• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:

    公开号:BR112013002925B1
    申请号:R112013002925-0
    申请日:2011-08-04
    公开日:2018-04-10
    发明作者:Borsotti Giampietro；Digioia Francesca
    申请人:Novamont S.P.A.；
    IPC主号:
    专利说明:

    (54) Title: PROCESS FOR THE SYNTHESIS OF 2,5-FURANDICARBOXYLIC ACID (51) Int.CI .: C07D 307/68; C07D 307/24; C07D 307/30 (52) CPC: C07D 307/68, C07D 307/24, C07D 307/30 (30) Unionist Priority: 06/08/2010 IT MI2010A001526 (73) Holder (s): NOVAMONT S.P.A.
    (72) Inventor (s): GIAMPIETRO BORSOTTI; FRANCESCA DIGIOIA t
    1/8
    Process for the synthesis of 2,5-furandicarboxylic acid
    description
    This invention relates to a process for the synthesis of 2,5-furandicarboxylic acid (FDCA) through the oxidation of 5-hydroxymethylfurfural (HMF).
    2,5-furandicarboxylic acid is an oxidized derivative of 5hydroxymethylfurfural, which is useful as a monomer in the production of plastics, in particular polyesters. In addition, as in turn, HMF is obtained from sugars, it is a derivative of raw materials that are widely available in nature.
    HMF oxidation processes are known in the literature, through which 2,5-furandicarboxylic acid can be obtained as the main product.
    US patent 4977283 (Hoechst) describes a method for oxidizing HMF in the presence of a metallic catalyst belonging to the platinum group, carried out in an aqueous medium at a pH between 6.5 and 8. The patent describes that by controlling the pH it is possible to influence the proportions between the various oxidation products and by-products. According to the information included in the patent, pH control can be achieved through bases such as sodium or potassium hydroxide, acidic solutions or buffers / buffer, according to a rule to maintain a pH below 8.
    US patent 2008/0103318 (Battelle) describes a method for oxidizing the supported platinum catalyzed HMF. Again in this case, the emphasis is placed on the variation in selectivity as a function of pH, which must be maintained at a value of no more than 7, possibly through the use of weak bases such as carbonates and bicarbonates. 2,5-furandicarboxylic acid is one of the described oxidation products.
    The metal catalysts used in the methods described above for the oxidation of HMF are, however, subject to contamination and consequent loss of catalytic activity. This means that, although supported catalysts, which can be easily recovered, are used, it is often necessary to replace or regenerate the catalyst, increasing costs due to the already expensive use of
    Λ precious metals such as platinum.
    . FR 2 669 634 provides an example of catalyst recycling to overcome this drawback. Said document describes a process for the synthesis of FDCA that comprises the oxidation of platinum-catalyzed HMF in an aqueous medium in an oxygen flow, in which recycling is possible due to the catalyst being enriched with specific amounts of lead.
    However, the described process requires the use of a considerable amount of catalyst, which is used in a proportion between 1:10 and 1:30 by weight in relation to HMF, equivalent to a molar ratio
    2/8 less than 1:50.
    However, a similar ratio between the catalyst and the HMF is necessary in order to achieve a high oxidation performance of the HMF in 2,5-furandicarboxylic acid, as will be seen from the data related to the processes according to the documents mentioned above. .
    The process for the synthesis of 2,5-furandicarboxylic acid according to the present invention has the particular advantage of providing a high yield of 2,5-furandicarboxylic acid using a limited amount of catalyst. The latter can also be recycled several times, maintaining its specific catalytic activity.
    This invention relates in particular to a process for the selective synthesis of 2,5-furandicarboxylic acid through the oxidation of 5hydroxymethylfurfural in an oxygen stream, catalyzed by a supported catalyst containing a platinum group metal, said process being carried out in aqueous solution at a weakly basic pH by adding a weak base. This process provides for the use of catalyst amounts between 1:60 and 1: 500, in moles with respect to HMF. It also provides for the possibility of recycling the catalyst several times in the reaction mixture, while maintaining the reaction yield above 90%.
    The terms "recycling" and "recycled" mean that the same catalyst is used more than once to repeat the same process.
