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CATAL . REV.-SCI. ENG., 25(1).

1-118 (1983)

Hydrocarbons from Methanol
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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

I . INTRODUCTION .................................... 2
I1 . GENERAL CONSIDERATIONS ....................... 2
A . Stoichiometric C o n s t r a i n t s ...................... 2
B . Thermochemistry ............................... 3
I11 . CATALYSTS ....................................... 4
A . E a r l y O b s e r v a t i o n s (pre-1960) .................. 4
B . Zeolite C a t a l y s t s ............................... 8
C . Nonzeolitic C a t a l y s t s ........................... 35
IV . REACTION KINETICS .............................. 36
V. REACTION MECHANISM ............................ 44
A . E t h e r Formation ................................ 44
B . Hydrocarbon Formation ......................... 48
VI . THE MOBIL METHANOL-TO-GASOLINE
(MTG) PROCESS ................................... 75
.
A Fixed-Bed Process ............................. 75
.
B Fluid-Bed P r o c e s s ............................. 84
........................
C . Product C h a r a c t e r i s t i c s 99
D . Olefin P r o d u c t i o n .............................. 100
VII . DUAL-FUNCTIONAL CATALYSIS ................... 103
VIII . POSTSCRIPT ...................................... 110
REFERENCES ...................................... 111

1

Copyright 0 1983 by Marcel Dekker. Inc . 0022-2348/83/250 1-0001%3.50/0

2 CHANG

I. INTRODUCTION

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
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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 con-
version 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 al-
ternative to classical synfuel processes such as the Fischer-
Tropsch 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 litera-
ture 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 for-
mates can also be written. However, with the possible exception
of methane formation, as discussed later, no clear-cut experimen-
tal examples of this reaction are known. For the present, there-
fore, 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 3

CHSOH * [CHZI + H2O ( 1)
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
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( n + l ) C H 3 0 H * CnH2n+2 + C + ( n + 1)HZO ( 2)

(2n + 1 ) C H 3 0 H + 2CnHzn+z iCO + 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 aro-
matic ring generated. The general equation for mononuclear aro-
matics 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/zeo-
lite 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 1-
olefin, and methylbenzenes formation at 316OC. The olefins curve,
which may also be considered representative of a balanced paraf-
fin-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 forma-
tion from methanol at 3 7 l o C , which is shown in Fig. 2 a s a func-
tion 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.

4 CHANG
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- 400
r PARAFFINS + C + H20

- 600 bl 2 4 6
CARBON NUMBER
8 10 12

FLG. 1. Hydrocarbon formation from methanol. Heats of re-
action for selected hydrocarbon products at 600 K .

111. CATALYSTS

A. Early Observations (pre- 1960)

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

HYDROCARBONS FROM METHANOL 5

lo3 I I 1 1 1 1 1 1 I I I l r l l l I I I I 1 1 1 1 1 1 I 1 I l l
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2
10

1 AT 100% CONVERSION: OHR -400 cal I g ( - I674 k J / kg 1

I I I I I I 1 I l l I 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-' 10' 3 10-2 10- I 1
LHSV-'

FIG. 2. Methanol conversion to hydrocarbons. Heat of reac-
tion 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
C

15 CH30H FUSED ZnC& '@
C
+ 3CH4+ I5yO

C

AG~"" = -265.2 kcal/rnol

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

6 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 propheti-
cally, in terms of V H , " condensing to benzene, followed by ex-
haustive ring methylation by a Friedel-Crafts reaction with CH,Cl
generated in situ.
In 1914 Sernagiotto [ 61 reported the decomposition of methanol
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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 prob-
ably be more accurately described as a reactant rather than a cat-
alyst 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 con-
.
version 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 acti-
vated 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 hydrocar-
bons 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 pres-
sure, 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.

0 C2H6 0. CoMoO. 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.1 Higher boiling products 30. Here the question arises a s to whether methanol is not simply a source of synthesis gas via dissociation. g .7 C. albeit in considerably lower yield.0 a 18%hexarnethylben zene based on MeOH converted. Oa Other - 7.0 1. e . modified with nickel chromite at 100-350°C at 70-1000 atm. HYDROCARBONS FROM METHANOL 7 TABLE 1 Conversion of Methanol to Hydrocarbons over Fused ZnC1.Suwon Campus] At: 10:27 12 February 2009 CH4 1. 166 atm) Mole percent MeOH converted to Downloaded By: [2007-2008-2009 Kyunghee University . [ 71 (425OC..4 100.6 1. and therefore whether the actual hydrocar- bon-forming reaction is a Fischer-Tropsch reaction. to 85OC (1.5 tom) 33.3 4. . .0 19.5 C4H8 0. Such is the case in an earlier study by Eidus [13] where methanol was reacted over a cobalt-thoria-kieselguhr catalyst under Fischer- Tropsch conditions and found to give the s a m e hydrocarbon products a s with CO + 2H2.4 1.

.2 i-C 26.4 i-Cs 11. This is balanced by (exchangeable) cations Mn+ in the structure.6 99. . 8 CHANG TABLE 2 Dimethyl Ether Conversion over Si02-A1. forming a three-dimensional framework. Zeolite Catalysts 1.. be elec- t rically neutral . leading to the general representation where n is the charge on the cation and z is the water of hydra- tion.03 [ 111 (37OoC. 151 and ZSM-11 [16. y / x ? 1. 5 < y /x 0 0 .H8 5. the synthetic zeolites ZSM-5 114.7 Downloaded By: [2007-2008-2009 Kyunghee University . of course. 171.Suwon Campus] At: 10:27 12 February 2009 C2H4 10. In general. e . 10 atm.2 C3H6 + C3H8 8.0 c7 3. 8 h-l QHSV) Products % CHI4 5.0 c 8+ 21. 6 . crystalline aluminosilicates composed of A104 and S O 4 tetrahedra. interconnected through shared oxy- gen atoms.1 n-C4H. Since every oxygen in such a structure (viewed a s an infinite lattice) is shared by two tetrahedra. the framework will possess a net negative charge. Introduction Zeolites are porous. g . the framework will. At ylx = w .6 Carbon 8. and in some exceptional cases. + C.8 B.

Suwon Campus] At: 10:27 12 February 2009 FIG.42 A. zeolites are unique in their ability to dis- criminate between reactant molecules and to control product se- lectivity. The . a. the zeolite becomes a strong Bronsted acid. A s catalysts. ZSM-5 and Related Zeolites The most extensive work on hydrocarbons from methanol has been done with ZSM-5 zeolite catalysts. Typical zeolite pore geometries. For comprehensive treatments of zeolite structure and chem- istry. 3. These are of molecular dimensions. Zeolite ZSM-5 [ 14. 15. 2. l o .. Structure of ZSM-5 and ZSM-11 The unique catalytic properties of ZSM. The catalytically most significant zeolites are those having pore openings characterized by 8-. depending on molecular size and shape. HYDROCARBONS FROM METHANOL 9 Erionite 8 Ring ZSM-5 10 Ring Y Zeolite 12 Ring (Stroight Channel1 Downloaded By: [2007-2008-2009 Kyunghee University . known as "shape-selective catalysis [ 18-22] . the reader is referred to the classic monographs of Breck 1231 and Rabo 1241.92.5 zeolites have been attributed to their crystal structure [ 1. and cages. This phenom- enon. b = 19. chan- nels. 1621. When M is a proton.07. Some typical pore geometries are shown in Fig. is a con- sequence of the well-defined geometry of zeolite pores. c = 13. There is little question that these are the most effective catalysts yet discovered for this reaction. and 12-rings of oxy- gen atoms. 3. 251 has orthorhombic symmetry Pnma with cell parameters a = 20.

. The framework is shown in Fig. Figure 5 shows a stereo-pair drawing of the ZSM-5 framework viewed along [ 0101. ZSM-Kchannel system. aromatics cycloparaffins +H20 C. 10 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . 6. 4. 3 5 A. 1 . 9. 1 X 5 . consists of intersecting straight channels.OCHS -C2'--C5'-. 8. 5 free dimension. with cell parameters a = 2 0 . shown in Fig. channel system. 251.General Reaction Path The conversion of methanol over ZSM-5 zeolites was investi- gated by Chang and Silvestri [ 21 who found the reaction to pro- ceed according to the following general reaction path: paraffins -H20 -H20 2CH3OH rCH. consists of straight chan- nels running parallel to 10101 and intersecting sinusoidal chan- nels parallel to [ 1001. c = 1 3 . 4 X 5. b. represented in F i g . Fig. 17. The channels are ellipsoidal with 10-ring openings. 4 1. 1 X 5 .Suwon Campus] At: 10:27 12 February 2009 FIG. confirming its intermediacy in the reaction sequence. shown in Fig. The channel structure. having the approximate free dimensions 5 . Closely related to ZSM-5 in structure and properties is ZSM-11 116. An essentially identical reaction path was obtained with DME as feed.6 w (straight channels) and 5 . 7. 4. with 5 .+ olefins Scheme A This was established by monitoring changes in product distribu- tion as a function of varying contact time. 4 1 (sinusoidal channels) based on oxygen radii of 1 . ZSM-11 has tetragonal symmetry I h 2 .

*P 1 viewed along (010J Secondary buildlng units: complex 5-1 Framework density: Channels: 1 7 . Pnma. .Si. HYDROCARBONS FROMMETHANOL 11 Downloaded By: [2007-2008-2009 Kyunghee University .~. a=20.Suwon Campus] At: 10:27 12 February 2009 ZSM-5 Pnma 8 T.6 .9 c = 1 3 . 9 T/1000 A3 { [OIO] 5. 4 x 5.1 b=19.O. 6 .Al.1 x 5. 4 A FIGURE 5 1251.16 H..t- Fault planes: (100) Type species: Mobil synthetic zeolite ZSM-5 Na.5r.. ZSM-11channel s y s t e m . .-.O with n c 27 and typically about 3 orthorhombic. [loo] - 10 5. FIG.

contains a direct path to olefins from methanol: 2CHjOH CH.O. Iam2. The modified scheme. 12 CHANG Downloaded By: [2007-2008-2009 Kyunghee University .16 H. 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. a=20.OCH.7 T/1000 A3 Channels: < 100. Scheme B .Al.1 x 5 . 5 * * * Fault planes: (100) Type species: Mobil synthetic zeolite ZSM-11 Na.4 A FIGURE 7 [25].O with n < 16 and typically about 3 tetragonal.. 5. + H2O \ J olefins Scheme B .Suwon Campus] At: 10:27 12 February 2009 viewed along [loo] Secondary building units: complex 5-1 Framework density: 17.Si. .1 c=13...

