1、Designation: D 5758 01 (Reapproved 2007)e1Standard Test Method forDetermination of Relative Crystallinity of Zeolite ZSM-5 byX-Ray Diffraction1This standard is issued under the fixed designation D 5758; the number immediately following the designation indicates the year oforiginal adoption or, in th
2、e case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.e1NOTEEditorial changes were made throughout in April 2007.1. Scope1.1 This test method covers a
3、procedure for determinationof the relative crystallinity of zeolite ZSM-5 using selectedpeaks from the X-ray diffraction pattern of the zeolite.1.2 The test method provides a number that is the ratio ofintensity of a portion of the XRD pattern of the sample ZSM-5to intensity of the corresponding por
4、tion of the pattern of areference ZSM-5. The intensity ratio, expressed as a percent-age, is then labeled percent XRD relative crystallinity/ZSM-5.This type of comparison is commonly used in zeolite technol-ogy and is often referred to as percent crystallinity.1.3 This standard does not purport to a
5、ddress all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 3906 Test
6、 Method for Determination of Relative X-rayDiffraction Intensities of Faujasite-Type Zeolite-Containing MaterialsD 5357 Test Method for Determination of Relative Crystal-linity of Zeolite Sodium A by X-ray DiffractionE 177 Practice for Use of the Terms Precision and Bias inASTM Test MethodsE 456 Ter
7、minology Relating to Quality and StatisticsE 691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method3. Summary of Test Method3.1 XRD patterns of the sample ZSM-5 and the referenceZSM-5 are obtained under the same conditions. From thesepatterns, there is a choi
8、ce from two procedures for calculationof relative crystallinity/ZSM-5.3.1.1 Procedure A (Integrated Peak Area Method)A com-parison is made of the sums of intensities (sample versusreference) of the strong peaks, having maxima between about23.1 and 24.3 2u.3.1.2 Procedure B (Peak Height Method)A comp
9、arison ismade of the absolute peak heights (sample versus reference) ofthe 24.3 2u peak.4. Significance and Use4.1 ZSM-5 is a siliceous zeolite that can be crystallized withSiO2/Al2O3ratio in the range of 20 to greater than 1000.ZSM-5, upon modification to the H-cation form (HZSM-5) ina post-crystal
10、lization step, has been used since the 1970s as ashape selective, acid-site catalyst for petroleum refining andpetrochemicals production, including such processes as alky-lation, isomerization, fluid cracking catalysis (FCC), andmethanol-to-gasoline. The most siliceous member of theZSM-5 family, som
11、etimes called silicalite, is hydrophobic andit is used for selective sorption of organic molecules fromwater-containing systems.4.2 This X-ray procedure is designed to allow a reporting ofthe relative degree of crystallization upon manufacture ofZSM-5. The relative crystallinity/ZSM-5 number has pro
12、venuseful in technology, research, and specifications.4.3 The Integrated Peak Area Method (Procedure A) ispreferred over the Peak Height Method (Procedure B) since itcalculates XRD intensity as a sum from several peaks ratherthan utilizing just one peak. Drastic changes in intensity ofindividual pea
13、ks in the XRD pattern of ZSM-5 can result fromchanges in distribution of electron density within the unit cellof the ZSM-5 zeolite. The electron density distribution isdependent upon the following factors:4.3.1 Extent of filling of pores with guest molecules and thenature of these guest molecules.4.
