Linear alpha olefin
Encyclopedia
Linear Alpha Olefins or Normal Alpha Olefins (NAO) are olefins or alkene
s with a chemical formula
C
xH
2x, distinguished from other mono-olefins with a similar molecular formula by linearity of the hydrocarbon
chain and the position of the double bond
at the primary or alpha position.
Linear alpha olefins are a range of industrially important alpha-olefins, including 1-butene
, 1-hexene
, 1-octene
, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and higher blends of C20-C24, C24-C30, and C20-C30 ranges.
and by Fischer-Tropsch synthesis followed by purification. Another route to linear alpha olefins which has been used commercially on small scale is dehydration
of alcohols. Prior to about the 1970s, linear alpha olefins were also manufactured by thermal cracking of waxes, whereas linear internal olefins were also manufactured by chlorination
/dehydrochlorination of linear paraffins.
There are seven commercial processes which oligomerize ethylene
to linear alpha olefins. Five of these processes produce wide distributions of linear alpha olefins. These are the Ethyl Corporation
(Ineos
) process, Gulf
(Chevron Phillips Chemical Company), Shell Oil Company
SHOP
process, the Idemitsu Petrochemical process and the SABIC
-Linde
α-Sablin process.
The newest commercial linear alpha olefin process is the Sabic-Linde α-Sablin process, commercialized by SABIC
in Saudi Arabia. The α-Sablin process is a low-pressure ethylene oligomerization process conducted over heterogeneous catalyst in a slurry bed. The process also makes a C4-C20+ distribution of alpha-olefins. Sabic announced the commercialization of a 150,000 metric tons per year plant using the α-Sablin process at their Jubail
plant on the Gulf coast of Saudi Arabia in 2009. The plant construction was managed by Linde’s subsidiary Linde-KCA-Dresden GmbH, Germany.
Two commercial processes make a single alpha-olefin carbon number. Phillips
(CP Chemical Company) ethylene trimerization process, produces only 1-hexene. Another commercial process, offered by a technology licensor IFP
, dimerizes ethylene to high purity 1-butene.
There are two alpha-olefin processes that have not been commercialized as of Q2, 2010. One is an ethylene oligomerization to a wide range of linear alpha olefins technology being offered by a technology licensor UOP
. The other is the DuPont
Versipol technology. To date, no commercial plants have been built using either UOP or DuPont's technology.
The only commercial process to isolate linear alpha olefins from synthetic crude is practiced by Sasol
Ltd., a South African oil and gas and petrochemical company. Sasol commercially employs Fischer-Tropsch synthesis to make fuels from synthesis gas derived from coal and recovers 1-hexene from these fuel streams, where the initial linear alpha olefin concentration in a narrow distillation
cut may be 60%, with the remainder being vinylidenes, linear and branched internal olefins, linear and branched paraffins, alcohols, aldehyde
s, carboxylic acid
s and aromatic compounds.
Dehydration of alcohols to linear alpha olefins by passing alcohols in a vapor phase over acidic alumina catalyst has been practiced periodically by Ethyl Corporation (later BP, now Ineos), Chevron Phillips, Sasol (formerly Vista Chemical) and Godrej Industries Ltd
, an Indian petro- and specialty chemical company. Normally, this process is not economical as the linear fatty alcohols are more valuable than the corresponding linear alpha olefins. However, the process has been applied whenever the value of fatty alcohols dipped below that of linear olefins because of market dynamics or regional supply-demand issues.
One of the problems of the linear alpha olefin industry is the wide range of products made by most of the processes. While the Ethyl process makes a Pseudo-Poisson distribution of products, most others, including the Sasol process, make a Schultz-Flory distribution. With 8-10 products being made at the same time, with most of them sold into different markets with different dynamics, it is difficult to balance the supply and the demand for all or even most products.
