EP2655639A1 - Procédé de préparation de composés organiques par fermentation d'une biomasse et par catalyse par une zéolithe - Google Patents

Procédé de préparation de composés organiques par fermentation d'une biomasse et par catalyse par une zéolithe

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Publication number
EP2655639A1
EP2655639A1 EP11813677.9A EP11813677A EP2655639A1 EP 2655639 A1 EP2655639 A1 EP 2655639A1 EP 11813677 A EP11813677 A EP 11813677A EP 2655639 A1 EP2655639 A1 EP 2655639A1
Authority
EP
European Patent Office
Prior art keywords
organic compounds
adsorption
gas
volatile organic
desorption
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP11813677.9A
Other languages
German (de)
English (en)
Inventor
Michael Zavrel
Oliver Franke
Oliver Richter
Michael Kraus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant Produkte Deutschland GmbH
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 Clariant Produkte Deutschland GmbH filed Critical Clariant Produkte Deutschland GmbH
Priority to EP11813677.9A priority Critical patent/EP2655639A1/fr
Publication of EP2655639A1 publication Critical patent/EP2655639A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/001—Processes specially adapted for distillation or rectification of fermented solutions
    • B01D3/003—Rectification of spirit
    • B01D3/004—Rectification of spirit by continuous methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • 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
    • C12P5/002—Preparation of hydrocarbons or halogenated hydrocarbons cyclic
    • 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
    • C12P5/002—Preparation of hydrocarbons or halogenated hydrocarbons cyclic
    • C12P5/005—Preparation of hydrocarbons or halogenated hydrocarbons cyclic aromatic
    • 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
    • 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
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
    • C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
    • 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
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/16—Butanols
    • 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
    • C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
    • 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
    • C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
    • C12P7/26—Ketones
    • C12P7/28—Acetone-containing products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
    • Y02T50/678—Aviation using fuels of non-fossil origin

Definitions

  • the invention relates to a process for the production of organic compounds from biomass.
  • the alcohol obtained by fermentation can be obtained by sorption to an adsorber from the fermentation broth, the sorption taking place directly in the fermentation broth.
  • a zeolite adsorber it is optionally possible to convert the loaded zeolite into a reaction zone in which the sorbed alcohol is catalytically reacted with the zeolite to give organic compounds. Reaction of alcohols to organic compounds having a lower oxygen to carbon ratio is particularly suitable for dehydration reactions. For this dehydration of alcohols ⁇ mostly ethanol) zeolites of type MF!
  • H-ZSM-5 zeolites In addition to H-ZSM-5 zeolites other types of zeolite types are other catalysts for the ethanol dehydration ⁇ US 4621164; Oudejans et al. , App. Catalysis Vol. 3, 1982, p.109), mesoporous molecular sieves (Volsli et al., Chem. Eng., Vol. 65, 2010, p.153) and hydroxyapatites (Tsuchida et al., Ind. Eng. Chem. Res. Vol.
  • the dehydration is carried out in a fixed bed reactor at temperatures between 150 ° C and 500 ° C, absolute pressures of 1 bar to 100 bar and liquid-hourly-space-velocities (LHSV volume flow liquid educt / volume catalyst) in the range of 0th , 5 h "1 to 50 h 1 (see, eg, US 4621164; Oudejans et al., App. Catalysis Vol. 3, 1982, p.
  • WO 2008/066581 A1 describes a process for preparing at least one butene, wherein sutanol and water are reacted.
  • the reagent may originate from a fermentation broth, it being possible in one embodiment to use gas-stripping for this purpose. This gas stream is either used directly for the reaction or previously subjected to distillation.
  • a disadvantage of all the prior art processes for producing organic compounds from sugars is that volatile fermentation by-products (e.g., furans) and volatile additives commonly used in fermentation (e.g., ammonia pH adjusters) can not be selectively separated. These lead to a deactivation of the ⁇ zeolite) catalyst in the downstream catalytic conversion and thus to a reduction in the catalyst activity and selectivity (see, for example, Hutchings, Studies in Surface Science and Catalysis Vol. 61, 1991, p.405).
  • volatile fermentation by-products e.g., furans
  • volatile additives commonly used in fermentation e.g., ammonia pH adjusters
  • the object of the present invention is to develop an economical process for the production of organic compounds from biomass, which eliminates the disadvantages of the prior art and allows a high yield of organic compounds with the least possible expenditure on equipment.
  • a process for the preparation of organic compounds comprising the following steps: a. the fermentative conversion of biomass to volatile organic compounds in a bioreactor;
  • the proportion of volatile organic compounds in the desorbate stream is preferably between 10% (w / w) and 90% (w / w), more preferably between 30% (w / w) and 70% (w / w) and still more preferably between 35% (w / w) and 60% (w / w).
  • the products of the catalytic reaction can then be worked up, for example, by condensation of the product stream and phase separation, preferably by decantation.
