EP2489780A1 - Procédé intégré pour le fractionnement sélectif et la séparation de la lignocellulose en ses principaux composants - Google Patents

Procédé intégré pour le fractionnement sélectif et la séparation de la lignocellulose en ses principaux composants Download PDF

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Publication number
EP2489780A1
EP2489780A1 EP20110154705 EP11154705A EP2489780A1 EP 2489780 A1 EP2489780 A1 EP 2489780A1 EP 20110154705 EP20110154705 EP 20110154705 EP 11154705 A EP11154705 A EP 11154705A EP 2489780 A1 EP2489780 A1 EP 2489780A1
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Prior art keywords
aqueous phase
solvent
organic phase
carboxylic acid
phase
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German (de)
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EP2489780B1 (fr
Inventor
Pablo Dominguez De Maria
Thorsten vom Stein
Philipp Grande
Walter Leitner
Fabrizio Sibilla
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Rheinisch-Westfaelische Technische Hochschule Aach
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Rheinisch Westlische Technische Hochschuke RWTH
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Priority to PCT/EP2012/000656 priority patent/WO2012110231A1/fr
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/222—Use of compounds accelerating the pulping processes

Definitions

  • the present invention relates to a method for processing lignocellulose, comprising the step of contacting a lignocellulosic substrate with a biphasic liquid system.
  • Lignocellulose in particular, but not restricted to, "wood" is mainly composed of three components: lignin, hemicellulose (composed of sugars: principally xylose, galactose, glucose), and cellulose (composed of glucose).
  • lignin hemicellulose
  • hemicellulose hemicellulose
  • glucose cellulose
  • a selective lignocellulose fractionation into these three components may lead to a number of useful chemicals and commodities. These compounds can be used as such, or conversely can be employed via further modifications, (bio)chemical derivatizations, etc.
  • lignin can be used in the fragrance or food industry, as a thermoplastic, as a source of phenolic derivatives, or directly as a biofuel.
  • xylose provides xylitol and furfural.
  • microorganisms able to metabolize C 5 sugars to produce fuels and other bio-based commodities.
  • cellulose pulps are used in pulp & paper industries, as well as a source of C 6 fermentable sugars (to produce fuels or chemical building blocks).
  • the cosolvents employed in the organosolv processes are miscible with water at least during the conditions under which the extraction is performed.
  • strong conditions of pressure and temperature must be applied, leading again to degradation problems.
  • alcoholic co-solvents have the disadvantage that etherification and by-product formation might happen under the acidic conditions of an organosolv process ( ChemSusChem, 2010, 3, 1349 ).
  • inert and bio-based, water-non-miscible solvents may represent an interesting approach for an efficient and in situ lignocellulose fractionation.
  • Tetrahydrofuran THF
  • Johansson et al., Biomass 1987, 13, 45-65 organosolv processes
  • problems of delignification may be expected under mild reaction conditions.
  • US 5,730,837 discloses a method for separating lignocellulosic material into (a) lignin, (b) cellulose, and (c) hemicellulose and dissolved sugars.
  • Wood or herbaceous biomass is digested at elevated temperatures in a single-phase mixture of alcohol, water and a water-immiscible organic solvent (e.g., a ketone). After digestion, the amount of water or organic solvent is adjusted so that there is a phase separation.
  • the lignin is present in the organic solvent
  • the cellulose is present in a solid pulp phase
  • the aqueous phase includes hemicellulose and any dissolved sugars.
  • WO 1995/18260 A1 is concerned with a method of delignifying wood or plant material, both virgin and post-consumer with a recyclable liquid composition
  • a recyclable liquid composition comprising sodium silicate up to 2.5%, sodium hydroxide up to 2.5%, alkyl or dialkyl glycol ether and/or diglycol ether and/or propylene glycol ether in an amount of 10 to 40%, hydrogen peroxide up to 10%, triethylamine and/or diethylmethylamine and/or dimethyl pyridine and/or methyl pyridine and/or methyl piperidine up to 10% and water to give 100%.
