WO2014087015A1 - Process for the isolation of levulinic acid and formic acid - Google Patents
Process for the isolation of levulinic acid and formic acid Download PDFInfo
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- WO2014087015A1 WO2014087015A1 PCT/EP2013/075961 EP2013075961W WO2014087015A1 WO 2014087015 A1 WO2014087015 A1 WO 2014087015A1 EP 2013075961 W EP2013075961 W EP 2013075961W WO 2014087015 A1 WO2014087015 A1 WO 2014087015A1
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- WIPO (PCT)
- Prior art keywords
- acid
- condensate
- levulinic acid
- aqueous phase
- washing
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- 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
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/40—Extractive distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
Definitions
- the present invention relates to a process for the isolation of levulinic acid and formic acid.
- Levulinic acid is a starting molecule for the synthesis of esters known as fuel additive and is known to be useful as plasticisers and solvents.
- Levulinic acid can be used to synthesize methyl tetrahydrofuran (MTHF) or can be used as a solvent.
- Other applications of levulinic acid are for example the synthesis of delta-amino levulinic acid used as herbicides and pesticides, diphenolic acid used to synthesize polycarbonates and succinic acid used to make polyesters.
- Levulinic acid can also be used to produce gamma valerolactone (5-methylbutyrolactone), which in turn can be used for production of adipic acid (1 ,6-hexanedioic acid).
- Formic acid is used as a preservative and antibacterial agent in livestock feed, in the production of leather, and in dyeing and finishing of textile. It is also used as coagulant in the production of rubber as well as cleaning agent assistant and potential future fuel for fuel cells.
- US2010/0324310 relates to the production of both formic acid and levulinic acid.
- a problem of the process of US2010/0324310 is that the yield, particular of levulinic acid, is insufficient.
- the invention provides an improved process for the isolation of levulinic acid and formic acid from a composition comprising formic acid and levulinic acid, said process comprising a solid-liquid separation step, a vapor removal step, and a solvent- solvent extraction step, wherein a vapor condensate and/or an aqueous phase from the solvent extraction is used to wash the solid fraction. Washing with a vapor condensate results in higher levulinic acid yields (higher levulinic acid recovery) as compared to washing with normal water. Washing with aqueous phase results in a less compressible filter cake. Washing first with aqueous phase and subsequently with vapor condensate results in even higher levulinic acid yields.
- the process is suitable for isolating levulinic acid and formic acid from compositions made by acid hydrolysis of a lignocellulosic biomass, and also from compositions made by acid hydrolysis of sugar such as glucose and fructose.
- the invention provides a process for the isolation of levulinic acid and formic acid from a composition comprising formic acid and levulinic acid, said process comprising a solid-liquid separation step, a vapor removal step, and a solvent-solvent extraction step, wherein a vapor condensate and/or an aqueous phase from the solvent-solvent extraction step is used to wash a solid fraction obtained by the solid- liquid separation step.
- the solid-liquid separation step and the vapor removal step can be done in any order.
- the order of the solid-liquid separation step and the vapor removal step has no effect of the washing with the condensate and/or the aqueous phase.
- the process is carried out as follows:
- composition comprising formic acid and levulinic acid to a solid- liquid separation to yield a solid fraction and a liquid fraction and recovering the liquid fraction;
- the condensate and/or the aqueous phase is used to wash the solid fraction.
- the process of the invention is carried out as follows: concentrating a composition comprising formic acid and levulinic acid to a vapor removal step to yield a concentrate and a vapor, and condensing said vapor to a condensate; subjecting the concentrate to a solid-liquid separation to yield a solid fraction and a liquid fraction and recovering the liquid fraction;
- the condensate and/or the aqueous phase is used to wash the solid fraction.
- the concentrate can be subjected to a further vapor concentration step, for example a second concentration step, a third concentration step, etceteras.
- composition comprising formic acid and levulinic acid to a solid- liquid separation to yield a solid fraction and a liquid fraction and recovering the liquid fraction;
- concentrating a composition comprising formic acid and levulinic acid to a first vapor removal step to yield a first concentrate and a first vapor, and condensing said first vapor to a first condensate;
- a condensate can refer to a single condensate, for example if the process comprises a single concentration step, or to a second, third condensate, etceteras, if the process comprises two or more concentration steps.
- the vapor of such concentration step(s) may be condensed e.g. by flashing, resulting in a condensate, and then used to wash the solid fraction. By washing of the solid fraction with condensate, any formic acid in the condensate is not be lost, but instead is retained.
- the solid fraction that is washed in the process of the invention are obtained by a solid-liquid separation such as centrifugation or filtration.
