CN100569367C - The australene isomerization catalyst and the preparation method of the high yield of a kind of monocycle terpenes - Google Patents

The australene isomerization catalyst and the preparation method of the high yield of a kind of monocycle terpenes Download PDF

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Publication number
CN100569367C
CN100569367C CNB2008100991884A CN200810099188A CN100569367C CN 100569367 C CN100569367 C CN 100569367C CN B2008100991884 A CNB2008100991884 A CN B2008100991884A CN 200810099188 A CN200810099188 A CN 200810099188A CN 100569367 C CN100569367 C CN 100569367C
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catalyst
hours
australene
preparation
zro
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CN101269337A (en
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李凝
王鹏
蒋锡福
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Guilin University of Technology
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Guilin University of Technology
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Abstract

The invention discloses a kind of australene isomerization catalyst and preparation method who improves monocycle terpenes yield.Catalyst consists of: the mass ratio of zirconia and neodymia is 1: 0.03～0.09.The Preparation of catalysts method is a base carrier for adopting meso-porous alumina, directly prepare the loaded nano complex carrier by infusion process at base carrier surface synthesis of nano zirconia and neodymia mixture, and adopt ultrasonic wave and microwave drying technology to handle complex carrier, and with this composite carrier load SO 4 2-The preparation solid acid catalyst is applied to the australene isomerization reaction, and the result shows, the conversion ratio of australene is that the percentage composition of monocycle terpenes more than 98%, in the isomerization product is more than 60%.Cost of the present invention is low, and environment and equipment are not polluted, and prepared catalyst has high activity, high selectivity and high stability.

