CN106431845B - A kind of method that doping type ceria catalysis acetone prepares phenolic compound - Google Patents
A kind of method that doping type ceria catalysis acetone prepares phenolic compound Download PDFInfo
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Abstract
The present invention relates to the methods that a kind of doping type ceria catalysis acetone prepares phenolic compound.This method reaction condition is as follows: it is carried out under normal pressure in fixed bed reactors, 340 DEG C~450 DEG C of reaction temperature, using acetone as raw material, and charging rate 0.01mLmin‑1~0.1mLmin‑1, nitrogen is carrier gas, flow velocity 20mLmin‑1~80mLmin‑1, mass spectrum determines that product forms after reaction, chromatogram quantification.This method is characterized in (1) reaction conversion ratio height, and the overall selectivity of phenolic compound reaches 64%；(2) using the ceria of doping as catalyst, catalyst is cheap, it is simple and high-efficient to prepare, and can have potential application prospect by regenerating after roasting carbon remover.
Description
Technical field
The present invention relates to a kind of methods for preparing phenolic compound, and in particular to using acetone as reactant, doping type two
The method that cerium oxide catalyst conversion prepares phenolic compound.
Background technique
Phenolic compound is a kind of important Organic Chemicals.Phenol is one of propylene important derivatives, is mainly used for
Produce phenolic resin, caprolactam, bisphenol-A, adipic acid, aniline, alkyl phenol, salicylic acid etc.；Sylvan is mainly used for phenolic aldehyde tree
Rouge, electrical apparatus insulation paint, dyestuff, surfactant and lube oil additive etc..In addition, phenolic compound is to human body, plant
Vital movement play the role of it is main, such as: it is anti-oxidant, antiviral etc..
Currently, the main source of phenolic compound is petrochemical industry crude oil and plant.Crude oil obtains light oil, warp through air-distillation
It crosses and adds hydrogen, then fractionation becomes the programs such as benzene, then sulfonated, melting, halogenated hydrocarbons alkali process, finally obtains phenolic compound, should
Process process is cumbersome, and has very strong dependence to fossil resources.In recent years, with the exhaustion of fossil resources, to logical
It crosses petrochemical industry route and prepares phenolic compound and propose challenge.In addition, it is (endogenous to be widely present phenolic compound in natural plant body
Property phenol), thus acquisition is extracted from plants in many phenolic compounds.Such as: the lignin depolymerization in raw matter object can get 4-
The phenolic compounds such as methoxyl group, o- methoxyl group phenol or 2,6- dimethoxy phenol.Although lignin route prepares phenolic compound
The dependence to petrochemical industry phenol is reduced, but still there are certain difficulties.Lignin depolymerization usually by adding hydrogen route to realize, is easy
The excessive hydrogenation for causing phenyl ring reduces the selectivity of phenolic compound.Therefore, the variation route that exploration prepares phenolic compound has
Important meaning.
Summary of the invention
It is an object of the invention to overcome prepare at present during phenolic compound there are the shortcomings that, specially provide one
The method that kind doping type ceria catalysis acetone prepares phenolic compound, the preparation method reaction process is simple, under normal pressure i.e.
Can, reaction conversion ratio and phenols selectivity are higher.
The technical solution of the present invention is as follows:
Using acetone as raw material, after the ceria that doping is filled in reaction tube, reaction tube is placed in fixed bed reactors
In, it is reacted under certain temperature, condition of normal pressure.