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

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

0 3. 36.0 A 11+ 0.0 12.3 0.2 25.2 11.0 c3 1.7 24.1 the higher aromatics.2.5 5. 5.8 13. become significant a s a result of secondary cracking.3 1.2 2.8 C 5 + aliphatic 2.0 8.3 c22.5-tetramethylbenzenes fall significantly short of their equilibrium values.*.4 1.1 0.5-trimethylbenzene.8 18.l ) is shown in Fig.7 4.2 14." a s was t h e sharp cut-off in product molecular weight.3. Below 3OOOC the main reaction is dehydration t o DME.3 5.1 1.3.5 1.2 26. 5. 9.5 4.7 0.2 9.4-. d.6 A.1 5.4 11.8 16.3 1. 1. and 1. This was attributed to zeolite "shape-selec- tivity. 1 LHSV) Hydrocarbon distribution (wt%) in Erionite ZSM-5 ZSM-11 ZSM-4 Mordenite Downloaded By: [2007-2008-2009 Kyunghee University .8 c.7 c.1 8.0 A10 3.9 A8 18. Above about 5OOOC t h e dissociation of methanol to H2 and CO becomes measurable.4 8. 1.5 c2 0.0 19.9 c. .6 0.0 . 1 atm.8 0.0 32.4 0.5 3.3 0.7 15.6 15.2.5 0.5 0.Suwon Campus] At: 10:27 12 February 2009 c.5 8. i0 121.4 4 7 10. With increasing temperature t h e sequence of Scheme A is followed. while above 45OOC light olefins and CHI.4 2.0 1. 39.2. Effect of Temperature The effect of temperature on ZSM-5 selectivity a t low w a c e velocity (LHSV = 0 . 6 .0 2.2 1. HYDROCARBONS FROM METHANOL 15 TABLE 3 [22] Methanol Conversion to Hydrocarbons over Various Zeolites (37OoC.2 6.8 0. 1.0 A3 7. 7 h .0 0.1 1.3.

0 22.5 [:3 123 0.7 m+P 4.9 Xylenes: 0 m P Trimethylbenzenes : 9.1 [ 0 0.4 a Diethylbenzenes + dimethylethylben zenes .Suwon Campus] At: 10:27 12 February 2009 Ben zene 4.8 10.0 [ [: I 33.1 2.2 Tetramethylbenzenes: 1234 1235 1245 0.1 Isopropylben zene 0.9 23. .1 Toluene 25.4 1. 16 CHANG TABLE 4 [2] Aromatics Distribution from Methanol Conversion over HZSM-5 Normalized Normalized Equilibrium distribution isomer distributions (wt %) distributions (371OC) Downloaded By: [2007-2008-2009 Kyunghee University .0 I::[ [":I 23.7 All+ 0.9 2.9 124 135 Ethyltoluenes : 11.6 Ethylben zene 1.4 Other Al0a 2.

10. HYDROCARBONS FROM METHANOL 17 I00 90 80 Downloaded By: [2007-2008-2009 Kyunghee University .6-0.04 and 50 atm. 11 and 1 2 for PMeOH = 0. 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 . 8 depicting the normal atmospheric reaction path. The sig- nificance of the shaded regions will b e discussed later.7 h-' LHSV. . e. Effect of temperature on methanol conversion over HZSM-5 (0.C 4 HYDROCARBONS 3 0 30 20 10 AROMATICS - 0 300 400 500 T E M P E R A T U R E 'C FIG. These plots may be compared with Fig. This is illustrated in Figs. while increasing pressure enhances the overlap of the two reactions. 1 atm) [ 2 ] .Suwon Campus] At: 10:27 12 February 2009 WATER I- 70 W V a W 60 c I '3 y 50 w 1 2 J 40 3 I C2 . aromatization steps [ 321 Decreasing pressure tends to decouple the two reactions.

.e. Its pref - erential formation is a consequence of zeolite shape-selectivity. v . 371OC) [321. durene possesses a critical di- ameter most compatible with the zeolite channel dimensions.-0. i. 11. durene is not the thermodynamically favored tetramethylbenzene isomer. f . Methanol reaction path at low pressure (HZSM-5 cat- alyst.O' 0 40- 2 30 . Clo equilibrium is attained. and is therefore more easily formed than the other Clo aromatics within the zeolite. it is the bulkiest isomer able to move with relative ease through the zeolite channel system. Thus at subatmospheric partial pressures. DIMETHYLETHER o / 5 3 0 0 g 20- . Among the tetramethylbenzenes . Modifications and Isotypes Kaeding and Butter [331 reported that ZSM-5 modified by treat- ment with phosphorus compounds showed high (70%) selectivity for .Suwon Campus] At: 10:27 12 February 2009 5 z .AROMATICS FIG. . The most striking effect of raising pressure above atmospheric is an increase in the degree of aromatic substitution. 18 CHANG '"I 60 .WATER 8 50- / Downloaded By: [2007-2008-2009 Kyunghee University . 10 - 0 . It is shown later that in large pore zeolites. especially in durene selectivity. A s shown in Table 4. . high selectivity to olefins is possible at complete conversion of methanol (Table 5).

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

2) (52.0 Propylene 4.4 21.0 20.7 1.17 0. 351. Representative data in Table 6 show that this catalyst be- haves similarly to ZSM-5.2 15.3 7.4 24.8 18.-C.0 39.7 Butenes 2.00 0. 8: 99+ 99+ 99+ 99+ Downloaded By: [2007-2008-2009 Kyunghee University .2 6.0 a Helium diluent at subatmospheric MeOH partial pressures.2 12.3 0.07 Conversion. 20 CHANG TABLE 5 Methanol Conversion at Low Pressures [ 1611 (427OC.2) (80. 1 atm total pressurea) Methanol partial pressure.4 (Total C.6) Methane 1.8 0.Suwon Campus] At: 10:27 12 February 2009 Hydrocarbon distribution.3 20. 371.2 26.4 0.3 Aromatics 41.6 18.9 2.3 2.6 C.6) (37.+ nonaromatic 3. wt %: Ethylene 3.OH Other than to reduce the activity of the ZSM-5 acid sites.7 2. CH30\ I P/OCH +CH . 3 6 .5 C2-C5paraffins 43.25 0. The conversion of ethanol over "Ultrasil" zeolite. has been described by Russian workers 128.6 0. . 1 LHSV. which is ZSM-8 [ 3 4 .5 0. the function of P-modification is unknown.5 38.5 Pent ene s 0. atm: 1.3 2. olefins) (10.4 17.

is hexagonal.03 2. 13-16.08 n-C. Other Zeolites a. HYDROCARBONS FROM METHANOL 21 TABLE 6 Methanol Conversion over "Ultrasil" Zeolite [ 361 Reaction conditions: Temperature.94 9. 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.69 4.39 31.88 14. the supercages is gained through 8-rings. The erionite structure. and between. which behaves similarly to ZSM. and higher 30.84 15.47 10.06 17.H.49 20.06 n-C4H10 1.He 3.97 21.33 1.48 1.74 8. 3.98 23.99 5.08 3.09 5.12 7. .29 2. containing "supercages" supported by columns of cancrinite units linked through double-6-rings (D6R). but deactivates quickly. torr 30 80 30 80 80 Downloaded By: [2007-2008-2009 Kyunghee University . 16.98 i-C 4H lo 22.62 3.80 Spencer and Whittam 1551 have described a high silica zeolite of unknown structure called Nu-1.5 in methanol conversion. 13.44 9.51 4.57 0..10 6.66 i-C. O C 300 300 450 4 50 4 50 Pressure.52 11. Fig.74 C2H4 + C2H6 4. Access to. Offretite is closely related to erionite except that the sequence of 6-rings is AABAAB [231 as compared to AABAAC in erionite. Structures of some of these small pore zeolites are illustrated in Figs..98 10.35 C3H6 5.81 37.54 10. min 60 60 60 3 60 Hydrocarbons.22 0.38 C.H.78 3.24 1.98 14.Suwon Campus] At: 10:27 12 February 2009 Time on stream. wt %: CH4 7.52 15.86 C4Hs 7.83 29.23 21.25 10.

1 A FIG. In the chabazite framework.O.6 T/l000 A3 Channels: -I [OOl] -8 3..). e. occur fre- quently..Suwon Campus] At: 10:27 12 February 2009 Secondary building units: single 6-rings in AABMC sequence (single 4-rings) Framework density: 15.Ca...Si. zeolite T . the D6R layer sequence is ABCABC. and the D6R units are linked together through tilted ..3 c=15. 27 H 2 0 hexagonal. Erionite.6 x 5.. a=13. P63/mmc. g. 14. Al. 13.2 *** Fault planes: (001) Type species: Erionite (Na2. Fig. 22 CHANG Downloaded By: [2007-2008-2009 Kyunghee University .. Intergrowths of erionite and offretite.

possibly triclinic) FIGURE 14 1251.Suwon Campus] At: 10:27 12 February 2009 CHABAZITE Rim 36 T[1] viewed along [OOl] hex Secondary building units: single 6-rings in AABBCC sequence (double 6.6 T/1000 A3 Cham els: - 1 [OOl] - 8 3. HYDROCARBONS FROM METHANOL 23 Downloaded By: [2007-2008-2009 Kyunghee University . These cavities a r e joined together via their 8-rings. a=13. forming a 3-dimensional channel sys- tem. 4-rings..Si. 16. Zeolite ZK-5. ..Al.2 c=15.6 x 3.1 A (True symmetry i s lower.. each entered through six 8-rings. a 40 HzO trigonal. consists of truncated cuboctahedra joined through D6R units in a body-centered structure.7**+ Fault planes: (0011 Type species: Chabazite Ca. 15). Rjm. The main channel system is defined by 8-rings.o r single 4-rings) Framework density: 14. The framework contains large ellipsoidal cavities (Fig. Fig.O.

based on drastic changes observed in the x-ray pattern. were mainly olefins. Cobb et al. The presence of signi- ficant amounts of methane in some experiments is symptomatic of coke laydown. (40. Both teams of investigators observed short-term catalyst deactivation due to coking. At 339-538OC the products. 431 studied methanol over the hydrogen form of zeolite T . range. observed long-term irrevers- ible deactivation. which was attributed to structural degradation. The conversion of methanol to light olefins over various cation- exchanged chabazites has been investigated by Cobb et al. Chabazite cavity. . Singh et al. 24 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . 1381. restricted largely to the C2-C. contended that their method of preparation led to an ffultrastableform of cha- .. Coking was rapid and was attributed to the forma- tion of nondesorbable cyclic hydrocarbons in the zeolite super- cages. Methanol conversion over a variety of small pore zeolites has been reported by Chang et 81. who saw no such deactivation in a three-month study comprising 21 regenerative cycles. but found the cat- alyst to be regenerable. 411. It was speculated that the discrepancy may have been due to differ- ences in ion-exchange procedures.Suwon Campus] At: 10:27 12 February 2009 FIG. [391 and Singh et al. This was disputed by Singh et al. Representative data are shown in Table 7. 15. bazite If Ceckiewicz [42.

6. 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. is ac- tive for converting methanol to C. ImJm. and gave the result shown in Table 8.or 8-rings) Framework density: 14.-C hydrocarbons at 30O-55O0C. Typical results are shown in Table 9.3% C2-C4olefins. * 98 H. Whittam and Spencer [45] report that "zeolite MCH.Si.7 T/1000 A3 Channels: < l o o > -8 3.6 vol%). and propene (22.Suwon Campus] At: 10:27 12 February 2009 ZK-5 lm3m 96 T[1] viewed along [loo] Secondary building units: double 6-rings (single 4-.2%). A methanol/water mixture (30 ~ 0 1 H %2 0 ) was reacted at 4OO0C. The product consists mainly of ethene (16.A1. .9***1 (100. S 3. HYDROCARBONS FROM METHANOL 25 Downloaded By: [2007-2008-2009 Kyunghee University . a=18.." which has an x-ray pattern similar to herschelite (isostructural with cha- bazite) but with line broadening due to small crystal size.7 A FIGURE 16 [25]..O cubic.4%).O..9*+* Fault planes: ---- Type species: synthetic zeolite ZK-5 Na3. The product was 66.propene (41.

