JPH02138232A - Production of alkyl-substituted aromatic hydrocarbon - Google Patents
Production of alkyl-substituted aromatic hydrocarbonInfo
- Publication number
- JPH02138232A JPH02138232A JP1203605A JP20360589A JPH02138232A JP H02138232 A JPH02138232 A JP H02138232A JP 1203605 A JP1203605 A JP 1203605A JP 20360589 A JP20360589 A JP 20360589A JP H02138232 A JPH02138232 A JP H02138232A
- Authority
- JP
- Japan
- Prior art keywords
- solid base
- catalyst
- aromatic hydrocarbon
- alkali metal
- potassium
- 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000007787 solid Substances 0.000 claims abstract description 98
- 239000002585 base Substances 0.000 claims abstract description 83
- 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 22
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 12
- 150000004645 aluminates Chemical class 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 230000002152 alkylating effect Effects 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 abstract description 22
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 229910000288 alkali metal carbonate Inorganic materials 0.000 abstract description 5
- 150000008041 alkali metal carbonates Chemical class 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002537 cosmetic Substances 0.000 abstract 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 29
- 229910052700 potassium Inorganic materials 0.000 description 29
- 229960003975 potassium Drugs 0.000 description 29
- 239000011591 potassium Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 26
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 24
- 238000003756 stirring Methods 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 19
- 239000012299 nitrogen atmosphere Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 description 12
- 235000011181 potassium carbonates Nutrition 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- -1 rubidium aluminate Chemical class 0.000 description 6
- 150000001339 alkali metal compounds Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- OTTZHAVKAVGASB-HYXAFXHYSA-N 2-Heptene Chemical compound CCCC\C=C/C OTTZHAVKAVGASB-HYXAFXHYSA-N 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical group CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- BEQGRRJLJLVQAQ-UHFFFAOYSA-N 3-methylpent-2-ene Chemical compound CCC(C)=CC BEQGRRJLJLVQAQ-UHFFFAOYSA-N 0.000 description 1
- 101100029851 Arabidopsis thaliana PIP1-3 gene Proteins 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- 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〉
本発明はアルキル置換芳香族炭化水素の製造方法に関し
、詳しくは特定の温度下でアルミナとアルカリ金属の炭
酸塩および／またはアルミン酸塩とアルカリ金属とを加
熱処理してなる固体塩基の存在下に、側鎖のα位に水素
原子を有する芳香族炭化水素とオレフィンとを反応させ
てα位をアルキル化せしめることによる、アルキル置換
芳香族炭化水素の製造方法に関するものである−ゆ〈従
来の技術〉
アルキ装置ＩＩＡ芳香族炭化水素は農・医薬品、化成品
等ファインケミカルズの中間原料として有用であり、塩
基触媒の存在下に側鎖のα位に水素を有する芳香族炭化
水素とオレフィンとを反応させることにより得られる。Detailed Description of the Invention <Industrial Application Field> The present invention relates to a method for producing an alkyl-substituted aromatic hydrocarbon, and more specifically, the present invention relates to a method for producing an alkyl-substituted aromatic hydrocarbon, and more specifically, the present invention relates to a method for producing an alkyl-substituted aromatic hydrocarbon, and more specifically, the present invention relates to a method for producing an alkyl-substituted aromatic hydrocarbon. Alkyl-substituted aromatic carbonization by reacting an aromatic hydrocarbon having a hydrogen atom at the α-position of the side chain with an olefin to alkylate the α-position in the presence of a solid base obtained by heat-treating a metal. This relates to a method for producing hydrogen. (Prior art) Alkylation device IIA Aromatic hydrocarbons are useful as intermediate raw materials for fine chemicals such as agricultural products, pharmaceuticals, and chemical products. It is obtained by reacting an aromatic hydrocarbon containing hydrogen with an olefin.
例えば、触媒として金属ナトリウムとクロルトルエンか
らなる触媒を用いる方法、金属ナトリウムを炭酸カリウ
ムに担持した触媒を用いる方法等が知られている（Ｊ、
Ａ＋、Ｃｈｅｍ、Ｓｏｃ、 、７８．４３１６（１９５
６）、英国特許第１２６９２８０号、特開昭６１−５３
２２９号公報）。For example, a method using a catalyst consisting of metallic sodium and chlorotoluene as a catalyst, a method using a catalyst in which metallic sodium is supported on potassium carbonate, etc. are known (J,
A+, Chem, Soc, , 78.4316 (195
6), British Patent No. 1269280, JP-A-61-53
Publication No. 229).
〈発明が解決しようとする課題〉
しかしながら、上記のような触媒を用いた場合、触媒活
性が充分ではなく、生成するアルキル置換芳香族炭化水
素の触媒光たりの収量が低いという問題、触媒と生成物
の分離が煩雑であるという問題、更には触媒が大気中の
空気、水分と接した場合に失活し易くまた発火の危険を
伴うという問題等があった。<Problems to be Solved by the Invention> However, when the above-mentioned catalyst is used, there are problems such as insufficient catalytic activity and a low yield of alkyl-substituted aromatic hydrocarbons per catalytic light; There are problems in that the separation of substances is complicated, and furthermore, there is a problem in that the catalyst is easily deactivated when it comes into contact with air or moisture in the atmosphere, and there is a risk of ignition.
＜ｉ！１題を解決するための手段〉
本発明者らは芳香族炭化水素のα位のアルキル化による
アルキル置換芳香族炭化水素の優れた製造方法を開発す
べく、アルキル化触媒について鋭意検討を重ねた結果、
アルミナとアルカリ金属の炭酸塩および／またはアルミ
ン酸塩とアルカリ金属を加熱処理して得られる特定の固
体塩基が、著しく高いアルキル化活性を示し、少ない触
媒量で効率良く目的とするアルキル置換芳香族炭化水素
を生成せしめ、しかも反応生成物との分離も容易であり
、そのうえ該固体塩基は大気中の空気、水分と接触して
も発火の危険が少なく、取扱いが極めて容易であること
を見出すとともに、更に種々の検討を加えて本発明を完
成した。<i! Means for Solving Problem 1> The present inventors have conducted intensive studies on alkylation catalysts in order to develop an excellent method for producing alkyl-substituted aromatic hydrocarbons by alkylating the α-position of aromatic hydrocarbons. result,
A specific solid base obtained by heat treating alumina and an alkali metal carbonate and/or aluminate and an alkali metal exhibits extremely high alkylation activity, and can efficiently produce target alkyl-substituted aromatics with a small amount of catalyst. It was discovered that hydrocarbons can be produced, and that they can be easily separated from the reaction products, and that the solid base has little risk of ignition even when it comes into contact with air or moisture in the atmosphere, and is extremely easy to handle. The present invention was completed after further various studies.
