WO2021081577A1 - Procédé de production d'éthylène - Google Patents

Procédé de production d'éthylène Download PDF

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WO2021081577A1
WO2021081577A1 PCT/AU2020/051148 AU2020051148W WO2021081577A1 WO 2021081577 A1 WO2021081577 A1 WO 2021081577A1 AU 2020051148 W AU2020051148 W AU 2020051148W WO 2021081577 A1 WO2021081577 A1 WO 2021081577A1
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succinic acid
biomass
carbohydrates
ethylene
hexose
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Muhammad Adeel Ghayur
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Muhammad Adeel Ghayur
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Publication of WO2021081577A1 publication Critical patent/WO2021081577A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/03—Acyclic or carbocyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • 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
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
    • 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
    • C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
    • C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
    • C12P5/026—Unsaturated compounds, i.e. alkenes, alkynes or allenes
    • 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
    • C12P7/46—Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid
    • 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
    • C12P7/54—Acetic acid
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • 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
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
    • C10L5/447—Carbonized vegetable substances, e.g. charcoal, or produced by hydrothermal carbonization of biomass
    • 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
    • C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin

Definitions

  • This disclosure relates to the production of renewable ethylene from biomass. More specifically the biorefinery process comprises a combination of biochemical, electrochemical and chemical routes. Feedstock carbohydrates are first separated into hexose and pentose carbohydrates for fermentation into succinic acid. Optionally pentose carbohydrates are fermented into acetic acid. A portion of succinic acid is converted to ethylene which can be value-added into ethylene derivatives like ethanol and/or polymers like polyethylene and poly(methyl methacrylate). Lignin and other unfermented feedstock are used in a thermal power station to produce heat and electricity for use in the biorefinery. Flue gas CO2 may be captured for the production of methanol.
  • Lignocellulose is the most abundant form of non-food biomass that is easily available for biofuel and biochemical production. Lignocellulose biomass may be categorised as: (1) wastes such as crop wastes, food wastes and other organic wastes; and (2) crops and trees grown specifically as biorefinery feedstock.
  • Lignocellulosic biomass consists of roughly 30-50% of cellulose, 10-30% of hemicellulose and 20-30% of lignin.
  • Cellulose contains majority of the hexose (C6) carbohydrates while hemicellulose contains majority of the pentose (C5) carbohydrates.
  • Ethylene is one of the chemicals that can be produced from biomass. Currently, nearly all of the ethylene is produced from fossil fuels. It is one of the most widely used hydrocarbons in the chemical industry. It is also a precursor to a wide range of polymers such as polyethylene, polyethylene terephthalate, polyethylene carbonate, poly(ethylene oxide), polyethylene glycol and poly(methyl methacrylate). Polyethylene itself is the most common polymer produced, primarily used in packaging, bottles, membranes, tubes and many other everyday items. Several types of polyethylene exist and are generally classified according to their density. In addition, there exists subcategories when the polyethylene is crosslinked or also according to its molecular weight.
  • biomass is fermented to ethanol - a process that wastes a significant portion of the sugar as CO2 - followed by dehydration into ethylene. It would be desirable to produce a precursor for ethylene production that does not waste sugar as CO2 during the fermentation process.
  • the present invention provides an integrated process for the valorisation of all fractions of the biomass.
  • This integrated process can utilise lignocellulosic, algal, microbial and other types of carbohydrates and fermentable feedstocks for the production of succinic acid and ethylene.
  • the lignocellulosic biomass is subjected to proper pretreatment conditioning including cleaning, washing and milling. Milling allows for size reduction which increases the efficiency of infiltration of the chemical reagents used in the subsequent hydrolysis and fermentation processes.
  • the present invention provides two-stage hydrolysis process to obtain fermentable sugars. In the first stage lignocellulosic biomass is subjected to a thermal or thermochemical treatment to achieve lignocellulose matrix fractionation and depolymerisation of the hemicellulose fraction. The aqueous phase resulting from the treatment contains mainly pentose sugars and may be followed by another hydrolysis treatment to further increase sugar monomers in this liquid hydrolysate.
  • the undissolved solids (consisting mainly cellulose and lignin) are separated and optionally followed by a hydrolysis treatment to depolymerise C6 polymers such as cellulose into monomers such as glucose. Following the hydrolysis, the two streams are sent to different fermenters.
  • the cellulose along with lignin are sent to the same hydrolysis tank and subsequently to the same fermenter. This avoids the cost of separation of the lignin from the cellulose.
