New Olefin Production Technologies in SINOPEC

19th World Petroleum Congress, Spain 2008
Forum 12: Progress in olefin production

World Petroleum Council
New olefin production technologies in SINOPEC
SRIPT

Mr Jiawei Teng, SINOPEC, China

Mr Rongwei Wang, SINOPEC, China
Mr Zaiku Xie, SINOPEC, China
Mr Yongsheng Gan, SINOPEC, China

Abstract
It is widely recognized that naphtha steam crackers and fluid catalytic cracking (FCC) units
are the main current sources of ethylene and propylene. On the condition of high crude oil
price, olefin producers are striving to develop new economical routes to produce ethylene and
propylene with low-cost feed stocks.

As is the case today, the new olefin production is projected to come from a number of
sources, which are methanol based, biological materials based or olefinic streams based.

SINOPEC SRIPT has developed a number of new olefin production technologies, these
alternatives can be categorized into the following three groups: <br>
Natural Gas or Methanol to Olefins (MTO and MTP)
Biological Ethanol to Olefins (ETO)
Olefin Conversion (Olefin Cracking and Metathesis)

Each of these alternatives can be the competitive route to ethylene and propylene in certain
situations. This paper provides an update from SINOPEC SRIPT on the latest development in
these technologies as well as a comparison of these alternatives. SINOPEC has the
technologies and experience to help you determine which routes to ethylene and propylene fit
your opportunities.

19th WPC preprint paper. For delegate use only. Do not circulate.

INTRODUCTION

Ethylene and propylene are the most important basic organic products. Almost all the
ethylene is supplied from thermal steam cracking of hydrocarbon feedstocks (primarily
naphtha and ethane). And the supply of propylene is more diversified than that of ethylene, as
shown in Figure 1. The naphtha steam cracking process is the main propylene source with
about 65% share in the primary production. Propylene could also be generated in FCC units,
increased production of light olefins directly from the FCC unit has been achieved through
changes in operations, base faujasite cracking catalyst and additive catalysts, and in
hardware design.
On the condition of high oil price, what is the best way to produce ethylene and propylene?
Olefin manufacturers are seeking cost effective options to increase the ethylene and
propylene production. There are more options available today than ever before for the
production of olefins, especially for the production of propylene. Each of these routes can
offer competitive economics in certain situations. Most importantly for a particular olefin
manufacturer is to understand how to select the right routes.

NEW OLEF

PRODUCTION TECHNOLOGIES DEVELOPED BY SINOPEC SRIPT

SINOPEC SRIPT has developed a number of new olefin production technologies, these
alternatives can be categorized into the following three groups:
Natural Gas or Methanol to Olefins (MTO and MTP)
Biological Ethanol to Olefins (ETO)
Olefin Conversion (Olefin Catalytic Cracking and Metathesis)
There are two types of methanol-to olefins (MTO) processes available. The first is the S-MTO,
which converts methanol to ethylene and propylene at 80% carbon selectivity in a fluidized
bed reactor. The second is a methanol-to-propylene (MTP) process, which produces
propylene.
METHANOL TO OLEFINS (MTO)

S-MTO Process (Figure 2) was developed by SINOPEC for selective production of ethylene
and propylene from methanol. The catalyst used in the process is based on a
silicoaluminophosphate, SAPO-34, which has very high carbon selectivity to lower olefins. An
industrial demonstration plant, which scale capacity is 100 tons methanol per day, was built
and stared up in 2007 in China. The experimental results show that S-MTO Process converts
methanol to ethylene and propylene at above 80% carbon selectivity in a fluid bed reactor
with continuous regeneration. The carbon selectivity approaches 90% if butenes are also
accounted for as part of the product. Other co-products include very small amounts of C
1
-C
4

paraffins, hydrogen, CO and CO
2
, as well as ppm levels of heavier oxygenates.
Figure 1 Propylene Supply in 2005 (Source: CMAI 2006)

Coke accumulates on the catalyst and must be removed to maintained catalyst activity. The
catalyst activity is maintained by continuous transfer of coked catalyst from the reaction
section to the regeneration section where the coke is burned with air.
Example results of tests performed in the fluid bed reactor with continuous regeneration
showed that variations in propylene-ethylene ratios are possible depending on catalyst
composition and operating conditions. Typically, the ratio of propylene- ethylene can range
from 0.6 to 1.3. When combined with the SINOPEC Olefin Catalytic Cracking process (to be
discussed later) to convert the heavier olefins, the overall yield of ethylene and propylene
increase to over 85% and propylene- ethylene ratios of more than 1.5 are achievable.

