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CATAL

. REV.-SCI.

ENG., 25(1). 1-118 (1983)

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Hydrocarbons from Methanol
CLARENCE D CHANG Mobil R e s e a r c h and Development C o r p o r a t i o n C e n t r a l R e s e a r c h Division P r i n c e t o n . New Jersey 08540

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.................................... GENERAL CONSIDERATIONS ....................... A . Stoichiometric C o n s t r a i n t s ...................... B . Thermochemistry ............................... CATALYSTS ....................................... A . E a r l y O b s e r v a t i o n s (pre-1960) .................. B . Zeolite C a t a l y s t s ............................... C . Nonzeolitic C a t a l y s t s ........................... REACTION KINETICS .............................. REACTION MECHANISM ............................ A . E t h e r Formation ................................ B . Hydrocarbon Formation .........................
INTRODUCTION THE MOBIL METHANOL-TO-GASOLINE (MTG) PROCESS ................................... A Fixed-Bed Process B Fluid-Bed P r o c e s s C . Product C h a r a c t e r i s t i c s D . Olefin P r o d u c t i o n

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VII . DUAL-FUNCTIONAL CATALYSIS
VIII . POSTSCRIPT REFERENCES

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Copyright 0 1983 by Marcel Dekker. Inc

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0022-2348/83/250 1-0001%3.50/0

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I.

INTRODUCTION

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The conversion of methanol to hydrocarbons is a remarkable reaction. The mechanism involves C-C bond formation from C, fragments generated in the presence of certain acidic catalysts and reagents. The precise nature of these reactive C1 species is unknown at present and is the subject of lively debate. The considerable diversity of current opinion will become apparent from the following account. Occasional reports of hydrocarbon formation from methanol, often as a minor side-reaction accompanying ether formation, can be found in the literature dating back as far a s 1880. However, it was not until the early 1970s that the industrial potential of the reaction emerged, due mainly to the confluence of two events: the discovery by workers at Mobil of the selective catalytic conversion of methanol to high octane gasoline over zeolite catalysts [l, 21, and the 1973 Arab oil embargo. The embargo instigated a worldwide reassessment of alternatives to petroleum. Since methanol can be made from coal (or virtually any carbon source) by proven technology, the Mobil development offered a new alternative to classical synfuel processes such as the FischerTropsch and Bergius. A sizable body of literature dealing with the theoretical and applied aspects of hydrocarbon formation from methanol has grown over the last decade and continues to expand. An attempt is made in this survey to cover the journal literature comprehensively, while the patent literature is, of necessity, treated with greater selectivity.
11. GENERAL CONSIDERATIONS

A.

Stoichiometric Constraints

Hydrocarbon formation from methanol requires the elimination of oxygen, which can occur via three modes: elimination a s H,O, CO, or CO, (elimination as 0,is prohibited by thermodynamics). Reactions involving the coproduction of oxygenates such as formates can also be written. However, with the possible exception of methane formation, as discussed later, no clear-cut experimental examples of this reaction are known. For the present, therefore, the discussion will be limited to hydrocarbons as the sole organic product. Depending on the nature of hydrocarbons formed, H 2 or coke may also be produced. In the simplest case, where H 2 is the only coproduct , the stoichiometry can be written a s follows:

HYDROCARBONS FROM METHANOL
CHSOH * [CHZI + H2O

3
( 1)

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Here [CH,] represents mono-olefins, cycloparaffins, or the average composition of a mixture of paraffins and aromatics. Acetylenic compounds o r polyenes have not been observed in significant amounts in studies reported to date. When paraffins a r e the sole hydrocarbon products, several reactions can be written. The principal reactions a r e ( n + l ) C H 3 0 H * CnH2n+2 + C + ( n + 1)HZO (2n + 1 ) C H 3 0 H
+

( 2)

2CnHzn+z

i CO

+ H20

(3)

n = 1 , , 2 , 3,

...

(4)

Equation ( 4 ) is derivable from ( 3 ) by allowing the water-gas shift reaction to occur and go to completion. In forming aromatics from methanol, 3 mol of H 2 (exclusive of H 2 in HzO) are necessarily eliminated or transferred for each aromatic ring generated. The general equation for mononuclear aromatics formation is nCHJOH + C n H z n - 6 + 3H, + nH,O, n = 6, 7 ,

. ..

( 5)

Although pure examples of (5) have not been observed to date, the enhancement of aromatics in the presence of certain metal/zeolite combinations, with concomitant H2 production, is known [ 31 .
B.

Thermochemistry

Hydrocarbon formation from methanol is an exothermic reaction. B y way of illustration. reaction enthalpies 141 associated with E q s . (11, ( 2 1 , and (5) are plotted in Fig. 1 for n-paraffin. linear 1olefin, and methylbenzenes formation at 316OC. The olefins curve, which may also be considered representative of a balanced paraffin-aromatic distribution ( i . e . , with no H, or coke make) is seen to level off at -AHR = 300-400 cal/g. This is in accord with the enthalpy data of Chang and Silvestri [21 for hydrocarbon formation from methanol at 3 7 l o C , which is shown in Fig. 2 a s a function of conversion. It is also apparent from Fig. 1 that the degree of exothermicity will vary depending on product distribution. From a practical standpoint, the control and removal of this large reaction heat is a major constraint in reactor design.

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- 400

r

- 600

bl
2
4
6 8 CARBON NUMBER 1 0

PARAFFINS + C

+ H20

12

FLG. 1. Hydrocarbon formation from methanol. Heats of reaction for selected hydrocarbon products at 600 K . 111.

CATALYSTS

A.

Early Observations (pre- 1960)

The earliest report of hydrocarbon formation from methanol n is that of LeBel and Greene [ 5 ] , who described i 1880 the

HYDROCARBONS FROM METHANOL
lo3
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5
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1

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1

1

1

1

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I l r l l l

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1 1 1 1 1

1

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1

I l l

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1 0

2

1
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AT 100% CONVERSION: OHR

-400 cal I g ( - I674 k J / kg 1

I I 1 I l l

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I

I I I I l l

1

I

I

I I 1 l I l

I

I 1 1 1 1 1 1

lo'

1'3 0

10-2

1 -I 0

1

LHSV-'

FIG. 2. Methanol conversion to hydrocarbons. Heat of reaction vs space-time at 371% [ 2 ] .

decomposition of methanol in molten ZnC1,. Hexamethylbenzene (HMB) and light gases, mostly CH,,, were identified as the main products, A possible equation for this extraordinary reaction is
1 CH30H 5
FUSED ZnC&

C

'@
C

C

+ 3CH4+

I5yO

AG~""

= -265.2 kcal/rnol

A s written, the reaction has AG = -261 kcalfmol of HMB at 283OC. the melting point of ZnC1,.

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CHANG

This large driving force for HMB formation has mechanistic a s well as process implications which are later discussed. LeBel and Creene interpreted their result, perhaps prophetically, in terms of V H , " condensing to benzene, followed by exhaustive ring methylation by a Friedel-Crafts reaction with CH,Cl generated in situ. In 1914 Sernagiotto [ 61 reported the decomposition of methanol by P,O, in a paper titled "On the Chemistry of Nascent Methylene." The vigorous reaction yielded a mixture of hydrocarbons with the general formula (CH,)n. Propene and butene were identified via bromination. Hexene and hexane, along with unidentified solid products, were also produced. For this example, P,O, would probably be more accurately described as a reactant rather than a catalyst in the true sense. A patent was later granted to Grosse and Snyder 171 for the conversion of methanol and DME to hydrocarbons over ZnC1, at 375-675OC and superatmospheric pressures. Table 1 contains typical results. The light hydrocarbons are mostly isobutane. The heavier fractions contained significant HMB Adkins and Perkins [8] studied the reactions of methanol over Al,O,. At 300-350°C methanol was quantitatively converted to DME, and above 350°C, CH,, CzH4 as well as C O , CO,, and H, were detected. Topchieva and Ballod [ 91 compared the activity of silica gel, Al$, and silica-alumina (Al,O, 30% Sio,70%), for methanol conversion to DME The aluminosilicate catalyst, after adsorbing methanol (0.58 mmol/g) at 20°C was heated to 4 O O O C and gave CO,, C2H4, CO. and C,H, in addition to DME, C , and unreacted methanol, Cullinane et al. [ 101 found that methanol contacted with activated Al,O, or Type-C Al,O, at 45OOC yielded small quantities of hexamethylbenzene. Gorin [ 111 reacted a mixture of dimethyl ether (18.2 mol%)and isobutane over amorphous silica-alumina at 37OoC, 150 psig, and 6.8 h-l GHSV. The conversion of dimethyl ether to hydrocarbons was 94.58, while no net change in isobutane occurred. The yield distribution on an isobutane-free basis is shown in Table 2. In the absence of isobutane, at higher temperature, lower pressure, and higher space velocity, considerable methane, CO , and carbon were produced, while the yield of C,+ hydrocarbon was less than 15%. Although no explanation of the role of isobutane was offered, one can surmise that it served to moderate the large reaction exotherm According to Gorin, methanol reacts more slowly and produces less liquid hydrocarbons, although no data were given.

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Suwon Campus] At: 10:27 12 February 2009 7 CH4 C2H6 1.1 30. ..0 a 18%hexarnethylben zene based on MeOH converted. albeit in considerably lower yield.0 0. CoMoO. g .4 1. e .HYDROCARBONS FROM METHANOL TABLE 1 Conversion of Methanol to Hydrocarbons over Fused ZnC1.7 C. A patent issued to Fawcett and Howk [12] claims the direct conversion of methanol to hydrocarbon wax in the presence of a metal rnolybdite catalyst.3 4. Such is the case in an earlier study by Eidus [13] where methanol was reacted over a cobalt-thoria-kieselguhr catalyst under FischerTropsch conditions and found to give the s a m e hydrocarbon products a s with CO + 2H2.5 tom) Higher boiling products Other 33. . modified with nickel chromite at 100-350°C at 70-1000 atm.6 1. and therefore whether the actual hydrocarbon-forming reaction is a Fischer-Tropsch reaction.4 - 100. [ 71 (425OC. Here the question arises a s to whether methanol is not simply a source of synthesis gas via dissociation. to 85OC (1.0 1. Oa 7. 166 atm) Mole percent MeOH converted to Downloaded By: [2007-2008-2009 Kyunghee University .0 19.5 C4H8 0.

Since every oxygen in such a structure (viewed a s an infinite lattice) is shared by two tetrahedra. + C. 151 and ZSM-11 [16. Zeolite Catalysts 1. In general. At ylx = w . crystalline aluminosilicates composed of A104 and S O 4 tetrahedra.6 99.H8 i-C i-Cs c 7 3.0 CHI4 C2H4 C3H6 + C3H8 n-C4H. . be elect rically neutral .03 [ 111 (37OoC.8 c 8+ Carbon B.1 5. 8 h-l QHSV) Products Downloaded By: [2007-2008-2009 Kyunghee University . 6 . and in some exceptional cases.2 26. the framework will possess a net negative charge. e . interconnected through shared oxygen atoms.8 CHANG TABLE 2 Dimethyl Ether Conversion over Si02-A1.6 8. forming a three-dimensional framework.7 10. leading to the general representation where n is the charge on the cation and z is the water of hydration. . 10 atm. the framework will..0 21. This is balanced by (exchangeable) cations Mn+ in the structure. g . Introduction Zeolites are porous.Suwon Campus] At: 10:27 12 February 2009 % 5.4 11.2 8. of course. 171. the synthetic zeolites ZSM-5 114. 5 < y /x 0 0 . y / x ? 1.

zeolites are unique in their ability to discriminate between reactant molecules and to control product selectivity. Structure of ZSM-5 and ZSM-11 The unique catalytic properties of ZSM. 2. ZSM-5 and Related Zeolites The most extensive work on hydrocarbons from methanol has been done with ZSM-5 zeolite catalysts. c = 13. For comprehensive treatments of zeolite structure and chemistry. Typical zeolite pore geometries. a.92. b = 19. The . There is little question that these are the most effective catalysts yet discovered for this reaction. 1621. the reader is referred to the classic monographs of Breck 1231 and Rabo 1241.42 A. l o . and cages.. When M is a proton. These are of molecular dimensions. channels.Suwon Campus] At: 10:27 12 February 2009 FIG. the zeolite becomes a strong Bronsted acid. known as "shape-selective catalysis [ 18-22] .5 zeolites have been attributed to their crystal structure [ 1. 3. Zeolite ZSM-5 [ 14.07. is a consequence of the well-defined geometry of zeolite pores. A s catalysts.HYDROCARBONS FROM METHANOL Erionite 8 Ring 9 Y Zeolite 1 Ring 2 ZSM-5 1 Ring 0 (Stroight Channel1 Downloaded By: [2007-2008-2009 Kyunghee University . This phenomenon. Some typical pore geometries are shown in Fig. 15. and 12-rings of oxygen atoms. 3. 251 has orthorhombic symmetry Pnma with cell parameters a = 20. The catalytically most significant zeolites are those having pore openings characterized by 8-. depending on molecular size and shape.

The framework is shown in Fig. 4 1 (sinusoidal channels) based on oxygen radii of 1 . Figure 5 shows a stereo-pair drawing of the ZSM-5 framework viewed along [ 0101. 17. represented in F i g . Fig. consists of intersecting straight channels. 4 X 5. 2CH3OH rCH. The channel structure. channel system. The channels are ellipsoidal with 10-ring openings. with cell parameters a = 2 0 . 4 1. confirming its intermediacy in the reaction sequence.+ olefins This was established by monitoring changes in product distribution as a function of varying contact time. An essentially identical reaction path was obtained with DME as feed. 3 5 A. shown in Fig. 1 X 5 . consists of straight channels running parallel to 10101 and intersecting sinusoidal channels parallel to [ 1001.6 (straight channels) and 5 . having the approximate free dimensions 5 . 6. 1 X 5 . 1 . with 5 . ZSM-11 has tetragonal symmetry I h 2 .Suwon Campus] At: 10:27 12 February 2009 FIG.10 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . 8. 5 free dimension. 251. 4. ZSM-Kchannel system. 4. Closely related to ZSM-5 in structure and properties is ZSM-11 116. .OCHS -C2'--C5'-- -H20 -H20 +H2 0 Scheme A paraffins aromatics cycloparaffins C. w General Reaction Path The conversion of methanol over ZSM-5 zeolites was investigated by Chang and Silvestri [ 21 who found the reaction to proceed according to the following general reaction path: b. shown in Fig. 9. 7. c = 1 3 .

t- Mobil synthetic zeolite ZSM-5 Na. ZSM-11channel s y s t e m .9 c = 1 3 . 9 T/1000 A3 { [OIO] (100) 5. 4 A FIGURE 5 1251.6 - [loo] 10 5. FIG. 4 x 5.16 H.. 6 ..Si.~.Suwon Campus] At: 10:27 12 February 2009 ZSM-5 Pnma viewed along (010J 8 T. .O.1 b=19.5r.-.Al. .*P 1 Secondary buildlng units: complex 5-1 Framework density: Channels: Fault planes: Type species: 1 7 .O wt ih n c 27 and typically about 3 orthorhombic.1 x 5.HYDROCARBONS FROMMETHANOL 11 Downloaded By: [2007-2008-2009 Kyunghee University . a=20. Pnma.

7 T/1000 A3 < 100.4 A FIGURE 7 [25]. .. Scheme B .1 x 5 ..O. a=20.OCH. 5 * * * Mobil synthetic zeolite ZSM-11 Na. The modified scheme. contains a direct path to olefins from methanol: 2CHjOH CH.16 H.Suwon Campus] At: 10:27 12 February 2009 viewed along Secondary building units: complex 5-1 [loo] Framework density: Channels: Fault planes: Type species: 17. (100) 5.O w t n < 16 and ih typically about 3 tetragonal. This reaction path has been confirmed in general by many work- ers [26-291 A variation has been proposed by Voltz and Wise [301 based on results from a fluid-bed kinetic study.. + H2O olefins \ J Scheme B .Al.12 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . Iam2.Si.1 c=13.

Reaction path for methanol conversion to hydrocarbons over HZSM-5 (371OC) [ 21. 8.Suwon Campus] At: 10:27 12 February 2009 70t / \ a DIMETHYL ETHER 1 ’ KY2 SPACEITME lo-’ I (m) I I0 FIG. .Downloaded By: [2007-2008-2009 Kyunghee University .

conversion of the intermediate olefins is essentially complete and the main products are isoparaffins and aromatics. as seen in Table 4.. It is evident that the xylene distribution is close to equilibrium.14 CHANG - d DIMETHYL ETHER a \ - Downloaded By: [2007-2008-2009 Kyunghee University . Product and Distribution Table 3 [22] contains typical hydrocarbon selectivities at 371OC for ZSM-5 and ZSM-11. At this stage of reaction. [31] for ethanol dehydration over alumina. This is formally identical to the mechanism of Balandin et al. Anderson et al. 9. The hydrocarbons span a relative narrow range of molecular weights. c. while among .4 . showing the general similarity between the two zeolites. terminating at about C l 0 .. which was elucidated by the kinetic isotope method. Reaction path for dimethyl ether conversion to hydrocarbons over HZSM-5 (371OC) 121. The relative kinetic significance of this auxiliary step is unknown. The aromatics are mostly methyl-substituted. Alm shown i s a comparison of the observed isomer distribution with their thermodynamic equilibrium values.- + Y 30 20 10 0 10' SPACE TIME 1( - 1 lo-' 1 FLG. [27] and Ceckiewicz I431 also recognized this possibility.-.Suwon Campus] At: 10:27 12 February 2009 5 m K 5 .

