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    • 专利摘要:
    A process for producing a carboxylic acid composition, and A process for producing a purified pulp stream comprising fdca is described for a process for producing a dry purified carboxylic acid product comprising furan-2,5-dicarboxylic acid (fdca). The process comprises oxidizing at least one oxidizable compound selected from the following group: 5- (hydroxymethyl) furfural (5-hmf), 5-hmf (5-r (co) och2-furfural esters where r = alkyl, cycloalkyl and aryl ), 5-hmf (5-r'och2-furfural, where r '= alkyl, cycloalkyl and aryl) ethers, 5-alkyl furfural (5-r "-furfural, where r" = alkyl, cycloalkyl and aryl) stocks 5-hmf and 5-hmf esters mixed feeds and 5-hmf and 5-ifm ethers mixed feed stocks and 5-hmf and 5-alkyl mixed feed stocks to generate a crude carboxylic acid slurry comprising dryness, removing impurities from the crude carboxylic acid slurry in a liquid displacement zone to form a low impurity slurry stream. The low impurity slurry stream is still treated in a secondary oxidation zone to produce a secondary oxidation slurry stream that is sent to a crystallization zone to form a crystallized slurry stream. the crystallized slurry stream is cooled in a cooling zone and the resulting cooled crystallized slurry stream is sent to a solid-liquid separation zone to generate a purified wet cake stream comprising fdca which is dried in a drying zone to generate a dry carboxylic acid product stream comprising purified fdca (mpdca).
    公开号:BR112014030065B1
    申请号:R112014030065
    申请日:2013-07-17
    公开日:2019-12-03
    发明作者:Shahanawaz Shaikh Ashfaq；Russell Bowers Bradford；Randolph Parker Kenny；Reynolds Partin Lee；Ejerssa Janka Mesfin；Charles Morrow Michael；Moody Paula
    申请人:Eastman Chem Co；
    IPC主号:
    专利说明:

    “PROCESS TO PRODUCE A PURIFIED PASTE CHAIN UNDERSTANDING FDCA” FIELD OF THE INVENTION
    [0001] The present invention relates to a process for producing a carboxylic acid composition. The process comprises the oxidation of at least one oxidizable compound in a stream of the oxidizable crude material in the presence of an oxidation gas stream, solvent stream and at least one catalyst system.
    [0002] More particularly, the process comprises oxidizing at least one oxidizable compound selected from the following group: 5- (hydroxymethyl) furfural (5-HMF), 5-HMF (5-R (CO) OCH2-furfural esters where R = alkyl, cycloalkyl and aryl), 5-HMF ethers (5-R'OCH2-furfural, where R '= alkyl, cycloalkyl and aryl), 5-alkyl furfural (5-R "-furfural, where R" = alkyl, cycloalkyl and aryl), mixed feed stocks of 5-HMF and 5-HMF esters and mixed feed stocks of 5-HMF and 5-HMF ethers and mixed feed stocks of 5-HMF and 5-alkyl fumes in the presence of oxygen , a saturated organic acid solvent having 2 to 6 carbon atoms and a catalyst system at a temperature of about 100 ° C to about 220 ° C to produce the carboxylic acid composition comprising furan-2,5- dicarboxylic acid to generate a crude carboxylic acid paste comprising FDCA, removing impurities from the c acid paste crude arboxylic in a liquid displacement zone to form a low impurity slurry stream. The low impurity slurry stream is still treated in a secondary oxidation zone to produce a secondary oxidation slurry stream that is sent to a crystallization zone to form a crystallized slurry stream. The crystallized paste stream is cooled in a cooling zone and the resulting cooled crystallized paste stream is sent to a solid-liquid separation zone to generate a purified wet pie stream comprising FDCA that is dried in a drying zone to generate a stream of dry carboxylic acid product comprising purified FDCA (pFDCA).
    BACKGROUND OF THE INVENTION
    [003] Aromatic dicarboxylic acids, such as terephthalic acid and isophthalic acid, are used to produce a variety of polyester products. Important examples of which are poly (ethylene terephthalate) and its copolymers. These aromatic dicarboxylic acids are synthesized by the catalytic oxidation of the corresponding dialkyl aromatic compounds that are obtained from fossil fuels, which is described in US Patent Application 2006/0205977 A1), which is incorporated in this by reference to extension and does not contradict the statements in this.
    [004] There is an interest in the development of the use of renewable sources as food stocks by the chemical industry mainly due to the progressive reduction of fossil reserves and their related environmental impacts. Furan-2,5-dicarboxylic acid (FDCA) is a versatile intermediate considered as the closest promising biofound alternative to terephthalic acid and isophthalic acid. Likewise, aromatic diacids, FDCA can be condensed with diols such as ethylene glycol to manufacture polyester resins similar to polyethylene tereflalate (PET) (Gandini, A .; Silvestre, A. J; Neto, CP; Sousa, AF; Gomes , MJ Poly. Sci. A 2009, 47, 295.). FDCA was prepared by oxidizing 5- (hydroxymethyl) furfural (5-HMF) under air using homogeneous catalysts as debugged in US2003 / 0055271 Al and in Partenheimer, W .; Grushin, V. V. Adv. Synth. Catai. 2001, 343, 102-111. However, reaching high yields had the difficulty proved. A maximum of 44.8% yield using Co / Mn / Br catalyst system and a maximum of 60.9% yield was listed using a combination of Co / Mn / Br / Zr catalysts.
    [005] The crude FDCA obtained by oxidation processes must be purified before they are suitable for end-use applications. JP Patent Application, JP209-242312A, describes the crude FDCA purification process using sodium hydroxide / sodium hypochloride and / or hydrogen peroxide followed by acid treatment of the disodium salt to obtain pure FDCA. This multi-stage purification process generates waste of by-products.
    [006] Therefore, there is a need in the chemical industry for a high-yield and cheap process for the purification of crude FDCA that does not produce waste products and lends itself to facilitating the separation steps.
    BRIEF DESCRIPTION OF THE DRAWINGS
    [007] Figure 1 illustrates different embodiments of the invention in which a process for producing a dried purified carboxylic acid 710 is provided.
    [008] Figure 2 illustrates an embodiment of the invention, showing the effect of temperature and reaction time in b *.
    DETAILED DESCRIPTION
    [009] It should be understood that the following is not intended to be an exclusive list of defined terms. Other definitions can be provided in the preceding description, such as, for example, when accompanying the use of a term defined in the context.
    [0010] As used in this, the terms "one," "one," and "o" mean one or more.
    [0011] As used in this, the term "and / or," when used in a list of two or more items, means that any of the items listed can be used alone or any combination of two or more of the items listed can be used. For example, if a composition is described as containing components A, B and / or C, the composition can contain A only; B only; C only; A and B in combination; A and C in combination, B and C in combination; or A, B and C in combination.
    [0012] As used herein, the terms "comprising," "comprises," and "comprising" are open transition terms used for the transition of a patient reported before the term to one or more related elements after the term, where the element or elements listed after the transition term are not necessarily just the elements that make up the individual.
    [0013] As used herein, the terms "having," "had," and "has" have the same open meaning as "comprising," "comprises," and "comprising" provided above.
    [0014] As used herein, the terms "including," "includes," and "including" have the same open meaning as "comprising," "comprises," and "comprising" provided above.
    [0015] The present description uses the numerical ranges to quantify certain parameters related to the invention. It should be understood that when numeric ranges are provided, such ranges will be constructed as providing literal support for claim limitations that only report the lower range value as well as claim limitations that only report the upper range value. For example, a numeric range described from 10 to 100 provides literal support for the reported claim "greater than 10" (with no upper link) and a reported claim "less than 100" (with no lower link).
    [0016] The present description uses specific numerical values to quantify certain parameters related to the invention, where specific numerical values are not expressly part of a numerical range. It should be understood that each specific numerical value provided in this is constructed as providing literal support over a narrow, intermediate and wide range. The wide range associated with each specific numerical value is the numerical value plus and minus 60 percent of the numerical value, rounded up to two significant digits. The intermediate range associated with each specific numerical value is the numerical value plus and minus 30 percent of the numerical value, rounded up to two significant digits. The narrow range associated with each specific numerical value is the numerical value plus and minus 15 percent of the numerical value, rounded to two significant digits. For example, if the specification describes a specific temperature of 62 ° F (16.67 ° C), such a description provides literal support for a wide numerical range from 25 ° F to 99 ° F (62 ° F +/- 37 ° F) (-3.89 ° C to 37.22 ° C (16.67 ° C +/- 2.78)), an intermediate number range from 43 ° F to 81 ° F (62 ° F +/- 19 ° F) (6.11 ° C to 27.22 ° C (16.67 ° C +/- -7.22 ° C) and a narrow number range from 53 ° F to 71 ° F (62 ° F + / - 9 ° F) (11.67 ° C to 21.67 ° C (16.67 ° C +/- 12.78 ° C)). These narrow, intermediate and wide numerical ranges should be applied not only to specific values, but should be applied to the differences between these specific values, so if the specification describes a first pressure of 110 psia (758.4 kPa abs.) and a second pressure of 48 psia (330.9 kPa abs.) (a difference of 62 psi (427, 4 kPa abs.), the narrow, intermediate and wide ranges for the pressure difference between these two currents should be 25 to 99 psi (172, 3 kPa abs. To 682.5 kPa abs.), 43 to 81 psi (296.4 kPa abs. at 558.4 kPa abs.) and 53 at 71 psi (365.4 kPa abs. at 489.5), respectively.
