PROCESS FOR MANUFACTURING A COMPOSITION OF DIALQUIL FURAN-2,5-DICARBOXILATE (DAFD)

专利摘要:
process for making a dialkyl furan-2,5-dicarboxylate (dafd) composition, and composition process for producing a purified dimethyl-furan-2,5-dicarboxylate (dmfd) by feeding dicarboxylic furan acid and methanol to a esterification zone to generate a crude diester composition and purification of the crude diester composition with a physical separation process followed by crystallization, solid liquid separation and, optionally, drying to produce a purified dmfd composition. a portion of the stream generated by solid-liquid separation can be dissolved and subjected to crystallization and solid-liquid separation repeatedly. the process is useful for producing a purified dmfd composition having a low b *, at least 98% by weight of dafd solids and a low concentration of 5- (methoxycarbonyl) furan-2-carboxylic acid (mcfc) and 5-formylfuran- Methyl 2-carboxylate (mffc).
公开号:BR112014030066B1
申请号:R112014030066-6
申请日:2013-06-10
公开日:2020-12-15
发明作者:Ashfaq Shahanawaz Shaikh；Kenny Randolph Parker；Lee Reynolds Partin；Mesfin Ejerssa Janka
申请人:Eastman Chemical Company；
IPC主号:

专利说明:

1. Field of the invention
[0001] The invention relates to processes for the production of purified dialkyl-furan-2,5-dicarboxylate (DAFD) and purified DAFD compositions made therefrom. 2. Basics of the invention
[0002] Aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid or their diesters, dimethyl terephthalate as, for example, are used to produce a variety of polyester products, important examples of which are poly (ethylene terephthalate) and their copolymers. Aromatic dicarboxylic acids are synthesized by the catalytic oxidation of the corresponding dialkyl aromatic compounds that are obtained from fossil fuels, such as those described in US 2006/0205977 A1. The esterification of diacids using excess alcohol that produces the corresponding diesters has been described in US2010 / 0210867A1. There is a growing interest in the use of renewable resources such as food stocks for the chemical industries 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 a biofounded alternative to terephthalic acid and isophthalic acid. As aromatic diacids, the FDCA can be condensed with diols such as ethylene glycol to make polyester resins similar to polyethylene terephthalate (PET) as described in Gandini, A .; Silvestre, A. J; Neto, C. P .; Sousa, A. F .; Gomes, M. J. Poly. Sci. A 2009, 47, 295. FDCA was prepared by oxidizing 5- (hydroxymethyl) furfural (5-HMF) under air using homogeneous catalysts as described in US2003 / 0055271 A1 and in Partenheimer, W .; Grushin, V. V. Adv. Synth. Catal. 2001, 343, 102-111. However, achieving high yields proved to be difficult. A maximum of 44.8% yield using the Co / Mn / Br catalyst system and a maximum of 60.9% yield was reported using a Co / Mn / Br / Zr catalyst combination.
[004] In US 2008 / 182944A1, new furan polyols are disclosed that can react to produce oligomers useful in binding applications, in addition to disclosing a method for producing furan-2,5-dicarboxylic acid dimethyl ester (FDME) by reaction of furan-2,5-dicarboxylic acid furan (FDCA) with methanol in a round bottom flask containing an acid catalyst (sulfuric acid). This mixture is refluxed for 30 hours, and the precipitate is then dissolved in 20% ethyl acetate and acetonitrile. The unreacted FDCA is absorbed on Amberlyst A-21 resin, and removed by filtration. The solvent is removed on a rotary evaporator and vacuum oven to give an off-white solid. This document does not describe or suggest a process for making furan-2,5-dicarboxylate dialkyl that uses a solid-liquid separation zone, in which at least a portion of the crystallized DAFD composition is washed in the solid-liquid separation zone with the wash composition to produce a purified DAFD product composition containing water.
[005] In Lewkowski et al., Polish J. Of Chem., Polskie Towarzystwo Chemiczne, PL, vol. 75, no. 12 (1 Jan. 2001), pp.1943-1946, XP09147732, ISSN: 0137-5083, methods for the preparation of FDCA methyl and ethyl esters are described in which a furan-2,5-dicarboxylic acid salt, i.e. ie, dichloride, is used as a starting material. The acid salt is dissolved in alcohol, (methanol or ethanol) and refluxed for 2 hours. The solvent is removed under cover and the solid residue is recrystallized from methanol. This document does not teach or suggest the use of purified FDCA or include the step of washing the DAFD in the solid-liquid separation zone with a washing composition to produce a purified DAFD product composition containing water.
[006] In Haworth, W. N. et al., J. of Chem. Society, Chemical Society, Letchworth, GB, no.1 (1 Jan. 1945), pp. 1-4, XP008122626, ISSN: 0368-1769, DOI: 10.1039 / JR9450000001, Methyl Furan 2,5-dicarboxylate, a process for making methyl furan-2,5-dicarboxylate is revealed by reacting FDCA with methyl hydrogen chloride - alcoholic for 6 hours. The product is crystallized, the solution is evaporated and the residue is re-crystallized from methyl alcohol. This document does not teach or suggest the step of washing the DAFD in a solid-liquid separation zone with a washing composition to produce a purified DAFD product composition containing water.
[007] And in Yoder, P.A. et al., Berichte der Deutschen Chemischen Gesellschaft Abteilung B: Abhandlungen, Wiley, DE, vol.34, no.3 (1 Oct. 1901), pp. 3446-3462, XP008148998, ISSN: 0365-9844, DOI: 10.1002 / CEBR.19010340329, the manufacture of diisobutyl-furan-2,5-dicarboxylic by reaction with FDCA, isobutyl alcohol and HCL is described. Although the ester is dissolved in ether and recrystallized, this document does not teach or suggest washing the DAFD in the solid-liquid separation zone with the washing composition to produce a purified DAFD product composition containing water.
[008] The crude FDCA obtained by oxidation processes must be purified before being suitable for end-use applications. JP patent application, JP209-242312A, described the process of purifying crude FDCA using sodium hydroxide / sodium hypochlorite and / or hydrogen peroxide followed by acid treatment of the disodium salt to obtain pure FDCA. The multi-stage purification process generates destructive by-products, it is difficult to classify a business process, and it has security interests at large scales.
[009] Therefore, there is a need for an inexpensive, high-yield process for the purification of crude FDCA that provides, on its own, more readily to a commercial-scale process and provides, in itself, easy separation steps. 3. Summary of the Invention
[0010] A process for the manufacture of the DAFD composition is now provided which comprises: a. feeding a furan-2,5-dicarboxylic acid (“FDCA”) composition to an esterification reactor; and b. in the presence of an alcohol compound, conduct an esterification reaction in the esterification reactor to react FDCA with said alcohol compound to form the crude diester composition comprising dialkyl furan-2,5-dicarboxylate ("DAFD") and the alcohol compound; and c. separating at least a portion of the alcohol compound from the crude diester composition into an alcohol separation zone using a physical separation process to produce a DAFD-rich composition comprising DAFD solids, wherein the concentration of DAFD in the DAFD-rich composition is greater than the concentration of DAFD in the crude diester composition in a combined solid and liquid base; and d. treating the DAFD-rich composition in a purification zone to produce a purified DAFD product composition.
[0011] A process is also provided for the preparation of the FDCA fed to the esterification reaction zone.
[0012] Also provided is the DAFD composition comprising: (i) at least 98% by weight of solids based on the weight of the composition, said solids comprising DAFD in an amount greater than 98% by weight based on the weight of solids, (ii) a b * of 5 or less, (iii) no more than 3% by weight of 5- (alkoxycarbonyl) furan-2-carboxylic acid (ACFC); and (iv) no more than 3% by weight alkyl 5-formylfuran-2-carboxylate (AFFC).
[0013] Also provided is a process that forms a very pure composition of DAFD on a commercial scale. The process is for the manufacture of a composition of furan-2,5-dicarboxylate and dialkyl (DAFD) having a yield of at least 1000 kg / day for any 30 days on a 24-hour / day basis, said process comprising: The. esterifying furan-2,5-dicarboxylic acid ("FDCA") with an alcohol in an esterification vessel to form the crude diester composition having a b * and comprising unreacted alcohol, water, dialkyl furan-2,5-dicarboxylate ("DAFD"); 5- (alkoxycarbonyl) furan-2-carboxylic acid (ACFC); Alkyl 5-formylfuran-2-carboxylate (AFFC); and b. purify the crude diester composition to form a purified DAFD product composition, wherein the purified DAFD product composition has: (i) a b * that is less than the b * of the crude diester composition by at least one 1 b unit *; and (ii) a higher DAFD concentration than the DAFD concentration in the crude diester composition by at least 200%; and (iii) an ACFC concentration lower than the ACFC concentration in the crude diester composition by at least 70%, without taking into account the amount of alcohol in the crude diester composition; and (iv) an AFFC concentration lower than the AFFC concentration in the crude diester composition by at least 70%. 4. Brief Description of the Drawings
[0014] Figure 1 is a process flow diagram for manufacturing both FDCA and DAFD.
[0015] Figure 2 is a flow diagram that describes the feed of raw materials to the esterification reactor.
[0016] Figure 3 is a flow diagram describing the process of crystallization, solid liquid separation and isolation of the DAFD composition and, optionally, dissolving and submitting the dissolved composition against crystallization.
[0017] Figure 4 is a flow diagram depicting the repeated stages of crystallization, solid-liquid separation and dissolution until the desired crystal purity is achieved. 5. Detailed Description of the Invention
[0018] 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.
[0019] As used in this, the terms "one," "one," and "o" mean one or more.
[0020] As used herein, 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.
[0021] 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.
[0022] As used herein, the terms "having," "had," and "has" have the same open meaning as "comprising," "comprises," and "comprising" provided above.
[0023] As used herein, the terms "including," "includes," and "including" have the same open meaning as "comprising," "comprises," and "comprising" provided above.
[0024] 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 top link) and a reported claim "less than 100" (with no bottom link).
[0025] 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 ° C)), 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 must 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 0.75 mPaa (110 psia) and a second pressure of 0.33 mPaa (48 psia) (a difference of 0.42 mPa (62 psi)), the narrow, intermediate and wide ranges due to the pressure difference between these two currents should be 0.17 to 0.68 mPa (25 to 99 psi), 0.29 to 0, 55 mPa (43 to 81 psi) and 0.36 to 0.48 mPa (53 to 71 psi), r expectantly.
[0026] The word "rich" in reference to a composition means that the concentration of the ingredient referred to in the composition is greater than the concentration of the same ingredient in the composition fed to the weight separation zone. For example, the DAFD rich composition means that the DAFD concentration in the DAFD rich composition is greater than the DAFD concentration in the crude diester stream that feeds the separation zone.
[0027] All quantities are by weight unless otherwise specified.
[0028] As illustrated in Figure 1, a carboxylic acid composition stream 410, which may be dried carboxylic acid solids or a wet carboxylic acid cake, in each case, the carboxylic acid comprising dicarboxylic furan ("FDCA") and an alcohol composition stream 520 are fed to the esterification reaction zone 500. The solid dicarboxylic acid composition 410 can be sent by truck, ship or railroad as solids to a plant or facility for manufacturing the composition of diester. The process for oxidizing the oxidizable material containing the furan group can be integrated with the process for making the diester composition. An integrated process includes colocalizing the two manufacturing facilities, one for oxidation and the other for esterification, within 10 miles (16.09 km) or within 5 miles (8.05 km) or within 2 miles (3 , 22 km) or within 1 mile (1.60 km) or within 1/2 mile (0.80 km) of each other. An integrated process also includes having the two manufacturing facilities in solid or fluid communication with each other. If a solid carboxylic acid composition is produced, the solids can be transported by any suitable means, such as air or belt, to the esterification plant. If a dicarboxylic acid composition of the wet cake is produced, the wet cake can be moved by belt or pumped as a liquid paste to the facility for esterification.
[0029] The esterification zone 500 contains at least one esterification reactor vessel. The dicarboxylic acid composition comprising FDCA is fed to an esterification zone and, in the presence of an alcohol compound, an esterification reaction is conducted in an esterification reactor by reacting the FDCA with said alcohol compound to form the composition crude diester comprising dialkyl furan-2,5-dicarboxylate ("DAFD"), the alcohol compound, alkyl 5- (alkoxycarbonyl) furan-2-carboxylic acid (ACFC), furan-2-carboxylate (AFC) and alkyl-5-formylfuran-2-carboxylate (AFFC). The crude diester composition can optionally contain a catalyst if a homogeneous esterification catalyst is used.
[0030] The alcohol composition is one or more types of the alcohol compound. Examples include compounds represented by the structure R-OH where R can vary from 1 to 6 carbons or 1 to 5 carbon atoms or 1 to 4 carbon atoms or 1 to 3 carbon atoms or 1 to 2 carbon atoms, preferably methanol. R can be branched or unbranched, saturated or unsaturated and cyclic or acyclic. Desirably, R is an unbranched, saturated, acyclic alkyl group. The alcohol composition contains at least 50% by weight or at least 60% by weight or at least 70% by weight or at least 80% by weight or at least 90% by weight or at least 95% by weight or at least 97 % by weight or at least 98% by weight or at least 99% by weight of alcohol compounds based on the weight of the alcohol composition. Desirably, the alcohol composition comprises methanol.
[0031] The crude diester composition produced in the esterification reactor is the reaction product of at least FDCA with the alcohol composition to produce DAFD, where the alkyl moiety is an alkyl group containing from 1 to 6 carbon atoms and at least a portion of the alkyl portion corresponds to the alcohol residue. In the case of a reaction between FDCA and methanol, the diester reaction product is dimethyl furan-2,5-dicarboxylate ("DMFD"). The esterification reaction of FDCA with methanol to produce DMFD comprises multiple reaction mechanisms as illustrated below. A reaction mechanism comprises reacting one mole of FDCA with one mole of MeOH to produce one mole of 5- (methoxycarbonyl) furan-2-carboxylic acid (MCFC) and water. One mole of MCFC can then be reacted with one mole of methanol to produce one mole of the desired DMFD product and water. Because both DMFD and MCFC are present in an esterification reaction zone, the crude diester composition will also contain MCFC in addition to the unreacted hydroxyl compounds and DAFD. A commercial process for producing purified DMFD must allow the separation of DMFD and MCFC downstream from the esterification zone. An example of a batch result for the esterification of crude FDCA with methanol is given in the experimental section.

