JPH0499736A - Production of dimethylnaphthalene isomer mixture containing concentrated 2,6-dimethylnaphthalene - Google Patents
Production of dimethylnaphthalene isomer mixture containing concentrated 2,6-dimethylnaphthaleneInfo
- Publication number
- JPH0499736A JPH0499736A JP21847590A JP21847590A JPH0499736A JP H0499736 A JPH0499736 A JP H0499736A JP 21847590 A JP21847590 A JP 21847590A JP 21847590 A JP21847590 A JP 21847590A JP H0499736 A JPH0499736 A JP H0499736A
- Authority
- JP
- Japan
- Prior art keywords
- dimethylnaphthalene
- concentration
- isomer mixture
- type zeolite
- isomer
- 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.)
- Granted
Links
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 title claims abstract description 55
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical class C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 25
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000012013 faujasite Substances 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 239000011973 solid acid Substances 0.000 claims abstract description 8
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 238000011282 treatment Methods 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 150000003752 zinc compounds Chemical class 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000010555 transalkylation reaction Methods 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
- SDDBCEWUYXVGCQ-UHFFFAOYSA-N 1,5-dimethylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1C SDDBCEWUYXVGCQ-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
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000013375 chromatographic separation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- ZDPJODSYNODADV-UHFFFAOYSA-N 1,2,3,4-tetramethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=C(C)C(C)=C21 ZDPJODSYNODADV-UHFFFAOYSA-N 0.000 description 1
- XYTKCJHHXQVFCK-UHFFFAOYSA-N 1,3,8-trimethylnaphthalene Chemical compound CC1=CC=CC2=CC(C)=CC(C)=C21 XYTKCJHHXQVFCK-UHFFFAOYSA-N 0.000 description 1
- 239000005967 1,4-Dimethylnaphthalene Substances 0.000 description 1
- INUWBHWKAMVTNU-UHFFFAOYSA-N 1-ethyl-2-methylnaphthalene Chemical compound C1=CC=C2C(CC)=C(C)C=CC2=C1 INUWBHWKAMVTNU-UHFFFAOYSA-N 0.000 description 1
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-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
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 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
- RJTJVVYSTUQWNI-UHFFFAOYSA-N beta-ethyl naphthalene Natural products C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野１
本発明はジメチルナフタレン異性体混合物の製造方法に
関するものであり、より詳しくは、２，６−ジメチルナ
フタレンの濃度を高めたジメチルナフタレン異性体混合
物の製造方法に関するものである。Detailed Description of the Invention [Industrial Application Field 1] The present invention relates to a method for producing a dimethylnaphthalene isomer mixture, and more specifically, a dimethylnaphthalene isomer mixture with an increased concentration of 2,6-dimethylnaphthalene. The present invention relates to a manufacturing method.
［従来の技術］
ジメチルナフタレン、例えば、２，６−ジメチルナフタ
レンは耐熱性およびガスバリアー性の高いポリエチレン
ナフタレート（ＰＥＮ）等の原料として使用され、ジメ
チルナフタレン異性体混合物を主要成分として含有する
原料油から分離されている。[Prior Art] Dimethylnaphthalene, for example, 2,6-dimethylnaphthalene, is used as a raw material for polyethylene naphthalate (PEN), etc., which has high heat resistance and gas barrier properties, and is a raw material containing a dimethylnaphthalene isomer mixture as a main component. Separated from oil.
ジメチルナフタレンは２つのメチル基がナフタレン骨格
に結合した化合物であり、種々の異性体が存在する。従
って、個々の異性体の濃度は低く、必要とする異性体の
分離後の異性体混合物の有効利用が必要であった。例え
ば、２，６−ジメチルナフタレンの全ジメチル体中に占
める熱力学的平衡濃度は１４％程度であり、これを分離
した後のラフィネートを有効利用するため、２，６−ジ
メチル体濃度を高めるための異性化あるいはトランスア
ルキル化等の変換反応が必要であった。Dimethylnaphthalene is a compound in which two methyl groups are bonded to a naphthalene skeleton, and various isomers exist. Therefore, the concentration of each isomer is low, and it is necessary to effectively utilize the isomer mixture after separation of the required isomers. For example, the thermodynamic equilibrium concentration of 2,6-dimethylnaphthalene in all dimethyl forms is about 14%, and in order to effectively utilize the raffinate after separating this, it is necessary to increase the concentration of 2,6-dimethyl forms. Conversion reactions such as isomerization or transalkylation were required.
