WO2015034948A1 - A process for manufacturing acrylic acid, acrylonitrile and 1,4-butanediol from 1,3-propanediol - Google Patents
A process for manufacturing acrylic acid, acrylonitrile and 1,4-butanediol from 1,3-propanediol Download PDFInfo
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- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
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- C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
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- C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
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- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
- C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
- C07C33/03—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond in beta-position, e.g. allyl alcohol, methallyl alcohol
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C07C51/50—Use of additives, e.g. for stabilisation
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- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Definitions
- This invention relates to a process for manufacturing bio-acrylic acid, bio-acrylonitrile and bio- 1,4-butanediol from bio- 1,3 -propanediol through simple one or two step chemical processes.
- the bio- 1,3-propanediol used as the starting materials in the present invention is obtained from one or other renewable carbon resources through microbial fermentation.
- the present invention provides novel methods for manufacturing bio- acrylic acid, bio- 1,4-butanediol and bio-acrylonitrile using biomass-derived 1,3-propanediol which is currently manufactured at commercial scale in a cost-effective way using biological feedstock.
- Acrylic acid and its esters are important commodity chemicals used in the production of polyacrylic esters, elastomers, superabsorbent polymers, floor polishes, adhesives, paints, and the like.
- acrylic acid has been produced by hydroxycarboxylation of acetylene. This method utilizes nickel carbonyl and high pressure carbon monoxide, both of which are expensive and considered environmentally unfriendly.
- Myriant Corporation and Procter & Gamble are also independently developing a process involving vapor phase dehydroxylation of biomass-derived lactic acid.
- Metabolix is attempting to manufacture bio-acrylic acid using its FAST (fast acting selective thermolysis) process.
- Genomatica has developed a novel method for bio-acrylic acid manufacturing using fumaric acid derived from fermentation process.
- Genomatica technology utilizes ethylene and fumaric acid to perform metathesis reaction to produce acrylic acid.
- This present invention provides a simple two-step scalable process for manufacturing bio-acrylic acid using biomass-derived 1,3-propanediol.
- Succinic acid derived from biological feedstock such as glucose, sucrose, glycerol and cellulosic hydrolysates is being considered as a suitable drop-in feedstock in the manufacture of useful industrial chemicals such as 1,4-butanediol (BDO), gamma- butryolactone (GBL) and tetrahydrofuran (THF).
- BDO 1,4-butanediol
- GBL gamma- butryolactone
- THF tetrahydrofuran
- BDO is currently used as an industrial solvent in the manufacture of plastics and polyesters and is a precursor to useful chemicals like GBL and THF. It is a protic polar solvent, which is miscible with water.
- GBL is suitable as a solvent, to replace environmentally harmful chlorinated solvents, in the preparation of pyrrolidones used as a raw material in the manufacture of herbicides, rubber additives, and pharmaceuticals, and in the production of biodegradable polymers.
- THF is an aprotic, water miscible solvent used in organic chemistry. It is also widely used in the production of resins and polymers.
- the typical process to produce BDO starts from petrochemical-derived acetylene which is reacted with formaldehyde using Reppe chemistry. The resulting 1, 4-butynediol is then hydrogenated to form BDO.
- BDO There are several other chemical routes to synthesize BDO, but one of the most economical routes starts from butane as a raw material.
- butane is oxidized to produce maleic anhydride.
- maleic anhydride can be converted to BDO via the BP/Lurgi Geminox process or the Davy Technology Process.
- the former process recovers maleic anhydride as maleic acid and performs liquid-phase hydrogenation to produce a mixture of BDO with THF and/or GBL.
- maleic anhydride is esterified to dimethyl maleate, which is then vaporized and fed to a vapor-phase hydrogenation system to produce dimethyl succinate.
- Dimethyl succinate undergoes hydrogenolysis reaction to produce GBL and BDO, which can be further converted into THF. These products are separated by distillation and methanol is recycled back to the esterification reactor.
- Acrylonitrile is yet another commodity chemical that can be manufactured according to the present invention using biomass-derived 1,3 -propanediol as the starting material.
- Acrylonitrile is widely used in large quantities in a number of commercial products and processes, notably in clothing and plastics. It is used in the production of many different synthetic polymers (ABS - Acrylonitrile butadiene styrene; ASA - Acrylonitrile styrene acrylate; NBR - Nitrile butadiene rubber; and SAN - Styrene acrylonitrile).
- ABS is used in everything from children's LEGO toys to golf club heads and car parts.
- NBR is probably most identifiable in non-latex gloves, but is also used in synthetic leather, gaskets, and seals. SAN is most commonly found in kitchen products because of its higher tolerance for heat.
- acrylonitrile is industrially used as a starting reagent for the production of acrylic acid.
- acrylonitrile is obtained from propylene through oxidation reaction using bismuthphosphomoiybdate catalyst.
- Propylene used in the manufacture of acrylonitrile is derived as a byproduct of petroleum and natural gas refining.
- bio-based acrylonitrile from renewable resources.
- the present invention provides a novel method for manufacturing bio-acrylonitrile using biomass-derived 1,3 -propanediol as the starting material.
- This present invention provides a process for manufacturing bio-acrylic acid, bio- acrylonitrile and bio-l,4-butanediol from bio- 1,3-propanediol through one or two simple chemical reactions.
- Bio- 1,3 -propanediol suitable for this invention is derived from renewable carbon resources through fermentation using a biocatalyst.
- bio-acrylic acid is derived from a renewable carbon source through a process carried out in two stages.
