JP6861289B2 - A catalyst for producing alkylene carbonate, a method for producing the same, and a method and apparatus for producing alkylene carbonate using the catalyst. - Google Patents
A catalyst for producing alkylene carbonate, a method for producing the same, and a method and apparatus for producing alkylene carbonate using the catalyst. Download PDFInfo
- Publication number
- JP6861289B2 JP6861289B2 JP2019543856A JP2019543856A JP6861289B2 JP 6861289 B2 JP6861289 B2 JP 6861289B2 JP 2019543856 A JP2019543856 A JP 2019543856A JP 2019543856 A JP2019543856 A JP 2019543856A JP 6861289 B2 JP6861289 B2 JP 6861289B2
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- Prior art keywords
- catalyst
- alkylene carbonate
- producing
- group
- reaction
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 112
- -1 alkylene carbonate Chemical compound 0.000 title claims description 86
- 238000004519 manufacturing process Methods 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 59
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 26
- 125000002947 alkylene group Chemical group 0.000 claims description 22
- 150000004820 halides Chemical class 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000001569 carbon dioxide Substances 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 16
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 12
- 125000004185 ester group Chemical group 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 5
- ZILVNHNSYBNLSZ-UHFFFAOYSA-N 2-(diaminomethylideneamino)guanidine Chemical compound NC(N)=NNC(N)=N ZILVNHNSYBNLSZ-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
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- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 4
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 claims description 3
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 claims description 3
- 125000003367 polycyclic group Chemical group 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 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 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 229960001126 alginic acid Drugs 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 239000000783 alginic acid Substances 0.000 claims description 2
- 150000004781 alginic acids Chemical class 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- 125000004429 atom Chemical group 0.000 claims 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims 1
- 238000002474 experimental method Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000012018 catalyst precursor Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 3
- 229940107816 ammonium iodide Drugs 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 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 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001502 inorganic halide Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LWLOKSXSAUHTJO-SYPWQXSBSA-N C[C@H](C(C)O1)OC1=O Chemical compound C[C@H](C(C)O1)OC1=O LWLOKSXSAUHTJO-SYPWQXSBSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
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- 239000011964 heteropoly acid Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0209—Esters of carboxylic or carbonic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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Description
本明細書は、アルキレンカーボネート製造用触媒、その製造方法、並びに前記触媒を用いたアルキレンカーボネートの製造方法及び装置に関する。 The present specification relates to a catalyst for producing an alkylene carbonate, a method for producing the same, and a method and an apparatus for producing an alkylene carbonate using the catalyst.
本発明を支援した国家研究開発事業
本研究は、未来創造科学部の支援の下、韓国研究財団主観の新技術融合型成長動力事業として行われたものであって、研究課題名は‘Ｏｒｔｈｏ−ｐａｒａ水素変換分析技術開発’である（研究期間：２０１５.７.１〜２０１６.６.３０）。
National R & D project that supported the present invention This research was conducted as a subjective new technology fusion type growth driving project of the Korea Research Foundation with the support of the Faculty of Future Creation Science, and the research project name is'Ortho-. Para hydrogen conversion analysis technology development'(Research period: 2015.7.1 to 2016.6.30).
エチレンカーボネート、プロピレンカーボネートなどのアルキレンカーボネートは、産業工程で溶媒や希釈剤として広く用いられており、化粧品原料物質や二次電池電解質としても用いられている。また、アルキレンオキサイドからアルキレングリコールの製造の際に中間体として使用可能であることから、最近、アルキレンカーボネートについての関心が増大しつつある。 Alkylene carbonates such as ethylene carbonate and propylene carbonate are widely used as solvents and diluents in industrial processes, and are also used as raw material substances for cosmetics and electrolytes for secondary batteries. In addition, since it can be used as an intermediate in the production of alkylene glycol from alkylene oxide, interest in alkylene carbonate has been increasing recently.
従来、アルキレンカーボネートの製造には、エチレングリコール（ｅｔｈｙｌｅｎｅ ｇｌｙｃｏｌ）とホスゲン（ＣＯＣｌ２）とを反応させる方法が用いられていた。この反応は室温で無触媒で進められる。しかし、原料物質であるホスゲンの猛毒性や環境汚染物質である塩化水素の副成という問題などのため、最近では、主にアルキレンオキサイドと二酸化炭素とを反応させる工程が用いられている。 Conventionally, a method of reacting ethylene glycol (ethylene glycol) with phosgene (COCl 2 ) has been used for the production of alkylene carbonate. This reaction proceeds uncatalyzed at room temperature. However, due to problems such as the violent toxicity of phosgene, which is a raw material, and the by-product of hydrogen chloride, which is an environmental pollutant, recently, a process of reacting alkylene oxide with carbon dioxide is mainly used.
しかし、アルキレンオキサイドと二酸化炭素とを反応させてアルキレンカーボネートを製造する反応工程は、室温で無触媒で進められるホスゲン工程とは異なり、高温・高圧下での反応が要求されるため、原料であるアルキレンオキサイドが分解又は重合して副生物が多量生成されるという問題とともに爆発の危険性もある。 However, unlike the phosgene process, which is carried out at room temperature without a catalyst, the reaction process for producing alkylene carbonate by reacting alkylene oxide with carbon dioxide requires a reaction at high temperature and high pressure, so it is a raw material. There is a risk of explosion as well as the problem that alkylene oxide is decomposed or polymerized to produce a large amount of by-products.
これらの問題点を解決するために多様な触媒が開発され、低温・低圧で反応させる研究が行なわれてきた。
例えば、日本特開平９−６７３６５号では、触媒としてＫＩを用いる方法を記述しており、また、日本特開昭５９−１３７７６号では、トリブチルホスホニウムヨージド（ｔｒｉｂｕｔｙｌ ｍｅｔｈｙｌｐｈｏｓｐｈｏｎｉｕｍ ｉｏｄｉｄｅ）及びテトラアルキルホスホニウムハライド（ｔｅｔｒａａｌｋｙｌ ｐｈｏｓｐｈｏｎｉｕｍ ｈａｌｉｄｅ）を用いる方法を記述している。
Various catalysts have been developed to solve these problems, and research has been conducted to react them at low temperature and low pressure.
For example, Japanese Patent Application Laid-Open No. 9-67365 describes a method of using KI as a catalyst, and Japanese Patent Application Laid-Open No. 59-13776 describes tributyl phosphonium iodide and tetraalkyl phosphonium halide ( It describes a method using a catalyst (tetraalkyl phosphate halide).
また、日本特開平９−２３５２５２号には、末端基に四級ホスホニウムハライドを有しているポリスチレン共重合高分子を用いる方法が開示されている。当該文献では、反応温度を１００〜１７０℃で１〜５時間反応させたとき、収率が５０〜９５％に達すると記述されている。 Further, Japanese Patent Application Laid-Open No. 9-235252 discloses a method using a polystyrene copolymer polymer having a quaternary phosphonium halide as a terminal group. The document describes that the yield reaches 50-95% when the reaction is carried out at a reaction temperature of 100-170 ° C. for 1-5 hours.