METHANOL TO PROPYLENE (MTP)

Methanol to Propylene (MTP) process was developed for selective production of propylene
from methanol. The catalyst used in the process is based on a proprietary SINOPEC ZSM-5
catalyst, which has very high carbon selectivity to propylene. Typical results show that MTP
process converts methanol to propylene at 40-50% carbon selectivity in a fixed-bed reactor
for single pass. The carbon selectivity approaches 65-70% if co-product hydrocarbons are
recycled. Other co-products include gasoline and very small amounts of C
1
-C
4
paraffins.
After a cycle approximately 600-800 hours of operation, the catalyst has to be regenerated by
burning coke with a nitrogen/air mixture. Catalyst regeneration is done in-situ. Nitrogen and
amount of air are mixed and introduced into the reactor to burn the coke deposits on the
catalyst. The regeneration is carried out at temperatures similar to the reaction itself, hence
the catalyst particles do not experience any temperature stress during the in-situ catalyst
regeneration procedure.
BIOLOGICAL ETHANOL TO OLEFINS (ETO)

SINOPEC ETO (S-ETO) process (Fig.3) was developed for selective production of ethylene
from biological ethanol. A number of catalysts are effective in promoting the reaction;
activated alumina and silica-alumina, are the most efficient catalysts in the reaction. The
activated alumina catalyst developed by SRIPT SINOPEC has very high carbon selectivity to
ethylene. Typical results show that ETO process converts ethanol to ethylene at 97% carbon
selectivity in a fixed-bed reactor, and the conversion of ethanol is over 99% for single pass.
Other co-products include very small amounts of C4 hydrocarbon, propylene and ethane.
Moreover, Coking tendency is suppressed efficiently, so no continuous catalyst regeneration
is required, and the catalyst cycle time is over one year.
The dehydration of ethanol to ethylene is a strong endothermic reaction, the temperature
control is important, since low temperature result in the presence of ether in the reactor
Figure 2 SINOPEC S-MTO Process


product and high temperature produce aldehydes. Temperatures in the range of 340-390
are suitable for the activated alumina catalyst
Compared with the other olefins production routes, the catalytic dehydration of ethanol to
olefins is a simple process, and S-ETO process gives very high carbon selectivity to ethylene,
only very small amounts of co-products was produced, so it does not require the sale or
utilization of co-products.

OLEFIN CATALYTIC CRACKING (OCC)

SINOPEC SRIPT has developed a process that allows high selective production of propylene
and ethylene by conversion of low value by-product streams containing C
4
/C
5
olefins from
crackers and refineries. Figure 4 depicts the reaction scheme of OCC. Low value olefins from
steam crackers or and refineries were catalytic cracked into propylene and ethylene on a
shape selective ZSM-5 type zeolite catalyst at the temperature of 500-600.

A simplified process flow diagram of OCC unit is shown in Figure 5. The liquid feedstock
containing olefins is vaporized and further heated
against the reactor effluent and in a fired heater
before entering the fixed-bed reactor. The effluent
from the reactor is cooled and compressed to do
further separation. Most of C
4
fraction is recycled to the OCC reactor to increase the total
propylene and ethylene yield. Part of the C
4
fraction is purged to avoid the accumulation of
paraffins in the system. The C
5
+
fraction is cut to further process as pyrolysis gasoline.
Separation facilities depend on how the unit is integrated into the processing system.

Cracker C
4
/C
5
FCC C
4
/C
5
FCC Gasoline
Ethylene
Propylene
Ethanol Waste
Water
Waste
Alkaline
Heavy
Ends
Ethylene
Product
Light
Ends
Water
Scrubber
Alkaline
Wash
Ethylene
Column Stripper
Purge
Reactor
Fired Heater
Olefin feed
C4 Recycle
C
5
+
Depropanizer Debutinizer
Light olefins
Figure 5 Process Flow Diagram of OCC Unit

