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Introduction
This whitepaper focuses on the issues concerning the shortage of propylene and its impact on the industry. Various feasible alternatives are discussed with a major emphasis on the production of GREEN propylene
100 80 60 40 20 2006 2007 2008 Ethylene 2009 2010 2011 2012 Propylene
The gap between propylene and ethylene prices have been widening since the beginning of 2006. The anticipated supply shortage of the monomer has been a major cause for the price difference, and demand from the polypropylene and other chemical sectors have been quite robust during this period.
Index
QuickFacts
Demand for propylene is expected to grow at an average annual growth rate of around 5% until 2015, and around 3% from 2015 to 2020, backed by demand from downstream derivatives such as polypropylene, acrylonitrile, acrylic acid, propylene oxide etc.
The supply demand gap has already started converging in the US and is expected to further tighten during the years to come. The propylene to ethylene price ratio has been on an increasing trend and the gap between the two is widening as propylene prices continue to rise. The impact of propylene prices are being felt on polypropylene prices and because of this many end-use segments are contemplating switching to either HDPE or polystyrene as possible substitutes.
Possible Solutions:
In the Asia-Pacific region where refineries still play a major role in the propylene production dynamics, FCC represents a major, growing share of the total propylene capacity. North American and European markets, at present, have a significant production of propylene from existing refineries, however, the lack of investment in new refineries and crackers leave no scope for improvement for the present scenario. In the Middle East, ethylene is given more importance than propylene and its downstream derivatives. Hence, massive ethane-crackers are being built for the major expansion of ethylene and other downstream products such as polyethylene. At present, about 5-10% of global propylene comes from purposive production techniques.
Since the steam cracker expansion cannot keep pace with the growth of propylene and polypropylene demand, various other alternatives need to be looked at for this purpose and on-purpose propylene technologies offer a solution. One basic approach, followed by many players in the industry, is to enhance the FCC unit operation. By modifying the zeolite catalyst and other operating conditions in existing FCC units, efficiency of the unit can be significantly improved, hence increasing the yield of propylene. The only disadvantage of this method is that the gasoline production is reduced significantly, i.e. by nearly 40% of the previous yield. Hence, when the gasoline demand is high, refiners will not be able to pump in the required quantities of gasoline into the market. Lummus and Honeywell are the major firms that are licensing their proprietary enhanced FCC technologies. There are other technologies coming up in the market that provides a more direct solution and is relatively independent of the current crude oil market situation. The technologies that are currently prevalent in the market are Propane Dehydrogenation, Olefin Metathesis and Methanol to Olefins.
QuickFacts
Nearly 30% of new crackers that were commercialized between 2003 and 2010, globally, were based on ethane and hence produce very little propylene.
The demand for MTO/MTP is robust in areas where there is an abundant availability of cheap feedstock such as natural gas and coal. Coal reserves of Russia, China and the US would prove to be the major hubs, going forward. However, the major stumbling block of a MTP is the humungous investment cost. A gasification unit that includes the production of syngas through coal, production of methanol through syngas and synthesis of propylene through methanol, together would cost close to 2 Billion USD. A coal gasification/gas reformation unit for the production of propylene would break even in about four years & six months for an annual capacity of around 600,000 MT, assuming it runs at around 80% operating rate.
QuickFacts
Sasol Technology has patented a heterogeneous auto metathesis process in which 1-butene is fed over a silica or tungsten catalyst. 2-butene is formed as a result of the isomerization of 1-butene, which further undergoes metathesis with the rest of the 1-butene, to produce propene and 2-pentene. 1-butene undergoes selfmetathesis to produce 3-hexene and ethylene. The ethylene formed undergoes metathesis with the 2-butenes and 2-pentenes to form more propene.
QuickFacts
Since the world might be heading to a shortage of propylene from conventional sources, more emphasis needs to be given to technologies that use renewable resources such as biomass.
Sugar Fermentation
Gasication
Econing
Gasication
Ethanol Dehydration
Butanol Dehydration
PDH
Recovery
Methanol Synthesis
Dimerization
Methanol to Propylene
Metathesis
Metathesis
Green P ropylene
Major Technologies:
There are two technology approaches for the production of green propylene. They are Biochemical and Thermo chemical. The biochemical approach employs biomass-based sugars for the synthesis of ethanol. Depending on the availability and the region, a variety of raw materials can be used for the fermentation process. Major commodities used for this purpose are corn starch, sugarcane, beet etc. Enzymes are used to convert the biomass into ethanol. Once the ethanol is obtained; they are processed and taken forward for the synthesis of olefins such as Ethylene and Butene, which further undergoes metathesis for the synthesis of propylene. CH2=CH2 + CH3CH=CHCH3 2 CH3CH=CH2 Ethylene Butene Propylene Ethanol Dehydration (post the processing of corn) and Butanol Dehydration (Biomass) can be considered as two possible solutions for the synthesis of green propylene. The thermo chemical technologies tend to use assorted materials as feedstocks that primarily include biomass (grass, agricultural wastes, and corn). These carbon rich materials undergo a gasification process in gasifiers for the production of syngas. The obtained syngas undergoes further processing for the production of methanol (Mega Methanol is used for this purpose, to achieve better process economics) and then MTP is employed for the synthesis of propylene. Bio-diesel and vegetable oils can be used for the production of green propylene as well. Bio-diesel is produced as a byproduct of vegetable oil, and propane gas is produced as a by-product of bio-diesel. This type of propane gas is called bio-propane and the propane is sent through a Propane Dehydrogenation Unit for the production of propylene.
Technology Integration:
Many companies are trying to integrate both the technologies. Combining the biochemical and thermo chemical processes, would help in achieving greater efficiency in terms of raw material usage. Sugar or starch, depending on the feedstock employed, can be fermented into ethanol and the remaining cellulosic parts like sugarcane bagasse or corn straw can be gasified for the production of syngas. Ethanol and syngas can then be used for the synthesis of propanol, which can be dehydrated for the synthesis of propylene. However, this technology combination has not yet been commercialized and is still under development. Once commercialized, this might be the best technology around, since there would be very little raw materials that are wasted and the output of propylene would be significantly higher. The other advantage of this combination is that, there is always a choice for the feedstock switch whenever a shortage is witnessed in one of the kind.
Biomass
P ropylene
Sugar / Starch
Sugar Fermentation
Cons
The usage of sugarcane/corn/wheat etc. for the production of chemical products results in a decrease in the availability of the staple food in those regions. The initial investment cost is slightly on the higher side as new facilities need to be set up for the synthesis of methanol from sugarcane, corn, sugar beet etc. The companies dealing with green propylene need to be completely backward integrated, to achieve greater efficiencies and reduce external dependency. Green propylene is effective only in areas that have an abundant supply of the feedstock, for example, if a green propylene plant is based on corn, the in-house capacity of corn must be high so that, the plant does not depend on imports for their raw material supply.
Results Achieved/Expected
intention from renewable feed is expected to be
During the first quarter of 2011, Dow A project for the production of propylene, to study and explore methods, for the announced in the near future. However, the production of their key feedstock, from exact route has not yet been finalized and as renewable resources. Dow Chemical of date, an array of raw materials is being is already involved in a project for the studied as a possible long term feedstock. production of ethylene and polyethylene, The location of the project has not yet been by using sugarcane ethanol in Brazil. Dow closed on and Brazil seems to be an open Chemicals R&D team is currently in the option. The assignment may be based either process of investigating various technology on ethanol or the gasification of biomass. routes for the manufacture of propylene and Dow Chemical also plans to develop second its downstream derivatives such as acrylic generation ethanol technologies. Usage of acid and other acrylates. More emphasis is bagasse and sugarcane waste would be their being given to propylene than on PP, since first priority. PP is relatively more commoditized and also since Dow has completely come out of the PP business.
DOW
Brazilian giants, Braskem have come up with The basic foundation of the project has the concept of using sugarcane ethanol for already been laid and the feasibility analysis the production of propylene. The essence of has already been done. Constructional the project was for the production of green activities are currently underway, which polypropylene. The green polypropylene reportedly began during early 2012; and would be produced at one of its plants that by the end of 2013 or early 2014, the use the Spheripol technology. The main commissioning of the plant is expected. aim of the project was to develop products This would be a small scale plant and the using the principles of low-carbon economy. capacity is expected to be around 30,000 Braskem has already demonstrated its MT/yr. The total investment for the venture capabilities on the green side, by installing a is expected to be at around $100 Million. sugarcane ethanol based ethylene plant for the production of green polyethylene at its site located in Triunfo, Brazil. Many major end-use consumers have already struck deals with Braskem for the supply of green PE; the most notable which include P&G, Tetra Pack and Shisiedo.
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Braskem
Conclusion
Earlier, the production economics of most alternate processes, based on sustainable and renewable materials, seemed completely out of scope and impossible, however, as the world might be witnessing a shortage of the most commonly used material, these alternate processes are bound to spring into action to cater to global demand. More emphasis needs to be given on green production techniques, so as to reduce dependence on the crude oil market and also reduce the amount of carbon emissions. Production of green propylene can be economically viable and a suitable option for many players in the segment dealing with propylene and its other downstream derivatives. However, for someone entering into this segment, it is extremely important to have a clear understanding of the market situation, based on a careful analysis of its limitations, by narrowing down on geographical locations and most important of all, the selection of the technology; to avoid strategic and economic losses. Though the production of propylene through the green route is relatively more expensive than the conventional method, green propylene provides long term advantages in terms of sustainability and emission control. In the green MTO process, over 75% of total energy required is biomass derived and this constitutes negative emissions. In the Sugarcane MTO process, in addition to utilizing biomass derived energy, the sugarcane plant co-generates electricity, and therefore it is a net energy producer resulting in negative emissions for fossil fuel. Green production techniques are for the future and by the end of 2020, the world will witness a paradigm shift that would be relatively independent of the wicked crude oil market.
References:
http://green-plastics.net/discussion/53-general/111-shades-of-green http://www.innovativeindustry.net/bioplastics-go-commercial-green-polypropylene-from-sugarcane http://biopol.free.fr/index.php/a-new-unit-to-produce-green-polypropylene-from-sugarcane
Disclaimer: Strictly no photocopying or redistribution is allowed without prior written consent from Beroe Inc. The information contained in this publication was derived from carefully selected sources. Any opinions expressed reflect the current judgment of the author and are subject to change without notice. Beroe Inc accepts no responsibility for any liability arising from use of this document or its contents.
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