[0032] The esterification by-products are also formed in the reaction zone of esterification reactor 500 and comprise chemicals with boiling points both higher and lower than DMFD. The esterification by-products formed in the esterification reaction zone comprise methyl acetate, alkyl furan-2-carboxylate (AFC), alkyl 5-formylfuran-2-carboxylate (AFFC) and 5- (alkoxycarbonyl) furan-2- acid carboxylic acid (ACFC). Many other by-products are possible depending on the impurities contained within the FDCA feed stock. A commercial process for producing a purified DAFD stream should allow the separation of impurities from the crude diester composition that comes out as the 510 stream. In addition, at least a portion of these impurities can be purged from the process in which the purging involves isolating the impurities and sends them from the process.
[0033] It is desirable to first mix the solid dicarboxylic acid composition with alcohol before conducting an esterification reaction under esterification conditions. As illustrated in Figure 2, a mixing zone 540 and esterification reactor 550 are provided within esterification zone 500. The solid dicarboxylic acid composition 410 comprising FDCA, a fresh or virgin feed of an alcohol composition such as stream 520 , optionally an alcohol recycling stream 802 comprising a recycled alcohol at least one of which is the same type of compounds as fed into stream 520, an optional esterification catalyst composition stream 530, is fed into the mixing zone 540 to generate the mixed reactor supply current 501. In one embodiment, the currents 802 and 520 comprise methanol.
[0034] Mixing in zone 540 can be performed by any equipment known in the art to mix liquids and solids, such as continuous in-line static mixers, agitated batch containers and or continuous agitated containers and others. The theoretical amount of alcohol required for the reaction with each mole of FDCA is two moles. The total amount of alcohol present in the esterification reactor 550 is desirably in excess of the theoretical amount required for the esterification reaction.
[0035] For example, the molar ratio of alcohol to moles of FDCA ranges from more than 2: 1 or at least 2.2: 1 or at least 2.5: 1 or at least 3: 1 or at least 4: 1 or at least 8: 1 or at least 10: 1 or at least 15: 1 or at least 20: 1 or at least 25: 1 or at least 30: 1 and can go as high as 40: 1. The appropriate molar ratios are within an alcohol range for FDCA from 10: 1 to 30: 1.
[0036] The mixing zone is also optionally supplied with an esterification catalyst system such as chain 530 if a catalyst is used. The catalyst can be heterogeneous in a fixed bed or desirably a homogeneous catalyst under the esterification reaction conditions and can also be homogeneous in the mixing zone. The known organometallic esterification catalysts can be used as cobalt acetate, copper and manganese and zinc in amounts conventionally used to esterify terephthalic acid. Other organic catalysts can be used, such as sulfuric acid.
[0037] Appropriate amounts of esterification catalyst range from 0.1 wt% to 5.0 wt% or 0.5 wt% to 2.0 wt%, based on the weight of the DAFD feed.
[0038] The mixed reactor feed stream 501 is sent to the esterification reactor 550 to generate a crude diester composition that exits the esterification reactor as the net crude diester stream 510. The crude diester composition, prior to separation of alcohol and water, desirably contains DAFD in an amount of at least 5% by weight or at least 8% by weight or at least 10% by weight or at least 15% by weight or at least 20% by weight, and up to 40% by weight or up to 35% by weight, based on the weight of the liquid phase of the crude diester composition. At high temperatures, high blood pressure and / or high alcohol concentration under esterification conditions, the DAFD present in the crude diester composition is solubilized and the solids concentration is, in general, no more than 5% by weight or no more than than 2% by weight or not more than 1% by weight or not more than 0.5% by weight or not more than 0.1% by weight, although the amount of solids may be higher when a concentration of unreacted alcohol decreased and the reaction temperature is reduced. If solids are present, at least 99% by weight of the solids are unreacted FDCA solids.
[0039] DAFD yield in the crude diester composition is desirably high. Suitable yields are at least 55 mol% or at least 60 mol% or at least 65% or at least 70 mol% or at least 75 mol% or at least 80 mol% or at least 85 mol% or at least 90 mol% or at least 95 mol% or at least 99 mol%. The yield of DAFD in the crude diester stream is calculated as follows: mol of DAFD in the crude diester composition in the liquid phase / initial mol of FDCA) * 100%.
[0040] The FDCA slurry stream can be fed to the esterification reactor at a rate corresponding to a desired yield in a continuous process for the production of a purified DAFD product composition. Examples of suitable rates for producing a purified DAFD product stream composition include an average of at least 1,000 kg / day or at least 10,000 kg / day or at least 20,000 kg / day or at least 50,000 kg / day or at least at least 75,000 kg / day or at least 100,000 kg / day or at least 200,000 kg / day of a purified DAFD product composition, on a 24-hour basis over the course of any three months.
[0041] The esterification can be carried out in batch or continuous reactors and comprises a reaction vessel or multiples that are capable of providing acceptable reaction residence time, temperature and pressure. The esterification reaction residence time ranges from 0.5 h to about 10 hours. The esterification temperature ranges from 150 ° C to below the supercritical temperature of the selected alcohol to ensure that the alcohol remains in the liquid phase at reaction temperatures. Suitable reaction temperatures can range from 150 ° C to 250 ° C or 150 ° C to 240 ° C or from 200 ° C to 230 ° C. Particularly suitable is an upper range of 240 ° C in the case, methanol is used as the alcohol. The esterification pressure inside the esterification reactor is sufficient to keep the alcohol compound in the liquid phase and will vary with the selected temperature. Suitable pressure ranges are about 1.72 mPa man (250 psig) to about 13.78 mPa man (2,000 psig) or 2.75 mPa man (400 psig) to about 10.34 mPa man ( 1,500 psig).
[0042] The crude diester composition is removed from the esterification reactor 550 as the current 510. As shown in Figure 1, the crude diester composition stream 510 is fed to an alcohol separation zone 600. At least a portion of the alcohol compound in the crude diester composition 510 is separated from the crude diester stream in the alcohol separation zone 600 in a physical separation process to produce a stream-rich composition of DAFD 620 containing liquid DAFD and in which the concentration of DAFD in the composition rich in DAFD, on a liquid basis, is greater than the concentration of DAFD in the crude diester composition on a liquid basis.
[0043] The crude diester composition 510 exits in the esterification zone 500 at elevated temperatures, typically at a temperature of at least 150 ° C or at least 170 ° C or at least 180 ° C or at least 190 ° C or at least 200 ° C or at least 210 ° C or at least 220 ° C or at least 230 ° C or at least 240 ° C, and in each case below the supercritical temperature of the alcohol. In order to take advantage of the sensitive heat energy already present in the crude diester composition, physical separation can be conducted more simply under a pressure that is less relative to the pressure on the crude diester current at the entrance to the separation zone and thus , removes alcohol through reduced pressure to produce a DAFD-rich composition like current 620. This can be done without applying additional heat energy to the separation vessel for the purposes of separation and thereby reduces energy consumption ( for example, sparkling adiabatic).
[0044] The alcohol separation zone 600 may comprise one or more containers operated in series or in parallel. For example, the alcohol separation zone 600 may comprise one or more scintillating evaporative unit operations or may comprise one or more distillation columns. The alcohol separation zone can comprise both a sparkling evaporation unit and a distillation column. The separation zone can be operated in a batch or continuous mode.
[0045] Desirably, the separation zone 600 contains at least one sparkling evaporation unit, such as a sparkling tank. Sparkling evaporation in stages in multiple containers can be conducted. The pressure in the sparkling unit operation can vary from 0 mPa man (0 psig) to about 1.03 mPa man (150 psig) or from 0 mPa man (0 psig) to about 0.34 mPa man (50 psig) or from 0 mPa man (0 psig) to 0.24 mPa man (35 psig). If alcohol is separated under a reduced pressure with respect to the pressure of the crude diester composition at the entrance to a physical separation vessel, it is desirable that the pressure inside the alcohol separation vessel is below the alcohol vapor pressure at the temperature of the stream of raw diester at the entrance to the alcohol separation vessel.
[0046] If desired, a sparkling evaporative unit should not be used first. For example, the crude diester composition stream 510 can be fed directly to a distillation column, heat energy is applied, if necessary, to separate the alcohol from the crude diester composition and the distilled alcohol can be removed as space upper gas, condenses and sends to the esterification zone as a recycling stream 802. The lower parts of the distillation column are removed as the current-rich composition of DAFD 620.
[0047] An alternative physical separation technique is a membrane separation unit operation, which can be used alone or in combination with at least one sparkling unit operation, to generate the 610 alcohol gas composition stream and the rich composition current of DAFD 620.
[0048] The temperature of the current-rich composition of DAFD 620 leaving the alcohol separation zone 600 is not particularly limited. This will be less than the temperature of the crude diester stream entering the alcohol separation zone if evaporative separation techniques that do not apply external heat energy are used for the separation, such as a sparkling tank, due to evaporative cooling. However, if distillation techniques are used, the temperature of the DAFD-rich composition can be the same or higher than the crude diester stream. In one embodiment, the temperature of the DAFD 620 current-rich composition is at least 5 ° C cooler or at least 20 ° C cooler or at least 50 ° C cooler or at least 75 ° C cooler or at least 100 ° C colder or at least 120 ° C colder than the raw temperature diester composition entering the 600 alcohol separation zone. If distillation is used, the DAFD 620 current-rich composition can be at least 5 ° C hotter or at least 10 ° C hotter than the temperature of the feed stream of the crude diester composition to the distillation column.
[0049] The alcohol that is quickly evaporated or distilled leaves the sparkling tank as a stream of 610 alcohol gas composition. The alcohol gas composition is desirably removed as an upper space. As the alcohol is evaporated quickly, the DAFD concentration increases to form the DAFD-rich stream. The water concentration also increases in the DAFD-rich stream with respect to the water concentration in the crude diester composition. Since the solubility of DAFD in water is much less than DAFD in alcohol, a smaller portion (for example, less than 20% by weight) of DAFD can precipitate out of solution. The gaseous upper space of alcohol comprises alcohol, some water and, typically, very little (e.g. less than 0.1% by weight) DAFD may also be present.
[0050] The alcohol gas stream 610 can be condensed in the alcohol recovery zone 800 and fed back to the esterification zone 500 as an alcohol recycling stream 802. This recycling stream may, however, contain some amount of water . If you want to purify the aqueous stream of alcohol 610 prior to recycling to the esterification zone 500, it can be fed to at least one distillation column in the alcohol recovery zone 800 to separate the alcohol compound as a distillate and recycle again to the esterification zone 500 or used as a portion or all of the washing composition 732 to the liquid solid separation zone (s), or used as a portion or all of the solvent feed 1010 to the dissolution zones or a combination of any of previous feeds. The distillation column can be dedicated to receive a supply of the gaseous alcohol stream or the condensed alcohol effluent. The distillation column is operated to separate water from alcohol to feed the esterification zone with the alcohol distillate as the 802 stream. The 802 alcohol recycle stream is desirably condensed to a liquid before feeding to the mixing zone 540 or the esterification reactor 550.
[0051] Alternatively, the gas stream of alcohol 610 or its condensate, can be fed to a distillation column divided into an alcohol recovery zone 800 which also receives the feed 721, 741 and / or 742. It is desirable to use a split column to reduce capital costs. As shown in Figure 1, a portion of the entire chain 721 can be fed first to a distillation column in an alcohol recovery zone 800.
[0052] The 802 alcohol recycling stream desirably contains less than 4% water by weight or less than 2% water by weight or less than 1% water by weight, based on the weight of the 802 alcohol recycling stream In one embodiment, the alcohol recycling stream 802 comprises methanol in an amount of at least 95% by weight or at least 98% by weight or at least 99% by weight. The alcohol composition stream 801 is a lower liquid composition from a distillation column comprising water and DAFD. A portion of the water composition stream 801, up to 100% by weight, can be sent from the process. A portion of the water composition stream 801, up to 100% by weight, can be recycled within the process to recover at least a portion of the DAFD in stream 801. A portion of the water composition stream 801, up to 100% by weight, can be added to the DAFD 620-rich stream or sent to the purification zone 700. The DAFD 620-rich stream composition comprises DAFD in a higher concentration than the amount of DAFD present in the raw diester stream leaving the esterification zone 500. The DAFD concentration in the DAFD-rich stream can be increased by at least 20% or at least 30% or at least 40% or at least 50% or at least 70% or at least 90% or at least 100% or at least 150% or at least 200% or at least 250% or at least 300% or at least 400% or at least 500%, in the concentration of DAFD in the crude diester composition. The DAFD-rich chain desirably contains DAFD in an amount of at least 10% by weight or at least 20% by weight or at least 30% by weight or at least 40% by weight or at least 50% by weight or at least 60 % by weight, and in each case up to 70% by weight or up to 80% by weight, in each case based on the weight of the DAFD rich composition. The DAFD-rich stream desirably does not contain solids. If present, the solids comprise unreacted DAFD and / or FDCA. The concentration of solids in a DAFD composition can contain no more than 55% by weight or up to 45% by weight or up to 35% by weight or up to 28% by weight or up to 15% by weight and, if present, an amount greater than zero or at least 5% by weight or at least 10% by weight, each based on the weight of the DAFD rich composition.
[0053] The current-rich composition of DAFD 620 also contains any alcohol that does not separate in the alcohol separation zone 600, water and a quantity of some or all of the by-products mentioned above. The amount of alcohol in the DAFD-rich chain can be at least 5% by weight or at least 10% by weight or at least 15% by weight, and up to 60% by weight or up to 50% by weight or up to 40% by weight. weight, based on the weight of the DAFD-rich chain.
[0054] The DAFD rich composition described as stream 620 is fed to a purification zone 700. In a purification zone 700, the solids in the DAFD rich composition is fed to a solid liquid separation zone when these are separated of the main and washed liquid to produce a stream of purified DAFD product 710. Optionally, the DAFD-rich composition is crystallized before solid-liquid separation. The DAFD-rich composition that is ultimately fed to the solid-liquid separation zone generally includes all of the following steps: (i) the DAFD-rich composition that is fed to the solid-liquid separation zone without going through one or more dissolution steps and / or crystallization, (ii) the DAFD-rich composition that undergoes one or more dissolution and crystallization steps to produce a DAFD-rich crystallized composition and (iii) the DAFD-rich composition that does not undergo dissolution but undergoes crystallization to produce a crystallized DAFD composition.
[0055] The purification zone 700 comprises at least the solid-liquid separation zone 713 as shown in Figure 3. If desired, the purification zone can also comprise a crystallization zone 712, a dissolution zone 711 or both a zone solution 711 as well as a crystallization zone 712. A portion of the purified DMFD purification stream 703 can optionally be fed to an optional dissolution zone 711 along with an amount of solvent stream 1010 sufficient to redissolve at least a portion of the solids of DAFD in the purified DMFD composition. The solvent stream can be any solvent effective to dissolve the DAFD solids, including a fresh alcohol feed or an 802 alcohol feed and recycle obtained from the alcohol recovery zone 800.
[0056] In the 711 dissolution zone, at least a portion of solids present in the purified DAFD composition 703 are dissolved. The purpose for re-dissolving solids after being subjected to solid / liquid separation in zone 713 and still purifying DAFD solids at the level of by-products and impurities trapped within the solids only one passage through the crystallizers remains undesirably high. Upon dissolution, such trapped by-products and impurities are released back into the solution.
[0057] The amount of solvent 1010 fed to the dissolution zone is dependent on the amount of solids to be dissolved, the solids concentration of the purified DAFD composition, the temperature within the dissolution zone and the type of solvent used. It is desired to use sufficient solvent under effective operating conditions to reduce the concentration of solids by at least 80% or at least 90% or at least 95% or at least 98% or at least 99% or by 100%.
[0058] As shown in Figure 3, the DAFD 620-rich stream is fed to a 712 crystallization zone. If a dissolution process is used, the product of the dissolution zone, a dissolved composition rich in DAFD 701, can be fed to the 712 crystallizer zone. The crystallization zone will generate a crystallized stream of DAFD 702 that comprises DAFD solids. At least a portion of DAFD in the DAFD 620 rich stream and at least a portion of the DAFD dissolved in the DAFD 701 current-rich dissolved composition comes from the solution to generate solid DAFD in the 712 crystallizer zone. In one embodiment, at least 80 % by weight or at least 90% by weight or at least 95% by weight or at least 98% by weight of DAFD in the DAFD 620 rich composition comes from the solution to form DAFD solids in the crystallized stream of DAFD 702. In another At least 80% by weight or at least 90% by weight or at least 95% by weight or at least 98% by weight of DAFD in the DAFD 620 rich composition and combined DAFD 701 current dissolved composition comes from the solution to form DAFD solids in the crystallized stream of DAFD 702.
[0059] Crystallization of DMFD in crystallization zone 712 can be performed by any crystallizer design known in the art. Examples include forced circulation evaporative crystallizer, surface cooled crystallizer with forced circulation deflector, crystallizer with air removal tube deflector or crystallizer by direct contact refrigeration. The crystallization zone contains at least one crystallizer and can contain multiple crystallizers, for example, 2 to 5 in series or multiple parallel trains. The generation of DMFD solids from the optional dissolved composition rich in DAFD 701 or a composition rich in DAFD 620, in crystallizer zone 712 comprises cooling and / or adding an antisolvent and / or removing a portion of the continuous liquid phase that comprises the solvent (for example, alcohol). If the solvent is removed in the crystallization zone 712 by evaporation, optionally under vacuum (for example, less than 1 atm), as a stream of crystallizing alcohol vapor 721, it can be recycled directly back to the esterification zone 500 or it can be sent to the alcohol separation zone 800 for further purification before feeding it to the esterification zone 500 or it can be used as a washing stream in the solid-liquid separation zone directly or after passing through the alcohol separation zone. alcohol separation 800.
[0060] The operating temperature of the liquid inside the crystallization reservoir can vary from about 5 ° C to about 100 ° C or 15 ° C to 65 ° C or 15 ° C to about 35 ° C. The crystallization temperature can be scaled down with each successive vessel if multiple vessels.
[0061] If desired, an antisolvent composition stream 731 can be fed to a crystallizer in a crystallization zone 712. The antisolvent composition is a liquid that promotes crystallization and / or precipitation of DAFD under operating conditions in the crystallizer. Such a stream may comprise water in an amount of at least 50% by weight or at least 60% by weight or at least 70% by weight or at least 80% by weight or at least 90% by weight or at least 98% by weight or 100% by weight, based on the weight of the anti-solvent chain 731. The solubility of DMFD in methanol and water varying temperature points ranging from about 1 ° C to about 61 ° C are shown in tables 3 and 4 DMFD has very low solubility in water compared to methanol so that it works as an excellent anti-solvent to promote crystallization.
[0062] From 1% to 45% or from 3% to 35%, of the liquid in the DAFD 620 rich stream and, if present, in the rich composition dissolved in the DAFD 701 stream, it is removed by evaporation from the crystallization vessel in the 712 crystallizer zone. If desired, any combination of cooling and / or adding antisolvent can be used in conjunction with removing a portion of the liquid continuous phase.
[0063] The crystallized DAFD composition 702 comprises solids in a concentration of at least 5% by weight or at least 10% by weight or at least 15% by weight or at least 20% by weight, and even an ability to pump the pulp, such as about 50% by weight to about 45% by weight. The solids comprise DAFD and the amount of DAFD present in the solids improves when a portion of the purified DAFD composition is removed to circulate in an additional dissolution and crystallization cycle. The amount of DAFD present in the solids is at least 90% by weight or at least 95% by weight or at least 98% by weight or at least 99% by weight or at least 99.5% by weight or at least 99.7 % by weight or at least 99.8% by weight or at least 99.9% by weight or at least 99.95% by weight or at least 99.97% by weight or at least 99.985% by weight or at least 99 , 99% by weight, based on the weight of the crystallized DAFD composition.
[0064] The stream of crystallized DMFD 702 produced in a crystallization zone 712 is fed to a solid-liquid separation zone 713. To the solid-liquid separation zone 713 is fed a stream of washing solvent 732. A stream of liquid main 722, washing liquid stream 741 comprising washing solvent and purified DAFD stream 703 are generated in the solid-liquid separation zone 713.
[0065] The solid-liquid separation zone 713 comprises at least one solid-liquid separation device capable of separating solids and liquids, washing solids with a washing stream 732, and reducing the percentage humidity in the washed solids to less than 50% by weight or less than 40% by weight or less than 30% by weight or less than 20% by weight, less than 15% by weight and preferably less than 10% by weight based on the weight of the composition of the purified DAFD stream 703.
[0066] The solid-liquid separation zone generates a main esterification liquid stream 722 containing the solvent (eg alcohol) and by-products and impurities. Desirably, the alcohol in a main esterification liquid stream 722 comprises methanol. Examples of by-products and impurities in the main liquid stream 722 comprise oxidation and / or esterification by-products. If desired, at least a portion of a main esterification liquid stream 722 can be directly fed back to the esterification reaction zone 500. From 5% to 95%, from 30% to 90% or from 40% to 80% of liquid main esterification present in the crystallized DAFD stream fed to the solid-liquid separation zone 713 is isolated in a main esterification liquid stream 722. The main esterification liquid stream 722 contains dissolved impurities removed from the feed to the separation zone liquid solid 713.