- suitable biocatalysts are used to produce bio- 1 ,3 -propanediol through biological fermentation.
- biomass-derived 1 ,3-propanediol is converted into acrylic acid through a two-step chemical reaction.
- bio- 1,3 -propanediol is subjected to catalytic dehydration reaction leading to production of bio-allyl alcohol which in turn is oxidized to yield bio-acrylic acid.
- Bio- 1 ,3 -propanediol used in this invention is obtained from renewable carbon sources including, among other things, glucose, sucrose, glycerol and cellulosic hydrolysates through fermentation involving biocatalysts.
- biomass-derived 1,3-propanediol is obtained from renewable carbon resources through fermentation involving biocatalysts.
- biomass-derived, 1,3-propanediol is subjected to catalytic dehydration reaction under mild oxidizing condition to yield a mixture of bio-allyl alcohol and bio-acrolein which are subsequently fully-oxidized to yield bio-acrylic acid.
- biomass-derived 1 ,3-propanediol reacts with oxygen via homogeneous pathways at 400°-500°K.
- 1 ,3-propanediol undergoes dehydration and oxidative dehydrogenation to form, almost exclusively, acrolein (ca. 90% selectivity).
- the acrolein thus formed as a result of homogeneous oxidation reaction is subjected to further oxidation in the presence of heterogeneous catalyst to yield acrylic acid.
- bio- 1,3 -propanediol is subjected to single step oxydehydration reaction to yield acrylic acid.
- biomass-derived 1,3 -propanediol is subjected to dehydration reaction to yield allyl alcohol which in turn is subjected to animation reaction to yield bio-allyl amine.
- bio-allyl amine is subjected to an oxidation reaction to yield bio-acrylonitrile.
- bio-allyl alcohol is subjected to a single step reaction involving ammoxidation catalyst to yield acrylonitrile.
- a two-stage process for the production of bio-l,4-butanediol from renewable carbon resources is provided.
- 1,3 -propanediol is derived from carbon sources including glucose, sucrose, glycerol and cellulosic hydrolysates using a biocatalyst.
- biomass-derived 1,3 -propanediol is subjected to a dehydration reaction leading to the production of bio-allyl alcohol, which in turn is subjected to hydro formylation and a hydrogenation reaction to yield bio-1 ,4-butanediol and 2-methyl-l ,3-propanediol.
- bio-allyl alcohol derived from bio- 1,3 -propanediol is used as drop-in chemical intermediate in the conventional acrylic acid manufacturing plant designed to utilize propylene feedstock leading to the production of bio- acrylic acid.
- bio-allyl alcohol derived from bio-1 ,3- propanediol is used as a drop-in chemical intermediate in the conventional 1 ,4-butanediol manufacturing plant designed to utilize propylene oxide feedstock leading to the production of bio-1 ,4-butanediol .
- FIG. 1 Bio- Acrylic acid and bio-acrylonitrile production from biomass-derived 1,3- propanediol through allyl alcohol.
- the 1 ,3-propanediol useful for the present invention is derived from renewable carbon sources including glucose, sucrose, glycerol and cellulosic hydrolysates through fermentation involving biocatalysts.
- Biomass-derived 1,3 -propanediol is subjected to dehydration reaction to yield bio-allyl alcohol. Upon oxidation reaction, bio-allyl alcohol yields bio-acrylic acid.
- FIG. 2 Simplified process configuration for bio-acrylic production and purification. Biomass-derived 1,3-propanediol is subjected to sequential catalytic dehydration and catalytic oxidation reactions to yield bio-acrylic acid.
- FIG. 3 Bio-acrylic acid production from biomass-derived 1,3-propanediol through bioacrolein as an intermediate. Biomass-derived, 1,3-propanediol is subjected to catalytic dehydration reaction under mild oxidizing condition to yield a mixture of bio-acrolein and bio- allyl alcohol which are subsequently fully-oxidized to yield bio-acrylic acid. Also shown in this figure is the pathway for oxydehydration reaction of 1,3-propanediol leading to the production of acrylic acid.
- FIG. 4 Simplified process configuration for the bio-acrylic acid production and purification. Biomass-derived 1,3-propanediol is subjected to a catalytic dehydration reaction under mild oxidizing condition to yield a mixture of bio-acrolein and bio-allyl alcohol which are subsequently fully-oxidized to yield bio-acrylic acid. (023) FIG. 5. Simplified process configuration for the bio-acrylic acid production and purification. Biomass-derived 1,3-propanediol is subjected to a single-step oxydehydration reaction to yield bio-acrylic acid.
- FIG. 6 Simplified process configuration for the bio-acrylic acid production and purification.
- Biomass-derived 1,3-propanediol is subjected homogeneous oxidation reaction, to form, almost exclusively, acrolein (ca. 90% selectivity).
- the acrolein thus formed as a result of homogeneous oxidation reaction is subjected to further oxidation in the presence of heterogeneous catalyst to yield acrylic acid.
- FIG. 7 Bio-acrylonitrile production from biomass-derived 1,3-propanediol through allyl alcohol intermediate. Biomass-derived 1,3-propanediol is subjected to dehydration reaction to yield bio-allyl alcohol. Bio-allyl alcohol thus produced is subjected to amination reaction to yield bio-allyl amine which in turn is subjected to an oxidation reaction to yield bio-acrylonitrile. Also shown in the figure is the single step ammoxidation reaction converting bio-ally alcohol into bio-acrylonitrile.