- solid fraction and “the solids” are understood to be the same, skilled person knows how to conduct solid-liquid separation. Suitable methods are filtration and centrifugation. If filtration is used, e.g. using a filter plate, die, or filter cloth, the solids are typically in the form of a filter cake. If centrifugation is used, the solids are typically in the form of a pellet.
- vapor condensate and “condensate” are understood to be the same.
- washing the solids with a condensate from a vapor results in higher yields of levulinic acid, as comparing to washing the solids with water.
- water is understood to be plain water and includes tap water and process water. It seems that a condensate is more efficient in recovering levulinic acid from solids than water. The state of the art is silent on this effect.
- US2010/0312006 mentions the formation of char, but is silent on a washing solids.
- Formic acid is isolated by extraction.
- US2010/0324310 relates to the production of both formic acid and levulinic acid.
- Example 3 the solid remaining at the end of the reaction is separated from the solution via vacuum filtration".
- US2010/0324310 is silent on recovering or washing of solids.
- US6,054,61 1 relates to the production of levulinic acid. It suggests that a cake be washed with water.
- US6,054,61 1 is silent on the isolation of formic acid and is silent on washing of solids with an aqueous phase or with a condensate, let alone that this would result in increased levulinic acid yields relative to washing with (plain) water.
- US8, 138,371 refers to formic acid obtained as a condensate stream". However, this condensate is not used to wash the solids, nor is any suggestion made thereto.
- the inventors also surprisingly found that washing with an aqueous phase results in a pellet or a filter cake which is less compressible, or less so, as compared to a filter cake or pellet which is obtained after washing with normal water.
- the skilled person knows how to wash the solids with condensate or aqueous phase.
- the resulting filter cake can be washed by passing condensate and/or aqueous phase over the filter cake.
- the solids-liquid separation comprises centrifugation, the resulting pellet can be washed by passing condensate and/or aqueous phase over said pellet.
- the pellet or filter cake can also be removed from the separation unit and be washed separately.
- washing of the solid fraction with condensate or with aqueous phase results in a washed solid fraction, and the remaining condensate or aqueous phase which is obtained after said washing is referred to as "the wash".
- the wash is typically in the form of a filtrate.
- the solid-liquid separation comprises centrifugation, the wash is typically in the form of a supernatant.
- the amount of condensate is not crucial. Already a little washing with condensate gives improved yield.
- One way to carry out washing is whilst monitoring the concentration of levulinic acid in the wash.
- the presence of levulinic acid in the wash indicates that, prior to the washing, the solid fraction comprises levulinic acid, and that this levulinic acid is recovered by the condensate.
- the concentration of the levulinic acid in the wash will decrease, until at a certain moment the concentration of levulinic acid in the wash remains more or less constant, preferably it approaches zero. Washing is preferably stopped when the concentration in the washe is more or less constant, or is or approaches zero.
- a constant concentration of levulinic acid in the wash may indicate presence of some levulinic acid in the vapor condensate, but preferably the condensate does not comprise any detectable amounts of levulinic acid.
- the skilled person can also determine the amount of formic acid in the filtrate. It is possible to combine washing with condensate and water. For example, the process may be carried out such that the solids are washed first with water, then with condensate. Alternatively, the process may be carried out such that the solids are washed first with condensate, then with water. In both embodiments, the levulinic acid will be increased as compared to washing only with water. It is also possible to combine washing with aqueous phase and water. For example, the process may be carried out such that the solids are washed first with water, then with aqueous phase. Alternatively, the process may be carried out such that the solids are washed first with aqueous phase, then with water. In both embodiments, the filter cake will be less compressible as compared to washing only with water.
- the process of the invention is particularly useful for operating in a continuous fashion.
- the condensate from the vapor concentration can simply be pumped to the solids using a pipe.
- the composition comprising formic acid and levulinic acid may comprise a biomass hydrolysate.
- said biomass comprises lignocellulosic biomass.
- the biomass may be or may be derived from grass, cereal, starch, algae, tree bark, hay, straw, leaves, paper pulp, paper sludge, or dung.
- Paper pulp, or simply pulp is a lignocellulosic fibrous material prepared by chemically or mechanically separating cellulose from wood, fibre crops or waste paper. Pulp is rich in cellulose and other carbohydrates.
- Paper sludge, or simply sludge is a lignocellulosic fibrous containing cellulose fibres too short for usage in the paper industry.
- the biomass may comprise lignocellulosic biomass.
- Lignocellulosic biomass typically has a fibrous nature and comprises a bran fraction that contains the majority of lignocellulosic (bran) fibers.