5 3. 2 ) .5 a De-aluminized . Si02/A1.4 21.7 25.1 2. Faujasites contain extremely large supercages ( ~ 1 1 3 diameter) entered into through 12-rings. mordenite. [ 4 6 .3 3.3 31. propane ( 6 .4 0.+ ( 7 .7 4. 17. 26 CHANG TABLE 7 Methanol Conversion over Small Pore Zeolites [ 381 Erionitea Zeolite T Chabazite ZK-5 Reaction conditions: Temperature.8) b b Conversion. b.1 30. and mazzite (ZSM-4).Suwon Campus] At: 10:27 12 February 2009 Pressure. butane ( 4 .2 13. The faujasite structure.0 10. % 9.6 C4HB 9. 471 synthesized an erionite-offretite catalyst by rapid crystallization in the presence of tetramethylammonium hy- droxide. 7 1 . Methanol (128 in N1) was reacted over the calcined (54OOC) material at 4OO0C. 5 ) at complete conversion. are large pore zeolites which have been found to catalyze methanol conversion to hydrocarbons. 1 pL MeOH in He. h-’ 1 (3. bPulse microreactor. is built up of truncated octa- hedra interconnected via D6R units.4 0 CzH4 36.6 11. g . Fig.0 21. 6 ) . wt %: CH 4 5. .4 22.8 0 33.8 C3H6 39.1 100 100 Hydrocarbons. 500 h .7 10.0 c 5+ 2. 4 1 . atm 1 1 1 1 LHSV (WHSV) . butene ( 1 9 . OC 3 70 341-378 538 538 Downloaded By: [2007-2008-2009 Kyunghee University .2 CH2H6 0. 7 ) .5 C4H10 5.l GHSV.Large Pore Zeolites Faujasite-type zeolites. X and Y .03 = 16. Inui et al.4 C3Ha 1.6 3. methane ( 4 . propene ( 3 2 . e .3 45.0 7. 1000 h .l GHSV and gave (m18) ethane ( 2 5 ) . and C. .2 3.

is characterized by a one-dimensional sys- tem of parallel elliptical channels.2 H20 s2. 1 co 0. Fig. which may account for the high methane selectivity. They reacted methanol over REX and ZnX at 330-390°C. the only hydrocarbon they reported (426OC) was 1- butene. [49] studied methanol dehydration to dimethyl ether over various alkali metal-exchanged X and Y faujasites. shown in Fig. Mazzite (ZSM-4).5 H2 5.7 Mordenite. In- terestingly. Attempts have been made to decrease the coking tendency of faujasites by cation exchange with numerous metal cations having hydrogenation activity [ 50. Topchieva et al. HYDROCARBONS FROM METHANOL 27 TABLE 8 Methanol Conversion over Mn-Exchanged Chabazite-Erionite I441 (40O0C. also has a one-dimensional system of parallel channels defined by 12-rings. and reported the data shown in Table 10. defined by 12-rings. 90%conversion) Products Vol % Downloaded By: [2007-2008-2009 Kyunghee University . 19. 1 Aromatics <o. 511.0 Dimethyl ether 4. 18. Schwart z and Ciric [ 481 were the first to achieve significant methanol conversion to hydrocarbons over zeolite catalysts.Suwon Campus] At: 10:27 12 February 2009 C2H4 3H6 C4HB CH4 C2H6 C3H8 C4H10 C sf nonaromatic <o. These efforts have met with . Coke formation was rapid.

A series of zeolites containing varying concentrations of Na and K ions was prepared.5-240OC. Mordenite and ZSM-4 were investigated by Chang et al. The effect of increasing hydrogenation activity of the metal component was mainly to enhance methanol dissocia- tion [51].2 i-C4Hlo 0 n-C4H10 4.4. Olefins were detected a t 24OOC . 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.7 i-C4H8 2.0 2-C4H8 4. sum- marizes the reaction conditions and hydrocarbon distributions . Table 3. exchanged with various cations. deactivation was rapid. 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. 28 CHANG TABLE 9 Methanol Conversion over Zeolite H -MCH [ 451 (45OoC. The acid strengths were determined by pyridine adsorption-desorption at different temperatures.Suwon Campus] At: 10:27 12 February 2009 CH4 3.6 C2H6 0.2 C2H4 16. but to have a short life-time.9 l-C4H8 2. [ 221 for methanol conversion.9 little success. was found by Zatorski and Krzyzanowski [ 541 to be highly active for meth- anol conversion to C1-C hydrocarbons at 350-500°C. however.6 c 3H8 22. and that the active sites must be of sufficient strength to retain pyridine at temperatures at least as high as 450OC. a s shown previously. Natural mordenite.4 C3H6 41. pulse microreactor) Products Vol % ~~~ ~ Downloaded By: [2007-2008-2009 Kyunghee University . The catalytic dehydration of methanol by synthetic H-mor- denite was studied by Swabb and Gates [ 531 a t 99. [ 521.

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

* 24 H. Cmcm. pore ( < 8 8 ) ZSM-4 and mordenite. The normalized aromatics distribution is shown in Fig. These results are consistent with the critical dimensions of the methyl-substituted benzenes. 7* Type species: Mordenite Na. 5 A FLGURE 18 [ 2 5 ] .9 x 5. a=18. some of which are listed in Table 11. 30 CHANG Downloaded By: [2007-2008-2009 Kyunghee University . produce this compound along with other aromatics.. that crystallographic pore dimensions cannot generally be used to gauge precisely what . 5 c=7.1 b=20.O orthorhombic.O.Si. which can accommodate mole- cules as bulky a s hexamethylbenzene. however.Al. It should be pointed out.0* tj I0101 - 8 2. 20 and serves to highlight the influence of pore size.7 x 7.Suwon Campus] At: 10:27 12 February 2009 1 MORDENITE Cmcm viewed along Secondary building units: complex 5-1 n Framework density: 17.2 T/1000 A’ Channels: [OOlI 12 6.

[m] viewed along [OOl] Secondary building units: complex 5-1 (or single 4-rings) Framework density: 16.1 T/1000 A 3 Channels: [OOl] 12 7.2 28 H. though still not an absolute. 12 T.6 A FIGURE 19 [ 251.4* Fault planes: (100) Type species: Mazzite Mg. a=18.O hexagonal. K2)3Al. . It has been found that for certain sorbate mole- cules.[1] . the kinetic diameter from the Lennard-Jones potential pro- vides a more satisfactory.(Ca. Molecules larger than the calculated aperture size of zeolites are sometimes freely sorbed. HYDROCARBONS FROM METHANOL 31 Downloaded By: [2007-2008-2009 Kyunghee University . P63/mmc.Suwon Campus] At: 10:27 12 February 2009 MAZZITE PGJmmc 24 T. molecules will be sorbed and what molecules excluded.oSiz60.4 c=7. match with zeolite pore dimensions [ 231.

7 3.0 7. CLiquid product mainly unreacted CH.7 2. and (CH. 1. Comparison is here made be- tween 1.0 i-CsHlz 6. It will be recalled that durene . fractions among the intermediate and large pore zeolites.3 2.OH to gaseous products 51 30 Gaseous product composition ( m l %) :C H2 Trace 10.8 - 100. b9.3 CH4 22.5 17.0 C2H4 24.46 w t % Zn. samples analyzed at 2-3 h on stream.8 i-C4Hlo 13.2 C3Hs 4.2.8 9.0 C2H6 2.) *O.9 C3H6 10.4.9 4.5 LHSV.5-tetramethylbenzene(durene) distributions in the Al. This demonstrates that the large pore zeolites per- m i t the attainment of equilibrium.4 C4Hs 8.0 100.O. 32 CHANG TABLE 10 1481 Methanol Decomposition over Metal Cat ion -Exchanged Paujasitesa Downloaded By: [2007-2008-2009 Kyunghee University .0 a Continuous-flow.5 43. Table 12.OH .Suwon Campus] At: 10:27 12 February 2009 Temperature (OC) 330-380 360-390 % conversion of CH. The nonequilibrium distribution of tetramethylbenzenes from ZSM-5 has already been noted. 1 atm.2 Hexanes 4. H.0 Other - 2.

however. Thermodynamic calculations [ 1721 reveal. HYDROCARBONS FROM METHANOL 33 loo vo:L ZSM-5 - ISM I I 75 - Downloaded By: [2007-2008-2009 Kyunghee University . 25 FIG. 50 25 . Aromatics distribution from methanol conversion over various zeolites [ 221. that . 20.Suwon Campus] At: 10:27 12 February 2009 50 - 25 0 0 A6 A? A6 A7 A8 A9 AIO All 100 I S M-4 MORDENITE 75 75 YO 50 . We have shown earlier that there is a large driving force for methanol to form hexamethylbenzene in the presence of acid cat- alysts. is the bulkiest molecule that can diffuse readily through ZSM-5 and ZSM-11.

Shape.0 ZSM-4 1.1 34.. Kinetic diameter % 2 .9 7.7 6.1 ’ 6 r.11 1.7 37. 34 CHANG TABLE 11 Critical Diameters of Selected Polymethylbenzenes [ 221 6.h.2 84.6 50.4 .5 1.1 Downloaded By: [2007-2008-2009 Kyunghee University .1 ZSM.6 Mor denite 0.2 Equilibrium (37OOC) 33.Suwon Campus] At: 10:27 12 February 2009 6.1 a Equilibrium diameters (rmin) estimated from Courtauld models.Selectivity of Various Zeolites %1245TMB in %1245TMB in Catalyst hydrocarbon A10 ZSM .4 6. TABLE 12 [22] A.

have a high coke toler- ance. HYDROCARBONS FROM METHANOL 35 TABLE 13 [ 1651 Coke Formation and Deactivation in Dimethyl Ether Conversion.3 HY 8 9. a 36-39%yield of hydrocarbons was obtained .15-0.SO.93% Fe203. An inverse correla- tion is evident between deactivation rate and coke selectivity. on the other hand. and H-mordenite.3% Mg. 0 3h-’ WHSV. heating methanol in the presence of 86%H. C. with the balance dimethyl ether. 0. Shape-selective zeolites such as ZSM-5 prevent the com- pletion of this reaction as a consequence of steric hindrance. Pearson [58] reported that when methanol or trimethyl phos- phate was heated with phosphorus pentoxide [ 61 andlor polyphos- phoric acid at 190°C.8 200 polymethylbenzenes formation must be a kinetically controlled phe- nomenon.1-43% A120. conversion was 85% and only ethene was detected in the reactor effluent.15 6. The intermediate pore zeo- lites such as ZSM-5.Suwon Campus] At: 10:27 12 February 2009 HZSM-5 90 1. This has been confirmed by Cormerais et al. Rollmann and Walsh [ 1641 have presented evidence that carbon formation in zeolites is a shape-selective reaction con- trolled by pore geometry. Table 13 summarizes the results obtained by these workers on the conversion of dimethyl ether over H-erionitel chabazite. at 135-140°C gives 2 . The cat - alyst required air regeneration after 15-20 h .5 0. + T i 0 2 . 1-1. Nonzeolitic Catalysts According to Dolgov [ 561.6 90 H-mordenite 0. and a trace of CuO deposited on clay pellets and calcined at 700-750OC. A t 100-15O0C.5 atm.3 40 H -erionite lchabazite 0. Matyushenskii and Freidlin [ 571 converted dimethyl ether to ethene by decomposition over a catalyst composed of 39. H Y . Catalyst deactivation due to coke deposition is fairly rapid in small pore and large pore zeolites.4 % ethene.15 8. 35OOC Residual Coke lhydro- Catalyst activity (8) Wt%coke carbons X l o 3 Downloaded By: [2007-2008-2009 Kyunghee University .83-0. and ~ 0 . [ 1651. HZSM-5. 0.