  • Microbes suited for the fermentation of C6 sugars like glucose ferment them into succinic acid leaving behind lignin and other unfermented biomass.
  • the other stream containing pentose sugars is sent to a separate fermenter to produce the desired organic acid e.g. succinic acid.
  • This process of separating C6 and C5 sugars into two streams and feeding them to microbes that preferentially consume the fed sugars overcomes the phenomenon of catabolite repression leading to an increase in the fermentation process efficiency.
  • Ethylene is one such valuable chemical with wide application in the chemical industry. It can be generated from succinic acid via Kolbe electrolysis. Kolbe electrolysis can be performed in the fermenter or on the aqueous medium extracted from the fermenter.
  • the lignin, unfermented biomass and microbial biomass are used to produced energy via thermochemical process. Combustion is typically used in today’s commercial biorefineries to generate energy to fulfil the biorefinery’s parasitic energy demands. In a preferred embodiment of this invention oxy-fuel combustion is used to generate heat and electricity, and flue gas CO2 is captured to produce methanol
  • FIG. l is a block diagram of one embodiment of the process of the present invention.
  • feedstock is subjected to a pretreatment step that includes cleaning, washing, sterilisation and milling.
  • a pretreatment step that includes cleaning, washing, sterilisation and milling.
  • two stage hydrolysis is carried out.
  • pentose carbohydrates are hydrolysed and separated from the cellulose and lignin fraction of the feedstock.
  • hexose carbohydrates are hydrolysed. Both streams are sent to different fermenters for the production of succinic acid.
  • the fermented broth is extracted from the fermenters and undergoes a multistep process of purification yielding a purified succinate stream and a second stream of unfermented feedstock.
  • Unfermented feedstock is sent to the preparation process to be converted into a solid biofuel.
  • Purified succinic acid is collected a product.
  • a portion of the succinate undergoes electrolysis generating ethylene.
  • CO2 is also produced and recycled to the fermenters.
  • Ethylene is collected as a product.
  • a portion of this ethylene is polymerised into polyethylene.
  • Another portion of the ethylene undergoes carboalkoxylation followed by condensation with formaldehyde to produce methyl methacrylate monomer that is polymerised into poly(methyl methacrylate).
  • Solid biofuel after preparation process is sent to the oxy-fuel combustion.
  • Oxygen is also fed to the oxy-fuel combustion.
  • Flue gas CO 2 is captured in the carbon capture process which is hydrogenated into methanol and collected as a product.
  • a portion of methanol is dehydrated to produce dimethyl ether.
  • Another portion of methanol is oxidised to generate formaldehyde for utilisation in the methyl me
  • the current invention does not depend upon a specific carbohydrate or biomass. It uses a combination of different processes to allow for the utilisation of a wide variety of carbohydrate and fermentable feedstock including lignocellulosic biomass.
  • the main fractions of the lignocellulose biomass are cellulose, hemicellulose and lignin, in addition to starch, protein, and other organic materials. Lignin is deposited between individual carbohydrate fibres and acts as an intercellular adhesive, binding the carbohydrates into the matrix. It is desirable to utilise all the major fractions, including the cellulose and hemicellulose, as well as the starch, protein and lignin in this invention.
  • Sterilised biomass is sent to the fractionation process to help break the lignocellulose matrix and allow for carbohydrate hydrolysis. Typically, these processes also carry out some level of hydrolysis of the carbohydrates.
  • a number of such processes are known in the art, any of which is suitable for this invention such as explosion hydrolysis.
  • Liquid explosion hydrolysis process may be used.
  • the best known of the liquid explosion processes is the so called “Masonite” process (U.S. Pat. No. 2,140,189).
  • Masonite process woodchips or biomass materials are pressurised by steam to pressures as high as 6.9 MPa (i.e. 69 atmosphere).
  • the fractionation process is combined with hydrolysis in a two-stage acid catalysed process.
  • Those skilled in the art are familiar with two-stage acid hydrolysis of lignocellulosic material.
  • Two-stage nitric acid hydrolysis is known in the art as a suitable process for lignocellulose hydrolysis (U.S. Pat. No. 5,221,357).
  • hemicellulosic component is hydrolysed and the slurry is washed with water and clarified using centrifuge or any of the other techniques known in the art, separating it into a solid Hexose Fraction and a liquid hydrolysed Pentose Fraction.
