YXY Building Blocks
Encyclopedia
YXY is a brand name for furan
based building blocks developed by the high throughput company Avantium. Furanics (e.g. 2,5-Furandicarboxylic acid
, HMF
, furfural
) have been referred to as “Sleeping Giants” because of their enormous market potential, as evidenced by the research of DuPont and DSM in this area and its position in the US Department of Energy top 12 of high-potential biobased products. YXY building blocks have a different manufacturing process than the traditional pursued routes towards HMF (minimizing the water content without using exotic solvents such as ionic liquids and DMSO
/MIBK). YXY is a trademark of Avantium of the Netherlands
.
and MMF
are key molecules into the conversion of carbohydrates into liquid biofuels, polymers and chemicals. Oxidation of HMF and MMF results in the formation of 2,5-furandicarboxylic acid
, which has been proposed as a replacement of terephthalic acid
for the production of a wide range of plastics including polyesters and polyamides. The potential applications of furan based building blocks for polymer
applications has been extensively reviewed by Gandini. In collaboration with NatureWorks
(subsidiary of Cargill
) the development of YXY polyesters was initiated. This collaboration has already demonstrated that YXY polyesters have properties that are very similar or even better (barrier properties) than regular PET
, allowing to develop a green version of this bulk polymer. Avantium has entered into a partnership with Teijin Aramid
, producer of Twaron
, to develop YXY for aramides
. HMF and MMF can be converted to a wide range of mono- and dialkoxymethyl ethers. The compounds can also further converted to 2,5-dimethylfuran
(DMF) and valeric biofuels. Several heavy duty Diesel engine tests have demonstrated the potential of YXY molecules as a green component to blend with Diesel fuel.
and HMF-derived intermediate chemicals in literature, HMF is still not produced on an industrial scale. Historically it is interesting to look at the two earlier HMF commercialization attempts that made it to the pilot plant stage. The main problem associated with producing HMF is that in principle HMF is an intermediate in the dehydration of hexoses to Levulinic acid and formic acid. In other words, HMF is not stable under the acidic conditions required for its formation. Both attempts used different strategies to handle this problem. The first of these is by Roquette Freres
in France who introduced a two-phase process in which the polar phase contained the hexose feed and an organic phase such as methylisobutyl ketone (MIBK) or dimethoxyethane (DME
) to extract the HMF out of the reactive phase directly after formation. The second approach by Südzucker
was based on water as diluent and conditions that maximized HMF selectivity, rather than maximizing HMF yield or hexose
conversion. The process involved the use of a homogeneous catalyst such as sulfuric acid and an ion-exchange resin to separate the catalyst from the reaction product. When under these conditions sucrose or glucose was used as a feed, no conversion to HMF is observed, which is a distinct disadvantage given the lower price and abundant availability of sucrose
and glucose
. Only in the presence of dimethylsulfoxide (DMSO), dimethylformamide
(DMF) and dimethylacetamide
(DMA), ionic liquids or in a sub- and supercritical mixture of acetone and water reasonable HMF yields from starting materials other than fructose
were obtained. Concluding, the known methods for the synthesis of HMF with economic potential mostly start from fructose and typically do not give high yield, partly attributable to the instability of HMF under the acidic reaction conditions required for HMF formation. Low conversion routes in water and in biphasic solvent systems both have disadvantages and no commercial process could be developed using these approaches.
process that enables the economic production of Furanics on basis of a wide range of carbohydrates. Its patented YXY technology that converts biomass into YXY building blocks (Figure 1) for both polymers as well as biofuels applications. It uses carbohydrates (C6 sugars) as feedstock to make biomaterials through a catalytic process of dehydration
, oxidation
and polymerization
. To make biofuels both C5 and C6 sugars can be used. Via dehydration and etherification / hydrogenation
you make components for Diesel, jetfuels and gasoline (Figure1). The necessary co-reactants (H2, methanol
, ethanol
) can be produced through gasification
/Fischer Tropsch synthesis of the humins/lignin
fraction. YXY shows attractive economics and a very promising environmental footprint. The process has a good fit with existing chemical production assets, allowing to retrofit existing production assets to switch from fossil feedstock
to renewable resources. Currently a pilot plant is being built on the Chemelot Campus in Geleen, the Netherlands (Figure 2). The objective of this pilot plant is to optimize the production process and to demonstrate the process at larger scale, as well as the production of trial quantities of YXY for product development purposes.