    [0017] In an embodiment of the invention, a process is provided to produce the composition of the carboxylic acid and / or dry purified carboxylic acid 710 comprising furan-2,5-dicarboxylic acid (FDCA). The embodiments of the process are shown in Figure 1. The process comprises the oxidation of at least one oxidizable compound in a stream of the oxidizable crude material 30 in the presence of an oxidation gas stream 10, solvent stream 20 and at least one catalyst system. The stream of oxidizable crude material 30 comprises at least one oxidizable compound suitable to produce a carboxylic acid composition 110 comprising FDCA. The amount of FDCA in the 110 carboxylic acid composition can vary by more than 10 percent by weight in the 110 carboxylic acid composition, by more than 20 percent by weight in the 110 carboxylic acid composition, by more than 30 percent by weight in the composition of the carboxylic acid 110. The composition of the carboxylic acid 110 comprises FDCA and solvent.
    [0018] In another embodiment of the invention, the process comprises the oxidation of at least one oxidizable compound in a stream of oxidizable crude material 30 in the presence of an oxidation gas stream 10, solvent stream 20 and at least one system of catalyst. The stream of oxidizable crude material 30 comprises at least one oxidizable compound selected from the group consisting of 5- (hydroxymethyl) furfural (5-HMF), 5-HMF (5-R (CO) OCH2-furfural esters where R = alkyl, cycloalkyl and aryl), 5-HMF ethers (5-R'OCH2-furfural, where R '= alkyl, cycloalkyl and aryl), 5-furfural (5-7 "-furfural, where R" = alkyl, cycloalkyl and aryl), mixed feed stocks of 5-HMF and 5-HMF esters, mixed feed stocks of 5-HMF and 5-HMF ethers, mixed feed stocks of 5-HMF and fufural 5-alkyls to generate an acid composition carboxylic acid comprising FDCA. The process includes removing impurities from the carboxylic acid composition 110 in a liquid displacement zone 225 to form a low impurity slurry stream 210. The low impurity slurry stream 210 can still be treated in an oxidation zone secondary 335 to produce a secondary oxidation paste stream 310 that can be directed to a crystallization zone 425 to form a crystallized paste stream 410. Crystallized paste stream 410 is cooled in a cooling zone 430 and the paste stream cooled crystallized 510 can be directed to a solid-liquid separation zone 625 to generate a purified wet cake stream 610 comprising FDCA which is dried in a drying zone 725 to generate a purified, dried carboxylic acid 710 comprising purified FDCA.
    [0019] In an embodiment of the invention, a process is provided to produce a purified, dried 710 carboxylic acid comprising purified, dried furan-2,5-dicarboxylic acid (FDCA) and comprises the following steps: [0020] Step ( a) comprises the oxidation of at least one oxidizable compound in a stream of oxidizable crude material 30 in the presence of an oxidation gas stream 10, solvent stream 20 and at least one catalyst system in a primary oxidation zone 125 comprising at least one primary oxidizing reactor to produce a carboxylic acid composition 110 comprising furan-2,5-dicarboxylic (FDCA); wherein the stream of oxidizable crude material 30 comprises at least one oxidizable compound selected from the group consisting of 5- (hydroxymethyl) furfural (5-HMF), 5-HMF (5-R (CO) OCH2-furfural esters where R = alkyl, cycloalkyl and aryl), 5-HMF ethers (5-R'OCH2-furfural, where R '- alkyl, cycloalkyl and aryl), 5-alkyl furfural (5-R "-furfural, where R" = alkyl, cycloalkyl and aryl), mixed feed stocks of 5-HMF and 5-HMF esters, mixed feed stocks of 5-HMF and 5-HMF ethers and mixed feed stocks of 5-HMF and fufural 5-alkyls. Structures for various compounds of oxidizable crude material are summarized below: Feeds derived from preferred 5-HMF [0021] Is 5-HMF or its derivatives oxidized with O elemental in the multistage reactions, eqs 1 and 2, to form FDCA with 5-formyl furan-2-carboxylic acid (FFCA) as a key intermediate.
    In an embodiment of this invention, currents directed to the primary oxidation zone 125 comprise an oxidation gas stream 10 comprising oxygen and a solvent stream 20 comprising solvent, a stream of oxidizable crude material 30 and a catalyst system. The stream of oxidizable crude material 30 comprises a continuous liquid phase. In another embodiment of the invention, the stream of oxidizable crude material 30, the oxidation gas stream 10, the solvent stream 20 and the catalyst system can be fed to the primary oxidation zone 125 as separate and individual or combined streams in any combination prior to entering primary oxidation zone 125 where said feed streams may enter a single location or multiple locations in primary oxidation zone 125. The carboxylic acid composition 110 comprises FDCA and FFCA. In another embodiment, the FFCA in the composition of carboxylic acid 110 ranges from 0.1% by weight (percent by weight) to about 4% by weight or 0.1% by weight to about 0.5% by weight, or 0.1% by weight to about 1% by weight. In another embodiment of the invention the carboxylic acid composition 110 comprises FDCA and FFCA and at least one of 2,5-diformylfuran in an amount ranging from 0% by weight to about 0.2% by weight, levulinic acid in a amount ranging from 0% by weight to 0.5% by weight, succinic acid in an amount ranging from 0% by weight to 0.5% by weight and acetoxy acetic acid in an amount ranging from 0% by weight to 0.5 % by weight.
    [0023] In another embodiment of the invention the carboxylic acid composition 110 comprises FDCA, FFCA and EFCA. In another embodiment of the invention EFCA in the composition of carboxylic acid 110 in a range of about 0.05% by weight to 4% by weight, or around 1% by weight to 2% by weight.
    [0024] The catalyst system comprises at least one catalyst suitable for oxidation. Any catalyst known in the art capable of oxidizing the oxidizable compound can be used. An example of suitable catalysts comprises at least one selected from, but not limited to, cobalt, bromine and manganese compounds, which are soluble in the selected oxidation solvent. In another embodiment of the invention, the catalyst system comprises cobalt, manganese and bromine in which the weight ratio of cobalt to manganese in the reaction mixture is about 10 to about 400 and the weight ratio of cobalt to bromine is about 0.7 to about 3.5. [0025] The oxidation gas stream comprises oxygen. Examples include, but are not limited to, purified air and oxygen. The amount of oxygen in the primary oxidation zone varies from 5 mol to 45 mol%, 5 mol to 60% mol to 5 mol% to 80 mol%.
    [0026] Suitable solvents include water and aliphatic solvents. In one embodiment of the invention, the solvents are aliphatic carboxylic acids in which they include, but are not limited to, aqueous solutions of C2 to C6 monocarboxylic acids, for example, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, trimethylacetic acid, caprylic acid and mixtures thereof. In another embodiment of the invention, the solvent is volatile under the oxidation reaction conditions to allow it to be removed as an effluent gas from the oxidation reactor. In yet another embodiment of the invention the selected solvent is also one in which the catalyst composition is soluble under the reaction conditions.
    [0027] The most common solvent used for oxidation is an aqueous acetic acid solution, typically having a concentration of 80 to 99% by weight. In especially preferred embodiments, the solvent comprises a mixture of water and acetic acid that has a water content of 0% to about 15% by weight. Additionally, a portion of the solvent feed to the primary oxidation reactor can be obtained from the recycling stream obtained by displacing around 80 to 90% of the main liquid substance removed from the stream of the crude reaction mixture discharged from the reactor. primary oxidation with fresh moist acetic acid containing about 0 to 15% water.
    [0028] Suitable solvents include, but are not limited to, aliphatic mono-earboxylic acids, preferably containing 2 to 6 carbon atoms and mixtures of these and mixtures of these compounds with water. Examples of aliphatic mono-carboxylic acids include, but are not limited to, acetic acid.
    [0029] Generally, the oxidation temperature can vary from about 100 ° C to about 220 ° C and from about 110 ° C to about 160 ° C.
    [0030] In another embodiment of the invention, a process is provided to produce furan-2,5-dicarboxylic acid (FDCA) in high yields by liquid phase oxidation which minimizes the loss of solvent and starting material by burning carbon. The process comprises the oxidation of at least one oxidizable compound in a stream of the oxidizable crude material 30 in the presence of an oxidation gas stream 10, solvent stream 20 and at least one catalyst system in a primary oxidation zone 125; wherein the oxidizable compound is at least one selected from the group consisting of H (C = O) -R- (C = O) H, HOH2C-R- (C = O) H and 5- (hydroxymethyl) furfural (5 -HMF). The oxidizable compound can be oxidized in a solvent comprising acetic acid with or without the presence of water with oxygen in the presence of a catalyst system comprising cobalt, manganese and bromine, where the weight ratio of cobalt to manganese in the reaction mixture is from about 10 to about 400 and the weight ratio of cobalt to bromine is about 0.7 to about 3.5. Such a catalyst system with improved Co: Mn ratio can lead to high FDCA yield. In this process, the oxidation temperature can vary from about 100 ° C to about 220 ° C, or another range from about 110 ° C to about 160 ° C, which can minimize the burning of carbon. The cobalt concentration of the catalyst can vary from about 1000 ppm to about 6000 ppm and the amount of manganese from about 2 ppm to about 600 ppm and the amount of bromine from about 300 ppm to about 4500 ppm with respect to to the total weight of the liquid in the reaction medium of the primary oxidation zone 125. As used herein, process temperature is the temperature of the reaction mixture within the primary oxidation zone where the liquid is present as the continuous phase. The primary oxidizing reactor will typically be characterized by a lower section where the gas bubbles are dispersed in a continuous liquid phase. Solids can be present in the bottom section. In the upper section of the primary oxidizer, the gas is in the continuous phase and the included liquid droplets may also be present.
    [0031] In various embodiments of the invention, the catalyst compositions used in the process of the invention comprise cobalt atoms, manganese atoms and bromine atoms, provided by any suitable means, further as described below. The catalyst composition is typically soluble in the solvent under the reaction conditions, or is soluble in the reagents fed through the oxidation zone. Preferably, the catalyst composition is soluble in the solvent at 40 ° C and 1 atm and is soluble in the solvent under the reaction conditions.
    [0032] Cobalt atoms can be supplied in ionic form as inorganic cobalt salts, such as cobalt bromide, cobalt nitrate, or cobalt chloride, or organic cobalt compounds such as cobalt salts of aliphatic or aromatic acids having 2-22 carbon atoms, including cobalt acetate, cobalt octanoate, cobalt benzoate, cobalt acetylacetonate and cobalt naphthalate.
