Research Article Phase Transformation of Zeolite P …downloads.hindawi.com/journals/jspec/2013/428216.pdfResearch Article Phase Transformation of Zeolite P to Y and Analcime Zeolites

Hindawi Publishing CorporationJournal of SpectroscopyVolume 2013 Article ID 428216 5 pageshttpdxdoiorg1011552013428216

Research ArticlePhase Transformation of Zeolite P to Y and Analcime Zeolitesdue to Changing the Time and Temperature

Seyed Naser Azizi Akram Alavi Daghigh and Maryam Abrishamkar

Analytical Division Faculty of Chemistry University of Mazandaran Babolsar 47416-95447 Iran

Correspondence should be addressed to Seyed Naser Azizi aziziumzacir

Received 6 June 2012 Accepted 14 January 2013

Academic Editor R P S Chakradhar

Copyright copy 2013 Seyed Naser Azizi et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

In the present study the synthesis of template free zeolite P under hydrothermal conditionwas investigatedThe effects of parameterssuch as SiAl ratios (3ndash45) crystallization temperatures (80ndash160∘C) and cry (40ndash60 h) on the synthesis of zeolite P were studiedThe phase transformation of zeolite P to two types of high crystallinity Y and analcime zeolites due to change of temperaturewas observed The effect of temperature on the achievement of two different zeolite types (Y and analcime) with a constant initialsynthetic composition under organic free synthesis of zeolite P was studied The zeolitic products were characterized by X-raydiffraction scanning electron microscopy and IR spectroscopy techniques

1 Introduction

Zeolitic materials are microporous high-internal-surfacecrystalline and hydrated aluminosilicates of alkali and alka-line earth cations with an infinite open and rigid three-dimensional structure [1] Breck et al in 1956 reported thesynthesis of ldquospecies very similar to gismodinerdquo [2] Laterthese types of zeolites were thought to belong to the har-motome-phillipsite group which is called P zeolites [3 4]Zeolite P is the synthetic analogue of the GIS-type (gob-binsite-NaP1) zeolites and has a two-dimensional pore systemwith two intersecting 8-ring channels [5] Zeolite P with SiAlratio of 1 has been described as a commercially detergentbuilder [6 7] On the other hand the analcime structure ismade up of small pores that are arranged in four- six- andeightfold ring The crystal structure of analcime for the firsttime was determined by Taylor [8] and refined by Calleri andFerraris [9] Analcime may be used in selective adsorptionreactions and in heterogeneous catalysis Zeolite Y is in thefaujasite (FAU) family with a framework containing double 6rings linked through sodalite cages that generate supercageswith average pore diameter of 74 A There are several appli-cations of FAU zeolites such as fluid cracking catalysts andsorbents for volatile organic removal [10]

Phase transformation processes include the transitionfrom one structure or symmetry into another structure orsymmetry and the intermediate phases can be observedby analysis techniques This means that from an initial gelwith defined composition one can obtain two or more puretypes of zeolite depending on the conditions of crystallizationsuch as alkalinity crystallization temperature and time andorganic additives (template) However such a possibility mayrepresent a serious disadvantage in the attempt to achieve thedesired group of zeolite in pure form without admixtures ofalternative types of zeolite Then it is possible to know theconditions under which a certain type of zeolite transforminto other ones in order to determine useful crystallizationconditions for synthesis of zeolites in pure form The role oforganic template on phase transformation process of Y zeoliteto zeolite P and analcime was reported in our previous work[11] Recently due to the poisonous effects and high expensesof organic templates for synthesis of zeolite the templatefree synthesis of zeolites has been frequently investigated andwhenever it comes to the commercial-scale production ofzeolites there is a high incentive for template free synthesesboth for ecological and economical reasons [12 13] In thisstudy the synthesis of template free zeolite P and its phasetransformation to two types of high crystalline zeolites Y

2 Journal of Spectroscopy

(a)

10120583m

(a)

(b)

10120583m

(b)

(c)

10120583m

(c)

(d)

10120583m

(d)

(e)

10120583m

(e)