かかる異性化あるいはトランスアルキル化反応は、１つ
の分子内の置換アルキル基の移動や二種の分子間の置換
アルキル基の移動に関するものであり、通常、アルミノ
シリケート、七オライド等の種々の固体酸触媒（例えば
、Ｋｏｚｏ Ｔａｎａｂｅ ｅｔａｌ、、”Ｎｅｗ ５
ｏｌｉｄ Ａｃ１ｄｓ ａｎｄ Ｂａ５ｅｓ” Ｋｏｄ
ａｎｓｈａ −Ｅｌｓｅｖｉｅｒ、 １９８９ 等参照
）あるいは塩化アルミニウム等の金属ハロゲン化物から
なるルイス酸触媒を用いて水素雰囲気下、気相または液
相で実施される。特に、ホージャサイト型ゼオライトを
用いて２．６−ジメチルナフタレンを得る方法としては
、例えば特開昭６３−１４７３７、特開昭６３−１４７
３８、特開昭６３−８３４４等が挙げられ、ホージャサ
イト型ゼオライトは、その構造からジメチルナフタレン
異性体混合物を製造する反応においては高い活性を示す
ことが知られている。Such isomerization or transalkylation reactions involve the transfer of substituted alkyl groups within one molecule or between two molecules, and are usually performed using various solid acids such as aluminosilicates and heptaolides. Catalysts (e.g., Kozo Tanabe et al., “New 5
olid Ac1ds and Ba5es” Kod
The reaction is carried out in a gas phase or a liquid phase in a hydrogen atmosphere using a Lewis acid catalyst consisting of a metal halide such as aluminum chloride or a metal halide such as aluminum chloride. In particular, methods for obtaining 2,6-dimethylnaphthalene using faujasite type zeolite include, for example, JP-A No. 63-14737 and JP-A No. 63-147.
38 and JP-A No. 63-8344, etc., and faujasite-type zeolite is known to exhibit high activity in the reaction for producing a dimethylnaphthalene isomer mixture due to its structure.
［発明が解決しようとする課題］
しかしながら、かかるホージャサイト型ゼオライトはス
ーパーケージ、即ち、細孔内部に大きな空隙を有する構
造のため、細孔内部でのコーク析出に伴う閉塞が生じ、
その結果、反応、活性が、セ、激に低下するという問題
があった。[Problems to be Solved by the Invention] However, since such faujasite-type zeolite has a supercage structure, that is, a structure with large voids inside the pores, clogging occurs due to coke precipitation inside the pores.
As a result, there was a problem in that the reaction and activity were drastically reduced.
［課題を解決するための手段１
そこで、本発明者等は、上記の課題を解消するべく鋭意
検討した結果、２，６−ジメチルナフタレンの濃度が熱
力学的平衡濃度よりも小さいジメチルナフタレン異性体
混合物を特定触媒の存在下反応させることにより、２，
６−ジメチルナフタレンの濃度を高めなジメチルナフタ
レン異性体混合物が長期的に亘り、安定的に取得できる
ことを見出し本発明に到達した。[Means for Solving the Problems 1] Therefore, as a result of intensive studies to solve the above problems, the present inventors have developed a dimethylnaphthalene isomer in which the concentration of 2,6-dimethylnaphthalene is lower than the thermodynamic equilibrium concentration. By reacting the mixture in the presence of a specific catalyst, 2,
The present invention was achieved by discovering that a dimethylnaphthalene isomer mixture without increasing the concentration of 6-dimethylnaphthalene can be stably obtained over a long period of time.
