JP5738517B2 - 5−アルコキシメチルフルフラルエーテルの合成方法及びそれらの使用 - Google Patents
5−アルコキシメチルフルフラルエーテルの合成方法及びそれらの使用 Download PDFInfo
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- JP5738517B2 JP5738517B2 JP2008558697A JP2008558697A JP5738517B2 JP 5738517 B2 JP5738517 B2 JP 5738517B2 JP 2008558697 A JP2008558697 A JP 2008558697A JP 2008558697 A JP2008558697 A JP 2008558697A JP 5738517 B2 JP5738517 B2 JP 5738517B2
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- Prior art keywords
- acid
- glucose
- catalyst
- ether
- hmf
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 16
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 29
- 239000008103 glucose Substances 0.000 claims description 29
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 28
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 26
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- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 16
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Saccharide Compounds (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description
連続フロー反応器内で、水/エタノール/10% H2SO4中に溶解させたスクロース10mmol/lを温度摂氏195度、滞留時間6秒〜60秒、及び流速10ml/分、即ち、反応器1つ当たり3.33ml/分で反応させた。6秒の時点では、主にフルクトース及びグルコースへの変換が観測されたが、長時間の滞留時間では、2つの主なフランピークがUVスペクトルにおいて観測された。質量分析により、これらの生成物は、25%の変換率(conversion)において90%を超える選択率を有するHMF及びEMFであると同定した。
連続フロー反応器内で、水/エタノール/10% H2SO4中に溶解させたグルコース10mmol/lを温度摂氏195度、滞留時間6秒〜60秒、及び流速10ml/分、即ち、反応器1つ当たり3.33ml/分で反応させた。30秒の時点で、2つの主なフランピークがUVスペクトルにおいて観測された。質量分析により、これらの生成物は、10%の変換率において90%を超える選択率を有するHMF及びEMFであると同定した。
4つの石英反応器から成る連続並行フロー反応器システム、例えば、温度レギュレータ及び流量レギュレータ、並びに3つのHPLCポンプを、銀製ヒーティングブロック内に装着した。ポンプのうち2つは液体を反応器へと送り、第3のポンプは回収前に反応生成物を希釈するのに使用される。
内標準(糖質(Sigma Aldrich))を用いたHPLC分析を利用して反応生成物を定量化した。UV検出器及びRI検出器を備えたMerck−Hitachi L7000クロマトグラフを使用した。固定相は、直列に接続した逆相C18(Sunfire 3.5μm、4.6×100mm(Waters))カラム、及び陽イオン交換(SupelcogelH、4.6×300mm(SigmaAldrich))カラムとした。一定流量0.6ml/分及び温度60℃における勾配溶出を以下のスキームに従って用いた。
水中又は88.7%エタノール中のグルコース(99.7%(Sigma Aldrich))の1.25重量%溶液を、不均一系触媒の固定床(200μl)に180℃で流した。流速は、空間速度が0.25/分又は0.5/分、即ち、接触時間が2分又は4分となるように選択した。反応器から出る液体を水とエタノールとの混合物(50:50)によって希釈して、管が遮断されないようにした。
図1A及び図1Bは、被験触媒について得られる変換率が76%(β型ゼオライト)となったことを示す。この触媒はHMF及びEMFに対する7%の選択率をもたらした。
β型ゼオライトの使用により、HMF及びEMFに対する約4%の選択率が、17%の変換率、低空間速度で得られた。他の被験触媒では、初めに現れる変換率が最大で20%であり、選択率が1%〜3%の範囲であった。優れたフラン誘導体は所望のEMFであった。
縮尺模型ディーゼルエンジンにおいて、燃料として通常の商業用ディーゼルを用いて、また1重量%、2重量%、3重量%、5重量%及び10重量%のHMF又はEMFのサンプルをそれぞれ添加した同じ商業用ディーゼルを用いて、比較試験を実施する。HMFを含むディーゼルサンプルは、外観検査においてあまり均一でなく(固体粒子は明らかに凝集したままである)、且つ5重量%を超えるHMFでは、固体沈積が観測されることがある。EMFは液体として添加され、如何なる混合又は凝集による問題も生じない。空になるまで燃料の設定容量(100mL)でエンジンを定常動作させる。HMF含有燃料は不規則に動作するのに対し、EMF含有燃料は規則的なペースでより長い時間(最大15%)動作する。エンジンの外観検査に関して、EMFでは目に見える汚れが少ない。
Claims (3)
- 触媒量又は化学量論量以下の均一系触媒もしくは不均一系酸触媒の存在下で、フルクトース及び/又はグルコース含有出発材料をメタノール、エタノール,及びその混合物のうちから選択された一種のアルコールと反応させることによって、5−ヒドロキシメチルフルフラルのエーテルを製造することを含み、前記反応は、前記アルコールに溶媒として添加された水の存在下で、前記アルコールと前記溶媒との比が20〜1の範囲で、175℃〜225℃の温度で、且つ連続フロープロセスで実施されることを特徴とする5−アルコキシメチルフルフラルエーテルの製造方法。
- 請求項1に記載の5−アルコキシメチルフルフラルエーテルの製造方法において、前記酸触媒が、有機酸およびハロゲン化有機酸、無機酸、塩、ルイス酸、イオン交換樹脂、ゼオライト、又はそれらの混合物及び/若しくは組合せから成る群から選択されることを特徴とする5−アルコキシメチルフルフラルエーテルの製造方法。
- 請求項1に記載の5−アルコキシメチルフルフラルエーテルの製造方法において、前記フルクトース及びグルコースの少なくとも一種の含有出発材料が、スクロース及びグルコースから選択されることを特徴とする5−アルコキシメチルフルフラルエーテルの製造方法。
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EP06075564.2 | 2006-03-10 | ||
EP06075564A EP1834950A1 (en) | 2006-03-10 | 2006-03-10 | Method for the synthesis of 5-alkoxymethylfurfural ethers and their use |
