JPH02282337A - Alkylation of benzene using super-strong solid acid catalyst - Google Patents
Alkylation of benzene using super-strong solid acid catalystInfo
- Publication number
- JPH02282337A JPH02282337A JP1101566A JP10156689A JPH02282337A JP H02282337 A JPH02282337 A JP H02282337A JP 1101566 A JP1101566 A JP 1101566A JP 10156689 A JP10156689 A JP 10156689A JP H02282337 A JPH02282337 A JP H02282337A
- Authority
- JP
- Japan
- Prior art keywords
- benzene
- catalyst
- silica
- dialkyl ether
- alumina
- 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 5
- 230000029936 alkylation Effects 0.000 title abstract description 3
- 239000011973 solid acid Substances 0.000 title 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 abstract description 25
- 150000001983 dialkylethers Chemical class 0.000 claims abstract description 17
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- -1 hydrogen ammonium fluoride Chemical class 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000007423 decrease Effects 0.000 abstract description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 5
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical class CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002168 alkylating agent Substances 0.000 description 4
- 229940100198 alkylating agent Drugs 0.000 description 4
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 4
- 239000003930 superacid Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SHHIADHOJKLUIZ-UHFFFAOYSA-N azane;molecular hydrogen Chemical compound N.[H][H] SHHIADHOJKLUIZ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/865—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an ether
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、固体超強酸触媒として、ぶつ化水素アンモニ
ウム担持シリカ・アルミナ触媒を用いてベンゼンとジア
ルキルエーテルを反応させアルキルベンゼンを得る方法
に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for obtaining alkylbenzene by reacting benzene and dialkyl ether using a silica/alumina catalyst supported on ammonium hydrogen fluoride as a solid super strong acid catalyst.
（従来の技術）
ベンゼンのアルキル化反応は、石油化学工業においてア
ルキルベンゼン製造のために広く利用されている。通常
、酸触媒として硫酸、リン酸、塩化アルミ、シリカ・ア
ルミナ、ゼオライトなどが用いられ、ベンゼンに対しア
ルキル化剤にはオレノィンやアルコールを使用している
。(Prior Art) Benzene alkylation reactions are widely used in the petrochemical industry to produce alkylbenzenes. Usually, sulfuric acid, phosphoric acid, aluminum chloride, silica/alumina, zeolite, etc. are used as acid catalysts, and oleinoin or alcohol is used as alkylating agent for benzene.
担持シリカ−アルミナ系超強酸触媒には、担持物として
五ふっ化アンチモン（Ｓ ｂ Ｆ５）を使用しているが
、それを用いてベンゼンのアルキル化反応を行った報告
は見当らない。〔田部浩三、野依良治、「超強酸・超強
塩基」講談社（１９８０）Ｐ３参照〕
（発明が解決しようとする課題）
従来用いられている固体超強酸触媒には、成分の一つと
して五ふっ化アンチモンが担持されているが、それは極
めて高価な薬品（試薬として５１当り４， ０ ０ ０
円）である。さらに、毒性や腐食性のためシリカ−アル
ミナに担持する際には熟練を必要とする。Although antimony pentafluoride (S b F5) is used as a support in a supported silica-alumina super acid catalyst, there have been no reports of alkylation of benzene using it. [Refer to Kozo Tabe, Ryoji Noyori, "Super Strong Acids and Super Strong Bases," Kodansha (1980), p. 3] (Problem to be solved by the invention) The conventionally used solid super strong acid catalyst contains five fluorine as one of its components. Antimony chloride is supported, but it is an extremely expensive chemical (4,000 per 51 as a reagent).
yen). Furthermore, due to its toxicity and corrosivity, skill is required when supporting it on silica-alumina.
本発明は、五ふつ化アンチモンを含まない、担持シリカ
・アルミナ系超強酸触媒を開発し、それを用いてベンゼ
ンとジアルキルエーテルらアルキルベンゼンを得ること
を目的としている。The purpose of the present invention is to develop a supported silica/alumina super acid catalyst that does not contain antimony pentafluoride, and to use it to obtain alkylbenzenes such as benzene and dialkyl ethers.