- FIG. 8 Simplified process configuration for bio-acrylonitrile production. Biomass- derived 1,3-propanediol is subjected to catalytic dehydration reaction to yield allyl alcohol which in turn is subjected to sequential amination and oxidation reactions to yield bio-acrylonitrile.
- FIG. 9 Simplified process configuration for bio-acrylonitrile production involving single-step amino-oxidation reaction in an ammoxidation reactor. Biomass-derived 1,3- propanediol is subjected to dehydration reaction to yield allyl alcohol which in turn is subjected to combined amination and oxidation reactions in a single step to yield bio-acrylonitrile.
- FIG. 10 Bio-l,4-butanediol, bio-2-methyl- 1,3 -propanediol juid bio-n-propanol production from biomass-derived 1,3-propanediol through allyl alcohol intermediate.
- the 1,3- propanediol useful for the present invention is derived from renewable carbon sources including glucose, sucrose, glycerol and cellulosic hydrolysates through fermentation involving biocatalysts. Biomass-derived 1,3-propanediol is subjected to dehydration reaction to yield bio- allyl alcohol.
- bio-allyl alcohol Upon hydroformylation reaction in the presence of Rh-Phosphine catalyst and [CO/H2] gas mixture, bio-allyl alcohol yields bio-hydroxybutanal, methylhydroxypropanal and propanal which are subjected to a hydrogenation reaction in the presence of Raney Nickel catalyst under hydrogen gas to yield bio- 1,4-butanediol, bio-2-methyl-l,3-propanediol and bio-n- propanol.
- FIG. 11 Simplified process configuration for production of bio- 1,4-butanediol and bio- 2-methyl- 1,3 -propanediol.
- Biomass-derived 1,3 -propanediol is subjected to dehydration reaction to yield allyl alcohol which in turn is subjected to hydroformylation and hydrogenation reactions to yield bio- 1,4-butanediol and bio-2-methyl- 1,3 -propanediol.
- FIG. 12 Use of biomass-derived 1,3 -propanediol as a drop-in chemical in the conventional process for the production of acrylic acid and acrylonitrile.
- propylene is oxidized to yield acrolein which in turn yields acrylic acid upon further oxidation.
- 1,3 -propanediol is derived from biomass- derived carbon sources through fermentation process involving biocatalysts. Upon dehydration reaction, biomass-derived 1,3 -propanediol yields bio-allyl alcohol which h turn is used as a drop-in chemical in the conventional process for the production of bio-acrylic acid involving acrolein as an intermediate.
- FIG. 13 Use of bio-allyl alcohol as a drop-in chemical in the conventional process for the production of 1 ,4-butanediol.
- propylene oxide is isoraerized to yield allyl alcohol which in turn is subjected to hydroformylation and hydrogenation reactions to yield 1,4-butanediol.
- 1,3 -propanediol is derived from biomass-derived carbon sources through fermentation process involving biocatalysts.
- FIG. 14 Elution profile of 1 ,3 -propanediol and allyl alcohol as detected under the HPLC conditions used in the present invention.
- FIG. 15 Elution profile of acrylic acid and allyl alcohol as detected under the HPLC conditions used in the present invention.
- the allyl alcohol (5.542 minute) and acrylic acid (9.156 minute) peaks were well separated under the experimental conditions described in Example 1.
- the present invention provides methods for producing bio-acrylic acid, bio-acrylonitrile and bio-l,4-butanediol using bio- 1,3-propanediol as the starting material.
- bio placed as a prefix to each of the commodity chemicals of the present invention means that the carbon atoms in each of those commodity chemicals are derived from renewable materials that are produced naturally in plants.
- the biomass-derived chemicals of the present invention including bio- 1,3 -propanediol, bio-acrylonitrile, bio-acrylic acid and bio- 1,4 butanediol have been traditionally manufactured from petroleum feedstock.
- the prefix "bio” is used in this patent specification for the purpose of distmguishing the products obtained by using the manufacturing process according to the present invention from similar products derived from the traditional manufacturing process involving petroleum feedstock.
- the bio-based commodity chemicals manufactured according to the present invention can be distinguished from the similar commodity chemicals manufactured following the traditional methods involving petroleum feedstock on the basis of their carbon 14 content following the method ASTM-D6866 provided by American Society of Testing and Materials.
- Cosmic radiation produces 14 C ("radiocarbon") in the stratosphere by neutron bombardment of nitrogen.
- 14 C atoms combine with oxygen atom in the atmosphere to form heavy 14 C0 25 which, except in the radioactive decay, is indistinguishable from the ordinary carbon dioxide.
- WO2009/155085 A2 provides isocyanate and polyisocyanate compositions comprising more than 10 percent of carbon derived from renewable biomass resources.
- U.S. Patent No. 6,428,767 provides a new polypropylene terephthalate composition.
- This new polypropylene terephthlate is comprised of 1,3 -propanediol and terephthalate.
- the 1,3 -propanediol used in this composition is produced by the bioconversion of a fermentable carbon source, preferably glucose.
- the resulting polypropylene terephthalate is distinguished from a similar polymer produced using petrochemical feedstock on the basis of dual carbon-isotopic fingerprinting which indicates the source and the age of the carbon.
- biomass refers to carbohydrates, sugars, glycerol and lignocellulosic materials derived from renewable plant resources which can be used in the fermentative production of commodity chemicals including 1,3-propanediol.
- dehydration or "dehydroxylation” as used in the present invention refers to a chemical reaction that removes one or more water molecules from a chemical compound.
- hydrolysis or “hydroxylation' as used in the present invention refers to a chemical reaction that adds one or more water molecules to a chemical compound.
