Fuel, Volume 111, September 2013, Pages 449–460
1-Butene oligomerization over ZSM-5 zeolite:
Part 1 – Effect of reaction conditions
A. Coelho (a), G. Caeiro (b), M.A.N.D.A. Lemos
(a), F. Lemos (a), F. Ramôa Ribeiro (a)
a IBB – Institute for Biotechnology and Bioengineering, Centre for Biological
and Chemical Engineering, Instituto Superior Técnico, UTL, Av. Rovisco Pais,
1049-001 Lisboa, Portugal
b Galp Energia, SGPS, S.A., Rua Tomás da Fonseca, 1600-209 Lisboa, Portugal
Abstract
The production of liquid fuels using a catalytic
cracker generates a significant amount of lighter fractions of olefinic nature.
The use of oligomerization reactions to convert lighter olefin cuts into middle
distillates to incorporate in the diesel pool is a promising process for the production
of clean diesel fractions.
Researchers studied 1-butene oligomerization
over H-ZSM-5 zeolite in a differential reactor operating at ambient pressure.
They examined the effect of reaction conditions, such as reaction temperature,
contact time and partial pressure, on the activity, selectivity and stability
of the catalyst. Their results reveal that an increase in the reaction
temperature and/or partial pressure and in the contact time produces an
improved catalyst activity.
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Wednesday, April 23, 2014
Analysis of Slurry-Phase Co-Polymerization of Ethylene and 1-Butene by Ziegler–Natta Catalysts Part 1: Experimental Activity Profiles
Macromolecular Reaction Engineering, Volume 7, Issue 8, pages 350–361,
August 2013
Analysis of Slurry-Phase Co-Polymerization of Ethylene and 1-Butene by Ziegler–Natta Catalysts Part 1: Experimental Activity Profiles
John T. McCoy (1), Joao B. P. Soares (2) and Randhir Rawatlal (1)
1 Department of Chemical Engineering, University of Cape Town, Cape Town, 7701, Republic of South Africa
2 Department of Chemical Engineering, Institute for Polymer Research, University of Waterloo, Waterloo, Ontario, Canada N2L 3G
randhir.rawatlal@uct.ac.za
Abstract
A rigorous method is developed to extract kinetic parameters describing catalyst activity from experimental polymerization rate profiles for Ziegler–Natta catalysts. The kinetic scheme used correlates the oxidation state with catalyst activity, eliminating the need for multiple site types to describe rate profiles. The method is applied to data from kinetic experiments performed in a lab-scale semi-batch reactor. Four parameters are required to describe the activity of the catalyst: the polymerization rate constant and three site transformation rate constants. The model is able to reproduce changes in the rate profiles in response to reactant concentrations. The fits of the model to the data are comparable to those in similar studies
Of primary interest to the current work is the correlation between polymerization activity and the oxidation state of the active sites, a concept most rigorously established by Soga et al. This correlation has been supported in more recent experimental and simulation studies.
With this correlation in mind, a rearrangement of the kinetic scheme was proposed. This scheme uses the oxidation state of titanium sites as an indicator for the activity of a single type of polymerizing site, predicts chain lengths via the pseudo-sites concept, and is described in the following section.
In the present work, a kinetic scheme to describe the activity of Ziegler–Natta catalysts is outlined. This is followed by the development of a general regression procedure designed for the scheme, and the application of this scheme to experimental data, including extraction of the kinetic parameters relating to activity from this data and analysis of some of the challenges of regression.
Free Full Text Source: http://onlinelibrary.wiley.com/doi/10.1002/mren.201200078/full
Analysis of Slurry-Phase Co-Polymerization of Ethylene and 1-Butene by Ziegler–Natta Catalysts Part 1: Experimental Activity Profiles
John T. McCoy (1), Joao B. P. Soares (2) and Randhir Rawatlal (1)
1 Department of Chemical Engineering, University of Cape Town, Cape Town, 7701, Republic of South Africa
2 Department of Chemical Engineering, Institute for Polymer Research, University of Waterloo, Waterloo, Ontario, Canada N2L 3G
randhir.rawatlal@uct.ac.za
Abstract
A rigorous method is developed to extract kinetic parameters describing catalyst activity from experimental polymerization rate profiles for Ziegler–Natta catalysts. The kinetic scheme used correlates the oxidation state with catalyst activity, eliminating the need for multiple site types to describe rate profiles. The method is applied to data from kinetic experiments performed in a lab-scale semi-batch reactor. Four parameters are required to describe the activity of the catalyst: the polymerization rate constant and three site transformation rate constants. The model is able to reproduce changes in the rate profiles in response to reactant concentrations. The fits of the model to the data are comparable to those in similar studies
Of primary interest to the current work is the correlation between polymerization activity and the oxidation state of the active sites, a concept most rigorously established by Soga et al. This correlation has been supported in more recent experimental and simulation studies.
With this correlation in mind, a rearrangement of the kinetic scheme was proposed. This scheme uses the oxidation state of titanium sites as an indicator for the activity of a single type of polymerizing site, predicts chain lengths via the pseudo-sites concept, and is described in the following section.
In the present work, a kinetic scheme to describe the activity of Ziegler–Natta catalysts is outlined. This is followed by the development of a general regression procedure designed for the scheme, and the application of this scheme to experimental data, including extraction of the kinetic parameters relating to activity from this data and analysis of some of the challenges of regression.
Free Full Text Source: http://onlinelibrary.wiley.com/doi/10.1002/mren.201200078/full
Process for workup of a stream comprising butene and/or butadiene (BASF)
PATENT
Process for workup of a stream comprising butene and/or butadiene (BASF)
Publication number US8420879 B2
Application number US 13/411,080
Publication date Apr 16, 2013
Also published as US20120226087
Inventors
Albena Kostova
Original Assignee
BASF Se
Abstract
The invention relates to a process for workup of a stream (1) comprising butene and/or butadiene, butane, hydrogen and/or nitrogen and carbon dioxide, comprising: •(a) absorption of stream (1) with a mixture (5) comprising 80 to 97% by weight of N-methylpyrrolidone and 3 to 20% by weight of water to obtain a stream (9) comprising N-methylpyrrolidone, water, butene and/or butadiene, butane, and optionally carbon dioxide, and a stream (7) comprising hydrogen and/or nitrogen and butane,
•(b) extractive distillation of stream (9) with a stream (13) comprising 80 to 97% by weight of N-methylpyrrolidone and 3 to 20% by weight of water to separate the stream (9) into a stream (17) comprising N-methylpyrrolidone, water, butene and/or butadiene, and a stream (15) comprising essentially butane, and optionally carbon dioxide,
•(c) distillation of stream (17) into a stream (23) comprising essentially N-methylpyrrolidone and water, and a stream (21) comprising butene and/or butadiene.
BACKGROUND OF THE INVENTION
The invention relates to a process for workup of a stream comprising butene and/or butadiene, butane, hydrogen and/or nitrogen, with or without carbon dioxide.
Butenes and butadiene can be prepared, for example by thermal cleavage (steam-cracking) of saturated hydrocarbons, typically proceeding from naphtha as a raw material. The steamcracking of naphtha gives a hydrocarbon mixture of methane, ethane, ethene, acetylene, propane, propene, propyne, allene, methylallene, and C5 and higher hydrocarbons.
A disadvantage of this process for producing butenes and butadiene is that relatively large amounts of unwanted coproducts are inevitably obtained. Alternatively, the butenes can be prepared from butane and butadiene from n-butene, by dehydrogenation.
DE-A 10 2004 059 356 discloses, for example, preparing butadiene by using n-butane as a feedstock. To prepare the butadiene, the n-butane is dehydrogenated in a dehydrogenation zone by nonoxidative catalytic dehydrogenation to give a stream comprising n-butane, 1-butene, 2-butene, butadiene, and hydrogen, with or without carbon dioxide and with or without water vapor. In a second dehydrogenation zone, the 1-butene and 2-butene are dehydrogenated further to butadiene. The stream obtained in the dehydrogenation is subsequently compressed and cooled in order to condense out water. A product stream comprising essentially butadiene is removed by extractive distillation from the residual stream comprising n-butane, butadiene, hydrogen, carbon dioxide and water vapor.
A corresponding process for preparing butadiene from n-butane is additionally also described in DE-A 10 2004 061 514.
A disadvantage of the process described here is that a different solvent than in the extractive distillation is used for the removal of an H2-rich stream in the absorption, and thus a desorption stage for the H2-rich gas is also needed. In addition there is no separation of CO2 and H2.
A further process for workup of a stream comprising butenes is also known from SU-A 1159915. In this process, the stream comprising butenes is subjected first to an absorption and then to an extractive distillation. The solvent used for the absorption and the extractive distillation is acetonitrile. A disadvantage in the case of the use of acetonitrile is that it does not dissolve any carbon dioxide. The use of acetonitrile therefore leads to the effect that the proportion of carbon dioxide in the gas increases since the carbon dioxide is recycled into the butane dehydrogenation together with the hydrogen and is not washed out in the absorption.
WO-A 2006/050969 describes a process for preparing butadiene from n-butane, in which the butadiene-comprising stream from the dehydrogenation is first cooled in order to condense out water. In a further compression stage and cooling, a condensate stream comprising n-butane, butadiene and water is obtained. n-Butane and butadiene are removed from the stream comprising water, n-butane and butadiene, and then separated into a product stream consisting essentially of butadiene and a recycle stream comprising n-butane.
A disadvantage here is that the C4 components are removed from the inert gases by a multistage compression and subsequent condensation. This process stage features a high energy requirement for the compression up to approx. 30 bar. The C4 condensation is effected at a temperature of 10° C., and thus a cooling unit is additionally required.
A process for preparing 1-butene is described, for example, in EP-B 1 682 468. In the process described here, a C4 stream is removed in a two-stage process by absorption and a subsequent desorption of inerts. A disadvantage of the process is that the absorption solvent (tetradecane) is different than the solvent used in the extractive distillation (NMP). Moreover, there is the risk of mixing of the two solvents, which results in a reduced selectivity of the absorption and extractive distillation stages. A further disadvantage here is that the absorbent is selective only for C4 and hence there is no removal of H2 and CO2. The use of different solvents in the absorption step entails a desorption of the C4 component with steam before it is passed on into the NMP extractive distillation column.
It is an object of the present invention to provide a process for workup of a stream comprising butene and/or butadiene, which can be implemented with less complexity and lower costs.
BRIEF SUMMARY OF THE INVENTION
The object is achieved by a process for workup of a stream comprising butene and/or butadiene, butane, hydrogen and/or nitrogen, with or without carbon dioxide, comprising the following steps:
•(a) absorption of the stream comprising butene and/or butadiene, butane, hydrogen and/or nitrogen, with or without carbon dioxide, with a mixture comprising 80 to 97% by weight of N-methylpyrrolidone and 3 to 20% by weight of water to obtain a stream comprising N-methylpyrrolidone, water, butene and/or butadiene, and butane, with or without carbon dioxide, and a stream comprising hydrogen and/or nitrogen and butane,
•(b) extractive distillation of the stream comprising N-methylpyrrolidone, water, butene and/or butadiene, and butane, with or without carbon dioxide, with a stream comprising 80 to 97% by weight of N-methylpyrrolidone and 3 to 20% by weight of water to separate the stream comprising N-methylpyrrolidone, water, butene and/or butadiene, and butane, with or without carbon dioxide, into a stream comprising N-methylpyrrolidone, water, butene and/or butadiene, and a stream comprising essentially butane, with or without carbon dioxide,
•(c) distillation of the stream comprising N-methylpyrrolidone, water, butene and/or butadiene into a stream comprising essentially N-methylpyrrolidone and water, and a stream comprising butene and/or butadiene.
According to the invention, a mixture of 80 to 97% by weight of N-methylpyrrolidone and 3 to 20% by weight of water, preferably a mixture of 90 to 93% by weight of N-methylpyrrolidone and 7 to 10% by weight of water and especially a mixture of 91 to 92% by weight of N-methylpyrrolidone and 8 to 9% by weight of water, for example a mixture of 91.7% by weight of N-methylpyrrolidone and 8.3% by weight of water, is used both as the solvent for the absorption in step (a) and as the extractant for the extraction in step (b).
Free Full Text Source: http://www.google.com/patents/US8420879
Process for workup of a stream comprising butene and/or butadiene (BASF)
Publication number US8420879 B2
Application number US 13/411,080
Publication date Apr 16, 2013
Also published as US20120226087
Inventors
Albena Kostova
Original Assignee
BASF Se
Abstract
The invention relates to a process for workup of a stream (1) comprising butene and/or butadiene, butane, hydrogen and/or nitrogen and carbon dioxide, comprising: •(a) absorption of stream (1) with a mixture (5) comprising 80 to 97% by weight of N-methylpyrrolidone and 3 to 20% by weight of water to obtain a stream (9) comprising N-methylpyrrolidone, water, butene and/or butadiene, butane, and optionally carbon dioxide, and a stream (7) comprising hydrogen and/or nitrogen and butane,
•(b) extractive distillation of stream (9) with a stream (13) comprising 80 to 97% by weight of N-methylpyrrolidone and 3 to 20% by weight of water to separate the stream (9) into a stream (17) comprising N-methylpyrrolidone, water, butene and/or butadiene, and a stream (15) comprising essentially butane, and optionally carbon dioxide,
•(c) distillation of stream (17) into a stream (23) comprising essentially N-methylpyrrolidone and water, and a stream (21) comprising butene and/or butadiene.
BACKGROUND OF THE INVENTION
The invention relates to a process for workup of a stream comprising butene and/or butadiene, butane, hydrogen and/or nitrogen, with or without carbon dioxide.
