JPS6383033A - Production of alkyltetralin - Google Patents
Production of alkyltetralinInfo
- Publication number
- JPS6383033A JPS6383033A JP61227757A JP22775786A JPS6383033A JP S6383033 A JPS6383033 A JP S6383033A JP 61227757 A JP61227757 A JP 61227757A JP 22775786 A JP22775786 A JP 22775786A JP S6383033 A JPS6383033 A JP S6383033A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- alkyltetralin
- hydrogenation
- dehydrogenation
- methyltetralin
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 36
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims abstract 2
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract 2
- 229910052721 tungsten Inorganic materials 0.000 claims abstract 2
- QIMMUPPBPVKWKM-UHFFFAOYSA-N beta-methyl-naphthalene Natural products C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- RJTJVVYSTUQWNI-UHFFFAOYSA-N 2-ethylnaphthalene Chemical compound C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 claims description 4
- UKAMWVYNAVUZEA-UHFFFAOYSA-N 2-butylnaphthalene Chemical compound C1=CC=CC2=CC(CCCC)=CC=C21 UKAMWVYNAVUZEA-UHFFFAOYSA-N 0.000 claims description 2
- TVYVQNHYIHAJTD-UHFFFAOYSA-N 2-propan-2-ylnaphthalene Chemical compound C1=CC=CC2=CC(C(C)C)=CC=C21 TVYVQNHYIHAJTD-UHFFFAOYSA-N 0.000 claims description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetraline Natural products C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims 6
- -1 alkyl tetralin Chemical compound 0.000 claims 3
- QIMMUPPBPVKWKM-RHRFEJLCSA-N 2-methylnaphthalene Chemical group C1=CC=[14CH]C2=CC(C)=CC=C21 QIMMUPPBPVKWKM-RHRFEJLCSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000004821 distillation Methods 0.000 abstract description 9
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 229910017318 Mo—Ni Inorganic materials 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- IVIDJLLPQYHHLM-UHFFFAOYSA-N 6-methyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=CC(C)=CC=C21 IVIDJLLPQYHHLM-UHFFFAOYSA-N 0.000 description 24
- WJRGJANWBCPTLH-UHFFFAOYSA-N 2-methyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2CC(C)CCC2=C1 WJRGJANWBCPTLH-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 9
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910017313 Mo—Co Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- KHARCSTZAGNHOT-UHFFFAOYSA-N naphthalene-2,3-dicarboxylic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 KHARCSTZAGNHOT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- APBBTKKLSNPFDP-UHFFFAOYSA-N 1-methyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2C(C)CCCC2=C1 APBBTKKLSNPFDP-UHFFFAOYSA-N 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur 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)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
この発明は、２−アルキルナフタレンを水素化して高収
率で２または６−アルキルテトラリンを製造する方法に
関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a method for hydrogenating 2-alkylnaphthalene to produce 2- or 6-alkyltetralin in high yield.
［従来の技術］
２−アルキルテトラリンをホルミル化して得られる２−
アルキル−６−ホルミルチトラリンは、脱水素および酸
化することにより容易に２．６−ナフタレンジカルボン
酸を生成する。２，６−ナフタレンジカルボン酸は、有
用な高分子合成原料てリ、例えば、これから導かれるポ
リエステルは、テレフタル酸を原料とするポリエステル
に比へ、機械的強度、耐熱性、寸法安定性など種々の点
で優れたフィルムや各種成型物を与えることが知られて
いる。[Prior art] 2- obtained by formylating 2-alkyltetralin
Alkyl-6-formyltitraline easily produces 2,6-naphthalene dicarboxylic acid by dehydrogenation and oxidation. 2,6-Naphthalene dicarboxylic acid is a useful raw material for polymer synthesis. For example, polyester derived from it has various properties such as mechanical strength, heat resistance, and dimensional stability compared to polyester made from terephthalic acid. It is known that it provides excellent films and various molded products.
