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    PROCESS FOR MANUFACTURING A DAFD STEAM, AND, COMPOSITION A process for producing a purified vapor comprising dialkyl-furan-2,5-dicarboxylate (DAFD) is described. Furan-2,5-dicarboxylic acid (FDCA) and an alcohol in an esterification zone to generate a crude diester stream containing dialkyl furan dicarboxylate (DAFD), unreacted alcohol, 5- (alkoxycarbonyl) furan-2-carboxylic acid ( Alkyl furan-2-carboxylate (AFC). The crude diester stream is fed to a rapid evaporation zone to produce a vapor alcohol composition and a first liquid DAFD-rich composition. At least a portion of the remaining alcohol can be separated from the first liquid DAFD-rich composition to produce a second alcohol vapor and a second liquid DAFD-rich composition, followed by the separation of AFC from the second liquid DAFD-rich composition to produce a vapor. AFC and a partially purified DAFD rich composition, followed by separating a portion of the DAFD from the partially purified DAFD rich composition to produce a purified DAFD vapor
    公开号:BR112014030071B1
    申请号:R112014030071-2
    申请日:2013-06-10
    公开日:2020-06-30
    发明作者:Lee Reynolds Partin；Ashfaq Shahanawaz Shaikh；Mesfin Ejerssa Janka；Kenny Randolph Parker
    申请人:Eastman Chemical Company；
    IPC主号:
    专利说明:

    [0001] [0001] The invention relates to processes for the production of purified dialkyl-furan-2,5-dicarboxylate (DAFD) steam and purified DAFD compositions made therefrom. BACKGROUND OF THE INVENTION
    [0002] [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.
    [0003] [0003] 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, CP; Sousa, AF; 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, VV 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 combination of Co / Mn / Br / Zr catalyst.
    [0004] [0004] The raw FDCA obtained by oxidation processes must be purified before being suitable for end-use applications. JP patent application, JP209-242312A, describes 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-step purification process generates destructive by-products.
    [0005] [0005] In Gonis, G. et al .; J. of Organic Chem., Vol.27, no.8 (1962), pp. 2946-2947 discloses a method for esterifying a furan-2,5-dicarboxylic acid by refluxing methanol and concentrated sulfuric acid, for 5 hours. After these hours, the solution is mixed with cold water to obtain a precipitate. This document also teaches condensing the vapor and refluxing liquid into the liquid reaction medium, and teaches that the formation of DAFD is only expected if all reagents are condensed and refluxed into the liquid reaction mixture and, in this case, the vapor phase component will be methanol.
    [0006] [0006] In Yoder, P. A. et al, Berichte der Deutschen Chemischen Gesellschaft Abteilung B: Abhandlungen, Wiley, DE, vol. 34, no. 3 (1901), pp. 3446-3462 the production of diisobutyl furan-2,5-dicarboxylic acid by reaction of FDCA, isobutyl alcohol and HCL is described.
    [0007] [0007] WO2011 / 023590 discloses a process for the preparation of esters of furan-2,5-dicarboxylic acid (FDCA) with isomeric C9 alcohols. This document teaches that in esterification of FDCA in order to shift the balance in favor of the ester, an old azeotrope can be used to help remove the reaction water from the batch. Such a document also reveals that mixtures of alcohols used for esterification boil at a lower temperature than furan dicarboxylic acid, its reactive derivatives, and its esters, and exhibit a range of miscibility with water, and are often used as an old azeotrope, and can be recycled into the process after removing water. In addition, it teaches that the amount of liquid to be recycled for the reaction can consist of all or part of the alcohols obtained by working with the distilled azeotrope.
    [0008] [0008] In Sanderson, R.D. et al., J. of Applied Polymer Science, vol. 53, no. 13 (1994), pp. 1785-1793 discloses the synthesis of several furan di-esters of furfural derivatives and the evaluation of di-esters as plasticizers in PVC. In addition, this document teaches the preparation of diesters by transesterification of dimethyl furan-2,5-dicarboxylate and 2-ethylhexanol (6a); or 2-octanol (6b); or hexanol (6c); or butanol (6d). It also describes that the reaction mixture is poured into water and extracted with ether, and that the excess ether and alcohol is removed by vacuum distillation.
    [0009] [0009] In Lewkowski et al .; Polish J. Chem., Vol. 75, no. 12 (2001), pp. 1943-1946 describes a process for making a dimethyl and dielty esters of furan-2,5-dicarboxylic acid, in which furan-2,5-dicarboxylic acid is dissolved in alcohol and the mixture is refluxed for a period of time. Then, the solid residue is re-crystallized from methanol. By definition and description, 100% of the vapor is returned to the liquid phase for continuous reaction. Furthermore, this document shows that the formation of DAFD is only expected if all reagents are condensed and refluxed into the liquid reaction mixture, and the vapor phase component can be alcohol, methanol, as described.
    [0010] [00010] W02010 / 077133 describes a method for the preparation of a polymer having a portion of furan-2,5-dicarboxylate in the polymer structure and teaches that, when preparing the polymer, it is essential that the first step is a step transesterification process in which alcohol, methanol or ethanol is removed at the top.
    [0011] [00011] In Haworth, W.N. et al., J. of the Chemical Society (1945), no. 1, pp. 1-4 the conversion of sucrose to furan compounds is disclosed, one compound is methyl furan-2,5-dicarboxylate which is prepared by boiling the dicarboxylic acid with 2% alcoholic methyl hydrogen chloride for 6 hours. This document teaches that most of the product is obtained by crystallization with a remainder obtained by neutralizing the filtrate with silver carbonate and evaporating the solution and recrystallizing the residue from methyl alcohol. This document does not teach or suggest making a purified DAFD from a vapor composition, but uses filtration and recrystallization from a solid phase and a liquid phase.
    [0012] [00012] Therefore, there is a need for an inexpensive, high-yield process for the purification of crude FDCA that minimizes the creation of additional waste products and lends itself to efficient separation steps. SUMMARY OF THE INVENTION
    [0013] (i) uma composição de álcool em vapor, que compreende o dito composto de álcool, retirado como uma corrente de espaço superior que é rica em uma concentração de álcool, com relação à concentração de álcool na alimentação da composição de diéster bruta na zona flash; e (ii) uma primeira composição rica em DAFD líquida, que compreende DAFD, ACFC, AFC e AFFC, que é rica na concentração total de DAFD com relação à concentração total de DAFD na alimentação da composição de diéster bruta na zona flash; e d. separar pelo menos uma porção de DAFD da primeira composição rica em DAFD líquida em uma zona de recuperação de produto; em que o processo produz: (i) uma composição de vapor de DAFD purificado rica em uma concentração de DAFD com relação à concentração de DAFD na primeira composição rica em DAFD líquida; e (ii) uma composição de ACFC líquida que é rica em uma concentração de ACFC com relação à concentração de ACFC na primeira composição rica em DAFD líquida; e (iii) uma composição de vapor AFC que compreende AFC que é rica em uma concentração de AFC com relação à concentração de AFC na primeira composição rica em DAFD líquida; e (iv) uma segunda composição de álcool que compreende álcool que é rica em uma concentração de álcool, com relação à primeira composição rica em DAFD líquida. [00013] A process for the manufacture of steam DAFD is now provided which comprises: The. feeding a furan-2,5-dicarboxylic acid (“FDCA”) composition to an esterification reaction zone; and B. in the presence of an alcohol compound, conduct an esterification reaction in the esterification reaction zone to react FDCA with said alcohol compound to form the crude diester composition comprising dialkyl furan-2,5-dicarboxylate ("DAFD") , the compound of alcohol, 5- (alkoxycarbonyl) furan-2-carboxylic acid (ACFC), alkyl furan-2-carboxylate (AFC) and alkyl-5-formylfuran-2-carboxylate (AFFC), and ç. separate at least a portion of the alcohol compound from the crude diester composition in a flash zone using a physical separation process to produce: (i) a vapor alcohol composition, comprising said alcohol compound, removed as an upper space stream that is rich in an alcohol concentration, with respect to the alcohol concentration in the feed of the raw diester composition in the flash zone ; and (ii) a first liquid DAFD-rich composition, comprising DAFD, ACFC, AFC and AFFC, which is rich in the total concentration of DAFD in relation to the total concentration of DAFD in the feed of the raw diester composition in the flash zone ; and d. separating at least a portion of DAFD from the first liquid DAFD-rich composition in a product recovery zone; where the process produces:(i) a purified DAFD vapor composition rich in a DAFD concentration with respect to the DAFD concentration in the first liquid DAFD rich composition; and (ii) a liquid ACFC composition that is rich in an ACFC concentration with respect to the concentration of ACFC in the first liquid DAFD-rich composition; and (iii) an AFC vapor composition comprising AFC that is rich in an AFC concentration with respect to the AFC concentration in the first liquid DAFD-rich composition; and (iv) a second alcohol composition comprising alcohol that is rich in an alcohol concentration, with respect to the first liquid DAFD-rich composition.
