JPH03284648A - Method for industrially producing naphthalene-2,6-dicarboxylic acid - Google Patents
Method for industrially producing naphthalene-2,6-dicarboxylic acidInfo
- Publication number
- JPH03284648A JPH03284648A JP8709290A JP8709290A JPH03284648A JP H03284648 A JPH03284648 A JP H03284648A JP 8709290 A JP8709290 A JP 8709290A JP 8709290 A JP8709290 A JP 8709290A JP H03284648 A JPH03284648 A JP H03284648A
- Authority
- JP
- Japan
- Prior art keywords
- naphthalene
- dicarboxylic acid
- acid
- salt
- potassium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 title claims description 49
- 238000000034 method Methods 0.000 title description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 53
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 34
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 33
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229960004365 benzoic acid Drugs 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- QAYXDWGFSMUTBJ-UHFFFAOYSA-L dipotassium;naphthalene-2,6-dicarboxylate Chemical compound [K+].[K+].C1=C(C([O-])=O)C=CC2=CC(C(=O)[O-])=CC=C21 QAYXDWGFSMUTBJ-UHFFFAOYSA-L 0.000 claims description 24
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 14
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 12
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 229910052700 potassium Inorganic materials 0.000 abstract description 40
- 239000011591 potassium Substances 0.000 abstract description 40
- 150000001875 compounds Chemical class 0.000 abstract description 14
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 abstract description 7
- 150000008064 anhydrides Chemical class 0.000 abstract description 3
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 abstract description 2
- WCBFEMZIZMFMPB-UHFFFAOYSA-L dipotassium;naphthalene-1,2-dicarboxylate Chemical compound [K+].[K+].C1=CC=CC2=C(C([O-])=O)C(C(=O)[O-])=CC=C21 WCBFEMZIZMFMPB-UHFFFAOYSA-L 0.000 abstract 2
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 abstract 1
- ZEAKTEHMYABQAH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid;potassium Chemical compound [K].C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 ZEAKTEHMYABQAH-UHFFFAOYSA-N 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 229960003975 potassium Drugs 0.000 description 39
- 239000000706 filtrate Substances 0.000 description 36
- 238000011084 recovery Methods 0.000 description 34
- -1 dicarboxylic acid dipotassium salt Chemical class 0.000 description 23
- 238000004458 analytical method Methods 0.000 description 18
- 238000004128 high performance liquid chromatography Methods 0.000 description 18
- GOMCKELMLXHYHH-UHFFFAOYSA-L dipotassium;phthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=CC=C1C([O-])=O GOMCKELMLXHYHH-UHFFFAOYSA-L 0.000 description 17
- 239000002244 precipitate Substances 0.000 description 17
- 238000005259 measurement Methods 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 150000002736 metal compounds Chemical class 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- SQJNKEHFJQEFFW-UHFFFAOYSA-M potassium;6-carboxynaphthalene-2-carboxylate Chemical compound [K+].C1=C(C([O-])=O)C=CC2=CC(C(=O)O)=CC=C21 SQJNKEHFJQEFFW-UHFFFAOYSA-M 0.000 description 8
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 7
- 235000015320 potassium carbonate Nutrition 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910052792 caesium Inorganic materials 0.000 description 6
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 5
- LRUDDHYVRFQYCN-UHFFFAOYSA-L dipotassium;terephthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 LRUDDHYVRFQYCN-UHFFFAOYSA-L 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 159000000001 potassium salts Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 3
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 3
- GIGWNNOCCCHECH-UHFFFAOYSA-L dipotassium;benzene-1,3-dicarboxylate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=CC(C([O-])=O)=C1 GIGWNNOCCCHECH-UHFFFAOYSA-L 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 235000010235 potassium benzoate Nutrition 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 241000894007 species Species 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 description 2
- 229940065285 cadmium compound Drugs 0.000 description 2
- 150000001662 cadmium compounds Chemical class 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- UBRZUHOUIISJAZ-UHFFFAOYSA-L dicesium;phthalate Chemical compound [Cs+].[Cs+].[O-]C(=O)C1=CC=CC=C1C([O-])=O UBRZUHOUIISJAZ-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001502 inorganic halide Inorganic materials 0.000 description 2
- 150000002601 lanthanoid compounds Chemical class 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004300 potassium benzoate Substances 0.000 description 2
- 229940103091 potassium benzoate Drugs 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- JAAGVIUFBAHDMA-UHFFFAOYSA-M rubidium bromide Chemical compound [Br-].[Rb+] JAAGVIUFBAHDMA-UHFFFAOYSA-M 0.000 description 2
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- KEDNSMBVYXSBFC-UHFFFAOYSA-N 6-bromo-2-chloroquinoline-4-carbonyl chloride Chemical compound C1=C(Br)C=C2C(C(=O)Cl)=CC(Cl)=NC2=C1 KEDNSMBVYXSBFC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- IJFCVSDHMYVPIF-UHFFFAOYSA-H C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Sc+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Sc+3] Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Sc+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Sc+3] IJFCVSDHMYVPIF-UHFFFAOYSA-H 0.000 description 1
- IGQZMZOMDHKGFC-UHFFFAOYSA-H C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Y+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Y+3] Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Y+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Y+3] IGQZMZOMDHKGFC-UHFFFAOYSA-H 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 229910016859 Lanthanum iodide Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- FCTMBHUXRGYAPT-UHFFFAOYSA-M [Cs+].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 Chemical compound [Cs+].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 FCTMBHUXRGYAPT-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001620 barium bromide Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- CBXLQVFLPVYSJW-UHFFFAOYSA-L barium(2+);naphthalene-1-carboxylate Chemical compound [Ba+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 CBXLQVFLPVYSJW-UHFFFAOYSA-L 0.000 description 1
- MTZOKGSUOABQEO-UHFFFAOYSA-L barium(2+);phthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O MTZOKGSUOABQEO-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910000011 cadmium carbonate Inorganic materials 0.000 description 1
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 description 1
- 229940075417 cadmium iodide Drugs 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 description 1
- AZLYQVQCKJEKBW-UHFFFAOYSA-L cadmium(2+);naphthalene-1-carboxylate Chemical compound [Cd+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 AZLYQVQCKJEKBW-UHFFFAOYSA-L 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- HOSISMMAWAHRDO-UHFFFAOYSA-L cadmium(2+);phthalate Chemical compound [Cd+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O HOSISMMAWAHRDO-UHFFFAOYSA-L 0.000 description 1
- MCQXGKSTPTWGSF-UHFFFAOYSA-N cadmium;terephthalic acid Chemical compound [Cd].OC(=O)C1=CC=C(C(O)=O)C=C1 MCQXGKSTPTWGSF-UHFFFAOYSA-N 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- KCVBJDWRXNEWRM-UHFFFAOYSA-L calcium;naphthalene-1-carboxylate Chemical compound [Ca+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 KCVBJDWRXNEWRM-UHFFFAOYSA-L 0.000 description 1
- PYSZASIZWHHPHJ-UHFFFAOYSA-L calcium;phthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O PYSZASIZWHHPHJ-UHFFFAOYSA-L 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- ZEDZJUDTPVFRNB-UHFFFAOYSA-K cerium(3+);triiodide Chemical compound I[Ce](I)I ZEDZJUDTPVFRNB-UHFFFAOYSA-K 0.000 description 1
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- KGOKDPWKDBWITQ-UHFFFAOYSA-K gadolinium(3+);tribromide Chemical compound Br[Gd](Br)Br KGOKDPWKDBWITQ-UHFFFAOYSA-K 0.000 description 1
- IZZTUGMCLUGNPM-UHFFFAOYSA-K gadolinium(3+);triiodide Chemical compound I[Gd](I)I IZZTUGMCLUGNPM-UHFFFAOYSA-K 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910001503 inorganic bromide Inorganic materials 0.000 description 1
- 229910001505 inorganic iodide Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- KYKBXWMMXCGRBA-UHFFFAOYSA-K lanthanum(3+);triiodide Chemical compound I[La](I)I KYKBXWMMXCGRBA-UHFFFAOYSA-K 0.000 description 1
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- DAOCFLYDQCOXGE-UHFFFAOYSA-L magnesium;naphthalene-1-carboxylate Chemical compound [Mg+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 DAOCFLYDQCOXGE-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- APLYTANMTDCWTA-UHFFFAOYSA-L magnesium;phthalate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O APLYTANMTDCWTA-UHFFFAOYSA-L 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- SCTINZGZNJKWBN-UHFFFAOYSA-M mercury(1+);fluoride Chemical compound [Hg]F SCTINZGZNJKWBN-UHFFFAOYSA-M 0.000 description 1
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 description 1
