WO2021136977A1 - A process for producing trimellitic acid from biomass - Google Patents

A process for producing trimellitic acid from biomass Download PDF

Info

Publication number
WO2021136977A1
WO2021136977A1 PCT/IB2020/051226 IB2020051226W WO2021136977A1 WO 2021136977 A1 WO2021136977 A1 WO 2021136977A1 IB 2020051226 W IB2020051226 W IB 2020051226W WO 2021136977 A1 WO2021136977 A1 WO 2021136977A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
reactant
group
trimellitic acid
biomass
Prior art date
Application number
PCT/IB2020/051226
Other languages
French (fr)
Inventor
Mohammad Ali Haider
TuhinSuvra KHAN
Mohammad Imteyaz Alam
Original Assignee
Indian Institute Of Technology, Delhi
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Indian Institute Of Technology, Delhi filed Critical Indian Institute Of Technology, Delhi
Publication of WO2021136977A1 publication Critical patent/WO2021136977A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
    • C12P17/02—Oxygen as only ring hetero atoms
    • C12P17/06—Oxygen as only ring hetero atoms containing a six-membered hetero ring, e.g. fluorescein
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/213—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by splitting of esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
    • C12P17/02—Oxygen as only ring hetero atoms
    • C12P17/04—Oxygen as only ring hetero atoms containing a five-membered hetero ring, e.g. griseofulvin, vitamin C
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/44—Polycarboxylic acids
    • C12P7/48—Tricarboxylic acids, e.g. citric acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C07D307/44—Furfuryl alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/30—Oxygen atoms, e.g. delta-lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
    • C07D309/38—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms one oxygen atom in position 2 or 4, e.g. pyrones