The ceria catalyst of the doping, doped chemical are as follows: aluminium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc,
Yttrium, zirconium, niobium, molybdenum, tin, ruthenium, palladium, rhodium, gold, platinum and lanthanide series metal；Metal-doped amount are as follows: 0.5wt% (weight ratio)~
10wt% (weight ratio)；
The ceria catalyst of the doping, preferable doped chemical are as follows: aluminium, titanium, vanadium, chromium, zinc, yttrium, zirconium, niobium, molybdenum,
Palladium, lanthanum, praseodymium, europium；Preferable metal-doped amount are as follows: 1wt% (weight ratio)~6wt% (weight ratio)；
The ceria catalyst of the doping, optimal doped chemical are as follows: aluminium, vanadium, zirconium, niobium, lanthanum, praseodymium；Best metal
Doping are as follows: 2wt% (weight ratio)~5wt% (weight ratio)；
The tube inner diameter are as follows: 5mm~9mm；Loading catalyst bed height is 5cm~30cm, reaction temperature 340
DEG C~450 DEG C；
Preferred scheme, the tube inner diameter are as follows: 6mm~8mm；Loading catalyst bed height is 8cm in reaction tube
~12cm, reaction temperature are 350 DEG C~400 DEG C；
The reaction solution charging rate of the acetone is 0.01mLmin-1~0.1mLmin-1；Nitrogen is carrier gas, stream
Speed is 20mLmin-1~80mLmin-1；
The reaction solution charging rate of the acetone is 0.01mLmin-1~0.05mLmin-1；Nitrogen is carrier gas, stream
Speed is 30mLmin-1~50mLmin-1；
Catalyst after the reaction regenerates 500 DEG C~600 DEG C of maturing temperature range, calcining time by roasting regeneration
For 2h~6h.
After extensive testing, it is 550 DEG C that the present invention, which selects preferable maturing temperature, calcining time 4h.
CeO as catalyst2Surface has Acid-Base pair, and its acid-base property is adjustable, CeO2It is middle to be used as a kind of modification mode
Hetero atom is mixed, heteroatomic incorporation can effectively improve the doping oxygen vacancy concentration of cerium base catalyst, and then regulating catalyst
Acid-base property.
The preparation method of the ceria catalyst of doping metals is coprecipitation and hydrothermal synthesis method.
The coprecipitation is to weigh a certain amount of soluble cerium salt and the soluble-salt of doping metals is dissolved in water,
Using precipitating reagent, regulation system pH=9~12 are dry by gained precipitation and centrifugal separation, 450 DEG C~700 DEG C roasting 3h~10h,
Up to doping type ceria.
The hydrothermal synthesis method is to weigh a certain amount of cerous nitrate, soluble doped metal salt and cetyl three respectively
Methyl bromide ammonium is dissolved in water, stirring, until being completely dissolved.Using precipitating reagent, above-mentioned system is added dropwise, until pH=9
~12.The mixture is put into synthesis reactor, 1~3d of crystallization at 80 DEG C~150 DEG C, after crystallization, is centrifuged, washs, it is dry, 450
DEG C~700 DEG C of roasting 3h~10h are to get ceria.
The present invention provides a kind of method, using acetone as reactant Heteroatom doping CeO2Catalytic action under, generate
Phenolic compound, the phenolic compound are 4- methylphenol, 2,4- xylenol and 2,4,6- pseudocuminols.
Speculating its catalytic pathway substantially includes following process: ceria acid-base catalysis of the acetone in Heteroatom doping
It reacts on center, generates ketenes or hydroxy-ketone, and then annulation occurs, hydrogen migration then occurs, thus most end form
At phenolic compound.
This reaction carries out in fixed bed reactors, carries out suitable control, including reactor inside diameter, charging to response parameter
The height of speed and catalyst filling bed, preferable response parameter are conducive to extend reaction substrate and stop in catalyst bed
The time is stayed, is overcome because of mass transfer bring low activity problem；In addition, temperature is also to influence the principal element of reaction effect, research
When showing that temperature is lower, principal product is ketone compounds and mesitylene；And temperature it is higher when, carbon distribution is serious, reduce product choosing
Poisoning effect is generated to catalyst again while selecting property.Therefore, suitable reaction temperature both can guarantee high selectivity, keep away simultaneously
Carbon distribution bring deactivation prob is exempted from.
It advantage of the invention and has the beneficial effect that
(1) reaction conversion ratio is high, and the overall selectivity of phenolic compound reaches 64%.
