• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    According to an example aspect of the present invention, there is provided both a continuous method and a batch method for producing furandicarboxylic acid (FDCA) and furandicarboxylic acid ester (FDCAE) from aldaric acid ester by utilizing cheap and available catalysts and bio-based solvents in an efficient manner.
    公开号:FI20186062A1
    申请号:FI20186062
    申请日:2018-12-10
    公开日:2020-06-11
    发明作者:David Thomas；Anneloes Berghuis；Strien Nicolaas Van
    申请人:Teknologian Tutkimuskeskus Vtt Oy；
    IPC主号:
    专利说明:

    [0001] [0001] The present invention relates to a synthesis method of furandicarboxylic acid (ester) from aldaric acid (ester) by using a heterogeneous, preferably rhenium-based catalyst and a bio-based solvent on a continuous flow reactor and/or a batch reactor.BACKGROUND
    [0002] [0002] Furan carboxylates have been traditionally used for example in pharmacology, where its diethyl ester has showed a strong anesthetic activity. Furandicarboxylic acid (FDCA) is also a very powerful chelating agent. In medicine, it is for example used to treat kidney stones, but also in the preparation of grafts having biological properties similar to those of natural tissues, and which are characterized by a lack of rejection after transplantation.
    [0003] [0003] FDCA has also been used as a basic monomer in the manufacture of polymers such as polyesters, polyamides, co-polymers or polyurethanes, for example for improving their mechanical properties. In polyesters, it is likely to be used in replacement of phthalates. In view of such a possibility, FDCA has been ranked among the 12 raw materials with the greatest industrial potential (Werpy and Peterson, 2004).
    [0004] [0004] Furan carboxylates are also realistic alternative to terephthalic acid, which is 00 S a monomer used in polyethylene terephthalate production and used, for example, in plastic
    [0007] [0007] Another prior art publication, WO 2015/189481, discloses a batch process for producing FDCA and its ester forms. The method comprises selective catalytic dehydroxylation of an aldaric acid by heating the aldaric acid with a solvent and a reductant in a pressurized container to temperatures between 90 to 300 °C in the presence of a transition metal catalyst for a pre-determined reaction time.
    [0008] [0008] One partly relating prior art publication, WO 2017/207875, describes a method for producing muconic acid from aldaric acids. The differences in the chemistry are however, that muconic acid is prepared by hydrodeoxygenation methodology, whereas FDCA is prepared by dehydration. FDCA also produces an aromatic compound rather than a linear conjugated system. In addition, FDCA is typically produced at temperatures over 200 °C and rather quickly (1 to 4 hours), whereas muconic acid is produced at a more gentle temperature of around 175 °C and more slowly (6 to 24 hours). Additionally, the solvents are different, since the muconic acid method uses butanol and FDCA method uses methanol.
    [0009] [0009] The available batch processes for the synthesis of FDCA and FDCAE are efficient, but are batch limited and currently carried out with only couple of different catalysts, with the most efficient p-toluene (para-toluene) sulphonic acid ethyl ester silica, being commercially available in only limited supply. There is a need to discover a new way to produce FDCA in good purity by using cheaper and readily available bio-based solvents and catalysts, which are up-scalable and fit for both a continuous production © process and a batch production process.
    [0010] [0010] The invention is defined by the features of the independent claims. Some specific embodiments are defined in the dependent claims.
    [0011] [0011] According to an aspect of the present invention, there is provided a continuous method for producing furandicarboxylic acid (FDCA) and furandicarboxylic acid ester (FDCAE) from aldaric acid or an ester thereof.
    [0012] [0012] According to another aspect of the present invention, there is provided a batch method for producing FDCA and FDCAE from aldaric acid or an ester thereof.
    [0013] [0013] These and other aspects together with the advantages thereof over the known solutions are achieved by the present invention, as hereinafter described and claimed.
    [0014] [0014] The continuous method of the present invention is mainly characterized by what is stated in the characterizing part of claim 1.
    [0015] [0015] The batch method of the present invention is mainly characterized by what is stated in the characterizing part of claim 10.
    [0016] [0016] Considerable advantages are obtained by means of the invention. This new approach employs cheap, widely available catalysts and bio-based solvents to prepare FDCA and FDCAE on either a continuous flow reactor or a batch reactor. This provides more efficient production and upscaling opportunities than what has earlier been developed. Different catalysts based on heterogeneous rhenium catalyst have been found to produce excellent yields of both FDCA and FDCAE. Careful selection of reaction © temperature and solvent allow optimum results to be obtained whether the process is N undertaken on batch or continuous flow methodologies.N
    [0017] [0017] Next, the present technology will be described more closely with reference to z certain embodiments. a © 3NEMBODIMENTS
    [0018] [0018] The present technology provides methods for preparing furandicarboxylic acid (FDCA) and furandicarboxylic acid ester (FDCAE) by employing widely available cheap catalysts and bio-based solvents on a continuous flow reactor and a batch reactor.