    [0014] d(i) uma segunda composição de álcool que é rica em uma concentração de álcool com relação à concentração de álcool na primeira composição rica em DAFD líquida; e d(ii) uma segunda composição rica em DAFD líquida que compreende DAFD que é rica em uma concentração de DAFD com relação à concentração de DAFD na primeira composição rica em DAFD líquida; e em que o dito processo ainda compreende: e. separar pelo menos uma porção de AFC da segunda composição rica em DAFD líquida usando-se um processo de separação física para produzir: e(i) uma composição de vapor AFC que é rica em uma concentração de AFC com relação à concentração de AFC na segunda composição rica em DAFD líquida; e e(ii) uma composição parcialmente purificada rica em DAFD líquida que compreende DAFD e ACFC que é rica em uma concentração de DAFD com relação à concentração de DAFD na segunda composição rica em DAFD líquida; e f. separar pelo menos uma porção do DAFD da composição rica parcialmente purificada em DAFD usando-se um processo de separação física para produzir: f(i) uma composição de vapor de DAFD purificado rica em uma concentração de DAFD com relação à concentração de DAFD na composição parcialmente purificada rica em DAFD líquida; e f(ii) uma composição de ACFC líquida que é rico na concentração de ACFC com relação à concentração de ACFC na composição parcialmente purificada rica em DAFD líquida. [00014] Step d further comprises separating at least a portion of alcohol from the first liquid DAFD-rich composition using a physical separation process to produce: d (i) a second alcohol composition that is rich in an alcohol concentration with respect to the alcohol concentration in the first liquid DAFD composition; and d (ii) a second liquid DAFD-rich composition comprising DAFD which is rich in a DAFD concentration with respect to the DAFD concentration in the first liquid DAFD-rich composition; and in which said process still comprises: and. separate at least a portion of AFC from the second liquid DAFD-rich composition using a physical separation process to produce: and (i) an AFC vapor composition that is rich in an AFC concentration with respect to the AFC concentration in the second liquid DAFD-rich composition; and and (ii) a partially purified liquid DAFD-rich composition comprising DAFD and ACFC which is rich in a concentration of DAFD with respect to the concentration of DAFD in the second liquid DAFD-rich composition; and f. separate at least a portion of the DAFD from the rich partially purified DAFD composition using a physical separation process to produce: f (i) a purified DAFD vapor composition rich in a concentration of DAFD with respect to the concentration of DAFD in the partially purified composition rich in liquid DAFD; and f (ii) a liquid ACFC composition that is rich in the concentration of ACFC with respect to the concentration of ACFC in the partially purified composition rich in liquid DAFD.
    [0015] [00015] A process for preparing FDCA is also provided which is fed to the esterification reaction zone.
    [0016] (i) pelo menos 99,5% em peso de DAFD; (ii) ácido 5-(alcoxicarbonil)furan-2-carboxílico (ACFC) presente e está presente em uma quantidade de não mais do que 1.000 ppm, e (iii) alquil-5-formilfuran-2-carboxilato (AFFC) presente e está presente em uma quantidade de não mais do que 1.000 ppm, em cada caso com base no peso da composição de vapor de DAFD. Também é fornecido uma composição de DAFD líquida purificada que compreende: (i) pelo menos 99,9% em peso de DAFD líquida; (ii) ácido 5-(alcoxicarbonil)furan-2-carboxílico (ACFC) presente e está presente em uma quantidade de não mais do que 1.000 ppm, e (iii) alquil-5-formilfuran-2-carboxilato (AFFC) presente e está presente em uma quantidade de não mais do que 1.000 ppm, (iv) não mais do que 1% em peso de água, e (v) não mais do que 1% em peso de sólidos, em cada caso com base no peso da composição de DAFD líquida purificada.[00016] A purified dialkyl furan carboxylate (DAFD) vapor composition is also provided which comprises: (i) at least 99.5% by weight of DAFD; (ii) 5- (alkoxycarbonyl) furan-2-carboxylic acid (ACFC) present and present in an amount of not more than 1,000 ppm, and (iii) alkyl-5-formylfuran-2-carboxylate (AFFC) present and present in an amount of no more than 1,000 ppm, in each case based on the weight of the DAFD vapor composition. A purified liquid DAFD composition is also provided which comprises: (i) at least 99.9% by weight of net DAFD; (ii) 5- (alkoxycarbonyl) furan-2-carboxylic acid (ACFC) present and present in an amount of not more than 1,000 ppm, and (iii) alkyl-5-formylfuran-2-carboxylate (AFFC) present and present in an amount of no more than 1,000 ppm, (iv) no more than 1% by weight of water, and (v) not more than 1% by weight of solids, in each case based on the weight of the purified liquid DAFD composition.
    [0017] (i) pelo menos 99,9% em peso de DAFD; (ii) ácido 5-(alcoxicarbonil)furan-2-carboxílico (ACFC) presente e está presente em uma quantidade de não mais do que 1.000 ppm, e (iii) alquil 5-formilfuran-2-carboxilato (AFFC) presente e está presente em uma quantidade de não mais do que 1.000 ppm, em que a composição contém não mais do que 1% em peso de água. [00017] A solid DAFD composition is also provided which comprises solid particles of DAFD, wherein said solids comprise: (i) at least 99.9% by weight of DAFD; (ii) 5- (alkoxycarbonyl) furan-2-carboxylic acid (ACFC) present and present in an amount of not more than 1,000 ppm, and (iii) alkyl 5-formylfuran-2-carboxylate (AFFC) present and present in an amount of no more than 1,000 ppm, wherein the composition contains no more than 1% by weight of water.
    [0018] [00018] Figure 1 is a process flow diagram for making both purified FDCA and DAFD.
    [0019] [00019] Figure 2 is a flow diagram that illustrates feeding raw materials to a mixing zone before feeding the slurry to an esterification reactor.
    [0020] [00020] Figure 3 is a flow diagram that describes the process of producing a purified DAFD vapor composition using a combination of separation zones. DETAILED DESCRIPTION OF THE INVENTION
    [0021] [00021] 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 previous description, such as, for example, when accompanying the use of a term defined in the context.
    [0022] [00022] As used herein, the terms "one," "one," and "o" mean one or more.
    [0023] [00023] 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.
    [0024] [00024] 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.
    [0025] [00025] As used herein, the terms "having," "had," and "has" have the same open meaning as "comprising," "comprises," and "comprising" provided above.
    [0026] [00026] As used herein, the terms "including," "includes," and "including" have the same open meaning as "comprising," "comprises," and "comprising" provided above.
    [0027] [00027] 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).
    [0028] [00028] 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 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 758.42 kPaa (110 psia) and a second pressure of 330.94 kPaa (48 psia) (a difference of 427.47 kPa (62 psi)), the narrow, intermediate and wide ranges due to the pressure difference between these two currents should be 172.36 to 682.58 kPa (25 to 99 psi), 296.47 to 558, 47 kPa (43 to 81 psi) and 365.42 to 489.52 kP a (53 to 71 psi), respectively.
    [0029] [00029] 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.
    [0030] [00030] All quantities are by weight unless otherwise specified.
    [0031] [00031] As illustrated in Figure 1, a carboxylic acid composition stream 410, which may be dried carboxylic acid solids or a wet cake containing carboxylic acid, 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 the manufacture of the diester composition. 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 into 1/2 miles (0.80 km). 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 wet cake dicarboxylic acid composition is produced, the wet cake can be belt-driven or pumped as a liquid slurry to the facility for esterification.
    [0032] [00032] The esterification zone 500 comprises at least one esterification reactor. 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 the esterification reaction zone to react FDCA with said alcohol compound to form the composition crude diester comprising dialkyl furan-2,5-dicarboxylate ("DAFD"), the alcohol compound, 5- (alkoxycarbonyl) furan-2-carboxylic acid (ACFC), alkyl 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.
    [0033] [00033] The alcohol composition comprises 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.
    [0034] [00034] The crude diester composition produced in an esterification zone 500 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 comprises 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 methanol 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 DMFD. A commercial process to produce purified DMFD must allow the separation of DMFD and MCFC downstream from the esterification zone.
    [0035] [00035] The esterification by-products are also formed in reaction zone 500 and comprise chemicals with boiling points that are 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-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.
    [0036] [00036] It is desirable to first mix the FDCA composition with the alcohol before conducting an esterification reaction under esterification conditions. As illustrated in Figure 2, a mixing zone 540 and esterification reactor 550 is provided within esterification zone 500. The dicarboxylic acid composition 410 comprising FDCA, an alcohol composition 520, optionally a catalyst esterification system 530 and 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 are mixed in the mixing zone 540 to generate the mixed reactor feed stream 501. In one embodiment , streams 520 and 802 comprise methanol.
    [0037] [00037] Mixing in zone 540 can be performed by any equipment known in the art for mixing 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 in an esterification zone, or the esterification reactor 550 or in the mixing zone 540, is two moles. The total amount of alcohol present in the mixing zone 540 is desirably in excess of the theoretical amount required for the esterification reaction.
    [0038] [00038] 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. Suitable molar ratios are within an alcohol range for FDCA from 10: 1 to 30: 1.
    [0039] [00039] Mixing zone 540 can also be fed with a catalyst esterification system such as chain 530 if a catalyst is used. The catalyst can be heterogeneous or desirably a homogeneous catalyst under the esterification reaction conditions and can also be homogeneous in the mixing zone.