. and con- tained a high percentage (49. olefins at 375-425OC).hydrocarbons were formed and about 56%(based on C feed) gas oil range (230-270OC) hydrocarbons were produced. ob- tained at 300°C. 36 CHANG with the average formula CH2. Very little aromatics were formed. The results of Cormerais et al.-C. [ 621 used supported aluminum dihydrogenphos- phate as catalyst to convert methanol into a predominantly olefinic product (20-608 yield of C. 2. Supported aluminum sulfate was found by Hargis and Kehoe [611 to catalyze methanol and dimethyl ether conversion to hy- drocarbons. K i m et al. Further. 163. IV. Apart from dimethyl ether. with little solid resi- due. Kikkawa et al. over a range CnH2n+z to CnHZn-10.12 X mol/h feedrate. substituted monoaromatics (maximal at C 1 2 ) .7%) of triptane. 671 that over a wide range of conversions the initial step of ether formation is much more rapid than the subsequent . Only small amounts of C. in view of the great complexity of the reaction. rigorous kinetic treat- ments may neither be practicable nor have much practical justi- fication. 66. The gasoline range ( C 5 - C15) fraction consisted mainly of branched paraffins. The kinetic scheme is simplified somewhat by the observation [30. Heavier fractions amounted to 2-3% based on C feed. and other compounds. Bell and Chang [ 591 found that coke formation during methanol/ dimethyl ether conversion to hydrocarbons in fused ZnC1. the large heat effects require special consid- eration. This has usually been neglected in the published ex- perimental work. (283OC) is suppressed by cofeeding hydrogen. and atmospheric pressure are shown in Table 14. [SO] converted methanol (>99%conversion) over bulk zinc iodide at 2OOOC to hydrocarbons. alkenes. [ 651 using silica-alumina cat- alyst will be discussed later in connection with reaction mechan- isms. The hydrocarbons were mostly in the C2-C5 range. the products contained alkanes. cyclo- alkanes. Global kinetic treatments are mainly found in the accessible literature. Typical data. Methyl chloride was s i m i - Downloaded By: [2007-2008-2009 Kyunghee University . However.Suwon Campus] At: 10:27 12 February 2009 larly converted to hydrocarbons in the fused salt. 641 to convert methanol. Heteropolyacids and salts of heteropolyacids have been used by On0 et al. REACTION KINETICS Relatively little has been published to date on the kinetics of hydrocarbon formation from methanol.

7 0 MeOMe 38.4 c5 12.7 7. Data from a pilot plant study of gasoline synthesis from meth- anol over ZSM-5 [SO] indicate that the rate of oxygenate dis- appearance is first-order in oxygenates.8 79.1 13. This work will be de- scribed in some detail later.5 3.4 a TP and TS indicate dodecatungstophosphate and dodecatung- stosilicate.2 26.9 9.3 C2H6 0.6 37.8 14.6 5.2 15.8 35.0 38.0 57.9 7.2 0.1 41.7 5.5 1.5 0.2 8 6 8.6 50.8 15. .6 7.0 1.1 61.9 4. %:b MeOH 1.1 Hydrocarbons 60. bCalculated on a carbon-number basis.0 9.7 8.7 5.9 Hydrocarbon distribution.9 0. olefin-forming step. Data illus- trating this fact appear in Fig.7 11.5 9.3 2.3 11.5 13.5 21. Thus the equilibrium oxy- genate mixture can be conveniently treated as a single kinetic species or "lump" [ 681 .0 10.3 c6 7.5 35.8 5.3 3.1 36.3 2.1 13.1 0 3. 21.9 c4 39.8 8.5 20. %:b CH4 3.3 39.3 8. HYDROCARBONS FROM METHANOL 37 TABLE 14 [63] Product Distribution of the Conversion of Methanol into Hydrocarbons Catalyst HTPa CuTP AgTP HTSa CUTS AgTS Downloaded By: [2007-2008-2009 Kyunghee University .3 8. and is essentially at equilibrium.3 C3H8 16.2 10.5 98.3 9.4 34. respectively.2 C2H4 11.2 9.Suwon Campus] At: 10:27 12 February 2009 Product distribution.

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

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

C = olefins.d.2 - 0 0 I I (a) Reactor: &in. catalyst : 1.d. and D = paraffins + aromatics. (c) Reactor : A-in.d. FIG. (b) Reactor: Q-in. 37OOC) 1691.8 . catalyst: 10% zeolite diluted with 7-alumina.).-o. The species B was assumed to have carbene-like character. 22. catalyst : 3% zeolite diluted with 50/50 copper powder and y-alumina.-0. 0 CATALYST (a) - A CATALYST (b) 0 CATALYST (c) VCATALYST (d) - Downloaded By: [2007-2008-2009 Kyunghee University .d. attacking both oxygenates and olefins.4% zeolite diluted with M/50 copper powder and y-alumina.-0. - - 0.o 1 kl lk2=. Autocatalysis in methanol conversion (HZSM-5cat- alyst. stainless steel . (d) Reactor: +in. Invoking the steady- .Suwon Campus] At: 10:27 12 February 2009 0. B = (:CH.-0. copper. copper . 40 CHAN G 1. copper. catalyst : 10% zeolite diluted with ?-alumina.02 k2-55 0. B+C k3 w C C A D where A = oxygenate.6 - 04.

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

Solid lines are theoretical [ 7 11 . and the intracrystalline Thiele modulus was less than unity for 0 . A t 115-2OO0Cthe kinetics of methanol conversion obeyed the rate law k l PH~ .OH r = 1 + k2P H2 0 with k . Hydrocarbon yield vs reaction time. no effect of crystal size on product distribu- tion was observed.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. 24. . = 6 X l o 5 exp (-80 y p )’ mol gesebar For dimethyl ether. 5 pm crystals. 42 CHANG Downloaded By: [2007-2008-2009 Kyunghee University .

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

+ b. initial C-C bond formation. The final stages. Several comprehensive surveys have been published [ 80. Ether Formation The mechanism of ether formation from alcohols over oxide cat- alysts. the literature on methanol dehydration is relatively sparse. sufficient differences may be found a s to warrant its dis- cussion here. have been well studied and proceed via classical carbenium mechanisms. however. = a. = Downloaded By: [2007-2008-2009 Kyunghee University .2 11 1 1 1 i l where moles of i produced for the j-th data point s. [ 791 on methanol and olefins conversion over ZSM-5 are pertinent. and H-transfer over acidic catalysts. + c x. Methanol etherification is similar in many respects to that of the higher alcohols.Suwon Campus] At: 10:27 12 February 2009 11 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.. V. The mechanism of the first two steps is discussed in this sec- tion. 44 CHANG accounts for catalyst deactivation and Sk is a selectivity function defined by S. These results are discussed in the following section. and Dejaifve et al. . In addition. since methanol lacks a parent olefin. REACTION MECHANISM The reaction path of acid-catalyzed hydrocarbon formation from methanol may be viewed essentially as composed of three key steps: ether formation. particularly Al2O3. The mechanism of polymethylbenzenes formation will.. papers by Galwey [781 on carbenium pathways in reactions of C2+ alcohols on montmorillonite. This topic will there- fore not be covered in detail here since it has been comprehensively treated in a number of excellent reviews [ 75-77]. In contrast. however. A. 81. comprising olefin condensation.has been extensively investigated. be discussed since these compounds are peculiar to the methanol transformation reaction. cyclization . The bulk of work has concentrated on alcohols having B-hydrogens. 841. and aromatization with ti-transfer.x.

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

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

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

Hydrocarbon Formation The mechanism of initial C-C bond formation from methanol is an unresolved question at present. Via Surface Alkoxyls Among contemporary investigators. A s of this writing. "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. and run the gamut from carbene to free radical schemes. 3. '%Thepositive value of the Taft reaction parameter for the for- mation of ether in contrast to negative values for the olefin formation on the same catalyst" [ 943 . B . 4. In summary. "Acetic acid and pyridine are poisons for the formation of ethers" [ 961. 2. 1. Arguments in support of this mechanism were summarized as follows: 1. second part of Statement 5 applies only to C2+ alcohols. The. Additional small amounts of dimethyl ether and s u r - face formate were also found after hydrolysis. to survey and discuss the diverse entries in this t'mech- anism sweepstakes. Hypothetical mechanisms abound in the literature. 48 CHANG Surface methoxyls could be hydrolyzed with water back to meth- anol at 25OC. 5. however. determined by IR spectroscopy" [ 1601. It seems appropriate. the first to consider this question were Topchieva and collaborators [ 91 in connection with . little supporting experimental evidence has appeared. 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 .Suwon Campus] At: 10:27 12 February 2009 by another molecule. the weight of evidence favors the intermediacy of surface alkoxyls in ether formation from alcohols. either from the gas phase or from a weakly adsorbed state. The speculation of the earliest workers [5. Beranek and Kraus [ 941 conclude that the mechanism involves essentially a nucleophilic substitution whereby the surface alkoxide is attacked Downloaded By: [2007-2008-2009 Kyunghee University . ttCorrelation between the rate of ether formation from ethanol and the surface concentration of ethoxide species. "The different degrees of water inhibition on the ether and olefin formation from ethanol on alumina. never- theless. 61 has already been acknowledged.

In a later study the thermal decomposition of methoxides of N a . CO..-Al..03 surfaces. CO. it was concluded that cleavage of the C .O.5 Major Major H. leaving a positively charged carbon moiety a s the reactive intermediate..1 Major Major C2H4 1.. Subsequently.5 Minor Minor (cH 3 ) 2 0 7.5 LHSV Downloaded By: [2007-2008-2009 Kyunghee University . It is seen that the main products are CH. SiO2-Al2O3.0. accompanied by dehydration and H-transfer. H. A free radical mechanism was rejected on the basis of negligible reactivity over nonacidic solids.0 bond is a heterolytic process. suggesting a cyclic transition state. 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.H.). quartz..3 Minor Minor C3H6 2.3 Minor Minor a study of the adsorption of methanol vapor on SiO. It was found that a portion of the methanol was irreversibly adsorbed on SiO. The mechanistic details of this condensation were not specified... with the flow of electrons in the direction of Al. Ethene was the only hydrocarbon prod- u ct ob served. Hydrocarbon formation was considered to occur by condensation of methoxy groups.. C.1 Major Major Other 0.H.03 at 45OoC.g.O.2 Major Major co 31. and A1. . A1203at 45OoC. Mg. at temperatures up to 45OOC. Based on the observation that Al(OCH. and CO.). and Al.5 LHSV 0.Q). (CH. e.] was reported by Pfeifer and Flora [981. as shown in Table 15..Suwon Campus] At: 10:27 12 February 2009 CH4 22. and A1 and the compound Na[Al(OMe). HYDROCARBONS FROM METHANOL 49 TABLE 15 Decomposition of Methyl Derivatives [ 951 C H 3 0 H over (CH3)zO over Al(OCH3)s at Al.. which upon heating and pumping to 4 O O O C evolved C. decomposed more readily than Al(OCH. and smaller amounts of C2H4 and C. Product 38 5OC (mol8) 0.H. The formation of surface methoxy groups was regarded as the pri- mary step. A negative activation entropy was observed. 35.

