JP4164459B2 - Methylnaphthalene production catalyst and production method - Google Patents
Methylnaphthalene production catalyst and production method Download PDFInfo
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- JP4164459B2 JP4164459B2 JP2004066966A JP2004066966A JP4164459B2 JP 4164459 B2 JP4164459 B2 JP 4164459B2 JP 2004066966 A JP2004066966 A JP 2004066966A JP 2004066966 A JP2004066966 A JP 2004066966A JP 4164459 B2 JP4164459 B2 JP 4164459B2
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- Prior art keywords
- naphthalene
- catalyst
- methanol
- alumina
- methylnaphthalenes
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- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 title claims description 130
- 239000003054 catalyst Substances 0.000 title claims description 71
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 141
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 132
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 27
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 23
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 17
- 230000011987 methylation Effects 0.000 claims description 11
- 238000007069 methylation reaction Methods 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 150000003657 tungsten Chemical class 0.000 claims description 2
- 230000001035 methylating effect Effects 0.000 claims 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical class C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 21
- 230000000694 effects Effects 0.000 description 19
- 239000006227 byproduct Substances 0.000 description 18
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- -1 for example Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011112 polyethylene naphthalate Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229930003448 Vitamin K Natural products 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- SHUZOJHMOBOZST-UHFFFAOYSA-N phylloquinone Natural products CC(C)CCCCC(C)CCC(C)CCCC(=CCC1=C(C)C(=O)c2ccccc2C1=O)C SHUZOJHMOBOZST-UHFFFAOYSA-N 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 235000019168 vitamin K Nutrition 0.000 description 3
- 239000011712 vitamin K Substances 0.000 description 3
- 150000003721 vitamin K derivatives Chemical class 0.000 description 3
- 229940046010 vitamin k Drugs 0.000 description 3
- QHJMFSMPSZREIF-UHFFFAOYSA-N 1,3-dimethylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC(C)=C21 QHJMFSMPSZREIF-UHFFFAOYSA-N 0.000 description 2
- APQSQLNWAIULLK-UHFFFAOYSA-N 1,4-dimethylnaphthalene Chemical compound C1=CC=C2C(C)=CC=C(C)C2=C1 APQSQLNWAIULLK-UHFFFAOYSA-N 0.000 description 2
- CBMXCNPQDUJNHT-UHFFFAOYSA-N 1,6-dimethylnaphthalene Chemical compound CC1=CC=CC2=CC(C)=CC=C21 CBMXCNPQDUJNHT-UHFFFAOYSA-N 0.000 description 2
- SPUWFVKLHHEKGV-UHFFFAOYSA-N 1,7-dimethylnaphthalene Chemical compound C1=CC=C(C)C2=CC(C)=CC=C21 SPUWFVKLHHEKGV-UHFFFAOYSA-N 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- WWGUMAYGTYQSGA-UHFFFAOYSA-N 2,3-dimethylnaphthalene Chemical compound C1=CC=C2C=C(C)C(C)=CC2=C1 WWGUMAYGTYQSGA-UHFFFAOYSA-N 0.000 description 2
- LRQYSMQNJLZKPS-UHFFFAOYSA-N 2,7-dimethylnaphthalene Chemical compound C1=CC(C)=CC2=CC(C)=CC=C21 LRQYSMQNJLZKPS-UHFFFAOYSA-N 0.000 description 2
- YXOVIGZJPGLNGM-UHFFFAOYSA-N 5-methyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=C1C=CC=C2C YXOVIGZJPGLNGM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- MFGWMAAZYZSWMY-UHFFFAOYSA-N (2-naphthyl)methanol Chemical compound C1=CC=CC2=CC(CO)=CC=C21 MFGWMAAZYZSWMY-UHFFFAOYSA-N 0.000 description 1
- 239000005967 1,4-Dimethylnaphthalene Substances 0.000 description 1
- XAABPYINPXYOLM-UHFFFAOYSA-N 1,8-dimethylnaphthalene Chemical compound C1=CC(C)=C2C(C)=CC=CC2=C1 XAABPYINPXYOLM-UHFFFAOYSA-N 0.000 description 1
- APBBTKKLSNPFDP-UHFFFAOYSA-N 1-methyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2C(C)CCCC2=C1 APBBTKKLSNPFDP-UHFFFAOYSA-N 0.000 description 1
- ONUWVTFBEJFWAS-UHFFFAOYSA-N 5,6-dimethyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=C(C)C(C)=CC=C21 ONUWVTFBEJFWAS-UHFFFAOYSA-N 0.000 description 1
- MDAXYSXRAMOWLY-UHFFFAOYSA-N 5,7-dimethyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=CC(C)=CC(C)=C21 MDAXYSXRAMOWLY-UHFFFAOYSA-N 0.000 description 1
- MHPANBVNWFIJJM-UHFFFAOYSA-N 6,7-dimethyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=C1C=C(C)C(C)=C2 MHPANBVNWFIJJM-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
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
Description
本発明は、メチルナフタレン類の製造触媒及び当該触媒を使用したメチルナフタレン類の製造法に関し、更に詳しくは、ナフタレンとメタノールからメチルナフタレン類の合成反応において、充分な活性と高いメチルナフタレン類の選択性、低いテトラヒドロナフタレン類の副生率を有するアルミナ担持酸化タングステン及びアルミナ担持硫酸触媒及びこれらの触媒を使用したメチルナフタレン類の製造法に関するものである。本発明は、様々な工業製品の中間原料として有用である、ナフタレン誘導体の合成技術の分野において、従来、メチルナフタレン類は、石油精製プロセスで得られる成分からの回収、ナフタレンのメチル化等により製造されていたが、触媒の十分な活性が得られず、副生成物が多いため、高い効率で、メチルナフタレン類を得ることは困難であったことを踏まえ、これらの問題点を確実に解決することが可能な、新しい触媒及び当該触媒を使用したメチルナフタレン類の製造方法を提供するものである。本発明で製造されるメチルナフタレン類は、高収率で、副生成物が少なく、しかも、硫黄等の不純物を含まないため、例えば、ビタミンＫの出発原料、ＰＥＴ樹脂の代替物として期待されている、ＰＥＮ樹脂等の中間原料、また、ナフトエ酸、蛍光増伯剤、界面活性剤、染料、医薬品等の中間原料として好適であり、これからの分野における、新技術の開発、新産業の創出に大きな推進力となるものとして有用である。 The present invention relates to a catalyst for producing methyl naphthalene and a method for producing methyl naphthalene using the catalyst, and more particularly, selection of methyl naphthalene having sufficient activity and high activity in the synthesis reaction of methyl naphthalene from naphthalene and methanol. The present invention relates to an alumina-supported tungsten oxide and an alumina-supported sulfuric acid catalyst having a low by-product rate of tetrahydronaphthalenes and a method for producing methylnaphthalenes using these catalysts. INDUSTRIAL APPLICABILITY The present invention is useful as an intermediate material for various industrial products. In the field of synthesis technology of naphthalene derivatives, methylnaphthalenes have been conventionally produced by recovery from components obtained in petroleum refining processes, methylation of naphthalene, and the like. However, it was difficult to obtain methylnaphthalene with high efficiency because sufficient activity of the catalyst could not be obtained and there were many by-products, and these problems were surely solved. The present invention provides a novel catalyst and a process for producing methylnaphthalenes using the catalyst. The methylnaphthalenes produced in the present invention are expected to be used as a starting material for vitamin K, an alternative to PET resin, for example, because it has a high yield, has few by-products, and does not contain impurities such as sulfur. It is suitable for intermediate raw materials such as PEN resin, and intermediate raw materials such as naphthoic acid, fluorescent thickeners, surfactants, dyes, and pharmaceuticals. For the development of new technologies and new industries in future fields It is useful as a big driving force.
