Studies in Surface Science and Catalysis, volume 147

X. Bao and Y. Xu (Editors)

9 Elsevier B.V. All rights reserved.

Most recent developments in ethylene and propylene

production from natural gas using the UOP/Hydro MTO
process
J. Q. Chen a, B. V. Vora a, P. R. Pujad6 a, ~. Gronvold b, T. Fuglerud b,
S. Kvisle b

aUOP LLC, P.O.Box 5017, Des Plaines, Illinois 60017-5017, USA

bNorsk Hydro ASA, P.O. Box 2560, N-3901 Porsgrunn, Norway

ABSTRACT

The UOP/Hydro MTO Process utilizes a SAPO-34-containing catalyst that

provides up to 80% yield of ethylene and propylene at near-complete methanol
conversion. The process has great flexibility to produce a product with a range
of ethylene/propylene ratios, depending on the operating conditions used. This
paper will discuss recent improvements related to the technology which have
increased the carbon selectivity from methanol to ethylene-plus-propylene to
about 85-90%.

1. INTRODUCTION

As worldwide natural gas reserves continue to increase, natural gas is expected

to become an increasingly important raw material for the chemical industry in
the 21 st century. Conversion of natural gas to syn-gas and higher value added
products such as methanol, ammonia and transportation fuels is currently being
practiced commercially. The combination of methanol production using state-of-
the-art mega-scale methanol technology and methanol-to-olefins (MTO)
technology developed by UOP and Norsk Hydro provides an economically
attractive route from natural gas to ethylene and propylene, two large-tonnage,
high-value petrochemicals. The MTO technology has been extensively
demonstrated at a large-scale facility owned by Norsk Hydro in Norway. The
process converts methanol or dimethyl ether (DME) to ethylene and propylene
at about 75-80% carbon selectivity ~. A world-scale MTO unit is currently under
design2'3. This paper will discuss recent improvements related to the MTO
technology which have increased the carbon selectivity from methanol to
ethylene-plus-propylene to about 85-90%.

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.

ZSM-5 molecular sieve used in methanol-to-gasoline (MTG) processes

produces much lower ethylene and propylene yields 4, primarily due to the larger
pore openings of the MFI structure (about 5.5 A) (Fig. 2).

Fig. 1. Frameworkstructure of SAPO-34 (CHA) and ZSM-5 (MFI) molecular sieves

50 !......... m
[] Mobil ZSM-5 MTG
,540 i B UOP/HYDRO SAPO-34 MTO
E
r
',," 35 I
30
25
::3
9'o
0
20
L
~ 15 Ii
9-= 10 ......

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.

3. PROCESS DESCRIPTION AND RECENT I M P R O V E M E N T S

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.

Conventional treating methods have been shown to be effective for

removing by-products to the specification levels required for olefin
polymerization processes.

Reactor operating conditions can be adjusted to the desired product

requirements. Pressure is normally dictated by mechanical considerations, with
lower methanol partial pressures resulting in higher overall yields. Thus, some
yield advantage can be obtained by using a crude methanol feed that typically
may contain around 20 wt% water. On the other hand, increased pressures may
be favored for the production of higher propylene ratios. Temperature is an
important control variable- higher temperatures are required to increase the
proportion of ethylene in the product relative to propylene, but higher
temperatures also result in a small reduction in the overall light olefin selectivity.
Temperature severity effects are best appreciated in Figure 3 where operating
temperatures range from 400 to about 550~ Figure 3 also shows that the
maximum (carbon-based) selectivity of ethylene plus propylene are just shy of
80% and occur at an ethylene-to-propylene ratio close to 1:1.