Below 3 O C the main reaction is dehydration t o DME. Effect of Temperature The effect of temperature on ZSM-5 selectivity a t low w a c e velocity (LHSV = 0 .5 1.9 c22c 3 11.HYDROCARBONS FROM METHANOL TABLE 3 [22] Methanol Conversion to Hydrocarbons over Various Zeolites (37OoC.1 0. 6 . 1. 1.3.8 5.5 0. 1 LHSV) Hydrocarbon distribution (wt%) in Downloaded By: [2007-2008-2009 Kyunghee University .2 3.0 c.6 0.1 5.Suwon Campus] At: 10:27 12 February 2009 15 Erionite ZSM-5 1.8 0.7 9.4 ZSM-4 8. i0 121.3 14.7 0.7 13.0 0.5-trimethylbenzene.2 1.6 0. c.3 6.0 5.4 8.1 0.9 15.0 32.3.0 2.5 16.*c.8 3.5 3.2 0. d. 1 atm.2 19.5 1.8 9.0 5.8 39.0 .4 25.0 7.0 15.5-tetramethylbenzenes fall significantly short of their equilibrium values. 7 h . while above 45OOC light olefins and CHI.2C 5 + aliphatic 2.l ) is shown in Fig.5 1.4 36.3 A." a s was t h e sharp cut-off in product molecular weight.3.7 8. and 1.2 4.3 0.5 18.1 A3 2.0 1.2. .8 18.4 0.0 2.8 Mordenite 4.0 24.2 12.6 A10 A 11+ the higher aromatics.4-.3 1. c 2 5.0 1.1 0. become significant a s a result of secondary cracking. 4 7 A8 10.2 26. With increasing OO temperature t h e sequence of Scheme A is followed.4 1.1 8. Above about 5 O C t h e dissociation of OO methanol to H2 and CO becomes measurable.5 c.2. This was attributed to zeolite "shape-selectivity.2 1.3 11.7 ZSM-11 0.

Suwon Campus] At: 10:27 12 February 2009 4.7 0.4 1.4 [: I 33.9 23.9 11.0 2.0 22.9 2.7 4.5 0.0 m P Trimethylbenzenes : 123 124 135 I::[ [":I 23.8 10.6 1.1 25. [:3 Ethyltoluenes : 0 0.1 0.9 9.1 2.1 [ [ .16 CHANG TABLE 4 [2] Aromatics Distribution from Methanol Conversion over HZSM-5 Equilibrium Normalized Normalized isomer distributions distribution (371OC) distributions (wt %) Ben zene Toluene Ethylben zene Xylenes: 0 Downloaded By: [2007-2008-2009 Kyunghee University .4 Other Al0a All+ a Diethylbenzenes + dimethylethylben zenes .2 m+P Isopropylben zene Tetramethylbenzenes: 1234 1235 1245 0.

e. 10.Suwon Campus] At: 10:27 12 February 2009 I W V WATER 70 W a 60 c I '3 y 50 w 2 I 3 J 3 1 40 C2 . .C 4 HYDROCARBONS 0 30 20 AROMATICS 10 500 0 300 400 T E M P E R A T U R E 'C FIG. while increasing pressure enhances the overlap 1 of the two reactions.6-0. These plots may be compared with Fig. Effect of temperature on methanol conversion over HZSM-5 (0. This is illustrated in Figs. 8 depicting the normal atmospheric reaction path. Effect of Pressure The main effect of varying reactant partial pressure on ZSM-5 selectivity is to change the relative rates of the olefin-forming and aromatization steps [ 321 Decreasing pressure tends to decouple the two reactions.04 and 50 atm. The significance of the shaded regions will b e discussed later.HYDROCARBONS FROM METHANOL I00 17 90 80 Downloaded By: [2007-2008-2009 Kyunghee University . 1 and 1 2 for PMeOH = 0. . 1 atm) [ 2 ] .7 h-' LHSV.

371OC) [321. . and is therefore more easily formed than the other Clo aromatics within the zeolite. high selectivity to olefins is possible at complete conversion of methanol (Table 5).WATER z 0 5 . A s shown in Table 4. The most striking effect of raising pressure above atmospheric is an increase in the degree of aromatic substitution. Modifications and Isotypes Kaeding and Butter [331 reported that ZSM-5 modified by treatment with phosphorus compounds showed high (70%) selectivity for . it is the bulkiest isomer able to move with relative ease through the zeolite channel system.18 CHANG 60 '"I / 8 50Downloaded By: [2007-2008-2009 Kyunghee University . Methanol reaction path at low pressure (HZSM-5 catalyst. O ' 40- 2 3 0 5 30 - DIMETHYLETHER / o 0 g 2010 . durene possesses a critical diameter most compatible with the zeolite channel dimensions. especially in durene selectivity. . Its pref erential formation is a consequence of zeolite shape-selectivity Among the tetramethylbenzenes . It is shown later that in large pore zeolites. v 0 . . durene is not the thermodynamically favored tetramethylbenzene isomer. Thus at subatmospheric partial pressures. i. Clo equilibrium is attained. f .AROMATICS FIG. 11.-0.Suwon Campus] At: 10:27 12 February 2009 - .e.

olefin formation from methanol. 371OC) [32]. The following was proposed as to the nature of trimethyl phosphite modification : H I O\ /o\*l/o\si/o 0 /si\o o/+. 12. 5 ! ? I - 0 30 I 3 0 0. Methanol reaction path at high pressure (HZSM-5 catalyst. 1 10 FIG.PARAFFINS V V 0 n K 20 200AROMATICS 10 10- 0 L 10-2 10-1 LHSV-' .\o o \ .HYDROCARBONS FROM METHANOL 19 Downloaded By: [2007-2008-2009 Kyunghee University .Suwon Campus] At: 10:27 12 February 2009 0 2- E 501 50 I / / / / I / I 5 m K 40 / . C2-CI. hr.

2) 17. 1 LHSV.7 21.+ nonaromatic Aromatics a 3.00 99+ 0. which is ZSM-8 [ 3 4 .7 18.5 2.4 (10.9 41.8 2.17 99+ 0. CH30\ P/OCH I +CH .4 26.8 39.6) 0.-C. 371. 8: Hydrocarbon distribution. The conversion of ethanol over "Ultrasil" zeolite. olefins) Methane C2-C5paraffins C.0 (52.5 43. .6 0.20 CHANG TABLE 5 Methanol Conversion at Low Pressures [ 1611 (427OC. wt %: Ethylene Propylene Butenes Pent ene s (Total C.4 2.0 3. 351. 1 atm total pressurea) Methanol partial pressure.2 4.2 6.3 20.4 (80.3 0. the function of P-modification is unknown.Suwon Campus] At: 10:27 12 February 2009 1.6 1. Representative data i Table 6 show that this catalyst ben haves similarly to ZSM-5.3 Helium diluent at subatmospheric MeOH partial pressures.4 18.0 38. atm: Downloaded By: [2007-2008-2009 Kyunghee University .5 15. has been described by Russian workers 128.OH Other than to reduce the activity of the ZSM-5 acid sites.3 (37.2 0.6) 1.7 20.3 0.2) 0.0 12.6 24.2 2.07 99+ Conversion.3 2. 3 6 .5 7.25 99+ 0.

He C3H6 i-C 4H lo n-C4H10 C4Hs i-C.98 3.52 21.35 14. which behaves similarly to ZSM.51 20.99 + C2H6 5.84 2..74 5. containing "supercages" supported by columns of cancrinite units linked through double-6-rings (D6R). 3.88 4. but deactivates quickly.66 10.47 29.H. torr Downloaded By: [2007-2008-2009 Kyunghee University .33 3. is hexagonal.Suwon Campus] At: 10:27 12 February 2009 21 300 30 60 300 80 60 450 30 60 4 50 80 3 4 50 80 60 Time on stream.09 15. and higher Spencer and Whittam 1551 have described a high silica zeolite of unknown structure called Nu-1.44 11.49 2.03 5. Structures of some of these small pore zeolites are illustrated in Figs.48 8. The erionite structure.08 17. Small Pore Zeolites Zeolites which sorb linear hydrocarbons and exclude branched ones have received attention as catalysts for methanol conversion to light hydrocarbons such as ethene and propene. min Hydrocarbons.57 7. O C Pressure. 13-16.69 1.39 10. Offretite is closely related to erionite except that the sequence of 6-rings i AABAAB [231 as compared to AABAAC in erionite.97 3. the supercages is gained through 8-rings.98 0.10 1.74 6.23 9.22 14.81 C.H.24 31.52 22. s .94 15.HYDROCARBONS FROM METHANOL TABLE 6 Methanol Conversion over "Ultrasil" Zeolite [ 361 Reaction conditions: Temperature.12 0.25 1.06 1.. Access to.86 10.38 10.80 4.78 30.98 23. Other Zeolites a.5 in methanol conversion. 13. n-C.08 16. wt %: CH4 C2H4 7. Fig. and between.98 3.29 37.83 7.54 21.62 9.06 4.

Ca.Suwon Campus] At: 10:27 12 February 2009 Secondary building units: single 6-rings in AABMC sequence (single 4-rings) 15..1 A FIG.. and the D6R units are linked together through tilted . occur frequently.6 x 5.2 *** (001) Erionite (Na2. zeolite T .O.. P63/mmc...3 c=15. e. a=13.. 27 H 2 0 hexagonal. 14. Fig. Erionite. 13.6 T/l000 A3 Framework density: Channels: Fault planes: Type species: I [OOl] 8 3. g. Intergrowths of erionite and offretite.Si. the D6R layer sequence is ABCABC. Al. In the chabazite framework..).22 CHANG Downloaded By: [2007-2008-2009 Kyunghee University .

O. .6 x 3. 4-rings.Al. Zeolite ZK-5. consists of truncated cuboctahedra joined through D6R units in a body-centered structure..1 A (True symmetry i s lower.Suwon Campus] At: 10:27 12 February 2009 CHABAZITE Rim viewed along [OOl] hex 36 T[1] Secondary building units: Framework density: Cham els: single 6-rings in AABBCC sequence (double 6. The main channel system is defined by 8-rings.o r single 4-rings) 14.HYDROCARBONS FROM METHANOL 23 Downloaded By: [2007-2008-2009 Kyunghee University .2 c=15.7**+ 8 Fault planes: Type species: (0011 Chabazite Ca. 15). Rjm. a=13. 16.. Fig..Si.3.6 T/1000 A3 1 [OOl] . forming a 3-dimensional channel system. These cavities a r e joined together via their 8-rings. The framework contains large ellipsoidal cavities (Fig. a 40 HzO trigonal. each entered through six 8-rings. possibly triclinic) FIGURE 14 1251.

Cobb et al. The conversion of methanol to light olefins over various cationexchanged chabazites has been investigated by Cobb et al. contended that their method of preparation led to an ffultrastable form of chabazite If Ceckiewicz [42.Suwon Campus] At: 10:27 12 February 2009 FIG. (40. based on drastic changes observed in the x-ray pattern. were mainly olefins. 15. Coking was rapid and was attributed to the formation of nondesorbable cyclic hydrocarbons in the zeolite supercages. . 431 studied methanol over the hydrogen form of zeolite T . [391 and Singh et al. observed long-term irreversible deactivation.. The presence of significant amounts of methane in some experiments is symptomatic of coke laydown. Chabazite cavity. Methanol conversion over a variety of small pore zeolites has been reported by Chang et 81.24 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . This was disputed by Singh et al. who saw no such deactivation in a three-month study comprising 21 regenerative cycles. restricted largely to the C2-C. 411. but found the catalyst to be regenerable. which was attributed to structural degradation. range. At 339-538OC the products. Both teams of investigators observed short-term catalyst deactivation due to coking. . Representative data are shown in Table 7. It was speculated that the discrepancy may have been due to differences in ion-exchange procedures. 1381. Singh et al.

-C hydrocarbons at 30O-55O0C. and gave the result % shown in Table 8.2%).7 T/1000 A3 < l o o > .3% C2-C4 olefins.O." which has an x-ray pattern similar to herschelite (isostructural with chabazite) but with line broadening due to small crystal size.. Wunder and Leupold [44] report that selectivity to ethene and propene is significantly enhanced over a mixture of chabazite and erionite when these zeolites are Mn-exchanged. cubic.3.7 A * 98 H. 6. Typical results are shown in Table 9..or 8-rings) Framework density: Channels: Fault planes: Type species: 14.A1. The product consists mainly of ethene (16. . a=18.4%). and propene (22. is active for converting methanol to C. Whittam and Spencer [45] report that "zeolite MCH.9*+* synthetic zeolite ZK-5 Na3.HYDROCARBONS FROM METHANOL 25 Downloaded By: [2007-2008-2009 Kyunghee University . ImJm.6 vol%).9***1 8 ---- (100. S 3.Suwon Campus] At: 10:27 12 February 2009 ZK-5 lm3m viewed along 96 T[1] [loo] Secondary building units: double 6-rings (single 4-. The product was 66. A methanol/water mixture (30 ~ 0 1 H 2 0 ) was reacted at 4OO0C.O FIGURE 16 [25]..propene (41.Si.

atm LHSV (WHSV) . 6 ) . and mazzite (ZSM-4).8 39. butene ( 1 9 .l GHSV.8 13. Faujasites contain extremely large supercages ( ~ 1 1 diameter) entered into through 12-rings. propane ( 6 . Fig. 1 pL MeOH in He.1 100 5.4 36.7 9. Inui et al.4 33.7 45. 500 h . . h-’ Conversion.1 5. [ 4 6 . Methanol (128 in N1) was reacted over the calcined (54OOC) material at 4OO0C. 2 ) .26 CHANG TABLE 7 Methanol Conversion over Small Pore Zeolites [ 381 Erionitea Reaction conditions: Temperature. 1000 h . Si02/A1.4 3.6 3.+ ( 7 . propene ( 3 2 . butane ( 4 . 17. and C.3 21. bPulse microreactor.0 C4HB 10. O C Pressure. 5 ) at complete conversion. g . is built up of truncated octahedra interconnected via D6R units.5 De-aluminized .2 0. .5 3. are large pore zeolites which have been found to catalyze methanol conversion to hydrocarbons. 471 synthesized an erionite-offretite catalyst by rapid crystallization in the presence of tetramethylammonium hydroxide.3 4.0 c 5+ a 7. 7 1 .0 2.5 22. 3 b.2 0. The faujasite structure. e .7 0 0 21.0 3.Suwon Campus] At: 10:27 12 February 2009 3 70 1 341-378 1 (3. methane ( 4 .2 10.3 1. % Hydrocarbons.4 31. 7 ) .4 25. wt %: CH 4 CH2H6 CzH4 Zeolite T Chabazite ZK-5 Downloaded By: [2007-2008-2009 Kyunghee University .6 C3Ha C3H6 C4H10 30.1 2. X and Y .03 = 16.8) 538 1 538 1 b 1 9.l GHSV and gave (m18) ethane ( 2 5 ) .6 b 100 11. 4 1 . Large Pore Zeolites Faujasite-type zeolites. mordenite.

1 0.Suwon Campus] At: 10:27 12 February 2009 Vol % C2H4 3H6 C4HB CH4 C2H6 C3H8 C4H10 C sf nonaromatic Aromatics <o. 1 <o. 90%conversion) Products Downloaded By: [2007-2008-2009 Kyunghee University . Fig.2 H20 Dimethyl ether s2. 18.5 co H2 5. also has a one-dimensional system of parallel channels defined by 12-rings. Schwart z and Ciric [ 481 were the first to achieve significant methanol conversion to hydrocarbons over zeolite catalysts. Interestingly.7 Mordenite. defined by 12-rings. 511. shown in Fig. Attempts have been made to decrease the coking tendency of faujasites by cation exchange with numerous metal cations having hydrogenation activity [ 50. Mazzite (ZSM-4). Topchieva et al. 19. Coke formation was rapid. and reported the data shown in Table 10. These efforts have met with . which may account for the high methane selectivity. [49] studied methanol dehydration to dimethyl ether over various alkali metal-exchanged X and Y faujasites. is characterized by a one-dimensional system of parallel elliptical channels. They reacted methanol over REX and ZnX at 330-390°C. the only hydrocarbon they reported (426OC) was 1butene.0 4.HYDROCARBONS FROM METHANOL 27 TABLE 8 Methanol Conversion over Mn-Exchanged Chabazite-Erionite I441 (40O0C.

28 CHANG TABLE 9 Methanol Conversion over Zeolite H -MCH [ 451 (45OoC. a s shown previously.7 2. summarizes the reaction conditions and hydrocarbon distributions . was found by Zatorski and Krzyzanowski [ 541 to be highly active for methanol conversion to C1-C hydrocarbons at 350-500°C. however. Table 3.9 l-C4H8 i-C4H8 2.6 0.Suwon Campus] At: 10:27 12 February 2009 CH4 C2H6 C2H4 c 3H8 C3H6 22.0 2-C4H8 4.9 little success.6 Downloaded By: [2007-2008-2009 Kyunghee University .2 i-C4Hlo n-C4H10 0 4. [ 221 for methanol conversion. The influence of acid strength of the protonic sites in zeolite Y on dimethyl ether conversion a t 35OOC was investigated by Cormerais et al. but to have a short life-time. exchanged with various cations. Natural mordenite.4 41. The catalytic dehydration of methanol by synthetic H-mordenite was studied by Swabb and Gates [ 531 a t 99. Mordenite and ZSM-4 were investigated by Chang et al.4. deactivation was rapid.2 16. I t was found that dimethyl ether reacted only when the total number of Na and K ions per unit cell was less than 16. and that the active sites must be of sufficient strength to retain pyridine at temperatures at least as high as 450OC. Olefins were detected a t 24OOC .5-240OC. The effect of increasing hydrogenation activity of the metal component was mainly to enhance methanol dissociation [51]. The acid strengths were determined by pyridine adsorption-desorption at different temperatures. pulse microreactor) Products ~~~ ~ Vol % 3. A series of zeolites containing varying concentrations of Na and K ions was prepared. [ 521.

