JPH0739357B2 - Method for isomerizing dimethylnaphthalene - Google Patents
Method for isomerizing dimethylnaphthaleneInfo
- Publication number
- JPH0739357B2 JPH0739357B2 JP58202249A JP20224983A JPH0739357B2 JP H0739357 B2 JPH0739357 B2 JP H0739357B2 JP 58202249 A JP58202249 A JP 58202249A JP 20224983 A JP20224983 A JP 20224983A JP H0739357 B2 JPH0739357 B2 JP H0739357B2
- Authority
- JP
- Japan
- Prior art keywords
- dmn
- reaction
- zeolite
- dimethylnaphthalene
- group
- 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 17
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 title claims description 14
- 239000010457 zeolite Substances 0.000 claims description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 17
- 238000006317 isomerization reaction Methods 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- -1 dimethylnaphthalene compound Chemical class 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000002441 X-ray diffraction Methods 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- WWGUMAYGTYQSGA-UHFFFAOYSA-N 2,3-dimethylnaphthalene Chemical compound C1=CC=C2C=C(C)C(C)=CC2=C1 WWGUMAYGTYQSGA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 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
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- RJTJVVYSTUQWNI-UHFFFAOYSA-N 2-ethylnaphthalene Chemical compound C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 2
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-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
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Chemical group 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 本発明はジメチルナフタレン（以下DMNと略称する）類
のうち同一環内にメチル基のある2,3−、1,3−、1,4−
及び1,2−の各DMNを主空洞の入口が酸素10員環よりなる
ゼオライトと接触させ、同一環内にあるメチル基の少な
くとも一つを隣接環に移行する方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention is a dimethylnaphthalene (hereinafter abbreviated as DMN) group having a methyl group in the same ring of 2,3-, 1,3-, 1,4-
And 1,2-DMNs are brought into contact with a zeolite having an oxygen 10-membered ring at the entrance of the main cavity, and at least one methyl group in the same ring is transferred to the adjacent ring.
DMNの主要な用途の一つはナフタレンジカルボン酸の製
造であり、この用途には特に2,6−異性体が好んで用い
られる。One of the main uses of DMN is the production of naphthalene dicarboxylic acid, for which the 2,6-isomer is particularly preferred.
DMNには10種の異性体があり、これら異性体は下記の４
つの組に分類でき、従来それぞれの組の内部では異性化
が容易であるが、組を超えての異性化は困難であつた。DMN has 10 isomers, and these isomers are
It can be classified into three groups, and conventionally, isomerization was easy inside each group, but isomerization beyond the group was difficult.
（１） 1,5−、1,6−、2,6−異性体 （２） 1,8−、1,7−、2,7−異性体 （３） 1,4−、1,3−、2,3−異性体 （４） 1,2−異性体 これに対して本発明者らは主空洞の入口が酸素10員環よ
りなるゼオライトを触媒に用いることにより上記の組を
超えての異性化、特に（１）の組から（２）の組へ、
（２）の組から（１）の組への異性化が容易に進行する
ことを見い出し先に出願した（特願昭57−196578）。(1) 1,5-, 1,6-, 2,6-isomer (2) 1,8-, 1,7-, 2,7-isomer (3) 1,4-, 1,3- , 2,3-isomer (4) 1,2-isomer By contrast, the inventors of the present invention exceeded the above set by using a zeolite whose main cavity inlet is composed of a 10-membered oxygen ring as a catalyst. Isomerization, especially from the set of (1) to the set of (2),
He found that the isomerization from the group of (2) to the group of (1) proceeded easily and filed a patent application (Japanese Patent Application No. 57-196578).
先の発明においては、（１）或いは（２）の組から
（３）の組及び／又は（４）の組への異性化は確かに進
行するもののその反応速度は、（１）の組から（２）の
組へ、或いはその逆の各異性化反応速度に比べはるかに
小さかつた。In the above invention, isomerization from the group of (1) or (2) to the group of (3) and / or the group of (4) certainly proceeds, but the reaction rate is from the group of (1). It was much smaller than each isomerization reaction rate to the group of (2) or vice versa.
