JPS6353194B2 - - Google Patents
Info
- Publication number
- JPS6353194B2 JPS6353194B2 JP54061571A JP6157179A JPS6353194B2 JP S6353194 B2 JPS6353194 B2 JP S6353194B2 JP 54061571 A JP54061571 A JP 54061571A JP 6157179 A JP6157179 A JP 6157179A JP S6353194 B2 JPS6353194 B2 JP S6353194B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- pyromellitic anhydride
- raw material
- oxide
- derivatives
- 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.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 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 14
- 239000000203 mixture Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WALBTDFSFTVXII-UHFFFAOYSA-N 2,3,4,5,6-pentamethylphenol Chemical compound CC1=C(C)C(C)=C(O)C(C)=C1C WALBTDFSFTVXII-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- FNYLWPVRPXGIIP-UHFFFAOYSA-N Triamterene Chemical compound NC1=NC2=NC(N)=NC(N)=C2N=C1C1=CC=CC=C1 FNYLWPVRPXGIIP-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 229960001288 triamterene Drugs 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- -1 hydroxyethyl group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000004685 tetrahydrates Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- FENOFCXZYHLMDU-UHFFFAOYSA-N (2-hydroxyphenyl)methanediol Chemical compound OC(O)C1=CC=CC=C1O FENOFCXZYHLMDU-UHFFFAOYSA-N 0.000 description 1
- DHQDXPIEOYLUBK-UHFFFAOYSA-N 2,6-bis(hydroxymethyl)-3,5-dimethylphenol Chemical compound CC1=CC(C)=C(CO)C(O)=C1CO DHQDXPIEOYLUBK-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
本発明は、無水ピロメリツト酸の新規な製造法
に関するものである。さらに詳しくは、ペンタア
ルキルフエノール、２，３，５，６―テトラアル
キルフエノールおよびこれらの誘導体の１種また
は２種以上の混合物を酸化することによつて無水
ピロメリツト酸を製造する方法に関するものであ
る。
従来、無水ピロメリツト酸の製造法として、
種々の原料を使用した種々の方法が提案されてい
る。これらの方法のなかで、最も一般的な方法は
ジユレン（１，２，４，５―テトラメチルベンゼ
ン）の酸化によるものである。しかし、この方法
では、原料として用いるジユレンが非常に入手困
難であるうえに、入手しうる原料は、ジユレンと
その異性体の混合物であるので、反応に供するに
は異性体を分離除去しなければならない。その他
の無水ピロメリツト酸の製造法も、そのほとんど
が１，２，４，５―テトラアルキルベンを原料と
して用いるものであつて、ジユレンと同じよう
に、原料の１，２，４，５―テトラアルキルベン
ゼンは入手が困難で、かつその異性体との混合物
から分離しなければならない。このように、既に
公知の一般的な方法では原料の入手および原料と
して反応に使用するために必要な異性体の分離除
去が困難である等の欠点を有し、これらの方法は
工業的にも、経済的にも満足しうる方法とは言え
ない。
本発明者らは、ポリアルキルフエノールの酸化
反応について詳細に研究した結果、ペンタアルキ
ルフエノール、２，３，５，６―テトラアルキル
フエノールおよびこれらの誘導体の１種または２
種以上の混合物を酸化することによつて、直接、
無水ピロメリツト酸が生成することを見い出し、
本発明の方法を完成した。
すなわち、本発明の方法はペンタアルキルフエ
ノール、２，３，５，６―テトラアルキルフエノ
ールおよびこれらの誘導体の１種または２種以上
の混合物を気相酸化触媒の存在下に酸素または酸
素含有ガスと接触させる気相接触酸化反応によつ
て無水ピロメリツト酸を製造するものである。
本発明の方法のようにペンタアルキルフエノー
ル、２，３，５，６―テトラアルキルフエノール
およびこれらの誘導体の１種または２種以上の混
合物、すなわち、４または５個のアルキルまた
は／および置換アルキル基を核置換基として有す
