Microporous and Mesoporous Materials 116 (2008) 210–215

Contents lists available at ScienceDirect

Microporous and Mesoporous Materials
journal homepage: www.elsevier.com/locate/micromeso

Comparison of four catalysts in the catalytic dehydration of ethanol to ethylene
Xian Zhang, Rijie Wang, Xiaoxia Yang *, Fengbao Zhang
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China

a r t i c l e

i n f o

Article history:
Received 29 November 2007
Received in revised form 18 March 2008
Accepted 2 April 2008
Available online 6 April 2008
Keywords:
Dehydration of ethanol
c-Al2O3
HZSM-5
SAPO-34
NiAPSO-34

a b s t r a c t
The aim of this study was to compare the activity and stability of c-Al2O3, HZSM-5 (Si/Al = 25), silicoaluminophosphate (SAPO-34) and Ni-substituted SAPO-34 (NiAPSO-34) as catalysts in the dehydration of
ethanol to ethylene. c-Al2O3- and HZSM-5 were commercial catalysts. SAPO-34 and NiAPSO-34 molecular
sieves had been synthesized with hydrothermal method in the laboratory, characterized with X-ray powder diffraction (XRD), Infrared Spectroscopy (FT-IR), H2 temperature-programmed reduction (H2–TPR)
technique and NH3 temperature-programmed desorption (NH3–TPD) technique. The incorporation of
Ni2+ into the SAPO-34 framework generated in NiAPSO-34 sample was proved by XRD, FT-IR and H2–
TPR techniques. NH3–TPD study had revealed that substitution of Ni2+ for Al3+ in the SAPO-34 framework
led to increase the weak and moderately strong acid strength and give rise to weak acid sites. Dehydration of ethanol was carried out over four catalysts and the results showed that conversion of ethanol and
selectivity to ethylene decreased in the order HZSM-5 > NiAPSO-34 > SAPO-34 > c-Al2O3. As to the stability of catalyst, NiAPSO-34 and SAPO-34 were better than other two catalysts. Considering the activity and
stability of the four catalysts comprehensively, NiAPSO-34 was the suitable catalyst in the dehydration of
ethanol.
Ó 2008 Elsevier Inc. All rights reserved.

1. Introduction
Ethylene is an important material for the organic chemistry
industry used in the preparation of polyethylene, ethylene oxide,
ethylene dichloride, etc. Conventionally, it has been commercially
produced by the thermal cracking of liquefied petroleum gas
(LPG) or naphtha [1]. This process is an endothermic reaction
requiring high temperature of 600–1000 °C. Compared to the conventional route, catalytic dehydration of ethanol to ethylene is
proving attractive as it requires lower temperature and offers higher ethylene yield [2,3]. Moreover, ethanol can be produced from
renewable sources, production of ethylene, therefore, does not depend on petroleum source.
Dehydration of ethanol can take place by two competitive paths.
One is the intramolecular dehydration of ethanol to ethylene and
the other is intermolecular dehydration of ethanol to diethyl ether.
At lower temperature, diethyl ether is produced in significant quantities, while, at the higher temperature, ethylene is the dominant
product. Ethanol dehydrogenation to produce acetaldehyde can
also occur as a side reaction at the higher temperature [4].
One of the early catalysts employed for the dehydration of ethanol was c-alumina (Al2O3) [5]. With Al2O3 catalyst, dehydration of
ethanol required higher reaction temperature (450 °C) and offered
lower ethylene yield (80%). At present, researchers studied on
dehydration of ethanol over HZSM-5 zeolite. Numerous papers
* Corresponding author. Tel./fax: +86 22 27401018.
E-mail addresses: xxytju@hotmail.com, gsarah@eyou.com (X. Yang).
1387-1811/$ - see front matter Ó 2008 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2008.04.004