- oxidation refers to the addition of an oxygen atom to a chemical compound or removal of hydrogen atoms.
- hydroformylation refers to the addition of a hydrogen atom and carbon monoxide to a chemical compound.
- hydrolysis refers to the addition of a hydrogen atom to a chemical compound.
- oxydehydration refers to a chemical reaction involving both dehydration and oxidation reaction.
- biocatalyst refers to a microbial organism that has been genetically modified to produce one or other industrially useful chemicals using biomass-derived sugars in a fermentative process.
- conversion refers to the percent of the reactant that has been used in a chemical conversion process. For example, when a compound "A” is converted into another compound “B” in a chemical reaction, the conversion efficiency of the chemical reaction is obtained using the Equation (1).
- selectivity refers to the percentage of a particular product formed in a chemical reaction among the plurality of the products formed in that particular chemical reaction. For example, when a chemical reaction yields products “A”, “B”, “C” and “D”, the selectivity of that chemical reaction to the product "A” is obtained using the Equation (2).
- a large number of carbohydrate materials derived from natural plant resources can be used as a feedstock in conjunction with the fermentative production of 1,3 -propanediol used as a starting material in the present invention.
- the cereal crops like maize and wheat contain starch as their primary carbohydrate material and require pre-hydrolysis step prior to sugar fermentation.
- the sugar crops such as sugar cane and sugar beet contain readily fermentable sucrose.
- the cereal crops and sugar crops are considered as the first generation feedstock in the manufacture of renewable chemicals including 1,3 -propanediol.
- first generation feedstock in the production of renewable chemicals is not sustainable in the long run due to the concerns about human food security and land-use issues. There has been effort to develop second generation feedstock which would reduce the cost of production of renewable chemicals further.
- second generation feedstock refers to non-food lignocellulosic biomass.
- Lignocellulose is the most abundant form of renewable carbon on the earth. Lignocellulosic biomass available for renewable chemical feedstock manufacturing can be grouped under two categories.
- Biowaste material including straws, corn residues (stover, fibers, and cobs), woody wastes/chipping, forestry residues, old paper/cardboard, bagasse, spent grain, municipal solid waste, agricultural residues (oil seed pulp, sugar beet pulp, etc.);
- Energy crops including but not limited to short rotation crops such as basket willow (Salix viminalis), energy grass (Miscanthus giganteus), alfalfa (Medicago sativa), switch grass (Panicumyigratum), reed canary grass (Arundo donax), rye grass etc.
- Lignocellulosic biomass consists of roughly 40-50% of hexose sugars and 10-30% of pentose sugars.
- the hexose sugars are known in the art as C6 sugars.
- the pentose sugars are known in the art as C5 sugars.
- the lignocellulosic materials yield a mixture of sugars that includes glucose, xylose, arabinose, mannose and galactose.
- the E. coli strain useful in the fermentative production of lactic acid described in U.S. Patent No. 7,223,567 uses a rich medium supplemented with glucose as the source of carbon.
- the E. coli strain KJ122 useful for the production of succinic acid described by Jantama et al (2008a; 2008b) and in the published PCT Patent Application Nos. WO/2008/021141 A2 and WO2010/115067 A2 and the U.S. Patent No. 8,691,539 requires a minimal medium supplemented with glucose.
- a method to make the microorganisms co- utilize the different sugars such as C5 and C6 sugars through a relief of catabolite repression during the production of industrial chemicals in a commercial scale would be critical to lowering the cost of industrial chemicals produced by fermentation.
- the C5 and C6 sugars from the lignocellulosic hydrolysate can be recovered in separate streams and subsequently fed to the biocatalysts at different times in order to maximize the use of both C5 and C6 fermentable sugars recovered from lignocellulosic biomass.
- Sucrose from cane and beet, glucose, whey containing lactose, maltose and dextrose from hydrolyzed starch, glycerol from biodiesel industry, sugars derived from the hydrolysis of variety of lignocellulosic materials and combinations thereof may be suitable for the fermentative production of 1,3-propanediol used as the starting material in the present invention.
- a microbial biocatalyst with ability to utilize both 6-carbon containing sugars such as glucose and 5-carbon containing sugars such as xylose simultaneously as provided in the U.S. Patent Application Publication No. 2012/0202259 is a preferred bacterial strain for developing a biocatalyst for the production of 1,3-propanediol.
- Bio- 1,3 -propanediol derived from biological feedstock using one or other biocatalysts described in one or other United States Patent document cited in this specification is suitable for use in several chemical applications as described in the present invention.
- Bio- 1,3 -propanediol can be used as a substrate in the formulation of polyesters, polyethers, polyurethanes, adhesives, composites laminates, coatings and moldings.
- bio- 1,3 -propanediol is useful as a solvent or antifreeze agent.
- Bio-l,3-propanediol is currently used in the commercial manufacture of Sorona® Polymer with acceptable levels of softness, stretch & recovery, vibrant colors and printability qualities.
- the present invention introduce yet another use for bio- 1,3- propanediol namely the manufacture of bio-acrylic acid, bio-acrylonitrile and bio-l,4-butanediol.
- Biocatalysts suitable for the industrial scale fermentative production of bio- 1,3- propanediol have been developed using metabolic engineering techniques and are currently in commercial use (Nakamura et al., Curr. Opin. Biotech. 14, 454 (2003); Raynaud et al., Proc. Natl. Aca. Sci. USA 100, 5010 (2003); Mendes et al., App. Microbio. Biotech. 92, 519 (2011); Nielsen, Nature Chem Biol. 7, 408 (2011); Zeng et al., Curr. Opin. Biotech. 22, 749 (2011)).
