Science and Technology in Catalysis 2002 109

Copyright 9 2003 by Kodansha Ltd.

16
Converting Natural Gas to Ethylene and
Propylene Using the UOP/HYDRO MTO
Process

Paul T. Barger, Bipin V. Vora, Peter R. Pujad6 and Qianjun Chen

UOP LLC
25. E Algonquin Road
Des Plaines, IL 60017 USA

Abstract
The development of new ways to convert natural gas, especially methane, to higher valued
products is one of the keys to increasing the utilization of this abundant natural resource. The
combination of methanol production using state-of-the-art mega methanol technology with the new
methanol-to-olefins (MTO) process developed by UOP and Norsk Hydro provides an economically
attractive route from natural gas to ethylene and propylene. These light olefins are feedstocks for a
wide variety of high-value petrochemicals and polymers.
The UOP/HYDRO MTO process utilizes a SAPO-34-containing catalyst, which 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. A major end use for both ethylene and propylene is the production of
polyolefins. Since polymerization catalysts are very sensitive to a wide variety of poisons, trace
by-products in the MTO light olefin effluent have been identified. Conventional treating methods
have been shown to be effective for removing these by-products to the specification levels required
for olefin polymerization processes. This work has shown that the ethylene and propylene
produced by the MTO process is a suitable feedstock for olefin polymerization.

1. INTRODUCTION

Natural gas is expected to become an increasingly important raw material for the production of
chemicals in the 21 st century. World gas reserves have continued to increase, although much of
them are in remote locations where transportation of gas is impractical. Effective utilization of the
methane content of the gas is particularly difficult problem. While no economically viable process
for direct conversion exists today, there are well-established commercial processes for the
production of synthesis gas (CO/H2) and methanol from methane. The subsequent conversion of
methanol to light olefins (ethylene and propylene) using shape-selective molecular sieve catalysts
provides a route for using natural gas to prepare high-value petrochemicals and polymers.

2. METHANOL-TO-OLEFINS (MTO) PROCESS AND CATALYST

The conversion of methanol to hydrocarbons over molecular sieves was discovered in the
early 1970s with ZSM-5 (MFI) based catalysts [1-4]. Although much of the focus at that time was
on the production of highly aromatic liquids for gasoline blending, process conditions were found
that gave good yields of light olefins, particularly propylene and butenes. In the 1980s, scientists at
Union Carbide discovered silicoaluminophosphate (SAPO) molecular sieves and found that several
of these materials, in particular SAPO-34 with the chabazite (CHA) structure, are excellent
110 P.T. Barger et al.

catalysts for the conversion of methanol to ethylene and propylene [5-7]. The structure of SAPO-
34 along with small organic molecules that are key to the MTO process are shown in Figure I. The
small (about 4 A) pore size of SAPO-34 restricts the diffusion of branched hydrocarbons, and this
leads to high selectivity to the desired small linear olefins.

Figure 1. Framework structure of SAPO-34 (CHA) molecular sieve

The acid sites of zeolitic molecular sieves arise from the substitution of A1+3 for Si+4 in the
mostly siliceous crystalline lattice with an acidic proton required to balance the charges. In the case
of SAPO molecular sieves the basic structure is AIPO4. Substitution of Si+4 and H + for a portion of
the framework p+5 introduces acid sites to the material. The acid strength of zeolitic materials is
typically greater than that of SAPO sieves. The impact of this acidity difference on MTO
performance has been shown by the comparison of the catalytic performances of SAPO-34 and
SSZ-13, which is a synthetic silicoaluminate that also has the chabazite structure [8]. Table 1
shows that SAPO-34 has significantly better stability due to a lower rate of coke formation than
SSZ-13 samples with comparable tetrahedral-atom substitutions and acid site densities. SSZ-13
also shows greater production of light paraffins, which is consistent with accelerated hydride
transfer for the catalyst with higher acidic strength.