すなわち本発明は、側鎖のα位に水素原子を有する芳香
族炭化水素をオレフィンでアルキル化して、アルキル置
換芳香族炭化水素を製造するに当たり、触媒として、ア
ルミナとアルカリ金属の炭酸塩および／またはアルミン
酸塩とアルカリ金属を不活性ガス雰囲気中、１８０乃至
８００’Ｃの温度下で加熱処理してなる固体塩基を用い
ることを特徴とする工業的に優れたアルキル置換芳香族
炭化水素の！！！遣方法を提供するものである。That is, the present invention uses alumina and an alkali metal carbonate and/or as a catalyst when alkylating an aromatic hydrocarbon having a hydrogen atom at the α-position of the side chain with an olefin to produce an alkyl-substituted aromatic hydrocarbon. An industrially excellent alkyl-substituted aromatic hydrocarbon product that uses a solid base obtained by heat-treating an aluminate and an alkali metal at a temperature of 180 to 800'C in an inert gas atmosphere! ! ! It provides a method for sending money.
本発明はアルミナとアルカリ金属の炭酸塩および／また
はアルミン酸塩とアルカリ金属を特定温度下で加熱処理
してなる固体塩基を用いることを特徴とするものである
が、アルミナとしてはα−アルミナ以外の種々の形態の
ものが使用し得、例えばγ−１χ−１ρ−型が挙げられ
る。アルミナは表面積の大きなアルミナが好ましく用い
られる。The present invention is characterized by using a solid base obtained by heat-treating alumina and an alkali metal carbonate and/or aluminate and an alkali metal at a specific temperature, but the alumina may be other than α-alumina. Various forms of can be used, such as γ-1χ-1ρ-type. Alumina having a large surface area is preferably used.
またアルカリ金属としては周期律表第１族のリチウム、
ナトリウム、カリウム、ルビジウム等のアルカリ金属が
用いられ、好ましくはナトリウム、カリウムもしくはこ
れ等の混合物、更に好ましくはカリウムが用いられる。Also, examples of alkali metals include lithium, which is in group 1 of the periodic table;
Alkali metals such as sodium, potassium and rubidium are used, preferably sodium, potassium or a mixture thereof, and more preferably potassium.
アルカリ金属の使用量はアルミナに対し通常２乃至１５
＋ｙｔχである。The amount of alkali metal used is usually 2 to 15 per alumina.
+ytχ.
アルカリ金属の炭酸塩、アルミン酸塩（以下、これらを
アルカリ金属化合物という、）としては、例えば炭酸リ
チウム、炭酸ナトリウム、炭酸カリウム、炭酸ルビジウ
ム、炭酸セシウム、炭酸水素リチウム、炭酸水素ナトリ
ウム、炭酸水素カリウム、炭酸水素ルビジウム、炭酸水
素セシウム、アルミン酸リチウム、アルミン酸ナトリウ
ム、アルミン酸カリウム、アルミン酸ルビジウム、アル
ミン酸セシウム等が挙げられるが、好ましくは炭酸ナト
リウム、炭酸カリウム、炭酸セシウム、アルミン酸ナト
リウム、アルミン酸カリウム等が用いられる。アルカリ
金属化合物は２種以上用いることもできる。使用量はア
ルミナに対し、通常５乃至４０榊ｔχである。Examples of alkali metal carbonates and aluminates (hereinafter referred to as alkali metal compounds) include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate. , rubidium hydrogen carbonate, cesium hydrogen carbonate, lithium aluminate, sodium aluminate, potassium aluminate, rubidium aluminate, cesium aluminate, etc., but preferably sodium carbonate, potassium carbonate, cesium carbonate, sodium aluminate, aluminate. Potassium acid etc. are used. Two or more types of alkali metal compounds can also be used. The amount used is usually 5 to 40 tχ based on alumina.
固体塩基を調製するに当たっては不活性ガス雰囲気下で
、先ずアルミナにアルカリ金属化合物を、次いで、アル
カリ金属を加熱作用させるのが好ましい。In preparing the solid base, it is preferable to first apply an alkali metal compound to alumina and then heat the alkali metal under an inert gas atmosphere.
不活性ガスとしては窒素、ヘリウム、アルゴン等が挙げ
られる。Examples of the inert gas include nitrogen, helium, and argon.
触媒鋼製温度は重要であり、通常１８０乃至８００℃１
好ましくはアルミナとアルカリ金属化合物とを作用せし
める温度は１８０乃至６００℃１より好ましくは２５０
乃至４８０℃である。アルカリ金属を作用せしめる温度
は、好ましくは２００乃至４５０℃である。Catalyst steel temperature is important, usually 180-800℃1
Preferably, the temperature at which alumina and the alkali metal compound are allowed to react is 180 to 600°C, preferably 250°C.
The temperature ranges from 480°C to 480°C. The temperature at which the alkali metal is applied is preferably 200 to 450°C.
加熱時間は選定する温度条件等にもよるが、アルカリ金
属化合物を作用せしめる工程は通常０．５乃至１０時間
で充分であり、アルカリ金属を作用せしめる工程は通常
１０乃至３００分である。The heating time depends on the selected temperature conditions, etc., but usually 0.5 to 10 hours is sufficient for the step of applying the alkali metal compound, and usually 10 to 300 minutes for the step of applying the alkali metal.
かくして、高活性なうえに流動性、操作性が良好でしか
も空気にふれても発火の危険性の少ない固体塩基が得ら
れる。In this way, a solid base can be obtained which is highly active, has good fluidity and operability, and has little risk of ignition even when exposed to air.