一方、ベンゼンのアルキル化に際しては、アルキル化剤
にオレフィンを用いると１００〜２００℃で反応が進行
する。しかし、オレフィンの重合が併発したり、原料オ
レフィンの貯蔵場所など問題点も多い。さらに、アルキ
ル化剤にアルコールを使用する場合は、反応温度が２５
０〜３００℃必要であり、反応したベンゼン１モル当り
に１モルの水が生成する。この水はルイス酸点を主な活
性点としている超強酸を被毒して活性低下をもたらす。On the other hand, when alkylating benzene, when an olefin is used as an alkylating agent, the reaction proceeds at 100 to 200°C. However, there are many problems such as co-occurrence of olefin polymerization and storage of raw material olefin. Furthermore, when alcohol is used as an alkylating agent, the reaction temperature is 25
The temperature is 0 to 300°C, and 1 mol of water is produced per 1 mol of reacted benzene. This water poisons super strong acids whose main active sites are Lewis acid sites, resulting in a decrease in activity.
本発明は、ぶつ化水素アンモニウム担持シリカ・アルミ
ナ触媒存在下、ベンゼンとジアルキルエーテルを反応さ
せれば、水の生成が減少し超強酸の被毒が弱められ、２
００℃以下でも効率良くアルキルベンゼンが得られる方
法を提供するものである。The present invention shows that by reacting benzene and dialkyl ether in the presence of ammonium hydrogen fluoride supported silica/alumina catalyst, the production of water is reduced and the poisoning of super strong acids is weakened.
The present invention provides a method for efficiently obtaining alkylbenzene even at temperatures below 00°C.
（課題を解決するための手段）
すなわち、本発明は、固体超強酸触媒としてぶつ化水素
アンモニウム担持シリカ・アルミナ触媒を用いて、ベン
ゼンとジアルキルエーテルカラアルキルベンゼンを得る
方法でアル。(Means for Solving the Problems) That is, the present invention provides a method for obtaining benzene and dialkyl ether coloralkylbenzene using a silica/alumina catalyst supported on ammonium hydrogen hydride as a solid super strong acid catalyst.
固体超強酸触媒とは、Ｚｏｏ ％硫酸よりも強い酸強度
を有する固体酸触媒と定義されている。A solid super acid catalyst is defined as a solid acid catalyst having a stronger acid strength than Zoo% sulfuric acid.
ハメットの酸度関数Ｈ８は、１００φ硫酸の場合Ｈａ−
１１，９３であるから、Ｈｏ（−１１，，９３の酸強度
を有するものが固体超強酸触媒である。この触媒は従来
よりも低い反応温度で触媒活性を有する他に、■触媒と
反応物の分離が容易、■触媒を繰り返し使用することが
可能、■触媒が反応器を腐食しないなどの特長がある。Hammett's acidity function H8 is Ha-
11,93, a solid superacid catalyst has an acid strength of Ho(-11,,93.This catalyst has catalytic activity at a lower reaction temperature than conventional catalysts. It has the following advantages: 1. The catalyst can be used repeatedly; 2. The catalyst does not corrode the reactor.
本発明において用いられる装置は、連続的な気相反応を
行うことから、常圧固定床流通系が好まし力。また、原
料の無用の酸化を避はアルキルベンゼンの収率を向上さ
せるために、酸素の存在しない条件下で反応を行うのが
望ましい。Since the apparatus used in the present invention performs a continuous gas phase reaction, an atmospheric pressure fixed bed flow system is preferable. Furthermore, in order to avoid unnecessary oxidation of raw materials and improve the yield of alkylbenzene, it is desirable to carry out the reaction under conditions in the absence of oxygen.
本明細書におけるジアルキルエーテルのアルキル基には
、エチル基、プロピル基、イソブチル基、ｎ−ブチル基
、イソブチル基がある。The alkyl group of dialkyl ether in this specification includes ethyl group, propyl group, isobutyl group, n-butyl group, and isobutyl group.
本発明において、反応系へ導入される原料の割合は、ベ
ンゼンのジアルキルエーテルに対するモル比で２０以下
が好ましい。In the present invention, the ratio of raw materials introduced into the reaction system is preferably 20 or less in molar ratio of benzene to dialkyl ether.
本発明において用いた触媒担体はシリカ・アルミナで、
ンリカ分が７０ｗｔ％以上の粉末状のものであり、所定
濃度のふり化水素アンモニウム水溶液に浸漬してぶつ化
水素アンモニウム担持シリカ・アルミナ触媒とすること
ができる。The catalyst carrier used in the present invention is silica alumina,
It is in the form of a powder having a phosphoric acid content of 70 wt % or more, and can be made into a silica/alumina catalyst supporting ammonium hydrogen fluoride by immersing it in an aqueous solution of ammonium hydrogen fluoride at a predetermined concentration.