    [0033] The oxidation state of cobalt when added as a compound to the reaction mixture is not limited and includes both the +2 and +3 oxidation states.
    [0034] Manganese atoms can be supplied as one or more inorganic manganese salts, such as manganese borates, manganese halides, manganese nitrates, or organometallic manganese compounds such as the manganese salts of the lower aliphatic carboxylic acids, including manganese acetate and manganese salts of beta-diketonates, including manganese acetylacetonate.
    [0035] The bromine component can be added as elemental bromine, in combined form, or as an anion. Suitable sources of bromine include hydrobromic acid, sodium bromide, ammonium bromide, potassium bromide and tetrabromoethane. Hydrobromic acid, or sodium bromide, can be preferred sources of bromine.
    [0036] In another embodiment of the invention, a process is provided to produce furan-2,5-dicarboxylic acid (FDCA) in high yields by liquid phase oxidation which minimizes the loss of solvent and starting material through burning of carbon. The process comprises the oxidation of at least one oxidizable compound in a comment of the oxidizable crude material 30 in the presence of an oxidation gas stream 10, solvent stream 20 and at least one catalyst system in a primary oxidation zone 125; wherein the oxidizable compound is selected from the group consisting of 5- (acetoxymethyl) furfural (5-AMF), 5- (ethoxymethyl) furfural (5-EMF), 5-methyl furfural (5-MF); wherein the solvent stream 20 comprises acetic acid with or without the presence of water; wherein the catalyst system comprising cobalt, manganese and bromine, where the weight ratio of cobalt to manganese in the reaction mixture ranges from about 10 to about 400 and the weight ratio of cobalt to bromine is about 0 , 7 to about 3.5. The catalyst system with improved Co: Mn ratio can lead to high FDCA yield. In this process, the oxidation temperature can vary from about 100 ° C to about 220 ° C, or from about 110 ° C to about 160 ° C to minimize the burning of carbon. The cobalt concentration in the catalyst system can vary from about 500 ppm to about 6000 ppm and the amount of manganese from about 2 ppm to about 600 ppm and the amount of bromine from about 300 ppm to about 4500 ppm with respect to the total weight of the liquid in the reaction medium. The mixed feed stocks of 5-AMF and 5-HMF or 5-EMF and 5-HMF or 5-MF and 5-HMF or 5-AMF, 5-EMF and 5-HMF, with component variation actions can be used and similar results can be obtained. [0037] In another embodiment of the invention, a process is provided to produce furan-2,5-dicarboxylic acid (FDCA) in high yields by liquid phase oxidation which minimizes the loss of solvent and starting material through burning of carbon. The process comprises the oxidation of at least one oxidizable compound in a stream of the oxidizable crude material 30 in the presence of an oxidation gas stream 10, solvent stream 20 and at least one catalyst system in a primary oxidation zone 125; wherein said oxidizable compound is 5- (hydroxymethyl) furfural (5-HMF); wherein said solvent stream comprises acetic acid with or without the presence of water; wherein said catalyst system comprising cobalt, manganese and bromine, wherein the weight ratio of cobalt to manganese in the reaction mixture is about 10 to about 400. In this process, the temperature can vary from about 100 ° C to about 220 ° C, from about 105 ° C to about 180 ° C and from about 110 ° C to about 160 ° C. The cobalt concentration of the catalyst system can vary from about 1000 ppm to about 6000 ppm and the amount of manganese can vary from about 2 ppm to about 600 ppm and the amount of bromine can vary from about 300 ppm to about 4500 ppm with respect to the total weight of the liquid in the reaction medium.
    [0038] In another embodiment of the invention, the process comprises oxidizing at least one oxidizable compound in a stream of the oxidizable crude material 30 in the presence of an oxidizing gas stream 10, solvent stream 20 and at least one system catalyst in a primary oxidation zone 125; wherein said oxidizable compound is 5- (hydroxymethyl) furfural (5-HMF); wherein said solvent stream comprises a saturated organic acid having 2 to 6 carbon atoms with or without the presence of water at a temperature of 100 ° C to 220 ° C to produce a dicarboxylic acid composition; wherein the primary oxidation zone 125 comprises at least one primary oxidation reactor and where the catalyst system comprises cobalt in a range of about 500 ppm by weight to about 6000 ppm by weight with respect to the weight of the liquid in the medium of reaction, manganese an amount ranging from about 2 ppm by weight to about 600 ppm by weight with respect to the weight of the liquid in the reaction medium and bromine in an amount ranging from about 300 ppm by weight to about 4500 ppm in weight in relation to the weight of the liquid in the reaction medium.
    [0039] In another embodiment of the invention, when a stream of oxidizable crude material 30 comprises 5-HMF, then the ratio of cobalt to manganese by weight is at least 10: 1, 15: 1, 20: 1.25: 1, 30: 1,40: 1 50: 1, 60: 1, or 400 to 1.
    [0040] In another embodiment of the invention, when the oxidizable material stream 30 comprises at least one oxidizable compound selected from the group consisting of 5-HMF (5-R (CO) OCH2-furfural esters where R = alkyl, cycloalkyl and aryl), 5-HMF ethers (5 - / Y C // - furfural, where R '= alkyl, cycloalkyl and aryl), 5-alkyl furfural (5-R "-furfural, where R" = alkyl , cycloalkyl and aryl), mixed feed stocks of 5-HMF and 5-HMF esters, mixed feed stocks of 5-HMF and 5-HMF ethers and mixed feed stocks of 5-HMF and 5-alkyls, the ratio cobalt and manganese by weight of the catalyst system is at least 1: 1, 10: 1, 20: 1,50: 1, 100: 1, or 400: 1.
    [0041] In another embodiment of this invention, furan-2,5-dicarboxylic acid (FDCA) can be obtained by oxidizing the liquid phase of 5- (hydroxymethyl) furfural (5-HMF), 5- (acetoxymethyl) furfural ( 5-AMF) and 5- (ethoxymethyl) furfural (5-EMF) with molecular oxygen using a Co / Mn / Br catalyst system in the acetic acid solvent. After oxidation of 5-HMF / 5-AMF / 5-EMF in the presence of acetic acid, the FDCA precipitates the solution. After filtration, washing with acetic acid and then with water and drying, solids were obtained with a minimum of 90%, 92%, 94%, 96% of the FDCA content by weight.
    [0042] In another embodiment of the invention, FDCA is obtained by oxidizing the liquid phase of 5-HMF, 5-AMF and 5-EMF with molecular oxygen using Co / Mn / Br catalyst system in the acetic acid solvent. After oxidation of 5-HMF 15-AMF / 5-EMF to acetic acid, the FDCA precipitates the solution. After filtration, washing with acetic acid and then with water and drying, solids were obtained with a minimum of 96% of the FDCA content and a maximum b * of 15, 16, 17, 18, 19, or 20.
    [0043] The b * is an attribute of three colors measured in an instrument based on spectroscopic reflectance. Color can be measured by any device known in the art. A Hunter Ultrascan XE instrument is typically the measuring device. Positive readings mean the degree of yellow (or absorbance of blue), while negative readings mean the degree of blue (or absorbance of yellow).
    [0044] In another embodiment of the invention, a process is provided to produce furan-2,5-dicarboxylic acid (FDCA) in minimum yields of 80% or 85% or 90% or more by liquid phase oxidation which minimizes the loss of solvent and starting material through the burning of carbon. As used in this, yield is defined as the mass of FDCA obtained divided by the theoretical amount of FDCA that must be produced based on the amount of use of the raw material. For example, if one mole or 126.11 grams of 5-HMF is oxidized, it should theoretically generate one mole or 156.09 grams of FDCA. If, for example, the current amount of FDCA formed is only 150 grams, the yield for this reaction is calculated to be = (1501156.09) times 100, which equals a yield of 96%. The same calculation applies to the oxidation reaction conducted using 5-HMF derivatives or mixed feeds.
    [0045] In another embodiment of this invention, a process is provided comprising oxidizing at least one oxidizable compound in a stream of the oxidizable crude material 30 in the presence of an oxidation gas stream 10, solvent stream 20 and at least one system catalyst in a primary oxidation zone 125; wherein said oxidizable compound is selected from the group consisting of H (C = O) -R- (C = O) H, HOH2C-R- (C = O) H, 5- (hydroxymethyl) furíural (5-HMF ); wherein said solvent stream comprises acetic acid with or without the presence of water; wherein said catalyst system comprises cobalt, manganese and bromine, where the weight ratio of cobalt to manganese in the reaction mixture is about 10 to about 400 and the weight ratio of cobalt to bromine is about 0.7 to about 3.5. Such a catalyst system with improved Co: Mn and Co: Br ratio can lead to high FDCA yield (minimum of 90%), decreases the formation of impurities (measured by b *) causing color in the downstream polymerization process while keeps the amount of CO and CO2 in the effluent gas to a minimum.
    [0046] The temperature in the primary oxidation zone can vary from about 100 ° C to about 220 ° and can range from about 110 ° C to about 160 ° C or can range from about 105 ° C to about 180 ° C or about 100 ° C to about 200 ° C, or about 100 ° C to about 190 ° C. An advantage of the primary oxidation conditions it describes is low carbon burning. The effluent gas stream from the oxidizer 120 is sent to the effluent gas treatment zone of the oxidizer 825 to generate an inert gas stream 810, liquid stream 820 comprising water and recovered solvent stream 830 comprising condensed solvent. In one embodiment, at least a portion of the recovered solvent stream 830 is sent by the wash feed stream 620 and the combined stream is sent to the solid-liquid separation zone 625 for the purpose of washing the solids present in the separation zone solid-liquid 625. In one embodiment, the inert gas stream 810 can be vented into the atmosphere. In another embodiment, at least a portion of the inert gas stream 810 can be used as an inert gas in the process to inert the containers and / or used to transport gas to the solids in the process.