ところが、（３）或いは（４）の組のDMN類を同様の触
媒に接触させたところ（１）及び（２）の組への異性化
反応が逆の異性化反応に比べ、数倍の速度で進行するこ
とを見い出し本発明に到達した。However, when DMNs of group (3) or (4) were contacted with the same catalyst, the isomerization reaction to groups (1) and (2) was several times faster than the reverse isomerization reaction. The present invention has been reached by finding out that the process proceeds.
即ち本発明は二個のメチル基を同一環内に有するDMN類
のメチル基の少なくとも一つを隣接環に移行する方法に
関するものである。That is, the present invention relates to a method of transferring at least one methyl group of DMNs having two methyl groups in the same ring to an adjacent ring.
以下本発明について詳細に説明する。The present invention will be described in detail below.
本発明方法で使用される原料としては、2,3−、1,3−、
1,4−及び1,2−DMNを各々単独で用いることもできる
が、混合物としても用いることもできる。混合物として
は石油系、石炭系のいずれの原料も使用でき、好適には
FCCプロセスのリサイクル油から蒸留分離されるDMN留分
が用いられる。The raw materials used in the method of the present invention include 2,3-, 1,3-,
Each of 1,4- and 1,2-DMN can be used alone or as a mixture. As the mixture, any of petroleum-based and coal-based raw materials can be used, and preferably
The DMN fraction that is distilled off from the recycled oil of the FCC process is used.
本発明方法で用いる触媒は、主空洞の入口が酸素10員環
よりなるゼオライトであり、粉末Ｘ線回折分析による回
折パターンが特開昭56−92114号公報の実施例１に記載
のものと同様で、回転角２θ＝23.25に最強のピークを
有し、２θ＝23.45に次に強いピークを有する。このタ
イプのゼオライトは通常ペンタシル構造を有しており、
またそのシリカ／アルミナのモル比は通常12以上であ
る。一般にゼオライトはその骨格構造がシリカ−アルミ
ナより成つているが、鉄、クロムその他の金属が骨格構
造の一部をなしている、即ち非交換性金属として含まれ
ているものも存在する。The catalyst used in the method of the present invention is a zeolite whose main cavity has an oxygen 10-membered ring, and the diffraction pattern by powder X-ray diffraction analysis is the same as that described in Example 1 of JP-A-56-92114. Thus, the rotation angle 2θ = 23.25 has the strongest peak, and 2θ = 23.45 has the next strongest peak. This type of zeolite usually has a pentasil structure,
The silica / alumina molar ratio is usually 12 or more. Zeolite generally has a skeleton structure of silica-alumina, but there are some zeolites in which iron, chromium, and other metals form part of the skeleton structure, that is, are contained as non-exchangeable metals.
本発明方法ではいずれのゼオライトを用いることもでき
るが、通常は骨格がシリカ−アルミナよりなるアルミノ
シリケートを用いる。これらのゼオライトは酸型体とし
て反応に用いられる。周知のように、酸型のゼオライト
とは、カチオンとしてプロトンや希土類イオン等の多価
カチオンを有するものである。通常は水素型のゼオライ
トとして反応に供する。なお、ゼオライトはそのままで
用いてもよく、シリカ、アルミナ、シリカ−アルミナそ
の他の助剤と共に成型して用いてもよい。Although any zeolite can be used in the method of the present invention, an aluminosilicate having a skeleton of silica-alumina is usually used. These zeolites are used in the reaction in the acid form. As is well known, the acid type zeolite has a polyvalent cation such as a proton or a rare earth ion as a cation. Usually, it is used as a hydrogen-type zeolite for the reaction. The zeolite may be used as it is, or may be molded together with silica, alumina, silica-alumina and other auxiliary agents.
本発明方法で触媒として用いる主空洞の入口が酸素10員
環よりなるゼオライトは、その製造条件により酸含有量
が異なる。本発明者らの検討によれば、後記する気体塩
基吸着法により求められる300℃での酸量が0.1mmol/g以
上のものを用いることが有利であり、特に0.45mmol/g以
上の酸量のものを用いるのが好ましいことが判明した。The acid content of the zeolite having a 10-membered oxygen ring at the main cavity inlet used as a catalyst in the method of the present invention varies depending on the production conditions. According to the study by the present inventors, it is advantageous to use an acid amount of 0.1 mmol / g or more at 300 ° C. determined by a gas base adsorption method described later, and particularly an acid amount of 0.45 mmol / g or more. It has been found that it is preferable to use the above.
