JPH0796505B2 - Indan manufacturing method - Google Patents
Indan manufacturing methodInfo
- Publication number
- JPH0796505B2 JPH0796505B2 JP62324711A JP32471187A JPH0796505B2 JP H0796505 B2 JPH0796505 B2 JP H0796505B2 JP 62324711 A JP62324711 A JP 62324711A JP 32471187 A JP32471187 A JP 32471187A JP H0796505 B2 JPH0796505 B2 JP H0796505B2
- Authority
- JP
- Japan
- Prior art keywords
- indane
- indene
- weight
- catalyst
- purity
- 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
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 title claims description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 60
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 45
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000011280 coal tar Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005909 Kieselgur Substances 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000005554 pickling Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- -1 as impurities Chemical compound 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 150000003939 benzylamines Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- BNRNAKTVFSZAFA-UHFFFAOYSA-N hydrindane Chemical compound C1CCCC2CCCC21 BNRNAKTVFSZAFA-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003756 stirring Methods 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、医薬、農薬などの原料として重要な化合物で
あるインダンの製造方法に関し、特にインデンを含む留
分から高純度のインダンを製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing indane, which is an important compound as a raw material for medicines, agricultural chemicals, etc., and particularly to a method for producing high-purity indane from a fraction containing indene. Regarding
＜従来の技術とその問題点＞ インダンは、一般にインデンの接触還元によって得られ
るが、インデンを含むコールタール留分から蒸留、ある
いは蒸留および晶析によって高純度のインデンを得るこ
とが困難であるため、高純度のインダンを得ることが困
難であった。<Prior art and its problems> Indane is generally obtained by catalytic reduction of indene, but it is difficult to obtain high-purity indene by distillation from a coal tar fraction containing indene or by distillation and crystallization. It was difficult to obtain high-purity indane.
すなわち、インデンを含むコールタール留分中には、イ
ンダンおよび不純物として主としてベンゾニトリルが、
その他クマロン、アニリン、フェノール等が含まれてお
り、これらのうちアニリンおよびフェノールはアルカリ
又は酸で洗浄することによって除去されるが、ベンゾニ
トリルは中性であるためアルカリ又は酸で洗浄しても除
去できず、第３物質を加え共沸蒸留して精製する方法も
あるが、インデンの純度を90重量％以上に高めることが
困難であるため高純度のインダンが得られなかったので
ある。That is, in coal tar fraction containing indene, indane and benzonitrile mainly as impurities,
It also contains coumarone, aniline, phenol, etc. Among them, aniline and phenol can be removed by washing with alkali or acid, but benzonitrile is neutral, so it can be removed even by washing with alkali or acid. There is also a method of refining by adding the third substance and performing azeotropic distillation, but it is difficult to increase the purity of indene to 90% by weight or more, and thus high-purity indane cannot be obtained.
なお、液体クロマトグラフィを用いてベンゾニトリルを
除く方法があるが、工業的には実施困難な方法である。Although there is a method of removing benzonitrile using liquid chromatography, it is an industrially difficult method.
さらに、インデンを含むコールタール留分を接触還元し
たものを精製してインダンの純度を高くすることも困難
であった。Furthermore, it was also difficult to improve the purity of indane by purifying a product obtained by catalytically reducing a coal tar fraction containing indene.
一般に試薬として市販されているインデンは、高純度の
ものが要求されるが、例えば第１表に示すようにその純
度は90.9重量％（和光純薬（株）製）に止まり、これを
接触還元して得たと考えられる市販のインダン試薬（和
光純薬（株）製）のインダンの純度は92.7重量％で2.8
重量％のベンゾニトリルを含んでいる。Generally, indene which is commercially available as a reagent is required to have high purity. For example, as shown in Table 1, the purity is 90.9% by weight (manufactured by Wako Pure Chemical Industries, Ltd.), and this is catalytically reduced. The commercially available indane reagent (manufactured by Wako Pure Chemical Industries, Ltd.), which is considered to have been obtained as described above, has a purity of 2.8 at 92.7% by weight.
Contains by weight benzonitrile.
＜発明の目的＞ 本発明は、従来技術におけるこれらの問題点を解決し、
インデンを含むコールタール留分を接触還元してインデ
ンを水添してインダンとすると同時に不純物として含ま
れているベンゾニトリルを水添したのち、酸洗すること
によってインダンの純度を大幅に向上したインダンを簡
便に製造する方法を提供することを目的とする。 <Object of the Invention> The present invention solves these problems in the prior art,
Coal tar fraction containing indene is catalytically reduced to hydrogenate indene to form indane, and at the same time, benzonitrile contained as an impurity is hydrogenated, followed by pickling to significantly improve the purity of indane. It is an object of the present invention to provide a method for easily producing
＜発明の構成＞ すなわち、本発明によれば、インデンを含むコールター
ル留分を、前記インデンがインダンに、不純物として含
むベンゾニトリルがそのベンジルアミン類になるよう接
触還元したのち、酸洗浄して前記ベンジルアミン類を除
去することを特徴とするインダンの製造方法が提供され
る。<Structure of the Invention> That is, according to the present invention, a coal tar fraction containing indene is catalytically reduced so that the indene becomes indane and benzonitrile contained as an impurity becomes its benzylamines, and then acid washed. There is provided a method for producing indane, which comprises removing the benzylamines.
以下に本発明を詳細に説明する。The present invention will be described in detail below.
本発明で用いるインデンを含むコールタール留分は、脱
酸、脱塩基したコールタール油を蒸留、あるいは蒸留お
よび晶析などによってインデンを濃縮したものを用いる
こトができる。The indene-containing coal tar fraction used in the present invention can be obtained by distilling deoxidized or debased coal tar oil, or concentrated indene by distillation and crystallization.
この留分にはインダンおよびベンゾニトリルが多く含ま
れてもかまわないが、それ以外の成分は少い方が好まし
い。蒸留は常圧、減圧のいずれで行ってもよく、エチレ
ングリコールなどの第３物質を加えた抽出蒸留や共沸蒸
留でもよい。This fraction may contain a large amount of indane and benzonitrile, but the other components are preferably smaller. Distillation may be carried out under normal pressure or reduced pressure, and extraction distillation or azeotropic distillation with addition of a third substance such as ethylene glycol may be carried out.
また、脱酸、脱塩基は蒸留前でなく蒸留後に行ってもよ
い。Deoxidation and debasing may be performed after distillation instead of before distillation.
本発明で用いる触媒は、通常の接触還元用の触媒、例え
ばニッケル／けいそう土またはこれに銅、クロムおよび
モリブデン、前記各金属の酸化物、アルカリおよびアル
カリ土類金属の中の１種または２種以上を加えた触媒、
銅−クロム酸化物またはこれにアルカリ金属およびアル
カリ土類金属の中の１種または２種以上を加えた触媒、
あるいはルテニウム、ロジウム、パラジウムまたは白金
を活性炭またはアルミナなどに担持させた触媒を用いる
ことができる。原料である前記インデンリッチ留分に対
する触媒比は0.01〜10重量％好ましくは0.5〜５重量％
である。これより少ないと反応速度が低下し、多いと過
剰水添されることがある。The catalyst used in the present invention is a conventional catalyst for catalytic reduction, such as nickel / diatomaceous earth or copper, chromium and molybdenum, oxides of each of the above metals, one or two of alkali and alkaline earth metals. A catalyst with more than one seed added,
Copper-chromium oxide or a catalyst obtained by adding one or more of alkali metals and alkaline earth metals thereto,
Alternatively, a catalyst in which ruthenium, rhodium, palladium or platinum is supported on activated carbon or alumina can be used. The catalyst ratio to the above-mentioned indene-rich fraction as a raw material is 0.01 to 10% by weight, preferably 0.5 to 5% by weight.
Is. If it is less than this range, the reaction rate may decrease, and if it is more than that, excessive hydrogenation may occur.
本発明における接触還元の反応条件は、インデンに対し
てはインダンを生成するがパーヒドロインデンまでは水
添されず、ベンゾニトリルに対してはベンジルアミン、
ジベンジルアミンあるいはトリベンジルアミンまで水添
されるように選定することが必要である。The reaction conditions of the catalytic reduction in the present invention are that indane is produced with respect to indene but not hydrogenated up to perhydroindene, and benzylamine with respect to benzonitrile.
It is necessary to choose such that even dibenzylamine or tribenzylamine can be hydrogenated.
すなわち、接触還元の反応温度は90〜200℃好ましくは9
0〜150℃であり、かつ水素圧力は常圧〜200kg/cm2好ま
しくは10〜50kg/cm2である。この理由は90℃未満の温度
で、かつ常圧の水素圧力ではベンゾニトリルの水添を完
全でなく、200℃超で、かつ200kg/cm2超の温度および水
素圧力ではパーヒドロインデンが生成するためである。That is, the reaction temperature for catalytic reduction is 90 to 200 ° C, preferably 9
The temperature is 0 to 150 ° C., and the hydrogen pressure is atmospheric pressure to 200 kg / cm 2, preferably 10 to 50 kg / cm 2 . The reason for this is that hydrogenation of benzonitrile is not complete at temperatures below 90 ° C and normal hydrogen pressure, and perhydroindene is produced at temperatures above 200 ° C and above 200 kg / cm 2 and hydrogen pressure. This is because.
溶媒は特に必要としないが、炭化水素類やアルコール、
エステル等を溶媒として用いてもよい。No solvent is required, but hydrocarbons, alcohols,
You may use ester etc. as a solvent.
接触還元用の装置としては、オートクレーブなどを用い
た回分式でも流通式でもよい。As a device for catalytic reduction, a batch type using an autoclave or a flow type may be used.
インデンリッチ留分を接触還元して得られた水添油は、
酸水溶液と混合することにより水添油中のベンジルアミ
ン、ジベンジルアミンおよびベンジルアミンなどの塩基
性成分が水層に抽出され分離される。酸水溶液として
は、通常の酸抽出に用いられる酸、例えば、硫酸、塩
酸、硝酸などを用いることができ、その濃度は数〜数十
重量％、好ましくは10〜25重量％である。水層に抽出さ
れて分離されたベンジルアミン、ジベンジルアミンおよ
びトリベンジルアミンなどは、アンモニア水などを加え
反応させることにより油層として回収できる。The hydrogenated oil obtained by catalytically reducing the inden rich fraction is
By mixing with an aqueous acid solution, basic components such as benzylamine, dibenzylamine and benzylamine in the hydrogenated oil are extracted and separated in the aqueous layer. As the aqueous acid solution, an acid used for ordinary acid extraction, for example, sulfuric acid, hydrochloric acid, nitric acid or the like can be used, and the concentration thereof is several to several tens wt%, preferably 10 to 25 wt%. The benzylamine, dibenzylamine, tribenzylamine and the like extracted and separated in the aqueous layer can be recovered as an oil layer by adding ammonia water and reacting.
酸で洗浄したあとの水添油には、全くベンジルアミンも
ジベンジルアミンもトリベジルアミンも存在せず、これ
らが除去された分だけインダンの純度が向上する。イン
ダンの純度は、インデンリッチ留分中のインダンおよび
ベンゾニトリル以外の不純物の量によって制約される
が、これらの不純物は通常インダンやベンゾニトリルに
比べて少量であるため、本発明により95〜99重量％純度
のインダンを工業的に得ることが可能となる。In the hydrogenated oil after washing with acid, benzylamine, dibenzylamine and tribedylamine were not present at all, and the purity of indane was improved by the amount removed. The purity of indane is limited by the amount of impurities other than indane and benzonitrile in the indene-rich fraction, but since these impurities are usually small compared to indane and benzonitrile, 95-99 wt% according to the present invention. It is possible to industrially obtain% purity indane.
＜実施例＞ 以下に、本発明を実施例に基づき具体的に説明する。<Examples> Hereinafter, the present invention will be specifically described based on Examples.