Butenes and butadiene can be prepared, for example by thermal cleavage (steam-cracking) of saturated hydrocarbons, typically proceeding from naphtha as a raw material. The steamcracking of naphtha gives a hydrocarbon mixture of methane, ethane, ethene, acetylene, propane, propene, propyne, allene, methylallene, and C5 and higher hydrocarbons.
A disadvantage of this process for producing butenes and butadiene is that relatively large amounts of unwanted coproducts are inevitably obtained. Alternatively, the butenes can be prepared from butane and butadiene from n-butene, by dehydrogenation.
DE-A 10 2004 059 356 discloses, for example, preparing butadiene by using n-butane as a feedstock. To prepare the butadiene, the n-butane is dehydrogenated in a dehydrogenation zone by nonoxidative catalytic dehydrogenation to give a stream comprising n-butane, 1-butene, 2-butene, butadiene, and hydrogen, with or without carbon dioxide and with or without water vapor. In a second dehydrogenation zone, the 1-butene and 2-butene are dehydrogenated further to butadiene. The stream obtained in the dehydrogenation is subsequently compressed and cooled in order to condense out water. A product stream comprising essentially butadiene is removed by extractive distillation from the residual stream comprising n-butane, butadiene, hydrogen, carbon dioxide and water vapor.
A corresponding process for preparing butadiene from n-butane is additionally also described in DE-A 10 2004 061 514.
A disadvantage of the process described here is that a different solvent than in the extractive distillation is used for the removal of an H2-rich stream in the absorption, and thus a desorption stage for the H2-rich gas is also needed. In addition there is no separation of CO2 and H2.
A further process for workup of a stream comprising butenes is also known from SU-A 1159915. In this process, the stream comprising butenes is subjected first to an absorption and then to an extractive distillation. The solvent used for the absorption and the extractive distillation is acetonitrile. A disadvantage in the case of the use of acetonitrile is that it does not dissolve any carbon dioxide. The use of acetonitrile therefore leads to the effect that the proportion of carbon dioxide in the gas increases since the carbon dioxide is recycled into the butane dehydrogenation together with the hydrogen and is not washed out in the absorption.
WO-A 2006/050969 describes a process for preparing butadiene from n-butane, in which the butadiene-comprising stream from the dehydrogenation is first cooled in order to condense out water. In a further compression stage and cooling, a condensate stream comprising n-butane, butadiene and water is obtained. n-Butane and butadiene are removed from the stream comprising water, n-butane and butadiene, and then separated into a product stream consisting essentially of butadiene and a recycle stream comprising n-butane.
A disadvantage here is that the C4 components are removed from the inert gases by a multistage compression and subsequent condensation. This process stage features a high energy requirement for the compression up to approx. 30 bar. The C4 condensation is effected at a temperature of 10° C., and thus a cooling unit is additionally required.
A process for preparing 1-butene is described, for example, in EP-B 1 682 468. In the process described here, a C4 stream is removed in a two-stage process by absorption and a subsequent desorption of inerts. A disadvantage of the process is that the absorption solvent (tetradecane) is different than the solvent used in the extractive distillation (NMP). Moreover, there is the risk of mixing of the two solvents, which results in a reduced selectivity of the absorption and extractive distillation stages. A further disadvantage here is that the absorbent is selective only for C4 and hence there is no removal of H2 and CO2. The use of different solvents in the absorption step entails a desorption of the C4 component with steam before it is passed on into the NMP extractive distillation column.
It is an object of the present invention to provide a process for workup of a stream comprising butene and/or butadiene, which can be implemented with less complexity and lower costs.
BRIEF SUMMARY OF THE INVENTION
The object is achieved by a process for workup of a stream comprising butene and/or butadiene, butane, hydrogen and/or nitrogen, with or without carbon dioxide, comprising the following steps:
•(a) absorption of the stream comprising butene and/or butadiene, butane, hydrogen and/or nitrogen, with or without carbon dioxide, with a mixture comprising 80 to 97% by weight of N-methylpyrrolidone and 3 to 20% by weight of water to obtain a stream comprising N-methylpyrrolidone, water, butene and/or butadiene, and butane, with or without carbon dioxide, and a stream comprising hydrogen and/or nitrogen and butane,
•(b) extractive distillation of the stream comprising N-methylpyrrolidone, water, butene and/or butadiene, and butane, with or without carbon dioxide, with a stream comprising 80 to 97% by weight of N-methylpyrrolidone and 3 to 20% by weight of water to separate the stream comprising N-methylpyrrolidone, water, butene and/or butadiene, and butane, with or without carbon dioxide, into a stream comprising N-methylpyrrolidone, water, butene and/or butadiene, and a stream comprising essentially butane, with or without carbon dioxide,
•(c) distillation of the stream comprising N-methylpyrrolidone, water, butene and/or butadiene into a stream comprising essentially N-methylpyrrolidone and water, and a stream comprising butene and/or butadiene.
According to the invention, a mixture of 80 to 97% by weight of N-methylpyrrolidone and 3 to 20% by weight of water, preferably a mixture of 90 to 93% by weight of N-methylpyrrolidone and 7 to 10% by weight of water and especially a mixture of 91 to 92% by weight of N-methylpyrrolidone and 8 to 9% by weight of water, for example a mixture of 91.7% by weight of N-methylpyrrolidone and 8.3% by weight of water, is used both as the solvent for the absorption in step (a) and as the extractant for the extraction in step (b).
Free Full Text Source: http://www.google.com/patents/US8420879
Ionic liquid enhanced alkylation of iso-butane and 1-butene
Catalysis Today, Volume 200, 1 February 2013, Pages 30–35 (Applications
of Ionic Liquids in Green Catalytic Processes)
Ionic liquid enhanced alkylation of iso-butane and 1-butene
Peng Cui (a), (b), Guoying Zhao (b), Hailing Ren (a), (b), Jun Huang (a) Suojiang Zhangb, ,
a State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, 210009 Nanjing, PR China
b Beijing Key Laboratory of Ionic Liquids Clean Process, Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, PR China
Abstract
Researchers catalyzed the alkylation of iso-butane with 1-butene by triflic acid (TFOH) coupled with a series of protic ammonium-based ionic liquids (AMILs). The addition of the AMILs dramatically enhanced the efficiency of TFOH for the alkylation reaction.
Up to 85.1% trimethylpentanes (TMP) selectivity and 98 research octane number (RON) were obtained with the optimized TFOH/AMIL catalyst. This was significantly better than that with the commercial H2SO4 catalyst and pure triflic acid.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S0920586112004506
Ionic liquid enhanced alkylation of iso-butane and 1-butene
Peng Cui (a), (b), Guoying Zhao (b), Hailing Ren (a), (b), Jun Huang (a) Suojiang Zhangb, ,
a State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, 210009 Nanjing, PR China
b Beijing Key Laboratory of Ionic Liquids Clean Process, Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, PR China
Abstract
Researchers catalyzed the alkylation of iso-butane with 1-butene by triflic acid (TFOH) coupled with a series of protic ammonium-based ionic liquids (AMILs). The addition of the AMILs dramatically enhanced the efficiency of TFOH for the alkylation reaction.
Up to 85.1% trimethylpentanes (TMP) selectivity and 98 research octane number (RON) were obtained with the optimized TFOH/AMIL catalyst. This was significantly better than that with the commercial H2SO4 catalyst and pure triflic acid.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S0920586112004506
The kinetics of oxidation of 1-butene to methylethylketone in the presence of a homogeneous catalyst (complex of palladium + Mo-V-P heteropoly acid)
Chemical Engineering Journal, Volume 230, 15 August 2013, Pages 308–313
The kinetics of oxidation of 1-butene to methylethylketone in the presence of a homogeneous catalyst (complex of palladium + Mo-V-P heteropoly acid)
E.G. Zhizhina, V.F. Odyakov
Boreskov Institute of Catalysis, SB RAS, pr. Akad. Lavrentieva, 5, 630090 Novosibirsk, Russia
Abstract
Describes a study of the kinetics of the direct oxidation of 1-butene to methylethylketone (MEK) in the presence of an aqueous solution of a Pd salt and Mo-V-P heteropoly acid having non-Keggin-type composition Н12P3Mo18V7O85 (HPA-7′), a novel homogeneous catalyst.
The catalyst (Pd + HPA-7′) is characterized by increased stability and high selectivity in MEK production. The process occurs in two stages. In stage (1), 1-butene reacts with the catalyst in a butylene reactor 1 with the formation of MEK and a reduced form of the catalyst. After stripping of the product, the reduced catalyst is oxidized by air in a reactor 2 under increased pressure. The experimental data enabled researchers to obtain the kinetic equation for the reaction rate of 1-butene oxidation used for the calculation of the tubular plug-flow reactor 1.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S138589471300867X
The kinetics of oxidation of 1-butene to methylethylketone in the presence of a homogeneous catalyst (complex of palladium + Mo-V-P heteropoly acid)
E.G. Zhizhina, V.F. Odyakov
Boreskov Institute of Catalysis, SB RAS, pr. Akad. Lavrentieva, 5, 630090 Novosibirsk, Russia
Abstract
Describes a study of the kinetics of the direct oxidation of 1-butene to methylethylketone (MEK) in the presence of an aqueous solution of a Pd salt and Mo-V-P heteropoly acid having non-Keggin-type composition Н12P3Mo18V7O85 (HPA-7′), a novel homogeneous catalyst.
The catalyst (Pd + HPA-7′) is characterized by increased stability and high selectivity in MEK production. The process occurs in two stages. In stage (1), 1-butene reacts with the catalyst in a butylene reactor 1 with the formation of MEK and a reduced form of the catalyst. After stripping of the product, the reduced catalyst is oxidized by air in a reactor 2 under increased pressure. The experimental data enabled researchers to obtain the kinetic equation for the reaction rate of 1-butene oxidation used for the calculation of the tubular plug-flow reactor 1.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S138589471300867X
Azeotropic and azeotrope-like compositions of Z-1,1,1,4,4,4-hexafluoro-2-butene, trans-1,2-dichloroethylene, and 1,1,1,3,3-pentafluorobutane (E I Du Pont De Nemours)
PATENT
Azeotropic and azeotrope-like compositions of Z-1,1,1,4,4,4-hexafluoro-2-butene, trans-1,2-dichloroethylene, and 1,1,1,3,3-pentafluorobutane (E I Du Pont De Nemours)
Publication number US8623233 B2
Application number US 13/519,004
Publication date Jan 7, 2014
Also published as CA2786031A1
Inventors
Mark L. Robin, Joan Ellen Bartelt
Original Assignee
E I Du Pont De Nemours And Company
Abstract
Azeotropic or azeotrope-like compositions are disclosed. The azeotropic or azeotrope-like compositions are mixtures of Z-1,1,1,4,4,4-hexafluoro-2-butene, trans-1,2-dichloroethylene and 1,1,1,3,3-pentafluorobutane. Also disclosed is a process of preparing a thermoplastic or thermoset foam by using such azeotropic or azeotrope-like compositions as blowing agents. Also disclosed is a process of producing refrigeration by using such azeotropic or azeotrope-like compositions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as solvents. Also disclosed is a process of producing an aerosol product by using such azeotropic or azeotrope-like compositions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as heat transfer media. Also disclosed is a process of extinguishing or suppressing a fire by using such azeotropic or azeotrope-like compositions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as dielectrics.
BACKGROUND OF THE INVENTION
1. Field of the Disclosure
The present disclosure relates to azeotropic or azeotrope-like compositions of Z-1,1,1,4,4,4-hexafluoro-2-butene, trans-1,2-dichloroethylene, and 1,1,1,3,3-pentafluorobutane.
2. Description of Related Art
Many industries have been working for the past few decades to find replacements for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). The CFCs and HCFCs have been employed in a wide range of applications, including their use as aerosol propellants, refrigerants, cleaning agents, expansion agents for thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. In the search for replacements for these versatile compounds, many industries have turned to the use of hydrofluorocarbons (HFCs).
The HFCs do not contribute to the destruction of stratospheric ozone, but are of concern due to their contribution to the “greenhouse effect”, i.e., they contribute to global warming. As a result of their contribution to global warming, the HFCs have come under scrutiny, and their widespread use may also be limited in the future. Thus, there is a need for compositions that do not contribute to the destruction of stratospheric ozone and also have low global warming potentials (GWPs). Certain hydrofluoroolefins, such as 1,1,1,4,4,4-hexafluoro-2-butene (CF3CH═CHCF3, FO-1336mzz), are believed to meet both goals.
SUMMARY OF THE INVENTION
This disclosure provides an azeotropic or azeotrope-like composition consisting essentially of (a) Z-FO-1336mzz, (b) trans-1,2-dichloroethylene (E-ClCH═CHCl, trans-1,2-DCE) and (c) 1,1,1,3,3-pentafluorobutane (CF3CH2CF2CH3); wherein the trans-1,2-dichloroethylene and the 1,1,1,3,3-pentafluorobutane are present in effective amounts to form an azeotropic or azeotrope-like mixture with Z-FO-1336mzz.
This disclosure also provides processes of using these azeotropic or azeotrope-like compositions as blowing agents, refrigerants, solvents, aerosol propellants, heat transfer medias, fire extinguishants, fire suppression agents or dielectrics.
Free Full Text Source: http://www.google.com/patents/US8623233
Azeotropic and azeotrope-like compositions of Z-1,1,1,4,4,4-hexafluoro-2-butene, trans-1,2-dichloroethylene, and 1,1,1,3,3-pentafluorobutane (E I Du Pont De Nemours)
Publication number US8623233 B2
Application number US 13/519,004
Publication date Jan 7, 2014
Also published as CA2786031A1
Inventors
Mark L. Robin, Joan Ellen Bartelt
Original Assignee
E I Du Pont De Nemours And Company
Abstract
Azeotropic or azeotrope-like compositions are disclosed. The azeotropic or azeotrope-like compositions are mixtures of Z-1,1,1,4,4,4-hexafluoro-2-butene, trans-1,2-dichloroethylene and 1,1,1,3,3-pentafluorobutane. Also disclosed is a process of preparing a thermoplastic or thermoset foam by using such azeotropic or azeotrope-like compositions as blowing agents. Also disclosed is a process of producing refrigeration by using such azeotropic or azeotrope-like compositions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as solvents. Also disclosed is a process of producing an aerosol product by using such azeotropic or azeotrope-like compositions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as heat transfer media. Also disclosed is a process of extinguishing or suppressing a fire by using such azeotropic or azeotrope-like compositions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as dielectrics.