[0067] The wash stream 732 fed to and used as the wash feed for the crystallized DAFD composition, comprises a liquid suitable to replace the wash the main liquid of the solids. For example, the washing solvent may comprise water, alcohol or water and alcohol, although the solvent is not limited to the use of alcohols. It is desirable that the wash solvent contains a solvent miscible with the alcohol remaining in the crystallized DAFD composition and can still be the same alcohol compound. The washing solvent stream may comprise an alcohol present in an amount of at least 5% by weight or at least 10% by weight or at least 20% by weight or at least 40% by weight or at least 60% by weight or at least 80% by weight or at least 90% by weight or at least 95% by weight and the remainder, if any, may be water. A mixture of alcohols can also be used.
[0068] The temperature of the washing solvent fed to the solid liquid separation zone is not limited and can vary from 10 ° C to below the boiling point of the washing solvent composition or up to 50 ° or up to 40 ° C. The amount of washing solvent used is defined as the washing ratio è equals the washing mass divided by the mass of solids in a batch or continuous base. The washing ratio, defined as the ratio of washing mass to mass of solids being washed, can vary from 0.25 to 5, 0.3 to 4 and 0.4 to 4. If desired, no washing is applied to the solids in a 713 liquid solid separation zone.
[0069] The liquid washing stream 741 comprising at least a portion of the washing solvent and at least a portion of by-products is purified and recycled or exits the process as a residual stream.
[0070] Equipment suitable for solid liquid separation may include centrifuges of all types, which includes, but is not limited to, decanter and disc stack centrifuges, solid bowl centrifuges, cyclone, rotary vacuum drum filter, filter vacuum belt optionally containing continuous co-current or counter-current washing steps, pressure leaf filter, candle filter and others and others. The preferred liquid solid separation device for the liquid solid separation zone is a continuous pressure drum filter optionally with continuous multi-stage co-current or counter-current washing or more specifically a continuous rotary pressure drum filter. The solid-liquid separator can be operated in batch or continuous mode, although it is estimated that for commercial processes, the continuous mode is preferred.
[0071] One or more washes can be implemented in the solid-liquid separation zone 713. In one embodiment, one or more of the washes, preferably at least the final wash, in the solid-liquid separation zone 713 can comprise a hydroxyl compound difunctional, such as ethylene glycol. By this method, the composition of the purified DAFD wet cake stream 703 is produced comprising the same functional hydroxyl compound in liquid form that should be used in polymerization to manufacture the polyester containing portions of FDCA and, by this method, the step of drying in the product isolation zone 714 can be avoided. However, if it is desired to produce a dry powder, then the washing liquids desirably are solvents that can easily volatize in a drying step and are effective for washing alcohol from DAFD. Such washing solvents include methanol, ethanol, propanol and butanol.
[0072] The washing and dehydration functions of the crystallized DAFD composition stream can be performed in a single solid-liquid separation device or multiple solid-liquid separation devices.
[0073] After the solids are washed in a solid liquid separation zone 713, these are dehydrated. Dehydration can happen in the solid-liquid separation zone and this can be part of or a device separate from the solid liquid separation mechanism. Dehydration involves replacing and reducing at least a portion of the moisture mass of any composition present with the solids to less than 50% by weight or less than 40% by weight or less than 30% by weight or less than 20 % by weight, less than 15% by weight and preferably less than 10% by weight based on the weight of the purified DAFD composition stream 703. Dehydration can be accomplished by passing a gas stream through the solids to replace the free liquid after the solids are washed with a washing solvent. Alternatively, dehydration can be achieved by centrifugal forces in a perforated basin or solid basin centrifuge.
[0074] The purified DAFD composition stream 703 may be in the form of a wet cake. All of the purified DAFD composition can be fed to the drying zone to form dry particles or powder or if a wet cake is desired as the final product, the drying zone can be bypassed or eliminated.
[0075] Optionally, a portion or all of the purified DAFD composition 703 can be fed to the dissolution zone 711 for dissolution or recrystallization. As shown in Figure 3, at least a portion of the purified DAFD composition stream 703 is removed as a feed for the dissolution zone 711. The solids in the purified DAFD composition are dissolved again in the dissolution zone 711 and the dissolved composition rich in DAFD 701 it is fed as a recycling arc back to the crystallization zone 712 for the recrystallization from DAFD. By this method, the concentration of DAFD in the solids is increased because a portion of the impurity by-products trapped in the DAFD solids from a purified DAFD composition 703 are released into the solution and after another passage through the solid separation mechanism -liquid, are directed into the main liquid stream 722. A portion of the purified DAFD composition stream 703 can be withdrawn continuously and a portion of the dissolved stream 701 returned to the crystallization zone 712 continuously.
[0076] At least 2% by weight or at least 5% by weight or at least 10% by weight or at least 15% by weight or at least 20% by weight or at least 30% by weight or at least 35% by weight or at least 40% by weight, and up to 95% by weight or up to 90% by weight or up to 85% by weight or up to 80% by weight or up to 75% by weight or up to 60% by weight or up to 50% by weight weight or up to 40% by weight or up to 30% by weight of the purified DAFD composition can be removed and fed to the 711 dissolution zone.
[0077] If desired, at least a portion of the slurry can be removed from the solid liquid separation zone 713 at any point after the main liquid stream 722 is separated from the DAFD 702-rich crystallized composition. For example, a portion of the slurry can be removed and fed to the dissolution zone 711 prior to the washing step in a solid liquid separation zone 713. However, it is desirable that a portion of the DAFD-rich crystallized composition be removed and fed to the dissolution zone 711 after the step of removing a main liquid stream and after the DAFD-rich crystallized composition in a solid liquid separation zone is washed and before the final drying step in a solid liquid separation zone. In this way, the stream was purified from at least a portion of the by-product impurities by both separation and washing.
[0078] If desired, the dissolved DAFD rich composition can be fed to a second crystallization zone instead of recirculated to the first 712 crystallization zone. As shown in Figure 4, the dissolved DAFD 701 rich composition can be fed to one in the crystallization zone 712 followed by feeding in the crystallized composition of DAFD 702n to one in the solid-liquid separation zone 713. This dissolution and recrystallization process can be repeated until the desired purity is obtained. The distinction between a different zone and multiple crystallizers and / or a solid liquid separation mechanism within a single zone is that the different zone is established when at least a portion of the feed composition in question is fed into two or more containers that hold the same function. Serial multiple devices, however, do not constitute multiple zones.
[0079] As shown in Figure 4, the DAFD 620-rich stream is fed to a first 712i crystallization zone. The product of the crystallization zone is a crystallized DAFD 702a stream comprising DAFD solids. At least a portion of DAFD in the DAFD 620-rich stream comes from the solution to generate solid DAFD in the 712i crystallizer zone. The solvent can be removed from the crystallization zone 712 by evaporation, optionally under vacuum (for example, less than 1 atm), as a stream of alcohol vapor from the crystallizer 721 i. The crystallized DMFD stream 702a produced in a crystallization zone 712i is fed to a first solid-liquid separation zone 713i. The solid-liquid separation zone 713i is fed with a washing solvent stream 732. A first main liquid stream 722i, a first liquid wash stream 741i comprising washing solvent and purified DAFD composition stream 703a are generated in the zone 713i solid-liquid separation system. The main esterification liquid stream 722i contains dissolved impurities removed from the feed to the solid liquid separation zone 713i. The wash stream 732 fed and used as the wash feed for the crystallized DAFD composition, comprises a liquid suitable for replacing and washing the main liquid from the solids. The liquid washing stream 741i which comprises at least a portion of the washing solvent and at least a portion of purified and recycled by-products or leaves the process as a residual stream. One or more washes can be implemented in the solid-liquid separation zone 713i. After the solids are washed in a liquid solid 713i separation zone, they are desirably dehydrated. The purified DAFD composition stream 703a can be in the form of a wet cake.
[0080] As shown in Figure 4, a portion or all of the purified DAFD composition 703a can be fed to the first dissolution zone 711i for dissolution using a solvent feed 1010 to produce a product suitable for recrystallization. At least a portion of the purified DAFD composition stream 703a is withdrawn as a dissolution feed 704a to the first dissolution zone 711i. The solids in the dissolution feed 704a (a portion or all of the purified DAFD composition) are redissolved in the first dissolution zone 711i to generate a dissolved composition rich in DAFD 701a which is fed into the crystallization zone 712n for the recrystallization from DAFD. "n" is an integer representing several cycles of crystallization, liquid-solid separation and dissolution and each cycle is a container number that accepts a feed of material such that with each additional cycle, the corresponding additional equipment is used to process the feed . The denomination "n" can be an integer from 0 to 5. For example, in the crystallizer zone 712n is a different zone from the first initial crystallizer zone 712i in which at least a portion of the dissolved DAFD 701a rich composition is fed to a different crystallization vessel within the 712n crystallization zone than the initial crystallization vessel within the first 712i crystallization zone. By feeding into a different crystallization vessel, a second or the crystallization zone is established.
[0081] When n = 0, a in the crystallization zone 712n and a in the liquid solid separation zone 713n and a in the dissolution zone 711n are not present and the dissolved DAFD 701a rich composition is fed into the final crystallizing zone 712f. When n = 1, a third liquid solid crystallization / separation is established (the initial 712i / 713i plus n = 1 plus the final 712f / 713f). When n = 2, then four solid liquid crystallization / separation zones are established, counting the initial and final zones, resulting in four cycles of crystallization and liquid solid separation.
[0082] Within the 712n crystallization zone, the dissolved DAFD 701a rich composition is crystallized using an anti-solvent composition 731 to generate one in the DAFD 702n rich crystallized composition, where n is the same integer as "in" number in the 712n crystallization zone. The DAFD 702n-rich crystallized composition is fed to one in the solid liquid separation zone 713n to perform solid liquid separation, washing with a washing composition 732 and optional dehydration steps and thereby generate one in the main liquid stream 722n, one in the washing liquid stream 741n, and one in the purified DAFD composition stream 703n.
[0083] A portion of the in the purified DAFD composition stream 703n can be removed and fed to the product isolation zone as shown in Figure 4. A portion or the entire composition of the DAFD 703n stream is fed to one in the dissolution zone 711n as in the dissolution feed 704n for dissolving at least a portion of the DAFD solids from the purified DAFD composition stream 703n. If n is an integer greater than 1, then a portion or all of it in the dissolved composition rich in DAFD 701n is fed to the in the 712n crystallizer zone. The in the composition dissolved in DAFD dissolved from feed through the 701n line will begin to follow, succeeding the highest digit of "n" to represent the next cycle and the additional crystallizing zone and liquid solid separation zone. Several additional crystallizing and solid liquid separation zones can be of any number ranging from 0 to 5 inclusive. With each new cycle, the process steps mentioned above are repeated.
[0084] Whether or not additional solid liquid crystallization and separation zones are established, a portion of the dissolved DAFD-rich composition can be fed to the final 712f crystallizing zone. If no additional liquid solid crystallization / separation zones are used, all of the dissolved DAFD-rich composition can be fed to the final 712f crystallizing zone. In the final crystallizing zone 712f, the dissolved DAFD-rich composition is crystallized to produce a final crystallized stream of DAFD 702f which is then fed to the final solid-liquid separation zone 713f to generate a final stream of purified DAFD composition 703f. The final purified DAFD composition stream 703f is fed, along with any in the purified DAFD composition stream 703n if any, to the product isolation zone 714.
[0085] As shown in Figures 3 to 4, the purified DMFD composition stream 703, and if more than one cycle is used, then 703a and 703f is fed to the DMFD isolation zone 714 to produce the composition stream of DMFD product 710 and a vapor stream 742 which comprises primarily washing solvent and, if present, some main liquid. In one embodiment, the DMFD 714 isolation zone comprises at least one dryer. Drying can be carried out by means known in the art being able to evaporate at least 50% of the volatiles remaining in the DMFD 703 composition stream. For example, direct contact dryers including a rotary steam tube dryer, a Single Shaft PorcupineTM dryer and a Bepex SolidaireTM dryer can be used. Direct contact dryers including a fluid bed dryer and drying on a conveyor line can be used for drying. For both batch and continuous dryers, a vacuum can be applied to facilitate the removal of steam from the dryer. A rotary air block valve can be used for the continuous discharge of the purified dried DMFD stream 710 from the continuous dryers.
[0086] The percentage of solids in the DAFD 710 product stream can be at least 65% by weight or at least 75% by weight or at least 80% by weight or at least 85% by weight or at least 90% by weight or at least 91% by weight or at least 92% by weight or at least 93% by weight or at least 94% by weight or at least 95% by weight or at least 99% by weight or at least 99.9% by weight or at least 99.99% by weight.
[0087] In one embodiment, a vacuum system can be used to pull the steam stream 742 from the product isolation zone 714. If a vacuum system is used in this way, the steam stream pressure 742 at the outlet of the dryer can vary from about 760 mmHg to about 400 mmHg, from about 760 mmHg to about 600 mmHg pressure gauge, from about 760 mmHg to about 700 mmHg, from about 760 mmHg to about 720 mmHg or from about 760 mmHga about 740 mmHg. The contents of the conduit enter the solid-liquid separation zone 713 and the product isolation zone 714 used to transfer the wet pie stream 703 comprises the wet pie stream 703 and gas where the gas is the continuous phase. The pressure at the outlet of the solid liquid separation zone 703 can, if desired, be close to that pressure where the vapor stream 742 exits the product isolation zone 714, where the closest is defined as within 13.7 kPa ( 2 psi) and can also be, if desired, within 5.51 kPa (0.8 psi) and preferably within 2.75 kPa (0.4 psi).
[0088] In another embodiment, the solids in streams 703, 703a and 703f can be heated, such that they melt and the purified DMFD product stream 710 leaves the process as a liquid melt without proceeding or using a dryer.
[0089] Steam stream 742, main liquid streams 722, 722n, 722f and steam streams 721, 721 i, and 721f all containing alcohol can be fed to an alcohol recovery zone 800 for the generation of a stream of 802 recycling alcohol and which generates water-rich lower streams containing water and other impurities contained within streams 742, 722, 722i, 722f, 721, 721i and 721f.
[0090] The DAFD 710 product composition desirably has a b * of no more than 15 or no more than 10 or no more than 5 or no more than 3 or no more than 2 or no more than 1 or not more than 0.5.
[0091] The DAFD product composition desirably has a composition profile as follows: at least 95% by weight of solids or at least 98% by weight of solids, said solids comprising DAFD in an amount greater than 98% by weight or at least 99% by weight or at least 99.5% by weight, each based on the weight of the solids; a b * of 5 or less or 4 or less or 3 or less or 2 or less, and at least 0; if in solid or liquid phase, not more than 3% by weight of 5- (alkoxycarbonyl) furan-2-carboxylic acid (ACFC) or not more than 2.5% by weight or not more than 2.0% by weight or not more than 1.8% by weight or not more than 1.5% by weight or not more than 1.3% by weight or not more than 1.0% by weight or not more than than 0.8% by weight or not more than 0.6% by weight or not more than 0.3% by weight ACFC or not more than 1000 ppm ACFC or not more than 500 ppm ACFC or not more than 250 ppm ACFC, based on the weight of the product composition; and if in the solid or liquid phase, not more than 3.0% by weight alkyl 5-formylfuran-2-carboxylate (AFFC) or not more than 2.5% by weight or not more than 2.0% in weight or not more than 1.8% by weight or not more than 1.5% by weight or not more than 1.3% by weight or not more than 1.0% by weight or not more than 0.8% by weight or not more than 1000 ppm or not more than 500 ppm or not more than 250 ppm AFFC, based on the weight of the product composition; and if in the solid or liquid phase, not more than 1% by weight of FDCA or not more than 0.1% by weight of FDCA or not more than 500 ppm FDCA or not more than 100 ppm FDCA or not more than 10 ppm FDCA or not more than 1 ppm FDCA; and optionally not more than 1.5% by weight water or not more than 1.2% by weight or not more than 1.0% by weight or not more than 0.9% by weight or not more than than 0.8% by weight or not more than 0.7% by weight or not more than 0.1% by weight or not more than 0.05% by weight or not more than 0.02% in water weight based on the weight of the product composition.
[0092] The process of the invention is able to improve the purity of the crude diester composition on a commercial scale. It is now possible to produce a purified DAFD product composition and DAFD product within the DAFD product composition at a rate of at least 1,000 kg / day or at least 3,000 kg / day or at least 5,000 kg / day or at least 10,000 kg / day or at least 20,000 kg / day or at least 50,000 kg / day or at least 75,000 kg / day or at least 100,000 kg / day or at least 200,000 kg / day or at least 400,000 kg / day or at least 500,000 kg / day, on a 24-hour basis over the course of any three months.
[0093] The DAFD product composition produced at these rates desirably has a lower b *, higher DAFD concentration and lower ACCF and AFFC concentration than each of its concentrations in the crude diester composition.
[0094] The DAFD product composition desirably has a b * that is less than the b * of the crude diester composition by at least one 1 b * unit or at least 2 b * units or at least 3 b * units or at least 4 b * units or at least 5 b * units or at least 6 b * units.
[0095] The process of the invention is able to improve the purity of the crude diester composition by increasing the concentration of DAFD. The DAFD product composition desirably has a higher DAFD concentration than the DAFD concentration in the crude diester composition by at least 20% or at least 40% or at least 50% or at least 70% or at least 80% or at least at least 100% or at least 120% or at least 150% or at least 200% or at least 250% or at least 300% or at least 400% or at least 500% or at least 600% or at least 700% or at least minus 800% or at least 900%, each as determined taking into account the difference in concentration between the DAFD product composition and the crude diester composition divided by the DAFD concentration in the crude diester composition multiplied by 100, each on a weight basis. For example, 99% by weight DAFD concentration of the final product, minus a 15% by weight DAFD concentration in the crude diester composition should equal 84% by weight divided by 15% by weight = 5.6 x 100 = 560% increase.
[0096] The process of the invention is able to improve the purity of the crude diester composition by decreasing the concentration of ACFC. The DAFD product composition desirably has a lower ACFC concentration than the concentration of ACFC in the crude diester composition. The DAFD product composition desirably has an ACFC concentration that is less than the concentration of ACFC in the crude diester composition, without taking into account the presence of alcohol, by at least 20% or at least 40% or at least 50% or at least 70% or at least 80% or at least 90% or at least 95% or at least 97% or at least 98% or at least 99% or at least 99.5%, as determined taking into account the difference in the concentration of ACFC in the composition of DAFD product and the concentration of ACFC in the composition of crude diester (calculated without taking into account the amount of alcohol present in the composition of crude diester) divided by the concentration of ACFC in the composition of DAFD product multiplied by 100 and each removed on a weight basis. To describe the calculation basis, an example is as follows: the concentration of ACFC in the composition of the final product of DAFD can be 0.02% by weight subtracted from the concentration of ACFC in the crude diester composition which can be 1.2% by weight (the% by weight of ACFC in the crude diester composition without taking into account the presence of alcohol alcohol) = 1.18% by weight divided by 1.2% by weight = 0.983 x 100 = 98.3% reduction.
[0097] The process of the invention is able to improve the purity of the crude diester composition by decreasing the concentration of AFFC. The DAFD product composition desirably has a lower AFFC concentration than the AFFC concentration in the crude diester composition. The DAFD product composition desirably has an AFCC concentration that is less than the AFFC concentration in the crude diester composition, regardless of the presence of alcohol, by at least 20% or at least 40% or at least 50% or at least 70% or at least 80% or at least 90% or at least 95% or at least 97% or at least 98% or at least 99% or at least 99.5%, as determined taking into account the difference in the concentration of AFFC in the composition of DAFD product and the concentration of AFFC in the composition of crude diester (calculated without taking into account the amount of alcohol present in the composition of crude diester) divided by the concentration of AFFC in the composition of DAFD product multiplied by 100 and each removed on a weight basis. To describe the basis of calculation, an example is as follows: the concentration of AFCC in the composition of the final product of DAFD can be 0.03% by weight subtracted from the concentration of AFCC in the crude diester composition which can be 2.8% by weight (the% by weight of AFFC in the crude diester composition without taking into account the presence of alcohol alcohol) = 2.77% by weight divided by 2.8% by weight = 0.989 x 100 = 98.9% reduction.
[0098] Advantageously, the esterification zone 500 is fed by a purified FDCA composition. The process for making FDCA will now be described in more detail.
[0099] The process comprises feeding an oxidizable composition to an oxidation zone, where the oxidizable composition contains a compound having a portion of furan. The furan portion can be represented by the structure:

[00100] The compounds having a furan moiety are such that, upon oxidation, they form functional groups of carboxylic acid in the compound. Examples of compounds having portions of furan include 5- (hydroxymethyl) furfural (5-HMF) and 5-HMF derivatives. such derivatives include 5-HMF esters, such as those represented by the formula 5- R (CO) OCH2-furfural where R = alkyl, cycloalkyl and aryl groups having 1 to 8 carbon atoms or 1 to 4 carbon atoms or 1 to 2 carbon atoms; 5-HMF ethers represented by the formula 5-R'OCH2-furfural, where R '= alkyl, cycloalkyl and aryl having 1 to 8 carbon atoms or 1 to 4 carbon atoms or 1 to 2 carbon atoms); Furfural 5-alkyl represented by the formula 5-R "-furfural, where R" = alkyl, cycloalkyl and aryl having 1 to 8 carbon atoms or 1 to 4 carbon atoms or 1 to 2 carbon atoms). In this way, the oxidizable composition can contain mixtures of 5-HMF and 5-HMF esters; 5-HMF and 5-HMF ethers; 5-HMF and 5-alkyl furfural or mixtures of 5-HMF and their esters, ether '' ~
alkyl.
[00101] The oxidizable composition, in addition to 5- (hydroxymethyl) furfural (5- HMF) or one of its derivatives, can also contain 5- (acetoxymethyl) furfural (5-AMF) and 5- (ethoxymethyl) furfural (5- EMF).
[00102] Specific examples of 5-HMF derivatives include those having the following structures: Preferred 5-HMF derived feeds Preferred 5-HMF derived feeds
One embodiment is illustrated in figure 1. An oxidizable composition is fed to a primary oxidation zone 100 and reacted in the presence of a solvent, a catalyst system and a gas that comprises oxygen, to generate a stream of crude carboxylic acid 110 that comprises acid furan-2,5-dicarboxylic (FDCA).
[00103] For example, the oxidizable composition containing 5-HMF, or its derivatives, or combinations thereof, is oxidized with elemental O2 in a multiple step reaction to form FDCA with 5-formyl furan-2-carboxylic acid (FFCA) as a key intermediary, represented by the following sequence:

[00104] If desired, the oxygen gas stream 10 comprising oxygen, a solvent stream 30 and the oxidizable stream 20 can be fed to the primary oxidation zone 100 as separate streams. Or, an oxygen stream 10 comprising oxygen as a stream and an oxidizable stream 20 comprising solvent, catalyst and oxidizable compounds as a second stream can be fed to the primary oxidation zone 100. Consequently, the solvent, oxygen gas comprising oxygen, catalyst system and oxidizable compounds can be fed to the primary oxidation zone 100 as individual and separate streams or combined in any combination before entering the primary oxidation zone 100 where these feed streams can enter the single or multiple locations in the primary oxidizer zone 100.
[00105] The catalyst can be a homogeneous solvent-soluble catalyst or a heterogeneous catalyst. The catalyst composition is desirably soluble in the solvent under the reaction conditions, or is soluble in the reactants fed to the oxidation zone. Preferably, the catalyst composition is soluble in the solvent at 40 ° C and 1 atm and is soluble under the reaction conditions.
[00106] The components of suitable catalysts comprise at least one selected from, but not limited to, cobalt, bromine and manganese compounds. Preferably a homogeneous catalyst system is selected. The preferred catalyst system comprises cobalt, manganese and bromine.
[00107] Cobalt atoms can be supplied in ionic form as inorganic cobalt salts, such as cobalt bromide compounds, cobalt nitrate, or cobalt chloride, or organic cobalt 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. 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.
[00108] Manganese atoms can be supplied as one or more inorganic manganese salts, such as manganese borate compounds, manganese halides, manganese nitrates, or organometallic manganese such as the manganese salts of the lower aliphatic carboxylic acids, including manganese acetate and manganese salts of beta-diketonates, including manganese acetylacetonate.
[00109] 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, may be preferred sources of bromide.
[00110] The amount of bromine atoms desirably varies from at least 300 ppm, or at least 2,000 ppm, or at least 2,500 ppm, or at least 3,000 ppm, or at least 3,500 ppm, or at least 3,750, ppm and up to 4,500 ppm, or up to 4,000 ppm, based on the weight of the liquid in the reaction medium of the primary oxidation zone. Bromine present in an amount of 2,500 ppm to 4,000 ppm, or 3,000 ppm to 4,000 ppm is especially desirable to promote high yield.
[00111] The amount of cobalt atoms can vary from at least 500 ppm, or at least 1,500 ppm, or at least 2,000 ppm, or at least 2,500 ppm, or at least 3,000 ppm, and up to 6,000 ppm, or up to 5,500 ppm , or up to 5,000 ppm, based on the weight of the liquid in the reaction medium of the primary oxidation zone.
[00112] Cobalt present in an amount of 2,000 to 6,000 ppm, or 2,000 to 5,000 ppm are especially desirable to promote high yield.
[00113] The amount of manganese atoms can vary from 2 ppm, or at least 10 ppm, or at least 30 ppm, or at least 50 ppm, or at least 70 ppm, or at least 100 ppm and in each case up to 600 ppm, or up to 500 ppm or up to 400 ppm, or up to 350 ppm, or up to 300 ppm, or up to 250 ppm, based on the weight of the liquid in the reaction medium of the primary oxidation zone. The manganese present in an amount ranging from 30 ppm to 400 ppm, or 70 ppm to 350 ppm, or 100 ppm to 350 ppm is especially desirable to promote high yield.
[00114] The weight ratio of cobalt atoms to manganese atoms in the reaction mixture can be from 1: 1 to 400: 1, or 10: 1 to about 400: 1. A catalyst system with improved Co: Mn ratio can lead to high FDCA yield. To increase the yield of FDCA, when the oxidizable composition fed to the oxidation reactor comprises 5-HMF, then cobalt the manganese weight ratio is at least 10: 1, or at least 15: 1, or at least 20: 1 , or at least 25: 1, or at least 30: 1, or at least 40: 1 or at least 50: 1, or at least 60: 1 and in each case up to 400: 1. However, in the case where the oxidizable composition comprises 5-HMF esters, 5-HMF ethers, or furfural 5-alkyl, or mixtures of any of these compounds together or with 5-HMF, the weight ratio of cobalt to manganese may be decreased while still obtaining the high yield of FDCA, such as the Co: Mn weight ratio of at least 1: 1, or at least 2: 1, or at least 5: 1, or at least 9: 1, or at least 10: 1, or at least 15: 1, or at least 20: 1, or at least 25: 1, or at least 30: 1, or at least 40: 1, or at least 50: 1, or at least minus 60: 1 and in each case up to 400: 1.
[00115] The weight ratio of cobalt atoms to bromine atoms is desirably at least 0.7: 1, or at least 0.8: 1, or at least 0.9: 1, or at least 1: 1, or at least 1.05: 1, or at least 1.2: 1, or at least 1.5: 1, or at least 1.8: 1, or at least 2: 1, or at least 2.2: 1, or at least 2.4: 1, or at least 2.6: 1, or at least 2.8: 1, and in each case up to 3.5, or up to 3.0, or up to 2.8.
[00116] The weight ratio of bromine atoms to manganese atoms is about 2: 1 to 500: 1.
[00117] Desirably, the weight ratio of cobalt to manganese is 10: 1 to 400: 1 and the weight ratio of cobalt to bromine atoms varies from 0.7: 1 to 3.5: 1. Such a catalyst system with improved Co: Mn and Co: Br ratio can lead to high yield of FDCA (minimum 90%), decreases the formation of impurities (measured by b *) causing color in the downstream polymerization process while maintaining the amount of CO and CO2 (carbon burning) in the effluent gas to a minimum.
[00118] Desirably, the amount of bromine present is at least 1000 ppm and up to 3500 ppm and the weight ratio of bromine to manganese is from 2: 1 to 500: 1. This combination has the advantage of high performance and low carbon burning.
[00119] Desirably, the amount of bromine present is at least 1000 ppm and up to 3000 ppm and the amount of cobalt present is at least 1000 ppm and up to 3000 ppm and the weight ratio of cobalt to manganese is 10: 1 to 100 :1. This combination has the advantage of high performance and low carbon burning.
[00120] Suitable solvents include aliphatic solvents. In one embodiment of the invention, the solvents are aliphatic carboxylic acids that include, but are not limited to, C2 to C6 monocarboxylic acids, for example, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, trimethylacetic acid , caprioic acid and mixtures thereof.
[00121] The most common solvent used for oxidation is a solution of aqueous acetic acid, typically having a concentration of 80 to 99% by weight. In especially preferred embodiments, the solvent comprises a mixture of water and acetic acid which has a water content of 0% to about 15% by weight. In addition, a portion of the solvent feed to the primary oxidation reactor can be obtained from a recycling stream obtained by displacing about 80 to 90% of the main liquid drawn from the crude reaction mixture stream discharged from the reactor. primary oxidation with moist, fresh acetic acid containing about 0 to 15% water.
[00122] The oxidation gas stream comprises oxygen. Examples include, but are not limited to, air and purified oxygen. The amount of oxygen in the primary oxidation zone ranges from about 5 mol% to 45 mol%, 5 mol% to 60 mol% 5 mol% to 80 mol%.
[00123] The temperature of the reaction mixture in the primary oxidation zone can vary from about 100 ° C to about 220 ° C. The temperature of the reaction mixture in the primary oxidation zone is at least 100 ° C, or at least 105 ° C, or at least 110 ° C, or at least 115 ° C, or at least 120 ° C, or at least 125 ° C, or at least 130 ° C, or at least 135 ° C, or at least 140 ° C, or at least 145 ° C, or at least 150 ° C, or at least 155 ° C, or at least 160 ° C and can be as high as 220 ° C, or up to 210 ° C, or up to 200 ° C, or up to 195 ° C, or up to 190 ° C, or up to 180 ° C, or up to 175 ° C, or up to 170 ° C, or up to 165 ° C, or up to 160 ° C, or up to 155 ° C, or up to 150 ° C, or up to 145 ° C, or up to 140 ° C, or up to 135 ° C, or up to 130 ° C . In other embodiments, the temperature ranges from 105 ° C to 180 ° C, or from 105 ° C to 175 ° C, or from 105 ° C to 160 ° C or from 105 ° C to 155 ° C or from 105 ° C to 150 ° C or 110 ° C a op ojuonyo SE§ op SOJOOJ so 'OEδuoAm up boneooid oj i' Do09l onb ° P joreui OEU no '3OÇ9 [onb op JOIEUI ufos OEU OEδuoi op EJΠJSILU up EinjEioduioj E orb ouf op uuπonb E IEZΠIΠUΠII EJEJ IbZlOO] • Do08l DoSΔl op πθ DoSΔl n DoOΔl OP in 3rd08l n DoOΔl op in DoQΔl E Do £ 9l op in jo £ j E Do99l op in DoQ8l n Do99l OP in jo0 £ j j E99 op no DoQ8l E Doç9i op no 3 99l AND 3 09l op no Do0Z, l AND DOQ9I op no Do9Zj and DOQ91 op no DoQ8l n Do09l op no DoQ9l E DOÇÇI op no ao99l u Doççi op no Do0Z, l AND DOÇÇI op no Do9Zj E 399l op no DoQ8l E Doggi op no u DoQgl ap no DoQ9l n Do09l op no ao99l u DoQgl ap no Do0Z, l E jo0 £ l op no Do9Zj u DoQgl op no 3rd08l n Do09l op no Do09l E DOÇH op no u op no DoQ9l n DoSPl op no ao99l u op no Do0Z, l E op no Do0Z, l E op no Do9Zj E Do9l7l op op DoQ8l E DOÇH op no Do9l7l u jθobl op no Do09l n DoOPl op no u jθobl op no DoQ9l E jθobl op no do99l u jθobl op no Doozj E DoOPl op no Do0Z, l E jθobl op no Do9Zj u jθobl op no DoQ8l E DoOPl op no DO9H E Do9 £ x op no Do09l E Sweet op op no u Doçn op no 3rd09l And Do9 £ i op no ao99l u 3rd9 £ i op no Doozj AND DO9 £ I op no Doozj DoSεi op no Do9Zj E Do9 £ x op no 3rdQ8l AND DO9 £ I op no DO9H AND 30 £ l op no no 3rd0 £ l E DoOEl op no u 30oεi np no 30o9l E 30oεi np no ao99l DoOεi op no Doozj E DoOEl op no Do9Zj u 30oεi np no 3rdQ8l E 30oεi op no DO9H E -JSU op no 3rd 0 £ l E -JSU op no u -JSU op no 30o9l Do9Zl op no 3rd99l u -JSU op no Doozj E -JSU op no Do9Zj u -JSU op no 3rd08l Do9Zl op no Do9l7l u Do0ZI op no 3rd0 £ l AND DO0ZI op no Do03l op no 3rd09l AND DOQZI op no no ao99l u Do0ZI op no Doozj AND DO0ZI op no Do9Zj E 3rd0Zl op no 3rdQ8l AND DO0ZI op no Do9l7l u jo9ll op no 3rd0 £ l DoOll op no 3rd99l E Do9π op no 30o9l E jo9ll op no 3rd ^ 9l u jo9ll op no Doozj E Do9π op no Do9Zj u jo9ll op no 3rdQ8l E Jo9π op no Do9l7l DoOll op no DoOSl E JOQH np no u jθon np no 3OQ9I AND JOQH op no 3rd99l E ao0lI o p in Do0Z, l E JOQH np in Do9Zj u DθOll op in 3rdQ8l oxidizer COx, where x is 1 or 2 and the amount of COx in the oxidizing effluent gas is less than 0.05 moles of COx per mol of the total oxidizable feed to the reaction medium, or no more than 4 moles of COx per mole of the total oxidizable feed to the reaction medium, or no more than 6 moles of COx per mole of the total oxidizable feed to the reaction medium. The carbon burn as determined by the COx generation rate can be calculated as follows: (moles of CO + moles of CO2) / moles of oxidizable feed. The low carbon burning generation rate in the process of the invention is achieved by combining the low reaction temperature and the molar weight ratios of the catalyst components as described above.
[00124] To minimize the burning of carbon, it is desired that the temperature of the reaction mixture is not greater than 165 ° C, or not greater than 160 ° C. In the process of the invention, the contents of the effluent gas from the oxidizer COx, where x is 1 or 2 and the amount of COx in the oxidizer effluent gas is less than 0.05 moles of COx per mol of the total oxidizable feed to the reaction medium , or not more than 4 moles of COx per mole of the total oxidizable feed to the reaction medium, or no more than 6 moles of COx per mole of the total oxidizable feed to the reaction medium. The carbon burn as determined by the COx generation rate can be calculated as follows: (moles of CO + moles of CO2) / moles of oxidizable feed. The low carbon burning generation rate in the process of the invention is achieved by combining the low reaction temperature and the molar weight ratios of the catalyst components as described above.
[00125] The oxidation reaction can be conducted under pressure ranging from 0.27 to 2.06 mPaa (40 psia to 300 psia). A bubble column is desirably operated under a pressure ranging from 0.27 to 1.03 mPaa (40 psia to 150 psia). In a stirred tank container, the pressure is desirably adjusted to 0.68 to 2.06 mPaa (100 psia to 300 psia).
[00126] The oxidizing effluent gas stream 120 containing COx (CO and CO2), water, nitrogen and vaporized solvent, is sent to the oxidizing effluent gas treatment zone 800 to generate an inert gas stream 810, liquid stream 820 comprising water and a recovered oxidation solvent stream 830 comprising condensed solvent. In one embodiment, the oxidizing effluent gas stream 120 can be fed directly or indirectly after separating condensables such as solvent from non-condensables such as COx and nitrogen in a separation column (eg distillation column with 10 to 200 trays), a an energy recovery device such as a turboexpander to drive an electric generator. Alternatively or in addition, the oxidizing effluent gas stream can be fed to a steam generator before or after the separation column to generate steam and if desired, then it can be fed to a turboexpander and preheated before entering the expander if necessary to ensure that the effluent gas does not condense in the turboexpander.
[00127] In another embodiment, at least a portion of the oxidation solvent stream 830 recovered from the oxidizer gas stream is sent to a filter and then to a wash solvent stream 320 to make a portion of the solvent stream washing 320 for the purpose of washing the solids present in the solid-liquid separation zone. In another embodiment, the inert gas stream 810 can be vented to 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 by the carrier gas for the solids in the process.
[00128] The oxidation can be conducted in a continuous agitated tank reactor or in a bubble column reactor.
[00129] The FDCA formed by the oxidation reaction desirably precipitates out of the reaction mixture. The reaction mixture comprises the oxidizable, solvent and catalyst composition if a homogeneous catalyst is used, otherwise it comprises the oxidizable and solvent composition.
[00130] The oxidation reaction product is a stream of crude carboxylic acid 110 comprising FDCA as a solid, FDCA dissolved in the solvent, solvent and by-products and intermediates and homogeneous catalyst system if used. Examples of the by-products include levulinic acid, succinic acid and acetoxy acetic acid. Examples of the intermediate products include 5-formyl furan-2-carboxylic acid (FFCA) and 2,5-diformylfuran.
[00131] The percentages of solids in the crude carboxylic acid stream ranges are at least 10% by weight, or at least 15% by weight, or at least 20% by weight, or at least 25% by weight, or at least 28% by weight, or at least 30% by weight, or at least 32% by weight, or at least 35% by weight, or at least 37% by weight, or at least 40% by weight. As long as there is no upper limit, as a practice, the amount will not exceed 60% by weight, or no more than 55% by weight, or no more than 50% by weight, or no more than 45% by weight, or not greater than 43% by weight, or not greater than 40% by weight, or not greater than 39% by weight.
[00132] The established amount of each of the following intermediates, products and impurities are based on the weight of the solids in the composition of the crude carboxylic acid produced in the primary oxidation reactor in an oxidation zone 100.
[00133] The amount of the FFCA intermediate present in the crude carboxylic acid stream is not particularly limited. Desirably, the amount is less than 4% by weight, or less than 3.5% by weight, or less than 3.0% by weight, or less than 2.5% by weight, or up to 2, 0% by weight, or up to 1.5% by weight, or up to 1.0% by weight, or up to 0.8% by weight.
[00134] Impurities, if present in the crude dicarboxylic acid composition, include such compounds as 2,5-diformylfuran, levulinic acid, succinic acid and acetoxy acetic acid. These compounds can be present, if at all, and in an amount from 0% by weight to about 0.2% by weight of 2.5 diformilfurane, levulinic acid in an amount ranging from 0% by weight to 0.5% in 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 and a cumulative amount of these impurities in an amount varying from 0% by weight to 1% by weight, or from 0.01% by weight to 0.8% by weight, or from 0.05% by weight to 0.6% by weight.
[00135] In another embodiment of the invention the composition of carboxylic acid 110 comprises FDCA, FFCA and 5- (ethoxycarbonyl) furan-2-carboxylic acid ("EFCA"). EFCA in the carboxylic acid composition 110 may be present in an amount of at least 0.05% by weight, or at least 0.1% by weight, or at least 0.5% by weight and in each case up to about 4% by weight, or up to about 3.5% by weight, or up to 3% by weight, or up to 2.5% by weight, or up to 2% by weight.
[00136] The yield of FDCA, on the basis of solids and measured after the drying zone, is at least 60% or at least 65% or at least 70% or at least 72% or at least 74% or at least 76% or at least 78% or at least 80% or at least 81% or at least 82% or at least 83% or at least 84% or at least 85% or at least 86% or at least 87% or at least 88% or at least 89% or at least 90%, or at least 91% or at least 92% or at least 94% or at least 95% and up to 99% or up to 98% or up to 97% or up to 96% or up to 95 % or up to 94% or up to 93% or up to 92% or up to 91% or up to 90% or up to 89%. For example, yield can range from 70% to 99% or 74% to 98% or 78% to 98% or 80% to 98% or 84% to 98%, or 86% to 98%, or 88% to 98 %, or 90% to 98%, or 91% to 98%, or 92% to 98% or 94% to 98% or 95% to 99%.
[00137] The yield is defined as FDCA mass 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 156.01 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 = (150 / 156.01) times 100, which equals a yield of 96%. The same calculation applies to the oxidation reaction conducted using 5- HMF derivatives or mixed feeds.
[00138] The purity of the product of the FDCA particles in a wet cake, or the purity of the dry solid particles FDCA, obtained, is at least 90% by weight of FDCA, or at least 92% by weight of FDCA, or at least 94% by weight of FDCA, or at least 96% by weight of FDCA, or at least 98% by weight of FDCA, based on the weight of the solids.
[00139] The maximum b * of dry solids, or wet cake, is not particularly limited. However, a b * no more than 20, or no more than 19, or no more than 18, or no more than 17, or no more than 16, or no more than 15, or no more than that 10, or no more than 8, or no more than 6, or no more than 5, or no more than 4, or no more than 3, is desirable without having subjected the crude carboxylic acid composition to hydrogenation. However, if decreased b * is important for a particular application, the crude carboxylic acid composition can be subjected to hydrogenation.
[00140] The b * is one of the attributes 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 negative readings white, yellow (or absorbance of blue) mean the degree of blue (or absorbance of yellow).
[00141] In the next step, which is an optional step, the crude carboxylic acid stream 110 can feed into a cooling zone 200 to generate a chilled crude dicarboxylic acid stream 210 and a 1st stream of solvent vapor 220 which comprises solvent vapor. The cooling of the raw carboxylic paste stream 110 can be accompanied by any means known in the art. Typically, cooling zone 200 is a sparkling tank. All or a portion of the crude carboxylic acid stream 110 can be fed to the cooling zone.
[00142] All or a portion of the crude carboxylic acid stream 110 can be fed to the solid-liquid separation zone 300 without first being fed to a cooling zone 200. In this way, none or only a portion can be cooled in the zone cooling temperature 200. The temperature of the current 210 leaving the cooling zone can vary from 35 ° C to 160 ° C, 55 ° C to 120 ° C and preferably from 75 ° C to 95 ° C.
[00143] The crude carboxylic acid stream 110, or 210 if sent through the cooling zone, is fed to a solid-liquid separation zone 300 to generate a moist crude carboxylic acid stream 310 comprising FDCA. The isolation, washing and dehydration functions of the crude carboxylic acid stream can be accompanied by a single solid-liquid separation device or multiple solid-liquid separation devices. The solid-liquid separation zone 300 comprises at least one solid-liquid separation device capable of separating solids and liquids, washing solids with a washing solvent stream 320 and reducing the% moisture in the washed solids to less than than 30% by weight. Desirably, the solid-liquid separation device is capable of reducing the moisture% to less than 20% by weight, or less than 15% by weight and preferably 10% by weight or less. Equipment suitable for the solid liquid separation zone can typically be comprised of, but not limited to, the following types of devices: centrifuges of all types including but not limited to a decanter and disc stack centrifuges, solid bowl centrifuges, cyclone , rotary drum filter, belt filter, pressure leaf filter, spark plug filter and others. The liquid solid separation device preferred by the liquid solid separation zone is a continuous pressure drum filter, or more specifically a continuous rotary pressure drum filter. The solid-liquid separator can be operated in batch or continuous mode, although it will be appreciated that by commercial processes, the continuous mode is preferred.