had already been published on the subject [6,7]. With HZSM-5 catalyst, at lower temperature (300 °C), 95% of ethylene was reported
in the reaction produce at a conversion level of 98% of ethanol. But
because of strong acidity of HZSM-5, catalyst easily occurred on
coking deactivation. Therefore, stability of HZSM-5 was worse.
In 1982, SAPO-34 had been synthesized by UCC [8]. Due to narrow
pores, extending in three dimensions and mild acidity, SAPO-34 was
successfully applied in the MTO (Methanol to Olefins) process [9–
11]. In previous studies, SAPO-34 was believed to be the best catalyst
in terms of activity and selectivity to light olefins [12]. Detailed research revealed that Ni-substituted SAPO-34 (NiAPSO-34) showed
excellent performance for ethylene production from methanol
[13–15]. However, for catalytic dehydration of ethanol to ethylene,
application of SAPO-34 and NiAPSO-34 was no reported.
In this work, we had devoted ourselves to investigations to look
for a catalyst capable of exhibiting high efficiency as well as stability in the formation of the final product ethylene. The selectivity
for catalytic dehydration of ethanol to ethylene of four catalysts,
Al2O3, HZSM-5, SAPO-34 and NiAPSO-34, was studied to find a suited catalyst in the activity and stability.

2. Experimental
2.1. Preparation of catalyst
Commercial Al2O3 and HZSM-5 (Si/Al = 25) were obtained from
Tianjin Research and Design Institute of Chemical Industry and the

Ni (NO3)26H2O (Tianjin Yaohua Chemical Reagent Co. / Microporous and Mesoporous Materials 116 (2008) 210–215 Table 1 Physical properties of the four catalysts Property 2 Surface area (m /g) Mean pore radius (Å) Cumulative pore volume (ml/g) Al2O3 HZSM-5 SAPO-34 NiAPSO-34 190 45.27 0. The products were filtrated. Catalytic reaction studies were performed in electrically heated fixed bed reactor (ID 10 mm.22 377 4. Tianjin Benchmark Chemical Reagent Co. respectively. Ltd. The products were analyzed on gas chromatograph (Agilent 6820) with FID using DB-WAX capillary column by programming the oven temperature between 60 °C and 150 °C at 15 °C/min.48 295 5 0.1.). The physical properties of samples were conducted using a Quantachrome Autosorb-1 physisorption machine. Characterization of SAPO-34 and NiAPSO-34 samples The elemental analyses of SAPO-34 and NiAPSO-34 samples were measured by XRF spectrometer as given in Table 2. Ltd.0SiO2: 0.211 X.0R:50H2O for SAPO-34 and 1. 3. where the surface area.0084 P N2 Reactor Micro pump Ethanol Gas chromatograph Fig.0R:50H2O for NiAPSO-34.72 0. washed. Results and discussion 3. The chemical composition of the starting gel was 1. SAPO-34 and NiAPSO-34 samples were prepared with hydrothermal method in the laboratory. Ltd. determined by home-made apparatus equipped with a thermal conductivity detector (TCD).28 0. The precursor gels were transferred to a stainless-steel autoclave and heated in static condition for 60 h at 200 °C under autogeneous pressure.73 – 0.0150NiO: 2.0P2O5:1.). The acidity of samples was estimated by tem- Table 2 Elemental analyses for SAPO-34 and NiAPSO-34 sample Sample Composition in crystals (atomic ratio) Al Si P Ni SAPO-34 NiAPSO-34 1. Ethanol was changed through a micro pump. FT-IR spectra of the samples were recorded on a Thermo Nicolet NEXUS FT-IR spectrophotometer using KBr pellet. nickel and template. colloidal silica (Beijing Hongxingguangsha Chemical Architectural Material Co. The ob- 2. The reducibility of samples was estimated by the temperature-programmed reduction (TPR) technique using home-made apparatus with a TCD.5 0. Usually the reactor charged 3 ml of catalyst. and dried at 110 °C for 8 h. Characterization X-ray diffraction analysis was carried out in a PANLytical X’Pery PRO diffractometer in the scan range of 2h between 5° and 50° using Co Ka as source. 1. mean pore radius and cumulative pore volume were calculated.00 0. phosphorus. Zhang et al. 1.0SiO2:2.) and morpholine (Tianjin Guangfu Fine Chemical Research Institute) were used as the sources of aluminum.0P2O5:1.3. respectively. .5 0.46 Catalyst Plant of Naikai University. length 420 mm).7 0. 2. perature-programmed desorption (TPD) profiles of pre-adsorbed NH3.49 358 4. silicon. The synthesis of SAPO-34 and NiAPSO-34 followed the procedure reported in the Literature [16]. orthophoshporic acid (85wt%.0Al2O3:1. The elemental analyses of the samples were done by X-ray fluorescence (XRF) in a SHIMADZU XRF-1800 spectrometer with Rh tube as excitation source. Unit cell parameters and volume were calculated using a standard least square refinement technique. The physical properties of the four catalysts were given in Table 1. Pseudoboehmite (Tianjin Research and Design Institute of chemical Industry).2.00 1. Catalyst experimental setup. Catalytic reaction Experimental setup used for this study is presented in Fig.0Al2O3:1. The peaks were identified with reference to JCPDS files (Joint Committee on Powder Diffraction Standards).