また、６−アルキルテトラリンをホルミル化して得られ
る６−アルキル−７−ホルミルチトラリンは、脱水素お
よび酸化することにより容易に６゜７ （２，３）−ナ
フタレンジカルボン酸に変化させることがでる。６，７
−ナフタレンジカルボン酸は、有用な高分子合成原料に
なり得ると予想されている。In addition, 6-alkyl-7-formyltitraline obtained by formylating 6-alkyltetraline can be easily converted into 6°7 (2,3)-naphthalene dicarboxylic acid by dehydrogenation and oxidation. . 6,7
- Naphthalene dicarboxylic acid is expected to be a useful raw material for polymer synthesis.
他方、２−アルキルナフタレンを水素化すれば、２−ア
ルキルテトラリンと６−アルキルテトラリンが生成する
ことは広く知られており、触媒あるいは反応条件によっ
て両者の選択率が変化することが報告されている。On the other hand, it is widely known that hydrogenation of 2-alkylnaphthalene produces 2-alkyltetralin and 6-alkyltetralin, and it has been reported that the selectivity of both changes depending on the catalyst or reaction conditions. .
（ただし、Ｒはアルキル基）
例えば、２−メチルナフタレンを２００°Ｃで、Ｐｄ、
Ｎｉ、Ｒｕ、Ｒｈ、Ｉｒ、Ｐｔ等の貴金属を含有する触
媒の存在下、還元すれば２−メチルテトラリンが第１表
に示す選択率で得られることが報告されている［Ａｄｖ
ａｎｃｅｓ ｉｎ ｃａｔａｌｙｓｉｓ ｖｏｌ。(However, R is an alkyl group) For example, when 2-methylnaphthalene is heated at 200°C, Pd,
It has been reported that 2-methyltetralin can be obtained with the selectivity shown in Table 1 by reduction in the presence of a catalyst containing a noble metal such as Ni, Ru, Rh, Ir, or Pt [Adv
ances in catalysis vol.
１８、４７ （１９６８） Ａｃａｄｅｍｉｃ ｐｒｅ
ｓｓ 、 Ｎｅｗ Ｙｏｒｋ ａｎｄＬｏｎｄｏｎ
コ。18, 47 (1968) Academic pre
ss, New York and London
Ko.
第 ｌ 表 （％）第１表に示
すとおり、２−メチルテトラリンの選択率の最大値は、
Ｐｄ／ＡＩ□０３の場合の６５％であるが、他は５０％
に達しない。Table l (%) As shown in Table 1, the maximum selectivity of 2-methyltetralin is:
It is 65% in case of Pd/AI□03, but 50% in other cases.
does not reach.
水素化触媒としては、前記貴金属以外に硫化ＭＯ−Ｎｉ
をＡｌ２Ｏ３に担持せしめた触媒が知られているが、２
−アルキルナフタレンの水素化においては、アルキル基
の付いた環の水素化速度が、アルキル基の付いていない
環の約１７３であることが報告されており（燃料協会誌
第６３巻第３号 ２＋１頁）、２−アルキルナフタレ
ンの水素化による２−アルキルテトラリンの選択率とし
ては、２５％程度であると予想される。In addition to the above-mentioned noble metals, sulfurized MO-Ni can be used as a hydrogenation catalyst.
A catalyst in which 2 is supported on Al2O3 is known, but 2
- In the hydrogenation of alkylnaphthalene, it has been reported that the hydrogenation rate of a ring with an alkyl group is about 173 times that of a ring without an alkyl group (Journal of Japan Fuel Association, Vol. 63, No. 3, 2+1 Page), the selectivity of 2-alkyltetralin by hydrogenation of 2-alkylnaphthalene is expected to be about 25%.
前記したとおり通常の２−アルキルナフタレンの水素化
反応では、６−アルキルテトラリンが副生ずるため、２
−アルキルテトラリンを８０％以上の収率で製造するこ
とは困難であった。As mentioned above, in the usual hydrogenation reaction of 2-alkylnaphthalene, 6-alkyltetralin is produced as a by-product.
- It was difficult to produce alkyltetralin with a yield of 80% or more.
また、生成する６−アルキルテトラリンを２−アルキル
テトラリンに転化させ、収率を向上せしめる経済的な方
法も提案されていない。Furthermore, no economical method has been proposed for converting the produced 6-alkyltetralin into 2-alkyltetralin to improve the yield.
