JP2900970B2 - Method for dehydrogenation of dimethyltetralin - Google Patents
Method for dehydrogenation of dimethyltetralinInfo
- Publication number
- JP2900970B2 JP2900970B2 JP5222448A JP22244893A JP2900970B2 JP 2900970 B2 JP2900970 B2 JP 2900970B2 JP 5222448 A JP5222448 A JP 5222448A JP 22244893 A JP22244893 A JP 22244893A JP 2900970 B2 JP2900970 B2 JP 2900970B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- catalyst
- platinum
- dmn
- activated carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 42
- 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 title claims description 32
- 238000006356 dehydrogenation reaction Methods 0.000 title description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 147
- 238000006243 chemical reaction Methods 0.000 claims description 96
- 239000003054 catalyst Substances 0.000 claims description 80
- 229910052697 platinum Inorganic materials 0.000 claims description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 50
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical class C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 24
- 239000002994 raw material Substances 0.000 description 19
- SDDBCEWUYXVGCQ-UHFFFAOYSA-N 1,5-dimethylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1C SDDBCEWUYXVGCQ-UHFFFAOYSA-N 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- SPUWFVKLHHEKGV-UHFFFAOYSA-N 1,7-dimethylnaphthalene Chemical compound C1=CC=C(C)C2=CC(C)=CC=C21 SPUWFVKLHHEKGV-UHFFFAOYSA-N 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000006317 isomerization reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- CBMXCNPQDUJNHT-UHFFFAOYSA-N 1,6-dimethylnaphthalene Chemical compound CC1=CC=CC2=CC(C)=CC=C21 CBMXCNPQDUJNHT-UHFFFAOYSA-N 0.000 description 11
- 238000009835 boiling Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 238000007086 side reaction Methods 0.000 description 8
- BMADLDGHUBLVMQ-UHFFFAOYSA-N 1,5-dimethyltetralin Chemical compound C1=CC=C2C(C)CCCC2=C1C BMADLDGHUBLVMQ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- XAABPYINPXYOLM-UHFFFAOYSA-N 1,8-dimethylnaphthalene Chemical compound C1=CC(C)=C2C(C)=CC=CC2=C1 XAABPYINPXYOLM-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000017858 demethylation Effects 0.000 description 5
- 238000010520 demethylation reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- -1 tetrahydronaphthalene compound Chemical class 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 230000020335 dealkylation Effects 0.000 description 3
- 238000006900 dealkylation reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KNQXALMJMHIHQH-UHFFFAOYSA-N 1,4-dimethyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2C(C)CCC(C)C2=C1 KNQXALMJMHIHQH-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
- WWGUMAYGTYQSGA-UHFFFAOYSA-N 2,3-dimethylnaphthalene Chemical compound C1=CC=C2C=C(C)C(C)=CC2=C1 WWGUMAYGTYQSGA-UHFFFAOYSA-N 0.000 description 2
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 description 2
- JFNIPAHFRAGYKF-UHFFFAOYSA-N 3,3-dimethyl-2,4,8,8a-tetrahydro-1h-naphthalene Chemical compound C1C=CC=C2CC(C)(C)CCC21 JFNIPAHFRAGYKF-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000005967 1,4-Dimethylnaphthalene Substances 0.000 description 1
- KWSOSNULPSERHY-UHFFFAOYSA-N 1,6-dimethyl-1,2,3,4-tetrahydronaphthalene Chemical compound CC1=CC=C2C(C)CCCC2=C1 KWSOSNULPSERHY-UHFFFAOYSA-N 0.000 description 1
- KVNZVXVZQFTXNA-UHFFFAOYSA-N 1,8-dimethyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC(C)=C2C(C)CCCC2=C1 KVNZVXVZQFTXNA-UHFFFAOYSA-N 0.000 description 1
- AOZLFGNQSVVKNN-UHFFFAOYSA-N 1-methyl-2-pent-2-enylbenzene Chemical compound CCC=CCC1=CC=CC=C1C AOZLFGNQSVVKNN-UHFFFAOYSA-N 0.000 description 1
- VRFKBBOWFOYOEY-UHFFFAOYSA-N 1-methyl-3-pent-3-enylbenzene Chemical compound CC=CCCC1=CC=CC(C)=C1 VRFKBBOWFOYOEY-UHFFFAOYSA-N 0.000 description 1
- LRQYSMQNJLZKPS-UHFFFAOYSA-N 2,7-dimethylnaphthalene Chemical compound C1=CC(C)=CC2=CC(C)=CC=C21 LRQYSMQNJLZKPS-UHFFFAOYSA-N 0.000 description 1
- ITGPTGUEFKGCJS-UHFFFAOYSA-N 4,4-dimethyl-2,3,8,8a-tetrahydro-1h-naphthalene Chemical compound C1C=CC=C2C(C)(C)CCCC21 ITGPTGUEFKGCJS-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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- YVNCCKPQDDILKX-ONEGZZNKSA-N [(E)-hex-4-en-2-yl]benzene Chemical compound C\C=C\CC(C)C1=CC=CC=C1 YVNCCKPQDDILKX-ONEGZZNKSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 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 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ジメチルテトラヒドロ
ナフタレン類を脱水素してジメチルナフタレン類を製造
する方法に関する。ジメチルナフタレン類は高分子材料
や医薬材料の原料として広範な用途を持っている。例え
ば、1,5-ジメチルテトラヒドロナフタレンを脱水素して
得られる1,5-ジメチルナフタレンは、異性化工程、酸化
工程を経て工業的に有用な2,6-ナフタレンジカルボン酸
に変換することができる。The present invention relates to a method for producing dimethylnaphthalenes by dehydrogenating dimethyltetrahydronaphthalenes. Dimethylnaphthalenes have a wide range of uses as raw materials for polymer materials and pharmaceutical materials. For example, 1,5-dimethylnaphthalene obtained by dehydrogenating 1,5-dimethyltetrahydronaphthalene can be converted to industrially useful 2,6-naphthalenedicarboxylic acid through an isomerization step and an oxidation step. .
【０００２】[0002]
【従来技術】テトラヒドロナフタレン化合物を貴金属担
持触媒粉末を用いて液相下で脱水素してナフタレン化合
物に変換する方法は、置換ナフタレン類の合成方法とし
て古くから知られている。例えば、Eberhardt らは J.O
rg.Chem., vol.30(1965), p82-84では、パラジウム担持
活性炭粉末を触媒に用いて1,5-、1,7-、または1,4-ジメ
チルテトラヒドロナフタレンを液相で脱水素して1,5-、
1,7-、または1,4-ジメチルナフタレンを製造する方法を
開示している。また、特表平３−５０００５２号、米国
特許５０１２０２４号には、同様な触媒を用い、反応系
から生成する水素を連続的に除去することで平衡をジメ
チルナフタレン側に有利にする方法が示されている。ま
た、米国特許４９９９３２６号には、同様の触媒を反応
に使用した後、活性の低下した触媒の活性賦活方法が示
されている。2. Description of the Related Art A method for converting a tetrahydronaphthalene compound into a naphthalene compound by dehydrogenation in a liquid phase using a noble metal-supported catalyst powder has long been known as a method for synthesizing substituted naphthalenes. For example, Eberhardt et al.
In rg.Chem., vol. 30 (1965), p82-84, 1,5-, 1,7-, or 1,4-dimethyltetrahydronaphthalene is dehydrogenated in the liquid phase using palladium-supported activated carbon powder as a catalyst. And 1,5-,
A method for producing 1,7- or 1,4-dimethylnaphthalene is disclosed. In addition, Japanese Patent Publication No. 3-500052 and U.S. Pat. No. 5,012,024 disclose a method of using the same catalyst to continuously remove hydrogen generated from the reaction system to make the equilibrium more favorable to the dimethylnaphthalene side. ing. U.S. Pat. No. 4,999,326 discloses a method for activating a catalyst whose activity has been reduced after the use of a similar catalyst in the reaction.