XRD patterns of as-synthesized SAPO-34 and NiAPSO-34 samples are shown in Fig.X. XRD patterns for as-synthesized samples (a) SAPO-34 and (b) NiAPSO-34. framework vibrations were characteristically similar to relevant reports [17. asymmetric. The H2–TPR profiles of SAPO-34 and NiAPSO-34 samples are shown in Fig. 640 cm 1.763 13. respectively. respectively. 4500 .91 2444. 2.) Sample (as-synthesized) tetrahedral SAPO-34 framework causes a slight expansion in the unit cell parameters and volume which is one of the evidences that Ni2+ is probably incorporated into the SAPO-34 framework. In NiAPOS-34 sample.18].Al)O4. FT-IR spectra of the as-synthesized samples in the framework vibration frequency region are shown in Fig. served framework chemical compositions for SAPO-34 and NiAPOS-34 samples suggested Si substitution for P. The appearance of the first peak (b) (a) 0 500 1000 1500 2000 2500 3000 3500 4000 Wavenumber / cm-1 Fig.u. The vibration frequencies had been assigned in Table 4. The replacement of Al3+ by the larger Ni2+ in the Table 3 Unit cell parameters and unit cell volume of samples SAPO-34 NiAPSO-34 Unit cell parameters Unit cell volume a/Å v/Å3b/Å c/Å 13. This is the supporting evidence for the presence of Ni2+ in the SAPO-34 framework. It was found that the unit cell parameters and volume increased for NiAPSO-34 sample.851 2431.786 13. FT-IR spectra of as-synthesized samples (a) SAPO-34 and (b) NiAPSO-34. symmetric. The position and the intensity of the diffraction peaks of both samples are well-matched with JCPDS files (PDF#47-0429). As shown in Table 4. protonated morpholine.823 14. 870 cm 1. This peak starting at 1100 °C. 530 cm 1.786 14. 4. IR band around 480 cm 1. 730 cm 1. a portion of Ni2+ in gel mixtures was incorporated into the SAPO-34 framework. [PO4]. Unit cell parameters and volume were calculated for as-synthesized samples and are listed in Table 3.34 Relative Absorbance (a.763 13. 2. It should be noticed that SAPO-34 sample presented one reduction of peak. / Microporous and Mesoporous Materials 116 (2008) 210–215 Relative Intensity (a. 3. 3. D-6 rings. compared with those of SAPO-34 sample. 570 cm 1. 1100 cm 1 exhibited by SAPO-34 sample can be attributed to stretching mode of [SiO4]. (Si. Zhang et al. The framework vibration frequencies of NiAPSO-34 sample shifted to position of lower wavenumber. The patterns indicated high crystallinity without obvious impurity. formed after the collapse of molecular sieves structures [19]. which was ascribed to the reduction of Al3+ in the SAPO-34 framework.u. which started at 1000 °C and 1100 °C. This result showed that incorporation of Ni into SAPO-34 framework was very difficult.) 212 (b) (a) SAPO-34(PDF#47-0429) 10 20 30 CoKα / 2θ (deg) 40 50 Fig. NiAPSO-34 sample was reduced in two regions.