シリカ・アルミナに対するぶつ化水素アンモニウムの担
持率は２ｗｔ％以上であるが、特に７ｗｔ係以上が好ま
しい。ぶつ化水素アンモニウム水溶液の濃度は１〜１．
５ｗｔ％が好ましく、シリカ・アルミナを７日間以上浸
漬した後、湯浴上で蒸発乾固しさらに１２０℃で２４時
間乾燥する。The supporting ratio of ammonium hydrogen fluoride to silica/alumina is 2 wt % or more, and particularly preferably 7 wt % or more. The concentration of the ammonium hydrogen fluoride aqueous solution is 1 to 1.
It is preferably 5 wt%, and after immersing the silica/alumina for 7 days or more, it is evaporated to dryness on a hot water bath and further dried at 120° C. for 24 hours.
本発明の具体的方法は、長さ６０ｃｍの透明石英製の反
応管（２０＋ｎ＋ａダ）の所定の位置に触媒を充てんし
、４００〜６００℃で乾燥空気を流通して触媒を活性化
する。次いで内部の空気を窒素で置換した後、マイクロ
フィーダーで原料を反応系へ供給する。A specific method of the present invention is to fill a predetermined position of a 60 cm long transparent quartz reaction tube (20+n+a) with a catalyst, and activate the catalyst by flowing dry air at 400 to 600°C. Next, after replacing the internal air with nitrogen, the raw material is supplied to the reaction system using a microfeeder.
本発明における反応温度は５０℃以上であるが特に２０
０〜２５０℃が好ましい。また反応時間は、１〜１０時
間で行われるが、１〜５時間で行うのが好都合である。The reaction temperature in the present invention is 50°C or higher, but especially 20°C.
0 to 250°C is preferred. The reaction time is 1 to 10 hours, but it is convenient to carry out the reaction for 1 to 5 hours.
本発明における生成物は無色透明の液体であり、その定
性・定量分析にはガスマス（島津製作所、ＬＫＢ−９０
００）、ガスクロマトグラフィー（島津製作所、ＧＣ−
６Ａ１ＧＣ−７Ａ１柳本製作所、Ｇ−８０）を適宜使用
した。The product of the present invention is a colorless and transparent liquid, and its qualitative and quantitative analysis is carried out using Gasmass (Shimadzu Corporation, LKB-900).
00), gas chromatography (Shimadzu, GC-
6A1GC-7A1 Yanagimoto Seisakusho, G-80) was used as appropriate.
生成物中ニハ、トルエン、エチルベンゼン、インプロピ
ルベンゼン、ｎ−７”ロビルベンゼン、ブチルベンゼン
類など化学工業原料として重要なアルキルベンゼンと、
ナフタレン、α−メチルナフタレン等の多環芳香族炭化
水素が存在している。生成物中におけるアルキルベンゼ
ンの割合は９５ｗｔ％以上を占め、蒸留を経て純品とし
て回収することができる。同時に未反応のベンゼンも回
収され、再使用することができる。The products contain alkylbenzenes that are important as raw materials for the chemical industry, such as niha, toluene, ethylbenzene, impropylbenzene, n-7'' lobylbenzene, and butylbenzenes.
Polycyclic aromatic hydrocarbons such as naphthalene and α-methylnaphthalene are present. The proportion of alkylbenzene in the product is 95 wt% or more, and it can be recovered as a pure product through distillation. At the same time, unreacted benzene is also recovered and can be reused.
反応終了後の触媒は、反応管から取り出すことなく、乾
燥空気気流中４５０〜５５０℃で焼成され再活性化の後
、再使用できる。The catalyst after the reaction is fired at 450 to 550° C. in a stream of dry air without being taken out from the reaction tube, and after reactivation, it can be reused.
本発明において、無触媒ではベンゼンとジアルキルエー
テルからアルキルベンゼンは生成しない。また、シリカ
・アルミナ担体存在下でベンゼンとジアルキルエーテル
の反応を行った場合、２００℃以下ではアルキルベンゼ
ンの生成ハはとんど見られない。さらに、シリカ、アル
ミナ担体にぶつ化アンモニウム（ＮＨ４Ｆ）を担持させ
た触媒も超強酸性を示さずアルキルベンゼンの生成には
活性がない。In the present invention, alkylbenzene is not produced from benzene and dialkyl ether without a catalyst. Furthermore, when benzene and dialkyl ether are reacted in the presence of a silica/alumina carrier, the formation of alkylbenzene is hardly observed at temperatures below 200°C. Further, a catalyst in which ammonium fluoride (NH4F) is supported on a silica or alumina carrier does not exhibit super acidity and is not active in producing alkylbenzene.
