Molecular Sieves - Science and Technology - Vol. 6 - Characterization II / 02-Thermal Analysis of Zeolites

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that observed in the case of H-ZSM-5 [106]. At about 670 K ammonia and propene were found to evolve simultaneously as decomposition products of 1-propylammonium cations. However, the thermal analysis of 1-propylamine adsorbed on a mixture pretreated at 973 K for 16 h in He pointed to a different behavior. Namely, the weight loss at about 670 K was much smaller than in the case of the sample pretreated at 848 K. MS data revealed that most of the ammonia eluted prior to propene. Nitriles (C3 and C6) and heavier residues were formed. The data strongly pointed to the replacement of protons by copper ions. Auto-reduction of CuO to Cu+ was suggested to be involved in this solid-state ion-exchange process.

Kanazirev et al. [110, 118] reported on the influence of gallium cations on the desorption-decomposition features of propylamines in ZSM-5 zeolites. Mixtures of Ga2O3 and H-ZSM-5 prepared by the impregnation technique or by grinding of the solid components were subjected to reductive solid-state ion exchange. Thus, Ga+ ions were introduced into cationic positions of the zeolite. TG results showed that, after adsorption of 1- propylamine at 323 K, more than one sorbate molecule per gallium cation was strongly held on reduced Ga-MFI at a temperature as high as 550 K. Furthermore, MS data clearly revealed that ammonia was released at temperatures about 160 K lower than those observed in the case of Ga-free H-ZSM-5. Thus, the release of ammonia and propene occurred in two separated steps, which indicated the occurrence of bimolecular transalkylation of 1-propylamine to dipropylamine. At higher temperatures, dehydrogenation reactions led to nitrile products. At 673 K propionitrile and propene were the main products. The decomposition of 2-propylamine in Ga-MFI was found to be completely different. Steric constraints do not allow that more than one 2-propylamine molecule is coordinatively bound to one gallium cation. In the plateau region of the TG curves (550–600 K) less 2-propylamine was measured than 1-propylamine. 2-PA may be converted to a limited degree to DPA, since some ammonia evolved at somewhat lower temperatures than propene. Nevertheless, the greater part of 2-PA decomposed simultaneously to ammonia and propene in a wide temperature range (between 550 and 750 K). At higher temperature, dehydrogenation, oligomerization, and cracking occurred.

A detailed comparative study of the interaction of 1-propylamine with H-, Ga-, In-, and Cu-MFI zeolites was also presented by Kanazirev et al. in [114]. The results illustrated well the advantages of using simultaneous TG-DTA-MS-GC techniques. Identification of the evolved products by MS/GC essentially contributed to the understanding of the physical and chemical processes giving rise to the observed weight losses and heat effects.

98	G. Pál-Borbély

8 Conclusions

Thermal analysis proved to be a highly effective tool for the characterization of zeolites and the investigation of intracrystalline processes accompanied by weight changes and/or heat effects (e.g. dehydration, dehydroxylation, deammoniation, phase transitions, crystal collapse, oxidation, or reduction of lattice constituents). In the case of thermal reactions associated with gas evolution it may be appropriate to analyze the volatile products by combination of TG and DTA with complementary techniques, e.g., titration methods, on-line MS, and/or on-line GC. Nature and consequences of thermochemical processes in zeolites are generally better understood when thermoanalytical techniques are complemented by, e.g., XRD, FTIRand/or MAS NMR spectroscopy applied to investigate zeolite specimens, in which changes in composition and structure may have occurred during previous thermoanalytical experiments. Also, TG and DTA may be successfully used, generally in combination with complementary techniques, to get insight into (i) the formation of coke during catalytic processes; (ii) the decomposition behavior of organic guest molecules introduced by adsorption and template molecules occluded during the synthesis in the channel system of zeolites; (iii) interactions of alkylamines and alcohols with “bridging” hydroxyls; and (iv) the hydrophobic and organophilic properties of high-siliceous zeolite varieties.

References

1.Cammenga HK, Epple M (1995) Angew Chem Int Ed Engl 34:1171

2.Auroux A (2002) Topics in Catalysis 19:205

3.Epple M (1994) J Therm Anal 42:559

4.Gimzewski E (1991) J Therm Anal 37:1251

5.Langier-Kuzniarowa A (1993) J Therm Anal 39:1169

6.Gabelica Z, Nagy BJ, Derouane EG, Gilson JP (1984) Clay Miner 19:803

7.Li C-Y, Rees LVC (1986) Zeolites 6:217

8.Muller JCM, Hakvoort G, Jansen JC (1998) J Therm Anal Calorim 53:449

9.Nyman M, Gu BX, Wang LM, Ewing RC, Nenoff TM (2000) Microporous Mesoporous Mater 40:115