本発明はかかる固体塩基を用いて、側鎖のα位に水素を
有する芳香族炭化水素とオレフィンとを反応させるもの
であるが、該芳香族炭化水素としては通常単環芳香族炭
化水素の他、縮合多環芳香族炭化水素が用いられる。側
鎖は結合して環を形成していても良い。The present invention uses such a solid base to react an aromatic hydrocarbon having hydrogen at the α-position of its side chain with an olefin. , a fused polycyclic aromatic hydrocarbon is used. The side chains may be combined to form a ring.
例えばトルエン、エチルベンゼン、イソプロピルベンゼ
ン、ｎ−プロピルベンゼン、ｎ−ブチルベンゼン、５ｅ
Ｃ−ブチルベンゼン、イソブチルベンゼン、キシレン、
シメン、ジイソプロピルベンゼン、メチルナフクレン、
テトラヒド口ナフタレン、インダン等が例示できる。ト
ルエン、エチルベンゼン、イソプロピルベンゼンが好ま
しく使用される。For example, toluene, ethylbenzene, isopropylbenzene, n-propylbenzene, n-butylbenzene, 5e
C-butylbenzene, isobutylbenzene, xylene,
Cymene, diisopropylbenzene, methylnafculene,
Examples include tetrahydro-naphthalene and indane. Toluene, ethylbenzene and isopropylbenzene are preferably used.
またオレフィンとしては炭素数が２〜２０のオレフィン
が通常用いられ、直鎖のもの、分岐のものいずれでも良
い、また二重結合が末端、内部いずれにあっても使用で
きる。末端オレフィンが好ましく用いられる。Further, as the olefin, an olefin having 2 to 20 carbon atoms is usually used, and it may be either a straight chain or a branched olefin, and it can be used even if the double bond is at the terminal or internally. Terminal olefins are preferably used.
これらの具体化合物としては、例えばエチレン、プロピ
レン、ｌ−ブテン、２−ブテン、イソブチレン、１−ペ
ンテン、２−ペンテン、１−ヘキセン、２−ヘキセン、
３−ヘキセン、１−ヘプテン、２−ヘプテン、３−ヘプ
テン、オクテン、ノネン、３−メチル−１−ブテン、２
−メチル−２−ブテン、３−メチル−１−ペンテン、３
−メチル−２−ペンテン等が挙げられる。Examples of these specific compounds include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1-hexene, 2-hexene,
3-hexene, 1-heptene, 2-heptene, 3-heptene, octene, nonene, 3-methyl-1-butene, 2
-Methyl-2-butene, 3-methyl-1-pentene, 3
-methyl-2-pentene and the like.
エチレン、プロピレン、ｌ−ブテン、２−７’テン等が
好ましく使用される。Ethylene, propylene, l-butene, 2-7'tene, etc. are preferably used.
アルキル化反応を実施するに当たっては、バッチ方式、
流動床、固定床を用いた流通方式いずれも採用できる。In carrying out the alkylation reaction, batch method,
Both distribution systems using fluidized beds and fixed beds can be adopted.
反応温度は通常０乃至３００℃１好ましくは２０乃至２
００℃であり、反応圧力は通常大気圧乃至２００Ｋｇ／
ｃｍＩ、好ましくは２乃至１００Ｋｇ／ｃｍ”である。The reaction temperature is usually 0 to 300°C, preferably 20 to 20°C.
00℃, and the reaction pressure is usually atmospheric pressure to 200Kg/
cmI, preferably 2 to 100 Kg/cm''.
また芳香族炭化水素に対するオレフィンのモル比は通常
０．１乃至１０、好ましくは０．２乃至５である。The molar ratio of olefin to aromatic hydrocarbon is usually 0.1 to 10, preferably 0.2 to 5.
バッチ方式における触媒の使用量は通常、使用する芳香
族炭化水素の０．０１乃至２０−１χ、好ましくは０．
０５乃至５ｗｔχであり、反応は通常０．５乃至５０時
間、好ましくは１乃至２５時間である。また流通反応に
おける芳香族炭化水素と脂肪族オレフィンの合計の供給
速度はＬ Ｉｔ Ｓ Ｖで通常０．１乃至６００ｈｒ−
好ましくは０．５乃至４００ｈｒ−’が採用される。The amount of catalyst used in the batch process is usually 0.01 to 20-1x, preferably 0.01 to 20-1x of the aromatic hydrocarbon used.
The reaction time is usually 0.5 to 50 hours, preferably 1 to 25 hours. In addition, the total feed rate of aromatic hydrocarbons and aliphatic olefins in the flow reaction is usually 0.1 to 600 hr-
Preferably, 0.5 to 400 hr-' is employed.
〈発明の効果〉
かくして、アルキル置換芳香族炭化水素が生成するが、
本発明によれば少ない触媒量で、しかも緩和な条件下で
も、極めて効率良く目的とするアルキル置換芳香族炭化
水素を製造し得る。<Effect of the invention> In this way, alkyl-substituted aromatic hydrocarbons are produced,
According to the present invention, target alkyl-substituted aromatic hydrocarbons can be produced extremely efficiently with a small amount of catalyst and even under mild conditions.
加えて、触媒の取扱いのみならず反応後の後処理も極め
て容易であるので、本発明方法はこの点でも有利である
。In addition, the method of the present invention is advantageous in this respect as not only the handling of the catalyst but also the post-treatment after the reaction is extremely easy.
〈実施例〉
以下、実施例により本発明をさらに詳細に説明するが、
本発明はこれら実施例のみに限定されるものではない。<Example> The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited only to these examples.
触媒調製例
（固体塩基Ａ−１）
４０〜２００メツシユに揃えた活性アルミナ（住良化学
工業■製ＮＫＩＩＤ−２４）２６．５ｇを炭酸カリウム
２．５ｇと水５０ｇからなる溶液に加え、次いでこれを
約７０℃減圧下、ロータリーエバポレーターを用いて蒸
発乾燥した。Catalyst Preparation Example (Solid Base A-1) 26.5 g of activated alumina (NKIID-24, manufactured by Sumira Chemical Co., Ltd.) arranged in a mesh size of 40 to 200 was added to a solution consisting of 2.5 g of potassium carbonate and 50 g of water, and then this was evaporated to dryness at about 70° C. under reduced pressure using a rotary evaporator.