Mg). 4. The intermediate pore ( < 6 (A> ZSM-5 and ZSM-11 truncate the hydrocarbon distribution at C..7 T/1000 A 3 <111> (1111 g 7. tivity in methanol conversion to hydrocarbons. .Si..Suwon Campus] At: 10:27 12 February 2009 FAUJASITE Fd3m viewed along (1111 192 T[1] Secondary building units: Framework density: Channels: Fault planes: double &rings (single 4.. cubic.. Ca.4*** Type species: Faujasite (Na. Included for comparison are results from small pore erionite and intermediate pore ZSM-5 and ZSM-11. Zeolite Shape-Selectivity Table 3 provides a concise illustration of zeolite shape-selec.. Small pore (4. obtained...or 6-rings) 12.7 A 240 H..3 A ) erionite.HYDROCARBONS FROM METHANOL 29 Downloaded By: [2007-2008-2009 Kyunghee University . Fd3m.O. a=24. as already shown. produces only low molecular weight hydrocarbons. while the large .Al.O FIGURE 17 [25]. It does not sorb benzene and therefore cannot produce aromatics.

7* 8 Type species: Mordenite Na. It should be pointed out.1 b=20.Suwon Campus] At: 10:27 12 February 2009 1 MORDENITE Cmcm viewed along Secondary building units: Framework density: Channels: complex 5-1 n 17. which can accommodate molecules as bulky a s hexamethylbenzene. 5 A FLGURE 18 [ 2 5 ] .30 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . 20 and serves to highlight the influence of pore size.O. These results are consistent with the critical dimensions of the methyl-substituted benzenes. that crystallographic pore dimensions cannot generally be used to gauge precisely what . pore ( < 8 8 ) ZSM-4 and mordenite.2. 5 c=7. produce this compound along with other aromatics.7 x 7.9 x 5. however.2 T/1000 A’ [OOlI 12 6. a=18..0* t j I0101 .Al. some of which are listed in Table 11. Cmcm. * 24 H. The normalized aromatics distribution is shown in Fig.O orthorhombic.Si.

. match with zeolite pore dimensions [ 231. the kinetic diameter from the Lennard-Jones potential provides a more satisfactory.1 T/1000 A 3 [OOl] (100) 12 7.Suwon Campus] At: 10:27 12 February 2009 MAZZITE PGJmmc viewed along [OOl] 24 T.O hexagonal.4 c=7.HYDROCARBONS FROM METHANOL 31 Downloaded By: [2007-2008-2009 Kyunghee University .4* Fault planes: Type species: Mazzite Mg.(Ca. molecules will be sorbed and what molecules excluded.[m] Secondary building units: Framework density: Channels: complex 5-1 (or single 4-rings) 16.oSiz60. It has been found that for certain sorbate molecules. Molecules larger than the calculated aperture size of zeolites are sometimes freely sorbed. K2)3Al. 12 T.6 A FIGURE 19 [ 251.2 28 H. a=18.[1] . P63/mmc. though still not an absolute.

Comparison is here made between 1.9 C3H6 10.2 C3Hs C4Hs 8.0 Continuous-flow. This demonstrates that the large pore zeolites perm i t the attainment of equilibrium.0 17. a The nonequilibrium distribution of tetramethylbenzenes from ZSM-5 has already been noted. CLiquid product mainly unreacted CH. b9.46 w t % Zn.3 CH4 C2H4 C2H6 43.5 LHSV. and (CH.5 2.32 CHANG TABLE 10 1481 Methanol Decomposition over Metal Cat ion -Exchanged Paujasitesa Downloaded By: [2007-2008-2009 Kyunghee University .3 2.0 2.0 13.8 4. fractions among the intermediate and large pore zeolites. 1 atm.0 Hexanes Other 4.5-tetramethylbenzene(durene) distributions in the Al.8 i-C4Hlo i-CsHlz 4.Suwon Campus] At: 10:27 12 February 2009 Temperature (OC) 330-380 51 360-390 30 % conversion of CH.5 24. It will be recalled that durene .7 100.2 7.OH .9 6.) *O.8 100. 1. H.O.0 2.0 3.2. samples analyzed at 2-3 h on stream.4.OH to gaseous products Gaseous product composition ( m l %) :C H2 Trace 22.7 10.4 9. Table 12.

Thermodynamic calculations [ 1721 reveal. W have shown earlier that there is a large driving force for e methanol to form hexamethylbenzene i the presence of acid catn alysts.HYDROCARBONS FROM METHANOL 33 Downloaded By: [2007-2008-2009 Kyunghee University .Suwon Campus] At: 10:27 12 February 2009 vo:L ZSM-5 75 loo ISM I I - - 50 - 25 0 0 A6 A? A6 A7 A8 A9 AIO All 10 0 I S M-4 MORDENITE 75 75 Y O 50 50 25 - 25 FIG. Aromatics distribution from methanol conversion over various zeolites [ 221. 20. is the bulkiest molecule that can diffuse readily through ZSM-5 and ZSM-11. however. that .

7 6.2 %1245TMB in A10 Catalyst ZSM .. Kinetic diameter % 2 .6 1.1 6.5 ZSM.1 0. Shape.1 ’ 6 r.11 50.6 37.2 Mor denite Equilibrium (37OOC) 33.Suwon Campus] At: 10:27 12 February 2009 6. TABLE 12 [22] A.1 a Equilibrium diameters (rmin) estimated from Courtauld models.9 7.h.0 ZSM-4 1.Selectivity of Various Zeolites %1245TMB in hydrocarbon 1.34 CHANG TABLE 11 Critical Diameters of Selected Polymethylbenzenes [ 221 Downloaded By: [2007-2008-2009 Kyunghee University .4 .1 84.7 34.4 6.

on the other hand. This has been confirmed by Cormerais et al. conversion was 85% and only ethene was detected in the reactor effluent. Catalyst deactivation due to coke deposition is fairly rapid in small pore and large pore zeolites. Shape-selective zeolites such as ZSM-5 prevent the completion of this reaction as a consequence of steric hindrance.83-0.1-43% A120. H Y .HYDROCARBONS FROM METHANOL 35 TABLE 13 [ 1651 Coke Formation and Deactivation in Dimethyl Ether Conversion. and a trace of CuO deposited on clay pellets and calcined at 700-750OC.3 40 90 200 0. 0.4 % ethene.Suwon Campus] At: 10:27 12 February 2009 Catalyst HZSM-5 HY H -erionite lchabazite H-mordenite Wt% coke Coke lhydrocarbons X l o 3 1. Pearson [58] reported that when methanol or trimethyl phosphate was heated with phosphorus pentoxide [ 61 andlor polyphosphoric acid at 190°C. C.15 polymethylbenzenes formation must be a kinetically controlled phenomenon. 3 O C 5O Residual activity (8) 90 8 Downloaded By: [2007-2008-2009 Kyunghee University . 0 3 h-’ WHSV.5 9. A t 100-15O0C.15-0.3 8. heating methanol in the presence of 86%H.3% Mg. The intermediate pore zeolites such as ZSM-5.6 6. An inverse correlation is evident between deactivation rate and coke selectivity. and H-mordenite. The cat alyst required air regeneration after 15-20 h . [ 1651. Table 13 summarizes the results obtained by these workers on the conversion of dimethyl ether over H-erionitel chabazite.SO.5 atm. 0. Nonzeolitic Catalysts According to Dolgov [ 561. a 36-39%yield of hydrocarbons was obtained .93% Fe203. HZSM-5. have a high coke tolerance. Matyushenskii and Freidlin [ 571 converted dimethyl ether to ethene by decomposition over a catalyst composed of 39. at 135-140°C gives 2 . and ~ 0 . with the balance dimethyl ether.15 0. + T i 0 2 .8 0. Rollmann and Walsh [ 1641 have presented evidence that carbon formation in zeolites is a shape-selective reaction controlled by pore geometry. 1-1.

-C. Very little aromatics were formed. with little solid residue. in view of the great complexity of the reaction. obtained at 300°C. The gasoline range ( C 5 C15) fraction consisted mainly of branched paraffins. the products contained alkanes. [SO] converted methanol (>99%conversion) over bulk zinc iodide at 2OOOC to hydrocarbons. substituted monoaromatics (maximal at C 1 2 ) . This has usually been neglected in the published experimental work. cycloalkanes. IV. [ 621 used supported aluminum dihydrogenphosphate as catalyst to convert methanol into a predominantly olefinic product (20-608 yield of C. (283OC) is suppressed by cofeeding hydrogen.36 CHANG Downloaded By: [2007-2008-2009 Kyunghee University .12 X mol/h feedrate. Methyl chloride was s i m i larly converted to hydrocarbons in the fused salt. 66. However.Suwon Campus] At: 10:27 12 February 2009 with the average formula CH2. The kinetic scheme is simplified somewhat by the observation [30. REACTION KINETICS Relatively little has been published to date on the kinetics of hydrocarbon formation from methanol. and atmospheric pressure are shown in Table 14. Apart from dimethyl ether. Kikkawa et al. 2. Only small amounts of C. and other compounds. Heavier i fractions amounted to 2-3% based on C feed. over a range CnH2n+z to CnHZn-10. alkenes.7%) of triptane. rigorous kinetic treatments may neither be practicable nor have much practical justification. Heteropolyacids and salts of heteropolyacids have been used by On0 et al. Typical data. The results of Cormerais et al. the large heat effects require special consideration. 163. olefins at 375-425OC). 671 that over a wide range of conversions the initial step of ether formation is much more rapid than the subsequent . K i m et al. Bell and Chang [ 591 found that coke formation during methanol/ dimethyl ether conversion to hydrocarbons in fused ZnC1.hydrocarbons were formed and about 56%(based on C feed) gas o l range (230-270OC) hydrocarbons were produced. [ 651 using silica-alumina catalyst will be discussed later in connection with reaction mechanisms. 641 to convert methanol.. and contained a high percentage (49. Further. The hydrocarbons were mostly in the C2-C5 range. Global kinetic treatments are mainly found in the accessible literature. Supported aluminum sulfate was found by Hargis and Kehoe [611 to catalyze methanol and dimethyl ether conversion to hydrocarbons.

0 9.5 35.5 38.1 7.3 12.1 37.5 50.1 CuTP AgTP HTSa CUTS AgTS 2.2 5.0 3.1 39.7 1.2 3.9 57.3 38.5 7.6 4.4 13. Data illustrating this fact appear in Fig.HYDROCARBONS FROM METHANOL TABLE 14 [63] Product Distribution of the Conversion of Methanol into Hydrocarbons Catalyst Downloaded By: [2007-2008-2009 Kyunghee University .3 11. This work will be described in some detail later.2 10.8 11.8 8.9 8.2 13.1 7.5 13. Thus the equilibrium oxygenate mixture can be conveniently treated as a single kinetic species or "lump" [ 681 Data from a pilot plant study of gasoline synthesis from methanol over ZSM-5 [SO] indicate that the rate of oxygenate disappearance is first-order in oxygenates.4 C3H8 c4 c 5 c6 TP and TS indicate dodecatungstophosphate and dodecatungstosilicate.3 21.7 35.8 0 20.5 8.9 Hydrocarbon distribution. a olefin-forming step.3 0.1 15.2 0.9 7. %:b MeOH MeOMe Hydrocarbons 1. %:b CH4 C2H4 C2H6 8 6 3.5 0.7 9.1 79.4 39.7 14.0 5. respectively.3 5.3 9.Suwon Campus] At: 10:27 12 February 2009 37 HTPa Product distribution. 21.2 8.3 16.0 26.5 8.7 9.3 61. .5 0 2.9 36.3 3.0 98.8 15.2 9. and is essentially at equilibrium.9 5.3 0.6 1. .8 34. bCalculated on a carbon-number basis.8 41.6 10.6 60.7 11.

371OC .] basis. CONTINUOUS FLOW ---. 21.Downloaded By: [2007-2008-2009 Kyunghee University . PULSE REACTOR DME FEED. CONTfNUCUS FLOW $ METHANOL FEED. Conversion of methanol and dimethyl ether to hydrocarbons over HZSM-5. normalized [CH.} MOM-DME EQUILIBRIA DM E Q nc F I G .Suwon Campus] At: 10:27 12 February 2009 0 METHANOL FEED.

proposed a sequence of two bimolecular reactions : where A and B are oxygenates and olefins. Figure 23 shows data obtained with catalysts of different activity. Autocatalysis was confirmed by Ono et al. [70. however. Neglecting k. 711. The kinetic scheme of Chen and Reagan was modified by Chang [ 681 to include an additional bimolecular term due to homologation of olefins : A + B .. at low conversions. With x = conversion of A and w = weight of catalysts. and demonstrating that the results were not due to autothermal effects. A linear correlation between k and intrinsic . Figure 22 shows the fit with data obtained using various catalyst loadings and reactor configurations.HYDROCARBONS FROM METHANOL 39 Chen and Reagan [ 691 discovered that the reaction is autocat alytic over ZSM-5. experimental data were fitted according to the expression giving characteristic sigmoidal curves. They proposed the following scheme: Downloaded By: [2007-2008-2009 Kyunghee University . and C = aromatics + paraffins. acid activity is indicated. Figure 24 shows the fit obtained at three temperatures.Suwon Campus] At: 10:27 12 February 2009 where A = oxygenates. respectively. these result i n where c1 = k1/k2 and f3 = [Bl. B = olefins. These workers.Ck2 . confirming reactor isothermicity./[A].

02 k2-55 0.o 1 kl lk2=. stainless steel . copper .d. (d) Reactor: +in. Invoking the steady- .6 - 04- 0.-o.4% zeolite diluted with M/50 copper powder and y-alumina. attacking both oxygenates and olefins. catalyst : 10% zeolite diluted with ?-alumina. (b) Reactor: Q-in.Suwon Campus] At: 10:27 12 February 2009 0 CATALYST A CATALYST 0 CATALYST VCATALYST (a) (b) (c) (d) - 0.-0.d. FIG.-0.8 - Downloaded By: [2007-2008-2009 Kyunghee University .d.d. The species B was assumed to have carbene-like character.2 0 0 I I (a) Reactor: &in. copper.40 CHAN G 1.-0. catalyst: 10% zeolite diluted with 7-alumina. copper. catalyst : 3% zeolite diluted with 50/50 copper powder and y-alumina. catalyst : 1. B+C C k3 w C A D where A = oxygenate. and D = paraffins + aromatics.). B = (:CH. Autocatalysis i methanol conversion (HZSM-5catn alyst. 22. 37OOC) 1691. C = olefins. (c) Reactor : A-in.

For catalyst identifications. Data a t three pressures were correlated with this model and are shown in Fig.Suwon Campus] At: 10:27 12 February 2009 FIG. and intrinsic catalyst acid activity [691 . Correlation between methanol rate constant k. and k.. state assumption on B and eliminating time. = k+/k. K1 = k . 22.HYDROCARBONS FROM METHANOL 7 . - 41 I I 7 1 1 0 CATALYST A A CATALYST B 0 CATALYST C Downloaded By: [2007-2008-2009 Kyunghee University . see Fig. . the following expression resulted: where u = C I A . 25. / k z . 23.

Suwon Campus] At: 10:27 12 February 2009 reaction timeh FIG. Doelle and co-workers 1721 studied both sorption and reaction kinetics of methanol and dimethyl ether conversion over ZSM-5. . Solid lines are theoretical [ 7 11 . and the intracrystalline Thiele modulus was less than unity for 0 . = 6 X l o 5 exp (-80 y p )’ mol gesebar For dimethyl ether. A t 115-2OO0Cthe kinetics of methanol conversion obeyed the rate law k l P ~ H .OH 1 + k2P r = H2 0 with k . Hydrocarbon yield vs reaction time. no effect of crystal size on product distribution was observed. 5 pm crystals. 24.42 CHANG Downloaded By: [2007-2008-2009 Kyunghee University .

Using curve-fitting techniques for model discrimination. [681.HYDROCARBONS FROM METHANOL 43 oxygenate Downloaded By: [2007-2008-2009 Kyunghee University . Solid lines are theoretical The conversion of methanol over chabazite was investigated by Anthony et al.oclPA)3 r A = where a= 1 1 + bt/SL . 25. [ 731. Methanol reaction path. it was found that the data could be represented by kloa3P A (1 + k.Suwon Campus] At: 10:27 12 February 2009 F I G .

These results are discussed in the following section. and aromatization with ti-transfer. The final stages.Suwon Campus] At: 10:27 12 February 2009 s. particularly Al2O3. + c x. The bulk of work has concentrated on alcohols having B-hydrogens. REACTION MECHANISM The reaction path of acid-catalyzed hydrocarbon formation from methanol may be viewed essentially as composed of three key steps: ether formation. papers by Galwey [781 on carbenium pathways in reactions of C2+ alcohols on montmorillonite. be discussed since these compounds are peculiar to the methanol transformation reaction. comprising olefin condensation. Methanol etherification is similar in many respects to that of the higher alcohols. 11 = moles of i produced for the j-th data point moles of methanol reacted for the j-th data point xj = conversion of methanol for the j-th data point The kinetics of dimethyl ether conversion over HZSM-5 was studied over the temperature range 227-300°C by van den Berg 1741. The mechanism of polymethylbenzenes formation will. and Dejaifve et al. This topic will therefore not be covered in detail here since it has been comprehensively treated in a number of excellent reviews [ 75-77]. A. initial C-C bond formation. the literature on methanol dehydration is relatively sparse. In addition.. sufficient differences may be found a s to warrant its discussion here. Ether Formation The mechanism of ether formation from alcohols over oxide catalysts. In contrast. = a.. [ 791 on methanol and olefins conversion over ZSM-5 are pertinent. V. and H-transfer over acidic catalysts. 841. however.2 11 i l 1 1 1 where Downloaded By: [2007-2008-2009 Kyunghee University .has been extensively investigated. . Several comprehensive surveys have been published [ 80. 81.44 CHANG accounts for catalyst deactivation and Sk is a selectivity function defined by S. since methanol lacks a parent olefin. however. + b. have been well studied and proceed via classical carbenium mechanisms.x. cyclization . The mechanism of the first two steps is discussed in this section.