逆に２−アルキルナフタレンの水素化によって、６−ア
ルキルテトラリンを回収時は、２−アルキルテトラリン
が副生ずるため、６−アルキルテトラリンを高収率で回
収することは困難であった。Conversely, when 6-alkyltetralin is recovered by hydrogenation of 2-alkylnaphthalene, 2-alkyltetralin is produced as a by-product, making it difficult to recover 6-alkyltetralin in a high yield.
［解決しようとする問題点］
この発明は、２−アルキルナフタレンの水素化による２
または６−アルキルテトラリンの製造において、高収率
でしかも効率よく２または６−アルキルテトラリンを製
造できる方法を提供するものである。[Problems to be Solved] This invention solves the problem by hydrogenating 2-alkylnaphthalene.
Another object of the present invention is to provide a method for producing 2- or 6-alkyltetralin with high yield and efficiency in the production of 6-alkyltetralin.
［発明の詳細な
説明者等は、前記２−アルキルナフタレンの水素化によ
り２または６−アルキルテトラリンを高収率でしかも効
率よく製造するについて種々試験研究の結果、副生ずる
６または２−アルキルテトラリンを系外に取り出すと、
結果的に２−アルキルナフタレンに対する２または６−
アルキルテトラリンの収率を低下させるので、副生ずる
６または２−アルキルテトラリンを系外へ取り出すこと
なく、脱水素することにより２−アルキルナフタレンに
転化し、水素化工程へ循環させることにより２または６
−アルキルテトラリンを高収率で製造できることを見い
出しこの発明に到達した。[Detailers of the invention have conducted various tests and studies to efficiently produce 2- or 6-alkyltetralin in high yield by hydrogenating the 2-alkylnaphthalene, and have found that 6- or 2-alkyltetralin as a by-produced When you take it out of the system,
Consequently, 2 or 6- to 2-alkylnaphthalene
Since this reduces the yield of alkyltetralin, the by-produced 6- or 2-alkyltetralin is not taken out of the system, but is converted into 2-alkylnaphthalene by dehydrogenation and recycled to the hydrogenation step.
-We have discovered that alkyltetralin can be produced in high yield and have arrived at this invention.
すなわちこの発明は、２−メチルナフタレンを触媒の存
在下、水素化して２または６−アルキルテトラリンを製
造する方法において、水素化生成物より２または６−ア
ルキルテトラリンを分離したのち、残部を触媒の存在下
、脱水素処理して水素化工程へ循環することを特徴とす
る２または６−アルキルテトラリンの製造方法である。That is, this invention provides a method for producing 2- or 6-alkyltetralin by hydrogenating 2-methylnaphthalene in the presence of a catalyst, in which 2- or 6-alkyltetralin is separated from the hydrogenated product, and the remainder is then treated with the catalyst. This is a method for producing 2- or 6-alkyltetralin, characterized by dehydrogenating it in the presence of hydrogen and recycling it to a hydrogenation step.
本発明方法における出発原料である２−アルキルナフタ
レンとしては、２−メチルナフタレン、２−エチルナフ
タレン、２−イソプロピルナフタレン、２−ブチルナフ
タレンを用いる。As the 2-alkylnaphthalene which is a starting material in the method of the present invention, 2-methylnaphthalene, 2-ethylnaphthalene, 2-isopropylnaphthalene, and 2-butylnaphthalene are used.
本発明で使用する水素化触媒としては、一般的な水素化
触媒であるＰｔ、Ｐｄ、Ｎｉ、Ｃｏ、等の貴金属を担持
せしめた触媒や、Ｍｏ−Ｎｉ、Ｗ−Ｎｉ、Ｍｏ−Ｃｏ等
の二元系触媒が使用できる。The hydrogenation catalyst used in the present invention includes catalysts supported with noble metals such as Pt, Pd, Ni, and Co, which are common hydrogenation catalysts, and catalysts supported with noble metals such as Mo-Ni, W-Ni, and Mo-Co. Binary catalysts can be used.
特に二元系触媒は、水素化脱硫触媒として一般的に使用
されており、硫黄分を含有した原料の核水素化に適して
おり、石炭系タール留分より分離した硫黄含有量の多い
２−メチルナフタレンの水素化に好適である。In particular, binary catalysts are commonly used as hydrodesulfurization catalysts, and are suitable for the nuclear hydrogenation of raw materials containing sulfur. Suitable for hydrogenation of methylnaphthalene.
