ASTM D5758-01(2015)

Standard Test Method for Determination of Relative Crystallinity of Zeolite ZSM-5 by X-Ray Diffraction

SIGNIFICANCE AND USE
4.1 ZSM-5 is a siliceous zeolite that can be crystallized with SiO2/Al2O3 ratio in the range of 20 to greater than 1000. ZSM-5, upon modification to the H-cation form (HZSM-5) in a post-crystallization step, has been used since the 1970s as a shape selective, acid-site catalyst for petroleum refining and petrochemicals production, including such processes as alkylation, isomerization, fluid cracking catalysis (FCC), and methanol-to-gasoline. The most siliceous member of the ZSM-5 family, sometimes called silicalite, is hydrophobic and it is used for selective sorption of organic molecules from water-containing systems.  
4.2 This X-ray procedure is designed to allow a reporting of the relative degree of crystallization upon manufacture of ZSM-5. The relative crystallinity/ZSM-5 number has proven useful in technology, research, and specifications.  
4.3 The Integrated Peak Area Method (Procedure A) is preferred over the Peak Height Method (Procedure B) since it calculates XRD intensity as a sum from several peaks rather than utilizing just one peak. Drastic changes in intensity of individual peaks in the XRD pattern of ZSM-5 can result from changes in distribution of electron density within the unit cell of the ZSM-5 zeolite. The electron density distribution is dependent upon the following factors:  
4.3.1 Extent of filling of pores with guest molecules and the nature of these guest molecules.  
4.3.2 Type of cations and extent of their presence (these cations may also affect the absorption of X rays by the ZSM-5 sample).  
4.3.3 In this XRD method, the guest molecule H2O completes the filling of the pores. Other guest molecule types may also be present, including one of numerous amines, diamines, and quarternary ammonium cations that can function as a template for crystallization of the ZSM-5 structure.  
4.3.4 Because of the factors mentioned in 4.3.1 to 4.3.3 that could vary the intensities of the XRD peaks in ZSM-5, this XRD method will provide the best de...
SCOPE
1.1 This test method covers a procedure for determination of the relative crystallinity of zeolite ZSM-5 using selected peaks from the X-ray diffraction pattern of the zeolite.  
1.2 The test method provides a number that is the ratio of intensity of a portion of the XRD pattern of the sample ZSM-5 to intensity of the corresponding portion of the pattern of a reference ZSM-5. The intensity ratio, expressed as a percentage, is then labeled percent XRD relative crystallinity/ZSM-5. This type of comparison is commonly used in zeolite technology and is often referred to as percent crystallinity.  
1.3 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.

General Information

• Status: Historical
• Publication Date: 30-Nov-2015
• ICS: 71.040.50 - Physicochemical methods of analysis
• Technical Committee: D32 - Catalysts
• Drafting Committee: D32.05 - Zeolites

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D5758 − 01 (Reapproved 2015)
Standard Test Method for
Determination of Relative Crystallinity of Zeolite ZSM-5 by
X-Ray Diffraction
This standard is issued under the fixed designation D5758; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope patterns, there is a choice from two procedures for calculation
of relative crystallinity/ZSM-5.
1.1 This test method covers a procedure for determination
3.1.1 Procedure A (Integrated Peak Area Method)—Acom-
of the relative crystallinity of zeolite ZSM-5 using selected
parison is made of the sums of intensities (sample versus
peaks from the X-ray diffraction pattern of the zeolite.
reference) of the strong peaks, having maxima between about
1.2 The test method provides a number that is the ratio of
23.1 and 24.3° 2θ.
intensityofaportionoftheXRDpatternofthesampleZSM-5
3.1.2 Procedure B (Peak Height Method)—Acomparison is
to intensity of the corresponding portion of the pattern of a
madeoftheabsolutepeakheights(sampleversusreference)of
reference ZSM-5. The intensity ratio, expressed as a
the 24.3° 2θ peak.
percentage, is then labeled percent XRD relative crystallinity/
ZSM-5. This type of comparison is commonly used in zeolite
4. Significance and Use
technology and is often referred to as percent crystallinity.