  • the liquid composition has a lower critical solution temperature between about 0 °C and about 100 °C and the method comprises heating said wood or plant material with an effective amount of said liquid composition to release lignin from said wood or plant material.
  • the above-mentioned international patent application also discloses a method of delignifying a lignin-containing plant-derived material with a recyclable liquid composition comprising water and an organic compound which can be azeotropically purified, said liquid composition having a lower critical solution temperature of between 0 °C and 100 °C above which lower critical solution temperature said liquid composition divides into a heavier aqueous phase and a lighter organic phase.
  • This method comprises treating said lignin-containing plant derived material with a lignin-removing amount of said liquid composition at a temperature between 100 °C and 210 °C for sufficient time to release lignin from said lignin containing plant-derived material.
  • the method according to the invention provides a novel approach for selective lignocellulose fractionation.
  • Carboxylic acid catalysts depolymerize hemicellulose selectively with the possibility of mild conditions being employed, whereas cellulose-pulp is not hydrolyzed.
  • the set-up of a two-phase system affords the selective hemicellulose hydrolysis, together with efficient in situ cellulose-pulp delignification and in situ lignin extraction into the organic phase. Water-soluble sugars remain in the aqueous phase and may be collected for further processing. Insoluble cellulose-pulp is then accessible for subsequent efficient enzymatic hydrolysis to afford glucose.
  • the reagents and solvents used can be derived from bio-based resources.
  • organic solvent for example bio-based 2-methyltetrahydrofuran (2-MTHF) may be used, showing excellent properties for lignin extraction, as well as for delignification of cellulose pulp fibers.
  • the lignocellulosic substrate (which may also be referred to as lignocellulosic feedstock) used may be any lignocellulose containing biomass such as wood or pre-processed lignocellulose.
  • lignocellulosic feedstock may be any lignocellulose containing biomass such as wood or pre-processed lignocellulose.
  • examples include, but are not limited to, non-woody plant biomass, cultivated crops such as, but not limited to grasses, for example, but not limited to, C4 grasses, such as switch grass, cord grass, rye grass, miscanthus, reed canary grass, or a combination thereof, sugar processing residues, for example, but not limited to, baggase, beet pulp, or a combination thereof, agricultural residues, for example, but not limited to, soybean stover, corn stover, rice straw, rice hulls, barley straw, corn cobs, wheat straw, canola straw, oat straw, oat
  • the lignocellulosic substrate may comprise cellulosic waste material or forestry waste materials such as, but not limited to, newsprint, cardboard and the like.
  • the lignocellulosic substrate may comprise one species of fiber or, alternatively, it may comprise a mixture of fibers that originate from different lignocellulosic feedstocks.
  • the lignocellulosic substrate may comprise fresh lignocellulosic feedstock, partially dried lignocellulosic feedstock, fully dried lignocellulosic feedstock, or a combination thereof.
  • the reaction vessel for step a) may be a batch reactor or a continuous reactor. Hence, the method according to the invention may be performed as a batch or a continuous process. If desired, the reaction vessel may be equipped with stirrers, solvent reflux or pressurizing installations.
  • the lignocellulosic substrate is contacted with a biphasic liquid system.
  • a biphasic liquid system This is to be understood as the liquid system having two distinct liquid phases under the conditions of the method according to the invention.
  • the initial lignocellulosic substrate is present as a third, solid phase.
  • Other solid phases such as heterogenous catalysts, molecular sieves, ion exchangers, solid-state acids and the like are also possible.
  • a gas phase for example for pressurizing the reactor, may also be present.
  • aqueous phase As a first constituent of the biphasic liquid system an aqueous phase is present. In the aqueous phase the catalyst is preferably dissolved.
  • the second constituent of the biphasic system is an organic phase which is at least partially immiscible with the aqueous phase.
  • at least partially immiscible means that two distinct liquid phases are visible to the naked eye of an observer.
  • the second, organic phase comprises a solvent selected from the group comprising esters, lactones, ethers and/or cyclic ethers.
  • the solvent should be chosen to award a desired lignin extraction under the other boundary conditions of the method such as solvent recovery temperatures and the like.
  • esters include bio-based polypropanediol di-esters with fatty acids and diethyl succinate.
  • An example for a bio-based ether is an end-capped polypropylene glycol polyether.
  • An example for a bio-based cyclic ether is methyltetrahydrofuran.
  • a further proviso is that said solvent does not comprise a hydroxyl group or hydroxyl groups. This is based on the reasoning that OH groups might lead to undesired side reactions with other alcohols, the lignocellulose or with components extracted therefrom during the method according to the invention.
  • carboxylic acid catalyst examples include monocarboxylic acids, dicarboxylic acids and tricarboxylic acids such as formic acid, acetic acid, propanic acid, butyric acid, malonic acid, succinic acid, glutaric acid, adipinic acid, maleic acid, fumaric acid, lactic acid, malic acid, tartaric acid, citric acid and/or oxalic acid.
  • An advantage of using carboxylic acid catalysts is that they may be recovered from aqueous solutions by crystallization.
  • carboxylic acid catalyst monoesters of carboxylic acids and diesters of carboxylic acids, provided that there is at least one remaining COOH functional group present in the molecule.
  • step a) is performed at a temperature of ⁇ 85 °C to ⁇ 150 °C. Below this temperature range the reaction rate might be slower than desired and above this range cellulose depolymerization might occur to an undesired extent.
  • a preferred temperature range is ⁇ 125 °C to ⁇ 140 °C.
  • step a) is performed under a pressure of ⁇ 5 bar to ⁇ 25 bar.
  • Preferred ranges are ⁇ 10 bar to ⁇ 20 bar.
  • Pressurizing the reaction system can afford the biphasic liquid system even if the process temperature is above the boiling point of one of the constituents of the biphasic system.
  • the pressure may be raised to a level at which 2-MTHF is liquid at 140 °C.
  • the pressure may be applied via gases such as CO 2 or N 2 .
  • step a) is performed for a duration of ⁇ 2 hours to ⁇ 6 hours.
  • a preferred duration is ⁇ 2.5 hours to ⁇ 3.5 hours.
  • the carboxylic acid catalyst is selected from the group comprising dicarboxylic acids and/or monoesters of dicarboxylic acids. It is preferred that the carboxylic acid catalyst comprises oxalic acid and most preferred that that the carboxylic acid catalyst is oxalic acid.
  • the carboxylic acid catalyst is present in an amount of ⁇ 0.5 weight-% to ⁇ 2 weight-% in the first, aqueous phase.
  • the weight percentage is to be understood as the amount of the catalyst in the aqueous phase before contacting the aqueous phase with other phases such as the organic phase or the lignocellulosic substrate.
  • the catalyst amount is ⁇ 0.9 weight-% to ⁇ 1.8 weight-%.
  • the catalyst loading may be expressed as the molar concentration in the total liquid volume of the first, aqueous phase.
  • the catalyst loading may be ⁇ 0.05 M (in total liquid volume) to ⁇ 0.15 M (in total liquid volume).
  • the solvent in the second, organic phase comprises 2-methyltetrahydrofuran and/or 3-methyltetrahydrofuran. It is preferred that the solvent in the second, organic phase is 2-methyltetrahydrofuran and/or 3-methyltetrahydrofuran. Most preferred is 2-methyltetrahydrofuran (2-MTHF) as an extractive phase, as it can be derived from biomass, exhibits a miscibility gap with water, and has a boiling point (ca. 80 °C) that enables straightforward separation and recycling by distillation.
  • 2-MTHF 2-methyltetrahydrofuran
  • a combination of 2-MTHF as the solvent in the second, organic phase and oxalic acid as the carboxylic acid catalyst has proven to be particularly suited for carrying out the method according to the invention.
  • steps b1) to b3) a recycling of the carboxylic acid catalyst is effected.
  • the catalyst may be recovered by crystallization.
  • the sugar-containing mother liquor can then be further processed.
  • steps c1) to c3) With the additional procedure of steps c1) to c3) a recycling of the organic solvent is possible. At the same time the lignin dissolved therein is collected.
  • suitable solvent removal techniques include distillation and membrane separation.
  • step a) The aforementioned steps of group b1 to b3) and of group c1 to c3) may be performed sequentially. It is also possible to perform them independent of each other. Another example for a suitable procedure is to perform a batch run according to step a), remove the obtained cellulose-pulp by filtration and then to recover and recycle the catalyst and the organic solvent.
  • FIG. 1 The overall process concept is shown schematically in FIG. 1 in which lignocellulosic biomass is subjected to mild (T ⁇ 150 °C) carboxylic acid catalyzed hydrolysis in a biphasic reaction mixture comprising an aqueous phase and an immiscible organic phase.
  • a reaction vessel 10 is charged with a biphasic reaction mixture comprising a first, aqueous phase 12 and an immiscible, second organic phase 11 in the form of a cyclic ether such as 2-methyltetrahydrofuran (2-MTHF).
  • the aqueous phase 12 comprises a dicarboxylic acid such as oxalic acid as a catalyst.
  • the temperature within the reaction vessel 10 may be preferably chosen to be between 80 °C and 140 °C.
  • the reaction vessel 10 is charged with a lignocellulosic biomass by way of stream 13.
  • the mild conditions together with the choice of, for example, oxalic acid as catalyst lead to the selective hydrolysis of amorphous hemicellulose yielding soluble sugars (mostly xylose) in the aqueous phase 12.
  • lignin is dissolved in the organic phase 11.
  • the product mixture is removed from the reaction vessel 10 via stream 14 and entered into a first separation unit 15.
  • the organic phase is entered as stream 16 into a second separation unit 19 which may be a distillation unit. Recovered organic phase is recycled into reaction vessel 10 via stream 21. Lignin obtained in the second separation unit 19 is carried out as stream 23.
  • the catalyst may be separated from the aqueous stream 18 leaving the first separation unit 15 by crystallization in a third separation unit 20 before further processing and is recycled into the process via stream 22.
  • Hemicellulose sugars may be extracted from the aqueous stream in the third separation unit 20 as stream 24.
  • the remaining biopolymers cellulose and lignin separate from each other owing to their very different structures and solubility properties.
  • the cellulose stays insoluble as solid pulp and can be filtered off as stream 17 from the fist separation unit 15 for subsequent enzymatic hydrolysis into glucose.
  • the pulp should be free of lignin, which is extracted in situ into the organic phase 11 of the biphasic reaction system as already described.
  • Oxalic acid, 2-methyltetrahydrofuran (2-MTHF), Avicel®, and reagents for PAHBAH colorimetric method were obtained from Sigma-Aldrich, and were used without further purification. Beech wood with a defined size (0.5-0.8 mm) was used. Accellerase-1500® was supplied by Genencor (the Netherlands).
  • Standard procedure for lignocellulose fractionation Wood loadings (50-100 gL -1 ) were suspended in water with oxalic acid (0.1 M) (5 mL). As organic phase, 2-MTHF (5 mL) was added, and the mixture transferred to a stainless steel high pressure reactor and pressurized with CO 2 (10-20 bar). The temperature was set between 125-150 °C for the indicated reaction time. After cooling and depressurization of the reactor, the organic phase was separated by decantation and 2-MTHF was evaporated to obtain the lignin fraction. The aqueous phase was filtered to isolate the cellulose pulp, and xylose and glucose concentrations were determined in the aqueous phase. The solid residue (mostly pulp) was washed with ethanol and dried until constant weight.
  • Enzymatic procedure Cellulose-pulp or Avicel® (20 gL -1 ) were suspended in citrate buffer pH 4.5 (20 mL), at 50 °C for several hours. Accellerase-1500® was then added (1 v%). Aliquots of the reactions were taken, heated to 100 °C for 5 minutes to denaturalize the enzymes and stop the process, and stored at -20 °C until colorimetric analysis was conducted. The amount of reducing ends was determined using the PABAH method ( M. Lever, Anal. Biochem.
  • Xylose and glucose determination HPLC: HPLC measurements were carried out on a Jasco HPLC equipped with a SUGARSH1011 column with 0.01 wt% aqueous acetic acid solution as eluent. Flow rate was set to 0.6 mL min -1 and samples of 30 ⁇ L were injected. Amounts of xylose and glucose present in the hemicellulose fraction were determined based on calibration curves built with commercially available real substrates.
  • Procedure for oxalic acid recycling The aqueous phases from a representative experiment for lignocellulose fractionation were concentrated 4-fold by evaporating water. The concentrated aqueous solution was stored at 10 °C for 15 h. Under these conditions up to 85% of oxalic acid crystallized in the form of needle-like crystals. The crystals were filtered off and subjected to HPLC and NMR analysis, and subsequently re-used directly in the process.
  • beech wood was taken as a prototypical lignocellulosic substrate with an approximate (variable) composition of 15-25% hemicellulose, 15-30% lignin, and 40-50% cellulose, together with some other minor components (salts, waxes, etc).
  • a first set of experiments was conducted with various variations of the multi-component reactive system and at different temperatures (85-150 °C). The reactions were carried out either under reflux conditions or in high-pressure reactors in the presence of additional CO 2 pressure to ensure a liquid reactive system at temperatures above the solvent's boiling point. Representative results are listed in Table 1.
  • Table 1 Oxalic acid-catalyzed fractionation of beech wood in an aqueous/organic biphasic reaction system. Typical reaction conditions: beech wood (0.5-0.8 mm, 100 g L -1 in aqueous phase), oxalic acid 0.1 M (in total liquid volume), biphasic system water-2-methyltetrahydrofuran (2-MTHF) (1:1 v/v, 10 mL total), 6 hours reaction time. Entry Organic phase T (°C) p CO 2 (bar) a Soluble Sugars b Lignin (wt%) c Solid residue (wt%) d Xylose (wt%) Glucose (wt%) 1 2-MTHF 85 Reflux 4.0 n.d.
  • beech wood 0.5-0.8 mm, 100 g L -1 in aqueous phase
  • oxalic acid 0.1 M in total liquid volume
  • biphasic system water-2-methyltetrahydrofuran (2-MTHF) (1:
  • glucose was also formed during the hydrolysis.
  • the amount of glucose was in the range of 2-3% at temperatures between 125-140 °C. This level is consistent with the glucose fraction in hemicellulose.
  • glucose formation increased rapidly when temperatures higher than 140 °C were set in the reactor. This additional glucose production is likely to have arisen from cellulose depolymerization, which is known to start at temperatures of 150 °C in the presence of organic acids.
  • higher temperatures lead to a decrease in selectivity for biomass fractionation, which adversely affects the potential as feedstock for the three main (pure) components of lignocellulose.
  • the aqueous phase in the experiments contained large amounts of the oxalic acid catalyst. Gratifyingly, this can be recovered and re-used in an efficient and clean manner. Under non-optimized conditions, it was observed that by reducing the volume of the aqueous phase to one fourth and cooling it down to 4 °C, approximately 85% of the originally charged oxalic acid crystallized within 15 hours and could be recovered by simple filtration. The oxalic acid showed high purity and could be used as catalyst again without further processing or activation.
  • the solid residue (mostly pulp) constituted the third feedstock stream from the separation method which was readily isolated by filtration from the reaction mixture after removal of the 2-MTHF, and washed with ethanol.
  • the mass of the crude material (50-58 wt%, Table 1) corresponds fairly well with the amount of cellulose in beech wood.

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EP11154705.5A 2011-02-16 2011-02-16 Procédé intégré pour le fractionnement sélectif et la séparation de la lignocellulose en ses principaux composants Not-in-force EP2489780B1 (fr)

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PCT/EP2012/000656 WO2012110231A1 (fr) 2011-02-16 2012-02-15 Processus intégré de fractionnement sélectif et de séparation de la lignocellulose en ses composants principaux

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WO2014132056A1 (fr) * 2013-02-27 2014-09-04 Bio-Sep Limited Opérations de procédé pour le fractionnement d'une biomasse
WO2014132055A1 (fr) * 2013-02-27 2014-09-04 Bio-Sep Limited Optimisation du traitement d'une biomasse
WO2014176531A2 (fr) 2013-04-27 2014-10-30 The Regents Of The University Of California Utilisation d'un co-solvant pour produire des intermédiaires réactifs à partir de biomasse
US20150176090A1 (en) * 2013-12-20 2015-06-25 Wisconsin Alumni Research Foundation Biomass pre-treatment for co-production of high-concentration c5- and c6-carbohydrates and their derivatives
EP3689847A1 (fr) * 2018-11-15 2020-08-05 CMP-Cimentos Maceira e Pataias S.A. Procédé thermochimique catalytique et continu de production de dérivés profitables à partir de matières organiques et de déchets
US11066525B2 (en) 2014-01-13 2021-07-20 Upm-Kymmene Corporation Method and apparatus for separating lignocellulose particle fraction and lignin particle fraction, lignin particle composition, lignocellulose particle composition and their use
WO2021245440A1 (fr) * 2020-06-02 2021-12-09 Cmp-Cimentos Maceira E Pataias , S.A. Procédé thermochimique et continu de production de dérivés de valeur à partir de matières et/ou de déchets organiques

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US20210269616A1 (en) 2018-06-25 2021-09-02 Katholieke Universiteit Leuven Fractionation and depolymerisation of lignocellulosic material
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US9863090B2 (en) 2013-02-27 2018-01-09 Bio-Sep Limited Process operations for biomass fractionation
WO2014132055A1 (fr) * 2013-02-27 2014-09-04 Bio-Sep Limited Optimisation du traitement d'une biomasse
CN105358581B (zh) * 2013-02-27 2019-03-15 保赛有限公司 生物质分级分离的工艺操作
CN105408544B (zh) * 2013-02-27 2018-10-19 保赛有限公司 生物质工艺优化
CN105408544A (zh) * 2013-02-27 2016-03-16 保赛有限公司 生物质工艺优化
US10000891B2 (en) 2013-02-27 2018-06-19 Bio-Sep Limited Biomass process optimisation
WO2014132056A1 (fr) * 2013-02-27 2014-09-04 Bio-Sep Limited Opérations de procédé pour le fractionnement d'une biomasse
EP2989207A4 (fr) * 2013-04-27 2016-11-23 Univ California Utilisation d'un co-solvant pour produire des intermédiaires réactifs à partir de biomasse
WO2014176531A2 (fr) 2013-04-27 2014-10-30 The Regents Of The University Of California Utilisation d'un co-solvant pour produire des intermédiaires réactifs à partir de biomasse
US10774394B2 (en) 2013-04-27 2020-09-15 The Regents Of The University Of California Co-solvent to produce reactive intermediates from biomass
US9359650B2 (en) * 2013-12-20 2016-06-07 Wisconsin Alumni Research Foundation Biomass pre-treatment for co-production of high-concentration C5- and C6-carbohydrates and their derivatives
US20150176090A1 (en) * 2013-12-20 2015-06-25 Wisconsin Alumni Research Foundation Biomass pre-treatment for co-production of high-concentration c5- and c6-carbohydrates and their derivatives
US11066525B2 (en) 2014-01-13 2021-07-20 Upm-Kymmene Corporation Method and apparatus for separating lignocellulose particle fraction and lignin particle fraction, lignin particle composition, lignocellulose particle composition and their use
EP3689847A1 (fr) * 2018-11-15 2020-08-05 CMP-Cimentos Maceira e Pataias S.A. Procédé thermochimique catalytique et continu de production de dérivés profitables à partir de matières organiques et de déchets
WO2021245440A1 (fr) * 2020-06-02 2021-12-09 Cmp-Cimentos Maceira E Pataias , S.A. Procédé thermochimique et continu de production de dérivés de valeur à partir de matières et/ou de déchets organiques

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