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. 19th World Petroleum Congress, Spain 2008 Forum 12: Progress in olefin production
World Petroleum Council 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) 19th WPC preprint paper. For delegate use only. Do not circulate. 19th World Petroleum Congress, Spain 2008 Forum 12: Progress in olefin production
World Petroleum Council 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
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World Petroleum Council 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
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World Petroleum Council 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
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World Petroleum Council 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. 19th WPC preprint paper. For delegate use only. Do not circulate. 19th World Petroleum Congress, Spain 2008 Forum 12: Progress in olefin production
World Petroleum Council 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
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World Petroleum Council 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. 19th WPC preprint paper. For delegate use only. Do not circulate. 19th World Petroleum Congress, Spain 2008 Forum 12: Progress in olefin production
World Petroleum Council
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
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World Petroleum Council
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
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Acetylene, the Principles of Its Generation and Use
A Practical Handbook on the Production, Purification, and Subsequent Treatment of Acetylene for the Development of Light, Heat, and Power