(2) China has rare earth resources abundant, and this process is with the CeO of doping type2For catalyst, catalyst is cheap,
Prepare it is simple and high-efficient, can by roasting carbon remover after regenerate, have potential industrial applications prospect.
Detailed description of the invention
In Fig. 1 for 4 products obtained therefrom of embodiment chromatography as a result, mass spectrometry phenolic compound mainly wraps as the result is shown
4- sylvan, 2,4- dimethyl phenol and 2,4,6- trimethyl phenol are included.
Specific embodiment
In order to which the present invention will be described in further detail, several specific implementation cases are given below, but the present invention is unlimited
In these embodiments.
Embodiment 1
It weighs 50g cerous nitrate and a certain amount of two hydrated stannous chloride is dissolved in 4L water, using the sodium carbonate of 25wt%
Gained precipitation and centrifugal separation is washed till neutrality as precipitating reagent, regulation system pH=10 by aqueous solution, dry, 500 DEG C of roasting 3h,
Up to 2wt%Sn-CeO2.By Sn-CeO2In the reaction tube that it is 7mm to internal diameter that molding sieve, which takes 14-25 mesh catalyst to fill, filling
15cm bed, under normal pressure, the charging rate of acetone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 350
12h is reacted at DEG C, uses chromatography after reaction.The conversion ratio of acetone is 85%, and the overall selectivity of phenolic compound is
48%.
Embodiment 2
It weighs 50g cerous nitrate and a certain amount of six nitric hydrates praseodymium is dissolved in 4L water, using the sodium carbonate of 25wt%
Gained precipitation and centrifugal separation is washed till neutrality as precipitating reagent, regulation system pH=10 by solution, dry, 500 DEG C of roasting 3h, i.e.,
Obtain 2wt%Pr-CeO2.By Pr-CeO2In the reaction tube that it is 8mm to internal diameter that molding sieve, which takes 14-25 mesh catalyst to fill, filling
25cm bed, under normal pressure, the charging rate of acetone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 350
12h is reacted at DEG C, uses chromatography after reaction.The conversion ratio of acetone is 100%, and the overall selectivity of phenolic compound is
38%.
Embodiment 3
It weighs 50g cerous nitrate and a certain amount of lanthanum nitrate hexahydrate is dissolved in 4L water, using the sodium hydroxide of 10wt%
Gained precipitation and centrifugal separation is washed till neutrality as precipitating reagent, regulation system pH=11 by solution, dry, 500 DEG C of roasting 3h, i.e.,
5wt%La-CeO2.By La-CeO2In the reaction tube that it is 10mm to internal diameter that molding sieve, which takes 14-25 mesh catalyst to fill, 30cm is filled
Bed, under normal pressure, the charging rate of acetone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, at 350 DEG C
12h is reacted, uses chromatography after reaction.The conversion ratio of acetone is 90%, and the overall selectivity of phenolic compound is 42%.
Embodiment 4
It weighs 50g cerous nitrate and a certain amount of six nitric hydrates praseodymium is dissolved in 4L water, using the ammonia spirit of 25wt%
As precipitating reagent, regulation system pH=11, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 2wt%Pr-
CeO2.By Pr-CeO2In the reaction tube that it is 7mm to internal diameter that molding sieve, which takes 14-25 mesh catalyst to fill, 9cm bed, normal pressure are filled
Under, the charging rate of acetone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C,
Chromatography is used after reaction.The conversion ratio of acetone is 89%, and the overall selectivity of phenolic compound is 64%.
Embodiment 5
It weighs 50g cerous nitrate and a certain amount of ammonium niobium oxalate is dissolved in 4L water, using the sodium hydroxide solution of 10wt%
As precipitating reagent, gained precipitation and centrifugal separation is washed till neutrality by regulation system pH=11.5, dry, 500 DEG C of roasting 3h to get
10wt%Nb-CeO2.By Nb-CeO2In the reaction tube that it is 6mm to internal diameter that molding sieve, which takes 14-25 mesh catalyst to fill, 25cm is filled
Bed, under normal pressure, the charging rate of acetone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, at 350 DEG C
12h is reacted, uses chromatography after reaction.The conversion ratio of acetone is 87%, and the overall selectivity of phenolic compound is 31%.
Embodiment 6
It weighs 50g cerous nitrate and a certain amount of two nitric hydrates oxygen zirconium is dissolved in 4L water, using the sodium carbonate of 25wt%
Gained precipitation and centrifugal separation is washed till neutrality as precipitating reagent, regulation system pH=10 by aqueous solution, dry, 500 DEG C of roasting 3h,
Up to 0.5wt%Zr-CeO2.By Zr-CeO2In the reaction tube that it is 7mm to internal diameter that molding sieve, which takes 14-25 mesh catalyst to fill, fill out
Fill 15cm bed, under normal pressure, the charging rate of acetone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1,
12h is reacted at 350 DEG C, uses chromatography after reaction.The conversion ratio of acetone is 78%, the overall selectivity of phenolic compound
It is 25%.
Embodiment 7
50g cerous nitrate, a certain amount of chromic nitrate and 36g cetyl trimethylammonium bromide are weighed respectively is dissolved in 5L water
In, stirring, until being completely dissolved.Using the ammonium hydroxide of 25wt% as precipitating reagent, above-mentioned system is added dropwise, until pH=
10.0.The mixture is put into synthesis reactor, crystallization 3d at 100 DEG C, after crystallization, is centrifuged, washs, it is dry, it is roasted at 500 DEG C
3h is to get 5wt%Cr-CeO2.By Cr-CeO2In the reaction tube that it is 8mm to internal diameter that molding sieve, which takes 14-25 mesh catalyst to fill, fill out
Fill 25cm bed, under normal pressure, the charging rate of acetone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1,
12h is reacted at 350 DEG C, uses chromatography after reaction.The conversion ratio of acetone is 88%, the overall selectivity of phenolic compound
It is 27%.
Embodiment 8
It weighs 50g cerous nitrate and a certain amount of six nitric hydrates europium is dissolved in 4L water, using the potassium hydroxide water of 15wt%
Gained precipitation and centrifugal separation is washed till neutrality as precipitating reagent, regulation system pH=11 by solution, dry, 500 DEG C of roasting 3h, i.e.,
Obtain 8wt%Eu-CeO2.By Eu-CeO2In the reaction tube that it is 10mm to internal diameter that molding sieve, which takes 14-25 mesh catalyst to fill, filling
30cm bed, under normal pressure, the charging rate of acetone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 350
12h is reacted at DEG C, uses chromatography after reaction.The conversion ratio of acetone is 92%, and the overall selectivity of phenolic compound is
38%.
Embodiment 9
It weighs 50g cerous nitrate and a certain amount of copper nitrate is dissolved in 5L water, made using the wet chemical of 25wt%
For precipitating reagent, gained precipitation and centrifugal separation is washed till neutrality by regulation system pH=10, dry, 500 DEG C of roasting 3h to get
1wt%Cu-CeO2.By Cu-CeO2In the reaction tube that it is 12mm to internal diameter that molding sieve, which takes 14-25 mesh catalyst to fill, 25cm is filled
Bed, under normal pressure, the charging rate of acetone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, at 350 DEG C
12h is reacted, uses chromatography after reaction.The conversion ratio of acetone is 82%, and the overall selectivity of phenolic compound is 48%.
Embodiment 10
It weighs 50g cerous nitrate and a certain amount of six nitric hydrates praseodymium is dissolved in 4L water, using the ammonium hydroxide conduct of 25wt%
Precipitating reagent, regulation system pH=11, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 2wt%Pr-CeO2.It will
Pr-CeO2It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 5mm to internal diameter, filling 15cm bed, under normal pressure, third
The charging rate of ketone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h, reaction knot are reacted at 350 DEG C
Chromatography is used after beam.The conversion ratio of acetone is 85%, and the overall selectivity of phenolic compound is 54%.