  • Process steps include:
  • biomass biological material comprising one or more of the following components: cellulose, hemicellulose, lignin, pectin, starch, sucrose, chitin, proteins and other biopolymers, as well as fats and oils.
  • this term also includes biological materials which contain sugars, in particular C5 and C6 sugars, amino acids, fatty acids and other biological monomers, or from which these monomers can be obtained, preferably by hydrolysis.
  • the solution contains less than 200 g / L of sugar, more preferably less than 100 g / L of sugar.
  • the solution contains sugars obtained from lignocellulosic biomass, more preferably these are obtained by previous enzymatic hydrolysis.
  • a likewise preferred procedure is the combination of the fermentation with the enzymatic hydrolysis, so that the hydrolysis and fermentation take place simultaneously. That is, if, as in the preferred embodiment described below, the fermentation proceeds concurrently with the subsequent steps, a combination of these embodiments is also possible, that is, both the hydrolysis and the fermentation occur simultaneously with the subsequent steps.
  • the perforation solution contains one or more low molecular weight carbon sources, and optionally one or more low molecular weight nitrogen sources.
  • Preferred low molecular weight carbon sources are monosaccharides such as glucose, fructose, galactose, xylose, arabinose, mannose, dissacidemde such as sucrose, lactose, maltose, cellobiose, sugar acids such as galacturonic acid, gluconic acid, polyols such as glycerol, sorbitol, as well as oils, fats and fatty acids.
  • Preferred nitrogen sources are ammonia, ammonium salts, nitrate salts, amino acids, urea and protein hydrolysates. Under In terms of low molecular weight, it is understood that the molecular weight is preferably less than 2500, and more preferably less than 1000.
  • Ammonia is particularly to be preferred as a nitrogen source, since. this also serves as a pK actuator, i. can be added if the pH is too low before fermentation.
  • ammonia may also be added during the fermentation if the pH drops as a result of the metabolic activity of the fermented microorganisms. As a result, the pH can be adjusted or regulated over the entire duration of the fermentation.
  • other additives such as other pH adjusters and antifoams with e1 can be added to the fermentation solution. Suitable microorganisms are yeasts, fungi and / or bacteria.
  • a volatile compound is understood to mean a compound which has a vapor pressure of more than 1.0 hPa, preferably more than 5.0 hPa, at 20 ° C. This includes compounds which have a vapor pressure equal to or greater than that of 1-butanol at 20 ° C, such as 2-butanol, tertiary-butanol, ethanol, 1-propanol, isopropanol and acetone.
  • the present invention comprises a process which is further characterized in that the volatile organic compounds are alcohols and / or ketones and / or aldehydes and / or organic acids, preferably ethanol and / or Butanol and / or acetone is.
  • Butanol unless further specified, includes all butanols, but more preferably 1-butanol.
  • the fermentation is typically carried out at temperatures between 10 and 70 ° C, preferably between 20 and 60 ° C, more preferably between 30 and 50 ° C.
  • the fermentation is preferably carried out in batch mode.
  • KTahrmedium is supplied continuously during the fermentation (fed-batch operation).
  • Further preferred is a continuous operation of the fermentation.
  • Also preferred are the operations repeated-batch and repeated-fed-batch, and two-step procedures and cascades.
  • the fermentation can be carried out by isolated enzymes added to the fermentation solution. However, it is preferred that the fermentation is carried out with the aid of at least one microorganism. This at least one microorganism is preferably selected from mesophilic and thermophilic organisms.
  • the mesophilic as well as the thermophilic organisms can in turn be selected from the group consisting of bacteria, archaea and eukaryotes, with eukaryotes in particular mushrooms, and especially yeasts are preferred.
  • mesophilic yeasts such as, for example, Saccharomyces cerevisiae, Pichia stipitis, Pichia segobiensis, Candida shehatae, Candida tropicalis, Candida boidinii, Candida tenuis, Pachysolen tannophilus, Hansenula polymorpha, Candida fa ata, Candida parapsilosis, Candida rugosa, Candida sonorensis , Issatchenka terricola, Kloeckera apis, Pichia barkeri, Pichia cactophila, Pichia deserticola, Pichia norvegensis, Pichia membranaefaciens, Pichia mexicana and TOru2aspora de
  • Thermophilic bacteria are, for example, Clostridium acetobutylicum, Clostridium beijerincki, Clostridium saccharobutylicum, Clostridium saccharoperbutylacetonicum, Escherichia coli, Zymomonas mobilis.
  • thermophilic organisms are used.
  • Thermophilic yeasts include, for example, Candida bovina, Candida picachoensis, Candida e berorur, Candida pintolopesi, Candida therophila, Kluyveromyces marxianus, Kluyveromyces fragilis, Kazachstania telluris, Issatchenkia orientalis and Lachancea thermotolerans.