すなわち、本発明の目的は、２，６−ジメチルナフタレ
ンの濃度を高めなジメチルナフタレン異性体混合物を効
率よく取得する方法を提供するものである。That is, an object of the present invention is to provide a method for efficiently obtaining a dimethylnaphthalene isomer mixture without increasing the concentration of 2,6-dimethylnaphthalene.
そして、かかる目的は、２，６−シメチルナフタレンの
濃度が熱力学的平衡濃度よりも小さいジメチルナフタレ
ン異性体混合物を固体酸触媒の存在下反応させることに
より、２，６−ジメチルナフタレンの濃度を高めたジメ
チルナフタレン異性体混合物を製造する方法において、
固体酸触媒としてその交換可能なカチオン部位が亜鉛で
イオン交換されたホージャサイト型ゼオライトを用いる
ことを特徴とする２、６−ジメチルナフタレンの濃度を
高めたジメチルナフタレン異性体混合物の製造方法によ
り容易に達成される。This purpose is achieved by reducing the concentration of 2,6-dimethylnaphthalene by reacting a mixture of dimethylnaphthalene isomers in which the concentration of 2,6-dimethylnaphthalene is lower than the thermodynamic equilibrium concentration in the presence of a solid acid catalyst. A method for producing a mixture of dimethylnaphthalene isomers with an increased concentration of 2,6-dimethylnaphthalene, characterized in that a faujasite type zeolite whose exchangeable cation sites are ion-exchanged with zinc is used as a solid acid catalyst. This is easily accomplished by a method for producing an enriched dimethylnaphthalene isomer mixture.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明における２、６−ジメチルナフタレンの濃度が熱
力学的平衡濃度よりも小さいジメチルナフタレン異性体
混合物とは、２，６−ジメチルナフタレンとその位置異
性体、即ち、２，７−ジメチルナフタレン、２，３−ジ
メチルナフタレン、１，３−ジメチルナフタレン、１．
８−ジメチルナフタレン、１．７−ジメチルナフタレン
、１，６−ジメチルナフタレン、１，５−ジメチルナフ
タレン、１，４−ジメチルナフタレン、および１，２−
ジメチルナフタレンの９種のうち少なくとも１種を含む
異性体混合物であり、全異性体中の２゜６−ジメチルナ
フタレンの濃度が異性体の熱力学的平衡濃度よりも小さ
いものである。In the present invention, the dimethylnaphthalene isomer mixture in which the concentration of 2,6-dimethylnaphthalene is lower than the thermodynamic equilibrium concentration refers to 2,6-dimethylnaphthalene and its positional isomer, that is, 2,7-dimethylnaphthalene, 2 , 3-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1.
8-dimethylnaphthalene, 1,7-dimethylnaphthalene, 1,6-dimethylnaphthalene, 1,5-dimethylnaphthalene, 1,4-dimethylnaphthalene, and 1,2-dimethylnaphthalene
It is an isomer mixture containing at least one of the nine types of dimethylnaphthalene, and the concentration of 2°6-dimethylnaphthalene in all isomers is lower than the thermodynamic equilibrium concentration of the isomers.
そして、かかる異性体混合物は、ジメチルナフタレン異
性体混合物を含む芳香族炭化水素原料油より、公知の方
法、例えば、特定の吸着剤と脱離剤を用いるカラムクロ
マトグラフィーや、更にこれと分離と晶析分離とを組み
合わせた２、６−ジメチルナフタレンの分離方法（特開
平１−１６８６２８ ）等によって容易に得られる。よ
り具体的には、ジメチルナフタレン全異性体中の２，６
−ジメチルナフタレンの濃度が０．１〜１０％、好まし
くは０．２〜５％程度であるようなものがよい。Such an isomer mixture can be obtained from an aromatic hydrocarbon feedstock containing a dimethylnaphthalene isomer mixture by a known method, such as column chromatography using a specific adsorbent and desorbing agent, or further separation and crystallization. It can be easily obtained by a method of separating 2,6-dimethylnaphthalene in combination with analytical separation (Japanese Patent Application Laid-open No. 1-168628). More specifically, 2,6 in all isomers of dimethylnaphthalene
- The concentration of dimethylnaphthalene is preferably about 0.1 to 10%, preferably about 0.2 to 5%.