Figure 3 Biological Ethanol to Olefins Process

Figure 4 Reaction Scheme of OCC


The OCC (Olefins Catalytic Cracking) process features fixed-bed adiabatic reactors operating
at temperatures 500-600 and pressures 0.1-0.2MPa. The main characteristic of OCC is that no
inert diluent is added into the system, at the same time, the catalyst can be operated at very
high space velocities. Accordingly, the reactor size and operating costs are minimized
notably.
The OCC process utilizes a proprietary ZSM-5 zeolite catalyst developed by SRIPT
SINOPEC. In the optimized process conditions, typically 28-30wt% propylene and 8-10wt%
ethylene are obtained in pilot plant for per pass. If the produced butylenes are recycled,
propylene yield can be increased to 45wt. % and ethylene yield can be increased to 12wt. %.
Other co-products include gasoline and very small amounts of C
1
-C
4
paraffins.
A swing reactor system is used for catalyst regeneration, catalyst regeneration is done in-situ.
Nitrogen and small amount of air are mixed and introduced into the reactor to burn the coke
deposits on the catalyst.
The catalyst exhibits little sensitivity to common impurities such as diolefins, sulphur
compounds and nitrogen compounds.

OLEFIN METATHESIS TECHNOLOGY (OMT)

The Olefin Metathesis Technology (OMT) from SINOPEC is used to combine n-butenes with
ethylene to produce polymer-grade propylene. Two chemical reactions take place: propylene
is formed by the metathesis of ethylene and butene-2; and butene-1 is isomerized to butene-2
as butene-2 is consumed in the metathesis reaction. OMT greatly enhances an excellent co-
product flexibility of cracker. When integrated with a grassroots steam cracker, the ratio of
propylene to ethylene can increase from the typical 0.5 to greater than 1.0. As propylene
demand continues to grow, the impact of OMT (Figure 6) in existing or grassroots ethylene
and/or refinery applications becomes evident.
The catalyst (WO
3
/SiO
2
and MgO) promotes the reaction of ethylene and butene-2 to form
propylene, and simultaneously isomerizes butene-1 to butene-2. The per-pass conversion of
butene is greater than 70%, with overall selectivity to propylene exceeding 95%. The product
from the metathesis reactor is primarily propylene and unreacted feed, the co-product include
very small amount of C
5
and C
6
olefins.
A small amount of coke is formed on the catalyst, so the beds are periodically regenerated
using nitrogen diluted air. Typically, the catalyst cycle time approaches 900 hours.
Purge
Reactor
C4 feed C4 Recycle
Ethylene
Colum
Ethylene
Recycle Ethylene
Propylene
Colum
Propylene
Purge
Guard Bed
Figure 6 OMT Process Flow Diagram


COMPARISONS OF NEW OLEFIN PRODUCTION ROUTES

Several factors must be considered when selecting a new olefin production routes. Process
economics are always an important factor, but on the condition of high oil price, each of the
abovementioned alternatives can be the competitive route to ethylene and propylene in
certain situations. Most importantly for a particular olefin manufacturer is to understand how to
select the right routes. The key factors to consider include:
Feedstock availability and cost
Olefins yield and co-product distribution
Applications
The key factors are compared between each of the alternative routes to olefins below.

FEEDSTOCKS

In the process of producing light olefins, the most significant component of the costs of
production is the cost of raw materials. The ability to effectively utilize a secure source of low-
cost feedstock is the most important factor in competitiveness, especially on the condition of
high crude oil price. Identifying the feedstocks that are available can greatly help narrow the
choice of the various routes.
One of main character of new olefin production technologies in SINOPEC SRIPT is the
diversity of raw materials. The feedstock for the abovementioned routes to producing ethylene
and propylene can be categorized into the following three groups:

Coal or natural gas based methanol (MTO, MTP)
Biology based ethanol (ETO)
C4 olefins from ethylene plant and/or refinery (OCC, OMT)

The proven reserve life time for coal is about 230 years, and the proven natural gas reserves
to production ratio, i.e. lifetime is about 100 years for Africa and 260 years for the Middle
East. Compared with the reserve lifetime of 41years for petroleum, there is no doubt that coal
and natural gas will be a key fuel component in the 21
th
century. In recent years, the Mega-
Methanol process for plants with a production of 5000 tons of methanol per day has made
great progress, methanol will be available at a constant low price in the foreseeable future. In
some areas of the world have abundant supplies of coal or natural gas but have very limited
local demand for its use, in those locations, the local price of coal or natural gas is very low.
This offers opportunities to access low-cost coal or natural gas for other applications such as
ethylene and propylene production via methanol combined with methanol to olefins (MTO,
MTP).
The feedstocks for ETO derive from local agricultural sources and thus avoid balance of
payment. Compared with the unrenewable fossil raw material, the feedstocks for biological
ethanol include corn, sugarcane, sugar beet, plant stalk etc. are renewable.
The OCC process can operate with different feedstocks, especially those feeds that are
available from steam crackers and refineries, the favourable feedstocks are as follows:

FCC or Coker C
4
Olefins
FCC C
5
Olefins
FCC gasoline
Steam cracking C
4
Olefins (Butadiene extraction or Selective hydrogenation)
C
4
Olefins from MTBE synthesis (FCC or Steam Cracker)
The mixture of the above hydrocarbons

In a word, the feedstock of OCC process is very flexible. There are several constrains for the
feedstock of OCC process with respect to purity and composition. Feedstocks containing high
or low concentrations of olefins can be processed. Naturally, feedstocks with higher olefins
content are more favourable. Paraffins, cycloalkanes, cycloalkenes and aromatics maybe
present in the feedstocks, these compounds are considered as non-convertibles. However,
the feedstock should be controlled to less than 1.0wt% of diolefins, these components are
contributed to coke formation.

The OMT is used to combine n-butenes with ethylene to produce polymer-grade propylene,
so the feedstocks for OMT include n-butenes and ethylene. The OMT can be used with a
variety of C
4
streams including the mixed C
4
s produced in stream cracking, raffinate C
4
s from
MTBE or butadiene extraction, and C
4
s produced in FCC units. The ethylene stream can very
from dilute ethylene typical from an FCC, to polymer-grade ethylene. Based on the reaction
stoichiometry, three tons of propylene is produced from two tons of butylenes and one ton of
ethylene.
OLEFINS YIELD AND CO-PRODUCTS

Each of the abovementioned routes to ethylene and propylene produces a different mixture of
products (Figure 7). Comparing co-product relative to the amount of ethylene and propylene
helps olefin producers to determine the best routes to light olefins.

MTO/MTP
MTO Process converts methanol to ethylene and propylene at about 80% carbon selectivity
with only about 0.15 tons of C
4
+
co-products per ton of light olefins. Moreover, the ratio of
propylene- ethylene can be adjusted in a broad range. This offers opportunity to adjust the
MTO product mixture when the ethylene/propylene market price changes and thereby
maximize profitability.
When combined with the SINOPEC OCC (Olefin Catalytic Cracking) process to convert the
heavier olefins, the overall yield of ethylene and propylene increase to over 85% and C
4
+
co-
products can be effectively eliminated, the product marketing is completely focus on the light
olefin or its derivatives.
MTP process converts methanol to propylene at about 65-70% carbon selectivity if co-product
hydrocarbons are recycled, and the main co-products is gasoline, MTP produces 0.3 tons of
gasoline for one ton of propylene produced. One of the unique features of MTP is its single
propylene product as compare with MTO, so its downstream PP plant is easy to have world
scale capacity.
ETO
One of the unique features of ETO is its 97% selectivity to ethylene. ETO offers very high
selectivity to ethylene with only about 0.03 tons of C
4
and fuel gas co-products per ton
ethylene. So it is not necessary for olefins producer to consider the utilization of the co-
products. The single feed, single product feature of ETO is one of the most attractive aspects
of this option, especially for the producer in an area where public policy encouraged the
development of a chemical industry based on local agricultural sources.
OCC
Olefin Catalytic Cracking (OCC) produces about 0.2tons of ethylene and 0.8 tons of
propylene for every ton of light olefin produced. The main co-product includes C
4
hydrocarbon
and C
5
+
gasoline. When integrated into an ethylene plant the C
4
hydrocarbon is well suited for
Figure 7 Olefins and Co-products Distribution


recycle to the furnaces to further enhance the light olefin yields, this allows stream cracker to
reduce the amount of naphtha feed and maintain the light olefin capacity at the same time.
The C
5
+
gasoline can be further processed as pyrolysis gasoline to increase the production of
BTX.
OMT
The Olefin Metathesis Technology (OMT) is a true on-purpose propylene producer and it
offers very high selectivity to propylene, the overall selectivity to propylene exceeds 95%. The
co-products include very small amount of C
5
and C
6
olefins.

