JPH03251545A - Production of 2,6-dimethylnaphthalene - Google Patents
Production of 2,6-dimethylnaphthaleneInfo
- Publication number
- JPH03251545A JPH03251545A JP2046857A JP4685790A JPH03251545A JP H03251545 A JPH03251545 A JP H03251545A JP 2046857 A JP2046857 A JP 2046857A JP 4685790 A JP4685790 A JP 4685790A JP H03251545 A JPH03251545 A JP H03251545A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- catalyst
- indium
- aluminum
- butene
- 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
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 229910052738 indium Inorganic materials 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
- RZEPECPPWVXGSY-UHFFFAOYSA-N 1-methyl-4-(2-methylbut-1-enyl)benzene Chemical compound CCC(C)=CC1=CC=C(C)C=C1 RZEPECPPWVXGSY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- XPCLINDRYZAPTJ-UHFFFAOYSA-N 1-methyl-4-(2-methylbutyl)benzene Chemical compound CCC(C)CC1=CC=C(C)C=C1 XPCLINDRYZAPTJ-UHFFFAOYSA-N 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000006297 dehydration reaction Methods 0.000 abstract description 5
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 4
- 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 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 2
- 239000002585 base Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910003437 indium oxide Inorganic materials 0.000 description 14
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 13
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910002090 carbon oxide Inorganic materials 0.000 description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002472 indium compounds Chemical class 0.000 description 4
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- ABIPNDAVRBMCHV-UHFFFAOYSA-N 4,4-dimethyl-2,3-dihydro-1h-naphthalene Chemical compound C1=CC=C2C(C)(C)CCCC2=C1 ABIPNDAVRBMCHV-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- HVDZMISZAKTZFP-UHFFFAOYSA-N indium(3+) trinitrate trihydrate Chemical compound O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVDZMISZAKTZFP-UHFFFAOYSA-N 0.000 description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- -1 polyethylene naphthalate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- ZULRWVHQERPKKV-UHFFFAOYSA-N 1-but-1-enyl-4-methylbenzene Chemical compound CCC=CC1=CC=C(C)C=C1 ZULRWVHQERPKKV-UHFFFAOYSA-N 0.000 description 1
- SBBKUBSYOVDBBC-UHFFFAOYSA-N 1-butyl-4-methylbenzene Chemical compound CCCCC1=CC=C(C)C=C1 SBBKUBSYOVDBBC-UHFFFAOYSA-N 0.000 description 1
- DXRBFZCGSZKZTL-UHFFFAOYSA-N 2,6-dimethyl-1,2,3,4-tetrahydronaphthalene Chemical compound CC1=CC=C2CC(C)CCC2=C1 DXRBFZCGSZKZTL-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- 241000511343 Chondrostoma nasus Species 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 239000000178 monomer Substances 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
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- 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、2,6−ナフタレンジカルボン酸の原料とし
て有用な2,6−ジメチルナフタレンを製造するための
触媒に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a catalyst for producing 2,6-dimethylnaphthalene, which is useful as a raw material for 2,6-naphthalene dicarboxylic acid.
2.6−ナフタレンジカルボン酸は、優れた引っ張り強
度と耐熱性を有するポリエチレンナフタレート繊維やフ
ィルム等の製造に用いられる高性能ポリエステルの原料
として工業的に重要な用途を持っている。2.6-Naphthalene dicarboxylic acid has industrially important uses as a raw material for high-performance polyester used in the production of polyethylene naphthalate fibers, films, etc., which have excellent tensile strength and heat resistance.
2.6−ジメチルナフタレンは、2,6−ナフタレンジ
カルボン酸の原料となるものであり、大量且つ安価に製
造できることが必要である。また高性能ポリエステル原
料としての2.6−ナフタレンジカルボン酸は異性体的
に高純度であることが要求されるので、その原料である
2、6−ジメチルナフタレンも異性体的に高純度である
ことが必要である。即ちジメチルナフタレンは2個のメ
チル基の位置により、2,6一体板外に、1,2−11
,3−11,4−11,5−11゜6−11,7−11
,8−22.3−12.7−の9個の異性体があり、こ
れら2,6一体板外の異性体を実質的に含まない2.6
−ジメチルナフタレンを大量且つ安価に製造する必要が
ある。2,6-dimethylnaphthalene is a raw material for 2,6-naphthalene dicarboxylic acid, and needs to be able to be produced in large quantities and at low cost. In addition, since 2,6-naphthalene dicarboxylic acid, which is a raw material for high-performance polyester, is required to be highly isomerically pure, the raw material, 2,6-dimethylnaphthalene, must also be isomerically pure. is necessary. That is, dimethylnaphthalene has a 1,2-11 structure outside the 2,6 monolithic plate due to the position of the two methyl groups.
,3-11,4-11,5-11゜6-11,7-11
, 8-22.3-12.7-, and there are 9 isomers of 2.6 that are substantially free of isomers outside of these 2,6 integral plates.
- There is a need to produce dimethylnaphthalene in large quantities and at low cost.
2.6−ジメチルナフタレンは従来タール留分から分離
する方法により取得されていた。しかしながら、タール
留分を対象とした場合には量的に少なく、また異性体混
合物が多く含まれているので分離精製も容易ではない。2,6-Dimethylnaphthalene has conventionally been obtained by separating it from a tar fraction. However, when targeting a tar fraction, it is small in quantity and contains a large amount of isomer mixtures, so it is not easy to separate and purify it.