Another significant use of C4-C8 linear alpha olefins is for production of linear aldehyde
via oxo synthesis (hydroformylation
) for later production of short-chain fatty acid
, a carboxylic acid, by oxidation of an intermediate aldehyde, or linear alcohols for plasticizer
application by hydrogenation
of the aldehyde.
The predominant application of 1-decene is in making polyalphaolefin synthetic lubricant
basestock (PAO) and to make surfactant
s in a blend with higher linear alpha olefins.
C10-C14 linear alpha olefins are used in making surfactants for aqueous detergent formulations. These carbon numbers may be reacted with benzene to make linear alkyl benzene
(LAB), which is further sulfonated to linear alkyl benzene sulfonate (LABS), a popular relatively low cost surfactant for household and industrial detergent applications.
Although some C14 alpha olefin is sold into aqueous detergent applications, C14 has other applications such as being converted into chloroparaffins. A recent application of C14 is as on-land drilling fluid
basestock, replacing diesel or kerosene
in that application. Although C14 is more expensive than middle distillates, it has a significant advantage environmentally, being much more biodegradable and in handling the material, being much less irritating to skin and less toxic.
C16 - C18 linear olefins find their primary application as the hydrophobes in oil-soluble surfactants and as lubricating fluids themselves. C16 - C18 alpha or internal olefins are used as synthetic drilling fluid base for high value, primarily off-shore synthetic drilling fluids. The preferred materials for the synthetic drilling fluid application are linear internal olefins, which are primarily made by isomerizing linear alpha-olefins to an internal position. The higher internal olefins appear to form a more lubricious layer at the metal surface and are recognized as a better lubricants. Another significant application for C16 - C18 olefins is in paper sizing. Linear alpha olefins are, once again, isomerized into linear internal olefins are then reacted with maleic anhydride
to make an alkyl succinic anhydride(ASA), a popular paper sizing
chemical.
C20 - C30 linear alpha olefins production capacity is only 5-10% of the total production of a linear alpha olefin plant. They are used in a number of reactive and non-reactive applications, including as feedstocks to make heavy linear alkyl benzene
(LAB) and low molecular weight polymers which are used to enhance properties of waxes.
Alkene
In organic chemistry, an alkene, olefin, or olefine is an unsaturated chemical compound containing at least one carbon-to-carbon double bond...
s with a chemical formula
Chemical formula
A chemical formula or molecular formula is a way of expressing information about the atoms that constitute a particular chemical compound....
C
Carbon
Carbon is the chemical element with symbol C and atomic number 6. As a member of group 14 on the periodic table, it is nonmetallic and tetravalent—making four electrons available to form covalent chemical bonds...
xH
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
2x, distinguished from other mono-olefins with a similar molecular formula by linearity of the hydrocarbon
Hydrocarbon
In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons from which one hydrogen atom has been removed are functional groups, called hydrocarbyls....
chain and the position of the double bond
Double bond
A double bond in chemistry is a chemical bond between two chemical elements involving four bonding electrons instead of the usual two. The most common double bond, that between two carbon atoms, can be found in alkenes. Many types of double bonds between two different elements exist, for example in...
at the primary or alpha position.
1-Butene
1-Butene is an organic chemical compound, linear alpha-olefin , and one of the isomers of butene. The formula is .-Stability:1-Butene is stable in itself but polymerizes exothermically. It is highly flammable and readily forms explosive mixtures with air...
, 1-hexene
1-Hexene
1-Hexene is an organic compound with the formula CH2CHC4H9. It is an alkene that is classified in industry as higher olefin and an alpha-olefin, the latter term meaning that the double bond is located at the alpha position, endowing the compound with higher reactivity and thus useful chemical...
, 1-octene
1-Octene
1-Octene is an organic compound with a formula CH2CHC6H13. The alkene is classified as a higher olefin and alpha-olefin, meaning that the double bond is located at the alpha position, endowing this compound with higher reactivity and thus useful chemical properties. 1-Octene is one of the...
, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and higher blends of C20-C24, C24-C30, and C20-C30 ranges.
Overview
Industrially, linear alpha olefins are commonly manufactured by two main routes: oligomerization of ethyleneEthylene
Ethylene is a gaseous organic compound with the formula . It is the simplest alkene . Because it contains a carbon-carbon double bond, ethylene is classified as an unsaturated hydrocarbon. Ethylene is widely used in industry and is also a plant hormone...
and by Fischer-Tropsch synthesis followed by purification. Another route to linear alpha olefins which has been used commercially on small scale is dehydration
Dehydration reaction
In chemistry and the biological sciences, a dehydration reaction is usually defined as a chemical reaction that involves the loss of water from the reacting molecule. Dehydration reactions are a subset of elimination reactions...
of alcohols. Prior to about the 1970s, linear alpha olefins were also manufactured by thermal cracking of waxes, whereas linear internal olefins were also manufactured by chlorination
Chlorination
Chlorination is the process of adding the element chlorine to water as a method of water purification to make it fit for human consumption as drinking water...
/dehydrochlorination of linear paraffins.
There are seven commercial processes which oligomerize ethylene
Ethylene
Ethylene is a gaseous organic compound with the formula . It is the simplest alkene . Because it contains a carbon-carbon double bond, ethylene is classified as an unsaturated hydrocarbon. Ethylene is widely used in industry and is also a plant hormone...
to linear alpha olefins. Five of these processes produce wide distributions of linear alpha olefins. These are the Ethyl Corporation
Ethyl Corporation
Ethyl Corporation is a fuel additive company headquartered in Richmond, Virginia. The company is a manufacturer, blender and distributor of fuel additives...
(Ineos
Ineos
INEOS Group Limited is a privately owned multinational chemicals company headquartered in Lausanne, Switzerland and with its registered office in Lyndhurst, United Kingdom...
) process, Gulf
Gulf Oil
Gulf Oil was a major global oil company from the 1900s to the 1980s. The eighth-largest American manufacturing company in 1941 and the ninth-largest in 1979, Gulf Oil was one of the so-called Seven Sisters oil companies...
(Chevron Phillips Chemical Company), Shell Oil Company
Shell Oil Company
Shell Oil Company is the United States-based subsidiary of Royal Dutch Shell, a multinational oil company of Anglo Dutch origins, which is amongst the largest oil companies in the world. Approximately 22,000 Shell employees are based in the U.S. The head office in the U.S. is in Houston, Texas...
SHOP
Shell higher olefin process
The Shell higher olefin process is a chemical process for the production of linear alpha olefins via ethylene oligomerization and olefin metathesis invented and exploited by Royal Dutch Shell. The olefin products are converted to fatty aldehydes and then to fatty alcohols, which are precursors...
process, the Idemitsu Petrochemical process and the SABIC
SABIC
SABIC is a diversified manufacturing company, active in chemicals and intermediates, industrial polymers, fertilizers and metals. It is the largest public company in Saudi Arabia as listed in Tadawul, but the Saudi government still owns 70% of its shares...
-Linde
The Linde Group
The Linde Group, registered as Linde AG is an international industrial gases and engineering company founded in Germany in 1879. Linde shares are traded on all the German stock exchanges and also in Zürich, and the Linde share price is included in the DAX 30 index...
α-Sablin process.
The newest commercial linear alpha olefin process is the Sabic-Linde α-Sablin process, commercialized by SABIC
SABIC
SABIC is a diversified manufacturing company, active in chemicals and intermediates, industrial polymers, fertilizers and metals. It is the largest public company in Saudi Arabia as listed in Tadawul, but the Saudi government still owns 70% of its shares...
in Saudi Arabia. The α-Sablin process is a low-pressure ethylene oligomerization process conducted over heterogeneous catalyst in a slurry bed. The process also makes a C4-C20+ distribution of alpha-olefins. Sabic announced the commercialization of a 150,000 metric tons per year plant using the α-Sablin process at their Jubail
Jubail
Jubail , is a city in the Eastern province on the Persian Gulf coast of Saudi Arabia. It consists of the Old Town of Al Jubail, which was originally a small fishing village, up to 1975 and the new industrial area....
plant on the Gulf coast of Saudi Arabia in 2009. The plant construction was managed by Linde’s subsidiary Linde-KCA-Dresden GmbH, Germany.