    [0019] [0019] FIGURE 1 is a comparison between the chemistry of the batch technology (starting from pectin) and the continuous technology (starting from glucose). However, both of these starting materials can be used for both processes, batch and continuous.
    [0020] [0020] FIGURE 2 is an NMR spectrum showing that for FDCA the plane of symmetry causes only two signals to be visible. The furan proton has an integral of one and the methyl protons have an integral of three, which confirms the spectra to be of FDCA methyl ester.
    [0021] [0021] The present invention relating to a continuous flow reaction is based on dissolving a soluble aldaric acid feedstock in a bio-based solvent, heating the solution to a desired temperature and pumping it then into a continuous flow reactor, where it passes a loaded catalyst held on a fixed bed. Reaction then occurs, and the formed product may be collected after a desired reaction time.
    [0022] [0022] According to one embodiment of the present invention, a continuous method for producing furandicarboxylic acid (FDCA) and furandicarboxylic acid ester (FDCAF) from aldaric acid is disclosed, wherein the method includes at least the steps of: - dissolving a soluble form of an aldaric acid into a bio-based solvent to form a liquid raw material solution, = - heating the liquid raw material solution to temperature between 175 °C and 250 °C N and mixing it with a nitrogen gas flow to form a mixture, - pumping the mixture into a continuous flow reactor, which comprises a loaded heterogeneous rhenium catalyst held on a fixed bed, a - running the reaction in the flow reactor for a reaction time between 1 and 5 hours, & - collecting the formed product from the flow reactor.
    [0024] [0024] According to another embodiment of the present invention, a batch method for producing furandicarboxylic acid (FDCA) and furandicarboxylic acid ester (FDCAF) from aldaric acid is disclosed, wherein the method includes at least the steps of: - adding an aldaric acid ester into a bio-based solvent to form a liguid raw material suspension in a pressure reactor, - adding a heterogeneous rhenium catalyst to the reactor, - heating the liguid raw material suspension and the catalyst mixture to temperature between 175 *C and 250 *C and mixing it under a pressure atmosphere, - running the reaction for a reaction time between 1 and 24 hours, - collecting the formed product from the batch reactor.
    [0025] [0025] In one embodiment of the present invention, the aldaric acid is a mucic acid or an ester thereof, for example mucic acid methyl ester. Solubility of the raw material is also a key factor, since the raw material needs to be fit for purpose of a batch production process.
    [0026] [0026] In one embodiment of the present invention, in both the batch and continuous process, a suitable solvent is selected from butanol, ethanol or methanol, preferably being butanol if a continuous process or methanol if a batch process. These solvents are bio- based, and thus provide environmentally friendly solution, yet capable of performing in an excellent manner.
    [0027] [0027] In one embodiment of the present invention, catalysts based around = heterogeneous rhenium catalysts, such as ammonium perrhenate, have surprisingly been 2 found out to produce excellent yields of both FDCA and FDCAE; with the latter being the 5 preferred form. One particularly advantageous catalyst is ammonium perrhenate. In a = preferred embodiment, the loaded fixed catalyst bed preferably consists of ammonium a perrhenate and coarse silicon carbide between quartz wool layers. © 3 [0028] The present invention works optimally with a careful selection of reaction > temperature and feedstock-solvent flow, together with a suitable catalyst. It is essential for high yields that the feedstock is not in the acid form but instead has been esterified to alter the reaction chemistries significantly. Without such careful selection, the reaction may not perform as it is supposed to, whereby a desired end-product may not produced. The examples provide few suitable selections, which have found to lead to a desired production process.
    [0029] [0029] According to one embodiment of the present invention, the continuous flow reactor is a sulphur free tube reactor. This has the advantage of avoiding potential poisoning of the catalyst. Precious metal catalysts, such as many rhenium catalysts can be poisoned by the presence of Sulphur and lose their activity and become inactive.
    [0030] [0030] Reference throughout this specification to one embodiment or an embodiment means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment. Where reference is made to a numerical value using a term such as, for example, about or substantially, the exact numerical value is also disclosed.