るポリアルキルフエノールおよび／またはこれら
の誘導体の酸化により直接一段で、しかも良好な
収率で無水ピロメリツト酸が得られることは驚く
べきことである。
すなわち、本発明の方法では、原料として用い
る４または５個の核置換基を有するポリアルキル
フエノールまたはこれらの誘導体の１種または２
種以上の混合物が、１，２，４，５―テトラアル
キルベンゼンを原料とする従来の製造法の問題で
ある原料としての入手困難さ、および反応に際し
ての異性体分離等の欠点もなく、かつ容易に製造
できるので、耐熱性樹脂の中間体として非常に有
用な無水ピロメリツト酸を工業的に極めて有利に
製造することができる。
本発明の方法で原料として用いられるペンタア
ルキルフエノール、２，３，５，６―テトラアル
キルフエノールおよびこれらの誘導体とは、
一般式（）
（式（）中、R1およびR4は水素原子または
アルキル基、またR2，R3，R5およびR6はアルキ
ル基であり、これらは互に同一の基であつても、
異なる基であつてもよい、ここでアルキル基と
は、炭素原子数１〜４のアルキル基、ハロゲン化
アルキル基、ヒドロキシアルキル基およびアセチ
ル基を示す。）で表わされる化合物である。
具体的には、メチル，エチル，ｎ―プロピル，
ｉ―プロピル，ｎ―ブチル，ｔ―ブチル等の低級
アルキル基を有するペンタアルキルフエノール、
２，３，５，６―テトラアルキルフエノールまた
はこれらのエステルおよびエーテル、また、水素
原子および炭素原子以外の原子または原子団を有
するアルキル基が核置換したポリアルキルフエノ
ールおよびそのエステルまたはエーテルであつ
て、一般式（）におけるR2〜R6のうち核置換
基として１個または２個以上のクロルメチル基、
ブロムエチル基等のハロゲン化アルキル基、ヒド
ロキシメチル基、ヒドロキシエチル基等のヒドロ
キシアルキル基、メトキシメチル基、エトキシメ
チル基等のアルコキシアルキル基およびアセチル
基を有する化合物およびこれらの混合物である。
これらの原料ポリアルキルフエノールおよびこれ
らのエステルまたはエーテルに、１，２，４，５
―テトラアルキルベンゼン、ペンタアルキルベン
ゼンおよびヘキサアルキルベンゼンが不純物とし
て混入することは何等差し支えない。
これらの原料ポリアルキルフエノールおよびそ
の誘導体は、フエノール、メチルフエニルエーテ
ル、フエニルアセテート等のメタノール、塩化メ
チル、ホルムアルデヒド等による公知のアルキル
化反応によつて製造できる。
本発明の方法で用いられる触媒は、一般に、気
相酸化触媒作用を有するものであつて、酸化バナ
ジウム、酸化モリブデン、酸化銀、酸化鉄、酸化
銅、酸化マンガン、酸化コバルト、酸化ニツケル
などの金属酸化物、白金、パラジウム、銀、銅、
ニツケルなどの金属、マンガン、コバルト、クロ
ム、銅などの有機酸塩が用いられる。とくに好ま
しくは、酸化バナジウム含有触媒であつて、酸化
バナジウム単独、またはこれにリン、リチウム、
ナトリウム、カリウム、マグネシウム、カルシウ
ム、クロム、モリブデン、タングステン、セレニ
ウム、ホウソ、アルミニウム、チタン、ゲルマニ
ウム、ジルコニウム、スズ、ニオブ、ビスマス、
亜鉛、鉄、コバルト、ニツケル、銅、銀等のの１
種または２種以上の元素の化合物、すなわち酸化
物または塩、の形で加えて、多元触媒としても用
いることができる。これらの触媒は、一般的には
半融アルミナ、軽石、炭化ケイ素などのような比
表面積の比較的小さい公知の担体に担持して用い
ることもできる。触媒の調製は、通常の酸化バナ
ジウム含有触媒調製法のいづれの方法によつても
よい。簡単には、例えば、バナジン酸アンモニウ
ムの水溶液または、その他の配合成分との混合水
溶液に担体をひたし、乾燥、焼成または焼成融触
して付着する方法をとることができる。触媒の用
い方は、固定床法、流動触媒法のいずれを採用し
てもよい。
酸素含有気体としては、空気が有利であるが、
酸素と他の希釈剤、例えば窒素、二酸化炭素、ヘ
リウムまたは水蒸気などとの混合ガスを使用する
こともできる。原料ボリアルキルフエノールと酸
素の使用割合は、モル比で１：100ないし１：
10000が望ましい。触媒に対する原料ガスの送入
速度は、触媒、反応温度等の反応条件により異な
るが、一般に触媒１当り毎時300〜30000（標
準状態）の範囲である。反応温度は、300〜650℃
の範囲、好ましくは、300〜550℃の範囲である。
反応終了し反応器より出る生成ガスを冷却するこ
とによつて、普通、結晶として無水ピロメリツト
酸を分離することができる。この無水ピロメリツ
ト酸は水と反応して容易にピロメリツト酸となる
ので、ピロメリツト酸としても取得することがで
きる。
以下、実施例により本発明を説明する。
実施例 １
メタバナジン酸アンモニウム（無水塩）0.9ｇ
とモリブデン酸アンモニウム（４水塩）1.2ｇの
混合水溶液にアナターゼ型酸化チタン60ｇを加
え、かく拌しながら加熱して、蒸発乾固させる。
これを成型後８〜10メツシユにくだき、空気中に
て500℃で４時間焼成して触媒とした。この触媒
15c.c.を内径17mmのパイレツクスガラス製Ｕ字管型
反応管に充填し、330℃に保持したナイター浴に
つけた。
蒸発器中の原料ジユレノール（２，３，５，６
―テトラメチルフエノール）を約150℃に加熱し
て完全に熔融させた後、空気を通じてジユレノー
ルを気化させ、さらに、これに二次空気を混合し
て反応管に導入した。ジユレノール0.2モル％を
含む空気を225／時（標準状態）の流速で触媒
層に通した結果、原料ジユレノールに対して72.5
重量％の無水ピロメリツト酸が得られた。
実施例 ２
シユウ酸（２水塩）50ｇを水に溶かし、これに
メタバナジン酸アンモニウム（無水塩）11ｇ、リ
ン酸二水素アンモニウム（無水塩）1.2ｇおよび
