CN102093222A - Method for performing toluene selective nitration under catalysis of solid acid catalyst SO42-/TiO2-HNbMoO6 - Google Patents

Method for performing toluene selective nitration under catalysis of solid acid catalyst SO42-/TiO2-HNbMoO6 Download PDF

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CN102093222A
CN102093222A CN2010106010140A CN201010601014A CN102093222A CN 102093222 A CN102093222 A CN 102093222A CN 2010106010140 A CN2010106010140 A CN 2010106010140A CN 201010601014 A CN201010601014 A CN 201010601014A CN 102093222 A CN102093222 A CN 102093222A
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toluene
nitrotoluene
acid
hnbmoo
tio
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何杰
唐元
张忠良
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Yangzhou Institute Of Chemistry And Chemical Engineering Of Nanjing University
Anhui University of Science and Technology
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Yangzhou Institute Of Chemistry And Chemical Engineering Of Nanjing University
Anhui University of Science and Technology
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Abstract

The invention relates to a method for performing toluene selective nitration under catalysis of a solid acid catalyst SO42-/TiO2-HNbMoO6. In the method, SO42-/TiO2-HNbMoO6 serves as the catalyst; the volume ratio of CC14 to acetic anhydride to toluene is 3:1.2:1; the molar ratio of fuming nitric acid to the toluene is 0.5-3:1; the using amount of the catalyst is 2 to 10 percent of the total mass of the toluene and nitric acid; the conversion rate of the toluene is 80 to 100 percent; and the mass ratio of paranitrotoluene to o-nitrotoluene is from 1.23 to 1.54.

