CN101337186A - Preparation method of meso-porous alumina and catalytic synthesis of alpha-tetralone - Google Patents

Preparation method of meso-porous alumina and catalytic synthesis of alpha-tetralone Download PDF

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CN101337186A
CN101337186A CNA2008100588501A CN200810058850A CN101337186A CN 101337186 A CN101337186 A CN 101337186A CN A2008100588501 A CNA2008100588501 A CN A2008100588501A CN 200810058850 A CN200810058850 A CN 200810058850A CN 101337186 A CN101337186 A CN 101337186A
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mesoporous
mal
tetralone
naphthane
cobalt
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王家强
马永平
段莉娜
王剑飞
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Yunnan University YNU
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Yunnan University YNU
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Abstract

The invention provides a method for preparing cobalt-doped mesoporous alumina by taking a rubber latex as a biological template, and a method for catalytically oxidizing tetralin into tetralone under liquid phase. The invention relates to the method for preparing the cobalt-doped mesoporous alumina by taking the rubber latex as the template, and the method for synthesizing tetralone. The invention aims to develop a method which is used for preparing the cobalt-doped mesoporous alumina by taking the rubber latex as the biological template and a high-conversion and high-selectivity method which is used for catalytically oxidizing tetralin into tetralone under the liquid phase, and comprises the following steps: a mesoporous material is taken as a heterogeneous catalyst, and tetralin is catalytically oxidized into tetralone under the low temperature liquid phase. The experimental results show that the conversion rate of the tetralin reaches 80.3 percent and the selectivity of tetralone reaches 74.5 percent.

Description

A kind of mesoporous Al 2O 3Preparation and be used for catalyzed synthesizing alpha-tetralone
Technical field
The invention belongs to technical field of chemical engineering, being specifically related to a kind of is the mesoporous alundum (Al of the doping cobalt of template preparation with the rubber latex, and the purposes of this product on the catalysis synthesizing tetralone.
Background technology
In catalysis subject development process, the aluminium oxide of various forms occupies an important position.Mesoporous nano aluminium oxide (Al 2O 3) molecular sieve has and non-porous Al 2O 3The excellent properties that nano material is different, it not only has skin effect, bulk effect, quantum size effect and the macro quanta tunnel effect of nano material uniqueness, and higher specific surface area arranged, arrange in the bigger aperture (poromerics relatively) and the hole of long-range order, at the catalysis ambit broad prospect of application is arranged.In recent years, synthesize meso-porous material adopt mainly that hydro-thermal is synthetic, room temperature synthetic, microwave is synthetic, wetly compose, phase transition method and method such as synthetic in non-aqueous system.Prepare mesoporous alundum (Al and mainly adopt template.For example, application number is 200410018502[1] be template in the Chinese invention patent application " a kind of mesoporous Mn/Al oxide catalyst, its preparation method and application " of .3 with surfactants such as P123, prepare mesoporous Mn/Al oxide catalyst with the equi-volume impregnating doped with manganese again, be used for catalytic hydrogenation.Application number is 01126878[1] Chinese invention patent " synthetic method of the even mesoporous aluminium oxide release agent of nano-scale " of .6 is the aluminium source with the aluminium isopropoxide, the P123 surfactant is that template prepares the meso-porous alumina ball.Application number is 200610122704[1] Chinese invention patent " a kind of synthetic method of mesoporous aluminum oxide molecular sieve " of .1 is the aluminium source with the organo-aluminium aluminium secondary butylate, the straight-chain carboxylic acid of 12~18 carbon atoms is the synthesising mesoporous aluminium oxide of template agent.Application number is 200710063718[1] Chinese invention patent " a kind of method for preparing ordered mesoporous aluminium oxide " of .5 does template with surfactant polyethylene.And be that the mesoporous alundum (Al of the doping cobalt of biological template preparation yet there are no report with the rubber latex.