- Bio-PDO biomass derived 1,3 -propanediol
- biocatalysts and the processes known in the art for the fermentative production of 1,3 -propanediol can be used to obtain bio-1,3- propanediol useful as the starting material for manufacturing bio-acrylic acid, bio-acrylonitrile and bio- 1,4-butanediol according to the present invention.
- glycerol that is currently obtained as a byproduct from biodiesel industry can be used as a starting raw material for the production of acrylic acid, acrylonitrile, and 1,4-butanediol according to the present invention.
- glycerol is used as a raw material in the synthesis of 1,3-propanediol. This can be achieved in two different ways. There are known methods for the chemical conversion of glycerol directly into 1 ,3-propanediol using either chemical catalysts or certain enzymes. Alternately, glycerol can be used as a carbon source for the fermentative production of 1,3- propanediol using certain biological catalysts.
- bio-acrylic acid from bio-l,3propanediol can be achieved through two different pathways each involving two different stages as illustrated in Figures 1 and 3.
- carbon sources such as glucose, sucrose, glycerol or cellulosic hydrolysates are subjected to fermentation involving biocatalysts leading to the production of bio- 1,3 -propanediol.
- both these pathways involve two distinct chemical reactions.
- bio-allyl alcohol is obtained as an intermediate through dehydration of bio-l,3-propanediol ( Figure 1).
- bio-allyl alcohol can also be obtained directly from glycerol through catalyst-mediated dehydration and hydrogenation reaction.
- the bio-allyl alcohol thus obtained is subsequently subjected to an oxidation reaction to yield acrylic acid ( Figure 1).
- biomass-derived 1,3 -propanediol is subjected to a dehydration reaction under milder oxidizing conditions to yield a mixture of bio-acrolein and bio-allyl alcohol ( Figure 3).
- Bio-acrolein is also obtained directly from glycerol through catalyst mediated dehydration reaction.
- Bio-acrolein can also be obtained from bio- 1,3 -propanediol through homogeneous oxidation reaction without the use of any catalyst ((Diaz et al., ChemSusChem 3, 1063 (2010)).
- the bio-acrolein + bio-allyl alcohol mixture obtained as an intermediate is subsequently oxidized to yield bio-acrylic acid ( Figures 3).
- bio-allyl alcohol and bio-acrolein derived from bio-based 1,3 -propanediol can be used as a drop-in chemical intermediate in the conventional petrochemical feedstock-based acrylic acid manufacturing plant ( Figure 12).
- Figure 12 In the conventional chemical process for the production of acrylic acid, propylene is oxidized to yield acrolein which in turn yields acrylic acid upon further oxidation.
- 1,3 -propanediol is derived from biomass- derived carbon sources through fermentation process involving biocatalysts.
- biomass-derived 1,3 -propanediol yields bio-allyl alcohol which upon milder oxidation yields acrolein which in turn is used as a drop-in chemical in the conventional process for the production of bio-acrylic acid involving bio-acrolein as an intermediate.
- FIG. 62 provides simplified process configuration for bio-acrylic production and purification.
- biomass-derived 1,3 -propanediol is subjected to sequential catalytic dehydration and catalytic oxidation reactions to yield bio-acrylic acid.
- FIG. 4 provides simplified process configuration for the bio -acrylic acid production and purification.
- Biomass-derived 1,3 -propanediol is subjected to a catalytic dehydration reaction under milder oxidizing condition to yield a mixture of bio-acrolein and bio-allyl alcohol which are subsequently fully-oxidized to yield bio-acrylic acid.
- FIG. 6 provides simplified process configuration for the bio-acrylic acid production and purification. Biomass-derived 1,3 -propanediol is subjected to a single-step oxy dehydration reaction to yield bio -acrylic acid.
- FIG. 6 provides simplified process configuration for the bio-acrylic acid production and purification.
- Biomass-derived 1,3 -propanediol is subjected homogeneous oxidation reaction, to form, almost exclusively, acrolein.
- the acrolein thus formed as a result of homogeneous oxidation reaction is subjected to further oxidation in the presence of heterogeneous catalyst to yield acrylic acid.
- Catalytic dehydration of bio-l,3-propanediol to produce allyl alcohol Catalytic conversion of 1,3 -propanediol into ally alcohol is well-known in the art and it is an endothermic reaction. Both the reactant (1,3 -propanediol) and the product (allyl alcohol) are symmetrical alcohols and are stable compounds. The catalytic conversion of 1,3 -propanediol into allyl alcohol results in minimal byproducts.
- Ce0 2 catalyzes the dehydration of 1,3 -diols into unsaturated alcohols (Vivier, L. and Duprez, D., ChemSusChem 3, 654 (2010)). Selective dehydration of diols to allylic alcohols catalyzed by Ceria has been reported. Ce0 2 catalyzed the dehydration of 1,3 -propanediol to 2- propen-l -ol (allyl alcohol) with the maximum selectivity of 98.9 mol% at 325°C (Sato et al., Catalysis Comm. 4, 77 (2003).
- Indium oxide (ln 2 0 3 ) with cubic bixbyite structure is another catalyst useful for the vapor-phase catalytic dehydration of 1,3 -propanediol to allyl alcohol in the temperature range of 300°C-375°C.
- the selectivity to allyl alcohol in the dehydration reaction of 1,3 -propanediol using ln 2 0 3 as a catalyst was higher than 90% with 2-propenal (acrolein) and acetaldehyde as the major byproducts (Segawa et al. dislike J. Mol. Cata. A: Chemical 310, 166 (2009).