10.Ray GJ, Nerheim AG, Donohue JA (1988) Zeolites 8:458

11.Anderson MW, Klinowski J (1986) J Chem Soc, Faraday Trans I 82:1449

12.Weitkamp J, Kleinschmit P, Kiss A, Berke CH (1993) In: von Ballmoos R, Higgins JB, Treacy MMJ (eds) Proc 9th Int Conf Zeolites, Montreal, 1992. ButterworthHeinemann, London, p 79

13.Long Y, Jiang H, Zeng H (1997) In: Chon H, Ihm S-K, Uh YS (eds) Progress in zeolite and microporous materials 1997, Proc 11th Int Zeolite Conf, Seoul, Korea, August 12–17, 1996. Elsevier, Amsterdam, Stud Surf Sci Catal 105:787

14.Yang H, Ping Z, Niu G, Jiang H, Long Y (1999) Langmuir 15(16):5382

15.Qian B, Jiang H, Sun Y, Long Y (2001) Langmuir 17:1119

Thermal Analysis of Zeolites

99

16.Fajula F, Pacheco VM, Figueras F (1987) Zeolites 7:203

17.Ernst S, Kokotailo GT, Weitkamp J (1987) Zeolites 7:180

18.Lee EFT, Rees LVC (1987) Zeolites 7:545

19.Li J, Qiu J, Sun Y, Long Y (2000) Microporous Mesoporous Mater 37:365

20.Li C-Y, Rees LVC (1986) Zeolites 6:60

21.Zi G, Yi T (1988) Zeolites 8:232

22.Abdillahi MM, Gharami MS, Siddiqui MAB (1994) J Therm Anal 42:1275

23.Esenli F, Kumbasar I (1994) In: Weitkamp J, Karge HG, Pfeifer H, Hölderich W (eds) Zeolites and related microporous materials: State of the art 1994, Proc 10th Int Zeolite Conf, Garmisch-Partenkirchen, Germany, July 17–22, 1994. Elsevier, Amsterdam, Stud Surf Sci Catal 84:645

24.Braunbarth CM, Behrens P, Felsche J, van de Goor G, Wildermuth G, Engelhardt G (1996) Zeolites 16:207

25.Ullrich B, Adolphi P, Zwahr H, Schomburg J (1989) Zeolites 9:412

26.Karge HG (1991) Coke Formation on Zeolites. In: van Bekkum H, Flanigen EM, Jansen JC (eds) Introduction to Zeolite Science and Practice. Stud Surf Sci Catal 58:531

27.Chen WH, Pradhan A, Jong SJ, Lee TY, Wang I, Tsai TC, Liu SB (1996) J Catal 163:436

28.Choudhary VR, Sivadinarayana C, Devadas P, Sansare SD, Magnoux P, Guisnet M (1998) Microporous Mesoporous Mater 21:91

29.Bauer F, Geidel E, Geyer W, Peuker Ch (1999) Microporous Mesoporous Mater 29:109

30.Zhuang Y, Ng FTT (2000) Appl Catal A: General 190:137

31.Liu H, Li T, Tian B, Xu Y (2001) Appl Catal A: General 213:103

32.Chen D, Gronvold A, Rebo HP, Moljord K, Holmen A (1996) Appl Catal A: General 137:L1

33.Zhu W, van de Graaf JM, van den Broeke LJP, Kapteijn F, Moulijn JA (1998) Ind Eng Chem Res 37:1934

34.Zhu W, Kapteijn F, Moulijn JA (2000) Phys Chem Chem Phys 2:1989

35.Zhu W, Kapteijn F, Moulijn JA (2001) Microporous Mesoporous Mater 47:157

36.Zhu W, Kapteijn F, van der Linden B, Moulijn JA (2001) Phys Chem Chem Phys 3:1755

37.Zhu W, Kapteijn F, Moulijn JA, Jansen JC (2000) Phys Chem Chem Phys 2:1773

38.Alexander SM, Bibby DM, Howe RF, Meinhold RH (1993) Zeolites 13:441

39.Aiello R, Crea F, Nastro A, Subotic B, Testa F (1991) Zeolites 11:767

40.Fejes P, Kiricsi I, Tasi Gy, Hannus I, Bertóti I, Székely T (1989) Zeolites 9:392

41.Karge HG, Beyer HK (1991) In: Jacobs PA, Jaeger NI, Kubelkova L, Wichterlova B (eds) Zeolite chemistry and catalysis, Proc Int Symp, Prague, Czechoslovakia September 8–13, 1991. Elsevier, Amsterdam, Stud Surf Sci Catal 69:43