更に、この異性体混合物には、ナフタレン、メチルナフ
タレン、エチルナフタレン、メチルエチルナフタレン、
トリメチルナフタレン、テトラメチルナフタレン、ビフ
ェニル、メチルビフェニル等の他の芳香族炭化水素を含
んでもよいが、これらは通常、全体の５０％以下、好ま
しくは１０％以下である。Furthermore, this isomer mixture includes naphthalene, methylnaphthalene, ethylnaphthalene, methylethylnaphthalene,
Other aromatic hydrocarbons such as trimethylnaphthalene, tetramethylnaphthalene, biphenyl, methylbiphenyl may also be included, but these usually account for 50% or less of the total, preferably 10% or less.
本発明では、かかる異性体混合物から出発して２゜６−
ジメチルナフタレンの濃度を高めなジメチルナフタレン
異性体混合物を取得するものである。ここで２，６−ジ
メチルナフタレンの濃度を高めたとは、出発原料である
異性体混合物中の２，６−ジメチルナフタレンの濃度よ
り大きくなることをいい、例えば、熱力学的平衡濃度付
近あるいはそれ以上、具体的にはジメチルナフタレン全
異性体中の２゜６−ジメチルナフタレンの濃度が１０〜
２０％程度となるようなものを意味する。In the present invention, starting from such an isomer mixture, 2°6-
A dimethylnaphthalene isomer mixture with a high concentration of dimethylnaphthalene is obtained. Here, "increasing the concentration of 2,6-dimethylnaphthalene" means that the concentration of 2,6-dimethylnaphthalene is higher than the concentration of 2,6-dimethylnaphthalene in the isomer mixture that is the starting material, for example, near the thermodynamic equilibrium concentration or higher. , specifically, the concentration of 2゜6-dimethylnaphthalene in all dimethylnaphthalene isomers is 10~
It means something that is about 20%.
本発明では、かかる２、６−ジメチルナフタレンの濃度
を高めなジメチルナフタレン異性体混合物を取得するた
めに使用する固体酸触媒としてその交換可能なカチオン
部位の少なくとも一部が亜鉛でイオン交換されたホージ
ャサイト型ゼオライトを用いる。ここで、その交換可能
なカチオン部位が亜鉛でイオン交換されたホージャサイ
ト型ゼオライトとしては、亜鉛がイオン交換された部位
に組み込まれたものである。そして、使用するホージャ
サイト型ゼオライトとしてはＸ型およびｌまたはＹ型ゼ
オライトを用いるのが好ましく、また、脱アルミニウム
処理等が施されたアルミニウム含量が少ない超安定化Ｙ
型ゼオライト（ＵＳＹゼオライト）等が好適に用いられ
る。In the present invention, as a solid acid catalyst used to obtain a dimethylnaphthalene isomer mixture with a high concentration of 2,6-dimethylnaphthalene, at least a part of its exchangeable cation sites is ion-exchanged with zinc. Site-type zeolite is used. Here, the faujasite type zeolite whose exchangeable cation sites are ion-exchanged with zinc is one in which zinc is incorporated into the ion-exchanged sites. As the faujasite type zeolite to be used, it is preferable to use X-type and l- or Y-type zeolites.
Type zeolite (USY zeolite) and the like are preferably used.
交換可能なカチオンサイトが亜鉛でイオン交換されたホ
ージャサイト型ゼオライトとしては、例えば特開昭６３
−１５０２３３に開示されたものが挙げられる。すなわ
ち、亜鉛化合物含有水溶液と接触させることにより得ら
れたホージャサイト型ゼオライトである。Faujasite type zeolites in which exchangeable cation sites are ion-exchanged with zinc include, for example, JP-A-63
-150233. That is, it is a faujasite type zeolite obtained by contacting it with an aqueous solution containing a zinc compound.