  • Thermophilic bacteria include Clostridium ther ocellum, Clostridium thermohydrosulphuricum, Clostridium ther osaccharolyticium,
  • Thermoanaerobacter ethanolicus Clostridium thermoaceticu, Clostridium thermoautotrophicum, Acetogenium kivui, Oesulfotomaculum nigrificans, and Desulfovibrio thermophilus, Thermoanaerobacter tengcongensis, Bacillus stearothermophilus and Thermoanaerobacter mathranii.
  • microorganisms are used which have been modified by genetic methods.
  • an overhead of the volatile constituents, in particular of the volatile organic products by stripping with a carrier gas in the gas phase.
  • gas stripping also called expulsion
  • the liquid phase by passing through Removed gas volatile compounds and transferred to the gaseous phase.
  • This transfer can take place continuously in a preferred embodiment.
  • Continuous removal of the volatile constituents refers to the removal of the volatile constituents by gas stripping, in parallel with their fermentative production.
  • Suitable carrier gases are inert gases such as carbon dioxide, helium, hydrogen, nitrogen or air, as well as mixtures of these gases. Gases that are very slow to react, ie can only participate in a few chemical reactions, are regarded as inert.
  • An advantage of the method according to the invention is that the fermentation waste gases formed during the fermentation can be used directly as carrier gas. It is therefore preferred in a particular embodiment that the fermentation exhaust gases are used as a carrier gas.
  • the fermentation and gas stripping is carried out in a reactor which is preferably selected from the group consisting of a stirred tank reactor, a loop reactor, an air-lift reactor or a bubble column reactor. Particularly preferred is the dispersion of the gas bubbles, which is achieved for example by a sparger and / or a suitable stirrer.
  • gas stripping is possible via an external gas-stripping column connected to the bioreactor, which optionally can be continuously fed with the fermentation solution and whose outlet can be returned to the bioreactor.
  • an external gas-stripping column is operated countercurrently and / or in combination with random packings, preferably with Raschig rings, for increasing the mass transfer rate.
  • the specific gassing rate is preferably between 0.1 and 10 vvm, more preferably between 0.5 and 5 vvm [vvm means volume gas / volume bioreactor / minute].
  • the gas stripping is preferably carried out at a pressure between 0.05 and 10 bar, more preferably between 0.5 and 1.3 bar. Most preferably, the gas stripping is carried out at reduced pressure (or negative overpressure), ie at a pressure which is lower than the reference pressure of the environment, which is typically about 1 bar.
  • the gas stripping preferably takes place at the fermentation temperature.
  • the gas-stripping is carried out so that the fermentation solution is additionally heated. This can be done by a design in which a part of the fermentation solution is passed into an external column in which the temperature is elevated and in which the gas-stripping takes place, whereby the gas-stripping is more efficient than at fermentation temperature.
  • a further advantage of the method according to the invention is that the enthalpy of vaporization transferred from the liquid into the gas phase by the passage of the volatile compounds contributes to the cooling of the bioreactor and thus the cooling capacity required for keeping the temperature in the bioreactor constant is reduced.
  • no cooling power is required any more since the sum of the enthaled evaporation enthalpy and heat loss to the environment is greater than the biologically produced heat.
  • the gas stream leaving the bioreactor is passed through one or more columns filled with one or more adsorbents.
  • Suitable adsorbents are zeolites, silicas, bentonites, silicalites, clays, hydrotalcites, aluminum silicates, oxide powders, mica, glasses, aluminates, clinoptolites, gismondines, quartzes, activated carbons, bone charcoal, montmorillonites, polystyrenes, polyurethanes, polyacrylamides, polymethacrylates and polyvinylpyridines or mixtures thereof ,
  • zeolites are used as adsorbents. Particular preference is given to zeolites of the beta or MFI type.
  • the zeolite has a Si0 2 / Ai 2 0 3 ratio of 5 to 1000, and particularly preferably a Si0 2 / Al 2 0i. Ratio of 100 to 900.
  • Particularly preferred are the synthetic zeolites according to US 7,244,409.
  • the mass ratio of adsorbent to adsorbed ethanol is preferably between 1 and 1000, more preferably between 2 and 20.
  • the temperature in the adsorption of the ethanol is preferably between 10 and 100 ° C, more preferably between 20 and 70 ° C.
  • the pressure is preferably between 0.5 and 10 bar, more preferably between 1 and 2 bar.
  • the adsorber material may be contained in one or more columns. Preferably, several, more preferably 2 or more, most preferably 2 to 6 columns are used. These columns can be connected in series or in parallel.
  • the advantage of the parallel connection is that a quasi-continuous operation is made possible by alternating two or more columns between the adsorption and the desorption described in more detail under point d, ie adsorption and desorption can be carried out simultaneously on different columns.
  • the columns are preferably provided in a turret arrangement. In a particularly preferred embodiment, 2 to 6 columns are switched so that the column or columns in which the adsorption takes place is switched in parallel to the column (s) in which the desorption proceeds. If adsorption occurs in more than one column, these columns can be connected in series or in parallel.