従ってタール留分から2゜6−ジメチルナフタレンを分
離する方法で大量且つ安価な2,6−ジメチルナフタレ
ンを工業的に供給することは困難である。Therefore, it is difficult to industrially supply 2,6-dimethylnaphthalene in large quantities and at low cost by separating 2.6-dimethylnaphthalene from the tar fraction.
近年、種々の原料から2,6−ジメチルナフタレンを製
造する方法が提案されている。しかしながら大量入手が
可能で安価な出発原料を用いて、2,6−ジメチルナフ
タレンを効率的かつ選択的に合成できる工業的製造法は
未だ確立されていない。In recent years, methods for producing 2,6-dimethylnaphthalene from various raw materials have been proposed. However, an industrial production method that can efficiently and selectively synthesize 2,6-dimethylnaphthalene using inexpensive starting materials that can be obtained in large quantities has not yet been established.
例えば特開昭49−18856号には2,6−ジメチル
テトラリンの脱水素による製造法かを示されている。For example, JP-A-49-18856 discloses a method for producing 2,6-dimethyltetralin by dehydrogenation.
この方法は原料ジメチルテトラリンの入手が困難である
。即ちタール留分から分離する場合は量的に少なく、ま
たアルキル或はアルケニルベンゼン類の環化によってジ
メチルテトラリンを製造する方法は、ジメチルテトラリ
ン収率が不十分であり、且つ2,6一体板外の異性体も
生成するので目的とする2、6一体を得るには、異性化
及び異性体混合物からの分離精製が必要である。For this method, it is difficult to obtain the raw material dimethyltetralin. That is, when separating from the tar fraction, the amount is small, and in the method of producing dimethyltetralin by cyclization of alkyl or alkenylbenzenes, the yield of dimethyltetralin is insufficient. Since isomers are also produced, isomerization and separation and purification from the isomer mixture are necessary to obtain the desired 2,6-unit.
また特開昭63−112527号には、ナフタリン或は
メチルナフタリンのメチル化による製造法が示されてい
る。この製造法でも2,6一体を選択的に得ることが困
難であり、異性化反応および、異性体混合物からの分離
精製が必要である。またナフタリン、メチルナフタリン
共に、量的な制約があり、工業原料として高価である。Further, JP-A-63-112527 discloses a production method by methylating naphthalene or methylnaphthalene. Even with this production method, it is difficult to selectively obtain 2,6 monomers, and an isomerization reaction and separation and purification from the isomer mixture are required. Furthermore, both naphthalene and methylnaphthalene have quantitative limitations and are expensive as industrial raw materials.
特公昭50−17983号、特公昭5047984号お
よび特公昭50−17985.号には5−(o−)リル
)ペンテン−2を原料とし、その脱水素環化による2、
6−ジメチルナフタレンの製造法が示されている。この
5−(o−)リル)ペンテン−2は一般には0−キシレ
ンと1.3−フタジエンから合成されるが、側鎖アルキ
ル化による5−(o−)リル)ペンテン−2の合成はそ
れ自体が容易ではない。即ち特公昭50−17985号
の実施例によれば、5−(o−トリル)ペンテン−2の
脱水素環化において2,6一体板外の1,5−11.6
一体の生成が著しく、2,6一体を得るには、1,5−
11,6一体の異性化及び異性体混合物の分離精製が必
要となる。Special Publication No. 50-17983, Special Publication No. 5047984, and Special Publication No. 50-17985. No. 5-(o-)lyl)pentene-2 is used as a raw material, and 2, which is produced by dehydrogenation cyclization.
A method for producing 6-dimethylnaphthalene is shown. This 5-(o-)lyl)pentene-2 is generally synthesized from 0-xylene and 1,3-phtadiene, but the synthesis of 5-(o-)lyl)pentene-2 by side chain alkylation is itself is not easy. That is, according to the example of Japanese Patent Publication No. 50-17985, in the dehydrocyclization of 5-(o-tolyl)pentene-2, 1,5-11.6 outside the 2,6 monolithic plate is
The formation of monoliths is remarkable, and in order to obtain 2,6 monoliths, 1,5-
11,6 integral isomerization and separation and purification of the isomer mixture are required.
また2−メチル−1−(p−1リル)−ブテンを環化脱
水素して2.6−ジメチルナフタレンを製造する方法と
して、特公昭53−5292号には酸化レニウムとアル
カリ金属酸化物またはアルカリ土類金属酸化物とアルミ
ナとからなる触媒を用いる方法が示されており、また特
公昭51−1701号にはアルカリ金属酸化物を含有す
るクロミア・アルミナ系触媒を用いる方法が示されてい
る。しかしながらこれらの触媒は何れも2.6−ジメチ
ルナフタレン収率が低く、また生成2.6−ジメチルナ
フタレンの異性体純度が十分でない。Furthermore, as a method for producing 2,6-dimethylnaphthalene by cyclodehydrogenation of 2-methyl-1-(p-1lyl)-butene, Japanese Patent Publication No. 53-5292 describes a method for producing 2,6-dimethylnaphthalene by cyclodehydrogenation of 2-methyl-1-(p-1lyl)-butene. A method using a catalyst consisting of an alkaline earth metal oxide and alumina is shown, and Japanese Patent Publication No. 51-1701 shows a method using a chromia-alumina catalyst containing an alkali metal oxide. . However, all of these catalysts have low yields of 2,6-dimethylnaphthalene, and the isomer purity of the produced 2,6-dimethylnaphthalene is insufficient.