42.Kanazirev V, Price GL, Dooley KM (1991) In: Jacobs PA, Jaeger NI, Kubelkova L, Wichterlova B (eds) Zeolite chemistry and catalysis, Proc Int Symp, Prague, Czechoslovakia September 8–13, 1991. Elsevier, Amsterdam, Stud Surf Sci Catal 69:277

43.Kanazirev V, Neinska Y, Tsoncheva T, Kosova L (1993) In: von Ballmoos R, Higgins JB, Treacy MMJ (eds) Proc 9th Int Zeolite Conf, Montreal, 1992. ButterworthHeinemann, London, p 461

44.Beyer HK, Mihályi RM, Minchev Ch, Neinska Y, Kanazirev V (1996) Microporous Materials 7:333

45.Mihályi RM, Beyer HK, Mavrodinova V, Minchev Ch, Neinska Y (1998) Microporous Mesoporous Mater 24:143

46.Ohgushi T, Niwa T, Araki H, Ichino S (1997) Microporous Materials 8:231

100	G. Pál-Borbély

47.Testa F, Crea F, Nastro A, Aiello R, Nagy BJ (1991) Zeolites 11:705

48.Zhao D, Qiu S, Pang W (1993) Zeolites 13:478

49.Howden MG (1993) Zeolites 13:315

50.Franklin KR, Lowe BM (1988) Zeolites 8:495

51.Araya A, Lowe BM (1986) Zeolites 6:111

52.Zones SI (1997) In: Occelli ML, Kessler H (eds) Synthesis of porous materials, zeolites, clays and nanostructures. Marcel Dekker Inc, New York, p 93

53.De Witte B, Patarin J, Guth JL, Cholley T (1997) Microporous Materials 10:247

54.Gies H, Marler B (1992) Zeolites 12:42

55.Crea F, Nastro A, Nagy BJ, Aiello R (1988) Zeolites 8:262

56.ElHage-Al Asswad J, Dewaele N, Nagy BJ, Hubert RA, Gabelica Z, Derouane EG, Crea F, Aiello R, Nastro A (1988) Zeolites 8:221

57.Soulard M, Bilger S, Kessler H, Guth JL (1987) Zeolites 7:463

58.Patarin J, Soulard M, Kessler H, Guth JL, Baron J (1989) Zeolites 9:397

59.Delmotte L, Soulard M, Kessler H (1990) Chem Lett 1215

60.Bilger S, Soulard M, Kessler H, Guth JL (1991) Zeolites 11:784

61.Soulard M, Bilger S, Kessler H, Guth JL (1991) Zeolites 11:107

62.Tavolaro A, Mostowicz R, Crea F, Nastro A, Aiello R, Nagy BJ (1992) Zeolites 12:756

63.Kosanovic C, Cizmek A, Subotic B, Smit I, Stubicar M, Tonejc A (1995) Zeolites 15:51

64.Yi KH, Ihm SK (1993) Microporous Materials 1:115

65.Occelli ML, Innes RA, Pollack SS, Sanders JV (1987) Zeolites 7:265

66.Araya A, Blake AJ, Harrison ID, Leach HF, Lowe BM, Whan DA, Collins SP (1992) Zeolites 12:24

67.Franco MJ, Perez Pariente J, Fornes V (1991) Zeolites 11:349

68.Wang B, Gao Q, Gao J, Ji D, Wang X, Suo J (2004) Appl Catal A: General 274:167

69.Feijen EJP, Matthijs B, Grobet PJ, Martens JA, Jacobs PA (1997) In: Chon H, Ihm S-K, Uh YS (eds) Progress in zeolite and microporous materials 1997, Proc 11th Int Zeolite Conf, Seoul, Korea, August 12–17, 1996. Elsevier, Amsterdam, Stud Surf Sci Catal 105:165

70.Goossens AM, Feijen EJP, Verhoeven G, Wouters BH, Grobet PJ, Jacobs PA, Martens JA (2000) Microporous Mesoporous Mater 35–36:555

71.Thangaraj A, Rajamohan PR, Ganapathy S, Ratnasamy P (1991) Zeolites 11:69

72.Franklin KR, Lowe BM (1988) Zeolites 8:501

73.Mostowicz R, Nastro A, Crea F, Nagy BJ (1991) Zeolites 11:732

74.Borade RB, Clearfield A (1994) Zeolites 14:458

75.Fjellvåg H, Lillerud KP, Norby P, Sørby K (1989) Zeolites 9:152

76.Schreyeck L, Caullet P, Mougenel JC, Guth JL, Marler B (1996) Microporous Materials 6:259

77.Pál-Borbély G, Szegedi Á, Beyer HK (2000) Microporous Mesoporous Mater 35– 36:573

78.Perez-Pariente J, Martens JA, Jacobs PA (1988) Zeolites 8:46

79.Perez-Pariente J, Martens JA, Jacobs PA (1987) Appl Catal 31:35

80.Hegde SG, Kumar R, Bhat RN, Ratnasamy P (1989) Zeolites 9:231

81.Camblor MA, Corma A, Valencia S (1998) Microporous Mesoporous Mater 25:59

82.Vaudry F, Di Renzo F, Fajula F, Schulz P (1994) In: Weitkamp J, Karge HG, Pfeifer H, Hölderich W (eds) Zeolites and related microporous materials: State of the art 1994, Proc 10th Int Zeolite Conf, Garmisch-Partenkirchen, Germany, July 17–22, 1994. Elsevier, Amsterdam, Stud Surf Sci Catal 84:163

83.Borade RB, Clearfield A (1996) Microporous Materials 5:289

84.Parker LM, Bibby DM, Patterson JE (1984) Zeolites 4:168

Thermal Analysis of Zeolites

101

85.Bourgeat-Lami E, Di Renzo F, Fajula F, Mutin PH, Des Courieres T (1992) J Phys Chem 96:3807

86.Kanazirev V, Price GL (1996) J Catal 161:156

87.Kosslick H, Tuan VA, Fricke R, Jedamzik J, Lanh HD (1991) J Therm Anal 37:2631

88.Nigro E, Crea F, Testa F, Aiello R, Lentz P, Nagy BJ (1999) Microporous Mesoporous Mater 30:199

89.Borade RB (1987) Zeolites 7:398

90.Testa F, Crea F, Diodati GD, Pasqua L, Aiello R, Terwagne G, Lentz P, Nagy BJ (1999) Microporous Mesoporous Mater 30:187

91.Jacob NE, Joshi PN, Shaikh AA, Shiralkar VP (1993) Zeolites 13:430

92.Chandwadkar AJ, Abdulla RA, Hegde SG, Nagy BJ (1993) Zeolites 13:470

93.Chandwadkar A, Bhat RN, Ratnasamy P (1991) Zeolites 11:42

94.Reddy JS, Reddy KR, Kumar R, Ratnasamy P (1991) Zeolites 11:553

95.Singh AP, Reddy KR (1994) Zeolites 14:290

96.Singh AP (1992) Zeolites 12:858

97.Borade RB, Adnot A, Kaliaguine S (1991) Zeolites 11:710

98.Camblor MA, Pérez-Pariente J, Fornes V (1992) Zeolites 12:280

99.Kumar R, Thangaraj A, Bhat RN, Ratnasamy P (1990) Zeolites 10:85

100.Occelli ML, Eckert H, Wölker A, Auroux A (1999) Microporous Mesoporous Mater 30:219

101.Borade RB, Clearfield A (1994) Microporous Materials 2:167

102.Borade RB, Clearfield A (1992) J Phys Chem 96:6729

103.Camblor MA, Corma A, Perez-Pariente J (1993) Zeolites 13:82

104.Tuel A, BenTaarit Y (1993) Zeolites 13:357

105.Tuel A, BenTaarit Y (1994) Zeolites 14:272

106.Parrillo DJ, Adamo AT, Kokotailo GT, Gorte RJ (1990) Appl Catal 67:107

107.Kofke TJG, Gorte RJ, Farneth WE (1988) J Catal 114:34

108.Kofke TJG, Gorte RJ, Kokotailo GT, Farneth WE (1989) J Catal 115:265

109.Kofke TJG, Gorte RJ, Kokotailo GT (1989) Appl Catal 54:177

110.Kanazirev V, Dooley KM, Price GL (1994) J Catal 146:228

111.Price GL, Kanazirev V (1997) Zeolites 18:33

112.Biaglow AI, Parrillo DJ, Kokotailo GT, Gorte RJ (1994) J Catal 148:213

113.Biaglow AI, Parrillo DJ, Gorte RJ (1993) J Catal 144:193

114.Kanazirev VI, Price GL, Dooley KM (1994) J Catal 148:164

115.Ruiz JAC, Ruiz VSO, Airoldi C, Pastore HO (2004) Appl Catal A: General 261:87

116.Parrillo DJ, Dolenec D, Gorte RJ, McCabe RW (1993) J Catal 142:708

117.Price GL, Kanazirev V, Church DF (1995) J Phys Chem 99:864

118.Kanazirev V, Price GL (1994) In: Weitkamp J, Karge HG, Pfeifer H, Hölderich W (eds) Zeolites and related microporous materials: State of the art 1994, Proc 10th Int Zeolite Conf, Garmisch-Partenkirchen, Germany, July 17–22, 1994. Elsevier, Amsterdam, Stud Surf Sci Catal 84C:1935