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ABSTRACT
1. INTRODUCTION
2. MTO CATALYST
The MTO process utilizes a molecular sieve, SAPO-34, that contains silicon,
aluminium, and phosphorous. The structure of SAPO-34 along with small
organic molecules that are key to the MTO process are shown in Figure 1. The
small pore size (about 4 ~) of SAPO-34 restricts the diffusion of branched
hydrocarbons, and this leads to high selectivity to the desired small linear olefins.
0
Ct-C4 ethylene propylene butenes C5+ &other
paraffins
Fig. 2. Comparativemaximum C2-- mode performance of SAPO-34 vs. ZSM-5
Another key feature of the SAPO-34 molecular sieve is its mild acidity
which reduces paraffinic by-product formation through the hydride transfer
reaction. This feature provides olefin purities of about 97% even without splitter
columns for further purification, and makes it easy to upgrade the olefins to
polymer grade.
The MTO process utilizes a circulating fluidized bed reactor that offers a
number of advantages. The moving bed of catalyst allows the continuous
movement of a portion of used catalyst to a separate regeneration vessel for the
removal of coke deposits by burning with air. Thus, a constant catalyst activity
and product composition can be maintained in the MTO reactor. A fluidized-bed
reactor also allows for better heat recovery from the exothermic methanol-to-
olefins reaction. Catalysts manufactured at the commercial scale have
demonstrated the required selectivity, long term stability, and attrition resistance.
100
= 90
O
.o
L 80
r
o 70
-~ 60
~-
r
50
~. 40
o}
30
.= 20
to
o
Low " High
Severity
I........................................................................................................................................................................................................................... /
i-,~ C2= ~ C3= ----~-----C2=+C3= - o - C2=+C3=+C4= I
Fig. 3. Light olefin selectivities from an MTO unit with high-purity methanol feed
100
95
o 90
~ 85
w 80
m 75
II
r
70
||
65
60
Lc ~w "- High
Severity
Fig. 4. Olefin selectivity vs. operating severity with and without OCP
The OCP unit makes use of a very robust catalyst that yields low levels of
coke as byproduct from the olefin cracking reaction. Thus, although the catalyst
is fully regenerable by using a standard carbon burn, it is not necessary to use a
fluidized bed with catalyst transport as used in the MTO unit; either a fixed bed
or a moving bed suffices in the OCP unit.
4. ECONOMICS
5. CONCLUSIONS
This paper has discussed some of the features of a typical process unit for
the conversion of methanol and/or DME to light olefins. Though based on a
relatively novel chemistry, the process configuration and recovery and
purification techniques are akin to those currently practiced in industry, either
for the production of olefins by fluidized catalytic cracking (FCC) of heavy
hydrocarbons or by steam cracking of LPG or naphtha fractions
REFERENCES
[1] B.V. Vora, et al, Studies in Surface Science and Catalysis, 107, (1997) 87-98.
[2] a. Chemical Week, October 2, 2002
b. European Chemical News, October 14-20, 2002
[3] London, CNI, 31-Mar-03
[4] Mobil data from 1992 "Eurogas Conference", Norway
[5] J.H. Gregor and W. Vermeiren, 5th EMEA Petrochemicals Technology Conference,
June 25-26, 2003, Paris