JP6772287B2 - 2,5−フランジカルボン酸製造用触媒、およびその触媒を用いた2,5−フランジカルボン酸の製造方法 - Google Patents
2,5−フランジカルボン酸製造用触媒、およびその触媒を用いた2,5−フランジカルボン酸の製造方法 Download PDFInfo
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- JP6772287B2 JP6772287B2 JP2018547912A JP2018547912A JP6772287B2 JP 6772287 B2 JP6772287 B2 JP 6772287B2 JP 2018547912 A JP2018547912 A JP 2018547912A JP 2018547912 A JP2018547912 A JP 2018547912A JP 6772287 B2 JP6772287 B2 JP 6772287B2
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- furandicarboxylic acid
- support
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- 239000003054 catalyst Substances 0.000 title claims description 58
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 30
- 229910000510 noble metal Inorganic materials 0.000 claims description 30
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 27
- 229910052596 spinel Inorganic materials 0.000 claims description 24
- 239000011029 spinel Substances 0.000 claims description 24
- -1 furan compound Chemical class 0.000 claims description 22
- 239000002082 metal nanoparticle Substances 0.000 claims description 20
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002028 Biomass Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 5
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- 239000010970 precious metal Substances 0.000 claims description 5
- 230000021523 carboxylation Effects 0.000 claims description 4
- 238000006473 carboxylation reaction Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910020632 Co Mn Inorganic materials 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 13
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- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910004283 SiO 4 Inorganic materials 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 239000007864 aqueous solution Substances 0.000 description 3
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- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 2
- 229910002521 CoMn Inorganic materials 0.000 description 2
- 229910015372 FeAl Inorganic materials 0.000 description 2
- 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 description 2
- 229910020068 MgAl Inorganic materials 0.000 description 2
- 229910010340 TiFe Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
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- 239000012467 final product Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
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- SAZOAKOUMNDGRF-UHFFFAOYSA-N (2-formylfuran-3-yl)methyl acetate Chemical compound CC(=O)OCC=1C=COC=1C=O SAZOAKOUMNDGRF-UHFFFAOYSA-N 0.000 description 1
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 1
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 1
- QVYAWBLDJPTXHS-UHFFFAOYSA-N 5-Hydroxymethyl-2-furfural Natural products OC1=CC=C(C=O)O1 QVYAWBLDJPTXHS-UHFFFAOYSA-N 0.000 description 1
- SHNRXUWGUKDPMA-UHFFFAOYSA-N 5-formyl-2-furoic acid Chemical compound OC(=O)C1=CC=C(C=O)O1 SHNRXUWGUKDPMA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000021433 fructose syrup Nutrition 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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Description
原料として、商業的に購入可能な65.3mmolの(CH3COO)2Co・4H2Oおよび32.6mmolの(CH3COO)2Mn・4H2O(Co:Mnのモル比は2:1)を400mLの水に溶かし、30分間撹拌して均質化する。