    [0031] [0031] As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though each member of the list is individually identified as a separate and unique member. While the forgoing examples are illustrative of the principles of the present invention in one or more particular applications, it will be apparent to those of ordinary skill in the art that numerous modifications in form, usage and details of implementation can be made without the exercise of inventive faculty, and without departing from the principles and concepts of the invention. Accordingly, it is not © intended that the invention be limited, except as by the claims set forth below. & A [0032] The verbs “to comprise” and “to include” are used in this document as open limitations that neither exclude nor reguire the existence of also un-recited features. The = features recited in depending claims are mutually freely combinable unless otherwise > explicitly stated. Furthermore, it is to be understood that the use of "a" or "an", that is, a & singular form, throughout this document does not exclude a plurality. 0NINDUSTRIAL APPLICABILITY
    [0033] [0033] At least some embodiments of the present invention find industrial application in generating a full value chain from the forest industry, agriculture, or food industry side streams to platform chemicals and end applications. In principle, this chain comprises production of aldaric acids from aldoses and side-stream carbohydrates, converting the aldaric acids (or specifically their esters) to dicarboxylic acids (or their esters), which in turn are used as platform chemicals for various bio-based applications, such as bio-based polyesters and nylon. According to one example, the present method produces 2,5-Furandicarboxylic acid for use in the production of polyethylene furanoate.
    EXAMPLES General method Continuous flow reaction Raw material in solution was drawn into a tube reactor with a HPLC pump. The mass flow rate was monitored by using a balance under the raw material vessel. Before the reactor, the liquid raw material was heated and mixed with a nitrogen gas flow. The volumetric gas flow rate was controlled with a flow controller. The reactor heating was done by using two 230 V ceramic electronic ovens. The reactor temperature was measured with a thermocouple probe inserted into the catalyst bed. The thermocouple probe measures © temperatures in six different points. After the reactor the products enter a pressure N controller and then a refrigerated sampling vessel. Product gasses are outgassed from the = sampling vessel to a ventilation duct. Liquid samples are drained from the sampling vessel 2 and analyzed with GC-FID for quantitative analysis of each furan compound. i The reactor used to study the continuous process was a sulphur free tube reactor. The O reactor is 38 cm long and has a diameter of 18 mm. The catalyst bed is supported in the 3 middle of the reactor by a metal rod.N
    Example 1: Ammonium perrhenate catalyst The general method was used, with a catalyst bed consisting of ammonium perrhenate (0,84 g) and coarse silicon carbide (2,60 g) between quartz wool layers (1,5 g) placed into the reactor and a 1:10 w/v solution of saccharic acid butyl ester diluted in 1-butanol. The reaction time was 4 h, with a reaction temperature of 175 °C. Raw material feed was 30 g/h and nitrogen feed 2 I/h. Liquid samples were collected every 30 minutes and samples of 1 h, 1.5 h and 4 h were concentrated in a rotary evaporator, silylated and analyzed using GC- FID. The method was repeated varying the reaction temperature and feed flow rate. The conditions and obtained reaction products are given in table 1. Table 1. Conditions and product yields of example 1: set 1 experiments Yield of FCA BE | Yield of FDCA BE Tm ow oo jk k. ww oma om k o The method was repeated varying the catalyst used and doubling the catalyst amount.
    © Reaction temperature was 220 °C, feed flow rate 15 g/h and total run time 5 h. Samples > were taken at 1h, 3h and Sh. The conditions and obtained reaction products are given in N table 2.
    I Table 2. Conditions and product yields of example 1: set 2 experiments a 3 : s [vey | ssa | | | |. 009 I sn | n
    Batch Process Reaction Mucic acid methyl ester (1 g, 4.2 mmol) was added to a hastalloy C-276 pressure reactor. To this was then added ammonium perrhenate (variable, see table 3) and methanol solvent. A stirrer bar was added and the reactor was then sealed and flushed with nitrogen before pressurizing to approximately 5 bar. The reactor then heated to the required temperature and stirred for a specific time. Once the reaction was completed, the reactor was cooled to room temperature and the contents removed. Vacuum filtration and evaporated of solvent (35 °C, below 10 mbar) afforded the product as an oil. The reaction product was purified by using known technology and was characterized by GC-MS and ‘H NMR. Table 3. Code | Reaction conditions Mass Purified isolated | yield
    FDCA methyl ester Catalyst | Solvent volume | Temperature | Hours wt-% mol-% (mol-%) (cm ) (°C) Eww we] = 1.97 15 15 175 24 46.6 7.9N
    N o NU — For FDCA, the plane of symmetry causes only two signals in the NMR spectrum to be
    I = visible (figure 2). The furan proton has an integral of one and the methyl protons have an S integral of three, which confirms the spectra to be of FDCA methyl ester. o coON
    Chemicals The chemicals used and their suppliers are shown on table 4. Saccharic acid butyl ester was produced in house. The synthesis was an esterification of D-saccharic acid potassium salt and 1-butanol in the presence of an acidic catalyst, for example, tosic acid silica, HSO4 or Amberlyst-catalyst. The product was an oily saccharic acid butyl ester and solid material which filtered using a porosity 3 glass filter. GC-FID analysis showed the solid material to be unreacted D-saccharic acid potassium salt. Table 4. Chemicals used and suppliers
    E o x a S Analysis 3 S Concentrated sample (5-13 mg) was transferred into a glass vial. Acetone (0.5 ml), pyridine (0.5 ml) and BSTFA (0.2 ml) were added into the vial, which was heated then at 60° for 30 min.