- HIJSSUKZLPXDPU-UHFFFAOYSA-L mercury(2+);carbonate Chemical compound [Hg+2].[O-]C([O-])=O HIJSSUKZLPXDPU-UHFFFAOYSA-L 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- ZDLZKHLDCVDPSE-UHFFFAOYSA-K naphthalene-1-carboxylate;yttrium(3+) Chemical compound [Y+3].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 ZDLZKHLDCVDPSE-UHFFFAOYSA-K 0.000 description 1
- LBWLQVSRPJHLEY-UHFFFAOYSA-K neodymium(3+);tribromide Chemical compound Br[Nd](Br)Br LBWLQVSRPJHLEY-UHFFFAOYSA-K 0.000 description 1
- DKSXWSAKLYQPQE-UHFFFAOYSA-K neodymium(3+);triiodide Chemical compound I[Nd](I)I DKSXWSAKLYQPQE-UHFFFAOYSA-K 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- ZVUVJTQITHFYHV-UHFFFAOYSA-M potassium;naphthalene-1-carboxylate Chemical class [K+].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 ZVUVJTQITHFYHV-UHFFFAOYSA-M 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- ICKYUJFKBKOPJT-UHFFFAOYSA-K samarium(3+);tribromide Chemical compound Br[Sm](Br)Br ICKYUJFKBKOPJT-UHFFFAOYSA-K 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- OJIKOZJGHCVMDC-UHFFFAOYSA-K samarium(iii) fluoride Chemical compound F[Sm](F)F OJIKOZJGHCVMDC-UHFFFAOYSA-K 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- APPHYFNIXVIIJR-UHFFFAOYSA-K scandium bromide Chemical compound Br[Sc](Br)Br APPHYFNIXVIIJR-UHFFFAOYSA-K 0.000 description 1
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 description 1
- 150000003326 scandium compounds Chemical class 0.000 description 1
- OEKDNFRQVZLFBZ-UHFFFAOYSA-K scandium fluoride Chemical compound F[Sc](F)F OEKDNFRQVZLFBZ-UHFFFAOYSA-K 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- NYMLCLICEBTBKR-UHFFFAOYSA-H scandium(3+);tricarbonate Chemical compound [Sc+3].[Sc+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NYMLCLICEBTBKR-UHFFFAOYSA-H 0.000 description 1
- HUIHCQPFSRNMNM-UHFFFAOYSA-K scandium(3+);triiodide Chemical compound [Sc+3].[I-].[I-].[I-] HUIHCQPFSRNMNM-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- 229910001625 strontium bromide Inorganic materials 0.000 description 1
- 229940074155 strontium bromide Drugs 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- KRIJWFBRWPCESA-UHFFFAOYSA-L strontium iodide Chemical compound [Sr+2].[I-].[I-] KRIJWFBRWPCESA-UHFFFAOYSA-L 0.000 description 1
- 229910001643 strontium iodide Inorganic materials 0.000 description 1
- OJXRUZAVBHFYRI-UHFFFAOYSA-L strontium naphthalene-1-carboxylate Chemical compound [Sr++].[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12 OJXRUZAVBHFYRI-UHFFFAOYSA-L 0.000 description 1
- KGCOMQDJRDGWDD-UHFFFAOYSA-L strontium;phthalate Chemical compound [Sr+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O KGCOMQDJRDGWDD-UHFFFAOYSA-L 0.000 description 1
- TYIZUJNEZNBXRS-UHFFFAOYSA-K trifluorogadolinium Chemical compound F[Gd](F)F TYIZUJNEZNBXRS-UHFFFAOYSA-K 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- XQKBFQXWZCFNFF-UHFFFAOYSA-K triiodosamarium Chemical compound I[Sm](I)I XQKBFQXWZCFNFF-UHFFFAOYSA-K 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- LSSJSIMBIIVSTN-UHFFFAOYSA-K ytterbium(3+);triiodide Chemical compound I[Yb](I)I LSSJSIMBIIVSTN-UHFFFAOYSA-K 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229940105965 yttrium bromide Drugs 0.000 description 1
- 229940105963 yttrium fluoride Drugs 0.000 description 1
- 229940105970 yttrium iodide Drugs 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- LFWQXIMAKJCMJL-UHFFFAOYSA-K yttrium(3+);triiodide Chemical compound I[Y](I)I LFWQXIMAKJCMJL-UHFFFAOYSA-K 0.000 description 1
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- MTYHLWRUYCUTPA-UHFFFAOYSA-L zinc;naphthalene-1-carboxylate Chemical compound [Zn+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 MTYHLWRUYCUTPA-UHFFFAOYSA-L 0.000 description 1
- UXDZLUCNRYCZCG-UHFFFAOYSA-L zinc;phthalate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O UXDZLUCNRYCZCG-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、高機能ポリマー原料として有用なナフタレン
−２，６−ジカルボン酸を製造する方法に間する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing naphthalene-2,6-dicarboxylic acid, which is useful as a raw material for high-performance polymers.
従来、ナフタレン−２，６−ジカルボン酸の製造方法と
しては、各種の方法が提唱されている。Conventionally, various methods have been proposed as methods for producing naphthalene-2,6-dicarboxylic acid.
その代表例として所謂ヘンケル法がある。すなわち、他
のナフタレンカルボン酸カリウム塩例えばα−またはβ
−ナフタレンモノカルボン酸のモノカリウム塩あるいは
ナフタレン−２，６−ジカルボン酸塩以外のナフタレン
ジカルボン酸類のジカリウム塩を不活性ガス下に加熱し
て、ナフタレン−２，６−ジカルボン酸ジカリウム塩を
得、これを酸性化する方法である（例えば、Ｋ、Ｆｕｊ
ｉｓｈｉｒ。A typical example is the so-called Henkel method. i.e. other naphthalene carboxylic acid potassium salts such as α- or β
- heating a monopotassium salt of naphthalene monocarboxylic acid or a dipotassium salt of a naphthalene dicarboxylic acid other than a naphthalene-2,6-dicarboxylic acid salt under an inert gas to obtain a dipotassium naphthalene-2,6-dicarboxylic acid salt; This is a method of acidifying this (for example, K, Fuji
ishir.
Ｓ、Ｍｉｔａｍｕｒａ、 Ｂｕｌｌ、Ｃｈｅａ＋、Ｊｐ
ｎ、 、６２．７８６−７９０（１９８９）並びにその
引用文献参照）、この方法を経済的に遂行するには、ナ
フタレン−２，６−ジカルボン酸ジカリウム塩から効率
よくカリウムを回収することが必要である。カリウム回
収法としては次の方法が知られている。■ヘンケル法の
反応に於いて生成したナフタレン−２，６−ジカルボン
酸ジカリウム塩を他のナフタレンカルボン酸でナフタレ
ン−２，６−ジカルボン酸モノカリウム塩と他のナフタ
レンカルボン酸のカリウム塩に変換し、ナフタレン−２
，６−ジカルボン酸モノカリウム塩は不均化によ゛リナ
フタレンー２．６−ジカルボン酸と該ジカルボン酸のジ
カリウム塩とし、他のナフタレンカルボン酸のカリウム
塩はヘンケル法の反応原料として利用する方法（特公昭
４９−２７１７６）、■ヘンケル法の反応に於いて生成
したナフタレン−２，６−ジカルボン酸ジカリウム塩を
炭酸ガスまたは亜硫酸ガスでナフタレン−２６−ジカル
ボン酸モノカリウム塩と炭酸水素カリウムまたは亜硫酸
水素カリウムに変換し、ナフタレン−２，６−ジカルボ
ン酸モノカリウム塩は不均化によりナフタレン−２，６
−ジカルボン酸と該ジカルボン酸のジカリウム塩とし、
炭酸水素カリウムまたは亜硫酸水素カリウムはナフタレ
ン２．６−ジカルボン酸以外のナフタレンカルボン酸と
作用させてナフタレンカルボン酸のカリウム塩に変換し
てヘンケル法の反応原料とする方法が知られている。（
特公昭５ｌ−４７７０６）。S, Mitamura, Bull, Chea+, JP
To carry out this process economically, it is necessary to efficiently recover potassium from naphthalene-2,6-dicarboxylic acid dipotassium salt. be. The following methods are known as potassium recovery methods. ■ Naphthalene-2,6-dicarboxylic acid dipotassium salt produced in the Henkel process reaction is converted with other naphthalenecarboxylic acids into naphthalene-2,6-dicarboxylic acid monopotassium salt and other potassium salts of naphthalenecarboxylic acids. , naphthalene-2
, 6-dicarboxylic acid monopotassium salt is disproportioned into ``linaphthalene-2,6-dicarboxylic acid and the dipotassium salt of the dicarboxylic acid, and other potassium salts of naphthalenecarboxylic acid are used as reaction raw materials in the Henkel method ( (Japanese Patent Publication No. 49-27176), ■ Naphthalene-2,6-dicarboxylic acid dipotassium salt produced in the Henkel process reaction is treated with naphthalene-26-dicarboxylic acid monopotassium salt and potassium hydrogen carbonate or hydrogen sulfite using carbon dioxide gas or sulfur dioxide gas. Naphthalene-2,6-dicarboxylic acid monopotassium salt is converted into potassium by disproportionation.
- a dicarboxylic acid and a dipotassium salt of the dicarboxylic acid;
A method is known in which potassium hydrogen carbonate or potassium hydrogen sulfite is reacted with a naphthalene carboxylic acid other than naphthalene 2,6-dicarboxylic acid to convert it into a potassium salt of naphthalene carboxylic acid, which is used as a reaction raw material for the Henkel process. (
Tokuko Sho 5l-47706).
［発明が解決しようとする課題］
以上のヘンケル法とそれに伴うカリウム回収法では、ナ
フタレンカルボン酸類が必要である。しかし、ナフタレ
ンカルボン酸類は生産量も少なく高価であり、従って従
来のヘンケル法を工業的に実施するためには製造コスト
が高くなり困難であった。[Problems to be Solved by the Invention] The Henkel method and the associated potassium recovery method described above require naphthalenecarboxylic acids. However, naphthalenecarboxylic acids are produced in small quantities and are expensive, making it difficult to implement the conventional Henkel method industrially due to high production costs.
最近ナフタレンとフタル酸ジカリウム塩の如きベンゼン
カルボン酸カリウム塩とを反応させ、ナフタレン−２，
６−ジカルボン酸ジカリウム塩を製造する方法が報告さ
れている（Ｙ、Ｋａｔａ、Ｓ、Ｍｉｔａｍｕｒａ、Ｔｈ
ｅ １９８９ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｈｅｍ
ｉｃａｌ Ｃｏｎｇｒｅｓｓｏｆ Ｐａｃｉｆｉｃ Ｂ
ａ５ｉｎ ５ｏｃｉｅｔｉｅｓ Ｈｏｎｏｌｕｌｕ Ｄ
ｅｃｅｍｂｅｒ １９８９．Ａｂｓｔｒ、、 ■、Ｎｏ
４０５．参照）、ナフタレン及びフタル酸は、いずれも
安価で工業的に大量生産されており、この方法はナフタ
レン−２，６−ジカルボン酸の工業的製造方法として極
めて適している。しかし、工業的に実施する場合には、
効率のよいカリウムの回収方法の確立が経済上極めて重
要であった。一般に、ナフタレン−２，６−ジカルボン
酸カリウム塩から遊離のナフタレン−２６−ジカルボン
酸を得るためには、強酸（例えば硫酸、塩酸、硝酸等）
を用いて塩溶液から酸を遊離すれば良いが、同時に得ら
れる強酸のカリウム塩を原料たるフタル酸ジカリウム塩
の如きベンゼンカルボン酸カリウム塩に変換することは
事実上不可能である０本発明者らはフタル酸の如きベン
ゼンカルボン酸類とナフタレン−２，６−ジカルボン酸
との酸解離定数及びこれらの塩の溶解度の差に着眼し、
カリウムを循環回収使用する工業的に有利な方法を開発
すべく鋭意検討した結果、工業的に有利にナフタレン−
２，６−ジカルボン酸を製造し且つカリウムを簡便に循
環回収使用することができる方法を見いだし、本発明に
到達したものである。Recently, naphthalene was reacted with potassium benzenecarboxylate such as dipotassium phthalate, and naphthalene-2,
A method for producing dipotassium 6-dicarboxylic acid salt has been reported (Y., Kata, S., Mitamura, Th.
e 1989 International Chem
ical Congress of Pacific B
a5in 5ocieties Honolulu D
1989. Abstr, ■, No
405. Reference), naphthalene and phthalic acid are both inexpensive and industrially produced in large quantities, and this method is extremely suitable as an industrial method for producing naphthalene-2,6-dicarboxylic acid. However, when implemented industrially,
Establishing an efficient method for recovering potassium was economically extremely important. Generally, in order to obtain free naphthalene-26-dicarboxylic acid from naphthalene-2,6-dicarboxylic acid potassium salt, a strong acid (e.g. sulfuric acid, hydrochloric acid, nitric acid, etc.) is used.
