EP3529299A1 - Composition pour le traitement aerobie de residus ligno-cellulosiques, procede associe et leur utilisation pour un pretraitement biologique desdits residus - Google Patents
Composition pour le traitement aerobie de residus ligno-cellulosiques, procede associe et leur utilisation pour un pretraitement biologique desdits residusInfo
- Publication number
- EP3529299A1 EP3529299A1 EP17794010.3A EP17794010A EP3529299A1 EP 3529299 A1 EP3529299 A1 EP 3529299A1 EP 17794010 A EP17794010 A EP 17794010A EP 3529299 A1 EP3529299 A1 EP 3529299A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- residues
- lignocellulosic
- composition according
- lignin
- treatment
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/02—Pretreatment of the raw materials by chemical or physical means
- D21B1/021—Pretreatment of the raw materials by chemical or physical means by chemical means
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
-
- 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
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
-
- 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
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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- 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
Definitions
- the present invention relates to the field of degradation of agricultural residues, and more particularly to the degradation of lignocellulosic agricultural residues, such as straws.
- the invention also relates to a composition for degrading these lignocellulosic residues, a treatment method implementing such a composition, and its use as a biological treatment of said residues.
- lignocellulosic residues are among the slowest to be degraded during anaerobic digestion.
- this lignocellulosic biomass comprises on the one hand cellulose fibers and hemi-cellulosic fibers, forming the holocellulose, and on the other hand a matrix based on lignin, a heteropolymer which constitutes a protective barrier of cellulose fibers and hemicellulose.
- the anaerobic biodegradation of straws (which are lignocellulosic residues) in the digesters (to produce methane) can be slow and exceed 40 days.
- a first object of the invention is therefore to provide a method of treating these lignocellulosic residues to facilitate or accelerate their digestion in anaerobic digesters such as methanizers.
- Another object of the invention is to provide an agent and a process for destructuring the lignin-based matrix of these lignocellulosic residues, with a view to increasing the accessibility of the cellulosic fibers, thereby allowing degradation of the cellulosic fibers. thus released.
- the present invention therefore relates to a composition for the treatment of agricultural plant residues, especially lignocellulosic residues, straw type, characterized in that it comprises a liquid mixture of an aqueous solution containing inorganic salts NPK, capable of forming a nutrient medium for endogenous microorganisms of said agricultural residues to be treated, and a lignin source derived from an alkaline delignification process of lignocellulosic biomasses.
- the source of lignin is lignin obtained from the Kraft process of the pulp industries, called Kraft lignin.
- the examples presented below show a synergy between the NPK nutrient salts and the Kraft lignin to increase the accessibility of cellulose to cellulases of lignocellulosic residues.
- the concentration of lignin in said liquid mixture is preferably between 0.1 g / l and 3 g / l, preferably between 1 g / l and 2.5 g / l, more preferably between 2 g / l and 2 g / l. , 5 g / L.
- Lignin preferably Kraft lignin, is advantageously added to the solution of NPK mineral salts.
- the aqueous solution containing the NPK mineral salts it preferably comprises from 10 to 300 mmol / L of potassium K, from 20 to 200 mmol / L of phosphorus P and from 5 to 100 mmol / L of nitrogen N.
- the aqueous solution containing the NPK inorganic salts comprises molar ratios N: P advantageously between 1: 10 and 1: 1 and P: K between 1: 5 and 10: 1.
- N is present in the form of ammonium ions and phosphorus P in the form of phosphate ions.
- the present invention also relates to the process for treating agricultural plant residues, in particular straw-like lignocellulosic residues, characterized in that it comprises a treatment step by contacting said lignocellulosic residue in an aerobic medium, with a composition as described above, said treatment leading to an increase in the accessibility of cellulose to cellulases of said lignocellulosic residue.
- Lignocellulosic agricultural plant residues may be selected from cereal straws, such as wheat, rapeseed, maize, barley, oat, rye straw, preferably rapeseed straw.
- This straw can be used raw, uncut, or cut only to reduce its size or adapt its length to the dimensions of the reactor. It does not require any special preparation.
- the process according to the invention is advantageously carried out in a reactor in which are placed said lignocellulosic residues, continuously impregnated with said aqueous mixture, having a redox potential greater than 100 mV, preferably between 150 mV and 500 mV.
- this aerobic treatment can be carried out only in the presence of endogenous microorganisms of said agricultural residues to be treated, that is to say without introducing into the reactor, other microorganisms than those initially present in said residues.
- the ratio of the chemical oxygen demand (COD) of the lignocellulosic residues to the chemical oxygen demand (COD) of the aqueous starting mixture is between 4 and 50, preferably between 5 and 20, more preferably between 6 and 10.
- composition according to the invention as well as the treatment method described above may in particular be used:
- Figure 1 is a diagram of a reactor for carrying out the method according to the invention
- Figure 2 groups diagrams showing the accessibility to cellulose of the various agents tested on rapeseed straw
- Figure 3 shows the relative proportions of the different fractions of the lignocellulosic residues after the various treatments (11 days) tested: soluble fractions, cellulose, hemicellulose and lignin (Van Soest method)
- composition according to the present invention is given by the mixture comprising the following constituents:
- M9 -mixture of nutrient salts called M9 (Sigma-Aldrich supplier reference M6030) comprising the following NKP mineral salts:
- Na2HPO4 6.8 g / L
- KH2PO4 3.0 g / L
- NaCl, 0.5 g / L
- NH4Cl 1.0 g / L-water
- FIG. 1 An example of a reactor used to implement the method according to the present invention is shown in FIG.
- the reactor 1 of cylindrical shape has two thermostatically controlled walls 2. It is equipped with a feed circuit 3 in aqueous solution (composition according to the invention of Example 1 or other test solution) which feeds said reactor by means of
- This aqueous supply circuit 3 comprises, in its upper part, a spray nozzle 5, and in its lower part, an outlet 6 taking up the liquid at the bottom 9 of the reactor 1.
- the lignocellulosic residues 11 to be treated are placed on a grid 10 disposed at a distance from the bottom 9 of the reactor. Since the treatment in said reactor 1 takes place in an aerobic environment, an injection of air is provided in the bottom 9 of the reactor by means of the air inlet 7. The exhaust air and the gases emitted escape from the reactor by the exit 8.
- the reactor is thermostated at a temperature of between 22 and 38.degree. C., more preferably around 30.degree.
- the pH of the solution is neutral (between 6.5 and 7.5).
- the redox potential of the solution which must be at least 100 mV, is monitored.
- the solid lignocellulosic residue on the grid 10 is permanently impregnated with the aqueous solution which is sprayed continuously over it, but separated from the stagnant solution at the bottom of the reactor prior to recycling.
- the amount of solution is of course adapted to the amount of lignocellulosic residues: in order to be able to humidify it permanently, the solid ratio of the mass of the residue relative to the quantity of the liquid must not be greater than 2.
- the flow rate of the aqueous solution is adjusted to around 100 ml per minute. Air is also permanently injected at a rate of 25 mL per minute.
- M9 nutrient solution (see formulation in example 1)
- Aerobic treatments were performed for 1 1 days with measurements at 3, 5, 7 and 11 days, respectively, the rate of accessibility to cellulose (CAC). This measure of the accessibility of residues to cellulase was carried out according to the method of Hong and Zhang (Langmuir, 23, 12535-12540, 2007), on samples immediately after sampling (not frozen).
- composition according to the invention allows a very significant increase in accessibility to cellulose after only three days of aerobic treatment.
- Fractionation was performed using the Van Soest method (Van Soest et al J Dairy Sci, 74, 3583-3597, 1991). This method makes it possible, by fractionating the residues chemically with the aid of neutral or acidic detergents, to determine the respective cellulosic, hemi-cellulosic or lignin fractions as well as the water-soluble fraction.
- the lignin fraction remains constant while the cellulosic and hemi-cellulosic fractions decrease.
- the increase in accessibility to cellulose by means of the composition according to the invention is therefore linked to a destructuration of this lignocellulosic biomass, which leads to a release of the cellulosic fibers.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Mechanical Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Paper (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Fertilizers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1660188A FR3057874B1 (fr) | 2016-10-20 | 2016-10-20 | Composition pour le traitement aerobie de residus ligno-cellulosiques, procede associe et leur utilisation pour un pretraitement biologique desdits residus |
| PCT/FR2017/052841 WO2018073524A1 (fr) | 2016-10-20 | 2017-10-16 | Composition pour le traitement aerobie de residus ligno-cellulosiques, procede associe et leur utilisation pour un pretraitement biologique desdits residus |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3529299A1 true EP3529299A1 (fr) | 2019-08-28 |
Family
ID=59381313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP17794010.3A Withdrawn EP3529299A1 (fr) | 2016-10-20 | 2017-10-16 | Composition pour le traitement aerobie de residus ligno-cellulosiques, procede associe et leur utilisation pour un pretraitement biologique desdits residus |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20190249362A1 (fr) |
| EP (1) | EP3529299A1 (fr) |
| CN (1) | CN109890874B (fr) |
| FR (1) | FR3057874B1 (fr) |
| WO (1) | WO2018073524A1 (fr) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2663628A (en) * | 1950-06-29 | 1953-12-22 | Alfred M Thomsen | Method of making a lignin fertilizer base |
| CN1164531C (zh) * | 2002-11-11 | 2004-09-01 | 张夫道 | 纳米级磺化木质素混聚物肥料包膜胶结剂生产方法 |
| CN101081795A (zh) * | 2006-06-02 | 2007-12-05 | 天津市汉沽区福祥肥料加工厂 | 利用造纸黑液制造肥料包膜胶结剂的方法 |
| EP2142573A4 (fr) * | 2007-04-19 | 2013-02-27 | Mascoma Corp | Prétraitement thermochimique combiné et raffinage de biomasse lignocellulosique |
| CN101985409B (zh) * | 2010-12-09 | 2013-02-27 | 福建省农业科学院土壤肥料研究所 | 一种胶粘型控释肥料及其制备方法 |
| CN104487405B (zh) * | 2012-03-07 | 2016-08-24 | 英派尔科技开发有限公司 | 木素基多用途肥料 |
| GB201303521D0 (en) * | 2013-02-27 | 2013-04-10 | Bio Sep Ltd | Process operations for biomass fractionation |
| US20160355444A1 (en) * | 2013-12-31 | 2016-12-08 | University Of Saskatchewan | Biomass processing methods and systems |
-
2016
- 2016-10-20 FR FR1660188A patent/FR3057874B1/fr active Active
-
2017
- 2017-10-16 WO PCT/FR2017/052841 patent/WO2018073524A1/fr not_active Ceased
- 2017-10-16 EP EP17794010.3A patent/EP3529299A1/fr not_active Withdrawn
- 2017-10-16 CN CN201780065017.7A patent/CN109890874B/zh active Active
- 2017-10-16 US US16/342,000 patent/US20190249362A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| CHEN YUEHUI ET AL: "Kraft lignin biodegradation by Novosphingobium sp. B-7 and analysis of the degradation process", BIORESOURCE TECHNOLOGY, vol. 123, 1 November 2012 (2012-11-01), AMSTERDAM, NL, pages 682 - 685, XP093062361, ISSN: 0960-8524, DOI: 10.1016/j.biortech.2012.07.028 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109890874A (zh) | 2019-06-14 |
| CN109890874B (zh) | 2021-08-13 |
| WO2018073524A1 (fr) | 2018-04-26 |
| FR3057874A1 (fr) | 2018-04-27 |
| FR3057874B1 (fr) | 2020-06-19 |
| US20190249362A1 (en) | 2019-08-15 |
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