dehydration of ethanol was incomplete and ethanol conversion was lower. the stronger the acid strength is. 5. SAPO-34 and NiAPSO-34. The desorption characteristics of zeolites are quite different from those of Al2O3. the acid site was important as well as the acid strength to catalytic activity for dehydration of ethanol to ethylene. With the increase in temperature. conversion of ethanol from each catalyst increased. respectively. the conversion of ethanol was 90.1% for Al2O3 sample. respectively. At 475 °C. 6 and Fig. Reduction temperature of Ni2+ in the extra framework is lower 800 °C. Al2O3 sample showed two peaks appearing from 150 °C to 400 °C and 400 °C to 600 °C. In general. Product distribution data at the optimal reaction condition of each catalyst are shown in Table 5.5% for SAPO-34.u. at lower temperature. Al)O4 PO4 D-6 rings 480 453 530 503 570 554 640 614 Symmetric stretch P–O (Al–O) Protonated morphiline stretch Asymmetric stretch O–P–O 730 714 870 846 1110 1086 220 ºC Relative Intensity (a. Zhang et al. This result indicated that the acidic property of HZSM-5 sample is stronger than that of SAPO-34 and NiAPSO-34 samples. The TPR profiles of samples confirmed the results of XRD and FT-IR. 6. the conversion of ethanol was 96. Acidic property of the four catalysts NH3–TPD was used to characterize the acidic properties of the four samples.) 430 ºC (b) 197 ºC 426 ºC 407 ºC (d) 185 ºC (c) (b) (a) (a) 150 400 600 800 1000 Temperature / ºC 1200 Fig. Catalytic performance of dehydration of ethanol Catalytic testing of ethanol dehydration was carried our over Al2O3. up to . The relative distribution of these two types of acid sites 1:5. NH3–TPD profiles of samples (a) Al2O3 (b) SAPO-34 (c) NiAPSO-34 and (d) HZSM-5. NiAPSO-34 sample exhibited higher desorption temperature of both weak and strong acid sites and possessed more weak acid sites due to incorporation of Ni2+ into the SAPO-34 framework. The higher desorption temperature is. 4.u. They are typically known as Lewis acid sites [20]. the first peak was associated to reduction of Ni2+ in the framework. The ethanol conversion and selectivity to ethylene were measured at different temperature. two distinctly resolved maxima NH3 desorption peaks sample at 185 °C and 407 °C. were observed. As shown in Fig. In contrast.3. HZSM-5. 5. As shown in Fig.) Relative Intensity (a.2. H2–TPR profiles of samples (a) SAPO-34 and (b) NiAPSO-34. sites present as surface hydroxyl groups.213 X. / Microporous and Mesoporous Materials 116 (2008) 210–215 Table 4 Assignment of the FT–IR bands in the framework vibration region of the as-synthesized samples Sample IR peaks wavenumber/cm 1 T–O bond SAPO-34 NiAPSO-34 SiO4 (Si. which were indication of the presence of acid sites in two different strengths. 5. For SAPO-34. Therefore. as estimated from the integrated areas of the two peaks. It was obvious that HZSM-5 sample showed highest desorption temperature of both weak and strong acid sites and most weak acid sites. The desorption peaks at low and high temperature corresponded to the weak and moderately strong acid sites in the molecular sieve framework. The desorption temperature indicates the acid strength of sample. This indicated that Ni2+ existed in the framework and was not easily reduced. attributed to the presence of Ni2+. At 375 °C. HZSM-5 sample possessing strong acidic property displayed the highest conversion of ethanol. suggesting the presence of a substantial amount of moderately strong acid sites in the SAPO-34 sample. 3. They are known to possess mainly the Brønsted acid sites. compared to SAPO-34 sample. 7. The moderately strong peak at 407 °C arose possibly from structural acidity [17]. NH3–TPD profiles of samples are shown in Fig. The acid amounts corresponding to the amounts of adsorbed NH3 were estimated from the areas underlying the NH3– TPD curves. 3. The results obtained are graphically illustrated in Fig.5% for NiAPSO-34 and 93. The first peak arose due to the weak acid 300 450 Temperature / ºC 600 750 Fig.