  • the Hexose Fraction stream comprises predominantly cellulose carbohydrates and lignin, and other water insoluble materials.
  • the liquid hydrolysed Pentose Fraction stream comprises predominantly of hydrolysed C5 sugars dissolved in water.
  • the acidic environment leads to a decrease in the pH value that needs to be increased.
  • ammonia and/or ammonium salts are used to bring the pH up, typically to pH 5 or above.
  • the process may be carried out in any suitable reactor/s such as screw reactor.
  • the sterilisation process is combined with the fractionation process and the hydrolysis process.
  • an additional enzymatic hydrolysis step may be carried out to convert carbohydrates in the Hexose Fraction stream into a media that is suitable for the metabolism of the microbes.
  • Synergetic actions of three cellulose enzymes namely: endo-b-glucanase, exo-b-glucanase and b-glucosidase are typically used for cellulose hydrolysis, working together to convert cellulose into glucose monomer.
  • Glucoamylase is typically used to complete the hydrolysis of the starch molecule. It only attacks the ends of the starch molecule as it is an exoenzyme, hydrolysing both 1,4 and 1,6 linkages, thereby, achieving nearly complete starch hydrolysis.
  • Optimal parameters range from 58-62 °C, pH 4.4-5.0 with a residence time of 24 to 48 hours. Longer residence times lead to the formation of non-fermentable disaccharides - a process called reversion and retrogradation.
  • Protease enzymes may be used for this purpose. These enzymes hydrolyse the proteins (of the feedstock or other sources) into smaller peptides and amino acids. These amino acids and peptides are a major nitrogen source for the fermentation microorganisms. Hydrolysis of the proteins also speeds up nitrogen assimilation during the fermentation.
  • the protein supplement for fermentation can come from the feedstock biomass as illustrated, or from other protein sources or a combination of both.
  • the hydrolysed slurry of Hexose Fraction is sent to the fermenter.
  • Any suitable bioreactor can be used as a fermenter including batch, fed-batch, cell recycle, single stage Continuous Stirred Tank Reactor (CSTR) or multi-step CSTR.
  • a combined hydrolysis and fermentation process can be carried out in a design called simultaneous saccharification and fermentation. This allows for the reduction of overall costs simultaneous saccharification and fermentation technology is utilised in the ethanol industry with starch enzymes. This technology is just as suitable for the cellulose enzymes and may also be used in the current invention. Product inhibition of the cellulases is avoided by conversion of the glucose into the desired fermentation product.
  • succinic acid producing microbes including bacteria or yeast are used to ferment the carbohydrates in the Hexose Fraction.
  • Succinic acid is a key intermediary in anaerobic fermentations by propionate-producing bacteria. This process, however, only produces it in low yields and in low concentrations.
  • Succinic acid is also produced by some anaerobic bacteria, yeast and fungi as a major product.
  • Succinic acid producing bacteria such as Mannheimia succinciproducens and Actinobacillus succinogens have been isolated from bovine rumen. These strains of rumen bacteria are capnophilic (CO 2 loving) and produce succinic acid as the major product from various carbon sources.
  • Anaerobiospir ilium succiniciproducens are anaerobically grown at a controlled pH between about 5.8 to about 6.6 in a fermenter with a medium containing carbohydrates; other nutrients, such as com steep liquor; tryptophan; and, calcium ions under a partial pressure of at least about 0.1 atmosphere CO 2 until a yield of about 75% weight (wt.) of succinate salt based on the weight of the carbohydrate is obtained and the fermentation broth contains at least about 20 g/1 of succinate.
  • the fermentation is carried out at a temperature between about 25° to about 45° C.
  • Optimum growth of the Anaerobiospiri Hum succiniciproducens organism is at about 39° C.
  • the typical concentration of carbohydrates in the medium is between about 20 g/1 to about 100 g 1, preferably between about 40 g/1 and about 80 g/1.
  • Carbohydrate concentrations above about 100 g/1 give solutions with such high osmotic pressures that the organisms do not grow well, while broths containing less than 20 g/1 generate succinic acid in concentration that is so low that its recovery usually is not practical.
  • the fermentation duration typically ranges from 10 to 48 hours.
  • any suitable base can be used to neutralise the fermentation such as Ca(OH) 2 , which can be supplied by CaO (lime) and calcium carbonate (CaC0 3 ) or NaOH or NH 4 OH or KOH.
  • CO 2 can be supplied to the fermentation medium in various ways and forms.