Furan
Furan is a heterocyclic organic compound, consisting of a five-membered aromatic ring with four carbon atoms and one oxygen. The class of compounds containing such rings are also referred to as furans....
based building blocks developed by the high throughput company Avantium. Furanics (e.g. 2,5-Furandicarboxylic acid
2,5-Furandicarboxylic acid
2,5-Furandicarboxylic acid , also known as dehydromucic acid, is an oxidized furan derivative. This organic compound was first obtained by Fittig and Heinzelmann in 1876. The first review by Henry Hill was already published in 1901. FDCA has also been detected in human urine. A healthy human...
, HMF
HMF
HMF may refer to:Horam Manor Fishery - A coarse fishery set in the sussex country side located in the quiet village of Horam.* HM Frigate: His Majesty's Frigate, a designation carried by Royal Navy frigates prior to the adoption of "HMS" * Norrlandsflyg * Hydroxymethylfurfural* Højbjerg...
, furfural
Furfural
Furfural is an organic compound derived from a variety of agricultural byproducts, including corncobs, oat, wheat bran, and sawdust. The name furfural comes from the Latin word , meaning bran, referring to its usual source....
) have been referred to as “Sleeping Giants” because of their enormous market potential, as evidenced by the research of DuPont and DSM in this area and its position in the US Department of Energy top 12 of high-potential biobased products. YXY building blocks have a different manufacturing process than the traditional pursued routes towards HMF (minimizing the water content without using exotic solvents such as ionic liquids and DMSO
Dimethyl sulfoxide
Dimethyl sulfoxide is an organosulfur compound with the formula 2SO. This colorless liquid is an important polar aprotic solvent that dissolves both polar and nonpolar compounds and is miscible in a wide range of organic solvents as well as water...
/MIBK). YXY is a trademark of Avantium of the Netherlands
Netherlands
The Netherlands is a constituent country of the Kingdom of the Netherlands, located mainly in North-West Europe and with several islands in the Caribbean. Mainland Netherlands borders the North Sea to the north and west, Belgium to the south, and Germany to the east, and shares maritime borders...
.
Uses
HMFHydroxymethylfurfural
Hydroxymethylfurfural , also 5-furfural, is an organic compound derived from dehydration of certain sugars. This yellow low-melting solid is highly water-soluble. The molecule consists of a furan ring, containing both aldehyde and alcohol functional groups...
and MMF
Methoxymethylfurfural
Methoxymethylfurfural , also 5-methoxymethylfuran-2-carbaldehyde, is an organic compound derived from dehydration of sugars and subsequent etherification with methanol. This colourless liquid is soluble in a wide range of solvents including lower alcohols. The molecule is a derivative of furan,...
are key molecules into the conversion of carbohydrates into liquid biofuels, polymers and chemicals. Oxidation of HMF and MMF results in the formation of 2,5-furandicarboxylic acid
2,5-Furandicarboxylic acid
2,5-Furandicarboxylic acid , also known as dehydromucic acid, is an oxidized furan derivative. This organic compound was first obtained by Fittig and Heinzelmann in 1876. The first review by Henry Hill was already published in 1901. FDCA has also been detected in human urine. A healthy human...
, which has been proposed as a replacement of terephthalic acid
Terephthalic acid
Terephthalic acid is the organic compound with formula C6H42. This colourless solid is a commodity chemical, used principally as a precursor to the polyester PET, used to make clothing and plastic bottles. Several billion kilograms are produced annually...
for the production of a wide range of plastics including polyesters and polyamides. The potential applications of furan based building blocks for polymer
Polymer
A polymer is a large molecule composed of repeating structural units. These subunits are typically connected by covalent chemical bonds...
applications has been extensively reviewed by Gandini. In collaboration with NatureWorks
NatureWorks LLC
NatureWorks LLC is a subsidiary of Cargill. NatureWorks produces a family of polymers derived entirely from annually renewable resources - namely plants - designed to compete with petroleum-based plastic packaging materials, consumer goods and fiber products...
(subsidiary of Cargill
Cargill
Cargill, Incorporated is a privately held, multinational corporation based in Minnetonka, Minnesota. Founded in 1865, it is now the largest privately held corporation in the United States in terms of revenue. If it were a public company, it would rank, as of 2011, number 13 on the Fortune 500,...
) the development of YXY polyesters was initiated. This collaboration has already demonstrated that YXY polyesters have properties that are very similar or even better (barrier properties) than regular PET
Polyethylene terephthalate
Polyethylene terephthalate , commonly abbreviated PET, PETE, or the obsolete PETP or PET-P, is a thermoplastic polymer resin of the polyester family and is used in synthetic fibers; beverage, food and other liquid containers; thermoforming applications; and engineering resins often in combination...
, allowing to develop a green version of this bulk polymer. Avantium has entered into a partnership with Teijin Aramid
Teijin Aramid
Teijin Aramid, formerly known as Teijin Twaron, is a company in The Netherlands that produces various high-strength fibers for industrial purposes, most notably their Kevlar-like para-aramid, Twaron. Twaron finds applications in numerous markets, such as automotive , aerospace, civil engineering,...
, producer of Twaron
Twaron
Twaron is the brandname of Teijin Aramid for a para-aramid. It is a heat-resistant and strong synthetic fibre developed in the early 1970s by the Dutch company AKZO, division Enka, later Akzo Industrial Fibers. The research name of the para-aramid fibre was originally Fiber X, but it was soon...
, to develop YXY for aramides
Aramides
Aramides is a genus of birds in the Rallidae family.It contains the following species:* Red-throated Wood Rail, Aramides gutturalis - doubtful species; extinct * Little Wood Rail, Aramides mangle...
. HMF and MMF can be converted to a wide range of mono- and dialkoxymethyl ethers. The compounds can also further converted to 2,5-dimethylfuran
2,5-Dimethylfuran
2,5-Dimethylfuran is a heterocyclic compound with the formula 2C4H2O. Although often abbreviated DMF, it should not be confused with dimethylformamide. A derivative of furan, this simple compound is a potential biofuel, being derivable from cellulose.-Production:Fructose can be converted into...
(DMF) and valeric biofuels. Several heavy duty Diesel engine tests have demonstrated the potential of YXY molecules as a green component to blend with Diesel fuel.
History
Already for many decades, the potential of furanic products, obtained from carbohydrates, has been identified. However, despite the impressive array of useful furfuralFurfural
Furfural is an organic compound derived from a variety of agricultural byproducts, including corncobs, oat, wheat bran, and sawdust. The name furfural comes from the Latin word , meaning bran, referring to its usual source....
and HMF-derived intermediate chemicals in literature, HMF is still not produced on an industrial scale. Historically it is interesting to look at the two earlier HMF commercialization attempts that made it to the pilot plant stage. The main problem associated with producing HMF is that in principle HMF is an intermediate in the dehydration of hexoses to Levulinic acid and formic acid. In other words, HMF is not stable under the acidic conditions required for its formation. Both attempts used different strategies to handle this problem. The first of these is by Roquette Freres
Roquette Freres
Roquette is a French based family owned company which produces more than 650 by-products from the starch extracted from corn, wheat, potatoes and peas....
in France who introduced a two-phase process in which the polar phase contained the hexose feed and an organic phase such as methylisobutyl ketone (MIBK) or dimethoxyethane (DME
Dimethoxyethane
Dimethoxyethane, also known as glyme, monoglyme, dimethyl glycol, ethylene glycol dimethyl ether, dimethyl cellosolve, and DME, is a clear, colorless, aprotic, and liquid ether that is used as a solvent. Dimethoxyethane is miscible with water.Dimethoxyethane is often used as a higher boiling...
) to extract the HMF out of the reactive phase directly after formation. The second approach by Südzucker
Südzucker
Südzucker AG is a German company, the largest sugar producer in Europe with an annual production of around 4.8 million tonnes.-Sugar segment:The company has 30 sugar factories and 3 refineries in Austria, Belgium, Czech Republic, France, Germany, Hungary, Moldova, Poland, Romania Slovakia and...
was based on water as diluent and conditions that maximized HMF selectivity, rather than maximizing HMF yield or hexose
Hexose
In organic chemistry, a hexose is a monosaccharide with six carbon atoms, having the chemical formula C6H12O6. Hexoses are classified by functional group, with aldohexoses having an aldehyde at position 1, and ketohexoses having a ketone at position 2....
conversion. The process involved the use of a homogeneous catalyst such as sulfuric acid and an ion-exchange resin to separate the catalyst from the reaction product. When under these conditions sucrose or glucose was used as a feed, no conversion to HMF is observed, which is a distinct disadvantage given the lower price and abundant availability of sucrose
Sucrose
Sucrose is the organic compound commonly known as table sugar and sometimes called saccharose. A white, odorless, crystalline powder with a sweet taste, it is best known for its role in human nutrition. The molecule is a disaccharide composed of glucose and fructose with the molecular formula...
and glucose
Glucose
Glucose is a simple sugar and an important carbohydrate in biology. Cells use it as the primary source of energy and a metabolic intermediate...
. Only in the presence of dimethylsulfoxide (DMSO), dimethylformamide
Dimethylformamide
Dimethylformamide is an organic compound with the formula 2NCH. Commonly abbreviated as DMF , this colourless liquid is miscible with water and the majority of organic liquids. DMF is a common solvent for chemical reactions...
(DMF) and dimethylacetamide
Dimethylacetamide
Dimethylacetamide is the organic compound with the formula CH3CN2. This colorless, water miscible, high boiling liquid is commonly used as a polar solvent in organic chemistry. DMAc is miscible with most other solvents, although it is poorly soluble in aliphatic hydrocarbons.The chemical reactions...
(DMA), ionic liquids or in a sub- and supercritical mixture of acetone and water reasonable HMF yields from starting materials other than fructose
Fructose
Fructose, or fruit sugar, is a simple monosaccharide found in many plants. It is one of the three dietary monosaccharides, along with glucose and galactose, that are absorbed directly into the bloodstream during digestion. Fructose was discovered by French chemist Augustin-Pierre Dubrunfaut in 1847...
were obtained. Concluding, the known methods for the synthesis of HMF with economic potential mostly start from fructose and typically do not give high yield, partly attributable to the instability of HMF under the acidic reaction conditions required for HMF formation. Low conversion routes in water and in biphasic solvent systems both have disadvantages and no commercial process could be developed using these approaches.
Production process
Furanics were never commercialized because they could not be produced in an economic fashion. Avantium has discovered a revolutionary chemical, catalyticCatalysis
Catalysis is the change in rate of a chemical reaction due to the participation of a substance called a catalyst. Unlike other reagents that participate in the chemical reaction, a catalyst is not consumed by the reaction itself. A catalyst may participate in multiple chemical transformations....
process that enables the economic production of Furanics on basis of a wide range of carbohydrates. Its patented YXY technology that converts biomass into YXY building blocks (Figure 1) for both polymers as well as biofuels applications. It uses carbohydrates (C6 sugars) as feedstock to make biomaterials through a catalytic process of dehydration
Dehydration reaction
In chemistry and the biological sciences, a dehydration reaction is usually defined as a chemical reaction that involves the loss of water from the reacting molecule. Dehydration reactions are a subset of elimination reactions...
, oxidation
Redox
Redox reactions describe all chemical reactions in which atoms have their oxidation state changed....
and polymerization
Polymerization
In polymer chemistry, polymerization is a process of reacting monomer molecules together in a chemical reaction to form three-dimensional networks or polymer chains...
. To make biofuels both C5 and C6 sugars can be used. Via dehydration and etherification / hydrogenation
Hydrogenation
Hydrogenation, to treat with hydrogen, also a form of chemical reduction, is a chemical reaction between molecular hydrogen and another compound or element, usually in the presence of a catalyst. The process is commonly employed to reduce or saturate organic compounds. Hydrogenation typically...
you make components for Diesel, jetfuels and gasoline (Figure1). The necessary co-reactants (H2, methanol
Methanol
Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a chemical with the formula CH3OH . It is the simplest alcohol, and is a light, volatile, colorless, flammable liquid with a distinctive odor very similar to, but slightly sweeter than, ethanol...
, ethanol
Ethanol
Ethanol, also called ethyl alcohol, pure alcohol, grain alcohol, or drinking alcohol, is a volatile, flammable, colorless liquid. It is a psychoactive drug and one of the oldest recreational drugs. Best known as the type of alcohol found in alcoholic beverages, it is also used in thermometers, as a...
) can be produced through gasification
Gasification
Gasification is a process that converts organic or fossil based carbonaceous materials into carbon monoxide, hydrogen, carbon dioxide and methane. This is achieved by reacting the material at high temperatures , without combustion, with a controlled amount of oxygen and/or steam...
/Fischer Tropsch synthesis of the humins/lignin
Lignin
Lignin or lignen is a complex chemical compound most commonly derived from wood, and an integral part of the secondary cell walls of plants and some algae. The term was introduced in 1819 by de Candolle and is derived from the Latin word lignum, meaning wood...
fraction. YXY shows attractive economics and a very promising environmental footprint. The process has a good fit with existing chemical production assets, allowing to retrofit existing production assets to switch from fossil feedstock
Fossil fuel
Fossil fuels are fuels formed by natural processes such as anaerobic decomposition of buried dead organisms. The age of the organisms and their resulting fossil fuels is typically millions of years, and sometimes exceeds 650 million years...
to renewable resources. Currently a pilot plant is being built on the Chemelot Campus in Geleen, the Netherlands (Figure 2). The objective of this pilot plant is to optimize the production process and to demonstrate the process at larger scale, as well as the production of trial quantities of YXY for product development purposes.