Figure 1 Scanning electron micrographs of synthesized zeolites at different temperatures (a) 90∘C (b) 96∘C (c) 100∘C (d) 110∘C and (e)130∘C

and analcime with changing crystallization temperature (80ndash160∘C) and additionally the effect of different SiAl ratios (3ndash45) and crystallization times (40ndash60 h) were investigated Tothe best of our knowledge this is the first time that organicfree synthesis of three pure phase zeolite types with the samesol-gel composition at certain crystallization times with onlychanging crystallization temperature was investigated Theaim of this work was to study the effect of temperature onthe phase transformation as a key factor on the organic freesynthesis of mentioned zeolites The syntheses were carriedout under hydrothermal conditions The obtained sampleswere characterized by X-ray diffraction (XRD) scanningelectron microscopy (SEM) and FT-IR spectroscopy techni-ques

2 Experiment

21 Synthesis The reagents silicic acid sodium hydroxideand aluminumpowder (all purchased fromMerck) were usedin the synthesis All aqueous solutions were prepared usingdeionized doubly distilled water The zeolite was synthesizedfrom gel with initial SiAl molar ratio in composition of 145The sol-gelmixture was prepared bymixing an aluminate anda silicate solution Then the synthesis gel was introduced toTeflon-lined stainless steel autoclave and sealed autoclave wasput into an air oven and heated for 60 hours at 100∘C Thesolid products were filtered andwashedwith deionizedwaterdried overnight at 100∘C and calcinated at 550∘C for 5 h in anelectric furnace

Journal of Spectroscopy 3C

ount

s

2120579 (deg)0 5 10 15 20 25 30 35 40 45 50

ANA

ANA

ANAANA

ANA ANA

P P P P P

PP

P P P

Y Y Y Y Y

(f)

(e)

(d)

(c)

(b)

(a)

Figure 2 X-ray patterns of synthesized zeolites at different tempera-tures (a) 85∘C (b) 90∘C (c) 96∘C (d) 100∘C (e) 110∘C and (f) 130∘C

2120579 (deg)0 5 10 15 20 25 30 35 40 45 50

(c)

(b)

(a)

Cou

nts

Figure 3 X-ray patterns of synthesized P zeolites after differentcrystallization times (a) 30 h (b) 40 h and (c) 60 h

22 Characterization Techniques The X-ray powder diffrac-tion (XRD) patterns were collected on a GBC MMA instru-ment The patterns were run with Ni-filtered CuK120572 radiation(120582 = 15418Angstrom) at 354 kV and 28mA with a scanningspeed of 2120579 = 10∘minminus1 FT-IR spectra were recorded at roomtemperature using FT-IR spectrometer (Vector 22-Bruker)over the range of 400ndash1500 cmminus1 with a resolution of 2 cmminus1on KBr pellets Scanning electronmicroscopy was performedon selected samples to determine the crystallite size andmor-phology using a JEOL JXA-840 SEM instrument

3 Results and Discussion

31 The Effect of Crystallization Temperature The crystalliza-tion temperature was varied from 80∘C to 160∘C in orderto find the appropriate temperature for the formation ofeach pure zeolitic phase The results indicated that the purezeolite P was obtained at 100∘C whereas the pure phasezeolite Y was produced at 90∘C and changing temperatureto 95ndash97∘C resulted in a mixture of zeolites Y and P Byincreasing temperature from 100∘C up to 110∘C a mixture ofzeolites P and analcime was produced The pure phase anal-cime can be obtained at 130∘C All investigations about theeffect of temperature were carried out with a same initial

2120579 (deg)0 5 10 15 20 25 30 35 40 45 50

Cou

nts

(c)

(d)

(e)

(b)

(a)P P P P

P

P P PP

P

PP

PP

PPP P

P

P

PPP

PP

YYY

Y Y Y YY

Figure 4 X-ray patterns of synthesized zeolites from initial syn-thetic gel with various SiAl mole ratios (a) 3 (b) 5 (c) 15 (d) 30and (e) 45

gel composition without using any organic additive Thescanning electron micrographs and XRD patterns whichshowed the effect of temperature on the synthesis of threetypes of mentioned zeolites are illustrated in Figures 1 and2 One can obtain the pure phase of zeolites Y P andanalcime at 90 100 and 130∘C with a parent composition inratio of 30 SiO

