Applied Catalysis.

72 t 19911 39-49
Elsevier Science Publishers B.V.. Amsterdam

39

Silicon species in a SAPO-5 molecular sieve

R. Wang and C.F. Lin
Department of Chemistry, National Tsing Hua University, Hsinchu. Taiwan 3004,3 (Tain,an. ROC)

Y.S. Ha and L.J. Leu

Refimng and Manufacturing Research Center, Chinese Petroleum Corporation. Chia- Yi, Taiu,an 60036 ( Taiwan, ROC)

and K.J. Chao*

Department of Chemisto, National Tsing Hua University, Hsinchu, Taiu,an 30043 (Taiwan, ROC) tel. (+886-35) 715131. lax. (+886-35) 711082
{Received 4 July 1990, revised manuscript received 3 December 1990

Abstract The incorporation of silicon into a AIPO4-5 molecular sieve modifies the acidity of the host without disrupting its microporous structure. The amount of silicon substitution in AIPO~-5 was found to be dependent on the silicon source and the template used in the synthesis condition. The silicon substitution of phosphorous was studied by -'gSi magic angle spinning-nuclear magnetic resonance and electron probe microanalysis. The strength and concentration of the Bronsted acidity of SAPO-5 were also studied by the temperature-programmed desorption of ammonia and IR spectroscopy.

Keywords: silicon, magic angle spinning-nuclear magnetic resonance, electron probe microanalysis,
Bronsted acidity, SAPO-5.

INTRODUCTION

Aluminophosphate molecular sieves (AIPO4) composed of alternating AIO4 and PO4 tetrahedra were recently discovered by workers at the Union Carbide Corporation [1,2]. The electrically neutral and acidic properties of the aluminophosphate framework can be modified by the incorporation of silicon. The incorporation of silicon into the AIPO4 framework leads to silico-aluminophosphate molecular sieves (SAPO) [3]. The framework structure of the number five families (AIPO4-5, SAPO-5) has been well characterized by Xray diffraction (XRD) and contains one-dimensional channels bounded by twelve-membered rings with a pore opening of 8 ~, [4,5]. The tetravalent silicon substitution of pentavalent phosphorous results in an anionic tetrahedral framework of SAPO which can be coupled with exchangeable cations or protons. In order to increase the ion-exchange capacity

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40 and Bronsted acidity, the SAPO-5 samples of high-silicon content were prepared by increasing the concentration of the silicon and varying the template source in the hydrothermal synthesis. However, the resulting high-silicon SAPO-5 materials usually contained a high percentage of amorphous silica impurities [6 ] or silica patch [7 ]. Therefore, their acidity is still quite low. The nature of the silicon reactant is one of the important parameters in the synthesis of aluminosilicate zeolites [8,9] and as such should play an important role in the introduction of silicon into the aluminophosphate framework. In this paper we report the results of SAPO-5 synthesis with monomeric organic silicon and polymeric colloidal silica and the characterization of a series of SAPO-5 samples. The nature of the silicon species in SAPO-5 was identified by 2~'Si nuclear magnetic reasonance ( N M R ) and the acidity was measured by means of temperature-programmed desorption ( T P D ) of ammonia with online titration and IR spectroscopy. EXPERIMENTAL

Sample preparation
The reactants were: 85% H.~PO4 {Merck:), aluminium hydroxide (pseudoboehmite Versal 450, Kaiser ), colloidal silica solution (Ludox AS-40, Du Pont ) with 40 wt.-% SlOe, tetraethyl orthosilicate Si(OEt )4 (Merck, 98% pure), tripropylamine (Fluka) and triethylamine (Wako). All reactant gels were prepared according to the following steps: the Ludox AS or tetraethyl oft hosilicate solution was added to a mixture of water and orthophosphoric acid while stirring; subsequently, aluminium hydroxide and template species (triethylamine or tripropylamine) were added to obtain a homogeneous gel with a pH of 3.03.5 and a molar composition of 0.62-0.85 Pr.~N or Et:~N: 1.0 P_,O~: 1.0 AI20.~: 0.13-0.27 SiO._, or S i ( O E t ) 4 : 3 0 H._,O {Table 1 ). The reactant gel in a teflon container was put into a stainless steel autoclave and heated at 170:C for 7 days. At the end of crystallization, the autoclaves were quenched to room temperature under tap water. The product was washed thoroughly with deionized water and a sodium hydroxide solution of pH--9.5, then dried at 80: C. The SAPO-5 precusor (1.5 g) was calcined at 600=C and ion exchanged with 100 ml of 1 N NH,C1 solution at room temperature to its NH4 form.