ゼオライトと接触させる亜鉛化合物としては、塩化亜鉛
、硝酸亜鉛あるいは、硫酸亜鉛等が挙げられる。Examples of the zinc compound to be brought into contact with the zeolite include zinc chloride, zinc nitrate, and zinc sulfate.
そして、かかる触媒において亜鉛の含有量はＺｎＯとし
て１〜２０重量％、好ましくは３〜１５重量％とするの
がよい。更に、必要に応じてモリブデン、タングステン
、ニッケルあるいはコバルト等の元素を硫化物あるいは
酸化物の形態で本発明の触媒に添加してもよい。かかる
化合物の添加量としては、０．５〜２０重量％重量％上
い。In such a catalyst, the content of zinc is preferably 1 to 20% by weight, preferably 3 to 15% by weight as ZnO. Furthermore, if necessary, elements such as molybdenum, tungsten, nickel, or cobalt may be added to the catalyst of the present invention in the form of sulfides or oxides. The amount of such a compound added is 0.5 to 20% by weight or more.
なお、かかる亜鉛でイオン交換されたホージャサイト型
ゼオライト触媒はコーク生成速度が低く長時間高活性を
維持するが、反応終了後に酸素含有ガスによる酸化処理
、あるいは水素含有ガスによる水素化処理によって再生
することができる。The faujasite-type zeolite catalyst ion-exchanged with zinc has a low coke formation rate and maintains high activity for a long time, but after the reaction is completed, it can be regenerated by oxidation treatment with an oxygen-containing gas or hydrogenation treatment with a hydrogen-containing gas. be able to.
本発明においては、かかるホージャサイト型ゼオライト
を触媒として使用し、上述した２、６ジメチルナフタレ
ンの濃度が熱力学的平衡濃度値よりも小さい値であるジ
メチルナフタレン異性体混合物から、２，６ジメチルナ
フタレンの濃度を高めたジメチルナフタレン異性体混合
物を取得するが、かかる反応帯域では異性化反応、不均
化反応、アルキル化反応あるいはトランスアルキル化反
応等の変換反応が複雑に生じ、反応終了の時点で、結果
として、２，６ジメチルナフタレンの濃度を高めたジメ
チルナフタレン異性体混合物が得られるものである。In the present invention, such a faujasite type zeolite is used as a catalyst to convert 2,6 dimethylnaphthalene from the dimethylnaphthalene isomer mixture in which the concentration of 2,6 dimethylnaphthalene is smaller than the thermodynamic equilibrium concentration value. However, complex conversion reactions such as isomerization, disproportionation, alkylation or transalkylation occur in the reaction zone, and at the end of the reaction As a result, a dimethylnaphthalene isomer mixture with an increased concentration of 2,6 dimethylnaphthalene is obtained.
そして、かかる反応の条件については、反応温度は特に
制限されるものではなく、通常２００〜５００°Ｃ１好
ましくは２５０〜４５０°Ｃの範囲から選択すればよい
。反応圧力は、常圧下あるいは加圧下のいずれでも実施
でき、また液相あるいは気相のいずれでも実施できる。Regarding the reaction conditions, the reaction temperature is not particularly limited and may be selected from the range of usually 200 to 500°C, preferably 250 to 450°C. The reaction pressure can be either normal pressure or increased pressure, and the reaction can be carried out in either a liquid phase or a gas phase.