    [0040] [00040] The known organometallic esterification catalysts can be used as acetate or other carboxylate or cobalt, copper and manganese glycolate, cadmium, lead, lithium and zinc in amounts conventionally used to esterify terephthalic acid. Other organic catalysts can be used, such as sulfuric acid, tosyl acid and Lewis acids.
    [0041] [00041] The mixed reactor supply stream 501 is sent to the esterification reactor 550 to generate a crude diester composition discharged from the esterification reactor 550 as the net crude diester stream 510. The crude diester composition 510 discharged from the esterification 500 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 total crude diester composition and desirably in each case based on the weight of the liquid phase. 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 95% by weight or at least 96% by weight or at least 97% by weight or at least 98% by weight or at least 99% by weight of the solids are unreacted FDCA solids.
    [0042] [00042] The yield of DAFD 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 mol or at least 90 mol% or at least 95 mol% or at least 99 mol%. The DAFD yield 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%.
    [0043] [00043] The raw 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 vapor composition. Examples of suitable rates for producing a purified DAFD vapor composition stream 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 75,000 kg / day or at least 100,000 kg / day or at least 200,000 kg / day of a purified DAFD vapor composition, on a 24-hour basis over the course of any three months.
    [0044] [00044] 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 residence time of the esterification reaction varies 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).
    [0045] [00045] The crude diester composition is removed from the esterification reactor in an esterification zone 500 in a stream 510 and fed to flash zone 600 as shown in Figure 1. At least a portion of the alcohol compound in the crude diester composition is separated from the crude diester stream in the flash zone 600 in a physical separation process to produce a first DAFD 620 stream-rich liquid composition containing liquid DAFD and where the concentration of DAFD in the DAFD-rich composition is greater than the concentration of DAFD in the feed of the crude diester composition in the flash zone 600. In the flash zone , the crude diester composition experiences a pressure left for the flash alcohol which also results in evaporative cooling.
    [0046] [00046] The crude diester composition 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 carried out 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 first liquid DAFD-rich composition like stream 620. This can be done without applying heat energy to the separation vessel for separation purposes, thereby reducing energy consumption (e.g., adiabatic flash ).
    [0047] [00047] The flash zone 600 may comprise one or more containers for flash separation by means of pressure reduction operated in series or in parallel without the application of external heat energy to carry out the separation. For example, flash zone 600 may comprise one or more evaporative flash unit operations or may comprise one or more distillation columns. The alcohol separation zone can comprise both a flash evaporation unit and a distillation column. The separation zone can be operated in a batch or continuous mode.
    [0048] [00048] Desirably, the flsah 600 zone contains at least one flash evaporation unit such as a flash tank . Flash evaporation can be conducted in stages in multiple containers. The pressure in the flash 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 physically separating container, it is desirable that the pressure inside the flash container is below the vapor pressure of the alcohol at the temperature of the diester stream gross at the entrance door to the flash container .
    [0049] [00049] The temperature of the first current-rich liquid composition of DAFD 620 discharged from flash zone 600 is not particularly limited. This will be less than the temperature of the crude diester stream entering the flash zone due to evaporative cooling. In one embodiment, the temperature of the first current-rich liquid composition of DAFD 620 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 cooler or at least 120 ° C cooler than the temperature of the raw diester composition entering the flash zone 600. A series of flash containers can be used having a small incremental temperature drop, such as that the cumulative temperature drop of all containers within the zone increases to at least these established values.
    [0050] [00050] An alcohol vapor composition stream 610 is generated in flash zone 600. The alcohol vapor composition stream 610 comprises alcohol, some water, and optionally a little (for example, less than 0.1% by weight) DAFD may also be present. The 610 alcohol vapor composition stream is rich in an alcohol concentration, with respect to the alcohol concentration in the 510 crude diester composition. Desirably, the alcohol concentration in the 610 alcohol vapor composition comprises at least 70% by weight alcohol or at least 80% by weight alcohol or at least 90% by weight or at least 95% by weight of alcohol.
    [0051] [00051] The alcohol vapor composition stream 610 is fed to an alcohol recovery zone 800. The alcohol recovery zone generates a purified alcohol stream 802 that comprises alcohol that is set aside in a water-alcohol concentration with respect to to the water concentration in the alcohol vapor composition stream 610 and generates a water stream 801 which is rich in a water concentration with respect to the water concentration in the alcohol vapor stream 610.
    [0052] [00052] The alcohol recovery zone 800 may comprise one or more distillation columns to carry out the separation of alcohol from water. The distillation column can be dedicated to receive a feed of the alcohol vapor composition 610 or the alcohol vapor composition 610 can first be condensed and fed to the distillation column. The purified alcohol composition 802 can be one or more steam distillates and if desired, at least a portion can be condensed and at least a portion can be fed as a recycling stream back to esterification zone 500.
    [0053] [00053] Alternatively, the upper gas stream of the 610 alcohol vapor composition or liquid if condensed, can be fed to a distillation column divided into an alcohol recovery zone 800 which also receives a feed from a second stream rich in alcohol 712 A split distillation mechanism is also desired to reduce capital costs.
    [0054] [00054] The first stream-rich liquid composition of DAFD 620 comprises rich DAFD (a higher concentration) in a concentration of DAFD with respect to the concentration of DAFD present in the crude diester stream 510 leaving the esterification zone 500. The concentration of DAFD 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 510. The DAFD-rich stream desirably contains DAFD in an amount of at least 5% by weight or 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.
    [0055] [00055] The first DAFD-rich liquid stream desirably does not contain solids. If present, the solids comprise unreacted DAFD and / or FDCA or other by-products that react with 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 or up to 10% by weight or up to 5% by weight or up to 3% by weight or up to 2% by weight and, if present, an amount greater than zero, each based on the weight of the first liquid DAFD 620 rich composition.
    [0056] [00056] The first stream-rich liquid composition of DAFD 620 also contains any alcohol that does not separate in flash zone 600, some water and a quantity of some or all of the by-products mentioned above. The amount of alcohol in the first DAFD-rich liquid stream is greater than zero or at least 1 wt% or at least 2 wt% or at least 3 wt% or at least 5 wt% or at least 10 wt% 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, based on the weight of the DAFD-rich chain.
    [0057] (i) uma composição de vapor de DAFD purificado rica em uma concentração de DAFD com relação à concentração de DAFD na primeira composição rica em DAFD líquida; e (ii) uma composição de ACFC líquida que é rica em uma concentração de ACFC com relação à concentração de ACFC na primeira composição rica em DAFD líquida; e (iii) uma composição de vapor AFC que compreende AFC que é rica em uma concentração de AFC com relação à concentração de AFC na primeira composição rica em DAFD líquida; e (iv) uma segunda composição de vapor de álcool, que compreende álcool, que é rica em uma concentração de álcool, com relação à primeira composição rica em DAFD líquida. [00057] As shown in Figure 1, the first current DAFD 620-rich liquid composition is fed to a product recovery zone 700 to separate at least a portion of DAFD from the first liquid DAFD-rich composition in the product recovery zone using one or more physical separation processes to produce: (i) a purified DAFD vapor composition rich in a DAFD concentration with respect to the DAFD concentration in the first liquid DAFD rich composition; and (ii) a liquid ACFC composition that is rich in an ACFC concentration with respect to the concentration of ACFC in the first liquid DAFD-rich composition; and (iii) an AFC vapor composition comprising AFC that is rich in an AFC concentration with respect to the AFC concentration in the first liquid DAFD-rich composition; and (iv) a second alcohol vapor composition, comprising alcohol, which is rich in an alcohol concentration, in relation to the first liquid DAFD rich composition.
    [0058] [00058] The product recovery zone 700 can contain one or more distillation columns to perform one or more separations.
    [0059] [00059] As an example, the product recovery zone 700 may contain an alcohol-water removal zone 710, as shown in Figure 3, which comprises a physical separation unit for separating alcohol from the first liquid DAFD-rich composition, thereby producing a second stream of alcohol composition 712 discharged from the top of the column that is rich in an alcohol concentration with respect to the alcohol concentration in the first stream rich liquid composition of DAFD 620, and a second stream rich liquid composition. of DAFD 711 comprising DAFD which is rich in a concentration of DAFD in relation to the concentration of DAFD in the first liquid composition rich in DAFD 620 stream. Desirably, the concentration of alcohol in the second liquid composition rich in DAFD is nullified (or less) regarding the alcohol concentration in the first liquid DAFD-rich composition. Also, desirably the concentration of DAFD in the second stream of alcohol composition 712 discharged from the top of the column is nullified with respect to the concentration of DAFD in the second liquid composition rich in DAFD stream 711.
    [0060] [00060] An example of a device suitable for separating alcohol from the first DAFD 620 stream-rich liquid composition is any type of distillation column (tray or packaged).
    [0061] [00061] The second alcohol composition stream 712 may, if desired, be fed directly to an alcohol recovery zone 800 as a vapor to separate water from the second alcohol composition stream 712. Alternatively, the second alcohol composition stream alcohol 712 can, if desired, be condensed, with a portion of the condensed alcohol composition fed back to the column as reflux and a portion of the condensed alcohol composition fed to the alcohol recovery zone 800 as a liquid. In this way, the stream 712 fed to the alcohol recovery zone 800 is a liquid and / or a vapor. The alcohol recovery zone 800 for alcohol of the second alcohol composition stream 712. The alcohol recovery zone 800 can also be used to accept a feed of the first alcohol vapor composition stream 610 to separate alcohol from the first composition stream of alcohol vapor 610 and the same distillation column can be used to accept feeds 610 and 712. Alternatively, a second distillation column can be used to accept feed 610.
    [0062] [00062] Throughout this description, it should be understood that any vapor stream generated in the process, such as in each distillation mechanism, can be condensed and condensation can occur inside the hill, outside the column, such as after the vapor is discharged from the grinding section of the distillation mechanism and this can be totally or partially condensed. Alternatively, the steam stream must not be fully condensed. It should also be understood that any values that describe the concentration of an ingredient in a vapor stream can be measured in a condensed liquid stream of the vapor stream in question if the condensables in the vapor stream are fully condensable.
    [0063] [00063] Alcohol recovery zone 800 generates a stream of purified alcohol composition 802 which is suitable for use as a recycling stream fed to esterification zone 500 if desired and the water-rich stream 801 which is enriched in a concentration of water with respect to the concentration of water in a stream of purified alcohol composition 802. The concentration of water in the stream rich in water 801 is desirably at least 98% by weight or at least 99% by weight or at least 99.5% in weight.
    [0064] [00064] Examples of devices suitable for separating alcohol from water in the alcohol recovery zone include a distillation column, with trays or packaged or both.
    [0065] [00065] The stream of purified alcoholic vapor composition 802, whether or not condensed for use as a recycling stream to the esterification zone, contains less than 10% by weight of water or less than 5% by weight of water or less than 1% by weight of water or less than 0.5% by weight of water and less than 0.001% by weight of DAFD or less than 0.0001% by weight of DAFD, each based on weight of a purified alcohol composition stream 802. In one embodiment, the purified alcohol recycling stream 802 comprises methanol in a purity greater than 99.0% by weight based on the weight of the purified alcohol composition stream.
    [0066] [00066] The second stream-rich liquid composition of DAFD 711 discharged from the alcohol water removal zone 710 contains DAFD in a concentration of at least 80% by weight or at least 85% by weight or at least 90% by weight or at least minus 92% by weight, and up to 99% by weight or up to 98% by weight or up to 97% by weight or up to 96% by weight, each based on the weight of the second stream-rich liquid composition of DAFD 711. A amount of alcohol in the second DAFD stream-rich liquid composition is desirably less than 1% by weight or less than 0.1% by weight or less than 0.01% by weight or less than 0.001% by weight. The amount of water in the second liquid DAFD-rich composition 711 is desirably less than 1% by weight or less than 0.5% by weight or less than 0.2% by weight. The concentration of DAFD in a second composition rich in DAFD 711 may be higher than the concentration of DAFD in the first liquid composition rich in chain DAFD 620 by at least 10% by weight or at least 20% by weight or at least 30 % by weight or at least 40% by weight. The cumulative concentration of water and alcohol in the second liquid DAFD-rich composition 711 is nullified with respect to the water concentration of an alcohol in the first liquid DAFD-rich composition 620 by a factor of at least 100x or at least 300x or at least 500x or at least minus 700x.
    [0067] [00067] The second current-rich liquid composition of DAFD 711 contains not only DAFD, but also ACFC, AFC and AFFC. As shown in Figure 3, the second liquid DAFD-rich composition 711 is fed to an AFC / AFFC 720 removal zone to separate at least a portion of AFC from the liquid DAFD-rich composition using a physical separation process to produce a AFC 722 rich vapor composition rich in an AFC concentration with respect to the AFC concentration in the second liquid DAFD 711 rich composition and a partially purified DAFD 721 current rich liquid composition comprising DAFD and ACFC which is rich in a concentration of DAFD in relation to the concentration of DAFD in the second composition rich in liquid DAFD 711. Since the vapor composition rich in AFC 722 is rich in a concentration of AFC in relation to the concentration of AFC in the second composition rich in liquid DAFD 711, also it is necessarily rich in a concentration of AFC in relation to the concentration of AFC in the first stream-rich liquid composition of DAFD 620. Since DAFD in the rich liquid composition partially Current purified agent of DAFD 721 is rich in a concentration of DAFD in relation to the concentration of DAFD in the second composition rich in liquid DAFD 711, it is also necessarily rich in a concentration of DAFD in relation to the concentration of DAFD in the first liquid composition rich in current of DAFD 620.
    [0068] [00068] An example of a suitable physical separation method is to distill the second liquid DAFD 711 rich composition. The appropriate distillation pot temperature ranges in the 720 zone of 200 ° C less than the boiling point of DAFD under operating conditions. Suitable temperatures range from 210 ° C to 280 ° C or 220 ° C to 260 ° C or 230 ° C to 250 ° C. The second liquid DAFD-rich composition is desirably vacuum distilled to degrade the DAFD product in the second DAFD-rich composition in the pot which must otherwise occur at higher temperatures. The second DAFD-rich composition can be distilled at pressures ranging from 6.89 kPaa (1 psia) to atmospheric pressure. The column desirably has 10 to 70 trays, 10 to 60 a trays, 10 to 50 trays, where a tray can be a valve tray, sieve tray, bubble cover tray or an equivalent height of a packed bed. The distillation operating temperature is desirably set to create an AFC vapor composition and desirably to remove AFC vapor as a distillate, which, optionally, can be partially or fully condensed and a portion returned to the column as reflux. In another embodiment, the distillation conditions can also be fixed to remove AFFC in addition to AFC as an upper vapor part, such that the AFFC concentration in the AFC 722 rich vapor composition is enriched in the AFFC concentration with respect to the concentration of AFFC in a second liquid stream rich in DAFD 711. In this embodiment, since the vapor composition rich in AFC 722 is rich in a concentration of AFFC in relation to the concentration of AFFC in the second composition rich in liquid DAFD 711, it is also necessarily rich in a concentration of AFFC in relation to the concentration of AFFC in the first current-rich liquid composition of DAFD 620.
    [0069] [00069] The reflux ratio to achieve the desired purities will vary with the number of trays and the mass of distillate produced.
    [0070] [00070] The composition of the vapor stream rich in AFC 722 contains AFC. The AFC rich vapor stream composition comprises at least 5% by weight AFC or at least 10% by weight AFC or at least 15% by weight AFC or at least 20% by weight AFC or at least 25% by weight AFC. The AFC rich vapor stream composition optionally comprises at least 2 wt% AFFC or at least 5 wt% AFFC or at least 10 wt% AFFC or at least 20 wt% AFFC or at least 30 % by weight of AFFC or at least 40% by weight of AFFC or at least 50% by weight of AFFC or at least 60% by weight of AFFC. The concentration of AFFC in the vapor stream rich in AFC 722 may be higher than the concentration of AFC, in some cases by a factor of 1.5x or 2x or 2.5x. The DAFD concentration in the AFC 722 rich vapor composition is negated with respect to the DAFD concentration in a second DAFD 711 current rich liquid composition. The DAFD concentration in the AFC 722 rich vapor composition can be less than 10 % by weight of DAFD or less than 5% by weight of DAFD or less than 4% by weight of DAFD or less than 3% by weight of DAFD or less than 2% by weight of DAFD or less than 1 % by weight of DAFD, each based on the weight of the AFC rich vapor composition. The concentration of AFC and AFFC in the AFC 722 rich vapor composition stream can be 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, each based on the weight of all ingredients in the AFC 722 rich vapor composition.
    [0071] [00071] The AFC concentration in the AFC 722 rich vapor composition stream is desirably increased by a factor of at least 5x or at least 10x or at least 15x and up to 80x or up to 70x or up to 50x, on a weight basis , regarding the AFC concentration in the second liquid DAFD 711 rich composition.
    [0072] [00072] The composition of the partially purified liquid stream rich in DAFD 721 contains DAFD and ACFC. The concentration of each of these ingredients based on the weight of the partially purified liquid stream rich in DAFD 721 is as follows: DAFD: at least 90% by weight or at least 92% by weight or at least 95% by weight or at least 97% by weight or at least 98% by weight, and up to 99.9% by weight or up to 99.5 % by weight or up to 99.0% by weight or up to 98.5% by weight or up to 98% by weight and ACFC: at least 0.05% by weight or at least 0.1% by weight or at least 0, 5% by weight or at least 1.0% by weight or at least 1.25% by weight, and up to 10% by weight or up to 7% by weight or up to 5.0% by weight or up to 4% by weight or up to 3% by weight and a cumulative amount of AFFC, AFC, water and alcohol less than 2% by weight or not more than 1.5% by weight or not more than 1.0% by weight or not more than than 0.5% by weight or not more than 0.1% by weight and, desirably, also AFC and AFFC in an amount of not more than 0.1% by weight or not more than 0.05% in weight or not more than 0,001% by weight.
    [0073] [00073] The concentration of DAFD in the partially purified composition rich in liquid DAFD 721 is greater than the concentration of DAFD in the second composition rich in liquid DAFD 711. The concentration of AFC in the partially purified liquid chain rich in DAFD 721 is desirably eliminated with with respect to the AFC concentration in the second liquid DAFD-rich composition 711 by a factor of at least 10x or at least 100x or at least 250x or at least 500x or at least 750x or at least 1000x.
    [0074] [00074] The temperature of the partially purified liquid stream rich in DAFD effluent 721 from the AFC / AFFC 720 removal zone is desirably at least 220 ° C or at least 230 ° C and up to 270 ° C or up to 260 ° C or up to 250 ° Ç.
    [0075] [00075] The DAFD 721 stream-rich partially purified liquid composition is fed to an ACFC 730 removal zone to separate at least a portion of the DAFD from the DAFD 721 partially purified rich composition using a physical separation process to produce a purified DAFD vapor composition 732 which is rich in a concentration of DAFD with respect to the concentration of DAFD in the partially purified composition rich in liquid DAFD 721 and a lower stream of liquid ACFC 731 which is rich in a concentration of ACFC with respect to to the concentration of ACFC in the partially purified composition rich in liquid DAFD 721, each by weight. Since the steam composition of purified DAFD 732 is rich in a concentration of DAFD with respect to the concentration of DAFD in the rich liquid composition partially purified in a stream of DAFD 721, it is also necessarily rich in a concentration of DAFD in relation to the concentration of DAFD in the first stream-rich liquid composition of DAFD 620. Since the bottom stream of liquid ACFC 731 is rich in a concentration of ACFC in relation to the concentration of ACFC in the rich liquid composition partially purified in stream of DAFD 721, it is also necessarily rich in a concentration of ACFC in relation to the concentration of ACFC in the first current-rich liquid composition of DAFD 620.
    [0076] [00076] An example of a suitable physical separation mechanism is a distillation column. The appropriate distillation pot temperature ranges in zone 730 range from 200 ° C less than the boiling point of ACFC under operating conditions. Desirably the temperature is displayed at least the boiling point of the DAFD compound under the conditions of the operation. Suitable pot temperatures range from 210 ° C to 280 ° C or 220 ° C to 260 ° C or 230 ° C to 255 ° C. The rich composition partially purified in liquid DAFD 721 is desirably distilled in a vacuum to prevent degradation of the DAFD product. The rich partially purified composition in liquid DAFD 721 can be distilled at pressures ranging from 6.89 kPaa (1 psia) at atmospheric pressure. The column desirably has 10 to 70 trays, 10 to 60 a trays or 10 to 50 trays, where a tray can be a valve tray, sieve tray, bubble cover tray or an equivalent height of a packed bed. The distillation operating temperature is desirably presented to create a purified DAFD vapor composition and desirably to remove DAFD steam as a distillate, which can optionally be partially or fully condensed and a portion taken back to the column as reflux. The reflux ratio will vary with the number of trays and the mass of the distillate produced.
    [0077] [00077] The vapor composition of the purified DAFD stream 732 contains DAFD. The concentration of each of these ingredients by weight based on the vapor weight of the purified DAFD stream is as follows: DAFD: at least 99.0% by weight or at least 99.2% 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, and up to 99.999% by weight or up to 99.995% by weight or at least 99.99% by weight; and ACFC, which if present in all, is present in an amount greater than zero and not more than 1000 ppm or not more than 100 ppm or not more than 10 ppm or not more than 1 ppm; and desirably AFFC, which if present in all, is present in an amount greater than zero and not more than 1000 ppm or not more than 100 ppm or not more than 50 ppm or not more than 20 ppm.
    [0078] [00078] Optionally, this composition also contains very low amounts or no amount of: AFC, which if present in all, is present in an amount of no more than 10 ppm or no more than 1 ppm or no more than 0 , 1 ppm; and alcohol, which if present in all, is present in an amount not more than 10 ppm or not more than 1 ppm or not more than 0.1 ppm and FDCA, if present in all, is present in an amount of no more than 1,000 ppm or no more than 100 ppm or no more than 10 ppm or no more than 1 ppm.
    [0079] [00079] Desirably, if water is present, it is present in an amount of no more than 1,000 ppm or no more than 100 ppm or no more than 10 ppm.
    [0080] [00080] The vapor concentration of ACFC in the purified DAFD stream 732 is annulled with respect to the concentration of ACFC in the partially purified composition rich in DAFD stream 721 by a factor of at least 10x or at least 50x or at least 100x or at least 200x.
    [0081] [00081] The composition of the liquid bottom composition ACFC 731 contains ACFC and DAFD. The ACFC liquid bottom composition comprises ACFC in an amount of at least 20% by weight or at least 30% by weight or at least 40% by weight based on the weight of the composition of the ACFC liquid bottom. The concentration of DAFD in the ACFC liquid bottom composition desirably contains DAFD in an amount of less than 70% by weight or less than 50% by weight or less than 40% by weight or less than 30% by weight, based on the weight of the ACFC liquid bottom composition. The amount of ACFC by weight is desirably at least 1.5x or at least 2.0x greater than the amount of DAFD in the ACFC liquid bottom stream.
    [0082] [00082] The concentration of ACFC in the composition of the liquid bottom ACFC 731 is desirably increased by a factor of at least 5x or at least 10x or at least 30x with respect to the concentration of ACFC in the partially purified composition rich in liquid DAFD 721.
    [0083] [00083] The composition of the purified DAFD vapor is desirably condensed in a condenser to produce a composition of the purified liquid DAFD product containing liquefied DAFD at a temperature below the boiling point of the DAFD compound and above its crystallization temperature in 1 atmosphere. The concentration of DAFD in the composition of the purified liquid DAFD product, based on the composition of the purified liquid DAFD product, is DAFD: at least 99.0% by weight or at least 99.2% 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, and up to 99.999% by weight or up to 99.995% by weight or at least 99.99% by weight; and ACFC, which if present in all, is in an amount of not more than 100 ppm or not more than 10 ppm or not more than 1 ppm; and desirably AFFC, which if present, is present in an amount of no more than 1,000 ppm or no more than 100 ppm or no more than 50 ppm or no more than 20 ppm, and optionally, AFC, which if present in all, is present in an amount of not more than 10 ppm or not more than 1 ppm or not more than 0.1 ppm; and optionally, alcohol, which if present in all, is present in an amount not more than 10 ppm or not more than 1 ppm or not more than 0.1 ppm; and desirably FDCA, if present in all, is present in an amount of no more than 1000 ppm or no more than 100 ppm or no more than 10 ppm or no more than 1 ppm.
    [0084] [00084] Desirably, if water is present in the composition of the purified liquid DAFD product, it is present in an amount of no more than 1000 ppm or no more than 100 ppm or no more than 10 ppm or no more than 5 ppm or not more than 1 ppm. The concentrations of solid in the composition of the purified liquid DAFD product is desirably 0, but if the solids are present, they are present in an amount of less than 0.1% by weight or not more than 0.01% by weight or not more than 0.001% by weight.
    [0085] [00085] If desired, the composition of the purified liquid DAFD product can be hot. The composition of the hot purified liquid DAFD product can be sent in a molten product storage tank, to a tank car or tank truck capable of containing and transferring the hot liquid material, and / or directly to a polyester process through a pipeline in that DAFD is mixed with a crude polyester material comprising a diol such as ethylene glycol and reacted with said diol to form the polymer comprising the polyester.
    [0086] [00086] Alternatively, the composition of the purified DAFD vapor can be condensed and crystallized to form the solid DAFD particles which comprise 99.9% by weight of DAFD on the solids basis as a slurry or instead of the slurry, can be dried to form the dry solids of the DAFD stream, which in each case has a purity of at least the same purity levels as in the 732 rich purified DAFD steam stream. Conversion of the purified liquid DAFD composition to a dry solid stream it can be accompanied by any methods known in the art including a cooled belt laminator, spray drying and the like. In this way, a solid DAFD composition is also provided which comprises solid particles of DAFD, wherein said solids comprise: (i) at least 99.9% by weight of DAFD or at least 99.95% by weight of DAFD or at least 99.99% by weight of DAFD; (ii) not more than 1000 ppm or not more than 100 ppm or not more than 10 ppm 5- (alkoxycarbonyl) furan-2-carboxylic acid ACFC, (iii) alkyl-5-formylfuran-2-carboxylate (AFFC) which, if present, is present in an amount of not more than 1000 ppm or not more than 100 ppm or not more than 10 ppm and optionally (iv) not more than 100 ppm or not more than 100 ppm or not more than 10 ppm, alkyl furan-2-carboxylate and wherein the composition contains not more than 1% by weight of water or not more than 0.5% by weight of water or not more than 0.1% by weight of water or not more than 0.01% by weight of water. Desirably, the composition contains less than 1000 ppm furan dicarboxylic acid (FDCA) or less than 500 ppm FDCA or less than 250 ppm FDCA or less than 100 ppm FDCA or less than 50 ppm FDCA or less than 20 ppm FDCA or less than 10 ppm FDCA or less than 5 ppm FDCA or less than 3 ppm FDCA.
    [0087] [00087] The process of the invention is described in further detail in this example obtained by modeling using an ASPEN program:
    [0088] [00088] For a given type of plant, the crude diester stream 510 is supplied which comprises 199.628 kg of methanol / day; 11,346 kg of water / day; 508 kg MFC / day; 1,490 kg MFFC / day; 50,614 kg DMFD / day; 954 kg MCFC / day; and 479 kg of FDCA impurities / day. The crude diester current 510 is at a temperature of 230 ° C and a pressure of 13.78 mPaa (2,000 psia). The crude diester stream is fed to a flash evaporation zone 600 where the stream pressure is reduced to 0.275 mPaa (40 psia) and by flash evaporation it is divided into two streams: a stream of 610 alcohol vapor comprising 164.502 kg of methanol / day; 7,959 kg of water / day; 87 kg MFC / day; 5 kg MFFC / day; and 134 kg of DMFD / day; and a first DAFD 620 stream-rich liquid composition comprising 35.126 kg of methanol / day; 3,387 kg of water / day; 421 kg MFC / day; 1,485 kg MFFC / day; 50,480 kg DMFD / day; 954 kg MCFC / day; and 479 kg of FDCA impurities / day.
    [0089] [00089] The first current-rich liquid composition of DAFD 620 is fed to a distillation column in the alcohol water removal zone 710 having 38 trays and adjusted to a pressure greater than 0.08 mPaa (12 psia). The liquid bottom temperature is 225 ° C. Methanol and water are removed as a second stream distilled from rich alcohol 712 which comprises 35.126 kg of methanol / day; 3,338 kg of water / day; and 18 kg of MFC / day. The net underflow of the distillation column, the second liquid DAFD-rich composition 711, comprises 49 kg of water / day; 403 kg MFC / day; 1,485 kg MFFC / day; 50,480 kg DMFD / day; 954 kg MCFC / day; and 479 kg of FDCA impurities / day.
    [0090] [00090] The alcohol vapor stream 610 and the second stream of rich alcohol 712 are fed to a distillation column in the alcohol recovery zone 800 by recovering the alcohol and purging water. The distillation column has 48 trays, is adjusted to an upper pressure of 0.05 mPaa (8 psia) and has a liquid bottom temperature of 95 ° C. The 802 alcohol recycling distillate stream comprises 199.627 kg of methanol / day; and 1,122 kg of water / day. The 801 subflow water-rich purge stream comprising 10,174 kg of water / day; 105 kg MFC / day; 5 kg MFFC / day; and 134 kg of DM FD / day.
    [0091] [00091] The second liquid rich stream in DAFD 711 is fed to a distillation column in the AFC / AFFC 720 removal zone. The distillation column has 48 trays, is adjusted to an upper pressure of 0.02 mPaa (3 psia) and has a liquid bottom temperature of 242 ° C. The column distillate stream, the AFC 722 rich steam composition, comprises 49 kg of water / day; 403 kg MFC / day; 1,484 kg MFFC / day; 73 kg DMFD / day; and 9 kg of FDCA impurities / day as a purge process for impurities. The column underflow stream, the rich composition partially purified in liquid DAFD 721, comprises 1 kg MFFC / day; 50,480 kg DMFD / day; 954 kg MCFC / day; and 470 kg of FDCA impurities / day.
    [0092] [00092] The rich partially purified liquid composition in DAFD 721 stream is fed to a distillation column in the ACFC 730 removal zone. The distillation column has 23 trays, is adjusted to a higher pressure of 6.89 kPaa (1 psia ) and has a liquid bottom temperature of 248 ° C. The column distillate stream, the vapor rich in DAFD 732, is the stream of the plant DMFD product and which comprises 1 kg MFFC / day; 50,000 kg of DMFD / day; 3 kg of MCFC / day; and 5 kg of FDCA impurities / day. The column underflow stream, ACFC 731 liquid bottom stream, comprises 408 kg DMFD / day; 951 kg MCFC / day; and 465 kg of FDCA impurities / day.
    [0093] [00093] The invention also includes a process for the manufacture of FDCA, which is one of the raw materials fed to the esterification zone 500. The process for the manufacture of FDCA will now be described in more detail.
    [0094] [00094] 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:
    [0095] [00095] 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) OCH 2 -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 its esters, ethers and alkyl derivatives.
    [0096] [00096] 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).
    [0097] [00097] Specific examples of 5-HMF derivatives include those having the following structures:
    [0098] [00098] 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 comprising oxygen, to generate a stream of crude carboxylic acid 110 which comprises furan-2,5-dicarboxylic acid (FDCA).
    [0099] [00099] 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:
    [0100] [000100] 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 area of the primary oxidizer 100.
    [0101] [000101] 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.
    [0102] [000102] 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.
    [0103] [000103] 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 to 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.
    [0104] [000104] 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.
    [0105] [000105] The bromine component can be added as elemental bromine, in combined form, or as an anion. Suitable sources of bromine include hydrobromic acid, sodium bromide, ammonium bromide, potassium bromide and tetrabromoethane. Hydrobromic acid, or sodium bromide can be preferred sources of bromide.
    [0106] [000106] 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.
    [0107] [000107] 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. Cobalt present in an amount of 2,000 to 6,000 ppm, or 2,000 to 5,000 ppm, is especially desirable to promote high yield.
    [0108] [000108] 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 desired to promote high yield.
    [0109] [000109] 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 5-alkyl furfural, or mixtures of any of these compounds together or with 5-HMF, the weight ratio of cobalt to manganese can 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.
    [0110] [000110] 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.
    [0111] [000111] The weight ratio of bromine atoms to manganese atoms is about 2: 1 to 500: 1.
    [0112] [000112] 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 FDCA yield (minimum 90%), decreases the formation of impurities (measured by b *) causing color in the downstream polymerization process while maintaining the amount of CO and CO 2 (carbon burning) in the effluent gas to a minimum.
    [0113] [000113] 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.
    [0114] [000114] 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.
    [0115] [000115] Suitable solvents include aliphatic solvents. In one embodiment of the invention, the solvents are aliphatic carboxylic acids that include, but are not limited to, C 2 to C 6 monocarboxylic acids, for example, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, trimethylacetic acid, caproic acid and mixtures thereof.
    [0116] [000116] 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 that 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 removed from the crude reaction mixture stream discharged from the reactor. primary oxidation with moist, fresh acetic acid containing about 0% to 15% water.
    [0117] [000117] The oxidation gas stream comprises oxygen. Examples include, but are not limited to, purified oxygen and air. The amount of oxygen in the primary oxidation zone varies from about 5 mol% to 45 mol%, 5 mol% to 60 mol% or 5 mol% to 80 mol%.
    [0118] [000118] 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 105 ° C to 175 ° C, or 105 ° C to 160 ° C, or 105 ° C to 165 ° C, or 105 ° C to 160 ° C, or 105 ° C to 155 ° C, or 105 ° C to 150 ° C, or 110 ° C to 180 ° C, or 110 ° C to 175 ° C, or 110 ° C to 170 ° C, or 110 ° C to 165 ° C, or 110 ° C to 160 ° C, or 110 ° C to 155 ° C, or 110 ° C to 150 ° C, or 110 ° C to 145 ° C, or 115 ° C to 180 ° C, or 115 ° C to 175 ° C, or 115 ° C to 170 ° C, or 115 ° C to 167 ° C, or 115 ° C to 160 ° C, or 115 ° C to 155 ° C, or 110 ° C to 150 ° C, or 115 ° C to 145 ° C, or 120 ° C to 180 ° C, or 120 ° C to 175 ° C, or 120 ° C to 170 ° C, or 120 ° C to 165 ° C, or 120 ° C to 160 ° C, or 120 ° C to 155 ° C, or 120 ° C to 150 ° C, or 120 ° C to 145 ° C, or 125 ° C to 180 ° C, or 125 ° C to 175 ° C, or 125 ° C to 170 ° C, or 125 ° C to 165 ° C, or 125 ° C to 160 ° C, or 125 ° C to 155 ° C, or 125 ° C to 150 ° C, or 125 ° C to 145 ° C, or 130 ° C to 180 ° C, or 130 ° C to 175 ° C, or 130 ° C to 170 ° C, or 130 ° C to 165 ° C, or 130 ° C to 160 ° C, or 130 ° C to 155 ° C, or 130 ° C to 1 50 ° C, or 130 ° C to 145 ° C, or 135 ° C to 180 ° C, or 135 ° C to 175 ° C, or 135 ° C to 170 ° C, or 135 ° C to 170 ° C, or 135 ° C to 165 ° C, or 135 ° C to 160 ° C, or 135 ° C to 155 ° C, or 135 ° C to 150 ° C, or 135 ° C to 145 ° C, or 140 ° C to 180 ° C, or 140 ° C to 175 ° C, or 140 ° C to 170 ° C, or 140 ° C to 170 ° C, or 140 ° C to 165 ° C, or 140 ° C to 160 ° C, or 140 ° C to 155 ° C, or 140 ° C to 150 ° C, or 140 ° C to 145 ° C, or 145 ° C to 180 ° C, or 145 ° C to 175 ° C, or 145 ° C to 170 ° C, or 145 ° C to 170 ° C, or 145 ° C to 165 ° C, or 145 ° C to 160 ° C, or 145 ° C to 155 ° C, or 145 ° C to 150 ° C, or 150 ° C to 180 ° C, or 150 ° C to 175 ° C, or 150 ° C to 170 ° C, or from 150 ° C to 165 ° C, or from 150 ° C to 160 ° C, or from 150 ° C to 155 ° C, or from 155 ° C to 180 ° C, or from 155 ° C to 175 ° C, or 155 ° C to 170 ° C, or 155 ° C to 165 ° C, or 155 ° C to 160 ° C, or 160 ° C to 180 ° C, or 160 ° C to 175 ° C, or 160 ° C to 170 ° C, or 160 ° C to 165 ° C, or 165 ° C to 180 ° C, or 165 ° C to 175 ° C, or 165 ° C to 170 ° C, or 165 ° C to 180 ° C, or 165 ° C to 175 ° C, or 165 ° C to 170 ° C, or 170 ° C to 180 ° C, or 170 ° C to 175 ° C, or 175 ° C to 180 ° C.
    [0119] [000119] 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 CO x in the oxidizer effluent gas is less than 0.05 moles of CO x per mol of the total oxidizable feed in half of reaction, or not more than 4 moles of CO x per mole of the total oxidizable feed to the reaction medium, or not more than 6 moles of CO x per mole of the total oxidizable feed to the reaction medium. The carbon burn as determined by the CO x generation rate can be calculated as follows: (moles of CO + moles of CO2) / moles of the 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.
    [0120] [000120] The oxidation reaction can be conducted under pressure ranging from 0.275 to 2.06 mPaa (40 to 300 psia). A bubble column is desirably operated under a pressure ranging from 0.275 to 1.03 mPaa (40 psia to 150 psia). In a stirred tank container, the pressure is desirably adjusted to 0.689 to 2.06 mPaa (100 psia to 300 psia).
    [0121] [000121] The oxidizer effluent gas stream 120 containing COx (CO and CO 2 ), water, nitrogen and vaporized solvent, is sent to the oxidizer effluent gas treatment zone 1000 to generate an inert gas stream 810, liquid stream 820 that it comprises water and a recovered oxidation solvent stream 830 which comprises 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 CO x and nitrogen in a separation column (eg distillation column with 10 to 200 trays), to 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 in the expander if necessary to ensure that the effluent gas does not condense in the turboexpander.
    [0122] [000122] 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 take 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 yet 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.
    [0123] [000123] Oxidation can be conducted in a continuous agitated tank reactor or in a bubble column reactor.
    [0124] [000124] 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.
    [0125] [000125] The oxidation reaction product is a stream of crude carboxylic acid 110 which comprises 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.
    [0126] [000126] 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 more than 43% by weight, or not more than 40% by weight, or not more than 39% by weight. Of the solids in the crude carboxylic acid stream, it is desirable that at least 80% by weight, or at least 85% by weight, or at least 90% by weight, or at least 95% by weight of the solids in each case is FDCA.
    [0127] [000127] 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.
    [0128] [000128] 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, based on the weight of the solids present in the crude carboxylic acid stream.
    [0129] [000129] 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 2.5 diformilfurane, levulinic acid in an amount ranging from 0% by weight to 0.5% by weight , succinic acid in an amount ranging from 0% by weight to 0.5% by weight and acetoxy acetic acid in an amount ranging from 0% by weight to 0.5% by weight and a cumulative amount of these impurities in an amount ranging 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, each based on the weight of the solids present in the crude carboxylic acid stream.
    [0130] [000130] In another embodiment of the invention the composition of the crude dicarboxylic acid 110 comprises FDCA, FFCA and 5- (ethoxycarbonyl) furan-2-carboxylic acid ("EFCA"). EFCA in the composition of crude dicarboxylic acid 110 can 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, based on the weight of the solids present in the crude carboxylic acid.
    [0131] [000131] 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 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% up to 98%, or 91% up to 98%, or 92% up to 98% or 94% up to 98% or 95% up to 99%.
    [0132] [000132] The yield is defined as mass of FDCA obtained divided by the theoretical amount of FDCA that must be produced based on the amount of use of the raw material. For example, if one mole or 126.11 grams of 5-HMF is oxidized, it should theoretically generate one mole or 156.01 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.
    [0133] [000133] The maximum b * of dry solids, or wet cake, is not particularly limited. However, ab * 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 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.
    [0134] [000134] B * is one of the three-color attributes measured on 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).
    [0135] [000135] In the next step, which is an optional step, the crude carboxylic acid stream 110 may be fed to a cooling zone 200 to generate a stream of the crude dicarboxylic acid slurry cooled 210 and a first vapor stream solvent 220 comprising solvent vapor. The cooling of the raw carboxylic slurry stream 110 can be accompanied by any means known in the art. Typically, the cooling zone 200 is a flash tank . All or a portion of the crude carboxylic acid stream 110 can be fed to the cooling zone.
    [0136] [000136] 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.
    [0137] [000137] 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 solid liquid separation device preferred by the solid liquid 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.
    [0138] [000138] 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 is preferably 75 ° C to 95 ° C.
    [0139] [000139] The washing stream 320 comprises a liquid suitable for displacing and washing the main liquid of 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.
    [0140] [000140] Here it can be multiple washes with the same washing solvent or with different washing solvents. For example, a first wash comprising acetic acid can be followed by a second wash comprising the alcohol used in the downstream esterification reaction zone.
    [0141] [000141] After the solids are washed in the solid liquid separation zone 300, they will be dehydrated. Dehydration can take place 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 the passage of 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.
    [0142] [000142] 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 hydroxyl functional 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 deviating, 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.
    [0143] [000143] 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 solid liquid separation zone 300.
    [0144] [000144] 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. 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 it is isolated in the solid-liquid separation zone 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.
    [0145] [000145] Sufficient hydroxyl functional compound such as an alcohol (for example methanol) is fed to a solid liquid separation zone 300 which is mixed with the resulting solids in a low impurity slurry stream 310 being pumped with% by weight of the solids ranging from 1% to 50%, 10% to 40% and preferably the% by weight of the solids in the stream 310 will vary from 25% to 38%.
    [0146] [000146] In one embodiment, from 5% to 100% by weight of the displaced main liquid stream 330 is sent to 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.
    [0147] [000147] Optionally, a portion up to 100% of the crude carboxylic acid composition can be sent directly into a secondary oxidation zone (not shown) before being subjected to a solid liquid separation zone 300.
    [0148] [000148] Generally, the 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.
    [0149] [000149] 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. 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.
    [0150] [000150] If a secondary oxidation zone is used, the secondary oxidation slurry can be crystallized to form a crystallized slurry 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.
    [0151] [000151] The crystallized slurry stream can then be subjected to a cooling zone 200 if desired and the process continued as described above.
    [0152] [000152] Instead of using a moist pie, one can produce a dry solid. The wet cake produced in the solid liquid 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.
    [0153] [000153] 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%.
    [0154] [000154] A vacuum system can be used to draw a stream of steam 420 from 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 where the pressure is measured in mmHg above absolute vacuum.
    [0155] [000155] The purified, dried carboxylic acid solids, 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.
    [0156] [000156] 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.
    [0157] [000157] 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. The% of moisture in the stream of crude carboxylic acid wet cake 310 typically range 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 the acetic acid before the esterification zone 500 because the acetic acid will react with the alcohol present in the 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 produce 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 it can be multiple and separate washes 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.
    [0158] [000158] The composition of solid dicarboxylic acid 410, which can 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 by 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 making the crude diester composition.
    [0159] [000159] 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 of the dicarboxylic acid composition is produced, the wet cake can be moved by the belt or pumped as a liquid slurry to the facility for esterification.
    权利要求:
    Claims (15)
    [0001]
    Process for the manufacture of a DAFD steam, characterized by the fact that it comprises: The. feeding a furan-2,5-dicarboxylic acid (“FDCA”) composition to an esterification reaction zone; and B. in the presence of an alcohol compound, conduct an esterification reaction in the esterification reaction zone to react FDCA with said alcohol compound to form the crude diester composition comprising dialkyl furan-2,5-dicarboxylate ("DAFD") , the compound of alcohol, 5- (alkoxycarbonyl) furan-2-carboxylic acid (ACFC), alkyl furan-2-carboxylate (AFC) and alkyl-5-formylfuran-2-carboxylate (AFFC), and ç. separating at least a portion of the alcohol compound from the crude diester composition into a flash zone comprising one or more containers for flash separation by reducing pressure to produce: (i) a vapor alcohol composition, comprising said alcohol compound, removed as an upper space stream that is rich in an alcohol concentration, with respect to the alcohol concentration in the feed of the raw diester composition in the flash zone , and (ii) a first liquid DAFD-rich composition, comprising DAFD, ACFC, AFC and AFFC, which is rich in the total concentration of DAFD in relation to the total concentration of DAFD in the feed of the raw diester composition in the flash zone; and d. separating at least a portion of DAFD from the first liquid DAFD-rich composition in a product recovery zone; where the process produces: (i) a purified DAFD vapor composition rich in a DAFD concentration with respect to the DAFD concentration in the first liquid DAFD rich composition and (ii) a liquid ACFC composition that is rich in an ACFC concentration with respect to the concentration of ACFC in the first liquid DAFD-rich composition; and (iii) an AFC vapor composition comprising AFC that is rich in an AFC concentration with respect to the AFC concentration in the first liquid DAFD-rich composition; and (iv) a second alcohol composition comprising alcohol that is rich in an alcohol concentration, with respect to the first liquid DAFD-rich composition.