    GC-FID analyses were carried out using an Agilent 6890 equipped with a FID: Column & length: HP-5 5% Phenyl Methyl Siloxane, 30 m, 0.32 mm, 0.25 um film, carrier gas: He, injector temperature: 250 °C, FID temperature: 300 °C, oven temperatures: Initial temp: 30 °C, Initial time: 1.00 min, Ramp: 13 °C/min to 300°C, final time 15 min. GC results were compared to reference standards, which were used to accurately determine the products obtained in the experiments.
    CITATION LIST Patent literature: WO 2016/166421 WO 2015/189481 WO 2017/207875 FT 20185118 Non-patent literature: Werpy, T., Peterson, G., 2004. Top Value Added Chemicals from Biomass, Vol. 1 pp. 26-
    28.
    coON
    N o
    I a a ol ©O
    O coON
    权利要求:
    Claims (14)
    [1] CLAIMS: I. A continuous method for producing furandicarboxylic acid (FDCA) and furandicarboxylic acid ester (FDCAE) from aldaric acid, characterized in that the method includes at least the steps of: - dissolving a soluble form of an aldaric acid into a bio-based solvent to form a liquid raw material solution, - heating the liquid raw material solution to temperature between 175 °C and 250 °C and mixing it with a nitrogen gas flow to form a mixture, - pumping the mixture into a continuous flow reactor, which comprises a loaded heterogeneous rhenium catalyst held on a fixed bed, - running the reaction in the flow reactor for a reaction time between 1 and 5 hours, - collecting the formed product from the flow reactor.
    [2] 2. The method according to claim 1, characterized that the aldaric acid is a saccharic acid or an ester thereof, for example saccharic acid butyl ester.
    [3] 3. The method according to claim 1 or 2, characterized in that the solvent is selected from butanol, ethanol or methanol, preferably butanol.
    [4] 4. The method according to any of the preceding claims, characterized in that the catalyst is ammonium perrhenate. ©
    [5] 5. The method according to any of the preceding claims, characterized in that the loaded > fixed catalyst bed preferably consists of ammonium perrhenate and coarse silicon carbide N between quartz wool layers.
    z
    [6] 6. The method according to any of the preceding claims, characterized in that the raw a N material feed flow rate is between 10 and 30 g/h. 2 =
    [7] 7. The method according to any of the preceding claims, characterized in that the nitrogen N feed flow rate is between 0,5 and 5 1/h, more preferably about 2 1/h.
    [8] 8. The method according to any of the preceding claims, characterized in that the continuous flow reactor is a sulphur free tube reactor.
    [9] 9. The method according to any of the preceding claims, characterized by using a raw material solution in a ratio of 1:10 w/v of saccharic acid butyl ester diluted in 1-butanol.
    [10] 10. A batch method for producing furandicarboxylic acid (FDCA) and furandicarboxylic acid ester (FDCAE) from aldaric acid, characterized in that the method includes at least the steps of: - adding an aldaric acid ester into a bio-based solvent to form a liguid raw material suspension in a pressure reactor, - adding a heterogeneous rhenium catalyst to the reactor, - heating the liquid raw material suspension and the catalyst mixture to temperature between 175 °C and 250 °C and mixing it under a pressure atmosphere, - running the reaction for a reaction time between 1 and 24 hours, - collecting the formed product from the batch reactor.
    [11] 11. The method according to claim 10, characterized that the aldaric acid is a mucic acid or an ester thereof, for example mucic acid methyl ester.
    [12] 12. The method according to claim 10 or 11, characterized in that the solvent is selected from butanol, ethanol or methanol, preferably methanol.
    [13] 13. The method according to any of claims 10 to 12, characterized in that the catalyst is © ammonium perrhenate.