BACKGROUND OF THE INVENTION
1. Field of the Disclosure
The present disclosure relates to azeotropic or azeotrope-like compositions of Z-1,1,1,4,4,4-hexafluoro-2-butene, trans-1,2-dichloroethylene, and 1,1,1,3,3-pentafluorobutane.
2. Description of Related Art
Many industries have been working for the past few decades to find replacements for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). The CFCs and HCFCs have been employed in a wide range of applications, including their use as aerosol propellants, refrigerants, cleaning agents, expansion agents for thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. In the search for replacements for these versatile compounds, many industries have turned to the use of hydrofluorocarbons (HFCs).
The HFCs do not contribute to the destruction of stratospheric ozone, but are of concern due to their contribution to the “greenhouse effect”, i.e., they contribute to global warming. As a result of their contribution to global warming, the HFCs have come under scrutiny, and their widespread use may also be limited in the future. Thus, there is a need for compositions that do not contribute to the destruction of stratospheric ozone and also have low global warming potentials (GWPs). Certain hydrofluoroolefins, such as 1,1,1,4,4,4-hexafluoro-2-butene (CF3CH═CHCF3, FO-1336mzz), are believed to meet both goals.
SUMMARY OF THE INVENTION
This disclosure provides an azeotropic or azeotrope-like composition consisting essentially of (a) Z-FO-1336mzz, (b) trans-1,2-dichloroethylene (E-ClCH═CHCl, trans-1,2-DCE) and (c) 1,1,1,3,3-pentafluorobutane (CF3CH2CF2CH3); wherein the trans-1,2-dichloroethylene and the 1,1,1,3,3-pentafluorobutane are present in effective amounts to form an azeotropic or azeotrope-like mixture with Z-FO-1336mzz.
This disclosure also provides processes of using these azeotropic or azeotrope-like compositions as blowing agents, refrigerants, solvents, aerosol propellants, heat transfer medias, fire extinguishants, fire suppression agents or dielectrics.
Free Full Text Source: http://www.google.com/patents/US8623233
Oxidative Dehydrogenation of 1-Butene with Lattice Oxygen of V-Mg-Al Complex Oxide
Chemeca
2013 : challenging tomorrow : 29 September – 2 October 2013, Brisbane
Convention & Exhibition Centre, Queensland / Chemical College, Engineers
Australia
Oxidative Dehydrogenation of 1-Butene with Lattice Oxygen of V-Mg-Al Complex Oxide
Naoki Ikenaga and Syo Onishi
Department of Chemical, Energy and Environmental Engineering and High Technology Research Center, Kansai University, 3-3-35 Yamate, Suita, Osaka 564-8680, JAPAN
ikenaga@kansai-u.ac.jp
Abstract
Oxidative dehydrogenation (ODH) of 1-butene to butadiene (BD), which is a major building block in the petrochemical industry, is an attractive alternative to the current steam cracking of naphtha. Since the ODH of 1-butene is an exothermic reaction, it can be carried out at a lower temperature than the steam cracking process.
A major problem of the ODH is deep oxidation of the reactant and the product to CO2. Therefore, in order to suppress the deep oxidation of them, the ODH of 1-butene with lattice oxygen of V-Mg complex oxide such as Mg3V2O8 and Mg2V2O7 instead of molecular oxygen were tried. The reactions were carried out with a fixed-bed flow reactor at 480 oC under atmospheric pressure.
The lattice oxygen of Mg3V2O8 and Mg2V2O7 could promote the ODH of 1-butene with very small amount of Al. V-Mg-Al complex oxide catalyst, the aluminum was introduced to Mg3V2O8 catalyst, afforded higher 1-butene conversion (43.0 %) and BD selectivity (41.5 %). Its catalytic activity was maintained for repeated runs on the ODH of 1-butene and the re-oxidation of the catalyst. When introducing a small amount of aluminum to Mg3V2O8, the specific surface area was increased and the abstraction of hydrogen from 1-butene could be promoted.
Free Full Text Source: http://www.conference.net.au/chemeca2013/papers/24898.pdf
Oxidative Dehydrogenation of 1-Butene with Lattice Oxygen of V-Mg-Al Complex Oxide
Naoki Ikenaga and Syo Onishi
Department of Chemical, Energy and Environmental Engineering and High Technology Research Center, Kansai University, 3-3-35 Yamate, Suita, Osaka 564-8680, JAPAN
ikenaga@kansai-u.ac.jp
Abstract
Oxidative dehydrogenation (ODH) of 1-butene to butadiene (BD), which is a major building block in the petrochemical industry, is an attractive alternative to the current steam cracking of naphtha. Since the ODH of 1-butene is an exothermic reaction, it can be carried out at a lower temperature than the steam cracking process.
A major problem of the ODH is deep oxidation of the reactant and the product to CO2. Therefore, in order to suppress the deep oxidation of them, the ODH of 1-butene with lattice oxygen of V-Mg complex oxide such as Mg3V2O8 and Mg2V2O7 instead of molecular oxygen were tried. The reactions were carried out with a fixed-bed flow reactor at 480 oC under atmospheric pressure.
The lattice oxygen of Mg3V2O8 and Mg2V2O7 could promote the ODH of 1-butene with very small amount of Al. V-Mg-Al complex oxide catalyst, the aluminum was introduced to Mg3V2O8 catalyst, afforded higher 1-butene conversion (43.0 %) and BD selectivity (41.5 %). Its catalytic activity was maintained for repeated runs on the ODH of 1-butene and the re-oxidation of the catalyst. When introducing a small amount of aluminum to Mg3V2O8, the specific surface area was increased and the abstraction of hydrogen from 1-butene could be promoted.
Free Full Text Source: http://www.conference.net.au/chemeca2013/papers/24898.pdf
Diesel and Jet Fuels Based on the Oligomerization of Butene (US Government As Represented By The Secretary Of Department Of The Navy)
PATENT
Diesel and Jet Fuels Based on the Oligomerization of Butene (US Government As Represented By The Secretary Of Department Of The Navy)
Publication number US20140051898 A1
Application number US 13/763,829
Publication date Feb 20, 2014
Inventors
Michael E. Wright, Benjamin G. Harvey, Roxanne L. Quintana
Original Assignee
US Government As Represented By The Secretary Of Department Of The Navy
Abstract
A renewable biofuel based on a highly efficient batch catalysis methodology for conversion of 1-butene to a new class of potential jet fuel blends. By tuning the catalyst and then using the dimer produced, the carbon use is about 95% or greater. This latter point will be particularly important in the future, where the source of raw materials (i.e., biomass/biofeedstock) is limited.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
The invention described herein may be manufactured and used by or for the government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.
FIELD OF THE INVENTION
A renewable biofuel for turbine engines based on a highly efficient batch catalysis methodology for conversion of 1-butene to a new class of fuels.
BACKGROUND OF THE INVENTION
We demonstrate that the quantitative conversion of 1-butene to a Schultz-Flory distribution of oligomers has been accomplished by use of Group 4 transition-metal catalysts in the presence of methylaluminoxane (MAO). The oligomerization reaction was carried out at ambient temperature in a sealed reaction vessel with complete conversion of 1-butene at catalyst turnover numbers greater than 17,000. The combination of high catalyst activity without concomitant production of high polymer led to a highly efficient production of new hydrocarbon jet fuel candidates. The reaction proceeds with high regioselectivity; however, because achiral catalysts were used, several diastereoisomeric structures were produced and observed in the gas chromatography-mass spectrometry (GC-MS) chromatograms. The single and specific dimer formed in the reaction, 2-ethyl-1-hexene, was easily removed by distillation and then was itself dimerized using acid catalysis to yield a mixture of mono-unsaturated C16 compounds. Changes in the oligomerization catalyst led to production of fuels with excellent cold-flow viscosity without the need for a high-temperature distillation. Thus, removal of the dimer followed by catalytic hydrogenation (PtO2) led to a 100% saturated hydrocarbon fuel with a density of 0.78 g/mL, a viscosity of 12.5 cSt at −20° C. (ASTM 445), and a calculated heat of combustion of 44+ MJ/kg. By back-addition of hydrogenated dimer in varying amounts (6.6, 11.5, and 17 wt %), it is possible to tailor the viscosity of the fuel (8.5, 7, and 6.5 cSt, respectively).
There exist several commercial and research programs around the world aimed at creating foil-performance jet fuels based on alternative feedstocks. Traditionally, jet propulsion (IP) fuels contain a complicated array of saturated and aromatic hydrocarbons that are highly refined to meet fuel specifications for a particular application. For instance, the Navy's JP-5 has a significantly higher flash point (60° C.) in comparison to the Air Force IP-8 and commercial jet fuel (about 38° C.). (Corporan, E.; DeWitt M. J.; Belovich, V.; Pawlik, R.; Lynch, A. C.; Gord, J. R.; Meyer, T. R. Energy Fuels 2607, 21, 2615-2626) (Chang, P. H.; Colbert, J. E.; Hardy, D. R.; Leonard, J. T. Prepr. Pap. Am Chem. Soc. Div. Pet. Chem. 2004, 49, 414). Syntroleum and Sasol have independently produced JP-5 and JP-8 equivalents based on gas-to-liquid (GTL) Fischer-Tropsch processes. (Freeks, R. L.; Muzzell, P. A. Prepr. Pap. Am Chem. Soc., Div. Pet. Chem. 2004, 49, 407-410) (Muzzell, P. A.; Feerks, R. L.; Baltrus, J. P.; Link, D. D. Prepr. Pap. Am Chem. Soc., Div. Pet. Chem. 2004, 49, 411-413) and (Lamprecht, D. Energy Fuels 2007, 21, 1448-1453). One of the most challenging aspects to making a jet fuel using Fischer-Tropsch chemistry (Fischer, F.; Tropsch, H. Brennst. Chem. 1923, 4, 276) has been to meet the required coldflow properties. To date, this has required significant postprocessing or “reforming” of the fuel to increase the iso/normal paraffin product ratio. Typically, the Chevron isocracking technology produces a predominance of methyl branching at the 2 position of a hydrocarbon chain; however, the chemical product distribution is quite complicated.
Conversion of propene and butylenes to dimers/oligomers was one of the first commercial processes in the petroleum industry. (Sehmerling, L.; Ipatieff, V. N. Adv. Catal. 1950, 21, 2). Some more recent approaches have looked at using mesoporous catalysts and newly designed large-pore acidic zeolite catalysts. (Catani, R.; Mandreoli, M.; Rossini, S.; Vaccari, A. Catal. Today 2002, 75, 125-131) (Schmidt, R.; Welch, M. B.; Randolph, B. B. Energy Fuels 2008, 22 (2), 1.148-1155). Transition-metal catalysts (homo- and heterogeneous), generally grouped into the category of Ziegler-Natta (ZN), have enjoyed a successful history for converting olefins, in particular, ethylene and propene, into oligomeric and polymeric materials. (Natta, G. J. Polym. Sci. 1955, 16, 143) (Natta, G.; Pino, P.; Corradti, P.; Danusso, F.; Mantica, E.; Mazzanti. G.; Moraglio, G. J. Am. Chem. Soc. 1955, 77, 1708) (Natta, G. Angew. Chem. 1956, 12, 3931 Ziegler, K. Angew. Chem. 1952, 64, 323) (Ziegler, K.; Holzkamp, E.; Breil, H.; Martin, H. Angew. Chem., 1955, 67, 541) (Janiak, C. Coord Chem. ReV. 2606, 250, 66-94) (Belov, G. P. Petrol. Chem. 1994, 34, 105). Studies using 1-butene can involve a co-polymerization reaction with more reactive olefins, such as ethylene or propene. (Janiak, C.; Blank, F. Macromol. Symp. 2006, 236, 14-22). A study by Kaminsky explored the oligomerization of 1-butene using selected chiral Group 4 transition-metal catalysts and methylaluminoxane (MAO). (Kaminsky, W. Macromol. Symp. 1995, 89, 283-219). In general, the catalysts studied required elevated reaction temperatures and typically led to incomplete conversion of the 1-butene. A study by Christoffers and Bergman reported that using an aluminum/zirconium ratio of 1/1 and with a nearly stoichiometric amount of zirconium “catalyst” that 1-butene could be converted selectively to dimer (2-ethyl-1-hexene). (Christoffers, J.; Bergman, R. G. Inorg. Chim. Acta 1998, 270, 20).
In undertaking this research our goal was to create a foil-performance IP-5/tactical biojet fuel that can be derived from a fully renewable and sustainable source of reduced carbon. Carbon dioxide is initially reduced via photosynthesis (e.g., cellulose and triglyceride oils). Further reduction can occur in a second fermentation or microbial treatment, to afford an alternative biofuel and/or biofeedstock. (Wright, M. E.; Harvey, B. G.; Quintans, R. Prepr. Pap. Am. Chem. Soc., Fuel Div. 2008, 53 (1), 252-253.)
It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not to be viewed as being restrictive of the invention, as claimed. Further advantages of this invention will be apparent after a review of the following detailed description of the disclosed embodiments which are illustrated schematically in the accompanying drawings and in the appended claims.