メチルナフタレン類は、メチルナフタレン（１−メチルナフタレンと２−メチルナフタレン）、ジメチルナフタレン（１，２−、１，３−、１，４−、１，５−、１，６−、１，７−、１，８−、２，３−、２，６−、２，７−ジメチルナフタレン）等の、（式１）で表される化合物の総称である。メチルナフタレン類は、有用な工業原料であり、例えば、２−メチルナフタレンは、ビタミンＫの原料として用いられており、また、２，６−ジメチルナフタレンは、ポリエチレンナフタレート（ＰＥＮ）樹脂の原料として用いられている。その他にも、このメチルナフタレン類は、医薬、農薬、染料、界面活性剤、蛍光増白剤等の原料として有用な工業原料である。 Methylnaphthalenes include methylnaphthalene (1-methylnaphthalene and 2-methylnaphthalene), dimethylnaphthalene (1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7 A general term for compounds represented by (formula 1) such as-, 1,8-, 2,3-, 2,6-, 2,7-dimethylnaphthalene). Methylnaphthalenes are useful industrial raw materials, for example, 2-methylnaphthalene is used as a raw material for vitamin K, and 2,6-dimethylnaphthalene is used as a raw material for polyethylene naphthalate (PEN) resin. It is used. In addition, these methylnaphthalenes are industrial raw materials useful as raw materials for pharmaceuticals, agricultural chemicals, dyes, surfactants, fluorescent brighteners and the like.
これらの化合物の中で、特に有用な化合物は、２−メチルナフタレン、２，６−ジメチルナフタレンであるが、２−メチルナフタレンは１−メチルナフタレンの異性化によって製造でき（特許文献１参照）、２，６−ジメチルナフタレンは２−メチルナフタレンのメチル化によって製造できるので（特許文献２参照）、メチルナフタレン類の混合物もまた有用な工業原料である。 Among these compounds, particularly useful compounds are 2-methylnaphthalene and 2,6-dimethylnaphthalene, but 2-methylnaphthalene can be produced by isomerization of 1-methylnaphthalene (see Patent Document 1). Since 2,6-dimethylnaphthalene can be produced by methylation of 2-methylnaphthalene (see Patent Document 2), a mixture of methylnaphthalenes is also a useful industrial raw material.
メチルナフタレン類は、従来、石炭のコーキングにより製造されるコールタールや、石油精製プロセスで得られるＬＣＯ（ｌｉｇｈｔ ｃｙｃｌｅ ｏｉｌ）に含まれる成分を精製して製造されており、その精製方法に関する報告がなされている（特許文献３〜７参照）。一方、化学反応によってメチルナフタレン類やメチルナフタレン類に富む留分を合成する報告もなされており、パラフィンの環化脱水素反応（特許文献８参照）によって、また、テトラリン類の環化脱水素（特許文献９参照）によって、ナフタレンとメチルナフタレン類の混合物を得る方法が報告されている。これらの方法、あるいはこれらの組み合わせによってメチルナフタレン類を製造することはできるが、需要の小さいナフタレンが副生・残余するという問題点がある。 Methylnaphthalenes are conventionally produced by refining components contained in coal tar produced by coal coking and LCO (light cycle oil) obtained by petroleum refining processes, and reports on the purification method have been made. (See Patent Documents 3 to 7). On the other hand, it has also been reported to synthesize methylnaphthalenes and fractions rich in methylnaphthalene by chemical reaction, and by paraffin cyclization dehydrogenation (see Patent Document 8), cyclization dehydrogenation of tetralins (see Patent Document 8). (See Patent Document 9), a method for obtaining a mixture of naphthalene and methylnaphthalene is reported. Methylnaphthalenes can be produced by these methods, or a combination thereof, but there is a problem that naphthalene with a small demand is produced as a by-product and remains.
そこで、固体酸触媒の存在下で、ナフタレンをメタノールによってメチル化する反応が有用と考えられ、既に報告がなされている。例えば、ナフタレン、メチルナフタレン類の混合物とメタノールから、２，６−ジメチルナフタレンを選択的に製造する方法が報告されている（特許文献１０〜１２参照）が、この反応ではナフタレンとメタノールからメチルナフタレン類を得る反応がその一部をなしている。これらの報告では、ナフタレンとメタノールからメチルナフタレン類を得る反応に対する触媒として、ゼオライト類が用いられている。しかし、ゼオライト類を触媒として用いると、（式２）で表される、テトラヒドロナフタレン類（例えば、１，２，３，４−テトラヒドロナフタレン、メチル−１，２，３，４−テトラヒドロナフタレン、ジメチル−１，２，３，４−テトラヒドロナフタレン等）の副生が避けられず、高い効率でメチルナフタレン類を得ることができないという問題点がある。 Thus, a reaction in which naphthalene is methylated with methanol in the presence of a solid acid catalyst is considered useful and has already been reported. For example, a method for selectively producing 2,6-dimethylnaphthalene from a mixture of naphthalene and methylnaphthalene and methanol has been reported (see Patent Documents 10 to 12). In this reaction, methylnaphthalene is converted from naphthalene and methanol. The kind of reaction is part of it. In these reports, zeolites are used as catalysts for the reaction of obtaining methylnaphthalenes from naphthalene and methanol. However, when zeolites are used as catalysts, tetrahydronaphthalenes represented by (formula 2) (for example, 1,2,3,4-tetrahydronaphthalene, methyl-1,2,3,4-tetrahydronaphthalene, dimethyl) -1,2,3,4-tetrahydronaphthalene and the like) are inevitable and methyl naphthalenes cannot be obtained with high efficiency.