    S N
    [14] 14. The method according to any of claims 10 to 13, characterized in heating the liguid raw material suspension and the catalyst mixture to temperature between 175 *C and 250 = °C and mixing it under a nitrogen pressure atmosphere between 1 and 10 bars. a 3 0
    N
    类似技术:
    公开号 | 公开日 | 专利标题
    Böhm et al.2001|Enantioselective synthesis of |-roccellaric acid
    Stadler et al.2001|The effect of microwave irradiation on carbodiimide-mediated esterifications on solid support
    EP3283471B1|2021-06-09|Method of producing furan carboxylates from aldaric acids by using solid heterogeneous catalysts
    FI127224B|2018-01-31|Method for producing muconic acids and furans from aldaric acids
    Kilroy et al.2005|Synthesis of Dihydrofurans Substituted in the 2‐Position
    Richter et al.1998|Substituted sulfonamides via a three component reaction on solid support
    VanBrunt et al.2000|A short total synthesis of |-Furanomycin
    Cox et al.2001|C-Glycosides to Fused Polycyclic Ethers. An Efficient Entry into the A− D Ring System of Gambierol
    Elliot et al.2017|Synthesis of a novel polyester building block from pentoses by tin-containing silicates
    Behr et al.2007|Application of carbonate solvents in the telomerisation of butadiene with carbon dioxide
    RU2402513C2|2010-10-27|Tricyclo-[6;6;0;0]-hexadecadiene-6,10 synthesis method
    US20190135727A1|2019-05-09|Continuous method for producing muconic acid from aldaric acid
    Palmieri et al.2013|Low impact synthesis of β-nitroacrylates under fully heterogeneous conditions
    KR20160136849A|2016-11-30|Method for preparing 2,5-furandicarboxylic acid
    FI128987B|2021-04-30|Synthesis of furandicarboxylic acid and ester thereof
    Caretto et al.2014|Upgrading of biobased lactones with dialkylcarbonates
    Kantin et al.2017|Efficient cyclodehydration of dicarboxylic acids with oxalyl chloride
    CN104169288A|2014-11-26|Method of making isoidide
    Dai et al.2020|Palladium-catalysed cyclisation of vinylethylene carbonates and anhydrides: a new approach to diverse medium-sized bislactones
    CN111056915A|2020-04-24|Synthesis method of 1, 2-dialkyl-1, 2-diaryl acetylene cyclobutane
    Kuppusamy et al.2021|Development of a Scalable Synthetic Route to BMS-986251. Part 1: Synthesis of the Cyclohexane Dicarboxylate Fragment
    CN109988143B|2021-07-16|Method for preparing functionalized chiral cyclic carbonate through biomass polyol
    CN108713015A|2018-10-26|The preparation of macrolide
    US10787427B2|2020-09-29|Synthesis of furan acids from xylonic acid
    Almeida et al.2008|Michael additions of thiocompounds to α, β-unsaturated carbonyl compounds in aqueous media: stereoselectivity with unambiguous characterization by NMR
    同族专利:
    公开号 | 公开日
    FI128987B|2021-04-30|
    WO2020120835A1|2020-06-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FI127224B|2014-06-13|2018-01-31|Teknologian Tutkimuskeskus Vtt Oy|Method for producing muconic acids and furans from aldaric acids|
    WO2016032403A1|2014-08-28|2016-03-03|Agency For Science, Technology And Research|Synthesis of aliphatic polycarboxylic acid|
    FI126387B|2015-04-17|2016-11-15|Teknologian Tutkimuskeskus Vtt Oy|A process for the preparation of furan carboxylates from aldaric acids using a solid heterogeneous catalyst|
    FI20165451A|2016-05-31|2017-12-01|Teknologian Tutkimuskeskus Vtt Oy|A continuous process for preparing muconic acid from aldaric acid|
    FI128780B|2018-02-09|2020-12-15|Teknologian Tutkimuskeskus Vtt Oy|Separation and purification of furan carboxylates|
    法律状态:
    2021-04-30| FG| Patent granted|Ref document number: 128987 Country of ref document: FI Kind code of ref document: B |
    优先权:
    申请号 | 申请日 | 专利标题
    FI20186062A|FI128987B|2018-12-10|2018-12-10|Synthesis of furandicarboxylic acid and ester thereof|FI20186062A| FI128987B|2018-12-10|2018-12-10|Synthesis of furandicarboxylic acid and ester thereof|
    PCT/FI2019/050876| WO2020120835A1|2018-12-10|2019-12-09|Synthesis of furandicarboxylic acid and ester thereof|
    [返回顶部]