以上のことから、ぶつ化水素アンモニウム担持シリカ・
アルミナ触媒の活性は、シリカ・アルミナ担体の表面水
酸基および構造内の酸素イオンとふっ化水素アンモニウ
ムの相互作用により、ブレンステッド酸性が強められ、
同時にアルミイオンのルイス酸性も強められているため
、超強酸触媒能が発現すると考察される。From the above, ammonium hydrogen fluoride-supported silica
The activity of the alumina catalyst is due to the interaction between the hydroxyl groups on the surface of the silica/alumina support and the oxygen ions in the structure and ammonium hydrogen fluoride, which strengthens the Brønsted acidity.
At the same time, the Lewis acidity of aluminum ions is also strengthened, so it is considered that super strong acid catalytic ability is developed.
したがって、本発明の反応機構は、ジアルキルエーテル
に対しブレンステッド酸点よリプロトン（Ｈ＋）が供給
されるカルボニウムイオン機構と、ルイス酸点により、
ジアルキルエーテルからハイドライドイオン（Ｈ−）が
引き抜かれるカルボニウムイオン機構の両者により、ジ
アルキルエーテルが分極された後ベンゼンと反応しアル
キルベンゼンを生成するものと考察される。Therefore, the reaction mechanism of the present invention is a carbonium ion mechanism in which a proton (H+) is supplied from a Brønsted acid site to a dialkyl ether, and a Lewis acid site.
It is considered that the dialkyl ether is polarized and then reacts with benzene to produce alkylbenzene due to both the carbonium ion mechanism in which a hydride ion (H-) is extracted from the dialkyl ether.
（実施例） 以下、実施例により本発明を説明する。(Example) The present invention will be explained below with reference to Examples.
実施例１
内容積５００−のプラスチ、り製容器内で、ぶつ化水素
アンモニウム１．１５ｆを純水１００−に溶解し、担体
として粉末状７リカ・アルミナ（シリカ分７２ｗｔ％）
１５グを７日間浸漬した。さらに湯浴上で蒸発乾固した
後、オーブン中１２０℃で２４時間乾燥してぶつ化水素
アンモニウム担持シリカ・アルミナ触媒（担持率７．６
ｗｔ％）を得た。Example 1 In a plastic container with an internal volume of 500 ml, 1.15 f of ammonium hydrogen fluoride was dissolved in 100 ml of pure water, and powdered 7 lyca alumina (silica content 72 wt%) was used as a carrier.
15 grams were soaked for 7 days. After further evaporating to dryness on a hot water bath, it was dried in an oven at 120°C for 24 hours to obtain a silica/alumina catalyst supported with ammonium hydrogen fluoride (support ratio 7.6).
wt%) was obtained.
超強酸であることの判定にはハメット指示薬を用いた。A Hammett indicator was used to determine whether it was a super strong acid.
すなわち、作製した触媒０．５２を乾燥空気気流中５５
０℃で３時間焼成した後、５分割して各々を十分脱水さ
れた塩化スルフリル液３−を入れた試験管中に投入した
。次いで、以下の５種類のハメット指示薬の１％ベンゼ
ン溶液を各々の試験管に数滴入れて、数回軽く振ってか
ら静置して触媒表面の変色の有無を肉眼で（７ン
観察した。ハメット指示薬には、ｍ−ニトロトルｘ ン
（ＰＫａ ＝−１１，９９）、ニトロベンゼン（ｐｘａ
１２．１４）、Ｐ−フルオｏ＝トロベンゼン（ＰＫａ１
２．４．４）、Ｐ−クロロニトロベンゼｙ（ｐｘａ＝１
２．７０）、ｍ−りｏｏ、＝、トロベンゼン（ｐＫａ＝
１３．１６）を使用したところ、すべての指示薬を変色
した。このことから、作製した触媒の酸強度はＨ８く〜
１３．１６であり、１００％硫酸の酸強度（Ｈｏ−１１
゜９３）の１７倍以上であることが示された。That is, 0.52% of the prepared catalyst was placed in a stream of dry air at 55%
After baking at 0°C for 3 hours, it was divided into 5 parts and each part was placed in a test tube containing sufficiently dehydrated sulfuryl chloride solution 3-. Next, a few drops of a 1% benzene solution of the following five types of Hammett indicators were added to each test tube, shaken lightly several times, and left to stand, and the presence or absence of discoloration on the surface of the catalyst was observed with the naked eye (7 times). Hammett indicators include m-nitrotorxone (PKa = -11,99), nitrobenzene (pxa
12.14), P-fluoro-trobenzene (PKa1
2.4.4), P-chloronitrobenzey (pxa=1
2.70), m-rioo,=, trobenzene (pKa=
13.16), all indicators changed color. From this, the acid strength of the prepared catalyst is H8 ~
13.16, the acid strength of 100% sulfuric acid (Ho-11
93).