Free Full Text Source: http://www.google.com/patents/US20140051898
Diesel and Jet Fuels Based on the Oligomerization of Butene (US Government As Represented By The Secretary Of Department Of The Navy)
Publication number US20140051898 A1
Application number US 13/763,829
Publication date Feb 20, 2014
Inventors
Michael E. Wright, Benjamin G. Harvey, Roxanne L. Quintana
Original Assignee
US Government As Represented By The Secretary Of Department Of The Navy
Abstract
A renewable biofuel based on a highly efficient batch catalysis methodology for conversion of 1-butene to a new class of potential jet fuel blends. By tuning the catalyst and then using the dimer produced, the carbon use is about 95% or greater. This latter point will be particularly important in the future, where the source of raw materials (i.e., biomass/biofeedstock) is limited.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
The invention described herein may be manufactured and used by or for the government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.
FIELD OF THE INVENTION
A renewable biofuel for turbine engines based on a highly efficient batch catalysis methodology for conversion of 1-butene to a new class of fuels.
BACKGROUND OF THE INVENTION
We demonstrate that the quantitative conversion of 1-butene to a Schultz-Flory distribution of oligomers has been accomplished by use of Group 4 transition-metal catalysts in the presence of methylaluminoxane (MAO). The oligomerization reaction was carried out at ambient temperature in a sealed reaction vessel with complete conversion of 1-butene at catalyst turnover numbers greater than 17,000. The combination of high catalyst activity without concomitant production of high polymer led to a highly efficient production of new hydrocarbon jet fuel candidates. The reaction proceeds with high regioselectivity; however, because achiral catalysts were used, several diastereoisomeric structures were produced and observed in the gas chromatography-mass spectrometry (GC-MS) chromatograms. The single and specific dimer formed in the reaction, 2-ethyl-1-hexene, was easily removed by distillation and then was itself dimerized using acid catalysis to yield a mixture of mono-unsaturated C16 compounds. Changes in the oligomerization catalyst led to production of fuels with excellent cold-flow viscosity without the need for a high-temperature distillation. Thus, removal of the dimer followed by catalytic hydrogenation (PtO2) led to a 100% saturated hydrocarbon fuel with a density of 0.78 g/mL, a viscosity of 12.5 cSt at −20° C. (ASTM 445), and a calculated heat of combustion of 44+ MJ/kg. By back-addition of hydrogenated dimer in varying amounts (6.6, 11.5, and 17 wt %), it is possible to tailor the viscosity of the fuel (8.5, 7, and 6.5 cSt, respectively).
There exist several commercial and research programs around the world aimed at creating foil-performance jet fuels based on alternative feedstocks. Traditionally, jet propulsion (IP) fuels contain a complicated array of saturated and aromatic hydrocarbons that are highly refined to meet fuel specifications for a particular application. For instance, the Navy's JP-5 has a significantly higher flash point (60° C.) in comparison to the Air Force IP-8 and commercial jet fuel (about 38° C.). (Corporan, E.; DeWitt M. J.; Belovich, V.; Pawlik, R.; Lynch, A. C.; Gord, J. R.; Meyer, T. R. Energy Fuels 2607, 21, 2615-2626) (Chang, P. H.; Colbert, J. E.; Hardy, D. R.; Leonard, J. T. Prepr. Pap. Am Chem. Soc. Div. Pet. Chem. 2004, 49, 414). Syntroleum and Sasol have independently produced JP-5 and JP-8 equivalents based on gas-to-liquid (GTL) Fischer-Tropsch processes. (Freeks, R. L.; Muzzell, P. A. Prepr. Pap. Am Chem. Soc., Div. Pet. Chem. 2004, 49, 407-410) (Muzzell, P. A.; Feerks, R. L.; Baltrus, J. P.; Link, D. D. Prepr. Pap. Am Chem. Soc., Div. Pet. Chem. 2004, 49, 411-413) and (Lamprecht, D. Energy Fuels 2007, 21, 1448-1453). One of the most challenging aspects to making a jet fuel using Fischer-Tropsch chemistry (Fischer, F.; Tropsch, H. Brennst. Chem. 1923, 4, 276) has been to meet the required coldflow properties. To date, this has required significant postprocessing or “reforming” of the fuel to increase the iso/normal paraffin product ratio. Typically, the Chevron isocracking technology produces a predominance of methyl branching at the 2 position of a hydrocarbon chain; however, the chemical product distribution is quite complicated.
Conversion of propene and butylenes to dimers/oligomers was one of the first commercial processes in the petroleum industry. (Sehmerling, L.; Ipatieff, V. N. Adv. Catal. 1950, 21, 2). Some more recent approaches have looked at using mesoporous catalysts and newly designed large-pore acidic zeolite catalysts. (Catani, R.; Mandreoli, M.; Rossini, S.; Vaccari, A. Catal. Today 2002, 75, 125-131) (Schmidt, R.; Welch, M. B.; Randolph, B. B. Energy Fuels 2008, 22 (2), 1.148-1155). Transition-metal catalysts (homo- and heterogeneous), generally grouped into the category of Ziegler-Natta (ZN), have enjoyed a successful history for converting olefins, in particular, ethylene and propene, into oligomeric and polymeric materials. (Natta, G. J. Polym. Sci. 1955, 16, 143) (Natta, G.; Pino, P.; Corradti, P.; Danusso, F.; Mantica, E.; Mazzanti. G.; Moraglio, G. J. Am. Chem. Soc. 1955, 77, 1708) (Natta, G. Angew. Chem. 1956, 12, 3931 Ziegler, K. Angew. Chem. 1952, 64, 323) (Ziegler, K.; Holzkamp, E.; Breil, H.; Martin, H. Angew. Chem., 1955, 67, 541) (Janiak, C. Coord Chem. ReV. 2606, 250, 66-94) (Belov, G. P. Petrol. Chem. 1994, 34, 105). Studies using 1-butene can involve a co-polymerization reaction with more reactive olefins, such as ethylene or propene. (Janiak, C.; Blank, F. Macromol. Symp. 2006, 236, 14-22). A study by Kaminsky explored the oligomerization of 1-butene using selected chiral Group 4 transition-metal catalysts and methylaluminoxane (MAO). (Kaminsky, W. Macromol. Symp. 1995, 89, 283-219). In general, the catalysts studied required elevated reaction temperatures and typically led to incomplete conversion of the 1-butene. A study by Christoffers and Bergman reported that using an aluminum/zirconium ratio of 1/1 and with a nearly stoichiometric amount of zirconium “catalyst” that 1-butene could be converted selectively to dimer (2-ethyl-1-hexene). (Christoffers, J.; Bergman, R. G. Inorg. Chim. Acta 1998, 270, 20).
In undertaking this research our goal was to create a foil-performance IP-5/tactical biojet fuel that can be derived from a fully renewable and sustainable source of reduced carbon. Carbon dioxide is initially reduced via photosynthesis (e.g., cellulose and triglyceride oils). Further reduction can occur in a second fermentation or microbial treatment, to afford an alternative biofuel and/or biofeedstock. (Wright, M. E.; Harvey, B. G.; Quintans, R. Prepr. Pap. Am. Chem. Soc., Fuel Div. 2008, 53 (1), 252-253.)
It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not to be viewed as being restrictive of the invention, as claimed. Further advantages of this invention will be apparent after a review of the following detailed description of the disclosed embodiments which are illustrated schematically in the accompanying drawings and in the appended claims.
Free Full Text Source: http://www.google.com/patents/US20140051898
Method for making hexafluoro-2-butene (Honeywell)
PATENT
Method for making hexafluoro-2-butene (Honeywell)
Publication number US8461401 B2
Application number US 13/045,926
Publication date Jun 11, 2013
Also published as CN102884030A
Inventors
Hsueh Sung Tung, Haiyou Wang
Original Assignee
Honeywell International Inc.
Abstract
Hexafluoro-2-butene (HFO-1336) is a low global warming potential blowing agent, refrigerant and solvent. This invention provides a method for making the compound, including the cis-isomer, from the readily available raw materials, carbon tetrachloride and 3,3,3-trifluoropropene. The trans-isomer formed in the process can be isomerized into cis-isomer by the use of an isomerization catalyst.
BACKGROUND OF THE INVENTION
Hexafluoro-2-butene (HFO-1336) is a low global warming potential blowing agent, refrigerant and solvent. This invention provides a method for making the compound, including the cis-isomer.
SUMMARY OF THE INVENTION
The present invention is a new process to produce hexafluoro-2-butene (HFO-1336) from readily available raw materials, carbon tetrachloride (CCl4) and 3,3,3-trifluoropropene (TFP). Hexafluoro-2-butene is produced through intermediates including, CF3CHClCH2CCl3, and CF3CHClCH2CF3. The trans-isomer formed in the process can be isomerized into cis-isomer by the use of an isomerization catalyst.
An embodiment of the present invention is a process for manufacturing cis-hexafluoro-2-butene comprising the steps of:
(a) contacting carbon tetrachloride with 3,3,3-trifluoropropene in the presence of an effective amount of a metal catalyst complex comprising a metal and an organic ligand under conditions effective to facilitate an addition reaction and to form a product stream comprising CF3CHClCH2CCl3,
(b) contacting HF with the CF3CHClCH2CCl3 formed in (a) in the presence or absence of a fluorination catalyst under conditions effective to facilitate a fluorination reaction and to form a product stream comprising 1,1,1,4,4,4-hexafluoro-2-butene and/or 1,1,1,4,4,4-hexafluoro-2-chlorobutane,
(c) optionally dehydrochlorinating the 1,1,1,4,4,4-hexafluoro-2-chlorobutane in the presence or absence of a dehydrochlorination catalyst under conditions effective to form a product stream comprising 1,1,1,4,4,4-hexafluoro-2-butene; and
(d) optionally but preferably, after isolating cis-1,1,1,4,4,4-hexafluoro-2-butene product from trans-1,1,1,4,4,4-hexafluoro-2-butene, contacting the trans-1,1,1,4,4,4-hexafluoro-2-butene with an isomerization catalyst under conditions effective to form substantial amount of cis-1,1,1,4,4,4-hexafluoro-2-butene.
DETAILED DESCRIPTION OF THE INVENTION
Starting with carbon tetrachloride and 3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336) can be prepared through the following reaction steps:
(a) CCl4+CF3CH═CH2→CF3CHClCH2CCl3
(b) CF3CHClCH2CCl3+HF→CF3CH═CHCF3 (HFO-1336)+CF3CHClCH2CF3+HCl
(c) CF3CHClCH2CF3→HCl+CF3CH═CHCF3 (HFO-1336)
Two isomers, i.e., cis-CF3CH═CHCF3 and trans-CF3CH═CHCF3, are generally produced during reactions of steps (b) and (c). The cis-isomer is the preferred product in numerous applications. Thus, to increase the single pass yield of the cis-isomer, the trans-1336 can be isomerized into cis-1336 with the help of an isomerization catalyst, adding another optional step to the process, namely:
(d) trans-1336→cis-1336
Detailed Process Descriptions
Step (a): CCl4+CF3CH═CH2→CF3CHClCH2CCl3
In this step, carbon tetrachloride is reacted with 3,3,3-trifluoropropene (TFP) in the presence of an effective amount of a metal catalyst complex comprising a metal and an organic ligand under conditions effective to facilitate an addition reaction and to form a product stream comprising CF3CHClCH2CCl3.
In preferred embodiment, the metal catalyst complex has a boiling point higher than that of CF3CHClCH2CCl3 product, the metal is a transition metal selected from a group consisting of copper and iron, and the organic ligand is selected from the group consisting of primary and secondary amines having a backbone of 4 or more carbon atoms, nitrites having a backbone of 3 or more carbon atoms, amides having a backbone of two or more carbon atoms, and phosphates or phosphites having a backbone of 3 or more carbon atoms. Particularly, preferred combinations of catalysts and organic ligands are provided in Table 1. Mixtures of the above combination (e.g., mixture of 17 and 18) can also work very well.
Free Full Text Source: http://www.google.com/patents/US8461401
Method for making hexafluoro-2-butene (Honeywell)
Publication number US8461401 B2
Application number US 13/045,926
Publication date Jun 11, 2013
Also published as CN102884030A
Inventors
Hsueh Sung Tung, Haiyou Wang
Original Assignee
Honeywell International Inc.
Abstract
Hexafluoro-2-butene (HFO-1336) is a low global warming potential blowing agent, refrigerant and solvent. This invention provides a method for making the compound, including the cis-isomer, from the readily available raw materials, carbon tetrachloride and 3,3,3-trifluoropropene. The trans-isomer formed in the process can be isomerized into cis-isomer by the use of an isomerization catalyst.
BACKGROUND OF THE INVENTION
Hexafluoro-2-butene (HFO-1336) is a low global warming potential blowing agent, refrigerant and solvent. This invention provides a method for making the compound, including the cis-isomer.
SUMMARY OF THE INVENTION
The present invention is a new process to produce hexafluoro-2-butene (HFO-1336) from readily available raw materials, carbon tetrachloride (CCl4) and 3,3,3-trifluoropropene (TFP). Hexafluoro-2-butene is produced through intermediates including, CF3CHClCH2CCl3, and CF3CHClCH2CF3. The trans-isomer formed in the process can be isomerized into cis-isomer by the use of an isomerization catalyst.
An embodiment of the present invention is a process for manufacturing cis-hexafluoro-2-butene comprising the steps of:
(a) contacting carbon tetrachloride with 3,3,3-trifluoropropene in the presence of an effective amount of a metal catalyst complex comprising a metal and an organic ligand under conditions effective to facilitate an addition reaction and to form a product stream comprising CF3CHClCH2CCl3,
(b) contacting HF with the CF3CHClCH2CCl3 formed in (a) in the presence or absence of a fluorination catalyst under conditions effective to facilitate a fluorination reaction and to form a product stream comprising 1,1,1,4,4,4-hexafluoro-2-butene and/or 1,1,1,4,4,4-hexafluoro-2-chlorobutane,
(c) optionally dehydrochlorinating the 1,1,1,4,4,4-hexafluoro-2-chlorobutane in the presence or absence of a dehydrochlorination catalyst under conditions effective to form a product stream comprising 1,1,1,4,4,4-hexafluoro-2-butene; and
(d) optionally but preferably, after isolating cis-1,1,1,4,4,4-hexafluoro-2-butene product from trans-1,1,1,4,4,4-hexafluoro-2-butene, contacting the trans-1,1,1,4,4,4-hexafluoro-2-butene with an isomerization catalyst under conditions effective to form substantial amount of cis-1,1,1,4,4,4-hexafluoro-2-butene.