2 Al2O3 24 Na

2O 1360 H

2O by the conven-

tional hydrothermal technique respectively The synthesisof analcime at 160∘C using NN1015840-dibenzyl-NNN1015840N1015840-tetra-methyl ethylene diamine (DBTMED) as organic template wasreported in our previous work [14] and nowwe can introducea new method to achieve pure phase analcime at lower tem-perature without using organic additive in initial syntheticsol-gel

32 Crystallization of Zeolite P versus Time The crystalliza-tion of zeolite P from initial gel composition of 30 SiO

2

Al2O3 24 Na

2O 1360 H

2O with different crystallization

times at a temperature of 100∘Cwas followed byX-ray powderdiffraction (Figure 3) The XRD patterns showed that after40 h a product with poor crystalline system was formed andthe high crystalline zeolite P could be obtained after 60 h at100∘C With an increase in the crystalization time at 100∘Czeolite P with high crystallinity was achieved whereas themixture of zeolite P and analcime was obtained with theincrease of crystallization time up to 60 hwhenD-Methioninewas used as organic template in initial gel composition [11]

33 The Effects of SiAl Ratio on the Synthesis of Zeolite P Inorder to synthesize zeolite P the initial gel composition 30SiO2 a Al2O3 24 Na

2O 1360 H

2O in which coefficient a

has been varied from 033 to 5 was investigated at 100∘C for60 hThe results indicated that the crystallinity of pure zeoliteP was increased from SiAl ratio of 3 followed by 5 and 15For higher SiAl ratio (SiAl = 30) a mixed phase of P andY zeolites was obtained An increase in the SiAl ratio to 45


(a)

(a)

(b)

(b)

Figure 5 SEM images of synthesized zeolites from initial synthetic gel compositions with SiAl mole ratios of (a) 15 and (b) 30

Inte

nsity

(au

)

1000 500

465

996

607

670739

400Wavenumber (cmminus1)

(a)

Inte

nsity

(au

)

1000

1004453

571691

500 400Wavenumber (cmminus1)

(b)

Inte

nsity

(au

)

937445

737

620

1000 500 400Wavenumber (cmminus1)

(c)

Figure 6 FT-IR spectra of synthesized three types of zeolites under template free condition from the same initial gel compositions (a) zeoliteY (b) zeolite P and (c) analcime

maximizes the intensity of zeolite Y peaks and for SiAl ratiogt45 no solid product was obtained One can see that the SiAlratio has a great influence in the phase transformation duringtemplate free synthesis of zeolite P (Figure 4) Figure 5 showsthe SEM images of obtained zeolitic products with the SiAlratios of 15 and 30 in initial synthetic compositions

34 FT-IR Spectra of Synthesized Zeolites Figure 6 illustratesthe FT-IR spectra of synthesized zeolitic samples of zeolitesP Y and analcime with initial gel composition of 30 SiO

2

Al2O3 24 Na

2O 1360 H

2O The FT-IR spectrum of zeolite

P is shown in Figure 6(a) The obtained peaks are similar tothose of zeolite P that were reported by Flanigen et al [15]The peaks at 453ndash571 cmminus1 and 996 cmminus1 were assigned toTndashO (T = Si Al) bending and SindashO AlndashO tetrahedral vib-ration respectively The band at 739 cmminus1 is attributed tosymmetrical stretching of SindashO (AlndashO) Figure 6(b) showsthe FT-IR spectrum of zeolite Y The signal at 453 cmminus1 isassigned to the structure insensitive internal TO

4tetrahedral

bending and the signal at 571 cmminus1 is attributed to thedouble ring external linkage band assigned to zeolite Y Thesignal at 691 cmminus1 is assigned to external linkage symmetrical

Journal of Spectroscopy 5

stretchingThe peak at 1004 cmminus1 is assigned to internal tetra-hedral asymmetrical stretching Figure 6(c) shows the FT-IRspectrum of analcime The band at about 937 cmminus1 is dueto internal vibrations of the (Si Al)O

4tetrahedral of anal-

cime whereas the band at about 1100 cmminus1 is due to vibrationsrelated to external linkages between tetrahedral The absorp-tion bands at 445 620 and 737 cmminus1 are related to TndashOndashTsymmetrical stretching mode