- US Patent No. 7,259,280 has provided improvements of the cerium-containing catalysts in the production of allyl alcohol for the purpose of making this catalytic production of allyl alcohol commercially viable.
- the disclosures of U.S. Patent No. 7,259,280 related to the cerium catalyst is incorporated herein by reference.
- cerium compounds including cerium oxides, hydroxides, nitrates, sulfates, halides and carboxylates, and mixtures thereof are useful for the dehydration of 1,3- propanediol to allyl alcohol.
- Cerium (IV) oxide, cerium (IV) hydroxide, cerium (IV) nitrate, cerium (IV) sulfate, cerium (IV) perchlorate, cerium (IV) acetate, cerium (IV) fluoride, cerium (IV) acetylacetate, cerium (IV)bromide, cerium (III) carbonate, cerium (III) chloride, and cerium (III) fluoride can be used in the preparation of the catalyst according to the present invention. It is necessary to convert any cerium compound to cerium oxide before the catalyst is used in the dehydration reaction.
- the cerium catalyst according to the present invention is supported on a carrier selected from alumina, silica, titania, zirconia, magnesia, carbonate, magnesium, carbonate, silica- alumina, silica-titania, silica-zirconia and carbon.
- alumina is preferred while alpha alumina is most preferred.
- the surface area for the carrier is in the range of 0.5 to 30 m 2 /g and the particle size of the carrier is in the range of 0.1 micrometer to 10 micrometer.
- Cerium compounds are supported on the carrier by impregnation, ion exchange, adsorption or precipitation. When necessary the impregnated carrier may be calcined in the temperature range of 300°C to 900°C.
- (071) For the purpose of improving the cerium oxide catalyst activity and/or selectivity, it is desirable to include other metal oxides such as aluminum, magnesium, calcium, barium, iron, cobalt, nickel, titanium, vanadium, scandium, yitrium, and the like and the resulting catalyst is referred as mixed metal oxide catalyst.
- Cerium oxide based catalyst as well as the mixed metal oxide catalyst comprising cerium oxide are used in the temperature range of 250°C to 450°C and 1,3-propanediol is preferably used as a gas under reaction condition.
- An inert gas may be used as carrier gas with an inert gas to 1,3-propanediol ratio in the range of 1 to 100.
- the catalyst is used either as a slurry or fluidized bed or a fixed bed; the catalytic process is performed in a continuous or semi-continuous or batch mode while the continuous flow mode is a preferred mode.
- Weight hourly space velocity (WHSV - grams of diol fed per gram of catalyst per hour) is in the range of 0.5 to 200 g/g catalyst/h.
- Japanese Patent Application Publication JP 2008-162907 provides a molybdenum vanadium catalyst for the preparation of acrylic acid from allyl alcohol by gas-phase catalytic oxidation.
- U. S. Patent Nos. 4,051,181, 4,107,204 and 4,144,398 provide supported two-metal catalyst, one metal being palladium and the other metal being copper or silver. Palladium is used in the amount of 0.01 to 5 weight percent and the other metal is used in the range of 0.001 to 10 weight percent.
- Alumina, silica, silicon carbide, carbon, titania, zirconia, and zeolite can be used as support.
- the oxidation reaction is carried out in the vapor phase by passing the reaction mixture through the heated catalyst at a temperature of 125°C to 320°C.
- Any one of the catalysts and the methods well-known in the art can be followed to carry out the oxidation of allyl alcohol to acrylic acid in an exothermic reaction.
- acrolein may accumulate as major by-product which may further be subjected to an oxidation reaction to produce acrylic acid.
- the catalysts and the conditions for the conversion of acrolein to acrylic acid is well known in the art and can be followed to achieve total conversion of allyl alcohol into acrylic acid. Further detail about the conditions and the catalysts useful for the oxidation of acrolein to acrylic acid is provided in the sections below.
- bio- 1,3-propanediol is first subjected to a dehydration reaction under milder oxidizing conditions leading to the production of acrolein / allyl alcohol mixture as an intermediate.
- the acrolein / allyl alcohol mixture thus produced is subjected to an oxidation reaction in the second stage leading to the production of acrylic acid.
- dehydration reaction and oxidation reactions are carried out using two different heterogeneous catalysts.
- 8,252,960 discloses a catalyst useful in the preparation of acrolein by dehydration of glycerol comprising as a main component, at least one compound in which protons on a heteropolyacid are exchanged at least partially with at least one cation selected from elements belonging to Group 1 to Group 16 of the Periodic Table of Elements.
- bio-acrolein + bio-allyl alcohol mixture is obtained from dehydration reaction involving 1 ,3-propanediol
- the bio-acrolein + bio-allyl alcohol mixture is subjected to oxidation reaction to yield acrylic acid.
- Oxidation catalysts for the conversion of acrolein to acrylic acid are well known in the scientific as well as in the patent literature. Oxidation of acrolein to acrylic acid on Mo/V/W-mixed oxide catalyst has been studied (Drochner et al., Chem. Eng. Tech. 37, 398 (2014)).
- the first step propene is substantially oxidized using a heterogeneous catalyst to produce acrolein.
- the acrolein produced in the first stage is oxidized using a different type of heterogeneous catalyst to produce acrylic acid.
- the heterogeneous catalyst suitable for the oxidation of acrolein to acrylic acid in the propene- based acrylic acid manufacturing plant is referred as multimetal oxides and these catalysts comprise the elements of Mo and V.