Description

The australene isomerization catalyst and the preparation method of the high yield of a kind of monocycle terpenes
Technical field
The present invention relates to catalysis material and heterogeneous catalysis field, particularly a kind of composition and preparation method who is used for improving the catalyst of australene isomerization reaction monocycle terpenes yield.
Background technology
Australene is the main component in the turpentine oil, and the content of general turpentine oil australene is more than 65%.Utilize the chemical property of australene, it can be carried out a series of deep processing developments such as oxidation, polymerization, isomerization and go out high fine chemical product of surcharge or chemical intermediate.Wherein the isomerization of australene is the useful approach that the turpentine oil deep processing is used.At present, the industrialized major obstacle of restriction australene isomerization is an isomerization catalyst, and from present present Research, that the catalysis scholar's research is many is zeolite-type molecular sieves, SO 4 2-/ M yO xType solid acid and heteropolyacid catalyst, though these catalyst have catalytic activity preferably, isomerization product distributes more, separates relatively difficulty.Isomerization product mainly contains amphene, forms about 45%, and the composition of monocycle terpenes is about 30%.
Summary of the invention
The composition and the preparation method that the purpose of this invention is to provide a kind of catalyst of the yield that is used for improving australene isomerization reaction monocycle terpenes.
The present invention is with the excellent properties and the mesoporous Al of nano material 2O 3ZrO in conjunction with a kind of support type of preparation 2-Nd 2O 3/ Al 2O 3Complex carrier.Give full play to nanometer ZrO on the one hand 2Excellent catalytic performance, utilize mesoporous Al on the other hand 2O 3Bigger specific area and suitable pore-size distribution.Simultaneously carry out modification at the nano zircite doping neodymium oxide, neodymia replaces Zr with the form of ion 4+Be present in ZrO 2In the time of in the lattice, can cause distortion of lattice and defective, and cause the uneven distribution of electric charge, this will directly influence SO 4 2-At ZrO 2On coordination mode, thereby change the acid site character of catalyst surface, improve the surface catalysis performance of nano zircite.And with this carrier loaded SO 4 -2Preparation solid acid catalyst SO 4 2-/ ZrO 2-Nd 2O 3/ Al 2O 3, the specific area and the aperture that increase catalyst help increasing the acid site number, improve activity of such catalysts and selectivity.
The composition of the catalyst that the present invention relates to: the mass ratio of zirconia and neodymia is 1: 0.03～0.09, and is distributed in the meso-porous alumina surface with nanoparticle form.
The Preparation of catalysts method concrete steps that the present invention relates to are:
With mesoporous Al 2O 3Place container and be evacuated to 0.01～0.03Mpa, add the 10ml percentage by weight after continuing to find time 4 hours and be 5～10% neopelex ethanolic solution and 10ml percentage by weight and be 6～10%, molecular weight is after 20000 polyethylene glycol stirs, by the mesoporous Al of every gram 2O 3The amount of load 0.6 gram zirconia and 0.018～0.054 gram neodymia adds zirconium nitrate and the neodymium nitrate solution of 1.0mol/L respectively, continuous stirring, flood after 4 hours that to add percentage by weight be 10% ammoniacal liquor, regulate pH=10～11, ageing is after 4 hours under 90 ℃ of temperature, handles 30 minutes in micro-wave oven dry 18 minutes then with ultrasonic wave, roasting is 4 hours under 600 ℃ of conditions, gets sample ZrO 2-Nd 2O 3/ Al 2O 3Complex carrier is with the H of 1mol/L 2SO 4Dipping ZrO 2-Nd 2O 3/ Al 2O 3Complex carrier 24 hours removes by filter excessive H 2SO 4Solution, microwave drying, 500 ℃ of roastings are 3 hours in Muffle furnace, SO 4 2-/ ZrO 2-Nd 2O 3/ Al 2O 3Catalyst.
Cost of the present invention is low, and environment and equipment are not polluted, and prepared catalyst has high activity, high selectivity and high stability.
The specific embodiment
Embodiment:
Consisting of of catalyst: the mass ratio of zirconia and neodymia is 1: 0.09.
Concrete steps: with mesoporous Al 2O 3Place container and be evacuated to 0.01～0.03Mpa, add the 10ml percentage by weight after continuing to find time 4 hours and be 5～10% neopelex ethanolic solution and 10ml percentage by weight and be 6～10%, molecular weight is after 20000 polyethylene glycol stirs, by the mesoporous Al of every gram 2O 3The amount of load 0.6 gram zirconia and 0.018～0.054 gram neodymia adds zirconium nitrate and the neodymium nitrate solution of 1.0mol/L respectively, continuous stirring, flood after 4 hours that to add percentage by weight be 10% ammoniacal liquor, regulate pH=10～11, ageing is after 4 hours under 90 ℃ of temperature, handles 30 minutes in micro-wave oven dry 18 minutes then with ultrasonic wave, roasting is 4 hours under 600 ℃ of conditions, gets sample ZrO 2-Nd 2O 3/ Al 2O 3Complex carrier is with the H of 1mol/L 2SO 4Dipping ZrO 2-Nd 2O 3/ Al 2O 3Complex carrier 24 hours removes by filter excessive H 2SO 4Solution, microwave drying, 500 ℃ of roastings are 3 hours in Muffle furnace, SO 4 2-/ ZrO 2-Nd 2O 3/ Al 2O 3Catalyst.Utilization XRD characterization technique result shows the ZrO of support type 2-Nd 2O 3/ Al 2O 3ZrO in the complex carrier 2There is ZrO with tetragonal phase structure 2Average grain diameter be 4.2nm.SO 4 2-/ ZrO 2-Nd 2O 3/ Al 2O 3The main physical and chemical performance of catalyst is as follows:
Table 1.SO 4 2-/ ZrO 2-Nd 2O 3/ Al 2O 3Physical and chemical performance
The performance title Performance indications
S BET 83.2-98.3m 2/g
Pore volume 1.25cc/g
Average pore size 6.346nm
In the 250ml there-necked flask of reflux condenser, electric mixer and thermometer is housed, add australene, acetic acid and catalyst by a certain percentage, stir and be heated to 150 ℃ of reaction 2h, filter.Sample is used the GC112A type gas chromatograph of the close instrument company of Nereid production and is analyzed FID ionic flame detector, OV-101 (30 * 0.3mm) capillary columns, 250 ℃ of detected temperatures, 250 ℃ of sample introduction temperature, temperature programming.The conversion ratio of australene is 98.42%, in the isomerization product percentage composition of monocycle terpenes more than 65%.