【０００３】一方、気相状態でジメチルテトラヒドロナ
フタレン類を脱水素してジメチルナフタレン類に変換す
る方法も知られている。例えば、特公昭５０−３０６１
６号、米国特許３７８１３７５号には、クロミア・アル
ミナ触媒を用いる方法が示されている。また、特開昭４
８−６７２６１号には、アルミナに担持したレニウムま
たはパラジウム触媒をジメチルテトラヒドロナフタレン
の気相脱水素に用いる方法が示されている。さらに、特
公昭６０−２７６９４号には、白金担持アルミナ触媒を
用いて水素気流中で脱水素する方法が示されている。[0003] On the other hand, a method is also known in which dimethyltetrahydronaphthalenes are dehydrogenated in a gas phase to convert them into dimethylnaphthalenes. For example, Japanese Patent Publication No. 50-3061
No. 6, US Pat. No. 3,781,375 discloses a method using a chromia-alumina catalyst. In addition, JP
8-67261 discloses a method in which a rhenium or palladium catalyst supported on alumina is used for gas phase dehydrogenation of dimethyltetrahydronaphthalene. Further, Japanese Patent Publication No. 60-27694 discloses a method of dehydrogenating in a hydrogen stream using a platinum-supported alumina catalyst.
【０００４】[0004]
【発明が解決しようとする課題】これらのうち貴金属担
持粉末触媒を用いて液相状態でジメチルテトラヒドロナ
フタレン類を脱水素する方法は、反応完結に比較的長い
時間を要し、また、触媒が微粉末であることから生成す
るジメチルナフタレン類と触媒との分離操作が非常に繁
雑であると云う欠点がある。また、パラジウム担持活性
炭触媒を液相状態で反応に用いる場合には、米国特許４
９９９３２６号に記載される如く触媒活性の低下が著し
いために頻繁に触媒再生を繰り返さざるを得ないもので
あり、工業的には満足される方法とはいえない。Among these, the method of dehydrogenating dimethyltetrahydronaphthalenes in a liquid phase using a noble metal-supported powder catalyst requires a relatively long time to complete the reaction, and the catalyst is fine. There is a disadvantage that the operation of separating the dimethylnaphthalenes formed from the powder and the catalyst is very complicated. In the case where a palladium-supported activated carbon catalyst is used in a reaction in a liquid phase, US Pat.
As described in Japanese Patent Application No. 999326, since the catalytic activity is remarkably reduced, the regeneration of the catalyst has to be repeated frequently, which is not industrially satisfactory.
【０００５】一方、気相状態でクロミア・アルミナ触媒
やアルミナに担持したレニウム触媒やパラジウム触媒を
用いて脱水素する方法、白金担持アルミナ触媒を用いて
気相下水素気流中でジメチルテトラヒドロナフタレンを
脱水素する方法は、充分な反応速度を維持するために
は、何れの場合も３５０〜４５０℃程度の高い反応温度
を必要とする。そのため反応中にジメチルナフタレンの
メチル基の移動による異性化、脱メチル化等の副反応が
起こりやすく、また、その反応条件下でジメチルテトラ
ヒドロナフタレン類、ジメチルナフタレン類が重合性を
示し、触媒上でのコークの生成による活性低下が起こり
易いという欠点がある。また、ジメチルテトラヒドロナ
フタレンからジメチルナフタレンへの脱水素反応はかな
り大きな吸熱反応であり、高い反応温度が必要であるこ
とによって工業装置での加熱方式が大きな問題となる。
すなわち、比較的低温の吸熱反応に一般的に用いられる
熱媒油を使用して多管式の等温反応器を用いる加熱方式
は、反応温度が高いために採用することが出来ない。ま
た、より高温の吸熱反応に広く用いられている断熱型の
反応方式を採用しようとすれば、実際に必要な反応温度
よりもかなり高い温度にジメチルテトラヒドロナフタレ
ン類を加熱し、触媒層へ導入する必要があり、そのため
メチル基の異性化や脱メチル化といった副反応が著しく
起こることになって好ましくない。On the other hand, a method of dehydrogenation using a chromia-alumina catalyst or a rhenium catalyst or a palladium catalyst supported on alumina in a gas phase, or dehydration of dimethyltetrahydronaphthalene in a gaseous hydrogen stream using a platinum-supported alumina catalyst. In any case, a high reaction temperature of about 350 to 450 ° C. is required in order to maintain a sufficient reaction rate. Therefore, during the reaction, side reactions such as isomerization and demethylation due to the transfer of the methyl group of dimethylnaphthalene tend to occur, and dimethyltetrahydronaphthalenes and dimethylnaphthalenes show polymerizability under the reaction conditions, and the However, there is a disadvantage that the activity is easily reduced due to the formation of coke. Further, the dehydrogenation reaction from dimethyltetrahydronaphthalene to dimethylnaphthalene is a rather large endothermic reaction, and a high reaction temperature is required, so that a heating method in an industrial apparatus becomes a serious problem.
That is, a heating method using a multitubular isothermal reactor using a heating medium oil generally used for a relatively low-temperature endothermic reaction cannot be adopted due to a high reaction temperature. In order to adopt an adiabatic reaction system widely used for higher temperature endothermic reactions, dimethyltetrahydronaphthalenes are heated to a temperature considerably higher than the actually required reaction temperature and introduced into the catalyst layer. It is necessary, and therefore, side reactions such as isomerization and demethylation of a methyl group occur remarkably, which is not preferable.
【０００６】以上に示したように、従来知られているジ
メチルテトラヒドロナフタレン類からジメチルナフタレ
ン類への脱水素方法は何れも多くの欠点があり、工業的
な方法とはなり得ないのが現状である。本発明者らは、
これら公知法における種々の問題点を解消するため、低
温で十分な反応速度をもってジメチルテトラヒドロナフ
タレン類を脱水素して、対応するジメチルナフタレン
を、長期に安定的に製造する触媒およびプロセスの開発
を目指して検討をおこない、活性炭に担持した白金およ
び／またはパラジウム触媒を用い、希釈媒の存在下気相
状態にて２００〜３５０℃の温度で反応をおこなう方法
を見出し、既に特願平０４ー２３１８９２にて特許出願
を行っている。しかしながら、同特願の方法では、触媒
として高価な貴金属を用いており、工業的な経済性の面
からは、貴金属の使用量を低減すること、或いは非常に
長期の触媒寿命が要求される。この触媒寿命の点から
は、先の方法は必ずしも満足できるものではなく、より
長期に高収率、高選択率を与える触媒およびプロセスの
開発が必要である。 本発明者らは、さらに長期に高活
性、高選択性を維持する触媒およびプロセスの開発を目
指して、先に出願した特許記載の触媒、プロセスの改良
に鋭意取り組み、本発明に到達した。即ち、本発明の目
的は、貴金属触媒を用い、ジメチルテトラヒドロナフタ
レン類を脱水素して対応するジメチルナフタレン類を製
造する方法において、非常に長期に、高収率、高選択率
を維持する触媒およびプロセスを提供することにある。As described above, any of the conventionally known methods for dehydrogenating dimethyltetrahydronaphthalenes to dimethylnaphthalenes have many disadvantages and cannot be industrialized at present. is there. We have:
In order to solve various problems in these known methods, we aim to develop catalysts and processes that stably produce the corresponding dimethylnaphthalene over a long period of time by dehydrogenating dimethyltetrahydronaphthalenes at a sufficient reaction rate at low temperatures. The present inventors have found a method of performing a reaction at a temperature of 200 to 350 ° C. in a gas phase in the presence of a diluent using a platinum and / or palladium catalyst supported on activated carbon. Has filed a patent application. However, in the method of this patent application, an expensive noble metal is used as a catalyst, and from the viewpoint of industrial economy, a reduction in the amount of the noble metal used or a very long catalyst life is required. From the viewpoint of the catalyst life, the above method is not always satisfactory, and it is necessary to develop a catalyst and a process that provide a high yield and a high selectivity over a longer period. The present inventors have worked diligently to improve the catalysts and processes described in the previously applied patents with the aim of developing catalysts and processes that maintain high activity and high selectivity for a longer period of time, and have reached the present invention. That is, an object of the present invention is to use a noble metal catalyst, a method for producing the corresponding dimethylnaphthalenes by dehydrogenating dimethyltetrahydronaphthalenes, for a very long time, a catalyst that maintains a high yield and a high selectivity, and To provide a process.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、ジメチル
テトラヒドロナフタレン類を脱水素してジメチルナフタ
レン類を製造するに際し、非常に長期に、高収率、高選
択率を維持する触媒およびプロセスを開発する目的で鋭
意検討を重ねた結果、活性炭に担持した白金触媒であっ
て、白金表面積が白金１ｇ当たり１００平方メートル以
上であるものを用い、気相状態で、希釈媒の存在下に２
００〜３５０℃で反応を行なうことで、ほぼ定量的に脱
水素反応が進行し、メチル基の移動による異性化、脱メ
チル化、脱アルキル化および不均化等の好ましくない副
反応に由来する副生物は反応液中にほとんど認められ
ず、さらに、非常に長期にわたってほとんど活性変化な
く安定的に反応を継続することが可能であることを見い
だし、本発明に到達した。すなわち本発明はジメチルテ
トラヒドロナフタレン類を脱水素してジメチルナフタレ
ン類を製造するに際し、活性炭に担持した白金触媒であ
り、かつ白金の表面積が白金１ｇ当たり１００平方メー
トル以上である触媒を用い、希釈媒の存在下、２００〜
３００℃の温度で反応をおこなうことを特徴とするもの
である。以下に本発明についてさらに説明する。DISCLOSURE OF THE INVENTION The present inventors have developed a catalyst and a process for maintaining a high yield and a high selectivity for a very long time in producing dimethylnaphthalenes by dehydrogenating dimethyltetrahydronaphthalenes. As a result of diligent studies for the purpose of developing a catalyst, a platinum catalyst supported on activated carbon having a platinum surface area of 100 square meters or more per gram of platinum was used in the gas phase in the presence of a diluent.