Definitions

  • the present invention relates to an eco-friendly method to produce trimellitic acid (TMA) from biomass based furans, pyrones and lactones.
  • TMA trimellitic acid
  • the present method relates to Diels-Alder cycloaddition with a specific dienophile to obtain cyclo-adduct which is be further dehydrated, dehydrogenated and/or oxidized to produce trimellitic acid anhydride.
  • TMA The market share of epoxy resins are estimated to be 15 billion USD worldwide.
  • the esters of TMA are also used as plasticizers in making the automobile interiors or in similar applications where resistance to high temperature is required.
  • Derivatives of TMA also have been suggested as potential drug for cancer and agrochemical applications.
  • TMA has been proposed to have application in the field of dental adhesive, anti-snake venom and HIV protection. There has been constant effort since the past decade or so to replace the petroleum based pathways with biomass routes for the production of essential chemicals.
  • terephthalic acid can be produced by reacting HMF and its derivatives with ethylene, to form an oxanorbornene intermediate, which can undergo dehydration reaction over a solid acid catalyst, to form its aromatic equivalent.
  • the resultant aromatic compound can be oxidized under mild condition, over low-cost oxide catalyst to obtain PTA [Chem. Rev. 2013, 113, 7421-7469].
  • trimellitic acid is produced in the industrial scale through catalytic oxidation of pseudocumene (1, 2, 4-Trimethylbenzene) over Co/Mn/Br catalyst using AMOCO process.
  • pseudocumene 1, 2, 4-Trimethylbenzene
  • AMOCO a trimellitic acid intramolecular anhydride
  • TMA trimellitic acid intramolecular anhydride
  • This process is conducted in highly corrosive acidic medium at a high temperature (175— 225°C).
  • Concerns over environmental and safety issues have driven studies to find milder process for the production of trimellitic acid.
  • low selectivity and conversion to a desired product remains a concern to be resolved.
  • U.S. Patent US9035018B2 provides a furan-based curable compound derived from carbohydrate-based biomass as a basic backbone, which may replace an aromatic compound produced through a petrochemical process.
  • the patent also provides a curable compound, which may reduce curing contraction ratio, and a method for preparing thereof with a combination of high yield and cost-effectiveness.
  • a method for preparing a furan-based curable compound derived from biomass comprising i. preparing a starting material wherein a furan-based compound derived from biomass is prepared as a starting material which may be obtained through oxidation or reduction reaction by using furfural or furfural derivatives as an intermediate which are converted from cellulose or hemicellulose extracted from carbohydrate-based biomass; and ii. mixing and stirring the furan-based compound derived from biomass and an epichlorhydrin.
  • the resultant molecules are proposed to be potential replacement of aromatic compounds produced through petrochemicals.
  • the examples 1-4 and the comparative example provide the photo curing behavior of the composition and the contraction ratio is measured during curing, in order to examine the applicability of a furan-based curable compound containing an epoxide functional group as a curing material which is synthesized according to the method described above. Therefore, the process and products as well as applications of the invention are entirely different from that of the present invention.
  • KR20160007506 discusses production of poly-carboxylic acid compounds from enzymatic treatment of lignocellulosic biomass. Biomass is treated with enzymes or other organisms to produce a mixture of poly-carboxylic acids as product. One of the compound in the poly-carboxylic acid mixture can be trimellitic acid. However, this process is not industrially feasible.
  • Said document teaches a method for producing a poly-carboxylic acid by treatment with a reduced degradation of lignoceric cellulose or cellulose material (reduced recalcitrance lignocellulosic or cellulosic material) with one or more enzymes and/or organism, and a method for manufacturing a product comprising the step of converting the poly- carboxylic acid as a product.
  • present invention does not disclose any enzymatic treatment of the lignocellulosic or cellulosic biomass.
  • WO20 16207403 relates to a recombinant Deinococcus bacterium expressing a heterologous polypeptide exhibiting 3-dehydroshikimate dehydratase activity and a heterologous polypeptide exhibiting protocatechuate decarboxylase activity, comprising a heterologous biosynthetic pathway converting 3-dehydroshikimate to catechol and/or cis, cis-muconic Acid; further comprising culturing above-mentioned recombinant Deinococcus bacterium under conditions suitable to produce cis-cis muconic acid, and optionally recovering said cis-cis muconic acid. Said application does not motivate a person skilled in the art to arrive at the present invention.
  • US8367858B2 relates to substituted and unsubstituted terephthalic acid and carboxylate derivatives and products prepared therefrom having a renewable content; processes for preparation thereof wherein a portion of the starting materials utilized is derived from renewable resources.
  • the invention also relates to cyclohexene based intermediates prepared in these processes and to conversion of these intermediates to substituted and unsubstituted cyclohexane-l,4-dicarboxylates and carboxylate derivatives thereof and different forms of the resulting products having renewable content.
  • the invention also relates to products prepared from substituted and unsubstituted terephthalic acid and carboxylate derivatives thereof derived from starting materials derived from renewable resources.
  • This patent application relates to a method for preparing a compound containing a benzene ring, the compound having formula (I)
  • R 1 is independently in each occurrence hydrogen or a hydrocarbyl group optionally containing a heteroatom containing functional group wherein the hydrocarbyl group does not interfere in the formation of the cyclohexene ring containing compound;
  • R 2 is independently in each occurrence hydrogen or a hydrocarbyl group optionally containing a heteroatom containing functional group wherein the hydrocarbyl group does not interfere in the formation of the cyclohexene ring containing compound;
  • R 3 is independently in each occurrence hydrogen or a hydrocarbyl group optionally containing a heteroatom containing functional group wherein the hydrocarbyl group does not interfere in the formation of the cyclohexene ring containing compound; or R 2 and R 3 combine to form a cyclic ring that can contain heteroatoms;
  • Z is independently in each occurrence an anion, oxygen, nitrogen, sulfur, halogen or nitrile; and b is independently in each occurrence 0, 1 or 2; with the proviso that b is 0 when Z is an anion, nitrile or halogen, that b is 1 when Z is oxygen or sulfur, and that b is 2 when Z in nitrogen.
  • WO 2010/148081 is the published application of the US patent discussed above.
  • trimellitic acid is produced through catalytic oxidation of pseudocumene (1,2,4-Trimethylbenzene) over Co/Mn/Br catalyst using AMOCO process.
  • TMA trimellitic acid intramolecular anhydride
  • This process is conducted in highly corrosive acidic medium at a high temperature (175-225 °C).
  • Concerns over environmental and safety issues have driven studies to find milder process for the production of trimellitic acid.
  • low selectivity and conversion to a desired product remains a concern to be resolved.
  • An objective of the present invention is to provide a process for production of trimellitic acid from biomass based lactones, pyrones and furans.
  • Another objective of the invention is to provide a catalytic process involving Diels-Alder cycloaddition with a dienophile to obtain cyclo-adduct, which can be further dehydrated, dehydrogenated and oxidized to produce the trimellitic acid anhydride.
  • a further objective of the invention is to obtain trimellitic acid anhydride from diels-alder reaction of isoprene obtained from biomass based Mevalonolactone and another biomass obtained maleic anhydride.
  • Another objective of the invention is to obtain trimellitic acid anhydride from diels-alder reaction of coumalic acid (or methyl coumalate) obtained from biomass and maleic anhydride.
  • a further objective of the invention is to obtain trimellitic acid anhydride from Diels- Alder reaction of biomass obtained furans and acrolein/acrylic aci d/methylacrylate.
  • Another objective of the invention is to provide an alternative process to the conventional fossil fuel based petrochemical route for production of trimellitic acid, with a relatively mild environmentally friendly process with high conversion and selectivity.
  • a process for the preparation of trimellitic acid comprising the steps of: a. obtaining a substrate from biomass; b. dissolving the substrate of step (a) in a solvent and heating at a temperature in the range of 80°C to 120°C to obtain a first reactant; c. adding a second reactant dissolved in solvent to the first reactant of step (b) to obtain a Diels-Alder adduct; and d.
  • step (c) subjecting the Diels-Alder adduct of step (c) to at least one of the reactions selected from a group consisting of oxidation, dehydrogenation, decarboxylation, and dehydration in presence of at least one catalyst to obtain trimellitic acid.
  • a process for the preparation of trimellitic acid from mevalonolactone comprising the steps of: a. obtaining mevalonolactone from biomass; b. dissolving the lactone of step (a) in a solvent and heating at a temperature of 80 to 100°C to obtain isoprene; c. adding a second reactant to isoprene of step (b) to obtain a Diels-Alder adduct; d. subjecting the Diels-Alder adduct of step (c) to oxidation in presence of a catalyst to obtain trimellitic acid.
  • a process for the preparation of trimellitic acid from hydroxyl methyl furan or its derivatives comprising the steps of: a. obtaining hydroxyl methyl furan or its derivatives from biomass; b. dissolving the hydroxyl methyl furan or its derivatives of step (a) in a solvent and heating at a temperature of 80 to 100°C to obtain a first reactant; c. adding a second reactant to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to dehydration and oxidation in presence of at least one catalyst to obtain trimellitic acid.
  • a process for the preparation of trimellitic acid from coumalic acid or its derivatives comprising the steps of: a. obtaining coumalic acid or its derivatives from biomass; b. dissolving the coumalic acid or its derivatives of step (a) in a first solvent and heating at a temperature of 80 to 100°C to obtain a first reactant; c. adding a second reactant to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to dehydrogenation and decarboxylation in presence of at least one catalyst to obtain trimellitic acid.
  • Figure 1 illustrates X H NMR spectrum showing complete conversion of maleic anhydride
  • Figure 2 illustrates X H NMR spectrum of Trimellitic Acid produced from Diels Alder adduct (right) and standard Trimellitic Acid (left)
  • Figure 3 illustrates HPLC chromatogram of Trimellitic Acid produced from Diels Alder adduct (right) and standard Trimellitic Acid (left)
  • the process can easily be integrated to an upstream fermentation reaction where the reactant furans, lactones, pyrones, melic anhydride, acrolein or propylene is obtained directly from biomass. Therefore, the novel integrated two/three-step process to produce trimellitic acid from biomass runs under relatively mild environmentally friendly conditions with high conversion and selectivity is proposed.
  • the present invention relates to a process for the preparation of trimellitic acid, the process comprising the steps of: a. obtaining a substrate from biomass; b. dissolving the substrate of step (a) in a solvent and heating at a temperature in the range of 80°C to 120°C to obtain a first reactant; c. adding a second reactant dissolved in solvent to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to at least one of the reactions selected from a group consisting of oxidation, dehydrogenation, decarboxylation, and dehydration in presence of at least one catalyst to obtain trimellitic acid.
  • the substrate is selected from the group consisting of lactones, furans and pyrones.
  • the substrate is lactone.
  • the substrate is pyrone.
  • the substrate is furan.
  • the substrate is obtained from biomass by at least one of fermentation, and acid hydrolysis.
  • the present invention relates to a process wherein the solvent is selected from a group consisting of polar and non-polar solvents, preferably selected from selected from water, tetrahydrofuran, 1,4-dioxane, acetonitrile, N-m ethyl pyrrolidone, dimethylacetamide, dimethyl sulfoxide, dimethyl acetamide, cyclohexane, hexane, toluene, xylene, benzene, chloroform, dichlormethane, acetone, aliphatic alcohol, aromatic alcohol, an ionic liquid.
  • polar and non-polar solvents preferably selected from selected from water, tetrahydrofuran, 1,4-dioxane, acetonitrile, N-m ethyl pyrrolidone, dimethylacetamide, dimethyl sulfoxide, dimethyl acetamide, cyclohexane, hexane,
  • the present invention relates to a process wherein the second reactant is selected from a group consisting of maleic anhydride, maleic acid, 2-butene, fumaric acid, mono-methyl fumarate, dimethyl fumarate, diethyl malate, mono-methyl malate, dimethyl malate, diethyl malate, acrolein, acrylic acid, methyl acrylate, ethyl acrylate, and propylene.
  • the second reactant is selected from a group consisting of maleic anhydride, maleic acid, 2-butene, fumaric acid, mono-methyl fumarate, dimethyl fumarate, diethyl malate, mono-methyl malate, dimethyl malate, diethyl malate, acrolein, acrylic acid, methyl acrylate, ethyl acrylate, and propylene.
  • the second reactant used in the process may be liquid or solid. During reaction the second reactant is dissolved in the solvent in which the substrate is dissolved and then added to the first reactant.
  • the present invention relates to a process wherein the at least one catalyst is selected from a group consisting of metal catalysts selected from palladium, platinum, nickel, rhodium, ruthenium and combinations thereof, acid catalysts such as zeolite selected from Sn-beta, Y-zeolite, beta-zeolite, ZSM-5, MCM-22, SAPO-5, SAPO-37, SAPO-34, USY, and metal oxides selected from Ce0 2 , MgO, A1 2 0 3 , Sn0 2 , W0 3 , Mo0 3 , Si0 2 , Ti0 2 , Zr0 2 , ZnO, Nb 2 0 3 , La 2 0 3 , Ta 2 Os, Y 2 0 3 , V 2 Os, Cr 2 0 3 , K 2 0/Cr 2 0 3 , Mn0 2 , Fe 2 0 3 , NiO, Ni 2 0 3 , Co 2 0 3 , CuO and combinations
  • the substrate of step (a) is dissolved in a solvent and heated at a temperature of 100°C to obtain a first reactant.
  • the step (d) is carried out at a temperature of 150°C. In another embodiment of the present process the step (d) is carried out at a temperature of 100°C.
  • the substrate is a lactone.
  • Lactone is obtained by microbial fermentation of biomass.
  • the microbial fermentation is carried out by microorganisms such as E.coli sp, Trichoderma sp, Saccharomyces sp, Yarrow ia sp, Geobactor sp, Shewanella sp, Enterococcus sp, Corynebacterium sp, Fusarium sp, Aspergillus sp, Candidas sp, Streptomyces sp, Pichia sp, Piromyces sp, Thermobifida sp, Rhodosporidium sp.
  • the lactone is mevanolactone
  • the solvent used in the process is tetrahydrofuran
  • the first reactant obtained in the process is isoprene.
  • the second reactant used in the process is maleic anhydride. Adding maleic anhydride to isoprene results in a solid white Diels-Alder adduct.
  • the Diels-Alder adduct is subjected to oxidation in presence of a catalyst, metal oxide to obtain trimellitic acid.
  • the substrate is a pyrone.
  • Pyrone is obtained by fermentation of biomass.
  • the pyrone is coumalic acid or its derivatives.
  • the pyrone is dissolved and heated in the solvent tetrahydrofuran to obtain the first reactant.
  • the second reactant used in the process is Maleic anhydride. Adding maleic anhydride to the first reactant results in a solid white Diels-Alder adduct.
  • the Diels-Alder adduct is subjected to dehydrogenation and decarboxylation in presence of catalysts, palladium and zeolite to obtain trimellitic acid.
  • the substrate is a furan.
  • Furan is obtained by acid hydrolysis of biomass.
  • the furan is hydroxylmethyl furan (HMF) or its derivatives.
  • the furan is dissolved and heated in the solvent tetrahydrofuran to obtain the first reactant.
  • the second reactant used in the process is acrolein. Adding acrolein to the first reactant results in a solid white Diels-Alder adduct.
  • the Diels-Alder adduct is subjected to dehydration and oxidation in presence of catalysts, zeolite and metal oxide to obtain trimellitic acid.
  • a process for the preparation of trimellitic acid from mevalonolactone comprising the steps of: a. obtaining mevalonolactone from biomass; b. dissolving the lactone of step (a) in a solvent and heating at a temperature of 80 to 100°C to obtain isoprene; c. adding a second reactant to isoprene of step (b) to obtain a Diels-Alder adduct; d. subjecting the Diels-Alder adduct of step (c) to oxidation in presence of a catalyst to obtain trimellitic acid.
  • the mevalonolactone is obtained from biomass by microbial fermentation.
  • the microorganisms used in the fermentation is selected from E. coli sp, Trichoderma sp, Saccharomyces sp, Yarrow ia sp, Geobactor sp, Shewanella sp, Enterococcus sp, Corynebacterium sp, Fusarium sp, Aspergillus sp, Candidas sp, Streptomyces sp, Pichia sp, Piromyces sp, Thermobifida sp, Rhodosporidium sp.
  • the solvent is selected from the group consisting of tetrahydrofuran, hexane, cyclohexane, toluene, methanol, ethanol, iso-propanol, acetone, acetonitrile, and water.
  • the solvent is tetrahydrofuran.
  • the second reactant is selected from the group consisting of maleic anhydride, maleic acid, dimethylacetylene dicarboxylate, 2-butene, fumaric acid, mono methyl fumarate, dimethyl fumarate, diethyl malate, mono-methyl malate, dimethyl malate, and diethyl malate.
  • the second reactant is maleic anhydride.
  • the catalyst is a metal oxide selected from the group consisting of Ce02,
  • the catalyst is K 2 0/Cr 2 0 3 .
  • the mevalonolactone of step (a) is dissolved in a first solvent and heated at a temperature of 100°C to obtain isoprene.
  • the Diels-Alder adduct is subjected to oxidation in presence of cerinium oxide at a temperature of 100°C for 20 hours to obtain trimellitic acid.
  • a process for the preparation of trimellitic acid from hydroxyl methyl furan or its derivatives comprising the steps of: a. obtaining hydroxyl methyl furan or its derivatives from biomass; b. dissolving the hydroxyl methyl furan or its derivatives of step (a) in a solvent and heating at a temperature of 80 to 100°C to obtain a first reactant; c. adding a second reactant to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to dehydration and oxidation in presence of at least one catalyst to obtain trimellitic acid.
  • the hydroxyl methyl furan derivatives are selected from the group consisting of dimethyl furan (DMF), bis-hydroxym ethyl furan (BHMF), 5-methylfurfural alcohol (MFA), furan dicarboxylic acid (FDCA), and methyl furan dicarboxylic acid (FDCA-Me-ester).
  • DMF dimethyl furan
  • BHMF bis-hydroxym ethyl furan
  • MFA 5-methylfurfural alcohol
  • FDCA furan dicarboxylic acid
  • FDCA-Me-ester methyl furan dicarboxylic acid
  • the hydroxyl methyl furan or its derivatives is obtained from biomass by acid hydrolysis.
  • the solvent is selected from the group consisting of tetrahydrofuran, hexane, cyclohexane, toluene, methanol, ethanol, iso-propanol, acetone, acetonitrile, and water.
  • the solvent is tetrahydrofuran.
  • the second reactant is selected from the group consisting of acrolein, acrylic acid, methyl acrylate, ethyl acrylate, and propylene. In a preferred embodiment, the second reactant is acrolein.
  • the at least one catalyst is selected from zeolites and metal oxides.
  • the zeolites are selected form the group consisting of Sn-beta, Y-zeolite, beta- zeolite, ZSM-5, MCM-22, SAPO-5, SAPO-37, SAPO-34, USY, and combination thereof
  • metal oxides are selected form the group consisting of CeC ⁇ , MgO, AI2O3, SnC> 2 , WO3, M0O3, S1O2, T1O2, ZrC> 2 , ZnO, Nb 2 0 3 , La 2 0 3 , Ta20s, Y2O3, V2O5, (3 ⁇ 40 3 , K 2 0/Cr 2 0 3 , MnC> 2 , Fe 2 0 3 , NiO, M 2 O 3 , C0 2 O 3 , CuO and combination thereof.
  • the zeolites are selected form the group consisting of Sn-beta, Y-zeolite, beta-
  • step (a) The hydroxyl methyl furan or its derivatives of step (a) is dissolved in a solvent and heated at a temperature of 100°C to obtain a first reactant.
  • the Diels-Alder adduct is subjected to dehydration in presence of ZSM-5 at a temperature of 150°C for 2 hours, followed by oxidation over K 2 0/Cr 2 0 3 catalyst at a temperature of 100°C for 20 hours to obtain trimellitic acid.
  • a process for the preparation of trimellitic acid from coumalic acid or its derivatives comprising the steps of: a. obtaining coumalic acid or its derivatives from biomass; b. dissolving the coumalic acid or its derivatives of step (a) in a first solvent and heating at a temperature of 80 to 100°C to obtain a first reactant; c. adding a second reactant to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to dehydrogenation and decarboxylation in presence of at least one catalyst to obtain trimellitic acid.
  • the coumalic acid derivatives are selected from the group consisting of methyl coumalate and ethyl coumalate.
  • the coumalic acid or its derivatives is obtained from biomass by fermentation.
  • fermentation of biomass results in the formation of malic acid which is heated to undergo dimerization to form coumalic acid or its derivatives.
  • the solvent is selected from the group consisting of tetrahydrofuran, hexane, cyclohexane, toluene, methanol, ethanol, iso-propanol, acetone, acetonitrile, and water.
  • the solvent is tetrahydrofuran.
  • the second reactant is selected from the group consisting of maleic anhydride, maleic acid, dimethylacetylene dicarboxylate, 2-butene, fumaric acid, mono methyl fumarate, dimethyl fumarate, diethyl malate, mono-methyl malate, dimethyl malate, and diethyl malate.
  • the second reactant is maleic anhydride.
  • the at least one catalyst is selected from the group consisting of metal catalysts, zeolites and metal oxides.
  • the metal catalysts are selected from the group consisting of palladium, platinum, nickel, rhodium, ruthenium and combinations thereof.
  • the zeolites are selected from the group consisting of Sn-beta, Y-zeolite, beta-zeolite, ZSM-5, MCM-22, SAPO-5, SAPO-37, SAPO-34, USY, and metal oxides are selected from the group consisting of Ce0 2 , MgO, A1 2 0 3 , Sn0 2 , W0 3 , Mo0 3 , Si0 2 , Ti0 2 , Zr0 2 , ZnO, Nb 2 0 3 , La 2 0 3 , Ta 2 Os, Y 2 0 3 , V 2 Os, Cr 2 0 3 , K 2 0/Cr 2 0 3 , Mn0 2 , Fe 2 0 3 , NiO, Ni 2 0 3 , Co 2 0 3 , CuO and combinations thereof.
  • step (a) The coumalic acid or its derivatives of step (a) is dissolved in a first solvent and heated at a temperature of 100°C to obtain a first reactant.
  • the Diels-Alder adduct is subjected to dehydrogenation and decarboxylation in presence of palladium and ZSM-5 zeolite catalyst at a temperature of 150°C for 2 hours to obtain trimellitic acid.
  • trimellitic acid as described herein results in the production of trimellitic acid with greater than 90% selectivity.
  • the present invention provides three different schemes starting from biomass based furan, lactone and pyrones to produce trimellitic acid in a green, environmental friendly and mild process.
  • the schemes are described in detail as follows:
  • Step 1 Dissolving Mevalonolactone in tetrahydrofuran and heating at 100°C to obtain isoprene in a round bottom flask.
  • Step 2 Adding Maleic anhydride dropwise with constant stirring which forms a solid white Diels-Alder adduct.
  • Step 3 Oxidizing resultant Diels-Alder adduct over K 2 0/Cr 2 0 3 catalyst at 100°C for 20 hours to obtain Trimellitic acid with >90% selectivity.
  • Step 1 Dissolving Coumalic acid (or methyl coumalate) in tetrahydrofuran and heating at 100°C.
  • Step 2 Adding Maleic anhydride dropwise with constant stirring which forms solid white Diels-Alder adduct.
  • Step 3 Dehydrogenating and decarboxylating resultant Diels-Alder adduct over a Pd/ZSM-5 catalyst at 150°C for 2 hours to obtain Trimellitic acid with >90% selectivity.
  • Step 1 Dissolving DMF (or HMF) in tetrahydrofuran and heating at 100°C.
  • Step 2 Adding Acrolein dropwise with constant stirring which forms a solid white Diels-Alder adduct.
  • Step 3 Dehydrating resultant Diels-Alder adduct over ZSM-5 catalyst at 150°C for 2 hours, followed by oxidating over K 2 0/Cr 2 0 3 catalyst 100°C for 20 hours to obtain Trimellitic acid with >90% selectivity.
  • the connection between the three schemes is that all the three routes start from biomass.
  • the starting substrate for the three scheme is obtained in three different biomass hydrolysis or fermentation process as shown in the scheme below:
  • the present invention relates to a green, environmental friendly and mild process, where corrosive acid is not required to convert biomass derived furans, lactones and pyrones in trimellitic acid production.
  • the process can easily be integrated to an upstream fermentation reaction where the reactant furans, lactones, pyrones, maleic anhydride, acrolein or propylene is obtained directly from biomass. Therefore, the novel-integrated two/three- step process to produce trimellitic acid from biomass runs at relatively mild environmentally friendly conditions with high conversion and selectivity is proposed. As depicted in the schemes three pathways to produce trimellitic acid/anhydride are explored. Mevalonolactone obtained from microbial fermentation of biomass, is dehydrogenated and decarboxyl ated to produce isoprene.
  • Isoprene was reacted with maleic anhydride (which can also be obtained from biomass fermentation) at mild temperature (T ⁇ 100 °C) to obtain Diels-Alder adduct with ⁇ 100 % yield.
  • the resultant adduct is oxidized over K 2 0/Cr 2 0 3 catalyst at 100°C for 20 hours to obtain trimellitic acid anhydride with 90 % yield and good selectivity (>90%).
  • coumalic acid / methyl coumalate obtained from fermentation of biomass sugars
  • maleic anhydride or dimethyl acetylene dicarboxylate obtained from fermentation of biomass sugars
  • Diels-alder adduct ⁇ 100 % yield
  • Pd/ZSM-5 catalyst oxidized over K 2 0/Cr 2 0 3 catalyst to produce Trimellitic acid anhydride with high yield (> 90 % yield).
  • HMF was reacted, which is produced from hydrolysis of biomass, with acrolein at temperature 100 °C to produce the Diels-Alder adduct which is dehydrated over an acidic zeolite catalyst (ZSM-5) to obtain the aromatic intermediate, which is oxidized over K 2 0/Cr 2 O, catalyst at 100°C for 20 hours to obtain Trimellitic acid with ⁇ 90 % yield.
  • ZSM-5 acidic zeolite catalyst

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Furan Compounds (AREA)

Abstract

Provided herein is a process for the preparation of trimellitic acid (TMA) from furans, pyrones and lactones obtained from biomass. The furans, pyrones and lactones are converted to a Diels-Alder adduct; and subsequently the Diels-Alder adduct follows either oxidation, dehydrogenation, decarboxylation, or dehydration in presence of at least one catalyst to obtain trimellitic acid.

Description

A PROCESS FOR PRODUCING TRIMELLITIC ACID FROM
BIOMASS
FIELD OF INVENTION
The present invention relates to an eco-friendly method to produce trimellitic acid (TMA) from biomass based furans, pyrones and lactones. Particularly, the present method relates to Diels-Alder cycloaddition with a specific dienophile to obtain cyclo-adduct which is be further dehydrated, dehydrogenated and/or oxidized to produce trimellitic acid anhydride.
BACKGROUND AND PRIOR ART
Depletion in the fossil fuel reserves and increase in the demand of chemical and energy products have necessitated efforts to explore alternative resources such as biomass, which is available in abundance for producing fuels and chemicals. While biomass can be directly gasified or pyrolysed to produce fuel and chemical range products, novel process integrations in which a platform molecule is produced via a bio-catalytic method and subsequently processed via a chemo-catalytic method into a desired product with high conversion and selectivity, represent the state-of-the-art in research. Trimellitic acid (TMA), used as the curing agent for manufacturing of epoxy resins, is one of the most sought after petroleum derived product. Epoxy resin finds its application as paints and coatings, adhesives, making industrial high-duty tools, electronics etc. The market share of epoxy resins are estimated to be 15 billion USD worldwide. The esters of TMA are also used as plasticizers in making the automobile interiors or in similar applications where resistance to high temperature is required. Derivatives of TMA also have been suggested as potential drug for cancer and agrochemical applications. Furthermore, TMA has been proposed to have application in the field of dental adhesive, anti-snake venom and HIV protection. There has been constant effort since the past decade or so to replace the petroleum based pathways with biomass routes for the production of essential chemicals.
Diels-Alder cycloaddition of biomass derived HMF and its derivatives with ethylene (C2H4) or acrolein (H2CCHCHO) followed by dehydration have been proposed as possible routes for the production of aromatics with different functionality by Davis et al. [WO2014/197195, US9108982B2, PNAS 2014. Ill (23) 8363-8367] and Toste et al. [Chem. Eur. J. 2011, 17, 12452 - 12457] Davis et al. [WO2014/197195, US9108982B2, PNAS 2014. Ill (23) 8363-8367] showed that terephthalic acid can be produced by reacting HMF and its derivatives with ethylene, to form an oxanorbornene intermediate, which can undergo dehydration reaction over a solid acid catalyst, to form its aromatic equivalent. The resultant aromatic compound can be oxidized under mild condition, over low-cost oxide catalyst to obtain PTA [Chem. Rev. 2013, 113, 7421-7469].
Further trimellitic acid is produced in the industrial scale through catalytic oxidation of pseudocumene (1, 2, 4-Trimethylbenzene) over Co/Mn/Br catalyst using AMOCO process. [Chem. Rev. 2013, 113, 7421-7469, Chinese Journal of Catalysis 35 (2014) 1641-1652] It has been observed that production and recovery of trimellitic acid intramolecular anhydride (TMA) is enhanced by conducting catalytic liquid phase oxidation of pseudocumene with air in the presence of 2 to 6 weight parts acetic acid having 2 to 5 weight percent water at a temperature of 325 to 450°F. [US 3,484,458] This process is conducted in highly corrosive acidic medium at a high temperature (175— 225°C). Concerns over environmental and safety issues have driven studies to find milder process for the production of trimellitic acid. In addition, low selectivity and conversion to a desired product remains a concern to be resolved.
U.S. Patent US9035018B2 provides a furan-based curable compound derived from carbohydrate-based biomass as a basic backbone, which may replace an aromatic compound produced through a petrochemical process. In addition, the patent also provides a curable compound, which may reduce curing contraction ratio, and a method for preparing thereof with a combination of high yield and cost-effectiveness.
According to an embodiment disclosed in column 3 lines 9-17, a method for preparing a furan-based curable compound derived from biomass comprising i. preparing a starting material wherein a furan-based compound derived from biomass is prepared as a starting material which may be obtained through oxidation or reduction reaction by using furfural or furfural derivatives as an intermediate which are converted from cellulose or hemicellulose extracted from carbohydrate-based biomass; and ii. mixing and stirring the furan-based compound derived from biomass and an epichlorhydrin.
The resultant molecules are proposed to be potential replacement of aromatic compounds produced through petrochemicals. Further the examples 1-4 and the comparative example provide the photo curing behavior of the composition and the contraction ratio is measured during curing, in order to examine the applicability of a furan-based curable compound containing an epoxide functional group as a curing material which is synthesized according to the method described above. Therefore, the process and products as well as applications of the invention are entirely different from that of the present invention.
KR20160007506 discusses production of poly-carboxylic acid compounds from enzymatic treatment of lignocellulosic biomass. Biomass is treated with enzymes or other organisms to produce a mixture of poly-carboxylic acids as product. One of the compound in the poly-carboxylic acid mixture can be trimellitic acid. However, this process is not industrially feasible.
Said document teaches a method for producing a poly-carboxylic acid by treatment with a reduced degradation of lignoceric cellulose or cellulose material (reduced recalcitrance lignocellulosic or cellulosic material) with one or more enzymes and/or organism, and a method for manufacturing a product comprising the step of converting the poly- carboxylic acid as a product. However, present invention does not disclose any enzymatic treatment of the lignocellulosic or cellulosic biomass.
WO20 16207403 relates to a recombinant Deinococcus bacterium expressing a heterologous polypeptide exhibiting 3-dehydroshikimate dehydratase activity and a heterologous polypeptide exhibiting protocatechuate decarboxylase activity, comprising a heterologous biosynthetic pathway converting 3-dehydroshikimate to catechol and/or cis, cis-muconic Acid; further comprising culturing above-mentioned recombinant Deinococcus bacterium under conditions suitable to produce cis-cis muconic acid, and optionally recovering said cis-cis muconic acid. Said application does not motivate a person skilled in the art to arrive at the present invention. US8367858B2 relates to substituted and unsubstituted terephthalic acid and carboxylate derivatives and products prepared therefrom having a renewable content; processes for preparation thereof wherein a portion of the starting materials utilized is derived from renewable resources. The invention also relates to cyclohexene based intermediates prepared in these processes and to conversion of these intermediates to substituted and unsubstituted cyclohexane-l,4-dicarboxylates and carboxylate derivatives thereof and different forms of the resulting products having renewable content. The invention also relates to products prepared from substituted and unsubstituted terephthalic acid and carboxylate derivatives thereof derived from starting materials derived from renewable resources.
This patent application relates to a method for preparing a compound containing a benzene ring, the compound having formula (I)
(I)
Figure imgf000005_0001
the method comprising:
(a) a one-pot reaction, isomerizing one or more of cis, cis and cis, trans muconic acids or carboxylate derivatives thereof to form trans, trans muconic acid or carboxylate derivatives thereof, and contacting the trans, trans muconic acid or carboxylate derivatives thereof with one or more dienophiles under conditions such that the trans, trans muconic acid or carboxylate derivatives thereof and the one or more dienophiles form one or more cyclohexene ring containing compounds; and
(b) contacting the one or more cyclohexene ring containing compounds with a dehydrogenation catalyst under conditions such that one or more compounds containing a benzene ring with carboxylate derivatives at the 1 and 4 position are formed; wherein said carboxylate derivatives contain group
Figure imgf000006_0001
Wherein R1 is independently in each occurrence hydrogen or a hydrocarbyl group optionally containing a heteroatom containing functional group wherein the hydrocarbyl group does not interfere in the formation of the cyclohexene ring containing compound;
R2is independently in each occurrence hydrogen or a hydrocarbyl group optionally containing a heteroatom containing functional group wherein the hydrocarbyl group does not interfere in the formation of the cyclohexene ring containing compound; and
R3is independently in each occurrence hydrogen or a hydrocarbyl group optionally containing a heteroatom containing functional group wherein the hydrocarbyl group does not interfere in the formation of the cyclohexene ring containing compound; or R2 and R3 combine to form a cyclic ring that can contain heteroatoms;
Z is independently in each occurrence an anion, oxygen, nitrogen, sulfur, halogen or nitrile; and b is independently in each occurrence 0, 1 or 2; with the proviso that b is 0 when Z is an anion, nitrile or halogen, that b is 1 when Z is oxygen or sulfur, and that b is 2 when Z in nitrogen.
WO 2010/148081 is the published application of the US patent discussed above.
Industrially trimellitic acid is produced through catalytic oxidation of pseudocumene (1,2,4-Trimethylbenzene) over Co/Mn/Br catalyst using AMOCO process. [Chem. Rev. 2013, 113, 7421-7469, Chinese Journal of Catalysis 35 (2014) 1641-1652] Production and recovery of trimellitic acid intramolecular anhydride (TMA) is enhanced by conducting catalytic liquid phase oxidation of pseudocumene with air in the presence of 2 to 6 weight parts acetic acid having 2 to 5 weight percent water at a temperature of 160°C to 230 °C. [US 3,484,458] This process is conducted in highly corrosive acidic medium at a high temperature (175-225 °C). Concerns over environmental and safety issues have driven studies to find milder process for the production of trimellitic acid. In addition, low selectivity and conversion to a desired product remains a concern to be resolved.
There is therefore a need to provide a better replacement of the conventional fossil fuel based petrochemical route for production of trimellitic acid by using biomass based reactants in the proposed method resulting in higher yield and hence saving the fossil fuels.
OBJECTIVES OF THE INVENTION
An objective of the present invention is to provide a process for production of trimellitic acid from biomass based lactones, pyrones and furans.
Another objective of the invention is to provide a catalytic process involving Diels-Alder cycloaddition with a dienophile to obtain cyclo-adduct, which can be further dehydrated, dehydrogenated and oxidized to produce the trimellitic acid anhydride.
A further objective of the invention is to obtain trimellitic acid anhydride from diels-alder reaction of isoprene obtained from biomass based Mevalonolactone and another biomass obtained maleic anhydride.
Another objective of the invention is to obtain trimellitic acid anhydride from diels-alder reaction of coumalic acid (or methyl coumalate) obtained from biomass and maleic anhydride.
A further objective of the invention is to obtain trimellitic acid anhydride from Diels- Alder reaction of biomass obtained furans and acrolein/acrylic aci d/methylacrylate. Another objective of the invention is to provide an alternative process to the conventional fossil fuel based petrochemical route for production of trimellitic acid, with a relatively mild environmentally friendly process with high conversion and selectivity.
SUMMARY OF THE INVENTION
The following presents a simplified summary of the invention in order to provide a basic understanding of some aspects of the invention. This summary is not an extensive overview of the present invention. It is not intended to identify the key/critical elements of the invention or to delineate the scope of the invention.
In an aspect of the present invention, there is provided a process for the preparation of trimellitic acid, the process comprising the steps of: a. obtaining a substrate from biomass; b. dissolving the substrate of step (a) in a solvent and heating at a temperature in the range of 80°C to 120°C to obtain a first reactant; c. adding a second reactant dissolved in solvent to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to at least one of the reactions selected from a group consisting of oxidation, dehydrogenation, decarboxylation, and dehydration in presence of at least one catalyst to obtain trimellitic acid.
In another aspect of the present invention, there is provided a process for the preparation of trimellitic acid from mevalonolactone, the process comprising the steps of: a. obtaining mevalonolactone from biomass; b. dissolving the lactone of step (a) in a solvent and heating at a temperature of 80 to 100°C to obtain isoprene; c. adding a second reactant to isoprene of step (b) to obtain a Diels-Alder adduct; d. subjecting the Diels-Alder adduct of step (c) to oxidation in presence of a catalyst to obtain trimellitic acid. In yet another aspect of the present invention, there is provided a process for the preparation of trimellitic acid from hydroxyl methyl furan or its derivatives, the process comprising the steps of: a. obtaining hydroxyl methyl furan or its derivatives from biomass; b. dissolving the hydroxyl methyl furan or its derivatives of step (a) in a solvent and heating at a temperature of 80 to 100°C to obtain a first reactant; c. adding a second reactant to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to dehydration and oxidation in presence of at least one catalyst to obtain trimellitic acid.
In a further aspect of the present invention, there is provided a process for the preparation of trimellitic acid from coumalic acid or its derivatives, the process comprising the steps of: a. obtaining coumalic acid or its derivatives from biomass; b. dissolving the coumalic acid or its derivatives of step (a) in a first solvent and heating at a temperature of 80 to 100°C to obtain a first reactant; c. adding a second reactant to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to dehydrogenation and decarboxylation in presence of at least one catalyst to obtain trimellitic acid.
BRIEF DESCRIPTION OF ACCOMPANYING DRAWINGS
The above and other aspects, features and advantages of the embodiments of the present disclosure will be more apparent in the following description taken in conjunction with the accompanying drawings, in which:
Figure 1 illustrates XH NMR spectrum showing complete conversion of maleic anhydride Figure 2 illustrates XH NMR spectrum of Trimellitic Acid produced from Diels Alder adduct (right) and standard Trimellitic Acid (left) Figure 3 illustrates HPLC chromatogram of Trimellitic Acid produced from Diels Alder adduct (right) and standard Trimellitic Acid (left)
DETAILED DESCRIPTION OF INVENTION
In the present invention, there is provided a green, environmental friendly and mild process to convert biomass derived furans, lactones and pyrones into trimellitic acid.
The process can easily be integrated to an upstream fermentation reaction where the reactant furans, lactones, pyrones, melic anhydride, acrolein or propylene is obtained directly from biomass. Therefore, the novel integrated two/three-step process to produce trimellitic acid from biomass runs under relatively mild environmentally friendly conditions with high conversion and selectivity is proposed.
The following description with reference to the accompanying drawings is provided to assist in a comprehensive understanding of various embodiments of the present disclosure as defined by the claims and their equivalents. It includes various specific details to assist in that understanding but these are to be regarded as merely exemplary. Accordingly, those of ordinary skill in the art will recognize that various changes and modifications of the various embodiments described herein can be made without departing from the scope and spirit of the present disclosure. In addition, descriptions of well-known functions and constructions may be omitted for clarity and conciseness.
The terms and words used in the following description and claims are not limited to the bibliographical meanings, but, are merely used by the inventor to enable a clear and consistent understanding of the present disclosure. Accordingly, it should be apparent to those skilled in the art that the following description of various embodiments of the present disclosure is provided for illustration purpose only and not for the purpose of limiting the present disclosure as defined by the appended claims and their equivalents.
It is to be understood that the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component surface" includes reference to one or more of such surfaces. The terminology used herein is for the purpose of describing particular various embodiments only and is not intended to be limiting of various embodiments. As used herein, the singular forms "a," "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising" used herein specify the presence of stated features, integers, steps, operations, members, components, and/or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, members, components, and/or groups thereof. Also, Expressions such as "at least one of," when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
The present disclosure will now be described more fully with reference to the accompanying drawings, in which various embodiments of the present disclosure are shown. The present disclosure may, however, be embodied in many different forms and should not be construed as being limited to the various embodiments set forth herein, rather, these various embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the present disclosure.
The present invention relates to a process for the preparation of trimellitic acid, the process comprising the steps of: a. obtaining a substrate from biomass; b. dissolving the substrate of step (a) in a solvent and heating at a temperature in the range of 80°C to 120°C to obtain a first reactant; c. adding a second reactant dissolved in solvent to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to at least one of the reactions selected from a group consisting of oxidation, dehydrogenation, decarboxylation, and dehydration in presence of at least one catalyst to obtain trimellitic acid.
As provided in the process, the substrate is selected from the group consisting of lactones, furans and pyrones. In one embodiment, the substrate is lactone. In another embodiment, the substrate is pyrone. In yet another embodiment, the substrate is furan.
Further, as provided by the present invention the substrate is obtained from biomass by at least one of fermentation, and acid hydrolysis.
The present invention relates to a process wherein the solvent is selected from a group consisting of polar and non-polar solvents, preferably selected from selected from water, tetrahydrofuran, 1,4-dioxane, acetonitrile, N-m ethyl pyrrolidone, dimethylacetamide, dimethyl sulfoxide, dimethyl acetamide, cyclohexane, hexane, toluene, xylene, benzene, chloroform, dichlormethane, acetone, aliphatic alcohol, aromatic alcohol, an ionic liquid.
The present invention relates to a process wherein the second reactant is selected from a group consisting of maleic anhydride, maleic acid, 2-butene, fumaric acid, mono-methyl fumarate, dimethyl fumarate, diethyl malate, mono-methyl malate, dimethyl malate, diethyl malate, acrolein, acrylic acid, methyl acrylate, ethyl acrylate, and propylene.
The second reactant used in the process may be liquid or solid. During reaction the second reactant is dissolved in the solvent in which the substrate is dissolved and then added to the first reactant.
The present invention relates to a process wherein the at least one catalyst is selected from a group consisting of metal catalysts selected from palladium, platinum, nickel, rhodium, ruthenium and combinations thereof, acid catalysts such as zeolite selected from Sn-beta, Y-zeolite, beta-zeolite, ZSM-5, MCM-22, SAPO-5, SAPO-37, SAPO-34, USY, and metal oxides selected from Ce02, MgO, A1203, Sn02, W03, Mo03, Si02, Ti02, Zr02, ZnO, Nb203, La203, Ta2Os, Y203, V2Os, Cr203, K20/Cr203, Mn02, Fe203, NiO, Ni203, Co203, CuO and combinations thereof.
In one embodiment of the present process the substrate of step (a) is dissolved in a solvent and heated at a temperature of 100°C to obtain a first reactant.
In one embodiment of the present process the step (d) is carried out at a temperature of 150°C. In another embodiment of the present process the step (d) is carried out at a temperature of 100°C.
In a preferred embodiment of the process, the substrate is a lactone. Lactone is obtained by microbial fermentation of biomass. The microbial fermentation is carried out by microorganisms such as E.coli sp, Trichoderma sp, Saccharomyces sp, Yarrow ia sp, Geobactor sp, Shewanella sp, Enterococcus sp, Corynebacterium sp, Fusarium sp, Aspergillus sp, Candidas sp, Streptomyces sp, Pichia sp, Piromyces sp, Thermobifida sp, Rhodosporidium sp. In a preferred embodiment, the lactone is mevanolactone, the solvent used in the process is tetrahydrofuran, and the first reactant obtained in the process is isoprene. The second reactant used in the process is maleic anhydride. Adding maleic anhydride to isoprene results in a solid white Diels-Alder adduct. The Diels-Alder adduct is subjected to oxidation in presence of a catalyst, metal oxide to obtain trimellitic acid.
In another preferred embodiment of the process, the substrate is a pyrone. Pyrone is obtained by fermentation of biomass. In a preferred embodiment, the pyrone is coumalic acid or its derivatives. The pyrone is dissolved and heated in the solvent tetrahydrofuran to obtain the first reactant. The second reactant used in the process is Maleic anhydride. Adding maleic anhydride to the first reactant results in a solid white Diels-Alder adduct. The Diels-Alder adduct is subjected to dehydrogenation and decarboxylation in presence of catalysts, palladium and zeolite to obtain trimellitic acid.
In another preferred embodiment of the process, the substrate is a furan. Furan is obtained by acid hydrolysis of biomass. In a preferred embodiment, the furan is hydroxylmethyl furan (HMF) or its derivatives. The furan is dissolved and heated in the solvent tetrahydrofuran to obtain the first reactant. The second reactant used in the process is acrolein. Adding acrolein to the first reactant results in a solid white Diels-Alder adduct. The Diels-Alder adduct is subjected to dehydration and oxidation in presence of catalysts, zeolite and metal oxide to obtain trimellitic acid.
In one embodiment of the present invention, there is provided a process for the preparation of trimellitic acid from mevalonolactone, the process comprising the steps of: a. obtaining mevalonolactone from biomass; b. dissolving the lactone of step (a) in a solvent and heating at a temperature of 80 to 100°C to obtain isoprene; c. adding a second reactant to isoprene of step (b) to obtain a Diels-Alder adduct; d. subjecting the Diels-Alder adduct of step (c) to oxidation in presence of a catalyst to obtain trimellitic acid.
In the process for the preparation of trimellitic acid from mevalonolactone, the mevalonolactone is obtained from biomass by microbial fermentation. The microorganisms used in the fermentation is selected from E. coli sp, Trichoderma sp, Saccharomyces sp, Yarrow ia sp, Geobactor sp, Shewanella sp, Enterococcus sp, Corynebacterium sp, Fusarium sp, Aspergillus sp, Candidas sp, Streptomyces sp, Pichia sp, Piromyces sp, Thermobifida sp, Rhodosporidium sp.
In an embodiment of the process for the preparation of trimellitic acid from mevalonolactone, the solvent is selected from the group consisting of tetrahydrofuran, hexane, cyclohexane, toluene, methanol, ethanol, iso-propanol, acetone, acetonitrile, and water. In a preferred embodiment, the solvent is tetrahydrofuran.
In an embodiment of the process for the preparation of trimellitic acid from mevalonolactone the second reactant is selected from the group consisting of maleic anhydride, maleic acid, dimethylacetylene dicarboxylate, 2-butene, fumaric acid, mono methyl fumarate, dimethyl fumarate, diethyl malate, mono-methyl malate, dimethyl malate, and diethyl malate. In a preferred embodiment, the second reactant is maleic anhydride.
In an embodiment of the process for the preparation of trimellitic acid from mevalonolactone the catalyst is a metal oxide selected from the group consisting of Ce02,
MgO, AI2O3, SnC>2, WO3, M0O3, S1O2, T1O2, ZrC>2, ZnO, ^C , La203, Ta20s, Y2O3, V2O5, Cr203, K20/Cr203, MnC , Fe203, NiO, M2O3, C02O3, CuO and combination thereof. In a preferred embodiment, the catalyst is K20/Cr203. The mevalonolactone of step (a) is dissolved in a first solvent and heated at a temperature of 100°C to obtain isoprene.
In one embodiment of the process for the preparation of trimellitic acid from mevalonolactone, the Diels-Alder adduct is subjected to oxidation in presence of cerinium oxide at a temperature of 100°C for 20 hours to obtain trimellitic acid.
In one embodiment of the present invention, there is provided a process for the preparation of trimellitic acid from hydroxyl methyl furan or its derivatives, the process comprising the steps of: a. obtaining hydroxyl methyl furan or its derivatives from biomass; b. dissolving the hydroxyl methyl furan or its derivatives of step (a) in a solvent and heating at a temperature of 80 to 100°C to obtain a first reactant; c. adding a second reactant to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to dehydration and oxidation in presence of at least one catalyst to obtain trimellitic acid.
The hydroxyl methyl furan derivatives are selected from the group consisting of dimethyl furan (DMF), bis-hydroxym ethyl furan (BHMF), 5-methylfurfural alcohol (MFA), furan dicarboxylic acid (FDCA), and methyl furan dicarboxylic acid (FDCA-Me-ester).
In the process for the preparation of trimellitic acid from hydroxyl methyl furan or its derivatives, the hydroxyl methyl furan or its derivatives is obtained from biomass by acid hydrolysis.
In an embodiment of the process for the preparation of trimellitic acid from hydroxyl methyl furan or its derivatives the solvent is selected from the group consisting of tetrahydrofuran, hexane, cyclohexane, toluene, methanol, ethanol, iso-propanol, acetone, acetonitrile, and water. In a preferred embodiment, the solvent is tetrahydrofuran. In an embodiment of the process for the preparation of trimellitic acid from hydroxyl methyl furan or its derivatives, the second reactant is selected from the group consisting of acrolein, acrylic acid, methyl acrylate, ethyl acrylate, and propylene. In a preferred embodiment, the second reactant is acrolein.
In an embodiment of the process for the preparation of trimellitic acid from hydroxyl methyl furan or its derivatives, the at least one catalyst is selected from zeolites and metal oxides. The zeolites are selected form the group consisting of Sn-beta, Y-zeolite, beta- zeolite, ZSM-5, MCM-22, SAPO-5, SAPO-37, SAPO-34, USY, and combination thereof, and metal oxides are selected form the group consisting of CeC^, MgO, AI2O3, SnC>2, WO3, M0O3, S1O2, T1O2, ZrC>2, ZnO, Nb203, La203, Ta20s, Y2O3, V2O5, (¾03, K20/Cr203, MnC>2, Fe203, NiO, M2O3, C02O3, CuO and combination thereof. In a preferred embodiment, the zeolite is ZSM-5 and metal oxide is K20/Cr203.
The hydroxyl methyl furan or its derivatives of step (a) is dissolved in a solvent and heated at a temperature of 100°C to obtain a first reactant.
In one embodiment of the process for the preparation of trimellitic acid from hydroxyl methyl furan or its derivatives, the Diels-Alder adduct is subjected to dehydration in presence of ZSM-5 at a temperature of 150°C for 2 hours, followed by oxidation over K20/Cr203 catalyst at a temperature of 100°C for 20 hours to obtain trimellitic acid.
In one embodiment of the present invention, there is provided a process for the preparation of trimellitic acid from coumalic acid or its derivatives, the process comprising the steps of: a. obtaining coumalic acid or its derivatives from biomass; b. dissolving the coumalic acid or its derivatives of step (a) in a first solvent and heating at a temperature of 80 to 100°C to obtain a first reactant; c. adding a second reactant to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to dehydrogenation and decarboxylation in presence of at least one catalyst to obtain trimellitic acid.
The coumalic acid derivatives are selected from the group consisting of methyl coumalate and ethyl coumalate.
In the process for the preparation of trimellitic acid from coumalic acid or its derivatives, the coumalic acid or its derivatives is obtained from biomass by fermentation. In a preferred embodiment, fermentation of biomass results in the formation of malic acid which is heated to undergo dimerization to form coumalic acid or its derivatives.
In an embodiment of the process for the preparation of trimellitic acid from coumalic acid or its derivatives, the solvent is selected from the group consisting of tetrahydrofuran, hexane, cyclohexane, toluene, methanol, ethanol, iso-propanol, acetone, acetonitrile, and water. In a preferred embodiment, the solvent is tetrahydrofuran.
In an embodiment of the process for the preparation of trimellitic acid from coumalic acid or its derivatives, the second reactant is selected from the group consisting of maleic anhydride, maleic acid, dimethylacetylene dicarboxylate, 2-butene, fumaric acid, mono methyl fumarate, dimethyl fumarate, diethyl malate, mono-methyl malate, dimethyl malate, and diethyl malate. In a preferred embodiment, the second reactant is maleic anhydride.
In an embodiment of the process for the preparation of trimellitic acid from coumalic acid or its derivatives, the at least one catalyst is selected from the group consisting of metal catalysts, zeolites and metal oxides. The metal catalysts are selected from the group consisting of palladium, platinum, nickel, rhodium, ruthenium and combinations thereof. The zeolites are selected from the group consisting of Sn-beta, Y-zeolite, beta-zeolite, ZSM-5, MCM-22, SAPO-5, SAPO-37, SAPO-34, USY, and metal oxides are selected from the group consisting of Ce02, MgO, A1203, Sn02, W03, Mo03, Si02, Ti02, Zr02, ZnO, Nb203, La203, Ta2Os, Y203, V2Os, Cr203, K20/Cr203, Mn02, Fe203, NiO, Ni203, Co203, CuO and combinations thereof.
The coumalic acid or its derivatives of step (a) is dissolved in a first solvent and heated at a temperature of 100°C to obtain a first reactant.
In one embodiment of the process for the preparation of trimellitic acid from coumalic acid or its derivatives, the Diels-Alder adduct is subjected to dehydrogenation and decarboxylation in presence of palladium and ZSM-5 zeolite catalyst at a temperature of 150°C for 2 hours to obtain trimellitic acid.
The process for preparation of trimellitic acid as described herein results in the production of trimellitic acid with greater than 90% selectivity.
Following the process of the present invention complete conversion of the reactants in the present invention is obtained with no impurities as evident from the NMR spectrum. Taking the error possible in NMR, the yield is expected to be ~ 90 %.
Particularly, the present invention provides three different schemes starting from biomass based furan, lactone and pyrones to produce trimellitic acid in a green, environmental friendly and mild process. The schemes are described in detail as follows:
Scheme 1: From bio-based lactones
Step 1: Dissolving Mevalonolactone in tetrahydrofuran and heating at 100°C to obtain isoprene in a round bottom flask.
Step 2: Adding Maleic anhydride dropwise with constant stirring which forms a solid white Diels-Alder adduct.
Step 3: Oxidizing resultant Diels-Alder adduct over K20/Cr203 catalyst at 100°C for 20 hours to obtain Trimellitic acid with >90% selectivity.
Scheme 2: From bio-based pyrones
Step 1: Dissolving Coumalic acid (or methyl coumalate) in tetrahydrofuran and heating at 100°C.
Step 2: Adding Maleic anhydride dropwise with constant stirring which forms solid white Diels-Alder adduct.
Step 3: Dehydrogenating and decarboxylating resultant Diels-Alder adduct over a Pd/ZSM-5 catalyst at 150°C for 2 hours to obtain Trimellitic acid with >90% selectivity.
Scheme 3: From bio-based furans
Step 1 : Dissolving DMF (or HMF) in tetrahydrofuran and heating at 100°C.
Step 2: Adding Acrolein dropwise with constant stirring which forms a solid white Diels-Alder adduct.
Step 3: Dehydrating resultant Diels-Alder adduct over ZSM-5 catalyst at 150°C for 2 hours, followed by oxidating over K20/Cr203 catalyst 100°C for 20 hours to obtain Trimellitic acid with >90% selectivity.
The schemes are depicted below as:
Scheme 1
Figure imgf000019_0001
Scheme 1: Preparation of trimellitic acid from bio-based lactones where (a) Mevalonolactone, (b) isoprene, (c) maleic anhydride (or maleic acid), (e) trimellitic acid anhydride (or trimellitic acid)
Scheme 2
Figure imgf000019_0002
o
Figure imgf000020_0001
a H, Me
Scheme 2: Preparation of trimellitic acid from bio-based pyrones where (f) coumalic acid (or methyl coumalate), (c) maleic anhydride (or maleic acid or (h) dimetylacetylene dicarboxylate), (g) and (i) cyclo-adduct, (e) trimellitic acid anhydride (or trimellitic acid)
Scheme 3
Figure imgf000020_0002
Scheme 3: Preparation of trimellitic acid from bio-based furans where (j) dimethyl furan (DMF), hydroxymethyl furan (HMF), bis-hydroxym ethyl furan (BHMF), 5- methylfurfural alcohol (MFA), hydroxymethyl furan (HMF), furan dicarboxylic acid (FDCA), methylfurandicarboxylic acid (FDCA-Me-ester) (k) acrolein, acrylic acid, methyl acrylate, (1) cyclo-adduct of (j) and (k); (m) Cg-aromatic intermediate (e) trimellitic acid anhydride (or trimellitic acid)
The connection between the three schemes is that all the three routes start from biomass. The starting substrate for the three scheme is obtained in three different biomass hydrolysis or fermentation process as shown in the scheme below:
Figure imgf000021_0001
Scheme 4: Preparation of the substrates from biomass
The present invention relates to a green, environmental friendly and mild process, where corrosive acid is not required to convert biomass derived furans, lactones and pyrones in trimellitic acid production. The process can easily be integrated to an upstream fermentation reaction where the reactant furans, lactones, pyrones, maleic anhydride, acrolein or propylene is obtained directly from biomass. Therefore, the novel-integrated two/three- step process to produce trimellitic acid from biomass runs at relatively mild environmentally friendly conditions with high conversion and selectivity is proposed. As depicted in the schemes three pathways to produce trimellitic acid/anhydride are explored. Mevalonolactone obtained from microbial fermentation of biomass, is dehydrogenated and decarboxyl ated to produce isoprene. Isoprene was reacted with maleic anhydride (which can also be obtained from biomass fermentation) at mild temperature (T ~ 100 °C) to obtain Diels-Alder adduct with ~ 100 % yield. The resultant adduct is oxidized over K20/Cr203 catalyst at 100°C for 20 hours to obtain trimellitic acid anhydride with 90 % yield and good selectivity (>90%). Similarly, coumalic acid / methyl coumalate (obtained from fermentation of biomass sugars) is reacted with maleic anhydride or dimethyl acetylene dicarboxylate, to obtain the Diels-alder adduct (~ 100 % yield), which is then decarboxyl ated and dehydrogenated over Pd/ZSM-5 catalyst or oxidized over K20/Cr203 catalyst to produce Trimellitic acid anhydride with high yield (> 90 % yield). In the third pathway HMF was reacted, which is produced from hydrolysis of biomass, with acrolein at temperature 100 °C to produce the Diels-Alder adduct which is dehydrated over an acidic zeolite catalyst (ZSM-5) to obtain the aromatic intermediate, which is oxidized over K20/Cr2O, catalyst at 100°C for 20 hours to obtain Trimellitic acid with ~ 90 % yield.
Henceforth, embodiments of the present disclosure are explained with one or more examples. However, such examples are provided for the illustration purpose for better understanding of the present disclosure and should not be construed as limitation on scope of the present disclosure.
Examples
Example 1: Preparation of trimelltic acid from bio-based lactones
100 mg of mevalonolactone was dissolved in tetrahydrofuran and heated at 100°C to obtain isoprene in a round bottom flask. A molar equivalent of maleic anhydride was added dropwise with constant stirring resulting in a solid white Diels-Alder adduct. The resultant Diels- Alder adduct is oxidized over K20/Cr203 catalyst at 100°C for 20 hours to obtain trimellitic acid with >90% selectivity.
Example 2: Preparation of trimelltic acid from bio-based pyrones
Coumalic acid (or methyl coumalate) was dissolved in tetrahydrofuran and heated at 100°C. A molar equivalent of maleic anhydride was added dropwise with constant stirring resulting in a solid white Diels-Alder adduct. The resultant Diels-Alder adduct was dehydrogenated and decarboxyl ated over a Pd/ZSM-5 catalyst at 150°C for 2 hours to obtain trimellitic acid with >90% selectivity.
When dimethyl acetylene dicarboxylate was used as an alternative to maleic anhydride, the resultant Diels-Alter product can be oxidized over K20/Cr203 catalyst at 150°C for 2 hours to obtain trimellitic acid with >90% selectivity. Example 3: Preparation of trimelltic acid from bio-based furans
100 mg of DMF (or HMF) was dissolved in tetrahydrofuran and heating at 100°C. A molar equivalent of Acrolein was added dropwise with constant stirring resulting in a solid white Diels-Alder adduct. The resultant Diels-Alder adduct was dehydrated over ZSM-5 catalyst at 150°C for 2 hours, followed by oxidating over K20/Cr203 catalyst 100°C for 20 hours to obtain trimellitic acid with >90% selectivity.
Example 4: Characterization of Trimellitic acid
All the reactants and products were analysed in 5mm NMR tubes. Prior to NMR analysis, 10-20 mg of each sample was dissolved in 0.6 mL deuterated solvent. The resultant spectrum was recorded on NMR machine and data were processed subsequently. The obtained XH NMR spectra of the reactant and/or product mixture were compared. 100 % conversion was stated when the characteristic peak of one of the reactant completely disappeared after the reaction. As observed from Figure 1, that is XH NMR spectrum, approximately 100% maleic anhydride is converted into the Diels Alder adduct (i.e. no peak for the reactant, maleic anhydride is seen). Further oxidation of the adduct produce Trimellitic Acid in yield high selectivity as shown in the H NMR spectrum in Figure 2 and HPLC chromatogram in Figure 3. Figure 2 showing the NMR data of the standard Trimellitic acid (purchased from Sigma Aldrich) in the left, whereas the NMR spectra of the as synthesized trimellitic acid using the process described herein is shown in the right. Figure 3 showing the HPLC chromatogram of the standard Trimellitic acid (purchased from Sigma Aldrich) in the left and the synthesized trimellitic acid using the process described herein is shown in the right. Figure 2 and 3 shows comparison of the produced Trimellitic Acid with standard Trimellitic Acid that confirms high yield selectivity of Trimellitic Acid produced by the process described herein.
The present invention is not to be limited in scope by the specific embodiments described herein. Indeed, various modifications of the invention, in addition to those described herein, will become apparent to those skilled in the art from the foregoing description and accompanying figures. Such modifications are intended to fall within the scope of the appended claims. The invention is, therefore, to be limited only by the terms of the appended claims along with the full scope of equivalents to which the claims are entitled.

Claims

1. A process for the preparation of trimellitic acid, the process comprising the steps of: a. obtaining a substrate from biomass; b. dissolving the substrate of step (a) in a solvent and heating at a temperature in the range of 80°C to 120°C to obtain a first reactant; c. adding a second reactant dissolved in solvent to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to at least one of the reactions selected from a group consisting of oxidation, dehydrogenation, decarboxylation, and dehydration in presence of at least one catalyst to obtain trimellitic acid.
2. The process as claimed in claim 1, wherein the substrate is selected from the group consisting of lactones, furans and pyrones.
3. The process as claimed in claim 1, wherein the substrate is obtained from biomass by at least one of fermentation, and acid hydrolysis.
4. The process as claimed in claim 1, wherein the solvent is selected from a group consisting of polar and non-polar solvents, preferably selected from water, tetrahydrofuran, 1,4-dioxane, acetonitrile, N-m ethyl pyrrolidone, dimethylacetamide, dimethyl sulfoxide, dimethyl acetamide, cyclohexane, hexane, toluene, xylene, benzene, chloroform, dichlormethane, acetone, aliphatic alcohol, aromatic alcohol, and ionic liquid.
5. The process as claimed in claim 1, wherein the second reactant is selected from a group consisting of maleic anhydride, dimethylacetylene di carboxyl ate, maleic acid, acrolein, acrylic acid, methyl acrylate, ethyl acrylate, and propylene.
6. The process as claimed in claim 1, wherein the at least one catalyst is selected from a group consisting of metal catalysts selected from palladium, platinum, nickel, rhodium, ruthenium and combinations thereof, acid catalysts such as zeolite selected from Sn-beta, Y-zeolite, beta-zeolite, ZSM-5, MCM-22, SAPO-5, SAPO-37, SAPO-34, USY, and metal oxides selected from Ce02, MgO, A1203, Sn02, W03, Mo03, Si02, Ti02, Zr02, ZnO, Nb203, La203, Ta2Os, Y203, V2Os, Cr203, K20/Cr203, Mn02, Fe203, NiO, Ni203, Co203, CuO and combinations thereof.
7. A process for the preparation of trimellitic acid from mevalonolactone, the process comprising the steps of: a. obtaining mevalonolactone from biomass; b. dissolving the lactone of step (a) in a solvent and heating at a temperature of 80 to 100°C to obtain isoprene; c. adding a second reactant to isoprene of step (b) to obtain a Diels-Alder adduct; d. subjecting the Diels-Alder adduct of step (c) to oxidation in presence of a catalyst to obtain trimellitic acid.
8. The process as claimed in claim 7, wherein the mevalonolactone is obtained from biomass by microbial fermentation.
9. The process as claimed in claim 7, wherein the solvent is selected from the group consisting of tetrahydrofuran, hexane, cyclohexane, toluene, methanol, ethanol, iso propanol, acetone, acetonitrile, and water.
10. The process as claimed in claim 7, wherein the second reactant is selected from the group consisting of maleic anhydride, maleic acid, dimethylacetylene di carboxyl ate, 2- butene, fumaric acid, mono-methyl fumarate, dimethyl fumarate, diethyl malate, mono methyl malate, dimethyl malate, and diethyl malate.
11. The process as claimed in claim 7, wherein the catalyst is a metal oxide selected from the group consisting of Ce02, MgO, A1203, Sn02, W03, Mo03, Si02, Ti02, Zr02, ZnO, Nb203, La203, Ta205, Y203, V2Os, Cr203, K20/Cr203, Mn02, Fe203, NiO, Ni203, Co203, CuO and combination thereof.
12. A process for the preparation of trimellitic acid from hydroxyl methyl furan or its derivatives, the process comprising the steps of: a. obtaining hydroxyl methyl furan or its derivatives from biomass; b. dissolving the hydroxyl methyl furan or its derivatives of step (a) in a solvent and heating at a temperature of 80 to 100°C to obtain a first reactant; c. adding a second reactant to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to dehydration and oxidation in presence of at least one catalyst to obtain trimellitic acid.
13. The process as claimed in claim 12, wherein the hydroxyl methyl furan derivatives are selected from the group consisting of dimethyl furan (DMF), bis-hydroxymethyl furan (BHMF), 5-methylfurfural alcohol (MFA), furan dicarboxylic acid (FDCA), and methyl furan dicarboxylic acid (FDCA-Me-ester).
14. The process as claimed in claim 12, wherein the hydroxyl methyl furan or its derivatives is obtained from biomass by acid hydrolysis.
15. The process as claimed in claim 12, wherein the solvent is selected from the group consisting of tetrahydrofuran, hexane, cyclohexane, toluene, methanol, ethanol, iso propanol, acetone, acetonitrile, and water.
16. The process as claimed in claim 12, wherein the second reactant is selected from the group consisting of acrolein, acrylic acid, methyl acrylate, ethyl acrylate, and propylene.
17. The process as claimed in claim 12, wherein the at least one catalyst is selected from zeolites and metal oxides.
18. A process for the preparation of trimellitic acid from coumalic acid or its derivatives, the process comprising the steps of: a. obtaining coumalic acid or its derivatives from biomass; b. dissolving the coumalic acid or its derivatives of step (a) in a first solvent and heating at a temperature of 80 to 100°C to obtain a first reactant; c. adding a second reactant to the first reactant of step (b) to obtain a Diels-Alder adduct; and d. subjecting the Diels-Alder adduct of step (c) to dehydrogenation and decarboxylation in presence of at least one catalyst to obtain trimellitic acid.
19. The process as claimed in claim 18, wherein the coumalic acid derivatives are selected from the group consisting of methyl coumalate and ethyl coumalate.
20. The process as claimed in claim 18, wherein coumalic acid or its derivatives is obtained from biomass by fermentation.
21. The process as claimed in claim 18, wherein the solvent is selected from the group consisting of tetrahydrofuran, hexane, cyclohexane, toluene, methanol, ethanol, iso propanol, acetone, acetonitrile, and water.
22. The process as claimed in claim 18, wherein the second reactant is selected from the group consisting of maleic anhydride, maleic acid, dimethylacetylene di carboxyl ate, 2- butene, fumaric acid, mono-methyl fumarate, dimethyl fumarate, diethyl malate, mono methyl malate, dimethyl malate, and diethyl malate.
23. The process as claimed in claim 18, wherein the at least one catalyst is selected from the group consisting of metal catalysts, zeolites and metal oxides.
PCT/IB2020/051226 2020-01-03 2020-02-14 A process for producing trimellitic acid from biomass WO2021136977A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN202011000319 2020-01-03
IN202011000319 2020-01-03

Publications (1)

Publication Number Publication Date
WO2021136977A1 true WO2021136977A1 (en) 2021-07-08

Family

ID=76687385

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2020/051226 WO2021136977A1 (en) 2020-01-03 2020-02-14 A process for producing trimellitic acid from biomass

Country Status (1)

Country Link
WO (1) WO2021136977A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5250724A (en) * 1991-05-17 1993-10-05 Alusuisse Italia S.P.A. Process for the preparation of trimellitic acid
EP0896960A2 (en) * 1997-07-16 1999-02-17 Mitsubishi Gas Chemical Company, Inc. Process for the production of trimellitic acid and process for the production of trimellitic acid anhydride

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5250724A (en) * 1991-05-17 1993-10-05 Alusuisse Italia S.P.A. Process for the preparation of trimellitic acid
EP0896960A2 (en) * 1997-07-16 1999-02-17 Mitsubishi Gas Chemical Company, Inc. Process for the production of trimellitic acid and process for the production of trimellitic acid anhydride

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RAJENDRAN ANNAMALAI, KUMAR GANESAN VINOTH: "Ultra-Rapid Green Microwave Assisted Diels-Alder Reactions Using Ionic Liquid", CURRENT MICROWAVE CHEMISTRY, BENTHAM SCIENCE PUBLISHERS, vol. 3, no. 1, 1 January 2016 (2016-01-01), pages 55 - 59, XP055838847 *

Similar Documents

Publication Publication Date Title
Van de Vyver et al. Emerging catalytic processes for the production of adipic acid
EP2576506B1 (en) Preparation of caprolactone, caprolactam, 2,5-tetrahydrofuran-dimethanol, 1,6-hexanediol or 1,2,6-hexanetriol from 5-hydroxymethyl-2-furfuraldehyde
Wojcieszak et al. Engineering the future: Perspectives in the 2, 5-furandicarboxylic acid synthesis
CA2922120C (en) A process for manufacturing acrylic acid, acrylonitrile and 1,4-butanediol from 1,3-propanediol
US10087161B2 (en) Synthesis of FDCA and FDCA precursors from gluconic acid derivatives
CN106660922B (en) Method for preparing muconic acid and furan from aldaric acid
US20100056832A1 (en) Method of making 2-butanol
US20030055271A1 (en) Oxidation of 5-(hydroxymethyl) furfural to 2,5-diformylfuran and subsequent decarbonylation to unsubstituted furan
Li et al. Highly selective catalytic conversion of furfural to γ-butyrolactone
Zhu et al. Bio-based 1, 4-butanediol and tetrahydrofuran synthesis: perspective
CN112645908B (en) Method for preparing maleic anhydride
EP3124462B1 (en) Use of rhenium-containing supported heterogeneous catalysts for the direct deoxydehydration of glycerol to allyl alcohol
CN111072601B (en) Method for preparing 2, 5-furan dicarbaldehyde from 5-hydroxymethylfurfural
CN113563289B (en) Method for preparing 2, 5-furandicarboxylic acid from furfural
Malu et al. Levulinic acid—a potential keto acid for producing biofuels and chemicals
WO2021136977A1 (en) A process for producing trimellitic acid from biomass
CN112920041B (en) Method for preparing hydroxy dibasic acid by catalyzing acetyl acid raw material to oxidize
CN112354542B (en) V (V) 2 O 5 -CuO/TiO 2 Catalyst, preparation method and application thereof
Si et al. Selective oxidation of 5-formyloxymethylfurfural to 2, 5-furandicarboxylic acid with Ru/C in water solution
WO2018146978A1 (en) Catalyst for reduction reaction of 3,4-dihydroxytetrahydrofuran, and method for producing 3,4-dihydroxytetrahydrofuran reduced product
CN108117472B (en) Method for preparing benzene ring-containing compound from pinacol
JP2013540109A (en) Improved process for epoxidizing fatty acids and their esters and mixtures thereof
JP2018039778A (en) Production method of carboxylic acid ester or carboxylic acid
Palai et al. Reaction Pathways for Synthesis of Four Carbon Chemicals from Sugars and Sugar Derived Platform Chemicals
CN112375052B (en) Method for preparing 2, 5-diformylfuran through glucose three-step cascade reaction

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20910025

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20910025

Country of ref document: EP

Kind code of ref document: A1