H.E. Curry-Hyde and R.F. Howe (Editors), Nalural Gas Conversion I1 1994 Elsevicr Science B.V.

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CONVERSION OF METHANOL TO LIGHT OLEFINS OVER SAPO-17 MOLECULAR SIEVE

Shah Nawaz*, Stein Kolboe* and Michael St6cker**

Department of Chemistry, University of Oslo, P.O.Box 1033, N-0315, Blindern, Oslo, Norway. **) Department of Hydrocarbon Process Chemistry, SINTEF-SI, P.O. Box 124, Blindern, N-03 14 Oslo, Norway.
*)

Abstract The zeolite erionite and its isostructural silicoaluminophosphateanalogue,SAPO- 17. were studied with respect to their catalytic behaviour in the MTO process, the emphasis being laid on SAPO-17.It proved superior to erionite both with respect to olefln selectivity and catalyst lifetime. Ethylene constituted almost 70 mol% and propylene almost 20 mol% of the product, compared to a maxtmum of 40 mol% ethylene and 30 mol% propylene with erionite. It was active for 10-20 the erionite for less than 2 h, h, and erionite exhibited ethylene/ propylene selectivity for only one hour. Experiments with SAPO- 1 in range 350-475OC 7 showed optimum behaviour around 425OC.Outside this temperature lifetime and selectivity deteriorated quickly. A deactivated sample of SAPO- 17 could be restored to full activity by calcination in air at 500-550C.
1. INTRODUCTION

Light olefins are important starting materials for the manufacture of many industrial products such as polymers, detergents, plasticizers etc. At present they are mainly obtained from crude oil based resources. Methanol, which may be obtained from coal or natural gas, may be an interesting alternative raw material. Protonated ZSM-5, in particular, is an excellent catalyst for converting methanol to hydrocarbons, but tends to produce a hydrocarbon mixture which i more useful for gasoline than as a light oleflns petrochemical feedstock [ 1-31. s Work aiming at stopping the reaction at the light olefin stage, e.g. by modifying the catalyst or by choosing optimum reaction conditions, has been reported [4-61. On the other hand, small pore zeolites like erionite, chabazite, ZK-5etc, with 8-oxygen ring pore openings are reported to be selective for an MTO process 1 1 7, but they deactivate quickly, so frequent regenerations are necessary. Modification by dealumination seems to alleviate the problem [8]. Recently a new class of zeotype molecular sieves based on aluminophosphates (ALP04,s) has been discovered 19-10). They are neutral, but acidity can be introduced by substituting some of the P5+ions by Si4+(forming SApOs) [ 1 1 - 1 1 2. The acidity i weaker, and the acid site density can be varied. They appear to be s promising catalysts for light olefln formation from methanol [ 1 1 Prominent 3. examples are SAPO-34 (chabazite structure) [ 13-14] and SAPO-17 (erionite structure). In this work SAPO-17and erionite were selected for further study.