However, it is virtually impossible to simultaneously convert the resulting potassium salt of a strong acid into the raw material potassium benzenecarboxylate salt such as dipotassium phthalate salt. focused on the difference in acid dissociation constant between benzenecarboxylic acids such as phthalic acid and naphthalene-2,6-dicarboxylic acid and the solubility of these salts,
As a result of intensive studies to develop an industrially advantageous method for recycling and using potassium, we found that naphthalene
The present invention was achieved by discovering a method for producing 2,6-dicarboxylic acid and easily recycling and recycling potassium.
すなわち、本発明は、溶媒量の水の存在下、ナフタレン
−２，６−ジカルボン酸ジカリウム塩またはモノカリウ
ム塩と、
（式中、ｍは１〜Ｇの整数であり、ｎは０〜５の整数で
ある。但しｍ＋ｎは１〜６の範囲にある。）で表される
ベンゼンカルボン酸類または相当するカルボン＃無水物
とを反応させ、ナフタレン−２゜６−ジカルボン酸と、
一般式
（式中、ｍ及びｎは前記に同じである。）で表されるベ
ンゼンカルボン酸カリウム塩とに変換する反応工程（工
程Ａ）と、結晶として析出したナフタレン−２，６−ジ
カルボン酸を水溶液から分離する分離工程（工程Ｂ）と
からなるナフタレン−２，６−ジカルボン酸の製造方法
である。That is, the present invention provides dipotassium salt or monopotassium salt of naphthalene-2,6-dicarboxylic acid in the presence of a solvent amount of water; (where m+n is in the range of 1 to 6. , m and n are the same as above.) A reaction step (Step A) of converting the naphthalene-2,6-dicarboxylic acid precipitated as crystals into a benzenecarboxylic acid potassium salt represented by This is a method for producing naphthalene-2,6-dicarboxylic acid, which comprises a separation step (step B).
更に本発明は、前記工程Ｂでナフタレン−２゜６−ジカ
ルボン酸を分離して得られた一般式（■）で示されるベ
ンゼンカルボン酸カリウム塩を溶解している水溶液から
回収したベンゼンカルボン酸カリウム塩と、ナフタレン
とを反応させてナフタレン−２，６−ジカルボン酸ジカ
リウム塩を住威させ（工程Ｃ）、生成したナフタレン−
２゜６−ジカルボン酸ジカリウム塩または必要により部
分中和して得られたナフタレン−２，６−ジカルボン酸
モノカリウム塩を、工程Ａの反応原料として使用するナ
フタレン−２，６−ジカルボン酸の製造方法である（第
１回参照）。尚、第１図中、ｍ及びｎは前記に同しであ
る。Furthermore, the present invention provides potassium benzenecarboxylate recovered from an aqueous solution in which potassium benzenecarboxylate represented by the general formula (■) obtained by separating naphthalene-2゜6-dicarboxylic acid in step B is dissolved. The salt and naphthalene are reacted to form naphthalene-2,6-dicarboxylic acid dipotassium salt (step C), and the generated naphthalene-
Production of naphthalene-2,6-dicarboxylic acid using 2゜6-dicarboxylic acid dipotassium salt or naphthalene-2,6-dicarboxylic acid monopotassium salt obtained by partial neutralization as a reaction raw material in Step A This is the method (see Part 1). In FIG. 1, m and n are the same as above.
前記工程Ａに於ける反応原料である前記一般式（１）で
表されるベンゼンカルボン酸Ｍ（以下、ベンゼンカルボ
ン酸ｆｆ（ｒ）ということがある）または相当するカル
ボン酸無水物としては、フタル酸、無水フタル酸、フタ
ル酸モノカリウム塩、安息香酸、トリメリット酸、無水
トリメリット酸、トリメリット酸モノカリウム塩、無水
トリメリット酸モノカリウム塩、ビロメリント酸、無水
ビロメリント酸、ピロメリット酸モノカリウム塩、ある
いはこれらの混合物が好適に使用できる。その使用量は
、ナフタレン−２，６−ジカルボン酸ジカリウム塩と反
応させる場合には、該ジカリウム塩１モルに対して２／
ｍモルであり、ナフタレン−２，６−ジカルボン酸モノ
カリウム塩と反応させる場合には、該モノカリウム塩１
モルに対して１／ｍモルである。すなわち、フタル酸、
無水フタル酸、フタル酸モノカリウム塩、安息香酸、無
水ピロメリット酸を例にとれば、ナフタレン−２６−ジ
カルボン酸塩１モルに対して、各々、１モル、１モル、
２モル、２モル、１／２モルでアリ、ナフタレン−２，
６−ジカルボン酸モノカリウム塩に対しては、各４１／
２モル、１／２モル、１モル、１モル、１／４モル使用
する。使用量がこれらの量より少ない場合には、ナフタ
レン−２６−ジカルボン酸ジカリウム塩またはモノカリ
ウム塩ヲ定量的にはナフタレン−２，６−ジカルボン酸
モノカリウム塩に変換できない。また、前記−ｉ式（１
）で表されるベンゼンカルボン酸類または相当するカル
ボン酸無水物に対する反応性が、ナフタレン−２，６−
ジカルボン酸ジカリウム塩またはモノカリウム塩よりも
低い塩が、反応系にあらかしめ溶解して存在することが
ありうるが、この場合にもベンゼンカルボン酸類（１）
または相当するカルボン酸無水物の使用量は、前述のと
おりで差し支えない、この様な塩としてはテレフタル酸
ジカリウム塩、イソフタル酸ジカリウム塩、フタル酸ジ
カリうム塩、安息香酸カリウム塩の如きベンゼンカルボ
ン酸カリウム塩類や、ヨウ化カリウム、ヨウ化セシウム
、塩化カリウム、塩化セシウム、臭化カリウム、臭化セ
シウムの如きハロゲン化アルカリ等が例示できる。一方
、炭酸ジカリウム塩、炭酸ジセシウム塩、水酸化カリウ
ム、水酸化セシウムの如きベンゼンカルボン酸類（■）
または相当するカルボン酸無水物に対する反応性がナフ
タレン−２，６−ジカルボン酸ジカリウム塩またはモノ
カリウム塩より高い塩基性化合物が反応系に存在して、
ベンゼンカルボン＃類（１）または相当するカルボンＭ
無水物を優先的に消費す場合には、ベンゼンカルボン酸
１ｆ（１）または相当するカルボン酸無水物をその分量
だけ過剰に使用すればよい。The benzenecarboxylic acid M represented by the general formula (1) (hereinafter sometimes referred to as benzenecarboxylic acid ff(r)) or the corresponding carboxylic acid anhydride, which is a reaction raw material in the step A, is phthalate. Acid, phthalic anhydride, monopotassium phthalate, benzoic acid, trimellitic acid, trimellitic anhydride, monopotassium trimellitic acid, monopotassium trimellitic anhydride, biromellitic acid, biromellitic anhydride, monopyromellitic acid Potassium salts or mixtures thereof can be preferably used. When reacting with naphthalene-2,6-dicarboxylic acid dipotassium salt, the amount used is 2/
m mol, and when reacting with naphthalene-2,6-dicarboxylic acid monopotassium salt, the monopotassium salt 1
It is 1/mmol to mole. i.e. phthalic acid,
Taking phthalic anhydride, phthalic acid monopotassium salt, benzoic acid, and pyromellitic anhydride as examples, per 1 mol of naphthalene-26-dicarboxylate, 1 mol, 1 mol,
2 mol, 2 mol, 1/2 mol of ant, naphthalene-2,
For 6-dicarboxylic acid monopotassium salt, each 41/
2 mol, 1/2 mol, 1 mol, 1 mol, and 1/4 mol are used. If the amount used is less than these amounts, the naphthalene-26-dicarboxylic acid dipotassium salt or monopotassium salt cannot be quantitatively converted into naphthalene-2,6-dicarboxylic acid monopotassium salt. In addition, the above-mentioned formula -i (1
) or the corresponding carboxylic acid anhydride is naphthalene-2,6-
A dicarboxylic acid dipotassium salt or a salt lower than the monopotassium salt may be present in some form dissolved in the reaction system, but in this case as well, benzenecarboxylic acids (1)
The amount of the corresponding carboxylic acid anhydride used may be as described above. Examples of such salts include benzenecarboxylate such as dipotassium terephthalate, dipotassium isophthalate, dipotassium phthalate, and potassium benzoate. Examples include acid potassium salts and alkali halides such as potassium iodide, cesium iodide, potassium chloride, cesium chloride, potassium bromide, and cesium bromide. On the other hand, benzenecarboxylic acids (■) such as dipotassium carbonate, discesium carbonate, potassium hydroxide, and cesium hydroxide
or a basic compound having higher reactivity toward the corresponding carboxylic acid anhydride than naphthalene-2,6-dicarboxylic acid dipotassium salt or monopotassium salt is present in the reaction system,
Benzene carbone #s (1) or corresponding carbone M
When anhydride is preferentially consumed, benzenecarboxylic acid 1f(1) or the corresponding carboxylic acid anhydride may be used in excess by that amount.