  • adsorption may proceed, column 4 may be heated for desorption, desorption may occur in column 5, and column 6 is allowed to cool changed when the adsorber loading reaches a predetermined value, but at the latest when a full load is reached and break the volatile organic compounds at the end of the column, so can not be fully adsorbed.
  • the gas stream contains more water than volatile organic compounds so that the adsorbers first saturate with water.
  • the volatile organic compound loading then increases continuously over a second period until saturation is reached. In this second period, the ratio of volatile organic compounds to water increases continuously.
  • a particularly preferred embodiment of the process is that, by choosing a suitable cycle time and / or a suitable adsorber amount, this ratio between the volatile organic compounds and water is adjusted so that it leads to a particularly suitable mixing ratio. ie, a particularly suitable or optimal proportion of the volatile organic compounds for the catalytic conversion comes.
  • the particularly favorable or optimal cycle times and / or adsorber quantities can be determined by preliminary experiments.
  • Particularly suitable levels of volatile organic compounds are between 10% (w / w) and 90% ⁇ w / w), especially preferably between 30% (w / w) and 70% (w / w) and more preferably between 35% (w / w) and 60% (w / w).
  • the remaining shares are composed of water and / or carrier gas.
  • the Adsorpt.ionsmaterial used is preferably capable of selective adsorption. By selective adsorption on an adsorption material is meant that the adsorption material from a gas stream can adsorb a higher mass fraction of the desired compound than the undesired compound. Desirable compounds for the purposes of this invention are the volatile organic compounds.
  • Unwanted compounds within the meaning of this invention are, for example, catalyst poisons such as ammonia, as specified in the next section. That is, when the gas flow is equal in mass fraction of the volatile organic compound and the undesired compound, more of the volatile organic compound is adsorbed by the undesired compound. Preferred is a ratio of volatile organic compound to the undesired compound of at least 5: 1, more preferably of at least 20: 1.
  • the adsorbent material is selected so that undesirable compounds, such as catalyst poisons, are adsorbed only in negligible or immeasurable amounts for subsequent catalytic conversion.
  • Typical undesirable compounds which may be used alone or in combination as catalyst poisons are ammonia, furans, furfural and its derivatives such as hydroxymethylfurfural (HMF).
  • HMF hydroxymethylfurfural
  • the adsorption of ammonia is largely or completely avoided when an adsorbent material is used which has few acid sites.
  • zeolites which have a SiO 2 / Al 2 O 3 ratio of at least 100 are suitable for this purpose. These zeolites are therefore particularly preferred as the adsorber material for this embodiment. If both the adsorber and the catalyst are a zeolite, it is preferable in one embodiment for the adsorber to have a SiO 2 / Al 2 O 3 ratio greater than that of the catalyst.
  • Examples 4 and 5 together show that zeolite is suitable for the selective adsorption of ethanol and that the adsorption of the undesired compound ammonia is negligible.
  • the depleted in volatile organic compounds gas stream exits the adsorber.
  • the undesirable compounds described above are depleted or removed from the product stream which is then subjected to the below d. and e. described further processed.
  • step d unlike, for example, the optional distillation described in WO 2008/066581 A1, undesired compounds can be effectively depleted or removed.
  • the gas stream can be fed back into the bioreactor after leaving the adsorption column and is then available again for gas-stripping.
  • the adsorption can be carried out in fluidized bed operation. Likewise, adial adsorbers or rotary adsorbers can be used. Since the recirculated gas stream is depleted in organic compounds in this embodiment, the concentration of volatile organic compounds in the fermentation medium can be kept low despite gas recirculation.
  • the concentration of the volatile organic compounds in the fermentation solution can be kept below a certain value over the entire fermentation time. This is particularly preferred when the volatile organic compounds exert an inhibiting or toxic effect on the microorganisms, such as ethanol, sutanol, or acetone.
  • the adsorption is preferably carried out at least during the entire duration of the production of the volatile organic compounds, ie as long as these volatile organic compounds are formed.
  • a low concentration of the volatile organic compounds in the fermentation medium means, for example, less than 10% (w / v) total volatile organic compounds in the fermentation medium, preferably less than 5% (w / v) volatile organic compounds in the fermentation medium, more preferably less than 3.5% ( w / v) volatile organic compounds in the fermentation medium, and most preferably less than 2% (w / v) volatile organic compounds in the fermentation medium.
  • the inventive method allows the desorption of the volatile organic compounds from the adsorbent.
  • the proportion of volatile organic compounds in process step d. of the process according to the invention in the desorbate stream preferably between 10% (w / w) and 90% (w / w), more preferably between 30% (w / w) and 70% (w / w) and even more preferably between 35% (w / w) and 60% (w / w).
  • Desorption can be accomplished by increasing the temperature and / or reducing the pressure within the column. Preference is given to temperatures between 25 and 300 ° C and absolute pressures between 0 and 10 bar. Particularly preferred are temperatures between 80 and 300 ° C, and absolute pressures between 0.1 and 3 bar.