以上の如〈従来技術の方法では、2.6−ナフタレンジ
カルボン酸の原料に適した異性体的に高純度の2,6−
ジメチルナフタレンを安価に且つ大量に製造することが
困難である。As described above, in the method of the prior art, isomerically high-purity 2,6-
It is difficult to produce dimethylnaphthalene inexpensively and in large quantities.
これらの従来技術に代わる方法として、トルエン、ブテ
ン、および−酸化炭素という極めて汎用な原料を出発物
質とし、p−)リルーsecブチルケトンを経由して2
,6−ジメチルナフタレンを製造する方法が見出され、
特許出願が行なわれている(特願昭63−239762
号)。An alternative to these conventional techniques is to start with the extremely versatile raw materials of toluene, butene, and -carbon oxide, and to convert 2
, 6-dimethylnaphthalene was discovered,
A patent application has been filed (Patent application No. 63-239762)
issue).
即ちこの方法は、トルエン、ブテン、−酸化炭素からp
−)リルーsecブチルケトンを製造し、そのカルボニ
ル基を水素化して対応するアルコールとし、このアルコ
ールを脱水して2−メチル−1−(p−トリル)−ブテ
ンを得、2−メチル−1−(p−トリル)−ブテンを環
化脱水素して2,6−ジメチルナフタレンを製造する方
法である。That is, this method converts toluene, butene, carbon oxide to p
-) lylu sec butyl ketone is prepared, its carbonyl group is hydrogenated to give the corresponding alcohol, and this alcohol is dehydrated to give 2-methyl-1-(p-tolyl)-butene, 2-methyl-1-( This is a method for producing 2,6-dimethylnaphthalene by cyclodehydrogenating p-tolyl)-butene.
この方法は、アシル化→水素化→脱水→環化脱水素の4
工程から成り、アシル化、水素化、脱水の各工程はいず
れも高収率、高選択率で進行し、異性体的に高純度な2
−メチル−1−(p−トリル)−ブテンが高収率で得ら
れる。しかしながらアルカリ金属酸化物を含有するクロ
ミア・アルミナ系触媒を用いる最終段の環化脱水素工程
では2.6−ジメチルナフタレン収率の点で十分とは言
えず、この工程の改良が望まれていた。This method consists of four steps: acylation → hydrogenation → dehydration → cyclodehydrogenation.
Each step of acylation, hydrogenation, and dehydration proceeds with high yield and high selectivity, producing isomerically pure 2
-Methyl-1-(p-tolyl)-butene is obtained in high yield. However, the final step of cyclodehydrogenation using a chromia-alumina catalyst containing an alkali metal oxide was not sufficient in terms of yield of 2,6-dimethylnaphthalene, and improvements in this process were desired. .
本発明者らは、2−メチル−1−(p4リル)−ブテン
等から異性体的に高純度な2,6−ジメチルナフタレン
を高収率で得る方法につき鋭意検討を行なった結果、イ
ンジウムとアルミニウムの酸化物をベースとする触媒を
用いることにより、異性体的に高純度な2.6−ジメチ
ルナフタレンを高収率で得ることができることを見出し
、本発明に到達した。The present inventors have conducted intensive studies on a method for obtaining isomerically pure 2,6-dimethylnaphthalene in high yield from 2-methyl-1-(p4lyl)-butene, etc., and have found that indium and The present invention has been achieved based on the discovery that isomerically pure 2,6-dimethylnaphthalene can be obtained in high yield by using a catalyst based on an oxide of aluminum.
即ち本発明は、2−メチル−1−(p−トリル)−ブテ
ン、2−メチル−1−(p−トリル)−ブタン、或はこ
れらの混合物を環化脱水素して2.6−ジメチルナフタ
レンを製造するに際し、(a)インジウム及びアルミニ
ウムの酸化物からなる触媒、(b)インジウム及びアル
ミニウムの酸化物と、アルカリ金属、アルカリ土類金属
から選ばれた一種以上の酸化物からなる触媒、(c)イ
ンジウム及びアルミニウムの酸化物と、鉄、錫、アンチ
モン、クロム、亜鉛、バナジウム、ニッケル、コバルト
より選ばれた一種以上の酸化物からなる触媒、或いは(
d)インジウム及びアルミニウムの酸化物と、鉄、錫、
アンチモン、クロム、亜鉛、バナジウム、ニッケル、コ
バルトより選ばれた一種以上の酸化物およびアルカリ金
属、アルカリ土類金属から選ばれた一種以上の酸化物か
らなる触媒を用いることを特徴とする2、6−ジメチル
ナフタレンの製造方法である。That is, the present invention cyclodehydrogenates 2-methyl-1-(p-tolyl)-butene, 2-methyl-1-(p-tolyl)-butane, or a mixture thereof to form 2,6-dimethyl When producing naphthalene, (a) a catalyst consisting of an oxide of indium and aluminum, (b) a catalyst consisting of an oxide of indium and aluminum and one or more oxides selected from alkali metals and alkaline earth metals, (c) A catalyst consisting of an oxide of indium and aluminum and one or more oxides selected from iron, tin, antimony, chromium, zinc, vanadium, nickel, and cobalt, or (
d) oxides of indium and aluminum and iron, tin,
2, 6 characterized by using a catalyst consisting of one or more oxides selected from antimony, chromium, zinc, vanadium, nickel, and cobalt and one or more oxides selected from alkali metals and alkaline earth metals. - A method for producing dimethylnaphthalene.