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

HYDROCARBONS FROMMETHANOL 51

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 reac-
tion 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
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event would be low, as demonstrated in studies on ketene photoly-
sis [ 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 hy-
dride abstraction from methanol, dimethyl ether, or hydrocar-
bons. The reaction

CH,+ + CH,OH + &H,OH + CH,,

is extremely rapid in the gas phase [102]. However, methane
normally accou t s for <l% of the hydrocarbons formed over ZSM-5.
2
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 electro-
static 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:

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 hydro-
1).
gens moves toward 0 ( e . g . , 0 - H , decreases from 2.04 to 1.79
Further, with increasing field strength H, becomes more nega-
tively charged while the methyl hydrogens become more positive.
A similar calculation was performed on a pair of colliding methanol
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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 silica-
alumina at 423 K . This compound could either be a key reaction
intermediate or simply a secondary product of the methanol-to-
ethene 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 un-
reactivity 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 re-
sults 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-nor-
ma1 ratio of product butanes [ 21 is significantly lowered. This is
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 thermo-
dynamic equilibrium i/n is 0 . 7 5 at the reaction conditions. However,
under the same conditions propane and isobutane were virtually in-
ert 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

HYDROCARBONS FROM METHANOL 53

Me8O
, MeOEt C2H4 MeOPr C,H, MeOBu C4H,...
4 1 4 1 A I
PHASE

PHASE
..It - It It - It I t It
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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 %P CH ,OH /He C H ,OH / C ,H8

CH, 0.86 0.90
C2O 0.93 0.90
cz2- 2.35 2.36
(C,O) -c -d
C,2- 3.63 4.53
i-Cbo 35.17 23.14
n-C,O 9.20 20.24
C,2- 1.88 2.34
C5+ aliphatic 21.32 20.98
Aromatics 24.66 24.62
100.00 100.00
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%.

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

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

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

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

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

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

2 Aromatics 34. MeEt benzenes. bEt benzene.6 12.1 c2 0. Figure 28 is an energy diagram comparing Routes A and B. is favored.Suwon Campus] At: 10:27 12 February 2009 Hydrocarbon distribution (wt 8) : C1 1.9 Wt%ethylbenzenesb in aromatics 0. 260 kJJmo1. in view of the behavior of the N-analogue [ 1141.6 4. LHSV = 1 .0 Wt%durene in aromatics 58. 2 h .8 1.assuming that the rearrangement proceeds through the 0-protonated oxirane : This is comparable to the expected energy barrier of Step A 2 .1 a T = 370 k l0C . According to van den Berg [ 741. P = 50 atrn.2 0.. kinetics of dimethyl ether reaction over HZSM-5 is zero-order at 227-300OC.8 6. and diEt ben- zenes. Chang and . diMeEt benzenes.4 17.0 7.8 40. involving the trimethyloxonium ion.8 33.l . It was concluded that Route A. Step A 3 is highly exothermic and. 60 CHANG TABLE 17 [32] The Conversion of Methanol and Ethanol to Hydrocarbons over ZSM-5 Class Zeolitesa Methanol Ethanol Percent age conversion 99+ 99 Downloaded By: [2007-2008-2009 Kyunghee University .8 0. is expected to have a low activation energy.3 C 5+ nonaromatic 44.

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

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

[ 1681 : Methanol conversion over phosphorus-modified ZSM.Suwon Campus] At: 10:27 12 February 2009 F I G . f Zeol . WHSV = 0. Methylene generated from diazomethane b y cuprous halide -catalyzed decomposition was similarly ineffectual [ 1091.5 was stud- ied by Kaeding and Butter [33]. 7 kPa.72 h-'. when the substrate contains an electron-with- drawing group. = 5 0 . However. + HZeol S CH3-0. P. N o insertion into alkyl ether is observed when the rnethylene is generated by mercury photosensitization. 29. who proposed the following mech- anism based also on oxonium intermediates : H @/ 8 CH.OCH. HYDROCARBONS FROM METHANOL 63 Downloaded By: [2007-2008-2009 Kyunghee University . 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. Arrhenius plot of the dimethyl ether conversion on zeolite HZSM-5 [74]. by ketene photolysis. a s in the fol- lowing reaction reported by Meerwein et al. reaction with diazomethane occurs.

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

’ 0 0 0 \ \ /O \ /O\ /O 0’ A1 \o 0 ’ Si ‘ 0 0 ’ A1 ‘00’ Si ‘ 0 . and in the following substitution reaction : R3C-H + CH3+ [R3C-+:l H 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.Suwon Campus] At: 10:27 12 February 2009 The transition state is believed to be a pentacoordinate carbonium ion. + + CH30R + \l>-cH30R] + CH. which are Bronsted acids. Based on their observation that methanol converts to hydro- r carbons over heteropolyacids and Nafion-H (perfluorinated sul- fonic acid resin). typified by the CH 5+ methanonium ion shown above.OR + H+ CH: Generation of the methyl cation was considered to occur by po- larization of surface methoxyl species: YH 3 CH. On0 and Mori [ 711 concluded that the mechanism involves methyl cations: + CH. HYDROCARBONS FROM METHANOL 65 Downloaded By: [2007-2008-2009 Kyunghee University .

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

carbenoid. 6. The "rake mechanism" of Ahn et al.Suwon Campus] At: 10:27 12 February 2009 Anderson et al. + reactive Cn -+ reactive Cn+.) was proposed. o r oxyme hylene species. who proposed a free radical mechanism: CH. a active C. The results of Matsushima and White [90] on deuterium exchange between CH30H and CD30D over alumina have already been mentioned. 5. and that therefore the reactive interme- diates a r e not carbene. which participates in a chain propagation mech- anism active C . moreover.)R H (R = H or CH. It will be recalled that these authors found little D-exchange below 237OC but complete scrambling at higher temperature (T 2 397OC). there is no exchange involving methyl hydrogens. 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. [128] and Cormerais et al. entity of the type (CH. [67].1 was investigated by Spencer and Whittam [ 551.OH -+ 6H. where Cn is an olefin. Thus their bearing on the mechanistic question may be somewhat tenuous.-C hydrocarbons over nat- ural mordenite was reported b y Zatorski and Krzyzanowski [ 541. However.+ nor oxonium ions were considered to be plausible. Chain Mechanisms Downloaded By: [2007-2008-2009 Kyunghee University . 2 6 ) . How- ever. From this it was inferred that in the methanol-to-hydrocarbon reaction. using deuterium labeling. found that in the methylation of benzene with methanol over HZSM-5 a t 207OC. a s has been noted [ 1231. the initial step does not involve lability of the C-H bond prior to C -C bond formation. species becomes somewhat of a moot question. In- b stead. + OH . They con- cluded that strong acidity is needed for t h e fast initial step and that cationic intermediates are involved. the precise nature of the C. In such a scheme. Other Schemes The conversion of methanol to C . This is a highly attractive scheme in that it is consistent with the observed autocatalysis of the r e - action [ 6 9 ] . [ 6 5 ] has already been mentioned (Fig. neither CH . HYDROCARBONS FROM METHANOL 67 The conversion of methanol over the alkylammonium zeolite Nu.

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

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

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

HYDROCARBONS FROM METHANOL 71 A [methanol 1 cycli zat ion cycloparaf fins ads ads ’ aromatics ads Downloaded By: [2007-2008-2009 Kyunghee University . Upon heat- ing to 97-197O. 25- 4OO0C. saturated hydro- carbons predominated. (c) crystal structure and pore geometry. olefinsg carbonaceous propyleneg and paraffinsg deposit ads In this scheme.-C. With HNaY . Also in the case of HZSM-5. IR. methyl-sub- stituted aromatics were evolved. competitive sorption between water and ethene was . and 13C-NMR. the presence of water altered the ratio of saturated to unsat- urated hydrocarbons in favor of saturates. [ 1321 studied the sorption activation of ethene by HZSM-5 using TGA. water vapor facilitated the desorption of products. ~3 t o r r ) .Suwon Campus] At: 10:27 12 February 2009 B cracking 4 C. Bolis et al. The different b e - havior of HZSM-5 was attributed to the following possible fac- tors: (a) different electrostatic field. at 197. and at 327-427O. with HZSM-5. C3-C7aliphatic hydrocarbons were evolved. alicyclic hydrocarbons. how- ever. [1311 who investigated the sorption reaction of ethene on HZSM-5 and HNaY zeolites by IR and MS. while HZSM-5 gave mainly unsaturates. Depending on zeolite pretreatment conditions. and Region B dynamic conditions (flowing He. ( b ) high Si:A1 ratio. especially aromatics. 0 Contrasting results were reported b y Novakova et al. They found that ethene is protonated (rate-determining step) on the Bronsted acid sites even near room temperature.2 9 7 O . Oligomerization was observed on both catalysts a t temperatures a s low a s 37OC. ~ 3 tom) . Water vapor did not affect the ethene reaction with NaHY. Region A represents static conditions (400°C.

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

31. + 59 psig - $ V 0. The overlap region is seen to increase with pressure. that the alkylation mechanism was kinetically feasible was shown in a study 11151 comparing plug-flow and backmixed reactor per- formance for methanol conversion over HZSM-5. wherein ring methylation by unconverted methanol /DME was assumed to occur [ 321. - 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). - 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 . First. HYDROCARBONS FROM METHANOL 73 700 OF 0.4- 0 . Evidence in support of this mechanism was twofold.Suwon Campus] At: 10:27 12 February 2009 u - I [ r - 353 psig 169 psig 0 !- I . ring methylation increased as illustrated in Fig. With 708 back- mixing. it was shown [32] that when ethanol was reacted under pressure. This is the anticipated result of the influence of back- mixing on the selectivity of a multistep sequential reaction. - . 8 and 12. Subsequent experiments indicated that the increase in poly- methylbenzenes with pressure is correlatable with the degree of overlap of the methanol/DME reaction curve and the aromatiza- tion curve in the reaction path. The shaded por- tion in these plots denotes this region of overlap. 0 - 0 n w 0 psig - .3. . which indicates a shift in distribution toward the higher aro- matics.5.61 I I I I I I ~ I I I I 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 - 2a 0. Second. 0 - 0. Figs.

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

where a near equilibrium MeOH /DME /H20 mixture was produced. Light gases were recycled to the second-stage reac- tor to control the temperature rise.5. A fixed-bed process with light gas recycle and the fluid-bed routes were selected for the initial process development studies.1401.000 barrels of gasoline per day. The heat of reaction varies with product distribution. Control and dissipation of this large reaction heat is a major constraint in reactor design. Initial operating conditions for a bench-scale version of the dual reactor system are shown in Table 18 [66]. 208of the total reaction heat is released in the first -stage and the balance in the second. THE MOBIL METHANOL-TO-GASOLINE (MTG) PROCESS The conversion of methanol to aromatic hydrocarbons over ZSM-5 zeolites is the basis of Mobil's MTG (methanol-to-gaso- . A s noted previously. Results of a 167-h test a r e shown in Tables 19 and 20. C 7 .-C.C 2 olefins . Depending on the recycle ratio. was a two-stage system consisting of a dehydration reactor. 32. hydrocarbon formation f r o m methanol is a highly exothermic process. 66. 1361. The feed was methanol containing 17%water to simulate crude product from a methanol plant. In this scheme. Fixed-Bed Process The fixed-bed unit [30. The plant will produce 13. have been extensively investigated in bench- Downloaded By: [2007-2008-2009 Kyunghee University . staged fixed-bed reactors 1135. line) process [ l ] Two versions of this process. and fluid-bed r e - actors [ 137. the fixed-bed and fluid-bed. A. 1411. C. including tubular heat exchanger reactors 11343. a AT < 95OC could be maintained in the second stage. followed by the hydrocarbon-forming reactor containing H ZSM. paraffins decrease. it may be noted that the Mobil team considered a variety of configurations. Al- though discussion of reactor design is outside the scope of this survey. which translates to an adiabatic tempera- t u r e rise of about 650OC [ 661. A s the cycle progresses. 1451.Suwon Campus] At: 10:27 12 February 2009 scale and pilot -plant studies. 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 . The fluid-bed process is scheduled for demonstration a s a lOO-bbl/d unit in West G e r - many 1133. shown in Fig. At 4OOOC it is 1510-1740 k J / k g of methanol converted. HYDROCARBONS FROM METHANOL 75 VI. The second-stage product was cooled and flashed in a high-pressure separator.

0 h .5-5. outlet Q454OC Pressure. 1 atrn Space velocity 1. inlet 343oc Temperature. Mobil methanol-to-gasoline process [661. outlet Q399OC Pressure. TABLE 18 Operating Conditions for Dual Reactor Fixed-Bed Process 1661 First Reactor Temperature.l .l . inlet 1 3 . WHSV Second Reactor Temperature. 76 CHANG ~~ Fixed Bed H20'-h Crude Methanol "'' --- Dehydration Reactor Compressor Gas Product + 334% Downloaded By: [2007-2008-2009 Kyunghee University . 6 .8OC .6-23.8 atm Space velocity 20 h .2 3 . WHSV Molar recycle ratio 3-4 (based on total fresh feed) SeDarator Temperature 37. inlet 13.Suwon Campus] At: 10:27 12 February 2009 HydrOca rbon Recycle Liquid Conversion Gas Product Reactor I Water 408'C FIG. inlet 316OC Temperature. 32.

726 Molecular weight 94.00 .3 100.04 CO2 0.0 100. psig 26 5 26 5 265 26 5 265 Product.4 94.8 93.22 Gasoline (including alkylate) : Reid vapor pressure. and Gasoline Propertiesa Time on stream ( h ) 8 47 95 142 167 Downloaded By: [2007-2008-2009 Kyunghee University .738 0.00 -0.3 94.4 3.2 93. 0.11 34. 648 648 663 665 660 perature.6 Pressure.08 0.3 3.08 0. 96. Run Conditions. OF Reactor 2 inlet tem.44 H2 0 63.00 100.02 0.746 0.0 9.69 99.00 0.65 36.00 Product. 77 1 768 769 768 735 perature.2 95.2 100.0 9.00 100.09 0.04 0. 626 625 624 625 625 perature.72 100.2 leaded Research octane. wt% of total product : Hydrochrbons 36.27 Dimethyl ether 0.00 0.76 100.28 35. 3 g 101.75 37.736 0. .3 3.Suwon Campus] At: 10:27 12 February 2009 Run conditions: Reactor 1 inlet tern. OF Reactor 2 outlet tem. Material Balance.00 100. process development unit.8 3.0 94.54 64.3 100. HYDROCARBONS FROM METHANOL 77 TABLE 19 [66] A Fixed Bed Aging Study.05 Methanol 0.05 0. wt % of feed 99. un.00 0.6 94.O) .00 0.00 0..3 lead Specific gravity 0.00 -0.3 94.09 0.45 101. 9.20 co 0.729 0.09 0.00 100. OF Reactor 1 outlet tem.00 100.0 9.3 3.18 63.3 catalyst Molar recycle ratio 3.0 9.6 3.13 62.8 a Feed crude methanol ( 17 wt%H.82 65. 862 8 57 888 891 8 19 perature.3 3.0 p sia Research octane. unit . OF WHSV (MeOH over 3.6 3.

0 Propane 11.Suwon Campus] At: 10:27 12 February 2009 Methane. The total test consisted of nine cycles.0 - 31.2.2 3. ethylene 2.4 100.9 82.6 4.5 8. 32. shown in Tables 22 and 23. A total of 208 d on stream was achieved. varying in length from 1 3 .9 n -Butane 5.0 c 5+ 68.3 4.3 .4 4.2 9 RVP gasoline including 75.1 - 28.2-96. Basis : Weight Percent Time on stream ( h ) 8 47 95 142 167 Downloaded By: [2007-2008-2009 Kyunghee University .1 73.7 74. so that the total of R V P gasoline selectivity was 75.1 1.6 C 3 .7 3. and aromatics remain fairly constant. For the final gasoline product.5 + increase.4 2. 78 C HAN G TABLE 20 [66] A Fixed Bed Aging Study.4 48.0 100.2 9. .8 88. with oxidative regenerations between cycles to re- move accumulated coke on catalyst.0 7. ethane.8 Aromatic s 33.C I .0 100.9 2. 1 d (first cycle) to 24.2 4.4 wt%.C 4 Olefins 2.7 7. C nonaromatic hydrocarbons increase significantly.6 5. during which 8000 lb meth- anol/lb catalyst was processed.6 and the recycle ratio increased from 3 . alkylate could be produced from the isobutane and C . are similar to the data in the preceding tables.5 2.0 42.9 2.2 88.1 78.2 4.1 42. Typical data.6 I sobu t ane 10.9-88.7 C 5+ Nonaromatics 35.7 - . . 4 . 8 to 9.9 81.9 d (Table 21).5 77. olefins.0 100.0 3.5 4.0 100. This product had an un- leaded research octane of 94.2 4.5 9. Hydrocarbon Product Distribution.0 2.4 alkylate Durene 2.3 50.5 2.8 - 27.7 8. 3 to 1. In a subsequent test [ 1421 the space velocity was lowered from 3 .

8 708 18.9 795 20.8 212. 2 Time ( d ) lb of cat 2.5 4011 103. .55 8 9 18 23.1 595 15. 2 Time (d) 212-48 1 50 1 13.2 8006 207.9 1105 28.1 212.9 1048 27. lb of MeOH/ lb of MeOHl lb of MeOHI Run no.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 Cumulative time on stream MeOH proc.0 808 21.5 212-50 3 643 16.56 9 920 24.1 895 23. MeOH proc.9 1046 27.8 2495 64.5 212-49 2 982 24.53 6 96 3 24. MeOH proc.3 212-51 4 695 18.3 5952 154.3 7000 181..5 595 15.6 a Methanol breakthrough taken as first material balance during which MeOH was detected in product water phase.8 212-54 7 810 21..4 212.0 3303 85. Time (d) Ib of cat..0 5057 130. Cycle lb of cat.0 1700 43.2 1006 26. Downloaded By: [2007-2008-2009 Kyunghee University .3 212-52 5 607 15.

. Downloaded By: [2007-2008-2009 Kyunghee University . psig 300 300 300 245 283 250 .. MeOH over conv.6 1. Dehydration reactor inlet temp.9 9.7 8.6 1. OF 779 776 773 771 771 774 Conversion reactor inlet temp. OF 648 652 649 652 650 651 Conversion reactor outlet temp.6 1.2 8.3 Pressure.. mol/mol of charge 9.8 9.2 8.6 1.6 Recycle ratio. OF 774 777 766 774 778 779 High pressure separator temp. 1.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 T h e on stream in cycle h 73 314 94 333 77 315 Cumulative charge. cat. OF 601 604 583 586 576 58 7 Dehydration reactor outlet temp..6 1. w t of MeOH/ 117 501 4162 4545 7123 7504 w t conv. cat.. OF 128 129 125 135 126 124 WHSV.

0 0.0 64.0 CO.07 Methanol 0. wt 0 of charge : Hydrocarbons 35.0 0.6 100.0 0.734 0. 0.3 a Gasoline includes alkylate .731 0.Suwon Campus] At: 10:27 12 February 2009 Products. properties are calculated from compositions. w t % of hydrocarbons 73.01 0.0 0.0 0.2 82.01 0. wt 90 98.6 92.0 Dimethyl ether 0.08 0.9 99.0 0.7 63.1 93.0 0.736 0.2 99.1 64.9 HZO 64.04 0.2 93.05 0.03 0.0 0.4 93.3 86.756 0.3 93.2 93.1 Specific gravity 0.2 63.01 0.01 0.8 64.4 97.5 35.9 35.01 0.4 99.728 0.8 98.2 0.0 0.9 99. Downloaded By: [2007-2008-2009 Kyunghee University .2 98.0 co 0.8 99.3 0.2 35.5 89.0 0.723 Molecular weight 95 95 95 95 94 94 Yield.0 0.0 0.0 Leaded octane ( R + 3) 100.3 36.4 0.0 85.3 99.0 Material balance.0 HZ 0.2 36.0 0. .0 9 RVP gaso1ine:a Research octane (R + 0) 95.

0 n -Pentane 2.6 3.6 20.2 1.3 0.3 2.0 1.1 1.7 2.9 8.0 0.4 10.3 6. Downloaded By: [2007-2008-2009 Kyunghee University .8 2.2 0.3 Isobutane 8. h 73 3 14 94 333 77 3 16 Cumulative charge.0 3.6 Pentenes 0.0 17.6 4.3 Ethene 0.3 11.4 Total C k 30.2 0.7 1.6 1.2 0.7 2.7 1.1 1.0 0.5 8.2 0.0 5.4 0.2 Isopentane 10.2 22. wt of MeOH/wt of conv.5 1. 117 50 1 4162 4545 7123 7504 Hydrocarbon composition.9 2. cat.1 0.2 0.4 0.6 0.0 19.9 0.1 11.9 .4 8. wt %: Methane 2.3 13.5 9.3 3.2 1.0 Prop m e 11.1 11.8 0.4 1.1 1.9 2.2 10.Suwon Campus] At: 10:27 12 February 2009 03 N TABLE 23 11421 Hydrocarbon Product Distribution in Long-Term Aging Test Cycle 1 Cycle 6 Cycle 9 Time on stream in cycle.1 2.7 0.0 Butenes 0.3 1.0 0.8 Ethane 1.0 0.0 0.6 6.3 n -Butane 5.6 3.9 0.9 Propene 0.