By performing the reaction at 00 to 350 ° C., the dehydrogenation reaction proceeds almost quantitatively, and is derived from undesired side reactions such as isomerization, demethylation, dealkylation, and disproportionation due to transfer of a methyl group. By-products were scarcely found in the reaction solution, and it was found that the reaction could be stably continued for a very long time with almost no change in activity, and the present invention was reached. That is, in the present invention, when producing dimethylnaphthalenes by dehydrogenating dimethyltetrahydronaphthalenes, a platinum catalyst supported on activated carbon and having a surface area of platinum of 100 square meters or more per gram of platinum is used as a diluent. In the presence, 200-
The reaction is performed at a temperature of 300 ° C. Hereinafter, the present invention will be further described.
【０００８】本発明の方法には、種々のジメチルテトラ
ヒドロナフタレンの異性体のうち、1,1-ジメチルテトラ
ヒドロナフタレン、2,2-ジメチルテトラヒドロナフタレ
ンを除く全てのジメチルテトラヒドロナフタレン類を使
用することができる。一方、同一の炭素にメチル基が２
つ結合した1,1-ジメチルテトラヒドロナフタレン、2,2-
ジメチルテトラヒドロナフタレンは、脱水素によってジ
メチルナフタレンに変換することができないために、本
発明には使用することができない。これらのジメチルテ
トラヒドロナフタレン類は、種々の方法で製造すること
ができる。 工業的に重要な製造方法としてEberhardt
らの J.Org.Chem., vol.30(1965), p82-84には、アルキ
ルベンゼン類に1,3-ブタジエンをアルカリ金属触媒を用
いて付加し、次いで生成したアルケニルベンゼン類を酸
触媒を用いて環化してジメチルテトラヒドロナフタレン
類を製造する方法が示されている。この方法では、例え
ばo-キシレンと1,3-ブタジエンとから 5-(o-トリル)-2-
ペンテンを経て1,5-ジメチルテトラヒドロナフタレンが
製造され、p-キシレンと1,3-ブタジエンとからは 5-(p-
トリル)-2-ペンテンを経由して1,7-ジメチルテトラヒド
ロナフタレンが製造される。エチルベンゼンからは5-フ
ェニル-2- ヘキセンを経て1,4-ジメチルテトラヒドロナ
フタレンが製造され、m-キシレンと1,3-ブタジエンから
製造される 5-(m-トリル)-2-ペンテンは環化して1,6-ジ
メチルテトラヒドロナフタレンと1,8-ジメチルテトラヒ
ドロナフタレンの混合物に変換することができる。In the method of the present invention, among the various isomers of dimethyltetrahydronaphthalene, all dimethyltetrahydronaphthalenes other than 1,1-dimethyltetrahydronaphthalene and 2,2-dimethyltetrahydronaphthalene can be used. . On the other hand, two methyl groups on the same carbon
1,1-dimethyltetrahydronaphthalene, 2,2-
Dimethyltetrahydronaphthalene cannot be used in the present invention because it cannot be converted to dimethylnaphthalene by dehydrogenation. These dimethyltetrahydronaphthalenes can be produced by various methods. Eberhardt as an industrially important manufacturing method
J. Org. Chem., Vol. 30 (1965), pp. 82-84, add 1,3-butadiene to an alkylbenzene using an alkali metal catalyst, and then add the resulting alkenylbenzene to an acid catalyst. And cyclization to produce dimethyltetrahydronaphthalenes. In this method, for example, 5- (o-tolyl) -2-from o-xylene and 1,3-butadiene is used.
1,5-Dimethyltetrahydronaphthalene is produced via pentene, and p-xylene and 1,3-butadiene are converted to 5- (p-
1,7-Dimethyltetrahydronaphthalene is produced via (tolyl) -2-pentene. 1,4-dimethyltetrahydronaphthalene is produced from ethylbenzene via 5-phenyl-2-hexene, and 5- (m-tolyl) -2-pentene produced from m-xylene and 1,3-butadiene is cyclized. To a mixture of 1,6-dimethyltetrahydronaphthalene and 1,8-dimethyltetrahydronaphthalene.
【０００９】また、ジメチルテトラヒドロナフタレン類
はジメチルナフタレン類の部分水素化によっても製造す
ることができる。この方法はジメチルナフタレン骨格を
新たに創出するものではないが、ジメチルナフタレン類
のメチル基の異性化方法として重要である。すなわち、
ジメチルナフタレンには１０種類の異性体が存在する
が、それらは次の４つの族に分けられ、 Ａ． 1,5-、1,6-、2,6-ジメチルナフタレン、 Ｂ． 1,7-、1,8-、2,7-ジメチルナフタレン、 Ｃ． 1,3-、1,4-、2,3-ジメチルナフタレン、 Ｄ． 1,2-ジメチルナフタレン、 その同一族内での異性化は比較的容易に起こるが、異族
間の異性化はナフタレン環の共鳴構造に由来する禁制の
ために非常に難しいことが知られている。例えば、Ｂ族
からＡ族に異性化する場合に直接異性化触媒と接触させ
ても反応速度が遅く、一方脱メチル化等の副反応が著し
くおこり、好ましい結果を得ることはできない。そのた
め、一旦、Ｂ族のジメチルナフタレン類を部分水素化し
てジメチルテトラヒドロナフタレンとし、禁制の無くな
った状態でメチル基を異性化し、次いで脱水素してジメ
チルナフタレンに戻すことでジメチルナフタレン類の族
間異性化を容易に行なう方法が提案されている（特開昭
４８−７６８５３号、特開昭４８−９６５６９号等）。
このような異族間異性化方法の脱水素工程に対して、
本発明の方法は問題なく適用でき、良好な反応成績と充
分な触媒寿命を得ることができる。ジメチルテトラヒド
ロナフタレン類の製造方法は、ここに挙げた方法に限ら
れるものではなく、種々の方法を採用することができ
る。Further, dimethyltetrahydronaphthalenes can also be produced by partial hydrogenation of dimethylnaphthalenes. Although this method does not newly create a dimethylnaphthalene skeleton, it is important as a method for isomerizing the methyl group of dimethylnaphthalenes. That is,
Dimethylnaphthalene has 10 isomers, which are divided into the following four groups. 1,5-, 1,6-, 2,6-dimethylnaphthalene, B. 1,7-, 1,8-, 2,7-dimethylnaphthalene, C.I. 1,3-, 1,4-, 2,3-dimethylnaphthalene; 1,2-Dimethylnaphthalene, isomerization within the same family occurs relatively easily, but isomerization between heterogeneous groups is known to be very difficult due to forbiddenness due to the resonance structure of the naphthalene ring . For example, in the case of isomerization from Group B to Group A, even if the isomerization catalyst is brought into direct contact with the isomerization catalyst, the reaction rate is low, while side reactions such as demethylation occur remarkably, and a favorable result cannot be obtained. Therefore, once the group B dimethylnaphthalenes are partially hydrogenated to dimethyltetrahydronaphthalene, the methyl group is isomerized in a state where prohibition is eliminated, and then dehydrogenated back to dimethylnaphthalene to obtain the inter-group isomerism of dimethylnaphthalenes. There have been proposed methods for easily carrying out the conversion (JP-A-48-76853, JP-A-48-96569, etc.).