前記工程Ａの反応に於いて、水は溶媒量使用する。すな
わち、水１重量部に対するナフタレン−２，６−ジカル
ボン酸ジカリウム塩またはモノカリウム塩と、ベンゼン
カルボン酸類（１）または相当するカルボン酸無水物と
の重量和は、反応原料の種類によって異なるが、通常０
．００１Ｍ量部〜３．００重量部の範囲が適当である。In the reaction of step A, water is used in a solvent amount. That is, the weight sum of naphthalene-2,6-dicarboxylic acid dipotassium salt or monopotassium salt and benzenecarboxylic acid (1) or the corresponding carboxylic acid anhydride relative to 1 part by weight of water varies depending on the type of reaction raw material, but Usually 0
．． A suitable range is from 0.001M parts to 3.00 parts by weight.
前記重量和が０．００１重量部以下では大量の水が必要
で、経済的観点からは好ましくない。一方、３゜００重
量部以上では、反応により生成する前記−般式（Ｕ）で
表されるベンゼンカルボン酸カリウム塩（以下、ベンゼ
ンカルボン酸カリウム塩（■）ということがある）がそ
の溶解度以上の濃度になるため結晶として析出し、ナフ
タレン−２゜６−ジカルボン酸との分離が困難となる。If the total weight is less than 0.001 parts by weight, a large amount of water is required, which is not preferable from an economical point of view. On the other hand, if the amount is 3.00 parts by weight or more, the benzenecarboxylic acid potassium salt represented by the general formula (U) (hereinafter sometimes referred to as benzenecarboxylic acid potassium salt (■)) produced by the reaction has a solubility higher than that. Since the concentration becomes , it precipitates as crystals, making it difficult to separate it from naphthalene-2°6-dicarboxylic acid.
前記工程への反応に於いて、反応温度はＯ″Ｃ〜２００
°Ｃ１好ましくは室温〜１５０℃の範囲である０反応時
間は、反応原料の種類や反応温度によって異なるが、通
常０，１〜１００時間の範囲である。反応温度が高い程
反応は速くなり、６０°Ｃ以上では３０分程度で充分で
あるが、より長時間でも反応結果に大差はない、圧力は
常圧で差しつかえないが、加圧下で１００°Ｃ以上の温
度で行うこともできる。In the reaction to the above step, the reaction temperature is O''C~200
The zero reaction time, which is preferably in the range of room temperature to 150°C, is usually in the range of 0.1 to 100 hours, although it varies depending on the type of reaction raw materials and reaction temperature. The higher the reaction temperature, the faster the reaction; at 60°C or higher, about 30 minutes is sufficient, but even longer times will not make a big difference in the reaction results. Normal pressure is fine, but under pressure 100°C. It can also be carried out at a temperature of C or higher.
前記工程への反応はスラリー状態で進行する。The reactions in the above steps proceed in a slurry state.
すなわち反応が進むにしたがい、ナフタレン−２６−ジ
カルボン酸が結晶として析出し、一方前記−Ｃ式（ｔｌ
）で表されるベンゼンカルボン酸カリウム塩が反応溶媒
の水に溶解した状態で生成する。That is, as the reaction progresses, naphthalene-26-dicarboxylic acid precipitates as crystals, while the -C formula (tl
) The benzenecarboxylic acid potassium salt represented by the following formula is produced in a state dissolved in water as a reaction solvent.
このため反応混合物を効率よく撹拌することが好ましい
。For this reason, it is preferable to stir the reaction mixture efficiently.
工程Ａの反応纒了後、工程Ｂの分離工程を行う。After the reaction in step A is completed, the separation step in step B is performed.
ここでは析出結晶を濾取し、必要ならば水洗してナフタ
レン−２，６−ジカルボン酸を単離する。Here, the precipitated crystals are collected by filtration and, if necessary, washed with water to isolate naphthalene-2,6-dicarboxylic acid.
一方、濾液に溶解するベンゼンカルボン酸カリウム塩（
ＩＩ）は、本発明者らの研究によれば、前記工程Ｃの反
応原料として使用することができる。On the other hand, benzenecarboxylic acid potassium salt (
According to the research of the present inventors, II) can be used as a reaction raw material in the step C above.
すなわち、所望ならばＰＨ副調整行った後、該濾液を加
熱乾固して水を完全に除去して、ベンゼンカルボン酸力
！ノウム塩（Ｉｔ）を固体残留物として得る。これを前
記工程Ｃの反応に供する。この際、該濾液には、前記工
程Ａの反応で生成したベンゼンカルボン酸カリウム塩（
Ｉｔ）の他に、前述のように次のような化合物が含有す
ることが可能である。それらは、テレフタル酸ジカリウ
ム塩、イソフタル酸ジカリウム塩、フタル酸ジカリウム
塩、安息香酸カリウム塩の如きベンゼンカルボン酸カリ
ウム塩類や、ヨウ化カリウム、ヨウ化セノウム、塩化カ
リウム、塩化セシウム、臭化カリウム、臭化セシウムの
如きハロゲン化アルカリや、炭酸ジカリウム塩、炭酸ジ
セシウム塩、水酸化カリウム、水酸化セシウムの如き塩
基性化合物とベンゼンカルボン酸１（１）または相当す
るカルボン酸無水物との反応生成物である。しかし、本
発明者等の検討によれば、これらの化合物をベンゼンカ
ルボン酸カリうム塩（ｎ）と分離せずに、該濾液を加熱
乾固し、止した固体残留物を前記工程Ｃの反応原料とし
て使用して差し支えない。That is, after performing minor pH adjustment if desired, the filtrate is heated to dryness to completely remove water, and the benzenecarboxylic acid strength is reduced. The noum salt (It) is obtained as a solid residue. This is subjected to the reaction in step C above. At this time, the filtrate contains benzenecarboxylic acid potassium salt (
In addition to It), the following compounds can be contained as mentioned above. They include potassium benzenecarboxylate salts such as dipotassium terephthalate, dipotassium isophthalate, dipotassium phthalate, potassium benzoate, potassium iodide, cenium iodide, potassium chloride, cesium chloride, potassium bromide, A reaction product of an alkali halide such as cesium chloride, a basic compound such as dipotassium carbonate, discesium carbonate, potassium hydroxide, or cesium hydroxide, and benzenecarboxylic acid 1(1) or a corresponding carboxylic acid anhydride. be. However, according to the studies of the present inventors, the filtrate was heated to dryness without separating these compounds from the benzenecarboxylic acid potassium salt (n), and the solid residue was collected in the above step C. It can be used as a reaction raw material.
前記工程Ｃの反応の遂行に当たっては、前記固体残留物
に触媒を加え、炭酸ガス加圧下で、ナフタレンと共に加
熱攪拌する。In carrying out the reaction in step C, a catalyst is added to the solid residue, and the mixture is heated and stirred together with naphthalene under pressure of carbon dioxide gas.
前記工程Ｃの反応の触媒としては、（ａ）Ｉｌｂ族金属
化合物並びに（ｂ）セシウム、Ｉｌａ及び■ａ族金属化
合物からなる群から選ばれた１種または２種以上の化合
物を使用する。■ｂ族金属化合物としては、フン化亜鉛
、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛の如きハロゲン化亜
鉛や、酸化亜鉛、炭酸亜鉛、フタル酸亜鉛やナフタレン
酸亜鉛の如き有機亜鉛化合物等の各種亜鉛化合物、フッ
化カドミウム、塩化カドミウム、臭化カドミウム、ヨウ
化カドミウム、の如きハロゲン化カドミウムや、酸化カ
ドミウム、炭酸カドミウム、フタル酸カドミウムやナフ
タレンカルボン酸カドミウムの如き有機カドミウム化合
物等の各種カドミウム化合物、フン化水銀、塩化水銀、
臭化水銀、ヨウ化水銀の如きハロゲン化水銀や、酸化水
銀、炭酸水銀等の各種水銀化合物を挙げることができる
が、好ましくは、Ｚｎ、Ｃｄの化合物である。これらの
ｎｂ族金属化合物の使用量は、前記ベンゼンカルボン酸
カリウム塩（Ｉｆ）に対して通常０．５〜３０モル％、
好ましくは５〜２５モル％の範囲である。As the catalyst for the reaction in step C, one or more compounds selected from the group consisting of (a) Ilb group metal compounds, and (b) cesium, Ila, and a group metal compounds are used. ■ Group B metal compounds include various zinc halides such as zinc fluoride, zinc chloride, zinc bromide, and zinc iodide, and organic zinc compounds such as zinc oxide, zinc carbonate, zinc phthalate, and zinc naphthalate. Various cadmium compounds such as zinc compounds, cadmium halides such as cadmium fluoride, cadmium chloride, cadmium bromide, and cadmium iodide, and organic cadmium compounds such as cadmium oxide, cadmium carbonate, cadmium phthalate, and cadmium naphthalene carboxylate; Mercury fluoride, mercury chloride,
Examples include mercury halides such as mercury bromide and mercury iodide, and various mercury compounds such as mercury oxide and mercury carbonate, but compounds of Zn and Cd are preferred. The amount of these nb group metal compounds used is usually 0.5 to 30 mol%, based on the benzenecarboxylic acid potassium salt (If).
Preferably it is in the range of 5 to 25 mol%.
３０モル％を超える大量使用は炭化物の副生を促進する
。Use of a large amount exceeding 30 mol % promotes the by-product of carbides.
前記工程Ｂの反応の触媒として、ｎｂ族金属化合物と共
に、セシウム、Ｉｌａ及びＩＩＩａ族金属の化合物を１
種または２種以上用いる。As a catalyst for the reaction in step B, a compound of cesium, Ila, and IIIa group metals is added together with an Nb group metal compound.
A species or two or more species are used.
セシウム化合物としてはフン化セシウム、塩化セシウム
、臭化セシウム、ヨウ化セシウムの如きハロゲン化セシ
ウムや、酸化セシウム、炭酸セシウム、フタル酸セシウ
ムやナフタレンカルボン酸セシウムの如き有機金属セシ
ウム化合物等の各種セシウム化合物あるいはこれらの混
合物を挙げることができる。Cesium compounds include various cesium compounds such as cesium halides such as cesium fluoride, cesium chloride, cesium bromide, and cesium iodide, and organometallic cesium compounds such as cesium oxide, cesium carbonate, cesium phthalate, and cesium naphthalene carboxylate. Alternatively, a mixture thereof can be mentioned.