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2. EXPERIMENTAL 2.1. Catalyst synthesis and characterization SAPO-17 was synthesized according to Lok et al. [ 111 and characterized by X-ray diffraction, elemental composition determined by X-ray fluorescence, TPD of ammonia, MAS NMR spectroscopy on 29Siand 31P, study of template removal during calcination, and thermogravimetric measurements. NH4-erionite was provided by VEB Chemie Kombinat Bitterfeld, Germany. It was converted to H-form by calcination at 550 O C . It was characterized using the same instrumentation as was used for SAPO-17. 2.2. Reactor testing The catalytic evaluation experiments were performed in a fixed-bed flow reactor using 0.4-1.0 g catalyst, which was placed between two layers of quartz wool. Methanol feed was evaporated and diluted with nitrogen. The measurements were carried out keeping a partial pressure of methanol and nitrogen mostly at 0.4 bar and 0.6 bar, respectively, and a Weight Hourly Space Velocity (WHSV)of 0.5 h-' unless speclfled otherwise. The reaction temperature was varied between 350-475OC. Al samples were activated in-situ at 4OO0C in an atmosphere of l nitrogen for one hour in the reactor oven before methanol feed was admitted. The products were analyzed on-line by gas chromatography. The reactor equipment and analytical systems have been described earlier [ 141. Deactivated catalysts were in some cases regenerated at 55OOC in a flow of air (75 ml/min) for 4 hours and retested. CO, CO, and hydrogen were analyzed, but the amounts were negligible. 2.3. Thermogravimetry Thermogravimetric studies were carried out using a Stanton Redcroft STA 785 instrument. The samples were heated (5'C/min) from 20 to 56OoC in flowing nitrogen (20 ml/min) and kept at that temperature until constant weight. The nitrogen flow was then replaced by air (15 ml/min) in order to study the rate of coke oxidation. 3. RESULTS AND DISCUSSION
3.1. Characterization Elemental composition: The elemental composition of the samples gave for erionite the ratio Si/Al =3.5 while in SAPO-17 the corresponding acidity determining ratio (AltPI/Si is 70, showing that the acid site density in erionite may be 20 times higher than in SAPO-17.

Powder X-rav diffraction: The X-ray diffraction pattern showed our SAPO-17 to contain a small admixture of, probably, SAPO-35 [11,15]. The erionite may contain an offretite intergrowth, but is otherwise pure.
3.2. Reactor testing Product distribution: The product distributions (including unconverted oxygenates) during the methanol conversion over SAPO-17 and erionite at 425 O are shown in Figs. 1 (a) and (b). Over both catalysts the olefln formation C increases with time on stream until it reaches a maximum and then declines sharply. The released hydrocarbons are in the C -C, range, with only small

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100

80

d, - 60

$
0

40

20
0 0

10

15

20

TOS fhours) (a)

25

TOS ( h o u r s )

(b1

Fig. 1 Product distribution in the reactor effluent and its dependence on t h e at . 425OC. (a) over SAPO-17; over erionite. (Note the different time scales for TOS). (b)
amounts of C,, In both cases. But there are also clear differences between the two catalysts. The catalysts lifetimes before deactivation are quite different. As seen from Fig. 1 a), SAPO- 17 was active for 20 hours before the activity declined while the erionite sample, as I seen from Fig. 1 b was active only a short time, s about 2 h. At peak activity, the amount of C,-C, olefins i about 85 mol% over SAPOs 17, whereas the erionite gave 70 %, and that was only in a short time interval. Furthermore, SAPO-17 was particularly selective for the formation of ethylene. During the active period of methanol conversion into hydrocarbons, the ethylene selectivity increased gradually with time on stream, up to above 60 mol%, while the formation of other hydrocarbons decreased correspondingly. Erionite did not show such a high selectivity. Saturated Hvdrocarbons: Also regarding formatton of saturated hydrocarbons erionite and SAPO-17 show very different behaviour. Erionite starts by giving propane as the dominating product, and propane, although declining, remains a major product during the whole peridd the erionite is active. Over SAPO17 propane is never a dominating product, and it falls almost to U MelhanelErionite - t PropanelSAPO-17 zero while ~ ~ ~ 0 is still7fully - 1 + Melhane/SAPO-17 active. Details are seen from Fig. $ 2. Methane is also formed over z 30 both catalysts, initially in a 2 similar quantity (< 5 mo1%). It E 20 falls to zero over erionite as the 5 catalyst deactivates. Over SAPO10 17 the methane formation remains stable, and it soon 0 becomes the major saturated 0 1 2 3 4 5 hydrocarbon (-3mol% 1. ExperiTime on stream (hours) ments with no catalyst, showed n .2. Methane and propane in the reactor g that the methane was not formed effluent over SAPO-17 and erionite at 425OC. on the reactor walls.