  • Gaseous form can be supplied either in the form of pure gaseous CO2 or CO2 mixed with other gases and sparged through the fermentation fluid, as long as the other gases employed do not interfere with the growth and metabolism of the microbes.
  • the inorganic carbon can be supplied in the form of carbonate or bicarbonate salts of various alkali and alkaline earth metals such as CaC0 3 , Ca(HC0 3 ) 2 , Na 2 C0 3 , NaHC0 3 , (NH 3 ) 2 C0 3 , NH 4 HC0 3 , K 2 C0 3 , KHC0 3 . It is well known in the art that depending on the pH of the medium, there is a definite ratio between the C0 3 -2 , HC0 3 -1 , and ftCCb and the corresponding cations.
  • inorganic carbon is supplied in the form of carbonate or bicarbonate salts of alkali and alkaline earth metals rather than the supply of gaseous CO2.
  • the solid form of inorganic carbon increases the inorganic carbon concentration in the fermentation medium beyond what could be achieved by the continuous supply of CO2 gas to the fermentation medium in a cost effective way.
  • the use of bicarbonate salt in place of gas phase CO2 also eliminates the issue related to the poor diffusion of CO2 from the gas phase into the aqueous phase.
  • growth inhibition occurs when excessive bicarbonate salts are added.
  • succinic acid reacts with the salt such as Na 2 CC> 3 to form succinate salt such as sodium succinate.
  • the broth exiting the fermenter contains salts of succinic acid, colouring matter, metabolic by-products, bacterial cell and cell materials, heavy metals and other inorganic materials.
  • the broth is clarified using centrifuge or any other techniques known in the art. In one embodiment of this invention disk stack centrifuge is used to separate out solids and liquids.
  • the insoluble stream (30% wt. moisture) containing lignin, undigested biomass, microbial biomass, other solid contaminants and a small percentage of succinate is separated for use as solid biofuel for energy generation.
  • the aqueous stream contains majority of the succinate and requires purification to extract succinic acid.
  • a further enzymatic hydrolysis of the hemicellulose in the Pentose Fraction stream may be carried out.
  • an admixture of enzymes is used to achieve complete hemicellulose hydrolysis.
  • the arabinose and glucuronic acids are removed from the xylose backbone using a-L-arabinofuranosidase and a- glucuronidase.
  • the xylose backbone is hydrolysed using endo-b-l,4-xylanase and b- xylosidase.
  • the broth is then sent to the fermenter.
  • the hydrolysed Pentose Fraction may be converted into a wide range of products such as organic acids, alcohols or biofuels. Any suitable bioreactor can be used as a fermenter.
  • microbes capable of fermenting pentose carbohydrates to succinic acid are used. Actinobacillus succinogenes is able to consume pentose sugars if the medium is lacking hexose sugars and produce succinic acid.
  • Genetically modified microorganisms like genetically modified Escherichia coli are also capable of producing succinic acid from pentose sugars.
  • the Pentose Fraction is fermented to acetic acid.
  • Acetic acid fermentation is done at a higher temperature, typically using thermophilic strains.
  • the acetogenic bacteria have been known and studied since the 1930s.
  • the acetogenic bacteria include members in the Clostridium, Acetobacterium, Peptostreptococcus and other lesser known species. Their habitats include the sewers, anaerobic digesters and natural sediments. They are also found in termite guts, rumens, and intestinal tracts of non ruminants including humans. Pathogenicity is rare. All of these organism are strict anaerobes, which means that contact with oxygen is often fatal to them.
  • Clostridium are spore formers. Spores are resistant to many sterilisation techniques. Special procedures have been established for handling spore-forming bacteria. Th e Acetobacterium and Peptostreptococcus species are not spore formers.
  • Acetogens which only produce acetic acid are called homofermentative organisms. In contrast there are acetogens which produce other organic products such as formic, propionic, succinic, etc. in addition to acetic acid. These acetogens are also able to metabolise glucose to pyruvate using the normal Embden-Meyerhof glycolytic pathway. Pyruvate is then converted into acetic acid and CO2 using the regular oxidation pathways. The released CO2 is then fixed by the acetogens to make an additional mole of acetic acid.
  • the aqueous succinic acid stream is passed through an ultrafiltration membrane to further remove any impurities. This stream is then treated with cation and anion exchangers, further purifying the succinic acid including the removal of any nitrogenous impurities (proteins and amino acids). This clean stream then goes through an evaporator and finally a drier.
  • the result is a succinic acid product with high purity.
  • the final product preferably will contain about 80 to about 99.5% succinic acid, on a dry basis, less than 1% nitrogenous impurities and less than 10 ppm of contaminating ions.
  • the succinic acid is value-added into chemicals and polymers with applications in chemical, food, pharmaceutical and biodegradable polymer industries.
  • Poly(butylene succinate) is a promising biodegradable polymer that can be made from succinic acid. It is a semi crystalline polyester with melting point at around 115 °C. It decomposes into water and CO2 easily. It can be blown into a foam for low density products.
  • Ethylene is another important chemical that can be produced from succinic acid via electrolysis.
  • a portion of the aqueous succinate salt stream is separated to produce ethylene via decarboxylation.
  • the aqueous stream containing succinate salt such as sodium succinate undergoes Kolbe electrolysis and is decarboxyl ated into ethylene (C4H4Na204 + ⁇ iO ® C2H4 + 2CO2 + 2NaOH + Eh).
  • the base such as NaOH and CO2 are recycled back to the fermenter.
  • Hydrogen is collected as a coproduct.
  • succinic acid electrolysis is carried out in a liquid medium to produce ethylene.
  • the Kolbe electrolysis may be carried out in the fermenter.
  • the Kolbe electrolysis reaction is one of the oldest and well-known electro-organic reactions, and electrolysis conditions are known in the art.
  • the Kolbe reaction is formally a decarboxylative dimerisation of two carboxylic acids (or carboxylate ions).
  • recovered ethylene is purified into a product suitable for generation of other products.
  • the purification process is well known in the art and produces ethylene with very high purity, typically 99.9% with very low levels of any residual impurities such as hydrogen, methane, and ethane ⁇ 2000 ppm (volume) and total carbon oxides such as CO and CO2, at approximately 1 ppm (volume) level.
  • low density polyethylene is prepared by random radical reactions initiated with oxygen or organic peroxides such as benzoyl peroxide.
  • the process is exothermic and controlled between 200-300 °C. Typical pressure range is 1,500 to 2,500 atmospheres.
  • the ethylene can be converted into a wide variety of other materials.
  • the ethylene can be used to produce ethylene oxide. It is well known in the art that this can be done by passing the ethylene and oxygen over silver on alumina catalyst, producing CO2 as a coproduct. The process is exothermic and process heat can be used in the biorefmery.
  • the ethylene oxide can be further value-added for example by producing ethylene glycol, ethanol amine and crown ethers.
  • polyethylene carbonate is synthesised by copolymerisation of ethylene oxide and CO2 using a catalyst system.
  • Polyethylene carbonate is a biodegradable polymer with medical applications as well. It can be used for controlled release of drugs, controlled exclusively by polymer degradation.
  • the ethylene is used to produce poly(methyl methacrylate). This is a multi-step process, well-known in the art. In this process the ethylene undergoes carboalkoxylation. In this step ethylene reacts with methanol and carbon monoxide in the presence of a catalyst to produce methyl propionate (C 2 H 4 + CO + CH 3 OH — »
  • the methyl propionate is then condensed with formaldehyde to produce monomer methyl methacrylate (C 4 H 8 O 2 + CH 2 O ® C 5 H 8 O 2 ).
  • the methyl methacrylate is then polymerised using any one of the many known processes (e g. U.S. Pat. No. 3,252,950).
  • ethylbenzene is produced by acid catalysed reaction of ethylene with benzene.
  • the ethylbenzene so formed can be catalytically dehydrogenated to give styrene and hydrogen.
  • This reaction involves passing ethylbenzene admixed with 10 to 15 times its volume of steam over a catalyst like iron oxide.
  • the process also produces hydrogen coproduct and byproducts like toluene.
  • the waste heat and steam from the process can be utilised in other processes of the biorefmery.
  • ethylene is converted into ethanol.
  • This process comprises the acid-catalysed hydration of ethylene to ethanol (C2H4 + H2O -A C2H6O).
  • the reaction is typically carried out in the presence of high pressure steam at 300 °C where a 5:3 ethylene to steam ratio is maintained.
  • the energy created as a consequence of the thermal process may be used to fulfil parasitic heat and electricity demand of the biorefmery and/or to sell to a customer.
  • the flue gas CO2 may be captured as a product to produce chemicals and fuels. This flue gas CO2 may be recycled to the succinic acid fermenter either in a gas form or in a carbonate salt form.
