining catalyst
activity until the end of run temperature is reached. The
predominant deactivation mechanisms are coking and poisoning. Other mechanisms can include fouling, pore blockage via coke or metals deposition, loss
of surface area, and active metals
agglomeration or collapse of the support via sintering. These mechanisms
can be grouped into two categories:
reversible and irreversible.

CRI uses 4-reactor Xytel pilot plants at its research


centres in Singapore and Texas to directly measure
regenerated catalyst performance.

Coking
One of the most common reversible
deactivation mechanisms is coking.
Active sites on the catalyst surface are
covered by carbon that is formed as the
feedstock is processed to remove sulfur, nitrogen and aromatic species.
There are many proposed mechanisms
for coke formation. One of the prevailing theories suggests that coke is
formed from intermediate reaction
products that condense or polymerise

Figure 1. Effect of arsenic on regenerated catalyst activity


(NiMo and CoMo hydrotreating catalysts).

HYDROCARBON ENGINEERING DECEMBER 1999

39

cult to assess the combined effects of


multiple poisons. Therefore, this article
will focus on the effects of single contaminants, arsenic and vanadium, on
catalyst performance.

Catalyst regeneration

Figure 2. Arsenic distribution on individual regenerated


NiMo catalyst pellets.

The catalyst regeneration process


eliminates the reversible deactivation
experienced during an operating cycle.
Coke contaminants can be effectively
removed from the catalyst by ex-situ
regeneration. This provides a controlled oxidation that removes the carbon and regulates catalyst particle
temperature. Effective temperature
control during regeneration is critical to
avoid irreversible damage like sintering
of catalytic metals, collapsing pores,
and reducing surface area. A regenerated catalyst that is relatively free of
metals poisons can usually be restored
to >90% of fresh catalyst activity.

Estimating
regenerated catalyst
performance
After shutdown, it is critical to quickly
assess the regeneration potential of a
representative cross section of spent
catalyst dumped from the unit. CRI typically performs laboratory scale regeneration on samples of the spent material and evaluates resultant physical
and chemical properties.
As ex-situ regeneration became
common in the late 1970s and 1980s,
a regenerated catalysts surface area
CRI analyses metals contaminants on spent catalyst using
recovery was used as the primary indiinductively coupled plasma spectroscopy (ICP).
cator of performance. However, both
the increase in complexity of catalysts
and the increased severity of the applications in which
Poisoning
these catalysts are used have made the regenerated cataCatalysts can also be subjected to irreversible deactivation
lyst evaluation process more difficult. Other physical propfrom permanent poisons, such as contaminant metals.
erties like pore volume, pore size distribution, bulk density,
These poisons degrade performance by occupying active
particle length distribution and crush strength are required
sites and blocking pores. Common contaminant metals and
to assist in the catalyst reuse evaluation process. The infortheir typical source are listed in Table 1.
mation in Table 2 describes the importance of these critical
There has been a general trend toward increased feed
catalyst properties.
metals contamination as refiners push for longer cycle
In many cases, physical and chemical properties alone
lengths while processing lower quality crudes. This results
are not enough to predict catalyst performance with a high
in higher contaminant metal levels on spent catalyst. The
enough degree of confidence. This frequently occurs when
metals tend to selectively deposit toward the reactor inlet
some physical and chemical property measurements narand diminish in concentration down the length of the bed.
rowly violate reuse criteria. In these situations, an activity
Depending on the severity of service and degree of feed
test using a hydrotreating pilot plant is required to more
contamination, the catalyst in the middle and bottom of the
accurately gauge catalyst performance.
catalyst system can often be regenerated and reused.
Not every metals contaminant deactivates the catalyst
Arsenic contamination
to the same degree. Some selective poisons like arsenic
Historically, very little data have been collected on the
greatly affect performance at low concentrations. This
effect of arsenic contamination on catalyst performance.
means that the contaminant is strongly coupled with the
Most prior data were developed from studies involving
active sites and not uniformly distributed across the catashale oil processing.
lyst surface. In other cases, contaminants like vanadium
More recently, CRI has observed an increase in arsenic
and nickel can concentrate at the entrance to catalyst
contaminated catalysts being evaluated for regeneration or
pores. The phenomenon of pore mouth plugging restricts
resale potential. This phenomenon is likely to be the result
molecular access to active sites, reducing the overall perof increased processing of both As containing crude oils
formance of the catalyst. Since the deactivation mechaand synthetic crudes generated from the processing of tar
nisms vary for different contaminants, it is extremely diffi40

HYDROCARBON ENGINEERING DECEMBER 1999

sands. In any event, the number of regenerated samples


evaluated by CRI was sufficient to develop a correlation for
both NiMo and CoMo catalysts. It is important to distinguish
the effects of both types of catalysts because catalyst functionality and processing objectives vary greatly for NiMo
and CoMo catalysts.
To quantify the effect of arsenic contamination on relative activity, only regenerated catalysts with good physical
properties and low levels of other contaminant metals were
examined. All performance data represents activity relative
to the fresh parent of the regenerated catalyst.
Table 1. Contaminant metals on hydroprocessing catalysts
Contaminant
Typical source
Silicon (Si)
Lighter boiling fractions from a coker
fractionator. Source of silicon is from
anti-foaming chemical addition.
Vanadium (V) and Nickel (Ni)
Naturally occurring in most crudes.
Typically concentrated in heavy VGO and
residuum boiling fractions or in heavy
products from a coker.
Arsenic (As)
Naturally present in many crude and
shale oils. Concentrated in lighter boiling
components.
Sodium (Na)
Found in many crudes. Poor crude
desalting can cause Na carryover to
hydroprocessing reactors.
Iron (Fe)
Often associated with the byproducts of
corrosion, but can also be naturally
occurring.

Table 2. Significance of catalyst physical properties


Catalyst property
Importance
Surface area
Regenerated catalyst surface area recovery is a
rough indicator of performance recovery. Absolute
surface area should not be used to compare
different catalysts.
Pore volume
Indicates available space within catalyst pores that
can be filled with coke and metals contaminants.
Pore size distribution Affects surface area, performance, stability and
ability to withstand contamination.
Bulk density
Increases with higher metals contamination
(higher particle density) and decreasing length
distribution (higher particle packing density).
Particle length
Assists in determination of catalyst losses and
distribution
expected unit pressure drop changes.
Crush strength
Indicates structural strength of catalyst particles
and tendency for breakage, which can result in
unacceptably high reactor pressure drop.

Table 3. Pilot plant test summary


CoMo evaluations
Feedstock properties
Straight run heavy gas
100
oil % by vol
Vacuum gas oil, % by vol
Light Cycle oil, % by vol
Gravity, API
32.0
Density @ 15 C, g/cc
0.8654
Sulfur, wt%
1.83
Nitrogen, wppm
386
GC distillation, C
IBP
172
10%
252
50%
315
90%
383
FBP
424
Operating conditions
Reactor inlet hydrogen
48
partial pressure, bar
Temperature, C
330
LHSV, hr-1
1.5
169
Treat gas rate, Nm3/m3

NiMo evaluations

34
67
21.5
0.9248
2.11
1145
138
327
509
69
330
1.5
337

HYDROCARBON ENGINEERING DECEMBER 1999

Arsenic deactivation on NiMo catalyst


The pilot plant activity data used to generate the NiMo
curves shown in Figure 1 are based on a single commercial hydrotreating catalyst. The data indicate that arsenic is
a fairly selective poison for NiMo catalysts; that is, it does
not take very high contamination levels to quickly reduce
catalyst performance. This is particularly true for the HDN
or saturation function of NiMo catalysts, which appear to be
very sensitive to arsenic poisoning. Regenerated NiMo catalysts with good physical and chemical properties and <0.2
wt% arsenic contamination may still provide acceptable
catalyst activity depending on the service requirements. In
general, any NiMo catalyst having contamination exceeding that level should not be reused.

Arsenic deactivation on CoMo catalyst


The CoMo activity data were generated using two different
commercial hydrotreating catalysts. The data show that the
effect of arsenic deactivation appears to be less selective
(but still significant) with CoMo catalysts, probably because
arsenic has a less inhibiting effect on desulfurisation reactions. Regenerated CoMo catalysts with good physical
properties but with higher levels (<0.4 wt%) of arsenic contamination can still provide acceptable catalyst activity.
In both the NiMo and CoMo evaluations, the question
arose regarding the homogeneity of and possible variation
of arsenic levels within a given sample. Was it possible that
a few highly contaminated pellets could skew the arsenic
levels, but have minimal impact on activity? To determine
the range of arsenic contamination within a sample, nine
catalyst pellets were randomly chosen from one of the
arsenic contaminated NiMo catalysts. As shown in Figure 2,
the range of arsenic contamination varied from 0.13 to
0.47 wt%. The average arsenic contamination of these pellets (0.28 wt%) agreed favourably with the arsenic contamination measured on the bulk composite sample (0.27 wt%).
The pellet analysis indicates that a range of arsenic contamination exists, but all particles appear to have measurable
levels of arsenic contamination. Thus, it does not appear
that a few highly contaminated pellets control the arsenic
level of the bulk catalyst system.

Vanadium contamination
Vanadium and nickel are much more common catalyst poisons than arsenic and affect catalyst performance in very
different ways. Vanadium and nickel appear together naturally, but since vanadium is typically higher in concentration
and is not a catalyst constituent like nickel, the author has
chosen to track vanadium for the purposes of this study.
Specific catalysts, called demet (demetallisation) catalysts, have been designed to capture vanadium and nickel
while also providing some catalytic performance for HDS
and HDN. These demet catalysts are commonly used in
guard and lead reactor beds, providing protection for downstream catalysts performing important HDS, HDN, HDCCR
and aromatic saturation functions. Demet catalysts are
usually disposed of following an operating cycle due to
heavy contamination, however the downstream catalyst
contaminated with much lower levels of vanadium are often
considered for reuse.
NiMo catalysts are predominant in units processing
vanadium contaminated feedstocks. CRI generated data in
Figure 3 represent performance of several different widely
used NiMo catalysts. In most cases, there were very low
levels of other metal contaminants so that the effect of
vanadium (and nickel) could be directly measured. All performance data represent activity relative to the fresh parent

41

alyst and activity maintenance should


always be considered when pre-existing
vanadium contamination is an issue.

Conclusion
To make good business decisions regarding
this disposition of spent catalyst, it is important to understand the quality of catalyst so
(1) reuse via regeneration can be determined and (2) placement in subsequent service can be made with confidence.
Using pilot plant activity data to assist
with evaluation of regenerated catalyst performance, a refiner can better determine
specifications for maximum acceptable
arsenic and vanadium contamination.
Generally speaking, specifications are:

Figure 3. Effect of vanadium on regenerated catalyst


activity (NiMo hydrotreating catalyst).
of the regenerated catalyst. Depending on the service
requirements, regenerated NiMo catalysts having <1 wt%
vanadium contamination with good physical and chemical
properties can still provide acceptable catalyst activity.
Placement of such catalysts in clean service having few
metals contaminants should be acceptable. Careful consideration should be given to placement of such catalyst in a
metals contaminated service. Catalysts having low levels of
existing contamination are frequently subject to pore mouth
plugging as they usually have a narrower pore structure
than demet catalysts. Initial catalyst performance is not
always the only criterion for placement of regenerated cat-

42

Arsenic < 0.4 wt% on CoMo catalyst


Arsenic < 0.2 wt% on NiMo catalyst
Vanadium < 1.0 wt% on NiMo catalyst

Refiners will need to assess their own


situation to set individual specifications using the data presented. CRI can provide assistance based on years of
experience in placing regenerated/resale catalysts with
many customers.

References
1.
2.
3.

NOWACKI P ed., 'Oil Shale Technical Data Handbook', Noyes Data


Company, 1981.
SPEIGHT J.G., 'The Chemistry and Technology of Petroleum', 2nd
edition, Marcel Dekker, Inc, 1991.
BUTT J.B and PETERSEN E.E., 'Activation, Deactivation, and
Poisoning of Catalysts', Academic Press, 1988.

Enquiry no: 18

HYDROCARBON ENGINEERING DECEMBER 1999