1 0.0 83.1 0.2 0.8 Ethylbenzene 0.1 0.2.9 0.6 0.9 1.3 6.5 29.5 1. 3 .4 0.2 0.and m .0 0.2 0.8 2.0 0.9 1.2 3.8 Cll A l k y l b e n z e n e s 0.8 2.6 p.3 7.5 31.2 Toluene 4.0 38.3 1.2 0.7 2.3 41.2 3.3 0.9 1.Suwon Campus] At: 10:27 12 February 2009 C yclopentane 0.0 0.0 28.2 0.8 0. Downloaded By: [2007-2008-2009 Kyunghee University .2 6.4.8 2.1 7.2 0.7 .7 7.2 1 .6 4.0 1.4 1.0 0.1 0.1 0.7 1. 5 .5 0.4 7.0 1.2 0.1 0.7 Naphthalenes 0.X y l e n e s 9.1 1.8 0.3 0.1 0.7 2.1 27.3 0.5 Methylethylben zenes 2.2 o -Xylene 2.6 3.2 0.5 6.4 80.8 2.+ 70.5-Tetramethylbenzene 3.3 0.4-Tetramethylbenzene 0.6 Propylben zenes 0.7 Total C.0 Total aromatics 36. 2 .1 0.1 Benzene 0.5 43.0 1.2 0.7 86.2 7.2.4 0.5 2.2 0.2 4.1 Unknowns 0.3 8.6 0.1 0.1 0.8 77.4 7.6 35.1 0.4 0.3 C6+ Nonaromatic 20.0 80.4 0.7 0.8 2.4 0.4 26.2 0.6 0.3.7 0.3 2.i 31.6 0.1 O t h e r C l o benzenes 1.T e t r a m e t hylben zene 1. 7 Trimethylbenzenes 8.6 1.1 1.

36 [ 1441. The reactor temperature profiles in Fig. The corresponding change in product distribution through a cycle is plotted in Fig. 34 (fifth cycle).8 0.0- 0.9 1 Fractional Bed Length FIG.2 0 0.2 0. due to progressive coking. B .Suwon Campus] At: 10:27 12 February 2009 0. A characteristic of this type of operation is catalyst band-aging.7 0. The fixed-bed process was subsequently scaled up to a 4 bblld pilot plant [ 1431. 33. Fluid-Bed Process Development of the fluid-bed process followed a course similar to the fixed-bed.6 0.8 - Downloaded By: [2007-2008-2009 Kyunghee University . The end of cycle occurs when the reaction front arrives at the reactor out- let. . 84 CHANG 1.3 0.1 0. 35 indicate identical aging patterns in the bench and pilot-plant tests.6 0. Band aging of methanol-to-gasoline catalyst in the first cycle of the long-term aging test [ 1421. exemplified in Fig.5 0.4 0. Initial studies were carried out in the bench- scale reactor illustrated in Fig. Data summarized in Tables 24 and 25 indicate that the bench-scale results were duplicated on the larger scale. 33.

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

6 8.1 i-Butane 8.73 Downloaded By: [2007-2008-2009 Kyunghee University .50-3.Suwon Campus] At: 10:27 12 February 2009 Water 56.00 Hydrocarbon product.2 R + O 95 95 Process conditions scoped were: 316-482OC.06 0.00 0.9 .l . Typical data a t 371°C.00 100.0-4. The changes in selectivity through a cycle a r e directionally similar to the fixed-bed. however.4 atm.75 43.00 0.03 0.02 Propane 8.00 Dimethylet her 0.8 75. 1.17 C o t CO2.1 2. wt8: Methane + ethane 2. 0.0 9 RVP gasoline Yield. 2 80. 86 CHANG TABLE 25 [143] MTG Scale-Up : Yield Comparison (average of first cycle) Product.1 Ethylene 0. 0. WHSV. w t % of HC 80.7 C 5+ Gasoline 75.0 100.10 Methanol 0. H. w t % MeOH 4 b b l l d unit Bench unit Hydrocarbons 43. - 100. In practice.00 100.19 56.4 8.5 h . 1 atm.2 n-B utane 4:2 4.5 But ene s 0. 1 WHSV a r e shown in Tables 26 and 27 and plotted in Figs.2 0. 37-40.5 Propylene 0.7 0. a fraction of .

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

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

30 64. 26-01 25-04 25-07 25-10 MeOH charged (Ib of MeOH/ 6 71 13 5 203 lb of cat.17 0. HYDROCARBONS FROM METHANOL 89 TABLE 26 f1441 Typical Material Balances in Fluid-Bed Pilot Planta Material balance no. - 0. CO.84 1. 0.54 55.21 7.07 0.64 6.21 .08 C O . 0.80 43. DME.24 c 5+ 63.15 .28 0.) Downloaded By: [2007-2008-2009 Kyunghee University .11 64.93 0.27 where PA^ = sum of the partial pressures of methanol.40 42.26 6.47 0..22 5.8 100. and H.37 Propene 5.64 5.54 Propane 3.23 - 99.92 But enes 4.71 13.17 0.O at a set of arbitrary reference conditions (1 atm.77 Ethane 0.81 0.Suwon Campus] At: 10:27 12 February 2009 Product (wt%of charge) : Methanol 0.90 0.08 2.98 7. while PA and p = ex- perimental values.20 Water 56.14 Ethylene 4. Figure 43 shows a plot of effluent methanol concentration vs .43 Hydrocarbons 42. po = gas density at reference conditions.83 2. 4OOOC) .84 5.65 3.32 0.41 5.30 10.25 1.78 n -Butane 1.20 42. H.81 55.77 55.62 63.14 12.8 Hydrocarbons (wt % of hydrocarbons) : Methane 0.02 0.15 0.82 Dimethyl ether 0.7 99.64 6.13 1.25 0.97 I sobut ane 15.2 99.48 1.

05 6.36 11.16 0.23 0.00 0.3.45 Other C .30 1.10 0.74 1.05 0.43 0.31 3.17 X ylenes 6.64 2.Suwon Campus] At: 10:27 12 February 2009 lb of cat.87 4.58 n .56 0.67 1.38 4.2.40 Dimethylbutanes 0.04 6.4.-PON 3.71 0.43 0.93 lI2.80 1.33 Naphthalenes 1.39 8.01 Other aromatics 2.43 0..50 0.11 0.5-Tetramethylbenzene 1.03 5.45 11.14 0.03 E t hylben zene 0.36 1. concentrations are w t % of total hydro- carbons..02 1.52 1.30 7.20 Methylethylben zenes 1.30 7.3.2.19 2. 0 psig.91 C.00 Toluene 1.34 1.44 0. .46 3. 14 5.33 Pentenes 2.02 5.43 2.25 C . 1 WHSV.31 Propylben zenes 0.15 2.02 0.29 Ce-PON 2.03 0.42 Met hylpentanes 5..) Isopentane 12.27 Benzene 0.-Benzenes 1.94 3.12 Cyclopentane 0.89 3.60 3.58 0.23 0.02 0.06 5.02 0.Hexane 4.07 n-Pentane 0.62 3.26 0.80 5.47 Cyclohexane 0.00 0.17 1.-benzenes 1. 26-01 25-04 25-07 25-10 MeOH charged (Ib of MeOH/ 6 71 13 5 203 Downloaded By: [2007-2008-2009 Kyunghee University .17 0.07 C .38 2.03 1.87 3.63 0.50 Trimet hylbenzenes 8.71 1.49 0.48 0. 90 CHANG TABLE 27 [144] Composition of Hydrocarbon Products from Fluid-Bed Pilot Planta Material balance no.99 1.72 0.38 2.46 6.43 0.41 0.67 0.97 1.86 '700°F.00 0.44 1.03 0.07 Methylcyclopent m e 0.39 0.04 3.18 0.00 0.18 1.06 10.00 Hexenes 0.12 2.30 5.22 0.20 CIO-PON 0.42 0.4-Tetramethylbenzene 0.5-Tetramethylbenzene 1.-PON 1.09 0.00 4.

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

.' and CSi hydrocarbons) 11441. 38. I X 100 200 I I00 i I00 2( METHANOL PROCESSED (LbMeOH/Lb Cot. 2.. 2.Suwon Campus] At: 10:27 12 February 2009 > r Y 0 c5+ x- X X .) METHANOL PROCESSED (Lb MeOH/Lb Cat.7 atm. ..) . METHANOL PROCESSED (Lb Me OH/Lb Cat.7 atm. Downloaded By: [2007-2008-2009 Kyunghee University . I WHSV 2 WHSV 2 WHSV FLG. I 371OC 371OC 399OC I atm. Fluid bed reactor ((2.

7 atm. W W .Suwon Campus] At: 10:27 12 February 2009 r I I $ 1 I PROPANE x P w n .) (Lb MeOH/Lb Cot. 39.7 atm.BUTANE -6-r METHANE +ETHANE 0 0 I00 2 20 I00 200 METHANOL PROCESSED METHANOL PROCESSED METHANOL PROCESSED (Lb MeOH/Lb Cat.) 371 OC 371 OC 399°C I atm. Fluid bed reactor (light paraffins) [ 1441. 1 (Lb McOH/Lb Cot. 2. Downloaded By: [2007-2008-2009 Kyunghee University . I WHSV 2 WHSV 2 WHSV FIG. 2.

Downloaded By: [2007-2008-2009 Kyunghee University .7 atm. 2. .Suwon Campus] At: 10:27 12 February 2009 Gj I0 - 0 w > E3t7 I . Fluid bed reactor (light olefins and durene) 11441. I WHSV 2 WHSV 2 WHSV FIG.) (Lb McOH/Lb Cat. 2 20 I00 200 0 100 200 0 I00 200 METHANOL PROCESSED METHANOL PROCESSED METHANOL PROCESSED (Lb McOH/Lb Cat. 40.) (Lb MeOH/Lb Cat. 2.7 atm.) 371 OC 371 O C 399OC I atm.

. HYDROCARBONS FROM METHANOL 95 Downloaded By: [2007-2008-2009 Kyunghee University . 42. Effect of temperature on methanol conversion at 25 psig [ 1441. 15- 25 psig 0 E 5 s 10- 50 Psig\ I 0 psig 5- K O 0 1 1 I I I l e FIG.Suwon Campus] At: 10:27 12 February 2009 1 ISC FIG. 41. 25 20 - - 8 -5. Effect of pressure on methanol conversion at 700°F [ 1441.

Comparison of calculated equilibrium and experimen- tal concentrations of methanol and dimethyl ether [ 1441.50 - 0. 96 CHANG Downloaded By: [2007-2008-2009 Kyunghee University .25 5 y 1.00 - 0 5 - 0.25 - I 0 1 2 3 Methanol (Wt %) FIG. 43. 44. Plot of methanol concentration versus @/@.11441.-E n 0. Observed - c Rediaed From Equilibrium -8 1.75 - .Suwon Campus] At: 10:27 12 February 2009 2 FIG. .