触媒成分としては、Ｍｏ１５重社％、Ｎｉ３重１％を、
Ａｌ２Ｏ３あるいはＡ１２０３−５ ｉ０２の担体に担
持せしめて使用する。As catalyst components, Mo 15%, Ni 3% 1%,
It is used by being supported on a carrier of Al2O3 or A1203-5 i02.
水素化方法は、特に限定するものではないが、上記触媒
を直径２關、長さ７ｍｍ程度の円柱状に成型し、固定床
に充填して原料２−アルキルナフタレンを供給して反応
させる方法や、触媒を粉末にして原料２−アルキルナフ
タレン中に懸濁させ反応させる方法が採用できる。The hydrogenation method is not particularly limited, but may include a method in which the above-mentioned catalyst is formed into a cylindrical shape with a diameter of about 2 mm and a length of about 7 mm, filled in a fixed bed, and the raw material 2-alkylnaphthalene is supplied and reacted. Alternatively, a method can be adopted in which the catalyst is made into powder and suspended in the raw material 2-alkylnaphthalene for reaction.
反応条件としては、Ｐｔ、Ｐｄ、Ｃｏ等の貴金属触媒使
用の場合は、１００〜２５０℃、また、Ｍｏ−Ｎ ｉ、
Ｍｏ−Ｃｏ等の二元系触媒使用の場合は、２５０〜４０
０℃の温度範囲が適当である。The reaction conditions are 100 to 250°C when noble metal catalysts such as Pt, Pd, and Co are used, and Mo-Ni,
When using a binary catalyst such as Mo-Co, 250 to 40
A temperature range of 0°C is suitable.
水素圧としては、３０〜１５０Ｊ／ ｃ ｔｎ’、好ま
しくは５０〜１００ｋｇ／ ｃ ｍ”の範囲である。原
料の触媒層中の滞留時間は１〜２時間で良い。The hydrogen pressure is in the range of 30 to 150 J/ctn', preferably 50 to 100 kg/cm''.The residence time of the raw material in the catalyst layer may be 1 to 2 hours.
反応装置としては、固定床の場合トリクルペット型反応
装置が、懸濁床の場合は完全混合型のオートクレーブ方
式の反応Ｈａがそれぞれ使用される。As the reactor, a trickle pet type reactor is used in the case of a fixed bed, and a complete mixing autoclave type reaction Ha is used in the case of a suspended bed.
水素化反応生成物から２または６−アルキルテトラリン
を分離回収する方法としては、精密蒸留が好適である。Precision distillation is suitable as a method for separating and recovering 2- or 6-alkyltetralin from the hydrogenation reaction product.
２−アルキルテトラリンと６−アルキルテトラリンは、
性質が非常に似かよっているが・沸点差が８℃あり、理
論段数４０段程度の蒸留塔によって純度９９％以上の２
または６−アルキルテトラリンを分離回収することが可
能である。2-alkyltetralin and 6-alkyltetralin are
Although their properties are very similar, there is a boiling point difference of 8°C, and a distillation column with about 40 theoretical plates produces 2.
Alternatively, it is possible to separate and recover 6-alkyltetralin.
精密蒸留により２または６−アルキルテトラリンを分離
回収したのち、残部の６または２−アルキルテトラリン
に富んだ留分の脱水素反応は、脱水素触媒として前期水
素化触媒と同一の触媒を使用するのが、同一反応装置で
連続的に脱水素、水素化反応を実施できるので有利であ
る。After separating and recovering 2- or 6-alkyltetralin by precision distillation, the remaining 6- or 2-alkyltetralin-rich fraction is dehydrogenated using the same catalyst as the previous hydrogenation catalyst as the dehydrogenation catalyst. However, it is advantageous because the dehydrogenation and hydrogenation reactions can be carried out continuously in the same reactor.
