JP2017039671A - Manufacturing method of 2-methyltetrahydrofuran - Google Patents
Manufacturing method of 2-methyltetrahydrofuran Download PDFInfo
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- JP2017039671A JP2017039671A JP2015163085A JP2015163085A JP2017039671A JP 2017039671 A JP2017039671 A JP 2017039671A JP 2015163085 A JP2015163085 A JP 2015163085A JP 2015163085 A JP2015163085 A JP 2015163085A JP 2017039671 A JP2017039671 A JP 2017039671A
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- methyltetrahydrofuran
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- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 107
- 239000002184 metal Substances 0.000 claims abstract description 107
- 239000003054 catalyst Substances 0.000 claims abstract description 72
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 36
- 229940040102 levulinic acid Drugs 0.000 claims abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 239000010948 rhodium Substances 0.000 claims abstract description 9
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 239000010937 tungsten Substances 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 229910021536 Zeolite Inorganic materials 0.000 claims description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 17
- 239000010457 zeolite Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 4
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 14
- 238000011282 treatment Methods 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- ZMCCBULBRKMZTH-UHFFFAOYSA-N molybdenum platinum Chemical compound [Mo].[Pt] ZMCCBULBRKMZTH-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WCJIUQVBQSTBDE-UHFFFAOYSA-N [Rh].[Re] Chemical compound [Rh].[Re] WCJIUQVBQSTBDE-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- DBJYYRBULROVQT-UHFFFAOYSA-N platinum rhenium Chemical compound [Re].[Pt] DBJYYRBULROVQT-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 229910002839 Pt-Mo Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- CZBGCSZGIMINPA-UHFFFAOYSA-N [Rh].[W] Chemical compound [Rh].[W] CZBGCSZGIMINPA-UHFFFAOYSA-N 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- ZCUTVPBDJKANGE-UHFFFAOYSA-N molybdenum rhodium Chemical compound [Mo].[Rh] ZCUTVPBDJKANGE-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- GRLYPOPFNDQSKV-UHFFFAOYSA-N rhenium ruthenium Chemical compound [Ru].[Re] GRLYPOPFNDQSKV-UHFFFAOYSA-N 0.000 description 1
- CQJFSGHLNFVVNS-UHFFFAOYSA-N rhodium vanadium Chemical compound [V].[Rh] CQJFSGHLNFVVNS-UHFFFAOYSA-N 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
Description
本発明は、温和な条件下、レブリン酸から２−メチルテトラヒドロフラン（以後、「ＭＴＨＦ」と称する場合がある）を選択的、且つ効率よく製造する方法に関する。 The present invention relates to a method for selectively and efficiently producing 2-methyltetrahydrofuran (hereinafter sometimes referred to as “MTHF”) from levulinic acid under mild conditions.
持続可能社会の構築に向けて、再生可能資源であるバイオマス由来の化学製品を利用することが望まれている。例えば、レブリン酸は木質系バイオマスのリグノセルロースから得られるケトカルボン酸であり、レブリン酸からラクトン、ジオール、環状エーテル等を製造することができる。 In order to build a sustainable society, it is desired to use biomass-derived chemical products that are renewable resources. For example, levulinic acid is a ketocarboxylic acid obtained from lignocellulose of woody biomass, and lactones, diols, cyclic ethers and the like can be produced from levulinic acid.
レブリン酸から得られる環状エーテルとしては、ＭＴＨＦが知られている。ＭＴＨＦは、テトラヒドロフラン（ＴＨＦ）に代わる溶媒として有用であり、ＭＴＨＦに水を加えるときれいに相分離する特性を有するため、溶媒として使用すると反応生成物の精製処理を容易に行うことができる。また、リチウムイオンバッテリーの電解液成分等としても有用である。 MTHF is known as a cyclic ether obtained from levulinic acid. MTHF is useful as a solvent in place of tetrahydrofuran (THF), and has a property of phase separation cleanly when water is added to MTHF. Therefore, when used as a solvent, the reaction product can be easily purified. It is also useful as an electrolyte component of a lithium ion battery.
レブリン酸からＭＴＨＦを得る反応としては、Ｒｕ−Ｔｒｉｐｈｏｓ錯体、Ｒｕ−Ｎ−Ｔｒｉｐｈｏｓ錯体等の均一系触媒を使用し、酸の存在下で反応させる方法が知られている。しかし、前記均一系触媒と酸を使用する方法では使用できる反応器の材質が限られる上、そのような反応器は非常に高価であること、反応終了後に前記酸を塩基で中和し、中和によって生成する塩を除去する等の精製処理を施す必要があり、精製処理に手間とコストがかかることが問題であった。その他、レブリン酸からＭＴＨＦを得る反応として、Ｐｄ−Ｒｅ／Ｃ、Ｎｉ−Ｃｕ／ＳｉＯ2等の固体触媒を使用し、気相流通系ワンパス反応を行う方法が知られている。前記固体触媒を使用する方法では、反応生成物の精製処理における手間とコストを削減することができるが、収率良くＭＴＨＦを得る為に高温及び／又は高水素圧条件下で反応を行う必要があった（非特許文献１〜５）。 As a reaction for obtaining MTHF from levulinic acid, a method of using a homogeneous catalyst such as Ru-Triphos complex, Ru-N-Triphos complex and reacting in the presence of an acid is known. However, in the method using the homogeneous catalyst and the acid, usable reactor materials are limited, and such a reactor is very expensive. After the reaction is completed, the acid is neutralized with a base. It is necessary to carry out a purification treatment such as removal of the salt produced by the sum, and it is a problem that the purification treatment takes time and cost. In addition, as a reaction for obtaining MTHF from levulinic acid, a method of performing a gas phase one-pass reaction using a solid catalyst such as Pd—Re / C, Ni—Cu / SiO 2 or the like is known. In the method using the solid catalyst, labor and cost in the purification process of the reaction product can be reduced, but it is necessary to perform the reaction under high temperature and / or high hydrogen pressure conditions in order to obtain MTH with high yield. (Non-Patent Documents 1 to 5).
従って、本発明の目的は、レブリン酸から、温和な条件下で、簡便且つ効率よくＭＴＨＦを製造する方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for easily and efficiently producing MTHF from levulinic acid under mild conditions.
本発明者等は上記課題を解決するため鋭意検討した結果、下記特定の固体触媒を使用すると、レブリン酸からＭＴＨＦを、温和な条件下でも、ワンポットで簡便に、効率よく、且つ安価に製造することができることを見いだした。本発明はこれらの知見に基づいて完成させたものである。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have produced MTHF from levulinic acid easily, efficiently and inexpensively in one pot even under mild conditions when the following specific solid catalyst is used. I found that I could do it. The present invention has been completed based on these findings.