  • a louggeraas is used for the discharge of the desorbed volatile organic compounds from the column.
  • the same inert carrier gas is used, which is also used for gas stripping.
  • the carrier gas in step b is the gas a gas A (which may be carbon dioxide)
  • the gas is in the embodiment of the "same" carrier gas also in step d, the gas ⁇ (which may be carbon dioxide).
  • step b. used gas stream in the subsequent step c. So when he leaves the adsorber, typically contains undesirable compounds, as described above.
  • the temperature and the absolute pressure of the carrier gas are adjusted according to the above-described temperatures and absolute pressures within the column. Suitable for this purpose upstream heat exchangers and / or throttles or compressors.
  • the desorption can be carried out in fluidized bed operation. Radial adsorbers or rotary adsorbers can also be used. e. Catalytic conversion
  • the Desorbatstrom described in section d is transferred to one or more catalyst-filled reactors, optionally by upstream heat exchangers and chokes or compressors, the input stream can be brought to reaction temperature and reaction pressure.
  • the input stream can be brought to reaction temperature and reaction pressure.
  • individual or mixtures of organic compounds are formed in the reactor, which can be assigned, inter alia, to the groups of olefins, aliphatics, aromatics, oxygenates.
  • Circulation reactors or fixed bed reactors are used. These reactors are briefly described within the scope of the preferred embodiments of this invention. It is also possible to combine several reactors of the same or different design.
  • Suitable catalysts are Brönsted and / or Lewis acidic substances, e.g. Zeolites, silica aluminas, aluminas, mesoporous molecular sieves,
  • Silicon aluminophosphates In a preferred embodiment
  • Zeolites used as a catalyst are zeolites of
  • the zeolite has a Si0 2 / Al 2 0 3 ratio of 5 or higher, such as from 5 to 1000, and most preferably a Si0 2 / Al 2 0 3 ratio of 20 to 200. It is preferred that both the adsorber and the catalyst is a zeolite, the catalyst zeolite a lower S1O / Al2O3 ratio than the
  • Adsorber Zeoli th Especially in this embodiment, but not limited to, the catalyst zeolite has a S1O2 / Al2O3 ratio of
  • GHSV gas hourly space velocity
  • the temperature is in a range from 250 to 350 ° C.
  • the absolute pressure in a range from 1 to 5 bar
  • the GHSV in a range from 2000 to 8000 h -1 .
  • An advantage of the method according to the invention over the prior art lies in the combination of the adsorption / desorption described in section c / d with the catalytic conversion described here.
  • By selective choice of the adsorption or desorption conditions it is now possible to adjust the proportion of water and the proportion of volatile organic compounds in the desorbate and thus in the input stream of the catalytic reaction.
  • By suitable choice of the proportion of volatile organic compounds the yield of liquid organic compounds and the water content of the deactivation behavior of the catalyst is significantly influenced.
  • undesired compounds can also be removed from the gas stream. This avoids that the catalyst is exposed to catalyst poisons to such an extent, as would happen, for example, in the method according to WO 2008/066581 Al, which does not comprise adsorption.
  • the catalytic reaction is preferably carried out at a temperature of 150 to 500 ° C, preferably between 250 and 350 ° C, an absolute pressure of 0.5 to 100 bar, preferably between 1 and 5 bar and a GHSV of 100 to 20,000 h _1 , preferably between 2000 and 8000 h "1 ,
  • the proportion of volatile organic compounds in the input stream is 10 to 90% (w / w), in a particularly preferred embodiment 30 to 70% (w / w) and in a still further preferred embodiment 35 to 60 % (w / w).
  • the remaining portions to 100% (w / w) are composed of the proportion of water or the carrier gas.
  • condensation in a preferred embodiment, the method according to the invention can furthermore be characterized in that, following the above-described method steps a to e, a condensation of the product stream takes place, which can optionally be done by lowering the temperature and / or increasing the pressure.
  • the temperature reduction is preferably to a temperature level below the ambient temperature, more preferably below 10 ° C.
  • heat exchangers can be used, which are operated in the DC, countercurrent or cross flow.
  • the condensation takes place in stages, so that a plurality of fractions having different compositions of matter is obtained.
  • the present invention also encompasses a process which is further characterized in that the carrier gas or the carrier gases can be recycled after the adsorption and / or after the catalytic conversion. It is preferred that the fermentation waste gases are used as the carrier gas.
  • the noncondensable portions of the gas stream are preferably further catalytically reacted, preferably by being recycled to the column of catalytic reaction.
  • these non-condensable fractions are used as starting materials for another chemical reaction or other chemical reactions, such as polymerization reactions. Particularly preferred is the polymerization of ethylene to polyethylene or propene to polypropylene. According to a further preferred embodiment, the non-condensable fractions are thermally utilized by being burned. In all of these embodiments, it is also possible to carry out a further adsorption with subsequent desorption to enrich the components.