ｎａ族金属化合物としては、フン化マグネシウム、塩化
マグネシウム、臭化マグネシウム、ヨウ化マグネシウム
の如きハロゲン化マグネシウムや、酸化マグネシウム、
炭酸マグネシウム、フタル酸マグネシウムやナフタレン
カルボン酸マグネシウムの如き有機金属マグネシウム化
合物等の各種マグネシウム化合物、フッ化カルシウム、
塩化カルシウム、臭化カルシウム、ヨウ化カルシウムの
如きハロゲン化カルシウムや、酸化カルシウム、炭酸カ
ルシウム、フタル酸カルシウムやナフタレンカルボン酸
カルシウムの如き有機金属カルシウム化合物等の各種カ
ルシウム化合物、フン化ストロンチウム、塩化ストロン
チウム、臭化ストロンチウム、ヨう化ストロンチウムの
如きハロゲン化ストロンチウムや、酸化ストロンチウム
、炭酸ストロンチウム、フタル酸ストロンチウムやナフ
タレンカルボン酸ストロンチウムの如き有機金属ストロ
ンチウム化合物等の各種ストロンチウム化合物、フン化
バリウム、塩化バリウム、臭化バリウム、ヨウ化バリウ
ムの如きハロゲン化バリウムや、酸化バリウム、炭酸バ
リウム、フタル酸バリウムやナフタレンカルボン酸バリ
ウムの如き有機金属バリウム化合物等の各種バリウム化
合物、あるいはこれらの混合物を挙げることができる。Examples of na group metal compounds include magnesium halides such as magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide, magnesium oxide,
Various magnesium compounds such as magnesium carbonate, organometallic magnesium compounds such as magnesium phthalate and magnesium naphthalene carboxylate, calcium fluoride,
Calcium halides such as calcium chloride, calcium bromide, and calcium iodide; various calcium compounds such as organometallic calcium compounds such as calcium oxide, calcium carbonate, calcium phthalate, and calcium naphthalene carboxylate; strontium fluoride; strontium chloride; Strontium halides such as strontium bromide and strontium iodide, various strontium compounds such as strontium oxide, strontium carbonate, organometallic strontium compounds such as strontium phthalate and strontium naphthalene carboxylate, barium fluoride, barium chloride, and bromide. Examples include various barium compounds such as barium, barium halides such as barium iodide, barium oxide, barium carbonate, organometallic barium compounds such as barium phthalate and barium naphthalenecarboxylate, or mixtures thereof.
ｍａ族金属の化合物としては、フッ化スカンジウム、塩
化スカンジウム、臭化スカンジウム、ヨウ化スカンジウ
ムの如きハロゲン化スカンジウムや、酸化スカンジウム
、炭酸スカンジウム、フタル酸スカンジウムやナフタレ
ンカルボン酸スカンジウムの如き有機金属スカンジウム
化合物等の各種スカンジウム化合物、フン化イツトリウ
ム′、塩化インドリウム、臭化イツトリウム、ヨウ化イ
ツトリウムの如きハロゲン化イツトリウムや、酸化イン
ドリウム、炭酸イツトリウム、フタル酸イツトリウムや
ナフタレンカルボン酸イツトリウムの如き有機金属イツ
トリウム化合物等の各種インドリウム化合物、あるいは
、ランタン、セリウム、プラセオジウム、ネオジウム、
ガドリニウム、サマリウム、インテルビウム等のランタ
ンイド金属のランタノイド化合物、あるいは、これらの
混合物を挙げることができる。このランタノイド化合物
としては、好ましくは、それらのハロゲン化物であるフ
ッ化ランタン、塩化ランタン、臭化ランタン、ヨウ化ラ
ンタン、フン化セシウム、塩化セリウム、臭化セリウム
、ヨウ化セリウム、フン化セシウム、塩化ネオジウム、
臭化ネオジウム、ヨウ化ネオジウム、フン化ガドリニウ
ム、塩化ガドリニうム、臭化ガドリニウム、ヨウ化ガド
リニウム、フン化サマリウム、塩化サマリウム、臭化サ
マリウム、ヨウ化サマリウム、フン化インテルビウム、
塩化インテルビウム、臭化インテルビウム、ヨウ化イッ
テルビウム等を挙げることができる。Compounds of MA group metals include scandium halides such as scandium fluoride, scandium chloride, scandium bromide, and scandium iodide, and organometallic scandium compounds such as scandium oxide, scandium carbonate, scandium phthalate, and scandium naphthalene carboxylate. various scandium compounds, yttrium halides such as yttrium fluoride, indium chloride, yttrium bromide, and yttrium iodide, and organometallic yttrium compounds such as indium oxide, yttrium carbonate, yttrium phthalate, and yttrium naphthalene carboxylate, etc. various indolium compounds, or lanthanum, cerium, praseodymium, neodymium,
Examples include lanthanide compounds of lanthanide metals such as gadolinium, samarium, and interbium, or mixtures thereof. The lanthanoid compounds preferably include their halides such as lanthanum fluoride, lanthanum chloride, lanthanum bromide, lanthanum iodide, cesium fluoride, cerium chloride, cerium bromide, cerium iodide, cesium fluoride, and chloride. neodymium,
Neodymium bromide, neodymium iodide, gadolinium fluoride, gadolinium chloride, gadolinium bromide, gadolinium iodide, samarium fluoride, samarium chloride, samarium bromide, samarium iodide, interbium fluoride,
Examples include interbium chloride, interbium bromide, and ytterbium iodide.
前記工程Ｃの反応の触媒としては、これらセシウム、Ｉ
Ｔａ及びｌ１ｌａ族金属化合物のいずれか１種または２
種以上を使用するが、前記ベンゼンカルボン酸カリウム
塩（Ｉｔ）に対して通常０．５〜３０モル％、好ましく
は５〜２５モル％の範囲である。０．５モル％以下の少
量使用ではその触媒作用が不十分であり、反対に３０モ
ル％を超える大量使用は炭化物の副生を促進する。また
、ｎｂ族金属化合物／（セシウム、ｎａ及びｍａ族金属
の化合物）で表されるモル比は０．２〜５の範囲が望ま
しい。As the catalyst for the reaction in step C, these cesium, I
Any one or two of Ta and l1la group metal compounds
Although more than one species is used, the amount is usually 0.5 to 30 mol%, preferably 5 to 25 mol%, based on the benzenecarboxylic acid potassium salt (It). When used in a small amount of 0.5 mol% or less, the catalytic action is insufficient, and on the contrary, when used in a large amount exceeding 30 mol%, the by-product of carbides is promoted. Further, the molar ratio expressed as nb group metal compound/(compound of cesium, na, and ma group metals) is preferably in the range of 0.2 to 5.
また、前記工程Ｃの反応に於いては、反応系に触媒であ
るｎｂ族金属化合物、並びに、セシウム、ｎａ及びｍａ
族金属の化合物以外の反応を促進させるような化合物を
添加しても差し支えない。反応を促進させるような化合
物としては、ハロゲン化物のような無機陰イオン化合物
、特に、無機ハロゲン化物が望ましい。無機ハロゲン化
物とじては、無機ヨウ化物及び無機臭化物が特に好まし
い。In addition, in the reaction of step C, the reaction system contains an Nb group metal compound as a catalyst, as well as cesium, na, and ma.
There is no problem in adding a compound that promotes the reaction other than the group metal compound. As the compound that promotes the reaction, inorganic anion compounds such as halides, particularly inorganic halides are desirable. Among the inorganic halides, inorganic iodides and inorganic bromides are particularly preferred.
例えば、ヨウ化リチウム、臭化リチウム、ヨウ化ナトリ
ウム、臭化ナトリウム、ヨウ化カリウム、臭化カリウム
、ヨウ化ルビジウム、臭化ルビジウム等を挙げることが
できる。反応を促進させるような化合物の添加は、触媒
としてテレフタル酸カドミウムとフタル酸セシウムを用
いたような、反応系に無機陰イオン化合物が存在しない
ような場合に特に有効である。その添加量は、触媒の使
用量と同様、前記ベンゼンカルボン酸カリウム塩（Ｉｆ
）に対して通常０．５〜３０モル％の範囲である。Examples include lithium iodide, lithium bromide, sodium iodide, sodium bromide, potassium iodide, potassium bromide, rubidium iodide, rubidium bromide, and the like. Addition of a compound that promotes the reaction is particularly effective when no inorganic anionic compound is present in the reaction system, such as when cadmium terephthalate and cesium phthalate are used as catalysts. The amount added is the same as the amount of the catalyst used, and the amount of the benzenecarboxylic acid potassium salt (If
) is usually in the range of 0.5 to 30 mol %.
前記工程Ｃの反応遂行に当たっては、前記ベンゼンカル
ボン酸カリウム塩（ｆｆ）と前記触媒とを反応に先駆け
て、予めよく混合しておくのがよい。In carrying out the reaction in step C, it is preferable to mix the benzenecarboxylic acid potassium salt (ff) and the catalyst thoroughly in advance of the reaction.
その方法として、例えば、ベンゼンカルボン酸カリウム
塩（ｎ）の水溶液に、前記触媒を加えてよく混合し、し
かる後に水を加熱留去する方法や、ベンゼンカルボン酸
カリウム塩（ｎ）と触媒とをボールミルでよく粉砕混合
する方法等を挙げることができる。Examples of this method include adding the catalyst to an aqueous solution of benzenecarboxylic acid potassium salt (n), mixing well, and then heating and distilling off the water, or adding the benzenecarboxylic acid potassium salt (n) and the catalyst. Examples include a method of thoroughly pulverizing and mixing with a ball mill.
前記工程Ｃの反応で使用するナフタレンの使用量は、前
記ベンゼンカルボン酸カリウム１（ＩＩ）に対して過剰
量、すなわち、ベンゼンカルボン酸カリウム塩（ＩＦ）
１モルに対して（ｍ＋ｎ）／２モル以上用いることが好
ましい。但し、大過剰の使用は、反応器が不必要に大き
くなり、また、反応混合物の加熱に多大な熱量を必要と
するため経済的でない、このような観点から、ナフタレ
ンの使用量は、通常ベンゼンカルボン酸カリウム塩（Ｉ
Ｉ）に対して重量で１〜１０倍量である。The amount of naphthalene used in the reaction in step C is an excess amount relative to the potassium benzenecarboxylate 1 (II), that is, potassium benzenecarboxylate (IF).
It is preferable to use (m+n)/2 moles or more per mole. However, the use of a large excess of naphthalene is not economical because the reactor becomes unnecessarily large and a large amount of heat is required to heat the reaction mixture.From this point of view, the amount of naphthalene used is usually lower than that of benzene. Carboxylic acid potassium salt (I
The amount is 1 to 10 times the weight of I).
前記工程Ｃの反応に於ける炭酸ガスの圧力は、反応温度
に於いて１０〜２００ｋｇ／ｄ−Ｇ、好ましくは２０〜
１５０ｋｇ／ｃｄ−Ｇの範囲である。また、反応温度は
、触媒の種類により若干異なるが、通常３００〜５００
’Ｃの範囲であり、反応を速やかに生起させ、かつ、
炭化物生成等の副反応を抑制する観点から３５０〜４５
０“Ｃの範囲が好ましい。反応時間は、反応温度により
異なるが、通常１〜５０時間の範囲である。The pressure of carbon dioxide gas in the reaction of step C is 10 to 200 kg/dG, preferably 20 to 200 kg/dG at the reaction temperature.
It is in the range of 150 kg/cd-G. In addition, the reaction temperature varies slightly depending on the type of catalyst, but is usually 300 to 500.
'C range, causes the reaction to occur quickly, and
350-45 from the viewpoint of suppressing side reactions such as carbide formation
A range of 0"C is preferable. The reaction time varies depending on the reaction temperature, but is usually in the range of 1 to 50 hours.
反応終了後、反応混合物に水を加えて、反応混合物中に
含有されるナフタレン−２，６−ジカルボン酸ジカリウ
ム塩を水に溶解させ、また、さらにトルエンやキシレン
の如き有機溶剤を加えて反応混合物中に含有される過剰
のナフタレンや反応時に副生ずるベンゼンを有機溶剤中
に溶解させ、水層と有ｔ１１溶剤層とを分液する。尚、
前記工程Ｃの反応触媒中のＵｂ族金属化合物は、水及び
有機剤のいずれにも不溶のｎｂ族金属の酸化物または炭
酸塩として、同様に水及び有機溶剤のいずれにも不溶な
副生炭化物とともに、濾過等の手段で容易に分離できる
０分液して得られた水層には、ナフタレン−２，６−ジ
カルボン酸ジカリウム塩の他に、反応で副生するテレフ
タル酸ジカリウム塩、イソフタル酸ジカリウム塩、フタ
ル酸ジカリウム塩、安息香酸カリウム塩の如きベンゼン
カルボン酸カリウム塩や、反応触媒や反応を促進させる
化合物のうち水溶性であるヨウ化カリウム、ヨウ化セシ
ウム、塩化カリウム、塩化セシウム、臭化カリウム、臭
化セシウムの如きハロゲン化アルカリや、分解生成物で
ある炭酸ジカリウム塩、炭酸ジセシウム塩、水酸化カリ
ウム、水酸化セシウムの如き塩基生花合物が含有するこ
とがある。しかし、これらは次に続く前記工程Ａを狙害
しないことは前述のとおりである。すなわち、分液して
得られた水層をそのままあるいは濃縮して、ナフタレン
−２，６−ジカルボン酸ジカリウム塩の水溶液として前
記工程Ａに供することができる。また必要ならば、分液
して得られた水層に酸を添加して含有するナフタレン−
２，６−ジカルボン酸ジカリウム塩を部分中和してナフ
タレン−２，６−ジカルボン酸モノカリウム塩に変換し
た後、前記工程Ａの反応に供することができる。この目
的で使用する酸としては、炭酸ガス、亜硫酸ガスの如き
無機の弱酸が好適に使用できる。After the reaction is completed, water is added to the reaction mixture to dissolve the naphthalene-2,6-dicarboxylic acid dipotassium salt contained in the reaction mixture, and an organic solvent such as toluene or xylene is further added to the reaction mixture. Excess naphthalene contained therein and benzene by-produced during the reaction are dissolved in an organic solvent, and an aqueous layer and a t11 solvent layer are separated. still,
The Ub group metal compound in the reaction catalyst in step C is an oxide or carbonate of the Nb group metal that is insoluble in both water and organic agents, and a by-product carbide that is also insoluble in both water and organic solvents. In addition, in addition to dipotassium naphthalene-2,6-dicarboxylic acid salt, dipotassium terephthalate salt and isophthalic acid, which are by-produced in the reaction, are contained in the aqueous layer obtained by dividing the liquid into 0 liquid, which can be easily separated by means such as filtration. Potassium benzenecarboxylic acid salts such as dipotassium salts, dipotassium phthalates, potassium benzoates, and water-soluble potassium iodide, cesium iodide, potassium chloride, cesium chloride, and odors among reaction catalysts and compounds that accelerate the reaction. It may contain alkali halides such as potassium chloride and cesium bromide, and base compounds such as dipotassium carbonate, cesium carbonate, potassium hydroxide, and cesium hydroxide, which are decomposition products. However, as described above, these do not aim at the subsequent step A. That is, the aqueous layer obtained by liquid separation can be used as it is or after being concentrated and subjected to the step A as an aqueous solution of dipotassium naphthalene-2,6-dicarboxylic acid salt. If necessary, an acid is added to the aqueous layer obtained by separating the naphthalene.
After the 2,6-dicarboxylic acid dipotassium salt is partially neutralized and converted into the naphthalene-2,6-dicarboxylic acid monopotassium salt, it can be subjected to the reaction in step A above. As the acid used for this purpose, inorganic weak acids such as carbon dioxide gas and sulfur dioxide gas can be suitably used.
以下、実施例により本発明を更に詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例Ｉ
ナフタレン−２，６−ジカルボン酸ジカリウム塩５．８
４ｇと無水フタル酸２．９６ｇを水５０ｍ１に懸濁せし
め還流温度で１２０分攪拌した後、室温まで冷却し、析
出物を濾過した。得られた結晶を水洗、乾燥後沈澱４．
１１ｇを得た。得られた結晶、濾液について、高速液ク
ロ分析、酸価測定を実施し以下の結果を得た。Example I Naphthalene-2,6-dicarboxylic acid dipotassium salt 5.8
4 g and 2.96 g of phthalic anhydride were suspended in 50 ml of water, stirred at reflux temperature for 120 minutes, cooled to room temperature, and the precipitate was filtered. The obtained crystals were washed with water and precipitated after drying 4.
11 g was obtained. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルポン酸回収率９５．９％ナ
フタレン〜２．６−ジカルボン酸純度 〉９９％カリウ
ム含有量（仕込みカリウム量に対して）０％
濾液
フタル酸ジカリウム塩回収率 〉９９％実施例２
ナフタレン−２，６−ジカルボン酸ジカリウム塩５．８
４ｇと無水フタル酸２．９６ｇを水１００ｍ１に懸濁せ
しめた以外は実施例１と同様の操作を行ない沈澱４．１
６ｇを得た。得られた結晶、濾液について、高速液クロ
分析、酸価測定を実施し以下の結果を得た。Crystalline naphthalene-2,6-dicarboxylic acid recovery rate 95.9% Naphthalene-2,6-dicarboxylic acid purity 〉99% Potassium content (relative to the amount of potassium charged) 0% Filtrate dipotassium phthalate salt recovery rate 〉99% Example 2 Naphthalene-2,6-dicarboxylic acid dipotassium salt 5.8
4g of phthalic anhydride and 2.96g of phthalic anhydride were suspended in 100ml of water.
6g was obtained. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルボン酸回収率９６．１％ナ
フタレン−２，６−ジカルボン酸純度 ９７，３％カリ
ウム含有量（仕込みカリウム量に対して）２．５％
濾液
フタル酸ジカリウム塩回収率 ９７．２％実施例３
ナフタレン−２，６−ジカルボン酸ジカリウム塩５．８
４ｇと無水フタル酸２．９６ｇを水１５ｍ１に懸濁せし
めた以外は実施例１と同様の操作を行ない沈澱４．５０
ｇを得た。得られた結晶、濾液について、高速液クロ分
析、酸価測定を実施し以下の結果を得た。Recovery rate of crystalline naphthalene-2,6-dicarboxylic acid 96.1% Naphthalene-2,6-dicarboxylic acid purity 97.3% Potassium content (relative to the amount of potassium charged) 2.5% Filtrate recovery rate of dipotassium phthalate salt 97.2% Example 3 Naphthalene-2,6-dicarboxylic acid dipotassium salt 5.8
The same procedure as in Example 1 was carried out except that 4 g and 2.96 g of phthalic anhydride were suspended in 15 ml of water, resulting in a precipitate of 4.50 g.
I got g. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルボン酸回収率９６．１％ナ
フタレン−２，６−ジカルボン酸純度 〉９９％カリウ
ム含有量（仕込みカリウム量に対して）１４．６％
濾液
フタル酸ジカリウム塩回収率 〉９９％実施例４
ナフタレン−２，６−ジカルボン酸ジカリウム塩５．８
４ｇと無水フタル酸２．９６ｇを水１７０ｍ１に懸濁せ
しめた以外は実施例１と同様の操作を行ない沈澱４．１
１ｇ得た。得られた結晶、濾液について、高速液クロ分
析、酸価測定を実施し以下の結果を得た。Recovery rate of crystalline naphthalene-2,6-dicarboxylic acid 96.1% Naphthalene-2,6-dicarboxylic acid purity 〉99% Potassium content (relative to the amount of potassium charged) 14.6% Filtrate dipotassium phthalate salt recovery rate 〉 99% Example 4 Naphthalene-2,6-dicarboxylic acid dipotassium salt 5.8
4g of phthalic anhydride and 2.96g of phthalic anhydride were suspended in 170ml of water.
I got 1g. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルポン酸回収率９６，１％ナ
フタレン−２，６−ジカルボン酸純度 〉９９％カリウ
ム含有量（仕込みカリウム量に対して）０％
濾液
フタル酸ジカワウム塩回収率 〉９９％実施例５
ナフタレン−２，６−ジカルボン酸ジカリウム塩５．８
４ｇと無水フタル酸２．９６ｇを水８００ｍ１に懸濁せ
しめた以外は実施例１と同様の操作を行ない沈澱３．９
６ｇを得た。得られた結晶、濾液について、高速液クロ
分析、酸価測定を実施し以下の結果を得た。Recovery rate of crystalline naphthalene-2,6-dicarboxylic acid 96.1% Naphthalene-2,6-dicarboxylic acid purity 〉99% Potassium content (based on the amount of potassium charged) 0% Filtrate recovery rate of diquaum phthalate salt 〉99% Example 5 Naphthalene-2,6-dicarboxylic acid dipotassium salt 5.8
The same procedure as in Example 1 was carried out except that 4 g and 2.96 g of phthalic anhydride were suspended in 800 ml of water, resulting in a precipitate of 3.9 g.
