JP2005132789A - Method for producing 1,2,3,4-butanetetracarboxylic acid - Google Patents
Method for producing 1,2,3,4-butanetetracarboxylic acid Download PDFInfo
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- JP2005132789A JP2005132789A JP2003372260A JP2003372260A JP2005132789A JP 2005132789 A JP2005132789 A JP 2005132789A JP 2003372260 A JP2003372260 A JP 2003372260A JP 2003372260 A JP2003372260 A JP 2003372260A JP 2005132789 A JP2005132789 A JP 2005132789A
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- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 139
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000012452 mother liquor Substances 0.000 claims abstract description 52
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 30
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 21
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 9
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 5
- 239000003456 ion exchange resin Substances 0.000 claims description 24
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 claims description 6
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- BCTWNMTZAXVEJL-UHFFFAOYSA-N phosphane;tungsten;tetracontahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.P.[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] BCTWNMTZAXVEJL-UHFFFAOYSA-N 0.000 claims description 3
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 abstract description 23
- 239000007788 liquid Substances 0.000 abstract description 15
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 22
- 238000012545 processing Methods 0.000 description 17
- 239000013078 crystal Substances 0.000 description 10
- 239000008213 purified water Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- -1 alkali metal salts Chemical class 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、１，２，４，５−テトラヒドロ無水フタル酸（以下、「ＴＨＰＡ」と略記する。）及び／又はその有水酸を過酸化水素により酸化して１，２，３，４−ブタンテトラカルボン酸（以下、「ＢＴＣ」と略記する。）を製造する方法に関する。さらに詳しくは、該製造で得られた反応母液を、繰り返し該製造に再使用してＢＴＣを製造する方法に関する。 In the present invention, 1,2,4,5-tetrahydrophthalic anhydride (hereinafter abbreviated as “THPA”) and / or its hydrous acid is oxidized with hydrogen peroxide to produce 1,2,3,4- The present invention relates to a method for producing butanetetracarboxylic acid (hereinafter abbreviated as “BTC”). More specifically, the present invention relates to a method for producing BTC by repeatedly reusing the reaction mother liquor obtained in the production for the production.
タングステン酸、モリブデン酸及びこれらのヘテロポリ酸触媒の存在下、過酸化水素を酸化剤として、ＴＨＰＡを酸化してＢＴＣを製造する方法は、従来の硝酸酸化法と比較して、有害ガス及び有害副生物の発生が無く、かつ比較的高収率で目的物が得られるため、工業的に極めて有利な反応方法である（特許文献１）。 In the presence of tungstic acid, molybdic acid, and these heteropolyacid catalysts, the method of producing BTC by oxidizing THPA using hydrogen peroxide as an oxidizing agent is more harmful than the conventional nitric acid oxidation method. Since there is no generation of organisms and the target product can be obtained in a relatively high yield, it is an industrially extremely advantageous reaction method (Patent Document 1).
これらの触媒は比較的高価であり、経済性の面から回収して再使用するのが望ましい。上記特許文献１の明細書中には、反応終了後に反応液を冷却し析出した目的物のカルボン酸を分離回収した後の反応母液中には、失活していない触媒の大部分が残存しており、再度反応に供することが有利であることを開示しているが、その方法については何ら具体的に記載されていない。 These catalysts are relatively expensive, and are desirably recovered and reused from the economical aspect. In the specification of the above-mentioned Patent Document 1, most of the catalyst that has not been deactivated remains in the reaction mother liquor after the reaction solution is cooled and separated after the reaction solution is separated and recovered. However, it is disclosed that it is advantageous to be subjected to the reaction again, but the method is not specifically described at all.
また、タングステン酸、リンタングステン酸若しくはそれらの塩を含む反応液又はＢＴＣを分離した後の反応母液を、弱塩基性陰イオン交換樹脂と接触させて、該触媒のみを選択吸着させ、回収、再使用する方法が提案されている（特許文献２）。 Further, a reaction solution containing tungstic acid, phosphotungstic acid or a salt thereof, or a reaction mother liquor after separation of BTC is brought into contact with a weakly basic anion exchange resin to selectively adsorb only the catalyst, and is recovered, recycled. A method to be used has been proposed (Patent Document 2).
しかしながら、この方法においては、１）触媒のみの回収・再使用であること、２）再使用回数が限られること、３)煩雑な操作が必要であること等の問題点を有しており、工業的製造方法としては必ずしも有利な方法とは言えないのが現状である。 However, this method has problems such as 1) recovery and reuse of the catalyst only, 2) limited number of reuses, and 3) complicated operation required. At present, it is not necessarily an advantageous method for industrial production.
本発明は、上記問題点を解消し、ＢＴＣの生成率を低下させることなく触媒及びＢＴＣを含有する反応母液を繰り返し該製造に再使用できる工業的に有利な１，２，３，４，−ブタンテトラカルボン酸の製造方法を提供することを目的とする。 The present invention eliminates the above-mentioned problems, and industrially advantageous 1,2,3,4,-, which allows a reaction mother liquor containing a catalyst and BTC to be repeatedly reused in the production without lowering the production rate of BTC. It aims at providing the manufacturing method of butanetetracarboxylic acid.
本発明者らは、上記の問題点を解決するため鋭意検討した。前記特許文献１には、触媒及び未析出のＢＴＣが含まれている反応母液を反応に再使用することが工業的に有利であることが記載されている。しかし、本発明者の研究によると、確かに繰り返し使用はできるものの、その繰り返し回数に反比例して徐々にＢＴＣの生成率は低下していき、必ずしも工業的に有利な方法として満足できるものではないことが判明した。 The present inventors diligently studied to solve the above problems. Patent Document 1 describes that it is industrially advantageous to reuse a reaction mother liquor containing a catalyst and undeposited BTC for the reaction. However, according to the research of the present inventor, although it can be used repeatedly, the production rate of BTC gradually decreases in inverse proportion to the number of repetitions, which is not always satisfactory as an industrially advantageous method. It has been found.
本発明者らは更に検討を重ねた結果、ＢＴＣの製造に使用した触媒及びＢＴＣを含有する反応母液をスルホン酸型陽イオン交換樹脂で処理して得られた処理液を該製造に再使用することにより、ＢＴＣを工業的に有利に製造できることを見いだし、係る知見に基づいて本発明を完成するに至った。 As a result of further investigations, the present inventors have reused the treatment liquid obtained by treating the reaction mother liquor containing the catalyst and BTC used in the production of BTC with a sulfonic acid type cation exchange resin. As a result, it was found that BTC can be produced industrially advantageously, and the present invention has been completed based on such knowledge.
即ち、本発明は、以下の１，２，３，４−ブタンテトラカルボン酸の製造方法を提供するものである。 That is, the present invention provides the following method for producing 1,2,3,4-butanetetracarboxylic acid.