PCT/EP2007/002145 WO2007104514A2 (en) | 2006-03-10 | 2007-03-12 | Method for the synthesis of 5-alkoxymethyl furfural ethers and their use |
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US (3) | US8133289B2 (ja) |
EP (5) | EP1834950A1 (ja) |
JP (1) | JP5738517B2 (ja) |
KR (1) | KR101449731B1 (ja) |
CN (2) | CN102161918B (ja) |
AP (1) | AP2008004633A0 (ja) |
AT (2) | ATE538111T1 (ja) |
AU (1) | AU2007224707B2 (ja) |
BR (1) | BRPI0707100A2 (ja) |
CA (2) | CA2644409C (ja) |
DE (1) | DE602007012422D1 (ja) |
EA (1) | EA021670B1 (ja) |
MX (1) | MX2008011592A (ja) |
MY (1) | MY157999A (ja) |
NZ (1) | NZ571517A (ja) |
UA (1) | UA98455C2 (ja) |
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CN111057594B (zh) * | 2019-12-30 | 2021-10-29 | 李旭 | 一种醇基燃料添加剂的制备方法 |
US11708343B2 (en) | 2021-07-16 | 2023-07-25 | Kse, Inc. | Method and integrated process for the carboxylation of furan derived carboxylic acids to 2,5-furandicarboxylic acid |
CN118119604A (zh) | 2021-10-21 | 2024-05-31 | 福兰尼克斯科技公司 | 用于制备糠醛衍生物的工艺 |
FR3131310B1 (fr) | 2021-12-23 | 2023-12-01 | Ifp Energies Now | Procédé de production d’une solution aqueuse de 5-hydroxyméthylfurfural (5-HMF) de pureté élevée |
FR3131313B1 (fr) | 2021-12-23 | 2023-12-01 | Ifp Energies Now | Procédé de production d’une solution aqueuse de 5-hydroxyméthylfurfural (5-HMF) |
FR3131309A1 (fr) | 2021-12-23 | 2023-06-30 | IFP Energies Nouvelles | Procédé de production d’une solution aqueuse d’au moins un composé furanique |
FR3131314A1 (fr) | 2021-12-23 | 2023-06-30 | IFP Energies Nouvelles | Procédé de production d’une solution aqueuse de 2,5-diformylfurane (DFF) |
FR3131311A1 (fr) | 2021-12-23 | 2023-06-30 | IFP Energies Nouvelles | Procédé de production d’une solution aqueuse d’au moins un composé furanique de pureté élevée |
FR3131312A1 (fr) | 2021-12-23 | 2023-06-30 | IFP Energies Nouvelles | Procédé de production d’une solution aqueuse de 2,5-diformylfurane (DFF) de pureté élevée |
FR3143605A1 (fr) | 2022-12-14 | 2024-06-21 | IFP Energies Nouvelles | Procédé de production de 5-HMF par conversion d’un sirop dans un solvant non aqueux avec extraction de l'eau du sirop en amont de la synthèse |
FR3143604A1 (fr) | 2022-12-14 | 2024-06-21 | IFP Energies Nouvelles | Procédé de production de 5-HMF par conversion de sucre dans un solvant non aqueux avec extraction de l'eau pendant la synthèse |
FR3143379A1 (fr) | 2022-12-14 | 2024-06-21 | IFP Energies Nouvelles | Procédé de production d’une solution aqueuse de 5-hydroxyméthylfurfural comportant une extraction liquide-liquide intégrant ou suivie d’une filtration |
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DE621517C (de) | 1933-12-22 | 1935-11-08 | Felten & Guilleaume Carlswerk | Anordnung zur Ermittlung des Fehlerortes von Druckrohranlagen fuer elektrische Druckkabel |
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RU2203279C1 (ru) * | 2001-10-22 | 2003-04-27 | Институт химии и химической технологии СО РАН | Способ получения простых эфиров 5-гидроксиметилфурфурола |
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US7393963B2 (en) * | 2004-12-10 | 2008-07-01 | Archer-Daniels-Midland Company | Conversion of 2,5-(hydroxymethyl)furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor |
EP1834950A1 (en) | 2006-03-10 | 2007-09-19 | Avantium International B.V. | Method for the synthesis of 5-alkoxymethylfurfural ethers and their use |
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