    It has indeed been surprisingly discovered that maintaining a weakly basic pH in the reaction environment, through the addition of a weak base, protects the catalyst from contamination. Under the conditions of the process according to the present invention, recycling of the catalyst does in fact make it possible to obtain 2,5-furandicarboxylic acid in high yields. This is the case, despite the use of smaller amounts of catalyst in relation to the HMF reagent, confirming that the selectivity of the process is substantial and that the catalytic activity is effectively maintained.
    The starting material in the process according to the present invention is 5-hydroxymethylfurfural (HMF). HMF can be obtained by dehydrating sugars, in particular hexoses, such as fructose and glucose. Said sugars can be obtained by hydrolysis and possible isomerization of cellulose or polysaccharides containing biomass. According to a preferred embodiment of the present invention, HMF is thus obtained, from cellulose or polysaccharides containing biomass. Cellulose or polysaccharides containing biomass are examples of raw materials that are widely available in nature and, as such, are a renewable source of HMF.
    3/8
    The dehydration reaction can be carried out by several techniques that generally use acid catalysts and may or may not use aqueous and non-aqueous solvents.
    The HMF used as a starting material for the process according to the invention may possibly contain by-products from the processing of cellulosic biomass, sugars or polysaccharides.
    In the process according to the present invention, HMF oxidation occurs in aqueous solution and does not require the aid of organic solvents, with pH conditions having the effect that the oxidation reaction product present in the dissociated form is easily soluble in water, as is the HMF. Advantageously, an aqueous solution in the HMF concentration of up to 30% by weight is used; HMF concentrations between 0.5 and 20% by weight are preferred, and HMF concentrations between 1 and 10% by weight are even more preferred.
    In the process according to the invention, the oxidizing substance responsible for the oxidation of HMF is oxygen or an oxygen-containing compound. Advantageously, the reaction is carried out by passing a flow of 02 inside the reactor.
    Advantageously, the catalyst used is based on platinum or a metal belonging to the platinum group, the use of platinum or palladium is particularly preferred. This catalyst is advantageously used in the supported form. The most suitable materials to provide a support for said catalyst are carbon or alumina. The support material may optionally be in the form of a nanostructure, and contain the catalyst in an amount that is preferably between 1 and 10% by weight.
    In a preferred form of the process according to the invention, the catalyst comprises 5% by weight of Pt supported on carbon.
    The catalyst used in the process according to the present invention is used in small amounts compared to the amount of reagent. Advantageously, the molar ratio between the HMF and the metal catalyst is between 60: 1 and 500: 1, preferably between 80: 1 and 350: 1, and even more preferably between 100: 1 and 250: 1.
    The catalyst used in the process according to the present invention is advantageously recycled at least once in the reaction mixture, and even more advantageously, at least four times, maintaining the reaction yield above 90%.
    The oxidation reaction of 5-hydroxymethylfurfural is carried out at a temperature between 80 and 120 ° C, preferably between 90 and 110 ° C and more
    preferably between 90 and 105 ° C, and at a pressure between atmospheric pressure and 10 * 10 5 Pa, advantageously between 2 * 10 5 and 8 * 10 5 Pa, more advantageously between 3 * 10 5 and 6 * 10 5 Pa .
    As is known, according to the theory of Brõnsted5 Lowry, weak bases are chemical bases that are not completely protonated in an aqueous solution, thus resulting in a higher concentration of hydrogen ions and a lower pH compared to strong bases. such as NaOH or KOH.
    The weak bases, whose presence is necessary for the implementation of the present invention, have a small base of dissociation constant (Kb), with a pK b £ 1.5 at 25 ° C in a diluted aqueous solution (s 1 mol / dm 3 ) preferably with a pK b > 1.8 and more preferably with a pK b > 2. In any case, said bases are used in quantities necessary to maintain, during the course of the HMF oxidation reaction, a pH greater than 7 in the reaction environment, but less than 12, in order to prevent the occurrence of unwanted side reactions, such as Cannizzaro reactions.
    The weak bases according to the invention are preferably selected from: sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, dibasic and tribasic phosphate buffer solutions and their mixtures.
    Maintaining a weakly basic pH in the reaction environment can be achieved both by adding the weak base before starting the HMF oxidation reaction and by adding part of the weak base before starting the HMF oxidation reaction and part after said reaction has started.
    When the weak base is added before starting the HMF oxidation reaction, the aqueous solution containing the HMF and said weak base advantageously has a pH value greater than or equal to 8 and less than 12, preferably greater than 8.5 and less than 11. The presence of the weak base maintains a slightly basic reaction environment in the course of the oxidation reaction, with an aqueous solution having a pH value greater than 7 and less than 11 in the end of the oxidation reaction. Under such conditions, it was unexpectedly discovered that the catalyst maintains its intrinsic catalytic activity practically unchanged and its reuse makes it possible to produce FDCA selectively with an almost total conversion of HMF. Recycling can be carried out several times, obtaining a clear final solution (colorless to slightly yellow) and maintaining an FDCA production yield of more than 90%.
    When part of the weak base is added to the mixture of
    5/8 reaction before the HMF oxidation reaction starts and part is added gradually, according to the pH variation, after the HMF oxidation reaction has started, the pH value is advantageously kept higher than 7 and lower than 11, preferably greater than 8 and less than or equal to 8.5.
    In a preferred embodiment of the invention, weak soluble bases are used. The term "poorly soluble weak bases" is intended for weak bases that have a water solubility of less than 20 g / 100 g H20, measured at 20 ° C and under a pressure of 1 * 10 5 Pa. Such poorly soluble bases can advantageously be added before starting the reaction and they gradually pass into the solution during the reaction, thereby balancing the pH changes due to the production of FDCA and maintaining a slightly basic reaction environment in the course of the oxidation reaction. Examples of poorly soluble weak bases are sodium bicarbonate, calcium and magnesium carbonates, magnesium hydroxides and mixtures thereof. Magnesium carbonate hydroxide is particularly preferred.
    In a preferred embodiment of the invention, the process provides for a preliminary step which comprises the preparation of an intermediate reaction by oxidizing the HMF without precious metal catalysts, such as, for example, copper.
    Advantageously, said intermediate is 5-hydroxymethylfuran-2-carboxylic acid, HMFA. The HMFA obtained through this preliminary step is easily purified, allowing oxidation according to the invention to be carried out using an intermediate reagent (HMFA), which is purer than the HMF, with a positive effect on the service life and the activity of the catalyst.
    In this case, it is necessary to use an adequate amount of the weak base to neutralize the acidity of the reaction intermediate.
    The 2,5-furandicarboxylic acid produced in accordance with the present invention is present in the aqueous solution, in dissociated form at the conclusion of the oxidation reaction. Once the catalyst has been separated by known techniques, the FDCA can be obtained as a precipitate by neutralizing the aqueous solution.
    The process according to the invention can be carried out in batches or continuously.
    The process according to the invention will now be described according to the following non-limiting examples.
    Example 1
    They were placed,
    - 0.5 g of catalyst containing 5% by weight of platinum supported on Degussa carbon type F101RA / W, (sold by Sigma-Aldrich; with a water content of 50%
    6/8 by weight);
    - 50 g to 2% by weight of aqueous HMF solution (HMF: Pt = 123: 1);
    - 1.5 g of NaHCO 3; in an autoclave equipped with a magnetic stirrer and with an inlet with an immersion tube to bubble in oxygen. The pH value of the aqueous solution was 8.1.
    The reactor was heated in an oil bath at 100 ° C and maintained at a pressure of 5 * 10 5 Pa, while O 2 was supplied to it at a flow rate of 20 L / h.
    After 4 hours, the HMF conversion was virtually complete. The colorless aqueous solution containing dissociated 2,5-furandicarboxylic acid had a pH value of about 9.
    The catalyst was filtered and washed with water; the aqueous solution was acidified in order to precipitate the FDCA. The production of FDCA was 95% of theoretical molar yield.
    The catalyst recovered by filtration was used again to repeat the reaction in the same way. After the first recycling step, the final solution still remained colorless and the yield of FDCA production was again 95% of the theoretical value, and kept above 90% during the four recycling steps.