これを窒素雰囲気下４５０’Ｃで３時間撹拌し、次いで
２９０℃に冷却した後、金属カリウム１．２５ｇを加え
て、同温度で０，２時 間撹拌した。これを室温まで放
冷して２４．７ｇの固体塩基へ−１を得た。This was stirred at 450'C for 3 hours under a nitrogen atmosphere, then cooled to 290°C, 1.25g of metallic potassium was added, and the mixture was stirred at the same temperature for 0.2 hours. This was allowed to cool to room temperature to obtain 24.7 g of solid base-1.
（固体塩基Ａ−２）
固体塩ｇ Ａ−１において、金属カリウムを２ｇ用いる
以外は固体塩基＾−１の調製例に準拠して実施し、２５
．５ｇの固体塩基Ａ−２を得た。(Solid base A-2) Solid salt g In A-1, the procedure was carried out according to the preparation example of solid base^-1 except that 2 g of metallic potassium was used, and 25
．． 5 g of solid base A-2 was obtained.
（固体塩基Ａ−３）
固体塩基＾−１において、金属カリウムを加える前の撹
拌温度を４５０℃から３００℃に変え、金属カリウムを
２ｇ用いる以外は固体塩基Ａ−１の調製例に準拠して実
施して固体塩基Ａ−３を得た。(Solid base A-3) In solid base ^-1, the stirring temperature before adding metallic potassium was changed from 450°C to 300°C and 2 g of metallic potassium was used. A solid base A-3 was obtained.
（固体塩基へ−４）
固体塩基Ａ−１において、金属カリウムを加える前の撹
拌温度を４５０’Ｃから１８０℃に変え、金属カリウム
を２．３８ｇ用いる以外は固体塩基Ａ−１のＥｍ Ｊ例
に準拠して実施して固体塩基Ａ−４を得た。(To solid base-4) Em J example of solid base A-1 except that in solid base A-1, the stirring temperature before adding metallic potassium was changed from 450'C to 180°C and 2.38 g of metallic potassium was used. Solid base A-4 was obtained.
（固体塩基Ａ−５）
固体塩基Ａ−１において、金属カリウムを加える前の撹
拌温度を４５０’Ｃから７００℃に変え、金属カリウム
を２ｇ用いる以外は固体塩基＾−１の調製例に準拠して
実施して固体塩基Ａ−５を得た。(Solid base A-5) In solid base A-1, the stirring temperature before adding metallic potassium was changed from 450'C to 700°C, and the preparation example of solid base ^-1 was followed except that 2 g of metallic potassium was used. Solid base A-5 was obtained.
（固体塩基Ａ−６）
固体塩＾−１で用いたと同じ活性アルミナ２６．５ｇと
炭酸カリウム２．５ｇとをｔ５）砕混合し、これをアル
ミナ坩堝にいれてマツフル炉で１２００℃下、３時間加
熱した０次いで２００℃まで冷却した後、窒素雲囲気下
デシケータ中で室温まで冷却したところ、微細な粉体が
得られた。(Solid base A-6) 26.5 g of the same activated alumina used in solid salt ^-1 and 2.5 g of potassium carbonate were ground and mixed (t5), and this was placed in an alumina crucible and heated at 1200°C in a Matsufuru furnace for 30 minutes. After heating at 0° C. for an hour and cooling to 200° C., the mixture was cooled to room temperature in a desiccator under a nitrogen cloud, yielding a fine powder.
このものを窒素雰囲気下２９０℃に加熱した後、撹拌し
ながらこれに金属カリウム２．０ｇを加えて同温度で０
．２時間撹拌した。これを室温まで冷却して固体塩基Ａ
−６を得た。After heating this material to 290°C under a nitrogen atmosphere, 2.0g of metallic potassium was added to it while stirring, and the mixture was heated to 290°C at the same temperature.
．． Stirred for 2 hours. Cool this to room temperature and make solid base A.
-6 was obtained.
（固体塩基Ａ−７）
固体塩基Ａ−１の調製例において、炭酸カリウムの代わ
りに炭酸ナトリウム２，５ｇを用い、金属カリウムを２
．４１ ｇ用いる以外は固体塩基Ａ−１の調製例に準
拠して実施して固体塩基Ａ−７を得た。(Solid base A-7) In the preparation example of solid base A-1, 2.5 g of sodium carbonate was used instead of potassium carbonate, and 2.5 g of metallic potassium was added.
．． Solid base A-7 was obtained in accordance with the preparation example of solid base A-1 except that 41 g was used.
（固体塩基Ａ−８）
固体塩基Ａ−１の調製例において、金属カリウムの代わ
りに金属ナトリウム２．１７ ｇを用いる以外は固体
塩基Ａ−１の調製例に準拠して実施して固体塩基Ａ−８
を得た。(Solid base A-8) In the preparation example of solid base A-1, solid base A was prepared according to the preparation example of solid base A-1 except that 2.17 g of metallic sodium was used instead of metallic potassium. -8
I got it.
（固体塩基Ａ−９）
固体塩基Ａ−１において、活性アルミナの代わりに４２
〜２００メツシユに揃えたシリカゲル（フジデビソン化
学Ｏ＠製＃５７）を用いる以外は固体塩基Ａ−１の調製
例に準拠して実施して固体塩基 Ａ−９を得た。(Solid base A-9) In solid base A-1, 42
Solid base A-9 was obtained in accordance with the preparation example of solid base A-1 except that silica gel (#57 manufactured by Fuji Davison Kagaku O@) having a mesh size of 200 was used.
（固体塩基へ−１０）
中心粒径８０マイクロメートルの活性アルミナ（住人化
学ｆｍ製ＢＫ−５７０） ５０ｇを炭酸セシウＡ５．
６ｇと水１００ｇからなる溶液に加えた後、これを約７
０’ＣＭ圧下にロータリーエバポレーターを用いて蒸発
乾燥した。(To solid base-10) 50 g of activated alumina (BK-570, manufactured by Sumitomo Chemical FM) with a center particle size of 80 micrometers was mixed with cesium carbonate A5.