このような状況の中で、本発明者らは、上記従来技術に鑑みて、工業的に有用な原料である、メチルナフタレン類の製造において、副生成物が少なく、高い効率で、メチルナフタレン類を得ることができる新しい合成システムを開発することを目標にして、鋭意研究を積み重ねた結果、アルミナ担持タングステン、又はアルミナ担持硫酸触媒を用いることにより、これらの問題点を確実に解決することが可能なことを見出し、本発明を完成させるに至った。即ち、本発明者らは、上記の課題を解決すべく、各種物質の上記反応に対する触媒作用を検討した結果、ナフタレンとメタノールからメチルナフタレン類を得る反応に対して、充分な活性と高いメチルナフタレン類選択性、低いテトラヒドロナフタレン類の副生率を有するアルミナ担持酸化タングステン及びアルミナ担持硫酸触媒を見出し、また、これらの触媒を使用して上記反応を行った結果、充分な反応速度と高いメチルナフタレン類選択性、低いテトラヒドロナフタレン類選択性を有するメチルナフタレン類の製造法を見出し、本発明を完成した。 Under such circumstances, the present inventors, in view of the above-mentioned prior art, have little by-products and high efficiency in the production of methylnaphthalenes, which are industrially useful raw materials, and methylnaphthalenes. As a result of intensive research aimed at developing a new synthesis system that can obtain the above, it is possible to reliably solve these problems by using alumina-supported tungsten or alumina-supported sulfuric acid catalyst. As a result, the present invention has been completed. That is, as a result of examining the catalytic action of various substances for the above reaction in order to solve the above-mentioned problems, the present inventors have found that methylnaphthalene having sufficient activity and high activity for the reaction of obtaining methylnaphthalene from naphthalene and methanol. As a result of finding the alumina-supported tungsten oxide and alumina-supported sulfuric acid catalyst having low selectivity and by-product rate of tetrahydronaphthalenes, and performing the above reaction using these catalysts, sufficient reaction rate and high methylnaphthalene were obtained. The inventors have found a method for producing methyl naphthalene having low selectivity and low tetrahydronaphthalene selectivity, and have completed the present invention.
即ち、本発明の目的は、ナフタレンとメタノールからメチルナフタレン類を製造する触媒及びメチルナフタレン類の製造方法を提供することである。
また、本発明の目的は、ナフタレンとメタノールからメチルナフタレン類を得る反応に対して、充分な活性を有し、メチルナフタレン類への選択性が高く、テトラヒドロナフタレン類の副生率が低い触媒を提供することである。
また、本発明の目的は、ナフタレンとメタノールからメチルナフタレン類の製造に好適な、アルミナ担持タングステン触媒、又はアルミナ担持硫酸触媒を提供することである。
更に、本発明の目的は、ナフタレンとメタノールからメチルナフタレン類を得る反応に関して、上記触媒を用いて、充分な反応速度を有し、メチルナフタレン類への選択性が高く、テトラヒドロナフタレン類の副生率が低いメチルナフタレン類の製造方法を提供することである。
That is, an object of the present invention is to provide a catalyst for producing methylnaphthalenes from naphthalene and methanol, and a method for producing methylnaphthalenes.
Another object of the present invention is to provide a catalyst that has sufficient activity for the reaction to obtain methylnaphthalenes from naphthalene and methanol, has high selectivity to methylnaphthalenes, and has a low byproduct rate of tetrahydronaphthalenes. Is to provide.
Another object of the present invention is to provide an alumina-supported tungsten catalyst or an alumina-supported sulfuric acid catalyst suitable for the production of methylnaphthalenes from naphthalene and methanol.
Further, the object of the present invention is to use the above catalyst for the reaction for obtaining methyl naphthalene from naphthalene and methanol, and has a sufficient reaction rate, high selectivity to methyl naphthalene, and by-product of tetrahydronaphthalene. The present invention provides a method for producing methylnaphthalenes having a low rate.
上記課題を解決するための、本発明は、以下の技術的手段から構成される。
（１）ナフタレンをメタノールによってメチル化してメチルナフタレン類を製造する反応に用いるナフタレンメチル化触媒であって、アルミナに、酸化タングステン又は硫酸を担持したことを特徴とするナフタレンメチル化触媒。
（２）アルミナの比表面積が１００ｍ２ｇ−１以上で、酸化タングステンの担持量が５〜４０ｗｔ％であることを特徴とする前記（１）に記載のナフタレンメチル化触媒。
（３）アルミナの比表面積が１００ｍ２ｇ−１以上で、硫酸の担持量が５〜２０ｗｔ％であることを特徴とする前記（１）に記載のナフタレンメチン化触媒。
（４）前記１から３のいずれかに記載のアルミナ担持酸化タングステン触媒又はアルミナ担持硫酸触媒の存在下に、ナフタレンとメタノールを反応させてメチルナフタレン類を製造すること特徴とするメチルナフタレン類の製造方法。
（５）ナフタレンとメタノールの反応を、反応温度３００〜５００℃で行うことを特徴とする前記（４）に記載のメチルナフタレン類の製造方法。
（６）原料の、ナフタレン／メタノールのモル比を、０．００５〜０．１とし、触媒１ｇに対して、０．０１〜５ｇｈ−１の供給量で反応を行うことを特徴とする前記（４）に記載のメチルナフタレン類の製造方法。
（７）ナフタレンとメタノールの反応を、気相で行うことを特徴とする前記（４）に記載のメチルナフタレン類の製造法。
（８）アルミナに、タングステン塩類、硫酸、スルホン酸類又は硫酸アンモニウムを担持させた後、３００〜６５０℃で焼成することを特徴とする、ナフタレンをメタノールによってメチル化してメチルナフタレン類を製造する反応に用いるナフタレンメチル化触媒の製造方法。
In order to solve the above problems, the present invention comprises the following technical means.
(1) A naphthalene methylation catalyst used in a reaction in which naphthalene is methylated with methanol to produce methyl naphthalene, wherein the alumina carries tungsten oxide or sulfuric acid.
(2) The naphthalene methylation catalyst as described in (1) above, wherein the specific surface area of alumina is 100 m 2 g −1 or more and the supported amount of tungsten oxide is 5 to 40 wt%.
(3) The naphthalene methination catalyst according to (1) above, wherein the specific surface area of alumina is 100 m 2 g −1 or more and the supported amount of sulfuric acid is 5 to 20 wt%.
(4) Production of methylnaphthalene, wherein naphthalene and methanol are reacted to produce methylnaphthalene in the presence of the alumina-supported tungsten oxide catalyst or alumina-supported sulfuric acid catalyst according to any one of 1 to 3 above. Method.
(5) The method for producing methylnaphthalenes as described in (4) above, wherein the reaction between naphthalene and methanol is performed at a reaction temperature of 300 to 500 ° C.