4.1 ZSM-5isasiliceouszeolitethatcanbecrystallizedwith
1.3 This standard does not purport to address all of the
SiO /Al O ratio in the range of 20 to greater than 1000.
2 2 3
safety concerns, if any, associated with its use. It is the
ZSM-5, upon modification to the H-cation form (HZSM-5) in
responsibility of the user of this standard to establish appro-
a post-crystallization step, has been used since the 1970s as a
priate safety and health practices and determine the applica-
shape selective, acid-site catalyst for petroleum refining and
bility of regulatory limitations prior to use.
petrochemicals production, including such processes as
alkylation, isomerization, fluid cracking catalysis (FCC), and
2. Referenced Documents
methanol-to-gasoline. The most siliceous member of the
2.1 ASTM Standards:
ZSM-5 family, sometimes called silicalite, is hydrophobic and
D3906Test Method for Determination of Relative X-ray
it is used for selective sorption of organic molecules from
Diffraction Intensities of Faujasite-Type Zeolite-
water-containing systems.
Containing Materials
4.2 ThisX-rayprocedureisdesignedtoallowareportingof
D5357Test Method for Determination of Relative Crystal-
the relative degree of crystallization upon manufacture of
linity of Zeolite Sodium A by X-ray Diffraction
ZSM-5. The relative crystallinity/ZSM-5 number has proven
E177Practice for Use of the Terms Precision and Bias in
useful in technology, research, and specifications.
ASTM Test Methods
4.3 The Integrated Peak Area Method (Procedure A) is
E456Terminology Relating to Quality and Statistics
preferred over the Peak Height Method (Procedure B) since it
E691Practice for Conducting an Interlaboratory Study to
calculates XRD intensity as a sum from several peaks rather
Determine the Precision of a Test Method
than utilizing just one peak. Drastic changes in intensity of
3. Summary of Test Method
individual peaks in the XRD pattern of ZSM-5 can result from
changes in distribution of electron density within the unit cell
3.1 XRD patterns of the sample ZSM-5 and the reference
of the ZSM-5 zeolite. The electron density distribution is
ZSM-5 are obtained under the same conditions. From these
dependent upon the following factors:
4.3.1 Extentoffillingofporeswithguestmoleculesandthe
This test method is under the jurisdiction of ASTM Committee D32 on
nature of these guest molecules.
Catalysts and is the direct responsibility of Subcommittee D32.05 on Zeolites.
4.3.2 Type of cations and extent of their presence (these
Current edition approved Dec. 1, 2015. Published December 2015. Originally
cations may also affect the absorption of X rays by the ZSM-5
approvedin1995.Lastpreviouseditionapprovedin2011asD5758–01(2011).DOI:
10.1520/D5758-01R15.
sample).
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
4.3.3 In this XRD method, the guest molecule H O com-
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
pletes the filling of the pores. Other guest molecule types may
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. also be present, including one of numerous amines, diamines,
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5758 − 01 (2015)
FIG. 1 X-Ray Diffraction Wide Scan Pattern of Zeolite ZSM-5—ASTM Z-20 (Reference)
and quarternary ammonium cations that can function as a 6. Reagents and Materials
template for crystallization of the ZSM-5 structure. 3
6.1 ZSM-5 Powder, as reference standard, preferably with
4.3.4 Because of the factors mentioned in 4.3.1 to 4.3.3 that
a mean particle diameter of less than 10 µm.
could vary the intensities of the XRD peaks in ZSM-5, this
XRD method will provide the best determination of relative
7. Procedure
crystallinity when the reference ZSM-5 and sample ZSM-5
7.1 Carry out steps 7.2 through 7.4, in an identical manner,
have a similar history of preparation and composition.
for both the sample ZSM-5 and the reference ZSM-5.
4.4 ZSM-5 can exist with either orthorhombic or mono-
7.2 Place about 1.5 g of finely divided ZSM-5 in the drying
clinic symmetry, depending upon the composition of the
ovenat105°Cfor2h.Coolthesampleinthehydratorandhold
precursorgelorpost-crystallizationmodificationconditions,or
thereatroomtemperatureandabout58%relativehumidityfor
both. In the orthorhombic type, the XRD peaks centered at
at least 16 h.
about23.1and23.8°2θareusuallysplitintodoublets,whereas
NOTE 2—Grinding of course-textured samples should be done gently.
thelesssymmetricmonoclinictypemayshowafurthersplitof
Overgrinding can lead to breaking up of fine crystals and destruction of
these peaks into triplets. The peak area intensities of these
the zeolite.
NOTE 3—Drying, followed by rehydration, results in filling the zeolite
peaks are unaffected by the crystalline form.The XRD peak at
pores with water of hydration but without an excess of moisture residing
24.3°2θfortheorthorhombicformisasingletandhenceisthe
on the surface of the zeolite particles.
mostsuitableforthePeakHeightMethod(ProcedureB).Ifthe
7.3 Pack the humidity-conditioned sample into an XRD
24.3° peak is split (doublet in the monoclinic form), then the
sample holder.
Integrated Peak Area Method (Procedure A) should be used.
7.4 ObtainanXRDpatternofthereferenceZSM-5andalso
4.5 IfcrystallinephasesotherthanZSM-5arepresentinthe
obtain a pattern of the sample ZSM-5 (in the same day), by
sample, their diffraction peaks may overlap with some of the
scanning over the angle range from 11 to 32° 2θ using
ZSM-5 peaks selected for the Integrated Peak Area Method
instrument parameters best suited to the X-ray diffractom
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM 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.
´1
Designation: D5758 − 01 (Reapproved 2011) D5758 − 01 (Reapproved 2015)
Standard Test Method for
Determination of Relative Crystallinity of Zeolite ZSM-5 by
X-Ray Diffraction
This standard is issued under the fixed designation D5758; 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.
ε NOTE—Updated ZSM-5 powder availability footnote editorially in October 2011.
1. Scope
1.1 This test method covers a procedure for determination of the relative crystallinity of zeolite ZSM-5 using selected peaks
from the X-ray diffraction pattern of the zeolite.
1.2 The test method provides a number that is the ratio of intensity of a portion of the XRD pattern of the sample ZSM-5 to
intensity of the corresponding portion of the pattern of a reference ZSM-5. The intensity ratio, expressed as a percentage, is then
labeled percent XRD relative crystallinity/ZSM-5. This type of comparison is commonly used in zeolite technology and is often
referred to as percent crystallinity.
1.3 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.
2. Referenced Documents
2.1 ASTM Standards:
D3906 Test Method for Determination of Relative X-ray Diffraction Intensities of Faujasite-Type Zeolite-Containing Materials
D5357 Test Method for Determination of Relative Crystallinity of Zeolite Sodium A by X-ray Diffraction
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 Test Method
3.1 XRD patterns of the sample ZSM-5 and the reference ZSM-5 are obtained under the same conditions. From these patterns,
there is a choice from two procedures for calculation of relative crystallinity/ZSM-5.
3.1.1 Procedure A (Integrated Peak Area Method)—A comparison is made of the sums of intensities (sample versus reference)
of the strong peaks, having maxima between about 23.1 and 24.3° 2θ.
3.1.2 Procedure B (Peak Height Method)—A comparison is made of the absolute peak heights (sample versus reference) of the
24.3° 2θ peak.
4. Significance and Use
4.1 ZSM-5 is a siliceous zeolite that can be crystallized with SiO /Al O ratio in the range of 20 to greater than 1000. ZSM-5,
2 2 3
upon modification to the H-cation form (HZSM-5) in a post-crystallization step, has been used since the 1970s as a shape selective,
acid-site catalyst for petroleum refining and petrochemicals production, including such processes as alkylation, isomerization, fluid
cracking catalysis (FCC), and methanol-to-gasoline. The most siliceous member of the ZSM-5 family, sometimes called silicalite,
is hydrophobic and it is used for selective sorption of organic molecules from water-containing systems.
4.2 This X-ray procedure is designed to allow a reporting of the relative degree of crystallization upon manufacture of ZSM-5.
The relative crystallinity/ZSM-5 number has proven useful in technology, research, and specifications.
This test method is under the jurisdiction of ASTM Committee D32 on Catalysts and is the direct responsibility of Subcommittee D32.05 on Zeolites.
Current edition approved Oct. 1, 2011Dec. 1, 2015. Published December 2011December 2015. Originally approved in 1995. Last previous edition approved in 20072011
ε1
as D5758–01(2007)D5758–01(2011). . DOI: 10.1520/D5758-01R11E01.10.1520/D5758-01R15.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5758 − 01 (2015)
4.3 The Integrated Peak Area Method (Procedure A) is preferred over the Peak Height Method (Procedure B) since it calculates
XRD intensity as a sum from several peaks rather than utilizing just one peak. Drastic changes in intensity of individual peaks in
the XRD pattern of ZSM-5 can result from changes in distribution of electron density within the unit cell of the ZSM-5 zeolite.
The electron density distribution is dependent upon the following factors:
4.3.1 Extent of filling of pores with guest molecules and the nature of these guest molecules.
4.3.2 Type of cations and extent of their presence (these cations may also affect the absorption of X rays by the ZSM-5 sample).
4.3.3 In this XRD method, the guest molecule H O completes the filling of the pores. Other guest molecule types may also be
present, including one of numerous amines, diamines, and quarternary ammonium cations that can function as a template for
crystallization of the ZSM-5 structure.
4.3.4 Because of the factors mentioned in 4.3.1 to 4.3.3 that could vary the intensities of the XRD peaks in ZSM-5, this XRD
method will provide the best determination of relative crystallinity when the reference ZSM-5 and sample ZSM-5 have a similar
history of preparation and composition.
4.4 ZSM-5 can exist with either orthorhombic or monoclinic symmetry, depending upon the composition of the precursor gel
or post-crystallization modification conditions, or both. In the orthorhombic type, the XRD peaks centered at about 23.1 and 23.8°
2θ are usually split into doublets, whereas the less symmetric monoclinic type may show a further split of these peaks into triplets.
The peak area intensities of these peaks are unaffected by the crystalline form. The XRD peak at 24.3° 2θ for the orthorhombic
form is a singlet and hence is the most suitable for the Peak Height Method (Procedure B). If the 24.3° peak is split (doublet in
the monoclinic form), then the Integrated Peak Area Method (Procedure A) should be used.
4.5 If crystalline phases other than ZSM-5 are present in the sample, their diffraction peaks may overlap with some of the
ZSM-5 peaks selected for the Integrated Peak Area Method (Procedure A). If there is reason to suspect the presence of such
components, then the Peak Height Method (Procedure B) should be chosen for analysis provided that there is no interference with
the 24.3° 2θ peak that is used for the calculation.
5. Apparatus
5.1 X-ray Diffractometer, equipped with computerized data acquisition and reduction capability, or with a strip chart recorder,
and using copper K-alpha radiation.
5.2 Drying Oven, set at 105 6 5°C.
5.3 Hydrator (Laboratory Desiccator), maintained at about 58 % relative humidity by a saturated solution of sodium bromide,
NaBr.
5.4 Planimeter.
NOTE 1—The planimeter will not be needed if the XRD instrument is equipped with computerized data acquisition and reduction capability.
6. Reagents and Materials
6.1 ZSM-5 Powder, as reference standard, preferably with a mean particle diameter of less than 10 μm.
7. Procedure
7.1 Carry out steps 7.2 through 7.4, in an identical manner, for both the sa
...