反応温度は、２５０〜４５０°Ｃ１好ましくは３００〜
４００℃である。反応圧力は、特に限定されないが、脱
水素反応を効率よ〈実施するためには、水素分圧をでき
るだけ低くし、場合によっては窒素雰囲気下で実施する
。The reaction temperature is 250 to 450°C, preferably 300 to
The temperature is 400°C. The reaction pressure is not particularly limited, but in order to carry out the dehydrogenation reaction efficiently, the hydrogen partial pressure is made as low as possible, and the reaction is carried out under a nitrogen atmosphere depending on the case.
反応装置としては、固定床、懸濁床いずれでも可能であ
るが、固定床の場合、気相で脱水素する方法も可能であ
る。懸濁床での脱水素は、完全混合型のオートクレーブ
方式の反応Ｖｚｅが採用されるが、水素化反応も同様の
方法で実施すれば、種々の利点がある。すなわち、反応
’Ａ＋’Ｗに６または２−アルキルテトラリンに富んだ
留分と粉末触媒を装入したのち、窒素雰囲気下、４００
℃で脱水案反応せしめ、そのままで温度を３５０℃まで
低下させ、原料２−アルキルナフタレンを添加し、水素
を追加正大して水素化反応せしめれば、同一触媒、同一
反応装置で連続的に脱水素、水素化反応を実施すること
が可能である。The reactor can be either a fixed bed or a suspended bed, but in the case of a fixed bed, a method of dehydrogenation in the gas phase is also possible. For dehydrogenation in a suspended bed, a completely mixed autoclave type reaction Vze is employed, but there are various advantages if the hydrogenation reaction is also carried out in a similar manner. That is, after charging the reaction 'A+'W with a fraction rich in 6 or 2-alkyltetralin and a powdered catalyst, 400
If the dehydration reaction is carried out at ℃, then the temperature is lowered to 350℃, the raw material 2-alkylnaphthalene is added, and hydrogen is added to increase the hydrogenation reaction, continuous dehydrogenation can be achieved using the same catalyst and the same reaction equipment. , it is possible to carry out the hydrogenation reaction.
さらにこの発明方法によれば、脱水素反応によって生成
した水素を水素化反応に利用できる利点がある。Furthermore, the method of this invention has the advantage that hydrogen produced by the dehydrogenation reaction can be used in the hydrogenation reaction.
［実施例コ
実施例１
５００ｃｃのオートクレーブに２−メチルテトラリンｌ
１ｇ、６−メチルテトラリン４７ｇ、２−メチルナフタ
レン４３ｇからなる原料と、硫化水素を用いて硫化した
Ｍｏ−Ｎ １−Ａｌ２０３系触媒ｌｏｇを仕込んだのち
、窒素雰囲気下、撹拌しながら３７０℃に昇温しで脱水
素反応せしめた。[Example Example 1 2-methyltetralin l was placed in a 500 cc autoclave.
After charging raw materials consisting of 1g of 6-methyltetralin, 47g of 6-methyltetralin, and 43g of 2-methylnaphthalene, and a log of Mo-N 1-Al203 catalyst sulfurized using hydrogen sulfide, the temperature was raised to 370°C with stirring under a nitrogen atmosphere. The dehydrogenation reaction was carried out at warm temperature.
２時間経過後十分に脱水素したことを確認したのぢ、温
度を２８０℃まで低下させ、水素ガスを圧人してｌｏｏ
ｋｇ／ｃｍ’まで昇圧し、２時間水素化反応せしめた。After 2 hours, it was confirmed that the hydrogen had been sufficiently dehydrogenated.The temperature was lowered to 280℃, and the hydrogen gas was compressed into a loo.
The pressure was increased to kg/cm', and a hydrogenation reaction was carried out for 2 hours.
この間水素圧が一定になるよう水素ガスを補給した。During this time, hydrogen gas was supplied to keep the hydrogen pressure constant.
反応終了後、オートクレーブを室温まで降温し、反応生
成物から触媒を濾過して分離したのち、ガスクロマトグ
ラフィーによりそのＭ１成を測定したところ、２−メチ
ルテトラリン３９ｇ、６−メチルテトラリン４７ｇ、２
−メチルナフタレン９ｇの割合であった。After the reaction was completed, the temperature of the autoclave was lowered to room temperature, the catalyst was filtered and separated from the reaction product, and its M1 composition was measured by gas chromatography. As a result, 39 g of 2-methyltetralin, 47 g of 6-methyltetralin,
- 9 g of methylnaphthalene.