Two commercial processes make a single alpha-olefin carbon number. Phillips
Chevron Phillips
Chevron Phillips is a chemical producer jointly owned by Chevron Corporation and ConocoPhillips. The company was formed July 1, 2000 by merging the chemicals operations of both Chevron Corporation and Phillips Petroleum Company. A 50/50 venture, the company continues to be governed by a board of...
(CP Chemical Company) ethylene trimerization process, produces only 1-hexene. Another commercial process, offered by a technology licensor IFP
IFP
IFP can stand for:* International Federation of Poker* Interwise Food Portal* Independent Feature Project* "The Illinois Functional Programming Interpreter", A.D. Robison, Proc 1987 SIGPLAN Conf on Interpreters and Interpretive Techniques , pp...
, dimerizes ethylene to high purity 1-butene.
There are two alpha-olefin processes that have not been commercialized as of Q2, 2010. One is an ethylene oligomerization to a wide range of linear alpha olefins technology being offered by a technology licensor UOP
UOP
UOP is an initialism that may stand for the following:* University of the People, an online university* University of Peradeniya in Sri Lanka* University of Peshawar, in Peshawar, Pakistan* University of Pune in India...
. The other is the DuPont
DuPont
E. I. du Pont de Nemours and Company , commonly referred to as DuPont, is an American chemical company that was founded in July 1802 as a gunpowder mill by Eleuthère Irénée du Pont. DuPont was the world's third largest chemical company based on market capitalization and ninth based on revenue in 2009...
Versipol technology. To date, no commercial plants have been built using either UOP or DuPont's technology.
The only commercial process to isolate linear alpha olefins from synthetic crude is practiced by Sasol
Sasol
Sasol Ltd. is a South African company involved in mining, energy, chemicals and synfuels. In particular, they produce petrol and diesel profitably from coal and natural gas using Fischer-Tropsch process...
Ltd., a South African oil and gas and petrochemical company. Sasol commercially employs Fischer-Tropsch synthesis to make fuels from synthesis gas derived from coal and recovers 1-hexene from these fuel streams, where the initial linear alpha olefin concentration in a narrow distillation
Distillation
Distillation is a method of separating mixtures based on differences in volatilities of components in a boiling liquid mixture. Distillation is a unit operation, or a physical separation process, and not a chemical reaction....
cut may be 60%, with the remainder being vinylidenes, linear and branched internal olefins, linear and branched paraffins, alcohols, aldehyde
Aldehyde
An aldehyde is an organic compound containing a formyl group. This functional group, with the structure R-CHO, consists of a carbonyl center bonded to hydrogen and an R group....
s, carboxylic acid
Carboxylic acid
Carboxylic acids are organic acids characterized by the presence of at least one carboxyl group. The general formula of a carboxylic acid is R-COOH, where R is some monovalent functional group...
s and aromatic compounds.
Dehydration of alcohols to linear alpha olefins by passing alcohols in a vapor phase over acidic alumina catalyst has been practiced periodically by Ethyl Corporation (later BP, now Ineos), Chevron Phillips, Sasol (formerly Vista Chemical) and Godrej Industries Ltd
Godrej Industries Ltd
Godrej Industries is one of the India's leading manufacturer of oleochemicals and makes more than a hundred chemicals for use in over two dozen industries. It also manufactures edible oils, vanaspati and bakery fats. Besides, it operates real estate. With global reach spreading across 40 countries...