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Effect of Methanol Partial Pressure: A number of catalytic testing experiments were performed on SAPO-17, where the partial pressure of methanol was varied. They were all performed at 40OoC. The partial pressures of methanol were 0.4, 0.2 and 0.1 bar. IGHSV was kept constant, so WHSV varied correspondingly.) From the plots of conversion versus time on stream (Fig. 31, it is apparent that the catalyst lifetime increased when the methanol pressure was lowered. The of hydrocarbons before regeneration became necessary was, however, essentially constant. This may suggest that coke formation is mechanistically connected with hydrocarbon formation. Effect of TemDerature: Experiments carried out at different temperatures showed the deactivation rate to be highly temperature dependent. This is shown in Fig. 4, where the conversion of methanol versus time on stream at 350,400, 425 and 475OC are presented. A rapid deactivation is observed both at the lowest and at the highest reaction temperatures. The longest catalyst lifetime was observed around 425 OC. We believe that two different catalyst deactivation mechanisms are operating at the two extremes of temperatures. Around 35OoC,we believe the deactivation to be due to the formation of long hydrocarbon chains formed by a series of condensation and poly-merization reactions of m e t h a n o l a n d / o r olefin molecules. Due to the low reaction temperature they do not decompose and hence they stay within the framework. The pores of the catalyst are thus filled with this complex and the catalyst is deactivated. On the other hand, around 45OoC and higher, the 0 20 40 60 80 1 I deactivation of the catalyst is Time on stream (hours) probably due to the formation of Fig. 3. Methanol Conversion over SAPO-17 at heat resistant, carbon rich "coke", various feed rates (and partial pressures). p r o b a b l y of polyaromatic character, which may render the active sites inaccessible, thus causing catalyst deactivation. In order to characterize the deactivating coke further, two samples of S M O - 17, deactivated at 350, respectively 425 O C , were put through thermogravimetric experiments. In each case, 32.6 mg of the sample was heated 0 5 10 15 from 2O-56O0Cat a programmed Time on stream (hours) heat-ing rate of 5'C/min in nitrogen flow (20 ml/min). The Fig. 4. Conversion of methanol into s a m p l e s were t h e n k e p t hydrocarbons at reactton temperatures of 350. 400, 425 and 475OC. The WHSV I 1.0 h' at s isothermally at 56OoC until a pMeoH=0.4 bar. constant weight

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was observed (about one 34 Ndragan+As hour), the carrier gas was 600 33Temp.'C then replaced by flowing air Y F 32- 450 2 Deactwated (350%) (15 ml/min). The weighta 31 losses in such experiments E 300 2 Q are shown in Fig. 5. Al30P 150 E though the total amount of 29: coke in the two samples is 28 0 very similar, the weight loss I 27 4 curves are quite diffgrent. 0 100 200 300 Both samples show a Time (min) weight loss slightly above 1 mg about 10 min after start Fig. 5. Thermal analysis of the carbonaceous of the experiment when the residues in two samples of SAPO-17 detemperature has reached activated by working at 350, respectively -100 OC, b u t this weight 425OC. Note initial use of N, (20 mL/min) and its replacement by ar (15 mL/min). i loss is undoubtedly due to loss of adsorbed water. The low temperature deactivated sample exhibits a pronounced weight loss starting C slightly below 450 O and tapering off slightly before the maximum temperature of 550 O is reached. The high temperature deactivated sample shows a hardly C noticeable weight loss in the same temperature range. When nitrogen is replaced by air,burning off of the residue remaining at this high temperature is seen to start immediately. The resistance to oxidation is, however, much higher in the sample deactivated at high temperature than in the low temperature deactivated one, which almost immediately attain a stable weight (coke free), whereas the former only slowly reaches a stable weight, which may be slightly lower, but is essentially the same as for the other sample. This indicates that the low temperature coke is rather different from the high temperature analogue, and this difference persists even after heating the coked catalysts to 550 OC, which is 125 O higher than the temperature where the high C temperature coke was formed. In a separate experiment a sample deactivated at 350 O was taken to 400 O C C (in N, stream), where a non-negligible weight loss takes place during a couple of hours. It could, however, not be revived to an active state by this procedure.