For the dehydrogenation step of such a heterogeneous isomerization method,
The method of the present invention can be applied without any problem, and good reaction results and sufficient catalyst life can be obtained. The method for producing dimethyltetrahydronaphthalenes is not limited to the methods described here, and various methods can be adopted.
【００１０】本発明の方法では、活性炭に担持した粒径
の小さい白金触媒が触媒として用いられる。白金は、脱
水素、水素化、環化等非常に多くの反応に触媒として使
用されている。これら種々の反応の成績に対し、白金の
粒径が影響を与えることは知られており、本反応と類似
のシクロヘキサンを脱水素してベンゼンを製造する反応
に対しては、例えば、触媒講座第５巻、１４４ページ、
１９８５年によれば、一般的に白金粒径の影響はないと
云われている。しかしながら、本発明者らがジメチルテ
トラリンを脱水素してジメチルナフタレンを製造する反
応について白金粒径の影響を調べたところ、白金粒径に
より反応成績、触媒寿命がいずれも影響を受けることが
わかった。そして、白金粒径が小さいとき、活性が高
く、触媒寿命が著しく長くなること、反応成績への影響
は比較的小さいが、触媒寿命への影響は非常に大きいこ
とを見出した。これが本発明を完成させる基礎となって
いる。白金粒径を表す際には、白金単位重量あたりの白
金表面積で表す方法が広く用いられている。この表示法
によれば、白金単位重量あたりの白金表面積が大きいほ
ど白金粒径が小さいことになる。白金表面積と平均白金
粒径との関係は、例えば白金表面積１４０ｍ2/ｇー Ｐｔ
の場合には平均白金粒径約２ｎｍ、白金表面積６０ｍ2/
ｇー Ｐｔ場合には平均白金粒径約５ｎｍに対応する。通
常工業的には白金表面積５０〜８０ｍ2/ｇー Ｐｔ程度の
担持白金触媒が広く用いられている。In the method of the present invention, a platinum catalyst having a small particle diameter supported on activated carbon is used as a catalyst. Platinum has been used as a catalyst in numerous reactions, including dehydrogenation, hydrogenation, and cyclization. It is known that the particle size of platinum has an effect on the performance of these various reactions, and for the reaction similar to this reaction for dehydrogenating cyclohexane to produce benzene, for example, 5 volumes, 144 pages,
According to 1985, it is generally said that there is no effect of the platinum particle size. However, when the present inventors investigated the effect of platinum particle size on the reaction for producing dimethylnaphthalene by dehydrogenating dimethyltetralin, it was found that both the reaction results and the catalyst life were affected by the platinum particle size. . And, when the platinum particle size is small, it has been found that the activity is high, the catalyst life is significantly prolonged, and the effect on the reaction result is relatively small, but the effect on the catalyst life is very large. This is the basis for completing the present invention. When expressing the platinum particle size, a method of expressing the platinum surface area per unit weight of platinum is widely used. According to this notation, the larger the platinum surface area per unit weight of platinum, the smaller the platinum particle size. The relationship between the platinum surface area and the average platinum particle size is, for example, a platinum surface area of 140 m 2 / g-Pt.
In the case of, the average platinum particle diameter is about 2 nm, and the platinum surface area is 60 m 2 /
In the case of g-Pt, this corresponds to an average platinum particle size of about 5 nm. Usually, a supported platinum catalyst having a platinum surface area of about 50 to 80 m 2 / g-Pt is widely used industrially.
【００１１】白金触媒の坦体としては、活性炭以外にア
ルミナ、シリカなどが広く工業的に用いられ、各種脱水
素反応用触媒として使用されているが、本発明の反応に
対しては、このうち活性炭に担持した触媒のみが有利に
用いられる。先の特願平０４ー２３１８９２にて、通常
工業的に用いられている担持白金触媒、即ち白金表面積
が５０〜８０ｍ2/ｇー Ｐｔ程度の担持白金触媒につい
て、白金をアルミナあるいはシリカに担持した触媒は、
活性炭に担持した触媒に比べ、活性が低く、高温が必要
であること、また、異性化、脱メチル化等の副反応が起
こり易く、あるいは反応中の活性変化が大きい欠点があ
ることを示した。アルミナあるいはシリカを担体とした
ときのこれらの欠点は、白金表面積の大きな担持白金触
媒を用いても変化はなく、本発明の白金表面積の大きな
担持白金触媒用の担体としては活性炭のみが有効である
ことがわかった。これは、活性炭の表面積がアルミナ、
シリカに比べ非常に大きいこともあるが、特に白金表面
積の大きな白金を用いた場合、白金と担体との相互作用
が大きくなることも一因である。As a carrier of the platinum catalyst, alumina, silica and the like are widely used industrially in addition to activated carbon, and are used as various dehydrogenation catalysts. Only catalysts supported on activated carbon are advantageously used. In Japanese Patent Application No. 04-231892, a supported platinum catalyst generally used industrially, that is, a supported platinum catalyst having a platinum surface area of about 50 to 80 m2 / g-Pt, in which platinum is supported on alumina or silica Is
Compared to the catalyst supported on activated carbon, it has low activity, requires high temperature, and has the disadvantage that side reactions such as isomerization and demethylation are likely to occur, or the activity change during the reaction is large. . These disadvantages when using alumina or silica as a carrier are the same even when a supported platinum catalyst having a large platinum surface area is used, and only activated carbon is effective as a carrier for a supported platinum catalyst having a large platinum surface area according to the present invention. I understand. This is because activated carbon has a surface area of alumina,
Although it may be much larger than silica, in particular, when platinum having a large platinum surface area is used, one factor is that the interaction between platinum and the carrier becomes large.
【００１２】本発明においては、担持白金触媒の白金表
面積は、白金源、担体の種類、担持方法等の触媒調製方
法により制御することができるが、調製方法によらずに
白金表面積のみに依存する。本発明では、白金１ｇ当た
り１００平方メートル以上、好ましくは１２０平方メー
トル/ ｇー Ｐｔの白金表面積を有する活性炭担持白金触
媒を用いる。白金表面積１００平方メートル/ ｇー Ｐｔ
よりも小さいものも、本反応に対し高い活性を示し、か
つ比較的長期に安定した成績を示すが、白金表面積１０
０平方メートル/ ｇー Ｐｔ以上の触媒に比べると、活
性、寿命共に不十分であり、その為同等の活性、寿命を
実現するためには白金担持量を多くするかまたは触媒の
使用量を多くする必要がある。本発明の触媒坦体として
用いる活性炭は、植物質および鉱物質を原料とする破砕
炭、成型炭、粉末炭等の様々な形態のものを使用するこ
とができる。本発明に用いる触媒の白金の活性炭坦体に
対する担持量は、重量で０．０５〜５％、好ましくは
０．１〜２％の範囲ある。それよりも白金の量が少ない
場合にも活性は示すが、反応速度が小さく実用的ではな
い。一方、それよりも多い場合にも充分な活性を示すこ
とは明らかであるが、触媒費が高価になりすぎて好まし
いものとは云えない。また、触媒中には他の金属成分が
少量含まれていても何等問題なく使用することができ
る。In the present invention, the platinum surface area of the supported platinum catalyst can be controlled by a catalyst preparation method such as a platinum source, a type of a carrier, and a supporting method, but depends only on the platinum surface area without depending on the preparation method. . In the present invention, an activated carbon-supported platinum catalyst having a platinum surface area of 100 square meters or more, preferably 120 square meters / g-Pt per gram of platinum is used. Platinum surface area 100 square meters / g-Pt
Although smaller ones show high activity for this reaction and show stable results for a relatively long time,
Compared to a catalyst of 0 square meters / g-Pt or more, both the activity and the life are insufficient. Therefore, in order to achieve the same activity and life, increase the amount of supported platinum or increase the amount of the catalyst used. There is a need. As the activated carbon used as the catalyst carrier of the present invention, various forms such as crushed charcoal, molded charcoal, powdered charcoal and the like made from plant and mineral substances can be used. The amount of platinum supported on the activated carbon carrier of the catalyst used in the present invention is in the range of 0.05 to 5%, preferably 0.1 to 2% by weight. Although the activity is exhibited when the amount of platinum is smaller than that, the reaction rate is small and not practical. On the other hand, it is apparent that sufficient activity is exhibited when the amount is larger than that, but the catalyst cost becomes too high, which is not preferable. Even if the catalyst contains a small amount of another metal component, it can be used without any problem.