触媒分離後の反応生成物を、理論段数４０段の蒸留装置
を使用し、還流比ｌＯで精密蒸留し、純度９９．８％の
２−メチルテトラリン２８ｇを留取した。残部の６−メ
チルテトラリン留分に富む留分６７ｇは、６−メチルテ
トラリン４７ｇ、２−メチルテトラリンｌ１ｇ、２−メ
チルナフタレン９ｇからなり、２−メチルナフタレン３
４ｇを追加すれば、そのまま脱水素原料として循環使用
が可能であった。The reaction product after catalyst separation was precisely distilled at a reflux ratio of 10 using a distillation apparatus having 40 theoretical plates, and 28 g of 2-methyltetralin with a purity of 99.8% was distilled. The remaining 6-methyltetralin-rich fraction (67 g) consists of 47 g of 6-methyltetralin, 1 g of 2-methyltetralin, and 9 g of 2-methylnaphthalene, and 2-methylnaphthalene 3
By adding 4 g, it was possible to recycle it as it is as a dehydrogenation raw material.
このことは、脱水素反応、水素化反応、精密蒸留の組み
合わせにより、２−メチルナフタレンから収率８２重層
％の高収率で２−メチルテトラリンをｔ！Ａ造できるこ
とを示すものである。This means that 2-methyltetralin can be produced from 2-methylnaphthalene in a high yield of 82% by a combination of dehydrogenation reaction, hydrogenation reaction, and precision distillation. This shows that A construction is possible.
しかも、水素化反応、脱水素反応を同一触媒、同−設備
で行うことができ、原料費、設備費の大巾な低減を図る
ことができることを示すものである。Moreover, this shows that the hydrogenation reaction and the dehydrogenation reaction can be carried out using the same catalyst and the same equipment, and that the cost of raw materials and equipment can be significantly reduced.
実施例２
２−メチルテトラリン１５重量％、６−メチルテトラリ
ン６１重量％、２−メチルナフタレン２２重位％からな
る原料を、Ｐｔ−Ａｌ２Ｏ３系触媒１６ｃｃを充填した
固定床に供給し、常圧下、４００℃で脱水素反応せしめ
た。得られた脱水素生成物の組成は、２−メチルテトラ
リンフ重量％、６−メチルテトラリン１５重量％、２−
メチルナフタレン７５ＭＭｔ％であった。Example 2 A raw material consisting of 15% by weight of 2-methyltetralin, 61% by weight of 6-methyltetralin, and 22% by weight of 2-methylnaphthalene was supplied to a fixed bed packed with 16cc of Pt-Al2O3-based catalyst, and under normal pressure, A dehydrogenation reaction was carried out at 400°C. The composition of the obtained dehydrogenation product was as follows: 2-methyltetralin 15% by weight, 2-methyltetralin 15% by weight, 2-methyltetralin 15% by weight
Methylnaphthalene content was 75MMt%.
この脱水素生成物１００部に２−メチルナフタレン４２
部を添加し、Ｐ ｔ−Ａ１２ｏ、系触媒を１６ｃｃ充填
した固寅床に供給し、反応温度２００℃、ＬＨ５Ｖ （
供７ｔＨＱｉ量（１／ｈｒ）／充填触媒量（１））２ｈ
ｒで水素化反応せしめた。42 parts of 2-methylnaphthalene was added to 100 parts of this dehydrogenation product.
was added to a solid bed packed with 16 cc of Pt-A12o and catalyst, and the reaction temperature was 200°C, LH5V (
Supply 7tHQi amount (1/hr)/Charged catalyst amount (1)) 2h
A hydrogenation reaction was carried out at r.
得られた水素化生成物の組成は、２−メチルテトラリン
３６重量％、６−メチルテトラリン４４重量％、２−メ
チルナフタレン１６重量％であった。The composition of the obtained hydrogenated product was 36% by weight of 2-methyltetralin, 44% by weight of 6-methyltetralin, and 16% by weight of 2-methylnaphthalene.