14、3.2 Type of cations and extent of their presence (thesecations may also affect the absorption of X rays by the ZSM-5sample).1This test method is under the jurisdiction of ASTM Committee D32 onCatalysts and is the direct responsibility of Subcommittee D32.05 on Zeolites.Current edition approved April
15、 1, 2007. Published May 2007. Originallyapproved in 1995. Last previous edition approved in 2001 as D 575801.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the sta
16、ndards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.4.3.3 In this XRD method, the guest molecule H2O com-pletes the filling of the pores. Other guest molecule types mayalso be present, incl
17、uding one of numerous amines, diamines,and quarternary ammonium cations that can function as atemplate for crystallization of the ZSM-5 structure.4.3.4 Because of the factors mentioned in 4.3.1 to 4.3.3 thatcould vary the intensities of the XRD peaks in ZSM-5, thisXRD method will provide the best de
18、termination of relativecrystallinity when the reference ZSM-5 and sample ZSM-5have a similar history of preparation and composition.4.4 ZSM-5 can exist with either orthorhombic or mono-clinic symmetry, depending upon the composition of theprecursor gel or post-crystallization modification conditions
19、, orboth. In the orthorhombic type, the XRD peaks centered atabout 23.1 and 23.8 2u are usually split into doublets, whereasthe less symmetric monoclinic type may show a further split ofthese peaks into triplets. The peak area intensities of thesepeaks are unaffected by the crystalline form. The XRD
20、 peak at24.3 2u for the orthorhombic form is a singlet and hence is themost suitable for the Peak Height Method (Procedure B). If the24.3 peak is split (doublet in the monoclinic form), then theIntegrated Peak Area Method (Procedure A) should be used.4.5 If crystalline phases other than ZSM-5 are pr
21、esent in thesample, their diffraction peaks may overlap with some of theZSM-5 peaks selected for the Integrated Peak Area Method(ProcedureA). If there is reason to suspect the presence of suchcomponents, then the Peak Height Method (Procedure B)should be chosen for analysis provided that there is no
22、interference with the 24.3 2u peak that is used for thecalculation.5. Apparatus5.1 X-ray Diffractometer, equipped with computerized dataacquisition and reduction capability, or with a strip chartrecorder, and using copper K-alpha radiation.5.2 Drying Oven, set at 105 6 5C.5.3 Hydrator (Laboratory De
23、siccator), maintained at about58 % relative humidity by a saturated solution of sodiumbromide, NaBr.5.4 Planimeter.NOTE 1The planimeter will not be needed if the XRD instrument isequipped with computerized data acquisition and reduction capability.6. Reagents and Materials6.1 ZSM-5 Powder,3as refere
24、nce standard, preferably witha mean particle diameter of less than 10 m.7. Procedure7.1 Carry out steps 7.2 through 7.4, in an identical manner,for both the sample ZSM-5 and the reference ZSM-5.7.2 Place about 1.5 g of finely divided ZSM-5 in the dryingoven at 105C for 2 h. Cool the sample in the hy
25、drator and holdthere at room temperature and about 58 % relative humidity forat least 16 h.NOTE 2Grinding of course-textured samples should be done gently.Overgrinding can lead to breaking up of fine crystals and destruction ofthe zeolite.NOTE 3Drying, followed by rehydration, results in filling the
26、 zeolitepores with water of hydration but without an excess of moisture residingon the surface of the zeolite particles.7.3 Pack the humidity-conditioned sample into an XRDsample holder.7.4 Obtain an XRD pattern of the reference ZSM-5 and alsoobtain a pattern of the sample ZSM-5 (in the same day), b
27、yscanning over the angle range from 11 to 32 2u usinginstrument parameters best suited to the X-ray diffractometer.The scan rate should not be greater than 1.0/min. The scanrange includes the diffraction peaks that are to be used in thecalculation for relative crystallinity. The XRD pattern of thesa
28、mple can also be used to check for crystalline phases otherthan ZSM-5 that might be present and might interfere with theutility of the calculation of Procedure A (see 4.5). Fig. 1 showsa pattern for the reference ZSM-5 (H+cation form) used in thetesting of this test method.7.4.1 If a strip chart rec
29、order is used, set the chart drive at 20mm/min. Select the scale factor (for amplification) for thereference ZSM-5 pattern so that the strongest peak at 23.1 2uis between 50 and 100 % of full scale. The same scale factorshould be used for the sample ZSM-5 pattern. However, if thesample gives conside
30、rably lower peak intensities, the scalefactor may be reduced (amplification increased) in order toprovide reasonable peak heights.8. Calculation8.1 Procedure A (Integrated Peak Area Method)Thiscalculation involves a comparison of the integrated peak areas3Available from ASTM Committee D32.FIG. 1 X-R
31、ay Diffraction Wide Scan Pattern of Zeolite ZSM-5ASTM Z-20 (Reference)D 5758 01 (2007)e12in the range of 22.5 to 25.0 2u (measured above background)from the patterns obtained in 7.4.8.1.1 Obtain an integrated peak area encompassing the threeto five strong peaks in the 22.5 to 25.0 2u range for both
32、thesample ZSM-5 and the reference ZSM-5. The area is generallydetermined in one of two ways:8.1.1.1 From the counts recorded by a digital integratingsystem that is used while obtaining the pattern.8.1.1.2 By measuring the area under the peaks with aplanimeter.8.1.2 Calculate the relative crystallini
33、ty using the equation:% XRD relative crystallinity ZSM-5 =SxSr3 100 (1)where:Sx= integrated peak area for the sample ZSM-5, andSr= integrated peak area for the reference ZSM-5.8.2 Procedure B (Peak Height Method)This calculationinvolves a comparison of the peak heights at 24.3 2u (mea-sured above ba
34、ckground) from the patterns obtained in 7.4.8.2.1 Construct a baseline from the center of the backgroundscatter at 21.2 2u to the center of the background scatter at25.0 2u on the XRD patterns (hardcopy or stripchart) of thesample ZSM-5 and reference ZSM-5. Determine the absoluteheights of the respe
35、ctive peaks centered at 24.3 2u; that is,measure the height, in millimetres, from the baseline to theapex of the peak. Fig. 2 shows an example of the peak heightdetermination.8.2.2 Calculate the relative crystallinity using the equation:% XRD relative crystallinity ZSM-5 =HsHr3 100 (2)where:Hs= peak
36、 height for the sample, andHr= peak height for the reference.NOTE 4Peak area or peak heights determined by the techniques in8.1.1.2 or 8.2.1 must be obtained from XRD patterns that have a linearintensity scale, and must have a correction factor applied if the scalefactors used for the ZSM-5 referenc
37、e and sample patterns are different; seeTest Method D 3906 and D 5357.NOTE 5Some samples of zeolite may be slightly more crystalline thana chosen reference material. Thus relative crystallinity values greater than100 % may be obtained.NOTE 6Peak broadening in XRD patterns of zeolites can occur for a
38、variety of reasons, including small crystal size (below about 0.2 m),disorder, absorption, and inconsistent sample packing density. ZSM-5products can be manufactured having a wide range of mean crystal sizes,including less than 0.2 m. Thus the percent XRD relative crystallinity ofthe small crystal Z
39、SM-5, when calculated by the Peak Height Method(Procedure B), may be erroneously low.9. Report9.1 Report the following information:9.1.1 Relative crystallinity of ZSM-5,9.1.2 The utilized procedure, that is, the Integrated PeakArea Method or the Peak Height Method, and9.1.3 Non-ZSM-5 peaks, if prese
40、nt (impurity identificaiton,if possible).10. Precision and Bias10.1 Test ProgramAn interlaboratory study was con-ducted in which the named property was measured in twoseparate test materials in ten separate laboratories. PracticeE 691, modified for non-uniform data sets, was followed forthe data red
41、uction. Analysis details are in the Research Report.10.2 PrecisionPairs of test results obtained by a proce-dure similar to that described in the study are expected to differin absolute value by less than 2.772 3 S, where 2.772 3 Sisthe 95 % probability interval limit on the difference betweentwo te
42、st results, and S is the appropriate estimate of standarddeviation. Definitions and usage are given in Practices E 456and E 177, respectively. See Table 1.10.3 BiasThis test method is without known bias.11. Keywords11.1 crystallinity; X-ray diffraction; zeolite ZSM-5FIG. 2 X-Ray Diffraction Short Sc
43、an Pattern of Zeolite ZSM-5ASTM Z-20 (Reference) (for Peak Height MethodProcedure B)D 5758 01 (2007)e13ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that d
44、etermination of the validity of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved
45、 or withdrawn. Your comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel
46、that your comments have not received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprin
47、ts (single or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).TABLE 1 Precision DataCalculationProcedureTest Result(consensusmean)95 %RepeatabilityInterval (withinlaboratory)95 %ReproducibilityInterval (betweenlaboratories)Integrated peakarea95.62 % 2.19 %(2.29 % of mean)5.04 %(5.27 % of mean)Peak height 91.11 % 5.33 %(5.84 % of mean)10.42 %(11.44 % of mean)D 5758 01 (2007)e14