Table 1. Comparison of SAPO-34 and SSZ-13 (Chabazite) Catalysts for MTO [8].

Material SAPO-34 SSZ-13 SSZ-13 SSZ-13

T atom % 10% Si 18% .....A1 10% AI 3.3%
...... AI
Selectivities '(%at 2 hr)
C2-C40lefins 96 69 75 87
Ci-C3_Paraffins .... 3 28
Stability
>40 6 13
(hr at >50% conv)
Coking 19 16'6 19.3 15.0
(% carbon on used cat) after 54 ha- after 18 hr after 18 hr after 18 hr
 111

3. UOP/HYDRO MTO PROCESS

UOP and Norsk Hydro have jointly developed and demonstrated a new MTO process utilizing a
SAPO-34 containing catalyst that provides up to 80% yield of ethylene and propylene at near-
complete methanol conversion [9]. Some of the key aspects of the work have included the
selection of reactor design for the MTO process and determination of the effects of process
conditions on product yield. The suitability of the MTO light olefin product as an olefin
polymerization feedstock has also been evaluated during the development of this process.
The MTO process utilizes a 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 removal of coke deposits by burning with air. Thus, a constant catalyst
activity and product composition can be maintained in the MTO reactor. Figure 2 demonstrates the
stability of a 90 day operation in the fluidized-bed MTO demonstration unit at the Norsk Hydro
Research Center in Porsgrtmn, Norway. A fluidized-bed reactor also allows for better heat recovery
from the exothermic methanol-to-olefins reaction. This type of reactor has been widely used in the
FCC area, particularly for catalyst regenerators.

Conversion
iv, 100

~-, 8O

r~ 60
0 Selectivity to C2--
o m Ill MI I m / iI Ii i U i i i i i n l m m m i m ii tl i i m m m ii ill m i

9,,,, 40
m m m m m m m ill i l l m ill m / / I m

Selectivity to ~=
~
0 2O

O l l l I 1 I I ... I

0 10 20 30 40 50 60 70 80 90
Time on-stream, days

Figure 2. Fluidized Bed MTO Performance in MTO Demonstration Unit

The UOP/HYDRO MTO process offers a wide range of flexibility for varying the ethylene and
propylene product ratio by adjusting the operating severity. The MTO process can be designed for
an ethylene to propylene ratio between 0.75 and 1.5 (Figure 3). Over the range of 0.8 to 1.3, the
overall yield of light olefins changes slightly with the highest yields achieved with about equal
amounts of ethylene and propylene. This region provides the lowest methanol requirements, but
the ratio can be adjusted to reflect the relative market demand and pricing for ethylene and
propylene. An example material balance is shown in Table 2 for the production of 600,000 MTA
of light olefins with equal amounts of ethylene and propylene. Approximately 3 tons of methanol
is required per ton of light olefins. This represents a carbon-based yield of almost 80%.
112 P.T. Barger et al.

100%
r~

r~

Ethylene + Propylene
m 80% - .......

O
t. 60% -

Propylene Ethylene
,t~
tim
40%

~ 2o~ _
increasing Severity ~'~
p,-

0 % ,,
| | | | | | | i

0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6
Ethylene / Propylene Ratio

Figure 3. MTO Reactor Yields as Function of Ethylene to Propylene Ratio and Severity

Table 2. MTO Material Balance for 600,000 MTA Ethylene and Propylene.