It may be appreciated though that, if butenes were included, the overall

carbon selectivity would be in the order of 90%. This lends itself to a modified
process scheme whereby the heavier olefins are fed to an ATOFINA/UOP
Olefin Cracking Process unit (OCP) based on technology developed and
demonstrated by ATOFINA and UOP 5. In essence, C4 to C6+ olefins generated
as byproducts from the MTO process unit can be fed to the OCP unit in which
these heavier olefins are cracked to ethylene plus propylene, but with a
preponderance of propylene. The fractionation scheme in the MTO unit remains
unchanged except that it has to be sized to accommodate the added circulation to
and from the OCP unit; a small purge removes the heavier or more refractory
components from the recycle loop. Figure 4 illustrates the carbon selectivity
pattern from high-purity methanol (99.85 wt% methanol) to ethylene plus
propylene with the incorporation of the OCP unit.

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

"" MTO only'~-~o'o MTO+OCP, Once T h r o u g h " e =- MTO+OCP, Recycle Mode

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.

The incorporation of an MTO unit with an OCP unit on a once-through basis

without recycle boosts the overall ethylene plus propylene selectivity to about
83% compared to 77-78% selectivity for an MTO unit by itself as in Figure 3
and 4 above. The addition of recycle around the OCP unit for maximum
conversion of the heavy olefins leads to an overall yield of about 89% (Fig. 4).
In the process, however, the points at which the maximum C2=+C3= yields are
achieved shift to higher C3-/C2 = ratios (on an overall MTO plus OCP basis) as
corresponds to the preferential production of propylene from the OCP unit.

4. ECONOMICS

An MTO unit designed to produce 400,000 MTA of polymer-grade ethylene and

400,000 MTA of polymer-grade propylene will also produce about 175,000
MTA of C4+ olefins which, although valuable in an integrated refining or
petrochemical complex, may only warrant fuel value in some remote locations.
If integrated with an OCP unit, the same MTO unit can produce about 426,000
MTA of polymer-grade ethylene and 500,000 MTA of polymer-grade propylene,
with a 78% decrease in the amount of C4+ byproduct to only 39,000 MTA. The
ISBL cost of the OCP unit with recycle of unconverted olefins is about $50
million and, in addition, some extra capacity is required in the fractionation and
recovery section of the MTO unit that amounts to another $10 million. Overall,
inclusive of OSBL incremental allowances, license fees, catalysts, etc., inclusion
of the OCP unit requires an incremental investment of about $70 million. Thus,
the overall investment for the integrated MTO/OCP complex increases from
about $425 million to about $495 million. Typical IRR rates are in the order of
20% or higher depending on the relative values assigned to the key products.

If additional propylene is desired, the production ratio of propylene to

ethylene can be further increased by reducing the operating severity of the MTO
unit and slightly increasing the size of the OCP unit. Thus, for example, with the
same methanol feed rate as in the previous example, the MTO unit could be
operated to produce about 340,000 MTA ethylene and 450,000 MTA propylene
(propylene/ethylene ratio ~ 1.33) without OCP. The operation can be further
shifted to produce about 370,000 MTA ethylene and 570,000 MTA propylene
(propylene/ethylene ratio ~ 1.54) by incorporating an OCP unit to convert about
200,000 MTA of C4+ olefins and reduce the Ca+ byproducts by almost 80%.
Note that, as seen in Figure 3, the amount of C4+ olefins increases and the yield
of C2=+C3= decreases slightly as operating severity decreases (increased
C3=/C2= ratio) in an MTO unit; however, by incorporating an OCP unit the
overall C2=+C3= yield actually increases at the lower operating severity (higher
C3=/C2 = ratio) as shown in Figure 4.

5. CONCLUSIONS

The MTO process provides an economically attractive alternative for the

production of light olefins, ethylene and propylene, and the corresponding
polyolefins from methanol or DME that can be produced at low cost and in large
quantities from natural gas or other hydrocarbon sources. The MTO process can
be operated over a relatively broad range of C3=/C2= ratios, but with slightly
lower C2=+C3= yields at the higher or lower C3=/C2-- ratios. The integration of
an MTO unit with an OCP unit increases the carbon-based yield of ethylene plus
propylene to almost 90% of the methanol feedstock. This essentially eliminates
the need to market less desirable C4+ byproducts and thereby provides a product
slate focused entirely on ethylene and propylene with high propylene/ethylene
ratios.

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