6g was obtained. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルボン酸回収率９２．３％ナ
フタレン−２，６−ジカルボン酸純度〉９９％カリウム
含有量（仕込みカリウム量に対して）１．７％
濾液
フタル酸ジカリウム塩回収率 〉９９％実施例６
反応温度を８０°Ｃにした以外は実施例１と同様の操作
を行ない沈ｉ１４．３０ｇを得た。得られた結晶、濾液
について、高速液クロ分析、酸価測定を実施し以下の結
果を得た。Crystalline naphthalene-2,6-dicarboxylic acid recovery rate: 92.3% Naphthalene-2,6-dicarboxylic acid purity: 99% Potassium content (relative to the amount of potassium charged): 1.7% Filtrate dipotassium phthalate salt recovery rate: 99% Example 6 14.30 g of precipitate i was obtained by carrying out the same operation as in Example 1 except that the reaction temperature was changed to 80°C. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルボン酸回収率９７．１％ナ
フタレン−２，６−ジカルボン酸純度 ９７．２％カリ
ウム含有量（仕込みカリウム量に対して）２．２％
濾液
フタル酸ジカリウム塩回収率 ９７．３％実施例７
反応温度を６０゛Ｃにした以外は実施例１と同様の操作
を行ない沈澱４．１７ｇを得た。得られた結晶、濾液に
ついて、高速液クロ分析、酸価測定を実施し以下の結果
を得た。Recovery rate of crystalline naphthalene-2,6-dicarboxylic acid 97.1% Naphthalene-2,6-dicarboxylic acid purity 97.2% Potassium content (based on the amount of potassium charged) 2.2% Filtrate recovery rate of dipotassium phthalate salt 97.3% Example 7 The same procedure as in Example 1 was carried out except that the reaction temperature was changed to 60°C to obtain 4.17 g of precipitate. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルポン酸回収率９４．１％ナ
フタレン−２，６−ジカルボン酸純度 ９６，９％カリ
ウム含有量（仕込みカリウム量に対して）１．３％
濾液
フタル酸ジカリウム塩回収率 ９７．２％実施例８
反応温度を４０℃にした以外は実施例１と同様の操作を
行ない沈澱４．３０ｇを得た。得られた結晶、濾液につ
いて、高速液クロ分析、酸価測定を実施し以下の結果を
得た。Recovery rate of crystalline naphthalene-2,6-dicarboxylic acid 94.1% Naphthalene-2,6-dicarboxylic acid purity 96.9% Potassium content (relative to the amount of potassium charged) 1.3% Filtrate recovery rate of dipotassium phthalate salt 97.2% Example 8 4.30 g of precipitate was obtained by carrying out the same operation as in Example 1 except that the reaction temperature was changed to 40°C. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルポン酸回収率９３．１％ナ
フタレン−２，６−ジカルボン酸純度 ９３．１％カリ
ウム含有ＩＣ仕込みカリウム量に対して）６．９％
濾液
フタル酸ジカリウム塩回収率 ９３．０％実施例９
反応時間を３０分にした以外は実施例１と同様の操作を
行ない沈澱４．３８ｇを得た。得られた結晶、濾液につ
いて、高速液クロ分析、酸価測定を実施し以下の結果を
得た。Recovery rate of crystalline naphthalene-2,6-dicarboxylic acid 93.1% Naphthalene-2,6-dicarboxylic acid purity 93.1% Potassium (based on the amount of potassium charged in IC) 6.9% Filtrate dipotassium phthalate salt recovery rate 93 .0% Example 9 The same operation as in Example 1 was carried out except that the reaction time was changed to 30 minutes to obtain 4.38 g of precipitate. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルポン酸回収率９９．１％ナ
フタレン−２，６−ジカルボン酸純度 〉９９％カリウ
ム含有Ｗ（仕込みカリウム量に対して）４．８％
濾液
フタル酸ジカリウム塩回収率 〉９９％実施例１０
反応温度を８０℃、反応時間を３０分にした以外は実施
例１と同様の操作を行ない沈澱４．２５ｇを得た。得ら
れた結晶、濾液について、高速液クロ分析、酸価測定を
実施し以下の結果を得た。Recovery rate of crystalline naphthalene-2,6-dicarboxylic acid 99.1% Naphthalene-2,6-dicarboxylic acid purity 〉99% Potassium content W (based on the amount of potassium charged) 4.8% Filtrate dipotassium phthalate salt recovery rate 〉 99% Example 10 4.25 g of precipitate was obtained by carrying out the same operation as in Example 1 except that the reaction temperature was 80° C. and the reaction time was 30 minutes. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルボン酸回収率９７．９％ナ
フタレン−２，６−ジカルボン酸純度 〉９９％カリウ
ム含有量（仕込みカリウム量に対して）４．８％
濾液
フタル酸ジカリウム塩回収率 〉９９％実施例１１
ナフタレン−２，６−ジカルボン酸ジカリウム塩５．８
４ｇと安息香酸２．４４ｇを水５０ｍ１に懸濁せしめた
以外は実施例１と同様の操作を行ない沈澱４．３ｇを得
た。得られた結晶、濾液について、高速液クロ分析、酸
価測定を実施し以下の結果を得た。Recovery rate of crystalline naphthalene-2,6-dicarboxylic acid 97.9% Naphthalene-2,6-dicarboxylic acid purity 〉99% Potassium content (relative to the amount of potassium charged) 4.8% Filtrate dipotassium phthalate salt recovery rate 〉 99% Example 11 Naphthalene-2,6-dicarboxylic acid dipotassium salt 5.8
4.3 g of precipitate was obtained by carrying out the same operation as in Example 1 except that 4 g of benzoic acid and 2.44 g of benzoic acid were suspended in 50 ml of water. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルボン酸回収率９８，７％ナ
フタレン−２，６−ジカルボン酸純度 ９７．９％カリ
ウム含有ｉｔ（仕込みカリウム量に対して〕４．８ ％
濾液
安息香酸カリウム塩回収率 ９８．９％実施例１２
ナフタレン−２，６−ジカルボン酸ジカリウム塩５．８
４ｇとイソフタル酸３．３２ｇを水５０ｍ１に懸濁せし
めた以外は実施例１と同様の操作を行ない沈澱４．３６
ｇを得た。得られた結晶、濾液について、高速液クロ分
析、酸価測定を実施し以下の結果を得た。Recovery rate of crystalline naphthalene-2,6-dicarboxylic acid 98.7% Naphthalene-2,6-dicarboxylic acid purity 97.9% Potassium content (relative to the amount of potassium charged) 4.8% Filtrate Recovery rate of potassium benzoate salt 98.9% Example 12 Naphthalene-2,6-dicarboxylic acid dipotassium salt 5.8
The same procedure as in Example 1 was carried out except that 4 g and 3.32 g of isophthalic acid were suspended in 50 ml of water, resulting in a precipitate of 4.36 g.
I got g. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルボン酸回収率９９６４％ナ
フタレン−２，６−ジカルボン酸純度 ９８．０％カリ
ウム含有量（仕込みカリウム量に対して）０％
濾液
イソフタル酸ジカリウム塩回収率 ９８．０％実施例１
３
ナフタレン−２，６−ジカルボン酸ジカリウム塩５．８
４ｇとトリメリット酸３．８４ｇを水５０ｍ１に懸濁せ
しめた以外は実施例１と同様の操作を行ない沈！４．２
３ｇを得た。得られた結晶、濾液について、高速液クロ
分析、酸価測定を実施し以下の結果を得た。Recovery rate of crystalline naphthalene-2,6-dicarboxylic acid 9964% Naphthalene-2,6-dicarboxylic acid purity 98.0% Potassium content (based on the amount of potassium charged) 0% Filtrate recovery rate of dipotassium isophthalate salt 98.0% Example 1
3 Naphthalene-2,6-dicarboxylic acid dipotassium salt 5.8
The same procedure as in Example 1 was carried out except that 4g of trimellitic acid and 3.84g of trimellitic acid were suspended in 50ml of water. 4.2
3g was obtained. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルボン酸回収率９９．５％ナ
フタレン−２，６−ジカルボン酸純度 〉９９％カリウ
ム含有量（仕込みカリウム量に対して）０％
濾液
トリメリット酸トリカリウム塩回収率 〉９９％実施例
１４
ナフタレン−２，６−ジカルボン酸ジカリウム塩５．８
４ｇとピロメリット酸４．３６ｇを水５０ｍ１に懸濁せ
しめた以外は実施例１と同様の操作を行ない沈Ｂ４゜２
１ｇを得た。得られた結晶、濾液について、高速液クロ
分析、酸価測定を実施し以下の結果を得た。Recovery rate of crystalline naphthalene-2,6-dicarboxylic acid 99.5% Naphthalene-2,6-dicarboxylic acid purity 〉99% Potassium content (relative to the amount of potassium charged) 0% Recovery rate of filtrate trimellitic acid tripotassium salt 〉 99% Example 14 Naphthalene-2,6-dicarboxylic acid dipotassium salt 5.8
Precipitate B4゜2 was prepared in the same manner as in Example 1, except that 4g of pyromellitic acid and 4.36g of pyromellitic acid were suspended in 50ml of water.
1g was obtained. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルボン酸回収率９９．０％ナ
フタレン−２，６−ジカルボン酸純度 〉９９％カリウ
ム含有量（仕込みカリウム量器二対して）２．８％
濾液
ピロメリット酸テトラカリウム塩回収率〉９９％実施例
１５
ナフタレン−２，６−ジカルボン酸モノカリウム塩４．
５７ｇとフタル酸モノカリウム塩３．６７ｇを水５０ｍ
１に懸濁せしめた以外は実施例】と同様の操作を行ない
沈Ｒ３，８６ｇを得た。得られた結晶、濾液について、
高速液クロ分析、酸価測定を実施し以下の結果を得た。Crystalline naphthalene-2,6-dicarboxylic acid Recovery rate: 99.0% Naphthalene-2,6-dicarboxylic acid purity: 〉99% Potassium content (based on the amount of potassium charged): 2.8% Filtrate: Tetrapotassium pyromellitic acid salt Recovery rate>99% Example 15 Naphthalene-2,6-dicarboxylic acid monopotassium salt 4.
57g and phthalic acid monopotassium salt 3.67g in 50ml of water.
86 g of precipitate R3 was obtained by carrying out the same operation as in Example except that the precipitate was suspended in 1. Regarding the obtained crystals and filtrate,
High performance liquid chromatography analysis and acid value measurement were performed and the following results were obtained.
結晶
ナフタレン−２，６−ジカルボン酸回収率９９．０％ナ
フタレン−２，６−ジカルボン酸純度 〉９９％カリウ
ム含有量（仕込みカリウム量に対して）５．７％
濾液
フタル酸ジカリウム塩回収率 〉９９％実施例１６
フタル酸ジカリウム塩１１．２ｇ、ナフタレン４７．５
ｇ、Ｃｄ１ｚ、７１ｇ１Ｃｓ１１．９２ｇを炭酸ガス加
圧１１８時間加熱した。得られた反応混合物を水並びに
トルエンで溶解し、分液した。Recovery rate of crystalline naphthalene-2,6-dicarboxylic acid 99.0% Naphthalene-2,6-dicarboxylic acid purity 〉99% Potassium content (based on the amount of potassium charged) 5.7% Filtrate dipotassium phthalate salt recovery rate 〉 99% Example 16 Phthalic acid dipotassium salt 11.2 g, naphthalene 47.5
g, Cd1z, 71g1Cs11.92g were heated under carbon dioxide gas for 118 hours. The resulting reaction mixture was dissolved in water and toluene, and the layers were separated.
得られた水層を濃縮乾固し、残留物の高速液クロ分析を
実施し、
ナフタレン−２，６−ジカルボン酸ジカリウム塩６．７
６ｇ
テレフタル酸ジカリウム塩 １．０３ｇ炭酸ジカリ
ウム塩 １．４７ｇ等が含有することが
判った。この濃縮固体と無水フタル酸４．２１ｇを水１
００ｍ１に懸濁し、還流温度で１２０分撹拌した後、室
温まで冷却し析出物を濾過した。得られた結晶を水洗、
乾燥後沈澱５．４ｇを得た。得られた結晶、濾液につい
て、高速液クロ分析、酸価測定を実施し以下の結果を得
た。The obtained aqueous layer was concentrated to dryness, and the residue was subjected to high-performance liquid chromatography analysis.
It was found that 6g of dipotassium terephthalate, 1.03g of dipotassium carbonate, and 1.47g of dipotassium carbonate were contained. Add this concentrated solid and 4.21 g of phthalic anhydride to 1 part of water.
After stirring at reflux temperature for 120 minutes, the mixture was cooled to room temperature and the precipitate was filtered. Wash the obtained crystals with water,
After drying, 5.4 g of precipitate was obtained. The obtained crystals and filtrate were subjected to high performance liquid chromatography analysis and acid value measurement, and the following results were obtained.
結晶
ナフタレン−２，６−ジカルボン酸回収率 ９８．２％
ナフタレン、２．６−ジカルボン酸純度 ９７．２％
カリウム含を量（仕込みカリウム量に対して）３．０％
濾液
フタル酸ジカリウム塩回収率 〉９９％この濾液は
無水フタル酸０．９２ｇとフタル酸ｃｄ２．０４ｇを加
え濃縮乾固し、ナフタレン４゜７５ｇを加え、炭酸ガス
加圧下１８時間加熱した。Crystalline naphthalene-2,6-dicarboxylic acid recovery rate 98.2%
Naphthalene, 2.6-dicarboxylic acid Purity 97.2%
Potassium content: 3.0% (relative to the amount of potassium charged) Recovery rate of dipotassium phthalate salt in filtrate: 〉99% This filtrate was concentrated to dryness by adding 0.92 g of phthalic anhydride and 2.04 g of phthalic acid CD. 75 g of the mixture was added and heated under pressure of carbon dioxide gas for 18 hours.
得られた反応混合物を水並びにトルエンで溶解し分液し
た。得られた水相を＊ｍ乾固し、残留物の高速液クロ分
析を実施し、
ナフタレン−２，６−ジカルボン酸ジカリウム塩６．６
１ｇ
テレフタル酸ジカリウム塩 １．１２ｇ炭酸ジカリ
ウム塩 １．３９ｇ等が含有することが判
った。これは、ナフタレン−２，６−ジカルボン酸に変
換する工程の反応原料として使用できる。The resulting reaction mixture was dissolved in water and toluene and separated into layers. The obtained aqueous phase was dried to dryness, and the residue was subjected to high-performance liquid chromatography analysis.
It was found that 1g of dipotassium terephthalate, 1.12g of dipotassium carbonate, and 1.39g of dipotassium carbonate were contained. This can be used as a reaction raw material in the step of converting it into naphthalene-2,6-dicarboxylic acid.
本発明の方法によって、高分子原料として有用なナフタ
レン−２，６−ジカルボン酸を工業的に安価に製造する
ことができる。By the method of the present invention, naphthalene-2,6-dicarboxylic acid useful as a polymer raw material can be produced industrially at low cost.
第１図は本発明の反応スキームを示す図面である。 FIG. 1 is a drawing showing the reaction scheme of the present invention.
Claims (3)
ルボン酸ジカリウム塩またはモノカリウム塩と、 一般式 ▲数式、化学式、表等があります▼−（ I ） （式中、ｍは１〜６の整数であり、ｎは０〜５の整数で
ある、但しｍ＋ｎは１〜６の範囲にある。） で表されるベンゼンカルボン酸類または相当するカルボ
ン酸無水物とを反応させ、ナフタレン−２，６−ジカル
ボン酸と、 一般式 ▲数式、化学式、表等があります▼−（II） （式中、ｍ及びｎは前記に同じである。） で表されるベンゼンカルボン酸カリウム塩とに変換する
反応工程（工程Ａ）と、結晶として析出したナフタレン
−２，６−ジカルボン酸を水溶液から分離する分離工程
（工程Ｂ）とを有することを特徴とするナフタレン−２
，６−ジカルボン酸の製造方法。(1) In the presence of a solvent amount of water, naphthalene-2,6-dicarboxylic acid dipotassium salt or monopotassium salt and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼-(I) (In the formula, m is 1 to 6, n is an integer of 0 to 5, provided that m+n is in the range of 1 to 6.) Naphthalene- 2,6-dicarboxylic acid and benzenecarboxylic acid potassium salt represented by the general formula ▲Mathematical formula, chemical formula, table, etc.▼-(II) (In the formula, m and n are the same as above.) Naphthalene-2 characterized by comprising a reaction step (step A) of converting the naphthalene-2, and a separation step (step B) of separating naphthalene-2,6-dicarboxylic acid precipitated as crystals from an aqueous solution.
, 6-dicarboxylic acid manufacturing method.
無水物が、フタル酸、無水フタル酸、フタル酸モノカリ
ウム塩、安息香酸、トリメリット酸、無水トリメリット
酸、トリメリット酸モノカリウム塩、無水トリメリット
酸モノカリウム塩、ピロメリット酸、無水ピロメリット
酸、あるいはこれらの混合物である請求項（１）記載の
ナフタレン−２，６−ジカルボン酸の製造方法。(2) Benzenecarboxylic acids or corresponding carboxylic acid anhydrides include phthalic acid, phthalic anhydride, monopotassium phthalate, benzoic acid, trimellitic acid, trimellitic anhydride, monopotassium trimellitic acid, trimellitic anhydride The method for producing naphthalene-2,6-dicarboxylic acid according to claim (1), wherein the acid monopotassium salt, pyromellitic acid, pyromellitic anhydride, or a mixture thereof.
離して得られた一般式（II）で示されるベンゼンカルボ
ン酸カリウム塩を溶解している水溶液から回収したベン
ゼンカルボン酸カリウム塩と、ナフタレンとを反応させ
てナフタレン−２，６−ジカルボン酸ジカリウム塩を生
成させ（工程Ｃ）、生成したナフタレン−２，６−ジカ
ルボン酸ジカリウム塩または必要により部分中和して得
られたナフタレン−２，６−ジカルボン酸モノカリウム
塩を、工程Ａの反応原料として使用する請求項（１）ま
たは（２）記載のナフタレン−２，６−ジカルボン酸の
製造方法。(3) potassium benzenecarboxylate salt recovered from an aqueous solution in which potassium benzenecarboxylate represented by general formula (II) obtained by separating naphthalene-2,6-dicarboxylic acid in step B is dissolved; Naphthalene-2,6-dicarboxylic acid dipotassium salt is produced by reacting with naphthalene (Step C), and the naphthalene-2,6-dicarboxylic acid dipotassium salt produced or naphthalene-2 obtained by partial neutralization if necessary. , 6-dicarboxylic acid monopotassium salt is used as a reaction raw material in step A.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8709290A JPH03284648A (en) | 1990-03-30 | 1990-03-30 | Method for industrially producing naphthalene-2,6-dicarboxylic acid |
| US07/678,425 US5175354A (en) | 1990-03-30 | 1991-04-01 | Process for preparing 2,6-naphthalene-dicarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8709290A JPH03284648A (en) | 1990-03-30 | 1990-03-30 | Method for industrially producing naphthalene-2,6-dicarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03284648A true JPH03284648A (en) | 1991-12-16 |
Family
ID=13905315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8709290A Pending JPH03284648A (en) | 1990-03-30 | 1990-03-30 | Method for industrially producing naphthalene-2,6-dicarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03284648A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115925531A (en) * | 2022-12-15 | 2023-04-07 | 沧州临港丰亚化工有限公司 | Method for preparing 2, 6-naphthalene dicarboxylic acid by using aromatic anhydride as raw material |
-
1990
- 1990-03-30 JP JP8709290A patent/JPH03284648A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115925531A (en) * | 2022-12-15 | 2023-04-07 | 沧州临港丰亚化工有限公司 | Method for preparing 2, 6-naphthalene dicarboxylic acid by using aromatic anhydride as raw material |
| CN115925531B (en) * | 2022-12-15 | 2023-07-11 | 信诺立兴(沧州渤海新区)化工有限公司 | Method for preparing 2,6 naphthalene dicarboxylic acid by taking aromatic anhydride as raw material |
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