Embodiment 11
It weighs 50g cerous nitrate and a certain amount of six nitric hydrates praseodymium is dissolved in 4L water, using the ammonium hydroxide conduct of 25wt%
Precipitating reagent, regulation system pH=11, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 2wt%Pr-CeO2.It will
Pr-CeO2It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 8mm to internal diameter, filling 25cm bed, under normal pressure, third
The charging rate of ketone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h, reaction knot are reacted at 350 DEG C
Chromatography is used after beam.The conversion ratio of acetone is 97%, and the overall selectivity of phenolic compound is 39%.
Embodiment 12
It weighs 50g cerous nitrate and a certain amount of six nitric hydrates praseodymium is dissolved in 4L water, using the ammonium hydroxide conduct of 25wt%
Precipitating reagent, regulation system pH=11, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 2wt%Pr-CeO2.It will
Pr-CeO2It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 8mm to internal diameter, filling 20cm bed, under normal pressure, third
The charging rate of ketone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h, reaction knot are reacted at 350 DEG C
Chromatography is used after beam.The conversion ratio of acetone is 92%, and the overall selectivity of phenolic compound is 50%.
Embodiment 13
It weighs 50g cerous nitrate and a certain amount of six nitric hydrates praseodymium is dissolved in 4L water, using the ammonium hydroxide conduct of 25wt%
Precipitating reagent, regulation system pH=11, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 2wt%Pr-CeO2.It will
Pr-CeO2It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 8mm to internal diameter, filling 25cm bed, under normal pressure, third
The charging rate of ketone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h, reaction knot are reacted at 350 DEG C
Chromatography is used after beam.The conversion ratio of acetone is 98%, and the overall selectivity of phenolic compound is 57%.
Embodiment 14
It weighs 50g cerous nitrate and a certain amount of six nitric hydrates praseodymium is dissolved in 4L water, using the ammonium hydroxide conduct of 25wt%
Precipitating reagent, regulation system pH=11, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 2wt%Pr-CeO2.It will
Pr-CeO2It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 10mm to internal diameter, filling 10cm bed, under normal pressure, third
The charging rate of ketone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h, reaction knot are reacted at 350 DEG C
Chromatography is used after beam.The conversion ratio of acetone is 82%, and the overall selectivity of phenolic compound is 46%.
Embodiment 15
It weighs 50g cerous nitrate and a certain amount of six nitric hydrates praseodymium is dissolved in 4L water, using the ammonium hydroxide conduct of 25wt%
Precipitating reagent, regulation system pH=11, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 2wt%Pr-CeO2.It will
Pr-CeO2It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 6mm to internal diameter, filling 15cm bed, under normal pressure, third
The charging rate of ketone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h, reaction knot are reacted at 350 DEG C
Chromatography is used after beam.The conversion ratio of acetone is 88%, and the overall selectivity of phenolic compound is 54%.
Embodiment 16
It weighs 50g cerous nitrate and a certain amount of six nitric hydrates praseodymium is dissolved in 4L water, using the ammonium hydroxide conduct of 25wt%
Precipitating reagent, regulation system pH=11, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 2wt%Pr-CeO2.It will
Pr-CeO2It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 11mm to internal diameter, filling 25cm bed, under normal pressure, third
The charging rate of ketone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h, reaction knot are reacted at 450 DEG C
Chromatography is used after beam.The conversion ratio of acetone is 95%, and the overall selectivity of phenolic compound is 47%.
Embodiment 17
It weighs 50g cerous nitrate and a certain amount of ferric trichloride is dissolved in 4L water, using the ammonium hydroxide of 25wt% as precipitating
Agent, regulation system pH=11, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 2wt%Fe-CeO2.By Fe-
CeO2It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 8mm to internal diameter, filling 25cm bed, under normal pressure, acetone
Charging rate is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 400 DEG C, after reaction
Using chromatography.The conversion ratio of acetone is 87%, and the overall selectivity of phenolic compound is 47%.
Embodiment 18
It weighs 50g cerous nitrate and a certain amount of ferric trichloride is dissolved in 4L water, using the ammonium hydroxide of 25wt% as precipitating
Agent, regulation system pH=11, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 2wt%Fe-CeO2.By Fe-
CeO2It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 8mm to internal diameter, filling 20cm bed, under normal pressure, acetone
Charging rate is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 300 DEG C, after reaction
Using chromatography.The conversion ratio of acetone is 62%, and the overall selectivity of phenolic compound is 48%.
Embodiment 19
It weighs 50g cerous nitrate and a certain amount of Nickelous nitrate hexahydrate is dissolved in 4L water, using the ammonium hydroxide conduct of 25wt%
Precipitating reagent, regulation system pH=9.5, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 5wt%Ni-CeO2。
By Ni-CeO2It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 7mm to internal diameter, filling 25cm bed, under normal pressure,
The charging rate of acetone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, is reacted
After use chromatography.The conversion ratio of acetone is 87%, and the overall selectivity of phenolic compound is 46%.
Embodiment 20
It weighs 50g cerous nitrate and zinc nitrate hexahydrate is dissolved in 4L water, using the ammonium hydroxide of 25wt% as precipitating reagent, adjust
Section system pH=9.5, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 8wt%Zn-CeO2.By Zn-CeO2At
In the reaction tube that it is 8mm to internal diameter that type sieve, which takes 14-25 mesh catalyst to fill, 25cm bed is filled, under normal pressure, the charging speed of acetone
Degree is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, uses color after reaction
Spectrum analysis.The conversion ratio of acetone is 73%, and the overall selectivity of phenolic compound is 58%.
Embodiment 21
It weighs 50g cerous nitrate and a certain amount of four nitric hydrates manganese is dissolved in 4L water, using the ammonium hydroxide of 25wt% as heavy
Shallow lake agent, regulation system pH=9.5, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 10wt%Mn-CeO2.It will
Mn-CeO2It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 6mm to internal diameter, filling 10cm bed, under normal pressure, third
The charging rate of ketone is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h, reaction knot are reacted at 450 DEG C
95% after beam, the overall selectivity of phenolic compound is 47%.
Embodiment 22
It weighs 50g cerous nitrate and a certain amount of hydrate ruthenium trichloride is dissolved in 4L water, using the ammonium hydroxide conduct of 25wt%
Precipitating reagent, regulation system pH=9.5, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 2wt%Ru-CeO2。
By Ru-CeO2It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 10mm to internal diameter, filling 25cm bed, under normal pressure,
The charging rate of acetone is 0.08mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 400 DEG C, is reacted
After use chromatography.The conversion ratio of acetone is 90%, and the overall selectivity of phenolic compound is 35%.
Embodiment 23
It weighs 50g cerous nitrate and a certain amount of vanadic sulfate is dissolved in 4L water, using the ammonium hydroxide of 25wt% as precipitating reagent,
Regulation system pH=9.5, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 5wt%V-CeO2.By V-CeO2At
In the reaction tube that it is 8mm to internal diameter that type sieve, which takes 14-25 mesh catalyst to fill, 12cm bed is filled, under normal pressure, the charging speed of acetone
Degree is 0.05mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 400 DEG C, uses color after reaction
Spectrum analysis.The conversion ratio of acetone is 82%, and the overall selectivity of phenolic compound is 55%.
Embodiment 24
50g cerous nitrate is weighed to be dissolved in 4L water, using the ammonium hydroxide of 25wt% as precipitating reagent, regulation system pH=9.5,
By gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get ceria.14-25 mesh is taken to urge ceria molding sieve
In the reaction tube that it is 7mm to internal diameter that agent, which is filled, 15cm bed is filled, under normal pressure, the charging rate of acetone is 0.1mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 400 DEG C, uses chromatography after reaction.Acetone turns
Rate is 89%, and the overall selectivity of phenolic compound is 48%.
Embodiment 25
It weighs 50g cerous nitrate and a certain amount of cabaltous nitrate hexahydrate and chromic nitrate is dissolved in 4L water, using 25wt%'s
Ammonium hydroxide is as precipitating reagent, and regulation system pH=9.5, by gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get 5wt%
Co-2wt%Cr-CeO2.By 5wt%Co-2wt%Cr-CeO2It is the anti-of 7mm that molding sieve, which takes 14-25 mesh catalyst to fill to internal diameter,
Ying Guanzhong fills 9cm bed, and under normal pressure, the charging rate of acetone is 0.1mLmin-1, nitrogen is carrier gas, flow velocity 80mL
min-1, 12h is reacted at 400 DEG C, uses chromatography after reaction.The conversion ratio of acetone be 76%, phenolic compound it is total
Selectivity is 54%.
Embodiment 26
It weighs 50g cerous nitrate and a certain amount of lanthanum nitrate hexahydrate and six nitric hydrate europiums is dissolved in 4L water, use
The ammonium hydroxide of 25wt% is as precipitating reagent, and regulation system pH=11 is dry by gained precipitation and centrifugal separation, 500 DEG C of roasting 3h, i.e.,
Obtain 2wt%La-2wt%Eu-CeO2.By 2wt%La-2wt%Eu-CeO2Shaping of catalyst sieve take 14-25 mesh catalyst fill to
Internal diameter is to fill 15cm bed in the reaction tube of 8mm, and under normal pressure, the charging rate of acetone is 0.1mLmin-1, nitrogen is to carry
Gas, flow velocity 50mLmin-1, 12h is reacted at 400 DEG C, uses chromatography after reaction.The conversion ratio of acetone is 69%,
The overall selectivity of phenolic compound is 45%.
Embodiment 27
It weighs 50g cerous nitrate and a certain amount of six nitric hydrates praseodymium and lanthanum nitrate hexahydrate is dissolved in 4L water, use
The ammonium hydroxide of 25wt% is as precipitating reagent, and regulation system pH=10 is dry by gained precipitation and centrifugal separation, 500 DEG C of roasting 3h, i.e.,
Obtain 2wt%Pr-2wt%La-CeO2.By 2wt%Pr-2wt%La-CeO2Shaping of catalyst sieve take 14-25 mesh catalyst fill to
Internal diameter is to fill 25cm bed in the reaction tube of 10mm, and under normal pressure, the charging rate of acetone is 0.04mLmin-1, nitrogen is
Carrier gas, flow velocity 60mLmin-1, 12h is reacted at 350 DEG C, uses chromatography after reaction.The conversion ratio of acetone is
78%, the overall selectivity of phenolic compound is 51%.
Embodiment 28
2wt%Pr-CeO after embodiment 4 to be reacted to 12h2, it is passed through air, flow velocity 50mLmin-1, roast at 550 DEG C
Burn 4h, the catalyst after being regenerated.
According to specific operation process described in embodiment 4, the sample after reusing regeneration carries out catalysis reaction 12h, acetone
Conversion ratio be 83%, selectivity be 58%.
Embodiment 29
2wt%Pr-CeO after embodiment 28 to be reacted to 12h2, it is passed through air, flow velocity 50mLmin-1, roast at 550 DEG C
Burn 4h, the catalyst after being regenerated.
According to specific operation process described in embodiment 4, the sample after reusing regeneration carries out catalysis reaction 12h, acetone
Conversion ratio be 84%, selectivity be 63%.
Embodiment 30
2wt%Pr-CeO after embodiment 29 to be reacted to 12h2, it is passed through air, flow velocity 50mLmin-1, roast at 550 DEG C
Burn 4h, the catalyst after being regenerated.
According to specific operation process described in embodiment 4, the sample after reusing regeneration carries out catalysis reaction 12h, acetone
Conversion ratio be 81%, selectivity be 60%.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of method that doping type ceria catalysis acetone prepares phenolic compound, it is characterised in that:
Using acetone as raw material, after the ceria that doping is filled in reaction tube, reaction tube is placed in fixed bed reactors, in
Certain temperature is reacted under condition of normal pressure；
Doped chemical is vanadium, chromium, manganese, iron, cobalt, nickel, zirconium, niobium, tin, ruthenium and group of the lanthanides in the doping type ceria catalyst
One or more of metal；Metal-doped amount is the wt% of 0.5 wt% ~ 10；
The tube inner diameter is the mm of 5 mm ~ 9；Loading catalyst bed height is the cm of 5 cm ~ 30, reaction temperature in reaction tube
Degree is 340 DEG C ~ 450 DEG C；
The charging rate of the acetone is the mLmin -1 of 0.01 mLmin -1 ~ 0.1；Nitrogen is carrier gas, flow velocity 20
mL·min -1~80 mL·min -1。
2. according to the method for claim 1, it is characterised in that: the preparation method of doping type ceria catalyst is coprecipitated
Shallow lake method or hydrothermal synthesis method.
3. according to the method for claim 1, it is characterised in that:
The tube inner diameter is the mm of 6 mm ~ 8；Loading catalyst bed height is the cm of 8 cm ~ 12, reaction temperature in reaction tube
Degree is 350 DEG C ~ 400 DEG C.
4. according to the method for claim 1, it is characterised in that:
The charging rate of the acetone is the mLmin -1 of 0.01 mLmin -1 ~ 0.05；Nitrogen is carrier gas, flow velocity 30
mL·min -1~50 mL·min -1。
5. according to the method for claim 1, it is characterised in that:
Catalyst after the reaction is by roasting regeneration, and regeneration maturing temperature is 500 DEG C ~ 600 DEG C, and calcining time is 2 h ~ 6
h。
6. according to the method for claim 1, it is characterised in that: acetone be prepared phenolic compound be 4- methylphenol,
2,4- xylenol and 2,4,6- pseudocuminol.
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| CN112824325A (en) * | 2019-11-20 | 2021-05-21 | 中国科学院大连化学物理研究所 | Porous cerium niobium oxide nano flaky material and preparation method thereof |
| CN114534734B (en) * | 2020-11-27 | 2024-02-27 | 万华化学集团股份有限公司 | Solid base catalyst for synthesizing 3, 5-dimethylphenol by acetone gas phase method, and preparation method and application thereof |
| CN114605216B (en) * | 2020-12-08 | 2023-06-27 | 中国科学院大连化学物理研究所 | Method for oxidative coupling of methane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3803249A (en) * | 1972-04-12 | 1974-04-09 | Atlantic Richfield Co | Vapor phase conversion of acetone to 3,5-xylenol in a single stage |
| CN103073395A (en) * | 2012-12-11 | 2013-05-01 | 浙江大学 | Technology for preparing micro-molecular phenolic compound through microwave reinforced continuous degradation of lignin in hydrogen donor |
-
2015
- 2015-08-11 CN CN201510489225.2A patent/CN106431845B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3803249A (en) * | 1972-04-12 | 1974-04-09 | Atlantic Richfield Co | Vapor phase conversion of acetone to 3,5-xylenol in a single stage |
| CN103073395A (en) * | 2012-12-11 | 2013-05-01 | 浙江大学 | Technology for preparing micro-molecular phenolic compound through microwave reinforced continuous degradation of lignin in hydrogen donor |
Non-Patent Citations (3)
| Title |
|---|
| Secondary reactions of the base-catalyzed aldol condensation of acetone;Sigrid Lippert等;《Journal of Molecular Catalysis》;19911231;第69卷;第199-214页 * |
| Surface Reactions of Acetone on Al2O3, TiO2, ZrO2, and CeO2: IR Spectroscopic Assessment of Impacts of the Surface Acid-Base Properties;M. I. Zaki等;《Langmuir》;20010301;第17卷;第768-774页 * |
| 丙酮气相一步合成3,5-二甲基苯酚;吕兴等;《科技导报》;20081231;第26卷(第22期);第63-65页 * |
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