反応形式は、回分法、連続法のいずれでもよい。なお、
反応雰囲気は水素が存在しないと触媒活性が劣化し易い
ので、触媒活性の維持の上からも水素ガスまたは硫化水
素ガスを含有する水素ガスの混合ガスの存在下で実施す
るのが好ましい。かかる混合ガス中の硫化水素ガス濃度
としては、通常１０容量％以下、好ましくは０．０１〜
５容量％の範囲であるのがよい。The reaction format may be either a batch method or a continuous method. In addition,
Since the catalyst activity tends to deteriorate in the absence of hydrogen in the reaction atmosphere, it is preferable to carry out the reaction in the presence of hydrogen gas or a mixed gas of hydrogen gas containing hydrogen sulfide gas in order to maintain the catalyst activity. The hydrogen sulfide gas concentration in such a mixed gas is usually 10% by volume or less, preferably 0.01 to 10% by volume.
It is preferably in the range of 5% by volume.
［実施例］
以下、本発明を実施例により具体的に説明するが、本発
明はその要旨を越えない限り下記の実施例に限定される
ものではない。[Examples] Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
実施例中のジメチルナフタレンについてはガスクロマト
グラフィーで分析を行なった。また、反応中に触媒に析
出するコーク量については燃焼法により定量を行なった
。なお、部および％は重量％を示す。Dimethylnaphthalene in the examples was analyzed by gas chromatography. Furthermore, the amount of coke deposited on the catalyst during the reaction was determined by the combustion method. Note that parts and % indicate weight %.
実施例１
塩化亜鉛（和光純薬（株）製） １３６．３ ｇを水に
溶解して１ｅとした。得られた水溶液３３０ｍ１にＮａ
ｍ Ｙゼオライト成型品（東ソー（株）製、組成［Ｓ
ｉＯ２： ６７．０％、Ａ１□０３：２０．５％、ＮＯ
２Ｏ１２，４％］、アルミナバインダー１３部対無水七
オライド１００部、粒径２５０〜４００１１ｍ球状品）
を３７．３ ｇ入れ、１００°０２時間、撹拌下、イオ
ン交換処理し、その後、ろ過、温水洗浄を行った。Example 1 136.3 g of zinc chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in water to prepare 1e. Add Na to 330ml of the resulting aqueous solution.
m Y zeolite molded product (manufactured by Tosoh Corporation, composition [S
iO2: 67.0%, A1□03:20.5%, NO
2O12.4%], 13 parts alumina binder to 100 parts anhydrous heptaolide, particle size 250-40011m spherical product)
37.3 g of was added and subjected to ion exchange treatment under stirring at 100°C for 2 hours, followed by filtration and washing with hot water.
以下、同様にイオン交換処理、ろ過及び洗浄をあと２回
繰り返した。Thereafter, the ion exchange treatment, filtration and washing were repeated two more times in the same manner.
次に、洗浄中にＣＩイオンが検出されなくなるまで、温
水洗浄した。しかる後、１２０°Ｃで一昼夜乾燥し、次
に、５４０°Ｃにて５時間、空気気流中で燃成して、Ｚ
ｎｎ交換上ゼオライト以下ｒＺｎ−ＹＪという）を得た
。このＺｎ−Ｙ５．５ｇを内径２０ｍｍのガラス製反応
管に充填し、常圧下、水素′ａ量１．６１／ｈｒ、反応
温度３５０°Ｃにてジメチルナフタレン異性体混合物を
１．７ｇ／ｈｒの流量で通液し、反応を行った。ここで
用いたジメチルナフタレン異性体混合物とは、クロマト
分離にて全ジメチルナフタレン中の２，６−シメチルナ
フタレン濃度が３．１％にまで減じられたものである。Next, hot water washing was performed until no CI ions were detected during washing. Thereafter, the Z
A zeolite (hereinafter referred to as rZn-YJ) was obtained on the exchange of nn. A glass reaction tube with an inner diameter of 20 mm was filled with 5.5 g of this Zn-Y, and a dimethylnaphthalene isomer mixture was added at a rate of 1.7 g/hr under normal pressure at a hydrogen'a amount of 1.61/hr and a reaction temperature of 350°C. The reaction was carried out by passing the solution at a high flow rate. The dimethylnaphthalene isomer mixture used here was one in which the concentration of 2,6-dimethylnaphthalene in the total dimethylnaphthalene was reduced to 3.1% by chromatographic separation.