Claims (1)

1. australene isomerization catalyst that improves monocycle terpenes yield, it is characterized in that the composition of catalyst: the mass ratio of zirconia and neodymia is 1: 0.03～0.09, and is distributed in the meso-porous alumina surface with nanoparticle form; Concrete preparation process is: with mesoporous Al 2O 3Place container and be evacuated to 0.01～0.03Mpa, add the 10ml percentage by weight after continuing to find time 4 hours and be 5～10% neopelex ethanolic solution and 10ml percentage by weight and be 6～10%, molecular weight is after 20000 polyglycol solution stirs, by the mesoporous Al of every gram 2O 3The amount of load 0.6 gram zirconia and 0.018～0.054 gram neodymia adds zirconium nitrate and the neodymium nitrate solution of 1.0mol/L respectively, continuous stirring, flood after 4 hours that to add percentage by weight be 10% ammoniacal liquor, regulate pH=10～11, ageing is after 4 hours under 90 ℃ of temperature, handles 30 minutes in micro-wave oven dry 18 minutes then with ultrasonic wave, roasting is 4 hours under 600 ℃ of conditions, gets sample ZrO 2-Nd 2O 3/ Al 2O 3Complex carrier is with the H of 1mol/L 2SO 4Dipping ZrO 2-Nd 2O 3/ Al 2O 3Complex carrier 24 hours removes by filter excessive H 2SO 4Solution, microwave drying, 500 ℃ of roastings are 3 hours in Muffle furnace, SO 4 2-/ ZrO 2-Nd 2O 3/ Al 2O 3Catalyst.
CNB2008100991884A 2008-05-13 2008-05-13 The australene isomerization catalyst and the preparation method of the high yield of a kind of monocycle terpenes Expired - Fee Related CN100569367C (en)

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CN105597825B (en) * 2015-11-02 2018-06-15 广东石油化工学院 A kind of monocyclic terpenes australene isomerization catalyst in high yield and preparation method and application
CN111203229A (en) * 2020-02-19 2020-05-29 中国科学院过程工程研究所 Preparation method and application of supported composite oxide catalyst
CN116102049A (en) * 2022-12-28 2023-05-12 常州市卓群纳米新材料有限公司 Preparation method of high-purity nano neodymium oxide

Citations (5)

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US4171288A (en) * 1977-09-23 1979-10-16 Engelhard Minerals & Chemicals Corporation Catalyst compositions and the method of manufacturing them
CN1171063A (en) * 1994-11-02 1998-01-21 波基达拉·格里戈洛瓦 Catalyst
CN1227854A (en) * 1997-12-15 1999-09-08 通用电气公司 Process for producing blends of tackifying resins with low molecular weight polyphenylene ethers
CN1241988A (en) * 1996-12-27 2000-01-19 阿南化成株式会社 Composite zirconium-cerium oxide, process for the preparation thereof, and cocatalyst for cleaning exhaust gas
CN1541764A (en) * 2003-04-29 2004-11-03 中国石油化工股份有限公司 Catalyst for isomerizing low-carbon paraffin and its preparing process

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4171288A (en) * 1977-09-23 1979-10-16 Engelhard Minerals & Chemicals Corporation Catalyst compositions and the method of manufacturing them
CN1171063A (en) * 1994-11-02 1998-01-21 波基达拉·格里戈洛瓦 Catalyst
CN1241988A (en) * 1996-12-27 2000-01-19 阿南化成株式会社 Composite zirconium-cerium oxide, process for the preparation thereof, and cocatalyst for cleaning exhaust gas
CN1227854A (en) * 1997-12-15 1999-09-08 通用电气公司 Process for producing blends of tackifying resins with low molecular weight polyphenylene ethers
CN1541764A (en) * 2003-04-29 2004-11-03 中国石油化工股份有限公司 Catalyst for isomerizing low-carbon paraffin and its preparing process

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Title
Phase diagram of the Al2O3-ZrO2-Nd2O3 system. S.M. Lakiza*, L.M. Lopato.Journal of the European Ceramic Society,Vol.26 . 2006
Phase diagram of the Al2O3-ZrO2-Nd2O3 system. S.M. Lakiza*, L.M. Lopato.Journal of the European Ceramic Society,Vol.26 . 2006 *

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