- corn fiber is a heterogeneous complex of carbohydrate polymers and lignin. It is primarily composed of the outer kernel covering or seed pericarp, along with 10-25% adherent starch. Carbohydrate analyses of corn fiber vary considerably according to the source of the material.
- the lignocellulosic biomass may comprise hemicellulose.
- the composition is a biomass hydrolysate made by acid hydrolysis of lignocellulosic biomass.
- the composition is a made by acid hydrolysis of C6 sugars, particularly of fructose or glucose or mixtures thereof.
- Sucrose C12H22O11
- Fructose can also be made by enzymatic isomerization of glucose.
- Sucrose is commonly produced from biomass such as beet, corn and cane.
- a biomass hydrolysate may be obtained by acid hydrolysis of biomass.
- Suitable acids in the acid hydrolysis of biomass or C6 sugars include sulphuric acid, hydrochloric acid, and phosphoric acid.
- a preferred acid is sulphuric acid, preferably diluted sulphuric acid, for example at a concentration between 1 .5 - 3%.
- the temperature in the acid hydrolysis may depend on the source of carbohydrates, and typically ranges between 120-250°C, preferably between 120-200°C. Said process may comprise one, two, or more stages.
- the pressure may also depend on the source of the biomass carbohydrates, as well as on the temperature, and may be anywhere between 1 and 50 bar, preferably between 5 and 40 bar, even more preferably between 10 and 30 bar.
- Suitable reactors include plugflow reactors, backmix reactors, and CSTR reactors. Different reactors for different stages may be used.
- the skilled person will understand that the reaction time for acid hydrolysis of biomass or C6 sugars depends on the reaction temperature, the pressure, as well as the source of biomass C6 sugars and the concentration of the acid. At higher reaction temperatures the reaction time may be shorter, whereas at lower reaction temperatures the reaction time may be longer. Likewise, at lower pressure, the reaction time may be longer whereas at higher pressure the reaction time may be shorter. The skilled person may therefore, without undue burden, establish suitable conditions with respect to temperature, reaction time, and pressure in order to obtain the biomass hydrolysate or C6 sugars acid hydrolysate.
- the reaction time may vary between one second and one day, preferably between 10 seconds and one hour.
- the composition preferably comprises solids which are removed by solid-liquid separation.
- the solids may comprise organic material from biomass, or tar, which are preferably removed as they are undesired in the final product (levulinic acid or formic acid).
- the composition may comprise humins.
- a problem associated with the production levulinic acid and formic acid by acid hydrolysis of biomass or C6 sugars is formation of tar or humins, which can be produced in amounts up to 10 to 50% w/w of the total reaction mixture, creating a high overall purification and separation effort.
- Tar and char represent organic material which is insoluble in water, which is dark in colour and which tends to become viscous and very dark to almost black when concentrated.
- Tar can be formed during heating of organic material, for example by pyrolysis, but is also formed when carbohydrates are subjected to acid hydrolysis, particularly when done at high temperatures.
- Char usually refers to solid material, for example the remains of solid biomass that has been incompletely combusted, such as charcoal if wood is incompletely burned.
- Tar usually refers (viscous) liquid, e.g. derived from the destructive distillation of organic matter.
- the presence of tar is undesired for a number of reasons. Firstly, its dark colour makes the product unattractive from the perspective of the user or customer. Secondly, the tar may negatively affect the performance of the bio-based product in the application. For this reason tar is preferably removed from the desired product. Yang and Sen (Chem. Sus. Chem.
- humins during production of fuels from carbohydrates such as fructose. They speculate that the humins are formed by acid-catalyzed dehydration. According to US7,896,944 the molecular weight of humins ranges from 2.5 to 300 kDa.
- Extraction takes advantage of differences in the chemical properties of the feed components, such as differences in polarity and hydrophobic/hydrophilic character to separate them (T.C. Frank, L.Dahuron, B.S. Holden, W.D. Prince, A.F. Seibert, L.C. Wilson, Liquid-liquid extraction and other liquid-liquid operations and equipment in Perry's Chemical Engineering Handbook, 8th Edition, Section 15).
- Extraction yields an aqueous phase and an organic phase.
- the organic phase preferably comprises levulinic acid and formic acid and can be used to wash the solids obtained after solid-liquid separation.
- the aqueous phase can be recovered to isolate levulinic acid from said aqueous phase, and optionally also formic acid.
- the aqueous phase can be recovered to wash the solid fraction.
- the skilled person knows how to recover the organic phase from the aqueous phase, e.g. by decanting.
- the organic solvent in the solvent-solvent extraction step comprises methyltetrahydrofuran (MTHF).
