CN106518628B - The method for preparing phenolic compound - Google Patents
The method for preparing phenolic compound Download PDFInfo
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- CN106518628B CN106518628B CN201510580108.7A CN201510580108A CN106518628B CN 106518628 B CN106518628 B CN 106518628B CN 201510580108 A CN201510580108 A CN 201510580108A CN 106518628 B CN106518628 B CN 106518628B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
Abstract
The present invention relates to a kind of methods for preparing phenolic compound.This method uses acetic acid, formaldehyde, or acetic acid, formaldehyde and methanol are as reactant, phenolic compound is prepared under the catalytic action of doping type ceria, the reaction carries out under normal pressure in fixed bed reactors, 300 DEG C~550 DEG C of reaction temperature, mass spectrum determines that product forms after reaction, chromatogram quantification.The reaction conversion ratio of the method for the present invention is high, and the maximum conversion of reaction reaches 100%, and the overall selectivity of phenolic compound reaches 95%;In addition the present invention selects doping type ceria for catalyst, and 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 acetic acid, formaldehyde or acetic acid, formaldehyde and
For methanol as reactant, doping type ceria is catalyst, the method that catalysis 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
Meaning of the present invention is to overcome prepare phenolic compound at present during there are the shortcomings that.The preparation method is anti-
Answer process simple, reaction conversion ratio and phenols selectivity are higher.
Phenolic compound of the present invention is prepared by following scheme:
The reaction solution prepared using a certain proportion of acetic acid, formaldehyde or acetic acid, formaldehyde and methanol is raw material, in reaction tube
Reaction tube is placed in fixed bed reactors after middle filling doping type ceria, is reacted under normal pressure, reaction temperature is
300 DEG C~550 DEG C, the reaction time is greater than 2h, preferred reaction time 6-72h.Catalyst after reaction can be by roasting again
It is raw;The doping type ceria catalyst, 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%~10wt%;The doping
Type ceria catalyst, preferable doped chemical are as follows: aluminium, titanium, vanadium, chromium, zinc, yttrium, zirconium, niobium, molybdenum, palladium, lanthanum, praseodymium, europium;Preferably
Metal-doped amount are as follows: 1wt%~6wt%;The tube inner diameter are as follows: 5mm~9mm;Loading catalyst bed height is 5cm
~30cm, reaction temperature are 300 DEG C~550 DEG C;The tube inner diameter are as follows: 6mm~8mm;Loading catalyst bed in reaction tube
Layer height is 8cm~12cm, and reaction temperature is 350 DEG C~450 DEG C;When the raw material is made of acetic acid and formaldehyde, acetic acid and first
The molar ratio of aldehyde is 1:1~1:10;When the raw material is made of acetic acid, formaldehyde and methanol, the molar ratio of acetic acid and formaldehyde is 1:1
~1:10, and the molar ratio of formaldehyde and methanol is 5:1~1:1.Reaction solution charging rate is 0.01mLmin-1~0.1mL
min-1;Nitrogen is carrier gas, flow velocity 20mLmin-1~80mLmin-1。
Catalyst after the reaction is by roasting regeneration, and 500 DEG C~600 DEG C of maturing temperature range, calcining time range
2h~10h.
Optimal regeneration maturing temperature is 550 DEG C, calcining time 4h.
The phenolic compound that the present invention is prepared includes o-cresol, 2,3- dimethyl phenol, 2,3,6- trimethyl phenol, 2,3,
4,6- tetramethyl phenol.
Ceria surface has Acid-Base pair, and its acid-base property is adjustable, and ceria mixes miscellaneous as a kind of modification mode
Atom, heteroatomic incorporation can effectively improve the doping oxygen vacancy concentration of cerium base catalyst, and then the acid-base property of regulating catalyst.
Doping type ceria is reacted as catalyst, thus it is speculated that its catalytic pathway substantially includes following process:
Acetic acid reacts on the ceria acid-base catalysis center of Heteroatom doping, generates acetone, carbon dioxide and water;Acetone with
Formaldehyde and acetone generate a variety of alkanones chemical combination from Aldol condensation reaction, and then dehydration occur under base catalysis
Object;Aliphatic ketone occurs annulation and forms six membered ring shape ketone compounds, hydrogen migration then occurs, to ultimately form phenol generalization
Close object.