Feedstocks, Products,
MTD MTD
Methanol 5,204
Ethylene 882
Propylene 882
Mixed Butenes 272
C5+ Hydrocarbons 100
Fuel Gas 88
Other (water, COx, coke, etc.) 2,980

Totals .,, 5,204 5,204

Because of the high olefin yields and low light ends make, the MTO process does not require
the high cost separation equipment of a conventional ethylene recovery unit. Figure 4 shows the
overall process design including product compression, fractionation and treatment that are
necessary to obtain polymer-grade ethylene and propylene products.
Modem olefin polymerization catalysts are sensitive to a wide variety of potential trace
impurities in the olefin feedstocks, such as oxygenates, acetylenes/dienes, 02, CO, CO2, COS and
arsine. Detailed analyses of the reactor effluent from the MTO demonstration unit has identified
the acetylenic, diolefinic and oxygenated compounds are present in the MTO product. No unusual
by-products have been found. In fact, a comparison of the oxygenates found in the effluents of an
MTO unit and an LPG cracker shows that the same oxygenates are present in both streams,
although at a higher level in the MTO product. The UOP/HYDRO MTO process includes
equipment to recover the major oxygenates and recycle them back to the reactor for conversion to
additional olefins. The remaining minor oxygenate impurities can be removed by conventional
technology, such as the UOP ORU process. Figure 5 shows that the ORU treatment is able to
remove all oxygenates in the light olefin product to below the 2 ppm detection limit of the GC
analysis. Acetylenes and diolefins can be selectively hydrogenated using conventional
technologies, such as the UOP SHP process.
 113

Figure 4. MTO Process Flow Scheme

Without ORU

1i ,i ,l

With ORU

C1 C2 C3 c4 Cs C6

Figure 5. Oxygenate Removal from MTO Product by ORU

In order to demonstrate the economic attractiveness of the production of light olefin polymers
from natural gas, an analysis has been conducted based on an MTO unit producing 300 KMTA
ethylene and 300 KMTA propylene. The economic analysis of an overall gas-to-polymers (GTP)
 114 P.T. Barger et al.

plant integrating this MTO unit with a mega methanol plant and conventional olefin polymerization
units is shown in Table 3. The economic viability of this integrated process is demonstrated by the
>20% pretax ROI.

Table 3. Economic Summary for Integrated GTP Complex.

Gas cost, $MM/year 30

Operating cost, $MM/year 99
Total cash cost, $MM/year i26
Product revenue, $MM/year 475
- Transportation costs, $MM/year 26
Net revenue, $MM/year 449
Gross profit, $MM/year 320
Investment, $MM 1210
Pretax ROI 21.4%

Basis: $0.50/MM BTU natural gas, $800/MT polyethylene, $705/MT

polypropylene and a remote location (U.S. Gulf Coast + 15%)

4. S U M M A R Y

The production of high-valued light olefins using molecular sieve catalysts has been an area of
active commercial developments over the last decade. The development of SAPO molecular sieves
with high selectivity to ethylene and propylene has lead to new MTO technology for natural gas
utilization that is on the verge of commercialization. The UOP/HYDRO MTO process provides,
for the first time, an economically viable route for the conversion of low-valued natural gas,
particularly remote or stranded gas, to high-valued petrochemical feedstocks. Some of the key
issues in the development of this process have included demonstration of the flexibility of the
fluidized bed reactor design and determination of the suitability of the MTO light olefin products as
feeds for olefin polymerization.

5. REFERNCES

I. Chang C. D., Lang W. H. and Silvestri A. J., U.S. Patent 4,062,905 (1977).
2. Chang C. D. and Silvestri A. J., J. Catal. 47 (1977), 249.
3. Chang C. D., Catal. Rev.-Sci. Eng. 26 (1984), 323.
4. Chang C. D., Hydrocarbons from Methanol (M. Dekker, New York, 1983).
5. Kaiser S. W., U.S. Patent 4,499,327 (1985).
6. Kaiser S. W.,ArabianJ. Sci. Eng. 10 (1985), 361.
7. Lewis j. M. O., in Catalysis 1987, ed. Ward J. W. (Elsevier, Amsterdam, 1988), 199.
8. Yuen L-T. et al, Microporous Mater. 2 (1994), 105.
9. Vora B. V. et al, in Natural Gas Conversion IV, ed. De Pontes M. et al (Elsevier, Amsterdam,
1997), 87.