OH CH30H. This was taken as evidence that the reaction over alumina involved s u r face methoxy groups: Downloaded By: [2007-2008-2009 Kyunghee University . The effect of a series of nitrogenous poisons (various amines and N -heterocycles) or dimethyl ether formation was monitored. forming stable quaternary ions.O + H 2 0 + H+ Figueras et al.Suwon Campus] At: 10:27 12 February 2009 /A1\ /A1\ /A1\ 0 0 0 P'\ Et This interpretation was based on the assumption that bases such as diethylamine dissociatively but reversibly chemisorb on alumina : Et I I H I Because of the greater nucleophilicity of N vs 0 .+ + CH30H (CH. [83] studied the kinetics of methanol dehydration over silica-alumina at 160-200°C and derived the rate expression . thereby inhibiting methoxylation. the nitrogenous base competes with methanol for the surface oxygen. the reaction over silica-alumina involves Bronsted sites. On the other hand.).HYDROCARBONS FROMMETHANOL ~~ ~~ ~~ 45 The dehydration of methanol on alumina and amorphous silicaalumina was studied by Parera and Figoli 1821. Silica-alumina was irreversibly poisoned. which are strongly poisoned by nitrogen base. + H+ -+ + CH. while alumina was reversibly poisoned.OH. According to these investigators ether formation over silica-alu mina may be represented by the following scheme: CH.

O or CH. which would lead to a rate equation of the form r = ke2 = k a P / ( l + aPI2 Downloaded By: [2007-2008-2009 Kyunghee University . could nevertheless influence the initial rate of dehydration by occupying active sites. and above 427OC.OCD. I //// - /////?-/$/.O.OH was carried out. were observed. proposed two modes of chemisorption. though not ether intermediates. both of which assumed the concerted action of acidic and basic centers [85-881. was significant.OD and CH.. gave only CH. which.. possibly the result of the initial formation of surface carboxylate groups [ 8 4 ] . At T > 77OC. Coadsorption of CD. and CH. Figueras et al.+. and therefore equilibrium with the undissociated species would b e readily established : H H C-H 0 H / \ H ! * H . the ether contained only CH. Another .OHad in the presence of gaseous CD. The thermal decomposition of methanol adsorbed on alumina was investigated by Matsushima and White [go] using deuterium labeling. significant concentrations of CH. CO was predominant while CH. Schmit z [ 911 studied the dehydration of methanol over silicaalumina at 289-418OC and found that the reaction becomes firstorder in methanol at the higher temperatures. Primary carbonium ions are much less stable than alkoxide structures. Thermal decomposition of CH.. CH. CH. Schmitz observed an induction period.OCH. must be reversibly adsorbed. Desorption of methanol started at 77OC. and CD.OCH.Suwon Campus] At: 10:27 12 February 2009 At low pressures the reaction order would be unity.. Nucleophilic attack on carbon by the basic site would generate CH. It was concluded that the rate-limiting step cannot be the interaction of two surface alcoholate groups.46 CHANG where Pa is the alcohol partial pressure.. H20. The observed half-order was rationalized on the ground that one of the species. which then interacts with an acid-generated surface methoxy group [89] to give ether. A I ///?/-. while at higher temperatures deuterium distribution became random. Under desorption at T < 237OC.. Interestingly. indicating that ether is formed by a bimolecular reaction between adjacent surface methoxides.OCH.OCD.OCD. which is not in agreement with the observed half-order.

HYDROCARBONS FROM METHANOL 47 Downloaded By: [2007-2008-2009 Kyunghee University . methanol can be completely removed and the CH bands are shifted to 2860 and 2960 cm-l. Upon evacuation. Derouane et al. Methanol ( 6 torr) was adsorbed on H -clinoptilolite at various temperatures. They a t tribute this to the formation of Bronsted sites from Lewis sites by hydration during reaction with methanol. the OH band did not reappear. At 25OC the 3620 cm-' band (acidic OH on clinoptilolite) disappears and two bands at 2950 and 2840 cm-' (CH stretching) appear.. This indicated that only weakly adsorbed methanol is removed. [931 observed partial methoxylation of the surface at 3OO0C. /O\ A . indicating the presence of surface methoxyls. O i S / . the CH bande decreased significantly . . The following mechanism was proposed : /Si. however. An Rideal-Eley mechanism was proposed. Absorption at 16OOC followed by evacuation caused only a partial disappearance of the 3620 cm-l band and a lower intensity of the 2950 and 2840 cm-I bands. The dehydration kinetics was also investigated in this study. l /\ . In a study of methanol reaction on synthetic germanic nearfaujasite using I3C-NMR. with ether formation.Suwon Campus] At: 10:27 12 February 2009 explanation might involve competitive sorption of product water prior to establishment of steady-state with respect to surface hydroxyl concentration. Detrekoy and Kallo [ 921 investigated the dehydration of methanol over clinoptilolite by infrared spectroscopy. At 4OO0C.\ A / CH OH 3 Further reaction would be catalyzed by the acidic OH groups thus generated. Detrekoy and Kallo found that methanol dehydration also occurs on dehydroxylated (at T > 400OC) clinoptilolite.

. Hypothetical mechanisms abound in the literature. In summary. Beranek and Kraus [ 941 conclude that the mechanism involves essentially a nucleophilic substitution whereby the surface alkoxide is attacked by another molecule. and run the gamut from carbene to free radical schemes. the first to consider this question were Topchieva and collaborators [ 91 in connection with . 2. "Similar products are obtained by the decomposition of metal alkoxides containing no B-hydrogens and by the reaction of corresponding alcohols on alumina at lower temperatures" [ 951. determined by IR spectroscopy" [ 1601. the weight of evidence favors the intermediacy of surface alkoxyls in ether formation from alcohols. The. 4. however. little supporting experimental evidence has appeared.Suwon Campus] At: 10:27 12 February 2009 Surface methoxyls could be hydrolyzed with water back to methanol at 25OC. 3. Via Surface Alkoxyls Among contemporary investigators. The speculation of the earliest workers [5. "Acetic acid and pyridine are poisons for the formation of ethers" [ 961 "The different degrees of water inhibition on the ether and olefin formation from ethanol on alumina. 1. Hydrocarbon Formation The mechanism of initial C-C bond formation from methanol is an unresolved question at present. nevertheless. It seems appropriate. ttCorrelation between the rate of ether formation from ethanol and the surface concentration of ethoxide species. Arguments in support of this mechanism were summarized as follows: 1. second part of Statement 5 applies only to C2+ alcohols. A s of this writing. 5. 61 has already been acknowledged.48 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . Additional small amounts of dimethyl ether and s u r face formate were also found after hydrolysis. and the agreement of ether /ethylene selectivity ratios found experimentally with those calculated by the Monte Carlo simulation of the hydrated surface of alumina" [ 971 . '%The positive value of the Taft reaction parameter for the formation of ether in contrast to negative values for the olefin formation on the same catalyst" [ 943 . to survey and discuss the diverse entries in this t'mechanism sweepstakes. B . either from the gas phase or from a weakly adsorbed state.

H. accompanied by dehydration and H-transfer. SiO2-Al2O3.H.5 LHSV (CH3)zO over A1203at 45OoC. The formation of surface methoxy groups was regarded as the primary step.03 at 45OoC. which upon heating and pumping to 4 O O O C evolved C.0. leaving a positively charged carbon moiety a s the reactive intermediate.Suwon Campus] At: 10:27 12 February 2009 CH4 22..0 bond is a heterolytic process.g.] was reported by 1 Pfeifer and Flora [981.5 LHSV Product Downloaded By: [2007-2008-2009 Kyunghee University . Ethene was the only hydrocarbon produ ct ob served . and A and the compound Na[Al(OMe).3 Major Major Major Minor Minor Major Minor Major Major Major Minor Minor Major Minor H. C.. A free radical mechanism was rejected on the basis of negligible reactivity over nonacidic solids. and Al. e. and smaller amounts of C2H4 and C. it was concluded that cleavage of the C .2 31.. It is seen that the main products are CH. It was found that a portion of the methanol was irreversibly adsorbed on SiO.5 (cH 3 ) 2 0 Other 7. with the flow of electrons in the direction of Al.O. In a later study the thermal decomposition of methoxides of N a .). Heiba and Landis [951 showed that the thermolysis products of aluminum alkoxides are virtually identical to the products of alumina-cataly zed decomposition of alcohols or ethers.O. 0. as shown in Table 15.1 0. H.Q).HYDROCARBONS FROM METHANOL 49 TABLE 15 Decomposition of Methyl Derivatives [ 951 Al(OCH3)s at 38 5OC (mol8) C H 3 0 H over Al. Subsequently.). at temperatures up to 45OOC..1 1. CO. CO.. ..-Al. quartz. and CO. and A1. (CH..3 a study of the adsorption of methanol vapor on SiO. Mg. Based on the observation that Al(OCH.03 surfaces..H. A negative activation entropy was observed. co C2H4 C3H6 2. Hydrocarbon formation was considered to occur by condensation of methoxy groups.5 35.. The mechanistic details of this condensation were not specified. suggesting a cyclic transition state. 0.. decomposed more readily than Al(OCH.

Salvador and Kladnig favored an a-elimination mechanism to explain olefin formation. A t room temperature. 3. JSiOCH. as observed by Schwart z and Ciric [48]. 4. n = 2 . a s reported by Mattox 1991. / -+ -SOH / \ + :CH. n:CH. GLC . .Suwon Campus] At: 10:27 12 February 2009 Venuto and Landis [ 751 proposed an a-elimination mechanism to account for olefins formed during methanol dehydration to dimethyl ether over NaX at 26OoC.). and around 25OOC secondary cracking reactions occur forming predominantly butane and propene. According to this view. which then polymerize to form olefins : H-CH. methoxylation of surface hydroxyl groups begins a t 2OoC.50 2. With HY. proposing that the generation of carbenoid species occurs by decomposition of the methoxylated surface : Q . and from methanol reaction over Rex and ZnX at 330-390°C. CHANG Carbenes and Carbenoids Downloaded By: [2007-2008-2009 Kyunghee University . Traces of olefin were detected at 240OC. and TGA techniques. reaching a maximum a t 130OC.. 5 Swabb and Gates [ 531 studied the dehydration of methanol over H-mordenite at 155-240OC. dimethyl ether formation begins and reaches a maximum at 21OoC. physical adsorption occurs on both zeolites. They differed with the acid-base mechanism of Swabb and Gates 1531. It was speculated that the olefins were formed by an a-elimination mechanism. This was accompanied by darkening of the catalyst due to coking which was enhanced with a further temperature increase. methanol adsorbed on the zeolite surface loses water to form a divalent carbenoid species. adsorption isotherm.-OH /3 -+ u H20 + :CH. + (CH. A t 12OoC. where bond scission is facilitated by cooperative action of acidic and basic sites in the zeolite lattice: Basic site Bronsted \ Salvador and Kladnig [ 1001 investigated the surface reactions of methanol on HY and NaY at 20-350°C using IR.

HYDROCARBONS FROMMETHANOL

51

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Condensation of the carbene would give olefin. Alkanes were a s sumed to arise via H -transfer reactions. An a-elimination mechanism involving a carbenoid intermediate was also proposed by Chang and Silvestri 121 for methanol reaction over ZSM-5. However, it was considered unlikely the olefins were formed by polymerization of the diradical intermediate. In view of the high reactivity of carbenes, the probability of such an event would be low, as demonstrated in studies on ketene photolysis [ 1013. By the same token, the presence of free carbenes would b e unlikely. Rather, a concerted reaction between methylene donor and acceptor was proposed involving simultaneous a-elimination and sp3 insertion into methanol or dimethyl ether as the primary step.
H

CHz

-+

CH,CH,OR' + R O H ,

R , R ' = H or alkyl

An ionic mechanism involving methyl cations was rejected since these species would be expected to form methane readily via hydride abstraction from methanol, dimethyl ether, or hydrocarbons. The reaction
CH,+ + CH,OH
+

&H,OH + CH,,

is extremely rapid in the gas phase [102]. However, methane of normally accou t s for <l% the hydrocarbons formed over ZSM-5. Note also that H,OH could deprotonate to formaldehyde, which is not observed over ZSM-5. Chang and Silvestri suggested that bond dissociation can be induced b y , or facilitated in the presence of the strong electrostatic field in the zeolite interior [ 103-1051 , the zeolite acting as a potent ionizing ''solvent .I1 This model prompted a theoretical study by Beran and Jiru [ 1061 of the influence of electrostatic field strength on the reactivity of methanol in the zeolite cavity. The small size of the methanol molecule permitted approximation of the zeolite field by a homogenous field. Computations were done by the INDO method. Orientation of the methanol molecule with respect to the external field is shown below:

2

52

CHANG

Upon indreasing the field strength from 0-8 V/& the 0 - H , bond length increases from 1.01 to 1.31 A, the C-0 bond is weakened by stretching from 1.33 to 1.38-1.40 8 , while one of the hydrogens moves toward 0 ( e . g . , 0 - H , decreases from 2.04 to 1.79 Further, with increasing field strength H, becomes more negatively charged while the methyl hydrogens become more positive. A similar calculation was performed on a pair of colliding methanol molecules to simulate ether formation. Beran and Jiru concluded that at 2-4 V / 8 the formation of dimethyl ether becomes possible while at 4-8 V/8 species such as CH,O and CH, can exist. The electrostatic field gradient has been estimated to be 1-3 V I A at 2.5-3.0 1 from surface cations, and in zeolites such as ZSM-5 can be much higher because of structural influences 1741. Pickert et al. [lo71 calculated a field strength of 6.3 VIA for points 2 1 from an occupied S,, site in Cay, with SiIA1 = 2. The presence of small amounts of methyl ethyl ether in the products of methanol conversion over ZSM-5 was reported by Chang and Silvestri [21. Cormerais et al. [65] found MeOEt among the products of dimethyl ether decomposition over silicaalumina at 423 K . This compound could either be a key reaction intermediate or simply a secondary product of the methanol-toethene reaction. From kinetic evidence, Cormerais et al. deduced that this compound was not formed via reaction of Me,O with ethene. It was determined that in the presence of excess ethene, amounting to 30X that of the products from Me,O, the rate of MeOEt formation from Me,O was increased by only a factor of 5. More significantly, the formation of propene from MeOEt was more than 10 times faster than from Me,O. In view of the observed unreactivity of ethene, it was concluded that propene is formed by two successive CH, insertions into Me,O, leading to MeOPr, which cleaves to propene. Another set of experiments gave analogous results for C, hydrocarbons. Cormerais et al. [65, 1281 proposed a chain growth "rake mechanism," Fig. 26, to explain their results. In this scheme, chain growth occurs by carbene insertion into surface alkoxy species, which are transformed into olefins via carbenium ions. Chang and Chu 11081 reported that when methanol is reacted over ZSM-5 in the presence of propane, the usual high iso-to-norma1 ratio of product butanes [ 2 is significantly lowered. This is 1 shown in Table 16 where the butane iln is seen to be 3.8 for the control experiment and 1.1 when propane is added. The thermodynamic equilibrium i/n is 0 . 7 5 at the reaction conditions. However, under the same conditions propane and isobutane were virtually inert in the absence of methanol. In the presence of l3CH3OH (90% l 3 C . 10% " C ) , it was found that the selectivity to singly-labeled butanes was 30-45 times higher than that expected from random

1).

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HYDROCARBONS FROM METHANOL
Me8 O , MeOEt
C2H4

53
C,H,
MeOBu
C4H,...

MeOPr

4 1
PHASE PHASE

4 1

A I

..It
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-

It

It

-

It

I t

It

Me2

FIC. 26. "Rake" mechanism for dimethyl ether conversion to hydrocarbons [ 651.

TABLE 16 Effect of Propane on Methanol Conversion over HZSM-5a [ 1081 (37OoC, 1 atm, 0.4 h-' LHSV (CH,OH)) Hydrocarbon product

(wt
CH,
C2O

%P

CH ,OH /He

C H ,OH / C ,H8

0.86 0.93 2.35 -c 3.63

0.90 0.90 2.36 -d 4.53 23.14 20.24 2.34 20.98 24.62
100.00

cz2(C,O) C,2-

i-Cbo n-C,O C,2C5+ aliphatic

35.17
9.20 1.88 21.32 24.66
100.00

Aromatics

i/n

c,'

3.8

1.1

'Three moles CH30H/1 mole diluent. bNormalized on a propane-free basis. CActual C = 25.36% of hydrocarbon. : dNet conversion of C 3° % 5%.

54 CHANG 3t Downloaded By: [2007-2008-2009 Kyunghee University . have iln % l . intermediate is carbene-like. It was concluded that propane methylation had occurred. is %2. The singly-substituted butanes. Further. 27.H. 27. distribution.8.close to the equilibrium value. and the mode of attack is insertion into an sp3 C-H bond. mostly the product of methylation. Such carbene insertions are indiscriminate in liquid phase. The iln of the 13C. as shown in Fig. and reflects the fact that they arise primarily from self-reaction of I 3 C H 3 0 H . the butane i l n increased with increasing I3C substitution. all C-H bonds of the substrate being subject to attack with equal probability [ 1091 : .Suwon Campus] At: 10:27 12 February 2009 i /n 0 n=O I 2 I3C" 3 4 FIG. Isolnormal ratio of -labeled butanes [ 1081 . From these considerations it was deduced that the reactive C .