- a series of alumina-supported polyoxometalate (Al20 3 -suported POM) catalysts was prepared by the impregnation method for the liquid phase catalytic oxydehydration of glycerol to acrylic acid in a batch reactor at low temperature (90°C).
- Al 2 03-supported POM catalysts Si/W/A1203 at 4 wt% loading exhibited the highest glycerol conversion of about 84% with a yield of acrylic acid of around 25% (Thanasli et al, J. Mol. Catalysis A: Chemical 380, 49 (2013)).
- the temperature suitable for this amination reaction may range from about 0°C to 400°C, preferably from about 150°C to 350°C.
- the catalysts suitable for this amination reaction are disclosed in U.S. Patent No. 4,036,881, U.S. Patent No. 3,869,526 and U.S. Patent No. 3,869,527 which are inculpated herein by reference.
- European Patent Specification No. 0,078,000 provides details about other experimental conditions for aminating allyl alcohol.
- ammoxidation catalysts have been disclosed in the U.S. Patent No. 3,907,859, U.S. Patent No. 3.962,309, U.S. Patent No. 3,993,680, U.S. Patent No. 4,018,712, U.S. Patent No. 4,263,449 and U.S. Patent No. 4,405,498. All of these U.S. Patent documents are herein incorporated by reference.
- Preferred ammoxidation catalysts suitable for the present invention have the formula: A a BbFe c Bi d C e Mo f O z wherein A is an alkali metal, alkaline earth metal Ti, In, rare earth metal or mixtures thereof; B is Ni, Co, Mg, or a mixture thereof; and C is phosphorus, arsenic, boron or antimony; and wherein a and e are independently 0-3; b is Oto 20; c and d are independently 0.1 to 10; /is about 8 to about 16 and x is the number of oxygen required to satisfy the valence requirements of the other elements present.
- a reprehensive example of an ammoxidation catalyst useful for the present invention contains at least the oxides of Bi and Mo, Te and Mo or mixtures thereof.
- Figure 10 provides a summary of the bio- 1,3 -propanediol to bio- 1,4-butanediol chemistry.
- 1,3-propanediol is subjected to a dehydration reaction to yield allyl alcohol as described in detail in the paragraphs above.
- HBA hydroxybutanal
- MHPA methylhydroxypropanal
- PA propanl
- NPA n-propanol
- BDO 1,4- butanediol
- MPDiol 2-methyl- 1,3-propanediol
- NPA n-propanol
- Effluent from Reactor 1 is sent to a Catalyst Extractor where it is mixed with water from Water Storage tank and the hydroformylation catalyst is recovered and recycled.
- the recovered product effluent stream from Catalyst Extractor is sent to Reactor -2 and subjected to hydrogenation reaction using hydrogenation catalyst.
- the effluent stream from Reactor-2 is sent to a Catalyst Separator where the hydrogenation catalyst is recovered and recycled while the recovered process water is recycled to the Process Water Storage.
- the recovered product effluent from Catalyst Separator is sent to a Distillation column to recover 1 ,4-Butanediol and 2- methyl 1,3 -propanediol through fractional distillation.
- U.S, Patent No. 4,465,873 provides a process for obtaining butanediol by distilling the same from an aqueous solution obtained by hydrogenation of a hydroformylated allyl alcohol carried out in the presence of a nickel catalyst
- the invention disclosed in this U.S. Patent provides a process involving distillation to separate 2 -methyl- 1,3 -propanediol, 1,4-butanediol and a high-boiling fraction from a butanediol mixture obtained from the hydrogenation reaction.
- U.S. Patent No. 4,567,305 provides conditions for hydroformylation of allyl alcohol with a gaseous mixture of hydrogen and carbon monoxide, in an aromatic hydrocarbon, in the presence of a rhodium complex and trisubsituted phosphine to hydroxybutyraldehydes which are separated from the reaction mixture within an aqueous medium. More specifically this U.S. Patent provides the way to select and control carbon monoxide partial pressure, the rate of consumption of carbon monoxide, the rate at which the carbon monoxide is dissolved in the reaction mixture, reaction temperature and the viscosity of the reaction mixture to give a high yield of 4-hydroxybutyraldehyde and reduced catalyst consumption.
- U.S. Patent No. 4,529,808 provides a bisolvent system for the hydroformylation of allyl alcohol using a rhodium catalyst.
- the bisolvent system may comprise materials such as p-xylene and acetamide.
- Such a bisolvent system provides for easy catalyst recovery since the rhodium catalyst is selectively soluble in the p-xylene whereas the desired product is conversely selectively soluble in the acetamide phase.
- U.S. Patent No. 4,590,311 provides a process for preparation of 1,4-butanediol involving reaction of allyl alcohol with carbon monoxide and hydrogen in the presence of a soluble rhodium catalyst, certain phosphine promoter and certain carbonitriles as solvent.
- U.S. Patent No. 5,290,743 provides a process for regenerating a deactivated hydroformulation catalyst system that contains a rhodium hybridocarbonyl tris(trisubstituted phosphiine) complex, a trisubstituted phosphine and a diphosphinoalkane.
- the process involves oxidation of the catalysts system, removal of the phosphine oxidation products, and regeneration of the catalyst system by syngas treatment, aqueous extraction, and addition of phosphine ligands.
- U.S. Patent No. 5,426,250 provides process in which the hydroformylation product is extracted with an alkaline aqueous solution in the presence of carbon monoxide and/or hydrogen. After the extraction, an extracted raffinate solution containing the rhodium complex in the organic solvent is recycled through the same hydrofromylation process while the extracted aqueous solution containing the hydroformylation product is subjected to a hydrogenation reaction in the presence of hydrogen, with a hydrogenation catalyst added, to produce 1,4- butanediol.
- U.S. Patent No. 5,981,810 provides a process for purifying crude 1,4-butanediol by subjecting it to melt crystallization.
- U.S. Patent No. 6,127,584 provided a process in which allyl alcohol is hydroformylated to 1,4-butanediol using a rhodium and trialkyl phosphine catalyst having at least 2 methyl groups, the reaction being carried out at milder conditions and subsequently at more, severe conditions.
- U.S. Patent No. 6,225,509 provides a process for reducing the undesirable make of C3 co-products in a hydroformylation reaction. According to this process, the CO concentration must be maintained above 4.5 nig mols/liter of reaction liquid, preferably above about 5.0 mg. mol/liter in order to achieve high 4-hydroxybutyaldehyde selectivities.
- U.S. Patent No. 6,426,437 provides a process giving high yield of l,4 ⁇ butanediol compared to 2-methyl-l,3-propanediol.
- U.S. Patent No. 6,969,780 provides a process for the reduction of hydrogenation catalyst deactivation and deterioration.
- U.S. Patent No. 7,271,295 provides a process comprising a rhodium complex and a 2,3- 0-isopropyUdene-2,3-dihydroxy-l,4bis[bis(3,5-di-n-alkylphenyl)phosphino]butane. This process gives high yield of 4-hydroxybutyraldehyde compared to 3-hydroxy-a- methylpropionaldehyde.
- U.S. Patent No. 7,279,606 provides a process comprising a rhodium complex and a trans- l,2-bis(bis)3-5-di-n-alkylphenyl)phosphinomethyl)-cyclobutane. This process gives high yield of 4-hydroxybutyraldehyde compared to 3-hydroxy-a-methylpropionaldehyde.
- U.S. Patent No. 6,969,780 provides a process for improving the catalytic hydrogenation of 4-hydroxybutyraldehyde and 2-methyl 3-hydroxypropionaldehyde.
- U.S. Patent Application Publication No. 2014/0135537 relates to system and methods for monitoring the feed and effluent streams during the production of 1,4-butanediol using Raman spectroscopy. (0102) All the U.S Patents and the U.S. Patent Application Publication listed in the paragraphs immediately above are incorporated herein by reference. With these disclosures related to the conversion of allyl alcohol to 1,4-butanediol provided in these patent documents, a person skilled in the art of manufacturing industrial commodity chemicals, particularly 1 ,4-butanediol will be able to able to carry out the hydroformylation and hydrogenation reactions with bio-allyl alcohol to manufacture bio-1 ,4-butnaediol.
- bio-allyl alcohol can be used as a drop-in chemical intermediate in the conventional BDO plant operated using petrochemical feedstock as provided in the Figure 13.
- the oven profile was maintained as follows: 40°C hold for 2 minutes; ramp 20°C/min to 230°C; hold for 8 minutes.
- 1,3 -propanediol, allyl alcohol and acrylic acid peaks were well-resolved thereby making it possible to monitor the dehydration and oxidation reactions precisely.
- Neat Bio 1,3-propanediol (PDO, DuPont Tate& Lyle 50 ml) was added to Ce02 (Aldrich, 7.8g) on a clean 250 ml round bottom flask kept at room temperature. The flask was attached to a short air condenser column followed by a distillation condenser and receiving flask. The contents were heated to 300°C jacket temperature. PDO started to boil at 250°C. Most of the PDO condensed at the air condenser, but low boiling allyl alcohol condensed at the distillation condenser. Bio- Allyl alcohol was collected at 2 ml an hour rate.
Abstract
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US14/915,554 US10035749B2 (en) | 2013-09-03 | 2014-09-03 | Process for manufacturing acrylic acid, acrylonitrile and 1,4-butanediol from 1,3-propanediol |
KR1020167008884A KR102266181B1 (en) | 2013-09-03 | 2014-09-03 | A process for manufacturing acrylic acid, acrylonitrile and 1,4-butanediol from 1,3-propanediol |
CN201480048789.6A CN105705647B (en) | 2013-09-03 | 2014-09-03 | Process for the production of acrylic acid, acrylonitrile and 1, 4-butanediol from 1, 3-propanediol |
EP14841656.3A EP3041942B1 (en) | 2013-09-03 | 2014-09-03 | A process for manufacturing acrylic acid, acrylonitrile and 1,4-butanediol from 1,3-propanediol |
CA2922120A CA2922120C (en) | 2013-09-03 | 2014-09-03 | A process for manufacturing acrylic acid, acrylonitrile and 1,4-butanediol from 1,3-propanediol |
JP2016540356A JP2016534131A (en) | 2013-09-03 | 2014-09-03 | Process for producing acrylic acid, acrylonitrile and 1,4-butanediol from 1,3-propanediol |
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EP3041942A4 (en) | 2017-04-26 |
US20160207865A1 (en) | 2016-07-21 |
JP2016534131A (en) | 2016-11-04 |
CA2922120A1 (en) | 2015-03-12 |
CN105705647B (en) | 2020-03-27 |
KR102266181B1 (en) | 2021-06-17 |
CA2922120C (en) | 2022-09-06 |
KR20160071376A (en) | 2016-06-21 |
EP3041942B1 (en) | 2020-07-01 |
EP3041942A1 (en) | 2016-07-13 |
CN105705647A (en) | 2016-06-22 |
US10035749B2 (en) | 2018-07-31 |
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