しかし、これらの触媒はイオン性液体で非常に高価のものであり、実際に商用化された均一系触媒を用いる工程では無機ハライド触媒を用いており、反応温度１８０℃、圧力１００気圧、反応時間８時間以上を要し、且つ原料である二酸化炭素及びアルキレンオキサイドの水分含量を数百ｐｐｍ以下に調節する必要があるなどの問題点を持っている。 However, these catalysts are ionic liquids and are very expensive. In the process of using a commercially available homogeneous catalyst, an inorganic halide catalyst is used, and the reaction temperature is 180 ° C., the pressure is 100 atm, and the reaction time is long. It takes 8 hours or more, and has problems such as the need to adjust the water content of carbon dioxide and alkylene oxide as raw materials to several hundred ppm or less.
また、無機ハライド物質は反応物と生成物に溶解される均一系（ｈｏｍｏｇｅｎｅｏｕｓ）触媒であるため、生成物と触媒とを分離するために真空蒸留し、しかも、分離された触媒はリサイクルが不可能であるため廃棄するようになる。 Further, since the inorganic halide substance is a homogeneous catalyst dissolved in the reactant and the product, vacuum distillation is performed to separate the product and the catalyst, and the separated catalyst cannot be recycled. Therefore, it will be discarded.
さらに、日本特開平７−２０６８４６号では、イオン交換樹脂を用いる方法としてイオン交換樹脂にＣｓＯＨ、ＲｂＯＨ、アンモニウムハライドを置換させた触媒を用いる方法を開示している。 Further, Japanese Patent Application Laid-Open No. 7-206846 discloses a method of using a catalyst in which CsOH, RbOH and ammonium hydroxide are substituted in an ion exchange resin as a method of using an ion exchange resin.
また、アメリカ特許第４,２３３,２２１号では、ダウエックス（Ｄｏｗｅｘ）とアンバーライト（Ａｍｂｅｒｌｉｔｅ）系のイオン交換樹脂を用いる方法を記述している。しかし、この方法ではアルキレンカーボネートの収率が３０〜８０％程度に過ぎないという実情である。 Further, US Pat. No. 4,233,221 describes a method using Dowex and Amberlite-based ion exchange resins. However, in this method, the yield of alkylene carbonate is only about 30 to 80%.
前述した触媒の他、アメリカ特許第５,２８３,３５６号では、Ｃｏ、Ｃｒ、Ｆｅ、Ｍｎ、Ｎｉ、Ｔｉ、Ｖ、Ｚｒなどを含むフタロシアニン（ｐｈｔｈａｌｏｃｙａｎｉｎｅ）を触媒として用いる方法を開示しており、また、日本特開平７−２０６５４７号では、ヘテロポリ酸（ｈｅｔｅｒｏｐｏｌｙ ａｃｉｄ）の水素イオンの代わりにルビジウム（Ｒｂ）又はセシウム（Ｃｓ）イオンを置換する触媒を用いる方法を提示している。しかし、両者の場合、いずれも高価の触媒を必要とし、反応温度は１２０〜１８０℃と温和な条件であるが、収率が３０〜９０％と充分ではない実情である。 Other of the aforementioned catalyst, in US Patent No. 5,283,356, Co, Cr, Fe, Mn, Ni, Ti, V, and phthalocyanine including Zr of (phthalocyanin e) discloses a method of using as a catalyst Further, Japanese Patent Application Laid-Open No. 7-206547 presents a method of using a catalyst for substituting rubidium (Rb) or cesium (Cs) ions instead of hydrogen ions of heteropoly acid. However, in both cases, an expensive catalyst is required, and the reaction temperature is mild at 120 to 180 ° C., but the yield is 30 to 90%, which is not sufficient.
以上のように、従来技術による方法でアルキレンカーボネートを量産するためには、高い温度と圧力、長い反応時間、原料の水分除去などの反応条件がややこしいだけでなく、選択性や収率が低いという問題点がある。 As described above, in order to mass-produce alkylene carbonate by the conventional method, not only the reaction conditions such as high temperature and pressure, long reaction time, and water removal of the raw material are complicated, but also the selectivity and yield are low. There is a problem.
また、従来技術の触媒の大半は熱安定性に劣っており、高温の反応又は蒸留精製過程で一部分解してハライドイオンを生成し、生成されたハライドイオンがアルキレンオキサイドと反応してハライド系副生物を生成する原因を提供したりもする。 In addition, most of the catalysts of the prior art are inferior in thermal stability, and are partially decomposed in a high temperature reaction or a distillation purification process to generate a halide ion, and the generated halide ion reacts with an alkylene oxide to form a halide-based sub. It also provides the cause of the production of organisms.
一方、より温和な条件で反応を進めるために改善された触媒として、マンガンハライド（ＭｎＸ２、Ｘ＝Ｃｌ、Ｂｒ、Ｉ）及びアルカリ金属ハライドからなる触媒（アメリカ特許第６,１６０,１３０号）と、インジウムと鉛ハライド、アルカリ金属ハライド（アメリカ特許第６,１５６,９０９号）からなる触媒などがあるが、いずれも均一系触媒であるため、触媒の回収及び再使用に問題点がある。 On the other hand, as a catalyst improved to proceed the reaction under milder conditions, a catalyst composed of manganese halide (MnX 2 , X = Cl, Br, I) and alkali metal halide (American Patent No. 6,160,130). There are catalysts composed of indium, lead halides, and alkali metal halides (American Patent No. 6,156,909), but since all of them are homogeneous catalysts, there is a problem in recovering and reusing the catalysts.
本発明の例示的な具現例では、一側面において、アルキレンオキサイドと二酸化炭素との反応を促進することで、低温及び低圧の温和な反応条件において短時間且つ高い収率でアルキレンカーボネートを製造することができるアルキレンカーボネート製造用触媒、その製造方法、並びに前記触媒を用いたアルキレンカーボネートの製造方法及び装置を提供することをその目的とする。 In an exemplary embodiment of the present invention, in one aspect, alkylene carbonate is produced in a short time and in a high yield under mild reaction conditions at low temperature and low pressure by accelerating the reaction between alkylene oxide and carbon dioxide. It is an object of the present invention to provide a catalyst for producing alkylene carbonate, a method for producing the same, and a method and an apparatus for producing alkylene carbonate using the catalyst.
本発明の例示的な具現例では、他の一側面において、耐久性に優れ、且つ触媒の回収及び再使用に有利であり、触媒を繰り返し再使用しても収率を保持することができるアルキレンカーボネート製造用触媒、その製造方法、並びに前記触媒を用いたアルキレンカーボネートの製造方法及び装置を製造する方法を提供することをその目的とする。 In the exemplary embodiment of the present invention, in another aspect, the alkylene is excellent in durability, advantageous for recovery and reuse of the catalyst, and can maintain the yield even if the catalyst is repeatedly reused. An object of the present invention is to provide a catalyst for producing a carbonate, a method for producing the same, and a method for producing an alkylene carbonate using the catalyst and a method for producing an apparatus.