DETAILED DESCRIPTION OF THE INVENTION
Starting with carbon tetrachloride and 3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336) can be prepared through the following reaction steps:
(a) CCl4+CF3CH═CH2→CF3CHClCH2CCl3
(b) CF3CHClCH2CCl3+HF→CF3CH═CHCF3 (HFO-1336)+CF3CHClCH2CF3+HCl
(c) CF3CHClCH2CF3→HCl+CF3CH═CHCF3 (HFO-1336)
Two isomers, i.e., cis-CF3CH═CHCF3 and trans-CF3CH═CHCF3, are generally produced during reactions of steps (b) and (c). The cis-isomer is the preferred product in numerous applications. Thus, to increase the single pass yield of the cis-isomer, the trans-1336 can be isomerized into cis-1336 with the help of an isomerization catalyst, adding another optional step to the process, namely:
(d) trans-1336→cis-1336
Detailed Process Descriptions
Step (a): CCl4+CF3CH═CH2→CF3CHClCH2CCl3
In this step, carbon tetrachloride is reacted with 3,3,3-trifluoropropene (TFP) in the presence of an effective amount of a metal catalyst complex comprising a metal and an organic ligand under conditions effective to facilitate an addition reaction and to form a product stream comprising CF3CHClCH2CCl3.
In preferred embodiment, the metal catalyst complex has a boiling point higher than that of CF3CHClCH2CCl3 product, the metal is a transition metal selected from a group consisting of copper and iron, and the organic ligand is selected from the group consisting of primary and secondary amines having a backbone of 4 or more carbon atoms, nitrites having a backbone of 3 or more carbon atoms, amides having a backbone of two or more carbon atoms, and phosphates or phosphites having a backbone of 3 or more carbon atoms. Particularly, preferred combinations of catalysts and organic ligands are provided in Table 1. Mixtures of the above combination (e.g., mixture of 17 and 18) can also work very well.
Free Full Text Source: http://www.google.com/patents/US8461401
1-Butene isomerization and metathesis over Mo/mordenite-alumina: Factors influencing product distribution and induction period
Journal of Energy Chemistry, Volume 22, Issue 1, January 2013, Pages
145–150
1-Butene isomerization and metathesis over Mo/mordenite-alumina: Factors influencing product distribution and induction period
Xiujie Li (a), Xiangxue Zhu (a), Dazhou Zhang (a), Fucun Chen (a), Peng Zeng (b), Shenglin Liu (a), Sujuan Xie (a), Longya Xu (a)
a Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
b Liaoning Branches, China Huanqiu Contracting & Engineering Corporation, Fushun 113006, Liaoning, China
Abstract
Describes a study of the effects of space velocity, reaction temperature and support acidity on product distribution and induction period in 1-butene isomerization and metathesis over Mo/mordenite-alumina. Results revealed that induction period and objective product were closely related to reaction conditions.
Lower space velocity led to longer induction period and higher propene yield. 1-Butene auto-metathesis predominated in the reaction network as the support with lower degree of sodium exchanged. Propene gradually became the dominant product when increasing the support sodium exchange degree. 6Mo/H100Na0M-30Al catalyst with a support of full sodium exchange degree displayed the highest propene yield.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S2095495613600194
1-Butene isomerization and metathesis over Mo/mordenite-alumina: Factors influencing product distribution and induction period
Xiujie Li (a), Xiangxue Zhu (a), Dazhou Zhang (a), Fucun Chen (a), Peng Zeng (b), Shenglin Liu (a), Sujuan Xie (a), Longya Xu (a)
a Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
b Liaoning Branches, China Huanqiu Contracting & Engineering Corporation, Fushun 113006, Liaoning, China
Abstract
Describes a study of the effects of space velocity, reaction temperature and support acidity on product distribution and induction period in 1-butene isomerization and metathesis over Mo/mordenite-alumina. Results revealed that induction period and objective product were closely related to reaction conditions.
Lower space velocity led to longer induction period and higher propene yield. 1-Butene auto-metathesis predominated in the reaction network as the support with lower degree of sodium exchanged. Propene gradually became the dominant product when increasing the support sodium exchange degree. 6Mo/H100Na0M-30Al catalyst with a support of full sodium exchange degree displayed the highest propene yield.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S2095495613600194
Propene yield enhancement from metathesis of ethene and 2-butene on mixed HBeta-alumina supported molybdenum-based catalysts using aluminum nitrate as alumina precursor
Bulgarian Chemical Communications, Volume 45, Number 2 (191 – 196) 2013
Propene yield enhancement from metathesis of ethene and 2-butene on mixed HBeta-alumina supported molybdenum-based catalysts using aluminum nitrate as alumina precursor
B. Netiworaruksa (1), S. Phatanasri (1), P. Praserthdam (1), W. Phongsawat (1), K. Suriye (2)
1 Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
2 SCG Chemicals Co.,Ltd. 1Siam-cement Rd, Bang sue, Bangkok 10800, Thailand
Abstract
The mixed HBeta-alumina supported molybdenum-based catalysts with 4 wt% Mo loading were prepared by incipient wetness impregnation method. Aluminum nitrate and aluminum oxide were used as alumina precursors in mixing with HBeta zeolite followed by calcination at 550ºC. The catalyst using aluminum nitrate as alumina precursor, Mo/AN+Hß(550), markedly outperformed its counterpart using aluminum oxide as precursor, Mo/AO+Hß(550), in both 2–butene conversion and propene selectivity from metathesis of ethene and 2–butene. The relatively higher metal-support interaction, as well as the derivation of surface tetrahedral molybdenum oxide species were discernible on Mo/ AN+Hß(550), as observed from H2-TPR and UV-vis spectra, respectively. In addition, the higher acidity obtained on Mo/AN+Hß(550), presumably due to the better protection of HBeta zeolite structure achieved by the optimum compatibility between Al using aluminum nitrate as alumina precursor and HBeta, was believed to play a significant role for the enhancement of propene yield by metathesis of ethene and 2–butene.
This work aims at investigating the enhancement of propene production by metathesis of ethene and 2-butene on mixed HBeta-alumina supported molybdenum-based catalyst by adopting aluminum nitrate as a precursor for alumina. All catalysts were prepared by incipient wetness impregnation of 4 wt % of molybdenum on a mixed HBeta-alumina support. The catalyst characterization was conducted by employing techniques of BET surface area assessment, X-Ray diffraction, NH3-TPD, UV-vis spectra and H2-TPR.
Free Full Text Source: http://www.bcc.bas.bg/BCC_Volumes/Volume_45_Number_2_2013/Volume_45_Number_2_2013_PDF/BCC-54-2-191-196.pdf
Propene yield enhancement from metathesis of ethene and 2-butene on mixed HBeta-alumina supported molybdenum-based catalysts using aluminum nitrate as alumina precursor
B. Netiworaruksa (1), S. Phatanasri (1), P. Praserthdam (1), W. Phongsawat (1), K. Suriye (2)
1 Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
2 SCG Chemicals Co.,Ltd. 1Siam-cement Rd, Bang sue, Bangkok 10800, Thailand
Abstract
The mixed HBeta-alumina supported molybdenum-based catalysts with 4 wt% Mo loading were prepared by incipient wetness impregnation method. Aluminum nitrate and aluminum oxide were used as alumina precursors in mixing with HBeta zeolite followed by calcination at 550ºC. The catalyst using aluminum nitrate as alumina precursor, Mo/AN+Hß(550), markedly outperformed its counterpart using aluminum oxide as precursor, Mo/AO+Hß(550), in both 2–butene conversion and propene selectivity from metathesis of ethene and 2–butene. The relatively higher metal-support interaction, as well as the derivation of surface tetrahedral molybdenum oxide species were discernible on Mo/ AN+Hß(550), as observed from H2-TPR and UV-vis spectra, respectively. In addition, the higher acidity obtained on Mo/AN+Hß(550), presumably due to the better protection of HBeta zeolite structure achieved by the optimum compatibility between Al using aluminum nitrate as alumina precursor and HBeta, was believed to play a significant role for the enhancement of propene yield by metathesis of ethene and 2–butene.
This work aims at investigating the enhancement of propene production by metathesis of ethene and 2-butene on mixed HBeta-alumina supported molybdenum-based catalyst by adopting aluminum nitrate as a precursor for alumina. All catalysts were prepared by incipient wetness impregnation of 4 wt % of molybdenum on a mixed HBeta-alumina support. The catalyst characterization was conducted by employing techniques of BET surface area assessment, X-Ray diffraction, NH3-TPD, UV-vis spectra and H2-TPR.
Free Full Text Source: http://www.bcc.bas.bg/BCC_Volumes/Volume_45_Number_2_2013/Volume_45_Number_2_2013_PDF/BCC-54-2-191-196.pdf
Effect of 2-Butene Cis/Trans Isomers in the Metathesis of Ethylene and 2-Butene Over WO3/SiO2 Catalysts
Catalysis Letters, March 2014
Effect of 2-Butene Cis/Trans Isomers in the Metathesis of Ethylene and 2-Butene Over WO3/SiO2 Catalysts
Narongrat Poovarawan, Kongkiat Suriye, Sirachaya Kunjara Na Ayudhya, Joongjai Punpranot, Francisco José Cadete Santos Aires, Piyasan Praserthdam
1. Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok, 10330, Thailand
2. SCG Chemicals Co., Ltd., 1 Siam Cement Road, Bangsue, Bangkok, 10800, Thailand
3. Institut de Recherches sur la Catalyse et l’Environnement de Lyon, UMR 5256, CNRS/Université Lyon1, 2 Avenue Albert Einstein, 69626, Villeurbanne Cedex, France
Abstract
Researchers used pure 2 % trans-2-butene and the mixture of 1 % cis- and 1 % trans-2-butene as feed to react with ethylene in metathesis reaction in order to produce propylene. Their purpose was to investigate the effect of feed on WO3/SiO2 catalysts with various tungsten oxide loadings.
They observed that at high tungsten oxide loading, when the mixture of cis- and trans-2-butene was used as the reaction feed, the conversion of 2-butene was lower than when pure trans-2-butene was used. However, the effect of cis-2-butene isomer on the conversion of 2-butene was less pronounced at low tungsten oxide loading.
Full Text Source (Subscription or Fee): http://link.springer.com/article/10.1007/s10562-014-1230-8#
Effect of 2-Butene Cis/Trans Isomers in the Metathesis of Ethylene and 2-Butene Over WO3/SiO2 Catalysts
Narongrat Poovarawan, Kongkiat Suriye, Sirachaya Kunjara Na Ayudhya, Joongjai Punpranot, Francisco José Cadete Santos Aires, Piyasan Praserthdam
1. Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok, 10330, Thailand
2. SCG Chemicals Co., Ltd., 1 Siam Cement Road, Bangsue, Bangkok, 10800, Thailand
3. Institut de Recherches sur la Catalyse et l’Environnement de Lyon, UMR 5256, CNRS/Université Lyon1, 2 Avenue Albert Einstein, 69626, Villeurbanne Cedex, France
Abstract
Researchers used pure 2 % trans-2-butene and the mixture of 1 % cis- and 1 % trans-2-butene as feed to react with ethylene in metathesis reaction in order to produce propylene. Their purpose was to investigate the effect of feed on WO3/SiO2 catalysts with various tungsten oxide loadings.
They observed that at high tungsten oxide loading, when the mixture of cis- and trans-2-butene was used as the reaction feed, the conversion of 2-butene was lower than when pure trans-2-butene was used. However, the effect of cis-2-butene isomer on the conversion of 2-butene was less pronounced at low tungsten oxide loading.
Full Text Source (Subscription or Fee): http://link.springer.com/article/10.1007/s10562-014-1230-8#
Intensifying Propylene Production by 1-Butene Transformation on a K Modified HZSM-5 Zeolite-Catalyst
Ind. Eng. Chem. Res., Article ASAP, DOI: 10.1021/ie500082v, Publication
Date (Web): March 10, 2014
Intensifying Propylene Production by 1-Butene Transformation on a K Modified HZSM-5 Zeolite-Catalyst
Eva Epelde *, Ana G. Gayubo , Martin Olazar , Javier Bilbao , and Andrés T. Aguayo
Chemical Engineering Department, University of the Basque Country, P.O. Box 644, 48080 Bilbao, Spain
eva.epelde@ehu.es
Abstract
Reports the effect that operating conditions have in the selective transformation of 1-butene into propylene. A catalyst of HZSM-5 zeolite (SiO2/Al2O3 = 280) modified with 1 wt % K and agglomerated with bentonite and alumina was used in the study.
Researchers conducted kinetic runs in a fixed bed reactor. They evaluated kinetic performance at zero time and throughout time on stream in order to find the suitable conditions to maximize propylene yield and selectivity and minimize deactivation by coke.
Full Text Source (Subscription or Fee): http://pubs.acs.org/doi/abs/10.1021/ie500082v
Intensifying Propylene Production by 1-Butene Transformation on a K Modified HZSM-5 Zeolite-Catalyst
Eva Epelde *, Ana G. Gayubo , Martin Olazar , Javier Bilbao , and Andrés T. Aguayo
Chemical Engineering Department, University of the Basque Country, P.O. Box 644, 48080 Bilbao, Spain
eva.epelde@ehu.es
Abstract
Reports the effect that operating conditions have in the selective transformation of 1-butene into propylene. A catalyst of HZSM-5 zeolite (SiO2/Al2O3 = 280) modified with 1 wt % K and agglomerated with bentonite and alumina was used in the study.