項１ １，２，４，５−テトラヒドロ無水フタル酸及び／又はその有水酸を、水性溶媒中、タングステン酸、モリブデン酸及びタングステン酸若しくはモリブデン酸を含有するヘテロポリ酸からなる群より選ばれる少なくとも１種の触媒存在下で過酸化水素により酸化し、１，２，３，４−ブタンテトラカルボン酸を製造する方法において、得られた反応液を冷却して析出した１，２，３，４−ブタンテトラカルボン酸を分離し、次いで得られた反応母液をスルホン酸型陽イオン交換樹脂で処理し、得られた処理液を該製造に再使用することを特徴とする１，２，３，４−ブタンテトラカルボン酸の製造方法。 Item 1 At least selected from the group consisting of 1,2,4,5-tetrahydrophthalic anhydride and / or its hydrous acid, in an aqueous solvent, consisting of tungstic acid, molybdic acid and heteropolyacid containing tungstic acid or molybdic acid In the process for producing 1,2,3,4-butanetetracarboxylic acid by oxidation with hydrogen peroxide in the presence of one kind of catalyst, the resulting reaction solution was cooled and precipitated 1,2,3,4 -Separating butanetetracarboxylic acid, then treating the resulting reaction mother liquor with a sulfonic acid type cation exchange resin, and reusing the obtained treating liquid for the production A method for producing 4-butanetetracarboxylic acid.
項２ スルホン酸型イオン交換樹脂１００容積部に対して、１，２，３，４−ブタンテトラカルボン酸を分離して得られた反応母液を１０〜５００容積部／ｈの条件で処理することを特徴とする上記項１に記載の１，２，３，４−ブタンテトラカルボン酸の製造方法。 Item 2: Treating the reaction mother liquor obtained by separating 1,2,3,4-butanetetracarboxylic acid under the condition of 10 to 500 parts by volume / h with respect to 100 parts by volume of the sulfonic acid type ion exchange resin. Item 2. The method for producing 1,2,3,4-butanetetracarboxylic acid according to Item 1 above.
項３ 触媒が、タングステン酸又は１２−タングストリン酸である上記項１又は項２に記載の１，２，３，４−ブタンテトラカルボン酸の製造方法。 Item 3. The method for producing 1,2,3,4-butanetetracarboxylic acid according to Item 1 or 2, wherein the catalyst is tungstic acid or 12-tungstophosphoric acid.
項４ 反応液中の過酸化水素の濃度が０．４〜１．５ｍｏｌ／ｋｇとなるように、過酸化水素を連続的に供給して行うことを特徴とする上記項１〜３のいずれかに記載の１，２，３，４−ブタンテトラカルボン酸の製造方法。 Item 4 The method according to any one of Items 1 to 3, wherein hydrogen peroxide is continuously supplied so that the concentration of hydrogen peroxide in the reaction solution is 0.4 to 1.5 mol / kg. A process for producing 1,2,3,4-butanetetracarboxylic acid as described in 1. above.
項５ 還流条件下で反応を行うことを特徴とする上記項１〜４のいずれかに記載の１，２，３，４−ブタンテトラカルボン酸の製造方法。 Item 5. The process for producing 1,2,3,4-butanetetracarboxylic acid according to any one of Items 1 to 4, wherein the reaction is carried out under reflux conditions.
本発明によれば、反応後冷却晶析してＢＴＣを分離して得られた反応母液をスルホン酸型イオン交換樹脂で処理し、得られた処理液を繰り返し再使用することにより、ＢＴＣの生成率を低下させることなく、また過酸化水素の使用量を増大させることなく、工業的に有利にＢＴＣを製造することができる。 According to the present invention, the reaction mother liquor obtained by cooling and crystallizing after the reaction and separating the BTC is treated with a sulfonic acid type ion exchange resin, and the obtained treatment liquid is repeatedly reused to produce BTC. BTC can be produced industrially advantageously without decreasing the rate and without increasing the amount of hydrogen peroxide used.
本発明に係るＢＴＣの製造は、１，２，４，５−テトラヒドロ無水フタル酸及び／又はその有水酸を、触媒存在下で過酸化水素により酸化する方法であれば、従来公知の方法により行うことができる。例えば、ＴＨＰＡを水性溶媒中、タングステン酸、モリブデン酸、及びタングステン酸又はモリブデン酸を含有するヘテロポリ酸からなる群より選ばれる少なくとも１種の触媒存在下で過酸化水素により酸化することにより行われる。 The production of BTC according to the present invention can be carried out by a conventionally known method as long as it is a method of oxidizing 1,2,4,5-tetrahydrophthalic anhydride and / or its hydrous acid with hydrogen peroxide in the presence of a catalyst. It can be carried out. For example, THPA is oxidized by oxidizing hydrogen peroxide in an aqueous solvent in the presence of at least one catalyst selected from the group consisting of tungstic acid, molybdic acid, and a heteropolyacid containing tungstic acid or molybdic acid.
本発明に係る触媒としては、タングステン酸、モリブデン酸又はタングステン若しくはモリブデン酸を含有するヘテロポリ酸が使用できる。ヘテロポリ酸は、２種以上の酸素酸からなる縮合酸でり、ポリ酸原子としては、タングステン及びモリブデンであり、ヘテロ原子としては、Ｐ、Ａｓ、Ｓｉ、Ｔｉ、Ｃｏ、Ｆｅ、Ｂ、Ｖ、Ｂｅ、Ｉ、Ｎｉ、Ｇａが使用でき、これらは混合配位であっても良い。尚、上記触媒の中でも、合成の容易さ、入手の容易さ、反応性の観点から、タングステン酸及びタングステン酸をポリ酸として含有するヘテロポリ酸が好ましく、より好ましくはタングステン酸及び１２−タングストリン酸が推奨される。 As the catalyst according to the present invention, tungstic acid, molybdic acid, or heteropolyacid containing tungsten or molybdic acid can be used. The heteropolyacid is a condensed acid composed of two or more oxygen acids, and the polyacid atoms are tungsten and molybdenum, and the heteroatoms are P, As, Si, Ti, Co, Fe, B, V, Be, I, Ni, and Ga can be used, and these may be mixed coordination. Among the above catalysts, heteropolyacids containing tungstic acid and tungstic acid as polyacids are preferred, more preferably tungstic acid and 12-tungstophosphoric acid, from the viewpoint of ease of synthesis, availability, and reactivity. Is recommended.
触媒として用いるタングステン酸、モリブデン酸又はタングステン酸若しくはモリブデン酸を含有するヘテロポリ酸は、水和物であってもよく、反応系内で上記の触媒を生成し得る化合物の形態であってもよい。 The tungstic acid, molybdic acid or heteropolyacid containing tungstic acid or molybdic acid used as a catalyst may be a hydrate or a compound capable of generating the above catalyst in the reaction system.
このような化合物としては、タングステン酸、モリブデン酸のカリウム、ナトリウム等のアルカリ金属塩、コバルト、ニッケル、マンガン、銅などの重金属塩、アンモニウム塩などの塩類などが挙げられ、更に、酸化物、塩化物、硫化物であってもよい。このような塩、塩化物、硫化物を使用する場合は、リン酸、塩酸、硫酸などの鉱酸を加え、ｐＨ４以下の酸性条件下で反応を行うことが好ましい。 Examples of such compounds include alkali metal salts such as tungstic acid, potassium molybdate and sodium, heavy metal salts such as cobalt, nickel, manganese and copper, and salts such as ammonium salts. Or sulfide. When such a salt, chloride, or sulfide is used, it is preferable to add a mineral acid such as phosphoric acid, hydrochloric acid, or sulfuric acid and perform the reaction under acidic conditions of pH 4 or less.
又、ヘテロポリ酸のアルカリ金属塩、アンモニウム塩、モノアルキルアンモニウム塩、ジアルキルアンモニウム塩、トリアルキルアンモニウム塩、テトラアルキルアンモニウム塩、アルキルピリジウム塩なども使用できる。 In addition, alkali metal salts, ammonium salts, monoalkyl ammonium salts, dialkyl ammonium salts, trialkyl ammonium salts, tetraalkyl ammonium salts, alkyl pyridium salts, and the like of heteropolyacids can also be used.
これらの触媒の使用量は、触媒活性が発揮される濃度であれば特に限定されないが、反応液中の遊離酸（タングステン酸、モリブデン酸又はタングステン酸若しくはモリブデン酸を含有するヘテロポリ酸）濃度が１〜５０ｇ／ｋｇの範囲が好ましく、より好ましくは３〜１０ｇ／ｋｇの範囲が好ましい。濃度が、１ｇ／ｋｇ未満であると工業的な反応速度が得られにくく、一方、５０ｇ／ｋｇを超える場合、添加量に見合う反応速度の向上効果は得られにくく、触媒コストの観点から不利である。 The amount of these catalysts used is not particularly limited as long as the catalyst activity is exerted, but the concentration of free acid (tungstic acid, molybdic acid, or heteropolyacid containing tungstic acid or molybdic acid) in the reaction solution is 1. The range of ˜50 g / kg is preferable, and the range of 3 to 10 g / kg is more preferable. If the concentration is less than 1 g / kg, it is difficult to obtain an industrial reaction rate. On the other hand, if it exceeds 50 g / kg, it is difficult to obtain an effect of improving the reaction rate commensurate with the amount added, which is disadvantageous from the viewpoint of catalyst cost. is there.
本発明に係るＢＴＣの製造において、ＴＨＰＡ及びその有水酸（以下、「基質」と略記する。）のいずれも使用することができ、有水酸は該製造において無水酸の加水分解により生成した有水酸であってもよい。反応時の基質濃度は特に制限が無く、反応温度において溶解している限り広い範囲から選択することができる。しかし反応終了後、反応液を冷却してＢＴＣを結晶化させて分離させる方法において、結晶の析出量及びその品質の観点から、反応終了時のＢＴＣの濃度が１５〜３５重量％、好ましくは２５〜３０重量％となるような基質濃度で行うことが好ましい。 In the production of BTC according to the present invention, both THPA and its hydrous acid (hereinafter abbreviated as “substrate”) can be used, and hydrous acid was produced by hydrolysis of acid anhydride in the production. Hydrous acid may be sufficient. The substrate concentration in the reaction is not particularly limited, and can be selected from a wide range as long as it is dissolved at the reaction temperature. However, after completion of the reaction, in the method of cooling the reaction solution to crystallize and separate BTC, the concentration of BTC at the end of the reaction is 15 to 35% by weight, preferably 25 from the viewpoint of the amount of precipitated crystals and the quality thereof. It is preferable to carry out at a substrate concentration of ˜30% by weight.
水性溶媒としては水が好ましく用いられる。本発明の効果を阻害しない範囲で水と混和可能な有機溶媒、例えばメタノール、エタノール等の炭素数１〜４のアルコール、酢酸等の炭素数１〜４のカルボン酸、ジオキサン、テトラヒドロフラン、Ｎ，Ｎ−ジメチルホルムアミド等と水の混合溶媒を用いることができる。 Water is preferably used as the aqueous solvent. Organic solvents that are miscible with water within a range that does not impair the effects of the present invention, such as alcohols having 1 to 4 carbon atoms such as methanol and ethanol, carboxylic acids having 1 to 4 carbon atoms such as acetic acid, dioxane, tetrahydrofuran, N, N -A mixed solvent of dimethylformamide or the like and water can be used.
本発明に係る過酸化水素は、過酸化水素水として該製造に供することができる。過酸化水素水の濃度は、工業的に入手可能なものであれば特に制限がなく、具体的には、３〜７０重量％、好ましくは３０〜６０重量％の過酸化水素水が推奨される。価格及び反応性の観点から特に６０重量％の過酸化水素水が好ましい。過酸化水素の化学量論量は、基質に対して４モルであるが、実際にはその１０〜５０モル％過剰、即ち４．４〜６．０モル使用するのが好ましい。反応液中の過酸化水素濃度は、０．１〜８モル／ｋｇが好ましく、より好ましくは０．４〜１．５モル／ｋｇが推奨される。過酸化水素の濃度が０．１モル／ｋｇ未満では十分な反応速度が得られず、一方、８モル／ｋｇを超える濃度で行うと、過反応、副反応又は過酸化水素の分解等により過酸化水素の消費量が増加する傾向が見られ好ましくない。反応液中の過酸化水素濃度をこの範囲内に保つために、過酸化水素を連続的又は間欠的に反応系に供給することが好ましい。 The hydrogen peroxide according to the present invention can be used for the production as a hydrogen peroxide solution. The concentration of the hydrogen peroxide solution is not particularly limited as long as it is industrially available. Specifically, 3 to 70% by weight, preferably 30 to 60% by weight of hydrogen peroxide solution is recommended. . In view of price and reactivity, 60% by weight of hydrogen peroxide is particularly preferable. The stoichiometric amount of hydrogen peroxide is 4 mol with respect to the substrate, but in actuality, it is preferable to use 10 to 50 mol% excess, that is, 4.4 to 6.0 mol. The hydrogen peroxide concentration in the reaction solution is preferably 0.1 to 8 mol / kg, more preferably 0.4 to 1.5 mol / kg. When the concentration of hydrogen peroxide is less than 0.1 mol / kg, a sufficient reaction rate cannot be obtained. On the other hand, when the concentration exceeds 8 mol / kg, excessive reaction, side reaction, decomposition of hydrogen peroxide, etc. A tendency to increase the consumption of hydrogen oxide is not preferable. In order to keep the hydrogen peroxide concentration in the reaction solution within this range, it is preferable to supply hydrogen peroxide continuously or intermittently to the reaction system.
反応は、通常、反応速度の観点から８０〜１１０℃の範囲で行われるが、還流条件下において行うと、反応温度の管理が不要になる上に、蒸発した水を適宜、系外に抜き出すことにより、反応液中の触媒濃度、基質濃度、過酸化水素濃度を一定に保ちやすく、好ましい方法として推奨される。 The reaction is usually carried out in the range of 80 to 110 ° C. from the viewpoint of the reaction rate. When the reaction is carried out under reflux conditions, the reaction temperature is not required to be controlled, and the evaporated water is appropriately extracted out of the system. Therefore, it is easy to keep the catalyst concentration, substrate concentration, and hydrogen peroxide concentration in the reaction solution constant, which is recommended as a preferable method.
反応時間は、基質、触媒及び過酸化水素の濃度、反応温度等によって適宜異なるが、通常１〜２４時間程度である。 The reaction time varies depending on the concentration of the substrate, catalyst and hydrogen peroxide, reaction temperature, etc., but is usually about 1 to 24 hours.
本発明に係る反応母液は、上記の方法により得られた反応液を冷却して析出したＢＴＣを分離することにより得ることができる。その方法については特に制限がなく、例えば、ＢＴＣの濃度、徐冷速度、晶析時間、冷却温度、使用する装置等を適宜選択して行うことができる。通常、冷却温度が低いほど析出量が増加するが、温度が低くなるにつれて固液分離性の悪い結晶が多く析出する傾向が見られる。これらの観点から、反応液は、０℃〜４０℃、より好ましくは５℃〜２５℃まで冷却した後、ＢＴＣを分離することが推奨される。 The reaction mother liquor according to the present invention can be obtained by cooling the reaction solution obtained by the above method and separating the deposited BTC. The method is not particularly limited, and for example, the BTC concentration, the slow cooling rate, the crystallization time, the cooling temperature, the apparatus to be used, etc. can be selected as appropriate. Usually, the amount of precipitation increases as the cooling temperature decreases, but as the temperature decreases, more crystals with poor solid-liquid separation tend to precipitate. From these viewpoints, it is recommended that the reaction solution is cooled to 0 ° C. to 40 ° C., more preferably 5 ° C. to 25 ° C., and then BTC is separated.
析出したＢＴＣと反応母液との分離は、例えば濾過、遠心分離等の慣用の方法により行なうことができる。分離したＢＴＣは精製水等の溶媒で洗浄するか、或いは再結晶により精製することができる。また、精製に用いた溶媒は反応母液とともに回収して発明に係るスルホン酸型イオン交換樹脂で処理することができる。 Separation of the precipitated BTC and the reaction mother liquor can be performed by a conventional method such as filtration or centrifugation. The separated BTC can be washed with a solvent such as purified water or purified by recrystallization. The solvent used for purification can be recovered together with the reaction mother liquor and treated with the sulfonic acid type ion exchange resin according to the invention.
かくして得られた反応母液は、そのまま本スルホン酸型陽イオン交換樹脂で処理することができる。本発明において、反応母液を該処理する頻度は、反応に供する度毎に行うことが好ましいが、該処理をすることなく、少なくとも１回以上該反応に再使用した後に処理してもよい。 The reaction mother liquor thus obtained can be directly treated with the sulfonic acid type cation exchange resin. In the present invention, the reaction mother liquor is preferably treated every time it is subjected to the reaction. However, the reaction mother liquor may be treated after being reused in the reaction at least once without performing the treatment.
反応母液中のＢＴＣの濃度については特に制限はないが、通常は３０重量％以下の範囲で処理するのが好ましい。３０重量％を超える反応母液は、配管、ポンプ、貯蔵槽又は処理槽等でＢＴＣを析出する虞があり好ましくない。ＢＴＣの濃度が高い場合には精製水などで希釈して処理することが好ましい。 Although there is no restriction | limiting in particular about the density | concentration of BTC in reaction mother liquid, Usually, it is preferable to process in the range of 30 weight% or less. A reaction mother liquor exceeding 30% by weight is not preferable because BTC may be precipitated in a pipe, a pump, a storage tank, a processing tank, or the like. When the concentration of BTC is high, it is preferable to dilute with purified water.
本発明に係るスルホン酸型陽イオン交換樹脂としては、官能基としてスルホン酸基を含有する市販の陽イオン交換樹脂が広く使用でき、例えば、三菱化学社製のダイヤイオン（Ｒ）のＳＫ、ＰＫ又はＵＢＫシリーズ、オルガノ社（Ｒｈｏｍ ＆ Ｈａａｓ）製のアンバーライト（Ｒ）ＩＲ１２０Ｂ Ｎａ、ＩＲ１２４ Ｎａ、２００ＣＴ Ｎａ又は２００ＣＰなどが挙げられる。市販の陽イオン交換樹脂は、スルホン酸Ｎａ塩形で販売されていることが多く、この場合はＮａイオンを水素イオンに置換して本発明に係るスルホン酸陽イオン交換樹脂とすることができる。Ｎａイオンから水素イオンへの交換は従来公知の方法が広く使用でき、例えば、カラムに充填したＮａイオン形の陽イオン交換樹脂に対して、２〜６倍容積の１〜２Ｎの塩酸を１〜２時間で通液することにより容易に得られる。さらにイオン交換樹脂と同容積の精製水を０．１〜１時間で通液することにより、塩素イオンも含まない水素イオン形のスルホン酸系陽イオン交換樹脂とすることができる。 As the sulfonic acid type cation exchange resin according to the present invention, commercially available cation exchange resins containing a sulfonic acid group as a functional group can be widely used. For example, SK (PK) of Diaion (R) manufactured by Mitsubishi Chemical Corporation Alternatively, UBK series, Amberlite (R) IR120B Na, IR124 Na, 200CT Na, or 200CP manufactured by Organ & Co. (Rom & Haas) can be used. Commercially available cation exchange resins are often sold in the sulfonic acid Na salt form, and in this case, Na ions can be substituted with hydrogen ions to obtain the sulfonic acid cation exchange resin according to the present invention. Conventionally known methods can be widely used for the exchange from Na ions to hydrogen ions. For example, 2 to 6 times the volume of 1 to 2 N hydrochloric acid is added to 1 to 2 volumes of Na ion type cation exchange resin packed in a column. It can be easily obtained by passing the solution in 2 hours. Further, by passing purified water having the same volume as the ion exchange resin in 0.1 to 1 hour, a hydrogen ion type sulfonic acid cation exchange resin containing no chlorine ions can be obtained.
反応母液をスルホン酸型陽イオン交換樹脂で処理する方法は、特に限定されず、例えば、反応母液と該イオン交換樹脂を所定の時間、混合撹拌した後に該イオン交換樹脂を濾別するバッチ方式、該イオン交換樹脂を充填した塔に反応母液を通液するカラム方法等が挙げられるが、単位時間当たりの処理速度が早い、処理操作が容易、設備が簡略等の点から、カラム方式が推奨される。 The method for treating the reaction mother liquor with the sulfonic acid type cation exchange resin is not particularly limited. For example, a batch method in which the reaction mother liquor and the ion exchange resin are mixed and stirred for a predetermined time, and then the ion exchange resin is separated by filtration. Examples include a column method in which the reaction mother liquor is passed through a column packed with the ion-exchange resin, but the column method is recommended because of its high processing speed per unit time, easy processing operation, simple equipment, etc. The
該イオン交換樹脂の使用量としては、当該イオン交換樹脂の見掛密度、交換容量、架橋密度、粒径、反応母液中のＢＴＣ濃度、触媒濃度、処理形式又は装置の形状などによって異なるが、例えば、カラム方式で充填塔に通液して処理する場合には、反応母液１００容積部に対して１〜５００容積部、好ましくは５〜２００容積部のスルホン酸型陽イオン交換樹脂を使用するのが好ましい。当該イオン交換樹脂の量が１容積部以下だと、十分な処理能力が得られにくい傾向がみられ、或いは処理を繰り返した際の能力低下が著しい傾向がみられる。一方、５００容積部を超えて使用しても顕著な処理効果の向上は認められず、該イオン交換樹脂の再生若しくは交換時の作業負担が大きくなり好ましくない。 The amount of the ion exchange resin used varies depending on the apparent density, exchange capacity, crosslinking density, particle size, BTC concentration in the reaction mother liquor, catalyst concentration, treatment type, or the shape of the apparatus. In the case of processing by passing through a packed tower in a column system, 1 to 500 parts by volume, preferably 5 to 200 parts by volume of a sulfonic acid type cation exchange resin is used with respect to 100 parts by volume of the reaction mother liquor. Is preferred. When the amount of the ion exchange resin is 1 part by volume or less, there is a tendency that a sufficient processing capacity cannot be obtained, or there is a remarkable tendency that the capacity decreases when the processing is repeated. On the other hand, even if it is used in excess of 500 parts by volume, no significant improvement in the treatment effect is recognized, and the work load during the regeneration or replacement of the ion exchange resin increases, which is not preferable.
カラム方式で処理をする場合、反応母液の処理速度は、当該イオン交換樹脂１００容積部に対して１０〜１０００容積部／ｈが好ましく、より好ましくは５０〜５００容積部／ｈが推奨される。この範囲において、生産性と処理効果が十分に得られる。
ましくない。
When processing by the column system, the processing rate of the reaction mother liquor is preferably 10 to 1000 parts by volume / h, more preferably 50 to 500 parts by volume / h, with respect to 100 parts by volume of the ion exchange resin. In this range, sufficient productivity and processing effect can be obtained.
It ’s not good.
処理温度は、反応母液からＢＴＣが析出しない温度より高く、当該イオン交換樹脂の耐熱温度以下であれば特に制限はないが、１０〜８０℃が好ましく、より好ましくは２０〜６０℃が推奨される。 The treatment temperature is not particularly limited as long as it is higher than the temperature at which BTC does not precipitate from the reaction mother liquor and is not higher than the heat resistant temperature of the ion exchange resin, but is preferably 10 to 80 ° C, more preferably 20 to 60 ° C. .
本発明に係るスルホン酸型陽イオン交換樹脂は、繰り返し当該処理に供することができる。繰り返し使用により、所望の効果が得られにくくなった場合は、該スルホン酸型イオン交換樹脂の調製に用いた方法と同一の操作を行うことにより、再度処理効果が得られることがある。 The sulfonic acid type cation exchange resin according to the present invention can be repeatedly subjected to the treatment. When it becomes difficult to obtain a desired effect by repeated use, a treatment effect may be obtained again by performing the same operation as the method used for the preparation of the sulfonic acid type ion exchange resin.
反応母液中に含有される過酸化水素の濃度が高いと、該イオン交換樹脂の酸化劣化で発生した微粉末により流路が閉塞して、反応母液の通液速度が低下したり、送液圧力が増大する傾向が見られる。また、塔内で過酸化水素の分解ガスが発生すると、反応母液と該イオン交換樹脂と接触面積の低下により、所望の効果が得られにくくなる傾向がある。そのため、該処理に用いる反応母液中の過酸化水素濃度は低い方が好ましい。推奨される過酸化水素の濃度は、少なくとも反応時より低濃度の８モル／ｋｇ以下、より好ましくは１．５モル／ｋｇ以下、特に好ましくは０．４モル／ｋｇ以下が推奨される。 If the concentration of hydrogen peroxide contained in the reaction mother liquor is high, the flow path is blocked by fine powder generated by oxidative degradation of the ion exchange resin, the reaction mother liquor flow rate decreases, or the liquid feeding pressure There is a tendency to increase. Further, when hydrogen peroxide decomposition gas is generated in the tower, there is a tendency that a desired effect is hardly obtained due to a decrease in contact area between the reaction mother liquor and the ion exchange resin. Therefore, it is preferable that the hydrogen peroxide concentration in the reaction mother liquor used for the treatment is low. The recommended hydrogen peroxide concentration is at least 8 mol / kg or less, more preferably 1.5 mol / kg or less, particularly preferably 0.4 mol / kg or less, which is at least a lower concentration than during the reaction.
かくして得られた該処理液は活性な触媒及び未析出のＢＴＣを含有しており、該製造の反応母液、即ち、触媒及びＢＴＣを含有した反応溶媒としてそのまま、或いは必要に応じて触媒、精製水を加えた後、再使用することができる。再使用する場合の該製造は上記記載の方法により行われ、この繰り返しにより、触媒コストの低減及びＢＴＣの収率が向上する。 The treatment liquid thus obtained contains an active catalyst and unprecipitated BTC. The reaction mother liquor of the production, that is, the reaction solvent containing the catalyst and BTC is used as it is, or as necessary, a catalyst, purified water. Can be reused. In the case of reuse, the production is carried out by the above-described method, and this repetition improves the catalyst cost and the yield of BTC.
以下、実施例を掲げて本発明を詳しく説明する。尚、本発明はこれら実施例により何らその範囲を制限されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples. The scope of the present invention is not limited by these examples.
過酸化水素濃度
ＪＩＳ Ｋ１４６３に準拠して測定した。
Hydrogen peroxide concentration was measured according to JIS K1463.
ＢＴＣ生成率
アジピン酸を内部標準とする液体クロマトグラフィー（ＨＰＬＣ）により測定した。
BTC production rate Measured by liquid chromatography (HPLC) using adipic acid as an internal standard.
スルホン酸型イオン交換樹脂の調製例１
陽イオン交換樹脂（三菱化学社製、商品名「ダイヤイオン（Ｒ） ＰＫ２１６」、官能基：スルホン酸のＮａイオン形）１００ｍｌをガラスカラムに充填した。２Ｎ−塩酸１０００ｍｌを１００ｍｌ／ｈの速度で通液しＮａイオンが溶出していないことを炎光分析により確認した。つづいて、蒸留水１０００ｍｌを１００ｍｌ／ｈの速度で通液し、スルホン酸型陽イオン交換樹脂Ａを調製した。
Preparation example 1 of sulfonic acid type ion exchange resin
A glass column was packed with 100 ml of a cation exchange resin (trade name “Diaion® PK216”, manufactured by Mitsubishi Chemical Corporation, functional group: Na ion form of sulfonic acid). By passing 1000 ml of 2N hydrochloric acid at a rate of 100 ml / h, it was confirmed by flame analysis that Na ions were not eluted. Subsequently, 1000 ml of distilled water was passed at a rate of 100 ml / h to prepare a sulfonic acid type cation exchange resin A.
スルホン酸型イオン交換樹脂の調製例２
陽イオン交換樹脂としてオルガノ社の商品名「アンバーライト（Ｒ） ２００ＣＴ Ｎａ」１００ｍｌを使用した他は、スルホン酸型イオン交換樹脂の調製例１と同様にしてスルホン酸型陽イオン交換樹脂Ｂを調製した。
Preparation example 2 of sulfonic acid type ion exchange resin
A sulfonic acid type cation exchange resin B was prepared in the same manner as in Preparation Example 1 of a sulfonic acid type ion exchange resin, except that 100 ml of the trade name “Amberlite (R) 200CT Na” of Organo Corporation was used as the cation exchange resin. did.
撹拌機、温度計及び冷却器付き２Ｌのガラス製フラスコ中に、１，２，４，５−テトラヒドロ無水フタル酸（以下、「ＴＨＰＡ」と略記する。）１５２ｇ（１．０モル）と１２−タングストリン酸・３０水和物４．５ｇを精製水５００ｇを入れ、加熱溶解した。常圧、還流下で６０％過酸化水素水２５５ｇ（４．５モル）を８時間かけて滴下すると共に、反応液量が概ね一定量に保たれるように蒸発水を適宜系外に留去しながら反応を行ったところ、反応液中のＴＨＰＡに対するＢＴＣの生成率は８８．２モル％であった。なお、反応中の反応液の過酸化水素濃度は、０．４〜０．８モル／ｋｇの範囲であった。得られた反応液を１０℃まで冷却し析出したＢＴＣの結晶を濾別し、精製水で洗浄してＢＴＣ湿結晶１８５ｇ（含水量２２重量％）と、濾液としてＢＴＣ（１２重量％）及び触媒を含有する反応母液５２０ｇ（４７０ｍｌ）を得た。室温下、この反応母液をスルホン酸型イオン交換樹脂Ａに５時間かけて通液して（スルホン酸型陽イオン交換樹脂１００ｍｌに対する処理速度１００ｍｌ／ｈ）、処理液４８０ｇを得た。該処理液にＴＨＰＡ７６ｇ（０．５モル）を加熱溶解し、還流下で６０％過酸化水素１３０ｇ（２．３モル）を７時間かけて連続的に滴下した。この間、反応液量が概ね一定量に保たれるように蒸発水を適宜系外に留去し、滴下終了１時間後に反応液をＨＰＬＣで分析したところ、ＴＨＰＡに対する新たなＢＴＣの生成率は９０．６モル％であった。なお、反応中、反応液の過酸化水素の濃度は、０．４〜０．８モル／ｋｇの範囲であった。 In a 2 L glass flask equipped with a stirrer, thermometer and cooler, 152 g (1.0 mol) of 1,2,4,5-tetrahydrophthalic anhydride (hereinafter abbreviated as “THPA”) and 12− 500 g of purified water was added to 4.5 g of tungstophosphoric acid 30 hydrate and dissolved by heating. Under normal pressure and reflux, 255 g (4.5 mol) of 60% aqueous hydrogen peroxide was added dropwise over 8 hours, and the evaporated water was appropriately distilled out of the system so that the amount of the reaction solution was maintained at a constant level. Then, the reaction was carried out, and the BTC production rate relative to THPA in the reaction solution was 88.2 mol%. The hydrogen peroxide concentration in the reaction solution during the reaction was in the range of 0.4 to 0.8 mol / kg. The obtained reaction solution was cooled to 10 ° C., and the precipitated BTC crystals were separated by filtration, washed with purified water, 185 g of BTC wet crystals (water content 22 wt%), BTC (12 wt%) and catalyst as the filtrate. Reaction mother liquor containing 520 g (470 ml) was obtained. This reaction mother liquor was passed through the sulfonic acid type ion exchange resin A for 5 hours at room temperature (treatment rate of 100 ml / h with respect to 100 ml of the sulfonic acid type cation exchange resin) to obtain 480 g of a treatment liquid. In this treatment solution, 76 g (0.5 mol) of THPA was dissolved by heating, and 130 g (2.3 mol) of 60% hydrogen peroxide was continuously added dropwise over 7 hours under reflux. During this time, evaporated water was appropriately distilled out of the system so that the amount of the reaction solution was maintained at a substantially constant amount, and the reaction solution was analyzed by HPLC 1 hour after the completion of the dropwise addition. As a result, the production rate of new BTC with respect to THPA was 90 It was 6 mol%. During the reaction, the concentration of hydrogen peroxide in the reaction solution was in the range of 0.4 to 0.8 mol / kg.
実施例１で得られた反応液を１０℃まで冷却して析出したＢＴＣの結晶を濾別し、精製水で洗浄してＢＴＣ湿結晶１６０ｇ（含水量２４重量％）と、濾液としてＢＴＣ（９重量％）及び触媒を含有する反応母液４８０ｇ（４６０ｍｌ）を得た。この反応母液を室温下で、スルホン酸型イオン交換樹脂Ｂに１時間かけて通液して（処理速度４６０ｍｌ／ｈ）、処理液４７０ｇを得た。該処理液にＴＨＰＡ７６ｇ（０．５モル）を加熱溶解し、常圧、還流下で６０％過酸化水素１３０ｇ（２．３モル）を７時間かけて連続的に滴下した。この間、反応液量が概ね一定量に保たれるように蒸発水を適宜系外に留去し、滴下終了１時間後に反応液をＨＰＬＣ分析したところ、ＴＨＰＡに対するＢＴＣの生成率は９０．２モル％であった。なお、反応中、反応液の過酸化水素の濃度は、０．４〜０．８モル／ｋｇの範囲であった。 The reaction solution obtained in Example 1 was cooled to 10 ° C., and the precipitated BTC crystals were filtered off, washed with purified water, and 160 g of BTC wet crystals (water content: 24% by weight), and BTC (9 %) And a reaction mother liquor containing 480 g (460 ml). The reaction mother liquor was passed through the sulfonic acid type ion exchange resin B at room temperature over 1 hour (processing speed: 460 ml / h) to obtain 470 g of processing liquid. In the treatment solution, 76 g (0.5 mol) of THPA was dissolved by heating, and 130 g (2.3 mol) of 60% hydrogen peroxide was continuously added dropwise over 7 hours under normal pressure and reflux. During this time, evaporated water was appropriately distilled out of the system so that the amount of the reaction solution was maintained at a substantially constant amount, and the reaction solution was subjected to HPLC analysis 1 hour after the completion of the dropwise addition. %Met. During the reaction, the concentration of hydrogen peroxide in the reaction solution was in the range of 0.4 to 0.8 mol / kg.
実施例１と同様の方法で反応及びＢＴＣの分離を行い、ＢＴＣ（１２重量％）及び触媒を含有する反応母液４９０ｇ（４４５ｍｌ）を得た。４０℃に加温した該反応母液をスルホン酸型イオン交換樹脂Ａに２．５時間かけて通液して（処理速度２００ｍｌ／ｈ）、処理液４８０ｇを得た。該処理液にＴＨＰＡ７６ｇ（０．５０モル）を加熱溶解し還流下で、６０％過酸化水素を１３０ｇ（２．３モル）を、２時間毎に４回に分けて添加した。この間、１３０ｇの蒸発水を適宜系外に留去し、最後の添加から２時間後に反応液をＨＰＬＣ分析したところ、ＴＨＰＡに対するＢＴＣの生成率は８８．７モル％であった。なお、反応中、反応液の過酸化水素濃度は、０．４〜１．２モル／ｋｇの範囲であった。 Reaction and BTC separation were performed in the same manner as in Example 1 to obtain 490 g (445 ml) of a reaction mother liquor containing BTC (12% by weight) and a catalyst. The reaction mother liquor heated to 40 ° C. was passed through the sulfonic acid type ion exchange resin A over 2.5 hours (processing speed 200 ml / h) to obtain 480 g of processing liquid. To the treatment solution, 76 g (0.50 mol) of THPA was dissolved by heating, and 130 g (2.3 mol) of 60% hydrogen peroxide was added in portions in 2 portions every 2 hours. During this time, 130 g of evaporated water was appropriately distilled out of the system, and the reaction mixture was analyzed by HPLC 2 hours after the last addition. As a result, the production rate of BTC relative to THPA was 88.7 mol%. During the reaction, the hydrogen peroxide concentration in the reaction solution was in the range of 0.4 to 1.2 mol / kg.
実施例３で得られた反応液を１０℃まで冷却して析出したＢＴＣの結晶を濾別し、精製水で洗浄してＢＴＣ湿結晶１４５ｇ（含水量２４重量％）と、濾液としてＢＴＣ（１１重量％）及び触媒を含有する反応母液４５０ｇ（４１０ｍｌ）を得た。この反応母液をスルホン酸型イオン交換樹脂Ｂに２時間かけて通液して（処理速度２２５ｍｌ／ｈ）、処理液４５０ｇを得た。該処理液にＴＨＰＡ７６ｇ（０．５モル）を加熱溶解し、９０℃で６０％過酸化水素１３０ｇ（２．３モル）を８時間かけて連続的に滴下しながら反応を行った。滴下終了１時間後、反応液をＨＰＬＣ分析したところ、ＴＨＰＡに対するＢＴＣの生成率は８９．８モル％であった。なお、反応中、反応液の過酸化水素の濃度は、０．３〜０．８モル／ｋｇの範囲であった。 The reaction solution obtained in Example 3 was cooled to 10 ° C., and the precipitated BTC crystals were filtered off, washed with purified water, and 145 g of BTC wet crystals (water content: 24% by weight), and BTC (11 %) And a reaction mother liquor containing 450 g (410 ml). This reaction mother liquor was passed through the sulfonic acid type ion exchange resin B over 2 hours (processing speed: 225 ml / h) to obtain 450 g of processing liquid. In this treatment solution, 76 g (0.5 mol) of THPA was dissolved by heating, and the reaction was performed at 90 ° C. while continuously dropping 130 g (2.3 mol) of 60% hydrogen peroxide over 8 hours. One hour after completion of the dropwise addition, the reaction solution was analyzed by HPLC. As a result, the production rate of BTC relative to THPA was 89.8 mol%. During the reaction, the concentration of hydrogen peroxide in the reaction solution was in the range of 0.3 to 0.8 mol / kg.
触媒としてタングステン酸２．０ｇを使用した以外は、実施例１と同様の方法で反応及びＢＴＣの分離を行い、ＢＴＣ（１２重量％）及び触媒を含有する反応母液５００ｇ（４５５ｍｌ）を得た。この反応母液をスルホン酸型イオン交換樹脂Ａに２時間かけて通液して（処理速度２５０ｍｌ／ｈ）、処理液４８０ｇを得た。該処理液にＴＨＰＡ７６ｇ（０．５モル）を加熱溶解し、還流下で６０％過酸化水素１３０ｇ（２．３モル）を８時間かけて連続的に滴下した。この間、反応液量が概ね一定量に保たれるように蒸発水を適宜系外に留去し、滴下終了１時間後、反応液をＨＰＬＣ分析したところ、ＴＨＰＡに対するＢＴＣの生成率は９０．２モル％であった。なお、反応中、反応液の過酸化水素の濃度は、０．４〜０．８モル／ｋｇの範囲であった。 Except for using 2.0 g of tungstic acid as a catalyst, the reaction and BTC were separated in the same manner as in Example 1 to obtain 500 g (455 ml) of a reaction mother liquor containing BTC (12 wt%) and the catalyst. This reaction mother liquor was passed through the sulfonic acid type ion exchange resin A over 2 hours (processing speed 250 ml / h) to obtain 480 g of processing liquid. In this treatment solution, 76 g (0.5 mol) of THPA was dissolved by heating, and 130 g (2.3 mol) of 60% hydrogen peroxide was continuously added dropwise over 8 hours under reflux. During this time, evaporated water was appropriately distilled out of the system so that the amount of the reaction solution was maintained at a substantially constant amount. One hour after the completion of the dropwise addition, the reaction solution was analyzed by HPLC. As a result, the BTC production rate relative to THPA was 90.2. Mol%. During the reaction, the concentration of hydrogen peroxide in the reaction solution was in the range of 0.4 to 0.8 mol / kg.
実施例１と同様の方法で、ＢＴＣの反応及び分離を行い、反応母液４８０ｇ（４３５ｍｌ）を得た。該反応母液に、ＴＨＰＡ７６ｇ（０．５モル）を加熱溶解し、還流下で６０％過酸化水素１６０ｇ（２．８モル）を７時間かけて連続的に滴下した以外は、実施例１と同様の方法により、ＢＴＣの分離と反応母液を得た。さらに、この反応母液をそのまま、再使用してＢＴＣの製造を繰り返し３回行ない、合計５回反応を繰り返した反応母液４６０ｇを得た。ＢＴＣ（１０重量％）及び触媒を含有する該反応母液を、室温下でスルホン酸型陽イオン交換樹脂に５時間かけて通液して（処理速度９０ｍｌ／ｈ）、処理液４５０ｇを得た。該処理液にＴＨＰＡｇ（０．５モル）を加熱溶解し、還流下で６０％過酸化水素１３０ｇ（２．３モル）を７時間かけて連続的に滴下した。この間、反応液量が概ね一定量に保たれるように蒸発水を適宜系外に留去し、滴下終了１時間後、反応液をＨＰＬＣ分析したところ、ＴＨＰＡに対するＢＴＣの生成率は９１．７モル％であった。なお、反応中、反応液の過酸化水素の濃度は、０．４〜０．８モル／ｋｇの範囲であった。 BTC was reacted and separated in the same manner as in Example 1 to obtain 480 g (435 ml) of a reaction mother liquor. In the same manner as Example 1 except that 76 g (0.5 mol) of THPA was dissolved by heating in the reaction mother liquor, and 160 g (2.8 mol) of 60% hydrogen peroxide was continuously added dropwise over 7 hours under reflux. By this method, BTC separation and reaction mother liquor were obtained. Further, this reaction mother liquor was reused as it was, and BTC production was repeated 3 times, to obtain 460 g of reaction mother liquor in which the reaction was repeated a total of 5 times. The reaction mother liquor containing BTC (10% by weight) and a catalyst was passed through a sulfonic acid type cation exchange resin at room temperature over 5 hours (treatment speed 90 ml / h) to obtain 450 g of a treatment liquid. THPAg (0.5 mol) was heated and dissolved in the treatment solution, and 130 g (2.3 mol) of 60% hydrogen peroxide was continuously added dropwise over 7 hours under reflux. During this time, evaporated water was appropriately distilled out of the system so that the amount of the reaction solution was maintained at a substantially constant amount. One hour after completion of the dropwise addition, the reaction solution was analyzed by HPLC. As a result, the production rate of BTC relative to THPA was 91.7. Mol%. During the reaction, the concentration of hydrogen peroxide in the reaction solution was in the range of 0.4 to 0.8 mol / kg.
比較例１
撹拌機、温度計及び冷却器付きガラス製フラスコ中に、１，２，４，５−テトラヒドロ無水フタル酸（以下、「ＴＨＰＡ」と略記する。）１５２ｇ（１．０モル）と１２−タングストリン酸・３０水和物４．５ｇを精製水５００ｇを入れ、加熱溶解した。還流下で６０％過酸化水素水２５５ｇ（４．５モル）を８時間かけて滴下すると共に、反応液量が概ね一定量に保たれるように蒸発水を適宜系外に留去しながら反応を行ったところ、反応液中のＴＨＰＡに対するＢＴＣの生成率は８８．２モル％であった。なお、反応中の反応液の過酸化物価から求めた過酸化水素濃度は、０．４〜０．８モル／ｋｇの範囲であった。得られた反応液を１０℃まで冷却し析出したＢＴＣの結晶を濾別し、精製水で洗浄してＢＴＣ湿結晶１６０ｇ（含水量２４重量％）と、濾液としてＢＴＣ（１２重量％）及び触媒を含有する反応母液５００ｇを得た。この反応母液にＴＨＰＡ７６ｇ（０．５モル）を加熱溶解し、還流下で６０％過酸化水素１３０ｇ（２．３モル）を７時間かけて連続的に滴下した。この間、反応液量が概ね一定量に保たれるように蒸発水を適宜系外に留去し、滴下終了１時間後、反応液をＨＰＬＣ分析したところ、ＴＨＰＡに対するＢＴＣの生成率は７０．７モル％であった。なお、反応中、反応液の過酸化水素の濃度は、０．４〜０．８モル／ｋｇの範囲であった。
Comparative Example 1
In a glass flask equipped with a stirrer, thermometer and condenser, 152 g (1.0 mol) of 1,2,4,5-tetrahydrophthalic anhydride (hereinafter abbreviated as “THPA”) and 12-tungstorin 4.5 g of acid / 30 hydrate was added to 500 g of purified water and dissolved by heating. While refluxing, 255 g (4.5 mol) of 60% aqueous hydrogen peroxide was added dropwise over 8 hours, and the reaction was carried out while appropriately distilling the evaporated water out of the system so that the amount of the reaction solution was maintained at a substantially constant level. As a result, the production rate of BTC relative to THPA in the reaction solution was 88.2 mol%. In addition, the hydrogen peroxide concentration calculated | required from the peroxide value of the reaction liquid in reaction was the range of 0.4-0.8 mol / kg. The obtained reaction solution was cooled to 10 ° C., and the precipitated BTC crystals were separated by filtration, washed with purified water, and 160 g of BTC wet crystals (water content: 24% by weight), and BTC (12% by weight) and catalyst as the filtrate. A reaction mother liquor containing 500 g was obtained. In this reaction mother liquor, 76 g (0.5 mol) of THPA was dissolved by heating, and 130 g (2.3 mol) of 60% hydrogen peroxide was continuously added dropwise over 7 hours under reflux. During this time, evaporated water was appropriately distilled out of the system so that the amount of the reaction solution was maintained at a substantially constant amount. One hour after the completion of the dropwise addition, the reaction solution was analyzed by HPLC. As a result, the BTC production rate relative to THPA was 70.7. Mol%. During the reaction, the concentration of hydrogen peroxide in the reaction solution was in the range of 0.4 to 0.8 mol / kg.
比較例２
実施例６と同様の方法により、合計５回反応を繰り返した反応母液を得た。該反応母液を何ら処理しなかった以外は、実施例６と同様の条件で反応を行った後、反応液をＨＰＬＣ分析したところ、ＴＨＰＡに対するＢＴＣの生成率は、５８．２％であった。
Comparative Example 2
In the same manner as in Example 6, a reaction mother liquor in which the reaction was repeated a total of 5 times was obtained. Except that the reaction mother liquor was not treated at all, the reaction was carried out under the same conditions as in Example 6, and then the reaction mixture was analyzed by HPLC. As a result, the production rate of BTC relative to THPA was 58.2%.
本発明に従い、ＢＴＣの製造に使用した触媒及びＢＴＣを含有する反応母液をスルホン酸型陽イオン交換樹脂で処理し、得られた処理液を反応に再使用することにより、ＢＴＣの生成率を低下させることなく工業的に有利に１，２，３，４−ブタンテトラカルボン酸を得ることができる。
特許出願人 新日本理化株式会社
In accordance with the present invention, the catalyst used for the production of BTC and the reaction mother liquor containing BTC are treated with a sulfonic acid type cation exchange resin, and the resulting treatment liquid is reused in the reaction, thereby reducing the production rate of BTC. In this manner, 1,2,3,4-butanetetracarboxylic acid can be obtained industrially advantageously.
Patent applicant New Nippon Rika Co., Ltd.
Claims (5)
The method for producing 1,2,3,4-butanetetracarboxylic acid according to any one of claims 1 to 4, wherein the reaction is carried out under reflux conditions.
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