New Technologies and Alternative Feedstocks in Petrochemistry and Refining

DGMK Conference October 9 – 11, 2013, Dresden, Germany

The Progress of SINOPEC Methanol-To-Olefins (S-MTO) Technology

Liu Hongxing, Xie Zaiku, Zhao Guoliang
Shanghai Research Institute of Petrochemical Technology SINOPEC, China

Abstract
It is widely recognized that naphtha steam crackers and FCC units are the main current
sources of ethylene and propylene. On the condition of high oil price, olefin producers are
striving to develop new economical routes to produce ethylene and propylene with low-cost
feedstocks.
Methanol to olefins (MTO) has aroused great attention in recent years, and SINOPEC
has developed a new kind of MTO process named S-MTO which features high olefins
selectivity, high methanol conversion and low catalyst consumption. Puyang Zhongyuan 200
KTA S-MTO has been in steady operation for more than 17 months. The catalyst used in the
process is based on a silicoaluminophosphate, SAPO-34, which has very high carbon
selectivity to low carbon olefins. Results from the commercial plant show that S-MTO
process converts methanol to ethylene and propylene at about 81% carbon selectivity. The
carbon selectivity approaches 92% if butenes are also accounted for as part of the product.
Typically, the ratio of propylene to ethylene can range from 0.6 to 1.3. When combined with
OCC（Olefin Catalytic Cracking）process to convert the heavier olefins, the overall yield of
ethylene and propylene can increase to 85%~87% and propylene-ethylene ratios of more
than 1.5 are achievable. Other co-products include very small amounts of C1-C4 paraffins,
hydrogen, CO and CO2, as well as heavier oxygenates only with ppm level.
Because of the quick deactivation of MTO catalyst, a kind of high efficiency fast fluidized
bed reactor is adopted. The activity of deactivated catalyst is recovered by burning the coke
in the regenerator.
This paper gives an updated introduction of S-MTO technology developed by SINOPEC
SRIPT .

Introduction
Light olefins such as ethylene and propylene are key components in the petrochemical
industry, which are widely used to make synthetic fiber, synthetic plastics and synthetic
rubber etc. Conventionally, the light olefins are produced by themal cracking of naphtha
consisting of C5-C12 alkanes which are from crude oil.
With the increase of crude oil price, the pursuit of new processes to produce light olefins
such as ethylene and propylene without using crude oil as feedstock is urgently neededAn
alternative way is the conversion of methanol to olefins (MTO). Because methanol can
readily be converted from coal, natural gas, or biomass via syngas,the process of MTO is
very promising and has aroused much attention within chemical industry1,2. In SINOPEC
Corporation, we have developed one MTO technology branded as S-MTO, which has been
commercialized in China.

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New Technologies and Alternative Feedstocks in Petrochemistry and Refining

The catalyst study

In order to improve the catalytic activity and ethene and propene selectivity, the catalyst
structure needs to be precisely controlled.

In the Fig.1(29Si MAS NMR), there is a strong line around -91ppm for both sample A and
B, which characterize Si(4Al) environment resulting from the substitution of a silicon atom for
phosphorus atom in SAPO-34(Substitution Mechanism II) 3. As for sample A, there are
signals around -95ppm,-100ppm and -110ppm which can be assigned to Si(3Al) , Si(2Al) ,
Si(4Si) respectively resulting from the synergistic effect of Substitution Mechanism II and
Substitution Mechanism III(two silicon atoms substitute for a pair of phosphorus and
aluminum atom)4. When mechanism II and III occur at the same time, it will form “silicon
island” in SAPO-34. Through the special synthesis system, we achieved the B molecular
sieve sample successfully, whose acidity is well controlled and has a better catalytic
performance.

A
-60 -70 -80 -90 -100 -110 -120 -130

Fig.1 29Si MAS NMR Spectra

There is general consensus that acidity, porosity and crystal morphology of zeolite
catalysts influence olefin diffusion ability, side reactions such as hydride transfer and coke
formation. Recently, using dry gel conversion technique, we synthesized SAPO-34 catalyst
with hierarchical porosity, which showed higher catalytic activity and stability than
conventional SAPO-34 for MTO reaction5.

Fig.2 A) SAPO-34 samples with various morphologies and porosity;

B) Yield of ethene and propene over various SAPO-34 catalysts.
We also examined SAPO-34 materials with various morphologies and porosity (Fig.2),
which demonstrated that small or lamellar crystals as well as the hierarchical porosity show
better catalytic performance. This is consistent with the kinetic Monte Carlo simulation
results, in which we also found that the diffusion of olefins in the pore of zeolites was very
sensitive to the morphology of zeolites and coke contents.

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New Tecchnologies and Alternativ
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We a also succee eded in increeasing the stability of zeolitic cattalysts by aadjusting the
e crystal
morpho ology and enhancing th he selectivitty of propylene by acid and poree modificatio ons6. As
for the studies on its chemic cal processs, we found d that maximum selecctivity of the e olefins
could bbe achieved d by balanc
ce control oof catalytic reaction an nd regenerration progrress, i.e.
control o
of its coking
g progress.

The Kinetics stu

udy

We stud e isothermal integral reaactor7. The lumping

died the kinetics of methanol to ollefins in the
idea wa as introducced into the kinetics study, in whichw the influence oof water an nd coke
depositiion was takken into connsideration. The equattions of kine etics on freesh and deaactivated
catalystt werecalculated. The obtained ge eneral kinettics equatio
ons could bbe used to calculate
c
the reaaction ratess of correspponding lum mp. Subse equently, the respectivve reaction rate of
ethylenee, propylene, butene inn any condiitions were calculated based on t he relation of ratios
between n olefins (e
ethylene/ pro
opylene and d propylene a reactionn temperatu
e/ butene) and ure. The
results sshowed thaat the error of statistica
al test and comparison n of calculaated values with the
experimmental valuees was in the allowable e range.

The lum
mp reaction kinetics equ
uations werre shown as
s follows:

The kine
etics equatiions thinking of deactivvation was shown
s as fo
ollows:

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New Technologies and Alternative Feedstocks in Petrochemistry and Refining

The performance of SMTO8

On the basis of laboratory research, in October 2007, SRIPT proceeded the 100
tons/day industrial test, and the results showed that the SMTO catalyst has high activity, high
selectivity and good hydrothermal stability.The methanol conversion reaches about 100%，
and the selectivity of (ethane+propene) is above 81%. These test results founded a good
technical basis for the design of large-scale MTO plants.

In October 2011, a commercial SMTO plant with capacity of 200 KTA in Puyang
Zhongyuan was started to run, and the qualified ethylene and propylene were achieved on
the day of start-up operation.
In the operation, because of the quick deactivation of MTO catalyst, a kind of high
efficiency fast fluidized bed reactor is adopted. The activity of deactivated catalyst is
recovered by burning the coke in the regenerator.
Up to now, Puyang Zhongyuan S-MTO plant has been operated steadily for more than
17 months. Results from the commercial plant show that S-MTO process converts methanol
to ethylene and propylene at about 81% carbon selectivity. The carbon selectivity
approaches 92% if butenes are also accounted for as part of the product. Typically, the ratio
of propylene toethylene can range from 0.6 to 1.3. When combined with OCC （ Olefin
Catalytic Cracking）process to convert the heavier olefins, the overall yield of ethylene and
propylene can increase to 85%~87% and propylene-ethylene ratios of more than 1.5 are
achievable. Other co-products include very small amounts of C1-C4 paraffins, hydrogen, CO
and CO2, as well as ppm levels of heavier oxygenates.

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