HYDROCARBONS FROM METHANOL 55 (75%) Downloaded By: [2007-2008-2009 Kyunghee University . classically. for example. carbene insertion will lead statistically to higher concentrations of n-butane relative to i-butane. addition to the double bond of propene generated from propane via dehydrogenation. it was believed possible that the unfavorable dehydrogenation equilibrium could be displaced by a "drain-off" reaction involving addition of a highly reactive species across the double bond of propene. If the attacking ~ p e c i e s were cationic. SbF 6 The alternative to sp3 C-H insertion. However. Attack by a cationic species such a s C H 3 + o r methyl oxonium ion according to an Olah-type mechanism (vide infra) . CH. The following pathway has been proposed to account for i-butane formation : ""'\ H II f H CH3 ?. methylcyclopropane [ 1091 . also received consideration. and i-butane is the major alkylation product. Carbene addition would yield. which will either yield 2-methylpropene via loss of a proton.He reaction. In the CH.F-SbF. will yield high i/n butane ratios due to stability of tertiary carbenium ions in the transition state. complex in S0.OH /C . branched products would similarly result : . namely C.Suwon Campus] At: 10:27 12 February 2009 (25%) although for a homogeneous gas-phase reaction there is some evidence of discrimination in favor of secondary over primary C-H bonds [ 1101. In the methylation of propene with the CH. is formed via H -transfer. Although propane itself is largely unreactive. CH. subsequent protonation and rearrangement gives preferentially the tertiary butyl cation. on the other hand. or i-butane via H-transfer.ClF [ 1111.

add to the C S N group. with propene as an intermediate.C=N + + -t CH3C=N-CH. It was also found that acetonitrile. In another attempt at "trapping" the reactive C. would attack the C Z N electron system exclusively. which would yield the same nitrilium ion in the presence of acidic catalysts.56 CHANG / \ C Downloaded By: [2007-2008-2009 Kyunghee University . intermediate. This is a Ritter-type sequence [ 1761 Carbene addition to the C G N group would result in a highly reactive azirine intermediate t 1771. Chang and Lang [1151 reacted methanol over HZSM-5 in the presence of acetonitrile. This alternative was therefore rejected as an explanation of the observed results. However. with or without the acetamides. A cationic intermediate.Suwon Campus] At: 10:27 12 February 2009 + RH C C-C-C I +R+ Another pathway involving propylium ion a s an electrophile can also be written: but leads to the same conclusion. can be invoked to explain the characteristic high i/n butane selectivity. Thus the sole presence in the final product of N-substituted acetamides would be evidence o a cationic intermediacy f (although the alternative of acetamide formation via reaction of amines with acetic acid from acetonitrile hydrolysis cannot be ruled out). must be taken a s a strong indication of carbene involvement. in the case of reaction of methanol alone. It was reasoned that a carbene would insert mainly into the C-H bonds and to a lesser extent. these mechanisms. On the other hand. . N-substituted acetamides would result. the presence of higher nitriles . . forming a nitrilium ion [ 173-1751 : CH3 + CH. Upon hydrolysis. on the other hand.

COOCH. the reactor effluent contained 16.N :CH.CH.CN. In their view. These 0.COOH. similar to the Simmons-Smith reagent (CH. Upon raising the temperature to 538OC. which reacts with alkenes to form cyclopropane derivatives via carbene addition to the double bond. H + RIRZN: + CH3CN * R.COOH + CH. while the N -methyl-w-aminonitries may result from an analogous nitrenium insertion [ 1781 where the nitrenium ion is generated from a methylamine precursor: R. CH. and N-substituted acetamides were i evidence.R. 4 % higher esters.HYDROCARBONS FROM METHANOL 57 Downloaded By: [2007-2008-2009 Kyunghee University . as n well as CH. etc. They postulated that the intermediate is a carbene complexed with the salt.R. and 3 .8% CH.6% CH. This is the result of acetonitrile hydrolysis and methanol amination. At 454OC an equimolar mixture of methanol and acetonitrile gave mostly acetic acid and methylamines (36%methanol conversion). a trimethyloxonium ion 111: . and methylamines.NCH*CN The reaction of methanol in the presence of zinc iodide at 2 O O O C was reported by Kim et al. hydrocarbons.. + Zn(Cu)) ..CH.CN is taken as evidence of carbene insertion.Suwon Campus] At: 10:27 12 February 2009 itself stable over the temperature range of interest. [ 1121.COOH + CH.0% 0. CH.R.3%hydrocarbons and 7.CH. [60] to yield highly branched hydrocarbons.CH. Particularly high selectivity to triptane was observed.CN + P I -H+ RlR.CN. 3. via 11. At 496OC ( 79% methanol conversion). which reacts with another molecule of dimethyl ether to form. 46.and N-compounds consisted of 12. The CH. 37.and N-compounds (exclusive of unreacted acetonitrile). Oxonium Ions and Ylids In their mechanism Chang and Silvestri left open the question of stabilization of the intermediate carbene in the transition state. pyrroles.COOCH.2% N-methyl-w-aminonitriles. A plausible resolution of this question may be found in the mechanism of van den Berg et al. served to moderate the reaction by competing strongly for the acid sites.I. dimethyl ether from methanol dehydration reacts with a Bronsted acid site to form a dimethyloxonium ion I .N * R1R2N: + :R. and after elimination of methanol.

O\ A1 -CH30H I1 I11 The critical step in their proposal is a Stevens-type intramolecular rearrangement of the trimethyloxonium ion 111 to a methyl ethyloxonium ion V : 4 0 111 IV V N VI VII .Suwon Campus] At: 10:27 12 February 2009 I /O\ si /O\-.58 CHANG H+ Downloaded By: [2007-2008-2009 Kyunghee University .

+ HZO + CH.HYDROCARBONS FROM METHANOL ~ ~~~ ~- 59 ~ Downloaded By: [2007-2008-2009 Kyunghee University . is seen to contain the stabilized C.Suwon Campus] At: 10:27 12 February 2009 Structure V I . In this variation t h e carboxonium ion is generated by hydride abstraction.OCH. ab initio calculations [ 1131 indicate that although the 1hydroxyethyl cation is more stable than the methoxymethyl cat ion. A s indicated previously.OH. the ab initio field calculations of Beran and Jiru [ 1061 lend support to this assumption.CH. Van den Berg presented the following scheme comparing the steps in the alkoxonium Route ( A ) and the carboxonium Route ( B ) . B41 Route A Route B The overall gas phase enthalpies of reaction of the various steps were calculated and are shown in Table 17. the energy barrier separating the two is on the order of .OH ~~l CZH. A major difference is found between Steps A 2 and B2.OH 4 + CHSOCH.0 leads to C -C bond for mation. + 1 + CH3-0-CH. + CH. An alternate cationic mechanism involving carboxonium ions was considered by van den Berg "741.H. Hf "i + + H. - C H 3 0 C H z C H 3 + CHBOH.-O-CH. Cis-insertion of the carbenoid into the adjacent C . which is equivalent to the oxonium ylid (CH.O+CH. + CH. The formation of ylid depends on the assumption that the conjugate basic sites in ZSM-5 a r e sufficiently strong to induce polarization of a C-H bond on a methyl group. + + CH. A2/ CH .CHOH B21 B3 i CH.OCH. carbenoid species. CH. Howe v e r .-.+ + C.).

Step A 3 is highly exothermic and.8 Aromatics Wt%durene in aromatics Wt%ethylbenzenesb in aromatics a 34.1 T = 370 k l0C . 260 kJJmo1. and diEt benzenes.6 Downloaded By: [2007-2008-2009 Kyunghee University . kinetics of dimethyl ether reaction over HZSM-5 is zero-order at 227-300OC. is expected to have a low activation energy. bEt benzene. LHSV = 1 .8 0. It was concluded that Route A. s According to van den Berg [ 741..2 44.assuming that the rearrangement proceeds through the 0-protonated oxirane : This is comparable to the expected energy barrier of Step A 2 . P = 50 atrn.1 1. Chang and . i favored.9 4. 2 h . in view of the behavior of the N-analogue [ 1141. MeEt benzenes.0 0.3 40. involving the trimethyloxonium ion.8 6.8 7. Figure 28 is an energy diagram comparing Routes A and B. diMeEt benzenes.0 12.l .2 0.Suwon Campus] At: 10:27 12 February 2009 Percent age conversion Hydrocarbon distribution (wt 8) : C1 c 2 99+ 1.4 C 5+ nonaromatic 17.60 CHANG TABLE 17 [32] The Conversion of Methanol and Ethanol to Hydrocarbons over ZSM-5 Class Zeolitesa Methanol Ethanol 99 0.6 33.8 58.

Suwon Campus] At: 10:27 12 February 2009 HYDROCARBONS FROM METHANOL 61 .Downloaded By: [2007-2008-2009 Kyunghee University .

van den Berg observed an anomalous temperature effect. the insertion of CH. CH3 m I o +H' CH~CH~ The Stevens rearrangement of oxonium compounds has not been reported up to this time. However. One such example is the formation of stilbene from benzyl mercaptan over Nal3X reported by Venuto and Landis [ 1161. [ 1171 studied the t her ma1 decomposition of met hylammonium cation exchanged Y-type faujasites. To explain this phenomenon it was proposed that at 227-26OoC.. However. with the oxonium ion as the transition state. suggestive of Langmuir-Hinshelwood behavior.N-dimethylpyrrolidinium bromide gives N -ethylpyrrolidine by carbene insertion : A / \ CH. a mechani s m involving a Stevens rearrangement followed by Hofmann elimination was proposed In another example (not involving zeolites) reported by Lepley and Giumanini [ 1181. It should be noted that ylid mechanisms have been earlier proposed to explain C-C bond formation from organic N and S compounds in the presence of zeolites. illustrated in the Arrhenius plot of Fig. 29. and increasing in order at higher conversions. ethene was observed among the products of decomposition. To account for this result. This is consistent with van den Berg's proposal that the formation of adsorbed alkoxyoxonium species is favored. C -C bond formation proceeds via the intramolecular rearrangement of trimethyloxonium ions while at higher temperatures a concerted reaction between dimethyl ether and alkyl cations. generated .62 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . Although these workers preferred an a-elimination mechanism for this reaction. with the C-C bond formation as the most demanding step. the thermolysis of N . At 275-45OoC.Suwon Campus] At: 10:27 12 February 2009 Lang [ 1151 found the reaction order of methanol decomposition over HZSM-5 at 371OC to be zero-order up to about 60%conversion. Wu et al. becomes significant. they recognized that a sulfonium ylid mechanism is also possible.

into C-H bonds of alkyl ethers is believed to occur via an ylid intermediate [ 1091. indicating that singlet methylene is involved in the attack [ 1091. @/ f Zeol 8 .72 h-'. = 5 0 . + HZeol S CH3-0. However. P. N o insertion into alkyl ether is observed when the rnethylene is generated by mercury photosensitization. when the substrate contains an electron-withdrawing group.5 was studied by Kaeding and Butter [33]. Arrhenius plot of the dimethyl ether conversion on zeolite HZSM-5 [74]. reaction with diazomethane occurs. a s in the following reaction reported by Meerwein et al. 7 kPa.Suwon Campus] At: 10:27 12 February 2009 F I G . WHSV = 0. [ 1681 : Methanol conversion over phosphorus-modified ZSM.OCH. who proposed the following mechanism based also on oxonium intermediates : H CH. 29. Methylene generated from diazomethane b y cuprous halide -catalyzed decomposition was similarly ineffectual [ 1091.HYDROCARBONS FROM METHANOL 63 Downloaded By: [2007-2008-2009 Kyunghee University . by ketene photolysis.

Perot et al. From this it was inferred that olefin formation was intermolecular.CH. The isotope distribution in the product ethene (at ~ 6 0 conversion) was % found to be random.64 CHANG CH3-0. However. 4. In agreement with van den Berg et al. Such reactions were first observed in superacid media by Olah and co-workers [ 119.OH t CH2=CH2 t HZeol The key step in this mechanism is the labilization of a C-H bond. - CH. Recently. assisted by anionic sites in the zeolite. data at low conversion were not given to confirm this interpretation.1211 and are exemplified by the remarkable reaction of methane : . it was proposed that the mechanism involves rearrangement of a trimethyloxonium ion which is formed by a bimolecular reaction between dimethyl ether and methanol or with another molecule of dimethyl ether.-0-CH. + HZeol I * CH3-0-CH2CH3Zeol e 8 H CH. The resultant nucleophilic species then attacks the Yncipient methyl carbonium ion" from protonated methyl ether (or methanol).CH2-OCH. Carbenium Ions and Superacid Chemistry Mechanisms based on electrophilic attack by methyl cations at saturated carbon are favored by some workers.CH. [ 1121 .OH + CH.O was reacted at 35OOC. i ' \ 'CH. Zeol Downloaded By: [2007-2008-2009 Kyunghee University .OCH.u I m - CH. A mixture of ( 12CH3)20 and ("CH.). [ 1271 carried out a 13C tracer study of dimethyl ether conversion over silica-alumina and HZSM-5.-HZeol t/ . + HZeol H CH.Suwon Campus] At: 10:27 12 February 2009 / ' 0 CH.-0-CH.

and in the following substitution reaction : H R3C-H + CH3+ [R3C-+:l CH 3 1 + R3C-CH3 + HS Pearson [58] proposed this as a possible mechanism of C-C bond formation in methanol decomposition by phosphorus pent oxide [6].CH. On0 and Mori [ 711 concluded that the mechanism involves methyl cations: CH. typified by the CH 5+ methanonium ion shown above. Based on their observation that methanol converts to hydrocarbons over heteropolyacids and Nafion-H (perfluorinated sulfonic acid resin).Suwon Campus] At: 10:27 12 February 2009 The transition state is believed to be a pentacoordinate carbonium ion. which are Bronsted acids. + + CH30R + r + \l>-cH30R] + CH.OR + H+ C: H Generation of the methyl cation was considered to occur by polarization of surface methoxyl species: YH 3 CH.’ 0 0 ’ A1 \ 0 \o 0 \ 0 Si /O ’ \ A1 /\ O Si /O ‘ 0 ‘ 0 0 ’ ‘0 0’ .HYDROCARBONS FROM METHANOL 65 Downloaded By: [2007-2008-2009 Kyunghee University .

I' The Olah superacid mechanism was also favored by Kagi [ 1221. who proposed a series of oxonium intermediates. and NbF. although Olah points out that similar carbocation transformations are observed in systems such a s HF-TaF. and therefore would not be potent oxidizing media.-catalyzed reaction gave more light hydrocarbons (>81% C1-C 5> than the TaF. Ono et al. were stable to hydrolysis under the reaction conditions or deactivated during the course of reaction. basic sites do not participate in the reaction. a twofold excess of methanol was converted to a mixture of paraffins and aromatics. in which the abstraction of a proton from a methyl group by basic sites is essential. + I t should be noted that neither CH. [70] rejected the posshility of carbene involvement. At 3OOOC in an autoclave. It has also been pointed out [ 1261 that SbF. [ 1251. They reasoned that since HC1 poisons base-catalyzed reactions.66 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . . Salem [ 1691 has reported the conversion of methanol and dimethyl ether to hydrocarbons over TaF.' nor C H . The NbF.Suwon Campus] At: 10:27 12 February 2009 Autocatalysis [ 691 involving condensation of methanol and olefins was cited as the reason why little methane is produced via hydride abstraction. which have high redox potentials. They found that HC1 did not poison the methanol reaction over HZSM-5. and NbF. They assert that these results "plead against the carbene mechanism.-C. However.. It was not clear whether the TaF.). Chang [ 1231 considered the bulky transition states arising from such reactions improbable in ZSM-5 on account of limitations due t o channel size. . e . reaction ( 5 3 %C. have thus far been directly observed in superacid solutions [ 124. a r e strong oxidizing species and could generate carbenium ions from alkanes by oxidation. g . and HF-BF. and SO. 1251.

HYDROCARBONS FROM METHANOL 67 The conversion of methanol over the alkylammonium zeolite Nu. the initial step does not involve lability of the C-H bond prior to C -C bond formation.-C hydrocarbons over natural mordenite was reported b y Zatorski and Krzyzanowski [ 541. [ 6 5 ] has already been mentioned (Fig. Instead. species becomes somewhat of a moot question. carbenoid. 6. using deuterium labeling. The "rake mechanism" of Ahn et al. o r oxyme hylene species. [67]. In such a scheme.) was proposed. The results of Matsushima and White [90] on deuterium exchange between CH30H and CD30D over alumina have already been mentioned. It will be recalled that these authors found little D-exchange below 237OC but complete scrambling at higher temperature (T 2 397OC). Other Schemes The conversion of methanol to C . found that in the methylation of benzene with methanol over HZSM-5 a t 207OC. who proposed a free radical mechanism: CH.Suwon Campus] At: 10:27 12 February 2009 . This is a highly attractive scheme in that it is consistent with the observed autocatalysis of the r e action [ 6 9 ] . Thus their bearing on the mechanistic question may be somewhat tenuous. the temperature a t which these D-labeling experiments were carried out was below the threshold for hydrocarbon formation from methanol in the presence of ZSM-5.1 was investigated by Spencer and Whittam [ 551. there is no exchange involving methyl hydrogens. They concluded that strong acidity is needed for t h e fast initial step and that cationic intermediates are involved. + reactive Cn -+ reactive Cn+. which participates in a chain propagation mechanism b active C . + OH . entity of the type (CH.OH + 6H. 2 6 ) . neither CH nor oxonium ions were considered to be plausible. the precise nature of the C.+ Chain Mechanisms Anderson et al. moreover. However. where Cn is an olefin. a active C. [128] and Cormerais et al. However. 5. Downloaded By: [2007-2008-2009 Kyunghee University .)R H (R = H or CH. From this it was inferred that in the methanol-to-hydrocarbon reaction. a s has been noted [ 1231. and that therefore the reactive intermediates a r e not carbene.