Characterization
The SAPO-5 is the only crystalline phase in the synthesized samples identified by XRD. The elemental analyses of products were carried out by using a Jole 840A electron probe microanalyzer ( E P M A ) and a GVM 1000 simultaneously inductively coupled plasma-atomic emission spectroscope ( ICP-AES ) [10], respectively. The crystal sizes and morphologies on the sample coated

41

TABLE 1 The compositions of reactants '' and SAPO-5 particles Sample No. Si in reactant wt.-% ) Silicon source EPMA ( w t . - ~ ) Si
1 ') 4.20 6.74

ICP-AES ( w t , - ~ ) Si
(hexagonal) csheaf-like (hexagonall Isheaf-like) (amorphous~ (hexagonalp (hexagonal) csheaf-like) (hexagonal) (hexagonal) (sheaf-likel qpebb[e-packed) 2.42 2.82

AI
22.0 20.6 20.7 20.1 19.2 20.4 2t).4 20.7 20.8 20.8 20.5 18.7

P
23.6 22.9 24.2 23.1 23.6 2:3.7 24.4 23,6 23,6 23,8 22,8 23.4

AI
17.98 17.27

P 18.97 17.98

Ludox AS Ludox AS

3 4 5 6

4.20 6.74 4.20 6.74

SilOEtp~ SiIOEt)4 SiIOEtt~ SicOEt)4

1.6 4.0 2.6 4.2 4.5 3.;3 2.6 3.2 3.1 2.9 4.2 5.2

1.95 2.29 3.24 3.56

18.18 20.08 16.97 18.86 18.11 17.17 18.89 18.51

"AI source: pseudoboehmite Versa1450: P source: 85% H:~PO~: template souce: tripropylamine for samples 1-4 and triethylamine for samples 5 and 6.

with a gold evaporation film were examined by means of an Hitachi S-570 scanning elect ton microscope. The 29Si-, 2~Al- and ~1P-MAS-NMR spectra were obtained on a Bruker MSL-200 N M R instrument. Typically, more than 13 000 free-induction decays, with 10 and 5 s recycle times were accumulated in -'9Si M A S - N M R and cross polarization ( C P ) - M A S - N M R , respectively. The NH4SAPO-5 sample (0.3 g} was placed into a quartz cell proceeding temperature-programmed desorption experiments. The adsorbed water was removed by a flow of dry argon (30 cm 3 min -1) at 150~C. Then, the temperature was increased at a rate of 5 = C / m i n from 150 to 600:C. The desorbed ammonia was trapped in a solution of saturated boric acid and 1 N NH4CI, and titrated by sulphamic acid [ 11 ]. A self-supported wafer (20 rag) was load into the IR cell which was capable of evacuation and programmed heating. The NH4SAPO-5 sample was first activated at 150:C for 12 h and then heated 10~C/min to 450:C and held at 450 :C overnight under vacuum. The sample was then cooled to ambient temperature and 200 scans were accumulated in an IR spectrum. Differential scanning calorimetry ( D S C ) and thermogravimetric thermal analyses were recorded in flowing argon on a Setaram TGDSC111 apparatus.
R E S U L T S AND D I S C U S S I O N

The X R D pattern of synthesized SAPO-5 is similar to that of A1PO4-5 with a = 13.720 (2) ,,, c = 8 . 4 3 9 (3} ,1, and a = 1 3 . 7 1 2 (3) .,, c = 8 . 4 4 5 (5) ~, respec-

42

"~\
~"
(/t

--:

,., ,,, .., ._.., ~ " " - ~ ~ " ' - , " "" ....~ ~ SAPO-51No.3~ ~ ~"~":" " ':'"-

-- SAPO-5(No.2~
:

ALP04-5

-5

o
0

-15

" ~= E 3o

/J

f/

o,
15

\j/
-15 0 -, 200 ,400 TEMPERATURE(C) , 600 800

Fig. l. TGA Itop ) and DSC qbottom I thermal analyses of AIPO4-5and SAPO-5. tively. This indicates that silicon incorporation has little effect on the framework structure of AIPO4-5. Fig. 1 shows the thermogravimetric analysis (TGA) and DSC results for SAPO-5 and AIPO4-5. AIPO4-5 have three distinct weight losses: 3 0 ~ 150C, 150 ~ 480:C and 480-650: C. The first endothermic loss is due to the desorption of water. The second loss is accompanied by an exotherm that indicates the decomposition of the organic template Pr.~N, which was confirmed by on-line mass spectrometry and acid titration analyses. The decomposition of the template on the No. 3 SAPO-5 sample was found at 390 and 430:C while the No. 2 SAPO-5 gave only one peak at 400: C. The two stage decomposition implies that the trialkylamine occupies two different sites in the No. 3 SAPO-5. One site will be in the channel with no nearby acid site while the other will be adjacent to a silicon site where the R:3NH + acts as a counter ion. The high temperature exotherm ( >600~C ), probably from carbon dioxide or organic compounds, is generated by the decomposition of the organic template.

