Escolar Documentos
Profissional Documentos
Cultura Documentos
1-118 (1983)
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
I. INTRODUCTION
A. Stoichiometric Constraints
( n + l ) C H 3 0 H * CnH2n+2 + C + ( n + 1)HZO ( 2)
n = 1 , , 2 , 3, ... (4)
B. Thermochemistry
- 400
r PARAFFINS + C + H20
- 600 bl 2 4 6
CARBON NUMBER
8 10 12
111. CATALYSTS
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
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
2
10
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
TABLE 1
Conversion of Methanol to Hydrocarbons over Fused ZnC1, [ 71
(425OC, 166 atm)
CH4 1.0
C2H6 0.4
1.3
4.0
1.0
19.6
1.5
C4H8 0.7
C, to 85OC (1.5 tom) 33.1
Higher boiling products 30. Oa
Other -
7.4
100.0
a
18%hexarnethylben zene based on MeOH converted.
TABLE 2
Dimethyl Ether Conversion over Si02-A1,03 [ 111
(37OoC, 10 atm, 6 . 8 h-l QHSV)
Products %
CHI4 5.7
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
C2H4 10.2
C3H6 + C3H8 8.1
n-C4H,, + C,H8 5.2
i-C 26.4
i-Cs 11.0
c7 3.0
c 8+ 21.6
Carbon 8.6
99.8
B. Zeolite Catalysts
1. Introduction
Zeolites are porous, crystalline aluminosilicates composed of
A104 and S O 4 tetrahedra, interconnected through shared oxy-
gen atoms, forming a three-dimensional framework. 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. This is balanced by (exchangeable) cations
Mn+ in the structure, leading to the general representation
paraffins
-H20 -H20
2CH3OH rCH,OCHS -C2'--C5'-- aromatics
cycloparaffins
+H20 C,+ olefins
Scheme A
Framework density:
Channels:
1 7 . 9 T/1000 A3
typically about 3
FIG. 6 . ZSM-11channel s y s t e m .
12 CHANG
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
FIGURE 7 [25].
70t
/
\a DIMETHYL ETHER 1’
KY2 lo-’ I I0
I
SPACEITME (m)
FIG. 8. Reaction path for methanol conversion to hydrocarbons over HZSM-5 (371OC) [ 21.
14 CHANG
- -
-d DIMETHYL ETHER
a\
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
5
m ,,----4-
+
K
Y
5
30
20
10
0
10' lo-' 1
1
SPACE TIME 1-(
TABLE 3 [22]
Methanol Conversion to Hydrocarbons over Various Zeolites
(37OoC, 1 atm, 1 LHSV)
d. Effect of Temperature
The effect of temperature on ZSM-5 selectivity a t low w a c e
velocity (LHSV = 0 . 6 - 0 . 7 h - l ) is shown in Fig. i0 121. Below
3OOOC the main reaction is dehydration t o DME. With increasing
temperature t h e sequence of Scheme A is followed, while above
45OOC light olefins and CHI, become significant a s a result of
secondary cracking. Above about 5OOOC t h e dissociation of
methanol to H2 and CO becomes measurable.
16 CHANG
TABLE 4 [2]
Aromatics Distribution from Methanol
Conversion over HZSM-5
Xylenes:
0
m
P
Trimethylbenzenes :
9.0
22.8
10.0
I::[ [":I
23.9 23.5
[:3
123 0.9
124
135
Ethyltoluenes :
11.1
2.1 [
0 0.7
m+P 4.1
Tetramethylbenzenes:
1234
1235
1245
0.4
1.9
2.0
[ [: I
33.4
All+ 0.4
a
Diethylbenzenes + dimethylethylben zenes .
HYDROCARBONS FROM METHANOL 17
I00
90
80
Downloaded By: [2007-2008-2009 Kyunghee University - 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 - 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
e. Effect of Pressure
The main effect of varying reactant partial pressure on ZSM-5
selectivity is to change the relative rates of the olefin-forming and
.
aromatization steps [ 321 Decreasing pressure tends to decouple
the two reactions, while increasing pressure enhances the overlap
of the two reactions. This is illustrated in Figs. 11 and 1 2 for
PMeOH = 0.04 and 50 atm. These plots may be compared with
Fig. 8 depicting the normal atmospheric reaction path. The sig-
nificance of the shaded regions will b e discussed later.
18 CHANG
'"I
60
- - -0- WATER
8 50-
/
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
5
z .O'
0
40-
2
30
- DIMETHYLETHER o
/
5
3
0
0
g 20-
,,
10 -
0 - v
- AROMATICS
E 501
/
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
50 /
/
2- /
0
5 40 I /
I
,
/
I
m
K
I-
5!?
0 30
I-
V
V 0- PARAFFINS
3
0
0
K 20-
20
n
0- AROMATICS
10-
10
0 L
10-2 10-1 1 10
LHSV-' , hr.