4 8. unit cell parameters and volume increased and the framework vibration frequencies shifted to position of lower wavenumber. SAPO-34 and NiAPSO-34 were employed as catalyst in the dehydration of ethanol. and provided 86. . With Al2O3. with four catalysts.9 0. 94. In NH3–TPD profiles of samples. (reaction condition: LHSV 3 h 1.7 atm. 98.7 0. 4. Table 5 Product distribution data at the optimal reaction condition of each catalyst* Product/% Catalyst Al2O3 HZSM-5 SAPO-34 NiAPSO-34 Optimal reaction temperature/°C Ethanol Ethylene Diethyl ether Acetaldehyde Unknown * 450 300 350 350 14. 97.214 X. As shown in Fig. LHSV 3 h 1. Effect of reaction temperature on selectivity to ethylene over different catalysts (reaction condition: LHSV 3 h 1. which showed the highest initial activity (93.1 92. SAPO-34. ethanol partial pressure 0. ethanol partial pressure 0. presented noticeable decrease of yield of ethylene after reaction for 60 h. / Microporous and Mesoporous Materials 116 (2008) 210–215 100 100 80 90 70 60 50 HZSM-5 NiAPSO-34 SAPO-34 Al2O3 40 30 200 250 300 350 400 450 Yield of Ethylene/% Conversion of Ethanol / % 90 80 HZSM-5 NiAPSO-34 70 SAPO-34 Al2O3 500 Temperature / ºC 60 Fig. 7.5 0. In contrast. the selectivity to ethylene begun to decrease due to the formation of outgrowth acetaldehyde produced by ethanol dehydrogenation.3%) at 450 °C. ethanol partial pressure 0. Al2O3 and HZSM-5 were commercial catalysts.9%. HZSM-5. Al2O3.4. the selectivity to ethylene increased with a concomitant decrease in the selectivity to diethyl ether. the selectivity to ethylene showed the same change tendency. NiAPSO-34 molecular sieve showed similar activity and better stability. at lower temperature (325 °C).5%. HZSM-5 catalyst. SAPO-34 and NiAPSO-34 were synthesized in the laboratory. As shown in Fig.3%. 98.7 6. For NiAPSO-34 sample. respectively. Zhang et al.1 – 4. LHSV 3 h 1.4 0.1%. (HZSM-5: reaction temperature 300 °C. 6. ethanol partial pressure 0. 7. which remained unchanged for 100 h of time on stream. The deactivation of H-ZSM catalyst was often reported in the literature [21]. In summary.8% to 62. An increase in temperature increased the selectivity to ethylene up to a certain temperature. after which it decreased. 0 20 40 60 80 100 Reaction time /h Fig. Compared to HZSM-5 catalyst. selectivity to ethylene was lower due to producing outgrowth diethyl ether. 8. 350 °C.7 atm). Al2O3 catalyst deactivated after reaction for 80 h and yield of ethylene decreased from 82. The stability of catalysts in the dehydration of ethanol The stability of Al2O3. At higher temperature. NiAPSO-34. Effect of reaction temperature on conversion of ethanol over different catalysts. 300 °C.8 86 4.7 atm Al2O3: reaction temperature 450 °C.3 – 6.4 78.7 atm SAPO-34 and NiAPSO-34: reaction temperature 350 °C. selectivity to ethylene was maximal (91. 3. Conclusions Dehydration of ethanol to ethylene was studied in this work. Comparison of the stability of catalysts. and is generally assigned to the possible strong acidic property of HZSM-5.7 atm).5 0. 100 Selectivity to Ethylene / % 90 80 70 60 50 HZSM-5 NiAPSO-34 SAPO-34 Al2O3 40 30 200 250 300 350 400 450 500 Temperature / ºC Fig. HZSM-5.1%). ethanol partial pressure 0.3% yield of ethylene.9 0. respectively.3 1. the conversion of ethanol and the selectivity to ethylene decreased in the order HZSM-5 > NiAPSO-34 > SAPO-34 > Al2O3. 8. At lower temperature. ethanol partial pressure 0. SAPO-34 and NiAPSO-34 exhibited effective catalytic activity and stability. 350 °C. Incorporation of Ni2+ into the framework generated in NiAPSO-34 sample was proved by XRD. NiAPSO-34 sample exhibited higher desorption temperature of both weak and strong acid sites and possessed more weak acid sites.9 93. HZSM-5 exhibited greater selectivity to ethylene than any of the catalysts at lower temperature.0% and 92. As the temperature increased. FT-IR and TPR techniques.2 Reaction condition: LHSV 3 h 1 .0 0. SAPO-34 and NiAPSO-34 was studied at the optimal reaction condition of each catalyst. LHSV 3 h 1.3%.7 atm). HZSM-5.