この水素化生成物を実施例１と同条件で精密蒸留し、軽
沸物と純度９９．８重量％の２−メチルテトラリンを留
取した。残油の組成は、２−メチルテトラリン１５重量
％、６−メチルテトラリン６１重量％、２−メチルナフ
タレン１２重量％で、脱水素原料として循環使用が可能
であった。This hydrogenated product was subjected to precision distillation under the same conditions as in Example 1, and light boilers and 2-methyltetralin with a purity of 99.8% by weight were distilled off. The composition of the residual oil was 15% by weight of 2-methyltetralin, 61% by weight of 6-methyltetralin, and 12% by weight of 2-methylnaphthalene, and could be recycled as a dehydrogenation raw material.
なお、２−メチルナフタレンに対する２−メチルテトラ
リンの収率は、ｌサイクル総計で８６％であった。The yield of 2-methyltetralin based on 2-methylnaphthalene was 86% in total for 1 cycle.
実施例３
実施例１で使用した５００ｃｃのオートクレーブに６−
メチルテトラリン１５ｇ、２−メチルテトラリン３５ｇ
、２−メチルナフタレン５２ｇからなる原料と、硫化水
素を用いて硫化したＭｏ−Ｎｉ−Ａｌ２０ｇ系触媒１０
ｇを仕込んだのち、窒素雰囲気下、攪拌しながら３７０
℃に昇温しで脱水素反応せしめた。２時間経過後十分に
脱水素したことを確認したのち、温度を３２０℃まで低
下させ、水素ガスを圧入して１００ｋｇ／ｃイまで昇圧
し、２時間水素化反応せしめた。この間水素圧が一定に
なるよう水素ガスを補給した。Example 3 In the 500cc autoclave used in Example 1, 6-
Methyltetralin 15g, 2-methyltetralin 35g
, a raw material consisting of 52 g of 2-methylnaphthalene and 20 g of Mo-Ni-Al catalyst 10 sulfurized using hydrogen sulfide.
After charging 370g of
The temperature was raised to ℃ to cause a dehydrogenation reaction. After confirming that sufficient dehydrogenation had occurred after 2 hours had elapsed, the temperature was lowered to 320° C., hydrogen gas was injected under pressure to increase the pressure to 100 kg/cm2, and a hydrogenation reaction was carried out for 2 hours. During this time, hydrogen gas was supplied to keep the hydrogen pressure constant.
反応終了後、オートクレーブを室温まで降温し、反応生
成物から触媒を濾過して分離したのち、ガスクロマトグ
ラフィーによりその組成を測定したところ、２−メチル
テトラリン３５ｇ、６−メチルテトラリン５１ｇ、２−
メチルナフタレン９ｇであった。After the reaction was completed, the temperature of the autoclave was lowered to room temperature, the catalyst was filtered and separated from the reaction product, and its composition was measured by gas chromatography. The following results were obtained: 35 g of 2-methyltetralin, 51 g of 6-methyltetralin, 2-methyltetralin.
It was 9g of methylnaphthalene.
触媒分離後の反応生成物を、実施例１と同じ蒸留装置を
使用し、還流比１０て精密蒸留し、純度９９．９％の６
−メチルテトラリン３６ｇを留取した。残りの２−メチ
ルテトラリンに富む留分は、２−メチルテトラリン３５
ｇ、６−メチルテトラリン１５ｇ、２−メチルナフタレ
ン９ｇからなり、２−メチルナフタレン４３ｇを追加す
れば、そのまま脱水素原料として循環使用が可能であっ
た。The reaction product after catalyst separation was precision distilled using the same distillation apparatus as in Example 1 at a reflux ratio of 10 to obtain 6.
- 36 g of methyltetralin was distilled off. The remaining 2-methyltetralin-rich fraction contains 2-methyltetralin 35
g, 15 g of 6-methyltetralin, and 9 g of 2-methylnaphthalene, and by adding 43 g of 2-methylnaphthalene, it was possible to recycle it as it was as a dehydrogenation raw material.
このことは、脱水素反応、水素化反応、精密蒸留を組み
合わせることにより、２−メチルナフタレンから６−メ
チルテトラリンを収率８４重量％て製造できることを示
すものである。This shows that 6-methyltetralin can be produced from 2-methylnaphthalene at a yield of 84% by weight by combining dehydrogenation, hydrogenation, and precision distillation.
Claims (5)
化して２または６−アルキルテトラリンを製造する方法
において、水素化生成物から２または６−アルキルテト
ラリンを分離したのち、残部を脱水素して水素化工程へ
循環することを特徴とするアルキルテトラリンの製造方
法。(1) In a method for producing 2- or 6-alkyltetralin by hydrogenating 2-alkylnaphthalene in the presence of a catalyst, 2- or 6-alkyltetralin is separated from the hydrogenated product, and then the remainder is dehydrogenated. A method for producing alkyltetralin, characterized in that the alkyltetralin is recycled to a hydrogenation step.
ン、２−エチルナフタレン、２−イソプロピルナフタレ
ン、２−ブチルナフタレンである特許請求の範囲第１項
記載のアルキルテトラリンの製造方法。(2) The method for producing alkyl tetralin according to claim 1, wherein the 2-alkylnaphthalene is 2-methylnaphthalene, 2-ethylnaphthalene, 2-isopropylnaphthalene, or 2-butylnaphthalene.
件を変化させることにより両反応を個々に生起させるこ
とを特徴とする特許請求の範囲第１項記載のアルキルテ
トラリンの製造方法。(3) The method for producing alkyl tetralin according to claim 1, characterized in that the hydrogenation catalyst and the dehydrogenation catalyst are the same, and both reactions are caused individually by changing reaction conditions.
Ｐｔ、Ｐｄ、Ｎｉ、Ｃｏから選ばれた金属を少なくとも
一種以上含有した触媒を使用することを特徴とする特許
請求の範囲第１項および第３項記載のアルキルテトラリ
ンの製造方法。(4) As a hydrogenation or dehydrogenation catalyst, Mo, W,
4. The method for producing alkyl tetralin according to claims 1 and 3, characterized in that a catalyst containing at least one metal selected from Pt, Pd, Ni, and Co is used.
程に循環使用することを特徴とする特許請求の範囲第１
項および第３〜４項記載のアルキルテトラリンの製造方
法。(5) Claim 1 characterized in that the hydrogen gas produced by the dehydrogenation reaction is recycled to the hydrogenation process.
5. A method for producing an alkyltetralin according to Items 3 and 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61227757A JPH0717531B2 (en) | 1986-09-25 | 1986-09-25 | Method for producing alkyltetralin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61227757A JPH0717531B2 (en) | 1986-09-25 | 1986-09-25 | Method for producing alkyltetralin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6383033A true JPS6383033A (en) | 1988-04-13 |
| JPH0717531B2 JPH0717531B2 (en) | 1995-03-01 |
Family
ID=16865896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61227757A Expired - Lifetime JPH0717531B2 (en) | 1986-09-25 | 1986-09-25 | Method for producing alkyltetralin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717531B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001198469A (en) * | 1999-11-05 | 2001-07-24 | Sekisui Chem Co Ltd | Metal carrying catalyst for storing/supplying hydrogen and hydrogen storage/supply system using the catalyst |
| JP2001354601A (en) * | 2000-06-14 | 2001-12-25 | Dainippon Ink & Chem Inc | Method for manufacturing fluorotetrahydronaphthalene derivative |
| JP2002003416A (en) * | 2000-06-26 | 2002-01-09 | Dainippon Ink & Chem Inc | Method for producing 1,2,3,4-tetrahydronaphthalene derivative |
-
1986
- 1986-09-25 JP JP61227757A patent/JPH0717531B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001198469A (en) * | 1999-11-05 | 2001-07-24 | Sekisui Chem Co Ltd | Metal carrying catalyst for storing/supplying hydrogen and hydrogen storage/supply system using the catalyst |
| JP2001354601A (en) * | 2000-06-14 | 2001-12-25 | Dainippon Ink & Chem Inc | Method for manufacturing fluorotetrahydronaphthalene derivative |
| JP2002003416A (en) * | 2000-06-26 | 2002-01-09 | Dainippon Ink & Chem Inc | Method for producing 1,2,3,4-tetrahydronaphthalene derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0717531B2 (en) | 1995-03-01 |
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