すなわち、本発明は、下記金属触媒の存在下でレブリン酸から２−メチルテトラヒドロフランを製造する２−メチルテトラヒドロフランの製造方法を提供する。
金属触媒：金属種として下記Ｍ1とＭ2が酸性担体に担持されてなる触媒
（Ｍ1）ロジウム、白金、ルテニウム、イリジウム、及びパラジウムからなる群より選択される少なくとも１種の金属
（Ｍ2）バナジウム、モリブデン、タングステン、及びレニウムからなる群より選択される少なくとも１種の金属
That is, this invention provides the manufacturing method of 2-methyltetrahydrofuran which manufactures 2-methyltetrahydrofuran from levulinic acid in presence of the following metal catalyst.
Metal catalyst: Catalyst in which M 1 and M 2 below are supported on an acidic support as metal species (M 1 ) At least one metal selected from the group consisting of rhodium, platinum, ruthenium, iridium, and palladium (M 2 ) At least one metal selected from the group consisting of vanadium, molybdenum, tungsten, and rhenium
本発明は、また、酸性担体が、ゼオライト、硫酸化ジルコニア、及びリン酸ジルコニウムからなる群より選択される少なくとも１種の担体である前記の２−メチルテトラヒドロフランの製造方法を提供する。 The present invention also provides the method for producing 2-methyltetrahydrofuran as described above, wherein the acidic carrier is at least one carrier selected from the group consisting of zeolite, sulfated zirconia, and zirconium phosphate.
本発明は、また、金属触媒が、金属種としてＭ1とＭ2を、Ｍ2１モルに対してＭ1を２〜１００モルの範囲で含有する前記の２−メチルテトラヒドロフランの製造方法を提供する。 The present invention also metal catalyst, the M 1 and M 2 as metal species, provides a method of manufacturing the 2-methyltetrahydrofuran containing M 1 in the range of 2 to 100 mol with respect to M 2 1 mole To do.
本発明は、また、金属触媒の使用量（Ｍ1金属換算）が、レブリン酸の０．０１〜３０モル％である前記の２−メチルテトラヒドロフランの製造方法を提供する。 The present invention also provides the process for producing 2-methyltetrahydrofuran as described above, wherein the amount of metal catalyst used (in terms of M 1 metal) is 0.01 to 30 mol% of levulinic acid.
本発明は、また、水の存在下で反応を行う前記の２−メチルテトラヒドロフランの製造方法を提供する。 The present invention also provides the method for producing 2-methyltetrahydrofuran described above, wherein the reaction is carried out in the presence of water.
本発明のＭＴＨＦの製造方法によれば、石油資源に代えて、バイオマス由来のレブリン酸からＭＴＨＦを、温和な条件下でも、ワンポットで簡便に、効率よく、且つ選択的に製造することができ、製造に要するエネルギー、手間、時間、及び試薬を最小限にとどめることができる。また、反応に酸を使用しないため、酸に耐性を有する、高価な反応器を使用する必要が無い。その上、中和処理など、反応に酸を使用することによって必要となる後処理も省略することができる。このようにして得られるＭＴＨＦは、ＴＨＦに代わる溶媒として有用である。その他、リチウムイオンバッテリーの電解液成分等としても有用である。従って、本発明のＭＴＨＦの製造方法は工業的にＭＴＨＦを製造する方法として好適である。 According to the method for producing MTHF of the present invention, instead of petroleum resources, MTHF from biomass-derived levulinic acid can be produced easily, efficiently and selectively in one pot even under mild conditions. Energy, labor, time, and reagents required for production can be minimized. In addition, since no acid is used for the reaction, there is no need to use an expensive reactor that is resistant to acid. In addition, post-treatments such as neutralization treatment that are required by using an acid in the reaction can be omitted. MTHF thus obtained is useful as a solvent instead of THF. In addition, it is also useful as an electrolyte component of a lithium ion battery. Therefore, the MTHF production method of the present invention is suitable as an industrial method for producing MTHF.
（金属触媒）
本発明のＭＴＨＦの製造方法は、下記金属触媒を使用することを特徴とする。
金属触媒：金属種として下記Ｍ1とＭ2が酸性担体に担持されてなる触媒
（Ｍ1）ロジウム、白金、ルテニウム、イリジウム、及びパラジウムからなる群より選択される少なくとも１種の金属
（Ｍ2）バナジウム、モリブデン、タングステン、及びレニウムからなる群より選択される少なくとも１種の金属
(Metal catalyst)
The MTHF production method of the present invention is characterized by using the following metal catalyst.
Metal catalyst: Catalyst in which M 1 and M 2 below are supported on an acidic support as metal species (M 1 ) At least one metal selected from the group consisting of rhodium, platinum, ruthenium, iridium, and palladium (M 2 ) At least one metal selected from the group consisting of vanadium, molybdenum, tungsten, and rhenium
本発明では、金属触媒として、触媒活性を有する上記金属種を担体に担持したものを使用する。それにより、金属種同士の界面面積を稼ぐことができ、触媒活性点を多く露出させることができる。そのため、本発明における金属触媒は優れた触媒活性を発揮することができる。 In the present invention, a metal catalyst having the above metal species having catalytic activity supported on a carrier is used. Thereby, the interface area between metal species can be earned, and a large number of catalytic active points can be exposed. Therefore, the metal catalyst in the present invention can exhibit excellent catalytic activity.
また、本発明における金属触媒は、金属種が担体に担持されたものであるので、反応終了後は、濾過、遠心分離等の物理的な分離手段により金属触媒を反応生成物から容易に、分離、回収することができ、反応生成物から触媒を除去する精製処理に要するコストを最小限とすることができる。また、分離し、回収された金属触媒は、そのままで、又は洗浄、乾燥等を施した後、再利用することができる。そのため、高価な金属触媒を繰り返し利用することができる。本発明のＭＴＨＦの製造方法は、前記効果を併せ持つ金属触媒を使用するため、ＭＴＨＦの製造コストを大幅に削減することができる。 In addition, since the metal catalyst in the present invention is a metal species supported on a carrier, after completion of the reaction, the metal catalyst can be easily separated from the reaction product by physical separation means such as filtration and centrifugation. Can be recovered, and the cost required for the purification treatment for removing the catalyst from the reaction product can be minimized. Further, the separated and recovered metal catalyst can be reused as it is or after being washed, dried and the like. Therefore, an expensive metal catalyst can be used repeatedly. Since the MTHF production method of the present invention uses a metal catalyst having the above effects, the production cost of MTHF can be greatly reduced.