Bun. [11] D. Carreras-Gracial. J. P. 223 (2004) 231–235. R. Catal. Duarte de Farias. SAPO-34 and NiAPSO-34 revealed that for conversion of ethanol and selectivity to ethylene.U. Appl. L. [10] L. Bilbao.V. S. Phys. Dhupatemiya. 28 (1999) 19–24. Ind. Runet. D. Guin.S. Borges. Synthetically. Catal. T. Appl. S. Datta. Today 107–108 (2005) 410–416. Roy. D.M. Mol. Patton.P. 36 (1997) 4466–4475. Ming-Teck. Eng. the decreasing order of preference of the catalysts was HZSM5 > NiAPSO-34 > SAPO-34 > Al2O3. S. Micropor. Technol. 58 (1990) 119–129. Nishiyama.G. Kang. Valle. Chem. Chakrabarty. Acta. J. Kang. B. Tsuruya. J. Ki-Won. Mater. Roque-Malherbe.D. [17] A. Sci. Mesopor. T. Parakash.F. Appel. Appl. Okagami. 150 (1999) 205–212. Zaki. O. Berteau. Ramos. . B. J.T.M. J. Pillai.L. Ashtekar. Bhat. [14] M. J. P. 90 (15) (1994) 2291–2296.S. Phatanasri.K. Fraga. Micropor. Catal. L.R. Atutxa. Obrzut. / Microporous and Mesoporous Materials 116 (2008) 210–215 A comparative study of Al2O3. Today 101 (2005) 39–44. B. US Patent 4.M.L. E. Messina. Chim. J.M. Zeolite 13 (1993) 481–484. Ossining. A: Chem. P. Liu. Faraday Trans. S. Process Nov (1976) 125–133. Inui.X. B. Cannan. S. Punnoose. J. Mater. Samuel. Unnikrishnau. J. [15] M. J. Gajek. A: General 329 (2007) 130– 136. Sousa-Aguiar. Monteiro. P. M. C. Mol. Catal. [18] S.N. R. A: Chem. References [1] [2] [3] [4] [5] [6] [7] [8] A.L. [12] S.A. Adekkanattu. R. NiAPSO-34 was the suitable catalyst in the dehydration of ethanol. [21] A. Nandi. Haggin. Lopez-Cordero. Ravindranathan. E. T. 160 (2000) 437–444. 1984. Colloid Interf. J. Soc.V.A.C. S. Eng. [19] R. J. 1970.M. of the four catalysts. Dutta. A. Seung-Chan. 83 (2003) 203–218. US Patent 3541179.A. [13] M. Matsuoka. Mao. Chem. Catal. taking the activity and stability of catalyst into account. Lok. Barger. S. Dubois. Gayubo. Gonzales-Morles. 215 [9] P. S. Thundimadathil.L. C. A. Phillips. Mol. Chilukuri. Wilson. June. Delmon. Aguayo. [20] F.440871. Chem. NiAPSO-34 and SAPO-34 appeared better stability than other catalysts. A. 59 (1990) 13. 98 (1994) 4878– 4883. HZSM-5. M. Onate-Martinez. R. J. Katonah. S.A. 29 (1999) 117–126. J. Winter. P. 284 (2005) 606–613. R. 124 (1987) 25–33.E. Catal.G.B. News 20 (1983) 36.R. Catal. A. T. M. Yun-Jo. M. M. Hydrocarb. A: Chem. Masai. M. Chem. Inoue. Mesopor.T. Seehra. Fule Process. L. [16] B. J.M. Nguyen. Res. Hung. Zhang et al. Catal.