After adding it to a solution consisting of 6 g and 100 g of water, this
It was evaporated to dryness using a rotary evaporator under 0'CM pressure.
これを窒素雰囲気下４８０℃で１時間撹拌し、次いで３
００″Ｃに冷却した後、金属カリウム２．８４ ｇを加
えて、同温度で０．５時間撹拌した。 これを室温まで
放冷して固体塩基へ−１０を得た。This was stirred at 480°C for 1 hour under nitrogen atmosphere, then 3
After cooling to 00''C, 2.84 g of metallic potassium was added and stirred at the same temperature for 0.5 hours. The mixture was allowed to cool to room temperature to obtain solid base-10.
（固体塩基Ａ−１１）
炭酸カリウム５０ｇを窒素雰囲気下、３５０ ’Ｃで２
時間撹拌した後、２５０″Ｃまで冷却して金属ナトリウ
ム１．２８ｇを加え、同温度で５時間撹拌した。(Solid base A-11) 50 g of potassium carbonate was added at 350'C under nitrogen atmosphere for 2
After stirring for an hour, the mixture was cooled to 250''C, 1.28 g of metallic sodium was added, and the mixture was stirred at the same temperature for 5 hours.
これを室温まで冷却して固体塩基＾−１１を得た。This was cooled to room temperature to obtain solid base ^-11.
（固体塩基Ａ−１２）
固体塩Ａ−１で用いたと同じ活性アルミナ２６．５８と
水酸化カリウム２．５ｇとを粉砕混合し、これをアルミ
ナ坩堝にいれてマツフル炉で１２００℃下、３時間加熱
した０次いで２００℃まで冷却した後、窒素雰囲気下デ
シケータ中で室温まで冷却したところ、微細な粉体が得
られた。(Solid base A-12) 26.58 g of the same activated alumina used in solid salt A-1 and 2.5 g of potassium hydroxide were pulverized and mixed, and this was placed in an alumina crucible and heated in a Matsufuru furnace at 1200°C for 3 hours. The mixture was heated to 0.degree. C., then cooled to 200.degree. C., and then cooled to room temperature in a desiccator under a nitrogen atmosphere, yielding a fine powder.
このものを窒素雰囲気下２９０’Ｃに加熱した後、撹拌
しながらこれに金属カリウム２．０ｇを加えて同温度で
０．５時間撹拌した。これを室温まで冷却して固体塩基
へ−１２を得た。After heating this material to 290'C under a nitrogen atmosphere, 2.0 g of metallic potassium was added thereto while stirring, and the mixture was stirred at the same temperature for 0.5 hour. This was cooled to room temperature to obtain solid base-12.
（固体塩基Ａ−１３）
固体塩基Ａ−１において、金属カリウムを加えた後の撹
拌時間を０４２時間から１時間に変える以外はは固体塩
基＾−１の調製例に準拠して実施し、固体塩基Ａ−１３
を得た。(Solid base A-13) Solid base A-1 was prepared according to the preparation example of solid base ^-1 except that the stirring time after adding metallic potassium was changed from 042 hours to 1 hour. Base A-13
I got it.
（固体塩基Ａ−１４）
固体塩基＾−１において、金属カリウムを加える前の撹
拌温度を４５０℃から４２０℃に変える以外は固体塩基
Ａ−１の調製例に準拠して実施し、固体塩基Ａ−１４を
得た。(Solid base A-14) Solid base A-1 was prepared according to the preparation example of solid base A-1 except that the stirring temperature before adding metallic potassium was changed from 450°C to 420°C. -14 was obtained.
（固体塩基＾−１５）
固体塩基Ａ−１において、炭酸カリウムを１．２５ｇ用
いる以外は固体塩基Ａ−１の調製例に準拠して実施し、
固体塩基へ−１５を得た。(Solid base ^-15) In solid base A-1, the procedure was carried out according to the preparation example of solid base A-1, except that 1.25 g of potassium carbonate was used.
Solid base-15 was obtained.
（固体塩基Ａ−１６）
固体塩基Ａ−１において、炭酸カリウムを５ｇ用いる以
外は固体塩基Ａ−１のｉＰ］製例にｍ拠して実施し、固
体塩基Ａ−１６を得た。(Solid base A-16) Solid base A-1 was carried out according to the iP example of solid base A-1 except that 5 g of potassium carbonate was used to obtain solid base A-16.
（固体塩基Ｂ−１）
４２〜２００メツシユに揃えた活性アルミナ（住人化学
工業■製ＮＫＩＩＤ−２４）２６．５ｇをアルミン酸カ
リウム２．５ｇと水５０ｇからなる溶液に加え、次いで
これを約７０℃減圧下、ロータリーエバボレークーを用
いて蒸発乾燥した。(Solid base B-1) 26.5 g of activated alumina (NKIID-24, manufactured by Sumima Kagaku Kogyo ■) arranged in 42 to 200 meshes was added to a solution consisting of 2.5 g of potassium aluminate and 50 g of water, and then this was mixed with about 70 g of activated alumina. It was evaporated and dried using a rotary evaporator under reduced pressure at ℃.
これを窒素雰囲気下４５０℃で３時間撹拌し、次いで２
９０″Ｃに冷却した後、金属カリウム２．０ｇを加えて
、同温度で０．２間撹拌した。これを室温まで放冷して
２５．５ｇの固体塩基Ｂ−１を得た。This was stirred at 450°C under nitrogen atmosphere for 3 hours, then 2 hours.
After cooling to 90''C, 2.0 g of metallic potassium was added and stirred at the same temperature for 0.2 hours. This was allowed to cool to room temperature to obtain 25.5 g of solid base B-1.
（固体塩基Ｂ−２）
固体塩基［１−１において、金属カリウムを加える時の
温度およびその後の撹拌温度を２９０℃から３５０℃に
代える以外は固体塩基Ｂ−１の調製例に準拠して実施し
、固体塩基Ｂ−２を得た。(Solid base B-2) Solid base [Producted according to the preparation example of solid base B-1 except that in 1-1, the temperature when adding metallic potassium and the subsequent stirring temperature were changed from 290°C to 350°C. Solid base B-2 was obtained.