金属種Ｍ1は、ロジウム、白金、ルテニウム、イリジウム、及びパラジウムからなる群より選択される少なくとも１種の金属（特に、貴金属）である。なかでも反応中間体であるγ−バレロラクトン（ＧＶＬ）の水素化反応を効率よく促進することができる点で、ロジウム、白金、ルテニウム、及びパラジウムからなる群より選択される少なくとも１種の金属が好ましく、特に副生物の生成量が極めて低く、高い選択率でＭＴＨＦを製造することができる点でロジウム、白金、及びパラジウムからなる群より選択される少なくとも１種の金属が好ましく、とりわけロジウム及び／又は白金が、より温和な温度、且つより短い反応時間で効率よくＭＴＨＦが得られる点で好ましい。 The metal species M 1 is at least one metal selected from the group consisting of rhodium, platinum, ruthenium, iridium, and palladium (particularly a noble metal). Among these, at least one metal selected from the group consisting of rhodium, platinum, ruthenium, and palladium is preferable in that the hydrogenation reaction of γ-valerolactone (GVL), which is a reaction intermediate, can be efficiently promoted. In particular, at least one metal selected from the group consisting of rhodium, platinum, and palladium is preferable in that MTH can be produced with extremely low production of by-products and high selectivity. Alternatively, platinum is preferable because MTHF can be efficiently obtained at a milder temperature and a shorter reaction time.
金属種Ｍ2は、バナジウム、モリブデン、タングステン、及びレニウムからなる群より選択される少なくとも１種の金属（特に、ルイス酸性を有する金属）である。 The metal species M 2 is at least one metal selected from the group consisting of vanadium, molybdenum, tungsten, and rhenium (particularly, a metal having Lewis acidity).
金属種Ｍ1とＭ2の組み合わせとしては、なかでも、パラジウム−レニウム、ルテニウム−レニウム、ロジウム−モリブデン、ロジウム−タングステン、ロジウム−バナジウム、ロジウム−レニウム、白金−モリブデン、白金−レニウムの組み合わせが、反応中間体であるＧＶＬの水素化反応を効率よく促進し、ＭＴＨＦを収率良く製造することができる点で好ましく、パラジウム−レニウム、ロジウム−レニウム、白金−モリブデン、白金−レニウムの組み合わせ（特に、パラジウム−レニウム、白金−モリブデンの組み合わせ）が、副生物の生成量が極めて低く、選択率にＭＴＨＦを製造することができる点で好ましく、とりわけ白金−モリブデンが、より温和な温度、且つより短い反応時間で効率よく選択的にＭＴＨＦを製造することができる点で好ましい。 Among the combinations of metal species M 1 and M 2 , palladium-rhenium, ruthenium-rhenium, rhodium-molybdenum, rhodium-tungsten, rhodium-vanadium, rhodium-rhenium, platinum-molybdenum, platinum-rhenium, among others, It is preferable in that the hydrogenation reaction of GVL which is a reaction intermediate can be efficiently promoted and MTHF can be produced with good yield, and a combination of palladium-rhenium, rhodium-rhenium, platinum-molybdenum, platinum-rhenium (particularly, The combination of palladium-rhenium and platinum-molybdenum) is preferable in that the amount of by-products generated is extremely low and MTHF can be produced with high selectivity. In particular, platinum-molybdenum has a milder temperature and a shorter reaction. To produce MTHF efficiently and selectively in time It is preferable in that it can be performed.
酸性担体としては、例えば、ゼオライト、硫酸化ジルコニア、リン酸ジルコニウム、モンモリロナイト、シリカ、アルミナ等を挙げることができる。本発明においては、なかでもゼオライト、硫酸化ジルコニア、又はリン酸ジルコニウムが好ましく、ＭＴＨＦを収率よく製造することができる点で、ゼオライト［例えば、β型ゼオライト（ＳｉＯ2／Ａｌ2Ｏ3（モル比）＝２５〜１５０）、Ｙ型ゼオライト（ＳｉＯ2／Ａｌ2Ｏ3（モル比）＝４〜２００）、ＺＳＭ−５型ゼオライト（ＳｉＯ2／Ａｌ2Ｏ3（モル比）＝２０〜１２００）、モルデナイト型ゼオライト（ＳｉＯ2／Ａｌ2Ｏ3（モル比）＝９〜１００）等が含まれる］、又は硫酸化ジルコニアが好ましく、特にβ型ゼオライトが、副生物の生成量が極めて低く、高い選択率でＭＴＨＦを製造することができる点で好ましい。 Examples of the acidic carrier include zeolite, sulfated zirconia, zirconium phosphate, montmorillonite, silica, alumina, and the like. In the present invention, zeolite, sulfated zirconia, or zirconium phosphate is preferable, and zeolite [for example, β-type zeolite (SiO 2 / Al 2 O 3 (mol Ratio) = 25-150), Y-type zeolite (SiO 2 / Al 2 O 3 (molar ratio) = 4-200), ZSM-5 type zeolite (SiO 2 / Al 2 O 3 (molar ratio)) = 20-1200 ), Mordenite-type zeolite (SiO 2 / Al 2 O 3 (molar ratio) = 9 to 100) and the like], or sulfated zirconia is preferred, and β-type zeolite, in particular, has a very low amount of by-products, It is preferable in that MTHF can be produced with high selectivity.
酸性担体の比表面積（ＢＥＴ法による）は、例えば１０〜１０００ｍ2／ｇ、好ましくは１００〜８００ｍ2／ｇ、特に好ましくは３００〜７００ｍ2／ｇである。 The specific surface area (by the BET method) of the acidic carrier is, for example, 10 to 1000 m 2 / g, preferably 100 to 800 m 2 / g, particularly preferably 300 to 700 m 2 / g.
酸性担体の平均粒子径（レーザー回折・散乱法による）は、例えば０．１〜５０μｍ、好ましくは０．１〜２０μｍ、特に好ましくは０．１〜０．５μｍである。 The average particle diameter (by laser diffraction / scattering method) of the acidic carrier is, for example, 0.1 to 50 μm, preferably 0.1 to 20 μm, and particularly preferably 0.1 to 0.5 μm.