  • oxy-fuel combustion is used to generate energy using unfermented feedstock, lignin and other organic materials.
  • the fuel is burned using pure oxygen instead of air as the primary oxidant.
  • nitrogen component of air is not heated, fuel consumption is reduced, and higher flame temperatures are possible.
  • oxygen is mixed with recycled flue gas or staged combustion is adopted.
  • Oxy-fuel combustion also produces considerably less flue gas than air fuelled combustion and generates flue gas primarily consisting of CO2 and water. This CO2 can be captured and used to produce chemicals and fuels.
  • oxygen for oxy-fuel combustion is produced via electrolysis and hydrogen is utilised in hydrogenation processes in the biorefmery.
  • Captured flue gas CO2 and CO2 generated in other biorefmery processes is hydrogenated to generate methanol which is utilised to fulfil biorefmery process demands.
  • Methanol can be dehydrated to produce dimethyl ether.
  • Dimethyl ether can also be produced via direct hydrogenation of CO2.
  • Dimethyl ether is a promising renewable fuel to generate electricity and/or substitute for natural gas.
  • a portion of methanol is catalytically oxidised to produce formaldehyde. The formaldehyde can be used during the production of said poly(methyl methacrylate).
  • the hydrogen, thus obtained from the electrolysis process can also be used to produce ammonia via Haber-Bosch process by reacting with nitrogen.
  • a portion of ammonia may be oxidised to nitric acid by the Ostwald process.
  • the ammonia and nitric acid produced are used to fulfil biorefmery’ s process demands such as during hydrolysis.
  • the ammonia may also be used to generate urea by reacting with CO2.
  • this CO2 is sourced from biorefmery processes. Urea production is also called the Bosch Meiser urea process after its discoverers. The process consists of two main equilibrium reactions. The first is carbamate formation wherein liquid ammonia reacts with gaseous CO2 at high temperature and pressure to form ammonium carbamate. The second reaction is urea conversion wherein ammonium carbamate is decomposed into urea and water.
  • ammonia is used to produce ammonium nitrate.
  • the industrial production of ammonium nitrate entails the acid-base reaction of ammonia with nitric acid.
  • the nitric acid is sourced from the said Ostwald process.
  • the feedstock is subjected to extraction with organic solvent in order to recover lignin in a highly pure form as a valuable product.
  • Lignin extraction can be done before, during or after the hydrolysis process.
  • lignin extraction is carried out on the solid biofuel before the treatment step.

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Abstract

L'invention concerne un procédé de bioraffinerie pour produire de l'éthylène comprenant une combinaison de voies biochimiques, chimiques et électrochimiques. Des hydrates de carbone comme produit de départ sont d'abord séparés en glucides d'hexose et de pentose pour la fermentation en acide succinique. Facultativement, des hydrates de carbone de pentose sont fermentés en acide acétique. Une partie de l'acide succinique est convertie en éthylène. La lignine et d'autres matières premières non fermentées sont utilisées dans une centrale thermique pour produire de la chaleur et de l'électricité pour une utilisation dans la bioraffinerie. Le gaz de combustion CO2 peut être capturé pour la production de méthanol.
PCT/AU2020/051148 2019-11-03 2020-10-25 Procédé de production d'éthylène WO2021081577A1 (fr)

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AU2019904137A AU2019904137A0 (en) 2019-11-03 Process for producing ethylene
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CN110016687A (zh) * 2019-04-08 2019-07-16 天津大学 一种乙烯的电化学制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110016687A (zh) * 2019-04-08 2019-07-16 天津大学 一种乙烯的电化学制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GHAYUR, A. ET AL.: "Techno-economic analysis of a succinic acid biorefinery coproducing acetic acid and dimethyl ether", JOURNAL OF CLEANER PRODUCTION. PUBLISHED, vol. 230, 16 May 2019 (2019-05-16), pages 1165 - 1175, XP085723386, DOI: 10.1016/j.jclepro.2019.05.180 *
RIVAROLO, M, BELLOTTI D, MAGISTRI L: "Methanol Synthesis from Renewable Electrical Energy: A Feasibility Study", BULGARIAN CHEMICAL COMMUNICATIONS, vol. 50, 2018, pages 114 - 122, XP055819672, Retrieved from the Internet <URL:http://www.bcc.bas.bg/bcc_volumes/Volume_50_Special_D_2018/BCCvol50_SpecD_paper14.pdf> *

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