    [0047] Step (b) comprises sending the crude carboxylic composition 110 and fresh solvent stream 220 to a liquid displacement zone 225 to produce a displaced main liquid substance stream 230 and low impurity slurry stream 210 comprising FDCA. The displaced main liquid substance stream 230 comprises solvent and soluble substance dissolved in the solvent comprising dissolved impurities and dissolved catalyst. In various embodiments of the invention, from about 5% to about 99%, from about 30% to about 90% and more preferably from about 50 to about 85% of the main liquid substance present in the acid composition carboxylic 110 is displaced by the liquid displacement zone 225 resulting in the dissolved substance comprising impurities present in the displaced main liquid substance not going forward in the process. The sufficient fresh solvent is fed to the liquid displacement zone 225 which is mixed with the resulting solids in a low impurity paste stream 210 being counted with% by weight of solids ranging from 1% to 50%, 10% to 40% and preferably% the weight of the solids in stream 210 will vary from 25% to 38%. [0048] The net displacement zone can be a single unit operation or multiple unit operations. In an embodiment of the invention, the liquid displacement zone 225 can be any liquid-solid separation device capable of generating a wet cake isolated from the feed slurry and then the isolated wet cake is mixed with fresh solvent in a separate mixing device to generate a low impurity paste stream 210. Examples of suitable solid-liquid separation devices, but are not limited to, a continuous pressure drum filter, solid blowing centrifuges including, but not limited to, disc stack decanters and centrifuges and batch pressure filters including, but not limited to, candle and leaf filters. The preferred solid-liquid separation device for this application is a continuous pressure drum filter. The solid-liquid separator is operated at temperatures between about 30 ° C to about 200 ° C, preferably 80 ° C to about 170 ° C. The solid-liquid separator in the liquid displacement zone 225 can be operated in batch or continuous mode, although it will be estimated that in commercial processes, the continuous mode is preferred. Alternatively, a portion of the main liquid substance in the stream 110 is displaced with the stream of fresh liquid substance 220 in a simple device to form a low impurity paste stream 210 without forming an isolated wet cake. Suitable devices for this embodiment include centrifuges, disk stack centrifuges and continuous wash columns.
    [0049] In one embodiment, 5% to 100% by weight of the displaced main liquid substance stream 230 is sent to a purge zone 235 in which a portion of the impurities present in stream 230 are isolated and exit the process as purge stream 920, wherein one portion is 5% by weight of the total impurities in stream 230 or more. The recovered solvent stream 910 comprises the solvent and the catalyst isolated from the stream 230 and is recycled to the process. In one embodiment, recovered solvent stream 910 is recycled to primary oxidation zone 125 and contains more than 30% of the catalyst that enters purging zone 235 in stream 230. In another embodiment, stream 910 is recycled to primary oxidation zone 125 and contains more than 50% by weight, contains more than 70% by weight and preferably more than 90% by weight of the catalyst that enters purging zone 235 in chain 230 on a batch basis or to be continued.
    [0050] In yet another embodiment, up to 100% of the feed to the purging zone 235 can be the primary liquid substance generated in a secondary liquid displacement zone located in some location downstream of the secondary oxidation zone 335. A displacement zone secondary liquid is not shown in Figure 1 and comprises the same equipment as that described by the liquid displacement zone 225 located after the primary oxidation zone 125 and must be located after the secondary oxidation zone 335.
    [0051] Step (c) comprises oxidation to the low impurity pulp stream 210 in the secondary oxidation zone 335 to form a purified pulp stream 310. In an embodiment of the invention, the low impurity pulp stream 210 is sent to a secondary oxidation zone 335 where it can be operated in any combination ranging from 110 ° C, or 115 ° C, or 120 ° C, or 125 ° C, or 130 ° C, or 135 ° C, or 145 ° C, 150 ° C, or 155 ° C, or 160 ° C, or 165 ° C, 170 ° C, at 175 ° C, or 180 ° C, or 185 ° C, or 190 ° C, or 195 ° C, or 200 ° C, or 210 ° C, or 215 ° C, or 220 ° C, or 225 ° C, or 230 ° C, or 235 ° C, or 240 ° C, or 245 ° C or 250 ° C and still oxidized with an oxidation gas, such as air, fed by line 320 to produce a stream of purified pulp 310. The secondary oxidation zone comprises at least one oxidation reactor vessel. In one embodiment, the secondary oxidation zone can be one or more oxidation containers. When the carboxylic acid in the low impurity slurry stream 210 comprises FDCA, the secondary oxidation zone can also be operated at a temperature ranging from about 115 ° C to about 220 ° C, preferably between about 120 ° C to about 200 ° C and stream 210 is further oxidized with an oxidation gas stream fed by line 320 to produce a purified paste stream 310.
    [0052] Generally, oxidation in the secondary oxidation zone 335 is at a higher temperature than the oxidation in the primary oxidation zone 125 to intensify the removal of impurity. In one embodiment, the secondary oxidation zone 335 is operated around 30 °, 20 ° C, 15 ° C and preferably 10 ° C higher than the oxidation temperature in the primary oxidation zone 125 to intensify removal impurity. The secondary oxidation zone 335 can be directly heated with solvent vapor, or vapor via stream 320, or indirectly by any means known in the art.
    [0053] Further purification of the low impurity slurry stream 210 is accompanied in the secondary oxidation zone by the mechanism involving the recrystallization or development of the crystal and oxidation of the impurities and intermediates including FFCA. One of the functions of the secondary oxidation zone is to convert FFCA to FDCA. FFCA is considered to be monofunctional relative to a polyester condensation reaction because it contains only one carboxylic acid. FFCA is present in the carboxylic acid composition stream 110 and the low impurity paste stream 210. FFCA is generated in the primary oxidation zone 125 because of the 5-HMF reaction to FFCA can be about eight times faster than that the FFCA reaction to the desired di-functional FDCA product. Molecular oxygen or additional air can be fed in stream 320 to a secondary oxidation zone 335 in an amount necessary to oxidize a substantial portion of partially oxidized products such as FFCA in stream 210 to the carboxylic acid corresponding to FDCA. Generally, at least 70% by weight of the FFCA present in the low impurity slurry stream 210 is converted to the FDCA in the secondary oxidation zone 335. Preferably, at least 80% by weight of FFCA present in the low impurity slurry stream 210 is converted to FDCA in the secondary oxidation zone 335 and more preferably, at least 90% by weight of the FFCA present in the low impurity slurry stream 210 is converted to the FDCA in the secondary oxidation zone 335. The significant concentrations of the monofunctional molecules equal to the FFCA in the purified, dry FDCA product they are particularly harmful to the polymerization processes as these act as chain terminators during the polyester condensation reaction. [0054] As in the primary oxidizer zone 125, the catalyst system in the low impurity slurry stream 210 comprises at least one catalyst suitable for oxidation. Any catalyst known in the art capable of oxidizing the oxidizable compound can be used. Catalysts that are suitable for the primary oxidation zone 125 can be used in the secondary oxidation zone 335. Example of suitable catalysts comprise at least one selected from, but are not limited to, cobalt, bromine and manganese compounds, which are soluble in the selected oxidation solvent. In another embodiment of the invention, the catalyst system comprises cobalt, manganese and bromine in which the weight ratio of cobalt to manganese in the reaction mixture is about 1 to about 400, or 1 to about 100, or 1 to about 40, or 1 to about 30, or 1 to about 20, or 1 to about 10. In another embodiment of the invention, the weight ratio of cobalt to bromine is about 0.7 at about 8, or 0.75 at about 3.5. The cobalt concentration of the catalyst can vary from about 10 ppm to about 600 ppm, or around 50 ppm to about 300 ppm and the amount of manganese from about 0.1 ppm to about 100 ppm, or manganese from about 1 ppm to about 50 ppm and the amount of bromine from about 3 ppm to about 600 ppm, or bromine from about 50 ppm to about 300 ppm with respect to the total weight of the liquid in the reaction medium secondary oxidation zone 335. Limiting catalysts loaded in stream 210 compared to streams 110 minimize the oxidation of organic molecule products to CO and CO2. This can be accompanied by the net displacement zone 225.
    [0055] The optional stream 340 can be used as a catalyst forming stream or solvent forming stream to adjust the concentrations of the catalysts in the secondary oxidation zone 335. The stream 340 comprises the same catalyst composition as in the primary oxidation zone 125. The feed stream temperature 340 can be kept close to the operating temperature of the secondary oxidation zone 335 to prevent the wide temperature drop from the secondary oxidation zone 335.
    [0056] As shown in tables 1 to 4 secondary oxidation stream 310 with less than 500 ppm FFCA and preferably less than 10 ppm FFCA can be achieved by using secondary oxidation / post-oxidation under the conditions described in this report . The combination of temperature, residence time and concentrations of catalysts set out in Tables 1 to 4 produces pDFCA with a very low FFCA content. As can be seen from the tables, crude FDCA from primary oxidation with varying levels of FFCA can be purified using the conditions (temperature and residence time) described in this invention. The raw FDCA with the even higher level of color as measured by b * can be purified using the longest reaction time and highest temperature set out in the tables.
    [0057] The amount of oxygen fed into the secondary oxidation zone 335 in the control to limit the burning of organic molecules to CO2. The amount of oxygen in stream 330 is monitored and used to control the amount of oxygen fed into stream 320. Another function of the secondary oxidation zone 335 is to dissolve and recrystallize the solids present in the low impurity slurry stream 210 fed to a secondary oxidation. At least 10% by weight, 25% by weight, 50% by weight and preferably at least 85% by weight of the solid impurities and oxidation by-products in stream 210 fed to a secondary oxidation zone 335 go into the solution when the FDCA particles are dissolved and recrystallized in the secondary oxidation zone 335. The effluent gas from the secondary oxidation zone is removed via line 330 and fed into a recovery system where the solvent is removed from the effluent gas comprising volatile organic compounds ( VOCs). VOCs including methyl bromide can be treated, for example, by incineration in a catalytic oxidation unit. The purified pulp stream 310 generated in the secondary oxidation zone is sent to the crystallization zone 425.
    [0058] Step (d) comprises crystallization of the secondary oxidation slurry 310 in the crystallization zone 425 to form a crystallized slurry stream 410. Generally, the crystallization zone 425 comprises at least one crystallizer. The vapor from the crystallization zone can be condensed in at least one condenser and returned to a crystallization zone 425 or always sent from the crystallization zone 425. Optionally, the condenser liquid or vapor product from the crystallization zone can be recycled , or it can be removed or sent to an energy recovery device. In addition, the off gas from the crystallizer is removed via the 420 line and can be sent to a recovery system where the solvent is removed and the effluent gas from the crystallizer comprises VOCs that can be treated, for example, by incineration in a catalytic oxidation, When the carboxylic acid is FDCA, the purified pulp stream 310 from the secondary oxidation zone 335 is fed to a crystallization zone 425 comprising at least one crystallizer where it cools to a temperature between about 40 ° C at about 175 ° C to form a crystallized paste stream 410, preferably at a temperature between about 50 ° C to about 170 ° C and more preferably from about 60 ° C to about 165 ° C.
    [0059] The crystallized paste stream 410 is then sent to a cooling zone 430 to generate a cooled crystallized paste stream 510. Cooling of the crystallized paste stream 410 can be accompanied by any means known in the art. Typically, the cooling zone 430 comprises a sparkling tank. The current temperature 510 can vary from 35 ° C to 160 ° C, 45 ° C to 120 ° C and preferably from 55 ° C to 95 ° C.
    [0060] In another embodiment, a portion of up to 100% of the secondary oxidation slurry stream 310 is sent directly to a cooling zone 430, thus the portion is not subjected to a crystallization zone 425. In yet another an embodiment, a portion of up to 100% of the crystallized pulp stream 410 is sent directly to a secondary liquid displacement zone which is not illustrated in Figure 1. Up to 100% of the pulp effluent comprising FDCA from a displacement zone secondary liquid can be sent to a solid-liquid separation zone 625 and / or sent directly to a cooling zone 430. The function of the secondary liquid displacement zone is to move a portion of the solvent in the crystallized paste stream 410 with fresh solvent and / or water in which one serving should be greater than 5 percent by weight. The secondary liquid displacement zone is separated and distinguished from the liquid displacement zone 225 located after primary oxidation zone 125. The same type can be used for both primary and secondary displacement zones. In yet another embodiment, crystallized paste stream 410 can be sent directly to a solid-liquid separation zone 625 without first being processed in the cooling zone 430.
    [0061] Step (e) comprises isolating, washing and removing water from the solids present in the crystallized paste stream, cooled 510 in the solid-liquid separation zone 625. These functions can be accompanied in a simple solid-liquid separation device or multiple solid-liquid separation devices. The solid-liquid separation zone 625 comprises at least one solid-liquid separation device capable of separating solids and liquids, washing the solids with a washing solvent stream 620 and reducing the% moisture in the washed solids to less than 30% by weight, less than 25% by weight, less than 20% by weight, less than 15% by weight and preferably less than 10% by weight.
    [0062] Equipment suitable for the liquid solid separation zone 625 can typically be comprised of, but not limited to, the following types of devices: centrifuges, cyclones, rotating drum filter, belt filters, pressure leaf filters , candle filters, etc. The preferred liquid solid separation device for the liquid solid separation zone 625 is a rotary pressure drum filter. The vapor temperature of the cooled crystallized paste 510 which is sent to the solid-liquid separation zone 625 can vary from 50 ° C to 140 ° C, 70 ° C to 120 ° C and is preferably from 75 ° C to 95 ° C . The washing solvent stream 620 comprises a liquid suitable for displacement and washing of the main liquid substance from the solids.
    [0063] In an embodiment of the invention, a suitable washing solvent comprises acetic acid and water. In another embodiment, a suitable solvent comprises up to 100% water in water. The temperature of the washing solvent can vary from 20 ° C to 135 ° C, 40 ° C and 110 ° C and preferably from 50 ° C to 90 ° C. The amount of the washing solvent used is defined as the washing ratio and equals the washing mass divided by the solid mass on a continuous or batch basis. The washing ratio can vary from about 0.3 to about 5, about 0.4 to about 4 and preferably about 0.5 to 3.
    [0064] After the solids are washed in the liquid solid separation zone, they have the water removed. The term water removal is defined as the reduction of the solvent from the wet cake and does not require the solvent to be water or contain water. The removal of water involves reducing the mass of moisture present with the solids to less than 30% by weight, less than 25% by weight, less than 20% by weight, less than 15% by weight and more preferably less than 10% by weight resulting in the generation of the purified wet pie stream 610. In one embodiment, the removal of water accompanied in a filter by the passage of a gas stream through the solids to displace the free liquid after the solids have been washed with the washing solvent. In another embodiment, water removal is achieved by centrifugal forces in a solid-bowl or perforated bowl centrifuge. The stream 630 generated in the solid-liquid separation zone 625 is a stream of main liquid substance comprising oxidation solvent, catalyst for some impurities and oxidation by-products. In one embodiment, a portion of the stream 630 is sent to a purge zone 235 and a portion is sent back to a primary oxidation zone 125 where a portion is at least 5% by weight. The washing liquid stream 640 is also generated in the solid-liquid separation zone 625 and comprises a portion of the main liquid substance present in stream 510 and the washing solvent where the mass ratio of the main liquid substance is the mass of solvent wash time is less than 3 and preferably less than 2. [0065] Step (f) comprises drying the purified wet pie stream 610 in a drying zone 725 to generate a dry purified carboxylic acid 710 and a steam stream 720. In one embodiment, steam stream 720 comprises steam from washing solvent. In another embodiment, vapor stream 720 comprises oxidizing solvent and washing solvent. Drying zone 725 comprises at least one dryer and may be accompanied by any means known in the art which is capable of evaporating at least 10% of the volatiles remaining in the purified wet cake stream 610 to produce a purified, dried carboxylic acid 710 comprising FDCA purified and a 720 steam stream. For example, indirect contact dryers include, but are not limited to, a rotary steam tube dryer, a Single Shaft Porcupine rtm dryer and a Bepex Solidaire rtm dryer · Direct contact dryers include , but are not limited to, a fluid bed dryer and drying on a conveyor line can be used by drying to produce the stream 710. The purified, dried carboxylic acid 710 comprising purified FDCA can be a carboxylic acid composition with less than 8% humidity, preferably less than 5% humidity and more preferably less than 1% humidity and even more preferable substantially less than 0.5% and even more preferably less than 0.1%. In another embodiment of this invention, if the liquid portion of the purified wet pie stream 610 comprises water and contains less than 0.1% by weight acetic acid, less than 500 ppm by weight acetic acid and preferably less than 200 ppm by weight of chain 610 can be fed directly to a polymerization zone without first being dried.
    [0066] In an embodiment of the invention, a vacuum system can be used to remove the steam stream 720 from the drying zone 725. If a vacuum system is used in this way, the current pressure 720 at the outlet of the dryer can range from about 760 mmHg to about 400 mmHg, from about 760 mmHg to about 600 mmHg, from about 760 mmHg to about 700 mmHg, from about 760 mmHg to about 720 mmHg and about from 760 mmHg to about 740 mmHg where pressure is measured in mmHg above absolute vacuum. The contents of the conduit between the solid-liquid separation zone 625 and drying zone 725 used to transfer a purified wet cake stream 610 comprises wet cake stream and gas in which the gas is the continuous phase. The pressure at the outlet of the liquid solid separation zone 625 may be close to the pressure where the vapor stream 720 exits the drying zone 725, where the closure is defined as within 2 psi (13.7 kPa abs.) , within 0.8 psi (5.51 kPa abs.) and preferably within 0.4 psi (2.75 kPa abs.) [0067] In an embodiment of the invention, the purified, dried carboxylic acid 710 has a b * less than about 9.0. In another embodiment of the invention, the color b * of the purified, dried carboxylic acid 710 is less than about 6.0. In another embodiment of the invention, the b * color of the purified, dried carboxylic acid 710 is less than about 5.0. In another embodiment of the invention, the b * color of the purified, dried carboxylic acid 710 is less than about 4.0. In another embodiment of the invention, the b * color of the purified, dried carboxylic acid 710 is less than about 2. The b * color is one of the three-color attributes measured on a spectroscopic reflectance based instrument. A Hunter Ultrascan XE instrument in reflectance mode is typically the measuring device. Positive readings mean the degree of yellow (or absorbance of blue), while negative readings mean the degree of blue (or absorbance of yellow).
    [0068] It should be estimated that the previously described process zones can be used in any other logical order to produce a purified, dried 710 carboxylic acid. It should also be estimated that when process zones are reordered, process conditions can change . It is also understood that all percentage values are percentages by weight.
    [0069] Step (g) is optionally a step comprising discoloration of the FDCA in this process or an FDCA esterified with a diol stream through hydrogenation. In one embodiment, the diol stream comprises ethylene glycol. In another embodiment, the diol stream comprises isomers of cyclohexane diol, preferably the isomer of 1-4 cyclohexane diol. Discoloration of the FDCA in this process or an esterified FDCA can be accompanied by any means known in the art and is not limited to hydrogenation. However, for example, in an embodiment of the invention, the discoloration can be accompanied by the reaction of a carboxylic acid that has undergone the esterification treatment, for example, with ethylene glycol, with molecular hydrogen in the presence of a hydrogenation catalyst in a reaction zone to produce a solution of the discolored carboxylic acid or a product of the discolored ester.
    [0070] For the reactor zone, there are no special limits on its shape or construction, subject to a provision that allows the supply of hydrogen to effect the intimate contact of the carboxylic acid or ester product with the catalyst in the reactor zone. Typically, the hydrogenation catalyst is usually a single metal group VIII or combination of the group of metals VIII. Preferably, the catalyst is selected from the group consisting of palladium, ruthenium, rhodium and a combination thereof. The reactor zone comprises a hydrogenation reactor that operates at a temperature and pressure sufficient to hydrogenate a portion of the compounds characteristically yellow to the colorless derivatives.
    [0071] Since the numerous modifications and changes will readily occur to that person skilled in the art, these are not desired to limit this invention to the exact process and operations illustrated and described above and consequently all modifications and suitable equivalents can be brought together, to be within the scope of the invention Examples [0072] This invention can still be illustrated by the following examples of the embodiments thereof, although it is understood that these examples are included for the purposes of the illustration only and are not intended to limit the scope of the invention other than otherwise specifically stated. Series of examples 1 [0073] In examples la-4b, glacial acetic acid, crude FDCA containing some FFCA and the catalyst components in the concentrations described in tables 1, 2, 3 and 4 were transferred to a 300 ml titanium autoclave equipped with a high pressure condenser and a deflector. Cobalt, manganese and ionic bromide were supplied as cobalt (II) acetate tetrahydrate, manganese (II) acetate and sodium bromide and / or aqueous hydrobromic acid respectively. The autoclave was pressurized with approximately 50 psig (344.7 kPa man.) Of nitrogen and the reaction mixture was heated to the desired temperature in a closed system (ie, with no gas flow) with stirring. At the reaction temperature, an air flow of 1500 sccm was introduced at the bottom of the solution and the reaction pressure was adjusted to the desired pressure. After 30 seconds from the beginning of the air supply, 1.0 g of peracetic acid in 5.0 ml of acetic acid was introduced using a blow-cycle to initiate the reaction. The reaction continued for the desired period of time and the air flow was stopped and the autoclave was cooled to room temperature and depressurized. The heterogeneous mixture was filtered to isolate the pFDCA. The filtrate mass was recorded. The pFDCA was washed with 60 ml of acetic acid twice and then twice with 100 ml of Dl water. The washed pFDCA was dried in an oven at 110 ° C under vacuum overnight and then weighed. The solid was analyzed by gas chromatography using the BSTFA, HPLC, ICP derivatization method and color measurement methods (b *). The filtrate was analyzed by gas chromatography using the BSTFA derivatization method only.
    [0074] The effluent gas was analyzed by CO and CO2 by ND-1R (ABB, Advanced Optima) and Cf by a paramagnetism detection system (Servomex, model 1440).
    Analytical [0075] Samples of the gas chromatography method process were analyzed using a Shimadzu 2010 gas chromatography model (or equivalent) equipped with a split / heated injector (300 ° C) and a flame ionization detector (300 ° C). A capillary column (60 meter x 0.32 mm ID) coated with (6% cyanopropylphenyl-methylpolysiloxane at 1.0 pm film thickness (such as DB-1301 or equivalent) was used. Helium was used as the gas loader with an initial column pressure of 29.5 psi (203.3 kPa) and an initial column flow of 3.93 mL / minute while the linear velocity of the carrier gas of 45 cm / second was kept constant throughout oven temperature program The column temperature was programmed as follows: The initial oven temperature was presented at 80 ° C and was maintained for 6 minutes, the stove was tilted up to 150 ° C at 4 ° C / minute and was maintained at 150 ° C for 0 minutes, the stove was tilted to 240 ° C at 10 ° C / minute and held at 240 ° C for 5 minutes, then the stove was tilted to 290 ° C at 10 ° C / minute and was maintained at 290 ° C for 17.5 minutes (total time was 60 mins) 1.0 μΐ of the prepared sample solution was injected with a split ratio 40: 1. The EZ-Chrom Elite chromatography data system software was used for data acquisition and data processing. Sample preparation was done by weighing 0.1 g (exactly 0.1 mg) of the sample in a GC flask and adding 200.0 μΐ of the ISTD solution (1% by volume of the decan in pyridine) and 1000 μΐ of BSTFA (N, O-bis (trimethylsilyl) trifluoroacetamide) with 1% TMSC1 (trimethylchlorosilane) to the GC vial. The contents were heated to 80 ° C for 30 minutes to ensure complete derivatization. 1.0 μΐ of this prepared sample solution was injected by GC analysis.
    [0076] Liquid chromatographic method for measuring the low level of FFCA in FDCA
    [0077] The samples are analyzed with an Agilent 1200 LC unit consisting of a quaternary pump, a self-sampler (3 uL injection), a thermostated column compartment (35 C) and a UV / vis series diode detector (280 nm). The chromatograph is fitted with a 150 mm x 4.6 mm Thermo Aquasil Cl8 column packed with 5 micron particles. The solvent flow program is shown in the table below: Channel A is 0.1% of phosphoric acid in water, channel B is acetonitrile and channel C is tetrahydrofuran (THF) Time (min)% A% B% C Flow (mi * min) Initial 95.0 0.0 5.0 1.50 7 95.0 0.0 5.0 1.50 10 15.0 80.0 5.0 1.50 12 15.0 80.0 5 , 0 1.50 12.1 95.0 0.0 5.0 1.50 15 95.0 0.0 5.0 1.50 Balance time: 1 minute [0078] EZChrom elite is used for processing control data and HPLC. A 5-point linear calibration is used in the (approximate) range of 0.25 to 100 ppm FFCA. The samples are prepared to dissolve -0.05 g (weighed exactly to 0.0001 g) in 10 ml of 50:50 DMF / THF; the weights of the larger sample can be used for samples where the FFCA is present at a very low level, as long as the solubility of FDCA is not exceeded. Sonification is used to ensure complete dissolution of the sample in the solvent. A portion of the prepared sample is transferred to a self-sampling vial by injection into the LC.
    Color measurement. 1) Assemble the Carver Press die as instructed in the directions — place the die on the base and place the bottom of the polished 40 mm cylinder face up. 2) Place a 40 mm plastic cup (Chemplex Plasticup, 39.7 x 6.4 mm) in the matrix. 3) Fill the beaker with the sample to be analyzed. The exact amount of sample added is not important. 4) Place the top 40 mm polished cylinder face down on the sample. 5) Insert the plunger into the matrix. No “canvas” should be displayed on the assembled matrix. 6) Place the die on the Carver Press, ensuring that it is close to the center of the upper press. Near the security door. 7) Raise the die until the upper press makes contact with the plunger. Apply> 20,000 lbs (9.07 tons) of pressure. To remain that the matrix remains under pressure for approximately 3 minutes (exact non-critical time). 8) Release the pressure and lower the lower press that holds the die. 9) Disassemble the matrix and remove the cup. Place the cup in a labeled plastic bag (Nasco Whirl-Pak 4 oz). 10) Use a HunterLab Colorquest XE colorimeter, create the following method (Hunterlab EasyQuest QC software, version 3.6.2 or later) Mode: RSIN-LAV (Reflectance Specular Included-barge Area View) measurements: CIE L * a * b * CIE XYZ 11) Standardize the nstrument as requested by the software using the light capture accessory and the certified white tile accessory compressed against the reflectance door. 12) Perform a green tile pattern using the certified white tile and compare the CIE X, Y and Z values obtained against the certified tile values. The values obtained must be ± 0.15 units in each scale of the established values. 13) Analyze the sample in the bag by compressing it against the reflectance port and obtaining the spectrum and values L *, a *, b *. Obtain duplicate readings and average values for the report.
    Interpretation of the results: [0079] During the oxidation of 5-HMF or its derivatives to FDCA in the primary oxidation zone 125 several impurities are produced particularly species of mono-carboxylic acid similar to 5-formyl furan-2-carboxylic acid (FFCA) . These mono-carboxylic acids are less desirable since they end the chain of a polyester produced from a crude dicarboxylic acid. Examples 1 a, to 4b (Tables 1, 2, 3 and 4) demonstrate that pFDCA with a very low level of FFCA and b * can be achieved by conducting a second oxidation of the raw pulp vapor FDCA 210 with catalyst systems consisting of cobalt, manganese and aqueous hydrobromic acid. The concentrations of the catalysts can be controlled to minimize the burning of carbon during the post-oxidation process in the secondary oxidation zone 335 compared to the primary oxidation zone 125. This can be achieved through liquid displacement with a fresh solvent vapor in the zone 225. Careful choice of catalyst compositions and reaction conditions results in the minimum level of organic burning as shown in tables 1 to 4. Various combinations of the longer reaction time, higher temperature or higher catalyst concentrations result in a pFDCA with less than 10 ppm FFCA, Table 1. As can be seen from Figure 2, longer reaction time and higher temperature are preferred to minimize the color of pFDCA as measured by b *.
    Table 1. Secondary oxidation of crude FDCA with 0.76% by weight of FFCA and b * of 8.68. * P = 130 psig (896.3 kPa, man.) Table 2 Secondary oxidation of crude FDCA with 1.08% by weight of FFCA and b * of 8.08. * P = 130 psig. (896.3 kPa. Man) Table 3. Secondary oxidation of crude FDCA with 1.93% by weight of FFCA and b * of 11.39. * P - 130 psig. (896.3 kPa. Man) Table 4. Secondary oxidation of crude FDCA with 0.43% by weight of FFCA and b * of 4.15. * P -130 psig (896.3 kPa. Man) Series of examples 2 [0080] In the examples 5a-7b, glacial acetic acid, crude FDCA containing some FFCA and the catalyst components in the concentrations described in tables 5, 6 and 7 were transferred to a 300 ml titanium autoclave equipped with a high pressure condenser and a deflector. Cobalt, manganese and ionic bromide were supplied as cobalt (II) acetate tetrahydrate, manganese (II) acetate and sodium bromide and / or aqueous hydrobromic acid respectively. The autoclave was pressurized with approximately 50 psig (344.7 kPa man.) Of nitrogen and the reaction mixture was heated to the desired temperature in a closed system (ie, with no gas flow) with stirring. At the reaction temperature, an air flow of 1500 sccm was introduced at the bottom of the solution and the reaction pressure was adjusted to the desired pressure. After 30 seconds from the beginning of the air supply, 1.0 g of peracetic acid in 5.0 ml of acetic acid was introduced using a blow-case to initiate the reaction. The reaction continued for the desired period of time and the air flow was stopped and the autoclave was cooled to room temperature and depressurized. The heterogeneous mixture was filtered to isolate the pFDCA. The filtrate mass was recorded. The pFDCA was washed with 60 ml of acetic acid twice and then twice with 100 ml of DL water. The washed pFDCA was dried in an oven at 110 ° C under vacuum overnight and then weighed. The solid was analyzed by gas chromatography using BSTFA derivatization method, HPLC, ICP and color measurement methods (b *). The filtrate was analyzed by gas chromatography using BSTFA derivatization method only.
    [0081] The effluent gas was analyzed by CO and CO2 by ND-1R (ABB, Advanced Optima) and O2 by a paramagnetism detection system (Servomex, model 1440).
    Analytical [0082] Samples of the gas chromatography method process were analyzed using a Shimadzu 2010 gas chromatography model (or equivalent) equipped with a split / heated injector (300 ° C) and a flame ionization detector (300 ° C). A capillary column (60 meter x 0.32 mm ID) coated with (6% cyanopropylphenyl) -methylpolysiloxane at 1.0 pm of the film thickness (such as DB-1301 or equivalent). Õ helium was used as the carrier gas with an upper column pressure of 29.5 psi (203.3 kPa man.) And an initial column flow of 3.93 mL / minute while the linear velocity of the carrier gas was 45 cm / second was kept constant throughout the oven temperature program. The column temperature was programmed as follows: The initial oven temperature was presented at 80 ° C and was maintained for 6 minutes, the oven was tilted up to 150 ° C at 4 ° C / minute and was kept at 150 ° C for 0 minute, the oven was tilted up to 240 ° C at 10 ° C / minute and held at 240 ° C for 5 minutes, then the oven was tilted up to 290 ° C at 10 ° C / minute and held at 290 ° C for 17.5 minutes (the total performance time was 60 mins). 1.0 pl of the prepared sample solution was injected with a 40: 1 split ratio. The EZ-Chrom Elite chromatography data system software was used for data acquisition and data processing. Sample preparation was done by weighing 0.1 g (exactly 0.1 mg) of the sample in a GC flask and adding 200.0 pl of the ISTD solution (1% by volume of the decan in pyridine) and 1000 pl of BSTFA (N, O-bis (trimethylsilyl) trifluoroacetamide) with 1% TMSC1 (trimethylchlorosilane) to the GC vial. The contents were heated to 80 ° C for 30 minutes to ensure complete derivatisation. 1.0 pl of this prepared sample solution was injected by GC analysis.
    [0083] Liquid chromatographic method by measuring the low level of FFCA in FDCA: The samples are analyzed with an Agilent 1200 LC unit consisting of a quaternary pump, a self-sampler (3 uL injection), a thermostated column compartment (35 C ) and a UV / vis diode series detector (280 nm). The chromatograph is fitted with a 150 mm x 4.6 mm Thermo Aquasil Cl 8 column packed with 5 micron particles. The solvent flow program is shown in the table below: Channel A is 0.1% of phosphoric acid in water, channel B is acetonitrile and channel C is tetrahydrofuran (THF) Time (min)% A% B% C Flow (ml / min) Initial 95.0 0.0 5.0 1.50 7 95.0 0.0 5.0 1.50 10 15.0 80.0 5.0 1.50 12 15.0 80.0 5 , 0 1.50 12.1 95.0 0.0 5.0 1.50 15 95.0 0.0 5.0 1.50 Balance time: 1 minute [0084] The EZChrom elite is used to control the data processing and HPLC. A 5-point linear calibration is used in the (approximate) range of 0.25 to 100 ppm FFCA. The samples are prepared to dissolve -0.05 g (weighed exactly to 0.000 lg) in 10 ml of 50:50 DMF / THF; the weights of the larger sample can be used for samples where the FFCA is present at a very low level, as long as the solubility of FDCA is not exceeded. Sonification is used to ensure complete dissolution of the sample in the solvent. A portion of the prepared sample is transferred to a self-sampling vial by injection into the LC.
    Color measurement. 1) Assemble the Carver Press die as instructed in the directions — place the die on the base and place the bottom of the polished 40 mm cylinder face up. 2) Place a 40 mm plastic cup (Chemplex Plasticup, 39.7 x 6.4 mm) in the matrix. 3) Fill the beaker with the sample to be analyzed. The exact amount of sample added is not important. 4) Place the top 40 mm polished cylinder face down on the sample. 5) Insert the plunger into the matrix. No “canvas” should be displayed on the assembled matrix. 6) Place the die on the Carver Press, ensuring that it is close to the center of the upper press. Near the security door. 7) Raise the die until the upper press makes contact with the plunger. apply> 20,000 Ibs of pressure. To remain that the matrix remains under pressure for approximately 3 minutes (exact non-critical time). 8) Release the pressure and lower the lower press that holds the die. 9) Disassemble the matrix and remove the cup. Place the cup in a labeled plastic bag (Nasco Whirl-Pak 4 oz). 10) Use a HunterLab Colorquest XE colorimeter, create the following method (Hunterlab EasyQuest QC software, version 3.6.2 or later) Mode: RSIN-LAV (Reflectance Specular Included-barge Area View) measurements: CIE L * a * b * CIEX YZ 11) Standardize the instrument as requested by the software using the light capture accessory and the certified white tile accessory compressed against the reflectance door. 12) Perform a green tile pattern using the certified white tile and compare the CIE X, Y and Z values obtained against the certified tile values. The values obtained must be ± 0.15 units in each scale of the established values. 13) Analyze the sample in the bag by compressing it against the reflectance port and obtaining the spectrum and values L *, a *, b *. Obtain duplicate readings and average values for the report.
    Interpretation of results: [0085] During the oxidation of 5-HMF or its derivatives to FDCA in the primary oxidation zone, several impurities are produced, particularly mono-carboxylic acid species similar to 5-formyl furan-2-carboxylic acid (FFCA). These mono-carboxylic acids are less desirable since they end the chain of a polyester produced from a crude dicarboxylic acid. Examples 5a, up to 7b (Tables 5, 6 and 7) demonstrate that pFDCA with less than 500 ppm FFCA and b * less than 5 can be achieved by conducting a second oxidation of crude FDCA with catalyst systems consisting of cobalt , manganese and aqueous hydrobromic acid.
    Table 5. Composition of pFDCA from secondary oxidation of crude FDCA which has 0.76% by weight of FFCA and b * of 8.68. * P = 130 psig Table 6. Composition of pFDCA from secondary oxidation of crude FDCA which has 1.08% by weight of FFCA and b * of 8.08. * P = 130 psig Table 7. Composition of pFDCA from secondary oxidation of crude FDCA which has 0.43% by weight of FFCA and b * of 4 , 15. * P = 130 psig CLAIMS NOT LIMITED TO THE DESCRIPTIONS
    [0086] The preferred forms of the invention described above are only illustrated as and should not be used in a limiting sense to interpret the scope of the present invention. The modifications to the exemplary embodiments, presented above, must be promptly made by that person skilled in the art without diverging from the spirit of the present invention.
    [0087] The inventors thereby establish their intention in the Doctrine of equivalents to determine and estimate the reasonably clear scope of the present invention when it relates to any mechanism that does not differ from but outside the literal scope of the invention as presented in the following claims .
    权利要求:
    Claims (4)
    [1]
    1. Process for producing a purified paste stream comprising FDCA, characterized by the fact that said process comprises: (a) oxidizing an oxidizable compound in a primary oxidation zone in the presence of a solvent stream, an oxidation gas stream and a catalyst system, wherein said stream of oxidizable crude material comprises at least one compound selected from the group consisting of 5- (hydroxymethyl) furfural (5-HMF), 5-HMF esters (5-RC (O) OCH2 -furfural where R = C1-C3 alkyl), 5-HMF ethers (5-R'OCH2-furfural, where R '= C1-C4 alkyl), 5-furfural ethers (5-R "-furfural, where R" = methyl), mixed feed stocks of 5-HMF and 5-HMF esters, mixed feed stocks of 5-HMF and 5-HMF ethers and mixed feed stocks of 5-HMF and 5-furfural alkyls to produce an acid composition carboxylic acid comprising furan-2,5-dicarboxylic acid (FDCA); (b) sending said carboxylic acid composition to a liquid displacement zone to produce a substituted main liquid stream and a low impurity content stream; (c) sending said low impurity pulp stream to a secondary oxidation zone to form a purified pulp stream; wherein said secondary oxidation zone comprises a secondary catalyst system; wherein said purified pulp stream comprises FDCA; wherein said oxidation temperature in said secondary oxidation zone is at least 10 ° C higher than the oxidation temperature in the primary oxidation zone: and wherein said secondary catalyst system comprises cobalt in a range of 10 ppm at 600 ppm with respect to the weight of the liquid in the secondary oxidation zone, manganese an amount ranging from 0.1 ppm to 100 ppm in weight with respect to the weight of the liquid in the secondary oxidation zone and bromine in an amount ranging from 3 ppm to 600 ppm by weight with respect to the weight of the liquid in the secondary oxidation zone; and where the catalyst system in the primary oxidation zone comprises cobalt in the range of 1000 ppm to 6000 ppm, manganese in the range of 2 ppm to 600 ppm and bromine in the range of 300 ppm to 4500 ppm with respect to the total weight of the liquid in the reaction medium of the primary oxidation zone.
    [2]
    Process according to claim 1, characterized in that said stream of oxidizable crude material comprises at least one compound selected from the group consisting of 5- (hydroxymethyl) furfural (5-HMF), 5-HMF esters ( 5-RC (O) OCH2-furfural where R = C1-C3 alkyl) and 5-HMF ethers (5-R'OCH2-furfural, where R '= C1-C4 alkyl) and where the yield of furan-2 acid , 5-dicarboxylic is greater than 90%.
    [3]
    Process according to claim 1, characterized by the fact that it still comprises sending said replaced main liquid to a purging zone.
    [4]
    Process according to claim 1, characterized in that said secondary catalyst system wherein said secondary catalyst system comprises cobalt in a range from 50 ppm to 300 ppm with respect to the weight of the liquid in the oxidation zone secondary, manganese an amount ranging from 1 ppm to 50 ppm by weight with respect to the weight of the liquid in the secondary oxidation zone and bromine in an amount ranging from 50 ppm to 300 ppm by weight with respect to the weight of the liquid in the secondary oxidation zone .
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    同族专利:
    公开号 | 公开日
    US20140024843A1|2014-01-23|
    EP3578552A1|2019-12-11|
    EP2875008A4|2015-12-09|
    US8809556B2|2014-08-19|
    BR112014030065A2|2017-06-27|
    WO2014014979A1|2014-01-23|
    EP2875008A1|2015-05-27|
    ES2744617T3|2020-02-25|
    EP2875008B1|2019-07-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2797197A|1956-07-02|1957-06-25|Sun Oil Co|Soluble oil and preparation|
    US3203963A|1963-04-18|1965-08-31|Atlas Chem Ind|Method of purifying dehydromucic acid|
    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|
    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|
    US7196215B2|2001-06-04|2007-03-27|Eastman Chemical Company|Process for the production of purified terephthalic acid|
    US6737481B1|2002-12-19|2004-05-18|E. I. Du Pont De Nemours And Company|Ester-modified dicarboxylate polymers|
    US7052764B2|2002-12-19|2006-05-30|E. I. Du Pont De Nemours And Company|Shaped articles comprising poly[ dicarboxylate] or poly(trimethylene-co-dianhydro-dicarboxylate with improved stability|
    US20040215036A1|2003-04-25|2004-10-28|Robert Lin|Method for heating a crude carboxylic acid slurry in a post oxidation zone by the addition of steam|
    US20060205977A1|2005-03-08|2006-09-14|Sumner Charles E Jr|Processes for producing terephthalic acid|
    US20070179312A1|2006-02-02|2007-08-02|O'meadhra Ruairi Seosamh|Process for the purification of a crude carboxylic axid slurry|
    EP2050742B1|2006-03-10|2010-07-07|Furanix Technologies B.V|Use of an organic acid esters of 5-hydroxymethylfurfural|
    EP1834950A1|2006-03-10|2007-09-19|Avantium International B.V.|Method for the synthesis of 5-alkoxymethylfurfural ethers and their use|
    JP2007261990A|2006-03-28|2007-10-11|Canon Inc|Method for producing furan-2,5-dicarboxylic acid|
    JP5006561B2|2006-03-28|2012-08-22|キヤノン株式会社|Method for producing furandicarboxylic acid|
    JP4804187B2|2006-03-28|2011-11-02|キヤノン株式会社|Method for producing furan-2,5-dicarboxylic acid|
    WO2007146636A1|2006-06-06|2007-12-21|Wisconsin Alumni Research Foundation|Catalytic process for producing furan derivatives from carbohydrates in a biphasic reactor|
    US7700788B2|2006-10-31|2010-04-20|Battelle Memorial Institute|Hydroxymethyl furfural oxidation methods|
    JP5147309B2|2007-06-21|2013-02-20|キヤノン株式会社|Process for producing 2,5-furandicarboxylic acid|
    JP2009013079A|2007-07-02|2009-01-22|Canon Inc|Method for producing furan-2,5-dicarboxylic acid|
    WO2009023174A2|2007-08-10|2009-02-19|Archer Daniels Midland Company|Enzymatic oxidation of hmf|
    CA2697796C|2007-09-07|2016-04-05|Furanix Technologies B.V.|Hydroxymethylfurfural ethers from sugars or hmf and mixed alcohols|
    WO2009030505A2|2007-09-07|2009-03-12|Furanix Technologies B.V.|Hydroxymethylfurfural ethers from hmf and olefins|
    WO2009030506A2|2007-09-07|2009-03-12|Furanix Technologies B.V.|Hydroxymethylfurfural ethers from sugars or hmf and branched alcohols|
    US20100218415A1|2007-09-07|2010-09-02|Furanix Technologies B.V.|Hydroxymethylfurfural ethers from sugars and higher alcohols|
    US7385081B1|2007-11-14|2008-06-10|Bp Corporation North America Inc.|Terephthalic acid composition and process for the production thereof|
    JP2011506478A|2007-12-12|2011-03-03|アーチャーダニエルズミッドランドカンパニー|Conversion of carbohydrates to hydroxymethylfurfural and derivatives|
    JP5252969B2|2008-03-31|2013-07-31|エア・ウォーター株式会社|Process for producing 2,5-furandicarboxylic acid|
    US8252953B2|2008-05-01|2012-08-28|Monsanto Technology Llc|Metal utilization in supported, metal-containing catalysts|
    NL2002382C2|2008-12-30|2010-07-01|Furanix Technologies Bv|A process for preparing a polymer having a 2,5-furandicarboxylate moiety within the polymer backbone and such polymers.|
    US8541616B2|2009-02-13|2013-09-24|Eastman Chemical Company|Addition of a methyl hydrogen terephthalate reactor to a dimethyl terephthalate process|
    EP2784069B2|2009-05-14|2019-05-01|Archer-Daniels-Midland Company|Oxidation of 5-alkoxy-furfural to 5-furan-2-carboxylic acid|
    CN102648191B|2009-10-07|2015-08-19|福兰尼克斯科技公司|Prepare the method for FDCA and ester thereof|
    JP5550303B2|2009-10-19|2014-07-16|キヤノン株式会社|Process for producing 2,5-furandicarboxylic acid|
    US8791278B2|2011-05-24|2014-07-29|Eastman Chemical Company|Oxidation process to produce a crude and/or purified carboxylic acid product|
    US20120302773A1|2011-05-24|2012-11-29|Eastman Chemical Company|Oxidation process to produce a crude and/or purified carboxylic acid product|US20120302768A1|2011-05-24|2012-11-29|Eastman Chemical Company|Oxidation process to produce a crude and/or purified carboxylic acid product|
    US9199958B2|2011-05-24|2015-12-01|Eastman Chemical Company|Oxidation process to produce a crude and/or purified carboxylic acid product|
    US8969404B2|2012-06-22|2015-03-03|Eastman Chemical Company|Purifying crude furan 2,5-dicarboxylic acid by hydrogenation|
    US8748479B2|2012-06-22|2014-06-10|Eastman Chemical Company|Process for purifying crude furan 2,5-dicarboxylic acid using hydrogenation|
    US9029580B2|2012-07-20|2015-05-12|Eastman Chemical Company|Oxidation process to produce a purified carboxylic acid product via solvent displacement and post oxidation|
    US8772513B2|2012-08-30|2014-07-08|Eastman Chemical Company|Oxidation process to produce a crude dry carboxylic acid product|
    US9156805B2|2012-11-20|2015-10-13|Eastman Chemical Company|Oxidative purification method for producing purified dry furan-2,5-dicarboxylic acid|
    US9573120B2|2014-05-08|2017-02-21|Eastman Chemical Company|Furan-2,5-dicarboxylic acid purge process|
    US9943834B2|2014-05-08|2018-04-17|Eastman Chemical Company|Furan-2,5-dicarboxylic acid purge process|
    US9944615B2|2014-05-08|2018-04-17|Eastman Chemical Company|Purifying crude furan 2,5-dicarboxylic acid by hydrogenation and a purge zone|
    US10010812B2|2014-05-08|2018-07-03|Eastman Chemical Company|Furan-2,5-dicarboxylic acid purge process|
    CN105214725B|2014-06-05|2018-02-16|湖南师范大学|Carbohydrate is effectively converted into the green catalysis method of 5 hydroxymethylfurfurals|
    CN105688988B|2014-12-16|2018-11-27|财团法人工业技术研究院|The oxidation reaction catalyst of furfural compounds and the method for oxidation of furfural compounds|
    WO2017076947A1|2015-11-04|2017-05-11|Basf Se|Process for preparing furan-2,5-dicarboxylic acid|
    WO2017123763A1|2016-01-13|2017-07-20|Rennovia Inc.|Processes for the preparation of 2,5-furandicarboxylic acid and intermediates and derivatives thereof|
    CN108299357A|2017-01-12|2018-07-20|中国科学院宁波材料技术与工程研究所|A kind of preparation method of disubstituted furan compound|
    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|
    US10421736B2|2017-07-20|2019-09-24|Eastman Chemical Company|Production of purified dialkyl-furan-2,5-dicarboxylatein a retrofitted DMT plant|
    US10344011B1|2018-05-04|2019-07-09|Eastman Chemical Company|Furan-2,5-dicarboxylic acid purge process|
    US10526301B1|2018-10-18|2020-01-07|Eastman Chemical Company|Production of purified dialkyl-furan-2,5-dicarboxylatein a retrofitted DMT plant|
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    2018-03-20| B06I| Technical and formal requirements: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2018-11-13| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2019-01-02| B15K| Others concerning applications: alteration of classification|Free format text: AS CLASSIFICACOES ANTERIORES ERAM: C07D 307/46 , C07D 307/48 , C07D 307/40 Ipc: C07D 307/60 (1974.07), C07D 307/68 (1974.07) |
    2019-05-21| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
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    US13/553,976|US8809556B2|2012-07-20|2012-07-20|Oxidation process to produce a purified carboxylic acid product via solvent displacement and post oxidation|
    PCT/US2013/050794|WO2014014979A1|2012-07-20|2013-07-17|An oxidation process to produce a purified carboxylic acid product via solvent displacement and post oxidation|
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