本発明は、インジウムとアルミニウムの酸化物の混合触
媒を用いることにより、2−メチル−1−(pトリル)
−ブテン等の環化脱水素による2、6−ジメチルナフタ
レンの生成が飛躍的に向上し、且っ2,6体以外への異
性化反応がほぼ完全に抑制されることを見出したことに
より成し遂げられたものである。The present invention produces 2-methyl-1-(p-tolyl) by using a mixed catalyst of indium and aluminum oxides.
-Achieved by discovering that the production of 2,6-dimethylnaphthalene through cyclodehydrogenation of butene, etc. was dramatically improved, and isomerization reactions other than the 2,6-isomer were almost completely suppressed. It is something that was given.
即ちアルミニウムの酸化物を単独で触媒として用いた場
合には、2−メチル−1−(p−)リル)−ブテンの一
部は環化脱水素によりジメチルナフタレンに変化するが
、著しい異性化を起し、また重合、分解等目的以外の反
応が支配的である。インジウムの酸化物を単独で触媒と
して用いた場合には2−メチル−1−(p−)リル)−
ブテンの環化脱水素は殆ど起らない。これに対して本発
明のインジウムとアルミニウムの酸化物の混合触媒を用
いた場合には2゜6一体板外への異性化反応が殆ど無く
、2.6−ジメチルナフタレンの生成が著しく向上する
。That is, when aluminum oxide is used alone as a catalyst, a part of 2-methyl-1-(p-)lyl)-butene is converted to dimethylnaphthalene by cyclodehydrogenation, but significant isomerization is not observed. Reactions other than the intended purpose, such as oxidation, polymerization, and decomposition, are predominant. When indium oxide is used alone as a catalyst, 2-methyl-1-(p-)lyl)-
Almost no cyclodehydrogenation of butene occurs. On the other hand, when the mixed catalyst of indium and aluminum oxides of the present invention is used, there is almost no isomerization reaction outside the 2.6 integral plate, and the production of 2,6-dimethylnaphthalene is significantly improved.
即ちそれぞれ単独では2,6−ジメチルナフタレン製造
触媒とはなり得ないアルミニウムとインジウムの酸化物
が、両者を混合することにより優れた2、6−ジメチル
ナフタレン製造触媒となる。また従来より2−メチル−
1−(p−トリル)−ブテンの環化脱水素に有効とされ
ているクロミア・アルミナ触媒、或はこれにアルカリ金
属を加えた触媒は水共存下では反応成績が悪化するのに
対し、本発明の触媒は水共存下でも反応成績の悪化は認
められない。That is, the oxides of aluminum and indium, which cannot be used alone as catalysts for producing 2,6-dimethylnaphthalene, become excellent catalysts for producing 2,6-dimethylnaphthalene by mixing them together. In addition, 2-methyl-
Chromia-alumina catalysts, which are said to be effective for the cyclodehydrogenation of 1-(p-tolyl)-butene, or catalysts containing alkali metals exhibit poor reaction performance in the coexistence of water; The catalyst of the invention shows no deterioration in reaction performance even in the coexistence of water.
従って、例えばトルエン、ブテン、−酸化炭素からp−
)リルーsecブチルケトンを製造し、そのカルボニル
基を水素化して対応するアルコールとなし、このアルコ
ールを脱水して得られる2−メチル−1(p−トリル)
−ブテンを原料とする場合において、クロミア・アルミ
ナ触媒、或はこれにアルカリ金属を加えた触媒を用いる
時には、脱水反応生成物から水を除去した後に環化脱水
素を行なう必要があるのに対し、本発明の触媒を用いる
場合は、脱水反応生成物をそのまま環化脱水素の原料と
して用いることができる。Thus, for example, toluene, butene, -carbon oxide to p-
) 2-methyl-1(p-tolyl) obtained by producing lylu-sec butyl ketone, hydrogenating its carbonyl group to form the corresponding alcohol, and dehydrating this alcohol.
- When using butene as a raw material, when using a chromia-alumina catalyst or a catalyst containing an alkali metal, it is necessary to perform cyclodehydrogenation after removing water from the dehydration reaction product. When using the catalyst of the present invention, the dehydration reaction product can be used as it is as a raw material for cyclization dehydrogenation.
本発明の触媒におけるインジウムとアルミニウムの比率
は、アルミニウム1原子に対しインジウムは0.005
〜0.5原子、好ましくは0.01〜063原子である
。The ratio of indium to aluminum in the catalyst of the present invention is 0.005 indium per 1 atom of aluminum.
~0.5 atoms, preferably 0.01-063 atoms.
この触媒の調製法は、反応に与かる触媒表面においてイ
ンジウムとアルミニウムが均一に分散されるような方法
であれば良く、特に制限はない。The method for preparing this catalyst is not particularly limited as long as it allows indium and aluminum to be uniformly dispersed on the surface of the catalyst participating in the reaction.