O\ /o\*l/o\si/o
0 /si\o o/+,\o o\
20 CHANG
TABLE 5
Methanol Conversion at Low Pressures [ 1611
(427OC, 1 LHSV, 1 atm total pressurea)
Hydrocarbon distribution, wt %:
Ethylene 3.2 12.4 17.4 21.0
Propylene 4.8 18.2 26.5 38.7
Butenes 2.2 6.3 7.6 18.5
Pent ene s 0.4 0.3 0.7 2.4
(Total C,-C, olefins) (10.6) (37.2) (52.2) (80.6)
Methane 1.5 0.8 0.6 0.5
C2-C5paraffins 43.0 39.4 24.2 15.6
C,+ nonaromatic 3.9 2.3 2.7 1.3
Aromatics 41.0 20.3 20.3 2.0
a
Helium diluent at subatmospheric MeOH partial pressures.
CH30\ I
P/OCH
+CH ,OH
Other than to reduce the activity of the ZSM-5 acid sites, the
function of P-modification is unknown.
The conversion of ethanol over "Ultrasil" zeolite, which is
ZSM-8 [ 3 4 , 351, has been described by Russian workers 128, 3 6 ,
371. Representative data in Table 6 show that this catalyst be-
haves similarly to ZSM-5.
HYDROCARBONS FROM METHANOL 21
TABLE 6
Methanol Conversion over "Ultrasil" Zeolite [ 361
Reaction conditions:
Temperature, O C 300 300 450 4 50 4 50
Pressure, torr 30 80 30 80 80
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
Hydrocarbons, wt %:
CH4 7.99 5.52 11.94 9.48 1.74
C2H4 + C2H6 4.97 21.84 15.74 8.10 6.38
C,He 3.03 2.09 5.24 1.47 10.35
C3H6 5.52 15.39 31.83 29.88 14.98
i-C 4H lo 22.25 10.12 7.69 4.98 23.06
n-C4H10 1.57 0.33 1.22 0.51 4.86
C4Hs 7.08 3.98 14.49 20.98 10.66
i-C,H,, 16.78 3.29 2.62 3.54 10.08
n-C,H,, and higher 30.81 37.44 9.23 21.06 17.80
3. Other Zeolites
a. 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. Structures of
some of these small pore zeolites are illustrated in Figs. 13-16.
The erionite structure, Fig. 13, is hexagonal, containing
"supercages" supported by columns of cancrinite units linked
through double-6-rings (D6R). Access to, and between, the
supercages is gained through 8-rings.
Offretite is closely related to erionite except that the sequence
of 6-rings is AABAAB [231 as compared to AABAAC in erionite.
22 CHANG
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
Cham els: -
1 [OOl] -
8 3.6 x 3.7**+
TABLE 7
Methanol Conversion over Small Pore Zeolites [ 381
Reaction conditions:
Temperature, OC 3 70 341-378 538 538
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
Pressure, atm 1 1 1 1
LHSV (WHSV) , h-’ 1 (3.8)
b b
Hydrocarbons, wt %:
CH 4 5.5 3.6 3.3 3.2
CH2H6 0.4 0.7 4.4 0
CzH4 36.3 45.7 25.4 21.4
C3Ha 1.8 0 33,3 31.8
C3H6 39.1 30.0 21.2 13.5
C4H10 5.7
10.4 22.6
C4HB 9.0 10.0
c 5+ 2.2 3.1 2.0 7.5
a
De-aluminized ; Si02/A1,03 = 16.
bPulse microreactor, 1 pL MeOH in He, 500 h - l GHSV.
TABLE 8
Methanol Conversion over Mn-Exchanged Chabazite-Erionite I441
(40O0C. 90%conversion)
Products Vol %
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
C2H4
3H6
C4HB
CH4
C2H6
C3H8
C4H10
C sf nonaromatic <o. 1
Aromatics <o. 1
co 0.5
H2 5.2
H20 s2.0
Dimethyl ether 4.7
TABLE 9
Methanol Conversion over Zeolite H -MCH [ 451
(45OoC, pulse microreactor)
Products Vol %
~~~ ~
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
CH4 3.6
C2H6 0.2
C2H4 16.6
c 3H8 22.4
C3H6 41.2
i-C4Hlo 0
n-C4H10 4.9
l-C4H8 2.7
i-C4H8 2.0
2-C4H8 4.9
FIGURE 17 [25].
4. Zeolite Shape-Selectivity
Table 3 provides a concise illustration of zeolite shape-selec;
tivity in methanol conversion to hydrocarbons, Small pore (4.3 A )
erionite, as already shown, produces only low molecular weight hy-
drocarbons. It does not sorb benzene and therefore cannot pro-
duce aromatics. The intermediate pore ( < 6 (A> ZSM-5 and ZSM-11
truncate the hydrocarbon distribution at C,, , while the large
30 CHANG
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
MORDENITE Cmcm
viewed along
FLGURE 18 [ 2 5 ] .