  • the adsorbent used here is preferably a zeolithiscb.es material. It is particularly preferable to use the same material as for the process steps described under c and / or e.
  • the resulting condensate is collected.
  • the resulting condensate is kept cool to avoid loss due to evaporation.
  • phase separation In a further preferred embodiment, the process described under f can be further characterized in that a phase separation takes place after the condensation. Due to the miscibility gap between the organic compounds and water, two phases preferably form after condensation, an organic and an aqueous phase. According to the method of the invention, the phases are separated from each other. This can be done by simple decanting or by centrifugation or by other liquid-liquid separation methods known to those skilled in the art.
  • the organic compounds are separated as a lighter phase, ie lighter than the aqueous phase.
  • a particular advantage of the method according to the invention is that thus a large amount of water can be separated from the product without high energy expenditure.
  • the aqueous phase can be recycled as process water to other process stages.
  • the aqueous phase is freed by gas stripping of any volatile hydrocarbons still dissolved therein.
  • these volatile hydrocarbons are recirculated either to adsorption from section c or to the catalytic conversion from section e, the carrier gas stream being either the same carrier gas stream as for the gas stripping of the bioreactor or used for the catalytic reaction.
  • the organic phase can be recovered either directly or after further processing as a product.
  • a preferred further treatment is the separation of the organic mixture into a plurality of fractions and / or components, each of which can be used differently.
  • Fuels can be gasoline, diesel, jet fuel or similar fuels.
  • use of the product as a fuel is possible, for example as heating oil.
  • An alternative use according to the invention is the further use for chemical follow-up reactions, particularly preferably for the preparation of polymers. parallel connection
  • FIG. la shows a possible embodiment of the method according to the invention.
  • An inert carrier gas stream (1) is blown into the bioreactor (2) for gas stripping.
  • biomass is fermented to volatile organic compounds, with adjuvants (3) are added as pH adjuster.
  • the gas leaving the bioreactor, which contains volatile organic compounds and other volatiles, is passed through an adsorption column (4) in which the volatile organic compounds are selectively adsorbed.
  • the depleted gas stream is then returned to the bioreactor.
  • two or more columns are connected in parallel and / or in series. Part of the carrier gas stream is removed due to the fermentation fermentation fermentation waste gases (5).
  • the carrier gas stream (10) necessary for the discharge of the desorbed volatile organic compounds is adjusted accordingly via a heat exchanger (6) and / or throttles.
  • the gas leaving the column during desorption is subsequently catalytically reacted in one or more reactors (7).
  • the organic products formed are condensed via a heat exchanger (8).
  • the condensate is then subjected to a phase separation (9).
  • the organic phase is removed as product (11) and the aqueous phase (12) can be used for further purposes.
  • the regenerated carrier gas stream (10) is recycled.
  • FIG. 1b shows a further possible embodiment of the method according to the invention, in which case gas stripping takes place in an external gas-stripping column (13) connected to the bioreactor. Fermentation solution is fed to the external gas-stripping column and the stripped solution is then returned to the bioreactor. All further process steps are analogous to Figure la.
  • the same Ak ivmaterial is used for the adsorption and the catalytic reaction in a particularly preferred embodiment as a carrier and catalyst.
  • Figure 2 shows another possible embodiment of the inventive method: the turret solution, in which four columns (A-D) or more are used.
  • columns A and B are in adsorption (1), which columns may be connected in series, but also in parallel.
  • Column C is in desorption (2) by bubbling a carrier gas stream at elevated temperatures or reduced pressure.
  • column D the catalytic reaction takes place, wherein the desorbed gas stream is blown.
  • column B is subjected to desorption (2), C to catalytic conversion (3) and D to adsorption (1).
  • the columns D and A are connected. Make as many cycle times as existing columns again the same column desorbed as at the beginning, so that a cycle is completed and a new beginning.
  • Figure 3 shows another possible embodiment of the process according to the invention, in which three columns (AC) or more are used and in which the desorption and the catalytic conversion take place simultaneously in the same column.
  • columns A and B are in adsorption (1), which columns may be connected in series, but also in parallel.
  • column C the volatile organic compounds are desorbed by increasing the temperature and at the same time catalytically reacted (3).
  • part of the desorbate gas stream is recycled to column C.
  • column B goes into desorption and catalytic conversion 12) and C into adsorption (1).
  • FIG. 4 shows another possible embodiment of the method according to the invention using a radial adsorber which consists of two zones.
  • zone A adsorption from the gas stream (1) containing the volatile organic compounds takes place in zone B, desorption and simultaneous catalytic conversion to the product gas stream (2).
  • zone B By rotating the apparatus, continuously charged adsorption material passes from the adsorption zone (A) to the desorption and catalytic conversion zone (B) and vice versa.
  • Figure 5 shows another possible embodiment of the process according to the invention using a fly-flow reactor which has an adsorption zone (A) and a reaction zone (B).
  • the adsorption zone (A) the adsorption of the volatile organic compounds from the gas stream (1) takes place in zone B by blowing a hot carrier gas stream (2) desorption and catalytic conversion, wherein the hot carrier gas stream entrains the particles and upwards within promoted the so-called riser.
  • Gas (dashed line) and particles (solid line) are conveyed in direct current.
  • a particle separation takes place. The particles then pass back into the adsorption zone (A), so that a total circulation of the particles is formed.
  • Figure 6 shows another possible embodiment of the process according to the invention using a moving bed reactor which has an adsorption zone (A) and a reaction zone (B).
  • the adsorption zone (A) the adsorption of the volatile organic compounds takes place from the carrier gas Ström (1).
  • the loaded particles then migrate into the warmer reaction zone (B), in which the desorption and the catalytic reaction take place.
  • the organic products are discharged from the reactor.
  • the particles are conveyed out of the reactor after the reaction zone and conveyed back into the adsorption zone (A) via suitable solids conveying techniques, so that a total circulation of the particles is produced.
  • the process according to this invention is further characterized in that one, preferably two, more preferably three, more preferably four, even more preferably five or more of the individual process steps are carried out under the following conditions:
  • the fermentation takes place at temperatures between 10 and 70 ° C, preferably between 20 and 60 ° C, particularly preferably between 30 and 50 ° C,
  • the specific gassing rate is between 0.1 and 10 vvm, preferably between 0.5 and 5 vvm,
  • the temperature during the adsorption is between 10 and 100 ° C, preferably between 20 and 70 ° C and the pressure between 0.5 and 10 bar, preferably between 1 and 2 bar,
  • the catalytic reaction is carried out at a temperature of 150 to 500 ° C, preferably between 250 and 350 ° C, an absolute pressure of 0.5 to 100 bar, preferably between 1 and 5 bar and a GHSV of 100 to 20,000 h "1 , preferably between 2000 and 8000 h "1 ,
  • Figure 1 shows embodiments of the method according to the invention with gas stripping in the bioreactor (la) and with gas stripping in an external gas-stripping column Elb).
  • Figure 2 shows an embodiment of the invention with turret configuration.
  • FIG. 3 shows an embodiment according to the invention with recycling of the desorbate gas stream into the same column.
  • Figure 4 shows an embodiment according to the invention with a radial adsorber.
  • FIG. 5 shows an embodiment according to the invention with a fly-flow reactor.
  • Figure 6 shows an embodiment of the invention with a moving bed reactor.
  • Figure 7 shows the adjustment of the ethanol content and the water content by different Adsorptionsteinperaturen according to Example 1.
  • FIG. 8 shows the comparison of two fermentations with Pachysolen tannophilus without (top) and with continuous separation of ethanol via gas-stripping and adsorption according to Example 2 (below), the short-dashed sum-ethanol curve takes into account the sum of ethanol in the solution and on the Adsorber bound).
  • FIG. 9 shows the influence of the ethanol content in the gaseous desorbate stream on the yield of the liquid organic phase, based on the amount of ethanol used according to Example 3.
  • Example 1 Gas-stripping and adsorption at different temperatures
  • the glass column was heated to a different temperature via a heating sleeve (Mohr & Co GmbH, Germany).
  • the gas-stripping in the gas washing bottle was carried out at 30 ° C.
  • the ethanol concentration was determined by gas chromatography (Trace GC, ThermoFischer, Germany) in the solution.
  • the gas chromatography Trace GC, ThermoFischer, Germany
  • Figure 7 shows the water content obtained and the proportions of volatile organic compounds as a function of the adsorption temperature. Accordingly, the water content or the proportion of the volatile organic compounds can be adjusted via the adsorption temperature.
  • Example 2 In situ fermentation with gas stripping and adsorption
  • Pachysolen tannophilus (DSM 70352, DSMZ, Braunschweig) was fermented with and without continuous separation of ethanol by gas stripping and adsorption under otherwise identical conditions for 100 hours at 30 ° C and pH 6.
  • the substrate used was pretreated and hydrolyzed lignocellulosic biomass containing about 70 g / L glucose and about 30 g / L xylose.
  • Bioreactors with a filling volume of 0.8 L each were used as the bioreactor.
  • the gas stripping was carried out with a specific gassing rate of 1 vvm using a membrane pump (KF, Germany). As in Example 1, the gas stream was passed through a glass column and then recycled.
  • the ethanol content was determined by gas chromatography and the sugars were quantified by HPLC.
  • the weight increase of the zeolite and the water content of the adsorbed mixture was determined by Karl Fischer titration (Schott Instruments, Germany). From preliminary experiments it is known that only water and ethanol are adsorbed under the given conditions. This can be deduced from the water content on the ethanol content.
  • Figure 8 shows the obtained concentration curves. It can be seen that the simultaneous implementation of fermentation, gas stripping and adsorption is advantageous and
  • the liquid model desorbate ⁇ 40% by weight EtOH, 60% by weight water) was metered into the reaction tube using an HPLC pump (Smartline Pump 100, Scientific Instrument Engineering Dr. Ing. Herbert Knauer GmbH), where it was used a heated pre-packing of inert Sic evaporated, mixed with nitrogen, so that 4 wt .-% of nitrogen were present, and was brought to the reaction temperature of 300 ° C and the absolute pressure of 3 bar.
  • the gaseous product stream was cooled to 10 ° C. in a gas / liquid separator downstream of the fixed bed reactor, the liquid products being condensed and separated from the gaseous products. Subsequently, the liquid organic phase was decanted from the aqueous phase.
  • the experiment was carried out in total via a ti e-on-stream (TOS) of 24 h.
  • TOS ti e-on-stream
  • the liquid organic phase obtained during this period was finally analyzed by gas chromatography with coupled wet-type spectrometry (for composition, see Table 1). As the evaluation showed, an ethanol conversion of> 99% and a yield of the liquid organic phase, based on the amount of ethanol used, of 34% by weight were achieved under these experimental conditions.
  • Example 1 With the structure described in Example 1 SOG mL of a 5% (w / v) ethanol-water solution for 24 hours at 3 ⁇ ° C at 1 vvm using a membrane pump (KNF Keuberger, Freiburg, Germany) and a volume flow regulator (Swagelok, Garching, Germany) stripped.
  • the gas stream was passed through a glass column (Gassner glass technology, Kunststoff, Germany), which was each filled with 200 g of adsorbent (zeolite with Si0 2 / Al 2 0 3 ).
  • the column was heated to 40 ° C. via a heating jacket (Mohr & Co GmbH, Germany).
  • the zeolite is therefore particularly well suited as adsorber At game 5
  • a zeolite according to the invention having a SiC> 2 / Al 2 O 3 ratio of 1000 are added to 400 ml of a 5% (w / v) aqueous ammonia solution.
  • the mixture is suspended for one hour at room temperature.
  • the zeolite is separated again.
  • 50 ml of the remaining solution are titrated four times with 5 molar hydrochloric acid, which is added by means of a burette, and methyl red as a pH indicator.
  • the added volume of hydrochloric acid is read. From this, the added amount of hydrochloric acid is calculated, which corresponds to the molar amount of ammonia; this in turn determines the concentration of the solution of ammonia.
  • Examples 4 and 5 together show that the zeolite is suitable for the selective adsorption of ethanol and at the same time the adsorption of the undesired compound ammonia on this adsorber is negligible.

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Abstract

L'invention concerne un procédé de production de composés organiques à partir d'une biomasse, les étapes de procédé d'extraction gazeuse, adsorption de la phase gazeuse et transformation catalytique étant adaptées les unes aux autres. Le procédé selon l'invention comporte de préférence les étapes de procédé de fermentation, extraction gazeuse, adsorption, désorption, transformation catalytique, condensation et décantation, qui peuvent se dérouler en parallèle. De plus, l'invention concerne le couplage de l'adsorption, de la désorption et de la transformation catalytique en utilisant le même matériau zéolithique pour l'adsorption et la transformation catalytique.
EP11813677.9A 2010-12-23 2011-12-23 Procédé de préparation de composés organiques par fermentation d'une biomasse et par catalyse par une zéolithe Withdrawn EP2655639A1 (fr)

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EP10196776.8A EP2468874B1 (fr) 2010-12-23 2010-12-23 Procédé de production des composés organiques via fermentation de biomasse et catalyse zéolitique
PCT/EP2011/073963 WO2012085275A1 (fr) 2010-12-23 2011-12-23 Procédé de préparation de composés organiques par fermentation d'une biomasse et par catalyse par une zéolithe
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EP2982703A1 (fr) 2014-08-06 2016-02-10 Clariant International Ltd. Procédé respectueux de l'environnement et énergétiquement efficace pour la production de composés chimiques cibles à partir d'un matériau cellulosique
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JP2014508120A (ja) 2014-04-03
US20140017751A1 (en) 2014-01-16
KR20130106871A (ko) 2013-09-30
CA2826421C (fr) 2015-11-24
JP5789306B2 (ja) 2015-10-07
PL2468874T3 (pl) 2014-11-28
WO2012085275A1 (fr) 2012-06-28
BR112013016073A2 (pt) 2016-10-04
KR101505878B1 (ko) 2015-03-25
SG192580A1 (en) 2013-09-30
UA105601C2 (uk) 2014-05-26
AU2011347168B2 (en) 2015-03-19
RU2573926C2 (ru) 2016-01-27
RU2013134233A (ru) 2015-01-27
EP2468874A1 (fr) 2012-06-27
ES2507240T3 (es) 2014-10-14
MY160137A (en) 2017-02-28
CN103370419A (zh) 2013-10-23
EP2468874B1 (fr) 2014-06-25
CA2826421A1 (fr) 2012-06-28

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