その結果、生成物である全ジメチルナフタレン異性体混
合物中の２，６−シメチルナフラタレン濃度は平衡濃度
（約１４％）を上回る１７．４％が得られた。As a result, the concentration of 2,6-dimethylnaphthalene in the total dimethylnaphthalene isomer mixture as a product was 17.4%, which exceeded the equilibrium concentration (about 14%).
実施例２
実施例１で得られたＺｎ −Ｙ３．２ｇを内径２０ ｍ
ｍのガラス製反応管に充填し、常圧下、水素流量３．６
１ ／計、反応温度３５０’Ｃにてジメチルナフタレン
異性体混合物を６．０ ｇ ／ ｈｒの流量で通液し、
反応を行なった。ここで用いたジメチルナフタレン異性
体混合物とは、クロマト分離にて全ジメチルナフタレン
中の２，６−シメチルナフタレン濃度が２．８％にまで
減じられたものである。結果を第１表に示す。Example 2 3.2 g of Zn-Y obtained in Example 1 was prepared with an inner diameter of 20 m.
Filled in a glass reaction tube of 3.0 m, hydrogen flow rate was 3.6 m under normal pressure.
1/meter, a dimethylnaphthalene isomer mixture was passed at a flow rate of 6.0 g/hr at a reaction temperature of 350'C,
The reaction was carried out. The dimethylnaphthalene isomer mixture used here was one in which the concentration of 2,6-dimethylnaphthalene in the total dimethylnaphthalene was reduced to 2.8% by chromatographic separation. The results are shown in Table 1.
比較例１
硝酸アンモニウム（和光純葉（株）製）１６０．０ｇを
水に、溶解して１ｅとした水容液３３０ｍ１に実施例
１で用いたＮａ型型上ゼオライト成型品３７．３ｇ入れ
、実施例１と同様の方法にてイオン交換処理を行い、更
に同様の方法で乾燥、焼成し、Ｈ型Ｙゼオライト（以下
ｒ Ｈ−Ｙ Ｊという）を得た。このＨＹを２．９ｇを
内径２０ｍｍのガラス製反応管に充填し、実施例 ２と
同様の方法にて反応を実施した。結果を第１表に示した
［発明の効果］
本発明によれば、２，６−シメチルナフタレンの濃度を
高めたジメチルナフタレン異性体混合物を長期間に亘り
安定的に取得することができ、工業的利用価値が高い。Comparative Example 1 Example by dissolving 160.0 g of ammonium nitrate (manufactured by Wako Junha Co., Ltd.) in water and adding 330 ml of aqueous solution to obtain 1e.
37.3 g of the Na-type upper zeolite molded product used in Example 1 was added, and ion exchange treatment was performed in the same manner as in Example 1. Further, it was dried and calcined in the same manner to obtain H-type Y zeolite (hereinafter referred to as r H- YJ) was obtained. 2.9 g of this HY was filled into a glass reaction tube with an inner diameter of 20 mm, and a reaction was carried out in the same manner as in Example 2. The results are shown in Table 1. [Effects of the Invention] According to the present invention, a dimethylnaphthalene isomer mixture with an increased concentration of 2,6-dimethylnaphthalene can be stably obtained over a long period of time. High industrial value.
Claims (2)
衡濃度よりも小さいジメチルナフタレン異性体混合物を
固体酸触媒の存在下反応させることにより、２，６−ジ
メチルナフタレンの濃度を高めたジメチルナフタレン異
性体混合物を製造する方法において、 固体酸触媒としてその交換可能なカチオン部位が亜鉛で
イオン交換されたホージャサイト型ゼオライトを用いる
ことを特徴とする２，６−ジメチルナフタレンの濃度を
高めたジメチルナフタレン異性体混合物の製造方法。(1) Dimethylnaphthalene with an increased concentration of 2,6-dimethylnaphthalene by reacting a dimethylnaphthalene isomer mixture in which the concentration of 2,6-dimethylnaphthalene is lower than the thermodynamic equilibrium concentration in the presence of a solid acid catalyst. A method for producing an isomer mixture, characterized in that a faujasite type zeolite whose exchangeable cation moieties are ion-exchanged with zinc is used as a solid acid catalyst, dimethylnaphthalene with an increased concentration of 2,6-dimethylnaphthalene. Method for producing isomer mixture.