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

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

the light olefins. and emissions. give final gasoline yields higher than that of the fixed-bed. drive- ability.8 f t l s Feed composition 83. Concentrations as high as 3% of durene were found to give no adverse engine effects.3 h-' Gas superficial velocity 0. Unlike commercial gasolines. MeOH 0. when alkylated with isobutane and blended back. However.Suwon Campus] At: 10:27 12 February 2009 WHSV. Table 30 presents a summary of the properties of MTG gasoline. the durene content of the gasoline must be controlled at suitable levels. The mechanism of durene formation has already been discussed. The one hydrocarbon in MTG gasoline not found in significant amounts in conventional gasoline is durene. Product Characteristics Extensive product quality testing has been conducted on the gasoline from the Mobil MTG process [ 1471.7-1.3OC). cold-start. Fleet testing confirmed that the MTG gasoline was comparable to commercial premium gasolines in road octane.4-3. depending on the ambient temperature. It is seen that the octane and volatility characteristics are ex- cellent.5-1.7 atm Downloaded By: [2007-2008-2009 Kyunghee University . C. Be- cause of its high melting point (79. HYDROCARBONS FROM METHANOL 99 TABLE 28 Operating Conditions for Fluid-Bed Pilot Plant 1 1461 -~ Temperature 388-427OC Pressure 2.100 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. so a s not to crystallize out of solution. S and N contaminants are totally absent. . It can be seen that the fluid-bed produces more light olefins and less C5' gasoline than the fixed-bed. In general the syn- thetic gasoline is identical in all major aspects to commercial high octane gasolines.

several techniques may be applied to maxi- mize olefin selectivity in methanol conversion over ZSM-5 zeolites. A third technique utilizes . 47.Suwon Campus] At: 10:27 12 February 2009 20 - c - C 15 B z c U c' . OF FIG. Fluid-bed reactor temperature profile [ 1461 I D . Olefin Production A s indicated earlier. 100 CHANG 25 Downloaded By: [2007-2008-2009 Kyunghee University .- c -B 10 t K 5 0 500 700 900 1 loo Temperature. Reduced partial pressure [ 321 and catalyst modification with phos- phorus compounds [ 331 are effective.

coz 0.3 C. kPa 2170 Recycle ratio (mol) 9. RVP = late) (96 R + 0.5 Water 56. kPa 275 Pressure.4 Hydrocarbons 43. w t % of methanol charged : charged : Methanol + ether 0.6 Propane 5. 5. HYDROCARBONS FROM METHANOL 101 TABLE 29 Comparison of Fixed.0 100.Suwon Campus] At: 10:27 12 February 2009 ture. - 100. Hydrocarbon product. wt % of methanol Yields.6 i-Butane 14.5 n -Butane 3.2 Hydrocarbons 43. OC 413 Inlet 360 Outlet 415 Pressure.2 Propylene 5. COZ 0.0 Hydrocarbon product.0 Gasoline (including alka.0 LP G 13.+ Gasoline 60.7 B u tene s 1. other 0.1 Butenes 7.0 100.0 Space velocity (WHSV) Yields.5 Propane 5.4 C O .9 Propylene 0.0 i-Butane 8.6 100. Gasoline (including alka- late) (93 R + 0. OC : Average bed tempera- Downloaded By: [2007-2008-2009 Kyunghee University .3 n-Butane 1. other -0.+ Gasoline 79.0 9 psi [ 6 2 kPa]) 88.and Fluid-Bed Yields [ 1631 ~~ Yields from methanol in Yields from methanol in 4 bbl/d fixed-bed reactor system fluid-bed pilot unit Temperature.0 .0 c o .2 100.0 .9 C.6 LPG 6.1 Coke.4 Light gas 5.4 Fuel gas 1.4 Fuel gas .0 2.2 Coke.0 100.0 Space velocity (WHSV) 1.0 Methanol + ether 0. wt%: wt %: Light gas 1. RVP = 9 psi [62 kPa]) 85.0 Water 56.

4 +3.17 g Pb/USG a s TEL 102.7 Existent gum.17 g PblUSG as TEL 103. mg/100 mL (ASTM D873. % evap.1 Reid vapor pressure.17 g Pb/USG as TML 103.17 g Pb/USG a s TML 96.1 Downloaded By: [2007-2008-2009 Kyunghee University .8 +3.17 g Pg/USG a s TEL 95. (ASTM 0 2 8 7 ) 62.1 Distribution octane number (ASTM D2886) : Unleaded 95. OF. alkylates and light hydrocarbons) API gravity. 5 h) 2.7 +3.8 +3.1 +3.3 Potential gum.4 +3.9 +3. lb (ASTM D323) 11.2 Research octane number (ASTM D2699) : Unleaded 96. (ASTM D86) : lBP 86 5% 102 10% 116 20 % 136 30 % 159 40 % 186 50 % 2 16 60 % 240 70 % 263 80 % 297 90 % 33 6 95% 3 58 End point 422 % Residue 1. 102 CHANG TABLE 30 [ 1471 Properties of Gasoline f r o m Methanol (yield proportions of liquid product from 4 bbl Id unit.5 (continued) .17 g Pb/USG as TML in distillation charge 96.2 Motor octane number (ASTM D2700) : Unleaded 87.9 Front end (IBP-212OF fraction) octane number: Unleaded 94. m g / 1 0 0 mL (ASTM D381) 1.17 g PblUSC as TML 104.Suwon Campus] At: 10:27 12 February 2009 Distillation.

Olefins are separated and unconverted feed recycled. vol % (ASTM D1319): Aromaticsa 27 Olefins 6 Saturates 67 Freeze point.Suwon Campus] At: 10:27 12 February 2009 Sulfur. Results are shown in Table 31. The methanol was diluted with various amounts of water.C . This question was investigated by Chang et al. Conditions a r e chosen to operate at partial conversion. Using methanol containing 17%water. 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. . A fluid-bed study was carried out a t partial conversion of methanol [ 1491. HYDROCARBONS FROM METHANOL 103 TABLE 30 (continued) Hydrocarbon type. [ 150. since the olefin distribution was not a s predicted b y thermodynamics under reaction conditions. 48%C 2 . olefins selec- tivity was obtained at 52%conversion. 1511.35 Downloaded By: [2007-2008-2009 Kyunghee University . wt % (Mobil method) Nil Nitrogen. 1481 . OF (ASTM D2386) . This was attributed to a kinetic effect. Increasing water dilution was found to improve ethene selectivity. VII. The overall ki- netics may be represented by The catalyst is composed of a metal oxide (methanol synthesis) component and an acidic ( zeolite) component. w t % (Mobil method) Nil a Includes 3 wt% durene the fact that olefins are intermediates in the MTG reaction path [ 2 .

8 27.4 0.6 27.6 P ropylene 17. the first reaction is subject to thermo- dynamic limitation.OH/ 16% CH. 104 CHANG TABLE 31 11491 Conversion of Methanol to Light Olefins 83% CH.3 20. P F 570 650 6 15 Pressure.2 Product yield.0 Per pass conversion. C O .5 16.8 Dimet hylet her 23.2 38.0 Coke.7 39.0 5. psig 6 6 27 Methanol WHSV 0.9 8.) 18.3 6.3 49.0 100. K = kl/kl' << 1 kl The transformations A -+ B and B -+ C are effected by different catalysts. - 100.5 6.1 2.7 17.0 100.5 23.0 16.Suwon Campus] At: 10:27 12 February 2009 Conditions : 1 2 3 Temperature. % 52 84 62 Hydrocarbon product. . A s indicated.6 Nonaromatics 19.5 The above kinetic scheme is a special case of a general class of polystep reactions 1521 represented by kl k2 A B -C.2 11.4 0.9 Water 38.1 Pentenes 2.5 Butenes 7.0 C2-C5 Olefins 47.9 1.2 - 100.8 24.1 7.OH/ Reactant composition 17% H 2 0 84% H 2 0 Downloaded By: [2007-2008-2009 Kyunghee University .1 0. wt 8: Ethylene 21.7 36.0 100. the second reaction provides a .3 Paraffins (C. C 0 2 .2 0. wt % of methanol : Hydrocarbons 22.9 52.2 Methanol 15.3 18. However.1 .7 Aroma tics 14.1 6. other 0.-C.9 26.0 100.

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

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

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

Zn/Cr = 0. 83 . H. 427OC. atm.Suwon Campus] At: 10:27 12 February 2009 z $20 I 10 60 50 40 8 5 >- I. GHSV = 1740. Influence of zeolite cracking activity. 108 CHANG 30 Downloaded By: [2007-2008-2009 Kyunghee University .34.l [ 1511 . 50. Syngas aromatization over ZnCrZSM-5. 5 230 l- 0 ! I In W 20 ? z c 3 10 I 0 3 1 10 IUU a FIG./CO = 1.1780 h .

3 c 9+ 19. [ 1571 in their study of syngas conversion over dual-functional catalysts.OH Catalyst ZnCra ZnCr + ZVK ZVK Downloaded By: [2007-2008-2009 Kyunghee University . HYDROCARBONS FROM METHANOL 109 TABLE 32 Conversion of Syngas and Methanol over Various Catalysts [ 1571 (350-380OC) ~~ Feed CO i2H2 CO + 2H.8 15. and 200-1000 h . Typical results are shown in Table 32. wt 8: CH4 Traces 8. Aharoni and Starer [ 1561 found evidence for a common precursor for methane and methanol. Syngas (H. 35O-38O0C.8 a 14.0 B en zene 2.23 c6 14.6 5.1 c.0 42. which also contains data from methanol con- version over zeolite ZVK for comparison.9 3. Addition of water suppressed double bond hydrogenation and increased ethene selectivity. A zinc- chromium methanol synthesis component was combined with a high silica zeolite ZVK.0 Et hylben zene 11.Suwon Campus] At: 10:27 12 February 2009 Pressure. This selectivity was attributed to the small pore size of erionite. Similar results have been reported by Ione et al. The conversion of syngas to light hydrocarbons over a dual- functional ZnO-CuO/H-erionite catalyst has been reported [ 1671 .1 8. A close similarity is evident.7 5.06 4. .9 Xylene 3. 1. indicating inter- ception and hydrogenation of olefinic intermediates./CO = 2) was reacted over this composite at 20 atm.I GHSV.79 Toluene 11.OH and mainly propane) at 35OOC. at m 20 20 1 Hydrocarbons. Paraffins were predominant. which is reported to be analogous to ZSM-5 11581.* At 322-458OC and 27-68 atm the product was entirely Cl-C4 hy- drocarbons.9 2.7 14.25% conversion (to CH.71 2.0 C8 2.1 1.0 Traces c2-c4 100 9. CH.

at what point during its career does this C . is the transfer and incorpora- tion of a six-electron CH. that ion solvation could (and probably will) drastically alter the picture in catalytic en- vironments. unit. reactions such a s have been studied by ion cyclotron resonance spectroscopy [ 1591. Direct obser- vation of the transition state seems beyond our capabilities at . I s it possible that.Suwon Campus] At: 10:27 12 February 2009 There is clearly a diversity of opinion concerning the mechan- i s m of initial C-C bond formation. in the case of CH. Downloaded By: [2007-2008-2009 Kyunghee University . e. even under the influence of high solvation energies. and a wide gap separating theory from experiment. such exercises may be useful heuris- tically. the reaction "bottom line. however. e . the formation of hydrocarbons from methanol raises a host of intriguing theoretical questions. have failed to provide unequivocal answers. 110 CHANG V I I I . It would seem there- fore that the central question is really concerned with timing. trapping of intermediates.')? Before. Regardless of the nature of the electron-donor substrate. i . Aside from its obvious practical implica- tions. completely analogous r e - actions with similar (net) energetics prevail in the zeolitic e n - vironment? Could this explain. Nevertheless. Nevertheless. at least during some stage of its existence. . for example." a s it were. . initially embedded in a stabilizing cationic environment. the anomalous tem- perature 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. and kinetic stud- ies. For example. tracer. classical methods of mechanism elucida- tion. intermediate is cationic in character. POSTSCRIPT 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. Such gas-phase reactions a r e extremely fast and apparently p m - ceed without activation energy. during. o r after C-C bond formation? It is extremely tempting to draw analogies with gas-phase ionic reactions. intermediate lose a proton (or H. into the substrate. recognizing.g. there seems to b e a majority consensus that the reactive C.

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