) The tungsten apparently has a dehydrogenation function. is then formed and subsequently polymerized to produce the olefins. indicating some degree of radical involvement. A possible mechanism is dissociation into a radical pair within a solvent cage [ 1661 : N o supporting evidence was given. + CH. [ 1291 studied methanol conversion over tungsten oxide on various supports including zeolite A .CH. 2CH. "These species then migrate to sites where the external bonding between the sites and the oxygen is stronger than the internal bonding between C+ and 0-. + CH. Langner [ 1701 has proposed the following imaginative mechan- >C=C< + CH30H 0 + CH20 -0 (H+) (H*) __c H<C-(-H + CH20 CH20H uCH3+ CH3OH (H+) CH20 OCH3 + .CH.H.Suwon Campus] At: 10:27 12 February 2009 -+ C.CH. .H. Downloaded By: [2007-2008-2009 Kyunghee University . Divalent specie C H .C I / N / R \ Lin et al. C. + CH. A mechanism involving the formation of a "HPC-O site" species as the rate-controlling step was proposed. and chabazite.Hlo CH3CH2 -+ C2H4 + H In this context it may be relevant that the Stevens rearrangement has b e n known to give rise to C I D N P spectra. R' \ \ + \. rnordenite. CHANG + C.68 CH. + CH.." (It was not specified how charge conservation is to be preserved.

hydride .. the Prins condensation of formaldehyde arid cycloolefin (Steps 2 ..HYDROCARBONS FROM METHANOL 69 CH30H -HzO CH3 +2CH30H -2H20) ( H*l * . CH3 a C H 3 (H+l (6) Downloaded By: [2007-2008-2009 Kyunghee University . Finally. According to Wu et al. 4. autocatalysis will minimize this reaction. species cannot be discounted as a source of at least some of the methane. and generation of olefins from the polymethyl cyclic intermediate via the "paring reaction" [ 1 7 1 ] (Step 6). from zeolite surface methoxy species may proceed by a "methyl disproportionation" reaction which produces formaldehyde as an intermediate. producing formaldehyde (Steps 1. However. The formation of methane deserves comment.. C O .Suwon Campus] At: 10:27 12 February 2009 - CH3 3 PROPYLENE -0 (H*) ISOBUTENE. PROPYLENE + CYCLOOLEFIN + PROPANE The critical steps are H-transfer from methanol to double bonds.. and H. usually present in minor amounts. 5) . [ 1171. the formation of methane. A s pointed out by Ono et al. dehydration of the hydroxymethyl substituent . 5). 5) . The initial cycloolefin is generated according to Step 7. ISOPENTENE. An intermolecular hydride transfer is envisioned : Zeol This reaction may also lead to coke formation: HCHO -f C + H20 Venuto and Landis [ 751 considered methane to be formed from methanol via radical pathways. [ 701 . hydride abstraction by the reactive C. followed by double-bond isomerization to the methyl derivative (Steps 3.

HY. Bragin et al. [ 1301 found that ethene-H. [27] utilized various ZSM-5 preparations in their study. olefins were identified. Anderson et al. According to Kaeding and Butter [ 331 . Chang and Silvestri [ 2 1 . the rate of propene formation from ethene was 100 times slower than from methanol. This was regarded as evidence that ethene could not be a primary intermediate. observed the propene band pattern but failed to detect ethene. in FTIR studies of methanol sorption on zeolite H-T a t 25-450°C. while methanol gave 20-25%hydrocarbons. over silica-alumina. and H-mordenite. The follow ing reaction network with propene a s the initial olefin was proposed : Downloaded By: [2007-2008-2009 Kyunghee University .70 CHANG abstraction could be significant during the induction period of such autocatalysis and account for methane a t low conversions. while ethene generally exhibited low reactivity. it was observed that certain catalyst preparations showed considerable activity in promoting ethene conversion. Jiru et al. alumina. Similarly. [ 271.Suwon Campus] At: 10:27 12 February 2009 . on the basis of similarity of product distributions. I s Ethene the Initial Olefin? Associated with the problem of C-C bond formation is the question of the nature of the "firstttolefin formed. C. [ 1281 were silica. silica-alumina. and van den Berg [ 741 considered ethene to be an active intermediate in the reaction sequence. The view that ethene is the initial olefin was challenged b y Ahn et al. The catalysts investigated b y Ahn et al. It was speculated that these particular catalysts may possess highly active sites which are easily poisoned. Derouane et al. 7. Ceckiewicz [ 431 . although the contact time of ethene was 10 times higher than methanol. however. [ 3 8 ] compared t h e reactions of ethene and methanol over ZSM-5 under various conditions and concluded. This question has generated some controversy. Further. Upon temperature-programmed desorption. However.O mixtures gave products identical with methanol over ZSM-5. less than 0 . 5 %ethene was reacted. At 35OoC. Consistent with this view. [ 1281 and Anderson et al. A t 4OOOC propene was readily converted to aromatic products. ethene is the initial olefin a t low methanol conversion in the presence of phosphorusmodified ZSM-5. [ 261.-C. They found ethene t o be substantially less reactive than propene over a variety of catalysts. that ethene is a primary intermediate in methanol transformation. They assumed that the phosphorus treatment did not alter t h e catalytic mechanism.

especially aromatics. Depending on zeolite pretreatment conditions. Contrasting results were reported b y Novakova et al. The different b e havior of HZSM-5 was attributed to the following possible factors: (a) different electrostatic field. ~ 3 tom) 0 . ( b ) high Si:A1 ratio. methyl-substituted aromatics were evolved. however. water vapor facilitated the desorption of products. 254OO0C. (c) crystal structure and pore geometry. IR. and 13C-NMR. Region A represents static conditions (400°C.-C. alicyclic hydrocarbons. [1311 who investigated the sorption reaction of ethene on HZSM-5 and HNaY zeolites by IR and MS. while HZSM-5 gave mainly unsaturates. and at 327-427O. C3-C7aliphatic hydrocarbons were evolved. at 197. with HZSM-5. Bolis et al. the presence of water altered the ratio of saturated to unsaturated hydrocarbons in favor of saturates.HYDROCARBONS FROM METHANOL A [methanol 71 1 cycli zat ion ads ’ cycloparaf fins ads aromatics ads Downloaded By: [2007-2008-2009 Kyunghee University . Upon heating to 97-197O. saturated hydrocarbons predominated. competitive sorption between water and ethene was .2 9 7 O . and Region B dynamic conditions (flowing He. Also in the case of HZSM-5. With HNaY . [ 1321 studied the sorption activation of ethene by HZSM-5 using TGA. olefinsg propyleneg and paraffinsg 4 carbonaceous deposit ads In this scheme. They found that ethene is protonated (rate-determining step) on the Bronsted acid sites even near room temperature. Water vapor did not affect the ethene reaction with NaHY. Oligomerization was observed on both catalysts a t temperatures a s low a s 37OC.Suwon Campus] At: 10:27 12 February 2009 B cracking C. ~3 t o r r ) .

In agreement with Novakova et al. based on desorption-adsorption of ethene as slow steps relative to reaction of the adsorbed species. Van den Berg [ 741 carried out detailed investigations on the sorption of light olefins in HZSM-5 using TGA and 13C-NMR. Origin of the Polymethylbenzenes It has already been noted that polymethylbenzenes are distinc tive products of methanol conversion to hydrocarbons over a variety of catalysts. This could explain the apparent low ethene reactivity reported by others. it was concluded that the chemisorption of olefins on HZSM-5 is an oligomerization process occurring readily even a t room tem perature. the reactions of C. is that of Dejaifve et al. With most unmodified zeolites. A series of experiments at different flow rates and pressures [66] ruled out the possibility that the degree of ring substitution was simply a consequence of increased contact time brought about by increased pressure.72 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . The plot demonstrates that chain-to-ring ratio is parametric in pressure. The most satisfactory explanation for this. methanol conversion gives product ethene to propene ratios less than unity.+(ads) are faster than i t s desorption as ethene. and desorption is faster than chemisorption of ethene from the gas phase. especially in ZSM-5 zeolites. Water may inhibit or retard the reaction a t low temperatures. [ 791. However. [ 791. In conclusion. 8. in light of the above-mentioned ethene studies. 3 molecules was adsorbed per Al-atom in the zeolite. C2H5+.H. This was confirmed by 13C-NMR which revealed that the ethene oligomer had an average chain length of 25 carbon atoms. At room temperature an average of 4 . allowing ethene chemisorption and reaction. These considerations support the view that ethene can act a s a primary intermediate. Their origin is discussed in the following pages. at temperatures used in methanol conversion to gasoline (227-377OC) the sorption equilibrium between water and the Bronsted acid sites will be shifted toward desorption. [ 1311. the results of Novakova [ 1311 and van den Berg [ 741 leave little doubt that ethene is extremely reactive in the presence of zeolites. Physisorbed water inhibited ethene sorption. and based on the shape of the sorption isotherms. .Suwon Campus] At: 10:27 12 February 2009 observed. 30 which plots aromatic chain-to-ring ratio. According to Dejaifve e t al. van den Berg observed an inhibitory effect of water vapor on ethene reactivity. against contact time. This is illustrated in Fig. Assuming that each Al-atom represents an active site. defined a s (alkyl C)/(aryl C ) .

Second.5a I r 353 psig 169 psig - - 0 ! - I 0.HYDROCARBONS FROM METHANOL 700 OF I I I ~ I I ~ I I I I I 73 0. 8 and 12. The shaded portion in these plots denotes this region of overlap. . Subsequent experiments indicated that the increase in polymethylbenzenes with pressure is correlatable with the degree of overlap of the methanol/DME reaction curve and the aromatization curve in the reaction path. that the alkylation mechanism was kinetically feasible was shown in a study 11151 comparing plug-flow and backmixed reactor performance for methanol conversion over HZSM-5.Suwon Campus] At: 10:27 12 February 2009 u [ 2 0. 31. Figs.3- - I I11111111111 I I11111111111 I I 1 1 l 1 1 1 1 1 1 1 1 I I I I I I I I I L I I . which indicates a shift in distribution toward the higher aromatics. First. With 708 backmixing. This is the anticipated result of the influence of backmixing on the selectivity of a multistep sequential reaction.4- $ V + 59 psig 0 n - 0 0 w 0 psig 0 0. wherein ring methylation by unconverted methanol /DME was assumed to occur [ 321. it was shown [32] that when ethanol was reacted under pressure. The overlap region is seen to increase with pressure. ring methylation increased as illustrated in Fig. Evidence in support of this mechanism was twofold.61 I I I I I I ~ I I I I I ~ I I I I I I I I I ~ ~ I ~ II 1 1 1 1 1 1 1 1 1 1 2 Downloaded By: [2007-2008-2009 Kyunghee University . the durene selectivity was exceedingly low a s compared with methanol feed at the same conditions (Table 17).

74 CHANG "1 Downloaded By: [2007-2008-2009 Kyunghee University . 31.Suwon Campus] At: 10:27 12 February 2009 PLUG FLOW 70% BACKMIXED FLOW CARBON NUMBER [ 1151 FIG. . Normalized aromatics distribution .

C. a AT < 95OC n could be maintained in the second stage. The plant will produce 13.5. C 7 .C 2 olefins . A s noted previously. Control and dissipation of this large reaction heat is a major constraint in reactor design.000 barrels of gasoline per day. 32. paraffins decrease. which translates to an adiabatic temperat u r e rise of about 650OC [ 661. Depending on the recycle ratio. where a near equilibrium MeOH /DME /H20 mixture was produced.HYDROCARBONS FROM METHANOL VI. shown in Fig. staged fixed-bed reactors 1135. 1411. and fluid-bed r e actors [ 137. At 4OOOC it is 1510-1740 k J / k g of methanol converted. The fixed-bed process has been selected by the government of N e w Zealand to convert natural gas from their extensive Maui field to gasoline via methanol [ 1331 . have been extensively investigated in benchscale and pilot -plant studies. Results of a 167-h test a r e shown in Tables 19 and 20. Fixed-Bed Process The fixed-bed unit [30. The feed was methanol containing 17%water to simulate crude product from a methanol plant. Although discussion of reactor design is outside the scope of this survey. the fixed-bed and fluid-bed. The fluid-bed process is scheduled for demonstration a s a lOO-bbl/d unit in West G e r many 1133. The heat of reaction varies with product distribution. including tubular heat exchanger reactors 11343. was a two-stage system consisting of a dehydration reactor. Initial operating conditions for a bench-scale version of the dual reactor system are shown in Table 18 [66]. THE MOBIL METHANOL-TO-GASOLINE (MTG) PROCESS 75 Downloaded By: [2007-2008-2009 Kyunghee University . it may be noted that the Mobil team considered a variety of configurations. 208of the total reaction heat is released in the first -stage and the balance i the second. 66.1401.-C. A s the cycle progresses. 1451. . followed by the hydrocarbon-forming reactor containing H ZSM. In this scheme. A. A fixed-bed process with light gas recycle and the fluid-bed routes were selected for the initial process development studies.Suwon Campus] At: 10:27 12 February 2009 The conversion of methanol to aromatic hydrocarbons over ZSM-5 zeolites is the basis of Mobil's MTG (methanol-to-gasoline) process [ l ] Two versions of this process. The second-stage product was cooled and flashed in a high-pressure separator. 1361. hydrocarbon formation f r o m methanol is a highly exothermic process. Light gases were recycled to the second-stage reactor to control the temperature rise.

5-5. inlet Space velocity Molar recycle ratio 343oc Q454OC 1 3 .0 h .6-23. WHSV Second Reactor Temperature.l .Suwon Campus] At: 10:27 12 February 2009 H20'-h + --Dehydration Reactor 334% Compressor Gas Product HydrOca rbon Liquid Product Conversion Reactor Recycle Gas 408'C I TABLE 18 Water FIG.76 ~~ CHANG Fixed Bed Crude Methanol "'' Downloaded By: [2007-2008-2009 Kyunghee University . inlet Temperature. 6 . 32. WHSV 3-4 (based on total fresh feed) SeDarator Temperature 37. inlet Space velocity 316OC Q399OC 13. Mobil methanol-to-gasoline process [661. 1 atrn 1.8OC . outlet Pressure.l . Operating Conditions for Dual Reactor Fixed-Bed Process 1661 First Reactor Temperature.2 3 . inlet Temperature. outlet Pressure.8 atm 20 h .

00 99. Material Balance.0 0.28 63.3 0.2 0.0 100.72 . 9.738 94.13 0.3 9.6 265 co H2 0 CO2 Methanol Dimethyl ether Product. psig Product. wt % of feed Gasoline (including alkylate) : Reid vapor pressure.3 3.729 93.27 0.3 0.2 101. and Gasoline Propertiesa Time on stream ( h ) 8 Downloaded By: [2007-2008-2009 Kyunghee University . O F WHSV (MeOH over catalyst Molar recycle ratio Pressure.04 0.8 9.0 94.6 100.2 100.18 0.45 100.82 65.6 26 5 625 735 660 8 19 3.00 0. unit .09 0.4 265 625 768 665 891 3.8 26 5 624 769 663 888 3.00 37.3 3.00 100. OF Reactor 1 outlet temperature. OF Reactor 2 outlet temperature.0 96.HYDROCARBONS FROM METHANOL TABLE 19 [66] A Fixed Bed Aging Study.6 26 5 625 768 648 8 57 3.Suwon Campus] At: 10:27 12 February 2009 77 47 95 142 167 Run conditions: Reactor 1 inlet ternperature.00 101.02 0.22 9.11 34. p sia Research octane.100.05 0.100.746 94. wt% of total product : Hydrochrbons 626 77 1 648 862 3.00 100.00 100.08 0.00 0.08 0.0 94.726 93. 3 g lead Specific gravity Molecular weight a 36.0 95.00 0.2 9.09 0.736 94. O F Reactor 2 inlet temperature. Run Conditions.69 35.4 .3 3. process development .3 3.20 0.44 63.04 0.3 100.00 0.09 0.00 0.00 .65 62.76 100.00 36.3 0.O) unit.54 0.3 3.75 64.05 0.8 Feed crude methanol ( 17 wt%H.0 94.00 99. unleaded Research octane.

5 5.78 C HAN G TABLE 20 [66] A Fixed Bed Aging Study. + .7 4. .0 74.2.5 c 5+ 9 RVP gasoline including alkylate Durene increase.0 Aromatic s 33.5 2.5 3.7 32.0 5.2 10.9 2.9 d (Table 21). varying in length from 1 3 .6 3.Suwon Campus] At: 10:27 12 February 2009 8 47 2. with oxidative regenerations between cycles to remove accumulated coke on catalyst.2 88.1 81.4 42. The total test consisted of nine cycles.4 4.2 2.6 2.2-96.0 9.5 82.2 4.4 142 1. so that the total of R V P gasoline selectivity was 75.5 68.5 35. 3 to 1. In a subsequent test [ 1421 the space velocity was lowered from 3 . 4 . C nonaromatic hydrocarbons increase significantly.1 28.9 9.0 78.4 wt%. Typical data.2 48.0 7.1 7.7 50. alkylate could be produced from the isobutane and C . shown in Tables 22 and 23. and aromatics remain fairly constant. For the final gasoline product.2 100.0 73.3 167 2.8 27. 8 to 9.9 4.1 88.6 3.C I .3 100.9-88.7 4. A total of 208 d on stream was achieved.3 . This product had an unleaded research octane of 94. during which 8000 lb methanol/lb catalyst was processed.8 4.6 and the recycle ratio increased from 3 . Hydrocarbon Product Distribution.0 100.0 31. Basis : Weight Percent Time on stream ( h ) Downloaded By: [2007-2008-2009 Kyunghee University .9 2.0 77. 1 d (first cycle) to 24.9 8.4 ----100. are similar to the data in the preceding tables. olefins.2 100. ethane.4 11.6 8.0 4.1 95 2.C 4 Olefins C 5+ Nonaromatics 2.7 42. ethylene Propane n -Butane I sobu t ane C 3 .7 75.8 Methane.

9 24.2 808 21.1 24.55 8 9 18 212.6 212-48 1 50 1 212-49 2 982 212-50 3 643 212-51 4 695 212-52 5 607 212..0 15. 2 Time (d) 15.0 23.5 64.56 9 920 Methanol breakthrough taken as first material balance during which MeOH was detected in product water phase.5 43. a .Downloaded By: [2007-2008-2009 Kyunghee University .8 130...8 1105 28.9 16.3 103.Suwon Campus] At: 10:27 12 February 2009 X TABLE 21 11421 Cycle Lengths of Long-Term Aging Test in Fixed Bed Unit Cycle length to MeOH breakthrou gha Total cycle length MeOH proc. Time (d) MeOH proc.0 795 20. lb of MeOHl Cumulative time on stream MeOH proc.9 18.8 154.4 207. 2 lb of cat 2.5 595 1700 2495 3303 4011 5057 5952 7000 8006 lb of MeOH/ Run no. Cycle lb of cat. Time ( d ) 13.1 181.1 23.8 24.3 27. lb of MeOHI Ib of cat.3 26.9 21.2 1006 1048 895 1046 708 18.3 85.0 595 15.53 6 96 3 212-54 7 810 212.5 27.