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Regeneration: SAPO- 1 7 which has converted methanol until deactivation may be regenerated. Samples deactivated by converting methanol to hydrocarbons a t 425OC, pmethanol=0.4 bar, WHSV = 1 h-' were regenerated by heating in air a t 55OoC for 4 hours. A renewed test under identical reaction conditions failed to show any change in catalytic properties or catalyst lifetime. This is in agreement with the result obtained by Kaiser [ 131, who also found that SAPO-17 (aswell as SAPO-34) can be repeatedly regenerated by calcination in air. We did, however, not carry out any long-term deactivation and regeneration experiments.
4. CONCLUSIONS

SAPO- is a promising catalyst for converting methanol to light olefms. It is 17

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particularly selective for forming ethylene which is the dominant product. It deactivates only moderately fast. The simultaneous catalytic testing of erionite and SAPO-17 clearly demonstrated that, in spite of being essentially isostructural, the two materials differ strongly in their catalytic properties. SAPO-17 is superior to erionite both with respect to catalyst lifetime and selectivity into light o l e h s when converting methanol. The resistance of SAPO- to deactivation has a maxlmum around 425 O and 17 C falls sharply at temperatures 50 O higher or lower. Deactivated SAPO-17 can be C fully regenerated.
6. ACKNOWLEDGEMENTS

S. Nawaz wishes to thank the "SPUNG Committee" of the Royal Norwegian Council for Scientific and Industrial Research and Norsk Hydro for financial support. Thanks are due to Dr. Frank RCSher, Leipdg (Germany) for providing the erionite sample.
6. REFERENCES

C. D. Chang and A. J. Silvestri, J. Catal., 47 (1977) 249. 1. 11 C. D. Chang, Catal. Rev.-Sci. Eng. 26 (1983) 2 11 S.Yurchak, Stud. Surface Sci. Catalysis, 36 ( 1988)25 1. 3 11 W. W. Kaeding and S. A. Butter, J. Catal., 61 (1980) 4 155. 11 C. D. Chang, C. T-W. Chu and R. F. Socha, J. Catal., 86 (1984) 5 289. 11 C. T-W. Chu and C. D. Chang, J. Catal., 86 (1984) 6 297. ( 1 C. D. Chang, W. H. Lang and A. J. Silvestri, U. S. Patent 4,062,905 7 (1977). 11 S.Cartlidge and R. Patel, Stud.Surface Sci. Catalysis, 49 (1989)1151. 8 [9] E. M.Flanigen, B. M. Lok, R.L. Patton and S. T. Wilson, Proc. 7 h Int. Zeolite t Conference, Tokyo 1986,Kodansha-Elsevier 1986,p. 103. [ 11 J. A. Rabo, Periodica Polytechnica Chemical Engineering, 32 ( 1988)21 1. 0 1111 B. M Lok, C. A. Messina, R. L. Patton, R. T. Gajek, T. R. Cannan,E. M.Flanigen, US. Patent. 4,440,871. 1 2 B. M. Lok, C. A. Messina, R. L. Patton, R. T. Gajek, T. R. Cannan, E. M. 11 Flanigen, J. Chem. SOC. 106 (1984) 6092. 0 361. 1 3 S.W. Kaiser, Arab. J. Sci. Eng. 1 (1985) 11 1 4 S.Nawaz, S. Kolboe, S. Kvisle, K. P. Lillerud, M. Stdcker and H. M. Bren, 11 Stud. Surface Sci. Catalysis, 61 ( 1991) 421. [15] Von Ballmoos and J. B. Higgins, Collection of simulated XRD Powder R. Patterns for Zeolites, Zeolites 10 (1990) 313-5 14.
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