（固体塩基Ｂ−３）
固体塩ｉ Ｂ−１において、金属カリウムを加える以前
の撹拌温度を４５０’Ｃから３００℃に代える以外は固
体塩基Ｂ−１の調製例に準拠して実施し、固体塩基Ｂ−
３を得た。(Solid base B-3) Solid salt i In B-1, the procedure was carried out in accordance with the preparation example of solid base B-1, except that the stirring temperature before adding metallic potassium was changed from 450'C to 300°C. Base B-
I got 3.
（固体塩基Ｂ−４）
固体塩５ Ｂ−１において、金属カリウムを加える以前
の撹拌温度を４５０℃から１８０”Ｃに代え、金属カリ
ウムを２．３５ｇ用いる以外は固体塩基［１−１の調製
例に準拠して実施し、固体塩基ト４杏得た。(Solid base B-4) Solid salt 5 Solid base [Preparation of 1-1 except that in B-1, the stirring temperature before adding metallic potassium was changed from 450°C to 180''C and 2.35 g of metallic potassium was used. The procedure was carried out according to the example, and 4 g of a solid base was obtained.
（固体塩基Ｂ−５）
固体塩基Ｂ−１において、金属カリウムを加える以前の
撹拌温度を４５０℃から７００℃に代える以外は固体塩
基Ｂ−１の調製例に準拠して実施し、固体塩基Ｂ−５を
得た。(Solid base B-5) Solid base B-1 was prepared according to the preparation example of solid base B-1 except that the stirring temperature before adding metallic potassium was changed from 450°C to 700°C. -5 was obtained.
（固体塩基Ｂ−６）
固体塩Ｂ−１で用いたと同じ活性アルミナ２６．５ ｇ
とアルミン酸カリウム２．５ｇとを＄５１砕混合し、こ
れをアルミナ坩堝にいれてマツフル炉で１２００’Ｃ下
、３時間加熱した０次いで２００’Ｃまで冷却した後、
窒素雰囲気下デシケータ中で室温まで冷却したところ、
微細な粉体が得られた。(Solid base B-6) 26.5 g of the same activated alumina used in solid salt B-1
and 2.5 g of potassium aluminate were crushed and mixed for $51, and this was placed in an alumina crucible and heated in a Matsufuru furnace at 1200'C for 3 hours. After cooling to 0 and 200'C,
When cooled to room temperature in a desiccator under a nitrogen atmosphere,
A fine powder was obtained.
このものを窒素雰囲気下２９０℃に加熱した後、撹拌し
ながらこれに金属カリウム２．２８ ｇを加えて同温度
で０．２時間撹拌した。これを室温まで冷却して固体塩
基Ｂ−６を得た。After heating this material to 290° C. under a nitrogen atmosphere, 2.28 g of metallic potassium was added thereto while stirring, and the mixture was stirred at the same temperature for 0.2 hours. This was cooled to room temperature to obtain solid base B-6.
（固体塩基Ｂ−７）
固体塩基Ｂ−６において、マツフル炉での加熱を９００
℃で実施し、金属カリウムの代わりに金属ナトリウム２
．２８ｇを用いる以外は固体塩基Ｂ−６の調製例に準拠
して実施し、固体塩基Ｂ−７を得た。(Solid base B-7) In solid base B-6, heating in a Matsufuru furnace was heated to 900°C.
carried out at ℃, with metallic sodium 2 instead of metallic potassium.
．． Solid base B-7 was obtained by carrying out the preparation according to the preparation example of solid base B-6 except that 28 g was used.
（固体塩基Ｂ−８）
固体塩基ト１において、アルミン酸カリウムの代わりに
アルミン酸ナトリウム２．５ｇを用い、金属カリウムを
２．２ｇ用いる以外は固体塩Ｉ Ｂ−１の調製例に準拠
して実施し、固体塩基ｎ−８を得た。(Solid base B-8) In accordance with the preparation example of solid salt I B-1, except that in solid base 1, 2.5 g of sodium aluminate was used instead of potassium aluminate, and 2.2 g of metallic potassium was used. The solid base n-8 was obtained.
（固体塩基Ｂ−９）
固体塩基Ｂ−１において、金属カリウムの代わり金属ナ
トリウムを２．３ｇ用いる以外は固体塩基Ｂ−１の調製
例に準拠して実施し、固体塩基Ｂ−９を得た。(Solid base B-9) Solid base B-1 was carried out in accordance with the preparation example of solid base B-1, except that 2.3 g of metallic sodium was used instead of metallic potassium, to obtain solid base B-9. .
実施例１
電磁撹拌器付６００ｄオートクレーブに窒素雰囲気下、
固体塩基Ａ−１０，６３ｇ、クメン２４０ｇを入れ、Ｉ
ＱＯＯｒ、ｐ、ｍ、撹拌下に４０℃に昇温後、同温度で
エチレンガスを１０にｇ７ｃｍ”−Ｇで供給しながら３
時間反応を行った。Example 1 In a 600d autoclave with a magnetic stirrer under a nitrogen atmosphere,
Add 10.63 g of solid base A and 240 g of cumene,
QOOr, p, m, after raising the temperature to 40°C with stirring, 3
A time reaction was performed.
反応後オートクレーブを冷却し、触媒を濾別した後、反
応液をガスクロマトグラフィーで分析した。 反応結果
を表１に示した。After the reaction, the autoclave was cooled, the catalyst was filtered off, and the reaction solution was analyzed by gas chromatography. The reaction results are shown in Table 1.
実施例２〜２０、比較例１〜５
実施例１において、表１に示す条件以外は実施例１に準
拠して実施した０反応結果を表１に示した。尚、実施例
１〜２０においては、反応終了後の触媒はなお活性であ
り、更に反応を行ったところ該反応が進行した。Examples 2 to 20, Comparative Examples 1 to 5 Table 1 shows the results of the zero reaction performed in Example 1 in accordance with Example 1 except for the conditions shown in Table 1. In Examples 1 to 20, the catalyst was still active after the reaction was completed, and when the reaction was further carried out, the reaction proceeded.