MeOH over conv.6 8.Suwon Campus] At: 10:27 12 February 2009 TABLE 22 11421 Operating Conditions and Products for Selected Cycles in Long-Term A g i n g Test Cycle 1 Cycle 6 Cycle 9 Conditions 73 117 601 779 648 774 128 1. OF O F High pressure separator temp. mol/mol of charge Pressure. WHSV..6 9.9 300 652 776 604 583 773 649 766 125 1.7 300 501 4162 314 94 333 4545 586 771 652 774 135 77 7123 576 771 650 778 126 315 7504 58 7 774 651 779 124 T h e on stream in cycle h Cumulative charge.6 9. w t of MeOH/ w t conv.. cat. psig .6 8. OF OF Dehydration reactor outlet temp. cat. 1.8 245 1. Dehydration reactor inlet temp.3 250 Recycle ratio..6 9. Conversion reactor inlet temp.Downloaded By: [2007-2008-2009 Kyunghee University .2 300 777 129 1.2 283 1.6 8.. OF Conversion reactor outlet temp..

w t % of hydrocarbons a Gasoline includes alkylate .0 0.3 Yield.6 00 .4 0. 0.8 0.4 99.0 99.2 HZ 0.6 99.756 95 Research octane (R + 0) 93.0 0.4 Dimethyl ether Material balance.03 0.0 Hydrocarbons 35.3 Leaded octane ( R + 3) Specific gravity Molecular weight 73.1 93.3 93.0 0. 98.0 100.2 97.1 0. w 90 t 9 RVP gaso1ine:a 95.0 00 .0 64.9 63.0 00 .2 0.8 0.728 95 92.3 0.0 0.01 0.0 63.2 0.04 64. wt 0 of charge : 35.01 0.2 100.1 0.0 0.3 0.01 0.0 93.8 Methanol 0.08 0.0 99.7 0.Downloaded By: [2007-2008-2009 Kyunghee University .4 0.2 99.0 CO.734 95 86.05 HZO 64.736 95 82.01 0.731 94 85. .3 36. 98.01 0.2 99. 98.5 35.2 36.0 0.0 co 0.9 64.2 35.0 0.9 0.9 0. 00 . properties are calculated from compositions.07 0.Suwon Campus] At: 10:27 12 February 2009 Products.723 94 89.5 93.

cat.4 0.9 0.6 0.2 2.Suwon Campus] At: 10:27 12 February 2009 03 TABLE 23 11421 N Hydrocarbon Product Distribution i Long-Term Aging Test n Cycle 1 Cycle 6 Cycle 9 Time on stream in cycle.0 1.9 0.1 1.3 0.0 6.0 Ethene Prop m e 11.Downloaded By: [2007-2008-2009 Kyunghee University .2 2.4 1.7 8. h 73 117 50 1 3 14 4162 4545 94 333 77 7123 3 16 7504 Cumulative charge.0 5.9 0.9 n -Butane Isobutane 8.9 1.1 0. Hydrocarbon composition.6 0.9 n -Pentane Isopentane Pentenes .6 1.4 0. wt %: Methane 2.0 Ethane 1.7 11.3 Propene 0.5 1.6 11.2 3.6 4.3 2.9 1.3 0.1 19.7 9.0 6.1 13. 0.0 1.3 0.1 0.2 8.3 17.6 3.0 2.5 30.5 0.0 1. wt of MeOH/wt of conv.3 07 .2 10.0 22.8 1.6 0.6 2.0 0.2 0.1 2.4 0.8 0.4 Butenes Total C k 20.2 10.0 0.1 5.2 3.8 0.3 11.2 1.2 2.7 10.3 1.0 3.4 8.3 2.

0 80.1 0.6 Propylben zenes 3.4 0.1 0.0 29.3 2.5-Tetramethylbenzene 1 .2 1.1 27.2 0.9 3.2 Toluene 4.8 1.2.6 1.3 0.T e t r a m e t hylben zene 0.7 0.5 6.2 1.0 6.8 0.5 31.2 38.3 0.4 1.9 Methylethylben zenes 0.6 Benzene 0.6 41.8 20.0 86.2 0.7 1.7 83.6 7.5 p. 7 6.1 1.and m .9 0.1 4.3 C6+ Nonaromatic 0.3 0.2 0.2 0.7 Total C.1 0.6 7.4 0. 3 .Downloaded By: [2007-2008-2009 Kyunghee University .5 0.3 0.6 0.6 0. 2 .1 0.1 Naphthalenes Unknowns 0.1 0.3 0.1 4.3 2.2 2.3 0.0 1.5 2.7 1.2 0.8 0.1 0.1 7.4 80.i 43.0 26.Suwon Campus] At: 10:27 12 February 2009 C yclopentane 0.2 0.0 7.7 7.2 2.1 1.2 0.3 3.2 3.1 1.1 1.7 0.8 77.7 0.4 0.4 2.6 0.1 0.4 0.0 1.7 Ethylbenzene 9.4 36.0 70.4 8.8 0.0 31.0 0. 5 .2.5 0.+ Total aromatics .6 Trimethylbenzenes 8.2 1.5 2.1 0.3.8 0.0 28.2 0.5 35.2 0.8 o -Xylene 2.2 2.3 2.4 0.X y l e n e s 7.9 0.8 0.2 2.8 0.7 0.4-Tetramethylbenzene O t h e r C l o benzenes Cll A l k y l b e n z e n e s 0.1 1.4.

Data summarized in Tables 24 and 25 indicate that the bench-scale results were duplicated on the larger scale. A characteristic of this type of operation is catalyst band-aging. 33. Fluid-Bed Process Development of the fluid-bed process followed a course similar to the fixed-bed. 0. 36 [ 1441.2 03 . exemplified in Fig.2 0 0. 34 (fifth cycle).4 0. 33.Suwon Campus] At: 10:27 12 February 2009 0. B .84 1. due to progressive coking. The fixed-bed process was subsequently scaled up to a 4 bblld pilot plant [ 1431.5 0. .6 0. Band aging of methanol-to-gasoline catalyst in the first cycle of the long-term aging test [ 1421. Initial studies were carried out in the benchscale reactor illustrated in Fig.6 0. 35 indicate identical aging patterns in the bench and pilot-plant tests. The reactor temperature profiles in Fig.1 0. The corresponding change in product distribution through a cycle is plotted in Fig.7 0.8 0.9 1 Fractional Bed Length FIG.0- CHANG 0.8 - Downloaded By: [2007-2008-2009 Kyunghee University . The end of cycle occurs when the reaction front arrives at the reactor outlet.

TABLE 24 [1431 Four Barrels-per -Day Fixed -Bed MTG Demonstration Plant Operating Conditions DME reactor inlet temperature. O C MTG reactor exit temperature.I ? s 0 20o 10- / 7 0 - - Olefins 0 I a L Time On Stream (Hours) FLG. OC 4 12 9 1. kPa Separator temperature. molar Catalyst WHSV (pure methanol basis) Reactor pressure. Changes in hydrocarbon composition during the fifth cycle of the long-term aging test [ 1421. O C 3 15 360 MTG reactor inlet temperature.HYDROCARBONS FROM METHANOL 50 I I I 85 1 > Downloaded By: [2007-2008-2009 Kyunghee University . O C Gas recycle ratio.6 2170 52 .Suwon Campus] At: 10:27 12 February 2009 40 _h \r lsoparaffins V r v - V Y m V I . 34.

00 0. w t % of HC 80.50-3. Typical data a t 371°C. n The changes in selectivity through a cycle a r e directionally similar to the fixed-bed.l .00 Hydrocarbon product.7 75.4 atm.4 0.10 0.1 0. In practice.00 0.0-4.6 0.5 8.00 0.00 100. 1 atm.86 TABLE 25 [143] MTG Scale-Up : Yield Comparison (average of first cycle) Product.7 75. Methanol Dimethylet her 0.17 Hydrocarbons Water 43. wt8: Methane Ethylene Propane Propylene + ethane 2.0 C 5+ Gasoline 100.06 C o t CO2. 2 95 80.2 n-B utane i-Butane But ene s 4. 1 WHSV a r e shown in Tables 26 and 27 and plotted i Figs.2 95 R + O Process conditions scoped were: 316-482OC.5 h .Suwon Campus] At: 10:27 12 February 2009 CHANG 4 b b l l d unit Bench unit 43.2 4:2 0.73 56.0 9 RVP gasoline Yield. 37-40.02 8.03 8. WHSV.8 - 0. H. a fraction of .75 56. however.00 100.9 100. 0.1 2. w t % MeOH Downloaded By: [2007-2008-2009 Kyunghee University . 1.1 8.5 0.19 0.

and q = relative catalyst activity expressed a s a function of initial activity q o . Fixed-bed MTG. To account for both inhibition and change in gas residence time due to . regenerated. and returned so that the selectivity would b e neld at a constant level. 41 and 4 2 the effects of temperature and pressure on methanol in the effluent a r e plotted against SC-’. r = dilution factor (moles reactant + moles diluent)l(moles reactant). Movement of temperature profiles [ 1431.HY DROC ARB 0 N S FROM METHANOL 87 Downloaded By: [2007-2008-2009 Kyunghee University . In Figs. An exponential deactivation was assumed. Conversion increases with increasing temperature and llSc. The pressure effect appeared not to b e first-order. S = experimental space velocity. the catalyst would be removed continuously. defined by where Sc = corrected space velocity.Suwon Campus] At: 10:27 12 February 2009 Fractional Bed Length FIG. This was assumed to be due to adsorption inhibition effects. 35.

n different pressures. the data were correlated with the group defined by -@= 00 (~+KAPA. Schematic of fluidized dense bed pilot plant [ 1441.) -( ~ + K A P A ) Sc PO .Suwon Campus] At: 10:27 12 February 2009 FIG. All dimensions are i inches.88 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . 36.

4OOOC) .26 2.) 89 26-01 6 25-04 71 25-07 13 5 25-10 203 Downloaded By: [2007-2008-2009 Kyunghee University .25 4.37 7.23 .07 42.7 0.40 56.02 42.20 55.97 10.17 6.80 55.78 0. while PA and p = experimental values. DME..30 1.Suwon Campus] At: 10:27 12 February 2009 Product (wt%of charge) : Methanol Dimethyl ether Hydrocarbons Water C O .15 99.24 64.82 0.2 1.54 1.62 0.84 3.08 5.81 0.92 6.64 63.15 42.54 2.13 0. 0.8 Hydrocarbons (wt % of hydrocarbons) : Methane Ethane Ethylene Propane Propene I sobut ane 0.64 63. H.14 1.27 n -Butane But enes c 5+ where PA^ = sum of the partial pressures of methanol.21 12.77 0.28 99.77 0.8 100.99.47 5.HYDROCARBONS FROM METHANOL TABLE 26 f1441 Typical Material Balances in Fluid-Bed Pilot Planta Material balance no.98 13.14 6. po = gas density at reference conditions.81 0.71 1.20 55.25 5.83 7.65 5.08 0.30 0.O at a set of arbitrary reference conditions (1 atm. and H.93 0.11 0.84 0. MeOH charged (Ib of MeOH/ lb of cat.17 5.32 0.64 3.41 15. Figure 43 shows a plot of effluent methanol concentration vs . CO.90 0.43 43.22 64.21 0.48 4.

07 0.11 0.10 0.02 2.20 0.38 0.80 0.30 8.17 5.46 2.39 0.40 1.64 0.4-Tetramethylbenzene Other C .47 0. carbons.09 4.56 1.91 2.-PON CIO-PON Benzene Toluene E t hylben zene X ylenes Trimet hylbenzenes Methylethylben zenes Propylben zenes 1.36 1.43 0.94 1..18 6.00 3.00 1.71 4.63 5.3.46 0.36 0.12 0.34 0.43 0. MeOH charged (Ib of MeOH/ lb of cat.86 0 psig.00 1.50 7.30 1.00 2.67 25-07 13 5 11.26 0. 1 WHSV.44 0.27 0.02 6.44 0.43 0.2. 0.38 0.50 1.39 1.03 1.58 Downloaded By: [2007-2008-2009 Kyunghee University .20 1.30 1.06 0.07 0.07 0.17 5.52 0.74 0.06 5.41 lI2.18 0.03 3.17 0.5-Tetramethylbenzene 0.58 5.42 3.38 1.05 8.45 0.02 0.48 0.) Isopentane n-Pentane Pentenes Cyclopentane Methylcyclopent m e n .4.-Benzenes Naphthalenes Other aromatics '700°F.49 2.03 3.72 1.25 4.15 0.99 0.19 0.3.97 0.Hexane Met hylpentanes Dimethylbutanes Hexenes Cyclohexane C ..02 0.16 6.03 0.01 1. 14 6.22 0.93 1.29 3.00 2.2.62 2.-PON 26-01 6 12.45 Ce-PON C.00 4.33 0.31 2.12 0.80 7.31 0.04 1.23 0.02 1.04 0.30 0.67 5.43 2.03 3.90 CHANG TABLE 27 [144] Composition of Hydrocarbon Products from Fluid-Bed Pilot Planta Material balance no.00 0.14 2.-benzenes C .89 1.5-Tetramethylbenzene 1.Suwon Campus] At: 10:27 12 February 2009 25-04 71 11.42 5. concentrations are w t % of total hydro- .71 1.05 0.43 25-10 203 10.87 3.60 0.87 1..33 3.23 3.

) METHANOL PROCESSED (Lb MeOH/Lb Cat.7 atm. Fluid bed reactor (total hydrocarbons and aromatics) [ 1441.) 371OC I atm.Downloaded By: [2007-2008-2009 Kyunghee University .7 atm.Suwon Campus] At: 10:27 12 February 2009 HYDROCARBONS a V I 30t AROMATICS -. I WHSV 371 "C 2. 2 WHSV FIG.) AROMATICS n DIMETHYLETHER1 O o D I ) DIMETHYLETHER 7 1 METHANOL PROCESSED (Lb MeOH/Lb Cat. 37. 0 METHANOL METHANOL PROCESSED (Lb Me OH/Lb Cat. 2 WHSV 399O c 2. .

7 atm.) I X 10 0 200 I METHANOL PROCESSED (LbMeOH/Lb Cot. .' and CSi hydrocarbons) 11441. 2 WHSV FLG.. 38. I WHSV 2 WHSV Fluid bed reactor ((2. i METHANOL PROCESSED (Lb MeOH/Lb Cat.. 371OC 2.) I00 2( METHANOL PROCESSED (Lb M OH/Lb Cat. I e 371OC I atm. 399OC 2.7 atm. I00 .Suwon Campus] At: 10:27 12 February 2009 > r Y 0 c5+ x- X X .Downloaded By: [2007-2008-2009 Kyunghee University .

Suwon Campus] At: 10:27 12 February 2009 r I w -6-r 0 METHANOL PROCESSED (Lb McOH/Lb Cot. Fluid bed reactor (light paraffins) [ 1441.Downloaded By: [2007-2008-2009 Kyunghee University .7 atm. I WHSV FIG.) I00 I $ 1 PROPANE I n . 2 WHSV 399°C 2.) 200 METHANOL PROCESSED (Lb MeOH/Lb Cat.7 atm.BUTANE x P 0 METHANE +ETHANE 2 20 I0 0 METHANOL PROCESSED (Lb MeOH/Lb Cot. 39. W W . 2 WHSV I atm. 1 3 1 OC 7 371 OC 2.

I WHSV 371 O C 2 7 atm. Fluid bed reactor (light olefins and durene) 11441. . .7 atm.) 0 10 0 I00 200 200 - E3t7 w > 2 20 I00 200 METHANOL PROCESSED (Lb McOH/Lb Cat.) METHANOL PROCESSED (Lb McOH/Lb Cat. 40.) 371 OC 2 WHSV I atm. 2 WHSV FIG.Downloaded By: [2007-2008-2009 Kyunghee University . 399OC 2.Suwon Campus] At: 10:27 12 February 2009 Gj I0 - 0 I 0 METHANOL PROCESSED (Lb MeOH/Lb Cat.

Suwon Campus] At: 10:27 12 February 2009 1 ISC FIG.HYDROCARBONS FROM METHANOL 95 Downloaded By: [2007-2008-2009 Kyunghee University . Effect of temperature on methanol conversion at 25 25 20 - 5 - 8 0 1525 psig 10- s E 5 50 Psig\ I 1 0 psig 5K O 0 1 I I I l e FIG. [ 1441. psig [ 1441. 42. 41. Effect of pressure on methanol conversion at 700°F .

96 CHANG Downloaded By: [2007-2008-2009 Kyunghee University .25 8 y 1. 11441.1. 44. .Suwon Campus] At: 10:27 12 February 2009 2 FIG.50 0.00 c - - Observed Rediaed From Equilibrium 5 5 0 0.25 I 0 1 2 3 Methanol (Wt %) FIG. Plot of methanol concentration versus @/@. 43. .75 E .n 0. Comparison of calculated equilibrium and experimental concentrations of methanol and dimethyl ether [ 1441.

The fluid-bed process was scaled up to a 4-bbl/d pilot plant [ 1461. Figure 44 plots DME vs methanol at the reactor exit. . The reactor-regenerator system is shown in Fig. 47. Comparison with the theoretical curve confirms that the initial etherification step is close to equilibrium.HYDROCARBONS FROM METHANOL -+ 97 To Product Recovery Disengager 4 0 - 16" x 3' Downloaded By: [2007-2008-2009 Kyunghee University . 45. Table 28 gives the range of operating conditions. Long-term demonstration runs of 34 and 75 d were conducted in the 4-bblJd pilot plant. 46. Unit 231 reactor-regenerator system [ 1461. A typical reactor temperature profile is displayed in Fig. indicating the uniform temperature achieved along the considerable length of the reactor for this highly exothermic reaction.Suwon Campus] At: 10:27 12 February 2009 Flue gas Regenerator lo" x 2%' Reactor Air 4" x 25' + N2 Hopper lo" x 2%' Scale: 1/4" = 1' Liquid Feed Vapor Feed - - FIG. 45 and a schematic flow diagram of the pilot plant is shown in Fig.