    Comparative Example
    They were placed,
    - 0.5 g of catalyst containing 5% by weight of platinum supported on carbon (Degussa type F101RA / W);
    - 50 g to 2% by weight of aqueous HMF solution (HMF: Pt = 123: 1);
    - 0.7 g of NaHCO 3; in the same autoclave used in example 1. The pH value of the aqueous solution was 8.
    The reactor was heated to 100 ° C in an oil bath and maintained at a pressure of 5 * 10 5 Pa, while the 02 was supplied with a flow rate of 20 L / h.
    After 5 hours, the aqueous solution had a pH value of about 3. The catalyst was filtered and washed with water. The yield of the FDCA production was 70% of the theoretical value, indicating a significant loss of activity in the catalyst.
    Example 2
    They were placed,
    - 0.50 g of catalyst containing 5% by weight of platinum supported on carbon (Degussa type F101RA / W);
    - 50 g to 2% by weight of aqueous HMF solution (HMF: Pt = 123: 1)
    7/8
    - 0.8 g of magnesium carbonate hydroxide (of course, sold by Sigma-Aldrich);
    in the same autoclave used in example 1. The autoclave was heated in an oil bath at 100 ° C and maintained at a pressure of 5 * 10® Pa, while O 2 was supplied in it with a flow of 20 L / h. After 5 hours, the HMF conversion was virtually complete. The pH value of the reaction solution changed from 10.4 to 8.0.
    The catalyst was filtered and washed with water, the colorless aqueous solution containing dissociated 2,5-furandicarboxylic acid was acidified in order to precipitate the FDCA. The yield of the FDCA production was 94% of the theoretical value.
    The catalyst recovered by filtration was used again to repeat the reaction in the same way. After five stages of recycling, the final solution was slightly yellow in color and the yield of FDCA production was again 92% of the theoretical value, and maintained above 90% in the next two stages of recycling.
    Example 3
    They were placed,
    - 0.5 g of catalyst containing 5% by weight of platinum supported on carbon (Degussa type F101RA / W);
    - 50 g to 4% by weight of aqueous HMF solution (HMF: Pt = 246: 1);
    - 2.7g NaHCO 3; in the same autoclave used in example 1. The pH value of the aqueous solution was 8.1.
    The reaction was carried out as in example 1. After 4 hours, the colorless aqueous solution containing dissociated 2,5-furandicarboxylic acid had a pH value of 8.96. The yield of the FDCA production was 92% of the theoretical value.
    The catalyst was recovered by filtration and washed with water was used again to repeat the reaction in the same way. After the first recycling step, the final solution still remained colorless and the yield of the FDCA production was again 92% of the theoretical value, and maintained above 90% in the next three recycling steps.
    Example 4
    They were placed,
    - 0.5 g of catalyst containing 5% by weight of platinum supported on Degussa-type carbon (F101 RA / W);
    - 50 g of water;
    - 2.84 g of hydroxy methyl furancarboxylic acid (HMFA);
    - 3.5 g of NaHCO 3 ;
    in an autoclave equipped with a magnetic stirrer and an inlet with an
    8/8 immersion to bubble in oxygen. The reactor was heated to 100 ° C in an oil bath and maintained at a pressure of 5 * 10 5 Pa. OO 2 was supplied in it with a flow of approximately 20 L / h. The pH value of the solution was 8.
    After 4 hours, the pH of the aqueous solution was 8.9 and 5 the yield of FDCA production was 96% of the theoretical value.
    By recycling the catalyst and reacting it in the same way, an yield of FDCA production of 94.5% of the theoretical value was provided.
    1/2
    权利要求:
    Claims (2)
    [1]
    Claims
    I. Process for the synthesis of 2,5-furandicarboxylic acid characterized by the oxidation of 5-hydroxymethylfurfural by an oxygen flow, catalyzed by a supported catalyst containing a metal of the platinum group,
    5 carried out in an aqueous solution whose pH is maintained above 7 and below 12 by adding a weak base selected from: sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate , magnesium carbonate, calcium hydroxide, magnesium hydroxide, dibasic and tribasic phosphate buffer solutions and their mixtures.