Researchers conducted kinetic runs in a fixed bed reactor. They evaluated kinetic performance at zero time and throughout time on stream in order to find the suitable conditions to maximize propylene yield and selectivity and minimize deactivation by coke.
Full Text Source (Subscription or Fee): http://pubs.acs.org/doi/abs/10.1021/ie500082v
Catalytic oxidative dehydrogenation of 1-butene to 1,3-butadiene using CO2
Catalysis Communications, Volume 46, 10 February 2014, Pages 208–212
Catalytic oxidative dehydrogenation of 1-butene to 1,3-butadiene using CO2
Wenjin Yan, Qing Yue Kouk, Jizhong Luo, Yan Liu, Armando Borgna
Institute of Chemical & Engineering Sciences, A-STAR, 1 Pesek Road, Jurong Island 627833, Singapore
Abstract
Demand for 1,3-Butadiene (BD) expected to increase dramatically. Catalytic oxidative dehydrogenation (ODH) of 1-butene offers an alternative route to produce BD.
Researchers employed a soft oxidant, CO2, instead of O2. They selected Fe2O3 from a preliminary screening using Temperature Programmed Surface Reaction (TPSR). They observed that catalytic performance was greatly improved by supporting Fe2O3 on Al2O3. Results of their study demonstrate that both Fe2O3 and CO2 are involved in the reaction. The main byproducts, trans/cis-2-butenes, can also be converted to BD with similar BD yield.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S1566736713004895
Catalytic oxidative dehydrogenation of 1-butene to 1,3-butadiene using CO2
Wenjin Yan, Qing Yue Kouk, Jizhong Luo, Yan Liu, Armando Borgna
Institute of Chemical & Engineering Sciences, A-STAR, 1 Pesek Road, Jurong Island 627833, Singapore
Abstract
Demand for 1,3-Butadiene (BD) expected to increase dramatically. Catalytic oxidative dehydrogenation (ODH) of 1-butene offers an alternative route to produce BD.
Researchers employed a soft oxidant, CO2, instead of O2. They selected Fe2O3 from a preliminary screening using Temperature Programmed Surface Reaction (TPSR). They observed that catalytic performance was greatly improved by supporting Fe2O3 on Al2O3. Results of their study demonstrate that both Fe2O3 and CO2 are involved in the reaction. The main byproducts, trans/cis-2-butenes, can also be converted to BD with similar BD yield.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S1566736713004895
Production of 1-butene and propylene from ethylene (Equistar Chemicals)
PATENT
Production of 1-butene and propylene from ethylene (Equistar Chemicals)
Publication number US8395005 B2
Application number US 12/903,794
Publication date Mar 12, 2013
Also published as
CN103153922A, US20120095275, US20130172647, WO2012051427A1
Inventors
Steven T. Coleman, Gary A. Sawyer, Robert S. Bridges
Original Assignee
Equistar Chemicals, Lp, Lyondell Chemical Technology, L.P.
Abstract
A process for producing propylene and 1-butene is disclosed. The process comprises dimerizing ethylene in the presence of a dimerization catalyst to produce a dimerization mixture comprising 1-butene and 2-butenes. The dimerization mixture is distilled to produce a 1-butene stream containing 1-butene and ethylene, a 2-butenes stream, and a heavy stream. The 2-butenes stream is reacted with ethylene in the presence of a metathesis catalyst to produce a metathesis mixture comprising propylene, ethylene, and 2-butenes. Propylene is separated from the metathesis mixture.
Description
FIELD OF THE INVENTION
The invention relates to a process for producing propylene and 1-butene from ethylene.
SUMMARY OF THE INVENTION
Steam cracking of hydrocarbon feedstocks produces ethylene, propylene, butenes (1-butene, isobutene, cis-2-butene, and trans-2-butene), butadiene, isoprene, aromatics, gasoline components, etc. Ethylene and propylene are important building blocks in the chemical industry. The relative proportions of ethylene and propylene produced in a steam cracking operation can be modulated to a certain extent by changing the nature of the feedstock and by modifying the operating conditions of the cracking to meet the market need. However, sometimes the market needs cannot be met by such modulation.
Metathesis reaction offers an opportunity to convert surplus olefins to other desirable olefins. For example, 2-butenes (cis-2-butene and trans-2-butene) can react with ethylene in the presence of a metathesis catalyst to produce propylene (U.S. Pat. Nos. 4,575,575, 5,120,894, 5,300,718, 6,586,649, 6,683,019, and 7,074,976). In one example, a mixture of 1-butene and 2-butenes obtained from a steam cracking process is reacted with ethylene to produce propylene. The process also generates heavier olefins such as pentenes and hexenes, which are useful gasoline blending components. In another example, ethylene is dimerized to form a dimerization mixture containing 1-butene and 2-butenes, which reacts with ethylene in a metathesis reaction to produce propylene. In this process, the 1-butene present in the dimerization mixture may react with 2-butene to form 2-pentene. 1-Butene can also form 3-hexene through metathesis.
It is desirable to reduce the amount of gasoline components formed and improve the yield of propylene from such processes.
SUMMARY OF THE INVENTION
This invention is a process for producing propylene and 1-butene. The process comprises dimerizing ethylene in the presence of a dimerization catalyst to produce a dimerization mixture comprising 1-butene and 2-butenes (cis-2-butene and trans-2-butene). The dimerization mixture is distilled to produce a 1-butene stream containing 1-butene and unreacted ethylene, a 2-butenes stream, and a heavy stream. The 2-butenes stream is reacted with ethylene in the presence of a metathesis catalyst to produce a metathesis mixture comprising propylene, ethylene, and 2-butenes. Propylene is separated from the metathesis mixture.
Free Full Text Source: http://www.google.com/patents/US8395005
Production of 1-butene and propylene from ethylene (Equistar Chemicals)
Publication number US8395005 B2
Application number US 12/903,794
Publication date Mar 12, 2013
Also published as
CN103153922A, US20120095275, US20130172647, WO2012051427A1
Inventors
Steven T. Coleman, Gary A. Sawyer, Robert S. Bridges
Original Assignee
Equistar Chemicals, Lp, Lyondell Chemical Technology, L.P.
Abstract
A process for producing propylene and 1-butene is disclosed. The process comprises dimerizing ethylene in the presence of a dimerization catalyst to produce a dimerization mixture comprising 1-butene and 2-butenes. The dimerization mixture is distilled to produce a 1-butene stream containing 1-butene and ethylene, a 2-butenes stream, and a heavy stream. The 2-butenes stream is reacted with ethylene in the presence of a metathesis catalyst to produce a metathesis mixture comprising propylene, ethylene, and 2-butenes. Propylene is separated from the metathesis mixture.
Description
FIELD OF THE INVENTION
The invention relates to a process for producing propylene and 1-butene from ethylene.
SUMMARY OF THE INVENTION
Steam cracking of hydrocarbon feedstocks produces ethylene, propylene, butenes (1-butene, isobutene, cis-2-butene, and trans-2-butene), butadiene, isoprene, aromatics, gasoline components, etc. Ethylene and propylene are important building blocks in the chemical industry. The relative proportions of ethylene and propylene produced in a steam cracking operation can be modulated to a certain extent by changing the nature of the feedstock and by modifying the operating conditions of the cracking to meet the market need. However, sometimes the market needs cannot be met by such modulation.
Metathesis reaction offers an opportunity to convert surplus olefins to other desirable olefins. For example, 2-butenes (cis-2-butene and trans-2-butene) can react with ethylene in the presence of a metathesis catalyst to produce propylene (U.S. Pat. Nos. 4,575,575, 5,120,894, 5,300,718, 6,586,649, 6,683,019, and 7,074,976). In one example, a mixture of 1-butene and 2-butenes obtained from a steam cracking process is reacted with ethylene to produce propylene. The process also generates heavier olefins such as pentenes and hexenes, which are useful gasoline blending components. In another example, ethylene is dimerized to form a dimerization mixture containing 1-butene and 2-butenes, which reacts with ethylene in a metathesis reaction to produce propylene. In this process, the 1-butene present in the dimerization mixture may react with 2-butene to form 2-pentene. 1-Butene can also form 3-hexene through metathesis.
It is desirable to reduce the amount of gasoline components formed and improve the yield of propylene from such processes.
SUMMARY OF THE INVENTION
This invention is a process for producing propylene and 1-butene. The process comprises dimerizing ethylene in the presence of a dimerization catalyst to produce a dimerization mixture comprising 1-butene and 2-butenes (cis-2-butene and trans-2-butene). The dimerization mixture is distilled to produce a 1-butene stream containing 1-butene and unreacted ethylene, a 2-butenes stream, and a heavy stream. The 2-butenes stream is reacted with ethylene in the presence of a metathesis catalyst to produce a metathesis mixture comprising propylene, ethylene, and 2-butenes. Propylene is separated from the metathesis mixture.
Free Full Text Source: http://www.google.com/patents/US8395005
NaOH modified WO3/SiO2 catalysts for propylene production from 2‐butene and ethylene metathesis
Chinese
Journal of Catalysis 35 (2014) 232–241
NaOH modified WO3/SiO2 catalysts for propylene production from 2‐butene and ethylene metathesis
Surasa Maksasithorn (a), Damien P. Debecker (b), Piyasan Praserthdam (a), Joongjai Panpranot (a),
Kongkiat Suriye (c), Sirachaya Kunjara Na Ayudhya (c)
a Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn
University, Bangkok 10330, Thailand
b Institute of Condensed Matter and Nanoscience – Molecules, Solids and Reactivity (IMCN/MOST), Université catholique de Louvain, Croix du Sud 2/17,
1348 Louvain‐La‐Neuve, Belgium
c SCG Chemicals, Co., Ltd., 1 Siam Cement Road, Bangsue, Bangkok 10800, Thailand
Abstract
A WO3/SiO2 catalyst is used in industry to produce propylene from 2‐butene and ethylene metathesis. Catalysts with various WO3 loading (4% to 10%) were prepared by impregnation and tested for the metathesis of ethene and trans‐2‐butene. Ion exchange of NaOH onto the WO3/SiO2 catalyst was used to mitigate the acidity of the catalysts in a controlled way. At low WO3 loading, the treatment with large amounts of NaOH resulted in a significant decrease in metathesis activity concomitant with significant W leaching and marked structural changes (XRD, Raman). At higher WO3 loading (6% to 10%), the treatment with NaOH mainly resulted in a decrease in acidity. FT‐IR experiments after adsorption of pyridine showed that the Lewis acidic sites were poisoned by sodium. Nevertheless, the metathesis activity remained constant after the NaOH treatment. This suggested that the remaining acidity on the catalyst was enough to ensure the efficient formation of the carbene active sites. Interestingly, Na poisoning resulted in some modification of the selectivity. The mitigation of acidity was shown to favor propene selectivity over the formation of isomerization products (cis‐2‐butene, 1‐butene, etc.). Moreover, treatment with NaOH led to a shorter induction period and reduced coke formation on the WO3/SiO2 catalyst.
In the present study, researchers tested WO3/SiO2 catalysts that have different loading under conditions close to the industrial ones to evaluate the impact of Na poisoning. Infrared spectroscopy of pyridine adsorption was used to evaluate the impact of Brönsted and Lewis sites on metathesis activity. Authors discuss the effect of Na poisoning on the undesired side reactions, catalyst stability, and coke formation.
Free Full Text Source: http://www.chxb.cn/CN/article/downloadArticleFile.do?attachType=PDF&id=21229
NaOH modified WO3/SiO2 catalysts for propylene production from 2‐butene and ethylene metathesis
Surasa Maksasithorn (a), Damien P. Debecker (b), Piyasan Praserthdam (a), Joongjai Panpranot (a),
Kongkiat Suriye (c), Sirachaya Kunjara Na Ayudhya (c)
a Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn
University, Bangkok 10330, Thailand
b Institute of Condensed Matter and Nanoscience – Molecules, Solids and Reactivity (IMCN/MOST), Université catholique de Louvain, Croix du Sud 2/17,
1348 Louvain‐La‐Neuve, Belgium
c SCG Chemicals, Co., Ltd., 1 Siam Cement Road, Bangsue, Bangkok 10800, Thailand
Abstract
A WO3/SiO2 catalyst is used in industry to produce propylene from 2‐butene and ethylene metathesis. Catalysts with various WO3 loading (4% to 10%) were prepared by impregnation and tested for the metathesis of ethene and trans‐2‐butene. Ion exchange of NaOH onto the WO3/SiO2 catalyst was used to mitigate the acidity of the catalysts in a controlled way. At low WO3 loading, the treatment with large amounts of NaOH resulted in a significant decrease in metathesis activity concomitant with significant W leaching and marked structural changes (XRD, Raman). At higher WO3 loading (6% to 10%), the treatment with NaOH mainly resulted in a decrease in acidity. FT‐IR experiments after adsorption of pyridine showed that the Lewis acidic sites were poisoned by sodium. Nevertheless, the metathesis activity remained constant after the NaOH treatment. This suggested that the remaining acidity on the catalyst was enough to ensure the efficient formation of the carbene active sites. Interestingly, Na poisoning resulted in some modification of the selectivity. The mitigation of acidity was shown to favor propene selectivity over the formation of isomerization products (cis‐2‐butene, 1‐butene, etc.). Moreover, treatment with NaOH led to a shorter induction period and reduced coke formation on the WO3/SiO2 catalyst.