例えば、アルミナにインジウム化合物を含浸し、乾燥・
焼成する方法、アルミニウムとインジウムの酸化物前駆
体を沈澱として別々に調製した後混合し乾燥・焼成する
方法、アルミニウムとインジラムの酸化物前駆体を共沈
澱として調製し乾燥・焼成する方法、インジウムの酸化
物前駆体或はインジウムの酸化物とアルミナゾルを混合
後、乾燥・焼成する方法等がある。For example, alumina is impregnated with an indium compound, dried and
A method in which oxide precursors of aluminum and indium are separately prepared as precipitates, then mixed, dried and fired; A method in which oxide precursors of aluminum and indium are prepared as a co-precipitate, dried and fired; There is a method of mixing an oxide precursor or indium oxide and alumina sol, followed by drying and firing.
アルミナにインジウム化合物を含浸する場合、またはイ
ンジウムの酸化物前駆体を沈澱として調製する場合は、
インジウム化合物には水やメタノール等の適当な有機溶
媒に溶解するインジウム化合物が用いられ、硝酸インジ
ウム、硫酸インジウム等が好適に使用できる。アルミニ
ウムの酸化物前駆体を沈澱として調製する場合は、アル
ミニウム化合物には水やメタノール等の適当な有機溶媒
に溶解する化合物が用いられ、硝酸アルミニウム、アル
ミン酸ナトリウム、硫酸アルミニウム、塩化アルミニウ
ム等が好適に使用できる。When impregnating alumina with an indium compound or preparing an oxide precursor of indium as a precipitate,
As the indium compound, an indium compound that dissolves in a suitable organic solvent such as water or methanol is used, and indium nitrate, indium sulfate, etc. can be suitably used. When preparing an aluminum oxide precursor as a precipitate, a compound soluble in an appropriate organic solvent such as water or methanol is used as the aluminum compound, and aluminum nitrate, sodium aluminate, aluminum sulfate, aluminum chloride, etc. are preferable. Can be used for
このようにして調製されたアルミニウムとインジウムの
酸化物からなる触媒は、それ自体2−メチル−1−(p
−トリル)−ブテンの環化脱水素に優れた活性を示す。The catalyst consisting of oxides of aluminum and indium thus prepared was itself 2-methyl-1-(p
Shows excellent activity in the cyclodehydrogenation of -tolyl)-butene.
アルミニウムとインジウムの酸化物からなる触媒に、ア
ルカリ金属、アルカリ土類金属酸化物から選ばれた少な
くとも1種の金属酸化物を加えた触媒、或は鉄、錫、ア
ンチモン、クロム、亜鉛、バナジウム、ニッケル、コバ
ルトから選ばれた一種以上の金属酸化物を加えた触媒、
或はこれに更にアルカリ金属、アルカリ土類金属酸化物
から選ばれた少なくとも1種の金属酸化物を加えた触媒
は、活性と選択性が更に向上する。A catalyst consisting of oxides of aluminum and indium, to which at least one metal oxide selected from alkali metals and alkaline earth metal oxides is added, or iron, tin, antimony, chromium, zinc, vanadium, A catalyst containing one or more metal oxides selected from nickel and cobalt,
Alternatively, a catalyst in which at least one metal oxide selected from alkali metal and alkaline earth metal oxides is further added has further improved activity and selectivity.
これらアルカリ金属、アルカリ土類金属、或は鉄、錫、
アンチモン、クロム、亜鉛、バナジウム、ニッケル、コ
バルトの添加量は、インジウム1原子に対し、0.1〜
10原子、好ましくは0.5〜5原子とする。これらの
金属酸化物の添加方法は、各成分が触媒表面に均一に分
散されれば良く、特に制限はない。例えば調製したアル
ミニウムとインジウムの酸化物からなる触媒にこれらの
金属塩溶液を含浸させる方法、混練する方法、アルミニ
ウムとインジウムの酸化物を作る際にこれらの金属塩溶
液を同時に添加する方法、インジウムとこれら金属の酸
化物前駆体とを予め調製しこれとアルミナゾルとを混合
する方法等、種々の方法を用いることができる。These alkali metals, alkaline earth metals, iron, tin,
The amount of antimony, chromium, zinc, vanadium, nickel, and cobalt added is 0.1 to 1 atom of indium.
The number is 10 atoms, preferably 0.5 to 5 atoms. The method of adding these metal oxides is not particularly limited as long as each component is uniformly dispersed on the catalyst surface. For example, a method of impregnating a prepared catalyst consisting of oxides of aluminum and indium with a solution of these metal salts, a method of kneading, a method of adding these metal salt solutions simultaneously when making oxides of aluminum and indium, a method of adding these metal salt solutions at the same time when making oxides of aluminum and indium, Various methods can be used, such as a method in which oxide precursors of these metals are prepared in advance and mixed with alumina sol.
このようにして調製された触媒前駆体混合物は、室温よ
り高い温度、好ましくは70〜130°Cで乾燥し、3
00〜800°Cで焼成した後、必要があれば成型し、
本発明の触媒として使用する。The catalyst precursor mixture thus prepared is dried at a temperature above room temperature, preferably from 70 to 130 °C, and
After baking at 00~800°C, mold if necessary.
Used as a catalyst in the present invention.
本発明の触媒を用いて、2−メチル−1−(p−トリル
)−ブテンの環化脱水素により2.6−ジメチルナフタ
レンを製造するに際しては、反応圧力は減圧、常圧、加
圧のいずれでもよいが、実用上は常圧〜2Kg/cm2
が好ましい。反応温度は350〜700°C1好ましく
は450〜650°Cである。なお2−メチル−1−(
p−)リル)−ブタンを原料とする場合には、2−メチ
ル−1−(p−)リル)−ブテンを環化脱水素する場合
に比べて反応性が多少低く、反応温度を上げるかS■を
下げる必要がある。目的生成物の2.6−ジメチルナフ
タレンは融点106℃の固体であり、反応操作上、また
重合等の副反応を抑制する意味からも、原料の2−メチ
ル−1−(p−)リル)−ブテンをトルエン、ベンゼン
、スチーム等に溶解あるいは希釈して反応に供するのが
好ましい。When producing 2,6-dimethylnaphthalene by cyclodehydrogenation of 2-methyl-1-(p-tolyl)-butene using the catalyst of the present invention, the reaction pressure is reduced, normal pressure, or elevated pressure. Any pressure is fine, but in practice, normal pressure to 2Kg/cm2
is preferred. The reaction temperature is 350-700°C, preferably 450-650°C. In addition, 2-methyl-1-(
When p-)lyl)-butane is used as a raw material, the reactivity is somewhat lower than when cyclodehydrogenating 2-methyl-1-(p-)lyl)-butene, and it is necessary to raise the reaction temperature. It is necessary to lower S■. The target product, 2,6-dimethylnaphthalene, is a solid with a melting point of 106°C, and the raw material, 2-methyl-1-(p-)lyl), is required for reaction operation and for suppressing side reactions such as polymerization. -Butene is preferably dissolved or diluted in toluene, benzene, steam, etc. and subjected to the reaction.
[発明の効果]
本発明の方法は、トルエン、ブテン、および−酸化炭素
という極めて汎用な原料を出発物質とする。[Effects of the Invention] The method of the present invention uses extremely versatile raw materials such as toluene, butene, and carbon oxide as starting materials.
また本発明の方法では、p−トリル−5ecブチルケト
ンを経由して2.6−ジメチルナフタレンを製造する方
法において、2.6一体板外の異性体が殆ど無く、著し
く高収率が得られる。Further, in the method of the present invention, in the method of producing 2,6-dimethylnaphthalene via p-tolyl-5ec butyl ketone, there is almost no isomer other than the 2.6 monolithic plate, and a significantly high yield can be obtained.
従って本発明により、トルエン、ブテン、および−酸化
炭素という極めて汎用な原料から、高純度の2.6−ジ
メチルナフタレンを安価且つ大量に製造することができ
るようになり、本発明の工業的な意義は極めて大きい。Therefore, according to the present invention, it has become possible to produce high-purity 2,6-dimethylnaphthalene at low cost and in large quantities from extremely general-purpose raw materials such as toluene, butene, and carbon oxide, and the industrial significance of the present invention is is extremely large.
[実施例]
以下実施例にて本発明を具体的に説明する。但し本発明
はこれらの実施例により制限されるものではない。なお
各実施例および比較例に従い調製した触媒は、石英製反
応管に充填し、常圧下で、2−メチル−1−(p−)リ
ル)−ブテンのトルエン溶液あるいは2−メチル−1−
(p−トリル)−ブタンのトルエン溶液を原料として反
応を行ない活性を確認した。[Example] The present invention will be specifically described below with reference to Examples. However, the present invention is not limited to these Examples. The catalysts prepared according to each of the Examples and Comparative Examples were packed into a quartz reaction tube and treated with a toluene solution of 2-methyl-1-(p-)lyl)-butene or 2-methyl-1-butene under normal pressure.
A reaction was carried out using a toluene solution of (p-tolyl)-butane as a raw material, and the activity was confirmed.
各実施例、比較例の結果を表1に示す。Table 1 shows the results of each example and comparative example.
実施例1
硝酸インジウム(3水塩)32gをイオン交換水400
m lに溶解し、200gのアルミナを加え、撹拌下4
5°Cにて2時間含浸後、70’Cで減圧乾燥し、空気
中550℃で焼成し、酸化インジウム・酸化アルミニウ
ム触媒を調製した。Example 1 32 g of indium nitrate (trihydrate) was mixed with 400 g of ion-exchanged water.
ml, add 200g of alumina, and stir under stirring for 4 hours.
After being impregnated at 5°C for 2 hours, it was dried under reduced pressure at 70'C and calcined in air at 550°C to prepare an indium oxide/aluminum oxide catalyst.
z隻別業
硝酸インジウム(3水塩) 60gと硝酸アルミニウム
(9水塩) 310gを2j2の純水に加えて溶解させ
、40°Cに保つ。別に炭酸ナトリウム170gを21
の純水に溶解させ、40°Cに保つ。撹拌下、内容物の
温度を40〜45°Cに保ったまま、両溶液を混合し、
8゜°Cに昇温した。生成した沈澱物を濾別し、純水に
て洗浄した後、110″Cで乾燥後、空気中550″C
で焼成し、酸化インジウム・酸化アルミニウム触媒を調
製した。Add 60 g of indium nitrate (trihydrate) and 310 g of aluminum nitrate (9 hydrate) to 2j2 of pure water, dissolve, and keep at 40°C. Separately, add 170g of sodium carbonate to 21
Dissolve in pure water and keep at 40°C. Mix both solutions while maintaining the temperature of the contents at 40-45 °C under stirring,
The temperature was raised to 8°C. The generated precipitate was filtered, washed with pure water, dried at 110"C, and then heated at 550"C in air.
An indium oxide/aluminum oxide catalyst was prepared.
実施例3
硫酸インジウム(9水塩) 50gをo、4!の純水に
加えて溶解させ、40°Cに保つ、別に炭酸ナトリウム
25gを0.41の純水に溶解させ、40℃に保つ。Example 3 Indium sulfate (nase hydrate) 50g was mixed with o, 4! 25g of sodium carbonate is dissolved in 0.41% pure water and kept at 40°C.
撹拌下、内容物の温度を40〜45°Cに保ったまま、
両溶液を混合し、80°Cに昇温した。生成した沈澱物
を濾別し、純水にて洗浄し、インジウムの酸化物前駆体
の沈澱を得た。沈澱中のインジウム濃度は27−tχで
あった。この沈澱60gとアルミナゾル(アルミナ含有
量10−1χ) 650gを混合し、110°Cで乾燥
後、空気中550°Cで焼成し、酸化インジウム・酸化
アルミニウム触媒を調製した。While stirring and keeping the temperature of the contents at 40-45°C,
Both solutions were mixed and heated to 80°C. The generated precipitate was filtered and washed with pure water to obtain a precipitate of an indium oxide precursor. The indium concentration in the precipitate was 27-tχ. 60 g of this precipitate and 650 g of alumina sol (alumina content: 10-1.chi.) were mixed, dried at 110.degree. C., and then calcined in air at 550.degree. C. to prepare an indium oxide/aluminum oxide catalyst.
2旌拠土
実施例1にて調製した触媒50gを酒石酸アンチモニル
カリウムの水溶液(酒石酸アンチモニルカリウム濃度5
wtχ) 124gに加え、撹拌下45℃にて2時間含
浸後、70°Cて減圧乾燥し、空気中550°Cで焼成
し、酸化インジウム・酸化アンチモン・酸化カリウム・
酸化アルミニウム触媒を調製した。2. 50g of the catalyst prepared in Example 1 was added to an aqueous solution of antimonylpotassium tartrate (antimonylpotassium tartrate concentration: 50g).
wtχ) and impregnated with stirring at 45°C for 2 hours, dried under reduced pressure at 70°C, and calcined in air at 550°C to form indium oxide, antimony oxide, potassium oxide,
An aluminum oxide catalyst was prepared.
亥111一
実施例1にて調製した触媒50gを硫酸第一錫の水溶液
(硫酸第一錫濃度5wtχ) 160gに加え、撹拌下
45°Cにて2時間含浸後、70°Cにて減圧乾燥し、
空気中550’Cで焼成して、酸化インジウム・酸化錫
・酸化アルミニウム触媒を調製した。50 g of the catalyst prepared in Example 1 was added to 160 g of an aqueous solution of stannous sulfate (concentration of stannous sulfate 5 wtχ), and the mixture was impregnated with stirring at 45°C for 2 hours, and then dried under reduced pressure at 70°C. death,
An indium oxide/tin oxide/aluminum oxide catalyst was prepared by firing in air at 550'C.
失施勇旦
硝酸ニッケル(6水塩)65gと硝酸インジウム160
gを21の純水に加えて溶解させ、40°Cに保つ。別
に炭酸ナトリウム100gを2!の純水に溶解させ、4
0″Cに保つ、撹拌下、内容物の温度を40〜45°C
に保ったまま、両溶液を混合し、80°Cに昇温した。Yudan Shishi nickel nitrate (hexahydrate) 65g and indium nitrate 160g
Add g to pure water of 21 to dissolve and keep at 40°C. Separately, add 100g of sodium carbonate! Dissolve in pure water,
Maintain temperature of contents at 0″C, under stirring, 40-45°C
Both solutions were mixed while maintaining the temperature at 80°C.
生成した沈澱物を濾別し、純水にて洗浄し、インジウム
とニッケルの酸化物前駆体の共沈澱を得た。共沈澱中の
インジウム濃度は16−tχ、ニッケル濃度は4.1w
tχであった。この共沈澱120gとアルミナゾル(ア
ルミナ含有量10−tχ) 1800gを混合し、11
0°Cで乾燥後、空気中550℃で焼成し、酸化インジ
ウム・酸化ニッケル・酸化アルミニウム触媒を調製した
。The generated precipitate was filtered and washed with pure water to obtain a coprecipitate of indium and nickel oxide precursors. The indium concentration in the coprecipitation was 16-tχ, and the nickel concentration was 4.1w.
It was tχ. 120 g of this coprecipitate and 1800 g of alumina sol (alumina content 10-tχ) were mixed,
After drying at 0°C, it was calcined in air at 550°C to prepare an indium oxide/nickel oxide/aluminum oxide catalyst.
1隻■に1見
計算量の各種金属の硝酸塩水溶液に、実施例1と同様に
して調製した酸化インジウム・酸化アルミニウム触媒を
計算量加え、撹拌下45°Cにて2時間含浸後、70°
Cて減圧乾燥し、空気中550”Cで焼成し、金属酸化
物・酸化インジウム・酸化アルミニウム触媒を調製した
。A calculated amount of indium oxide/aluminum oxide catalyst prepared in the same manner as in Example 1 was added to a calculated amount of nitrate aqueous solution of various metals in one boat.
The mixture was dried under reduced pressure at 50°C and calcined in air at 550"C to prepare a metal oxide/indium oxide/aluminum oxide catalyst.
スJli−肚二13
計算量の各種金属の硝酸塩水溶液に、実施例3と同様に
して調製した酸化インジウム・酸化アルミニウム触媒を
計算量加え、撹拌下45℃にて2時間含浸後、70°C
て減圧乾燥し、空気中550″Cで焼成し、金属酸化物
・酸化インジウム・酸化アルミニウム触媒を調製した。Su Jli-Duji 13 A calculated amount of indium oxide/aluminum oxide catalyst prepared in the same manner as in Example 3 was added to a calculated amount of nitrate aqueous solution of various metals, and after impregnation at 45°C for 2 hours with stirring, the mixture was heated to 70°C.
The mixture was dried under reduced pressure and calcined in air at 550''C to prepare a metal oxide/indium oxide/aluminum oxide catalyst.
ル較■土
硝酸クロム(9水塩) 169gと硝酸カリウム28.
4gをイオン交換水400m lに溶解し、これに20
0gのアルミナを加え、撹拌下45℃にて2時間含浸後
、7゜°Cて減圧乾燥し、空気中550″Cで焼成し、
酸化カリウム・酸化クロム・酸化アルミニウム触媒を調
製した。Comparison of soil chromium nitrate (9 hydrate) 169g and potassium nitrate 28.
Dissolve 4g in 400ml of ion-exchanged water, add 20ml to this
0 g of alumina was added and impregnated for 2 hours at 45°C with stirring, dried under reduced pressure at 7°C, calcined at 550"C in air,
Potassium oxide, chromium oxide, and aluminum oxide catalysts were prepared.
比較例2 実施例1でのアルミナをそのまま触媒とした。Comparative example 2 The alumina used in Example 1 was used as a catalyst.
Claims (1)
ル−1−(p−トリル)−ブタン、或はこれらの混合物
を環化脱水素して2,6−ジメチルナフタレンを製造す
るに際し、(a)インジウム及びアルミニウムの酸化物
からなる触媒、(b)インジウム及びアルミニウムの酸
化物と、アルカリ金属、アルカリ土類金属から選ばれた
一種以上の酸化物からなる触媒、(c)インジウム及び
アルミニウムの酸化物と、鉄、錫、アンチモン、クロム
、亜鉛、バナジウム、ニッケル、コバルトより選ばれた
一種以上の酸化物からなる触媒、或いは(d)インジウ
ム及びアルミニウムの酸化物と、鉄、錫、アンチモン、
クロム、亜鉛、バナジウム、ニッケル、コバルトより選
ばれた一種以上の酸化物およびアルカリ金属、アルカリ
土類金属から選ばれた一種以上の酸化物からなる触媒を
用いることを特徴とする2,6−ジメチルナフタレンの
製造方法In producing 2,6-dimethylnaphthalene by cyclodehydrogenation of 2-methyl-1-(p-tolyl)-butene, 2-methyl-1-(p-tolyl)-butane, or a mixture thereof. , (a) a catalyst consisting of an oxide of indium and aluminum, (b) a catalyst consisting of an oxide of indium and aluminum and one or more oxides selected from alkali metals and alkaline earth metals, (c) a catalyst consisting of indium and A catalyst consisting of an oxide of aluminum and one or more oxides selected from iron, tin, antimony, chromium, zinc, vanadium, nickel, and cobalt, or (d) an oxide of indium and aluminum, and iron, tin, antimony,
2,6-dimethyl characterized by using a catalyst consisting of one or more oxides selected from chromium, zinc, vanadium, nickel, and cobalt and one or more oxides selected from alkali metals and alkaline earth metals. Method for manufacturing naphthalene
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2046857A JPH03251545A (en) | 1990-02-27 | 1990-02-27 | Production of 2,6-dimethylnaphthalene |
DE90313073T DE69004542T2 (en) | 1989-12-01 | 1990-11-30 | Process for the preparation of 2,6-dimethylnaphthalene. |
CA002031257A CA2031257A1 (en) | 1989-12-01 | 1990-11-30 | Process for producing 2,6-dimethylnaphthalene |
EP90313073A EP0430714B1 (en) | 1989-12-01 | 1990-11-30 | Process for producing 2,6-dimethylnaphthalene |
US07/621,260 US5068480A (en) | 1989-12-01 | 1990-12-03 | Process for producing 2,6-dimethylnaphthalene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2046857A JPH03251545A (en) | 1990-02-27 | 1990-02-27 | Production of 2,6-dimethylnaphthalene |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03251545A true JPH03251545A (en) | 1991-11-11 |
Family
ID=12759011
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2046857A Pending JPH03251545A (en) | 1989-12-01 | 1990-02-27 | Production of 2,6-dimethylnaphthalene |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03251545A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993002995A1 (en) * | 1991-08-08 | 1993-02-18 | Teijin Limited | Process for producing dialkylnaphthalene |
US5276230A (en) * | 1991-12-06 | 1994-01-04 | Mitsubishi Gas Chemical Company, Inc. | Process for production of 2,6-dimethylnaphthalene |
-
1990
- 1990-02-27 JP JP2046857A patent/JPH03251545A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993002995A1 (en) * | 1991-08-08 | 1993-02-18 | Teijin Limited | Process for producing dialkylnaphthalene |
US5365001A (en) * | 1991-08-08 | 1994-11-15 | Teijin Limited | Method for preparing dialkylnaphthalene |
US5276230A (en) * | 1991-12-06 | 1994-01-04 | Mitsubishi Gas Chemical Company, Inc. | Process for production of 2,6-dimethylnaphthalene |
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