- MTHF methyltetrahydrofuran
- Washing with the condensate or with the aqueous phase may reduce water consumption as no or little external water is required.
- the washed solid fraction has been found to contain less minerals and is therefore easier and less expensive to dispose of, than when the solids are not washed, or if they are washed with water.
- the filter cake becomes surprisingly dark in colour and less compressible than if the solids were not washed, or if they were washed with condensate or with plain water.
- the process includes washing the solids with the condensate and with the aqueous phase, such that the solids are washed first with the aqueous phase and subsequently with the condensate. Washing with an organic phase and, and subsequently with a condensate has a synergistic effect.
- the inventors have found washing solids with the aqueous phase results in a washed solid fraction which is less compressible and much easier to wash, particularly when in the form of a filter cake, and when such washed solid fraction is subsequently washed with a condensate, the efficacy of the condensate to increase the levulinic acid yield is enhanced. In other words, the yield of levulinic acid after washing is further increased.
- Washing with condensate and aqueous phase can be combined with washing with water.
- the process may be carried out such that the solids are washed first with water, then with aqueous phase, then with condensate.
- the process may be carried out such that the solids are washed first with aqueous phase, then with water, then with condensate.
- the process may be carried out such that the solids are washed first with aqueous phase, then with condensate, then with water.
- the process may be carried out such that the solids are washed first with aqueous phase, then with water, then with condensate, then with water.
- the process may be carried out such that the solids are washed first with water, then with aqueous phase, then with water, then with condensate, then with water.
- Multiple washing steps with condensate and aqueous phase is also possible. It is even possible to have a washing with condensate prior to washing with aqueous phase, but in this case it is preferred to have at least one washing with condensate after said washing with aqueous phase, as the synergistic effect described above, that is, the further increase of levulinic acid when washing with aqueous phase and condensate, is achieved when at least one washing of solids is done prior to at least one washing with condensate.
- washing with both condensate and aqueous phase also advantageously results in lower sulfur content in the washed solid fraction.
- Example 1 100g wood chips were impregnated for 90 minutes. After impregnation, the temperature was raised to the reaction temperature and the slurry was hydrolyzed in the presence of approximately 5 wt% hydrosulphuric acid without stirring. The resulting biomass hydrolysate suspension was subjected to solid/liquid separation. Results of the liquid fraction and the reaction conditions are stated in Table 2.
- the liquid fraction of the biomass hydrolysate of Example 1 can be cooled via evaporation resulting in a vapor.
- the resulting vapor can be condensed resulting in an aqueous solution (to give a condensate) comprising 0.8 - 1 % formic acid, 0.02 - 0.4% acetic acid and 0 - 0.02 % levulinic acid.
- 365g of a biomass hydrolysate made according to Example 1 was filtered over a filter cloth with a pressure difference of 0.1 bar.
- the filter cake was washed three times with 50g tap water at 25°C.
- the conductivity of the wash water, an indication for the ion content (organic acids and sulfuric acid) was measured to be 225.2 mS/cm in the first filtrate, 30.02 mS/cm in the first wash, 3.52 mS/cm in the second wash and 0.786 mS/cm in the third.
- Example 2 401 g of a biomass hydrolysate made according to Example 1 was filtered over a filter cloth with a pressure difference of 0.3bar. The filter cake was washed five times with 76g of the condensate of Example 2. The concentration of levulinic acid, acetic acid and formic acid in the wash are stated in Table 3. The washing efficiency is show in Table 4. The cake is dried after the washing and analyzed. The cake is dried after the washing and analyzed. The analysis data is found in Table 5.
- Example 4 403g of a biomass hydrolysate made according to Example 1 was filtered over a filter cloth with a pressure difference of 0.3 bar. The filter cake was washed five times with 76g of a solution described in Example 6, which is an aqueous phase obtain after extraction. The concentration of levulinic acid, acetic acid and formic acid in the wash water are stated in Table 3. The washing efficiency is show in Table 4. The cake is dried after the washing and analyzed. The cake is dried after the washing and analyzed. The analysis data is found in Table 5.
- Example 3 (condensate)
- Example 4 (aqueous phase)
- a biomass hydrolysate according to Example 1 was enriched with pure levulinic acid to a levulinic acid concentration of 9.07wt% with a formic acid concentration of 1 .89wt% to simulate the flash step in Example 2.
- 2.1 kg reaction solution was 5 times extracted 1 .7kg of fresh Methyltetrahydrofuran at 60°C. After the fifth extraction 99.1 % of the levulinic acid and 98.8% of the formic acid present in the reaction solution could be collected in the organic layer.