In the present study, researchers tested WO3/SiO2 catalysts that have different loading under conditions close to the industrial ones to evaluate the impact of Na poisoning. Infrared spectroscopy of pyridine adsorption was used to evaluate the impact of Brönsted and Lewis sites on metathesis activity. Authors discuss the effect of Na poisoning on the undesired side reactions, catalyst stability, and coke formation.
Free Full Text Source: http://www.chxb.cn/CN/article/downloadArticleFile.do?attachType=PDF&id=21229
Production Of Isoprene From Iso-Butanol (Total Research & Technology)
PATENT
Production Of Isoprene From Iso-Butanol (Total Research & Technology)
United States Patent Application 20130217942
Inventors:
Vermeiren, Walter (Houthalen, BE)
Gonzalez, José Castor (Jette, BE)
Application Number: 13/825749
Publication Date: 08/22/2013
Assignee:
Total Research & Technology Feluy (B-7181 Seneffe (Feluy), BE)
Abstract:
The present invention is a process to make isoprene comprising: •◦a) providing a reaction zone comprising an acidic aqueous solution,
◦b) introducing, continuously or intermittently, in said reaction zone
a mixture comprising (i) isobutanol and optionally (ii) t-butanol or an iso-butene precursor which is not isobutanol and not t-butanol or iso-butene or any combination of two or three of these (ii) components,
an aqueous solution of formaldehyde,
◦c) operating said reaction zone at conditions effective to dehydrate isobutanol and optionally (ii) t-butanol and optionally the iso-butene precursor to iso-butene and produce isoprene by reaction of formaldehyde and iso-butene while distilling away a mixture comprising produced isoprene, water, unreacted starting materials and other low boiling point components from this reaction zone to the outside of the reaction zone.
In another embodiment isobutanol provides 10% or more of the iso-butene for the isoprene synthesis.
In another embodiment isobutanol provides 20% or more of the iso-butene for the isoprene synthesis.
In another embodiment isobutanol provides 30% or more of the iso-butene for the isoprene synthesis.
In another embodiment isobutanol provides 40% or more of the iso-butene for the isoprene synthesis. In another embodiment isobutanol provides 50% to 100% of the iso-butene for the isoprene synthesis.
FIELD OF THE INVENTION
The present invention relates to a process for producing isoprene from iso-butanol, preferably obtained from renewable resources. Isoprene is used as a basic chemical starting material for various chemical products and elastomers. The limited supply and increasing cost of crude oil has prompted the search for alternative processes for producing hydrocarbon products such as isoprene. Iso-butanol can be obtained by fermentation of carbohydrates or by condensation of lighter alcohols, obtained by fermentation of carbohydrates. Made up of organic matter from living organisms, biomass is the world's leading renewable energy source.
BACKGROUND OF THE INVENTION
Conventionally isoprene is produced by extraction from pyrolysis gasoline, which is a byproduct of steamcracking of naphtha. The yield is typically very low, of the order of 1-3% of the produced ethylene. Hence it is difficult to justify this capital-intensive technology for only a small production capacity of isoprene. The process to isolate isoprene from pyrolysis gasoline consist first in the removal of cyclopentadiene by dimerisation and distillation. Next the pipirylenes are separated by superfractionation. The last steps consist in an extractive distillation using a solvent. Moreover the quality of isoprene obtained from pyrolysis gasoline is hard to guarantee as the specifications with respect to cyclopentadiene and pipirylenes are very severe and these compounds are plentiful present in the same pyrolysis gasoline. As pyrolysis gasoline contains only small amounts of isoprene (10-20%), a lot of byproducts (dicyclopentadiene and pipirylene) are produced according to the same laborious manner while their market value is not necessary in line with the evolution of the market value of isoprene.
Recently, there is a tendency to shift to lighter feedstock for steamcracking feeding. Most new steamcrackers are using ethane as feedstock that does not produce pyrolysis gasoline as byproduct. Also many naphtha-based steamcrackers are shifting to lighter feedstock because of its abundant availability and competitive advantage.
Other routes to produce isoprene are the isolation of isoamylenes from refinery and petrochemical cuts and perform a dehydrogenation into isoprene. This process is typically done over iron oxide catalyst promoted with potassium compounds at temperatures above 600° C. in presence of water steam and reduced pressure. As this reaction is limited by a thermodynamic equilibrium, only partial conversions can be obtained.
Isoprene can also be produced from isopentane by a double dehydrogenation.
In still another process, isoprene is produced by a two-step process. In the first step iso-butene, tertiary-butanol, di-t-butyl ether, methyl-t-butyl ether or ethyl-t-butyl ether is condensed with two molecules of formaldehyde to form dimethyloxirane. The dimethyloxirane is separated and purified. In the second step the dimethyloxirane is decomposed under appropriate conditions into isoprene and one molecule of formaldehyde. An improvement on the latter two-step process is a one-step process, in which iso-butene, tertiary-butanol, di-t-butyl ether, methyl-t-butyl ether or ethyl-t-butyl ether is directly reacted with formaldehyde into isoprene.
The U.S. Pat. No. 4,511,751 describes a process for producing isoprene in good yield. The process is characterized in that iso-butene and/or tertiary butanol and a formaldehyde source are fed, together with water, into an acidic aqueous solution continuously or intermittently while maintaining the reaction pressure in an adequate range and at the same time distilling off the product isoprene and unreacted starting materials, together with water, from the reaction zone.
The U.S. Pat. No. 4,593,145 describes a process for producing isoprene, characterized in that an alkyl-t-butyl ether and a formaldehyde source are fed, together with water, into an acidic aqueous solution continuously or intermittently while maintaining the reaction pressure in an adequate range and at the same time distilling off the product isoprene, unreacted starting materials, iso-butene and tertiary butanol, together with water, from the reaction zone.
EP106323 describes a process for producing isoprene by reacting iso-butene and/or tertiary butanol and/or an alkyl tertiary butyl ether which gives iso-butene and/or tertiary butanol under the reaction conditions with formaldehyde in an acidic aqueous solution, under such conditions (a) that the acidic aqueous solution is present in the reaction zone, (b) that iso-butene and/or tertiary butanol and/or the alkyl tertiary butyl ether, a formaldehyde source and water are fed to said reaction zone continuously or intermittently, and (c) that isoprene, water, unreacted starting materials and other low-boiling components are distilled off from said reaction zone, wherein a glycol ether is added, in an amount of 5 to 15 percent by weight, to the acid aqueous solution. It is specified that the presence of a solvent in the reactor improves the solubility of iso-butene in the aqueous phase and hence the contact with the acid catalyst that is substantially dissolved in the aqueous solution.
EP 1 614 671 A1 describes process for producing isoprene, which includes continuously or intermittently supplying iso-butene and/or t-butanol, formaldehyde and water into an acidic aqueous solution, and reacting the reaction mixture while distilling away a mixture containing produced isoprene, water, unreacted starting materials and other low boiling point components from this reaction mixture to the outside of the reaction system, wherein the reaction is carried out while controlling the concentration of high boiling point byproducts, which is produced and accumulated in the reaction mixture, to fall within the range of 0.5-40 mass %.
EP 2 157 072 A1 describes a method to obtain isoprene by way of liquid-phase interaction between trimethyl carbinol (also known as t-butanol, or its water solutions) and formaldehyde (or its source substances) in the presence of acidic catalyzer water solution; this can be made in one or several contacting stages, with use (at the final contacting stage) of separation reactor containing a heat supply zone, a reaction zone and a separation zone, with reaction products and water taken, out of the separation zone, in the form of a vapor flow to be subsequently cooled down, condensed and separated and with liquid flow of the catalyzer water solution put out for extraction and, after this, put back into the heating zone. As it goes from the reaction zone into the separation zone, the reactive flow is throttled. In the reaction zone, temperature is maintained at the level of 140-180° C., while pressure is 8-25 atmospheres; in the separation zone, pressure is 1.2-9.5 atmospheres. The separation reactor contains two or three separation zones. The balance quantity of water is put out of catalyzer water solution, which is circulating along the circuit, by way of its evaporation as the flow is throttled into the separation zone (zones) during regulation of the quantity of the circulating liquid phase in the interval of 0.2-6.0 parts of the total reaction zone area.
US 2010 0216958 A1 relates, in one embodiment, to a method of preparing butadiene comprising (a) providing an alcohol mixture comprising one or more butanols; (b) contacting the alcohol mixture with a dehydration catalyst, thereby forming an olefin mixture comprising one or more linear butenes and isobutene; (c) contacting the olefin mixture of step (b) with a dehydrogenation catalyst, thereby forming a di-olefin mixture comprising butadiene and isobutene; and (d) isolating butadiene from the di-olefin mixture of (c).
In another embodiment, it relates to a method of preparing isoprene comprising (a) providing an olefin mixture comprising one or more pentenes, with the proviso that at least a portion of the olefin mixture comprises one or more methylbutenes; (b) contacting the olefin mixture of (a) with a dehydrogenation catalyst, thereby forming a mixture comprising isoprene; and (c) isolating isoprene from the mixture of (b).
In still another embodiment, it relates to a method of preparing monomers, comprising: (a) providing an olefin mixture comprising one or more linear butenes and isobutene; (b) contacting the olefin mixture of step (a) with a dehydrogenation catalyst, thereby forming a di-olefin mixture comprising butadiene and isobutene; (c) isolating isobutene from the mixture of step (b); and (dl)) converting the isobutene to methyl t-butyl ether, ethyl t-butyl ether, isooctane, methacrolein, methyl methacrylate, butyl rubber, butylated hydroxytoluene, or butylated hydroxyanisole.
In still other embodiments, it relates to methods for preparing isobutene or isoprene as described herein, wherein the olefin mixture is prepared by dehydration of a renewable alcohol mixture comprising one or more renewable C4 or C5 alcohols.
Iso-butanol (2-methyl-1-propanol) has historically found limited applications and its use resembles that of 1-butanol. It has been used as solvent, diluents, wetting agent, cleaner additive and as additive for inks and polymers. Recently, iso-butanol has gained interest as fuel or fuel component as it exhibits a high octane number (Blend Octane R+M/2 is 102-103) and a low vapor pressure (RVP is 3.8-5.2 psi).
Iso-butanol is often considered as a byproduct of the industrial production of 1-butanol (Ullmann's encyclopedia of industrial chemistry, 6th edition, 2002). It is produced from propylene via hydroformylation in the oxo-process (Rh-based catalyst) or via carbonylation in the Reppe-process (Co-based catalyst). Hydroformylation or carbonylation makes n-butanal and iso-butanal in ratios going from 92/8 to 75/25. To obtain iso-butanol, the iso-butanal is hydrogenated over a metal catalyst. Iso-butanol can also be produced from synthesis gas (mixture of CO, H2 and CO2) by a process similar to Fischer-Tropsch, resulting in a mixture of higher alcohols, although often a preferential formation of iso-butanol occurs (Applied Catalysis A, general, 186, p. 407, 1999 and Chemiker Zeitung, 106, p. 249, 1982). Still another route to obtain iso-butanol, is the base-catalysed Guerbet condensation of methanol with ethanol and/or propanol (J. of Molecular Catalysis A: Chemical 200, 137, 2003 and Applied Biochemistry and Biotechnology, 113-116, p. 913, 2004).
Recently, new biochemical routes have been developed to produce selectively iso-butanol from carbohydrates. The new strategy uses the highly active amino acid biosynthetic pathway of microorganisms and diverts its 2-keto acid intermediates for alcohol synthesis. 2-Keto acids are intermediates in amino acid biosynthesis pathways. These metabolites can be converted to aldehydes by 2-keto-acid decarboxylases (KDCs) and then to alcohols by alcohol dehydrogenases (ADHs). Two non-native steps are required to produce alcohols by shunting intermediates from amino acid biosynthesis pathways to alcohol production (Nature, 451, p. 86, 2008 and US patent 2008/0261230). Recombinant microorganisms are required to enhance the flux of carbon towards the synthesis of 2-keto-acids. In the valine biosynthesis 2-ketoisovalerate is on intermediate. Glycolyse of carbohydrates results in pyruvate that is converted into acetolactate by acetolactate synthase. 2,4-dihydroxyisovalerate is formed out of acetolactate, catalysed by isomeroreductase. A dehydratase converts the 2,4-dihydroxyisovalerate into 2-keto-isovalerate. In the next step, a keto acid decarboxylase makes isobutyraldehyde from 2-keto-isovalerate. The last step is the hydrogenation of isobutyraldehyde by a dehydrogenase into iso-butanol.
Of the described routes towards iso-butanol above, the Guerbet condensation, the synthesis gas hydrogenation and the 2-keto acid pathway from carbohydrates are routes that can use biomass as primary feedstock. Gasification of biomass results in synthesis gas that can be converted into methanol or directly into iso-butanol. Ethanol is already at very large scale produced by fermentation of carbohydrates or via direct fermentation of synthesis gas into ethanol. So methanol and ethanol resourced from biomass can be further condensed to iso-butanol. The direct 2-keto acid pathway can produce iso-butanol from carbohydrates that are isolated from biomass. Simple carbohydrates can be obtained from plants like sugar cane, sugar beet. More complex carbohydrates can be obtained from plants like maize, wheat and other grain bearing plants. Even more complex carbohydrates can be isolated from substantially any biomass, through unlocking of cellulose and hemicellulose from lignocelluloses.
It is the object of the present invention to use of iso-butanol for the production of isoprene by condensation with formaldehyde. Without willing to be bound to any theory, it is believed that the t-butyl-carbocation is the reactive specie that attacks formaldehyde and that its presence in the aqueous solution where resides also the acid catalyst and the formaldehyde is essential for high reaction rates for the selective condensation reaction. The decomposition of iso-butanol is significantly slower than that of t-butanol under the reaction conditions and as a consequence iso-butanol will serve as efficient solvent that improves the solubility of iso-butene and enhances the presence of t-butyl-carbocations in the aqueous phase. t-Butanol tends to dehydrate too fast so that most of the iso-butene escapes from the aqueous reaction medium and hence a lot of recycling is required.