    2. Process according to claim 1, characterized in that part of the weak base is added to the reaction mixture before the 5-hydroxymethylfurfural oxidation reaction begins and part is gradually added after said reaction is initiated, and the pH of the aqueous solution is maintained above 7 and below 11.
    Process according to claim 1 characterized by
    15 the fact that the weak base is a weak soluble base.
    4. Process according to claim 1, characterized by the fact that said weak sparingly soluble base is selected from sodium bicarbonate, calcium and magnesium carbonates, magnesium hydroxides and mixtures thereof.
    Process according to any one of claims 20 to 1 to 4, characterized by the fact that metallic catalyst amounts between 1:60 and 1: 500 in moles are used in relation to 5-hydroxymethylfurfural.
    6. Process according to any one of claims 1 to 5, characterized by the fact that the catalyst is Pt or Pd supported on carbon or alumina.
    7. Process according to any one of claims 1 to 6, characterized by the fact that the catalyst is recycled in the reaction mixture.
    8. Process according to claim 7, characterized by the fact that the catalyst is recycled at least four times.
    Process according to any one of claims 30 to 1 to 8, characterized in that it is carried out at a temperature between 80 and 120 ° C and at a pressure between atmospheric pressure and 10 * 10 5 Pa.
    Process according to any one of claims 1 to 9, characterized in that it comprises a preliminary oxidation step of 5-hydroxymethylfurfural catalyzed by non-precious metals, in order to obtain an intermediate of
    35 easily purified reaction.
    II. Process according to the previous claim, characterized by the fact that said intermediate is 5-hydroxymethylfuran-2-carboxylic acid.
    12. Process according to any one of the claims
    Petition 870170091199, of 11/24/2017, p. 5/10
    [2]
    2/2 from 1 to 11, characterized by the fact that said 5-hydroxymethylfurfural is obtained from cellulose or polysaccharides containing biomass.
    Petition 870170091199, of 11/24/2017, p. 6/10
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112013002925B1|2018-04-10|2,5-FURANDIC CARBOXYLIC ACID SYNTHESIS PROCESS
    JP5252969B2|2013-07-31|Process for producing 2,5-furandicarboxylic acid
    US10385033B2|2019-08-20|Process for preparing furan-2,5-dicarboxylic acid
    RU2703511C2|2019-10-18|Method for selective oxidation of 5-hydroxymethylfurfural
    JP6100757B2|2017-03-22|Process for producing 5-hydroxymethylfurfural
    PT2220021E|2012-08-31|Process for the preparation of terephthalic acid
    BR122017024876B1|2020-11-10|oxidation method of furan aldehydes
    JP2014515037A5|2015-06-11|
    BR112019009884A2|2019-08-13|method and system for producing glycolic acid and / or glycolate
    US9365531B2|2016-06-14|Method for selectively oxidizing 5-hydroxymethyl furaldehyde
    CN108484545B|2021-01-12|Method and system for continuously synthesizing furan dicarboxylic acid
    JP2013203666A|2013-10-07|Method of producing 5-hydroxymethylfurfural oxide
    JP2013126967A|2013-06-27|Method for producing succinic acid
    TW201700168A|2017-01-01|Catalyst system and process
    JP5207680B2|2013-06-12|Process for producing 2,5-furandicarboxylic acid
    CN104829449B|2020-06-02|Method for synthesizing 2,5-dihydroxy terephthalic acid
    JP4951957B2|2012-06-13|Method for producing furfurals
    CN105820054A|2016-08-03|Preparation method of 3-methoxy-2-nitrobenzoate
    JP6638934B2|2020-02-05|Method for producing furfural or furfural derivative
    WO2015054756A1|2015-04-23|Integrated 2,5-furandicarboxylic acid production method
    BR102012032839B1|2018-02-06|INTEGRATED PROCESS FOR 2.5 - DICARBOXYLIC ACID PRODUCTION
    BRPI0820238B1|2017-08-08|PROCESS OF PRODUCTION OF TEREFTALIC ACID AND THEIR COMPOSITIONS
    TH81961A|2006-12-21|A method for producing acetic acid, which is composed of at least one metal salt as a catalyst stabilizer.