【００１３】本発明においてジメチルテトラヒドロナフ
タレン類からジメチルナフタレン類の脱水素反応は、希
釈媒の存在下に原料であるジメチルテトラヒドロナフタ
レン類および生成物のジメチルナフタレン類が実質的に
気相となるような条件下で行なわれる。液相状態でジメ
チルテトラヒドロナフタレン類と本発明に示す活性炭に
担持した白金触媒とを接触させた場合にも脱水素反応は
起こるが、反応速度は小さく、また経時的に活性が低下
し好ましくない。これに対して気相状態で希釈媒の存在
下に反応を行なう場合には液相状態で反応を行なう場合
に比較して著しい反応速度の向上が見られ、副反応も少
なく、長期間にわたって安定的に高収率で反応を維持す
ることができるようになることを見いだした。In the present invention, the dehydrogenation reaction of dimethyltetrahydronaphthalenes from dimethylnaphthalenes is carried out in such a manner that dimethyltetrahydronaphthalene as a raw material and dimethylnaphthalene as a product are substantially in a gas phase in the presence of a diluent. It is performed under conditions. When dimethyltetrahydronaphthalenes and the platinum catalyst supported on activated carbon shown in the present invention are brought into contact with each other in the liquid phase, the dehydrogenation reaction occurs, but the reaction rate is low and the activity decreases with time, which is not preferable. In contrast, when the reaction is carried out in the presence of a diluent in the gas phase, the reaction rate is significantly improved compared to the case where the reaction is carried out in the liquid phase, and there are few side reactions, and the reaction is stable for a long period of time It has been found that the reaction can be maintained at a high yield.
【００１４】本発明に用いる希釈媒としては、窒素、ア
ルゴン、ヘリウム等の不活性ガスおよび反応条件下にお
いて気体となる脂肪族炭化水素類、芳香族炭化水素類が
挙げられる。希釈媒は単独で用いても、また数種類の希
釈媒を混合して用いることもできる。ここで用いる脂肪
族炭化水素類は、反応条件下において気体となるもので
あって、生成物であるジメチルナフタレン類よりも沸点
が低いものが好ましく用いられる。具体的には炭素数１
から１５の直鎖および分岐したパラフィン類が用いら
れ、特に好ましいのは生成物である水素およびジメチル
ナフタレン類との分離が容易である炭素数６から１０の
直鎖および分岐したパラフィン類である。本発明で希釈
媒に用いる芳香族炭化水素類は、反応条件下において気
体となるもので、生成物であるジメチルナフタレン類よ
りも沸点が低く、室温において液体であるものが特に好
ましく用いられる。具体的にはベンゼン、トルエン、o-
キシレン、m-キシレン、p-キシレン、エチルベンゼン、
プソイドキュメン、メシチレン、n-プロピルベンゼン、
キュメン等が挙げられる。本発明に用いる希釈媒の使用
量は、原料であるジメチルテトラヒドロナフタレンに対
してモル比で０．１〜１００、好ましくは０．５〜２０
である。Examples of the diluting medium used in the present invention include inert gases such as nitrogen, argon and helium, and aliphatic hydrocarbons and aromatic hydrocarbons which become gas under the reaction conditions. The diluents can be used alone or as a mixture of several types. The aliphatic hydrocarbons used here are gaseous under the reaction conditions, and those having a boiling point lower than that of the product dimethylnaphthalene are preferably used. Specifically, carbon number 1
To 15 straight-chain and branched paraffins are used, and particularly preferred are straight-chain and branched paraffins having 6 to 10 carbon atoms which can be easily separated from the product hydrogen and dimethylnaphthalenes. Aromatic hydrocarbons used as a diluent in the present invention are gaseous under reaction conditions, and those having a boiling point lower than that of dimethylnaphthalene as a product and being liquid at room temperature are particularly preferably used. Specifically, benzene, toluene, o-
Xylene, m-xylene, p-xylene, ethylbenzene,
Pseudocumen, mesitylene, n-propylbenzene,
Cumen and the like. The amount of the diluent used in the present invention is 0.1 to 100, preferably 0.5 to 20 in molar ratio to dimethyltetrahydronaphthalene as a raw material.
It is.
【００１５】本発明の反応を実施するに当っての反応方
式としては、反応原料を気相状態で固体状の触媒と接触
させることのできる方式、例えば固定層方式、移動層方
式、流動層方式等の種々の反応方式を採用することがで
きる。このうち特に好ましいのは触媒を反応管に充填
し、原料を流通させる固定層方式の反応方式である。本
発明の方法における脱水素反応は、２００〜３５０℃の
範囲で実施するのが好ましく、さらに好ましくは２４０
〜３００℃の範囲である。この温度範囲であれば熱媒油
による加熱が可能であり、工業操作上きわめて好適なプ
ロセスを構築することができる。３５０℃よりも反応温
度が高い場合にはジメチルテトラヒドロナフタレン類お
よびジメチルナフタレン類の脱アルキル化、異性化、重
合反応などの副反応が顕著に起こり、また、触媒の活性
低下が著しく好ましくない。この高温下での副反応の増
大は活性金属である白金が高温において種々の好ましく
ない反応を引き起こすと同時に、担体に用いている活性
炭が高温下において様々な反応活性を発現することによ
るものである。活性炭は種々の表面官能基を有してお
り、高温下で炭化水素類の脱アルキル化、脱水素等の反
応の触媒となることは従来から知られている。一方、２
００℃より反応温度が低い場合には充分な反応速度を得
ることができず、好ましくない。As a reaction system for carrying out the reaction of the present invention, a system in which a reaction raw material can be brought into contact with a solid catalyst in a gaseous state, for example, a fixed bed system, a moving bed system, a fluidized bed system And various other reaction systems. Among them, particularly preferred is a fixed bed type reaction system in which a catalyst is filled in a reaction tube and a raw material is circulated. The dehydrogenation reaction in the method of the present invention is preferably performed at a temperature in the range of 200 to 350 ° C, more preferably 240 to 350 ° C.
~ 300 ° C. In this temperature range, heating with a heating medium oil is possible, and a process extremely suitable for industrial operation can be constructed. When the reaction temperature is higher than 350 ° C., side reactions such as dealkylation, isomerization, and polymerization of dimethyltetrahydronaphthalenes and dimethylnaphthalenes occur remarkably, and a decrease in the activity of the catalyst is not preferred. This increase in side reactions at high temperatures is due to the fact that platinum, which is an active metal, causes various undesired reactions at high temperatures, and the activated carbon used as a carrier exhibits various reaction activities at high temperatures. . Activated carbon has various surface functional groups, and it has been conventionally known that it can act as a catalyst for reactions such as dealkylation and dehydrogenation of hydrocarbons at high temperatures. Meanwhile, 2
If the reaction temperature is lower than 00 ° C., a sufficient reaction rate cannot be obtained, which is not preferable.
【００１６】本発明で反応を実施する圧力は、絶対圧で
０．１気圧から１０気圧の範囲が好ましく、より好まし
くは０．５気圧から３気圧の範囲である。なお、反応温
度と反応圧力は上記範囲内で、原料であるジメチルテト
ラヒドロナフタレン類およびジメチルナフタレン類が希
釈媒の存在下において気相状態となるように選択される
べきものである。本発明で原料であるジメチルテトラヒ
ドロナフタレン類の供給速度は、時間あたり触媒重量に
対して０．１〜１０倍重量が好ましく、より好ましくは
０．２〜５倍重量である。The pressure at which the reaction is carried out in the present invention is preferably in the range of 0.1 to 10 atm in absolute pressure, more preferably in the range of 0.5 to 3 atm. The reaction temperature and reaction pressure should be selected within the above ranges so that the starting materials dimethyltetrahydronaphthalenes and dimethylnaphthalenes are in a gas phase in the presence of a diluent. The feed rate of dimethyltetrahydronaphthalene as a raw material in the present invention is preferably 0.1 to 10 times, more preferably 0.2 to 5 times, the weight of the catalyst per hour.