タングステン酸アンモニウム（５水塩）5.1ｇを
加えて完全に溶解させた。この溶液に８〜10メツ
シユのアランダム90ｇを加え、かく拌しながら加
熱して蒸発乾固させた後、空気気流中にて500℃
で４時間焼成した。このようにして得られた触媒
20c.c.を実施例１と同じ反応管に充填し、450℃に
保持したナイター浴につけた。
蒸発器中の原料ペンタメチルフエノールを約
150℃に加熱して熔融させた後、空気を通じてペ
ンタメチルフエノールを気化させ、さらに、これ
に二次空気を混合して反応管に導入した。ペンタ
メチルフエノール0.1モル％を含む空気を150／
時（標準状態）の流速で触媒層に通した結果、原
料ペンタメチルフエノールに対して60.5重量％の
無水ピロメリツト酸が得られた。
実施例 ３
シユウ酸（２水塩）10ｇを水に溶解し、これに
メタパナジン酸アンモニウム（無水塩）6.5ｇ）、
リン酸二水素アンモニウム（無水塩）0.64ｇ、モ
リブデン酸アンモニウム（４水塩）0.98ｇを加え
て均一溶液とした。
さらに、これに四塩化チタン0.53ｇを加えた
後、８〜10メツシユのアランダム100ｇを入れて
かく拌しながら加熱して、蒸発乾固させた。
これを空気気流中にて500℃で６時間焼成した
後、実施例１と同じ反応管にこの触媒15c.c.を充填
し、430℃に保持したナイター浴につけた。実施
例１で実施した方法に準じて、３，５―ジメチル
２，６―ジヒドロキシメチルフエノール0.15モル
％を含む空気を120／時（標準状態の流速で触
媒層に通した結果、原料３，５−ジメチル２，６
−ジヒドロキシメチルフエノールに対して62.8重
量％の無水ピロメリツト酸が得られた。
実施例 ４〜５
実施例１と同様にして、下記の原料ポリアルキ
ルフエノールおよびその誘導体の酸化反応を行な
つた。第１表に結果を示す。
The present invention relates to a novel method for producing pyromellitic anhydride. More specifically, it relates to a method for producing pyromellitic anhydride by oxidizing pentaalkylphenol, 2,3,5,6-tetraalkylphenol, and one or a mixture of two or more of these derivatives. . Conventionally, as a method for producing pyromellitic anhydride,
Various methods using various raw materials have been proposed. Among these methods, the most common method is by oxidation of diurene (1,2,4,5-tetramethylbenzene). However, in this method, it is very difficult to obtain diurene used as a raw material, and the available raw materials are a mixture of diurene and its isomers, so the isomers must be separated and removed before being used for the reaction. It won't happen. Most of the other methods for producing pyromellitic anhydride use 1,2,4,5-tetraalkylben as a raw material, and like diurene, 1,2,4,5-tetraalkylben is used as a raw material. Alkylbenzenes are difficult to obtain and must be separated from mixtures with their isomers. As described above, the already known general methods have drawbacks such as difficulty in obtaining raw materials and separating and removing isomers necessary for use as raw materials in reactions, and these methods are not suitable for industrial use. This cannot be said to be an economically satisfactory method. As a result of detailed research on the oxidation reaction of polyalkylphenols, the present inventors found that pentaalkylphenols, 2,3,5,6-tetraalkylphenols, and one or two of these derivatives.
directly by oxidizing a mixture of more than one species;
discovered that pyromellitic anhydride was produced,