    [0002]
    Process according to claim 1, characterized in that the physical separation in step c comprises a flash tank .
    [0003]
    Process according to claim 2, characterized in that the physical separation in step d comprises at least two distillation columns.
    [0004]
    Process according to claim 1, characterized in that the concentration of DAFD in the first composition rich in liquid DAFD is increased by at least 250% in the concentration of DAFD in the crude diester composition.
    [0005]
    Process according to claim 1, characterized in that the AFC vapor composition comprises AFC and AFFC in a cumulative amount of at least 90% by weight based on the weight of the AFC vapor composition.
    [0006]
    Process according to claim 1, characterized in that the AFC concentration in the AFC vapor composition is increased by a factor of at least 15x with respect to the AFC concentration in the second liquid DAFD composition.
    [0007]
    Process according to claim 1, characterized in that the vapor composition of purified DAFD comprises DAFD in an amount greater than 99.0% by weight and less than 1000 ppm ACFC, each based on the weight of the vapor composition of purified DAFD.
    [0008]
    Process according to any one of claims 1 to 7, characterized in that step d comprises separating at least a portion of alcohol from the first liquid DAFD-rich composition using a physical separation process to produce: d (i) a second alcohol composition that is rich in the alcohol concentration with respect to the alcohol concentration in the first liquid DAFD-rich composition; and d (ii) a second liquid DAFD-rich composition comprising DAFD which is rich in a DAFD concentration with respect to the DAFD concentration in the first liquid DAFD-rich composition; and in which said process still comprises: and. separate at least a portion of AFC from the second liquid DAFD-rich composition using a physical separation process to produce: and (i) an AFC vapor composition that is rich in an AFC concentration with respect to the AFC concentration in the second liquid DAFD-rich composition; and and (ii) a partially purified liquid DAFD-rich composition comprising DAFD and ACFC which is rich in a concentration of DAFD with respect to the concentration of DAFD in the second liquid DAFD-rich composition; and f. separate at least a portion of the DAFD from the rich partially purified DAFD composition using a physical separation process to produce: f (i) a purified DAFD vapor composition rich in a concentration of DAFD with respect to the concentration of DAFD in the partially purified composition rich in liquid DAFD; and f (ii) a liquid ACFC composition that is rich in a concentration of ACFC with respect to the concentration of ACFC in the partially purified composition rich in liquid DAFD.
    [0009]
    Process according to claim 8, characterized in that the concentration of DAFD in the second composition rich in liquid DAFD is greater than the concentration of DAFD in the first composition rich in liquid DAFD by at least 30% by weight.
    [0010]
    Process according to claim 8, characterized in that the concentration of DAFD in the partially purified composition rich in liquid DAFD is at least 95% by weight and up to 99.9% by weight and the amount of ACFC is at least 1.0% by weight, each based on the weight of the partially purified liquid DAFD-rich composition.
    [0011]
    Process according to claim 8, characterized in that the concentration of AFC in the partially purified composition rich in liquid DAFD is canceled with respect to the concentration of DAFD in the second composition rich in liquid DAFD by a factor of at least 750x.
    [0012]
    Process according to claim 8, characterized by the fact that the AFC concentration in the AFC vapor composition is greater than the AFC concentration in the second liquid DAFD composition is a factor of at least 15x.
    [0013]
    Process according to claim 8, characterized in that the concentration of ACFC in the liquid ACFC composition is greater than the concentration of ACFC in the partially purified composition rich in liquid DAFD by a factor of at least 10x.
    [0014]
    Process according to claim 8, characterized in that the concentration of ACFC in the vapor composition of DAFD is canceled with respect to the concentration of in the partially purified composition rich in liquid DAFD by a factor of at least 200x.
    [0015]
    Process according to any of claims 1 to 7, characterized by the fact that the FDCA composition is obtained in a colocalized oxidation process within 10 miles (16.09 km) from the process for producing the DAFD composition .
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    同族专利:
    公开号 | 公开日
    EP2864305A1|2015-04-29|
    US8658810B2|2014-02-25|
    EP3590930A1|2020-01-08|
    BR112014030071A2|2017-09-19|
    EP2864305B1|2017-05-31|
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    WO2013191940A1|2013-12-27|
    US20130345447A1|2013-12-26|
    EP3239140A1|2017-11-01|
    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|
    DE850751C|1950-10-28|1952-09-29|Basf Ag|Process for the preparation of furan-2,5-dicarboxylic acid esters|
    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|
    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|
    DE19538700A1|1995-10-18|1997-04-24|Hoechst Ag|Polymers forming cholesteric phases, process for their preparation and 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|
    US6063465A|1998-04-23|2000-05-16|Hna Holdings, Inc.|Polyester container and method for making same|
    US5958581A|1998-04-23|1999-09-28|Hna Holdings, Inc.|Polyester film 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|
    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|
    US6063495A|1998-04-23|2000-05-16|Hna Holdings, Inc.|Polyester fiber and methods for making same|
    US6025061A|1998-04-23|2000-02-15|Hna Holdings, Inc.|Sheets formed from polyesters including isosorbide|
    US6063464A|1998-04-23|2000-05-16|Hna Holdings, Inc.|Isosorbide containing polyesters and methods for making same|
    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|
    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|
    US6737481B1|2002-12-19|2004-05-18|E. I. Du Pont De Nemours And Company|Ester-modified dicarboxylate polymers|
    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|US8912349B2|2012-06-22|2014-12-16|Eastman Chemical Company|Method for producing purified dialkyl-furan-2,5-dicarboxylate separation and solid liquid separation|
    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|
    BR112015004491B1|2012-08-31|2021-07-27|SOCIETE ANONYME DES EAUX MINERALES D'EVIAN et en abrégé "S.A.E.M.E."|BOTTLE, METHOD OF MANUFACTURING A BOTTLE|
    CN105246958B|2012-12-20|2018-02-02|阿彻丹尼尔斯米德兰德公司|The esterification of 2,5 furan dicarboxylic acids|
    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.|
    US9944615B2|2014-05-08|2018-04-17|Eastman Chemical Company|Purifying crude furan 2,5-dicarboxylic acid by hydrogenation and a purge zone|
    US9573120B2|2014-05-08|2017-02-21|Eastman Chemical Company|Furan-2,5-dicarboxylic acid purge process|
    US10010812B2|2014-05-08|2018-07-03|Eastman Chemical Company|Furan-2,5-dicarboxylic acid purge process|
    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|
    WO2016186505A1|2015-05-21|2016-11-24|Avantium Knowledge Centre B.V.|Process for the purification of a carboxylic acid-containing composition|
    EP3297995B1|2015-05-21|2019-07-10|Avantium Knowledge Centre B.V.|Process for the preparation of an aromatic dicarboxylic acid|
    WO2017123763A1|2016-01-13|2017-07-20|Rennovia Inc.|Processes for the preparation of 2,5-furandicarboxylic acid and intermediates and derivatives thereof|
    BR112020000611A2|2017-07-12|2020-07-14|Stora Enso Oyj|purified products via 2,5-furanedicarboxylic acid pathway|
    US20190023675A1|2017-07-20|2019-01-24|Eastman Chemical Company|Method for producing purified dialkyl-furan-2,5-dicarboxylate|
    US10421736B2|2017-07-20|2019-09-24|Eastman Chemical Company|Production of purified dialkyl-furan-2,5-dicarboxylatein a retrofitted DMT plant|
    US10344011B1|2018-05-04|2019-07-09|Eastman Chemical Company|Furan-2,5-dicarboxylic acid purge process|
    US20190390004A1|2018-06-25|2019-12-26|Eastman Chemical Company|Oxidation process to produce 5 methyl 5-methylfuran-2-carboxylate |
    CN112585123A|2018-08-31|2021-03-30|伊士曼化工公司|Production of purified dialkyl furan-2, 5-dicarboxylatein modified DMT plant|
    US10526301B1|2018-10-18|2020-01-07|Eastman Chemical Company|Production of purified dialkyl-furan-2,5-dicarboxylatein a retrofitted DMT plant|
    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-07-02| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-07-16| B15K| Others concerning applications: alteration of classification|Free format text: A CLASSIFICACAO ANTERIOR ERA: C07D 307/68 Ipc: C07D 307/24 (1974.07), C07D 307/46 (1974.07), C07D |
    2020-04-28| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-06-30| 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:
    申请号 | 申请日 | 专利标题
    US13/530,738|US8658810B2|2012-06-22|2012-06-22|Method for producing purified dialkyl-furan-2,5-dicarboxylate vapor|
    US13/530738|2012-06-22|
    PCT/US2013/044922|WO2013191940A1|2012-06-22|2013-06-10|Method for producing purified dialkyl-furan-2,5-dicarboxylate vapor|
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