本発明方法によるDMN類の異性化は、気相、液相いずれ
でも行なうことができる。気相法について以下記述す
る。反応は通常固定床反応装置を用いて行なわれるが、
流動床や移動床等を用いて行なうこともできる。反応温
度は250〜550℃、好ましくは300〜450℃であり、圧力は
0.1〜100気圧、好ましくは常圧〜20気圧である。DMNは
単独でまたは水素、窒素、炭酸ガス、あるいは水蒸気で
希釈して接触させる。全ガス空間速度は標準条件（NT
P）で100〜10,000hr-1、好ましくは500〜5000hr-1程度
であり、DMNの液重量空間速度（WHSV）は通常0.01〜100
ml/g−cat・hr、好ましくは0.1〜10ml/g−cat・hrであ
る。次に液相法について記述する。反応は通常固定床あ
るいは懸濁床反応装置を用いて行なわれる。反応温度は
通常250〜550℃、好ましくは300〜450℃であり、圧力は
経済的あるいは技術上の配慮によつて指定されるが、常
圧〜50atmが好ましい。本反応は回分法、流通法のいず
れでも行なうことができる。回分法の場合、原料に対す
る触媒の仕込み割合は通常0.5〜50重量パーセント、好
ましくは１〜20重量パーセント、反応時間は0.1〜10時
間位で行なわれる。流通法の場合DMNの液空間速度（LHS
V）は0.1〜100hr-1の範囲内で適宜選択することができ
る。ジメチルナフタレンは単独でまたは水素、窒素、炭
酸ガス等の雰囲気下で触媒と接触させる。The isomerization of DMNs by the method of the present invention can be carried out in either a gas phase or a liquid phase. The vapor phase method will be described below. The reaction is usually carried out using a fixed bed reactor,
It is also possible to use a fluidized bed or a moving bed. The reaction temperature is 250 to 550 ° C, preferably 300 to 450 ° C, and the pressure is
The pressure is 0.1 to 100 atm, preferably atmospheric pressure to 20 atm. DMN is contacted alone or diluted with hydrogen, nitrogen, carbon dioxide, or steam. All gas space velocities are standard conditions (NT
P) is 100 to 10,000 hr -1 , preferably about 500 to 5000 hr -1 , and the liquid weight space velocity (WHSV) of DMN is usually 0.01 to 100.
ml / g-cat · hr, preferably 0.1 to 10 ml / g-cat · hr. Next, the liquid phase method will be described. The reaction is usually carried out using a fixed bed or suspension bed reactor. The reaction temperature is usually 250 to 550 ° C., preferably 300 to 450 ° C., and the pressure is specified by economic or technical considerations, but normal pressure to 50 atm is preferable. This reaction can be performed by either a batch method or a distribution method. In the case of the batch method, the charging ratio of the catalyst to the raw materials is usually 0.5 to 50% by weight, preferably 1 to 20% by weight, and the reaction time is 0.1 to 10 hours. In the case of the distribution method DMN liquid hourly space velocity (LHS
V) can be appropriately selected within the range of 0.1 to 100 hr -1 . Dimethylnaphthalene is contacted with the catalyst alone or under an atmosphere of hydrogen, nitrogen, carbon dioxide gas or the like.
本発明により、2,3−、1,3−、1,4−及び1,2−DMNがDMN
の中で特に有用な2,6−DMNの原料となり得ることが判明
し、原料の拡大化が確認された。According to the present invention, 2,3-, 1,3-, 1,4- and 1,2-DMN are DMN.
Among them, it was found that it could be a particularly useful raw material for 2,6-DMN, and it was confirmed that the raw material was expanded.
以下に実施例により本発明をさらに詳細に説明するが、
本発明はその要旨を超えない限り、以下の実施例に限定
されるものではない。Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist.
また、実施例における転化率および選択率は、ガスクロ
マトグラフイーにより検出した下記の成分に基いて、下
記式により算出した。Further, the conversion rate and selectivity in the examples were calculated by the following formulas based on the following components detected by gas chromatography.
検出成分：ナフタレン、αおよびβ−メチルナフタレ
ン、αおよびβ−エチルナフタレン、ジメチルナフタレ
ンの各異性体、 実施例１ （ｉ） ゼオライトの合成 内容積100のステンレス製圧力容器に、コロイド状シ
リカ（シリカ分20.4重量％）32.471Kg、水18.8Kg、およ
びジグリコールアミン7.228Kgを加え撹拌した。これ
に、水10Kgにアルミン酸ナトリウム（含有量90.3重量
％）499.3gおよび水酸化ナトリウム726gを溶解した溶液
を加え、密閉後、撹拌しながら160℃に３日間加熱し
た。得られた生成物を約100Kgの水で洗浄し、130℃で乾
燥した。得た生成物は、シリカ／アルミナ比が27で、粉
末Ｘ線回折分析による回折パターンは表１に示すもので
特開昭56−92114号公報の実施例１に記載のものと同様
であり、主空洞の入口が酸素10員環よりなるペンタシル
型ゼオライトであることを確認した。Detection components: naphthalene, α and β-methylnaphthalene, α and β-ethylnaphthalene, dimethylnaphthalene isomers, Example 1 (i) Synthesis of zeolite To a stainless steel pressure vessel having an internal volume of 100, 32.471 kg of colloidal silica (silica content: 20.4% by weight), 18.8 kg of water, and 7.228 kg of diglycolamine were added and stirred. A solution prepared by dissolving 499.3 g of sodium aluminate (content: 90.3% by weight) and 726 g of sodium hydroxide in 10 kg of water was added thereto, and after sealing, the mixture was heated to 160 ° C. for 3 days while stirring. The product obtained was washed with about 100 Kg of water and dried at 130 ° C. The obtained product has a silica / alumina ratio of 27, and the diffraction pattern by powder X-ray diffraction analysis is shown in Table 1 and is the same as that described in Example 1 of JP-A-56-92114. It was confirmed that the inlet of the main cavity was a pentasil-type zeolite consisting of a 10-membered oxygen ring.
（ii） 酸型ゼオライトへの転化 塩化アンモニウム53.3gを水200mlに溶解した水溶液中に
上記のゼオライトを36g仕込み、２時間還流を行なつ
た。過したのち、同様の還流操作を更に２回繰返し
た。ついで脱塩水を用い、塩素イオンがなくなるまで洗
浄した（塩素イオンの検出は、0.1N硫酸銀水溶液により
行なつた）。その後、130℃で乾燥し、粉末打錠成型機
により成型後、破砕して24〜42メツシユに整粒した。こ
れを500℃で３時間空気中で加熱焼成して酸型のゼオラ
イトとした。 (Ii) Conversion to acid-type zeolite 36 g of the above zeolite was charged into an aqueous solution in which 53.3 g of ammonium chloride was dissolved in 200 ml of water, and the mixture was refluxed for 2 hours. After passing, the same reflux operation was repeated twice more. Then, it was washed with demineralized water until chlorine ions were eliminated (chlorine ions were detected with a 0.1N silver sulfate aqueous solution). Then, it was dried at 130 ° C., molded by a powder tableting molding machine, crushed and sized to 24-42 mesh. This was heated and calcined in air at 500 ° C. for 3 hours to obtain an acid type zeolite.
（ii） 反応 上記で得られた酸型のゼオライト7.3ml（4.2g）を内径1
9mmのガラス製反応管に充填し、350℃、常圧下溶融した
2,3−DMN及びN2ガスを導入した。溶融した2,3−DMNは12
0℃に温度調節されたSUS 304製注射器により1.33g/hr
の流量でN2ガス、2.8/hr（NTP）と同時に予熱器を通
して触媒層に導入された。反応管より流出した反応生成
液は還流状態のトルエン中に捕集した。反応開始から30
分後までの反応生成液を捕集し、一部抜き出してガスク
ロマトグラフイーにより分析した。結果を表−１に示
す。(Ii) Reaction Add 7.3 ml (4.2 g) of the acid-type zeolite obtained above to the inner diameter 1
It was filled in a 9 mm glass reaction tube and melted at 350 ° C under normal pressure.
2,3-DMN and N 2 gas were introduced. Molten 2,3-DMN is 12
1.33 g / hr with SUS 304 syringe whose temperature is controlled to 0 ℃
N 2 gas at a flow rate of 2.8 / hr (NTP) was simultaneously introduced into the catalyst layer through a preheater. The reaction product liquid flowing out from the reaction tube was collected in refluxing toluene. 30 from the start of the reaction
The reaction product solution until the minute was collected, a part of it was extracted and analyzed by gas chromatography. The results are shown in Table-1.
実施例２ 原料を1.3−DMNに変更したこと以外は実施例１と同様の
方法で反応を行なつた。結果を表−１に示す。Example 2 The reaction was performed in the same manner as in Example 1 except that the raw material was changed to 1.3-DMN. The results are shown in Table-1.
比較例１ 原料を2,6−DMMで変更したこと以外は実施例１と同様の
方法で反応を行なつた。結果を表−１に示す。Comparative Example 1 A reaction was performed in the same manner as in Example 1 except that the raw material was changed to 2,6-DMM. The results are shown in Table-1.
実施例と比較例より2,3−DMN或いは1,3−DMNのメチル基
の隣接環への移行速度（（DMN）Ｎ）は、2,6−DMNから
同一環ジメチル体への移送速度（（DMN）Ｓ）より２倍
以上大きいことが明らかである。From the examples and the comparative examples, the transfer rate of the methyl group of 2,3-DMN or 1,3-DMN to the adjacent ring ((DMN) N ) was the transfer rate from 2,6-DMN to the same ring dimethyl compound ( It is clear that it is more than twice as large as (DMN) S ).
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭54−52699（ＪＰ，Ａ) 特開 昭56−92114（ＪＰ，Ａ) 特開 昭48−75554（ＪＰ，Ａ) 特開 昭47−37415（ＪＰ，Ａ) 特公 昭47−37420（ＪＰ，Ｂ１) 特公 昭47−37418（ＪＰ，Ｂ１) 石油学会誌 第24巻 第３号 1981年 第160〜166頁 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-54-52699 (JP, A) JP-A-56-92114 (JP, A) JP-A-48-75554 (JP, A) JP-A-47- 37415 (JP, A) JP-B 47-37420 (JP, B1) JP-B 47-37418 (JP, B1) Journal of Japan Petroleum Institute, Vol. 24, No. 3, 1981, pp. 160-166
Claims (1)
有するジメチルナフタレン類を、主空洞の入口が酸素10
員環よりなり、Ｘ線回折において、回転角２θ＝23.25
に最強のピークを有し、２θ＝23.45に次に強いピーク
を有するゼオライトと接触させ、上記ジメチルナフタレ
ン類のメチル基の少なくとも一つを隣接環に移行させる
ことを特徴とするジメチルナフタレン類の異性化方法。1. A dimethylnaphthalene compound having a methyl group on only one of the naphthalene rings, the main cavity having an oxygen content of 10
It consists of a member ring and has a rotation angle of 2θ = 23.25 in X-ray diffraction.
Isomerization of dimethylnaphthalene, characterized in that at least one of the methyl groups of the dimethylnaphthalene is transferred to an adjacent ring by contacting with a zeolite having the strongest peak at 2θ = 23.45 and the next strongest peak at 2θ = 23.45. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58202249A JPH0739357B2 (en) | 1983-10-28 | 1983-10-28 | Method for isomerizing dimethylnaphthalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58202249A JPH0739357B2 (en) | 1983-10-28 | 1983-10-28 | Method for isomerizing dimethylnaphthalene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6094926A JPS6094926A (en) | 1985-05-28 |
| JPH0739357B2 true JPH0739357B2 (en) | 1995-05-01 |
Family
ID=16454414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58202249A Expired - Lifetime JPH0739357B2 (en) | 1983-10-28 | 1983-10-28 | Method for isomerizing dimethylnaphthalene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0739357B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007102047A (en) * | 2005-10-07 | 2007-04-19 | Dainippon Printing Co Ltd | Product management tag |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855328A (en) * | 1971-12-14 | 1974-12-17 | Sun Research Development | Isomerization and/or transalkylation and/or disproportionation of alkylnaphthalenes |
| US4108881A (en) * | 1977-08-01 | 1978-08-22 | Mobil Oil Corporation | Synthesis of zeolite ZSM-11 |
| JPS5692114A (en) * | 1979-12-25 | 1981-07-25 | Mitsubishi Chem Ind Ltd | Manufacture of synthetic crystalline aluminosilicate zeolite |
-
1983
- 1983-10-28 JP JP58202249A patent/JPH0739357B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 石油学会誌第２４巻第３号１９８１年第１６０〜１６６頁 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6094926A (en) | 1985-05-28 |
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