The method of the present invention has been completed. That is, the method of the present invention involves treating one or a mixture of pentaalkylphenol, 2,3,5,6-tetraalkylphenol, and their derivatives with oxygen or an oxygen-containing gas in the presence of a gas-phase oxidation catalyst. Pyromellitic anhydride is produced by a gas phase catalytic oxidation reaction. As in the process of the invention, one or a mixture of two or more of pentaalkylphenols, 2,3,5,6-tetraalkylphenols and their derivatives, i.e. 4 or 5 alkyl or/and substituted alkyl groups It is surprising that pyromellitic anhydride can be obtained directly in one step and in good yields by oxidation of polyalkylphenols and/or derivatives thereof having as a nuclear substituent. That is, in the method of the present invention, polyalkylphenols having 4 or 5 nuclear substituents or one or two derivatives thereof used as raw materials
It is easy to prepare a mixture of more than 1,2,4,5-tetraalkylbenzene without the disadvantages of difficulty in obtaining raw materials and separation of isomers during reaction, which are problems of conventional production methods using 1,2,4,5-tetraalkylbenzene as a raw material. Therefore, pyromellitic anhydride, which is very useful as an intermediate for heat-resistant resins, can be produced industrially with great advantage. Pentaalkylphenol, 2,3,5,6-tetraalkylphenol and their derivatives used as raw materials in the method of the present invention have the general formula () (In formula (), R 1 and R 4 are hydrogen atoms or alkyl groups, and R 2 , R 3 , R 5 and R 6 are alkyl groups, and even if these are the same groups,
The alkyl group here refers to an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group, a hydroxyalkyl group, and an acetyl group, which may be different groups. ) is a compound represented by Specifically, methyl, ethyl, n-propyl,
Pentaalkylphenol having a lower alkyl group such as i-propyl, n-butyl, t-butyl,
2,3,5,6-tetraalkylphenols or their esters and ethers, and polyalkylphenols whose nucleus is substituted with an alkyl group having an atom or atomic group other than a hydrogen atom and a carbon atom, and their esters or ethers. , one or more chloromethyl groups as a nuclear substituent among R 2 to R 6 in the general formula (),
These are compounds having a halogenated alkyl group such as a bromoethyl group, a hydroxyalkyl group such as a hydroxymethyl group and a hydroxyethyl group, an alkoxyalkyl group such as a methoxymethyl group and an ethoxymethyl group, and an acetyl group, and mixtures thereof.