(6) The molar ratio of naphthalene / methanol as a raw material is 0.005 to 0.1, and the reaction is performed at a supply amount of 0.01 to 5 gh −1 with respect to 1 g of the catalyst. The method for producing methylnaphthalene according to 4).
(7) The process for producing methylnaphthalenes as described in (4) above, wherein the reaction of naphthalene and methanol is carried out in a gas phase.
(8) Tungsten salt, sulfuric acid, sulfonic acid or ammonium sulfate is supported on alumina and then calcined at 300 to 650 ° C., which is used for the reaction for producing methylnaphthalene by methylation of naphthalene with methanol. A method for producing a naphthalene methylation catalyst.
次に、本発明を、更に詳細に説明する。
本発明の触媒及びその製造方法について説明すると、本発明においては、アルミナ担持酸化タングステン及び／又はアルミナ担持硫酸を触媒として使用する。アルミナとしては、好適には，純度の高いαアルミナ、例えば、触媒学会供給の参照触媒ＪＲＣ−ＡＬＯ４、ＪＲＣ−ＡＬＯ８、日揮化学株式会社製造販売のＮ６１１Ｎ、等が例示され、１００ｍ２ｇ−１以上の比表面積を有するものが好適に使用される。比表面積が小さいと活性が低く、好ましくない。本発明では、これらは単独で、又は両方を併用して使用される。
Next, the present invention will be described in more detail.
The catalyst of the present invention and the production method thereof will be described. In the present invention, alumina-supported tungsten oxide and / or alumina-supported sulfuric acid is used as a catalyst. Suitable examples of the alumina preferably include high-purity α-alumina, for example, reference catalysts JRC-ALO4 and JRC-ALO8 supplied by the Catalysis Society of Japan, N611N manufactured and sold by JGC Chemical Co., Ltd., and the like is 100 m 2 g −1 or more. Those having a specific surface area of 5 are preferably used. If the specific surface area is small, the activity is low, which is not preferable. In the present invention, these are used alone or in combination.
酸化タングステン（ＷＯ３）の含有量としては、アルミナ担持酸化タングステンの重量に対して、５〜４０％の範囲であることが好ましく、更に好ましくは、１０〜３０％の範囲である。硫酸（Ｈ２ＳＯ４）の含有量としては、アルミナ担持硫酸の重量に対して、５〜２０％の範囲であることが好ましい。この範囲にあれば、ナフタレンとメタノールからメチルナフタレン類を得る反応に対して、充分な活性と、高いメチルナフタレン類の選択性、低いテトラヒドロナフタレン類の副生率を有する触媒を得ることができる。 The content of tungsten oxide (WO 3 ) is preferably in the range of 5 to 40%, more preferably in the range of 10 to 30%, based on the weight of the alumina-supported tungsten oxide. The content of sulfuric acid (H 2 SO 4 ) is preferably in the range of 5 to 20% with respect to the weight of the alumina-supported sulfuric acid. If it is in this range, it is possible to obtain a catalyst having sufficient activity, high selectivity for methylnaphthalene, and low by-product rate of tetrahydronaphthalene for the reaction for obtaining methylnaphthalene from naphthalene and methanol.
酸化タングステンをアルミナに担持する方法としては、例えば、タングステンを含む塩類の水溶液にアルミナを投入し、加熱によって蒸発乾固し、焼成する方法、タングステンを含む塩類の水溶液にアルミナを投入し、前駆体を吸着させた後に濾過や遠心分離によって水を除去し、焼成する方法等が例示される。タングステンを含む塩類としては、例えば、タングステン酸アンモニウム（５（ＮＨ４）２Ｏ・１２ＷＯ３）、及びその水和物のタングステン酸アンモニウム５水和物（５（ＮＨ４）２Ｏ・１２ＷＯ３・５Ｈ２Ｏ）等が例示される。焼成条件としては、溶媒が蒸発し、タングステンを含む塩類が酸化タングステンに転化する条件であれば良く、例えば、酸素あるいは空気中で、３００〜６５０℃、好ましくは、３５０〜５００℃、での焼成が例示される。焼成温度が高すぎると、触媒の比表面積が失われ、活性が低下するので好ましくない。 As a method of supporting tungsten oxide on alumina, for example, alumina is introduced into an aqueous solution of a salt containing tungsten, evaporated to dryness by heating, and fired. Alumina is introduced into an aqueous solution of a salt containing tungsten, and a precursor. Examples of the method include removing water by filtration or centrifugal separation after adsorbing and firing. Examples of the salt containing tungsten include ammonium tungstate (5 (NH 4 ) 2 O · 12WO 3 ) and ammonium hydrate tungstate pentahydrate (5 (NH 4 ) 2 O · 12WO 3 · 5H 2 O) and the like. The firing conditions may be any conditions as long as the solvent evaporates and the salt containing tungsten is converted to tungsten oxide. For example, firing at 300 to 650 ° C., preferably 350 to 500 ° C. in oxygen or air. Is exemplified. If the calcination temperature is too high, the specific surface area of the catalyst is lost and the activity is lowered, which is not preferable.
硫酸を担持する方法としては、具体的には、例えば、硫酸、有機スルホン酸、硫酸アンモニウム等を含む溶液中にアルミナを投入し、加熱によって蒸発乾固し、焼成する方法が例示される。有機スルホン酸を含む溶液としては、例えば、２−ナフタレンスルホン酸水溶液が例示される。焼成条件としては、溶媒が蒸発する温度に加熱するが、有機スルホン酸を原料とする場合には、有機スルホン酸が硫酸根に転化する条件であれば良く、例えば、酸素あるいは空気中で、３００〜６５０℃、好ましくは、３５０〜５００℃の焼成が例示される。焼成温度が高すぎると、触媒の比表面積が失われ、活性が低下するので好ましくない。酸化タングステンあるいは硫酸を担持する方法としては、上記溶液中にアルミナを投入し、溶液中で吸着させたのちに濾過する方法も例示される。 Specific examples of the method for supporting sulfuric acid include a method in which alumina is put into a solution containing sulfuric acid, organic sulfonic acid, ammonium sulfate, etc., evaporated to dryness by heating, and calcined. Examples of the solution containing an organic sulfonic acid include a 2-naphthalenesulfonic acid aqueous solution. As the firing conditions, the solvent is heated to a temperature at which the solvent evaporates. However, when organic sulfonic acid is used as a raw material, it may be any condition as long as the organic sulfonic acid is converted into sulfate radicals. Illustrated is baking at ˜650 ° C., preferably 350 ° C. to 500 ° C. If the calcination temperature is too high, the specific surface area of the catalyst is lost and the activity is lowered, which is not preferable. Examples of the method for supporting tungsten oxide or sulfuric acid include a method in which alumina is introduced into the above solution, adsorbed in the solution, and then filtered.