The reaction carries out in fixed bed reactors, the control of suitable response parameter, including reactor inside diameter, charging speed
Degree and catalyst filling bed be highly advantageous for extend reaction substrate in the residence time of catalyst bed, overcome because pass
Matter bring low activity problem;In addition, temperature is also to influence the principal element of reaction effect.Studies have shown that when temperature is lower, it is main
Product is other ketone compounds that acetic acid decomposes the acetone generated and Aldol condensation reaction generates;And temperature it is higher when, product
Carbon is serious, generates poisoning effect to catalyst again while reducing the selectivity of product.Therefore, suitable reaction temperature can protect
High selectivity is demonstrate,proved, while avoiding carbon distribution bring deactivation prob.
The method of the invention has the beneficial effect that
(1) this method prepares the dependence that phenolic compound overcomes conventional method to fossil energy, avoids cumbersome work
Skill process, has potential application.
(2) raw material sources are extensive, using acetic acid and acetone cheap and easy to get as raw material, reaction conversion ratio and selectivity compared with
Height, the maximum conversion of reaction reach 100%, and the overall selectivity of phenolic compound reaches 95%.
(3) China has rare earth resources abundant, and this process is using the ceria of doping type as catalyst, and catalyst is honest and clean
Valence prepares simple and high-efficient, can realize regulation to catalyst acid alkalinity by the modulation to doping condition, and can pass through roasting
It is regenerated after burn off carbon distribution.
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
Acetic acid, formaldehyde and ethyl alcohol according to the reaction solution that molar ratio 1:5:1 is prepared are raw material, charging rate under normal pressure by 15cm bed
For 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, after reaction through liquid separation,
Obtained oil phase and water phase, is respectively adopted chromatography.Acetic acid conversion is 85%, and the overall selectivity of phenolic compound is
80%.
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
Acetic acid and formaldehyde according to the reaction solution that molar ratio 1:5 is prepared are raw material, charging rate is under normal pressure by 25cm bed
0.03mL·min-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, after reaction through liquid separation, is obtained
The oil phase and water phase arrived, is respectively adopted chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 83%.
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
Acetic acid, formaldehyde and ethyl alcohol according to the reaction solution that molar ratio 1:1:1 is prepared are raw material, charging rate is under normal pressure by bed
0.03mL·min-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, after reaction through liquid separation, is obtained
The oil phase and water phase arrived, is respectively adopted chromatography.Acetic acid conversion is 90%, and the overall selectivity of phenolic compound is 93%.
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 reaction solution that acetic acid, formaldehyde and methanol are prepared according to molar ratio 1:5:1 is raw material, charging rate 0.03mL
min-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, after reaction through liquid separation, obtained oily phase
And water phase, chromatography is respectively adopted.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 95%.
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
Acetic acid, formaldehyde and methanol according to the reaction solution that molar ratio 1:5:1 is prepared are raw material, charging rate is under normal pressure by bed
0.03mL·min-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, after reaction through liquid separation, is obtained
The oil phase and water phase arrived, is respectively adopted chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 84%.
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
It fills 15cm bed, according to the reaction solution that molar ratio 1:5:1 is prepared is raw material, charging speed by acetic acid, formaldehyde and methanol under normal pressure
Degree is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, react 12h at 350 DEG C, after reaction through point
Liquid, obtained oil phase and water phase, is respectively adopted chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is
85%.
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
It fills 25cm bed, according to the reaction solution that molar ratio 1:5:1 is prepared is raw material, charging speed by acetic acid, formaldehyde and methanol under normal pressure
Degree is 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, react 12h at 350 DEG C, after reaction through point
Liquid, obtained oil phase and water phase, is respectively adopted chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is
82%.
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
Acetic acid, formaldehyde and methanol according to the reaction solution that molar ratio 1:5:1 is prepared are raw material, charging rate under normal pressure by 30cm bed
For 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, after reaction through liquid separation,
Obtained oil phase and water phase, is respectively adopted chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is
90%.
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
Acetic acid, formaldehyde and methanol according to the reaction solution that molar ratio 1:5:1 is prepared are raw material, charging rate is under normal pressure by bed
0.03mL·min-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, after reaction through liquid separation, is obtained
The oil phase and water phase arrived, is respectively adopted chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 88%.
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, it, will under normal pressure
Acetic acid and formaldehyde are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:5 is prepared-1, nitrogen is to carry
Gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, and after reaction through liquid separation, obtained oil mutually and water phase, is respectively adopted
Chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 94%.
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, it, will under normal pressure
Acetic acid, formaldehyde and ethyl alcohol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:1:1 is prepared-1, nitrogen
Gas is carrier gas, flow velocity 30mLmin-1, react 12h at 350 DEG C, after reaction through liquid separation, obtained oil mutually and water phase, point
It Cai Yong not chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 89%.
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, it, will under normal pressure
Acetic acid, formaldehyde and methanol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:2:1 is prepared-1, nitrogen
Gas is carrier gas, flow velocity 30mLmin-1, react 12h at 350 DEG C, after reaction through liquid separation, obtained oil mutually and water phase, point
It Cai Yong not chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 80%.
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, it, will under normal pressure
Acetic acid, formaldehyde and methanol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:3:1 is prepared-1, nitrogen
Gas is carrier gas, flow velocity 30mLmin-1, react 12h at 350 DEG C, after reaction through liquid separation, obtained oil mutually and water phase, point
It Cai Yong not chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 85%.
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, it, will under normal pressure
Acetic acid, formaldehyde and methanol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:2:2 is prepared-1, nitrogen
Gas is carrier gas, flow velocity 30mLmin-1, react 12h at 350 DEG C, after reaction through liquid separation, obtained oil mutually and water phase, point
It Cai Yong not chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 91%.
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, it, will under normal pressure
Acetic acid, formaldehyde and methanol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:5:5 is prepared-1, nitrogen
Gas is carrier gas, flow velocity 30mLmin-1, react 12h at 350 DEG C, after reaction through liquid separation, obtained oil mutually and water phase, point
It Cai Yong not chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 94%.
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, it, will under normal pressure
Acetic acid, formaldehyde and methanol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:5:1 is prepared-1, nitrogen
Gas is carrier gas, flow velocity 30mLmin-1, react 12h at 450 DEG C, after reaction through liquid separation, obtained oil mutually and water phase, point
It Cai Yong not chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 93%.
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, by second
Acid, formaldehyde and methanol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:5:1 is prepared-1, nitrogen
For carrier gas, flow velocity 30mLmin-1, react 12h at 400 DEG C, after reaction through liquid separation, obtained oil mutually and water phase, respectively
Using chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 77%.
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, by second
Acid, formaldehyde and methanol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:5:1 is prepared-1, nitrogen
For carrier gas, flow velocity 30mLmin-1, react 12h at 300 DEG C, after reaction through liquid separation, obtained oil mutually and water phase, respectively
Using chromatography.Acetic acid conversion is 90%, and the overall selectivity of phenolic compound is 88%.
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 reaction solution that acetic acid, formaldehyde and methanol are prepared according to molar ratio 1:5:1 is raw material, charging rate 0.03mLmin-1,
Nitrogen is carrier gas, flow velocity 30mLmin-1, react 12h at 350 DEG C, after reaction through liquid separation, obtained oil mutually and water phase,
Chromatography is respectively adopted.Acetic acid conversion is 90%, and the overall selectivity of phenolic compound is 75%.
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, by acetic acid, formaldehyde
The reaction solution prepared with methanol according to molar ratio 1:5:1 is raw material, charging rate 0.03mLmin-1, nitrogen is carrier gas,
Flow velocity is 30mLmin-1, 12h is reacted at 350 DEG C, and after reaction through liquid separation, mutually and water phase, color is respectively adopted in obtained oil
Spectrum analysis.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 80%.
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, it, will under normal pressure
Acetic acid, formaldehyde and methanol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:5:1 is prepared-1, nitrogen
Gas is carrier gas, flow velocity 30mLmin-1, react 12h at 550 DEG C, after reaction through liquid separation, obtained oil mutually and water phase, point
It Cai Yong not chromatography.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 72%.
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 reaction solution that acetic acid, formaldehyde and methanol are prepared according to molar ratio 1:5:1 is raw material, charging rate 0.08mLmin-1,
Nitrogen is carrier gas, flow velocity 30mLmin-1, react 12h at 400 DEG C, after reaction through liquid separation, obtained oil mutually and water phase,
Chromatography is respectively adopted.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 85%.
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, by acetic acid, formaldehyde
The reaction solution prepared with methanol according to molar ratio 1:5:1 is raw material, charging rate 0.05mLmin-1, nitrogen is carrier gas,
Flow velocity is 30mLmin-1, 12h is reacted at 400 DEG C, and after reaction through liquid separation, mutually and water phase, color is respectively adopted in obtained oil
Spectrum analysis.Acetic acid conversion is 100%, and the overall selectivity of phenolic compound is 85%.
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, by acetic acid, formaldehyde and methanol according to molar ratio
The reaction solution that 1:5:1 is prepared is raw material, charging rate 0.1mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1,
12h is reacted at 400 DEG C, after reaction through liquid separation, chromatography is respectively adopted in obtained oil phase and water phase.Acetic acid conversion
It is 85%, the overall selectivity of phenolic compound is 81%.
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, according to the reaction solution that molar ratio 1:5:1 is prepared is former by acetic acid, formaldehyde and methanol under normal pressure
Material, charging rate 0.1mLmin-1, nitrogen is carrier gas, flow velocity 80mLmin-1, 12h is reacted at 400 DEG C, and reaction terminates
By liquid separation, chromatography is respectively adopted in obtained oil phase and water phase.Acetic acid conversion is 98%, total choosing of phenolic compound
Selecting property is 84%.
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, acetic acid, formaldehyde and methanol are prepared according to molar ratio 1:5:1
Reaction solution be raw material, charging rate 0.1mLmin-1, nitrogen is carrier gas, flow velocity 50mLmin-1, anti-at 400 DEG C
12h is answered, after reaction through liquid separation, chromatography is respectively adopted in obtained oil phase and water phase.Acetic acid conversion is 95%, phenol
The overall selectivity of class compound is 85%.
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, acetic acid, formaldehyde and methanol are prepared according to molar ratio 1:5:1
Reaction solution be raw material, charging rate 0.04mLmin-1, nitrogen is carrier gas, flow velocity 60mLmin-1, at 350 DEG C
12h is reacted, after reaction through liquid separation, chromatography is respectively adopted in obtained oil phase and water phase.Acetic acid conversion is 100%,
The overall selectivity of phenolic compound is 94%.
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 is carried out
Catalysis reaction 12h, acetic acid conversion 100%, selectivity are 83%.
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 is carried out
Catalysis reaction 12h, acetic acid conversion 100%, selectivity are 84%.
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 is carried out
Catalysis reaction 12h, acetic acid conversion 100%, selectivity are 80%.
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 (9)
1. a kind of method for preparing phenolic compound, it is characterised in that:
Reaction tube is placed in fixed bed reactors after filling doping type ceria in reaction tube, is carried out under normal pressure anti-
It answers, reaction temperature is 300 DEG C~550 DEG C;
Reaction raw materials are acetic acid, formaldehyde and the first of the acetic acid of certain mol proportion, the reaction solution that formaldehyde is prepared or certain mol proportion
The reaction solution that alcohol is prepared;
When the raw material is made of acetic acid and formaldehyde, the molar ratio of acetic acid and formaldehyde is 1:1~1:10;The raw material by acetic acid,
When formaldehyde and methanol form, the molar ratio of acetic acid and formaldehyde is 1:1~1:10, and the molar ratio of formaldehyde and methanol is 5:1~1:
1;
In the doping type ceria catalyst doped chemical be aluminium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium,
One or more of zirconium, niobium, molybdenum, tin, ruthenium, palladium, rhodium, gold, platinum and lanthanide series metal;Metal-doped amount are as follows: 0.5wt%
~10wt%.
2. according to the method for claim 1, it is characterised in that:
In the doping type ceria catalyst preferable doped chemical be aluminium, titanium, vanadium, chromium, zinc, yttrium, zirconium, niobium, molybdenum, palladium,
One or more of lanthanum, praseodymium, europium;Preferable metal-doped amount are as follows: 0.5wt%~6wt%.
3. method according to claim 1 or 2, it is characterised in that:
The preparation method of doping type ceria catalyst is coprecipitation or hydrothermal synthesis method.
4. according to method described in claim 1 or 3, it is characterised in that:
The coprecipitation is to weigh a certain amount of soluble cerium salt and the soluble-salt of doping metals is dissolved in water, and is used
Precipitating reagent, regulation system pH=9~12 are dry by gained precipitation and centrifugal separation, and 450~700 DEG C of roasting 3h~10h are to get mixing
Miscellaneous type ceria;
The hydrothermal synthesis method is to weigh a certain amount of cerous nitrate, soluble doped metal salt and cetyl trimethyl respectively
Ammonium bromide 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, 450~700
DEG C roasting 3h~10h to get doping type ceria.
5. according to the method for claim 1, it is characterised in that: the tube inner diameter is 5mm~9mm;Loading catalyst
Bed height is 5cm~30cm.
6. according to the method for claim 1, it is characterised in that:
The tube inner diameter is 6mm~8mm;Loading catalyst bed height is 8cm~12cm in reaction tube, and reaction temperature is
350 DEG C~450 DEG C.
7. according to the method for claim 1, it is characterised in that:
Reaction solution charging rate is 0.01mLmin-1~0.1mLmin-1;Nitrogen is carrier gas, flow velocity 20mLmin-1
~80mLmin-1。
8. according to the method for claim 1, it is characterised in that:
Catalyst after the reaction can pass through roasting regeneration.
9. according to the method for claim 1, it is characterised in that: the phenolic compound includes o-cresol, 2,3- dimethyl
Phenol, 2,3,6- trimethyl phenol, 2,3,4,6- tetramethyl phenol.
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