Description

Solid acid catalyst SO＜sub〉4＜/sub〉＜sup〉2-＜/sup 〉/TiO＜sub〉2＜/sub 〉-HNbMoO＜sub〉6＜/sub〉the nitrated method of catalysis methylbenzene selective
One, technical field
The present invention relates to a kind of SO 4 2-/ TiO 2-HNbMoO 6Solid acid catalyst is used for the nitrated method of methylbenzene selective.
Two, background technology
The para-nitrotoluene ratio is to study focus at present in the nitrated raising product of methylbenzene selective, and solid acid catalyst substitutes sulfuric acid often can improve para-nitrotoluene ratio in the product.Liu Lirong etc. (Liu Lirong, Lv Chunxu, Li Xia. toluene is nitrated under the solid Niobic Acid, applied chemistry .2007,24 (12): 1374～1377) studied niobic acid (Nb 2O 5.nH 2O) go up the nitric acid selective nitration of toluene,, Ortho Nitro Toluene ratio is reached 0.79, reaction conversion ratio is 99.3%.Stratiform niobium molybdic acid (HNbMoO 6) all character and the former acidity that almost have a stratiform niobic acid is better than the latter far away.(Caio Tagusagawa, Atsushi Takagaki.Catal.Today.2009 267-231) have studied HNbMoO to Caio Tagusagawa in 2009 6Catalysis toluene and benzylalcohol are paid the gram alkylated reaction, and the result shows that catalytic activity is higher than Nb 2O 5-MoO 3, niobic acid (Nb 2O 5.nH 2O).
Three, summary of the invention
The invention provides a kind of SO 4 2-/ TiO 2-HNbMoO 6The method that solid acid catalyst catalysis methylbenzene selective is nitrated.Methylbenzene selective nitration reaction: in container, add CCl 4, acetic anhydride, toluene, massfraction be 95% nitrosonitric acid and SO 4 2-/ TiO 2-HNbMoO 6Catalyzer, CCl 4, acetic anhydride and toluene volume ratio be 3: 1.2: 1, the mol ratio of nitrosonitric acid and toluene is 0.5～3: 1, catalyst levels is the 2-10% of toluene and nitric acid total mass, stir, 30-50 ℃ drips nitrosonitric acid down, after dropwising, temperature of reaction is controlled at 30-50 ℃, continue to stir 0.5-2 hour, reaction finishes after-filtration and tells liquid phase, liquid phase NaHCO 3The aqueous solution is neutralized to neutrality, tells organic phase, organic phase with anhydrous sodium sulfate drying after, filter and to obtain the nitrotoluene mixture, the gas-chromatography sample introduction is analyzed.Analytical results: toluene conversion reaches 80～100%, and the mass ratio of para-nitrotoluene and Ortho Nitro Toluene reaches 1.23～1.54.
Figure BDA0000040083620000011
Solid acid SO 4 2-/ TiO 2-HNbMoO 6Synthetic: under the room temperature 19.32g tetrabutyl titanate slowly is added drop-wise in the 200mL1mol/L hydrochloric acid soln, dripped 2.5 hours, continue to stir and obtained mixed solution in 0.5 hour, restrain C 2 4H 9NH 2-HNbMoO 6(reference: N.S.P.Bhuvanesh, J.Gopalakrishnan.Inorg.Chem.1995,34,3160-3164) join in the mixed solution and to stir 3 hours, filtering separation is washed to no chlorion, and drying at room temperature obtains solid acid TiO 2-HNbMoO 6With 1.2 gram TiO 2-HNbMoO 6Place container, add 1.8mL 0.4mol/L sulfuric acid and mix, evaporate to dryness in 80 ℃ of water-baths, 500 ℃ of roastings obtained solid acid SO in 3 hours 4 2-/ TiO 2-HNbMoO 61 gram.
Four, embodiment
Embodiment 1: the methylbenzene selective nitration reaction: add CCl in container 415mL, acetic anhydride 6mL, toluene 5mL and SO 4 2-/ TiO 2-HNbMoO 6Catalyzer 1 gram stirs, and it is 95% nitrosonitric acid 5mL that 40 ℃ of water-baths drip massfraction down, and after dropwising, temperature of reaction is controlled at 40 ℃, continues to stir 1.5 hours, and reaction finishes after-filtration and tells liquid phase, liquid phase NaHCO 3The aqueous solution is neutralized to neutrality, tells organic phase, organic phase with anhydrous sodium sulfate drying after, filter and to obtain the nitrotoluene mixture.The gas-chromatography sample introduction is analyzed, and toluene conversion reaches 100%, and the mass ratio of para-nitrotoluene and Ortho Nitro Toluene reaches 1.54.
Embodiment 2: the methylbenzene selective nitration reaction: add CCl in container 415mL, acetic anhydride 6mL, toluene 5mL and SO 4 2-/ TiO 2-HNbMoO 6Catalyzer 0.45 gram stirs, and it is 95% nitrosonitric acid 5mL that 40 ℃ of water-baths drip massfraction down, and after dropwising, temperature of reaction is controlled at 40 ℃, continues to stir 1.5 hours, and reaction finishes after-filtration and tells liquid phase, liquid phase NaHCO 3The aqueous solution is neutralized to neutrality, tells organic phase, organic phase with anhydrous sodium sulfate drying after, filter and to obtain the nitrotoluene mixture.The gas-chromatography sample introduction is analyzed, and toluene conversion reaches 80%, and the mass ratio of para-nitrotoluene and Ortho Nitro Toluene reaches 1.23.
Embodiment 3: the methylbenzene selective nitration reaction: add CCl in container 415mL, acetic anhydride 6mL, toluene 5mL and SO 4 2-/ TiO 2-HNbMoO 6Catalyzer 1 gram stirs, and it is 95% nitrosonitric acid 2mL that 40 ℃ of water-baths drip massfraction down, and after dropwising, temperature of reaction is controlled at 40 ℃, continues to stir 1.5 hours, and reaction finishes after-filtration and tells liquid phase, liquid phase NaHCO 3The aqueous solution is neutralized to neutrality, tells organic phase, organic phase with anhydrous sodium sulfate drying after, filter and to obtain the nitrotoluene mixture.The gas-chromatography sample introduction is analyzed, and toluene conversion reaches 86%, and the mass ratio of para-nitrotoluene and Ortho Nitro Toluene reaches 1.37.
Embodiment 4: the methylbenzene selective nitration reaction: add CCl in container 415mL, acetic anhydride 6mL, toluene 5mL and SO 4 2-/ TiO 2-HNbMoO 6Catalyzer 1 gram stirs, and it is 95% nitrosonitric acid 5mL that 40 ℃ of water-baths drip massfraction down, and after dropwising, temperature of reaction is controlled at 40 ℃, continues to stir 0.5 hour, and reaction finishes after-filtration and tells liquid phase, liquid phase NaHCO 3The aqueous solution is neutralized to neutrality, tells organic phase, organic phase with anhydrous sodium sulfate drying after, filter and to obtain the nitrotoluene mixture.The gas-chromatography sample introduction is analyzed, and toluene conversion reaches 93%, and the mass ratio of para-nitrotoluene and Ortho Nitro Toluene reaches 1.26.