, an Indian petro- and specialty chemical company. Normally, this process is not economical as the linear fatty alcohols are more valuable than the corresponding linear alpha olefins. However, the process has been applied whenever the value of fatty alcohols dipped below that of linear olefins because of market dynamics or regional supply-demand issues.
One of the problems of the linear alpha olefin industry is the wide range of products made by most of the processes. While the Ethyl process makes a Pseudo-Poisson distribution of products, most others, including the Sasol process, make a Schultz-Flory distribution. With 8-10 products being made at the same time, with most of them sold into different markets with different dynamics, it is difficult to balance the supply and the demand for all or even most products.
Ineos (Ethyl) Process
Ethyl linear alpha olefin process is commonly called stoichiometric Ziegler process. It is a two-step process. In the first step, a stoichiometric quantity of triethyl aluminium in olefin diluent is reacted with excess ethylene at high pressure (above 1000 psig) and relatively low temperature (below 400 °F). On the average, nine moles of ethylene are added per mole of triethyl aluminium, resulting in, on average, a tri-octyl aluminium. The distribution of alkyl chains on the aluminium is determined by statistical bell curve distribution except for some smearing to the light side due to the kinetic phenomena and some smearing to the heavy side due to some incorporation of heavier olefins into the chain. Excess ethylene and olefin diluent are flashed off. The heavy aluminium tri-alkyls are reacted with ethylene again in a displacement or a tranalkylation reaction, but at high temperature (over 400 °F) and at low pressure (less than 1000 psig) to recover triethyl aluminium and a statistical distribution of linear alpha olefins, which serve as the olefin diluent in the chain-growth step.CP Chemicals (Gulf) Process
The Gulf linear alpha olefin process is commonly called a catalytic Ziegler process. Triethyl aluminium is used as a catalyst, but in catalytic amounts and the process is a single-step process. Tri-ethyl aluminium and excess ethylene are fed to a plug flow-reactor. The reaction is conducted at high pressure and high temperature. Excess ethylene is flashed off. The tri-ethyl aluminium catalyst is washed out of the product with caustic and the linear alpha olefins are separated. The product distribution is a Schultz-Flory distribution typical of catalytic processes.Applications
There is a wide range of applications for linear alpha olefins. The lower carbon numbers, 1-butene, 1-hexene and 1-octene are overwhelmingly used as comonomers in production of polyethylene. High density polyethylene (HDPE) and linear low density polyethylene (LLDPE) use approximately 2-4% and 8-10% of comonomers, respectively.Another significant use of C4-C8 linear alpha olefins is for production of linear aldehyde
Aldehyde
An aldehyde is an organic compound containing a formyl group. This functional group, with the structure R-CHO, consists of a carbonyl center bonded to hydrogen and an R group....
via oxo synthesis (hydroformylation
Hydroformylation
Hydroformylation, also known as oxo synthesis or oxo process, is an important industrial process for the production of aldehydes from alkenes. This chemical reaction entails the addition of a formyl group and a hydrogen atom to a carbon-carbon double bond...
) for later production of short-chain fatty acid
Fatty acid
In chemistry, especially biochemistry, a fatty acid is a carboxylic acid with a long unbranched aliphatic tail , which is either saturated or unsaturated. Most naturally occurring fatty acids have a chain of an even number of carbon atoms, from 4 to 28. Fatty acids are usually derived from...
, a carboxylic acid, by oxidation of an intermediate aldehyde, or linear alcohols for plasticizer
Plasticizer
Plasticizers or dispersants are additives that increase the plasticity or fluidity of the material to which they are added; these include plastics, cement, concrete, wallboard, and clay. Although the same compounds are often used for both plastics and concretes the desired effects and results are...
application by hydrogenation
Hydrogenation
Hydrogenation, to treat with hydrogen, also a form of chemical reduction, is a chemical reaction between molecular hydrogen and another compound or element, usually in the presence of a catalyst. The process is commonly employed to reduce or saturate organic compounds. Hydrogenation typically...
of the aldehyde.