APPLICATIONS

The abovementioned routes to light olefins offer a wide variety of opportunities to produce
ethylene and propylene. Each of these alternatives can be the best route to light olefins in
certain situations. Most importantly for a particular olefin manufacturer is to understand how to
select the right routes.
MTO/MTP
MTO and MTP are driven by the desire to utilize natural gas or coal and the market demands
for ethylene and propylene. Natural gas or coal prices are generally independent of crude oil
and naphtha market prices, so MTO and MTP provides another means for olefin producers to
diversity the cost structure for their feedstocks. MTO and MTP can provide much lower costs
of production and higher returns on investment than oil based routes on the condition of high
crude oil price.
MTO and MTP process may benefit from economies of integration with mega-methanol
production processes. First, the amount of methanol required for an MTO or MTP project is
consistent with the methanol production from the latest mega-methanol plant (5000 t/d
methanol or more). Second, the use of crude methanol directly from the methanol converter
may eliminate the need for the usual fractionation requirements for producing chemical grade
or fuel grade methanol. Typical commercial methanol specifications limiting DME co-product
production may become less of a factor in methanol converter design and operating
conditions, which may lead to further methanol production economies.
Perhaps the optimum integration option would be the location of an entire mega-
methanol/MTO or MTP/PE or PP production complex in the vicinity of a natural gas or coal
production location. This may be particularly advantageous for extremely remote locations
where transportation conditions may limit the desirability of any products other than the solid
polyethylene or polypropylene products.
ETO
The Ethanol to Olefin (ETO) is a true on-purpose ethylene alternative which is based on local
agricultural sources. As compared with hydrocarbon pyrolysis, it is a simple process, it can
utilize a local produced feedstock derived from agricultural sources and thus avoid balance-
of-payment problems, it is suitable for small-scale installation, and it does not require the sale
or utilization of co-products. ETO is of interest in some locations, where there are abundant
agricultural sources and government incentives are provided to reduce dependence on
imported hydrocarbons.
OCC
The OCC process was developed to utilize low value by-product streams containing olefins
from steam crackers and refineries.
Steam Cracker Integration
There are several possible integration schemes for an OCC unit into a steam cracker. The
simplest option is that product separation is done completely at the ethylene plant. The
integration scheme is shown in Figure 8.


C
4
stream from butadiene extraction or Selective hydrogenation or MTBE synthesis units are
fed into the OCC unit. The effluent from the reaction section is processed by the separation of
the ethylene plant. To avoid the accumulation of paraffins in the system, part of the C
4
fraction
is purged in the option. This integration maybe the most economic solution for a new-building
plant, where additional capacity required separating the effluent from OCC unit can be
reserved in the ethylene plant. Therefore, no independent separation system for OCC unit is
needed to build.
Another option features integrating OCC unit with its own separation system. Only C
3
-
or C
2
-

fraction is processed by the separation system of ethylene plant. The option is favourable for
an existing ethylene plant, where the additional capacity is limited.
Refinery Integration
The refinery integration scheme is shown in Figure 9. The OCC converts C
4
fraction or
cracking gasoline to desirable light olefins, mostly propylene and ethylene. The volume of
olefins in the gasoline stream is lowered from 45% to 15%, at the same time, the octane
number is improved at least retained due to a mount of aromatics formed.

Figure 8 Steam Cracker Integration



OMT
OMT is generally economical when propylene is valued
higher than or equal to ethylene, though approximately 0.33
tons of ethylene are consumed per ton of propylene
produced, 0.67 tons of low-valued C
4
olefins are converted to high-valued propylene per ton
of propylene produced. OMT unit can be integrated with a steam cracker or a refinery.
OMT combined with a steam cracker can significantly vary the propylene-to-ethylene product
ration and improve overall plant flexibility and economics. Typical steam crackers with liquid
feedstocks operate with a propylene-to-ethylene ratio range of 0.45-0.65, depending on
cracking severity. If butadiene in not required as a product, it can be selectively hydrogenated
to butenes to provide additional butylenes feed for metathesis. The steam cracker/OMT
combination can result in propylene-to-ethylene ratios exceeding 1.0 as determined by the
quantity of butylenes available.
FCC unit profitability is significantly enhanced by operating at higher propylene production
rates. A low cost, reliable ethylene recover system is needed, and then ethylene recover
followed by butylenes/ethylene metathesis to propylene can improve overall FCC plant
economics.
SUMMARY

On condition of high crude oil price, the new olefin production technologies, which are
methanol based, biological materials based or olefin streams based, offer a wide variety of
opportunities for olefins producer to produce ethylene and propylene. Each of these routes
can offer competitive economics in certain situations. Most importantly for a particular olefin
manufacturer is to understand how to select the right routes. SINOPEC has the technologies
and experience to help you determine which routes to ethylene and propylene fit your
opportunities.

Figure 9 Refinery Integration


New Olefin Production Technologies in SINOPEC

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19th World Petroleum Congress, Spain 2008

Forum 12: Progress in olefin production

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