ASTM D4463/D4463M-96(2012)e1
(Guide)Standard Guide for Metals Free Steam Deactivation of Fresh Fluid Cracking Catalysts
Standard Guide for Metals Free Steam Deactivation of Fresh Fluid Cracking Catalysts
SIGNIFICANCE AND USE
In general, steam treatment of FCC catalyst can be used either to compare a series of cracking catalysts at a simulated equilibrium condition or conditions, or to simulate the equilibrium condition of a specific cracking unit and a specific catalyst. This guide gives an example for the first purpose and an approach for the latter purpose.
SCOPE
1.1 This guide covers the deactivation of fresh fluid catalytic cracking (FCC) catalyst by hydrothermal treatment prior to the determination of the catalytic cracking activity in the microactivity test (MAT).
1.2 The hydrothermal treatment of fresh FCC catalyst, prior to the MAT, is important because the catalytic activity of the catalyst in its fresh state is an inadequate measure of its true commercial performance. During operation in a commercial cracking unit, the catalyst is deactivated by thermal, hydrothermal and chemical degradation. Therefore, to maintain catalytic activity, fresh catalyst is added (semi) continuously to the cracking unit, to replace catalyst lost through the stack or by withdrawal, or both. Under steady state conditions, the catalyst inventory of the unit is called equilibrium catalyst. This catalyst has an activity level substantially below that of fresh catalyst. Therefore, artificially deactivating a fresh catalyst prior to determination of its cracking activity should provide more meaningful catalyst performance data.
1.3 Due to the large variations in properties among fresh FCC catalyst types as well as between commercial cracking unit designs or operating conditions, or both, no single set of steam deactivation conditions is adequate to artificially simulate the equilibrium catalyst for all purposes.
1.3.1 In addition, there are many other factors that will influence the properties and performance of the equilibrium catalyst. These include, but are not limited to: deposition of heavy metals such as Ni, V, Cu; deposition of light metals such as Na; contamination from attrited refractory linings of vessel walls. Furthermore, commercially derived equilibrium catalyst represents a distribution of catalysts of different ages (from fresh to >300 days). Despite these apparent problems, it is possible to obtain reasonably close agreement between the performances of steam deactivated and equilibrium catalysts. It is also recognized that it is possible to steam deactivate a catalyst so that its properties and performance poorly represent the equilibrium. It is therefore recommended that when assessing the performance of different catalyst types, a common steaming condition be used. Catalyst deactivation by metals deposition is not addressed in this guide.
1.4 This guide offers two approaches to steam deactivate fresh catalysts. The first part provides specific sets of conditions (time, temperature and steam pressure) that can be used as general pre-treatments prior to comparison of fresh FCC catalyst MAT activities (Test Method D3907) or activities plus selectivities (Test Method D5154).
1.4.1 The second part provides guidance on how to pretreat catalysts to simulate their deactivation in a specific FCCU and suggests catalyst properties which can be used to judge adequacy of the simulation. This technique is especially useful when examining how different types of catalyst may perform in a specific FCCU, provided no other changes (catalyst addition rate, regenerator temperature, contaminant metals levels, etc.) occur. This approach covers catalyst physical properties that can be used as monitors to indicate the closeness to equilibrium catalyst properties.
1.5 The values stated in either SI units or inch-pound units are to be regarded separately as standard. The values stated in each system may not be exact equivalents; therefore, each system shall be used independently of the other. Combining values from the two systems may result in non-conformance with the standard.
1.6 This standard does not purport to address a...
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´1
Designation: D4463/D4463M − 96(Reapproved 2012)
Standard Guide for
Metals Free Steam Deactivation of Fresh Fluid Cracking
Catalysts
This standard is issued under the fixed designation D4463/D4463M; the number immediately following the designation indicates the
year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last
reapproval. A superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
´ NOTE—Updated units statement and made a combined standard editorially in April 2012.
1. Scope fresh to >300 days). Despite these apparent problems, it is
possible to obtain reasonably close agreement between the
1.1 This guide covers the deactivation of fresh fluid cata-
performancesofsteamdeactivatedandequilibriumcatalysts.It
lytic cracking (FCC) catalyst by hydrothermal treatment prior
is also recognized that it is possible to steam deactivate a
to the determination of the catalytic cracking activity in the
catalyst so that its properties and performance poorly represent
microactivity test (MAT).
the equilibrium. It is therefore recommended that when assess-
1.2 The hydrothermal treatment of fresh FCC catalyst, prior
ing the performance of different catalyst types, a common
to the MAT, is important because the catalytic activity of the
steaming condition be used. Catalyst deactivation by metals
catalyst in its fresh state is an inadequate measure of its true
deposition is not addressed in this guide.
commercial performance. During operation in a commercial
1.4 This guide offers two approaches to steam deactivate
cracking unit, the catalyst is deactivated by thermal, hydrother-
fresh catalysts. The first part provides specific sets of condi-
mal and chemical degradation. Therefore, to maintain catalytic
tions (time, temperature and steam pressure) that can be used
activity, fresh catalyst is added (semi) continuously to the
as general pre-treatments prior to comparison of fresh FCC
cracking unit, to replace catalyst lost through the stack or by
catalyst MAT activities (Test Method D3907) or activities plus
withdrawal, or both. Under steady state conditions, the catalyst
selectivities (Test Method D5154).
inventory of the unit is called equilibrium catalyst. This
1.4.1 The second part provides guidance on how to pretreat
catalyst has an activity level substantially below that of fresh
catalysts to simulate their deactivation in a specific FCCU and
catalyst. Therefore, artificially deactivating a fresh catalyst
suggests catalyst properties which can be used to judge
prior to determination of its cracking activity should provide
more meaningful catalyst performance data. adequacy of the simulation. This technique is especially useful
whenexamininghowdifferenttypesofcatalystmayperformin
1.3 Due to the large variations in properties among fresh
a specific FCCU, provided no other changes (catalyst addition
FCC catalyst types as well as between commercial cracking
rate, regenerator temperature, contaminant metals levels, etc.)
unit designs or operating conditions, or both, no single set of
occur. This approach covers catalyst physical properties that
steam deactivation conditions is adequate to artificially simu-
canbeusedasmonitorstoindicatetheclosenesstoequilibrium
late the equilibrium catalyst for all purposes.
catalyst properties.
1.3.1 In addition, there are many other factors that will
influence the properties and performance of the equilibrium
1.5 The values stated in either SI units or inch-pound units
catalyst. These include, but are not limited to: deposition of
are to be regarded separately as standard. The values stated in
heavy metals such as Ni,V, Cu; deposition of light metals such
each system may not be exact equivalents; therefore, each
as Na; contamination from attrited refractory linings of vessel
system shall be used independently of the other. Combining
walls. Furthermore, commercially derived equilibrium catalyst
values from the two systems may result in non-conformance
represents a distribution of catalysts of different ages (from
with the standard.
1.6 This standard does not purport to address all of the
This guide is under the jurisdiction ofASTM Committee D32 on Catalysts and
safety concerns, if any, associated with its use. It is the
is the direct responsibility of Subcommittee D32.04 on Catalytic Properties.
responsibility of the user of this standard to establish appro-
Current edition approved April 1, 2012. Published July 2012. Originally
priate safety and health practices and determine the applica-
approved in 1985. Last previous edition approved in 2006 as D4463–96(2006).
DOI: 10.1520/D4463_D4463M-96R12E01. bility of regulatory limitations prior to use.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
´1
D4463/D4463M − 96 (2012)
2. Referenced Documents 5.4 In fixed bed steaming, the temperature gradient through
2 the catalyst bed should be kept as small as possible and should
2.1 ASTM Standards:
not exceed 4°C [7.2°F]. In fluid bed steaming the bed tempera-
D3663 Test Method for Surface Area of Catalysts and
ture must be homogeneous.
Catalyst Carriers
D3907 Test Method for Testing Fluid Catalytic Cracking
5.5 Heating and cooling of the catalyst must be performed
(FCC) Catalysts by Microactivity Test in the reactor under a flow of dry nitrogen.
D3942 Test Method for Determination of the Unit Cell
5.6 Precautions must be taken to achieve uniform contact of
Dimension of a Faujasite-Type Zeolite
the steam with the bed.
D4365 Test Method for Determining Micropore Volume and
Zeolite Area of a Catalyst
6. Sampling
D5154 TestMethodforDeterminingActivityandSelectivity
6.1 Asuitable sampling procedure is needed. Practice E105
of Fluid Catalytic Cracking (FCC) Catalysts by Microac-
is appropriate.
tivity Test
E105 Practice for Probability Sampling of Materials
7. Sample Preparation
E177 Practice for Use of the Terms Precision and Bias in
ASTM Test Methods
7.1 No sample preparation is necessary if the catalyst is
E456 Terminology Relating to Quality and Statistics
heated slowly during preheating (non-shock steaming).
E691 Practice for Conducting an Interlaboratory Study to
7.2 If the sample is introduced directly into a preheated
Determine the Precision of a Test Method
steaming reactor, (shock-steaming) it is desirable to predry the
sample for about one hour at about 550°C [1022°F] to prevent
3. Summary of Guide
excessive catalyst loss.
3.1 A sample of fresh fluid cracking catalyst is placed in a
reactor, either fixed bed or preferably fluid bed, and is
8. Procedure
contacted with steam at elevated temperature. This treatment
8.1 Procedure for fluid bed and fixed bed steam treatment
causes partial deactivation of the catalyst.
(non-shock steaming):
NOTE 1—In a fixed bed reactor, material containing sulfates, chlorides,
8.1.1 With the reactor heated to 300°C [572°F] or lower,
etc. can result in significant additional chemical deactivation.
load the reactor with catalyst.
3.2 The catalyst is withdrawn from the reactor and may be
8.1.2 Start nitrogen flow to the reactor at a flow velocity of
subjected to an activity or activity plus selectivity
3 cm/s [0.1 ft/s].
determination, by using the microactivity test (Test Methods
8.1.3 Heat the reactor at the maximum rate until a tempera-
D3907 or D5154).
ture of 600°C [1112°F] is reached.
8.1.4 Keep the temperature constant at 600°C [1112°F] for
4. Significance and Use
30 min in order to remove volatile material from the catalyst.
4.1 In general, steam treatment of FCC catalyst can be used
8.1.5 Heat the reactor at the maximum rate until the desired
either to compare a series of cracking catalysts at a simulated
steaming temperature is reached; for example, at 760, 788 or
equilibrium condition or conditions, or to simulate the equilib-
800°C [1400, 1450 or 1472°F] 6 2°C [6 3.6°F].
rium condition of a specific cracking unit and a specific
8.1.6 Stop the nitrogen flow and start a flow of undiluted
catalyst. This guide gives an example for the first purpose and
steam at atmospheric pressure and at constant temperature of
an approach for the latter purpose.
760, 788 or 800°C [1400, 1450 or 1472°F]. Continue this
steam flow for 5 hours. For fixed bed operation, keep the steam
5. Apparatus
flow velocity at 5 6 1 cm/s [0.16 6 0.03 ft/s] at the desired
5.1 Fixed bed o
...
This document is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation:D4463–96 (Reapproved 2006) Designation: D4463/D4463M – 96
´1
(Reapproved 2012)
Standard Guide for
Metals Free Steam Deactivation of Fresh Fluid Cracking
Catalysts
This standard is issued under the fixed designation D4463/D4463M; the number immediately following the designation indicates the
year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last
reapproval. A superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
´ NOTE—Updated units statement and made a combined standard editorially in April 2012.
1. Scope
1.1 This guide covers the deactivation of fresh fluid catalytic cracking (FCC) catalyst by hydrothermal treatment prior to the
determination of the catalytic cracking activity in the microactivity test (MAT).
1.2 The hydrothermal treatment of fresh FCC catalyst, prior to the MAT, is important because the catalytic activity of the
catalyst in its fresh state is an inadequate measure of its true commercial performance. During operation in a commercial cracking
unit, the catalyst is deactivated by thermal, hydrothermal and chemical degradation. Therefore, to maintain catalytic activity, fresh
catalystisadded(semi)continuouslytothecrackingunit,toreplacecatalystlostthroughthestackorbywithdrawal,orboth.Under
steady state conditions, the catalyst inventory of the unit is called equilibrium catalyst. This catalyst has an activity level
substantially below that of fresh catalyst. Therefore, artificially deactivating a fresh catalyst prior to determination of its cracking
activity should provide more meaningful catalyst performance data.
1.3 Due to the large variations in properties among fresh FCC catalyst types as well as between commercial cracking unit
designs or operating conditions, or both, no single set of steam deactivation conditions is adequate to artificially simulate the
equilibrium catalyst for all purposes.
1.3.1 In addition, there are many other factors that will influence the properties and performance of the equilibrium catalyst.
These include, but are not limited to: deposition of heavy metals such as Ni, V, Cu; deposition of light metals such as Na;
contamination from attrited refractory linings of vessel walls. Furthermore, commercially derived equilibrium catalyst represents
a distribution of catalysts of different ages (from fresh to >300 days). Despite these apparent problems, it is possible to obtain
reasonably close agreement between the performances of steam deactivated and equilibrium catalysts. It is also recognized that it
is possible to steam deactivate a catalyst so that its properties and performance poorly represent the equilibrium. It is therefore
recommended that when assessing the performance of different catalyst types, a common steaming condition be used. Catalyst
deactivation by metals deposition is not addressed in this guide.
1.4 This guide offers two approaches to steam deactivate fresh catalysts.The first part provides specific sets of conditions (time,
temperature and steam pressure) that can be used as general pre-treatments prior to comparison of fresh FCC catalyst MAT
activities (Test Method D3907) or activities plus selectivities (Test Method D5154).