1, 2, 4, 5 to these raw material polyalkyl phenols and their esters or ethers.
- There is no problem with the inclusion of tetraalkylbenzene, pentaalkylbenzene, and hexaalkylbenzene as impurities. These raw material polyalkylphenols and their derivatives can be produced by a known alkylation reaction of phenol, methyl phenyl ether, phenyl acetate, etc. with methanol, methyl chloride, formaldehyde, etc. The catalyst used in the method of the present invention generally has a gas phase oxidation catalytic action, and is a metal such as vanadium oxide, molybdenum oxide, silver oxide, iron oxide, copper oxide, manganese oxide, cobalt oxide, nickel oxide, etc. oxide, platinum, palladium, silver, copper,
Metals such as nickel, organic acid salts such as manganese, cobalt, chromium, and copper are used. Particularly preferred is a vanadium oxide-containing catalyst, in which vanadium oxide alone or vanadium oxide, phosphorus, lithium,
Sodium, potassium, magnesium, calcium, chromium, molybdenum, tungsten, selenium, borax, aluminum, titanium, germanium, zirconium, tin, niobium, bismuth,
1 of zinc, iron, cobalt, nickel, copper, silver, etc.
It can be added in the form of species or compounds of two or more elements, ie oxides or salts, and can also be used as a multi-component catalyst. These catalysts can also be generally used by being supported on a known carrier having a relatively small specific surface area, such as semi-fused alumina, pumice, silicon carbide, or the like. The catalyst may be prepared by any conventional method for preparing vanadium oxide-containing catalysts. Simply, for example, a method can be used in which the carrier is immersed in an aqueous solution of ammonium vanadate or a mixed aqueous solution with other compounded components, and then dried, baked, or baked and melted to adhere. The catalyst may be used by either a fixed bed method or a fluidized catalyst method. Air is advantageous as the oxygen-containing gas, but
It is also possible to use gas mixtures of oxygen and other diluents such as nitrogen, carbon dioxide, helium or water vapor. The molar ratio of raw material polyalkylphenol to oxygen is 1:100 to 1:
10000 is preferable. The feed rate of raw material gas to the catalyst varies depending on the catalyst and reaction conditions such as reaction temperature, but is generally in the range of 300 to 30,000 per hour (standard state) per catalyst. Reaction temperature is 300~650℃
, preferably in the range of 300 to 550°C.
Pyromellitic anhydride can usually be separated as crystals by cooling the product gas exiting the reactor after the reaction is completed. Since this pyromellitic anhydride easily reacts with water to become pyromellitic acid, it can also be obtained as pyromellitic acid. The present invention will be explained below with reference to Examples. Example 1 Ammonium metavanadate (anhydrous salt) 0.9g
Add 60 g of anatase-type titanium oxide to a mixed aqueous solution of 1.2 g of ammonium molybdate (tetrahydrate) and evaporate to dryness by heating with stirring.
After molding, this was cut into 8 to 10 meshes and calcined in air at 500°C for 4 hours to obtain a catalyst. this catalyst
15 c.c. was filled into a Pyrex glass U-shaped reaction tube with an inner diameter of 17 mm and placed in a night bath maintained at 330°C. Raw material diurenol (2, 3, 5, 6) in the evaporator
-tetramethylphenol) was heated to about 150°C to completely melt it, diurenol was vaporized through air, and secondary air was mixed with this and introduced into the reaction tube. As a result of passing air containing 0.2 mol% of diulenol through the catalyst bed at a flow rate of 225/hour (standard state), the air containing 0.2 mol% of diulenol was 72.5 mol% relative to the raw diulenol.
% by weight of pyromellitic anhydride was obtained. Example 2 50 g of oxalic acid (dihydrate) was dissolved in water, and 11 g of ammonium metavanadate (anhydrous salt), 1.2 g of ammonium dihydrogen phosphate (anhydrous salt) and 5.1 g of ammonium tungstate (pentahydrate) were dissolved in water. and completely dissolved. Add 90 g of 8-10 meshes of alundum to this solution, heat with stirring to evaporate to dryness, and then heat to 500°C in an air stream.
It was baked for 4 hours. Catalyst thus obtained
The same reaction tube as in Example 1 was filled with 20 c.c. and placed in a night bath maintained at 450°C. The raw material pentamethylphenol in the evaporator is approximately
After heating to 150°C and melting, pentamethylphenol was vaporized through air, and secondary air was mixed with this and introduced into the reaction tube. Air containing 0.1 mol% of pentamethylphenol
As a result, 60.5% by weight of pyromellitic anhydride was obtained based on the pentamethylphenol raw material. Example 3 10 g of oxalic acid (dihydrate) was dissolved in water, and 6.5 g of ammonium metapanadate (anhydrous salt) was added to the solution.
0.64 g of ammonium dihydrogen phosphate (anhydrous salt) and 0.98 g of ammonium molybdate (tetrahydrate) were added to form a homogeneous solution. Further, 0.53 g of titanium tetrachloride was added thereto, followed by 100 g of alundum of 8 to 10 meshes, and heated while stirring to evaporate to dryness. After calcining this in an air stream at 500°C for 6 hours, the same reaction tube as in Example 1 was filled with 15 c.c. of this catalyst and placed in a nighter bath maintained at 430°C. According to the method carried out in Example 1, air containing 0.15 mol% of 3,5-dimethyl-2,6-dihydroxymethylphenol was passed through the catalyst bed at a flow rate of 120/hour (standard condition), and as a result, the raw material 3,5 -dimethyl 2,6
-62.8% by weight of pyromellitic anhydride based on dihydroxymethylphenol was obtained. Examples 4 to 5 In the same manner as in Example 1, oxidation reactions of the following raw material polyalkylphenols and derivatives thereof were carried out. Table 1 shows the results.
【表】
リ−メチルフエノール
[Table] Li-methylphenol
Claims (1)
―テトラアルキルフエノールおよびこれらの誘導
体の１種または２種以上の混合物を気相酸化触媒
の存在下、酸素含有気体と接触させて無水ピロメ
リツト酸を製造する方法。 ２ 気相酸化触媒が酸化バナジウム含有触媒であ
る特許請求の範囲第１項に記載の方法。[Claims] 1. Pentaalkylphenol, 2,3,5,6
- A method for producing pyromellitic anhydride by contacting one or more mixtures of tetraalkylphenols and their derivatives with an oxygen-containing gas in the presence of a gas-phase oxidation catalyst. 2. The method according to claim 1, wherein the gas phase oxidation catalyst is a catalyst containing vanadium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6157179A JPS55154966A (en) | 1979-05-21 | 1979-05-21 | Preparation of pyromellitic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6157179A JPS55154966A (en) | 1979-05-21 | 1979-05-21 | Preparation of pyromellitic anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55154966A JPS55154966A (en) | 1980-12-02 |
| JPS6353194B2 true JPS6353194B2 (en) | 1988-10-21 |
Family
ID=13174936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6157179A Granted JPS55154966A (en) | 1979-05-21 | 1979-05-21 | Preparation of pyromellitic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55154966A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6424491U (en) * | 1987-08-03 | 1989-02-09 |
-
1979
- 1979-05-21 JP JP6157179A patent/JPS55154966A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6424491U (en) * | 1987-08-03 | 1989-02-09 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55154966A (en) | 1980-12-02 |
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