4 Conclusion

In this study a newmethod for organic free synthesis of zeoliteP under hydrothermal condition was investigated The effectof temperature on the phase transformation of the structureof zeolite p to analcime and to zeolite Ywas studied By chang-ing temperature the Y and analcime zeolitic phases wereobservedThe organic free synthesis of analcime and zeolite Ythrough synthesis of zeolite P with changing temperature forthe first time in this study was reported The effect of heatingtime SiAl ratios in the initial gel and heating temperatureon the obtained zeolite were investigated A mixture of Pand Y zeolites was obtained in 95ndash97∘C and this mixturewas transferred to high crystalline zeolites P and analcimephases with the increase of temperature to 100∘ and 130∘Crespectively

References

[1] H Kazemian HModarres and H GMobtaker ldquoIranian natu-ral clinoptilolite and its synthetic zeolite P for removal of ceriumand thorium fromnuclear wastewatersrdquo Journal of Radioanalyt-ical and Nuclear Chemistry vol 258 no 3 pp 551ndash556 2003

[2] D W Breck W G Eversole and R M Milton ldquoNew syntheticcrystalline zeolitesrdquo Journal of the American Chemical Societyvol 78 no 10 pp 2338ndash2339 1956

[3] W C Beard ldquoLinde type B zeolites and relatedmineral and syn-thetic phasesrdquoAdvances in Chemistry vol 101 pp 237ndash249 1971

[4] E M Flanigen H Khatami and H A Szymanski ldquoInfraredstructural studies of zeolite frameworksrdquo Advances in Chem-istry vol 101 pp 201ndash229 1971

[5] R Szostak Handbook of Molecular Sieves Van Nostrand Rein-hold New York NY USA 1992

[6] A Araya ldquoThe invention describes a process for preparing Pzeolites in which aluminate and silicate solutions are reacted inthe presence of a P-zeolite seedrdquo US Pattent 5362466 1994

[7] C J Adams A Araya S W Carr et al ldquoZeolite map a newdetergent builderrdquo Studies in Surface Science and Catalysis vol98 pp 206ndash207 1995

[8] W H Taylor ldquoThe structure of analcime (NaAlSi2

O6

sdot H2

O)rdquoZeitschrift fur Kristallographie vol 74 pp 1ndash19 1930

[9] M Calleri andG Ferraris ldquoStruttura dellıanalcime NaAlSi2

O6

sdot

H2

Ordquo Atti della Accademia delle Scienze di Torino vol 98 pp821ndash846 1964

[10] C S Cundy and P A Cox ldquoThe hydrothermal synthesis ofzeolites Precursors intermediates and reaction mechanismrdquoMicroporous and Mesoporous Materials vol 82 no 1-2 pp 1ndash78 2005

[11] S N Azizi and S E Tilami ldquoRecrystallization of zeolite Y toanalcime and zeolite P with D-methionine as structure-direct-ing agent (SDA)rdquo Zeitschrift fur Anorganische und AllgemeineChemie vol 635 no 15 pp 2660ndash2664 2009

[12] W Chang C H Lee M Y Kim and B J Ahn Journal of Indus-trial and Engineering Chemistry vol 7 p 121 2001

[13] R A Rakoczy M Breuninger M Hunger Y Traa and J Weit-kamp ldquoContentsrdquo Chemical Engineering amp Technology vol 25no 1 pp 3ndash8 2002

[14] S N Azizi and M Yousefpour ldquoSynthesis of aluminum-richanalcime using an ethylene diamine derivative as templaterdquoZeitschrift fur anorganische und allgemeine Chemie vol 635 no11 pp 1654ndash1658 2009

[15] E M Flanigen H Khatami and H A Szymanksi ldquoInfraredstructural studies of zeolite frameworksrdquo in Molecular SieveZeolites-I E M Flanigen and L B Sand Eds Adv Chem SerNo 101 p 201 ACS Washington DC USA 1971

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CatalystsJournal of


(a)

10120583m

(a)

(b)

10120583m

(b)

(c)

10120583m

(c)

(d)

10120583m

(d)

(e)

10120583m

(e)

Figure 1 Scanning electron micrographs of synthesized zeolites at different temperatures (a) 90∘C (b) 96∘C (c) 100∘C (d) 110∘C and (e)130∘C

and analcime with changing crystallization temperature (80ndash160∘C) and additionally the effect of different SiAl ratios (3ndash45) and crystallization times (40ndash60 h) were investigated Tothe best of our knowledge this is the first time that organicfree synthesis of three pure phase zeolite types with the samesol-gel composition at certain crystallization times with onlychanging crystallization temperature was investigated Theaim of this work was to study the effect of temperature onthe phase transformation as a key factor on the organic freesynthesis of mentioned zeolites The syntheses were carriedout under hydrothermal conditions The obtained sampleswere characterized by X-ray diffraction (XRD) scanningelectron microscopy (SEM) and FT-IR spectroscopy techni-ques

2 Experiment

21 Synthesis The reagents silicic acid sodium hydroxideand aluminumpowder (all purchased fromMerck) were usedin the synthesis All aqueous solutions were prepared usingdeionized doubly distilled water The zeolite was synthesizedfrom gel with initial SiAl molar ratio in composition of 145The sol-gelmixture was prepared bymixing an aluminate anda silicate solution Then the synthesis gel was introduced toTeflon-lined stainless steel autoclave and sealed autoclave wasput into an air oven and heated for 60 hours at 100∘C Thesolid products were filtered andwashedwith deionizedwaterdried overnight at 100∘C and calcinated at 550∘C for 5 h in anelectric furnace


ount

s

2120579 (deg)0 5 10 15 20 25 30 35 40 45 50

ANA

ANA

ANAANA

ANA ANA

P P P P P

PP

P P P

Y Y Y Y Y

(f)

(e)

(d)

(c)

(b)

(a)


2120579 (deg)0 5 10 15 20 25 30 35 40 45 50

(c)

(b)

(a)

Cou

nts





2120579 (deg)0 5 10 15 20 25 30 35 40 45 50

Cou

nts

(c)

(d)

(e)

(b)

(a)P P P P

P

P P PP

P

PP

PP

PPP P

P

P

PPP

PP

YYY

Y Y Y YY



2 Al2O3 24 Na

2O 1360 H

2O by the conven-



2

Al2O3 24 Na

2O 1360 H




2O 1360 H




(a)

(a)

(b)

(b)


Inte

nsity

(au

)

1000 500

465

996

607

670739


(a)

Inte

nsity

(au

)

1000

1004453

571691


(b)

Inte

nsity

(au

)

937445

737

620


(c)




2

Al2O3 24 Na

2O 1360 H



4tetrahedral






4 Conclusion


References









O6

sdot H2



O6

sdot

H2

















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


ount

s

2120579 (deg)0 5 10 15 20 25 30 35 40 45 50

ANA

ANA

ANAANA

ANA ANA

P P P P P

PP

P P P

Y Y Y Y Y

(f)

(e)

(d)

(c)

(b)

(a)


2120579 (deg)0 5 10 15 20 25 30 35 40 45 50

(c)

(b)

(a)

Cou

nts





2120579 (deg)0 5 10 15 20 25 30 35 40 45 50

Cou

nts

(c)

(d)

(e)

(b)

(a)P P P P

P

P P PP

P

PP

PP

PPP P

P

P

PPP

PP

YYY

Y Y Y YY



2 Al2O3 24 Na

2O 1360 H

2O by the conven-



2

Al2O3 24 Na

2O 1360 H




2O 1360 H




(a)

(a)

(b)

(b)


Inte

nsity

(au

)

1000 500

465

996

607

670739


(a)

Inte

nsity

(au

)

1000

1004453

571691


(b)

Inte

nsity

(au

)

937445

737

620


(c)




2

Al2O3 24 Na

2O 1360 H



4tetrahedral






4 Conclusion


References









O6

sdot H2



O6

sdot

H2

















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


(a)

(a)

(b)

(b)


Inte

nsity

(au

)

1000 500

465

996

607

670739


(a)

Inte

nsity

(au

)

1000

1004453

571691


(b)

Inte

nsity

(au

)

937445

737

620


(c)




2

Al2O3 24 Na

2O 1360 H



4tetrahedral






4 Conclusion


References









O6

sdot H2



O6

sdot

H2

















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





4 Conclusion


References









O6

sdot H2



O6

sdot

H2

















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Documents

Research Article Phase Transformation of Zeolite P …downloads.hindawi.com/journals/jspec/2013/428216.pdfResearch Article Phase Transformation of Zeolite P to Y and Analcime Zeolites