（実施例１） 脱酸、脱塩基したコールタールナフサ油を蒸留および晶
析して得たインデン90.2重量％、インダン4.4重量％、
ベンゾニトリル3.5重量％、その他1.9重量％からなるイ
ンデンリッチ留分150gとニッケル／けいそう土触媒1.5g
を内容積400mlの誘導回路攪拌式オートクレーブに入
れ、気相を窒素でバージしたのち、120℃の温度および
水素圧力30kg/cm2で２時間反応させた。得られた水添油
の組成は、インダン94.6重量％、ベンジルアミン、ジベ
ンジルアミンおよびトリベジルアミンの合計が3.4重量
％、その他が2.0重量％であった。この水添油を25重量
％硫酸溶液50mlで処理した水層を分離した油層には、9
8.2重量％のインダンを含まれていた。水添後および酸
洗後の各組成は第２表の通りであった。(Example 1) 90.2% by weight of indene and 4.4% by weight of indane obtained by distillation and crystallization of deoxidized and debased coal tar naphtha oil
150 g of indene-rich fraction consisting of 3.5% by weight of benzonitrile and 1.9% by weight of others, and 1.5 g of nickel / diatomaceous earth catalyst
Was placed in an induction circuit stirring autoclave having an internal volume of 400 ml, and the gas phase was barged with nitrogen, and then reacted at a temperature of 120 ° C. and hydrogen pressure of 30 kg / cm 2 for 2 hours. The composition of the obtained hydrogenated oil was 94.6% by weight of indane, 3.4% by weight of the total of benzylamine, dibenzylamine and tribedylamine, and 2.0% by weight of others. This hydrogenated oil was treated with 50 ml of 25% by weight sulfuric acid solution.
It contained 8.2% by weight of indane. The respective compositions after hydrogenation and after pickling are shown in Table 2.
また、前記水層をアンモニア水で処理し、ベンジルアミ
ン、ジベンジルアミンおよびトリベンジルアミンあわせ
て5.3gが得られた。Further, the aqueous layer was treated with aqueous ammonia to obtain 5.3 g of benzylamine, dibenzylamine and tribenzylamine in total.
（実施例２） 脱酸、脱塩基したコールタールナフサ油を蒸留して得た
インデン80.2重量％、インダン9.5重量％、ベンゾニト
リル6.9重量％からなるインデンリッチ留分150gとニッ
ケル／けいそう土触媒1.5gを用いた以外は実施例１と同
様の操作で水添および酸洗を行った。(Example 2) 150 g of an indene-rich fraction composed of 80.2% by weight of indene obtained by distilling deoxidized and debased coal tar naphtha oil, 9.5% by weight of indane, and 6.9% by weight of benzonitrile, and a nickel / diatomaceous earth catalyst. Hydrogenation and pickling were performed in the same manner as in Example 1 except that 1.5 g was used.
酸洗後の各組成は第２表の通りであった。The compositions after pickling are shown in Table 2.
（実施例３〜８） 実施例１と同じインデンリッチ留分を用い、第３表に示
す触媒および反応条件を用いた以外は、実施例１と同様
の操作で水添および酸洗を行った。酸洗後のインダ純度
な第３表の通りであった。なお、各実施例の触媒量はい
ずれも用いたインデンリッチ留分に対して１重量％とし
た。(Examples 3 to 8) Hydrogenation and pickling were performed in the same manner as in Example 1 except that the same indene rich fraction as in Example 1 was used and the catalyst and reaction conditions shown in Table 3 were used. . The inda purity after pickling was as shown in Table 3. The amount of catalyst used in each example was 1% by weight based on the inden rich fraction used.
（比較例１） 実施例１と同じインデンリッチ留分を150gとニッケル／
けいそう土触媒1.5gを用い、80℃の温度および水素圧力
10kg/cm2とした以外は実施例１と同様の操作で水添およ
び酸洗を行った。水添後および酸洗後の各組成は第２表
の通りであった。(Comparative Example 1) 150 g of the same indene rich fraction as in Example 1 and nickel /
Using diatomaceous catalyst 1.5g, temperature of 80 ℃ and hydrogen pressure
Hydrogenation and pickling were performed in the same manner as in Example 1 except that the amount was 10 kg / cm 2 . The respective compositions after hydrogenation and after pickling are shown in Table 2.
第２表および第３表から明らかなように、本発明の実施
例ではいずれも高純度のインダンが得られており、実施
例２のようにインデンが80重量％のインデンリッチ留分
からも高純度のインダンが得られた。 As is clear from Tables 2 and 3, high-purity indane was obtained in all of the examples of the present invention, and the high-purity indene-rich fraction having an indene content of 80 wt% as in Example 2 was also obtained. I got Indan of.
＜発明の効果＞ 本発明によれば、インデンを含むコールタール留分を接
触還元してインデンを水添してインダンとすると同時に
不純物のベンゾニトリルを水添したのち、酸洗するとい
う簡便な操作によって高純度のインダンを製造すること
ができる。<Effects of the Invention> According to the present invention, a simple operation of catalytically reducing a coal tar fraction containing indene to hydrogenate indene to give indane, hydrogenated impurities benzonitrile, and then pickling Thus, high-purity indane can be produced.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 23/44 Ｘ 23/46 ３０１ Ｘ ３１１ Ｘ 23/755 23/78 Ｘ Ｃ０７Ｂ 61/00 ３００ (56)参考文献 特開 昭52−85109（ＪＰ，Ａ) 特開 昭60−87230（ＪＰ，Ａ) 特公 昭40−15001（ＪＰ，Ｂ１)Continuation of the front page (51) Int.Cl. 6 Identification number Internal reference number for FI FI technical display location B01J 23/44 X 23/46 301 X 311 X 23/755 23/78 X C07B 61/00 300 (56) Reference References JP-A-52-85109 (JP, A) JP-A-60-87230 (JP, A) JP-B-4015001 (JP, B1)
Claims (3)
インデンがインダンに、不純物として含むベンゾニトリ
ルがそのベンジルアミン類になるように接触還元したの
ち、酸洗浄して前記ベンジルアミン類を除去することを
特徴とするインダンの製造方法。1. A coal tar fraction containing indene is catalytically reduced so that the indene becomes indane and the benzonitrile contained as an impurity becomes its benzylamine, and then acid washed to remove the benzylamine. A method for producing indane, which is characterized in that
たはこれに銅、クロムおよびモリブデン、前記各金属の
酸化物、アルカリおよびアルカリ土類金属の中の１種ま
たは２種以上を加えた触媒、銅一クロム酸化物またはこ
れにアルカリ金属およびアルカリ土類金属の中の１種ま
たは２種以上を加えた触媒、あるいはルテニウム、ロジ
ウム、パラジウムまたは白金を活性炭またはアルミナに
担持させた触媒である特許請求の範囲第１項記載の製造
方法。2. A catalyst for catalytic reduction comprising nickel / diatomaceous earth or a catalyst obtained by adding one or more of copper, chromium and molybdenum, oxides of the above metals, alkalis and alkaline earth metals. , Copper-chromium oxide or a catalyst obtained by adding one or more of alkali metal and alkaline earth metal to it, or ruthenium, rhodium, palladium or platinum supported on activated carbon or alumina The manufacturing method according to claim 1.
水素圧力が常圧〜200kg/cm2である特許請求の範囲第１
項または第２項記載の製造方法。3. The method according to claim 1, wherein the temperature of the catalytic reduction reaction is 90 to 200 ° C., and the hydrogen pressure is atmospheric pressure to 200 kg / cm 2 .
Item 2. The method according to item 2 or item 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62324711A JPH0796505B2 (en) | 1987-12-22 | 1987-12-22 | Indan manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62324711A JPH0796505B2 (en) | 1987-12-22 | 1987-12-22 | Indan manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01165532A JPH01165532A (en) | 1989-06-29 |
| JPH0796505B2 true JPH0796505B2 (en) | 1995-10-18 |
Family
ID=18168855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62324711A Expired - Lifetime JPH0796505B2 (en) | 1987-12-22 | 1987-12-22 | Indan manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0796505B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10737993B2 (en) | 2017-04-18 | 2020-08-11 | Mitsubishi Gas Chemical Company, Inc. | Method for producing indancarbaldehyde |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1464657A1 (en) | 2003-03-06 | 2004-10-06 | ATOFINA Research | Hydrogenated metallocene catalyst |
| CN112642423B (en) * | 2020-12-14 | 2023-08-11 | 辽宁铭鑫环境工程有限公司 | Preparation and application of high-temperature coal tar-based palladium carbon |
-
1987
- 1987-12-22 JP JP62324711A patent/JPH0796505B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10737993B2 (en) | 2017-04-18 | 2020-08-11 | Mitsubishi Gas Chemical Company, Inc. | Method for producing indancarbaldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01165532A (en) | 1989-06-29 |
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