β型ゼオライトとしては、例えば、商品名「ＪＲＣ−Ｚ−ＨＢベータ」（触媒学会参照触媒）、商品名「ｚｅｏｌｉｔｅ ｂｅｔａ（Ｈ−ｂｅｔａ）」（ｚｅｏｌｙｓｔ社製）等の市販品を好適に使用することができる。 As the β-type zeolite, for example, commercially available products such as trade name “JRC-Z-HB beta” (catalyst society reference catalyst), trade name “zeolite beta (H-beta)” (manufactured by zeolist) and the like are preferably used. be able to.
担体に担持される金属種Ｍ1とＭ2の態様は特に限定されることがなく、例えば、金属単体、金属塩、金属酸化物、金属水酸化物、又は金属錯体等を挙げることができる。 The aspect of the metal species M 1 and M 2 supported on the carrier is not particularly limited, and examples thereof include a simple metal, a metal salt, a metal oxide, a metal hydroxide, or a metal complex.
金属種Ｍ1の担持量（金属換算）は、上記担体の、例えば０．１〜２０重量％程度、好ましくは０．５〜１５重量％、特に好ましくは１〜１０重量％である。担持量が上記範囲を上回ると、活性点が減少するためか、触媒活性が低下してＭＴＨＦの収率が低下する傾向がある。一方、担持量が上記範囲を下回ると、十分な触媒活性が得られ難くなる傾向がある。 The amount of metal species M 1 supported (in metal) is, for example, about 0.1 to 20% by weight, preferably 0.5 to 15% by weight, and particularly preferably 1 to 10% by weight of the above support. If the supported amount exceeds the above range, the active point may decrease, or the catalytic activity may decrease and the yield of MTHF tends to decrease. On the other hand, if the loading amount is below the above range, sufficient catalytic activity tends to be difficult to obtain.
金属種Ｍ1の担持量（金属換算）は、Ｍ2１モルに対して、例えば２〜１００モルの範囲であり、その上限は、好ましくは９０モル、より好ましくは７０モル、更に好ましくは５０モル、特に好ましくは３０モル、最も好ましくは１８モルである。下限は、好ましくは５モル、特に好ましくは８モル、最も好ましくは１２モルである。金属触媒は、金属種Ｍ1とＭ2の界面に活性点を有すると考えられる。そして、金属種Ｍ1とＭ2の含有割合が上記範囲を外れ、Ｍ1とＭ2の一方が過剰になると、過剰の金属種によってもう一方の金属種が覆われて界面が減少し、活性点が減少するためか、触媒活性が低下してＭＴＨＦの収率が低下する傾向がある。 The supported amount of metal species M 1 (in metal conversion) is, for example, in the range of 2 to 100 mol with respect to 1 mol of M 2 , and the upper limit thereof is preferably 90 mol, more preferably 70 mol, still more preferably 50. Mol, particularly preferably 30 mol, most preferably 18 mol. The lower limit is preferably 5 mol, particularly preferably 8 mol, and most preferably 12 mol. The metal catalyst is considered to have an active site at the interface between the metal species M 1 and M 2 . When the content ratio of the metal species M 1 and M 2 is out of the above range and one of M 1 and M 2 becomes excessive, the other metal species is covered by the excess metal species, and the interface decreases, and the activity This is because the number of points is decreased, and the catalytic activity is decreased and the yield of MTHF tends to be decreased.
本発明における金属触媒は、例えば、含浸法により調製することができる。 The metal catalyst in the present invention can be prepared, for example, by an impregnation method.
含浸法は、上記金属種を含む化合物（＝金属化合物）を溶解して得られる溶液（例えば、水溶液）に担体を浸漬して前記金属化合物を含浸させた後、乾燥させ、更に焼成することにより金属種を担体に担持させる方法である。溶液中の金属化合物濃度や、担体の浸漬時間等を調整することにより、担持量を制御することができる。 In the impregnation method, the carrier is immersed in a solution (for example, an aqueous solution) obtained by dissolving the compound containing the metal species (= metal compound), impregnated with the metal compound, dried, and further fired. In this method, a metal species is supported on a carrier. The loading amount can be controlled by adjusting the concentration of the metal compound in the solution, the immersion time of the carrier, and the like.
金属種として上記Ｍ1とＭ2を含有する金属触媒は、担体に金属種Ｍ1を含む化合物を溶解して得られる溶液（以後、「Ｍ1含有溶液」と称する場合がある）とＭ2を含む化合物を溶解して得られる溶液（以後、「Ｍ2含有溶液」と称する場合がある）を順次含浸させる方法（＝逐次含浸法）や担体にＭ1含有溶液とＭ2含有溶液を同時に含浸させる方法（＝共含浸法）により調製することができる。逐次含浸法により金属触媒（２）を調製する場合は、担体をＭ1含有溶液とＭ2含有溶液に順次浸漬し、その都度焼成を行う。共含浸法により金属触媒を調製する場合は、Ｍ1含有溶液とＭ2含有溶液の混合液中に担体を含浸し、その後焼成を行う。 The metal catalyst containing M 1 and M 2 as the metal species includes a solution obtained by dissolving a compound containing the metal species M 1 on a carrier (hereinafter, sometimes referred to as “M 1 -containing solution”) and M 2. A method of sequentially impregnating a solution obtained by dissolving a compound containing a compound (hereinafter sometimes referred to as “M 2 -containing solution”) (= sequential impregnation method) or a carrier containing an M 1 -containing solution and an M 2 -containing solution It can be prepared by an impregnation method (= co-impregnation method). When the metal catalyst (2) is prepared by the sequential impregnation method, the support is sequentially immersed in the M 1 -containing solution and the M 2 -containing solution, and calcined each time. When the metal catalyst is prepared by the co-impregnation method, the support is impregnated in a mixed solution of the M 1 -containing solution and the M 2 -containing solution, and then calcined.
本発明における金属触媒としては、共含浸法により金属種Ｍ1とＭ2を担持して得られたものが、ＭＴＨＦをより選択的に製造することができる点で好ましい。 As the metal catalyst in the present invention, one obtained by supporting the metal species M 1 and M 2 by the co-impregnation method is preferable in that MTH can be more selectively produced.
例えばＭ1としてのＰｔとＭ2としてのＭｏが、担体としてのβ型ゼオライト（Ｈ−ｂｅｔａ）に、共含浸法により担持された金属触媒（例えば、Ｐｔ−Ｍｏ／Ｈ−ｂｅｔａ）は、Ｐｔ化合物（例えば、Ｈ2ＰｔＣｌ6等）とＭｏ化合物［例えば、（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ等］を水に溶解して得られる溶液中にβ型ゼオライトを浸漬し、その後、引き揚げて乾燥させ、更に焼成することにより調製することができる。 For example, a metal catalyst (for example, Pt-Mo / H-beta) in which Pt as M 1 and Mo as M 2 are supported by β-type zeolite (H-beta) as a support by a co-impregnation method is Pt. A β-type zeolite is immersed in a solution obtained by dissolving a compound (for example, H 2 PtCl 6 ) and a Mo compound [for example, (NH 4 ) 6 Mo 7 O 24 · 4H 2 O, etc.] in water, It can be prepared by lifting, drying, and further firing.
Ｍ1としてＲｈを含有する金属触媒を製造する場合は、Ｐｔ化合物に代えてＲｈ化合物（例えば、ＲｈＣｌ3・ｘＨ2Ｏ等）を使用し、Ｍ1としてＲｕを含有する金属触媒を製造する場合は、Ｐｔ化合物に代えてＲｕ化合物（例えば、ＲｕＣｌ3等）を使用し、Ｍ1としてＩｒを含有する金属触媒を製造する場合は、Ｐｔ化合物に代えてＩｒ化合物（例えば、ＩｒＣｌ3・ｘＨ2Ｏ等）を使用し、Ｍ1としてＰｄを含有する金属触媒を製造する場合は、Ｐｔ化合物に代えてＰｄ化合物（例えば、Ｐｄ（ＮＯ3）2等）を使用すればよい。 When producing a metal catalyst containing Rh as M 1 , using a Rh compound (for example, RhCl 3 · xH 2 O) instead of the Pt compound and producing a metal catalyst containing Ru as M 1 In the case of using a Ru compound (for example, RuCl 3 or the like) instead of the Pt compound and producing a metal catalyst containing Ir as M 1 , an Ir compound (for example, IrCl 3 .xH 2 ) is used instead of the Pt compound. In the case where a metal catalyst containing Pd as M 1 is used, a Pd compound (eg, Pd (NO 3 ) 2 etc.) may be used instead of the Pt compound.
また、Ｍ2としてＶを含有する金属触媒を製造する場合は、Ｍｏ化合物に代えてＶ化合物（例えば、ＶＣｌ3等）を使用し、Ｍ2としてＷを含有する金属触媒を製造する場合は、Ｍｏ化合物に代えてＷ化合物（例えば、Ｈ42Ｎ10Ｏ42Ｗ12・ｘＨ2Ｏ等）を使用し、Ｍ2としてＲｅを含有する金属触媒を製造する場合は、Ｍｏ化合物に代えてＲｅ化合物（例えば、ＮＨ4ＲｅＯ4等）を使用すればよい。 Further, when producing a metal catalyst containing V as M 2 , a V compound (for example, VCl 3 ) is used instead of the Mo compound, and when producing a metal catalyst containing W as M 2 , W compounds in place of the Mo compound (e.g., H 42 N 10 O 42 W 12 · xH 2 O , etc.) when using, to produce a metal catalyst containing Re as M 2 is, Re compound in place of the Mo compound (For example, NH 4 ReO 4 or the like) may be used.
前記溶液中に担体を浸漬する際の温度は、例えば室温（１〜３０℃）が好ましい。 The temperature at which the carrier is immersed in the solution is preferably room temperature (1 to 30 ° C.), for example.
前記溶液中に担体を浸漬する時間は、例えば１〜３０時間程度、好ましくは１〜５時間である。 The time for immersing the carrier in the solution is, for example, about 1 to 30 hours, preferably 1 to 5 hours.
乾燥は、例えば乾燥機等を使用して、８０〜１５０℃で１〜１０時間程度加熱乾燥することが好ましい。 The drying is preferably performed by heating at 80 to 150 ° C. for about 1 to 10 hours using, for example, a dryer.
焼成は、例えばマッフル炉等を使用して、３００〜７００℃で１〜５時間加熱することが好ましい。 Firing is preferably performed at 300 to 700 ° C. for 1 to 5 hours using, for example, a muffle furnace.
また、焼成後、更に還元処理を施してもよい。還元処理に使用する還元剤としては、例えば、水素（Ｈ2）等を挙げることができる。 Moreover, you may perform a reduction process after baking. Examples of the reducing agent used for the reduction treatment include hydrogen (H 2 ).
還元処理温度及び時間としては、例えば０〜６００℃（好ましくは、１００〜２００℃）の温度で、０．５〜５時間程度（好ましくは、０．５〜２時間）である。 The reduction treatment temperature and time are, for example, 0 to 600 ° C. (preferably 100 to 200 ° C.) and about 0.5 to 5 hours (preferably 0.5 to 2 hours).
上記調製方法により得られた金属触媒は、その後、洗浄処理（水や有機溶媒等により洗浄）、乾燥処理（真空乾燥等により乾燥）等を施してもよい。 Thereafter, the metal catalyst obtained by the above preparation method may be subjected to a washing treatment (washing with water, an organic solvent or the like), a drying treatment (drying by vacuum drying or the like) or the like.
［ＭＴＨＦの製造方法］
本発明のＭＴＨＦの製造方法は、上記金属触媒の存在下でレブリン酸から２−メチルテトラヒドロフランを製造することを特徴とする。
[Method for producing MTHF]
The method for producing MTHF according to the present invention is characterized in that 2-methyltetrahydrofuran is produced from levulinic acid in the presence of the metal catalyst.
本発明のＭＴＨＦの製造方法では、レブリン酸（ＬＡ）からγ−バレロラクトン（ＧＶＬ）、１，４−ペンタンジオール（１，４−ＰｅＤ）を経てＭＴＨＦを製造する（下記式（１）参照）。本発明では上記金属触媒を使用し、前記金属触媒における金属種Ｍ1とＭ2が下記式（１）中の水素化反応を促進し、酸性担体が下記式（１）中の分子内脱水反応を促進する作用を有するため、レブリン酸からワンポットでＭＴＨＦを製造することができ、多段階合成反応に比べて製造に要するエネルギー、手間、時間、及び試薬を最小限にとどめることができる。
金属触媒の使用量（金属触媒に含まれるＭ1金属換算、２種以上使用する場合はその総量）は、レブリン酸の、例えば０．０１〜３０モル％程度、好ましくは０．１〜１０モル％、特に好ましくは０．５〜５モル％である。金属触媒の使用量が上記範囲を下回るとＭＴＨＦを高収率で得ることが困難となる傾向がある。 The amount of the metal catalyst (M 1 in terms of metal contained in the metal catalyst, if used two or more kinds thereof total) is levulinic acid, for example, about 0.01 to 30 mol%, preferably 0.1 to 10 moles %, Particularly preferably 0.5 to 5 mol%. When the amount of the metal catalyst used is less than the above range, it tends to be difficult to obtain MTHF in a high yield.
反応に使用する水素の供給は、例えば水素雰囲気下で反応を行う方法や、水素ガスをバブリングする方法等により行われる。 Supply of hydrogen used for the reaction is performed by, for example, a method of performing a reaction under a hydrogen atmosphere or a method of bubbling hydrogen gas.
本発明では上記金属触媒を使用するため温和な条件下で速やかに反応を進行させることができ、反応時の水素圧は、例えば、１０ＭＰａ以下（例えば、０．１〜１０ＭＰａ、好ましくは１〜１０ＭＰａ）、好ましくは５ＭＰａ以下（例えば、０．１〜５ＭＰａ、好ましくは１〜５ＭＰａ）である。 In this invention, since the said metal catalyst is used, reaction can be advanced rapidly on mild conditions, The hydrogen pressure at the time of reaction is 10 MPa or less (for example, 0.1-10 MPa, for example, preferably 1-10 MPa) ), Preferably 5 MPa or less (for example, 0.1 to 5 MPa, preferably 1 to 5 MPa).
また、反応温度は、例えば５０〜２００℃、好ましくは１００〜１８０℃、特に好ましくは１１０〜１５０℃、最も好ましくは１１０〜１４０℃である。 Moreover, reaction temperature is 50-200 degreeC, for example, Preferably it is 100-180 degreeC, Most preferably, it is 110-150 degreeC, Most preferably, it is 110-140 degreeC.
反応時間は、例えば１〜４８時間程度、好ましくは５〜３６時間、特に好ましくは１０〜２４時間、最も好ましくは１５〜２４時間であり、反応温度によって適宜調整することができる。例えば、反応温度が低め（例えば１３０℃以下、好ましくは１１０〜１３０℃）の場合は、反応時間を長め（例えば、２０〜２４時間）に設定し、反応温度が高め（例えば１３０℃超、好ましくは１３０℃を超え１５０℃以下）の場合は、反応時間を短め（例えば、８〜１５時間）に設定することでＭＴＨＦを収率良く製造することができる。 The reaction time is, for example, about 1 to 48 hours, preferably 5 to 36 hours, particularly preferably 10 to 24 hours, and most preferably 15 to 24 hours, and can be appropriately adjusted depending on the reaction temperature. For example, when the reaction temperature is low (for example, 130 ° C. or lower, preferably 110 to 130 ° C.), the reaction time is set longer (for example, 20 to 24 hours), and the reaction temperature is increased (for example, more than 130 ° C., preferably Is higher than 130 ° C. and 150 ° C. or lower), MTHF can be produced with good yield by setting the reaction time short (for example, 8 to 15 hours).
本発明では、反応を酸（例えば、トリフルオロメタンスルホン酸、ｐ−トルエンスルホン酸、安息香酸、酢酸等の有機酸；硝酸、リン酸、硫酸等の無機酸；酸性イオン液体等のルイス酸；及びこれらの塩から選択される少なくとも１種）の存在下で行う必要が無く、バッチ式で反応を行う場合の反応系に存在する前記酸の濃度は、例えば反応液全重量の０．５重量％以下程度、好ましくは０．１重量％以下、特に好ましくは０．０１重量％以下である。尚、前記酸の濃度の下限はゼロ重量％である。そのため、耐酸性を有する高価な反応器を使用する必要が無く、反応終了後に酸を中和する処理も必要無い。 In the present invention, the reaction is carried out with an acid (eg, organic acids such as trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzoic acid, acetic acid; inorganic acids such as nitric acid, phosphoric acid, sulfuric acid; Lewis acids such as acidic ionic liquids; and It is not necessary to carry out in the presence of at least one selected from these salts, and the concentration of the acid present in the reaction system when the reaction is carried out batchwise is, for example, 0.5 wt% It is about below, preferably 0.1% by weight or less, particularly preferably 0.01% by weight or less. The lower limit of the acid concentration is zero weight percent. Therefore, it is not necessary to use an expensive reactor having acid resistance, and there is no need to neutralize the acid after completion of the reaction.
反応はバッチ式、セミバッチ式、連続式などの何れの方法で行うこともできる。 The reaction can be carried out by any method such as batch, semi-batch and continuous methods.
反応は液相で行うことが好ましい。すなわち、本発明の反応は液相反応が好ましい。レブリン酸の沸点が高いので、気相で反応を行うと反応生成物が分解し、ＭＴＨＦの収率が低下する傾向がある。 The reaction is preferably carried out in the liquid phase. That is, the reaction of the present invention is preferably a liquid phase reaction. Since the boiling point of levulinic acid is high, when the reaction is carried out in the gas phase, the reaction product is decomposed and the yield of MTHF tends to decrease.
液相で反応を行う場合、溶媒としては、例えば、水、メタノール、エタノール、２−プロパノール、１−ブタノール、１，４−ジオキサン、ＴＨＦ、１，２−ジメトキシエタン、ジエチルエーテル、トルエン、ヘキサン、ドデカン、１，２−ジクロロエタン、ジクロロメタン等を挙げることができる。 When performing the reaction in the liquid phase, examples of the solvent include water, methanol, ethanol, 2-propanol, 1-butanol, 1,4-dioxane, THF, 1,2-dimethoxyethane, diethyl ether, toluene, hexane, Examples include dodecane, 1,2-dichloroethane, and dichloromethane.
溶媒としては、なかでも、水が最も好ましい。すなわち、本発明の反応は水の存在下で行うことが好ましい。溶媒としてメタノール、エタノール、ジエチルエーテルを使用した場合は、副生物の生成量が上昇する傾向があり、２−プロパノール、１，４−ジオキサンを使用した場合は、ＧＶＬの水素化反応速度が低下する傾向がある。 Of these, water is most preferred as the solvent. That is, the reaction of the present invention is preferably performed in the presence of water. When methanol, ethanol, or diethyl ether is used as a solvent, the amount of by-products tends to increase, and when 2-propanol or 1,4-dioxane is used, the hydrogenation rate of GVL decreases. Tend.
溶媒（特に、水）の使用量は、バッチ式で反応させる場合はレブリン酸の初期濃度が例えば０．０１〜１０重量％程度となる範囲が好ましい。 The amount of the solvent (especially water) used is preferably in the range where the initial concentration of levulinic acid is, for example, about 0.01 to 10% by weight when the reaction is carried out batchwise.
反応終了後、反応生成物は、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、カラムクロマトグラフィーなどの分離手段や、これらを組み合わせた分離手段により分離精製できる。 After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.
本発明のＭＴＨＦの製造方法によれば、レブリン酸を効率よく転化して、ＭＴＨＦを選択的且つ高収率で製造することができる。レブリン酸の転化率は、例えば８０％以上、好ましくは９０％以上、特に好ましくは９５％以上である。ＭＴＨＦの選択率は、例えば４５％以上、好ましくは６５％以上、より好ましくは８０％以上、更に好ましくは８５％以上である。また、ＭＴＨＦの収率は、例えば１０％以上、好ましくは２０％以上、より好ましくは３０％以上、特に好ましくは５０％以上、最も好ましくは７０％以上、とりわけ好ましくは８０％以上である。 According to the MTHF production method of the present invention, levulinic acid can be efficiently converted to produce MTHF selectively and in high yield. The conversion of levulinic acid is, for example, 80% or more, preferably 90% or more, particularly preferably 95% or more. The selectivity for MTHF is, for example, 45% or more, preferably 65% or more, more preferably 80% or more, and still more preferably 85% or more. The yield of MTHF is, for example, 10% or more, preferably 20% or more, more preferably 30% or more, particularly preferably 50% or more, most preferably 70% or more, and particularly preferably 80% or more.
以下、実施例により本発明をより具体的に説明するが、本発明はこれらの実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.
実施例１
（金属触媒の調製：共含浸法）
Ｈ2ＰｔＣｌ6 ０．０５ｍＭ水溶液４ｍＬと（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ ２．４ｍｇを水５０ｍＬに溶解して得られた溶液中に、室温（２５℃）条件下で、モルデナイト型ゼオライト（商品名「ＪＲＣ−Ｚ−ＨＭ９０」、ＳｉＯ2／Ａｌ2Ｏ3（モル比）＝９０、触媒学会参照触媒、比表面積：４５０ｍ2／ｇ超）１ｇを４時間浸漬した。浸漬後、減圧下でロータリーエバポレーターを使用して水を留去し、１１０℃の乾燥機で５時間乾燥させ、得られた粉末を空気雰囲気下、マッフル炉を使用し５００℃で３時間焼成して金属触媒（１）［Ｐｔ担持量：５重量％、Ｍｏ担持量：１重量％］を得た。
Example 1
(Preparation of metal catalyst: co-impregnation method)
Mordenite in a solution obtained by dissolving 4 mL of H 2 PtCl 6 0.05 mM aqueous solution and 2.4 mg of (NH 4 ) 6 Mo 7 O 24 · 4H 2 O in 50 mL of water at room temperature (25 ° C.). 1 g of type zeolite (trade name “JRC-Z-HM90”, SiO 2 / Al 2 O 3 (molar ratio) = 90, catalyst catalyst reference catalyst, specific surface area: more than 450 m 2 / g) was immersed for 4 hours. After immersion, water is distilled off using a rotary evaporator under reduced pressure, dried for 5 hours with a dryer at 110 ° C., and the resulting powder is baked for 3 hours at 500 ° C. using a muffle furnace in an air atmosphere. Thus, metal catalyst (1) [Pt loading: 5 wt%, Mo loading: 1 wt%] was obtained.
（ＭＴＨＦの製造）
テフロン（登録商標）製内筒を備えた、５０ｍＬステンレス製オートクレーブに、レブリン酸１ミリモルと金属触媒（１）１００ｍｇ[レブリン酸の２モル％（Ｐｔ金属換算）]、及び水３ｍＬを仕込み、水素圧５ＭＰａの条件下、１５０℃で４時間反応させて反応生成物を得た。ガスクロマトグラフ質量分析計（ＧＣ−ＭＳ）を使用して原料の転化率（conv.［％］）及び各反応生成物の収率（yield［％］）を測定した。
(Production of MTHF)
A 50 mL stainless steel autoclave equipped with a Teflon (registered trademark) inner cylinder was charged with 1 mmol of levulinic acid, 100 mg of metal catalyst (1) [2 mol% of levulinic acid (in terms of Pt metal)], and 3 mL of water, hydrogen Reaction was carried out at 150 ° C. for 4 hours under a pressure of 5 MPa to obtain a reaction product. Using a gas chromatograph mass spectrometer (GC-MS), the conversion rate of raw materials (conv. [%]) And the yield of each reaction product (yield [%]) were measured.
実施例２〜９
Ｍ1とＭ2の組み合わせを下記表１に記載の通りに変更した触媒を使用した以外は実施例１と同様に行った。
The same operation as in Example 1 was performed except that a catalyst in which the combination of M 1 and M 2 was changed as described in Table 1 below was used.
実施例１０〜１４
担体を下記表２に記載の通りに変更した触媒を使用し、下記式（３）に記載の反応条件で反応を行った以外は実施例１と同様に行った。
The same procedure as in Example 1 was carried out except that the catalyst was changed as described in Table 2 below and the reaction was carried out under the reaction conditions described in the following formula (3).
実施例１５〜２１
担体をβ型ゼオライト（商品名「ｚｅｏｌｉｔｅ ｂｅｔａ（Ｈ−ｂｅｔａ）」、ｚｅｏｌｙｓｔ社製、ＳｉＯ2／Ａｌ2Ｏ3（モル比）＝２５）に変更し、金属種ＰｔとＭｏのモル比を下記表３に記載の通りに変更した触媒を使用し、下記式（４）に記載の反応条件で反応を行った以外は実施例１と同様に行った。
The support was changed to β-type zeolite (trade name “zeolite beta (H-beta)”, manufactured by zeolist, SiO 2 / Al 2 O 3 (molar ratio) = 25), and the molar ratio of the metal species Pt and Mo was as follows: The same procedure as in Example 1 was carried out except that the catalyst changed as described in Table 3 was used and the reaction was performed under the reaction conditions described in the following formula (4).
実施例２２〜２５
金属種ＰｔとＭｏのモル比（Ｐｔ：Ｍｏ）を１５：１として、担体への金属種Ｐｔの担持量を下記表４に記載の通りに変更した触媒を使用し、下記式（５）に記載の反応条件で反応を行った以外は実施例１と同様に行った。尚、金属量が一定となるように金属触媒の使用量を調整した。
Using a catalyst in which the molar ratio of metal species Pt to Mo (Pt: Mo) was 15: 1 and the amount of metal species Pt supported on the support was changed as shown in Table 4 below, the following formula (5) The reaction was performed in the same manner as in Example 1 except that the reaction was performed under the described reaction conditions. The amount of metal catalyst used was adjusted so that the amount of metal was constant.
実施例２６〜３２
溶媒を下記表５に記載の通りに変更し、下記式（６）に記載の反応条件で反応を行った以外は実施例１と同様に行った。
The solvent was changed as described in Table 5 below, and the same procedure as in Example 1 was performed except that the reaction was performed under the reaction conditions described in the following formula (6).
実施例３３〜３９
反応温度、反応時間、及び水素圧を下記表６に記載の通りに変更し、下記式（７）に記載の反応条件で反応を行った以外は実施例１と同様に行った。
The reaction temperature, reaction time, and hydrogen pressure were changed as described in Table 6 below, and the reaction was performed in the same manner as in Example 1 except that the reaction was performed under the reaction conditions described in the following formula (7).
実施例４０
下記式（８）に記載の金属触媒（Ｆｒｅｓｈ）、及び反応条件で反応を行った以外は実施例１と同様に行った。
Example 40
It carried out like Example 1 except having reacted with the metal catalyst (Fresh) of following formula (8), and reaction conditions.
実施例４１
実施例４０の反応終了後、遠心分離により金属触媒と反応液を分離し、上澄みを除いた後、残った金属触媒に何も処理を施さず、これを金属触媒（１ｓｔ Ｒｅｕｓｅ）として再使用した以外は実施例４０と同様に行った。
Example 41
After completion of the reaction in Example 40, the metal catalyst and the reaction solution were separated by centrifugation, and after removing the supernatant, no treatment was applied to the remaining metal catalyst, which was reused as a metal catalyst (1st Reuse). Except for this, the same procedure as in Example 40 was performed.
実施例４２
実施例４１の反応終了後、遠心分離により金属触媒と反応液を分離し、上澄みを除いた後、残った金属触媒に何も処理を施さず、これを金属触媒（２ｎｄ Ｒｅｕｓｅ）として再使用した以外は実施例４０と同様に行った。
Example 42
After completion of the reaction of Example 41, the metal catalyst and the reaction solution were separated by centrifugation, and after removing the supernatant, no treatment was performed on the remaining metal catalyst, which was reused as a metal catalyst (2nd Reuse). Except for this, the same procedure as in Example 40 was performed.
実施例４３
実施例４２の反応終了後、遠心分離により金属触媒と反応液を分離し、上澄みを除いた後、残った金属触媒に何も処理を施さず、これを金属触媒（３ｒｄ Ｒｅｕｓｅ）として再使用した以外は実施例４０と同様に行った。
After completion of the reaction in Example 42, the metal catalyst and the reaction solution were separated by centrifugation, and after removing the supernatant, no treatment was performed on the remaining metal catalyst, which was reused as a metal catalyst (3rd Reuse). Except for this, the same procedure as in Example 40 was performed.
実施例４４、比較例１〜２
下記表８に記載の金属触媒、及び下記式（９）に記載の反応条件で反応を行った以外は実施例１と同様に行った。
It carried out similarly to Example 1 except having reacted on the metal catalyst of the following Table 8, and the reaction conditions of the following formula (9).
実施例４５、参考例１〜５
本発明に係るレブリン酸からＭＴＨＦを製造する方法と、非特許文献１〜５に記載のレブリン酸からＭＴＨＦを製造する方法について、使用する触媒、反応温度、水素圧、溶媒、レブリン酸の転化率、及びＭＴＨＦの収率を下記表に記載した。下記表からわかるように、本発明の方法では、参考例１〜５の方法より温和な条件下（低い温度、低い水素圧）で、参考例１〜５の方法と同等の収率でＭＴＨＦを製造することができる。また、参考例１、２、４、５の方法では有機溶媒を使用するため、比例費の増加に伴い製造コストが上昇したり、厳しい排水の排出規制を受ける等の問題が発生するが、本発明の方法では水を溶媒として使用するため、比例費の増加による製造コストの上昇を抑制することができる。また、排水の排出規制を受けることもない。更に、参考例３〜５では酸の存在下で反応を行うが、本発明の方法では酸を必要としない。
Regarding the method for producing MTHF from levulinic acid according to the present invention and the method for producing MTHF from levulinic acid described in Non-Patent Documents 1 to 5, the catalyst used, reaction temperature, hydrogen pressure, solvent, conversion of levulinic acid , And the yield of MTHF are listed in the table below. As can be seen from the table below, in the method of the present invention, MTHF was obtained in a yield equivalent to that of the methods of Reference Examples 1 to 5 under milder conditions (lower temperature and lower hydrogen pressure) than those of Reference Examples 1 to 5. Can be manufactured. In addition, since the organic solvent is used in the methods of Reference Examples 1, 2, 4, and 5, there are problems such as an increase in production cost due to an increase in proportional cost and severe wastewater discharge regulations. Since the method of the invention uses water as a solvent, an increase in production cost due to an increase in proportional cost can be suppressed. In addition, there are no restrictions on wastewater discharge. Further, in Reference Examples 3 to 5, the reaction is performed in the presence of an acid, but the method of the present invention does not require an acid.
Claims (5)
金属触媒：金属種として下記Ｍ1とＭ2が酸性担体に担持されてなる触媒
（Ｍ1）ロジウム、白金、ルテニウム、イリジウム、及びパラジウムからなる群より選択される少なくとも１種の金属
（Ｍ2）バナジウム、モリブデン、タングステン、及びレニウムからなる群より選択される少なくとも１種の金属 The manufacturing method of 2-methyltetrahydrofuran which manufactures 2-methyltetrahydrofuran from levulinic acid in presence of the following metal catalyst.
Metal catalyst: Catalyst in which M 1 and M 2 below are supported on an acidic support as metal species (M 1 ) At least one metal selected from the group consisting of rhodium, platinum, ruthenium, iridium, and palladium (M 2 ) At least one metal selected from the group consisting of vanadium, molybdenum, tungsten, and rhenium
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110479366A (en) * | 2019-08-06 | 2019-11-22 | 南方医科大学 | A kind of catalyst being used to prepare diethyl carbonate |
| CN110479366B (en) * | 2019-08-06 | 2021-06-08 | 南方医科大学 | Catalyst for preparing diethyl carbonate |
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