Suwon Campus] At: 10:27 12 February 2009 98 t 313A33U SVZ) 1HE)Il CHANG .Downloaded By: [2007-2008-2009 Kyunghee University .

However. T It is seen that the octane and volatility characteristics are excellent.Suwon Campus] At: 10:27 12 February 2009 388-427OC 2. and emissions.3 h-' 0. S and N contaminants are totally absent. Fleet testing confirmed that the M G gasoline was comparable T to commercial premium gasolines in road octane. so a s not to crystallize out of solution. Product Characteristics Extensive product quality testing has been conducted on the gasoline from the Mobil M G process [ 1471.3OC). cold-start. Because of its high melting point (79.8 f t l s 83.5-1.100 wt%MeOH In Table 29 [ 1631 representative product yields are shown and compared with typical data obtained from the 4-bblld fixed-bed pilot plant. driveability. give final gasoline yields higher than that of the fixed-bed.7-1.4-3. Unlike commercial gasolines. C. Table 30 presents a summary of the properties of M G gasoline. the durene content of the gasoline must be controlled at suitable levels. The one hydrocarbon in M G gasoline not found T in significant amounts in conventional gasoline is durene. Concentrations as high as 3% of durene were found to give no adverse engine effects. It can be seen that the fluid-bed produces more light olefins and less C5' gasoline than the fixed-bed. depending on the ambient temperature. In general the synT thetic gasoline is identical in all major aspects to commercial high octane gasolines. The mechanism of durene formation has already been discussed.7 atm WHSV. .HYDROCARBONS FROM METHANOL TABLE 28 Operating Conditions for Fluid-Bed Pilot Plant 1 1461 -~ 99 Temperature Pressure Downloaded By: [2007-2008-2009 Kyunghee University . the light olefins. MeOH Gas superficial velocity Feed composition 0. when alkylated with isobutane and blended back.

Olefin Production A s indicated earlier. Fluid-bed reactor temperature profile [ 1461 I D .Suwon Campus] At: 10:27 12 February 2009 20 C c 15 z U B c . several techniques may be applied to maximize olefin selectivity in methanol conversion over ZSM-5 zeolites. Reduced partial pressure [ 321 and catalyst modification with phosphorus compounds [ 331 are effective. 47.100 25 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . OF 900 1 loo FIG. A third technique utilizes .c B 10 K c' t 5 0 500 700 Temperature.

other 0.6 3.4 5.1 79.2 43.0 100.0 . wt%: Light gas Propane Propylene i-Butane n -Butane B u tene s C.6 5.6 Gasoline (including alkalate) (96 R + 0.and Fluid-Bed Yields [ 1631 ~~ Yields from methanol in fixed-bed reactor system Downloaded By: [2007-2008-2009 Kyunghee University .4 0.+ Gasoline 5.5 56.9 5.0 43.0 14.Suwon Campus] At: 10:27 12 February 2009 Yields from methanol in 4 bbl/d fluid-bed pilot unit Average bed temperature.2 - 360 413 275 1.3 60. RVP = 9 psi [ 6 2 kPa]) LPG 88. RVP = 9 psi [62 kPa]) LP G Fuel gas 85.5 1.3 1.0 6.Fuel gas 100.0 1.1 0.0 0.0 Methanol + ether Hydrocarbons Water C O . coz Coke.4 5. wt % of methanol charged : Methanol + ether Hydrocarbons Water c o . O : C Inlet Outlet Pressure.0 415 2170 9.5 0.0 100.0 Gasoline (including alkalate) (93 R + 0. other 0. O C Pressure. w t % of methanol charged : Temperature.HYDROCARBONS FROM METHANOL 101 TABLE 29 Comparison of Fixed.7 7.4 56.2 100.0 0.2 8.0 13.0 Light gas Propane Propylene i-Butane n-Butane Butenes C. COZ Coke.+ Gasoline Hydrocarbon product.0 Hydrocarbon product.9 100.0 2.6 100. wt %: 1. kPa Recycle ratio (mol) Space velocity (WHSV) Yields. kPa Space velocity (WHSV) Yields.4 .

17 g Pb/USG as TML Motor octane number (ASTM D2700) : Unleaded +3. (ASTM D86) : lBP 5% 10% 20 % 30 % 40 % 50 % 60 % 70 % 80 % 90 % 95% End point % Residue Research octane number (ASTM D2699) : Unleaded +3.9 103.4 95. alkylates and light hydrocarbons) API gravity. m g / 1 0 0 mL (ASTM D381) Potential gum.9 94.17 g Pb/USG a s TEL +3. OF.8 102.2 96.1 11.2 87. 5 h) 86 102 116 136 159 186 2 16 240 263 297 33 6 3 58 422 1.17 g PblUSG as TEL +3.1 95.7 1.17 g Pb/USG a s TML Distribution octane number (ASTM D2886) : Unleaded +3.8 103.4 104. (ASTM 0 2 8 7 ) Reid vapor pressure.102 CHANG TABLE 30 [ 1471 Properties of Gasoline f r o m Methanol (yield proportions of liquid product from 4 bbl Id unit. lb (ASTM D323) Downloaded By: [2007-2008-2009 Kyunghee University .5 (continued) . % evap.1 Distillation. mg/100 mL (ASTM D873.17 g PblUSC as TML Front end (IBP-212OF fraction) octane number: Unleaded +3.17 g Pg/USG a s TEL +3.Suwon Campus] At: 10:27 12 February 2009 62.7 96.17 g Pb/USG as TML in distillation charge Existent gum.1 96.3 2.

DUAL-FUNCTIONAL CATALYSIS It is natural to inquire whether the two reactions of methanol synthesis and subsequent hydrocarbon formation could b e done in a single step over a dual-functional catalyst. w t % (Mobil method) a Nil Nil Includes 3 wt% durene the fact that olefins are intermediates in the MTG reaction path [ 2 . Results are shown in Table 31.35 Freeze point. . [ 150. Using methanol containing 17%water. 48%C 2 .HYDROCARBONS FROM METHANOL TABLE 30 (continued) Hydrocarbon type. vol % (ASTM D1319): Aromaticsa Olefins Saturates Downloaded By: [2007-2008-2009 Kyunghee University . Conditions a r e chosen to operate at partial conversion. olefins selectivity was obtained at 52%conversion. since the olefin distribution was not a s predicted b y thermodynamics under reaction conditions. Olefins are separated and unconverted feed recycled. 1511. wt % (Mobil method) Nitrogen. 1481 .C . VII. O (ASTM D2386) F Sulfur. Increasing water dilution was found to improve ethene selectivity. A fluid-bed study was carried out a t partial conversion of methanol [ 1491.Suwon Campus] At: 10:27 12 February 2009 103 27 6 67 . The overall kinetics may be represented by The catalyst is composed of a metal oxide (methanol synthesis) component and an acidic ( zeolite) component. This was attributed to a kinetic effect. This question was investigated by Chang et al. The methanol was diluted with various amounts of water.

A s indicated.3 24.OH/ 84% H 2 0 3 6 15 27 0. wt % of methanol : Hydrocarbons Methanol Dimet hylet her Water Coke.9 5.2 0.9 38. K = kl/kl' << 1 The transformations A -+ B and B -+ C are effected by different catalysts.0 39.7 The above kinetic scheme is a special case of a general class of polystep reactions 1521 represented by kl A kl k2 B -C.0 0. other Per pass conversion.0 52.8 11. % Hydrocarbon product. However.9 23.1 1.5 6.5 100.8 7.2 7.1 Conditions : Temperature.) Aroma tics Nonaromatics C2-C5 Olefins 2 650 6 0.3 0.9 20.104 TABLE 31 11491 Conversion of Methanol to Light Olefins 83% CH.1 2.0 38. C O .0 47.7 15. psig Methanol W S HV Product yield.4 36.6 17.6 16.Suwon Campus] At: 10:27 12 February 2009 16% CH.2 26.5 2.0 100. P F Pressure.0 84 18.2 100.5 19. wt 8: Ethylene P ropylene Butenes Pentenes Paraffins (C.5 100. the first reaction is subject to thermodynamic limitation.0 62 27.7 6.0 52 21.-C. the second reaction provides a .4 22.6 8.1 18.7 6.2 100.OH/ 17% H 2 0 1 570 6 0.1 CHANG Reactant composition Downloaded By: [2007-2008-2009 Kyunghee University .9 100.2 27. C 0 2 .3 17.8 16.3 23.3 14.1 49.

however. This is illustrated for the ZnCrZSM-5 catalyst in Fig. A s the ZnJCr is lowered. 8. At ZnICr = 4 . [ 1511 found that the polystep reaction of interest contained an undesirable side-reaction : hydrogenation of the intermediate olefins. the syngas conversion activity drops. a s reflected in the conversion behavior. . In some cases. and the selectivity changes in a pattern similar to the methanol-to-hydrocarbon pathway in Fig. it was determined that the unwanted side-reaction became significant whenever the rates of methanol formation and aromatization were not pmperly matched. which is optimum for methanol synthesis 11531. 50 which plots a conversion and selectivity vs the activity parameter a. 48. By varying the activity of each catalyst component. aromatics formation becomes evident.Suwon Campus] At: 10:27 12 February 2009 dN @ RT r2 =(=)(pi)(o) < = diffusivity of the intermediate (cm2/s) where D r Pi (dN/dt) R T = mean diffusing distance. It was found that the interception of the olefins could be controlled simply by changing the activity of the metal component. only light paraffins are observed. . diffusive transport will not significantly influence the polystep reaction rate. only light paraffins were produced via this competitive pathway. the efficiency of the "drain-off" mechanism increases. The effect of increasing zeolite activity is shown in Fig. or particle radius (cm) = intermediate species partial pressure (atm) = reaction rate (mol sec-' cm-') = gas constant (cm' atm mole-' OK-') = reaction temperature (OK) When Q is <1.It can be seen that with increasing a. and it can be shown [ 1521 that the attainable conversion of the coupled system can exceed the product of the conversions of the constituent reactions. Weisz t 1521 has given the following general criterion : Downloaded By: [2007-2008-2009 Kyunghee University . In addition to activity considerations. which is a measure of the relative n-hexane cracking acid activity [1541. Chang et al.HYDROCARBONS FROM METHANOL 105 "drain-off" equilibrium displacement. certain diffusional criteria must be met before the maximum polystep kinetics are realized. Figure 49 shows a strong correlation between the specific hydrogenation activity (for pmpene) of the ZnCr component and the aromatization selectivity of the composite.

An interesting result. 50. 1800 h-’ GHSV [ 1511. is the suppression of methane with increasing a. The follqwing mechanism was proposed : . 48. as seen in Fig. 1200 psig. Syngas aromatization over ZnCrZSM-5. Effect of metals composition. H.Suwon Campus] At: 10:27 12 February 2009 t i TYPICAL HIGH PRESSURE tMETHANOL SYNTHESIS I I CATALYST I ATOM PERCENT FIG. 800°F. its suppression was believed to be achieved by interception of a precursor.106 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . Since methane is thermodynamically stable. which was common also to methanol./CO = 1.

k. Correlation of catalyst hydrogenation activity with aromatics selectivity [ 1511.HYDROCARBONS FROM METHANOL 7c 107 6C 0 Downloaded By: [2007-2008-2009 Kyunghee University . In support of this proposal. [ 1551 showing that methanation and methanol formation a r e parallel r e actions on methanol synthesis catalysts was cited. Furthermore. hr-' FIG. the result of Vlasenko et al. . W A v) 30 -I 0 5 4 4 g 20 1 0 0 SPECIFIC PROPENE HYDROGENATION RATE.40 - i. 49.Suwon Campus] At: 10:27 12 February 2009 50 z 5 c. Syngas aromatization over ZnCrZSM-5.

H. GHSV = 1740./CO = 1.34.Suwon Campus] At: 10:27 12 February 2009 30 z $20 I 1 0 60 50 8 40 5 > I - 230 5 0 l - I W n ! I 20 ? z c 3 1 0 I 0 3 1 1 0 a IUU FIG. Influence of zeolite cracking activity. . 50. Zn/Cr = 0. 83 atm.1780 h .108 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . 427OC.l [ 1511 . Syngas aromatization over ZnCrZSM-5.

wt 8: CH4 c2-c4 ZnCra 20 ZnCr + ZVK 20 Traces 100 c6 c.1 2.0 9. [ 1571 in their study of syngas conversion over dual-functional catalysts.1 2. which also contains data from methanol conversion over zeolite ZVK for comparison. 35O-38O0C. This selectivity was attributed to the small pore size of erionite. and 200-1000 h . CH.OH and mainly propane) at 35OOC. Paraffins were predominant. The conversion of syngas to light hydrocarbons over a dualfunctional ZnO-CuO/H-erionite catalyst has been reported [ 1671 At 322-458OC and 27-68 atm the product was entirely Cl-C4 hydrocarbons. . at m Hydrocarbons.I GHSV.0 2.9 1. Syngas (H. Similar results have been reported by Ione et al.71 2.8 19.0 1.* .OH ZVK 1 Catalyst Pressure.Suwon Campus] At: 10:27 12 February 2009 CO i 2H2 CO + 2H. Typical results are shown in Table 32.7 14.1 Traces 42. Aharoni and Starer [ 1561 found evidence for a common precursor for methane and methanol. indicating interception and hydrogenation of olefinic intermediates.79 14.25% conversion (to CH. Addition of water suppressed double bond hydrogenation and increased ethene selectivity.3 8.0 5. C8 B en zene Toluene Xylene Et hylben zene c 9+ a 8.9 11.HYDROCARBONS FROM METHANOL TABLE 32 Conversion of Syngas and Methanol over Various Catalysts [ 1571 (350-380OC) ~~ 109 Feed Downloaded By: [2007-2008-2009 Kyunghee University . A zincchromium methanol synthesis component was combined with a high silica zeolite ZVK. which is reported to be analogous to ZSM-5 11581./CO = 2) was reacted over this composite at 20 atm.06 11.7 3. A close similarity is evident.23 3.8 14.0 15.6 5.9 4.

Nevertheless. for example. the reaction "bottom line. the formation of hydrocarbons from methanol raises a host of intriguing theoretical questions. in the case of CH. trapping of intermediates." a s it were. intermediate is cationic in character. There is clearly a diversity of opinion concerning the mechani s m of initial C-C bond formation. . have failed to provide unequivocal answers. e .110 V I I I . at least during some stage of its existence. and a wide gap separating theory from experiment. recognizing. classical methods of mechanism elucidation. even under the influence of high solvation energies. Aside from its obvious practical implications. is the transfer and incorporation of a six-electron CH. Such gas-phase reactions a r e extremely fast and apparently p m ceed without activation energy. Direct observation of the transition state seems beyond our capabilities at . intermediate lose a proton (or H. during. such exercises may be useful heuristically. e. initially embedded in a stabilizing cationic environment. Regardless of the nature of the electron-donor substrate. at what point during its career does this C . however. POSTSCRIPT CHANG Downloaded By: [2007-2008-2009 Kyunghee University . i . reactions such a s have been studied by ion cyclotron resonance spectroscopy [ 1591.g. .')? Before. It would seem therefore that the central question is really concerned with timing. unit.Suwon Campus] At: 10:27 12 February 2009 This survey has provided a documentary account of the history and nature of a catalytic reaction which h a s become the object of widespread attention. I s it possible that. that ion solvation could (and probably will) drastically alter the picture in catalytic environments. the anomalous temperature dependency observed by van den Berg [ 741 during the early stages of dimethyl ether reaction? Because of the high exothermicity and fast kinetics of the methanol transformation. For example. o r after C-C bond formation? It is extremely tempting to draw analogies with gas-phase ionic reactions. and kinetic studies. there seems to b e a majority consensus that the reactive C. tracer. completely analogous r e actions with similar (net) energetics prevail in the zeolitic e n vironment? Could this explain. Nevertheless. into the substrate.

U. Patent 2. 142 (1948). Westrum. and W . Phys. M . S. A m . D . C . 249 (1977). Nauk.. Chem. Gorin.702. The literature on this question has grown apace. L . and A . 119 (1978). . B . Grosse and J. LeBel and W . E . D. D . Akad. Nauk SSSR Izv. J . 6. 20 ( 1880). W . J . Lawton. Lechthaler. P . J. Sernagiotto. E . Nature. R . Meisel. S. Patent 2. J .275. SOC.894. U s .584 (1948). and W . Catal. L . Perkins. Patent 3. Nature. L .104 ( 1975). 86 (1976). Eidus. Chu. H . N . S. C . W .. E. Jr. 2. J. 67. Ya. 32. G . Topchieva and A . C . Landolt. Chemtech. 75. New York. and R . Weisz. C. J. and P. U. 1. Chang and A . Stull. Sinke.S. F . 47. M . Ind. U. F. U. The Chemical Thermodynamics of Organic Compounds. Lawton. K h i m . Patent 2. G .979 (1973). 247 (1950). J. D.HYDROCARBONS FROM METHANOL 111 Downloaded By: [2007-2008-2009 Kyunghee University . V. H . H . Ballod. Howk. Lang.. Argauer and G .Suwon Campus] At: 10:27 12 February 2009 present. Chem. The solution to the C-C bond problem remains an open challenge at present. V. REFERENCES S. Chem.886 (1972). Fawcett and B. H . it is even conceivable that the C-C bond formation may involve a continuous spectrum of transition states.744. K . . Chart. J . C.S. Meatyard. Meier. 1969.. McCullough. Silvestri. Adkins and P. Gorin and%. Kokotailo. Chim. T. Wiley . E. Patent 3. A . . J . Snyder.. 272. T.456. Indeed. M . Chang. S. R . Kokotailo. 44(I). Ital.151 (1956). Meier. 437 (1978). V . Olson. Dokl. Patent 3.492. P. Silvestri. 2 2 1 (1928). Akad. T . A . H . a situation that is not too appealing to mechanist. Nauk E R .S. It seems certain that significant progress will b e made even a s this s u r vey goes to press. 65 (1943).709. 587 (1914). and G . P. D. Chu. Otd. U.S. Cullinane.984 (1950). S. Gazz. H . Greene.. J .

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