表１
＊実施例Ｎｏ、３ は２Ｋｇ／ｃｖａ”−Ｇ ”ｔｅｘ
チレンガスを供給した。Table 1 *Example No. 3 is 2Kg/cva”-G”tex
Chilled gas was supplied.
比較例Ｎｏ、３は１６０ ｇのクメンを用いた。Comparative Example No. 3 used 160 g of cumene.
ＴＡＢ ＝ ｔｅｒｔ−アミルベンゼン比較例６
窒素雰囲気下で電磁撹拌器付２００ ｍオートクレーブ
に、あらかじめ４００’Ｃ１窒素雰囲気下で２時間焼成
した無水炭酸カリウム８．１９ｇ、ナトリウム０．３０
ｇ 、クメン２６．７ ｇを加えた後、１９０℃に昇
温し、同温度で２時間１０００ｒ、ｐ、ｍ、で撹拌を続
けた。TAB = tert-amylbenzene Comparative Example 6 8.19 g of anhydrous potassium carbonate and 0.30 g of sodium carbonate were previously calcined for 2 hours under a 400'C1 nitrogen atmosphere in a 200 m autoclave with a magnetic stirrer under a nitrogen atmosphere.
After adding 26.7 g of cumene and 26.7 g of cumene, the temperature was raised to 190°C, and stirring was continued at the same temperature for 2 hours at 1000 r, p, m.
次いでオートクレーブを冷却し、クメン５３．３ｇを追
加した後、１０００ｒ、ｐ、ｍ、撹拌下１６０℃に昇温
し、同温度でエチレンガス１０Ｋｇ／ｃｍ”Ｇで供給し
ながら３時間反応を行った。 反応後、ガスクロマトグ
ラフィーで分析したところクメン転化率１９．４％、Ｔ
ＡＢ ３Ａ沢率７３．９％であった。Next, the autoclave was cooled, and after adding 53.3 g of cumene, the temperature was raised to 160°C with stirring at 1000 r, p, m, and the reaction was carried out for 3 hours while supplying ethylene gas at 10 kg/cm"G at the same temperature. After the reaction, gas chromatography analysis revealed that the cumene conversion rate was 19.4%.
The AB 3A ratio was 73.9%.
実施例２１
Ｔｒｉ、 ＫＩＩ撹拌器付３００ａ＋ｊ！オートクレー
ブに窒素雰囲気下、固体塩基Ａ−１０，８４ｇ、クメン
８０ｇを入れ、液化プロピレン９０ｄを圧入した後、１
６０℃で２４時間撹拌を続けた。Example 21 Tri, 300a+j with KII stirrer! 84 g of solid base A-1 and 80 g of cumene were placed in an autoclave under a nitrogen atmosphere, and 90 d of liquefied propylene was pressurized.
Stirring was continued for 24 hours at 60°C.
反応終了後、オートクレーブを冷却した後、反応液を実
施例１と同様にしてガスクロマドグー７フイーで分析し
た０反応結果を表２に示した。After the reaction was completed, the autoclave was cooled, and the reaction solution was analyzed using a gas chromatography Goo 7F in the same manner as in Example 1. The reaction results are shown in Table 2.
実施例２２〜２４、比較例７
実施例２１において、表２に示す条件で実施する以外は
実施例２１に準拠して行った。結果を表２に示した。
尚、実施例２１〜２５において、反応終了後の触媒はな
お活性であり、さら゛に反応を行なったところ反応が進
行した。Examples 22 to 24, Comparative Example 7 The same procedures as in Example 21 were carried out except that the conditions shown in Table 2 were used. The results are shown in Table 2.
In Examples 21 to 25, the catalyst was still active after the reaction was completed, and when the reaction was further carried out, the reaction proceeded.
比較例８
窒素雰囲気下で電磁撹拌器付３００ ｍオートクレーブ
に、あらかじめ４００℃２窒素雰囲気下で２時間焼成し
た無水炭酸カリウム８．８６ｇ、ナトリウム０．３０ｇ
、クメン８１．２ ｇを加えた後、１９０℃に昇温し、
同温度で２時間１０００ｒ、ｐ、ｍ、で撹拌を続けた。Comparative Example 8 8.86 g of anhydrous potassium carbonate and 0.30 g of sodium were calcined in advance at 400°C for 2 hours in a 300 m autoclave equipped with a magnetic stirrer under a nitrogen atmosphere.
, after adding 81.2 g of cumene, the temperature was raised to 190°C,
Stirring was continued at 1000 r, p, m for 2 hours at the same temperature.
次いでオートクレーブを冷却し、液化プロピレン７０ｓ
＋ １を圧入した後、１６０℃、１０００ｒ、ｐ、ｍ、
撹拌下で２４時間撹拌した。結果を表２に示した。The autoclave was then cooled and liquefied propylene 70s
After press-fitting +1, 160℃, 1000r, p, m,
Stir for 24 hours under stirring. The results are shown in Table 2.
表２
ＴＭＰＢ・１，１．２− トリメチルプロピルベンゼン
実施例２５
電磁撹拌器付３００ｓｊ！オートクレーブに窒素雰囲気
下、固体塩基Ａ−１２，５３ｇ、トルエン７９．４ ｇ
を入れ、液化プロピレン７０ｄを圧入した後、１６４°
ｃ、ｔｏｏ。Table 2 TMPB・1,1.2-Trimethylpropylbenzene Example 25 300sj with magnetic stirrer! In an autoclave under nitrogen atmosphere, 53 g of solid base A-1 and 79.4 g of toluene.
164° after press-fitting 70d of liquefied propylene.
c, too.
ｒ、ｐ、ｍ、撹拌下で６時間反応を続けた。The reaction was continued for 6 hours under stirring.
反応後、ガスクロマトグラフィーで分析した。After the reaction, it was analyzed by gas chromatography.
その結果を表３に示した。The results are shown in Table 3.
表３
した、 尚、実施例２５〜３２において、反応終了後の
触媒はなお活性であり、さらに反応を行なったところ反
応が進行した。Table 3 In Examples 25 to 32, the catalyst was still active after the reaction was completed, and when the reaction was further carried out, the reaction proceeded.