Silicon species
Scanning electron micrographs of SAPO-5 and AIPO4-5 are shown in Figs. 2 and 3a. There are four different kinds of particle morphology including hex-

43

Fig. '2. Scanning electron micrographs of SAPO-5, sample Nos. 1-6: (a)- (f). Hexagonal (a,b}; sheaf-like (c,e); pebble packed (d,f} particles.

44

Fig. 3. Scanning electron micrographs of AIPO4-5 (a) and a cloud-like particle in the SAPO-5 sample (b).

2&
vJ 1111
! I I

4.2O%

6.74%
It.

,~,,.,~ I.udox-AS

i Bi((]El 14

[/
M

B; IOEt]4

-100 ppm

-200

-100 ppm

-200

Fig. 4.~gSiMAS-NMR spectra ofSAPO-5, sample Nos. l-6:(al-lfh

agonal, sheaf-like, pebble-packed and cloud-like forms. The alternation in reactant composition was accompanied by the change in morphology from sample 1 to sample 6. Particles from Si (OEt)4 preparations appear to be made

45
93 ~ 104

'+~,

L 1.

- 1O0 ppm

-2 O0

Fig. 5. -'gSn MAS-NMR spectra of synthesized (a) and calcined (b) No. 5 SAPO-5; CP MASNMR spectrum of calcined No. 5 SAPO-5 (c).
92

- 1O 0 P~

-200

Fig. 6.29Si MAS-NMR of No. 6 SAPO-5 (a) and Si(OEt )4 treated No. 6 SAPO-5 (b). up of a large n u m b e r of small c o m p o n e n t p a r t s a g g l o m e r a t e d in sheaf-like or p e b b l e - p a c k e d f o r m s a n d / o r i n t e r g r o w n together. I n c r e a s i n g the silicon cont e n t in the L u d o x AS p r e p a r a t i o n s results in the f o r m a t i o n of the cloud-like particles. T h e silicon c o n t e n t of t h e particles are in the o r d e r of hexagonal < sheaf-like < cloud-like < pebble-packed (Table 1 ). O f all the particles, only the cloud-like ones can not p r o d u c e e l e c t r o n diffraction p a t t e r n s and are a m o r -

46
b

150

35

-80

50

ppm

-25 ppm

-100

Fig. 7.~TAIqat and.~p IbD MAS-NMR of SAPO-5.

phous ~Fig. 3b). No. 2 SAPO-5 had the highest concentration of amorphous material, No. 5 SAPO-5 the lowest. The A I P O c 5 sample had no detectable impurities. Fig. 4 shows the z9Si M A S - N M R spectra of samples. They consist principally of three peaks: at ca. - 9 2 , - 1 0 5 and - 1 1 2 ppm except the 29Si N M R spectrum of sample 6. The silicon substitutions of one silicon atom for one phosphorus atom and two silicon atoms for an aluminium plus a phosphorus atom are more likely in the SAPO framework [3,6]. Based on the results of their composition analysis, Appleyard et al. [6] suggested that the - 9 2 ppm peak is probably from silicon atoms in a QO (4A1) environment. The intensity of the - 9 2 ppm peak in the -'gsi M A S - N M R spectrum of calcined No. 5 SAPO5 was enhanced significantly by CP techniques (Fig. 5). This indicates that the silicon species related to the - 9 2 ppm peak probably has a proton nearby. It is clear that the - 9 2 ppm line can be assigned as one silicon for one phosphorus substitution. Sample No. 6 were impregnated with very dilute Si (OEt)4 aqueous solution and heated to 150: C. The '29Si N M R spectrum of the Si ~OEt )4 treated No. 6 SAPO-5 sample shows a strong signal at - 105 ppm compared with that of No. 6 SAPO-5 (Fig. 6). Therefore, the peak at ca. - 105 ppm is assigned to the coating behaviour of unreacted silicon sources. If the pair substitution of two silicon for one aluminium and one phosphorus were possible, at least two 29Si signals would be observed corresponding to Si ( 3A1 ) and Si (3P). The absence of these two peaks shows that there is no such substitution mechanism taking place. According to the literature [6], the peak at - 1 1 2 ppm reflects some amorphous SiO.,. The .rip_ and ~TAI-MAS-NMR spectra were recorded for samples 1-6. The typical e:Al and :~P N M R spectra are shown in Fig. 7. One broad line is observed for the 2VAl or :~P N M R spectrum of each sample. The chemical shift values varied from 34.6 to 38.7 ppm and from - 29.4 to - 30.3 ppm respectively for the 2:A1 and 3~P NMR. These chemical shift values are typical for tetrahedral aluminium AI(4P) or phosphorous P(4AI) [12]. This also indicates

47

that there are no significant aluminium or phosphorus octahedral amorphous materials in any of our samples.