TABLE 10 1481
Methanol Decomposition over Metal
Cat ion -Exchanged Paujasitesa
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
H2 Trace 10.3
CH4 22.5 43.0
C2H4 24.5 17.0
C2H6 2.7 2.9
C3H6 10.8 9.2
C3Hs 4.4
a
Continuous-flow; 1 atm; 1.5 LHSV; samples analyzed at 2-3 h
on stream.
b9.46 w t % Zn.
CLiquid product mainly unreacted CH,OH , H,O, and (CH,) *O.
loo
vo:L
ZSM-5 -
ISM I I
75 -
Downloaded By: [2007-2008-2009 Kyunghee University - 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 - 50
25 - 25
TABLE 11
Critical Diameters of Selected Polymethylbenzenes [ 221
6.1
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
6.4
6.7
6.9
7.1
a
Equilibrium diameters (rmin) estimated from Courtauld models.
Kinetic diameter % 2 - 1 ’ 6 r,h.
TABLE 12 [22]
A,, Shape- Selectivity of Various Zeolites
%1245TMB in %1245TMB in
Catalyst hydrocarbon A10
TABLE 13 [ 1651
Coke Formation and Deactivation in Dimethyl
Ether Conversion, 35OOC
C. Nonzeolitic Catalysts
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 - Suwon Campus] At: 10:27 12 February 2009
a
TP and TS indicate dodecatungstophosphate and dodecatung-
stosilicate, respectively.
bCalculated on a carbon-number basis.
MOM-DME EQUILIBRIA
---- }
DM E nc
Q
F I G . 21. Conversion of methanol and dimethyl ether to hydrocarbons over HZSM-5. 371OC
normalized [CH,] basis.
HYDROCARBONS FROM METHANOL 39
A + B - Ck2
40 CHAN G
1.o 1
kl lk2=.02 k2-55
0.6 -
04- -
-
0.2 -
0
0 I I
B+C k3 w C
C A D
7 . - I 7 I 1 1
0 CATALYST A
A CATALYST B
0 CATALYST C
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
reaction timeh
k l PH~ ,OH
r =
1 + k2P
H2 0
with
oxygenate
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
kloa3P
A
r =
A (1 + k,oclPA)3
where
1
a=
1 + bt/SL
44 CHANG
V. REACTION MECHANISM
The reaction path of acid-catalyzed hydrocarbon formation from
methanol may be viewed essentially as composed of three key steps:
ether formation, initial C-C bond formation, and aromatization with
ti-transfer.
The mechanism of the first two steps is discussed in this sec-
tion. The final stages, comprising olefin condensation, cyclization ,
and H-transfer over acidic catalysts, have been well studied and
proceed via classical carbenium mechanisms. 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 addition,
papers by Galwey [781 on carbenium pathways in reactions of C2+
alcohols on montmorillonite, and Dejaifve et al. [ 791 on methanol
and olefins conversion over ZSM-5 are pertinent.
The mechanism of polymethylbenzenes formation will, however,
be discussed since these compounds are peculiar to the methanol
transformation reaction.
A. Ether Formation
/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
CH,OH + H+ + CH,OH,+
r = ke2 = k a P / ( l + aPI2
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
pears and two bands at 2950 and 2840 cm-' (CH stretching) ap-
pear. Upon evacuation, the CH bande decreased significantly ;
however, the OH band did not reappear. This indicated that
only weakly adsorbed methanol is removed. 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, At 4OO0C, methanol can be completely removed and the
CH bands are shifted to 2860 and 2960 cm-l, indicating the pres-
ence of surface methoxyls.
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. The following mech-
anism was proposed :
/Si, /O\ A
, ,l /O\ ,iS/ ,A\
/ CH OH
3
B . Hydrocarbon Formation
TABLE 15
Decomposition of Methyl Derivatives [ 951
/3
H-CH,-OH -+ H20 + :CH,
u
n:CH, + (CH,),, n = 2 , 3, 4, 5
Basic Bronsted
site \
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
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
Me8O
, MeOEt C2H4 MeOPr C,H, MeOBu C4H,...
4 1 4 1 A I
PHASE
PHASE
..It - It It - It I t It
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
Me2
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
3t
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
i /n
0I
n=O I 2 3 4
I3C"
(75%) (25%)
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
""'\ H
II
f H - ?, SbF 6
CH3 CH,
C
/ \
-
C
RH I
C-C-C +R+
+
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
+ +
CH3 + CH,C=N -t CH3C=N-CH,
+
R,R,R,N * R1R2N: + :R,
H
+ PI
RIRZN: + CH3CN * R,R,N :CH,CN --H+
RlR,NCH*CN
H+
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
/O\ /O\-,O\
si
I1
A1
--CH30H
I11
4 0
111 IV V
N
VI VII
HYDROCARBONS FROM METHANOL 59
~ ~~~ ~- ~
CH,-O-CH,
+ 1
Hf
"i
CH3-0-CH,
+
+ H,
A2/
B21 +
CH ,CHOH
B3 i-CH,OCH,
+ 4 +
C H 3 0 C H z C H 3 + CHBOH, CH,CH,OH + CHSOCH,
~~l
CH,OH,+ + C,H, + CH,OH
B41
CZH, + HZO + CH,OCH,
+
Route A Route B
TABLE 17 [32]
The Conversion of Methanol and Ethanol to Hydrocarbons
over ZSM-5 Class Zeolitesa
Methanol Ethanol
a
T = 370 k l0C ; P = 50 atrn; LHSV = 1 . 2 h - l .
bEt benzene, MeEt benzenes, diMeEt benzenes, and diEt ben-
zenes.
A m o +H'
/ \ I
CH, CH3 CH~CH~
H
@/ 8
CH,OCH, + HZeol S CH3-0, f Zeol
64 CHANG
CH3-0,
i
' -
'\
'CH,
CH,OH + CH,CH2-OCH, + HZeol
Zeol CH,-0-CH,
0
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
H
I
CH,OCH,CH, + HZeol * CH3-0-CH2CH3Zeol 8
H
I
CH,-0-CH,CH,-HZeol
t/ .u
m e
- CH,OH t CH2=CH2 t HZeol
CH 3
1+
R3C-CH3 + HS
r
carbons over heteropolyacids and Nafion-H (perfluorinated sul-
fonic acid resin), which are Bronsted acids, On0 and Mori [ 711
concluded that the mechanism involves methyl cations:
+
CH, + + CH30R + \l>-cH30R] + CH,CH,OR + H+
CH:
Generation of the methyl cation was considered to occur by po-
larization of surface methoxyl species:
YH 3 CH,’
0 0 0
\ \ /O \ /O\ /O
0’ A1
\o 0 ’
Si
‘
0 0
’
A1
‘00’
Si
‘
0
66 CHANG
5. Chain Mechanisms
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
6. Other Schemes
The conversion of methanol to C ,-C hydrocarbons over nat-
ural mordenite was reported b y Zatorski and Krzyzanowski [ 541,
who proposed a free radical mechanism:
CH,OH -+ 6H, + OH
68 CHANG
2CH,CH, -+ C,Hlo
CH3CH2 -+ C2H4 + H
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
R' R
+
\..N - C I /
\ \ / \
Lin et al. [ 1291 studied methanol conversion over tungsten ox-
ide on various supports including zeolite A , rnordenite, and cha-
bazite. A mechanism involving the formation of a "HPC-O site"
species as the rate-controlling step was proposed. "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-. Divalent specie C H , is then formed and sub-
sequently polymerized to produce the olefins." (It was not speci-
fied how charge conservation is to be preserved.) The tungsten
apparently has a dehydrogenation function.
Langner [ 1701 has proposed the following imaginative mechan-
>C=C< + -
CH30H
(H+)
H<C-(-H + CH20
-
(H+l ( H*l CH3
-0
CH3
Zeol
HCHO -f C + H20
Venuto and Landis [ 751 considered methane to be formed from
methanol via radical pathways.
Finally, hydride abstraction by the reactive C, species can-
not be discounted as a source of at least some of the methane,
usually present in minor amounts. A s pointed out by Ono et al.
[ 701 , autocatalysis will minimize this reaction. However, hydride
70 CHANG
Derouane et al. [ 261, and van den Berg [ 741 considered ethene
to be an active intermediate in the reaction sequence. Consis-
tent with this view, Jiru et al. [ 1301 found that ethene-H,O mix-
tures gave products identical with methanol over ZSM-5. Simi-
larly, Bragin et al. [ 3 8 ] compared t h e reactions of ethene and
methanol over ZSM-5 under various conditions and concluded,
on the basis of similarity of product distributions, that ethene
is a primary intermediate in methanol transformation.
According to Kaeding and Butter [ 331 , ethene is the initial
olefin a t low methanol conversion in the presence of phosphorus-
modified ZSM-5. They assumed that the phosphorus treatment
did not alter t h e catalytic mechanism.
The view that ethene is the initial olefin was challenged b y
Ahn et al. [ 1281 and Anderson et al. [ 271. They found ethene
t o be substantially less reactive than propene over a variety of
catalysts. This was regarded as evidence that ethene could not
be a primary intermediate.
The catalysts investigated b y Ahn et al. [ 1281 were silica,
alumina, silica-alumina, HY, and H-mordenite. At 35OoC, over
silica-alumina, although the contact time of ethene was 10 times
higher than methanol, less than 0 . 5 %ethene was reacted, while
methanol gave 20-25%hydrocarbons. Further, the rate of pro-
pene formation from ethene was 100 times slower than from meth-
anol.
Anderson et al. [27] utilized various ZSM-5 preparations in
their study. A t 4OOOC propene was readily converted to aro-
matic products, while ethene generally exhibited low reactivity.
However, it was observed that certain catalyst preparations
showed considerable activity in promoting ethene conversion.
It was speculated that these particular catalysts may possess
highly active sites which are easily poisoned.
Ceckiewicz [ 431 , in FTIR studies of methanol sorption on
zeolite H-T a t 25-450°C, observed the propene band pattern
but failed to detect ethene. Upon temperature-programmed de-
sorption, however, C,-C, olefins were identified. The follow -
ing reaction network with propene a s the initial olefin was
proposed :
HYDROCARBONS FROM METHANOL 71
[methanol 1
cycli zat ion cycloparaf fins
ads
ads ’ aromatics
ads
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
cracking
4
C,-C, olefinsg carbonaceous
propyleneg and paraffinsg deposit
ads
700 OF
0.61 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 0.5- -
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
u -
I
[ r -
353 psig
169 psig
0
!-
I - + 59 psig -
$
V
0.4-
0
- 0 -
0 n
w 0 psig -
- 0 -
0.3- -
- -
I I11111111111 I I11111111111 I I 1 1 l 1 1 1 1 1 1 1 1 I I I I I I I I I L I I .
CARBON NUMBER
A. Fixed-Bed Process
The fixed-bed unit [30, 66, 1411, shown in Fig. 32, was a
two-stage system consisting of a dehydration reactor, where a
near equilibrium MeOH /DME /H20 mixture was produced, followed
by the hydrocarbon-forming reactor containing H ZSM- 5. The
second-stage product was cooled and flashed in a high-pressure
separator. Light gases were recycled to the second-stage reac-
tor to control the temperature rise. In this scheme, 208of the
total reaction heat is released in the first -stage and the balance
in the second. Depending on the recycle ratio, a AT < 95OC
could be maintained in the second stage.
Initial operating conditions for a bench-scale version of the
dual reactor system are shown in Table 18 [66]. The feed was
methanol containing 17%water to simulate crude product from a
methanol plant.
Results of a 167-h test a r e shown in Tables 19 and 20. A s
the cycle progresses, C,-C, paraffins decrease, C 7 - C 2 olefins
76 CHANG
~~
Fixed Bed
H20'-h
Crude
Methanol
"'' ---
Dehydration
Reactor
Compressor
Gas Product
+ 334%
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
HydrOca rbon
Recycle Liquid
Conversion Gas Product
Reactor
I
Water
408'C
TABLE 18
Operating Conditions for Dual Reactor Fixed-Bed Process 1661
First Reactor
Temperature, inlet 316OC
Temperature, outlet Q399OC
Pressure, inlet 13.6-23,8 atm
Space velocity 20 h - l , WHSV
Second Reactor
Temperature, inlet 343oc
Temperature, outlet Q454OC
Pressure, inlet 1 3 . 6 - 2 3 . 1 atrn
Space velocity 1.5-5.0 h - l . WHSV
Molar recycle ratio 3-4 (based on total fresh feed)
SeDarator
Temperature 37.8OC
HYDROCARBONS FROM METHANOL 77
TABLE 19 [66]
A Fixed Bed Aging Study. Run Conditions, Material Balance,
and Gasoline Propertiesa
Time on stream ( h )
8 47 95 142 167
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
Run conditions:
Reactor 1 inlet tern- 626 625 624 625 625
perature, OF
Reactor 1 outlet tem- 77 1 768 769 768 735
perature, OF
Reactor 2 inlet tem- 648 648 663 665 660
perature, OF
Reactor 2 outlet tem- 862 8 57 888 891 8 19
perature, OF
WHSV (MeOH over 3.3 3.3 3.3 3.3 3.3
catalyst
Molar recycle ratio 3.6 3.8 3.4 3.6 3.6
Pressure, psig 26 5 26 5 265 26 5 265
Product, wt% of total
product :
Hydrochrbons 36.28 35.75 37.65 36.11 34.44
H2 0 63.54 64.13 62.18 63.82 65.20
co 0.09 0.04 0.08 0.02 0.04
CO2 0.09 0.08 0.09 0.05 0.05
Methanol 0.00 0.00 0.00 0.00 0.27
Dimethyl ether 0.00 0.00
- - 0.00 -0.00 -0.00
100.00 100.00 100.00 100.00 100.00
Product, wt % of feed 99.72 100.45 101.69 99.76 100.22
Gasoline (including
alkylate) :
Reid vapor pressure, 9.0 9.0 9.0 9.0 9.0
p sia
Research octane, un- 96.2 95.0 94.3 94.6 94.2
leaded
Research octane, 3 g 101.0 100.3 100.2 100.3 100.3
lead
Specific gravity 0.746 0.738 0.736 0.729 0.726
Molecular weight 94.3 94.4 94.2 93.8 93.8
a
Feed crude methanol ( 17 wt%H,O) ; unit ; process development
unit.
78 C HAN G
TABLE 20 [66]
A Fixed Bed Aging Study. Hydrocarbon Product Distribution.
Basis : Weight Percent
Time on stream ( h )
8 47 95 142 167
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
+
increase, C nonaromatic hydrocarbons increase significantly,
and aromatics remain fairly constant.
For the final gasoline product, alkylate could be produced
from the isobutane and C , - C I , olefins, so that the total of R V P
gasoline selectivity was 75.9-88.4 wt%. This product had an un-
leaded research octane of 94.2-96.2.
In a subsequent test [ 1421 the space velocity was lowered from
3 . 3 to 1.6 and the recycle ratio increased from 3 . 4 - 3 . 8 to 9. A
total of 208 d on stream was achieved, during which 8000 lb meth-
anol/lb catalyst was processed. The total test consisted of nine
cycles, varying in length from 1 3 . 1 d (first cycle) to 24.9 d
(Table 21), with oxidative regenerations between cycles to re-
move accumulated coke on catalyst. Typical data, shown in
Tables 22 and 23, are similar to the data in the preceding tables.
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
X
TABLE 21 11421
Cycle Lengths of Long-Term Aging Test in Fixed Bed Unit
a
Methanol breakthrough taken as first material balance during which MeOH was detected in product
water phase.
Downloaded By: [2007-2008-2009 Kyunghee University - 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
Conditions
T h e on stream in cycle h 73 314 94 333 77 315
Cumulative charge, w t of MeOH/ 117 501 4162 4545 7123 7504
w t conv. cat.
Dehydration reactor inlet temp., OF 601 604 583 586 576 58 7
Dehydration reactor outlet temp., OF 779 776 773 771 771 774
Conversion reactor inlet temp., OF 648 652 649 652 650 651
Conversion reactor outlet temp., OF 774 777 766 774 778 779
High pressure separator temp., OF 128 129 125 135 126 124
WHSV, MeOH over conv. cat. 1.6 1.6 1.6 1.6 1.6 1.6
Recycle ratio, mol/mol of charge 9.2 8.9 9.7 8.8 9.2 8.3
Pressure, psig 300 300 300 245 283 250
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
Products, wt 0 of charge :
Hydrocarbons 35.5 35.3 36.2 35.2 36.9 35.9
HZO 64.1 64.2 63.8 64.7 63.0 64.0
HZ 0.01 0.01 0.0 0.0 0.0 0.0
co 0.04 0.03 0.01 0.01 0.01 0.0
CO, 0.4 0.3 0.0 0.05 0.08 0.07
Methanol 0.0 0.2 0.0 0.0 0.0 0.0
Dimethyl ether 0.0 0.0 0.0 0.0 0.0 0.0
Material balance, wt 90 98.4 97.8 98.2 98.6 100.2 99.0
9 RVP gaso1ine:a
Research octane (R + 0) 95.1 93.3 93.4 93.2 93.2 93.0
Leaded octane ( R + 3) 100.8 99.4 99.9 99.3 99.9 99.1
Specific gravity 0.756 0.734 0.736 0.728 0.731 0.723
Molecular weight 95 95 95 95 94 94
Yield, w t % of hydrocarbons 73.3 86.2 82.6 92.0 85.5 89.3
a
Gasoline includes alkylate ; properties are calculated from compositions.
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
03
N
TABLE 23 11421
Hydrocarbon Product Distribution in Long-Term Aging Test
1.0-
0.8 -
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
0.6
0.2
B . Fluid-Bed Process
50 I I I 1
- 40 - _h
V v
lsoparaffins
r
- V Y
m
V
> \r
-
-
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
7
I
.I-
? 20-
s
0
o / 0 Olefins
10-
0 I a L
TABLE 24 [1431
Four Barrels-per -Day Fixed -Bed MTG Demonstration
Plant Operating Conditions
Separator temperature, OC 52
86 CHANG
TABLE 25 [143]
MTG Scale-Up : Yield Comparison
(average of first cycle)
TABLE 26 f1441
Typical Material Balances in Fluid-Bed Pilot Planta
TABLE 27 [144]
Composition of Hydrocarbon Products from
Fluid-Bed Pilot Planta
lb of cat.)
Isopentane 12.36 11.45 11.06 10.07
n-Pentane 0.49 0.43 0.42 0.33
Pentenes 2.19 2.60 3.04 3.12
Cyclopentane 0.44 0.05 0.10 0.07
Methylcyclopent m e 0.71 0.67 0.63 0.58
n - Hexane 4.06 5.02 5. 14 5.42
Met hylpentanes 5.46 6.04 6.03 5.40
Dimethylbutanes 0.99 1.17 1.18 1.00
Hexenes 0.26 0.39 0.43 0.47
Cyclohexane 0.03 0.23 0.09 0.25
C ,-PON 3.31 3.87 4.00 4.29
Ce-PON 2.89 3.62 3.46 3.91
C,-PON 1.64 2.43 2.15 2.20
CIO-PON 0.11 0.22 0.43 0.27
Benzene 0.00 0.00 0.00 0.00
Toluene 1.38 2.12 2.38 4.03
E t hylben zene 0.16 0.18 0.17 0.17
X ylenes 6.05 6.30 5.80 5.50
Trimet hylbenzenes 8.39 8.30 7.30 7.20
Methylethylben zenes 1.34 1.44 1.30 1.31
Propylben zenes 0.02 0.03 0.02 0.03
1,2,4,5-Tetramethylbenzene 1.94 3.38 2.87 3.93
lI2,3,5-Tetramethylbenzene 1.52 1.80 1.74 1.02
1,2,3,4-Tetramethylbenzene 0.56 0.50 0.41 0.45
Other C ,,,-benzenes 1.36 1.23 0.97 1.07
C ,,-Benzenes 1.72 0.48 0.43 0.33
Naphthalenes 1.14 0.02 0.00 0.01
Other aromatics 2.58 0.67 1.71 1.86
HYDROCARBONS
-
a
I
V 30t
AROMATICS -0.
AROMATICS
O D
n o
I DIMETHYLETHER 7
1 DIMETHYLETHER- 1
METHANOL
FIG. 37. Fluid bed reactor (total hydrocarbons and aromatics) [ 1441.
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
>
r
Y
0
c5+ x-
X
X
.. ..
I X
100 200
I
I00 i I00 2(
METHANOL PROCESSED
(LbMeOH/Lb Cot.)
METHANOL PROCESSED
(Lb MeOH/Lb Cat.)
- METHANOL PROCESSED
(Lb Me OH/Lb Cat. I
FLG. 38. Fluid bed reactor ((2,' and CSi hydrocarbons) 11441.
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
r I I $ 1 I
PROPANE x
P
w n - BUTANE
-6-r
METHANE +ETHANE
0
0 I00 2 20 I00 200
METHANOL PROCESSED METHANOL PROCESSED METHANOL PROCESSED
(Lb MeOH/Lb Cat. 1 (Lb McOH/Lb Cot.) (Lb MeOH/Lb Cot.)
W
W
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
Gj I0 -
w
>
E3t7
I - 2 20 I00 200
0 100 200 0 I00 200
METHANOL PROCESSED METHANOL PROCESSED METHANOL PROCESSED
(Lb McOH/Lb Cat.) (Lb MeOH/Lb Cat.) (Lb McOH/Lb Cat.)
FIG. 40. Fluid bed reactor (light olefins and durene) 11441.
HYDROCARBONS FROM METHANOL 95
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
1 ISC
25
20 -
-
8
-5- 15-
25 psig
0
E
5
s 10-
50 Psig\
I 0 psig
5-
K O
0 1 1 I I I l e
Observed
-
c
Rediaed From
Equilibrium
-8 1.25
5
y 1.00 -
0
5
-
0.75 -
.-E
n
0.50 -
0.25 -
I
0 1 2 3
Methanol (Wt %)
-+ To Product Recovery
4
Disengager
0 -
16" x 3'
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
Flue gas
Regenerator
lo" x 2%'
Reactor
Air + N2
4" x 25'
-
Hopper
lo" x 2%'
Liquid Feed -
Vapor Feed -
98
t
313A33U SVZ) 1HE)Il
CHANG
HYDROCARBONS FROM METHANOL 99
TABLE 28
Operating Conditions for Fluid-Bed Pilot Plant 1 1461
-~
Temperature 388-427OC
C. Product Characteristics
25
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
20
-
c
-
C
15
B
z
c
U
c'
.-
c
-B
10
t
K
0
500 700 900 1 loo
Temperature, OF
D . Olefin Production
TABLE 29
Comparison of Fixed- and Fluid-Bed Yields [ 1631
~~
ture, OC 413
Inlet 360
Outlet
415 Pressure, kPa 275
Pressure, kPa 2170
Recycle ratio (mol) 9.0
2.0 Space velocity (WHSV) 1.0
Space velocity (WHSV)
TABLE 30 [ 1471
Properties of Gasoline f r o m Methanol (yield proportions of liquid
product from 4 bbl Id unit, alkylates and light hydrocarbons)
(continued)
HYDROCARBONS FROM METHANOL 103
TABLE 30 (continued)
a
Includes 3 wt% durene
the fact that olefins are intermediates in the MTG reaction path
[ 2 , 1481 . Conditions a r e chosen to operate at partial conversion.
Olefins are separated and unconverted feed recycled.
A fluid-bed study was carried out a t partial conversion of
methanol [ 1491. The methanol was diluted with various amounts
of water. Results are shown in Table 31.
Using methanol containing 17%water, 48%C 2 - C , olefins selec-
tivity was obtained at 52%conversion. Increasing water dilution
was found to improve ethene selectivity. This was attributed to
a kinetic effect, since the olefin distribution was not a s predicted
b y thermodynamics under reaction conditions.
TABLE 31 11491
Conversion of Methanol to Light Olefins
Conditions : 1 2 3
Temperature, P F 570 650 6 15
Pressure, psig 6 6 27
Methanol WHSV 0.4 0.4 0.2
Product yield, wt % of methanol :
Hydrocarbons 22.7 36.6 27.2
Methanol 15.9 8.9 26.8
Dimet hylet her 23.0 5.1 7.9
Water 38.3 49.2 38.0
Coke, C O , C 0 2 , other 0.1 0.2 0.1
- - -
100.0 100.0 100.0
Per pass conversion, % 52 84 62
Hydrocarbon product, wt 8:
Ethylene 21.3 18.8 27.6
P ropylene 17.2 11.7 17.5
Butenes 7.1 6.5 6.1
Pentenes 2.1 2.9 1.3
Paraffins (C,-C,) 18.3 20.8 24.7
Aroma tics 14.5 16.3 6.6
Nonaromatics 19.5 23.0 16.2
-
100.0 100.0 100.0
C2-C5 Olefins 47.7 39.9 52.5
kl k2
A B -C; K = kl/kl' << 1
kl
dN RT r2
@ =(=)(pi)(o)
<
t itTYPI
I
I
CAL HIGH PRESSURE
METHANOL SYNTHESIS
CATALYST
ATOM PERCENT
7c
6C
0
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
50
z
5
c-
-
40
i,
A
W
30
v)
0
-I
4
5
g 20
4
10
0
SPECIFIC PROPENE HYDROGENATION RATE, k, hr-'
30
Downloaded By: [2007-2008-2009 Kyunghee University - Suwon Campus] At: 10:27 12 February 2009
z
$20
I
10
60
50
40
8
5
>-
I- 5
230
l-
0
!
I
In
W
20 ?
z
c
3
10 I
0 3
1 10 IUU
a
TABLE 32
Conversion of Syngas and Methanol over Various
Catalysts [ 1571 (350-380OC)
~~
Pressure, at m 20 20 1
Hydrocarbons, wt 8:
CH4 Traces 8.0 Traces
c2-c4 100 9.0 42.6
5.7 5.23
c6 14.9 3.1
c, 1.71 2.0
C8 2.1 1.0
B en zene 2.9 2.79
Toluene 11.7 14.9
Xylene 3.06 4.0
Et hylben zene 11.8 15.3
c 9+ 19.1 8.8
a
14.25% conversion (to CH,OH and mainly propane) at 35OOC.
V I I I . POSTSCRIPT
REFERENCES
S. Ceckiewicz, React.
~- Kinet. Catal. Lett., 16(1), 11
(1981).
S. Ceckiewicz, J. Chem. Soc., Faraday Trans., 1, 77,
269 (1981).
F. A . Wunder and E . I. Leupold, Angew. Chem., Int.
Ed. Engl., 19(2), 126 (1980).
T. V . Whittam and M . S. Spencer, U . K . Patent Appl.
GB 2,061,999A.
T. Inui, T. Ishihara, and Y. Takegami, J . Chem. Soc.,
Chem. Commun., p. 936 (1981).
T. Inui, H. Matsuda, N . Morinaga, G . Takeuchi,
T . Ishihara, and Y. Takegami, Japan-Soviet Catal.
Seminar, 6th Osaka, p. 196 (1981).
A. B . Schwartz and J . Ciric, in Ref. 75.
K . V . Topchieva, A . A . Kubasov, and T . V . Dao,
Vestn. Mosk. Univ., Khim.,- - 27(6), 628 (1972).
N . Davidova, D. Shopov, N . Jaeger, and G . Schulz-
Ekloff, React. Kinet. Catal. Lett., 12(3), 229 (1979).
S. Hochevar, G . V . Echevskii, B . Szaj, and K . G .
Ione, Ibid., 13(4), 425 (1980).
F. X. Cormerais, Y. S. Chen, M . Kern, N . S . Gnep,
G . Perot, and M. Guisnet, J . Chem. Res., ( 5 ) , 290
(1981).
F. A . Swabb and B . C . Gates, Ind. Eng. Chem., Fun-
dam., 11, 540 (1972). .
K Z a t G s k i and S. Krzyzanowski, Acta Phys. Chem.,
29, 347 (1978).
S. Spencer and T . V . Whittam, Ibid., 29, 307 (1978).
B . N . Dolgov, Die Katalyse in der Oyanischen Chemie,
DVW, Berlin, 1963, p. 439.
B . V . Matyushenskii and G . N . Freidlin, Zh. Vses. Khim.
Obshchestv., 12(6), 710 (1967).
D. E. PearsonrJ. Chem. Soc., Chem. Commun., p. 397
(1974).
W. K . Bell and C. D. Chang, U.S. Patent 3,969,427
( 1976) .
114 CHANG