比較例１０
窒素雰囲気下で電磁撹拌器付２００ ｍオートクレーブ
に、あらかじめ４００℃１窒素雰囲気下で２時間焼成し
た無水炭酸カリウム８．４５ ｇ 、ナトリウム０．３
０ ｇ 。Comparative Example 10 8.45 g of anhydrous potassium carbonate and 0.3 g of sodium were calcined in advance at 400°C for 2 hours under a nitrogen atmosphere in a 200 m autoclave equipped with a magnetic stirrer under a nitrogen atmosphere.
0g.
トルエン２６．６ ｇを加えた後、１９０℃で２時間１
０００ｒ。After adding 26.6 g of toluene, heat at 190°C for 2 hours.
000r.
ｐ、ｍ、で撹拌を続けた。Stirring was continued at p, m.
次いでオートクレーブを冷却してトルエン５３．２ｇを
追加し、液化プロピレン７０ｍを圧入した後、１６０℃
で６時間撹拌した。 結果を表３に示した。Next, the autoclave was cooled, 53.2 g of toluene was added, 70 m of liquefied propylene was injected, and the temperature was increased to 160°C.
The mixture was stirred for 6 hours. The results are shown in Table 3.
１［１［１ イソブチルベンゼン 実施例２６〜３２、比較例９1[1[1 isobutylbenzene Examples 26-32, Comparative Example 9
Claims (1)
ィンでアルキル化して、アルキル置換芳香族炭化水素を
製造するに当たり、触媒として、アルミナとアルカリ金
属炭の酸塩および／またはアルミン酸塩とアルカリ金属
を不活性ガス雰囲気中、１８０乃至８００℃の温度下で
加熱処理してなる固体塩基を用いることを特徴とするア
ルキル置換芳香族炭化水素の製造方法。When producing an alkyl-substituted aromatic hydrocarbon by alkylating an aromatic hydrocarbon having a hydrogen atom at the α-position of the side chain with an olefin, alumina and an acid salt and/or aluminate of an alkali metal carbon are used as a catalyst. A method for producing an alkyl-substituted aromatic hydrocarbon, comprising using a solid base obtained by heat-treating an alkali metal at a temperature of 180 to 800° C. in an inert gas atmosphere.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/399,974 US5043507A (en) | 1988-08-31 | 1989-08-29 | Process for preparing alkyl-substituted aromatic hydrocarbons |
| EP89116003A EP0357031B1 (en) | 1988-08-31 | 1989-08-30 | Process for preparing alkyl-substituted aromatic hydrocarbons |
| CA000609796A CA1326863C (en) | 1988-08-31 | 1989-08-30 | Process for preparing alkyl-substituted aromatic hydrocarbons |
| DE68912460T DE68912460T2 (en) | 1988-08-31 | 1989-08-30 | Process for the preparation of alkyl substituted aromatic hydrocarbons. |
| KR1019890012549A KR0148564B1 (en) | 1988-08-31 | 1989-08-31 | Process for preparing alkyl substituted aromatic hydrocarbons |
| US07/699,586 US5202515A (en) | 1988-08-31 | 1991-05-14 | Process for preparing alkyl-substituted aromatic hydrocarbons |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-219503 | 1988-08-31 | ||
| JP21950388 | 1988-08-31 | ||
| JP63-219502 | 1988-08-31 | ||
| JP21950288 | 1988-08-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02138232A true JPH02138232A (en) | 1990-05-28 |
| JP2745706B2 JP2745706B2 (en) | 1998-04-28 |
Family
ID=26523164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1203605A Expired - Fee Related JP2745706B2 (en) | 1988-08-31 | 1989-08-04 | Method for producing alkyl-substituted aromatic hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2745706B2 (en) |
-
1989
- 1989-08-04 JP JP1203605A patent/JP2745706B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2745706B2 (en) | 1998-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2748631B2 (en) | Method for producing alkyl-substituted aromatic hydrocarbon | |
| JPH02138232A (en) | Production of alkyl-substituted aromatic hydrocarbon | |
| EP0612706B1 (en) | Process for producing monoalkenylbenzenes | |
| US4962254A (en) | Process for preparing alkyl-substituted aromatic hydrocarbons | |
| EP0328940B1 (en) | Process for preparing alkyl-substituted aromatic hydrocarbons | |
| EP0569742B1 (en) | Process for producing monoalkenyl aromatic hydrocarbon compound | |
| JP2748646B2 (en) | Method for producing alkyl-substituted aromatic hydrocarbon | |
| US5043507A (en) | Process for preparing alkyl-substituted aromatic hydrocarbons | |
| JP2625985B2 (en) | Method for producing alkyl-substituted aromatic hydrocarbon | |
| JP2792132B2 (en) | Process for producing alkyl-substituted aromatic hydrocarbons | |
| JPH02250837A (en) | Production of alkyl-substituting aromatic hydrocarbons | |
| JP2596108B2 (en) | Preparation of alkyl-substituted aromatic hydrocarbons | |
| JPH02138231A (en) | Production of alkyl-substituted aromatic hydrocarbon | |
| JPH02138230A (en) | Production of alkyl-substituted aromatic hydrocarbon | |
| US5227559A (en) | Process for preparing alkyl-subtituted aromatic hydrocarbons | |
| US5436381A (en) | Process for producing a monoalkenyl aromatic hydrocarbon compound | |
| JPS61221133A (en) | Method of side chain alkylation of alkyl-substituted aromatic hydrocarbon | |
| US5347062A (en) | Process for preparing alkyl-substituted aromatic hydrocarbons | |
| JPH06199B2 (en) | Preparation method of catalyst loaded with alkali metal | |
| US5202515A (en) | Process for preparing alkyl-substituted aromatic hydrocarbons | |
| KR0148564B1 (en) | Process for preparing alkyl substituted aromatic hydrocarbons | |
| JP3028020B2 (en) | Method for producing monoalkenylbenzenes | |
| JPH02138228A (en) | Preparation of inner olefin | |
| JPS6357537A (en) | Production of arylalkene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |