WO2008049440A1 - Production of organic solvents, monomers and polymers from fermentable carbohydrate materials - Google Patents

Production of organic solvents, monomers and polymers from fermentable carbohydrate materials Download PDF

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WO2008049440A1
WO2008049440A1 PCT/EE2006/000008 EE2006000008W WO2008049440A1 WO 2008049440 A1 WO2008049440 A1 WO 2008049440A1 EE 2006000008 W EE2006000008 W EE 2006000008W WO 2008049440 A1 WO2008049440 A1 WO 2008049440A1
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lactic acid
process according
salts
esters
monomers
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PCT/EE2006/000008
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French (fr)
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Valeriy Shvets
Juriy Suchkov
Roman Kozlovskiy
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Oü Nordbiochem
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/02Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/18Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/40Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/40Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/56Lactic acid

Definitions

  • This invention relates to preparing organic solvents, monomers and polymers from fermentable carbohydrate materials, particularly, lactic acid, acrylic acid propionic acid, and its esters, acetone, propylene glycols, polylactates, polypropylene and polyacrylates.
  • Lactic acid is currently receiving a great deal of attention as the feedstock monomer for biodegradable polylactic acid polymer production.
  • lactic acid has both a carboxylic acid function and a hydroxyl group, making it reactive in a variety of chemical conversions to useful products - esters, propylene glycol, propionic acid, acrylic acid and its ester and etc.
  • PatXML 2 5847_1869
  • a side benefit of these chemicals is that all of them are the non-toxical substances decaying in an environment under action of microorganisms.
  • Lactic acid dehydration in supercritical or near-critical water is promising, as liquid-like densities at 300-400 0 C suppress degradation reactions.
  • McCrackin and Lira achieved acrylic acid yields of 55% with the addition of small quantities of phosphate salts to lactic acid feed solution.
  • the lactic acid and/or ammonium lactate is contacted in the vapor phase while admixed with 0.1 to 50, usually 0.5 to 50, moles of steam per mole of lactic acid and/or ammonium lactate, with a solid aluminum phosphate catalyst that has been treated with an aqueous inorganic base, and calcinated at a temperature in the range from 300 to 650 0 C.
  • Zhang et al. examined the metal-catalyzed hydrogenation of lactic acid to propylene glycol in aqueous solution (5-20%) in a stirred batch reactor and in a continuous trickle-bed reactor. Ruthenium on an inert support is identified as an active catalyst for the reaction, with nearly complete conversion achieved at reaction temperatures of 100-170 0 C and hydrogen pressures of 3.4-16.5 MPa.
  • ZHANG et al. Aqueous-phase hydrogenation of lactic acid to propylene glycol, Applied Catalysis A. General. 2001 , no.219, p.89-98. ; WO 00/30744 (MICHIGAN STATE UNIVERSITY) 2.06.2000 )
  • Lactic acid is hydrogenated over silica-supported copper at total pressures between 0.10 and 0.72MPa and temperatures between 413 and 493 K to predominately 1 ,2-propanediol, with formation of smaller amounts of 2- hydroxy propionaldehyde, propionic acid, and propyl alcohols. Deactivation of the Cu/SiO2 catalyst does not appear to be significant under these reaction conditions. The production of 1 ,2-propandiol is favored at higher hydrogen partial pressures. At 473K and a hydrogen partial pressure of 0.72MPa, complete conversion of lactic acid was observed, with 88 mol% of the lactic acid converted to 1 ,2-propanediol.
  • the invention provides a cost-effective process for producing a organic solvents, monomers and polymers from fermentable carbohydrate materials, including esters of lactic and acrylic acids, diols and derivatives thereof, from starting materials in high yields.
  • aqueous solutions of a lactic acid and/or ammonium lactate and/or ethers of a lactic acid and/or polylactate can be used.
  • the two or more products may be synthesized.
  • the invention is provided of the dehydration and/or hydrogenation and esterification optionally at the presence of an alcohol and carbon dioxide.
  • the process includes heating a starting material in the presence of catalyst and an alcohol and carbon dioxide to a mixture that includes acrylic and lactic acids and their esters.
  • the process includes heating a starting material in the presence of catalyst and an alcohol, hydrogen and carbon dioxide to a mixture that includes esters of a lactic acid and diol.
  • aqueous solutions of lactic acid and/or ammonium lactate and/or polylactate can be converted to the mixture lactic, acrylic acid and their esters, optionally in the presence of an alcohol and carbon dioxide, by passing them through a heated reactor containing fixed-bed catalyst.
  • the aqueous solutions of lactic acid and/or ammonium lactate and/or polylactate can be converted to the mixture lactic acid, esters and 1 ,2-propandiol (propylene glycol) in the presence of hydrogen and optionally an alcohol, carbon dioxide, by passing them through a heated reactor containing fixed-bed catalyst.
  • catalysts some layers of various type catalysts or one layer of the bifunctional catalyst can be used.
  • Use of the bifunctional catalysts containing two types of the active centers, is preferable at carrying out of process at the presence of hydrogen.
  • useful bifunctional catalysts may include solid state metals and metal oxides. Specific examples are catalysts based upon Rh, Ru, Rh, Pd, Re, Cu, Ni and AI2O3, Si ⁇ 2, Zr ⁇ 2 and aluminosilicates.
  • the layers catalyst may include AI2O3, SiO2, Zr ⁇ 2, aluminosilicates, phosphates and carbonates metal II, Ilia, IVb, VIII and/or the iron groups of the Periodic Table (Na, K, Ca, Ba, Al is preferable), and metal Rh, Ru, Rh, Pd, Re, Cu, Ni and heteropolyacids deposited on an inert support (microporous carbon is preferable).
  • the process is conducted at a temperature and pressure of 180 to 400 0 C and 1-50 bar.
  • the preferred range temperature and pressure of the process at the presence of hydrogen is 190-350 0 C and 15-50 bar.
  • temperature and pressure of the process in absence of hydrogen is 230- 350 0 C and 1-5 bar.
  • Figure 1 shows a process for the conversion of starting material to esters of lactic and acrylic acids, diols in a continuous flow reactor.
  • the process comprises a reactor 1 which contains one or more layers fixed-bed of catalyst 2.
  • the top of a reactor was packed an inert material 3.
  • the resulting mixture (III) fed in ultrasonic generator 5 where transformed into an aerosol.
  • the reactor effluent stream (Vl) cooled to 20-60 0 C in a heat exchanger 6 a suitable fluid such as water (VIl).
  • a suitable fluid such as water (VIl).
  • the cooled effluent stream (VIII) passed through a gas-liquid separator 7, wherein the fluid separated into an overhead gas stream (IX) and a bottom liquid stream (X).
  • the overhead stream (IX) containing mainly carbon dioxide or hydrogen recycled to reactor 1.
  • the starch of the whole meal flour suspension was hydrolysed to glucose (15.1 %), using enzymological processing with alpha-amylase and glycoamylase. Using Novo-Nordisk Flavourzyme (5 u/g, 50 0 C, 20") for that purpose, the grain proteins were converted into a blend of amino acids to the extent of 30% in the initial stage of liquefaction of starch.
  • Cultivation was carried out in anaerobic conditions by mixing at 62 rpm, 56 0 C, pH value in the stationary regime at 6.3, NH 4 + was used as a neutralizer. The duration of the cultivation cycle was 41 hours. After the end of fermentation, the cells were centrifuged out and the ammonium lactate in the supernatant was concentrated by distillation to 30-70%. The distilled water was condensed and collected for following experiments.
  • the vertical tubular jacketed reactor (inner diameter of 16 mm and of 300 mm in length) was charged with of one layer of inert material (10 cc) and of two layers of the catalyst (of the first layer - 15 cc 5% wt.H3PWi2 ⁇ 4 o/Al2 ⁇ 3, of the second layer - 20 cc AIPO 4 ). Temperature controlled with a temperature controller and regulated in each layer of an inert material and of layers of the catalyst.
  • Temperature of the layer of the inert material was kept at 240-250 0 C 1 of the first layer of the catalyst was kept at 240-250 0 C and of the second layer of the catalyst was kept at 320-330 0 C.
  • Pressure in reactor was kept at 3-5 bar.
  • the reactor effluent stream is cooled to 25 0 C and fed in a heat exchanger and passed through a gas-liquid separator.
  • the resulting bottom liquid was mixed with diethyl ether and the top liquid layer was analyzed by gas chromatography using a 2 m stainless steel column (6 mm outside diameter) packed with polyethylene glycol (nominal molecular weight 20,000) on Chromosorb PAW, a helium gas flow rate of 30 ml/minute and a thermal conductivity detector.
  • the vertical tubular jacketed reactor (inner diameter of 16 mm and of 300 mm in length) was charged with of one layer of inert material (10 cc) and of two layers of the catalyst (of the first layer - 10 cc Zr ⁇ 2, of the second layer - 25 cc 5% wt. Ru/C). Temperature controlled with a temperature controller and regulated in each layer of an inert material and of layers of the catalyst.
  • Temperature of the layer of the inert material was kept at 240-250 °C, of the first layer of the catalyst was kept at 240-250 0 C and of the second layer of the catalyst was kept at 215-225 0 C.
  • Pressure in reactor was kept at 40-45 bar.
  • the reactor effluent stream is cooled to 25 0 C and fed in a heat exchanger and passed through a gas-liquid separator.
  • the resulting bottom liquid was mixed with diethyl ether and the top liquid layer was analyzed by gas chromatography.
  • the vertical tubular jacketed reactor (inner diameter of 16 mm and of 300 mm in length) was charged with of one layer of inert material (10 cc) and of two layers of the catalyst (of the first layer - 15 cc AIPO 4 , of the second layer - 20 cc 8%wt. Cu/SiO 2 ).
  • Temperature of the layer of the inert material was kept at 250-260 0 C, of the first layer of the catalyst was kept at 230-240 0 C and of the second layer of the catalyst was kept at 200-210 0 C.
  • Pressure in reactor was kept at 30-32 bar.
  • the reactor effluent stream is cooled to 25 0 C and fed in a heat exchanger and passed through a gas-liquid separator.
  • the resulting bottom liquid was mixed with diethyl ether and the top liquid layer was analyzed by gas chromatography.
  • Methyl acrylate of example 2 was used for synthesis polymers.
  • the polymerization is conduct in the presence of a solvent (50-70 %wt.) to avoid the viscosity of the crude polymerizate rising above a value where the polymerization becomes uncontrollable. It is also preferred to conduct the polymerization in the presence of a free radical agent (0,01-0,1 %wt.) to minimize the concentration of the polymer chains containing terminally unsaturated carbons.
  • Methyl lactate of example 2 was used for synthesis lactide. The process is conducted at 22O 0 C. Gaseous stream of nitrogen and methyl lactate was fed to reactor charged of a solid catalyst (SnO supported on a solid carrier PatXML 12 5847_1869
  • the resulting gaseous reaction product stream comprising N2, lactide, methanol and unreacted feed material (methyl lactate) passes into scrubber containing a scrubbing solvent, such as isopropyl alcohol.
  • a scrubbing solvent such as isopropyl alcohol.
  • the solvent-scrubbing action produces a slurry of solid lactide particle in isopropyl alcohol.
  • the slurry is removed and filtered.
  • Solid cyclic ester is removed from the filter.
  • the cyclic ester can be further purified if necessary by any means known.

Abstract

The present invention relates to processes for producing organic solvents, different monomeric and polymeric chemical substances from fermentable carbohydrate materials (starch, cellulose, hemicellulose), particularly, a lactic acid and its esters, acrylic acid and its esters, propylene glycol, polypropylene, polylactate and polyacrylates, which comprises microbiological fermentation of carbohydrate materials up to a lactic acid and its salts, isolation of lactic acid and its salts, chemical conversion of lactic acid and its salts to organic alcohols aldehydes and ketones, acids, esters, glycols, polymers (i.e. polypropylenes, polylactates and polyacrylates). One or more the steps of the chemical conversion of a lactic acid and its salts carry out joint synthesis of two or more final products.

Description

PRODUCTION OF ORGANIC SOLVENTS, MONOMERS AND POLYMERS FROM FERMENTABLE CARBOHYDRATE MATERIALS
Technical Field
[0001] This invention relates to preparing organic solvents, monomers and polymers from fermentable carbohydrate materials, particularly, lactic acid, acrylic acid propionic acid, and its esters, acetone, propylene glycols, polylactates, polypropylene and polyacrylates.
Background Art
[0002] Given the increase in greenhouse gas emissions due to the use of petroleum (and other fossil fuels) and the impending limits of this nonrenewable resource as evidenced by petrol price increases, there is a need to develop renewable resources such as biomass as the feedstock for the chemical industry and as an energy source.
[0003] In fact, all forms of biomass, including carbohydrates, are a potential renewable source.
[0004] The advantages of deriving our chemical production, and energy needs, from renewable sources including biomass are obvious and crucial to our way of life. The switch to the use of biomass as a feedstock and an energy source is an important global initiative in getting the world onto a sustainable trajectory.
[0005] The use of renewable feedstocks such as carbohydrates is a key issue in the development of sustainable large-scale production processes. Today, only a small number of chemicals are produced from renewable resources. The biotechnological production of lactic acid, acetic acid butanol and ethanol are the only processes which are currently applied in technical scales and which can compete with petrochemical routes.
[0006] Lactic acid is currently receiving a great deal of attention as the feedstock monomer for biodegradable polylactic acid polymer production. However, lactic acid has both a carboxylic acid function and a hydroxyl group, making it reactive in a variety of chemical conversions to useful products - esters, propylene glycol, propionic acid, acrylic acid and its ester and etc. PatXML 2 5847_1869
A side benefit of these chemicals is that all of them are the non-toxical substances decaying in an environment under action of microorganisms.
[0007] The chemical conversions of lactic acid and lactate has been described on numerous occasions in the literature.
[0008] a) Conversion of lactic acid and esters to acrylic acid and acrylates. Dehydration of lactic acid to acrylic acid has long been of interest, as acrylic acid and its esters are the primary building blocks of all acrylate polymers and plastics. Currently 100% of acrylic acid is produced from fossil fuels. Although acrylic acid and chemicals associated with acrylics have a world market volume of almost 3*106 tonnes per annum, relatively few attempts have been made to produce acrylic acid from of lactic acid.
[0009] Vapor-phase conversion of lactic to acrylic at temperatures within the range of about 250-550 0C was first reported over several salt catalysts in a patent of Holmen R. E. et al. The most effective catalyst was CaSCWNa2SO4 (400 0C), which gave a yield of 68% of theoretical. ( US 2859240 (MINNESOTA MINING ) 4.11.1958 ), Production of acrylates by catalytic dehydration of lactic acid and acrylates, 1958).
[0010] In 1984, Garcia reported a 68% acrylic acid yield at 300 0C on a support consisting of insoluble phosphates of elements of II, Ilia, IVb, VIII and/or the iron groups of the Periodic Table. ( ES 8400383 (MERCADOS QUIMICOS IND) 16.01.1984 ), Preparation of α-,β-unsaturated acids and their esters)
[0011] In 1988, Sawicki reported a 58% acrylic acid yield at 350 0C using
Na2HPO4 on silica/alumina with NaHCO3 as a pH adjuster. ( US 4729978 (TEXACO INC) 8.03.1988 )
[0012] Lactic acid dehydration in supercritical or near-critical water is promising, as liquid-like densities at 300-400 0C suppress degradation reactions.
[0013] Mok et al. reacted 0.1 M lactic acid in water at 385 0C and 34 MPa and found that decarbonylation to acetaldehyde predominates with the addition of H2SO4. Adding NaOH, in contrast, led to the formation of more carbon dioxide, hydrogen, and acrylic acid. ( MOK, et al. Formation of Acrylic Acid from Lactic Acid in Supercritical Water. Org. Chem. 1989, no.54, p.4596. ). PatXML 3 5847_1869
[0014] McCrackin and Lira achieved acrylic acid yields of 55% with the addition of small quantities of phosphate salts to lactic acid feed solution. ( MCCRACKIN, LIRA. Conversion of Lactic Acid to Acrylic Acid in Supercritical Water. Ind. eng, chem. res.. 1993, no.32, p.2608. ). They showed that the overall effect of the phosphate is to suppress acetaldehyde formation rather than to enhance dehydration.
[0015] Walkup at al. developed a two-stage process for producing lactate esters following fermentation and then converting those esters to acrylates ( US 5071754 (BATTELLE MEMORIAL INSTITUTE) 10.12.1991 , US 5252473 (BATTELLE MEMORIAL INSTITUTE) 12.10.1993 ).
[0016] The adjustment of pH during fermentation is done with ammonia, and then esterification is carried out in a single step directly from ammonium lactate. Dehydration of lactate esters to acrylate is carried out at 350-410 0C over CaSO4 catalyst in a fixed bed reactor; the highest per pass yields achieved are 53% of theoretical.
[0017] Formation of salts or esters of lactic acid prior to conversion gives materials that are easier to handle and which dehydrate more favorably than the acid. For instance, Paparizos obtained 61 % yield of acrylic acid from ammonium lactate versus 43% from lactic acid ( US 4786756 (STANDARD OIL CO OHIO) 22.11.1988 ).
[0018] According to the process of the present invention the lactic acid and/or ammonium lactate is contacted in the vapor phase while admixed with 0.1 to 50, usually 0.5 to 50, moles of steam per mole of lactic acid and/or ammonium lactate, with a solid aluminum phosphate catalyst that has been treated with an aqueous inorganic base, and calcinated at a temperature in the range from 300 to 650 0C.
[0019] Unfortunately, the chemical conversion of lactic acid or lactate to acrylic acid gives rather low yields due to decarbonylation, decarboxylation, hydrogenation and condensation reactions which mainly lead to acetaldehyde, propanoic acid and penta-2,3-dione and other unidentified products to reduce acrylic acid yield.
[0020] b) Conversion of lactic acid and esters to Propylene Glycol.
1 ,2-propanediol is a desired commodity chemical used as a de-icing fluids, PatXML 4 5847_1869
antifreeze (green replacement for ethylene glycol), for the production of unsaturated polyester resins, and in the production of drugs, cosmetics, and foods. Currently, 1 ,2-propanediol is produced from the hydration of propylene oxide. Propylene oxide is produced through the selective oxidation of propylene with 50% of the US propylene oxide production through the chlorohydrin process involving the use of hypochlorous acid. Accordingly, the direct hydrogenation of lactic acid would provide an alternative green process for the production of 1 ,2-propanediol. Furthermore, production of the necessary carbohydrate source results in the fixation of carbon dioxide (a greenhouse gas), this production route would lower the amount of carbon dioxide as well as produce desired commodity chemicals.
[0021] Surprisingly little prior work has been reported on the hydrogenation of lactic acid. Adkins and co-workers ( BOWDEN, E.; ADKINS1 H.. Hydrogenation of Optically Active Compounds over Nickel and Copper- Chromium Oxide. J.Am. Chem. Soc. 1934, no.56, p.689. ; ADKINS, H.; BILLICA, H. R.. Effect of Ratio of Catalyst and Other Factors upon the Rate of Hydrogenation. J. Am. Chem. Soc. 1948, no.70, p.3118. , ADKINS, H.; BILLICA, H. R.. The Hydrogenation of Esters to Alcohols at 25-150 0C. J. Am. Chem. Soc. 1948, no.70, p.3121. ) conducted several studies of carboxylic acid ester hydrogenation to alcohols in the 1930s and 1940s. They achieved 80% yields of propylene glycol from ethyl lactate over copper/chromium oxide and Raney nickel catalysts at 150-250 0C and extremely high hydrogen pressures (20-30 MPa).