Free Full Text Source: http://www.freepatentsonline.com/y2013/0217942.html
Production Of Isoprene From Iso-Butanol (Total Research & Technology)
United States Patent Application 20130217942
Inventors:
Vermeiren, Walter (Houthalen, BE)
Gonzalez, José Castor (Jette, BE)
Application Number: 13/825749
Publication Date: 08/22/2013
Assignee:
Total Research & Technology Feluy (B-7181 Seneffe (Feluy), BE)
Abstract:
The present invention is a process to make isoprene comprising: •◦a) providing a reaction zone comprising an acidic aqueous solution,
◦b) introducing, continuously or intermittently, in said reaction zone
a mixture comprising (i) isobutanol and optionally (ii) t-butanol or an iso-butene precursor which is not isobutanol and not t-butanol or iso-butene or any combination of two or three of these (ii) components,
an aqueous solution of formaldehyde,
◦c) operating said reaction zone at conditions effective to dehydrate isobutanol and optionally (ii) t-butanol and optionally the iso-butene precursor to iso-butene and produce isoprene by reaction of formaldehyde and iso-butene while distilling away a mixture comprising produced isoprene, water, unreacted starting materials and other low boiling point components from this reaction zone to the outside of the reaction zone.
In another embodiment isobutanol provides 10% or more of the iso-butene for the isoprene synthesis.
In another embodiment isobutanol provides 20% or more of the iso-butene for the isoprene synthesis.
In another embodiment isobutanol provides 30% or more of the iso-butene for the isoprene synthesis.
In another embodiment isobutanol provides 40% or more of the iso-butene for the isoprene synthesis. In another embodiment isobutanol provides 50% to 100% of the iso-butene for the isoprene synthesis.
FIELD OF THE INVENTION
The present invention relates to a process for producing isoprene from iso-butanol, preferably obtained from renewable resources. Isoprene is used as a basic chemical starting material for various chemical products and elastomers. The limited supply and increasing cost of crude oil has prompted the search for alternative processes for producing hydrocarbon products such as isoprene. Iso-butanol can be obtained by fermentation of carbohydrates or by condensation of lighter alcohols, obtained by fermentation of carbohydrates. Made up of organic matter from living organisms, biomass is the world's leading renewable energy source.
BACKGROUND OF THE INVENTION
Conventionally isoprene is produced by extraction from pyrolysis gasoline, which is a byproduct of steamcracking of naphtha. The yield is typically very low, of the order of 1-3% of the produced ethylene. Hence it is difficult to justify this capital-intensive technology for only a small production capacity of isoprene. The process to isolate isoprene from pyrolysis gasoline consist first in the removal of cyclopentadiene by dimerisation and distillation. Next the pipirylenes are separated by superfractionation. The last steps consist in an extractive distillation using a solvent. Moreover the quality of isoprene obtained from pyrolysis gasoline is hard to guarantee as the specifications with respect to cyclopentadiene and pipirylenes are very severe and these compounds are plentiful present in the same pyrolysis gasoline. As pyrolysis gasoline contains only small amounts of isoprene (10-20%), a lot of byproducts (dicyclopentadiene and pipirylene) are produced according to the same laborious manner while their market value is not necessary in line with the evolution of the market value of isoprene.
Recently, there is a tendency to shift to lighter feedstock for steamcracking feeding. Most new steamcrackers are using ethane as feedstock that does not produce pyrolysis gasoline as byproduct. Also many naphtha-based steamcrackers are shifting to lighter feedstock because of its abundant availability and competitive advantage.
Other routes to produce isoprene are the isolation of isoamylenes from refinery and petrochemical cuts and perform a dehydrogenation into isoprene. This process is typically done over iron oxide catalyst promoted with potassium compounds at temperatures above 600° C. in presence of water steam and reduced pressure. As this reaction is limited by a thermodynamic equilibrium, only partial conversions can be obtained.
Isoprene can also be produced from isopentane by a double dehydrogenation.
In still another process, isoprene is produced by a two-step process. In the first step iso-butene, tertiary-butanol, di-t-butyl ether, methyl-t-butyl ether or ethyl-t-butyl ether is condensed with two molecules of formaldehyde to form dimethyloxirane. The dimethyloxirane is separated and purified. In the second step the dimethyloxirane is decomposed under appropriate conditions into isoprene and one molecule of formaldehyde. An improvement on the latter two-step process is a one-step process, in which iso-butene, tertiary-butanol, di-t-butyl ether, methyl-t-butyl ether or ethyl-t-butyl ether is directly reacted with formaldehyde into isoprene.
The U.S. Pat. No. 4,511,751 describes a process for producing isoprene in good yield. The process is characterized in that iso-butene and/or tertiary butanol and a formaldehyde source are fed, together with water, into an acidic aqueous solution continuously or intermittently while maintaining the reaction pressure in an adequate range and at the same time distilling off the product isoprene and unreacted starting materials, together with water, from the reaction zone.
The U.S. Pat. No. 4,593,145 describes a process for producing isoprene, characterized in that an alkyl-t-butyl ether and a formaldehyde source are fed, together with water, into an acidic aqueous solution continuously or intermittently while maintaining the reaction pressure in an adequate range and at the same time distilling off the product isoprene, unreacted starting materials, iso-butene and tertiary butanol, together with water, from the reaction zone.
EP106323 describes a process for producing isoprene by reacting iso-butene and/or tertiary butanol and/or an alkyl tertiary butyl ether which gives iso-butene and/or tertiary butanol under the reaction conditions with formaldehyde in an acidic aqueous solution, under such conditions (a) that the acidic aqueous solution is present in the reaction zone, (b) that iso-butene and/or tertiary butanol and/or the alkyl tertiary butyl ether, a formaldehyde source and water are fed to said reaction zone continuously or intermittently, and (c) that isoprene, water, unreacted starting materials and other low-boiling components are distilled off from said reaction zone, wherein a glycol ether is added, in an amount of 5 to 15 percent by weight, to the acid aqueous solution. It is specified that the presence of a solvent in the reactor improves the solubility of iso-butene in the aqueous phase and hence the contact with the acid catalyst that is substantially dissolved in the aqueous solution.
EP 1 614 671 A1 describes process for producing isoprene, which includes continuously or intermittently supplying iso-butene and/or t-butanol, formaldehyde and water into an acidic aqueous solution, and reacting the reaction mixture while distilling away a mixture containing produced isoprene, water, unreacted starting materials and other low boiling point components from this reaction mixture to the outside of the reaction system, wherein the reaction is carried out while controlling the concentration of high boiling point byproducts, which is produced and accumulated in the reaction mixture, to fall within the range of 0.5-40 mass %.
EP 2 157 072 A1 describes a method to obtain isoprene by way of liquid-phase interaction between trimethyl carbinol (also known as t-butanol, or its water solutions) and formaldehyde (or its source substances) in the presence of acidic catalyzer water solution; this can be made in one or several contacting stages, with use (at the final contacting stage) of separation reactor containing a heat supply zone, a reaction zone and a separation zone, with reaction products and water taken, out of the separation zone, in the form of a vapor flow to be subsequently cooled down, condensed and separated and with liquid flow of the catalyzer water solution put out for extraction and, after this, put back into the heating zone. As it goes from the reaction zone into the separation zone, the reactive flow is throttled. In the reaction zone, temperature is maintained at the level of 140-180° C., while pressure is 8-25 atmospheres; in the separation zone, pressure is 1.2-9.5 atmospheres. The separation reactor contains two or three separation zones. The balance quantity of water is put out of catalyzer water solution, which is circulating along the circuit, by way of its evaporation as the flow is throttled into the separation zone (zones) during regulation of the quantity of the circulating liquid phase in the interval of 0.2-6.0 parts of the total reaction zone area.
US 2010 0216958 A1 relates, in one embodiment, to a method of preparing butadiene comprising (a) providing an alcohol mixture comprising one or more butanols; (b) contacting the alcohol mixture with a dehydration catalyst, thereby forming an olefin mixture comprising one or more linear butenes and isobutene; (c) contacting the olefin mixture of step (b) with a dehydrogenation catalyst, thereby forming a di-olefin mixture comprising butadiene and isobutene; and (d) isolating butadiene from the di-olefin mixture of (c).
In another embodiment, it relates to a method of preparing isoprene comprising (a) providing an olefin mixture comprising one or more pentenes, with the proviso that at least a portion of the olefin mixture comprises one or more methylbutenes; (b) contacting the olefin mixture of (a) with a dehydrogenation catalyst, thereby forming a mixture comprising isoprene; and (c) isolating isoprene from the mixture of (b).
In still another embodiment, it relates to a method of preparing monomers, comprising: (a) providing an olefin mixture comprising one or more linear butenes and isobutene; (b) contacting the olefin mixture of step (a) with a dehydrogenation catalyst, thereby forming a di-olefin mixture comprising butadiene and isobutene; (c) isolating isobutene from the mixture of step (b); and (dl)) converting the isobutene to methyl t-butyl ether, ethyl t-butyl ether, isooctane, methacrolein, methyl methacrylate, butyl rubber, butylated hydroxytoluene, or butylated hydroxyanisole.
In still other embodiments, it relates to methods for preparing isobutene or isoprene as described herein, wherein the olefin mixture is prepared by dehydration of a renewable alcohol mixture comprising one or more renewable C4 or C5 alcohols.
Iso-butanol (2-methyl-1-propanol) has historically found limited applications and its use resembles that of 1-butanol. It has been used as solvent, diluents, wetting agent, cleaner additive and as additive for inks and polymers. Recently, iso-butanol has gained interest as fuel or fuel component as it exhibits a high octane number (Blend Octane R+M/2 is 102-103) and a low vapor pressure (RVP is 3.8-5.2 psi).
Iso-butanol is often considered as a byproduct of the industrial production of 1-butanol (Ullmann's encyclopedia of industrial chemistry, 6th edition, 2002). It is produced from propylene via hydroformylation in the oxo-process (Rh-based catalyst) or via carbonylation in the Reppe-process (Co-based catalyst). Hydroformylation or carbonylation makes n-butanal and iso-butanal in ratios going from 92/8 to 75/25. To obtain iso-butanol, the iso-butanal is hydrogenated over a metal catalyst. Iso-butanol can also be produced from synthesis gas (mixture of CO, H2 and CO2) by a process similar to Fischer-Tropsch, resulting in a mixture of higher alcohols, although often a preferential formation of iso-butanol occurs (Applied Catalysis A, general, 186, p. 407, 1999 and Chemiker Zeitung, 106, p. 249, 1982). Still another route to obtain iso-butanol, is the base-catalysed Guerbet condensation of methanol with ethanol and/or propanol (J. of Molecular Catalysis A: Chemical 200, 137, 2003 and Applied Biochemistry and Biotechnology, 113-116, p. 913, 2004).
Recently, new biochemical routes have been developed to produce selectively iso-butanol from carbohydrates. The new strategy uses the highly active amino acid biosynthetic pathway of microorganisms and diverts its 2-keto acid intermediates for alcohol synthesis. 2-Keto acids are intermediates in amino acid biosynthesis pathways. These metabolites can be converted to aldehydes by 2-keto-acid decarboxylases (KDCs) and then to alcohols by alcohol dehydrogenases (ADHs). Two non-native steps are required to produce alcohols by shunting intermediates from amino acid biosynthesis pathways to alcohol production (Nature, 451, p. 86, 2008 and US patent 2008/0261230). Recombinant microorganisms are required to enhance the flux of carbon towards the synthesis of 2-keto-acids. In the valine biosynthesis 2-ketoisovalerate is on intermediate. Glycolyse of carbohydrates results in pyruvate that is converted into acetolactate by acetolactate synthase. 2,4-dihydroxyisovalerate is formed out of acetolactate, catalysed by isomeroreductase. A dehydratase converts the 2,4-dihydroxyisovalerate into 2-keto-isovalerate. In the next step, a keto acid decarboxylase makes isobutyraldehyde from 2-keto-isovalerate. The last step is the hydrogenation of isobutyraldehyde by a dehydrogenase into iso-butanol.
Of the described routes towards iso-butanol above, the Guerbet condensation, the synthesis gas hydrogenation and the 2-keto acid pathway from carbohydrates are routes that can use biomass as primary feedstock. Gasification of biomass results in synthesis gas that can be converted into methanol or directly into iso-butanol. Ethanol is already at very large scale produced by fermentation of carbohydrates or via direct fermentation of synthesis gas into ethanol. So methanol and ethanol resourced from biomass can be further condensed to iso-butanol. The direct 2-keto acid pathway can produce iso-butanol from carbohydrates that are isolated from biomass. Simple carbohydrates can be obtained from plants like sugar cane, sugar beet. More complex carbohydrates can be obtained from plants like maize, wheat and other grain bearing plants. Even more complex carbohydrates can be isolated from substantially any biomass, through unlocking of cellulose and hemicellulose from lignocelluloses.
It is the object of the present invention to use of iso-butanol for the production of isoprene by condensation with formaldehyde. Without willing to be bound to any theory, it is believed that the t-butyl-carbocation is the reactive specie that attacks formaldehyde and that its presence in the aqueous solution where resides also the acid catalyst and the formaldehyde is essential for high reaction rates for the selective condensation reaction. The decomposition of iso-butanol is significantly slower than that of t-butanol under the reaction conditions and as a consequence iso-butanol will serve as efficient solvent that improves the solubility of iso-butene and enhances the presence of t-butyl-carbocations in the aqueous phase. t-Butanol tends to dehydrate too fast so that most of the iso-butene escapes from the aqueous reaction medium and hence a lot of recycling is required.
Free Full Text Source: http://www.freepatentsonline.com/y2013/0217942.html
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