Acidic property
The Bronsted acid strength and the concentration of SAPO-5 and the zeolites can be detected by the ammonium decomposition temperature and the amount of ammonia desorption from its NH4 form sample measured by T P D with on-line titration. The acid amounts and the temperature of peak maximum concerning the six SAPO-5 samples are calculated and listed in Table 2. As mentioned in Table 1, sample 1 and 3 or sample 2 and 4 were prepared in an identical manner but with different silicon reactant. The acid amounts in sample 3 and 4 are greater than those in sample 1 and 2. The use of tetraethyl orthosilicate instead of Ludox AS as a silicon source leads to an increase in Bronsted acidity of the SAPO-5. Ludox AS is a polymeric silica material in contrast to Si(OEt )4 and needs to be broken into small components in order to be incorporated into the AIPO4-5 framework. Therefore, our results indicate that S i ( O E t ) 4 is a better reactant than Ludox AS for synthesizing highly acidic SAPO-5. The relative intensity of the peak at - 9 2 ppm on the 29Si N M R of the samples from Si(OEt )4 preparations is higher than that from Ludox AS preparations. Therefore, we can conclude that the - 9 2 ppm peak originated from one silicon substitution for one phosphorous and related to the Bronsted acidity of SAPO-5. Table 2 also shows that the Bronsted acidity on SAPO-5 can be increased by using triethylamine instead of tripropylamine as the template agent. The ammonium decomposition temperatures of NH4SAPO-5 indicates that the Bronsted acidity of SAPO-5 is between that of Y and ZSM-5. The acid values of No. 5 and 6 NH4SAPO-5 (0.56 and 0.58 mmol/g) are comparable with that of ZSM-5 (0.45 mmol/g) with an Si/AI atomic ratio of 24

[13].
The IR spectra of the hydroxyl groups of calcined SAPO-5 No. 2 and No. 6 are shown in Fig. 8. There are four adsorption bands with maxima at 3744, 3670, 3623 and 3520 c m - ~ on No. 6 SAPO-5. The band at 3744 cm - ~, considered to be attributed to the SiOH groups from extra-crystalline silica impurities, is smaller in the No. 6 SAPO-5 than in the SAPO-5 sample synthesized
TABLE 2 Temperature-programmed desorption of ammonia on NH4SAPO-5 samples Sample No. Acid amount (mmol/g): Tm~J :C b 1 0.02 2 0.07 392 3 0.23 340 4 0.28 348 5 0.56 325 6 0.58 318

48 0.03
a: b:

SAPO-5(No:2) SAPO-5(No:6)
Q

Z .< "s o9 Z

0.02

3744

0.01

31lifo

!U;2.3

3~1~

0.00 4000

5750 3500 WAVENUMBER (crn -1 )

3250

Fig. 8. Hydroxyl groups of SAPO-5 No. 2 qa) and No. (3 (b).

by Halik et al. [ 14 ]. With similar amounts of samples, the intensities of the two bands at 3623 and 3520 c m - ' were shown to be much weaker on the No. 2 SAPO-5 than on the No. 6 SAPO-5. These two bands probably arise from SiOHA1 groups generated by the substitution of silicon for phosphorous and have also been observed by Halik et al. [ 14 ] and Hedge et al. [ 15 ]. Halik et al. [ 14 ] suggested that only the SiOHAI groups corresponding to the band at 3623 c m - ~ pointing into the main channels of the framework could be accessed by large reactants such as benzene. The frequency value of this band is close to those of bridged acidic OH groups on SAPO-37 (3640 c m - l ) [16], HY (3640 c m - ] ) and HZSM-5 13610 c m - ] ). If the higher frequency of the 3600 -~ 3640 band comes from the weaker Bronsted acidic site, the acidic strength in the order of HZSM-5 > HSAPO-5 > HSAPO-37-- HY [ 16,17 ] can be confirmed. The relative intensities of the 3623 and 3520 c m - 1 bands are higher than that of the 3744 c m - 1 band on No. 6 SAPO-5 which shows an increase in silicon substitution for phosphorus by using tet raethylort hosilicate as the silicon source for synthesizing SAPO-5.
ACKNOWLEDGEMENTS

We are grateful to Mr. L.H. Lin for the TGA and DSC measurements. This work was partially supported by the National Science Council of the Republic of China.

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