上記で製造されたスピネル構造のMnCo2O4支持体5gおよび1Ruが触媒全体を基準に4.0重量%となるように、0.432gのRuCl3・3H2Oを、冷却浴(bath)に浸した約20ml水入りの二口丸底フラスコ(100ml)に入れる。前記混合物をN2雰囲気下で12時間撹拌する。その後、撹拌を行いながら、RuCl3・3H2Oの量の10倍以上の量でNaBH4水溶液を前記フラスコ内に一滴ずつ滴下し、反応がすべて行われるように室温、およびN2雰囲気下で一日中500rpmの速度で撹拌を行う。前記反応を介して、Ru()がRu(0)に還元されてナノ粒子を形成する。最終的に前記反応を介して得られた触媒を濾別し、エタノールで洗浄する。上述した過程を行い、乾燥したダークブラック色のスピネル構造のMnCo2O4支持体にナノルテニウム貴金属粒子が含まれている触媒を得た。前記触媒を分析するために、エネルギー分散X線(EDX/EDS)スペクトロメータ、Quantax200で測定を行い、その結果を図4に示す。図4に示されるように、ルテニウム貴金属がスピネル構造のMnCo2O4支持体に含まれることを確認することができた。
[実施例1]
100mLのステンレススチール製高圧反応器にマグネチックスターラーおよび電気ヒーターを備える。5−ヒドロキシメチルフルフラール(HMF)(0.2513g、2.0mmol)と溶媒としての水20mlを仕込み、表1に示すように添加される触媒を投入し、撹拌速度を100rpmに維持したまま、少なくとも5分間室温で混合を行った後、空気を反応器内に連続的に供給しながら、反応器の温度を120℃、容器内の圧力を150psiに維持した後、600rpmで撹拌を行いながら、最終的に反応器内の空気圧力を350psiに設定し、120℃で10時間反応させた。反応中、反応器内の圧力が一定に維持できるように、リザーブタンク(reservoir tank)に連結された背圧レギュレーター(back pressu reregulator)で圧力を調節した。反応が完了したら、反応混合物を室温に冷却し、濾過して固体生成物を分離した。この時、分離された固体生成物を真空オーブンで完全に乾燥させた。乾燥後、生成されたFDCAの重量を測定した。その中の一部をH2SO4(0.0005M)の含まれている水に溶かした後、HPLC分析(Agilent Technologies 1200 series、Bio-Rad Aminex HPX-87 H pre-packed column、およびUV検出器UV-detector)によって、HMF転換率(C)、FDCA生成収率(Y)、およびFDCA、FFCA、DFFの選択率(S)を下記数式のように算出した(FFCA、DFFの選択率(S)の場合は、下記数式3でFFCA、DFFの収率で代替して算出する)。実施例1のHPLC結果を図6に示し、計算された結果を表1に示す。
実施例1と同様の条件で実験を行うが、触媒の量、反応温度、反応時間を変えて行った結果を表1に示す。実施例1〜4の反応開始後の容器内のpHは3〜4であって、酸性条件でもFDCAが高収率で製造できることが分かる。
実施例1と同様の条件で実験を行うが(温度120℃、反応時間10hr)、HMF/金属のモル比を変えて実施した結果を表2に示す。
実施例6と同様の条件で実験を行うが(温度120℃、反応時間10hr)、空気圧を変えて実施した結果を表3に示す。
実施例6と同様の条件で実験を行うが(温度120℃、反応時間10hr、圧力350psi)、本願触媒の触媒全体重量に対するRuナノ金属の重量%を変えて実施した結果を表4に示す。
スピネル構造の支持体の製造の際に、(CH3COO)2Co・4H2Oのモル数および(CH3COO)2Mn・4H2Oを1:2に変えてCo:Mnのモル比を1:2にして支持体を製造し、前記支持体内にRuナノ金属を4重量%で含ませた後、実施例6と同様に実験を行った(温度120℃、反応時間10hr、圧力350psi)結果を表5に示す。
全ての条件を実施例6と同様にするが、基質としてHMFの代わりにAMF(2-acetoxymethyl-5-furfural)を用いたときの結果を表6に示す。AMFを基質として用いた場合にも、FDCAが高収率で生成されることを確認することができた。
実施例1と同様の条件で実験を行うが、Ru金属なしに触媒としてMnCo2O4のみを用い、温度および反応時間を変えて行った結果を表7に示す。
実施例1と同様の条件で実験を行うが、表8に示すように、ナノ金属粒子をAuとし、支持体をMnCo2O4とし、反応時間および温度を変えて実施した。その結果を表8に示す。
実施例6と同様の条件で実験を行うが、触媒としてAu金属/CeO2支持体を用い、表9に示すように一部の実験条件を変えて行った。比較例6の場合は、溶媒として水の代わりに酢酸:メタノール=8:2の混合溶媒を用いた。
実施例1と同様の条件で実験を行うが、触媒としてRu金属/MgAl2O4支持体を用いた。
実施例6と同様の条件で実験を行うが、触媒としてRu金属/炭素を用い、塩基性物質であるNa2CO3とNaHCO3を反応容器内に添加した。比較例9の反応開始後の容器内のpHは7〜8であった。また、同じ触媒(Ru金属/炭素)で行うが、すべての条件を実施例6と同様にして(ベース−フリーで)実験を行った。
支持体の種類を下記表12のとおりに変えた以外は実施例6と同様にして、表8に示すように実験を行った。
Claims (14)
- ヒドロキシ基およびカルボニル基を含むフラン系化合物またはその誘導体のカルボキシル化触媒であって、
MnCo2O4およびCoMn2O4の1種以上であるスピネル構造の支持体内に貴金属ナノ粒子が含まれており、貴金属が、白金、パラジウム、およびルテニウムからなる群から選択された1種以上である、2,5−フランジカルボン酸(FDCA)製造用触媒。 - 支持体が、2.0〜4.0μmの平均粒径(D50)を有する、請求項1に記載の2,5−フランジカルボン酸(FDCA)製造用触媒。
- 貴金属が、ルテニウムである、請求項1に記載の2,5−フランジカルボン酸(FDCA)製造用触媒。
- フラン系化合物が、5−ヒドロキシメチルフルフラール(HMF)である、請求項1に記載の2,5−フランジカルボン酸(FDCA)製造用触媒。
- 誘導体が、2−アセトキシメチル−5−フルフラール(AMF)である、請求項1に記載の2,5−フランジカルボン酸(FDCA)製造用触媒。
- 貴金属ナノ粒子が、触媒全体重量を基準に0.1〜10重量%で含まれる、請求項1に記載の2,5−フランジカルボン酸(FDCA)製造用触媒。
- MnCo2O4およびCoMn2O4の1種以上であるスピネル構造の支持体内に、白金、パラジウム、およびルテニウムからなる群から選択された1種以上である貴金属ナノ粒子が含まれている触媒の存在下で、ヒドロキシ基およびカルボニル基を含むフラン系化合物またはその誘導体をカルボキシル化させることを含む、2,5−フランジカルボン酸(FDCA)の製造方法。
- ヒドロキシ基およびカルボニル基を含むフラン系化合物が、5−ヒドロキシメチルフルフラール(HMF)である、請求項7に記載の2,5−フランジカルボン酸(FDCA)の製造方法。
- 誘導体が、2−アセトキシメチル−5−フルフラール(AMF)である、請求項7に記載の2,5−フランジカルボン酸(FDCA)の製造方法。
- フラン系化合物の酸化が、100〜200℃の温度、551580.56〜6894757Paの空気圧、および3〜12時間の反応時間の条件下で行われる、請求項7に記載の2,5−フランジカルボン酸(FDCA)の製造方法。
- 貴金属ナノ粒子:フラン系化合物のモル比が、1:5〜200である、請求項7に記載の2,5−フランジカルボン酸(FDCA)の製造方法。
- フラン系化合物の酸化が、ベースフリー(base-free)環境で溶媒として水を用いて単一容器内で行われる、請求項7に記載の2,5−フランジカルボン酸(FDCA)の製造方法。
- 5−ヒドロキシメチルフルフラール(HMF)が、セルロースまたは多糖類を含有するバイオマスから得られる、請求項8に記載の2,5−フランジカルボン酸(FDCA)の製造方法。
- 貴金属ナノ粒子が、触媒全体重量を基準に0.1〜10重量%で含まれる、請求項7に記載の2,5−フランジカルボン酸(FDCA)の製造方法。
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