[0022] They also found that hydrogenation proceeded faster and at much lower temperatures (down to 100 0C) if very high loadings of catalyst, approaching 1 :1 on a molar basis with substrate, were used.
[0023] Broadbent et al. ( BROADBENT, et al. Rhenium and Its Compounds as Hydrogenation Catalysts. III. Rhenium Heptoxide. J. Org. Chem.. 1959, no.24, p.1847. ) showed that propylene glycol yields as high as 80% could be achieved from ethyl lactate in 8 h batch reaction at 150 0C over rhenium black catalysts, but again at 25 MPa hydrogen pressure. PatXML 5 5847_1869
[0024] In a related study, Carnahan et al. ( CARNAHAN, et al. Ruthenium- catalyzed hydrogenation of acids to alcohols. J. Am. Chem. Soc. 1955, no.77, p.3766. ) examined hydrogenation of glycolic acid (2-hydroxyacetic acid) to ethylene glycol over ruthenium catalysts but made no mention of lactic acid. Recent patents by Kitson et al. ( US 4777303 (BP CHEM INT LTD) 11.10.1988 ; US 4985572 (BRITISH PETROLEUM CO PLC) 15.01.1991 ; US 5149680 (BRITISH PETROLEUM CO PLC) 22.09.1992 ) and Kipax et al. ( DE 3443277 (DAVY MCKEE LTD) 5.06.1985 ) describe mixed metal catalysts for hydrogenating carboxylic acids and esters at the present of minor amount of carbon dioxide to alcohols but make only passing mention of lactate as a substrate and give no yield information.
[0025] Zhang et al. examined the metal-catalyzed hydrogenation of lactic acid to propylene glycol in aqueous solution (5-20%) in a stirred batch reactor and in a continuous trickle-bed reactor. Ruthenium on an inert support is identified as an active catalyst for the reaction, with nearly complete conversion achieved at reaction temperatures of 100-170 0C and hydrogen pressures of 3.4-16.5 MPa. ( ZHANG, et al. Aqueous-phase hydrogenation of lactic acid to propylene glycol, Applied Catalysis A. General. 2001 , no.219, p.89-98. ; WO 00/30744 (MICHIGAN STATE UNIVERSITY) 2.06.2000 )
[0026] Selectivity to propylene glycol in excess of 90% at 95% lactic acid conversion has been obtained at optimal reaction conditions. Potassium and calcium lactate salts cannot be directly converted to PG, but simple addition of sulfuric acid suffices to convert the salt to free acid, which is then hydrogenated. With ammonium lactate at the same conditions, observed a small HPLC peak for propylene glycol.
[0027] Cortright at al. showed possibility to produce 1 ,2-propanediol (a high demand commodity chemical) in high yields via the vapor-phase catalytic hydrogenation of biomass-derived lactic acid. This catalytic process provides an environment-friendly route for the production of 1 ,2- propanediol from renewable resources. ( CORTRIGHT, et al. Conversion of biomass to 1 ,2-propanediol by selective catalytic hydrogenation of lactic acid over silica-supported copper, Applied Catalysis B. Environmental. PatXML 6 5847_1869
2002, no.39, p.353-359. ; US 6455742 (WISCONSIN ALUMNI RES FOUND) 24.09.2002 ; WO 01/16063 (WISCONSIN ALUMNI RES FOUND) 8.03.2001 ).
[0028] Lactic acid is hydrogenated over silica-supported copper at total pressures between 0.10 and 0.72MPa and temperatures between 413 and 493 K to predominately 1 ,2-propanediol, with formation of smaller amounts of 2- hydroxy propionaldehyde, propionic acid, and propyl alcohols. Deactivation of the Cu/SiO2 catalyst does not appear to be significant under these reaction conditions. The production of 1 ,2-propandiol is favored at higher hydrogen partial pressures. At 473K and a hydrogen partial pressure of 0.72MPa, complete conversion of lactic acid was observed, with 88 mol% of the lactic acid converted to 1 ,2-propanediol.
Disclosure of Invention
[0029] In general, the invention provides a cost-effective process for producing a organic solvents, monomers and polymers from fermentable carbohydrate materials, including esters of lactic and acrylic acids, diols and derivatives thereof, from starting materials in high yields.
[0030] As a starting material aqueous solutions of a lactic acid and/or ammonium lactate and/or ethers of a lactic acid and/or polylactate can be used.
[0031] According to present invention the two or more products may be synthesized. The invention is provided of the dehydration and/or hydrogenation and esterification optionally at the presence of an alcohol and carbon dioxide.
[0032] In one aspect, the process includes heating a starting material in the presence of catalyst and an alcohol and carbon dioxide to a mixture that includes acrylic and lactic acids and their esters.