1.4.1 The second part provides guidance on how to pretreat catalysts to simulate their deactivation in a specific FCCU and
suggests catalyst properties which can be used to judge adequacy of the simulation. This technique is especially useful when
examining how different types of catalyst may perform in a specific FCCU, provided no other changes (catalyst addition rate,
regenerator temperature, contaminant metals levels, etc.) occur. This approach covers catalyst physical properties that can be used
as monitors to indicate the closeness to equilibrium catalyst properties.
1.5The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.
1.5 The values stated in either SI units or inch-pound units are to be regarded separately as standard. The values stated in each
system may not be exact equivalents; therefore, each system shall be used independently of the other. Combining values from the
two systems may result in non-conformance with the standard.
1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use.
This guide is under the jurisdiction of ASTM Committee D32 on Catalysts and is the direct responsibility of Subcommittee D32.04 on Catalytic Properties.
Current edition approved Oct.April 1, 2006.2012. Published November 2006.July 2012. Originally approved in 1985. Last previous edition approved in 20012006 as
D4463–96(20016). DOI: 10.1520/D4463_D4463M-96R12E061.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
´1
D4463/D4463M – 96 (2012)
2. Referenced Documents
2.1 ASTM Standards:
D3663 Test Method for Surface Area of Catalysts and Catalyst Carriers
D3907 Test Method for Testing Fluid Catalytic Cracking (FCC) Catalysts by Microactivity Test
D3942 Test Method for Determination of the Unit Cell Dimension of a Faujasite-Type Zeolite
D4365 Test Method for Determining Micropore Volume and Zeolite Area of a Catalyst
D5154 TestMethodforDeterminingActivityandSelectivityofFluidCatalyticCracking(FCC)CatalystsbyMicroactivityTest
E105 Practice for Probability Sampling of Materials
E177 Practice for Use of the Terms Precision and Bias in ASTM Test Methods
E456 Terminology Relating to Quality and Statistics
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
3. Summary of Guide
3.1 Asample of fresh fluid cracking catalyst is placed in a reactor, either fixed bed or preferably fluid bed, and is contacted with
steam at elevated temperature. This treatment causes partial deactivation of the catalyst.
NOTE 1—In a fixed bed reactor, material containing sulfates, chlorides, etc. can result in significant additional chemical deactivation.
3.2 The catalyst is withdrawn from the reactor and may be subjected to an activity or activity plus selectivity determination,
by using the microactivity test (Test Methods D3907 or D5154).
4. Significance and Use
4.1 In general, steam treatment of FCC catalyst can be used either to compare a series of cracking catalysts at a simulated
equilibriumconditionorconditions,ortosimulatetheequilibriumconditionofaspecificcrackingunitandaspecificcatalyst.This
guide gives an example for the first purpose and an approach for the latter purpose.
5. Apparatus
5.1 Fixed bed or fluid bed steaming reactors can be used for the hydrothermal treatment of FCC catalyst.
5.2 In the steaming reactor, temperatures of the catalyst can be maintained at selected constant mean levels between 700°C
(1292°F)[1292°F] and 850°C (1562°F)[1562°F] 6 2°C (6 3.6°F)[6 3.6°F] during the steam treatment.
5.3 Temperature control during steam treatment is critical, as temperature variations of 62°C (63.6°F)[63.6°F] can lead to 61
wt. % conversion changes or more, especially at higher temperatures.
5.4 In fixed bed steaming, the temperature gradient through the catalyst bed should be kept as small as possible and should not
exceed 4°C (7.2°F).[7.2°F]. In fluid bed steaming the bed temperature must be homogeneous.
5.5 Heating and cooling of the catalyst must be performed in the reactor under a flow of dry nitrogen.
5.6 Precautions must be taken to achieve uniform contact of the steam with the bed.
6. Sampling
6.1 A suitable sampling procedure is needed. Practice E105 is appropriate.
7. Sample Preparation
7.1 No sample preparation is necessary if the catalyst is heated slowly during preheating (non-shock steaming).
7.2 If the sample is introduced directly into a preheated steaming reactor, (shock-steaming) it is desirable to predry the sample
for about one hour at about 550°C (1022°F)[1022°F] to prevent excessive catalyst loss.
8. Procedure
8.1 Procedure for fluid bed and fixed bed steam treatment (non-shock steaming):
8.1.1 With the reactor heated to 300°C (572°F)[572°F] or lower, load the reactor with catalyst.
8.1.2 Start nitrogen flow to the reactor at a flow velocity of 3 cm/s (0.1 ft/s).[0.1 ft/s].
8.1.3 Heat the
...
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