【００１７】[0017]
【発明の効果】本発明の方法により、ジメチルテトラヒ
ドロナフタレン類を脱水素して工業的に有用なジメチル
ナフタレン類を高収率かつ高選択率で、さらに長期にわ
たって安定的に製造できるものであり、その工業的意義
は大きい。According to the method of the present invention, industrially useful dimethylnaphthalenes can be stably produced over a long period of time by dehydrogenating dimethyltetrahydronaphthalenes with high yield and high selectivity. Its industrial significance is great.
【００１８】[0018]
【実施例】以下に実施例にて本発明を具体的に説明する
が、本発明はこれら実施例に限定されるものではない。
各実施例中では、ジメチルテトラヒドロナフタレンをＤ
ＭＴ、ジメチルナフタレンをＤＭＮと略記した。 ま
た、白金表面積をＭＳＡと略記した。その単位はｍ2/ｇ
ー Ｐｔである。なお、当該脱水素反応による軽沸分、高
沸分の生成はほとんど観察されないことから、反応率、
収率及び選択率は反応前後の液成分のモル数が変わらな
いものとして、原料液および生成液の組成からそれぞれ
次のようにして求めた。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In each example, dimethyltetrahydronaphthalene was replaced with D
MT and dimethylnaphthalene are abbreviated as DMN. The platinum surface area is abbreviated as MSA. Its unit is m 2 / g
-Pt. In addition, since the formation of light boiling components and high boiling components by the dehydrogenation reaction is hardly observed, the reaction rate,
The yield and selectivity were determined as follows from the compositions of the raw material liquid and the product liquid, assuming that the number of moles of the liquid component before and after the reaction did not change.
【００１９】実施例１ 内径13mmφ、長さ 350mmＬの石英ガラス製反応管に、0.
5 〜1.0mm に粒度を揃えた0.5wt%白金／活性炭触媒（Ｎ
Ｅケムキャット社製、ＭＳＡ＝１７１）4.0gを充填し
た。触媒層の上部にはガラスビーズを 200mmの高さで充
填した。反応管を280 ℃に加熱し、ガラスビーズの上か
ら表１に示すような1,5-ジメチルテトラリンを主成分と
する原料液の32％n-ヘプタン溶液を７g/時の供給速度で
供給し、脱水素反応を行った。反応は約4000時間継続し
た。各通液時間での反応成績を表１にまとめて示す。 Example 1 A quartz glass reaction tube having an inner diameter of 13 mmφ and a length of 350 mmL was placed in a quartz tube.
0.5wt% platinum / activated carbon catalyst (N
E Chemcat, MSA = 171) 4.0 g was filled. The upper part of the catalyst layer was filled with glass beads at a height of 200 mm. The reaction tube was heated to 280 ° C., and a 32% n-heptane solution of a raw material liquid containing 1,5-dimethyltetralin as a main component as shown in Table 1 was supplied at a supply rate of 7 g / hour from the top of the glass beads. A dehydrogenation reaction was performed. The reaction lasted about 4000 hours. Table 1 summarizes the reaction results at each passing time.
【００２０】実施例２ 0.5wt%白金/ 活性炭触媒（ＭＳＡ＝１７１）の代りに1%
白金／活性炭触媒（ＮＥケムキャット社製、ＭＳＡ＝１
３２）を用いたこと以外は実施例１と同様に反応を行
い、活性の変化を調べた。結果を表２に示す。 Example 2 1% instead of 0.5 wt% platinum / activated carbon catalyst (MSA = 171)
Platinum / activated carbon catalyst (NE Chemcat, MSA = 1
A reaction was carried out in the same manner as in Example 1 except that 32) was used, and a change in activity was examined. Table 2 shows the results.
【００２１】実施例３ 表３に示すような1,5-ジメチルテトラヒドロナフタレン
の３２％n-ヘプタン溶液を１９ｇ/ 時の供給速度で供給
した以外は実施例１と同様に反応を行った。結果を表３
に示す。 Example 3 A reaction was carried out in the same manner as in Example 1 except that a 32% solution of 1,5-dimethyltetrahydronaphthalene in n-heptane as shown in Table 3 was supplied at a supply rate of 19 g / hour. Table 3 shows the results
Shown in
【００２２】比較例１ 0.5wt%白金/ 活性炭触媒（ＭＳＡ＝１７１）の代わりに
0.5wt%白金／活性炭触媒（ＮＥケムキャット社製、ＭＳ
Ａ＝８０）を用いたこと以外は実施例３と同様に反応を
行い、活性を調べた。 結果を実施例３と比較して表３
に示す。白金表面積の小さい白金／活性炭触媒を用いる
場合にも反応初期には白金表面積の大きい触媒とほぼ同
等の反応成績が得られるが、活性低下が大きいことがわ
かる。COMPARATIVE EXAMPLE 1 Instead of 0.5 wt% platinum / activated carbon catalyst (MSA = 171)
0.5wt% platinum / activated carbon catalyst (NE Chemcat, MS
The reaction was carried out in the same manner as in Example 3 except that A = 80) was used, and the activity was examined. Table 3 compares the results with Example 3.
Shown in Even when a platinum / activated carbon catalyst having a small platinum surface area is used, almost the same reaction results as those of a catalyst having a large platinum surface area can be obtained in the initial stage of the reaction, but it can be seen that the activity is greatly reduced.
【００２３】実施例４ 内径17mmφ、長さ 300mmＬのステンレス製反応管に、1.
0 〜2.63mmに揃えた0.5wt%白金/ 活性炭触媒（ＮＥケム
キャット社製、ＭＳＡ＝１７１）を 10g充填し、窒素を
通じながら 290℃に加熱した。反応管内部の圧力を0.5k
g/cm2Gに保ち窒素ガス 20cc/分と同時に表１に示す組成
の原料液を10g/時の速度で導入し、反応成績を調べた。
この反応条件では反応液はすべて気化し、反応は気相状
態で行われている。結果を表４に示す。 Example 4 A stainless steel reaction tube having an inner diameter of 17 mmφ and a length of 300 mmL was placed in a stainless steel reaction tube.
10 g of 0.5 wt% platinum / activated carbon catalyst (MSA = 171, manufactured by NE Chemcat) adjusted to 0 to 2.63 mm was charged and heated to 290 ° C. while passing nitrogen. 0.5k pressure inside the reaction tube
The raw material liquid having the composition shown in Table 1 was introduced at a rate of 10 g / hour at the same time as 20 cc / min of nitrogen gas while maintaining the g / cm 2 G, and the reaction results were examined.
Under these reaction conditions, all of the reaction solution is vaporized, and the reaction is performed in a gas phase. Table 4 shows the results.
【００２４】比較例２ 反応管内部の圧力を5.0kg/cm2Gとし、窒素ガスを導入し
なかったこと以外は実施例４と同様にして反応を行っ
た。 この条件では反応液は液体の状態を保っている。
結果を実施例４と比較して表４に示す。 Comparative Example 2 A reaction was carried out in the same manner as in Example 4 except that the pressure inside the reaction tube was 5.0 kg / cm 2 G and nitrogen gas was not introduced. Under these conditions, the reaction liquid is kept in a liquid state.
The results are shown in Table 4 in comparison with Example 4.
【００２５】実施例５ 内径 8mmφ、長さ 300mmＬのパイレックスガラス製反応
管に、実施例２で用いた触媒と同一の触媒1.0gを充填し
た。触媒層の上部にはα−アルミナ球を 150mmの高さで
充填した。反応管を 280℃に加熱し、α−アルミナ球の
上から表５に示すような1,5-ＤＭＴを主成分とする原料
液の 32%n-ヘプタン溶液を1.56g/時の供給速度で供給
し、脱水素反応を行った。 反応は約500 時間継続し
た。各通液時間での反応成績を表５に示す。 Example 5 A reaction tube made of Pyrex glass having an inner diameter of 8 mmφ and a length of 300 mmL was filled with 1.0 g of the same catalyst as used in Example 2. The upper portion of the catalyst layer was filled with α-alumina spheres at a height of 150 mm. The reaction tube was heated to 280 ° C., and a 32% n-heptane solution of a raw material liquid containing 1,5-DMT as a main component as shown in Table 5 was supplied from above the α-alumina spheres at a supply rate of 1.56 g / hour. The mixture was supplied to perform a dehydrogenation reaction. The reaction lasted about 500 hours. Table 5 shows the reaction results at each passing time.
【００２６】比較例３〜４ 0.5％白金／アルミナ触媒（ＭＳＡ＝１３８）、0.5 ％
白金／シリカ触媒（ＭＳＡ＝１４２）を用いたこと以外
は実施例５と同様に反応を行い活性の変化を調べた。各
通液時間での反応成績を実施例５と比較して表５に示
す。 Comparative Examples 3-4 0.5% platinum / alumina catalyst (MSA = 138), 0.5%
A reaction was carried out in the same manner as in Example 5 except that a platinum / silica catalyst (MSA = 142) was used, and a change in activity was examined. Table 5 shows the results of the reaction at each liquid passing time in comparison with Example 5.
【００２７】実施例６ 表１に示す1,5-ジメチルテトラリンを主成分とする原料
液の 32%n-ヘプタン溶液の代わりに、表６に示す1,5-ジ
メチルテトラリンを主成分とする原料液の 32%トルエン
溶液を用いた以外は実施例１と同様に反応を行った。反
応は約2000時間継続した。各通液時間での反応成績を表
６に示す。 Example 6 Instead of a 32% n-heptane solution of a raw material liquid containing 1,5-dimethyltetralin as a main component shown in Table 1, a raw material containing 1,5-dimethyltetraline as a main component shown in Table 6 was used. The reaction was carried out in the same manner as in Example 1 except that a 32% toluene solution of the solution was used. The reaction lasted about 2000 hours. Table 6 shows the reaction results at each passing time.
【００２８】[0028]
【表１】 ──────────────────────────────────── 原料組成 反応時間 0〜2000時間 1,5-+1,8-DMT 95.2%, 1,6-+1,7-DMT 1.0% 1,5-DMN 0.3%, 1,6-DMN 0.04%, 軽沸分 3.5% 反応時間 2000 時間以降 1,5-+1,8-DMT 97.9%, 1,6-+1,7-DMT 0.2% 1,5-DMN 0.2%, 1,6-DMN 0%, 軽沸分 1.7% ──────────────────────────────────── 通液時間(hr) 65 380 1170 2154 3380 4107 ──────────────────────────────────── 温度( ℃) 280 280 280 280 280 280 原料組成( ％) 1,5-+1,8-DMT 95.2 95.2 95.2 97.9 97.9 97.9 1,6-+1,7-DMT 1.0 1.0 1.0 0.2 0.2 0.2 1,5-DMN 0.3 0.3 0.3 0.2 0.2 0.2 1,6-DMN 0.04 0.04 0.04 0 0 0 軽沸 3.5 3.5 3.5 1.7 1.7 1.7 ──────────────────────────────────── DMN 収率( ％) 1,5-DMN 97.9 98.3 98.1 98.7 98.5 98.4 1,6-DMN+ 1.1 1.0 1.0 0.2 0.2 0.2 1,7-DMN 1,8-DMN 0.3 0.2 0.3 0.3 0.3 0.2 反応率( ％) 99.5 99.6 99.5 99.3 99.1 98.8 DMN 選択率( ％) 99.8 99.9 99.9 99.9 99.9 99.9 ────────────────────────────────────[Table 1] 原料 Raw material composition Reaction time 0-2000 hours 1, 5- + 1,8-DMT 95.2%, 1,6- + 1,7-DMT 1.0% 1,5-DMN 0.3%, 1,6-DMN 0.04%, light boiling point 3.5% , 5- + 1,8-DMT 97.9%, 1,6- + 1,7-DMT 0.2% 1,5-DMN 0.2%, 1,6-DMN 0%, light boiling 1.7% ───── ─────────────────────────────── Flow time (hr) 65 380 1170 2154 3380 4107 ─────── ───────────────────────────── Temperature (° C) 280 280 280 280 280 280 Raw material composition (%) 1,5- + 1 , 8-DMT 95.2 95.2 95.2 97.9 97.9 97.9 1,6- + 1,7-DMT 1.0 1.0 1.0 0.2 0.2 0.2 1,5-DMN 0.3 0.3 0.3 0.2 0.2 0.2 1,6-DMN 0.04 0.04 0.04 0 0 0 3.5 3.5 3.5 1.7 1.7 1.7 ──────────────────────────────────── DMN yield (%) 1, 5-DMN 97.9 98.3 98.1 98.7 98.5 98.4 1,6-DMN + 1.1 1.0 1.0 0.2 0.2 0.2 1,7-DMN 1,8-DMN 0.3 0.2 0.3 0.3 0.3 0.2 Reaction rate (%) 99.5 99.6 99.5 99.3 99.1 98.8 DMN selectivity (%) 99.8 99.9 99.9 99.9 99.9 99.9 ────────────────────────────────────
【００２９】[0029]
【表２】 ──────────────────────────────────── 原料組成 1,5-+1,8-DMT 94.3%, 1,6-+1,7-DMT 2.0% 1,5-DMN 1.0%, 1,6-DMN 0.1%, 軽沸分 2.6% ──────────────────────────────────── 通液時間(hr) 85 350 1050 1970 3240 4300 温度( ℃) 280 280 280 280 280 280 ──────────────────────────────────── DMN 収率( ％) 1,5-DMN 96.5 96.9 96.7 96.6 96.5 96.4 1,6-DMN 2.0 2.0 2.1 1.9 1.9 1.9 + 1,7-DMN 1,8-DMN 0.5 0.5 0.5 0.4 0.5 0.4 反応率( ％) 99.0 99.5 99.3 99.0 99.0 98.7 DMN 選択率( ％) 100 99.9 100 99.9 99.9 100 ────────────────────────────────────[Table 2] 原料 Raw material composition 1,5- + 1,8 -DMT 94.3%, 1,6- + 1,7-DMT 2.0% 1,5-DMN 1.0%, 1,6-DMN 0.1%, light boiling 2.6% ──────────── ──────────────────────── Flow time (hr) 85 350 1050 1970 3240 4300 Temperature (° C) 280 280 280 280 280 280 280 ──────────────────────────────── DMN yield (%) 1,5-DMN 96.5 96.9 96.7 96.6 96.5 96.4 1 , 6-DMN 2.0 2.0 2.1 1.9 1.9 1.9 + 1,7-DMN 1,8-DMN 0.5 0.5 0.5 0.4 0.5 0.4 Reaction rate (%) 99.0 99.5 99.3 99.0 99.0 98.7 DMN selectivity (%) 100 99.9 100 99.9 99.9 100 ────────────────────────────────────
【００３０】[0030]
【表３】 ──────────────────────────────────── 原料組成 1,5-+1,8-DMT 95.1%, 1,6-+1,7-DMT 0.8% 1,5-DMN 0.2%, 1,6-DMN 0.1%, 軽沸分 3.8% ──────────────────────────────────── 実施例３ 比較例１ 通液時間(hr) 25 188 415 22 170 385 温度( ℃) 280 280 280 280 280 280 ──────────────────────────────────── DMN 収率( ％) 1,5-DMN 96.6 94.8 92.2 95.3 88.3 80.5 1,6-DMN+ 0.8 0.7 0.7 0.8 0.7 0.7 1,7-DMN 1,8-DMN 0.3 0.3 0.2 0.3 0.2 0.2 反応率( ％) 97.7 95.8 93.1 96.4 89.2 81.4 DMN選択率( ％) 100 100 100 100 100 100 ────────────────────────────────────[Table 3] 原料 Raw material composition 1,5- + 1,8 -DMT 95.1%, 1,6- + 1,7-DMT 0.8% 1,5-DMN 0.2%, 1,6-DMN 0.1%, light boiling 3.8% ──────────── ──────────────────────── Example 3 Comparative Example 1 Flow time (hr) 25 188 415 22 170 385 Temperature (° C) 280 280 280 280 280 280 ──────────────────────────────────── DMN yield (%) 1,5-DMN 96.6 94.8 92.2 95.3 88.3 80.5 1,6-DMN + 0.8 0.7 0.7 0.8 0.7 0.7 1,7-DMN 1,8-DMN 0.3 0.3 0.2 0.3 0.2 0.2 Reaction rate (%) 97.7 95.8 93.1 96.4 89.2 81.4 DMN selectivity (%) 100 100 100 100 100 100 ────────────────────────────────────
【００３１】[0031]