[0033] In a second aspect, the process includes heating a starting material in the presence of catalyst and an alcohol, hydrogen and carbon dioxide to a mixture that includes esters of a lactic acid and diol.
[0034] Optionally, a starting material and alcohol fed into the reactor as an aerosol. The carbon dioxide and hydrogen fed into the reactor as gas. PatXML 7 5847_1869
[0035] The process of the present invention is most conveniently carried out in a continuous manner, although semi-continuous operations may also be employed.
Best Mode for Carrying Out the Invention
[0036] We have found surprisingly that the joint synthesis of two or more products in the same reactor to decrease of the formation by-products.
[0037] The aqueous solutions of lactic acid and/or ammonium lactate and/or polylactate can be converted to the mixture lactic, acrylic acid and their esters, optionally in the presence of an alcohol and carbon dioxide, by passing them through a heated reactor containing fixed-bed catalyst.
[0038] Similarly, the aqueous solutions of lactic acid and/or ammonium lactate and/or polylactate can be converted to the mixture lactic acid, esters and 1 ,2-propandiol (propylene glycol) in the presence of hydrogen and optionally an alcohol, carbon dioxide, by passing them through a heated reactor containing fixed-bed catalyst.
[0039] As catalysts some layers of various type catalysts or one layer of the bifunctional catalyst can be used. Use of the bifunctional catalysts containing two types of the active centers, is preferable at carrying out of process at the presence of hydrogen. When carry out process in absence of hydrogen, two types of the catalyst is preferable.
[0040] In general, useful bifunctional catalysts may include solid state metals and metal oxides. Specific examples are catalysts based upon Rh, Ru, Rh, Pd, Re, Cu, Ni and AI2O3, Siθ2, Zrθ2 and aluminosilicates.
[0041] The layers catalyst may include AI2O3, SiO2, Zrθ2, aluminosilicates, phosphates and carbonates metal II, Ilia, IVb, VIII and/or the iron groups of the Periodic Table (Na, K, Ca, Ba, Al is preferable), and metal Rh, Ru, Rh, Pd, Re, Cu, Ni and heteropolyacids deposited on an inert support (microporous carbon is preferable).
[0042] The process is conducted at a temperature and pressure of 180 to 400 0C and 1-50 bar.
[0043] The preferred range temperature and pressure of the process at the presence of hydrogen is 190-350 0C and 15-50 bar. The preferred range PatXML 8 5847_1869
temperature and pressure of the process in absence of hydrogen is 230- 350 0C and 1-5 bar.
[0044] Figure 1 shows a process for the conversion of starting material to esters of lactic and acrylic acids, diols in a continuous flow reactor.
[0045] The process comprises a reactor 1 which contains one or more layers fixed-bed of catalyst 2. The top of a reactor was packed an inert material 3. A starting material (I) mixed with alcohol (II) at mixer 4. The resulting mixture (III) fed in ultrasonic generator 5 where transformed into an aerosol. An aerosol (IV) mixed with carbon dioxide and/or hydrogen (V) and fed to top of a reactor 1.
[0046] After the reaction, the reactor effluent stream (Vl) cooled to 20-60 0C in a heat exchanger 6 a suitable fluid such as water (VIl). The cooled effluent stream (VIII) passed through a gas-liquid separator 7, wherein the fluid separated into an overhead gas stream (IX) and a bottom liquid stream (X). The overhead stream (IX) containing mainly carbon dioxide or hydrogen recycled to reactor 1.
[0047] The bottom liquid stream (X) mixed with diethyl ether and the top liquid layer analyzed by gas chromatography. EXAMPLES
[0048] Example 1
[0049] The starch of the whole meal flour suspension was hydrolysed to glucose (15.1 %), using enzymological processing with alpha-amylase and glycoamylase. Using Novo-Nordisk Flavourzyme (5 u/g, 50 0C, 20") for that purpose, the grain proteins were converted into a blend of amino acids to the extent of 30% in the initial stage of liquefaction of starch.
[0050] According to then in hydrine reaction, the total content of amino acids was 1.3%. The derived feed was clarified using centrifugation and the supernatant was fermented with termophilic bacterium. 96% of the fermented glucose was converted into L-lactate, which accumulates in the fermentation medium as ammonium lactate, resulting in the final concentration of lactic acid of 9.8%. Additional sources of mineral substances and nitrogen compounds were not used. PatXML 9 5847_1869
[0051] Cultivation was carried out in anaerobic conditions by mixing at 62 rpm, 56 0C, pH value in the stationary regime at 6.3, NH4 + was used as a neutralizer. The duration of the cultivation cycle was 41 hours. After the end of fermentation, the cells were centrifuged out and the ammonium lactate in the supernatant was concentrated by distillation to 30-70%. The distilled water was condensed and collected for following experiments.
[0052] Example 2
[0053] The vertical tubular jacketed reactor (inner diameter of 16 mm and of 300 mm in length) was charged with of one layer of inert material (10 cc) and of two layers of the catalyst (of the first layer - 15 cc 5% wt.H3PWi2θ4o/Al2θ3, of the second layer - 20 cc AIPO4). Temperature controlled with a temperature controller and regulated in each layer of an inert material and of layers of the catalyst.
[0054] 7 g/h of 70% ammonium lactate solution mixed to 7 g/h methanol were fed in ultrasonic generator. The resulted an aerosol (14 g/h) and 9.6 g/h carbon dioxide were fed into the top of the reactor containing two layers fixed-bed catalyst. The mole ratio of lactate ammonium/water/methanol/ carbon dioxide being 1/2.6/4.8/4.8.
[0055] Temperature of the layer of the inert material was kept at 240-250 0C1 of the first layer of the catalyst was kept at 240-250 0C and of the second layer of the catalyst was kept at 320-330 0C. Pressure in reactor was kept at 3-5 bar.
[0056] The reactor effluent stream is cooled to 25 0C and fed in a heat exchanger and passed through a gas-liquid separator. The resulting bottom liquid was mixed with diethyl ether and the top liquid layer was analyzed by gas chromatography using a 2 m stainless steel column (6 mm outside diameter) packed with polyethylene glycol (nominal molecular weight 20,000) on Chromosorb PAW, a helium gas flow rate of 30 ml/minute and a thermal conductivity detector.
[0057] As the result of analyzing the solution produced in 24 hours after the reaction started, the conversion of ammonium lactate was 91.3%, and the selectivity to methyl acrylate was 74.1% and the selectivity to methyl lactate was 18.2%. PatXML 10 5847_1869
[0058] Example 3
[0059] The vertical tubular jacketed reactor (inner diameter of 16 mm and of 300 mm in length) was charged with of one layer of inert material (10 cc) and of two layers of the catalyst (of the first layer - 10 cc Zrθ2, of the second layer - 25 cc 5% wt. Ru/C). Temperature controlled with a temperature controller and regulated in each layer of an inert material and of layers of the catalyst.
[0060] 7 g/h mixture of ammonium lactate (10%wt.), lactic acid (25%wt.), water (30%wt.) and ethanol (35%wt.) were fed in ultrasonic generator. The resulted an aerosol, 2 g/h carbon dioxide and 2 g/h hydrogen were fed into the top of the reactor containing two layers fixed-bed catalyst. The mole ratio of (lactate ammonium + lactic acid)/water/ethanol/carbondioxide/ hydrogen being 1/4.5/2.05/1.76/39.
[0061] Temperature of the layer of the inert material was kept at 240-250 °C, of the first layer of the catalyst was kept at 240-250 0C and of the second layer of the catalyst was kept at 215-225 0C. Pressure in reactor was kept at 40-45 bar.
[0062] The reactor effluent stream is cooled to 25 0C and fed in a heat exchanger and passed through a gas-liquid separator. The resulting bottom liquid was mixed with diethyl ether and the top liquid layer was analyzed by gas chromatography.
[0063] As the result of analyzing the solution produced in 20 hours after the reaction started, the conversion of ammonium lactate and lactic acid - 90.3% and the selectivity to propylene glycol was 58.1 % and the selectivity to ethyl lactate was 18.2%.
[0064] Example 4
[0065] The vertical tubular jacketed reactor (inner diameter of 16 mm and of 300 mm in length) was charged with of one layer of inert material (10 cc) and of two layers of the catalyst (of the first layer - 15 cc AIPO4, of the second layer - 20 cc 8%wt. Cu/SiO2).
[0066] 6 g/h mixture of polylactate (10%wt), lactic acid (25%wt.), water (35%wt.) and methanol (30%wt.) were fed into the top of the reactor (on the layer of the inert material). 0.5 g/h carbon dioxide and 2 g/h hydrogen were fed into PatXML 11 5847_1869
the top of the reactor. The mole ratio of (polylactate + lactic acid)/water/ methanol/carbon dioxide/hydrogen being 1/5/2.4/0.5/42.9.
[0067] Temperature of the layer of the inert material was kept at 250-260 0C, of the first layer of the catalyst was kept at 230-240 0C and of the second layer of the catalyst was kept at 200-210 0C. Pressure in reactor was kept at 30-32 bar.
[0068] The reactor effluent stream is cooled to 25 0C and fed in a heat exchanger and passed through a gas-liquid separator. The resulting bottom liquid was mixed with diethyl ether and the top liquid layer was analyzed by gas chromatography.
[0069] As the result of analyzing the solution produced in 24 hours after the reaction started, the conversion of polylactate and lactic acid - 93.3% and the selectivity to propylene glycol was 71.1 % and the selectivity to methyl lactate was 21.2%.
[0070] Example 5
[0071] Methyl acrylate of example 2 was used for synthesis polymers. The polymerization is conduct in the presence of a solvent (50-70 %wt.) to avoid the viscosity of the crude polymerizate rising above a value where the polymerization becomes uncontrollable. It is also preferred to conduct the polymerization in the presence of a free radical agent (0,01-0,1 %wt.) to minimize the concentration of the polymer chains containing terminally unsaturated carbons.
[0072] The 0.25 g benzoyl peroxide dissolved in toluene (10g) was added at the reaction temperature (65 0C) to 10 g of methyl acrylate dissolved in toluene (13 g). Stirring was carried out for 27 minutes. After the reaction time stated, the reaction was stopped with methanol and the solvent was removed under reduced pressure, the residue was taken up in benzene and the solution was filtered and freeze-dried. As the result 8 g polyarcylate (MM = 10000) was produced.
[0073] Example 6
[0074] Methyl lactate of example 2 was used for synthesis lactide. The process is conducted at 22O0C. Gaseous stream of nitrogen and methyl lactate was fed to reactor charged of a solid catalyst (SnO supported on a solid carrier PatXML 12 5847_1869
- Siθ2). The resulting gaseous reaction product stream comprising N2, lactide, methanol and unreacted feed material (methyl lactate) passes into scrubber containing a scrubbing solvent, such as isopropyl alcohol. The solvent-scrubbing action produces a slurry of solid lactide particle in isopropyl alcohol. The slurry is removed and filtered. Solid cyclic ester is removed from the filter. The cyclic ester can be further purified if necessary by any means known.

Claims

PatXML 13 5847_1869Claims
1. A process for production a organic solvents, monomers and polymers from fermentable carbohydrate materials, comprising
- microbiological fermentation of vegetative raw materials or products of its partial splitting at the presence of lactic bacteria up to a lactic acid and/or its salts,
- isolation of lactic acid and/or its salts,
- one or more steps chemical conversion of a lactic acid and/or its salts into organic solvents and/or a monomers, and
- conversion of lactic acid or monomers into polymeric materials, wherein at least on one of the steps of chemical conversion of a lactic acid and/or its salts carry out joint synthesis of two or more products.
2. A process according to claim 1 , wherein said an organic solvents are esters and alcohols.
3. A process according to claim 1 , wherein said a monomers are acrylic acid or its esters.
4. A process according to claim 1 , wherein said a polymers are polylactates and poiyacrylates.
5. A process according to claim 1 , wherein said a vegetative raw materials are starches selected from wheat, rye, triticale, oat, barley, corn, potatoes, etc, and/or celluloses and hemicelluloses selected from wood, straw, etc.
6. A process according to claim 1 , wherein said a products of partial splitting vegetative raw materials are a starch, cellulose, hemicellulose and sugar.
7. A process according to claim 1 , wherein microbiological synthesis is carried out with thermotolerant bacteria.
8. A process according to claim 1 , wherein joint synthesis of two or more products carry out in one reaction chamber.
9. A process according to claim 1, wherein joint synthesis carry out in reactor containing at least two types of the catalyst.
10. A process according to claim 1 , wherein joint synthesis carry out in reactor containing at least two fixed-bed catalyst of various types.
11. A process according to claim 1 , wherein joint synthesis carry out in reactor at the presence of the bifunctional catalyst.
PCT/EE2006/000008 2006-10-26 2006-10-26 Production of organic solvents, monomers and polymers from fermentable carbohydrate materials WO2008049440A1 (en)

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WO2016148930A1 (en) * 2015-03-13 2016-09-22 The Procter & Gamble Company Bicomponent catalyst and method for dehydrating lactic acid to acrylic acid
WO2020099430A1 (en) * 2018-11-14 2020-05-22 Shell Internationale Research Maatschappij B.V. Regeneration of catalyst for lactic acid dehydration
IT201900001899A1 (en) * 2019-02-11 2020-08-11 Liberty Chemicals S R L SOLVENT COMPOSITION
EP3693418A1 (en) * 2019-02-11 2020-08-12 Liberty Chemicals S.r.l. A solvent composition
CN112442006A (en) * 2019-08-28 2021-03-05 上海东庚化工技术有限公司 Method for continuously synthesizing L-lactide

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WO2016148930A1 (en) * 2015-03-13 2016-09-22 The Procter & Gamble Company Bicomponent catalyst and method for dehydrating lactic acid to acrylic acid
CN107531605A (en) * 2015-03-13 2018-01-02 宝洁公司 For the bicomponent catalyst and method by acid by dehydrating lactic into acrylic acid
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CN107531605B (en) * 2015-03-13 2020-11-20 宝洁公司 Two-component catalyst and process for dehydration of lactic acid to acrylic acid
WO2020099430A1 (en) * 2018-11-14 2020-05-22 Shell Internationale Research Maatschappij B.V. Regeneration of catalyst for lactic acid dehydration
IT201900001899A1 (en) * 2019-02-11 2020-08-11 Liberty Chemicals S R L SOLVENT COMPOSITION
EP3693418A1 (en) * 2019-02-11 2020-08-12 Liberty Chemicals S.r.l. A solvent composition
CN112442006A (en) * 2019-08-28 2021-03-05 上海东庚化工技术有限公司 Method for continuously synthesizing L-lactide

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