[00144] The temperature of the crude carboxylic acid slurry stream, if cooled as stream 210, fed to a solid-liquid separation zone 300 can vary from 35 ° C to 160 ° C, 55 ° C to 120 ° C and it is preferably from 75 ° C to 95 ° C. The washing stream 320 comprises a liquid suitable for displacing and washing the main liquid from the solids. For example, the washing solvent comprises acetic acid, or acetic acid and water, an alcohol, or water, in each case up to an amount of 100%. The temperature of the washing solvent can vary from 20 ° C to 180 ° C, or 40 ° C and 150 ° C, or 50 ° C to 130 ° C. The amount of washing solvent used is defined as the washing ratio equal to the washing mass divided by the mass of the solids on a continuous or batch basis. The weight ratio can vary from about 0.3 to about 5, about 0.4 to about 4 and preferably about 0.5 to 3.
[00145] After the solids are washed in the solid liquid separation zone 300, they will be dehydrated. Dehydration can happen in the solid-liquid separation zone or it can be a device separated from the solid-liquid separation device. Dehydration 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 and more preferably less than 15% by weight in order to generate a wet cake stream of crude carboxylic acid 310 comprising FDCA. Dehydration can be accompanied on a filter by passing a gas stream through the solids to move the free liquid after the solids are washed with a washing solvent. Alternatively, dehydration can be achieved by centrifugal forces in a solid bowl or perforated bowl centrifuge.
[00146] One or more washes can be implemented in the solid-liquid separation zone 300. One or more of the washes, preferably at least the final wash, in the solid-liquid separation zone 300 comprises a hydroxyl functional compound as defined further down, such as an alcohol (for example methanol). By this method, a moist pie stream 310 is produced which comprises the functional hydroxyl compound such as methanol in liquid form. The amount of the hydroxyl functional compound in liquid form in the wet cake can be at least 50% by weight, or at least 75% by weight, or at least 85% by weight, or at least 95% by weight of the hydroxyl functional compound. such as methanol based on the weight of the liquids in the wet pie stream. The advantage of adopting this washing technique with a functional hydroxyl compound is that portion or all of the wet cake that can be fed to the esterification zone 500 without suffering or bypass, a step of feeding the wet cake to a container by drying the cake wet in a drying zone 400 after the solid-liquid separation zone.
[00147] In one embodiment, 100% of the wet cake stream 310 is fed to the esterification reaction zone 500 without suffering or submitting the wet cake to a container by drying the wet cake from the liquid solid separation zone 300.
[00148] The stream 330 generated in the solid-liquid separation zone 300 is a stream of the main liquid substance comprising oxidation solvent, catalyst and impurities. If desired, a portion of the main liquid stream 330 can be fed to a purge zone 900 and a portion can be fed back to a primary oxidation zone 100, where a portion is at least 5% by weight based on weight of the liquid. The washing liquid stream 340 is also generated in the solid-liquid separation zone 300 and comprises a portion of the main liquid present in the stream 210 and washing solvent where the weight ratio of the mass of the main liquid to the mass of solvent is washing in the washing liquid stream is less than 3 and preferably less than 2.
[00149] From 5% to 95%, from 30% to 90% and more preferably from 40% to 80% of the main liquid present in the crude carboxylic acid stream fed to a solid-liquid separation zone 200 is isolated in the zone solid-liquid separation 300 to generate a main liquid stream 330 resulting in the dissolved substance comprising impurities present in the displaced main liquid not advancing in the process. The main liquid stream 330 contains dissolved impurities removed from the crude dicarboxylic acid.
[00150] Sufficient washing solvent is fed to the solid liquid separation zone 300 which becomes mixed with the resulting solids in a low impurity slurry stream 310 being pumpable with% by weight of the solids ranging from 1% to 50 %, 10% to 40% and preferably the weight% of the solids in stream 310 will vary from 25% to 38%.
[00151] In one embodiment, from 5% to 100% by weight of the displaced main liquid stream 330 is sent in a purge zone 900 in which a portion of impurities present in the stream 330 are isolated and come out of the process as a purge stream 920, wherein one portion is 5% by weight or more. The recovered solvent stream 910 comprises the solvent and the catalyst isolated from stream 330 and is recycled to the process. The recovered solvent stream 910 can be recycled to a primary oxidation zone 100 and contains more than 30% of the catalyst that enters the purge zone 900 in stream 330. Stream 910 recycled to a primary oxidation zone 100 can contain more than 50% by weight, or more than 70% by weight, or more than 90% by weight of the catalyst entering the purge zone 900 in stream 330 on a batch or continuous basis.
[00152] Optionally, a portion up to 100% of the crude carboxylic acid composition can be sent directly to a secondary oxidation zone (not shown) before being subjected to a 300 liquid solid separation zone.
[00153] Generally, oxidation in the secondary oxidation zone is at a higher temperature than the oxidation in the primary oxidation zone 100 to intensify the removal of impurity. In one embodiment, the secondary oxidation zone is operated at about 30 ° C, 20 ° C and preferably 10 ° C higher than the oxidation temperature in the primary oxidation zone 100 to enhance the removal of impurity. The secondary oxidation zone can be heated directly with solvent vapor, or vapor through the stream, or indirectly by any means known in the art.
[00154] Further purification of the crude carboxylic acid stream can be accompanied in the secondary oxidation zone by the mechanism involving recrystallization or crystal development and oxidation of impurities and intermediates including FFCA. One of the functions of the secondary oxidation zone is to convert FFCA to FDCA. FFCA is considered monofunctional relative to a polyester condensation reaction because it contains only one carboxylic acid. FFCA is present in the crude carboxylic acid chain composition. FFCA is generated in the primary oxidation zone 100 because the reaction of 5-HMF to FFCA can be about eight times faster than the reaction of FFCA to the desired difunctional product FDCA. The additional air or molecular oxygen can be fed to a secondary oxidation zone in an amount necessary to oxidize a substantial portion of the partially oxidized products such as FFCA to the corresponding carboxylic acid FDCA. Generally, at least 70% by weight, or at least 80% by weight, or at least 90% by weight of the FFCA present in the crude carboxylic acid composition leaving a primary oxidation zone can be converted to FDCA in the secondary oxidation zone. The significant concentrations of FFCA-like monofunctional molecules in the purified, dried FDCA product are particularly harmful to polymerization processes as these can act as chain terminators during the polyester condensation reaction.
[00155] If a secondary oxidation zone is used, the secondary oxidation paste can be crystallized to form a crystallized paste stream. The vapor from the crystallization zone can be condensed in at least one condenser and returned to the crystallization zone or recycled, or it can be removed or sent to an energy recovery device. The effluent gas from the crystallizer can be removed and sent to a recovery system where the solvent is removed and effluent gas from the crystallizer containing VOC's can be treated, for example, by incineration in the catalytic oxidation unit. The crystallizer can be operated by cooling the secondary oxidation slurry to a temperature between about 40 ° C to about 175 ° C to form a crystallized slurry stream.
[00156] The crystallized paste stream can then be subjected to a cooling zone 200 if desired and the process continued as described above.
[00157] Instead of using a moist pie, one can produce a dry solid. The wet cake produced in the liquid solid separation zone 300 can be dried in a drying zone 400 to generate a dry purified carboxylic acid solid 410 and a vapor stream 420. The vapor stream 420 typically comprises the washing solvent vapor used in the solid liquid separation zone and may additionally contain the solvent used in the primary oxidation zone. Drying zone 400 comprises at least one dryer and can 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 to produce the purified, dried carboxylic acid solids. For example, indirect contact dryers include, but are not limited to, a rotary steam tube dryer, a Single Shaft Porcupine dryer and a Bepex Solidaire dryer. Direct contact dryers include, but are not limited to, a fluid bed dryer and drying on a conveyor line.
[00158] The purified, dried carboxylic acid solids comprising purified FDCA may be a composition of the carboxylic acid with less than 8% moisture, preferably less than 5% moisture and more preferably less than 1% moisture and even more preferably less than 0.5% and even more preferably less than 0.1%.
[00159] A vacuum system can be used to draw a stream of steam 420 from the drying zone 400. If a vacuum system is used in this way, the pressure at the outlet of the dryer can vary 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 from about 760 mmHg to about 740 mmHg in which pressure is measured in mmHg above absolute vacuum.
[00160] The solids of the purified, dried carboxylic acids, or the solids in the wet cake, desirably have a b * less than about 9.0, or less than about 6.0, or less than about 5 , 0, or less than about 4.0 or less than about 3.
[00161] It should be appreciated that the process zones previously described can be used in any other logical order to produce the purified, dried carboxylic acid. It should also be appreciated that when process zones are reordered that process conditions can change. It is also understood that all percentage values are percentages by weight.
[00162] A function of drying zone 400 is to remove by evaporation oxidation solvent which comprises a monocarboxylic acid with 2 to 6 carbons that may be present in the moist crude carboxylic acid stream 310.% of the moisture in the stream of crude carboxylic acid wet cake 310 typically ranges from 4.0% by weight to 30% by weight depending on the operating conditions of the solid-liquid separation zone 300. If, for example, the liquid portion of stream 310 is about 90% acetic acid, the amount of acetic acid present in stream 310 can vary from about 3.6% by weight to 27% by weight. It is desirable to remove acetic acid before esterification zone 500 because the acetic acid will react with the alcohol present in zone 500 to create unwanted by-products. For example, if methanol is fed to esterification zone 500 for the purpose of reacting with FDCA, it will also react with acetic acid present to form methyl acetate and therefore consume methanol and generate an unwanted by-product. It is desirable to minimize the acetic acid content of the crude carboxylic acid stream comprising FDCA which is fed to the esterification zone 500 to less than 3.6% by weight, preferably less than 1% by weight and more preferably less than 0.5% by weight and more preferably less than 0.1% by weight. One method to achieve this is to dry a wet pie stream of crude carboxylic acid 310 comprising acetic acid before sending the crude carboxylic acid to esterification zone 500. Another method for minimizing the oxidizing solvent comprising monocarboxylic acid with carbons ranging from 2 to 5 in the stream of crude carboxylic acid 410 sent to an esterification zone 500 at an acceptable level without using the dryer zone 400 is to conduct washing or washing with non-monocarboxylic acid in the solid-liquid separation zone 300 for washing an oxidizing solvent from the solids with a wash comprising any washing solvent compatible with a chemical esterification zone 500 to generate a suitable crude carboxylic acid 310 moist stream by sending it directly to esterification zone 500 without being dried in drying zone 400. Acceptable washing solvents include solvents that do not manufacture independent by-products in the esterification zone 500. For example, water is an acceptable washing solvent for displacing acetic acid from the solids in the solid-liquid separation zone 300. Another acceptable washing solvent is an alcohol that will be used as a reagent in the esterification zone 500. Here, multiple and separate washes can be used in the solid liquid separation zone 300. A wash feed can comprise water up to 100% by weight. A washing feed can comprise an alcohol of up to 100% by weight. A wash feed can comprise up to 100% methanol. A wash feed may comprise the same alcohol used in esterification zone 500 by reacting with FDCA to form the diester product. In one embodiment, the wet cake dehydration step can be used after the wet cake is formed in the solid liquid separation zone 300 and then any non-acetic acid wash is used. This dehydration step will minimize the liquid content of the wet cake before washing with a non-acetic acid washing solvent such as water and or methanol as described above, thereby minimizing the cost of separating any mixtures of acetic acid and washing solvents from the non-acetic acid that are generated in the solid-liquid separation zone 300.
[00163] The composition of solid dicarboxylic acid 410, which may be dried carboxylic acid solids or wet cake, comprising FDCA and the alcohol composition stream 520 are fed to an esterification reaction zone 500. The composition of dicarboxylic acid solid 410 can be shipped via truck, ship or rail as solids. However, an advantage of the invention is that the process by oxidizing the oxidizable material containing the furan group can be integrated with the process for the manufacture of the crude diester composition.
[00164] An integrated process includes colocalizing the two manufacturing facilities, one for oxidation and the other for esterification, within 10 miles (16.09 km), or within 5 miles (8.05 km), or within 2 miles (3.22 km), or within 1 mile (1.60 km), or within 1/2 mile (0.80 km) of each other. An integrated process also includes having the two manufacturing facilities communicate solid or fluid with each other. If a composition of the solid dicarboxylic acid is produced, the solids can be transported by any suitable means, such as air or belt, to the esterification installation. If the wet cake from the dicarboxylic acid composition is produced, the wet cake can be moved by the belt or pumped as a liquid paste to the esterification facility.
[00165] The process of the invention is further described in the following examples.
[00166] Example 1 and 2: 5-HMF semi-stack oxidation 5-HMF air oxidation using cobalt, manganese and ionic bromide catalysts in the acetic acid solvent in the quantities shown in table 1 were conducted under the following conditions of reaction in a reactor presented as described below: Reactor conditions: 132 ° C Reaction pressure: 0.89 mPa man (130 psig)
[00167] Reactor presentation: a 300 ml autoclave was equipped with a high pressure condenser, a deflector and an Isco pump. The autoclave was pressurized with approximately 0.34 mPa man (50 psig) of nitrogen and then the homogeneous mixture was heated to the desired temperature in a closed system (that is, with no gas flow) with stirring. At the reaction temperature, an air flow of 1,500 sccm was introduced at the bottom of the solution and the reaction pressure was adjusted to the desired pressure. A solution of 5-HMF in acetic acid was fed to the mixture at a rate of 0.833 mL / min via an Isco high pressure pump (ie t = 0 for the time period). After 30 seconds from the start of the 5-HMF feed, 1.0 g of peracetic acid in 5.0 mL of acetic acid was introduced using a blow-case to initiate the reaction. The feeding was interrupted after 1 h and the reaction continued for 1 more hour under the same conditions of air flow, temperature and pressure. After the period of time was finished, the air flow was interrupted and the autoclave was cooled to room temperature and depressurized. After the reaction, the heterogeneous mixture was filtered to isolate the crude FDCA. The crude FDCA was washed with acetic acid twice and then twice with deionized water. The washed raw FDCA was dried in an oven at 110 ° C under vacuum overnight. The solid and the filtrate were analyzed by gas chromatography using the BSTFA derivative method. The b * of the solid was measured using a Hunter Ultrascan XE instrument by the following method: 1) Assemble the Carver Press matrix as instructed in the directions --- place the matrix on the base and place the bottom of the polished 40 mm cylinder with the face facing 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 time not critical). 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 measurements (Reflectance Specular Included-barge Area View): CIE L a * b * CIE XYZ 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 values of the tile. 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. As shown in Table 1, we have found conditions to generate FDCA yields up to 89.4%, b * <6 and low carbon burn (<0.0006 mol / min CO + CO2). 1 a and 1 b experiments are repeated to show consistency and minor deviation in results. Experiments 2a and 2b are also repeated experiments. TABLE 1
* P = 130 psig, COx (mol / min) = CO (mol / min) + CO2 (mol / min). Example 3: Synthesis of DMFD 100.0 g of FDCA contains some FFCA. 410 g of MeOH and the FDCA were mixed in a clean and dry autoclave 1 L in a molar ratio of methanol to FDCA of 20: 1 and no esterification catalyst was added. The autoclave mixture was heated to 180 ° C in a closed system to allow pressure to develop. After 3 h at 180 ° C the reaction mixture was cooled to room temperature. The volatiles were removed to obtain 114 g of the crude product. The GC analysis of the crude product showed the following composition: 95.64% by weight of DMFD based on the weight of the reaction product, 0.50% by weight of 5- (methoxycarbonyl) furan-2-carboxylic acid (MCFC) with based on the weight of the product, 1.78% by weight of _methyl 5-formylfuran-2-carboxylate (MFFC) based on the weight of the product and 0.74% by weight of water. Example 4: Solubility of DMFD in water and methanol 1) The solubility of DMFD in water and methanol was tested according to the following procedure: the 20 ml jacketed solubility cells equipped with a condenser, a digital thermometer, a nitrogen blanket and connected to a circulation bath capable of heating / cooling was loaded with FDCA and water or methanol. The heterogeneous mixture was heated to the desired temperature and the sample was taken using the preheated calcined glass pipette. The samples were analyzed using gas chromatography. The results are listed in Tables 3 and 4. Table 3. Measurements of DMFD solubility (% by weight) in Methanol
Table 4. Measurements of DMFD solubility (% by weight) in water
BDL, below the detection limit Example 5: Recrystallization of crude DMFD using methanol A 150 mL three-necked round-bottom flask equipped with an overhead stirrer, a nitrogen line and a condenser was charged with 6.0 g of FDMC and 54.0 g of methanol. The solid was dissolved by heating the mixture to 55 ° C. the homogeneous solution was cooled to 2 ° C over a period of 3 h. Then the solid was filtered and washed with 20 g of methanol pre-cooled to 2 ° C twice. It was dried under vacuum overnight. The same experiment was repeated at 5 ° C and 10 ° C. The b * of each sample was measured and the results are reported in Table 5. Table 5. Recrystallization of crude DMFD using cold methanol.

权利要求:
Claims (15)
[0001]
1. Process for the manufacture of a dialkyl furan-2,5-dicarboxylate (DAFD) composition, characterized by the fact that it comprises: a. feeding a furan-2,5-dicarboxylic acid (“FDCA”) composition to an esterification reactor; and b. in the presence of an alcohol compound, conduct an esterification reaction at a temperature of 150 ° C to 250 ° C and a pressure of 1.72 mPa man (250 psig) to 13.78 mPa Man (2,000 psig) for 0, 5 hours to 10 hours in the esterification reactor to form the crude diester composition comprising dialkyl furan-2,5-dicarboxylate ("DAFD") and the alcohol compound; ç. separating at least a portion of the alcohol compound from the crude diester composition into an alcohol separation zone using a physical separation process to produce a DAFD-rich composition comprising DAFD solids, wherein the concentration of DAFD in the DAFD-rich composition is greater than the concentration of DAFD in the crude diester composition in a combined solid and liquid base; and d. treating the DAFD-rich composition in a purification zone to produce a purified DAFD product composition, wherein the purification zone comprises: d (i) a crystallization zone and at least a portion of the DAFD-rich composition is crystallized in the zone crystallization to generate a crystallized DAFD composition comprising DAFD solids, and (ii) the liquid solid separation zone and at least a portion of the crystallized DAFD composition is washed in the liquid solid separation zone with a washing composition to produce a purified DAFD product composition containing water.
[0002]
Process according to claim 1, characterized in that the physical separation comprises the rapid evaporation of at least a portion of the alcohol compound from the crude diester composition in the alcohol separation zone to produce a gaseous composition of alcohol.
[0003]
Process according to claim 2, characterized in that the alcohol vapor is first purified in a distillation column to produce a recycling alcohol composition, at least a portion of which is fed directly or indirectly to the reactor. or the mixing zone that powers the esterification reactor.
[0004]
Process according to claim 3, characterized in that the purification zone further comprises: d (iii) a dissolution zone in which at least a portion of the purified product composition is fed and contacts the purge stream within of the dissolution zone with a solvent effective to dissolve at least a portion of the DAFD solids to thereby produce a dissolved DAFD composition comprising the DAFD compounds in said solvent.
[0005]
Process according to claim 4, characterized in that a portion of the solvent of the dissolved DAFD-rich composition is recovered in the crystallization zone and recycled indirectly to the esterification zone or used as at least a portion of the wash composition in the solid-liquid separation zone or both.
[0006]
Process according to claim 4, characterized in that at least a portion of the dissolved DAFD composition is fed to the same crystallizer zone when accepting a feed of the DAFD-rich composition.
[0007]
7. Process according to claim 4, characterized in that the DAFD-rich composition is fed to a first crystallization zone and the dissolved DAFD composition is fed to a crystallization zone, where n is any integer that ranges from 0 to 5 inclusive and N is not the first crystallization zone.
[0008]
Process according to claim 7, characterized in that the No. of crystallizer container generates an NA crystallized DAFD composition, at least a portion of which is fed to a No. of liquid solid separation vessel to generate an NA purified DAFD composition and at least a portion of the purified DAFD composition is fed to a product isolation zone and / or at least a portion of the purified DAFD composition is subjected to repeated cycles of dissolution, crystallization, and solid separation net by any number of N times.
[0009]
Process according to claim 1, characterized in that the DAFD-rich composition comprising DAFD solids undergoes crystallization, separation of solids from the liquid, washing and dehydration in a purification zone to produce a composition of Purified DAFD having less than 20% by weight of moisture based on the weight of the purified DAFD composition.
[0010]
Process according to claim 9, characterized in that the DAFD-rich composition is crystallized, washed in a liquid solid separation zone with a washing composition comprising alcohol and subsequently dehydrated to produce a wet cake of composition purified DAFD product, each within the purification zone.
[0011]
Process according to claim 1, characterized in that the purified DAFD product composition is dried by evaporation to produce a DAFD product composition with isolated solids having a water content of not more than 1.5% in water weight based on the weight of the DAFD product composition.
[0012]
Process according to any one of claims 1 to 11, characterized in that the DAFD compounds comprise dimethyl furan dicarboxylate ("DMFD") and the alcohol compound comprises methanol.
[0013]
13. Process according to claim 1, characterized by the fact that the FDCA composition is obtained in an oxidation process that is co-located within 16,093.44 meters from the process for the production of the DAFD composition.
[0014]
14. Process according to claim 1, characterized by the fact that it has a yield of at least 1,000 kg / day calculated on a 24-hour basis over the course of any three months, said process comprising: a. esterify furan-2,5-dicarboxylic acid ("FDCA") with an alcohol at a temperature of 150 ° C to 250 ° C and a pressure of 1.72 mPa man (250 psig) to 13.78 mPa Man (2,000 psig ) for 0.5 hours to 10 hours in an esterification vessel to form the crude diester composition, said crude diester composition having a b * and comprising unreacted alcohol, water, dialkyl furan-2,5-dicarboxylate ( "DAFD"); 5- (alkoxycarbonyl) furan-2-carboxylic acid (ACFC); alkyl 5-formylfuran-2-carboxylate (AFFC); and b. purifying the crude diester composition to form a purified DAFD product composition, wherein the purified DAFD product composition has: i. a b * which is less than the b * of the crude diester composition of at least one 1 b * unit; and ii. a higher DAFD concentration than the DAFD concentration in the crude diester composition by at least 200%; and iii. an ACFC concentration lower than the ACFC concentration in the crude diester composition by at least 70%, calculated on a basis that does not factor the amount of alcohol in the crude diester composition; and iv. an AFFC concentration lower than the AFFC concentration in the crude diester composition by at least 70%.
[0015]
Process according to claim 14, characterized in that the purified DAFD product composition has: i. a b * that is less than the b * of the crude diester composition by at least 3 b * units; and ii. a higher DAFD concentration than the DAFD concentration in the crude diester composition by at least 400%; and iii. an AFFC concentration lower than the AFFC concentration in the crude diester composition by at least 97%.

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EP2864302A1|2015-04-29|

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EP3333158B1|2019-12-18|

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EP3653612A1|2020-05-20|

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EP3333158A1|2018-06-13|

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PL3333158T3|2020-07-13|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

GB621971A|1946-11-12|1949-04-25|James Gordon Napier Drewitt|Improvements in polymers|

---

US3225066A|1963-04-18|1965-12-21|Atlas Chem Ind|Process for the preparation of tetrahydrofuran-cis, 2,5-dicarboxylic acid and salts thereof|

---

US3845100A|1970-02-13|1974-10-29|Standard Oil Co|Process for conversion of para-xylene to high purity dimethyl terephthalate|

---

US3852247A|1970-11-02|1974-12-03|Fiber Industries Inc|Polymerization catalyst|

---

JPS6248989B2|1980-06-23|1987-10-16|Adeka Argus Chemical Co Ltd|

---

EP0294863A1|1987-05-13|1988-12-14|Stamicarbon B.V.|Aromatic polyester|

---

DE3826073A1|1988-07-30|1990-02-01|Hoechst Ag|METHOD FOR THE OXIDATION OF 5-HYDROXYMETHYLFURFURAL|

---

FR2723946B1|1994-08-24|1996-10-18|Ard Sa|PROCESS FOR THE MANUFACTURE OF A DIESTER OF 2,5-FURANE DICARBOXYLIC ACID|

---

IT1273617B|1995-05-05|1997-07-08|Enichem Spa|POLYOLEFINS MODIFIED WITH AN UNSATURATED GLYCIDYL ESTER|

---

DE19538700A1|1995-10-18|1997-04-24|Hoechst Ag|Polymers forming cholesteric phases, process for their preparation and use|

---

CA2235270A1|1995-10-18|1997-04-24|Hoechst Research & Technology Deutschland Gmbh & Co. Kg|Polymers which form cholesteric phases, process for their preparation, and their use|

---

WO1998050447A1|1997-05-06|1998-11-12|Ciba Specialty Chemicals Holding Inc.|Modified epoxy resin and its use as a formulating component for heat-curable compositions, especially for powder coatings|

---

US6342300B1|1999-02-20|2002-01-29|Celanese Ventures Gmbh|Biodegradable polymers based on natural and renewable raw materials especially isosorbite|

---

US6140422A|1998-04-23|2000-10-31|E.I. Dupont De Nemours And Company|Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers|

---

US6063464A|1998-04-23|2000-05-16|Hna Holdings, Inc.|Isosorbide containing polyesters and methods for making same|

---

US6126992A|1998-04-23|2000-10-03|E.I. Dupont De Nemours And Company|Optical articles comprising isosorbide polyesters and method for making same|

---

US5959066A|1998-04-23|1999-09-28|Hna Holdings, Inc.|Polyesters including isosorbide as a comonomer and methods for making same|

---

US5958581A|1998-04-23|1999-09-28|Hna Holdings, Inc.|Polyester film and methods for making same|

---

US6063495A|1998-04-23|2000-05-16|Hna Holdings, Inc.|Polyester fiber and methods for making same|

---

US6063465A|1998-04-23|2000-05-16|Hna Holdings, Inc.|Polyester container and method for making same|

---

US6025061A|1998-04-23|2000-02-15|Hna Holdings, Inc.|Sheets formed from polyesters including isosorbide|

---

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|

---

US6914120B2|2002-11-13|2005-07-05|Eastman Chemical Company|Method for making isosorbide containing polyesters|

---

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|

---

US20060205977A1|2005-03-08|2006-09-14|Sumner Charles E Jr|Processes for producing terephthalic acid|

---

JP4881127B2|2005-11-07|2012-02-22|キヤノン株式会社|Polymer compound and synthesis method thereof|

---

US8247582B2|2006-02-07|2012-08-21|Battelle Memorial Institute|Esters of 5-hydroxymethylfurfural and methods for their preparation|

---

US20090018264A1|2007-07-12|2009-01-15|Canon Kabushiki Kaisha|Resin composition|

---

US20080081883A1|2006-09-28|2008-04-03|Battelle Memorial Institute|Polyester Polyols Derived From 2,5-Furandicarboxylic Acid, and Method|

---

US7700788B2|2006-10-31|2010-04-20|Battelle Memorial Institute|Hydroxymethyl furfural oxidation methods|

---

US7638592B2|2007-01-16|2009-12-29|Battelle Memorial Institute|Formaldehyde free binders|

---

JP5233390B2|2007-04-24|2013-07-10|三菱化学株式会社|Method for producing polyester resin containing furan structure|

---

JP2008308578A|2007-06-14|2008-12-25|Canon Inc|Process for preparing polyarylate resin containing furan ring|

---

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|

---

JP5371259B2|2008-02-20|2013-12-18|キヤノン株式会社|POLYESTER RESIN, PROCESS FOR PRODUCING THE SAME, COMPOSITION FOR MOLDED ARTICLE AND MOLDED ARTICLE|

---

JP2009215467A|2008-03-11|2009-09-24|Canon Inc|Manufacturing method of polyethylene-2,5-furan dicarboxylate|

---

ITMI20080507A1|2008-03-26|2009-09-27|Novamont Spa|BIODEGRADABLE POLYESTER, ITS PREPARATION PROCESS AND PRODUCTS INCLUDING THE POLYESTER.|

---

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|

---

JP5120944B2|2008-04-25|2013-01-16|独立行政法人産業技術総合研究所|Biodegradable high molecular weight aliphatic polyester and method for producing the same|

---

IT1387503B|2008-05-08|2011-04-13|Novamont Spa|ALYPATIC-AROMATIC BIODEGRADABLE POLYESTER|

---

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|

---

JP5517494B2|2009-06-03|2014-06-11|キヤノン株式会社|Polyester, production method thereof, and molded product|

---

US8314267B2|2009-06-26|2012-11-20|Uop Llc|Carbohydrate route to para-xylene and terephthalic acid|

---

DE102009028975A1|2009-08-28|2011-03-03|Evonik Oxeno Gmbh|Ester derivatives of 2,5-furandicarboxylic acid and their use as plasticizers|

---

CA2775319C|2009-10-07|2018-08-28|Furanix Technologies B.V.|Method for the preparation of 2,5-furandicarboxylic acid and for the preparation of the dialkyl ester of 2,5-furandicarboxylic 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|

---

EP2481733A1|2011-01-28|2012-08-01|Süd-Chemie AG|Process for manufacturing esters of 2,5-furandicarboxylic acid|

---

US8658810B2|2012-06-22|2014-02-25|Eastman Chemical Company|Method for producing purified dialkyl-furan-2,5-dicarboxylate vapor|US8859788B2|2012-06-22|2014-10-14|Eastman Chemical Company|Esterification of furan-2,5-dicarboxylic acid to a dialkyl-furan-2,5-dicarboxylate vapor with rectification|

---

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.|

---

WO2015155784A1|2014-04-09|2015-10-15|Natco Pharma Limited|Process for the preparation of 2,5-furandicarboxylic acid and its ester derivative|

---

KR101926436B1|2014-11-10|2018-12-07|신비나 씨.브이.|Process for purifying a crude composition of dialkyl ester of 2,5-furandicarboxylic acid|

---

WO2016076711A1|2014-11-10|2016-05-19|Furanix Technologies B.V.|Preparation of dialkyl esters of 2,5-furandicarboxylic acid|

---

US9321714B1|2014-12-05|2016-04-26|Uop Llc|Processes and catalysts for conversion of 2,5-dimethylfuran derivatives to terephthalate|

---

DE112016001317T5|2015-03-20|2018-01-04|Stanford University|Carbonate-assisted carboxylation reaction for the synthesis of valuable organic compounds|

---

EP3325459A1|2015-07-24|2018-05-30|E. I. du Pont de Nemours and Company|Multi-stage esterification process|

---

US20190031633A1|2015-07-24|2019-01-31|E I Du Pont De Nemours And Company|Low pressure, high temperature process for forming 2,5-furandicarboxylic acid dialkyl ester|

---

US20190084952A1|2015-07-24|2019-03-21|E I Du Pont De Nemours And Company|Process for producing 2,5-furandicarboxylic acid dialkyl ester|

---

US11114194B2|2015-10-01|2021-09-07|Audacious Inquiry|Network-based systems and methods for providing readmission notifications|

---

WO2017123763A1|2016-01-13|2017-07-20|Rennovia Inc.|Processes for the preparation of 2,5-furandicarboxylic acid and intermediates and derivatives thereof|

---

BR112020000611A2|2017-07-12|2020-07-14|Stora Enso Oyj|purified products via 2,5-furanedicarboxylic acid pathway|

---

US20190390004A1|2018-06-25|2019-12-26|Eastman Chemical Company|Oxidation process to produce 5 methyl 5-methylfuran-2-carboxylate |

---

WO2022035610A1|2020-08-12|2022-02-17|Archer Daniels Midland Company|Purification of 2,5-furandicarboxylic acid, dimethyl ester and other esterified products|

法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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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. |

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2019-07-02| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2019-07-16| B15K| Others concerning applications: alteration of classification|Free format text: A CLASSIFICACAO ANTERIOR ERA: C07D 307/24 Ipc: C07D 307/24 (1974.07), C07D 307/46 (1974.07), C07D |

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2020-04-28| 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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2020-09-01| B09A| Decision: intention to grant|

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2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/530,765|US8912349B2|2012-06-22|2012-06-22|Method for producing purified dialkyl-furan-2,5-dicarboxylate separation and solid liquid separation|

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US13/530,765|2012-06-22|

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PCT/US2013/044927|WO2013191942A1|2012-06-22|2013-06-10|Method for producing purified dialkyl-furan-2,5-dicarboxylate by physical separation and solid liquid separation|

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