【表４】 ────────────────────────────── 原料組成 1,5-+1,8-DMT 93.7%, 1,6-+1,7-DMT 1.2% 1,5-DMN 1.7%, 1,6-DMN 0.2%, 軽沸分 3.2% ────────────────────────────── 実施例４ 比較例２ 温度( ℃) 290 290 圧力(kg/cm2G) 0.5 5.0 N2導入量(cc/min) 20 0 反応相 気相 液相 ────────────────────────────── 通液時間 20 時間での成績 DMN収率( ％) 1,5-DMN 96.1 82.5 1,6-DMN 1.4 1.1 + 1,7-DMN 1,8-DMN 0.3 0.3 反応率( ％) 98.0 84.2 選択率( ％) 99.8 99.6 ──────────────────────────────[Table 4] 原料 Raw material composition 1,5- + 1,8-DMT 93.7%, 1 , 6- + 1,7-DMT 1.2% 1,5-DMN 1.7%, 1,6-DMN 0.2%, light boiling 3.2% ────────────────── ──────────── Example 4 Comparative Example 2 Temperature (℃) 290 290 Pressure (kg / cm2G) 0.5 5.0 N2 introduction amount (cc / min) 200 0 Reaction phase Gas phase Liquid phase ──成績 Performance after 20 hours DMN yield (%) 1,5-DMN 96.1 82.5 1 , 6-DMN 1.4 1.1 + 1,7-DMN 1,8-DMN 0.3 0.3 Reaction rate (%) 98.0 84.2 Selectivity (%) 99.8 99.6 ───────────────── ─────────────
【００３２】[0032]
【表５】 ──────────────────────────────────── 原料組成 1,5-+1,8-DMT 95.1%, 1,6-+1,7-DMT 0.9%, 1,5-DMN 0.5% 1,6-DMN 0.2 軽沸分 3.3% ──────────────────────────────────── 実施例５ 比較例３ 比較例４ 触媒 0.5%Pt/ 活性炭 0.5%Pt/Al2O3 0.5%Pt/SiO2 ──────────────────────────────────── 通液時間(hr) 20 85 480 10 32 3 28 温度( ℃) 270 270 270 270 270 270 270 ──────────────────────────────────── DMN収率( ％) 1,5-DMN 97.5 97.6 97.5 97.2 86.9 96.9 87.4 1,6-DMN+ 0.9 1.0 1.0 0.8 0.7 0.6 0.6 1,7-DMN 1,8-DMN 0.3 0.3 0.2 0.3 0.2 0.2 0.2 反応率( ％) 98.8 99.0 98.8 98.4 87.8 97.9 88.3 DMN 選択率( ％) 99.9 99.9 99.9 99.9 100 99.8 99.9 ────────────────────────────────────[Table 5] 原料 Raw material composition 1,5- + 1,8 -DMT 95.1%, 1,6- + 1,7-DMT 0.9%, 1,5-DMN 0.5% 1,6-DMN 0.2 Light boiling 3.3% ────────────── ────────────────────── Example 5 Comparative Example 3 Comparative Example 4 Catalyst 0.5% Pt / Activated carbon 0.5% Pt / Al 2 O 3 0.5% Pt / SiO 2 ──────────────────────────────────── Flow time (hr) 20 85 480 10 32 3 28 Temperature (° C) 270 270 270 270 270 270 270 270 ──────────────────────────────────── DMN yield (%) 1,5-DMN 97.5 97.6 97.5 97.2 86.9 96.9 87.4 1,6-DMN + 0.9 1.0 1.0 0.8 0.7 0.6 0.6 1,7-DMN 1,8-DMN 0.3 0.3 0.2 0.3 0.2 0.2 0.2 Reaction rate (%) 98.8 99.0 98.8 98.4 87.8 97.9 88.3 DMN selectivity (%) 99.9 99.9 99.9 99.9 100 99.8 99.9 ────────────── ──────────────────────
【００３３】[0033]
【表６】 ──────────────────────────────────── 原料組成 1,5-+1,8-DMT 93.0%, 1,6-+1,7-DMT 0.8%, 1,5-DMN 0.3% 1,6-DMN 0.2%, 軽沸分 5.7% ──────────────────────────────────── 通液時間(hr) 48 270 625 1020 2015 温度( ℃) 280 280 280 280 280 ──────────────────────────────────── DMN 収率( ％) 1,5-DMN 98.5 98.6 98.4 98.3 98.2 1,6-DMN+ 0.9 0.8 0.8 0.8 0.7 1,7-DMN 1,8-DMN 0.2 0.2 0.2 0.2 0.2 反応率( ％) 99.6 99.6 99.5 99.4 99.2 DMN 選択率( ％) 100 100 99.9 99.9 99.9 ────────────────────────────────────[Table 6] 原料 Raw material composition 1,5- + 1,8 -DMT 93.0%, 1,6- + 1,7-DMT 0.8%, 1,5-DMN 0.3% 1,6-DMN 0.2%, light boiling point 5.7% ──────────── ──────────────────────── Flow time (hr) 48 270 625 1020 2015 Temperature (° C) 280 280 280 280 280 ────── ────────────────────────────── DMN yield (%) 1,5-DMN 98.5 98.6 98.4 98.3 98.2 1,6- DMN + 0.9 0.8 0.8 0.8 0.7 1,7-DMN 1,8-DMN 0.2 0.2 0.2 0.2 0.2 Reaction rate (%) 99.6 99.6 99.5 99.4 99.2 DMN selectivity (%) 100 100 99.9 99.9 99.9 ──────── ────────────────────────────
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 15/24 B01J 23/42 B01J 35/10 C07C 5/367 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) C07C 15/24 B01J 23/42 B01J 35/10 C07C 5/367
Claims (3)
素してジメチルナフタレン類を製造するに際し、白金表
面積が白金１ｇ当り１００平方メートル以上である、活
性炭に担持した白金触媒を用い、気相状態で、希釈媒の
存在下に２００〜３５０℃の温度で反応を行なうことを
特徴とするジメチルナフタレン類の製造方法。1. A method for producing dimethylnaphthalenes by dehydrogenating dimethyltetrahydronaphthalenes, using a platinum catalyst supported on activated carbon having a platinum surface area of 100 square meters or more per gram of platinum, using a diluent in a gas phase. Wherein the reaction is carried out at a temperature of 200 to 350 ° C. in the presence of dimethylnaphthalene.
不活性気体である請求項１記載の方法。2. The method according to claim 1, wherein the diluting medium is an inert gas such as nitrogen, argon and helium.
脂肪族炭化水素類、芳香族炭化水素類である請求項１記
載の方法。3. The method according to claim 1, wherein the diluting medium is an aliphatic hydrocarbon or an aromatic hydrocarbon which becomes a gas under the reaction conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5222448A JP2900970B2 (en) | 1993-09-07 | 1993-09-07 | Method for dehydrogenation of dimethyltetralin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5222448A JP2900970B2 (en) | 1993-09-07 | 1993-09-07 | Method for dehydrogenation of dimethyltetralin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0776532A JPH0776532A (en) | 1995-03-20 |
| JP2900970B2 true JP2900970B2 (en) | 1999-06-02 |
Family
ID=16782568
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5222448A Expired - Lifetime JP2900970B2 (en) | 1993-09-07 | 1993-09-07 | Method for dehydrogenation of dimethyltetralin |
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| JP (1) | JP2900970B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2813304B1 (en) * | 2000-08-23 | 2002-11-29 | Inst Francais Du Petrole | PROCESS FOR DEHYDROGENATION OF ORGANIC COMPOUNDS IN THE PRESENCE OF A SUPPORTED BIMETALLIC CATALYST HAVING A STRONG INTERACTION BETWEEN A GROUP VIII METAL AND TIN |
| JP2006070000A (en) * | 2004-09-06 | 2006-03-16 | Mitsubishi Gas Chem Co Inc | Preparation method of dimethyl naphthalenedicarboxylate |
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1993
- 1993-09-07 JP JP5222448A patent/JP2900970B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0776532A (en) | 1995-03-20 |
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