- the extracted aqueous solution can be concentrated by the evaporation of water to yield a solution with concentration of levulinic acid of 0.6 wt%, of formic acid of 0.3wt%, of acetic acid of 0.6wt% and of sulfuric acid of 6.2wt%.
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/648,437 US9908836B2 (en) | 2012-12-07 | 2013-12-09 | Process for the isolation of levulinic acid and formic acid |
CN201380063521.5A CN104854075A (en) | 2012-12-07 | 2013-12-09 | Process for the isolation of levulinic acid and formic acid |
CA2891402A CA2891402A1 (en) | 2012-12-07 | 2013-12-09 | Process for the isolation of levulinic acid and formic acid |
EP13802369.2A EP2928857B1 (en) | 2012-12-07 | 2013-12-09 | Process for the isolation of levulinic acid and formic acid |
KR1020157017593A KR20150091155A (en) | 2012-12-07 | 2013-12-09 | Process for the isolation of levulinic acid and formic acid |
BR112015012823A BR112015012823A2 (en) | 2012-12-07 | 2013-12-09 | process for isolating levulinic acid and formic acid |
EA201500606A EA201500606A1 (en) | 2012-12-07 | 2013-12-09 | METHOD FOR ISOLATION OF LEVULINIC ACID AND FORMIC ACID |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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US201261734523P | 2012-12-07 | 2012-12-07 | |
US61/734,523 | 2012-12-07 | ||
EP12196080.1 | 2012-12-07 | ||
EP12196080 | 2012-12-07 | ||
EP13168025.8 | 2013-05-16 | ||
EP13168025 | 2013-05-16 |
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WO2014087015A1 true WO2014087015A1 (en) | 2014-06-12 |
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PCT/EP2013/075961 WO2014087015A1 (en) | 2012-12-07 | 2013-12-09 | Process for the isolation of levulinic acid and formic acid |
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US (1) | US9908836B2 (en) |
EP (1) | EP2928857B1 (en) |
KR (1) | KR20150091155A (en) |
CN (1) | CN104854075A (en) |
BR (1) | BR112015012823A2 (en) |
CA (1) | CA2891402A1 (en) |
EA (1) | EA201500606A1 (en) |
WO (1) | WO2014087015A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3115351A1 (en) * | 2015-07-10 | 2017-01-11 | GFBiochemicals Ltd. | Levulinic acid compositions |
EP3689847A1 (en) | 2018-11-15 | 2020-08-05 | CMP-Cimentos Maceira e Pataias S.A. | Catalytic and continuous thermochemical process of production of valuable derivatives from organic materials and waste |
WO2021245440A1 (en) | 2020-06-02 | 2021-12-09 | Cmp-Cimentos Maceira E Pataias , S.A. | Catalytic and continuous thermochemical process of production of valuable derivatives from organic materials and/or waste |
EP4265592A1 (en) | 2022-04-22 | 2023-10-25 | Indian Oil Corporation Limited | Method for producing levulinic acid |
Families Citing this family (1)
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CA2918150C (en) * | 2013-07-17 | 2021-03-09 | Dsm Ip Assets B.V. | Process for the isolation of levulinic acid |
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2013
- 2013-12-09 EP EP13802369.2A patent/EP2928857B1/en active Active
- 2013-12-09 KR KR1020157017593A patent/KR20150091155A/en not_active Application Discontinuation
- 2013-12-09 BR BR112015012823A patent/BR112015012823A2/en not_active IP Right Cessation
- 2013-12-09 US US14/648,437 patent/US9908836B2/en active Active
- 2013-12-09 EA EA201500606A patent/EA201500606A1/en unknown
- 2013-12-09 CA CA2891402A patent/CA2891402A1/en not_active Abandoned
- 2013-12-09 WO PCT/EP2013/075961 patent/WO2014087015A1/en active Application Filing
- 2013-12-09 CN CN201380063521.5A patent/CN104854075A/en active Pending
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WO2021245440A1 (en) | 2020-06-02 | 2021-12-09 | Cmp-Cimentos Maceira E Pataias , S.A. | Catalytic and continuous thermochemical process of production of valuable derivatives from organic materials and/or waste |
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CA2891402A1 (en) | 2014-06-12 |
CN104854075A (en) | 2015-08-19 |
US20150299087A1 (en) | 2015-10-22 |
EP2928857A1 (en) | 2015-10-14 |
BR112015012823A2 (en) | 2017-07-11 |
US9908836B2 (en) | 2018-03-06 |
KR20150091155A (en) | 2015-08-07 |
EA201500606A1 (en) | 2015-09-30 |
EP2928857B1 (en) | 2019-01-23 |
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