Claims (1)

1. solid acid catalyst SO 4 2-/ TiO 2-HNbMoO 6The method that the catalysis methylbenzene selective is nitrated,
In container, add CCl 4, acetic anhydride, toluene, massfraction be 95% nitrosonitric acid, it is characterized in that using SO 4 2-/ TiO 2-HNbMoO 6Make catalyzer, CCl 4, acetic anhydride and toluene volume ratio be 3:1.2:1, the mol ratio of nitrosonitric acid and toluene is 0.5 ~ 3:1, catalyst levels is the 2-10% of toluene and nitric acid total mass, stir, 30-50 ℃ drips nitrosonitric acid down, after dropwising, temperature of reaction is controlled at 30-50 ℃, continue to stir after 0.5-2 hour, filter and tell liquid phase, liquid phase NaHCO 3The aqueous solution is neutralized to neutrality, tells organic phase, organic phase with anhydrous sodium sulfate drying after, filter and to obtain the nitrotoluene mixture, the mass ratio of para-nitrotoluene and Ortho Nitro Toluene reaches 1.23 ~ 1.54 in the nitrotoluene mixture, toluene conversion reaches 80 ~ 100%.
CN2010106010140A 2010-12-23 2010-12-23 Method for performing toluene selective nitration under catalysis of solid acid catalyst SO42-/TiO2-HNbMoO6 Pending CN102093222A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106146357A (en) * 2015-04-14 2016-11-23 上海合丽亚日化技术有限公司 A kind of preparation method of DSD acid

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0092372A1 (en) * 1982-04-16 1983-10-26 Sumitomo Chemical Company, Limited Process for nitration of benzene
CN1995014A (en) * 2006-12-21 2007-07-11 黑龙江大学 Method for preparing 2-nitro-4-methyl p-tolyl sulfone using solid superstrong acid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0092372A1 (en) * 1982-04-16 1983-10-26 Sumitomo Chemical Company, Limited Process for nitration of benzene
CN1995014A (en) * 2006-12-21 2007-07-11 黑龙江大学 Method for preparing 2-nitro-4-methyl p-tolyl sulfone using solid superstrong acid

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
《Catalysis Today》 20081219 Caio Tagusagawa Evaluation of strong acid properties of layered HNbMoO6 and catalytic activity for Friedel-Crafts alkylation 267-271 1 第142卷, *
CAIO TAGUSAGAWA: "Effects of Transition-Metal Composition of Protonated, Layered Nonstoichiometric Oxides H1-xNb1-xMo1+xO6 on Heterogeneous Acid Catalysis", 《JOURNAL OF PNYSICAL CHEMISTRY C》, vol. 113, no. 40, 11 September 2009 (2009-09-11), pages 17421 - 17427 *
CAIO TAGUSAGAWA: "Evaluation of strong acid properties of layered HNbMoO6 and catalytic activity for Friedel–Crafts alkylation", 《CATALYSIS TODAY》, vol. 142, 19 December 2008 (2008-12-19), pages 267 - 271, XP026061354, DOI: doi:10.1016/j.cattod.2008.10.045 *
刘丽荣: "固体铌酸催化下甲苯的硝化", 《应用化学》, vol. 24, no. 12, 31 December 2007 (2007-12-31) *
刘丽荣: "铌酸及其改性催化剂上甲苯的区域选择性硝化", 《精细化工》, vol. 24, no. 10, 31 October 2007 (2007-10-31), pages 988 - 995 *
潘声成: "SO42-/TiO2固体超强酸催化甲苯硝化的研究", 《精细石油化工进展》, vol. 4, no. 6, 30 June 2003 (2003-06-30), pages 18 - 2 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106146357A (en) * 2015-04-14 2016-11-23 上海合丽亚日化技术有限公司 A kind of preparation method of DSD acid
CN106146357B (en) * 2015-04-14 2017-12-26 上海合丽亚日化技术有限公司 A kind of preparation method of DSD acid

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