実施例２゜
実施例１で得られた触媒４５７を、長さ６０口の透明石
英製の反応管（２０ｍ＋ｎＯ）の所定の位置に充てんし
、その上部には原料拡散層としてガラスピーズを入れた
。その反応管を５５０℃の電気炉にセ、トシた後、乾燥
空気を１００ｍ６／ｍｉｎ以上、３時間流通し触媒を活
性化した。次いで窒素ガスを２時間流通して内部の空気
を置換した後、反応温度を２００℃にセットした。Example 2 The catalyst 457 obtained in Example 1 was filled in a predetermined position in a 60-neck transparent quartz reaction tube (20 m + nO), and glass beads were placed in the upper part as a raw material diffusion layer. . After the reaction tube was placed in an electric furnace at 550° C., dry air was passed through it at a rate of 100 m 6 /min or more for 3 hours to activate the catalyst. Next, nitrogen gas was passed through the reactor for 2 hours to replace the air inside, and then the reaction temperature was set at 200°C.
反応原料は、ベンゼン／ジエチルエーテルのモル比が２
で反応系へ供給されるように、二台のマイクロフィーダ
ーを用いて反応管上部より窒素ガスと共に送入した。捷
だ、接触時間（Ｗ／Ｆ）は、９６．１ Ｓ’ −ｃａｔ
−ｈｒ／ｍｏｌとなるように調節した。The reaction raw materials have a benzene/diethyl ether molar ratio of 2.
Two microfeeders were used to feed the nitrogen gas together with nitrogen gas from the top of the reaction tube. The contact time (W/F) is 96.1 S'-cat
-hr/mol.
液体生成物および未反応原料は、反応管下部の冷却器で
凝縮され、氷冷されたサンプルビンに最初の１滴が落下
した時を反応開始とし、９０分間反応させた。液収率は
過大原料に対し８゜ｗｔ％であった。液収率が低いのは
主にジエチルエーテルが分解され、気体となって散逸し
たことが原因である。液体生成物の収率は、酢酸イソア
ミルを内標準物質としてガスクロマトグラフィーで定量
し、送入ベンゼン基準で表わした。The liquid product and unreacted raw materials were condensed in a condenser at the bottom of the reaction tube, and the reaction was started when the first drop fell into an ice-cooled sample bottle, and the reaction was continued for 90 minutes. The liquid yield was 8°wt% based on the excess raw material. The low liquid yield is mainly due to diethyl ether being decomposed and dissipated as a gas. The yield of the liquid product was determined by gas chromatography using isoamyl acetate as an internal standard and expressed on the basis of fed benzene.
その結果、エチルベンゼン（５，０ｗｔ％）、イソプロ
ピルベンゼン（０，１ｗｔ％）、インブチルベンゼン（
０，２ｗｔ％）、ｎ−ブチルベンゼン（０，５ｗｔ％）
、ナフタリン（０，１ｗｔ％）、α−メチルナフタリン
（０，１，ｗｔ％）であり、エチルベンゼンの選択率が
極めて高い結果を得た。また、反応装置が流通系のため
、接触時間の増加により収率の増大を計ることができる
。As a result, ethylbenzene (5.0 wt%), isopropylbenzene (0.1 wt%), inbutylbenzene (
0.2wt%), n-butylbenzene (0.5wt%)
, naphthalene (0.1 wt%), and α-methylnaphthalene (0.1 wt%), resulting in extremely high selectivity for ethylbenzene. Furthermore, since the reaction apparatus is a flow system, it is possible to increase the yield by increasing the contact time.