α-tetralone, it is a kind of organic intermediate of important biologically active, be mainly used in the synthetic of medicines such as pesticide sevin, antidepressant Sertraline, anti-inflammatory class, antirheumatic, anti-diabetic class, anti-hypertension class, be widely used in various fields such as agricultural chemicals, medicine, auxiliary agent.Its prior synthesizing method is that to be raw material in acidic catalyst (as alchlor) effect friedel-crafts acylation reaction takes place down synthesizes [Chem.PhamBull., 1989 with benzene and gamma-butyrolacton; 37 (9): 2334-2337; J.Am.Chem.Soc, 1952; 74:4721]; Be that raw material is through multisteps such as acidylate, reduction, cyclization synthetic [Liu Daxue, Wang He, Ningxia University's journal (natural science edition), 1997 perhaps with benzene and succinic anhydride; 18 (4): 351].The former raw material is expensive, the cost height; Latter's complex steps, productive rate is low, and a large amount of waste gas waste residue of this method generation, causes serious environmental to pollute.
CrO such as Radhika 3The oxidation tetrahydronaphthalene synthesizes α-tetralone, and productive rate is 68% (J.Org.Chem., 1985; 50:2435-2438); But because the naphthane of oxidation 1mol need add 8mol CrO 3, chromium causes serious environmental to pollute.Liu Changkun etc. have reported and have utilized cobalt chromium composite oxides as the catalyst liquid-phase catalytic oxidation of tetralin, tetralone productive rate low (less than 20%) [petroleum journal (PETROLEUM PROCESSING) the 13rd the 2nd phase of volume of June in 1997], and this method is also used chromium, still can cause environmental pollution.
Human Co-DMEDA such as Chung (DMEDA=N, N '-dimethyl-ethylenediamine) are oxygen source with the molecular oxygen, the autoxidation of catalysis naphthane under water/organic two-phase system, the selectivity of α-tetralone is 68% o'clock, and the conversion ratio of naphthane has only 24.2%, and the productive rate of tetralone is also low.(J.Mol.Catal.1999,137:23~29); Yasutaka Ishii group study finds that N monohydroxy phthalimide (NHPI) oxidable naphthane under 1 atmospheric pressure oxygen is α-tetralone, and yield is 37%; (science and technology and engineering such as Xu Jie, 2006,6 (18): 2870~2871) with NHPI and 1,4 one diaminourea--2, the catalyst system and catalyzing that 3--dichloroanthraquinone (DADCAQ) is formed feeds 0.3MPa in having the teflon-lined autoclave oxygen carries out catalytic oxidation to naphthane, the conversion ratio of naphthane can reach 89.4%, and selectivity is 84.7%; (application number is 200610114399.1 Chinese patent) conversion ratio and selectivity are higher in its patent, but the method needs to carry out in autoclave, to the requirement height of equipment.
At present, still nobody carries out the synthetic α-tetralone of catalytic oxidation with mesoporous material to naphthane.It is that template prepares mesoporous alundum (Al and is used for catalytic oxidation of tetralin that the present invention lays particular emphasis on the plant latex, different with another invention " method of synthesizing tetralone by liquid-phase catalytic oxidation of tetralin " emphasis, it is that mesoporous titanium, the silicon materials that template prepares carry out catalytic oxidation to naphthane that another invention lays particular emphasis in order to surfactant or plant peel.
Summary of the invention
The objective of the invention is: (1) provides the invention product, promptly a kind of mesoporous alundum (Al of using the doping cobalt of biological template rubber latex preparation; (2) provide the purposes of this invention product, promptly be used as catalyst and realize the synthetic α-tetralone of high conversion highly selective.
Product of the present invention is the meso-porous alumina (Co/MAl of doping cobalt 2O 3), it is characterized in that making as follows: the ammoniacal liquor or the ethylenediamine of 1 part of volume are mixed with the rubber latex of 1~10 part of volume, add 2~6 parts of volumes, molar concentration is 1~3molL -1Sodium metaaluminate (NaAlO 2) in the aqueous solution, stirred 0.1~2 hour, under stirring condition, dripping the aluminium salt of 3~7 parts of volumes and the mixed aqueous solution of cobalt salt again, the molar concentration of aluminium salt is 0.2~0.7molL in the mixed aqueous solution of used aluminium salt and cobalt salt -1, and the molar concentration of cobalt salt is 0.02~0.5molL -1, stirred 0.4~2 hour, left standstill 0.5~24 hour, crystallization 10~72 hours, suction filtration, washing, drying, roasting must the mesoporous Co/MAl of invention product after 2~24 hours 2O 3
More than said aluminium salt and cobalt salt can be corresponding sulfate, nitrate, chloride, acetate etc., preferably nitrate.
The purposes of product of the present invention is to do the synthetic α-tetralone of catalyst.
Product of the present invention is used for the catalytic oxidation of tetralin synthesizing tetralone can carry out according to the following steps: naphthane, product of the present invention, organic or inorganic solvent are added container successively, under the low temperature liquid phase situation, add oxidant, question response finishes, and separate the back, the collection tetralone, reaction temperature is 40 ℃-110 ℃, and the reaction time is 4-12h.
Described organic solvent can be the polar solvent of one of acetic acid, propionic acid, ethanol or benzene, carbon tetrachloride one of non-polar solven.
Described oxidant can be hydrogen peroxide (H 2O 2), air or oxygen.
Further the technical scheme of optimizing is:
Solvent is an acetic acid, and oxidant is 30%H 2O 2, reaction temperature is controlled in 40-110 ℃, reaction time 4-12h, naphthane and mesoporous Co/MAl 2O 3Mol ratio is 1: 0.0002~0.005, and naphthane and acetic acid mol ratio are 1: 4~70, naphthane and H 2O 2Mol ratio is 1: 2~8.
According to experimental result, the mesoporous Co/MAl of product of the present invention 2O 3Catalytic effect fine.Reason is to be the mesoporous Co/MAl of template preparation with the rubber latex 2O 3The aperture be more suitable for the absorption of naphthane and the desorb of tetralone, simultaneously, make Co to disperse better because Co can better enter into the skeleton of mesoporous carrier.
When acetic acid is made solvent, the mesoporous Co/MAl of catalyst 2O 3Catalytic performance to get well than other solvent.In addition, the acetic acid amount increases, and the selectivity of tetralone also increases, and this is because the amount of solvent is big more, just easy more dispersion H 2O 2And tetralone, thereby make that the concentration of tetralone is relatively low and prevent that effectively tetralone and tetralol from forming balance and transform.Yet the conversion ratio of naphthane no longer increases when a certain amount of when solvent is increased to, this be since quantity of solvent too big after, the unit concentration of naphthane reduces, so its conversion ratio can't obviously increase.
According to the oxidant contrast, we obtain using H 2O 2Reaction is ideal when making oxidant.With the mesoporous Co/MAl of catalyst 2O 3, acetic acid, H 2O 2Be used for this reaction, derive, the mesoporous Co/MAl of catalyst from experimental result 2O 3, acetic acid, H 2O 2Certainly exist synergy.
Reaction temperature also has tangible influence to the oxidation of naphthane, description of test is in catalyst, oxidant, solvent and reaction time one timing, when reaction temperature is controlled at 100 ℃, the conversion ratio of naphthane is up to 80.3%, and the selectivity of tetralone has reached 74.5% simultaneously.
When reaction temperature, solvent, oxidant and catalyst one timing, the reaction time influences the efficient of ground catalytic reaction significantly.When the time was controlled at 8 hours, the conversion ratio of naphthane was best, and the selectivity of tetralone is also best simultaneously.
It is that the mesoporous material of template preparation is a heterogeneous catalysis that the present invention adopts with the rubber latex, and under the low temperature liquid phase condition, catalytic oxidation of tetralin is to tetralone, and experimental result shows that the selectivity of the conversion ratio of naphthane and tetralone is very high.
Beneficial effect of the present invention: providing a kind of is the mesoporous alundum (Al of template preparation with the rubber latex; The invention product is used for the catalysis synthesizing tetralone, and conversion ratio height, selectivity are good, the reaction condition gentleness, and catalyst easily reclaims, and does not have pollution of chromium, less demanding to equipment.
The specific embodiment
Only the present invention is described further for following examples, but the present invention will be not limited thereto.
Embodiment 1
Measure 5 milliliters of ammoniacal liquor and 5 milliliters of rubber latexs, adding is dissolved with 0.03 mole of NaAlO 210 ml waters in, stirred 0.1 hour, will be dissolved with 0.008 mole of Co (NO again 3) 2With 0.01 mole of Al (NO 3) 315 ml water solution under stirring fast, be added drop-wise in the aforementioned solution, stirred 0.4 hour, leave standstill 0.5 hour after, crystallization is after 10 hours in the crystallization of packing into the bottle, suction filtration washs, drying, in Muffle furnace at 300 ℃ of sintering 2h.Get the mesoporous alundum (Al material C o/MAl of light blue doping cobalt 2O 3(1: 5).
Embodiment 2
Measure 5 milliliters of ammoniacal liquor and 5 milliliters of rubber latexs, adding is dissolved with 0.03 mole of NaAlO 230 ml waters in, stirred 2 hours, will be dissolved with 0.0008 mole of CoSO again 4With 0.01 mole of Al 2(SO 4) 345 ml water solution under stirring fast, be added drop-wise in the aforementioned solution, stirred 2 hours, leave standstill 24 hours after, crystallization is after 72 hours in the crystallization of packing into the bottle, suction filtration washs, drying, in Muffle furnace at 700 ℃ of sintering 24h.Get the mesoporous alundum (Al material C o/MAl of light blue doping cobalt 2O 3(1: 50).
Embodiment 3
Measure 5 milliliters of ethylenediamines and 5 milliliters of rubber latexs, adding is dissolved with 0.03 mole of NaAlO 230 ml waters in, stirred 1 hour, will be dissolved with 0.0016 mole of CoCl again 2With 0.01 mole of AlCl 320 ml water solution under stirring fast, be added drop-wise in the aforementioned solution, stirred 1 hour, leave standstill 12 hours after, crystallization is after 24 hours in the crystallization of packing into the bottle, suction filtration washs, drying, in Muffle furnace at 500 ℃ of sintering 4h.Get the mesoporous alundum (Al material C o/MAl of light blue doping cobalt 2O 3(1: 25).
Embodiment 4
Measure 5 milliliters of ammoniacal liquor and 5 milliliters of rubber latexs, adding is dissolved with 0.03 mole of NaAlO 230 ml waters in, stirred 1 hour, will be dissolved with 0.004 mole of Co (OAc) again 2With 0.01 mole of Al (OAc) 320 ml water solution under stirring fast, be added drop-wise in the aforementioned solution, stirred 1 hour, leave standstill 12 hours after, crystallization is after 48 hours in the crystallization of packing into the bottle, suction filtration washs, drying, in Muffle furnace at 500 ℃ of sintering 4h.Get the mesoporous alundum (Al material C o/MAl of light blue doping cobalt 2O 3(1: 10).
Embodiment 5
Take by weighing the naphthane of 1g, the mesoporous Co/MAl of 10mg successively 2O 3The acetic acid of (1: 5) catalyst and 2ml joins in the three-necked bottle of 50ml, is heated to 40 ℃, stirs and add slowly the H of 2ml 2O 2, behind the question response 4h, stop reaction, filter, separate.Sample is through the gas chromatograph-mass spectrometer analysis, and the result is: the conversion ratio of naphthane is 49.5%, and the selectivity of tetralone is 56.2%, and the selectivity of tetralol is 4.2%, and other has part phenol and acetic acid that esterification has taken place, and also has a small amount of other accessory substances.
Embodiment 6
Take by weighing the naphthane of 1g, the mesoporous Co/MAl of 200mg successively 2O 3The acetic acid of (1: 10) catalyst and 30ml joins in the three-necked bottle of 100ml, is heated to 110 ℃, stirs and add slowly the H of 7ml 2O 2, behind the question response 12h, stop reaction, filter, separate.Sample is through the gas chromatograph-mass spectrometer analysis, and the result is: the conversion ratio of naphthane is 52.2%, and the selectivity of tetralone is 69.3%, and the selectivity of tetralol is 5.8%, and other has part phenol and acetic acid that esterification has taken place, and also has a small amount of other accessory substances.
Embodiment 7
Take by weighing the naphthane of 1g, the mesoporous Co/MAl of 20mg successively 2O 3The acetic acid of (1: 25) catalyst and 15ml joins in the three-necked bottle of 100ml, is heated to 100 ℃, stirs and add slowly the H of 5ml 2O 2, behind the question response 8h, stop reaction, filter, separate.Sample is through the gas chromatograph-mass spectrometer analysis, and the result is: the conversion ratio of naphthane is 79.8%, and the selectivity of tetralone is 74.0%, and the selectivity of tetralol is 4.8%, and other has part phenol and acetic acid that esterification has taken place, and also has a small amount of other accessory substances.
Embodiment 8
Take by weighing the naphthane of 1g, the mesoporous Co/MAl of 40mg successively 2O 3The acetic acid of (1: 50) catalyst and 15ml joins in the three-necked bottle of 100ml, is heated to 100 ℃, stirs and add slowly the H of 5ml 2O 2, behind the question response 8h, stop reaction, filter, separate.Sample is through the gas chromatograph-mass spectrometer analysis, and the result is: the conversion ratio of naphthane is 80.3%, and the selectivity of tetralone is 74.5%, and the selectivity of tetralol is 4.5%, and other has part phenol and acetic acid that esterification has taken place, and also has a small amount of other accessory substances.
Embodiment 9
Be catalytic oxidation in the different solvents, take by weighing the naphthane of 1g, the mesoporous Co/MAl of 50mg successively 2O 3The solvent of catalyst and 15ml joins in the three-necked bottle of 100ml, and the H that also adds 5ml is slowly stirred in heating 2O 2Be oxidant, behind the question response 8h, stop reaction, filter, separate.Sample is through the gas chromatograph-mass spectrometer analysis, and the conversion ratio of naphthane and the selectivity of tetralone such as following table also have a small amount of other accessory substances.
Solvent (15mL) Temperature (℃) The conversion ratio of naphthane (%) The selectivity of tetralone (%)
Propionic acid 100 45.6 54.0
Ethanol 78 10.2 98.6
Benzene 80 1.2 95.4
Carbon tetrachloride 75 0.5 98.2
Embodiment 10
Take by weighing the naphthane of 1g, the mesoporous Co/MAl of 80mg successively 2O 3The acetic acid of (1: 50) catalyst and 15ml joins in the three-necked bottle of 100ml, is heated to 100 ℃, stirs and add slowly the H of 5ml 2O 2, behind the question response 8h, stop reaction, filter, separate.Sample is through the gas chromatograph-mass spectrometer analysis, and the result is: the conversion ratio of naphthane is 62.8%, and the selectivity of tetralone is 76.8%, and the selectivity of tetralol is 4.3%, and other has part phenol and acetic acid that esterification has taken place, and also has a small amount of other accessory substances.
Embodiment 11
Take by weighing the naphthane of 1g, the mesoporous Co/MAl of 120mg successively 2O 3The acetic acid of (1: 50) catalyst and 15ml joins in the three-necked bottle of 100ml, is heated to 100 ℃, stirs and add slowly the H of 5ml 2O 2, behind the question response 8h, stop reaction, filter, separate.Sample is through the gas chromatograph-mass spectrometer analysis, and the result is: the conversion ratio of naphthane is 75.4%, and the selectivity of tetralone is 69.3%, and the selectivity of tetralol is 5.2%, and other has part phenol and acetic acid that esterification has taken place, and also has a small amount of other accessory substances.
Embodiment 12
Take by weighing the naphthane of 1g, the mesoporous Co/MAl of 80mg successively 2O 3The acetic acid of (1: 50) catalyst and 15ml joins in the three-necked bottle of 100ml, is heated to 100 ℃, and aerating oxygen behind the question response 8h, stops reaction, filters, and separates.Sample is through the gas chromatograph-mass spectrometer analysis, and the result is: the conversion ratio of naphthane is 43.6%, and the selectivity of tetralone is 62.5%, and the selectivity of tetralol is 9.2%, and other has part phenol and acetic acid that esterification has taken place, and also has a small amount of other accessory substances.

Claims (7)

1, a kind of is the meso-porous alumina Co/MAl of the doping cobalt of template preparation with the rubber latex 2O 3, it is characterized in that it being to make as follows: the ammoniacal liquor or the ethylenediamine of 1 part of volume are mixed with the rubber latex of 1~10 part of volume, add 2~6 parts of volumes, molar concentration is 1~3mol.L -1The sodium metaaluminate aqueous solution in, stirred 0.1~2 hour, under stirring condition, drip the aluminium salt of 3~7 parts of volumes and the mixed aqueous solution of cobalt salt again, the molar concentration of aluminium salt is 0.2~0.7molL in the mixed aqueous solution of said aluminium salt and cobalt salt -1, and the molar concentration of cobalt salt is 0.02~0.5mol.L -1, stirred 0.4~2 hour, left standstill crystallization 10~72 hours, suction filtration, washing, drying, roasting 2~24 hours 0.5~24 hour.
2, as the said mesoporous Co/MAl of claim 1 2O 3, it is characterized in that said aluminium salt is sulfate, nitrate, chloride, acetate etc., cobalt salt is sulfate, nitrate, chloride, acetate etc.
3, as the said mesoporous Co/MAl of claim 1 2O 3Purposes be to do the synthetic α of catalyst-tetrahydrochysene ketone.
4, as the said mesoporous Co/MAl of claim 3 2O 3Purposes, it is characterized in that according to the following steps: naphthane, product of the present invention, organic or inorganic solvent are added container successively, add oxidant under the low temperature liquid phase situation, question response finishes, and separate the back, the collection tetralone, reaction temperature is 40 ℃-110 ℃, and the reaction time is 4-12h.
5, as the said mesoporous Co/MAl of claim 4 2O 3Purposes, it is characterized in that described organic solvent be the polar solvent of one of acetic acid, propionic acid, ethanol or benzene, carbon tetrachloride one of non-polar solven.
6, as the mesoporous Co/MAl of claim 4 Suo Said 2O 3Purposes, it is characterized in that described oxidant is H 2O 2, air or oxygen.
7, as the mesoporous Co/MAl of claim 4 Suo Said 2O 3Purposes it is characterized in that solvent is that acetic acid, oxidant are 30%H 2O 2, reaction temperature is controlled in 40-110 ℃, reaction time 4-12h, naphthane and mesoporous Co/MAl 2O 3Mol ratio is 1: 0.0002~0.005, and naphthane and acetic acid mol ratio are 1: 4~70, naphthane and H 2O 2Mol ratio is 1: 2~8.
CNA2008100588501A 2008-08-27 2008-08-27 Preparation method of meso-porous alumina and catalytic synthesis of alpha-tetralone Pending CN101337186A (en)

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CN109420507A (en) * 2017-08-31 2019-03-05 中国石油天然气股份有限公司 Hydrodesulfurization catalyst containing macroporous alumina carrier and preparation method thereof
CN109420506B (en) * 2017-08-31 2021-07-30 中国石油天然气股份有限公司 Catalyst for removing mercaptan from gasoline and preparation method thereof
CN109420507B (en) * 2017-08-31 2021-08-27 中国石油天然气股份有限公司 Hydrodesulfurization catalyst containing macroporous alumina carrier and preparation method thereof
CN109261175A (en) * 2018-10-18 2019-01-25 乳源东阳光氟有限公司 A kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst and its preparation method and application
CN116102410A (en) * 2023-02-03 2023-05-12 爱斯特(成都)生物制药股份有限公司 Method for synthesizing alpha-tetralone by continuous flow

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