JP2009242312A - Process for producing 2,5-furandicarboxylic acid - Google Patents
Process for producing 2,5-furandicarboxylic acid Download PDFInfo
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- JP2009242312A JP2009242312A JP2008091762A JP2008091762A JP2009242312A JP 2009242312 A JP2009242312 A JP 2009242312A JP 2008091762 A JP2008091762 A JP 2008091762A JP 2008091762 A JP2008091762 A JP 2008091762A JP 2009242312 A JP2009242312 A JP 2009242312A
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- 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 abstract description 98
- 238000000034 method Methods 0.000 title claims description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000007789 gas Substances 0.000 claims abstract description 57
- 230000001590 oxidative effect Effects 0.000 claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 27
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 25
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 25
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 23
- 238000010521 absorption reaction Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 26
- 239000010941 cobalt Substances 0.000 claims description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 11
- -1 bromine ions Chemical class 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 238000003916 acid precipitation Methods 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 17
- SHNRXUWGUKDPMA-UHFFFAOYSA-N 5-formyl-2-furoic acid Chemical compound OC(=O)C1=CC=C(C=O)O1 SHNRXUWGUKDPMA-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229930091371 Fructose Natural products 0.000 description 5
- 239000005715 Fructose Substances 0.000 description 5
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 150000001649 bromium compounds Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011437 continuous method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000010451 perlite Substances 0.000 description 2
- 235000019362 perlite Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- 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 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZBICJTQZVYWJPB-UHFFFAOYSA-N [Mn].[Co].[Br] Chemical compound [Mn].[Co].[Br] ZBICJTQZVYWJPB-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical class [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
本発明は、植物由来プラスチックの原料、あるいは医薬、農薬の原料として利用価値の高い２，５−フランジカルボン酸の製造方法に関する。 The present invention relates to a method for producing 2,5-furandicarboxylic acid, which is highly useful as a raw material for plant-derived plastics, or as a raw material for pharmaceuticals and agricultural chemicals.
２，５−フランジカルボン酸（ＦＤＣＡ）は、植物に多く含まれるフルクトース（果糖）から合成可能でありながら、ＰＥＴなどプラスチックの原料物質として使用されるテレフタル酸の代替物質となりうるものであり、また、その誘導体は医薬品や農薬としても使用しうる。このため、ＦＤＣＡは、米国エネルギー省（Ｄｅｐａｒｔｍｅｎｔ ｏｆ Ｅｎｅｒｇｙ）が選定したバイオリファイナリーのビルディングブロック材料の１つに選定されている。 2,5-furandicarboxylic acid (FDCA) can be synthesized from fructose (fructose) abundant in plants, and can be an alternative to terephthalic acid used as a raw material for plastics such as PET. The derivatives can also be used as pharmaceuticals and agricultural chemicals. For this reason, FDCA has been selected as one of the biorefinery building block materials selected by the US Department of Energy (Department of Energy).
このＦＤＣＡのフルクトースからの合成は、フルクトースを脱水環化し、５−ヒドロキシメチルフルフラール（５ＨＭＦ）とした後に、５ＨＭＦを酸化することによってＦＤＣＡに誘導する方法が一般的である。 In general, FDCA is synthesized from fructose by dehydrating and cyclizing fructose into 5-hydroxymethylfurfural (5HMF) and then oxidizing 5HMF to FDCA.
５ＨＭＦの酸化方法としては、ＫＭｎＯ４、硝酸、酸化銀などの酸化性固体や、酸素、空気等の酸化性気体など酸化剤を使用した例が報告されている（たとえば非特許文献１参照。)が、経済性、及び環境への影響の点から、空気を酸化剤として使用する方法が優れている。 As an oxidation method of 5HMF, an example using an oxidizing agent such as an oxidizing solid such as KMnO 4 , nitric acid or silver oxide, or an oxidizing gas such as oxygen or air has been reported (for example, see Non-Patent Document 1). However, the method of using air as an oxidizing agent is excellent from the viewpoints of economy and influence on the environment.
空気を酸化剤として使用する例としては特許文献１や非特許文献２に、金属臭素化物、Ｃｏ，Ｍｎ触媒の存在下、酢酸溶媒中７ＭＰａの空気により酸化する例が記載されている。
特許文献１および非特許文献２に記載される方法は、空気を酸化剤として使用する点で他の酸化剤を使用する方法より優れているが、収率は７０ｍｏｌ％に達しておらず、工業的に採用しうる方法とはいえない。また酸化中間体である５−ホルミル−２−フランカルボン酸（ＦＦＣＡ）が残留しており、収率、品質共に満足できる方法ではない。 The methods described in Patent Document 1 and Non-Patent Document 2 are superior to the methods using other oxidizing agents in that air is used as the oxidizing agent, but the yield does not reach 70 mol%, It cannot be said that this method can be adopted. Further, 5-formyl-2-furancarboxylic acid (FFCA), which is an oxidation intermediate, remains, which is not a satisfactory method in terms of yield and quality.
そこで、本発明は、５ＨＭＦを酸化してＦＤＣＡを製造する方法について、工業的に採用しうる高い収率、および好ましくは高い純度で製造する方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method for producing FDCA by oxidizing 5HMF with a high yield that can be industrially employed, and preferably with a high purity.
上記課題を解決すべく、本発明者が鋭意研究した結果、酢酸等を溶媒として５ＨＭＦおよびコバルト−マンガン−臭素系の触媒を含む反応液に、分子状酸素を含む酸化性気体（典型的には空気）を供給して酸化するにあたって、その触媒における金属換算コバルトおよび金属換算マンガンの原子比が特定の範囲（２：１〜４：１）である場合には、反応液に対する酸化性気体の吸収がなくなった、すなわち分子状酸素の吸収終了点に到達した後に、酸化性気体の供給をさらに行って反応液における酸化反応を継続させることにより、収率を工業的に採用しうる７０ｍｏｌ％以上にまで高めることが可能であることを見出した。 As a result of intensive research conducted by the present inventors in order to solve the above problems, an oxidizing gas (typically containing molecular oxygen) is added to a reaction solution containing 5HMF and a cobalt-manganese-bromine catalyst using acetic acid as a solvent. When the atomic ratio of metal-converted cobalt and metal-converted manganese in the catalyst is within a specific range (2: 1 to 4: 1) when oxidizing by supplying air), the oxidizing gas is absorbed into the reaction solution. After reaching the end point of absorption of molecular oxygen, the oxidizing gas is further supplied to continue the oxidation reaction in the reaction solution, whereby the yield can be increased to 70 mol% or more which can be industrially adopted. It was found that it is possible to increase up to.
本発明は係る知見に基づくものであり、コバルト、マンガン、および臭素を含む触媒を含む反応液中で、５−ヒドロキシメチルフルフラールを分子状酸素により酸化する２，５−フランジカルボン酸の製造方法において、触媒における金属換算コバルトおよび金属換算マンガンの原子比が２：１〜４：１であって、分子状酸素を含む酸化性気体を前記反応液に供給しつつ計測した排気ガス（反応器から排出される気体）の酸素濃度（分子状酸素の濃度）に基づいて、反応液に対する分子状酸素の吸収終了点に達したと判定した後に、さらに酸化性気体の供給を行って酸化反応を継続させることを特徴とする２，５−フランジカルボン酸の製造方法である。 The present invention is based on such knowledge, and in a method for producing 2,5-furandicarboxylic acid in which 5-hydroxymethylfurfural is oxidized with molecular oxygen in a reaction solution containing a catalyst containing cobalt, manganese, and bromine. The exhaust gas (exhaust from the reactor) was measured while supplying an oxidizing gas containing molecular oxygen to the reaction solution, the atomic ratio of metal-converted cobalt and metal-converted manganese in the catalyst being 2: 1 to 4: 1 Gas) is determined based on the oxygen concentration (molecular oxygen concentration), and after reaching the absorption end point of molecular oxygen to the reaction solution, an oxidizing gas is further supplied to continue the oxidation reaction. This is a process for producing 2,5-furandicarboxylic acid.
ここで、反応液に添加される触媒が、５−ヒドロキシメチルフルフラール１ｍｏｌに対する金属換算コバルトの比率が０．０１〜０．３グラム原子、かつコバルトおよびマンガンの金属換算総和１グラム原子に対する臭素イオンの比率が０．０５〜２０ｍｏｌであるようにすることが好ましい。 Here, the catalyst added to the reaction solution has a ratio of cobalt equivalent to 0.01 to 0.3 gram atom of metal per 1 mol of 5-hydroxymethylfurfural, and bromine ions of 1 gram atom of the total metal equivalent of cobalt and manganese. The ratio is preferably 0.05 to 20 mol.
また、酸化性気体の酸化により得られた粗ＦＤＣＡをアルカリ金属水酸化物の水溶液に溶解し、次亜塩素酸ナトリウムおよび過酸化水素から選ばれる一種または二種で処理した後、酸析することによって、さらに高純度のＦＤＣＡを得ることが可能である。 In addition, the crude FDCA obtained by oxidizing the oxidizing gas is dissolved in an alkali metal hydroxide aqueous solution, treated with one or two kinds selected from sodium hypochlorite and hydrogen peroxide, and then acidified. Thus, it is possible to obtain FDCA with higher purity.
本発明によれば、酸化反応の収率を、工業的に採用可能なレベルである７０ｍｏｌ％以上に高めることが可能である。また、酸化反応による生成した粗ＦＤＣＡを効率的に高純度化することも可能である。 According to the present invention, the yield of the oxidation reaction can be increased to 70 mol% or more, which is a level that can be industrially adopted. It is also possible to efficiently purify the crude FDCA produced by the oxidation reaction.
以下、本発明のＦＤＣＡの製造方法について詳細に説明する。
１．反応液
（１）５ＨＭＦ
出発原料として使用する５ＨＭＦの製法には制限は無い。セルロース、デンプンなどの六糖類、ショ糖、マルトース、セロビオース、ラクトースなどの少糖類、フルクトース、グルコースなどの単糖類の脱水反応によって得られる植物由来品を使用してもよい。
Hereafter, the manufacturing method of FDCA of this invention is demonstrated in detail.
1. Reaction solution (1) 5HMF
There is no restriction | limiting in the manufacturing method of 5HMF used as a starting material. Plant-derived products obtained by dehydration reaction of hexasaccharides such as cellulose and starch, oligosaccharides such as sucrose, maltose, cellobiose and lactose, and monosaccharides such as fructose and glucose may be used.
（２）溶媒
本発明に係る酸化反応のための反応液の溶媒としては、従来技術に係る酸化反応の場合と同様に、酢酸、プロピオン酸または酢酸/無水酢酸の混合溶媒を使用する。この溶媒は少量の水を含有していてもよい。溶媒の使用量は重量比で出発原料（５ＨＭＦ）の３〜２０倍とするのが好ましい。
(2) Solvent As the solvent of the reaction solution for the oxidation reaction according to the present invention, acetic acid, propionic acid or a mixed solvent of acetic acid / acetic anhydride is used as in the case of the oxidation reaction according to the prior art. This solvent may contain a small amount of water. The amount of solvent used is preferably 3 to 20 times that of the starting material (5HMF) by weight.
（３）触媒
本発明では、酸化触媒としてコバルト触媒、マンガン触媒および臭素化合物からなる触媒系を用いる。コバルトおよびマンガン触媒としては、反応温度において反応溶媒に溶解可能なものであれば特に制限されない。
(3) Catalyst In the present invention, a catalyst system comprising a cobalt catalyst, a manganese catalyst and a bromine compound is used as the oxidation catalyst. The cobalt and manganese catalysts are not particularly limited as long as they are soluble in the reaction solvent at the reaction temperature.
例えば、コバルトでは、その無機酸（例えば、臭素化物、炭酸塩等）および有機酸塩（例えば、酢酸塩、プロピオン酸塩等）からなる群から選ばれる一種または二種以上を使用すればよい。同様にマンガンも、その無機酸（例えば、臭素化物、炭酸塩等）および有機酸塩（例えば、酢酸塩、プロピオン酸塩等）からなる群から選ばれる一種または二種以上を使用すればよい。 For example, for cobalt, one or more selected from the group consisting of inorganic acids (for example, bromides, carbonates, etc.) and organic acid salts (for example, acetates, propionates, etc.) may be used. Similarly, manganese may be used alone or in combination of two or more selected from the group consisting of inorganic acids (for example, bromides, carbonates, etc.) and organic acid salts (for example, acetates, propionates, etc.).
臭素化合物としては、反応温度において反応溶媒に溶解して臭素イオンを供給できるものであればよく、具体例としては、臭素、臭化水素、アルカリ金属およびアンモニウムの臭化物(例、臭化カリウム、臭化アンモニウム)、臭化コバルトなどの無機化合物、ならびに臭化ベンジル、ブロモエタンなどの有機臭化物が挙げられる。なお、臭化コバルトはコバルト触媒と臭化化合物の両方を兼ねる。 The bromine compound is not particularly limited as long as it can be dissolved in the reaction solvent at the reaction temperature to supply bromine ions. Specific examples include bromine, hydrogen bromide, alkali metal and ammonium bromides (eg, potassium bromide, odors). Inorganic compounds such as ammonium chloride) and cobalt bromide, and organic bromides such as benzyl bromide and bromoethane. Cobalt bromide serves as both a cobalt catalyst and a bromide compound.
触媒を構成する各物質の含有量に関し、本発明では、コバルト触媒およびマンガン触媒におけるコバルト金属およびマンガン金属の原子比を２：１〜４：１とする。コバルト金属のグラム原子数がマンガン金属のグラム原子数に対して２倍未満となると、収率が低下する傾向を示すようになる。一方、コバルトがマンガンに対して多くなっても収率には影響しないものの、コバルトは比較的高価であるから、経済的観点での不利益が大きくなる。 Regarding the content of each substance constituting the catalyst, in the present invention, the atomic ratio of cobalt metal and manganese metal in the cobalt catalyst and the manganese catalyst is 2: 1 to 4: 1. When the number of gram atoms of cobalt metal is less than twice the number of gram atoms of manganese metal, the yield tends to decrease. On the other hand, even if cobalt increases with respect to manganese, it does not affect the yield, but since cobalt is relatively expensive, the disadvantage from an economic viewpoint becomes large.
さらに、次の範囲とすると、ＦＤＣＡを高い収率で得ることが安定的に実現される。
まず、原料物質（５ＨＭＦ）１ｍｏｌに対するコバルト触媒（コバルト金属換算）の比率を０．０１〜０．３グラム原子とすることが好ましく、０．０３〜０．２グラム原子とすれば特に好ましい。この範囲から過剰に小さくなると、収率が低下する傾向を示す。なお、コバルト触媒の使用量を酸化反応の溶媒に対して規定すれば、コバルト金属換算で０．０８重量%以上とすることが好ましい。より好ましくは０．１４〜０．５４重量％である。
Furthermore, when it is set as the following range, obtaining FDCA with a high yield is stably realized.
First, the ratio of the cobalt catalyst (in terms of cobalt metal) to 1 mol of the raw material (5HMF) is preferably 0.01 to 0.3 gram atom, and particularly preferably 0.03 to 0.2 gram atom. When it becomes excessively small from this range, the yield tends to decrease. In addition, if the usage-amount of a cobalt catalyst is prescribed | regulated with respect to the solvent of an oxidation reaction, it is preferable to set it as 0.08 weight% or more in conversion of a cobalt metal. More preferably, it is 0.14-0.54 weight%.
また、コバルト触媒およびマンガン触媒（いずれも金属換算）の総和の１グラム原子に対する臭素イオンの比率を、０．０５〜２０ｍｏｌとすることが好ましく、０．１〜５ｍｏｌとすれば特に好ましい。なお、臭素イオン量をコバルト触媒量に対して規定すれば、コバルト金属１グラム原子に対して臭素イオン量は０．２〜２．０ｍｏｌとすることが好ましい。 Moreover, it is preferable that the ratio of the bromine ion with respect to 1 gram atom of the sum total of a cobalt catalyst and a manganese catalyst (both metal conversion) shall be 0.05-20 mol, and it is especially preferable if it shall be 0.1-5 mol. If the bromine ion amount is defined with respect to the cobalt catalyst amount, the bromine ion amount is preferably 0.2 to 2.0 mol with respect to 1 gram atom of cobalt metal.
２．酸化反応
（１）概要
本発明に係る製造方法では、上記の反応液に酸化性気体を供給して、原料物質である５ＨＭＦを酸化することによりＦＤＣＡを製造する。この液相での空気酸化反応により５ＨＭＦのアルコール部位（ＡｒＣＨ２ＯＨ）がアルデヒド（ＡｒＣＨＯ）を経緯してカルボン酸（ＡｒＣＯＯＨ）に変換され、アルデヒド部位もカルボン酸に変換されたＦＤＣＡが生成する。
2. Oxidation reaction (1) Outline In the production method according to the present invention, an oxidizing gas is supplied to the reaction solution, and 5HMF as a raw material is oxidized to produce FDCA. By this air oxidation reaction in the liquid phase, the alcohol part (ArCH 2 OH) of 5HMF is converted into carboxylic acid (ArCOOH) through aldehyde (ArCHO), and FDCA in which the aldehyde part is also converted into carboxylic acid is generated.
本発明に係る製造方法では、分子状酸素を含む酸化性気体を供給しつつ、排気ガスの酸素濃度を計測し反応液に対する分子状酸素の吸収終了点に達したと判定した後に、さらに酸化性気体の供給を行って酸化反応を継続させることで収率を工業的に採用しうる７０ｍｏｌ％以上にまで高めることを安定的に実現する。 In the production method according to the present invention, the oxygen concentration of the exhaust gas is measured while supplying an oxidizing gas containing molecular oxygen, and after determining that the molecular oxygen absorption end point for the reaction solution has been reached, the oxidizing method is further increased. By continuously supplying the gas and continuing the oxidation reaction, the yield can be stably increased to 70 mol% or more which can be industrially adopted.
（２）酸化性気体
酸化性気体とは、原料物質である５ＨＭＦを酸化することができる分子状酸素を含む気体であり、最も典型的には空気が例示される。
(2) Oxidizing gas The oxidizing gas is a gas containing molecular oxygen that can oxidize 5HMF, which is a raw material, and most typically air.
ここで、酸化性気体に含まれる分子状酸素の濃度（酸素濃度）は、たとえば実験室レベルなどにおいて、オートクレーブを用いて爆発の危険性を低下させた状態で酸化する場合には、約２１体積％の酸素を含む空気をそのまま用いてもよいし、純酸素のように酸素濃度をさらに高めて酸化させてもよい。一方、工業的には、排気ガスの酸素濃度が爆発限界を超えない、すなわち１１体積％未満となるように、窒素などいわゆる不活性気体によって空気を希釈して酸化性気体としてもよい。 Here, the molecular oxygen concentration (oxygen concentration) contained in the oxidizing gas is, for example, about 21 volumes in the laboratory level or the like when oxidation is performed using an autoclave while reducing the risk of explosion. % Of oxygen-containing air may be used as it is, or may be oxidized by further increasing the oxygen concentration like pure oxygen. On the other hand, industrially, air may be diluted with a so-called inert gas such as nitrogen to form an oxidizing gas so that the oxygen concentration of the exhaust gas does not exceed the explosion limit, that is, less than 11% by volume.
（３）酸化性気体の供給方法、圧力、流量
酸化性気体の供給方法は、所定の圧力・流量で供給されることが実現されれば、特に制限されない。典型的には、空気と希釈用不活性ガス（窒素、アルゴンなど）とを公知の混合器により混合し、酸素濃度が制御された混合ガスとして所定圧力および／または所定流量で反応器に供給する。
(3) Oxidizing gas supply method, pressure, and flow rate The oxidizing gas supply method is not particularly limited as long as it can be supplied at a predetermined pressure and flow rate. Typically, air and an inert gas for dilution (nitrogen, argon, etc.) are mixed by a known mixer and supplied to the reactor as a mixed gas with a controlled oxygen concentration at a predetermined pressure and / or a predetermined flow rate. .
酸化性気体の圧力は、反応溶媒が反応温度において液相を保つことができるのであれば、高ければ高いほど反応性が高まるため好ましい。しかしながら、圧力が過剰に高い場合には、機密性確保のための設備投資が大きくなってしまう。また、反応前後の準備時間が長くなる場合が多いため、生産性の低下を招く可能性が高まる。これらの観点から、酸化性気体の圧力は、１〜４０ｋｇ／ｃｍ２とすることが好ましく、１０〜３０ｋｇ／ｃｍ２(いずれもゲージ圧)程度とすれば特に好ましい。 As long as the pressure of the oxidizing gas can maintain the liquid phase at the reaction temperature, the higher the pressure of the oxidizing gas, the higher the reactivity, which is preferable. However, if the pressure is excessively high, capital investment for securing confidentiality will increase. In addition, since the preparation time before and after the reaction often becomes long, the possibility of causing a decrease in productivity is increased. From these viewpoints, the pressure of the oxidizing gas is preferably in a 1~40kg / cm 2, particularly preferred if the degree (gauge pressure both) 10~30kg / cm 2.
酸化性気体の流量は、大きければ大きいほど反応性は高まるものの、流量が過剰に大きい場合には供給のための設備投資が大きくなる上に、排気ガス量も多くなるため、生産性の低下を招く。したがって、酸化性気体の流量は、仕込みの５ＨＭＦ１ｍｏｌ当たり１〜２０Ｌ／分とすることが好ましく、２〜１０Ｌ／分とすれば特に好ましい。 As the flow rate of the oxidizing gas increases, the reactivity increases. However, if the flow rate is excessively large, the capital investment for supply increases and the amount of exhaust gas also increases. Invite. Therefore, the flow rate of the oxidizing gas is preferably 1 to 20 L / min per 1 mol of 5HMF charged, and particularly preferably 2 to 10 L / min.
（４）反応形式
酸化反応は、回分式、半連続式、および連続式のいずれの方式で実施してもよい。回分式は、原料物質（５ＨＭＦ）および触媒の全量を反応器に予め装入しておき、酸化性気体を反応液に通気して酸化反応を行い、反応終了後に反応液を一度に回収する方法である。
(4) Reaction format The oxidation reaction may be carried out by any of batch, semi-continuous and continuous methods. The batch method is a method in which the raw material (5HMF) and the total amount of the catalyst are charged in the reactor in advance, an oxidizing gas is passed through the reaction solution to carry out the oxidation reaction, and the reaction solution is recovered at once after the reaction is completed. It is.
半連続式は、例えば、触媒の全量を反応器に装入し、原料物質と酸化性気体を連続的に反応器に供給しながら酸化反応を行い、反応終了後に反応液を一度に回収する方法である。 The semi-continuous method is, for example, a method in which the entire amount of the catalyst is charged into the reactor, the oxidation reaction is performed while continuously supplying the raw material and oxidizing gas to the reactor, and the reaction solution is recovered at once after the reaction is completed. It is.
連続式は、原料物質、触媒および酸化性気体のすべてを連続的に反応器に供給しながら酸化反応を行い、反応液を連続的に回収する方法である。
工業的実施においては、連続式または半連続式が操業効率の点から好ましい。
The continuous method is a method in which the reaction solution is continuously recovered by performing an oxidation reaction while continuously supplying all of the raw material, catalyst and oxidizing gas to the reactor.
In industrial implementation, a continuous type or a semi-continuous type is preferable from the viewpoint of operation efficiency.
（５）反応温度、時間
本発明に係る酸化反応は９０〜１５０℃の範囲の温度で実施することが好ましく、９０〜１３０℃とすれば特に好ましい。また、反応開始の１時間または１時間半を９０℃に保ち、その後１３０℃に昇温するといった具合に反応温度を多段とする制御を行ってもよい。
(5) Reaction temperature and time The oxidation reaction according to the present invention is preferably carried out at a temperature in the range of 90 to 150 ° C, particularly preferably 90 to 130 ° C. In addition, the reaction temperature may be controlled in multiple stages such that the reaction start is kept at 90 ° C. for 1 hour or an hour and a half and then raised to 130 ° C.
酸化反応時間は温度、圧力、触媒組成等の条件により適宜設定され、通常は３〜６時間程度である。
（６）排気ガスの酸素濃度計測
本発明に係る酸化反応では、上記のように酸化性気体が所定の流量で反応器に供給されるため、反応器から排出されるガス（排気ガス）の酸素濃度は、反応器内での酸化反応の進行状況を図るためにもっとも適切なパラメータの一つである。本発明に係る酸化反応は、液相にある原料物質（５ＨＭＦ）が液相にある触媒を用いて気相にある分子状酸素と反応するものであるから、分子状酸素の溶媒への溶解度が反応の進みやすさに大きく影響する。しかしながら、この酸素の溶解度は反応溶媒、温度、圧力、触媒などの影響を受けやすいため、必ずしも制御が容易でない。そこで、本発明に係る製造方法では、排気ガスの酸素濃度を計測し、その結果から供給された分子状酸素がどの程度吸収されたかの情報を得て、反応の進行程度を把握することとしている。この酸素濃度の計測は公知の方法により行うことができ、たとえば自動酸素濃度分析装置を用いて、連続的または定期的に計測すればよい。
The oxidation reaction time is appropriately set depending on conditions such as temperature, pressure, and catalyst composition, and is usually about 3 to 6 hours.
(6) Oxygen concentration measurement of exhaust gas In the oxidation reaction according to the present invention, since the oxidizing gas is supplied to the reactor at a predetermined flow rate as described above, oxygen in the gas (exhaust gas) discharged from the reactor The concentration is one of the most appropriate parameters for the progress of the oxidation reaction in the reactor. In the oxidation reaction according to the present invention, since the source material (5HMF) in the liquid phase reacts with molecular oxygen in the gas phase using the catalyst in the liquid phase, the solubility of molecular oxygen in the solvent is high. This greatly affects the progress of the reaction. However, since the solubility of oxygen is easily affected by the reaction solvent, temperature, pressure, catalyst, etc., it is not always easy to control. Therefore, in the production method according to the present invention, the oxygen concentration of the exhaust gas is measured, information on how much molecular oxygen supplied has been absorbed is obtained from the result, and the progress of the reaction is grasped. This oxygen concentration can be measured by a known method. For example, the oxygen concentration may be measured continuously or periodically using an automatic oxygen concentration analyzer.
さらに、本発明に係る製造方法では、この計測の結果に基づいて、分子状酸素が反応液に吸収されなくなった吸収終了点に達したか否かを判定する。
吸収終了点とは分子状酸素が反応液に吸収されなくなったときである。分子状酸素が反応液に吸収されている場合には、供給された酸化性気体の酸素濃度（供給酸素濃度）よりも排気ガスの酸素濃度（排気酸素濃度）の方が低くなっているが、分子状酸素が吸収されなくなると究極的には供給酸素濃度と排気酸素濃度とは同一の値となるため、この同一となったときが原理的な吸収終了点である。ただし、実務上は、計測誤差や計測時間遅れなどを考慮して、供給酸素濃度と排気酸素濃度との差が所定の数値以内になったときに吸収終了点に到達したと判定してもよい。この場合の例として、供給する空気（酸素濃度が２１体積％）であるときに差を１％に設定して、吸収終了点の排気酸素濃度を２０体積％とすることが挙げられる。
Furthermore, in the manufacturing method according to the present invention, based on the result of this measurement, it is determined whether or not the molecular oxygen has reached the absorption end point at which it is no longer absorbed by the reaction solution.
The absorption end point is when molecular oxygen is no longer absorbed by the reaction solution. When molecular oxygen is absorbed in the reaction solution, the oxygen concentration of the exhaust gas (exhaust oxygen concentration) is lower than the oxygen concentration of the supplied oxidizing gas (supply oxygen concentration). When molecular oxygen is no longer absorbed, the supply oxygen concentration and the exhaust oxygen concentration ultimately become the same value, and when this is the same, the fundamental absorption end point. However, in practice, it may be determined that the absorption end point has been reached when the difference between the supply oxygen concentration and the exhaust oxygen concentration is within a predetermined value in consideration of measurement errors and measurement time delays. . As an example in this case, it is possible to set the difference to 1% when supplying air (oxygen concentration is 21% by volume) and to set the exhaust oxygen concentration at the end of absorption to 20% by volume.
（７）ポストオキシデーション
本発明に係る製造方法は、反応液に対する酸化性気体の吸収がなくなった吸収終了点に到達したと判定した後に、酸化性気体の供給をさらに行って、反応液における酸化反応を継続させる（ポストオキシデーション）。
(7) Post-oxidation In the manufacturing method according to the present invention, after determining that the absorption end point at which the absorption of the oxidizing gas with respect to the reaction solution has ended is reached, the oxidizing gas is further supplied to oxidize the reaction solution. The reaction is continued (post oxidation).
このポストオキシデーションにおいて供給する酸化性気体の条件（酸素濃度、流量など）は、吸収終了点到達前の供給条件と同一でもよいし、異なっていてもよい。その他の条件（温度、圧力など）も吸収終了点到達前の供給条件と同一でもよいし、異なっていてもよい。ポストオキシデーションの時間はその条件により適宜設定されるべきものであるが、０．５〜２時間程度が一般的であり、最も典型的には１時間である。 The conditions (oxidation concentration, flow rate, etc.) of the oxidizing gas supplied in this post-oxidation may be the same as or different from the supply conditions before reaching the absorption end point. Other conditions (temperature, pressure, etc.) may be the same as or different from the supply conditions before reaching the absorption end point. The post-oxidation time should be appropriately set according to the conditions, but is generally about 0.5 to 2 hours, most typically 1 hour.
なお、上記の回分式および半連続式ではこのポストオキシデーションを追加することは容易である。連続式においても、原料物質および触媒の供給を一時的に停止し、酸化性気体の供給のみを継続することによってポストオキシデーションを行うようにすればよい。 In addition, it is easy to add this post-oxidation in said batch type and semi-continuous type. Even in the continuous type, post-oxidation may be performed by temporarily stopping the supply of the raw material and the catalyst and continuing the supply of the oxidizing gas.
３．酸化剤による処理
本発明に係る製造方法は、好適態様として、上記のポストオキシデーションを含む５ＨＭＦの液相での酸化反応により得られたＦＤＣＡ（以下「粗ＦＤＣＡ」という。）を、酸化剤によって処理することにより、粗ＦＤＣＡの純度を高める。
3. Treatment with Oxidizing Agent As a preferred embodiment of the production method according to the present invention, FDCA (hereinafter referred to as “crude FDCA”) obtained by an oxidation reaction in the liquid phase of 5HMF including the post-oxidation is used with an oxidizing agent. By processing, the purity of the crude FDCA is increased.
前述のように、本発明に係る酸化反応では、原料の５ＨＭＦはそのヒドロキシメチル基およびアルデヒド基のそれぞれが酸化されてＦＤＣＡとなるが、その反応中間体の一つとして、ヒドロキシメチル基だけがカルボン酸基まで酸化された５−ホルミル−２−フランカルボン酸（ＦＦＣＡ）が形成される。上記の酸化反応により得られたＦＤＣＡを固液分離法(例、濾過、遠心分離、沈降)により溶媒から単離すると、得られた粗ＦＤＣＡには０．１〜２０重量％のＦＦＣＡが含まれている。 As described above, in the oxidation reaction according to the present invention, 5HMF as a raw material is oxidized to FDCA by oxidizing each of its hydroxymethyl group and aldehyde group. However, as one of the reaction intermediates, only hydroxymethyl group is carboxylic acid. 5-Formyl-2-furancarboxylic acid (FFCA) oxidized to the acid group is formed. When the FDCA obtained by the above oxidation reaction is isolated from a solvent by a solid-liquid separation method (eg, filtration, centrifugation, sedimentation), the obtained crude FDCA contains 0.1 to 20% by weight of FFCA. ing.
そこで、酸化剤、典型的には次亜塩素酸ナトリウムおよび／または過酸化水素を粗ＦＤＣＡと次のような方法で反応させることにより、残留するＦＦＣＡがＦＤＣＡに変換し、粗ＦＤＣＡの純度を高めることが実現される。 Therefore, by reacting an oxidizing agent, typically sodium hypochlorite and / or hydrogen peroxide, with the crude FDCA in the following manner, the remaining FFCA is converted to FDCA and the purity of the crude FDCA is increased. Is realized.
まず、空気酸化で得られたＦＦＣＡを含有する粗ＦＤＣＡを、アルカリ金属水酸化物の水溶液に溶解させる。使用するアルカリ金属水酸化物としては経済性の観点で水酸化ナトリウムが好ましい。アルカリ金属水酸化物の量は溶解させるＦＦＣＡに対して２倍以上のモル数であればよい。アルカリ金属水酸化物の水溶液濃度は操作性の面から２〜１０重量％とすることが好ましい。 First, crude FDCA containing FFCA obtained by air oxidation is dissolved in an aqueous solution of an alkali metal hydroxide. As the alkali metal hydroxide to be used, sodium hydroxide is preferable from the viewpoint of economy. The amount of the alkali metal hydroxide may be at least twice the number of moles of FFCA to be dissolved. The aqueous solution concentration of the alkali metal hydroxide is preferably 2 to 10% by weight from the viewpoint of operability.
なお、アルカリ金属水酸化物の水溶液に溶解した時点で不溶分がある場合には濾過して除いても良い。
次に、この粗ＦＤＣＡを含むアルカリ金属水酸化物の水溶液に次亜塩素酸ナトリウムおよび／または過酸化水素を添加する。添加する次亜塩素酸ナトリウムおよび／または過酸化水素の濃度に制限は無い。市販品をそのまま使用でき、場合によっては希釈して使用することも可能である。次亜塩素酸ナトリウムおよび／または過酸化水素水の添加量は、粗ＦＤＣＡ中に残留するＦＦＣＡに対してモル数換算で等量以上とすればよい。好ましくはモル数換算で２〜１０倍である。反応温度は２０〜８０℃の範囲で実施できる。
反応時間は反応温度や使用する酸化剤の量により変わるが通常０．５〜１０時間である。
In addition, when there exists an insoluble content at the time of melt | dissolving in the aqueous solution of an alkali metal hydroxide, you may filter and remove.
Next, sodium hypochlorite and / or hydrogen peroxide is added to the alkali metal hydroxide aqueous solution containing the crude FDCA. There is no restriction | limiting in the density | concentration of the sodium hypochlorite and / or hydrogen peroxide to add. Commercially available products can be used as they are, and in some cases they can be used after dilution. The amount of sodium hypochlorite and / or hydrogen peroxide solution added may be equal to or greater than the equivalent amount in terms of moles with respect to FFCA remaining in the crude FDCA. Preferably, it is 2 to 10 times in terms of the number of moles. Reaction temperature can be implemented in the range of 20-80 degreeC.
The reaction time varies depending on the reaction temperature and the amount of oxidizing agent used, but is usually 0.5 to 10 hours.
残存するＦＦＣＡをＦＤＣＡに酸化した後、酸析を行う。使用する酸の種類やその濃度には制限は無く、公知の方法にしたがって行えばよい。こうして着色の少ない高純度のＦＤＣＡが得られるが、必要に応じて水で再結晶を行えば、アルカリ金属の除去も可能である。 After remaining FFCA is oxidized to FDCA, acid precipitation is performed. There is no restriction | limiting in the kind of acid to be used, and its density | concentration, What is necessary is just to follow according to a well-known method. In this way, high-purity FDCA with little coloration can be obtained, but alkali metal can be removed by recrystallization with water as necessary.
以下に実施例、比較例によって本発明をより具体的に説明をするが、これらの例により本発明は何ら制限されるものではない。
（比較例１）
攪拌機、ガス吹込み管、還流冷却器付き排ガス抜出し管、原料導入管、および温度計を取り付けた内容積５００ｍｌのチタン製オートクレーブに、純度９８．０重量％の５−ヒドロキシメチルフルフラール２５ｇ、酢酸２２５ｇ、酢酸コバルト４水和物１．４６ｇ、酢酸マンガン４水和物１．３９ｇ、および臭化カリウム０．６７ｇを仕込んだ。このときの、コバルト化合物のコバルト金属換算グラム原子数：マンガン化合物のマンガン金属換算グラム原子数：臭素イオンモル数（以下「触媒モル比」という。）は１：１：１であった。
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
(Comparative Example 1)
A titanium autoclave having an internal volume of 500 ml equipped with a stirrer, a gas blowing pipe, an exhaust gas extraction pipe with a reflux condenser, a raw material introduction pipe, and a thermometer, 25 g of 5-hydroxymethylfurfural with a purity of 98.0 wt% and 225 g of acetic acid. , 1.46 g of cobalt acetate tetrahydrate, 1.39 g of manganese acetate tetrahydrate, and 0.67 g of potassium bromide were charged. Cobalt metal conversion gram atom number of the cobalt compound at this time: Manganese metal conversion gram atom number of the manganese compound: Bromine ion mole number (hereinafter referred to as “catalyst molar ratio”) was 1: 1: 1.
オートクレーブ内雰囲気を窒素で置換した後、攪拌下に加熱して１２０℃まで昇温させてから、排ガス流量が１．０Ｌ／分となるようにガス吹込み管を通じて空気を導入し始め、反応系を温度１２０℃、圧力３．０ＭＰａに保ちながら空気の供給を継続した。こうして反応させながら排気ガスの酸素濃度を計測したところ、排気ガスの酸素濃度は約１体積％であった。 After substituting the atmosphere in the autoclave with nitrogen, the mixture was heated to 120 ° C. with stirring, and then air was introduced through the gas blowing tube so that the exhaust gas flow rate was 1.0 L / min. Was maintained at a temperature of 120 ° C and a pressure of 3.0 MPa. When the oxygen concentration of the exhaust gas was measured while reacting in this way, the oxygen concentration of the exhaust gas was about 1% by volume.
１時間経過後、排気ガスの酸素濃度が５体積％となったため、空気の供給は維持しつつ、オートクレーブ内の温度を１５０℃に昇温し２時間反応を継続すると排気ガスの酸素濃度が２０体積％に達した。この時点から更に１時間空気の供給を行い、その後、空気の導入を停止し、オートクレーブを冷却した。 After 1 hour, the oxygen concentration of the exhaust gas became 5% by volume. Therefore, when the temperature inside the autoclave was raised to 150 ° C. and the reaction was continued for 2 hours while maintaining the supply of air, the oxygen concentration of the exhaust gas was 20 Reached volume%. From this point, air was supplied for another hour, after which the introduction of air was stopped and the autoclave was cooled.
オートクレーブの冷却後、内容物を取り出して結晶を濾別し、２，５−フランジカルボン酸を含むケーキと濾液とを得た。得られたケーキを同体積の酢酸で洗浄した後、真空乾燥し、淡褐色の２，５−フランジカルボン酸２２．４ｇを得た。以下に示す装置および測定条件で高速液体クロマトグラフィー（ＨＰＬＣ）により分析したところ、ＬＣ純度は８７．５重量％であり、収率は６４．８ｍｏｌ％であった。また、５−ホルミル−２−フランカルボン酸が２．９９重量％ケーキ内に残留した。 After cooling the autoclave, the contents were taken out and the crystals were separated by filtration to obtain a cake containing 2,5-furandicarboxylic acid and a filtrate. The obtained cake was washed with the same volume of acetic acid and then vacuum-dried to obtain 22.4 g of light brown 2,5-furandicarboxylic acid. When analyzed by high performance liquid chromatography (HPLC) with the following apparatus and measurement conditions, the LC purity was 87.5 wt% and the yield was 64.8 mol%. In addition, 5-formyl-2-furancarboxylic acid remained in the 2.99 wt% cake.
分析機器：高速液体クロマトグラフィー
カラム：昭和電工（株）製 Ｓｈｏｄｅｘ ＳｕｇａｒＳＨ１００１１
検出器：ＵＶ（２８４ｎｍ）
溶離液：３ｍＭ過塩素酸水溶液
流量：０．６ｍＬ／分 （０〜２０分）、１．４ｍＬ／分 （２０〜３５分）
内部標準物質：フタル酸
Analytical instrument: High performance liquid chromatography Column: Shodex Sugar SH10011 manufactured by Showa Denko K.K.
Detector: UV (284 nm)
Eluent: 3 mM perchloric acid aqueous solution Flow rate: 0.6 mL / min (0-20 min), 1.4 mL / min (20-35 min)
Internal standard: phthalic acid
（実施例１）
比較例１において酢酸コバルト４水和物の仕込量を２．９２ｇにし、触媒モル比を２：１：１にした以外は同様の操作を行い、淡紫色の２，５−フランジカルボン酸２６．２ｇを得た。そのＬＣ純度は８９．１重量％であり、収率は７７．１ｍｏｌ％であった。また、５−ホルミル−２−フランカルボン酸が４．０１重量％ケーキ内に残留した。
Example 1
The same procedure as in Comparative Example 1 was carried out except that the amount of cobalt acetate tetrahydrate charged was 2.92 g and the catalyst molar ratio was 2: 1: 1. 2 g was obtained. Its LC purity was 89.1 wt% and the yield was 77.1 mol%. In addition, 5-formyl-2-furancarboxylic acid remained in the 4.01 wt% cake.
（実施例２）
実施例１において酢酸コバルト４水和物の仕込み量を５．８４ｇにし、触媒モル比を４：１：１にした以外は同様の操作を行い、淡紫色の２，５−フランジカルボン酸２７．５ｇを得た。そのＬＣ純度は８５．８重量％であり、収率は７７．７ｍｏｌ％であった。また、５−ホルミル−２−フランカルボン酸が３．６６重量％ケーキ内に残留した。
(Example 2)
The same procedure as in Example 1 was carried out except that the amount of cobalt acetate tetrahydrate charged was 5.84 g and the catalyst molar ratio was 4: 1: 1. 5 g was obtained. Its LC purity was 85.8 wt% and the yield was 77.7 mol%. In addition, 5-formyl-2-furancarboxylic acid remained in the 3.66 wt% cake.
（実施例３）
実施例１において反応温度を９０℃として１．５時間反応させた後に、１３０℃で反応を２時間継続し酸素の吸収がほぼ無くなった時点から更に１時間反応を継続した以外は同様の操作を行い、淡紫色の２，５−フランジカルボン酸２６．２ｇを得た。そのＬＣ純度は９０．２重量％であり、収率は７６．７ｍｏｌ％であった。また、５−ホルミル−２−フランカルボン酸が６．５４重量％ケーキ内に残留した。
(Example 3)
In Example 1, the reaction temperature was 90 ° C. and the reaction was carried out for 1.5 hours, then the reaction was continued at 130 ° C. for 2 hours, and the reaction was further continued for 1 hour from the point where oxygen absorption was almost lost. 26.2 g of pale purple 2,5-furandicarboxylic acid was obtained. Its LC purity was 90.2 wt% and the yield was 76.7 mol%. In addition, 5-formyl-2-furancarboxylic acid remained in the 6.54% by weight cake.
（実施例４）
攪拌機、温度計を取り付けた内容積５００ｍＬのガラス製３つ口フラスコに、純度９７重量％の水酸化ナトリウム１１．５ｇおよび水３００ｇを仕込んだ。
Example 4
11.5 g of sodium hydroxide having a purity of 97% by weight and 300 g of water were charged into a 500-mL glass three-necked flask equipped with a stirrer and a thermometer.
実施例２で得られた２，５−フランジカルボン酸２０ｇをその３つ口フラスコに添加し、撹拌下、反応系を温度２５℃の状態で約１時間反応を継続した。
得られたフラスコ内容物についてパーライトを用いて濾過を行い、固体および濾液を得た。得られた濾液を攪拌機、還流冷却器、滴下ロート、および温度計を取り付けた内容積５００ｍＬのガラス製４つ口フラスコに仕込んだ。
20 g of 2,5-furandicarboxylic acid obtained in Example 2 was added to the three-necked flask, and the reaction was continued for about 1 hour at 25 ° C. with stirring.
The obtained flask contents were filtered using perlite to obtain a solid and a filtrate. The obtained filtrate was charged into a 500 mL glass four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer.
撹拌下に加熱して６０℃まで昇温させ、１０重量％の次亜塩素酸ナトリウム水溶液を２８．５ｇ添加して、反応系を温度６０℃の状態で約７時間反応を継続した。
その後、加熱を停止し、フラスコを冷却した。冷却後、過剰量の次亜塩素酸ナトリウムを失活するために１０重量％の亜硫酸水素ナトリウム水溶液を１．０２ｇ添加して、撹拌下、反応系を温度２５℃の状態で３０分間還元反応を行った。
The mixture was heated to 60 ° C. with stirring, 28.5 g of a 10% by weight aqueous sodium hypochlorite solution was added, and the reaction was continued for about 7 hours at a temperature of 60 ° C.
Thereafter, heating was stopped and the flask was cooled. After cooling, 1.02 g of 10% by weight aqueous sodium hydrogen sulfite solution was added to deactivate the excess amount of sodium hypochlorite, and the reaction was carried out for 30 minutes with stirring at a temperature of 25 ° C. went.
３０分間経過後、３５%塩酸３２．４ｇを滴下して、撹拌下、反応系を温度２５℃の状態で約1時間反応を継続した。
内容物を取り出して結晶を濾別し、２，５−フランジカルボン酸を含むケーキと濾液とを得た。得られたケーキを水１００ｇで洗浄した後、攪拌機、温度計を取り付けた内容量３００ｍＬの３つ口フラスコにケーキを加え、水１０７ｇを仕込んだ。
After 30 minutes, 32.4 g of 35% hydrochloric acid was added dropwise, and the reaction was continued for about 1 hour at 25 ° C. with stirring.
The contents were taken out and the crystals were separated by filtration to obtain a cake containing 2,5-furandicarboxylic acid and a filtrate. The obtained cake was washed with 100 g of water, and then the cake was added to a 300 mL three-necked flask equipped with a stirrer and a thermometer to charge 107 g of water.
撹拌下に加熱して温度を３０℃に昇温して、反応系を温度３０℃に保ち約1時間撹拌を継続した。その後、加熱を停止し、フラスコを冷却した。
内容物を取り出して結晶を濾別し、２，５−フランジカルボン酸を含むケーキと濾液とを得た。３０℃にあらかじめ加熱しておいた水１００ｇで得られたケーキを洗浄した。この３０℃での水洗工程を３回繰り返した後、得られたケーキを真空乾燥し、白色の２，５−フランジカルボン酸１５．０ｇを得た。ＬＣ純度は９９．９重量％であり、収率は８７．６ｍｏｌ％であった。
The mixture was heated with stirring to raise the temperature to 30 ° C., and the reaction system was kept at 30 ° C. and stirring was continued for about 1 hour. Thereafter, heating was stopped and the flask was cooled.
The contents were taken out and the crystals were separated by filtration to obtain a cake containing 2,5-furandicarboxylic acid and a filtrate. The cake obtained was washed with 100 g of water preheated to 30 ° C. After repeating this water washing process at 30 ° C. three times, the obtained cake was vacuum-dried to obtain 15.0 g of white 2,5-furandicarboxylic acid. The LC purity was 99.9% by weight and the yield was 87.6 mol%.
（実施例５）
攪拌機、温度計を取り付けた内容積５００ｍＬのガラス製３つ口フラスコに、純度９７重量％の水酸化ナトリウム１１．５ｇおよび水３００ｇを仕込んだ。
(Example 5)
11.5 g of sodium hydroxide having a purity of 97% by weight and 300 g of water were charged into a 500-mL glass three-necked flask equipped with a stirrer and a thermometer.
実施例３で得られた２，５−フランジカルボン酸２０ｇをフラスコ内に添加し、撹拌下、反応系を温度２５℃の状態で約１時間反応を継続した。
得られたフラスコ内容物についてパーライトを用いて濾過を行い、固体および濾液を得た。得られた濾液を攪拌機、還流冷却器、滴下ロート、および温度計を取り付けた内容積５００ｍＬのガラス製４つ口フラスコに仕込んだ。
20 g of 2,5-furandicarboxylic acid obtained in Example 3 was added to the flask, and the reaction was continued for about 1 hour under stirring at a temperature of 25 ° C.
The obtained flask contents were filtered using perlite to obtain a solid and a filtrate. The obtained filtrate was charged into a 500 mL glass four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer.
撹拌下に加熱して３０℃まで昇温させ、３０重量％の過酸化水素水溶液を８．６８ｇ添加して、反応系を温度３０℃の状態で約６時間反応を継続した。
その後、ｔ−ブチルメチルケトンを１８．２ｇ添加し、加熱して６０℃まで昇温した。昇温後、３５％塩酸３１．５ｇを滴下し、４つ口フラスコをオイルバスから外し、撹拌下で１時間保持した。
The mixture was heated with stirring to 30 ° C., 8.68 g of a 30 wt% aqueous hydrogen peroxide solution was added, and the reaction was continued for about 6 hours at a temperature of 30 ° C.
Thereafter, 18.2 g of t-butyl methyl ketone was added and heated to 60 ° C. After raising the temperature, 31.5 g of 35% hydrochloric acid was added dropwise, the four-necked flask was removed from the oil bath, and held for 1 hour with stirring.
１時間経過後、フラスコ内の内容物を取り出して結晶を濾別して得られたケーキの真空乾燥を行い。白色の２，５−フランジカルボン酸を１７．０ｇ、収率９３．６ｍｏｌ％で回収した。回収した１７．０ｇ中、５ｇを水で再結晶を行うと収率９１．８ｍｏｌ％で白色の２，５−フランジカルボン酸が回収され、そのＬＣ純度は９９．９重量％であった。 After 1 hour, the contents in the flask were taken out and the cake obtained by filtering the crystals was vacuum-dried. 17.0 g of white 2,5-furandicarboxylic acid was recovered in a yield of 93.6 mol%. When 5 g of the recovered 17.0 g was recrystallized with water, white 2,5-furandicarboxylic acid was recovered in a yield of 91.8 mol%, and its LC purity was 99.9 wt%.
Claims (3)
前記触媒における金属換算コバルトおよび金属換算マンガンの原子比が２：１〜４：１であって、
分子状酸素を含む酸化性気体を前記反応液に供給しつつ計測した排気ガスの酸素濃度に基づいて、前記反応液に対する分子状酸素の吸収終了点に達したと判定した後に、さらに酸化性気体の供給を行って酸化反応を継続させること
を特徴とする２，５−フランジカルボン酸の製造方法。 In a method for producing 2,5-furandicarboxylic acid in which 5-hydroxymethylfurfural is oxidized with molecular oxygen in a reaction solution containing a catalyst containing cobalt, manganese, and bromine,
The atomic ratio of metal-converted cobalt and metal-converted manganese in the catalyst is 2: 1 to 4: 1,
Based on the oxygen concentration of the exhaust gas measured while supplying the oxidizing gas containing molecular oxygen to the reaction solution, after determining that the molecular oxygen absorption end point for the reaction solution has been reached, the oxidizing gas is further added. A process for producing 2,5-furandicarboxylic acid, characterized in that the oxidation reaction is continued by supplying
５−ヒドロキシメチルフルフラール１ｍｏｌに対する金属換算コバルトの比率が０．０１〜０．３グラム原子、かつコバルトおよびマンガンの金属換算総和１グラム原子に対する臭素イオンの比率が０．０５〜２０ｍｏｌである、請求項１記載の２，５−フランジカルボン酸の製造方法。 The catalyst added to the reaction solution is
The ratio of cobalt in terms of metal to 1 mol of 5-hydroxymethylfurfural is 0.01 to 0.3 gram atom, and the ratio of bromine ions to 1 gram atom in total of metal in terms of cobalt and manganese is 0.05 to 20 mol. 2. The method for producing 2,5-furandicarboxylic acid according to 1.
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| CN109293608A (en) * | 2018-09-21 | 2019-02-01 | 中国科学技术大学 | A kind of preparation method of 5- formoxyl furancarboxylic acid |
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| CN112898251A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院宁波材料技术与工程研究所 | Method for preparing 2, 5-furandicarboxylic acid |
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| WO2023125067A1 (en) * | 2021-12-30 | 2023-07-06 | 中国石油天然气股份有限公司 | Catalyst, preparation method therefor and method for preparing 2,5-furandicarboxylic acid from catalyst |
| CN116408081A (en) * | 2021-12-30 | 2023-07-11 | 中国石油天然气股份有限公司 | Catalyst and preparation method thereof, and method for preparing 2, 5-furandicarboxylic acid by using catalyst |
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