本発明のアルミナ担持酸化タングステン及びアルミナ担持硫酸は、粉末で用いても、また、成型して用いても良い。成型体とするには、既に成型されたアルミナ担体を原料として用いても良いし、酸化タングステンあるいは硫酸を担持した後に成型しても良い。成型方法としてはこれらの物質の純粋な試料を圧縮成型しても良いし、バインダーを用いても良い。 The alumina-supported tungsten oxide and the alumina-supported sulfuric acid of the present invention may be used as a powder or may be used after being molded. In order to form a molded body, an already molded alumina carrier may be used as a raw material, or may be molded after supporting tungsten oxide or sulfuric acid. As a molding method, a pure sample of these substances may be compression molded, or a binder may be used.
次に、本発明の触媒を使用して、メチルナフタレン類を製造する方法につい説明すると、本発明は、上記のようにして製造したアルミナ担持酸化タングステン及び／又はアルミナ担持硫酸触媒を用いて、ナフタレンとメタノールからメチルナフタレン類を製造する。本発明で原料として使用するナフタレンとしては、精製されたナフタレンでも、ナフタレン及びメチルナフタレン類を含む混合物でも良く、例えば、石炭のコーキングにより製造されるコールタールや、石油精製プロセスで得られるＬＣＯ（ｌｉｇｈｔ ｃｙｃｌｅ ｏｉｌ）、あるいはこれらを精製したものでも良い。 Next, a method for producing methyl naphthalenes using the catalyst of the present invention will be described. The present invention is directed to naphthalene using the alumina-supported tungsten oxide and / or the alumina-supported sulfuric acid catalyst produced as described above. Methylnaphthalene is produced from methanol and methanol. The naphthalene used as a raw material in the present invention may be refined naphthalene or a mixture containing naphthalene and methylnaphthalene. For example, coal tar produced by coking of coal, LCO (light cycle oil) or a purified product thereof.
本発明の方法により、アルミナ担持酸化タングステン及びアルミナ担持硫酸を用いてナフタレンとメタノールからメチルナフタレン類を製造するに際し、その反応は気相でも液相でも行うことができる。メチルナフタレン類を高収率で得るには、反応温度を３００〜５００℃、好ましくは３５０〜４５０℃とする。反応温度が３００℃以下では、充分な反応速度が得られないばかりか、生成物が触媒表面から脱離せず、失活の原因となるおそれがある。反応温度が５００℃以上では、反応物や生成物の重合によって炭素質が多く生成して触媒表面を被毒し、失活のおそれがあり、また、メチルナフタレン類の選択性を下げる。反応は液相でも気相でも行えるが、前記のような反応温度で実施するためには、気相が好ましい。反応圧力は、常圧、加圧、減圧のいずれでも良いが、減圧や大きな加圧では圧力を変えるための装置やエネルギーコストがかかるばかりで何ら利点はないので、１〜５気圧が好ましい。 In producing the methylnaphthalene from naphthalene and methanol using the alumina-supported tungsten oxide and the alumina-supported sulfuric acid by the method of the present invention, the reaction can be carried out in a gas phase or a liquid phase. In order to obtain methylnaphthalenes in high yield, the reaction temperature is 300 to 500 ° C, preferably 350 to 450 ° C. When the reaction temperature is 300 ° C. or lower, not only a sufficient reaction rate can be obtained, but also the product is not detached from the catalyst surface, which may cause deactivation. When the reaction temperature is 500 ° C. or higher, a large amount of carbonaceous matter is produced by polymerization of the reactants and products, poisoning the catalyst surface, there is a risk of deactivation, and the selectivity of methylnaphthalenes is lowered. The reaction can be carried out in the liquid phase or in the gas phase, but the gas phase is preferred in order to carry out the reaction at the reaction temperature as described above. The reaction pressure may be any of normal pressure, pressurization, and depressurization. However, the depressurization or large pressurization requires a device for changing the pressure and energy costs, and has no advantage, so 1 to 5 atm is preferable.
原料として用いるナフタレンとメタノールの混合比率については、ナフタレン／メタノールモル比が０．００５より小さいと、大量のメタノールを反応後に生成物から回収して再利用しなければならず、装置とエネルギーコストが高くなる。一方、ナフタレン／メタノールモル比が、０．１より大きいと、ナフタレンの重合により炭素質が多く生成し、触媒表面を被毒し、失活のおそれがあり、また、メチルナフタレン類の選択性を下げる。したがって、ナフタレン／メタノールモル比は、０．００５〜０．１が好ましく、更に好ましくは０．０１〜０．０５である。ナフタレン・メタノール混合物の供給量は、触媒１ｇに対して０．０１ｇｈ−１以下では生産効率が低く、５ｇｈ−１以上では充分な転化率が得られない。したがって、ナフタレン・メタノール混合物の供給量は、触媒１ｇに対して０．０１〜５ｇｈ−１であることが好ましく、更に好ましくは０．０５〜２ｇｈ−１である。 As for the mixing ratio of naphthalene and methanol used as a raw material, if the naphthalene / methanol molar ratio is less than 0.005, a large amount of methanol must be recovered from the product after the reaction and reused. Get higher. On the other hand, if the naphthalene / methanol molar ratio is larger than 0.1, a large amount of carbonaceous matter is produced by the polymerization of naphthalene, the catalyst surface may be poisoned and deactivated, and the selectivity of methylnaphthalenes is increased. Lower. Therefore, the naphthalene / methanol molar ratio is preferably 0.005 to 0.1, and more preferably 0.01 to 0.05. When the supply amount of the naphthalene / methanol mixture is 0.01 gh −1 or less with respect to 1 g of the catalyst, the production efficiency is low, and when it is 5 gh −1 or more, sufficient conversion cannot be obtained. Accordingly, the supply amount of the naphthalene-methanol mixture is preferably 0.01～5Gh -1 the catalyst 1g, more preferably from 0.05~2gh -1.
本発明では反応は、連続式、回分式のいずれであっても良いが、工業的見地から連続法で行うことが望ましい。連続法で行う場合には、例えば、触媒を充填塔に詰め、これにナフタレンとメタノールの混合物を供給する方法、あるいはナフタレンとメタノールを別個に供給する方法、あるいはこれらを不活性な溶媒に溶かして供給する方法等が挙げられる。また、これらの原料を不活性な希釈ガス（例えば、窒素）とともに供給する方法も挙げられる。 In the present invention, the reaction may be either a continuous type or a batch type, but it is desirable to carry out the reaction by a continuous method from an industrial point of view. In the case of the continuous method, for example, the catalyst is packed in a packed column and a mixture of naphthalene and methanol is supplied to this, or a method of supplying naphthalene and methanol separately, or these are dissolved in an inert solvent. The method of supplying etc. are mentioned. Moreover, the method of supplying these raw materials with an inert diluent gas (for example, nitrogen) is also mentioned.
ナフタレンとメタノールの混合物を供給する方法としては、例えば、ナフタレンをメタノールに溶解し、この液体を蒸発器に供給し、気体混合物として供給する方法、あるいは液化したナフタレン中にメタノール蒸気を流通させ、気体混合物を得て供給する方法、液化したナフタレンとメタノールを別々に蒸発器に供給し、気体混合物として供給する方法等が例示される。 As a method of supplying a mixture of naphthalene and methanol, for example, a method of dissolving naphthalene in methanol and supplying this liquid to an evaporator and supplying it as a gas mixture, or circulating methanol vapor in liquefied naphthalene, Examples thereof include a method of obtaining and supplying a mixture, a method of separately supplying liquefied naphthalene and methanol to an evaporator, and supplying them as a gas mixture.
反応器から取り出した気体生成物には、通常、過剰量のメタノールと未反応のナフタレン類が含まれる。この気体生成物からメチルナフタレン類を取り出すには、気体生成物を冷却し、最初に析出するナフタレンとメチルナフタレン類を回収し、回収物から蒸留によってメチルナフタレン類を分離精製する方法が例示される。 The gaseous product removed from the reactor usually contains an excess amount of methanol and unreacted naphthalene. In order to take out methylnaphthalenes from this gaseous product, there is exemplified a method in which the gaseous product is cooled, firstly precipitated naphthalene and methylnaphthalene are recovered, and methylnaphthalenes are separated and purified from the recovered product by distillation. .
以上説明したように、本発明は、ナフタレンとメタノールからメチルナフタレン類を製造する反応に使用するための、副生物の生成が少ない新規な触媒、及び当該触媒を用いたメチルナフタレン類の製造方法を提供するものである。本発明が、従来技術と比較して、優れた効果を奏するための基本的な機構については、次のように説明することができる。従来知られていたゼオライト触媒類は、高活性ではあるが、テトラヒドロナフタレン類を副生する。これは、ゼオライトが有する強酸点によって、メタノールから一酸化炭素と水素が発生し、この水素がナフタレンを水素化するため、あるいはメタノールからナフタレンへの水素の移行が気相水素を経ないで直接起きるためと考えられる。一方、ナフタレンのメチル化に対しては、本発明のアルミナ担持酸化タングステン及びアルミナ担持硫酸は、不要な強い酸点を持たず、弱い酸点のみを有するが、弱い酸点でも充分な活性を持つために、メチルナフタレン類を製造するには、充分な活性と、高い選択性を持つものと推測される。 As described above, the present invention provides a novel catalyst for producing methylnaphthalenes from naphthalene and methanol with little by-product formation, and a method for producing methylnaphthalenes using the catalyst. It is to provide. The basic mechanism for the present invention to provide superior effects compared to the prior art can be described as follows. Conventionally known zeolite catalysts are highly active, but by-produce tetrahydronaphthalenes. This is because carbon monoxide and hydrogen are generated from methanol by the strong acid point of zeolite and this hydrogen hydrogenates naphthalene, or the hydrogen transfer from methanol to naphthalene occurs directly without gas phase hydrogen. This is probably because of this. On the other hand, for methylation of naphthalene, the alumina-supported tungsten oxide and the alumina-supported sulfuric acid of the present invention do not have unnecessary strong acid sites and have only weak acid sites, but have sufficient activity even at weak acid sites. Therefore, it is presumed to have sufficient activity and high selectivity for producing methylnaphthalenes.
一方、本発明者らは、以前の論文（Ｊ．ｐｈｙｓ．Ｃｈｅｍ．，Ｂ，Ｖｏｌ．１０３，ｐ．７２０６−７２１３（１９９９）及びＪ．Ｐｈｙｓ．Ｃｈｅｍ．，Ｂ，Ｖｏｌ．１０４，ｐ．５５１１−５５１８（２０００））において、１００ｍ２ｇ−１程度の比表面積を有するジルコニア（ＺｒＯ２）に、酸化タングステンを１０〜３０ｗｔ％、もしくは硫酸を５〜２０ｗｔ％担持して３００〜６５０℃で焼成すると、酸化タングステンもしくは硫酸の単分子層が表面を覆い、単分子層特有の酸性質を発現することを報告しているが、本発明では、酸化タングステンを１０〜３０ｗｔ％、もしくは硫酸を５〜３０ｗｔ％担持して３００〜６５０℃で焼成した際に、単分子層特有の酸性質を発現し、上記のような好適な性質を示すことを見出したものである。 On the other hand, the present inventors have previously published papers (J. phys. Chem., B, Vol. 103, p. 7206-7213 (1999) and J. Phys. Chem., B, Vol. 104, p. 5511). -5518 (2000)), zirconia (ZrO 2 ) having a specific surface area of about 100 m 2 g −1 carries 10 to 30 wt% tungsten oxide or 5 to 20 wt% sulfuric acid and calcined at 300 to 650 ° C. Then, it has been reported that the monomolecular layer of tungsten oxide or sulfuric acid covers the surface and expresses the acid properties peculiar to the monomolecular layer. In the present invention, 10 to 30 wt% of tungsten oxide, or 5 to 5 of sulfuric acid is reported. It was found that when it was supported at 30 wt% and calcined at 300 to 650 ° C., it exhibited the acid properties peculiar to the monolayer and exhibited the above-mentioned suitable properties. Those were.
本発明により、１）メチルナフタレン類の製造触媒及びその製造方法を提供することができる、２）ナフタレンとメタノールからメチルナフタレン類を得る反応に対して、充分な活性を有し、メチルナフタレン類への選択性が高く、テトラヒドロナフタレン類の副生率が低い触媒を提供できる、３）当該触媒を用い、充分な反応速度を有し、メチルナフタレン類への選択性が高く、テトラヒドロナフタレン類の副生率が低い、ナフタレンとメタノールからメチルナフタレン類を製造方法を提供できる、という格別の効果が奏される。 According to the present invention, 1) a catalyst for producing methylnaphthalenes and a method for producing the same can be provided, and 2) a compound having sufficient activity for the reaction to obtain methylnaphthalenes from naphthalene and methanol. 3) Using the catalyst, the catalyst has a sufficient reaction rate, a high selectivity to methylnaphthalenes, and a side effect of tetrahydronaphthalenes. The exceptional effect is that the production rate can be provided from naphthalene and methanol.
以下に、本発明の触媒、その調製法、及びその触媒を用いた反応例を実施例に基づいて具体的に説明するが、本発明は、これらの実施例によって何ら限定されるものではない。 EXAMPLES The catalyst of the present invention, its preparation method, and reaction examples using the catalyst are specifically described below based on examples, but the present invention is not limited to these examples.
実施例１〜６
表１に記載した量の、タングステン酸アンモニウム５水和物（和光純薬製造販売）を、１００ｃｍ３のビーカー中で、水５０ｃｍ３に溶解し、比表面積１５１ｍ２ｇ−１を有する触媒学会配付のアルミナ参照触媒ＪＲＣ−ＡＬＯ４を１ｇ投入し、１６０℃のホットプレート上で加熱、水を蒸発させた。得られた固体を、空気中、４００℃で４時間焼成して、本発明の触媒を作製した。
Examples 1-6
Amounts listed in Table 1 of ammonium tungstate pentahydrate (manufactured and sold by Wako Pure Chemical Industries, Ltd.) dissolved in 50 cm 3 of water in a 100 cm 3 beaker and having a specific surface area of 151 m 2 g −1 1 g of alumina reference catalyst JRC-ALO4 was added and heated on a hot plate at 160 ° C. to evaporate water. The obtained solid was calcined in the air at 400 ° C. for 4 hours to produce the catalyst of the present invention.
次に、上記触媒０．２ｇを内径８ｍｍのパイレックス（登録商標）ガラス製反応管に詰め、４１０℃で５０ｃｍ３ｍｉｎ−１のヘリウム（イワタニガス製造販売）気流中で１時間前処理した後、４１０℃で５０ｃｍ３ｍｉｎ−１のヘリウムを流通させつつ、ナフタレン（和光純薬製造販売）とメタノール（和光純薬製造販売）の混合溶液（ナフタレン／メタノールモル比０．０１）を、１．０６ｇｈ−１の速度で供給し、反応管出口に現れた生成物を、０℃に冷やして液体・固体を捕集し、キャピラリーカラム（信和化工製ＤＭＮ−２６７）を備えたガスクロマトグラフ（島津製作所製ＧＣ−２０１０）を用いて分析した。表１に、得られたメチルナフタレン類の収率及びテトラヒドロナフタレン類の副生率を示した。 Next, 0.2 g of the above catalyst was packed in a Pyrex (registered trademark) glass reaction tube having an inner diameter of 8 mm, and pretreated for 1 hour in a helium (manufactured and sold by Iwatani gas) air flow at 410 ° C. in 50 cm 3 min −1 . While passing 50 cm 3 min −1 helium at 410 ° C., 1.06 gh of a mixed solution of naphthalene (manufactured and sold by Wako Pure Chemical Industries) and methanol (manufactured and marketed by Wako Pure Chemical Industries) (naphthalene / methanol molar ratio 0.01) was added. The gas chromatograph (GC manufactured by Shimadzu Corporation) equipped with a capillary column (DMN-267 manufactured by Shinwa Kako) was collected by cooling the product that was supplied at a speed of -1 and cooled to 0 ° C. -2010). Table 1 shows the yield of the obtained methylnaphthalene and the byproduct rate of tetrahydronaphthalene.
表１中、メチルナフタレン類の収率は、１−メチルナフタレン、２−メチルナフタレン、１，２−ジメチルナフタレン、１，３−ジメチルナフタレン、１，４−ジメチルナフタレン、１，６−ジメチルナフタレン、１，７−ジメチルナフタレン、１，８−ジメチルナフタレン、２，３−ジメチルナフタレン、２，６−ジメチルナフタレン、２，７−ジメチルナフタレンの収量の合計をナフタレンの供給量で除した数値で示した。但し、他のメチルナフタレン類の収量は、極めて低い値であったので無視した。 In Table 1, the yields of methylnaphthalenes are 1-methylnaphthalene, 2-methylnaphthalene, 1,2-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1,6-dimethylnaphthalene, The total yield of 1,7-dimethylnaphthalene, 1,8-dimethylnaphthalene, 2,3-dimethylnaphthalene, 2,6-dimethylnaphthalene, and 2,7-dimethylnaphthalene is shown as a numerical value obtained by dividing by the amount of naphthalene supplied. . However, the yields of other methylnaphthalenes were extremely low and were ignored.
また、テトラヒドロナフタリン類の副生率は、１，２，３，４−テトラヒドロナフタレン、５−メチル−１，２，３，４−テトラヒドロナフタレン、６−メチル−１，２，３，４−テトラヒドロナフタレン、５，６−ジメチル−１，２，３，４−テトラヒドロナフタレン、５，７−ジメチル−１，２，３，４−テトラヒドロナフタレン、５，８−ジメチル−１，２，３，４−テトラヒドロナフタレン、６，７−ジメチル−１，２，３，４−テトラヒドロナフタレン収量の合計を、ナフタレンの供給量で除した数値で示した。但し、他のテトラヒドロナフタレン類の収量は、極めて低い値であったので無視した。 Further, the by-product rate of tetrahydronaphthalene is 1,2,3,4-tetrahydronaphthalene, 5-methyl-1,2,3,4-tetrahydronaphthalene, 6-methyl-1,2,3,4-tetrahydro. Naphthalene, 5,6-dimethyl-1,2,3,4-tetrahydronaphthalene, 5,7-dimethyl-1,2,3,4-tetrahydronaphthalene, 5,8-dimethyl-1,2,3,4- The sum of the yields of tetrahydronaphthalene and 6,7-dimethyl-1,2,3,4-tetrahydronaphthalene was shown by a value obtained by dividing by the amount of naphthalene supplied. However, the yields of other tetrahydronaphthalenes were very low and were ignored.
表１に示したように、メチルナフタレン類の収率は５％以上と充分高く、テトラヒドロナフタレン類副生率は１％以下と低い値であった。中でも、酸化タングステン含有量が１０〜３０％の範囲にある実施例２〜６では、メチルナフタレン類収率が１０％以上と高い値であった。 As shown in Table 1, the yield of methylnaphthalenes was sufficiently high as 5% or more, and the byproduct rate of tetrahydronaphthalenes was as low as 1% or less. Especially, in Examples 2-6 in which the tungsten oxide content is in the range of 10-30%, the methylnaphthalene yield was a high value of 10% or more.
実施例７〜１０及び比較例１
表１に記載の量の、硫酸を含む０．５ｍｏｌｄｍ−３の硫酸（和光純薬製造販売）を、１００ｃｍ３のビーカー中で、水２０ｃｍ３に希釈し、触媒学会配付のアルミナ参照触媒ＪＲＣ−ＡＬＯ４を１ｇ投入し、１６０℃のホットプレート上で加熱、水を蒸発させた。得られた固体を空気中、４００℃で４時間焼成して、本発明の触媒を作製した。
Examples 7 to 10 and Comparative Example 1
The sulfuric acid-containing 0.5 moldm -3 sulfuric acid (manufactured and sold by Wako Pure Chemical Industries) in the amount shown in Table 1 was diluted to 20 cm 3 in water in a 100 cm 3 beaker, and the alumina reference catalyst JRC- distributed by the Catalytic Society of Japan was used. 1 g of ALO4 was added and heated on a hot plate at 160 ° C. to evaporate water. The obtained solid was calcined in the air at 400 ° C. for 4 hours to produce the catalyst of the present invention.
上記触媒を用いて実施例１〜６と同様の操作を行ない、メチルナフタレン類を製造した。 表１に示したとおり、硫酸の担持量が２．９ｗｔ％である比較例１では、メチルナフタレン収率が２．８％と低いが、硫酸担持量が５〜２０ｗｔ％である実施例７〜１０では、メチルナフタレン収率が４％以上と高く、テトラヒドロナフタレン類副生率は０．６％以下で低い値であった。 The same operation as in Examples 1 to 6 was performed using the above catalyst to produce methylnaphthalenes. As shown in Table 1, in Comparative Example 1 where the supported amount of sulfuric acid is 2.9 wt%, the yield of methyl naphthalene is as low as 2.8%, but the supported amount of sulfuric acid is 5 to 20 wt% in Examples 7 to In No. 10, the methylnaphthalene yield was as high as 4% or more, and the tetrahydronaphthalene by-product rate was 0.6% or less, which was a low value.
比較例２
ゼオライトベータ（ＶＡＬＦＯＲ ＣＰ ８１１ＢＬ−２５、ＰＱ Ｃｏｒｐ．製造販売）を用いて、実施例１〜６と同様の操作を行った。その結果、メチルナフタレン収率が１２．９％で、実施例３等と同程度であるのに対し、テトラヒドロナフタレン類の副生率が７７．１％と極めて高い値であった。
Comparative Example 2
The same operation as in Examples 1 to 6 was performed using zeolite beta (VALFOR CP 811BL-25, PQ Corp. production and sales). As a result, the methylnaphthalene yield was 12.9%, which was similar to Example 3 and the like, while the byproduct rate of tetrahydronaphthalene was 77.1%, which was an extremely high value.
実施例１１
２−ナフタレンスルホン酸０．１３２ｇを、１００ｃｍ３のビーカー中で水５０ｃｍ３に溶解し、触媒学会供給のアルミナ参照触媒ＪＲＣ−ＡＬＯ４を１ｇ投入し、１８０℃のホットプレート上で加熱、水を蒸発させた。得られた固体を５０ｃｍ３ｍｉｎ−１の純酸素（イワタニガス製造販売）気流中、４００℃で２４時間焼成して、本発明の触媒を作製した。得られたアルミナ担持硫酸触媒中の、硫酸の計算量は、実施例７と同じく、５．８ｗｔ％である。この触媒を用いて実施例１〜６と同様の操作を行ったところ、メチルナフタレン類収率は４．９％と高く、テトラヒドロナフタレン類副生率は１．３４％と低い値であった。
Example 11
2-Naphthalenesulfonic acid (0.132 g) is dissolved in 50 cm 3 of water in a 100 cm 3 beaker, 1 g of alumina reference catalyst JRC-ALO4 supplied by the Catalysis Society of Japan is added, heated on a hot plate at 180 ° C., and water is evaporated. I let you. The obtained solid was calcined for 24 hours at 400 ° C. in a stream of pure oxygen (Iwatani gas production and sales) of 50 cm 3 min −1 to produce the catalyst of the present invention. The calculated amount of sulfuric acid in the obtained alumina-supported sulfuric acid catalyst is 5.8 wt%, as in Example 7. When this catalyst was used in the same manner as in Examples 1 to 6, the methylnaphthalene yield was as high as 4.9%, and the tetrahydronaphthalene byproduct rate was as low as 1.34%.
以上詳述したように、本発明は、メチルナフタレン類製造触媒及びその製造方法に係るものであり、本発明により、ナフタレンとメタノールからメチルナフタレン類を得る反応に対して、充分な活性と高いメチルナフタレン類選択性、低いテトラヒドロナフタレン類の副生率を有するアルミナ担持酸化タングステン及びアルミナ担持硫酸触媒、及びこれらの触媒を使用したメチルナフタレン類の製造方法を提供することができる。本発明は、様々な工業製品の中間原料として有用であるナフタレン誘導体のなかで、従来、メチルナフタレン類の工業的製造技術では、触媒の十分な活性が得られず、副生成物が多いため、高い効率でメチルナフタレン類を得ることが困難である等の従来技術の問題点を確実に解決することが可能な、新規な触媒、及び当該触媒を用いたメチルナフタレン類の製造技術を提供することを可能とするものである。本発明は、例えば、ビタミンＫの出発原料、耐熱性、ガスバリアー性に優れＰＥＴ樹脂の代替物として期待されているＰＥＮ（ポリエチレンナフタレート）樹脂、また、ナフトエ酸、蛍光増伯剤、界面活性剤等の中間原料として好適なメチルナフタレン類の製造技術を提供するものとして有用である。
As described above in detail, the present invention relates to a catalyst for producing methylnaphthalenes and a method for producing the same. According to the present invention, the present invention has sufficient activity and high methylation for the reaction for obtaining methylnaphthalenes from naphthalene and methanol. There can be provided an alumina-supported tungsten oxide and an alumina-supported sulfuric acid catalyst having a naphthalene selectivity and a low by-product ratio of tetrahydronaphthalene, and a method for producing methylnaphthalenes using these catalysts. The present invention is a naphthalene derivative that is useful as an intermediate material for various industrial products. Conventionally, in the industrial production technology of methylnaphthalenes, sufficient activity of the catalyst cannot be obtained, and there are many by-products. PROBLEM TO BE SOLVED: To provide a novel catalyst capable of surely solving the problems of the prior art such as difficulty in obtaining methyl naphthalene with high efficiency, and a technology for producing methyl naphthalene using the catalyst. Is possible. The present invention is, for example, a PEN (polyethylene naphthalate) resin, which is excellent as a starting material for vitamin K, has excellent heat resistance and gas barrier properties, and is expected as a substitute for a PET resin, naphthoic acid, fluorescent thickener, surface activity It is useful as a technique for producing methylnaphthalenes suitable as an intermediate raw material for agents.
Claims (8)
Naphthalene methylation used in a reaction for producing methylnaphthalenes by methylating naphthalene with methanol, which is characterized in that tungsten salt, sulfuric acid, sulfonic acid or ammonium sulfate is supported on alumina and then calcined at 300 to 650 ° C. A method for producing a catalyst.
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