The predominant application of 1-decene is in making polyalphaolefin synthetic lubricant
Lubricant
A lubricant is a substance introduced to reduce friction between moving surfaces. It may also have the function of transporting foreign particles and of distributing heat...
basestock (PAO) and to make surfactant
Surfactant
Surfactants are compounds that lower the surface tension of a liquid, the interfacial tension between two liquids, or that between a liquid and a solid...
s in a blend with higher linear alpha olefins.
C10-C14 linear alpha olefins are used in making surfactants for aqueous detergent formulations. These carbon numbers may be reacted with benzene to make linear alkyl benzene
Linear alkyl benzene
Linear alkylbenzene is a family of organic compounds with the formula C6H5CnH2n+1. Typically, n lies between 10 and 16, although generally supplied as a tighter cut, such as C12-C15, C12-C13 and C10-C13, for detergent use. The CnH2n+1 chain is unbranched. They are sometimes called LAB's. They are...
(LAB), which is further sulfonated to linear alkyl benzene sulfonate (LABS), a popular relatively low cost surfactant for household and industrial detergent applications.
Although some C14 alpha olefin is sold into aqueous detergent applications, C14 has other applications such as being converted into chloroparaffins. A recent application of C14 is as on-land drilling fluid
Drilling fluid
In geotechnical engineering, drilling fluid is a fluid used to aid the drilling of boreholes into the earth. Often used while drilling oil and natural gas wells and on exploration drilling rigs, drilling fluids are also used for much simpler boreholes, such as water wells. Liquid drilling fluid...
basestock, replacing diesel or kerosene
Kerosene
Kerosene, sometimes spelled kerosine in scientific and industrial usage, also known as paraffin or paraffin oil in the United Kingdom, Hong Kong, Ireland and South Africa, is a combustible hydrocarbon liquid. The name is derived from Greek keros...
in that application. Although C14 is more expensive than middle distillates, it has a significant advantage environmentally, being much more biodegradable and in handling the material, being much less irritating to skin and less toxic.
C16 - C18 linear olefins find their primary application as the hydrophobes in oil-soluble surfactants and as lubricating fluids themselves. C16 - C18 alpha or internal olefins are used as synthetic drilling fluid base for high value, primarily off-shore synthetic drilling fluids. The preferred materials for the synthetic drilling fluid application are linear internal olefins, which are primarily made by isomerizing linear alpha-olefins to an internal position. The higher internal olefins appear to form a more lubricious layer at the metal surface and are recognized as a better lubricants. Another significant application for C16 - C18 olefins is in paper sizing. Linear alpha olefins are, once again, isomerized into linear internal olefins are then reacted with maleic anhydride
Maleic anhydride
Maleic anhydride is an organic compound with the formula C2H22O. It is the acid anhydride of maleic acid and in its pure state it is a colourless or white solid with an acrid odour....
to make an alkyl succinic anhydride(ASA), a popular paper sizing
Sizing
Sizing or size is any one of numerous specific substances that is applied to or incorporated in other material, especially papers and textiles, to act as a protecting filler or glaze....
chemical.
C20 - C30 linear alpha olefins production capacity is only 5-10% of the total production of a linear alpha olefin plant. They are used in a number of reactive and non-reactive applications, including as feedstocks to make heavy linear alkyl benzene
Linear alkyl benzene
Linear alkylbenzene is a family of organic compounds with the formula C6H5CnH2n+1. Typically, n lies between 10 and 16, although generally supplied as a tighter cut, such as C12-C15, C12-C13 and C10-C13, for detergent use. The CnH2n+1 chain is unbranched. They are sometimes called LAB's. They are...
(LAB) and low molecular weight polymers which are used to enhance properties of waxes.