    同族专利:
    公开号 | 公开日
    US9359318B2|2016-06-07|
    CA2805574A1|2012-02-09|
    EP2601182A1|2013-06-12|
    BR112013002925A2|2016-06-07|
    CA2805574C|2018-05-01|
    JP2013534219A|2013-09-02|
    EP2601182B1|2015-09-16|
    JP6069199B2|2017-02-01|
    MX346052B|2017-03-02|
    CN103068809B|2016-04-06|
    CN103068809A|2013-04-24|
    MX2013001432A|2013-03-12|
    ES2555989T3|2016-01-12|
    WO2012017052A1|2012-02-09|
    US20130137882A1|2013-05-30|
    IT1401911B1|2013-08-28|
    KR20130095748A|2013-08-28|
    ITMI20101526A1|2012-02-07|
    KR101936966B1|2019-01-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3326944A|1964-03-09|1967-06-20|Atlas Chem Ind|Method of producing dehydromucic acid|
    DE3826073A1|1988-07-30|1990-02-01|Hoechst Ag|METHOD FOR THE OXIDATION OF 5-HYDROXYMETHYLFURFURAL|
    FR2669634B1|1990-11-22|1994-06-10|Furchim|PROCESS FOR THE MANUFACTURE OF 2-5-FURANE DICARBOXYLIC ACID.|
    WO2001072732A2|2000-03-27|2001-10-04|E.I. Dupont De Nemours And Company|Oxidation of 5- furfural to 2,5-diformylfuran and subsequent decarbonylation to unsubstituted furan|
    JP5006561B2|2006-03-28|2012-08-22|キヤノン株式会社|Method for producing furandicarboxylic acid|
    JP5217142B2|2006-10-04|2013-06-19|三菱化学株式会社|Method for producing furan derivatives|
    US7700788B2|2006-10-31|2010-04-20|Battelle Memorial Institute|Hydroxymethyl furfural oxidation methods|
    JP5072348B2|2006-12-27|2012-11-14|キヤノン株式会社|Method for producing furan ring compound|
    JP5207680B2|2007-07-27|2013-06-12|キヤノン株式会社|Process for producing 2,5-furandicarboxylic acid|
    JP5078490B2|2007-07-30|2012-11-21|キヤノン株式会社|Method for producing carboxylic acid|
    CN101386611A|2007-09-14|2009-03-18|中国科学院大连化学物理研究所|Method for preparing 5-hydroxymethyl-furfural|
    CN101456850A|2007-12-12|2009-06-17|中国科学院大连化学物理研究所|Method for preparing 5-hydroxymethyl-furfural|CN103626726B|2012-08-23|2016-08-03|中国科学院大连化学物理研究所|A kind of method preparing 5-HMFA and FDCA|
    FR2995898B1|2012-09-27|2019-07-26|Roquette Freres|PROCESS FOR SYNTHESIZING DICARBOXYLIC 2,5-FURANIC ACID FROM A COMPOSITION CONTAINING FURANE-2,5-DIALDEHYDE|
    US9029579B2|2012-11-08|2015-05-12|Eastman Chemical Company|Method of synthesizing low color furan diesters|
    US9006470B2|2012-11-08|2015-04-14|Eastman Chemical Company|Method of synthesizing low color furan diesters|
    FR3001970B1|2013-02-11|2015-02-27|Centre Nat Rech Scient|PROCESS FOR THE PREPARATION OF DICARBOXYLIC 2,5-FURANE ACID|
    WO2014158838A1|2013-03-14|2014-10-02|Archer Daniels Midland Company|Process for making 2,5-furandicarboxylic acid|
    MX2016002618A|2013-08-30|2016-06-06|Furanix Technologies Bv|Process for purifying an acid composition comprising 2-formyl-furan-5-carboxylic acid and 2,5-furandicarboxylic acid.|
    CN105555774B|2013-09-19|2018-08-28|花王株式会社|The manufacturing method of 2,5- furan dicarboxylic acids|
    WO2015056270A1|2013-10-17|2015-04-23|Natco Pharma Limited|Process for the preparation of 2,5-furandicarboxylic acid|
    WO2015054756A1|2013-10-17|2015-04-23|Petróleo Brasileiro S.A. - Petrobras|Integrated 2,5-furandicarboxylic acid production method|
    WO2015155784A1|2014-04-09|2015-10-15|Natco Pharma Limited|Process for the preparation of 2,5-furandicarboxylic acid and its ester derivative|
    AU2015276185B2|2014-06-17|2019-04-18|Annikki Gmbh|Process for the selective oxidation of 5-hydroxymethylfurfural|
    WO2015197699A1|2014-06-25|2015-12-30|Basf Se|Process for preparing furan-2,5-dicarboxylic acid|
    US9598780B2|2015-01-08|2017-03-21|Wisconsin Alumni Research Foundation|Electrochemical and photoelectrochemical oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and 2,5-diformylfuran|
    US9885119B2|2015-02-12|2018-02-06|Wisconsin Alumni Research Foundation|Electrochemical and photoelectrochemical reduction of furfurals|
    US9321744B1|2015-06-26|2016-04-26|Industrial Technology Research Institute|Method for preparing 2,5-furan dicarboxylic acid|
    CA2991075A1|2015-07-22|2017-01-26|Basf Se|Process for preparing furan-2,5-dicarboxylic acid|
    KR20180093922A|2015-12-15|2018-08-22|쉘 인터내셔날 리써취 마트샤피지 비.브이.|Method and system for removing alkyl iodide impurities from a recycle gas stream during the production of ethylene oxide|
    EP3391446A4|2015-12-18|2019-08-21|Rhodia Operations|Selective oxidation of furan based alcohols via electro-generative process|
    WO2017123763A1|2016-01-13|2017-07-20|Rennovia Inc.|Processes for the preparation of 2,5-furandicarboxylic acid and intermediates and derivatives thereof|
    CN108314667B|2017-01-18|2021-10-26|中国科学院过程工程研究所|Preparation method of non-alkaline system bio-based 2, 5-furandicarboxylic acid|
    BR112020000611A2|2017-07-12|2020-07-14|Stora Enso Oyj|purified products via 2,5-furanedicarboxylic acid pathway|
    US10669639B2|2017-09-05|2020-06-02|Wisconsin Alumni Research Foundation|Eletrochemical oxidation of 5-hydroxymethylfurfural using copper-based anodes|
    US11142833B2|2017-10-09|2021-10-12|Wisconsin Alumni Research Foundation|Electrochemical oxidation of aromatic aldehydes in acidic media|
    KR102009467B1|2018-01-08|2019-08-09|한국화학연구원|Heterogeneous catalyst for producing 2,5-furandicarboxylic acid based on Chitosan support and its preparation method|
    IT201800007204A1|2018-07-13|2020-01-13|PROCESS FOR THE PRODUCTION AND SEPARATION OF 5-HYDROXIMETHYLFURFURAL WITH QUATERNAR AMMONIC SALTS "|
    CN109046349B|2018-08-01|2021-07-23|西华大学|Monoatomic palladium catalyst, preparation method thereof and method for preparing 2,5-FDCA by catalytic oxidation of 5-HMF|
    TWI725347B|2018-10-18|2021-04-21|遠東新世紀股份有限公司|Preparation method of 2,5-furandicarboxylic acid|
    WO2021123240A1|2019-12-20|2021-06-24|Novamont S.P.A.|Process for the synthesis of 2,5-furandicarboxylic acid|
    法律状态:
    2016-06-28| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2017-08-29| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2017-10-17| B15K| Others concerning applications: alteration of classification|Ipc: C07D 307/68 (1974.07), C07D 307/24 (1974.07), C07D |
    2018-02-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2018-04-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/08/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    ITMI2010A001526A|IT1401911B1|2010-08-06|2010-08-06|PROCESS FOR SYNTHESIS OF 2,5-FURANDICARBOSSIC ACID|
    ITMI2010A001526|2010-08-06|
    PCT/EP2011/063482|WO2012017052A1|2010-08-06|2011-08-04|Process for the synthesis of 2,5-furandicarboxylic acid.|
    [返回顶部]