比較例１
担持シリカ・アルミナ超強酸触媒には、担持物として五
ふっ化アンチモンを使用する場合が多い。実施例１のぶ
つ化水素アンモニウムの代わりに五ふっ化アンチモンを
用いて、五ふっ化アンチモン担持シリカ・アルミナ触媒
を作製した。しかし、酸強度は■。〈−１２４４であり
超強酸性を示したが、ぶつ化水素アンモニウム担持シリ
カ・アルミナ触媒よりは酸性が弱い結果を示した。さら
に、五ふっ化アンチモン担持シリカ・アルミナ存在下、
実施例２と同条件で、ベンゼンとジエチルエーテルの反
応を行ったところ、生成物は、エチルベンゼン（２，３
ｗｔ％）、イノブチルベンゼン（０，２ｗｔ％）、ｎ−
ブチルベンゼン（０，２ｗｔ％）で、他の生成物は０．
１ｗｔ％以下でちった。Comparative Example 1 Supported silica/alumina Antimony pentafluoride is often used as a support for super strong acid catalysts. An antimony pentafluoride-supported silica/alumina catalyst was prepared by using antimony pentafluoride in place of ammonium hydrogen fluoride in Example 1. However, the acid strength is ■. <-1244, indicating super acidity, but weaker acidity than the ammonium hydrogen fluoride supported silica/alumina catalyst. Furthermore, in the presence of antimony pentafluoride-supported silica/alumina,
When benzene and diethyl ether were reacted under the same conditions as in Example 2, the product was ethylbenzene (2,3
wt%), inobutylbenzene (0.2 wt%), n-
Butylbenzene (0.2 wt%), other products 0.
It was less than 1wt%.
（発明の効果）
以上のように、本発明方法によれば、安価なぶつ化水素
アンモニウム担持シリカ・アルミナ触媒存在下で、ベン
ゼンとジアルキルエーテルから２００℃程度の反応温度
で高収率、高選択率でアルキルベンゼンを得ることがで
きる。(Effects of the Invention) As described above, according to the method of the present invention, benzene and dialkyl ether are reacted with high yield and high selectivity at a reaction temperature of about 200°C in the presence of an inexpensive ammonium hydrogen fluoride supported silica/alumina catalyst. Alkylbenzene can be obtained at a high rate.
触媒作製においても、ぶつ化水素アンモニウムの取扱い
は危険がなく、再現性の良い活性を得ることができる。In the production of catalysts, ammonium hydrogen fluoride is not dangerous to handle, and activity can be obtained with good reproducibility.
さらに、アルキル化剤にジアルキルエーテルを用いるの
でアルコールの場合と比べて水の生成が減少し、触媒の
活性を持続させることができる。Furthermore, since a dialkyl ether is used as an alkylating agent, the production of water is reduced compared to the case of alcohol, and the activity of the catalyst can be sustained.
また、製造には連続反応装置を使用できるため、経済的
効果が大きく極めて有利な工業的プロセスとして利用す
ることができる。Furthermore, since a continuous reaction apparatus can be used for production, it can be used as an extremely advantageous industrial process with great economic effects.
Claims (1)
カ、アルミナ触媒存在下、ベンゼンとジアルキルエーテ
ルを加熱してアルキル化反応を生起させアルキルベンゼ
ンを得る方法。A method to obtain alkylbenzene by heating benzene and dialkyl ether in the presence of ammonium hydrogen fluoride (NH_4F・HF) supported silica and alumina catalyst to cause an alkylation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1101566A JPH0639422B2 (en) | 1989-04-24 | 1989-04-24 | Alkylation of benzene using solid superacid catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1101566A JPH0639422B2 (en) | 1989-04-24 | 1989-04-24 | Alkylation of benzene using solid superacid catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02282337A true JPH02282337A (en) | 1990-11-19 |
| JPH0639422B2 JPH0639422B2 (en) | 1994-05-25 |
Family
ID=14303961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1101566A Expired - Lifetime JPH0639422B2 (en) | 1989-04-24 | 1989-04-24 | Alkylation of benzene using solid superacid catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0639422B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010229104A (en) * | 2009-03-27 | 2010-10-14 | Mitsubishi Chemicals Corp | Method for producing alkyl aromatic compound |
-
1989
- 1989-04-24 JP JP1101566A patent/JPH0639422B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010229104A (en) * | 2009-03-27 | 2010-10-14 | Mitsubishi Chemicals Corp | Method for producing alkyl aromatic compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0639422B2 (en) | 1994-05-25 |
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