はＹ型ゼオライトであることを特徴とする請求項１記載
の方法。(2) The method according to claim 1, wherein the faujasite-type zeolite is an X-type and/or Y-type zeolite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2218475A JP2767994B2 (en) | 1990-08-20 | 1990-08-20 | Method for producing dimethylnaphthalene isomer mixture with increased 2,6-dimethylnaphthalene concentration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2218475A JP2767994B2 (en) | 1990-08-20 | 1990-08-20 | Method for producing dimethylnaphthalene isomer mixture with increased 2,6-dimethylnaphthalene concentration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0499736A true JPH0499736A (en) | 1992-03-31 |
| JP2767994B2 JP2767994B2 (en) | 1998-06-25 |
Family
ID=16720513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2218475A Expired - Fee Related JP2767994B2 (en) | 1990-08-20 | 1990-08-20 | Method for producing dimethylnaphthalene isomer mixture with increased 2,6-dimethylnaphthalene concentration |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2767994B2 (en) |
-
1990
- 1990-08-20 JP JP2218475A patent/JP2767994B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2767994B2 (en) | 1998-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5342596A (en) | Process for making theta-1 zeolite | |
| US3700744A (en) | Simultaneous recovery and production of pure xylenes from a c aromatic mixture | |
| EP2931686B1 (en) | Aromatic transalkylation using uzm-44 aluminosilicate zeolite | |
| KR100517593B1 (en) | Catalysts and methods for the conversion of aromatic hydrocarbons and their use in the production of aromatic hydrocarbons | |
| WO2009008876A1 (en) | Process for xylene production | |
| AU592790B2 (en) | Highly active and highly selective aromatization catalyst | |
| US8049051B2 (en) | Process for production of aromatic hydrocarbons | |
| JPH0291031A (en) | Isomerization of xylene | |
| EP0493040A2 (en) | Process for the production of aromatic hydrocarbons from aliphatic hydrocarbons | |
| US3629351A (en) | Catalytic rearrangement of alkyl aromatics | |
| EP0002824A1 (en) | Rhenium containing hydroalkylation catalyst, process for its production and its use | |
| US4423280A (en) | Selective sorption by zeolites | |
| WO2020050092A1 (en) | Method for producing xylene | |
| JPH0499736A (en) | Production of dimethylnaphthalene isomer mixture containing concentrated 2,6-dimethylnaphthalene | |
| JP2767993B2 (en) | Process for producing dimethylnaphthalene isomer mixture with increased 2,6-dimethylnaphthalene concentration | |
| Sastre et al. | Isomerization of meta-xylene over offretite catalysts | |
| US3576895A (en) | Conversion of alkyl aromatics | |
| CN104437592A (en) | Alumisilicate molecular sieve catalyst with MWW structure and preparation method of alumisilicate molecular sieve catalyst with MWW structure | |
| GB2162534A (en) | Silicalite reforming process | |
| DE3878626T2 (en) | METHOD FOR PRODUCING M-XYLOL FROM O-XYLOL. | |
| JPH05500352A (en) | Zeolite (B) SSZ-24 | |
| JP2767997B2 (en) | Method for producing dimethylnaphthalene isomer mixture with increased 2,6-dimethylnaphthalene concentration | |
| JP3139119B2 (en) | Method for isomerizing dialkylnaphthalene | |
| JPH0541611B2 (en) | ||
| WO1998024745A1 (en) | Method for isomerizing halogenated ethylbenzene and method for separating halogenated ethylbenzene isomers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |