JPH0735344B2 - Catalytic isomerization method of dimethylnaphthalenes containing methylnaphthalene - Google Patents
Catalytic isomerization method of dimethylnaphthalenes containing methylnaphthaleneInfo
- Publication number
- JPH0735344B2 JPH0735344B2 JP58206779A JP20677983A JPH0735344B2 JP H0735344 B2 JPH0735344 B2 JP H0735344B2 JP 58206779 A JP58206779 A JP 58206779A JP 20677983 A JP20677983 A JP 20677983A JP H0735344 B2 JPH0735344 B2 JP H0735344B2
- Authority
- JP
- Japan
- Prior art keywords
- dmn
- reaction
- dimethylnaphthalenes
- zeolite
- catalytic isomerization
- 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
- 238000006317 isomerization reaction Methods 0.000 title claims description 11
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical class C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 title claims description 9
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 title claims description 8
- 230000003197 catalytic effect Effects 0.000 title claims description 5
- 238000000034 method Methods 0.000 title description 17
- 239000010457 zeolite Substances 0.000 claims description 20
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 16
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical class C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 rare earth ion Chemical class 0.000 description 3
- XYTKCJHHXQVFCK-UHFFFAOYSA-N 1,3,8-trimethylnaphthalene Chemical compound CC1=CC=CC2=CC(C)=CC(C)=C21 XYTKCJHHXQVFCK-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 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
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 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
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002739 metals Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 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
- 239000006227 byproduct Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Chemical group 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 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
- 230000001035 methylating effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001961 silver nitrate 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
- 239000005720 sucrose Substances 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５〜40重量％のメチルナフタレン（以下MNと略
す）を含むジメチルナフタレン（以下DMNと略す）類の
接触異性化方法に関するものであり、詳しくはMNおよび
DMN異性体の混合物から、2,6-DMN異性体を優先的に製造
するのに好適な接触異性化方法に関するものである。The present invention relates to a method for catalytic isomerization of dimethylnaphthalene (hereinafter abbreviated as DMN) containing 5 to 40% by weight of methylnaphthalene (hereinafter abbreviated as MN).
The present invention relates to a catalytic isomerization method suitable for preferentially producing 2,6-DMN isomers from a mixture of DMN isomers.
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-DMN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 2,6-DMN isomers are particularly preferred.
従来、DMNには10種の異性体があり、これらの異性体は
下記の４つの組に分類できる。それぞれの組の内部にお
ける異性化は、容易であるが、組を超えての異性化は困
難であつた。Conventionally, DMN has 10 kinds of isomers, and these isomers can be classified into the following four groups. The isomerization within each set was easy, but the isomerization beyond the set 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、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た場合、上記の組を超え
て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号）。しかしながら上記触媒を用
い接触異性化させる際には、異性化と同時にDMNの不均
化反応等が起こり高沸点生成物が生じ、それに比例して
カーボンが触媒上に析出するという問題があつた。この
カーボンの析出は、触媒の寿命を短かくする主要な原因
となる為、その前駆体である高沸点生成物の副生を抑制
することは経済上極めて重要である。(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, when the present invention uses a zeolite having a 10-membered oxygen ring at the inlet of the main cavity as a catalyst, it exceeds the above set. It was found that the isomerization of sucrose easily proceeded and applied for it (Japanese Patent Application No. 57-196578). However, in the case of catalytic isomerization using the above catalyst, DMN disproportionation reaction and the like occur simultaneously with the isomerization to generate a high boiling point product, and in proportion thereto, carbon is deposited on the catalyst. Since the precipitation of carbon is a major cause of shortening the life of the catalyst, it is economically extremely important to suppress the by-product of the high boiling point product which is the precursor thereof.
本発明者らは上記実情に鑑み、鋭意検討を重ねた結果、
原料中に、DMN異性体以外にMNを加え上記触媒と接触さ
せたところ、高沸点生成物を減少せしめ、DMNの副反応
を抑制するという効果を見い出し本発明に到達した。In view of the above situation, the present inventors have made extensive studies,
When MN was added to the raw material in addition to the DMN isomer and brought into contact with the above catalyst, the effect of reducing the high boiling point product and suppressing the side reaction of DMN was found, and the present invention was reached.
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.
本発明で使用される原料としては、ナフタレン（以下NL
と略す）やMNをメチル化して得られる合成DMN類や、石
油留分を種々の方法でクラツキングして得られるクラツ
キング油から蒸留分離したDMN留分、あるいはこれらDMN
留分の異性化物から所望の異性体を分取した後の残渣等
に、MNを所定の割合で添加して反応に供せられる。MNの
添加量は多すぎると目的生成物であるDMNの収量が下が
り、少なすぎるとMNの効果が現われないため、MNの含有
量としては全原料の５〜40重量％好ましくは、10〜30重
量％が適当である。MNはα−体およびβ−体のいずれで
も良く、MN源としては異性化反応の際同時に起こる不均
化反応により得られるものを再使用する方法が経済上最
も好ましい。The raw material used in the present invention is naphthalene (hereinafter referred to as NL
Abbreviated) and synthetic DMNs obtained by methylating MN, DMN fractions obtained by distillation separation from cracking oil obtained by cracking petroleum fractions by various methods, or these DMNs.
MN is added at a predetermined ratio to the residue or the like after the desired isomer has been separated from the isomerized product of the fraction, and the mixture is provided for the reaction. If the amount of MN added is too large, the yield of the target product, DMN, decreases, and if it is too small, the effect of MN does not appear, so the content of MN is 5 to 40% by weight of the total raw material, preferably 10 to 30%. Weight percent is suitable. The MN may be in the α-form or the β-form, and the most preferable economically method is to reuse the MN source obtained by the disproportionation reaction that occurs simultaneously during the isomerization reaction.
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る。このようなゼオライトは公
知であり、その代表的なものにはモービル社より公表さ
れたZSM-5、８、11等のゼオライトがある。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. Such zeolites are known, and typical examples thereof include zeolites such as ZSM-5, 8 and 11 published by Mobil. This type of zeolite usually has a pentasil structure and its 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、液相のいず
れにおいて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
（NTP）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
〜100ml/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決定され、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％、好ましくは
１〜20重量％、反応時間は0.1〜10時間程度で行なわれ
る。流通法の場合DMNの液空間速度（LHSV）は0.1〜100h
r-1の範囲で選択される。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 the gas phase or the liquid phase. The vapor phase method will be described below. The reaction is usually carried out using a fixed bed reactor, but it can also be carried out using a fluidized bed, a moving bed or the like.
The reaction temperature is 250 to 550 ° C, preferably 300 to 450 ° C,
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. Total gas hourly space velocity 100～10,000Hr -1 at standard conditions (NTP), preferably 500～5000Hr -1
The liquid weight space velocity (WHSV) of DMN is usually 0.01.
-100 ml / g-cat-hr, preferably 0.1-10 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., the pressure is determined by economic or technical considerations, and 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 about 0.1 to 10 hours. In the case of the distribution method, the liquid hourly space velocity (LHSV) of DMN is 0.1 to 100h
Selected in the range of r -1 . Dimethylnaphthalene is brought into contact with the catalyst alone or under an atmosphere of hydrogen, nitrogen or carbon dioxide.
本発明方法によれば、高沸点生成物の生成を抑制し、ジ
メチルナフタレンの収率を向上させる効果が認められ
る。According to the method of the present invention, the effects of suppressing the production of high boiling point products and improving the yield of dimethylnaphthalene are recognized.
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.
実施例１ （ｉ）ゼオライトの合成 内容積100l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を加え攪拌した。これに、
水10kgにアルミン酸ナトリウム（含有量90.3重量％）49
9.3g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、攪拌しながら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。Example 1 (i) Synthesis of Zeolite 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 to a stainless steel pressure vessel having an internal volume of 100 l and stirred. to this,
Sodium aluminate (content 90.3% by weight) 49 in 10 kg of water 49
A solution in which 9.3 g and 726 g of sodium hydroxide were dissolved was added, sealed, and then heated at 160 ° C. for 3 days while stirring. The product obtained was washed with about 100 kg of water and dried at 130 ° C. The product obtained is a powder X with a silica / alumina ratio of 27.
The diffraction pattern obtained by the line diffraction analysis was the same as that described in Example 1 of JP-A-56-92114, and it was confirmed that the inlet of the main cavity was a pentasil-type zeolite having 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硝酸銀水溶液により
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 nitrate 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.
（iii）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のガラス製反応器に充填し、350℃常圧下2-MNを添加
した溶融状態の2,6-DMN（2,6-DMN/2-MN＝6.65/1.63（mo
l/mol））及びN2ガスを導入した。溶融原料は120℃に温
度調節されたSUS304製注射器により1.27g/hrの流量で、
N2ガス、28l/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、一部を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。(Iii) Reaction Add 7.3 ml (4.2 g) of the acid-type zeolite obtained above to the inner diameter 1
Fill a 9 mm glass reactor and add 2-MN under normal pressure at 350 ° C to melt 2,6-DMN (2,6-DMN / 2-MN = 6.65 / 1.63 (mo
l / mol)) and N 2 gas were introduced. The molten raw material is a SUS304 syringe whose temperature is regulated at 120 ° C at a flow rate of 1.27 g / hr,
At the same time as N 2 gas, 28 l / hr (NTP), it was introduced into the catalyst layer through a preheater. The reaction product liquid flowing out from the reaction tube was collected in refluxing toluene. The reaction product solution was collected from 30 minutes after the start of the reaction, and a part thereof was extracted and analyzed by gas chromatography. The results are shown in Table-1.
比較例１ 2,6-DMNを原料として使用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 The reaction was carried out in the same manner as in Example 1 except that 2,6-DMN was used as a raw material. The results are shown in Table-1.
上記実施例１及び比較例１より、MNを添加すると、仕込
みDMNの損失及びTMN（トリメチルナフタレン）の生成を
抑制することが認められる。From the above-mentioned Example 1 and Comparative Example 1, it is recognized that the addition of MN suppresses the loss of charged DMN and the generation of TMN (trimethylnaphthalene).
実施例２ 表−２に示す2,6-DMNを抜き出したDMN混合物に2-MNを添
加した原料を用い、原料を室温で供給したこと以外は実
施例１と同様の方法で反応を行なつた。反応開始30〜60
分後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−２に示す。Example 2 A reaction was performed in the same manner as in Example 1 except that a raw material prepared by adding 2-MN to a DMN mixture obtained by extracting 2,6-DMN shown in Table 2 was used and the raw material was supplied at room temperature. It was Reaction start 30-60
The reaction product liquid after the collection was collected, a part of the liquid was extracted and analyzed by gas chromatography. The results are shown in Table-2.
比較例２ 2-MNを殆んど含まない表−２に示す原料を用いたこと以
外は、実施例２と同様の方法で反応を行なつた。結果を
表−２に示す。Comparative Example 2 The reaction was performed in the same manner as in Example 2 except that the raw materials shown in Table 2 containing almost no 2-MN were used. The results are shown in Table-2.
実施例２及び比較例２より、MNを添加すると原料中の全
DMNの損失及び高沸点生成物の生成が抑制されることが
認められる。From Example 2 and Comparative Example 2, when MN was added,
It is observed that the loss of DMN and the formation of high boiling products are suppressed.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 朝日 佳男 神奈川県横浜市緑区鴨志田町1000番地 三 菱化成工業株式会社総合研究所内 (56)参考文献 特開 昭48−75554（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshio Asahi 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Sanryo Kasei Kogyo Co., Ltd. (56) Reference JP-A-48-75554 (JP, A)
Claims (1)
メチルナフタレン類と主空洞の入口が酸素10員環よりな
るゼオライトとを接触させることを特徴とするメチルナ
フタレンを含むジメチルナフタレン類の接触異性化法1. Catalytic isomerization of dimethylnaphthalenes containing methylnaphthalene, characterized in that dimethylnaphthalenes containing 5 to 40% by weight of methylnaphthalene are brought into contact with zeolite having a 10-membered ring of oxygen at the main cavity inlet. Chemical law
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58206779A JPH0735344B2 (en) | 1983-11-02 | 1983-11-02 | Catalytic isomerization method of dimethylnaphthalenes containing methylnaphthalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58206779A JPH0735344B2 (en) | 1983-11-02 | 1983-11-02 | Catalytic isomerization method of dimethylnaphthalenes containing methylnaphthalene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6097923A JPS6097923A (en) | 1985-05-31 |
| JPH0735344B2 true JPH0735344B2 (en) | 1995-04-19 |
Family
ID=16528943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58206779A Expired - Lifetime JPH0735344B2 (en) | 1983-11-02 | 1983-11-02 | Catalytic isomerization method of dimethylnaphthalenes containing methylnaphthalene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0735344B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513146B (en) * | 2011-11-23 | 2013-05-08 | 开滦能源化工股份有限公司 | Catalyst for compounding 2, 6-dimethylnaphthalene and preparing method thereof |
Family Cites Families (2)
| 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 |
| JPS5692114A (en) * | 1979-12-25 | 1981-07-25 | Mitsubishi Chem Ind Ltd | Manufacture of synthetic crystalline aluminosilicate zeolite |
-
1983
- 1983-11-02 JP JP58206779A patent/JPH0735344B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6097923A (en) | 1985-05-31 |
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