本発明の例示的な具現例では、アルキレンカーボネート製造用触媒であって、カルボニル基（−Ｃ＝Ｏ−）又はエステル基（−ＣＯＯ−）；及びハライド、アミン基（−ＮＨ２）、ヒドロキシ基（−ＯＨ）をいずれも含むアルキレンカーボネート製造用触媒を提供する。 In an exemplary embodiment of the present invention, the catalyst for producing an alkylene carbonate is a carbonyl group (-C = O-) or an ester group (-COO-); and a halide, amine group (-NH2), hydroxy group (-NH2). Provided is a catalyst for producing an alkylene carbonate containing both −OH).
本発明の例示的な具現例では、他の一側面において、アルキレンカーボネート製造用触媒の製造方法であって、ハライド、アミン基、ヒドロキシ基を含む化合物をカルボン酸前駆体（又はエステル前駆体）と反応させる段階;を含むアルキレンカーボネート製造用触媒の製造方法を提供する。 In an exemplary embodiment of the present invention, in another aspect, a method for producing a catalyst for producing an alkylene carbonate, wherein a compound containing a halide, an amine group, and a hydroxy group is referred to as a carboxylic acid precursor (or ester precursor). Provided is a method for producing a catalyst for producing an alkylene carbonate, which comprises a step of reacting;
本発明の例示的な具現例では、さらに、前記アルキレンカーボネート製造用触媒の下でアルキレンオキサイドと二酸化炭素とを反応させてアルキレンカーボネートを製造するアルキレンカーボネートの製造方法及び装置を提供する。 An exemplary embodiment of the present invention further provides a method and apparatus for producing an alkylene carbonate by reacting an alkylene oxide with carbon dioxide under the catalyst for producing an alkylene carbonate.
本発明の例示的な具現例によれば、アルキレンオキサイドと二酸化炭素との反応を促進することで、既存の触媒による反応条件に比べて低温、低圧での反応が可能であり且つ反応時間を短縮させることができ、高い収率でアルキレンカーボネートを得ることが可能である。 According to an exemplary embodiment of the present invention, by accelerating the reaction between the alkylene oxide and carbon dioxide, the reaction can be performed at a low temperature and a low pressure as compared with the reaction conditions using an existing catalyst, and the reaction time is shortened. It is possible to obtain an alkylene carbonate in a high yield.
また、本発明の例示的な具現例による触媒は反応物と生成物に溶解しない不均一系（ｈｅｔｅｒｏｇｅｎｅｏｕｓ）触媒であって、反応後に生成物と触媒とを単純沈殿及びろ過にて分離可能であるため分離が容易であり、分離された触媒もリサイクルが可能であるため経済的な観点からも長所がある。また、触媒の耐久性が高く且つ触媒を繰り返し再使用しても触媒収率を保持することができる。 Further, the catalyst according to the exemplary embodiment of the present invention is a heterogeneous catalyst that does not dissolve in the reactant and the product, and the product and the catalyst can be separated by simple precipitation and filtration after the reaction. Therefore, it is easy to separate, and the separated catalyst can be recycled, which is advantageous from an economical point of view. In addition, the durability of the catalyst is high, and the catalyst yield can be maintained even if the catalyst is repeatedly reused.
以下、本発明の例示的な具現例について詳しく説明することにする。 Hereinafter, exemplary embodiment of the present invention will be described in detail.
本明細書において、アルキル基は、直鎖状若しくは分岐状の炭化水素を意味し、例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシルなどが含まれるが、これらに限定されるものではない。 In the present specification, the alkyl group means a linear or branched hydrocarbon, and includes, but is not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl and the like.
本明細書において、アリール基は、芳香族基とヘテロ芳香族基及びそれらの部分的に還元された誘導体をすべて含むものであってよい。芳香族基は、５〜１５角形からなる単環式又は縮合環式のものであり、ヘテロ芳香族基は、酸素、硫黄又は窒素を１つ以上含む芳香族基を意味する。 As used herein, the aryl group may include all aromatic groups, heteroaromatic groups and partially reduced derivatives thereof. The aromatic group is a monocyclic or condensed ring type consisting of 5 to 15 squares, and the heteroaromatic group means an aromatic group containing one or more oxygen, sulfur or nitrogen.
代表的なアリール基の例としては、フェニル、ベンジル、ナフチル、ピリジニル（ｐｙｒｉｄｉｎｙｌ）、フラニル（ｆｕｒａｎｙｌ）、チオフェニル（ｔｈｉｏｐｈｅｎｙｌ）、インドリル（ｉｎｄｏｌｙｌ）、キノリニル（ｑｕｉｎｏｌｉｎｙｌ）、イミダゾリニル（ｉｍｉｄａｚｏｌｉｎｙｌ）、オキサゾリル（ｏｘａｚｏｌｙｌ）、チアゾリル（ｔｈｉａｚｏｌｙｌ）、テトラヒドロナフチルなどがあるが、これらに限定されるものではない。 Examples of typical aryl groups are phenyl, benzyl, naphthyl, pyridinyl, furanyl, thiophenyl, indole, quinolinyl, imidazolyl, oxazolyl, and oxalyl. , Thiazolyl, tetrahydronaphthyl and the like, but are not limited thereto.
本明細書において、ハロアルキル基は１つ又はそれ以上の水素がハロゲンで置換されたアルキル基を意味し、例えば、トリフルオロメチル、クロロメチルなどを含むが、これらに限定されるものではない。 As used herein, a haloalkyl group means an alkyl group in which one or more hydrogens are substituted with halogen, and includes, but is not limited to, for example, trifluoromethyl, chloromethyl, and the like.
本発明の例示的な具現例では、アルキレンカーボネート製造用触媒であって、カルボニル基（−Ｃ＝Ｏ−）又はエステル基（−ＣＯＯ−）；アミン基（−ＮＨ２）、ヒドロキシ基（−ＯＨ）、ハライド成分をともに含む。該触媒においてカルボニル基（−Ｃ＝Ｏ−）又はエステル基（−ＣＯＯ−）は、アミン基、ヒドロキシ基、ハライドのうちの１つ以上の化学結合を強くする役割をし、炭素、酸素、水素などの有機物鎖を長くすることで高温・高圧で触媒が溶け難くなるようにするため、該触媒が不均一系触媒特性を示すと判断される。すなわち、該触媒は不均一系触媒である。 In an exemplary embodiment of the present invention, the catalyst for producing an alkylene carbonate is a carbonyl group (-C = O-) or an ester group (-COO-); an amine group (-NH 2 ), a hydroxy group (-OH). ), Contains both the halide component. In the catalyst, the carbonyl group (-C = O-) or ester group (-COO-) plays a role in strengthening the chemical bond of one or more of amine group, hydroxy group and halide, and carbon, oxygen and hydrogen. It is judged that the catalyst exhibits heterogeneous catalytic properties in order to make it difficult for the catalyst to dissolve at high temperature and high pressure by lengthening the organic chain such as. That is, the catalyst is a heterogeneous catalyst.
このように、前記アルキレンカーボネート製造用触媒は、既存の触媒と異なり、触媒中にカルボニル基（−Ｃ＝Ｏ−）又はエステル基（−ＣＯＯ−）の化学結合で固定化されたアミン基、ヒドロキシ基、ハライド物質が存在して、二酸化炭素の吸収促進、アルキレンオキサイド中の Ｏ−ｒｉｎｇをｏｐｅｎｉｎｇして二酸化炭素の添加反応を生じさせる。 As described above, unlike the existing catalyst, the catalyst for producing alkylene carbonate is an amine group, hydroxy, which is immobilized by a chemical bond of a carbonyl group (-C = O-) or an ester group (-COO-) in the catalyst. A group, a halide substance, is present, which promotes the absorption of carbon dioxide and opens the O-ring in the alkylene oxide to cause an addition reaction of carbon dioxide.
また、触媒のエステル基（−ＣＯＯ−）又はカルボニル基（−Ｃ＝Ｏ−）がアミン基、ヒドロキシ基、ハライドの化学結合を強くして、反応物及び生成物に触媒が溶解しないようにすることができるため、触媒反応性及び耐久性が向上され得る。 In addition, the ester group (-COO-) or carbonyl group (-C = O-) of the catalyst strengthens the chemical bond of the amine group, hydroxy group and halide to prevent the catalyst from dissolving in the reactants and products. Therefore, catalytic reactivity and durability can be improved.
例示的な一具現例において、前記触媒は、ＦＴ−ＩＲスペクトルで３２００〜３６００ｃｍ−１において−ＯＨピークを示し、１６３０〜１６８０ｃｍ−１において−Ｃ＝Ｏ−ピークを示し、１５１５〜１５７０ｃｍ−１において−Ｃ−Ｎ−Ｈピークを示し、１２１１〜１３４０ｃｍ−１において−Ｃ−Ｏ−ピークを示す。特に、前記触媒は、ＦＴ−ＩＲスペクトルで３３２５ｃｍ−１において−ＯＨピークを示し、１６３２ｃｍ−１において−Ｃ＝Ｏ−ピークを示し、１５５８ｃｍ−１において−Ｃ−Ｎ−Ｈピークを示し、１３３５ｃｍ−１において−Ｃ−Ｏ−ピークを示す。 In an exemplary an embodiment, the catalyst shows the -OH peaks in 3200～3600Cm -1 in FT-IR spectrum shows a -C = O-peak at 1630～1680Cm -1, in 1515～1570Cm -1 It shows a -C-N-H peak and a -C-O- peak at 1211-1340 cm -1. In particular, the catalyst shows the -OH peak at 3325cm -1 in FT-IR spectrum shows a -C = O-peak at 1632cm -1, indicate the -C-N-H peak at 1558cm -1, 1335cm - The −CO— peak is shown at 1.
例示的な一具現例において、前記触媒は、下記の化学式１又は化学式２又は化学式３又は化学式４で表される触媒であってよい。
化学式１〜化学式４中、ｎは、それぞれ繰り返し単位である。
In
前記化学式１〜化学式４に見られるように、アルキレンカーボネート製造用触媒は、カルボニル基（−Ｃ＝Ｏ−）又はエステル基（−ＣＯＯ−）を含み、さらに、アミン基、ヒドロキシ基（−ＯＨ）、ハライド成分を含む。
As seen in the
前記化学式１〜化学式４においてハライド（ｈａｌｉｄｅ）は、Ｆ、Ｃｌ、Ｂｒ又はＩであり、エポキシド Ｏｒｉｎｇ ｏｐｅｎｉｎｇ及び二酸化炭素の添加反応効果が大きいという面から、好ましくは、Ｂｒ又はＩ又はＣｌである。
In the
本発明の例示的な具現例では、他の一側面において、アルキレンカーボネート製造用触媒の製造方法であって、ハライド、アミン基、ヒドロキシ基をいずれも含む触媒化合物を重縮合反応前駆体であるカルボン酸前駆体（又は、エステル前駆体）と反応させる段階;を含むアルキレンカーボネート製造用触媒の製造方法を提供する。 In an exemplary embodiment of the present invention, in another aspect, a method for producing a catalyst for producing an alkylene carbonate, wherein a catalyst compound containing any of a halide, an amine group, and a hydroxy group is a carboxylic acid as a polycondensation reaction precursor. Provided is a method for producing a catalyst for producing an alkylene carbonate, which comprises a step of reacting with an acid precursor (or an ester precursor).
例示的な一具現例において、前記方法は、アミン前駆体、アルデヒド前駆体、及びアンモニウムハライドからハライド、アミン基、ヒドロキシ基を含む触媒化合物を生成する段階；前記触媒化合物をカルボン酸前駆体（又は、エステル前駆体）と反応させて前記触媒化合物にカルボニル基又はエステル基を生成する段階;をさらに含んでいてよい。 In one exemplary embodiment, the method is the step of producing a catalytic compound containing a halide, an amine group, a hydroxy group from an amine precursor, an aldehyde precursor, and an ammonium halide; the catalytic compound is a carboxylic acid precursor (or). , Ester precursor) to form a carbonyl group or ester group in the catalyst compound;
例示的な一具現例において、アミン前駆体は、尿素（ｕｒｅａ）、メラミン（ｍｅｌａｍｉｎｅ）、ジシアンジアミド（ｄｉｃｙａｎｄｉａｍｉｄｅ）、シアンアミド（ｃｙａｎａｍｉｄｅ）、グアニジン（ｇｕａｎｉｄｉｎｅ）、ビグアニジン（ｂｉｇｕａｎｉｄｉｎｅ）、グアニル尿素（ｇｕａｎｙｌｕｒｅａ）、多環グアニジン（ｐｏｌｙｃｙｃｌｉｃ ｇｕａｎｉｄｉｎｅ）などが含まれた１種以上の物質が用いられてよい。 In an exemplary an embodiment, the amine precursor, urea (urea), a melamine (melamine), cyanogen diamide (dicyandiamide), cyanamide (Cyanamide), guanidine (guanidine), biguanidine (biguanidine), guanyl urea (guanylurea) , One or more substances containing polycyclic guanidine and the like may be used.
例示的な一具現例において、アルデヒド前駆体としては、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ブチルアルデヒド、ベンズアルデヒド、グルタルアルデヒド（ｇｌｕｔａｒａｌｄｅｈｙｄｅ）、グリオキサール（ｇｌｙｏｘａｌ）、マロンジアルデヒド（ｍａｌｏｎｄｉａｌｄｅｈｙｄｅ）、コハク酸ジアルデヒド（ｓｕｃｃｉｎｄｉａｌｄｅｈｙｄｅ）、フタルアルデヒド（ｐｈｔｈａｌａｌｄｅｈｙｄｅ）などのアルデヒド類と知られた１種以上の物質が用いられてよい。 In one exemplary embodiment, the aldehyde precursors include formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, benzaldehyde, glutaraldehyde, glyoxal, malondialdide, and succindialdehyde. ), One or more substances known as aldehydes such as phthalaldehyde may be used.
例示的な一具現例において、アンモニウムハライドとしては、例えば、ＮＨ４Ｉ、ＮＨ４Ｂｒ、ＮＨ４Ｃｌなどから選ばれる１種以上が用いられてよい。 In one exemplary embodiment, as the ammonium halide, for example, one or more selected from NH 4 I, NH 4 Br, NH 4 Cl and the like may be used.
例示的な一具現例において、前記カルボン酸前駆体（又は、エステル前駆体）は、ギ酸、酢酸、プロピオン酸、ｎ−酪酸、イソ酪酸、ｎ−吉草酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、ポリアクリル酸（ｐｏｌｙａｃｒｙｌｉｃ ａｃｉｄ、ＰＡＡ）、酸化グラフェン（ｇｒａｐｈｅｎｅ ｏｘｉｄｅ）、アルギン酸（ａｌｇｉｎｉｃ ａｃｉｄ）などのカルボキシル基を含む物質から選ばれる１種以上であってよい。 In one exemplary embodiment, the carboxylic acid precursor (or ester precursor) is formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, hexanoic acid, heptanic acid, octanoic acid, It may be one or more selected from substances containing a carboxyl group such as nonanoic acid, polyacrylic acid (PAA), graphene oxide, and alginic acid.
本発明の例示的な具現例では、また、前記アルキレンカーボネート製造用触媒の下でアルキレンオキサイドと二酸化炭素とを反応させてアルキレンカーボネートを製造するアルキレンカーボネートの製造方法を提供する。 An exemplary embodiment of the present invention also provides a method for producing an alkylene carbonate by reacting an alkylene oxide with carbon dioxide under the catalyst for producing an alkylene carbonate.
本発明の例示的な具現例では、さらに、アルキレンオキサイドと二酸化炭素とを反応させてアルキレンカーボネートを製造するアルキレンカーボネートの製造装置であって、前記触媒を含む装置を提供する。 An exemplary embodiment of the present invention further provides an apparatus for producing an alkylene carbonate by reacting an alkylene oxide with carbon dioxide to produce an alkylene carbonate, which comprises the catalyst.
例示的な一具現例において、前記アルキレンオキサイドは、下記の化学式５で表されるものであってよく、アルキレンカーボネートは、下記の化学式６で表される化合物であってよい。
前記化学式５及び化学式６中、Ｒ１及びＲ２は、それぞれ独立に、水素、炭素数１〜６のアルキル基、炭素数１〜６のハロアルキル基又はアリール基であってよく、結合されている炭素原子とともに六角形環を形成していてよい。 In the chemical formulas 5 and 6, R1 and R2 may be independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an aryl group, and are bonded carbon atoms. May form a hexagonal ring with.
例示的な一具現例において、前記化学式５で表されるアルキレンオキサイドは、例えば、エチレンオキサイド、プロピレンオキサイド、エピクロロヒドリン、ブチレンオキサイド、スチレンオキサイド、シクロへキシレンオキサイドなどを含むが、これらに限定されるものではない。 In one exemplary embodiment, the alkylene oxide represented by Chemical Formula 5 includes, but is limited to, for example, ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide, styrene oxide, cyclohexylene oxide and the like. It is not something that is done.
例示的な一具現例において、前記触媒の使用量は、アルキレンオキサイド１００重量に対し、好ましくは、０．０００１〜２０重量部、より好ましくは、０．１〜５重量部で用いられてよい。０．０００１重量部未満である場合は、反応速度が遅くなりすぎることがあり、また、２０重量部を超える場合は、さらなる反応速度や選択性の向上が得られないことがあるため経済的利得がない。 In one exemplary embodiment, the amount of the catalyst used may be preferably 0.0001 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the alkylene oxide. If it is less than 0.0001 parts by weight, the reaction rate may be too slow, and if it exceeds 20 parts by weight, further improvement in reaction rate and selectivity may not be obtained, which is an economic gain. There is no.
例示的な一具現例において、前記反応の反応温度は、４０〜１５０℃又は８０〜１５０℃であってよい。反応温度が低すぎると、反応速度が遅くなることがあり、また、反応温度が高すぎると、アルキレンオキサイドが自己高分子化反応（ｓｅｌｆ−ｐｏｌｙｍｅｒｉｚａｔｉｏｎ）を引き起こすため反応選択性が低下することがある。 In one exemplary embodiment, the reaction temperature of the reaction may be 40-150 ° C or 80-150 ° C. If the reaction temperature is too low, the reaction rate may slow down, and if the reaction temperature is too high, the alkylene oxide may cause a self-polymerization reaction (self-polymerization), which may reduce the reaction selectivity. ..
例示的な一具現例において、前記反応の反応圧力は１０〜３０気圧である。反応圧力が１０気圧未満になると、反応速度が遅くなることがあり、また、３０気圧を超えると、さらなる反応速度の向上効果が得られないだけでなく、装置コストの過多所要につながることがある。 In one exemplary embodiment, the reaction pressure of the reaction is 10 to 30 atmospheres. If the reaction pressure is less than 10 atm, the reaction rate may be slowed down, and if it exceeds 30 atm, not only the effect of further improving the reaction rate cannot be obtained, but also the equipment cost may be excessively required. ..
例示的な一具現例において、前記反応の収率は９０〜９９％である。 In one exemplary embodiment, the yield of the reaction is 90-99%.
例示的な一具現例において、前記反応の反応時間は３〜５時間である。 In one exemplary embodiment, the reaction time for the reaction is 3-5 hours.
例示的な一具現例において、前記反応の際に反応溶媒を用い、反応溶媒としては、生成物と同一のアルキレンカーボネートを用いてよい。その理由は、反応物であるアルキレンオキサイドが反応性が高くて爆発危険性があるため、生成物である安定したアルキレンカーボネートを混合することで工程安全性を向上させることができるからである。 In one exemplary embodiment, a reaction solvent may be used in the reaction, and the same alkylene carbonate as the product may be used as the reaction solvent. The reason is that the reactant alkylene oxide is highly reactive and has an explosion risk, so that the process safety can be improved by mixing the stable alkylene carbonate which is the product.
以下、本発明の具現例に係る具体的な実施例についてより詳細に説明する。なお、本発明が下記の実施例によって限定されるものではなく、添付の特許請求の範囲内で種々の形態の実施例が具現でき、下記の実施例は単に本発明の開示を完全にさせるとともに当業界で通常の知識を有する者にとって発明の実施が容易にできるようにするためのものであることが理解できるであろう。 Hereinafter, specific examples according to the embodiment of the present invention will be described in more detail. It should be noted that the present invention is not limited to the following examples, and various embodiments can be embodied within the scope of the appended claims, and the following examples merely complete the disclosure of the present invention. It will be appreciated that it is intended to facilitate the implementation of the invention by those with ordinary knowledge in the industry.
実施例１
新規な触媒の製造例１
温度計、還流冷却器、及び滴下装置が設けられた三口フラスコに、ビグアニジン５ｇ、ヨウ化アンモニウム２．２ｇと５０％ グルタルアルデヒド５．２ｇを入れ、反応温度７５℃、ｐＨ３で１時間撹拌する。滴下装置にて５０％ グルタルアルデヒド５．２gをさらに加え、２０％ 塩酸溶液でｐＨ４．０に調節してから１２時間反応させる。
Example 1
Production example of a
Put 5 g of biguanidine, 2.2 g of ammonium iodide and 5.2 g of 50% glutaraldehyde in a three-necked flask equipped with a thermometer, a reflux condenser, and a dropping device, and stir at a reaction temperature of 75 ° C. and pH 3 for 1 hour. Further, 5.2 g of 50% glutaraldehyde is added by a dropping device, and the pH is adjusted to 4.0 with a 20% hydrochloric acid solution, and then the reaction is carried out for 12 hours.
還流装置が取り付けられた１００ｍＬ二口フラスコに、前記した方法によって合成された触媒前駆物質１．５ｇと蒸留水５０ｇ、ポリアクリル酸０．５ｇを充填し、６０℃で撹拌しながら２時間反応を進めた。 A 100 mL two-necked flask equipped with a reflux device is filled with 1.5 g of the catalyst precursor synthesized by the above method, 50 g of distilled water, and 0.5 g of polyacrylic acid, and the reaction is carried out for 2 hours while stirring at 60 ° C. I proceeded.
反応後、水はロータリーエバポレータ（Ｒｏｔａｒｙ Ｅｖａｐｏｒａｔｏｒ）を用いて減圧下で除去し、カルボニル基を含む新規な触媒粉末（化学式１）を合成した。 After the reaction, water was removed under reduced pressure using a rotary evaporator to synthesize a novel catalyst powder containing a carbonyl group (Chemical Formula 1).
実施例２
新規な触媒の製造例２
温度計、還流冷却器、及び滴下装置が設けられた三口フラスコに、尿素３．６ｇ、ヨウ化アンモニウム２．２ｇとグリオキサール（ｇｌｙｏｘａｌ）３．８ｇ、ジエチレントリアミン０．０５gを入れ、反応温度７５℃、ｐＨ３で１時間撹拌する。滴下装置にてグリオキサール３．８ｇをさらに加え、２０％ 塩酸溶液でｐＨ４．０に調節してから１２時間反応させる。
Example 2
Production example 2 of a new catalyst
In a three-necked flask equipped with a thermometer, a reflux condenser, and a dropping device, 3.6 g of urea, 2.2 g of ammonium iodide, 3.8 g of glyoxal, and 0.05 g of diethylenetriamine were placed, and the reaction temperature was 75 ° C. Stir at pH 3 for 1 hour. Further, 3.8 g of glyoxal is added by a dropping device, and the pH is adjusted to 4.0 with a 20% hydrochloric acid solution, and then the reaction is carried out for 12 hours.
還流装置が取り付けられた１００ｍＬ二口フラスコに、前記した方法によって合成された触媒前駆物質１．５ｇと蒸留水５０ｇ、酸化グラフェン０．５ｇを充填し、６０℃で撹拌しながら２時間反応を進めた。 A 100 mL two-necked flask equipped with a reflux device is filled with 1.5 g of the catalyst precursor synthesized by the above method, 50 g of distilled water, and 0.5 g of graphene oxide, and the reaction proceeds for 2 hours while stirring at 60 ° C. It was.
反応後、水はロータリーエバポレータ（Ｒｏｔａｒｙ Ｅｖａｐｏｒａｔｏｒ）を用いて減圧下で除去し、カルボニル基を含む新規な触媒粉末（化学式２）を合成した。 After the reaction, water was removed under reduced pressure using a rotary evaporator to synthesize a novel catalyst powder containing a carbonyl group (Chemical Formula 2).
実施例３
新規な触媒の製造例３
温度計、還流冷却器、及び滴下装置が設けられた三口フラスコに、ジシアンジアミド２．８ｇ、臭化アンモニウム１．９ｇとコハク酸ジアルデヒド（ｓｕｃｃｉｎｄｉａｌｄｅｈｙｄｅ）４．５ｇ、ジエチレントリアミン０．０５ｇを入れ、反応温度７５℃、ｐＨ３で１時間撹拌する。滴下装置にてコハク酸ジアルデヒド（ｓｕｃｃｉｎｄｉａｌｄｅｈｙｄｅ）４．５ｇをさらに加え、２０％ 塩酸溶液でｐＨ４．０に調節してから１２時間反応させる。
Example 3
Production example 3 of a new catalyst
A three-necked flask equipped with a thermometer, a reflux condenser, and a dropping device was charged with 2.8 g of dicyandiamide, 1.9 g of ammonium bromide, 4.5 g of succinaldehyde dialdehyde, and 0.05 g of diethylenetriamine, and the reaction temperature was increased. Stir at 75 ° C. and pH 3 for 1 hour. Further, 4.5 g of succinaldehyde dialdehyde is added by a dropping device, and the pH is adjusted to 4.0 with a 20% hydrochloric acid solution, and then the reaction is carried out for 12 hours.
還流装置が取り付けられた１００ｍＬ二口フラスコに、前記した方法によって合成された触媒前駆物質１．５ｇと蒸留水５０ｇ、プロピオン酸０．５ｇを充填し、６０℃で撹拌しながら２時間反応を進めた。 A 100 mL two-necked flask equipped with a reflux device is filled with 1.5 g of the catalyst precursor synthesized by the above method, 50 g of distilled water, and 0.5 g of propionic acid, and the reaction proceeds for 2 hours while stirring at 60 ° C. It was.
反応後、水はロータリーエバポレータ（Ｒｏｔａｒｙ Ｅｖａｐｏｒａｔｏｒ）を用いて減圧下で除去し、カルボニル基を含む新規な触媒粉末（化学式３）を合成した。 After the reaction, water was removed under reduced pressure using a rotary evaporator to synthesize a novel catalyst powder containing a carbonyl group (Chemical Formula 3).
実施例４
新規な触媒の製造例４
温度計、還流冷却器、及び滴下装置が設けられた三口フラスコに、尿素３．６ｇ、ヨウ化アンモニウム２．２ｇと３５％ ホルムアルデヒド５．０ｇ、ジエチレントリアミン０．０５ｇを入れ、反応温度７５℃、ｐＨ３で１時間撹拌する。滴下装置にて３５％ ホルムアルデヒド５．０ｇをさらに加え、２０％ 塩酸溶液でｐＨ４．０に調節してから１２時間反応させる。
Example 4
Production example of a new catalyst 4
In a three-necked flask equipped with a thermometer, a reflux condenser, and a dropping device, 3.6 g of urea, 2.2 g of ammonium iodide, 5.0 g of 35% formaldehyde, and 0.05 g of diethylenetriamine were placed, and the reaction temperature was 75 ° C. and pH 3 Stir for 1 hour. Further, 5.0 g of 35% formaldehyde is added by a dropping device, and the pH is adjusted to 4.0 with a 20% hydrochloric acid solution, and then the reaction is carried out for 12 hours.
還流装置が取り付けられた１００ｍＬ二口フラスコに、前記した方法によって合成された触媒前駆物質１．５ｇと蒸留水５０ｇ、ポリアクリル酸０．５ｇ（又は、酸化グラフェン０．５ｇ）を充填し、６０℃で撹拌しながら２時間反応を進めた。 A 100 mL two-necked flask equipped with a reflux device was filled with 1.5 g of the catalyst precursor synthesized by the above method, 50 g of distilled water, and 0.5 g of polyacrylic acid (or 0.5 g of graphene oxide). The reaction proceeded for 2 hours with stirring at ° C.
反応後、水はロータリーエバポレータ（Ｒｏｔａｒｙ Ｅｖａｐｏｒａｔｏｒ）を用いて減圧下で除去し、エステル基を含む新規な触媒粉末（化学式４）を合成した。 After the reaction, water was removed under reduced pressure using a rotary evaporator to synthesize a novel catalyst powder containing an ester group (Chemical Formula 4).
図１は、本発明の実施例１〜３で製造された触媒のＦＴ−ＩＲ測定結果である。 FIG. 1 is an FT-IR measurement result of the catalyst produced in Examples 1 to 3 of the present invention.
図１のＦＴ−ＩＲ測定結果から、製造された触媒は、−ＮＨ２、Ｃ＝Ｎ、−ＯＨ、−ＣＯＯ−、−Ｃ−Ｎ−Ｈ、−Ｃ−Ｏ−などが確認された。また、−Ｃ＝Ｏ−からカルボニル基の存在を確認することができた。 From the FT-IR measurement results in FIG. 1, it was confirmed that the produced catalysts were -NH 2 , C = N, -OH, -COO-, -C-N-H, -C-O- and the like. In addition, the presence of a carbonyl group could be confirmed from -C = O-.
アルキレンカーボネートの製造
１００ｍＬ高圧反応器に、反応物であるプロピレンオキサイド（ＰＯ、１０ｇ、０．１７ｍｏｌ）と実施例１で得られた新規な触媒（０．２ｇ）を充填した後、二酸化炭素（ＣＯ２）で満たして温度を１３０℃に上げる。
Production of alkylene carbonate A 100 mL high pressure reactor is filled with propylene oxide (PO, 10 g, 0.17 mol) as a reactant and the novel catalyst (0.2 g) obtained in Example 1, and then carbon dioxide (CO). Fill with 2 ) and raise the temperature to 130 ° C.
再び二酸化炭素を加え、反応器の圧力が２０気圧になるようにした。４時間反応させてから反応器を室温で冷却し、触媒を回収して、８０℃で１２時間乾燥した後、重さを測定し、触媒を４回繰り返し再使用した。 Carbon dioxide was added again to bring the reactor pressure to 20 atm. After reacting for 4 hours, the reactor was cooled at room temperature, the catalyst was recovered, dried at 80 ° C. for 12 hours, weighed, and the catalyst was reused 4 times repeatedly.
図２〜５は、本発明の実施例１において、４回の繰り返し実験のＧＣ／ＭＳ分析結果である。図２が第１回目、図３が第２回目、図４が第３回目、図５が第４回目の実験についての分析結果である。 FIGS. 2 to 5 show the results of GC / MS analysis of four repeated experiments in Example 1 of the present invention. 2 is the analysis result of the first experiment, FIG. 3 is the second experiment, FIG. 4 is the third experiment, and FIG. 5 is the analysis result of the fourth experiment.
図２〜５から分かるように、ＧＣ／ＭＳによる生成物質の分析結果、４回の実験結果ともに、プロピレンカーボネートの収率は９９．９％であって（ＰＯ→ＰＣ収率９９．９％保持）、ハライド系不純物は生成されなかった。参考までに、ここで、収率は次の式にて求められる。
収率（％）＝（アルキレンカーボネートの生成モル数／原料アルキレンオキサイドのモル数）×１００
As can be seen from FIGS. 2 to 5, the yield of propylene carbonate was 99.9% (PO → PC yield maintained at 99.9%) in all the results of analysis of the product by GC / MS and the results of four experiments. ), Halide impurities were not produced. For reference, here, the yield is calculated by the following formula.
Yield (%) = (number of moles of alkylene carbonate produced / number of moles of raw material alkylene oxide) x 100
同様に、実施例２及び３の触媒を用いて、１回のアルキレンカーボネート製造実験を行った。図６は、本発明の実施例２において、１回実験のＧＣ／ＭＳ分析結果である。図７は、本発明の実施例３において、１回実験のＧＣ／ＭＳ分析結果である。図６及び７でも図２〜５と同様に、ハライド系不純物が生成されることなく９９．９％の高い収率を得ることができた。 Similarly, one alkylene carbonate production experiment was performed using the catalysts of Examples 2 and 3. FIG. 6 shows the results of GC / MS analysis of one experiment in Example 2 of the present invention. FIG. 7 shows the results of GC / MS analysis of one experiment in Example 3 of the present invention. Similar to FIGS. 2 to 5, high yields of 99.9% could be obtained in FIGS. 6 and 7 without forming halide-based impurities.
このように、本発明の例示的な具現例の触媒を用いる場合、既存の触媒による反応条件に比べて低温、低圧で反応が可能であり且つ反応時間を短縮することができ、高い収率でアルキレンカーボネートを得ることが可能である。また、触媒の耐久性を向上することができ、繰り返し再使用しても高い触媒収率を保持することができる。 As described above, when the catalyst of the exemplary embodiment of the present invention is used, the reaction can be performed at a low temperature and a low pressure as compared with the reaction conditions using the existing catalyst, the reaction time can be shortened, and the yield is high. It is possible to obtain an alkylene carbonate. In addition, the durability of the catalyst can be improved, and a high catalyst yield can be maintained even after repeated reuse.
アルキレンカーボネート製造用触媒、その製造方法、並びに前記触媒を用いたアルキレンカーボネートの製造方法及び装置が提供される。当該触媒は、既存の触媒による反応条件に比べて低温、低圧で反応が可能であり且つ反応時間を短縮させることができ、高い収率でアルキレンカーボネートを得ることが可能である。また、触媒の耐久性を向上することができるのみならず、生成物との分離が容易であることから再使用が可能であり、触媒を繰り返し再使用しても触媒収率を保持することができる。 Provided are a catalyst for producing an alkylene carbonate, a method for producing the same, and a method and an apparatus for producing an alkylene carbonate using the catalyst. The catalyst can be reacted at a low temperature and a low pressure as compared with the reaction conditions using an existing catalyst, the reaction time can be shortened, and an alkylene carbonate can be obtained in a high yield. Moreover, not only the durability of the catalyst can be improved, but also the catalyst can be reused because it can be easily separated from the product, and the catalyst yield can be maintained even if the catalyst is repeatedly reused. it can.
Claims (18)
カルボニル基（−Ｃ＝Ｏ−）又はエステル基（−ＣＯＯ−）；アミン基（−ＮＨ２）、ヒドロキシ基（−ＯＨ）、ハライドを含み、
前記触媒は、ＦＴ−ＩＲスペクトルで３２００〜３６００ｃｍ −１ において−ＯＨピークを示し、１６３０〜１６８０ｃｍ −１ において−Ｃ＝Ｏ−ピークを示し、１５１５〜１５７０ｃｍ −１ において−Ｃ−Ｎ−Ｈピークを示し、１２１１〜１３４０ｃｍ −１ において−Ｃ−Ｏ−ピークを示すことを特徴とするアルキレンカーボネート製造用触媒。 A catalyst for producing alkylene carbonate
Carbonyl group (-C = O-) or an ester group (-COO-); amine group (-NH 2), hydroxy (-OH), an halide seen including,
The catalyst showed the -OH peaks in 3200～3600Cm -1 in FT-IR spectrum shows a -C = O-peak at 1630～1680Cm -1, a -C-N-H peak at 1515～1570Cm -1 A catalyst for producing an alkylene carbonate, which is characterized by showing a -CO- peak at 1211-1340 cm- 1.
前記触媒は、次の化学式１〜化学式４のいずれか一つで表されることを特徴とするアルキレンカーボネート製造用触媒。
（前記化学式１〜化学式４中、ｎは繰り返し単位である。） A catalyst for producing alkylene carbonate
The catalyst characteristics and to luer Ruki alkylene carbonate production catalyst by being represented by any one of the following Chemical Formulas 1 to 4.
(In the chemical formulas 1 to 4, n is a repeating unit.)
ハライド、アミン基、ヒドロキシ基を含む触媒化合物をカルボン酸前駆体と反応させる段階;を含むことを特徴とする、アルキレンカーボネート製造用触媒の製造方法。 The method for producing a catalyst for producing an alkylene carbonate according to claim 1 or 2.
A method for producing a catalyst for producing an alkylene carbonate, which comprises a step of reacting a catalytic compound containing a halide, an amine group, and a hydroxy group with a carboxylic acid precursor;
前記触媒化合物をカルボン酸前駆体と反応させて前記触媒化合物にカルボニル基（−Ｃ＝Ｏ−）又はエステル基（−ＣＯＯ−）を生成する段階;を含むことを特徴とする、請求項４に記載のアルキレンカーボネート製造用触媒の製造方法。 The method is the step of producing a catalytic compound containing a halide, an amine group, a hydroxy group from an amine precursor, an aldehyde precursor, and ammonium halide; and reacting the catalytic compound with a carboxylic acid precursor to carbonyl to the catalytic compound. The method for producing a catalyst for producing an alkylene carbonate according to claim 4 , further comprising a step of forming a group (-C = O-) or an ester group (-COO-).
アミン前駆体、アルデヒド前駆体、及びアンモニウムハライドからハライド、アミン基、ヒドロキシ基を含む触媒化合物を生成する段階；及び
前記触媒化合物をカルボン酸前駆体と反応させて前記触媒化合物にカルボニル基（−Ｃ＝Ｏ−）又はエステル基（−ＣＯＯ−）を生成する段階;を含み、
前記アミン前駆体は、尿素（ｕｒｅａ）、メラミン（ｍｅｌａｍｉｎｅ）、ジシアンジアミド（ｄｉｃｙａｎｄｉａｍｉｄｅ）、シアンアミド（ｃｙａｎａｍｉｄｅ）、グアニジン（ｇｕａｎｉｄｉｎｅ）、ビグアニジン（ｂｉｇｕａｎｉｄｉｎｅ）、グアニル尿素（ｇｕａｎｙｌｕｒｅａ）、多環グアニジン（ｐｏｌｙｃｙｃｌｉｃ ｇｕａｎｉｄｉｎｅ）からなる群より選ばれる一つ以上であることを特徴とする、アルキレンカーボネート製造用触媒の製造方法。 A method for producing a catalyst for producing an alkylene carbonate.
The step of producing catalytic compounds containing halides, amine groups, hydroxy groups from amine precursors, aldehyde precursors, and ammonium halides; and
The step of reacting the catalyst compound with a carboxylic acid precursor to form a carbonyl group (-C = O-) or an ester group (-COO-) in the catalyst compound;
The amine precursors are urea, melamine, dicyandiamide, cyanamide, guanidine, biguanidine, guanylurea, polycyclic guanidine, and polycyclic guanidine. and characterized in that from one or more selected group consisting of the method of a Ruki alkylene carbonate production catalyst.
アミン前駆体、アルデヒド前駆体、及びアンモニウムハライドからハライド、アミン基、ヒドロキシ基を含む触媒化合物を生成する段階；及び
前記触媒化合物をカルボン酸前駆体と反応させて前記触媒化合物にカルボニル基（−Ｃ＝Ｏ−）又はエステル基（−ＣＯＯ−）を生成する段階;を含み、
前記アルデヒド前駆体は、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ブチルアルデヒド、ベンズアルデヒド、グルタルアルデヒド（ｇｌｕｔａｒａｌｄｅｈｙｄｅ）、グリオキサール（ｇｌｙｏｘａｌ）、マロンジアルデヒド（ｍａｌｏｎｄｉａｌｄｅｈｙｄｅ）、コハク酸ジアルデヒド（ｓｕｃｃｉｎｄｉａｌｄｅｈｙｄｅ）、フタルアルデヒド（ｐｈｔｈａｌａｌｄｅｈｙｄｅ）からなる群より選ばれる一つ以上であることを特徴とする、アルキレンカーボネート製造用触媒の製造方法。 A method for producing a catalyst for producing an alkylene carbonate.
The step of producing catalytic compounds containing halides, amine groups, hydroxy groups from amine precursors, aldehyde precursors, and ammonium halides; and
The step of reacting the catalyst compound with a carboxylic acid precursor to form a carbonyl group (-C = O-) or an ester group (-COO-) in the catalyst compound;
The aldehyde precursors include formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, benzaldehyde, glutaraldehyde, glyoxal, malondialdide, dialdehyde succinate, phthalaldehyde, and phthalaldehyde. and characterized in that from one or more selected group consisting of the method of a Ruki alkylene carbonate production catalyst.
（前記化学式５及び化学式６中、Ｒ１及びＲ２は、それぞれ独立に、水素、炭素数１〜６のアルキル基、炭素数１〜６のハロアルキル基又はアリール基であってよく、結合されている炭素原子とともに六角形環を形成していてよい。） Alkylene oxide are those represented by Chemical Formula 5 below, wherein the alkylene carbonate is a compound represented by Chemical Formula 6 below, a manufacturing method of an alkylene carbonate according to claim 1 0.
(In the chemical formula 5 and the chemical formula 6, R1 and R2 may be hydrogen, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an aryl group, respectively, and are bonded carbons. It may form a hexagonal ring with the atom.)
請求項１又は２に記載のアルキレンカーボネート製造用触媒を含むことを特徴とする、アルキレンカーボネートの製造装置。 An alkylene carbonate production device that produces alkylene carbonate by reacting alkylene oxide with carbon dioxide.
An apparatus for producing alkylene carbonate, which comprises the catalyst for producing alkylene carbonate according to claim 1 or 2.
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