CN106518627B - A method of preparing phenolic compound - Google Patents
A method of preparing phenolic compound Download PDFInfo
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- CN106518627B CN106518627B CN201510577993.3A CN201510577993A CN106518627B CN 106518627 B CN106518627 B CN 106518627B CN 201510577993 A CN201510577993 A CN 201510577993A CN 106518627 B CN106518627 B CN 106518627B
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- acetic acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a kind of methods for preparing phenolic compound.This method using acetic acid, formaldehyde or acetic acid, formaldehyde and methanol as reactant, in ceria (CeO2) catalytic action under prepare phenolic compound.The reaction carries out under normal pressure in fixed bed reactors, and reaction temperature is 300 DEG C~550 DEG C, and 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 85%；In addition present invention selection CeO2For 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 acetic acid, formaldehyde and/or methanol as instead
Answer object, 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
Middle catalyst filling CeO2Reaction tube is placed in fixed bed reactors afterwards, is reacted under fixed bed reactors normal pressure, instead
Answering temperature is 300 DEG C~550 DEG C.Reaction time is greater than 2h, preferred reaction time 6-72h.Catalyst after reaction can pass through
Roasting regeneration；
The CeO2Catalyst can be using one-step calcinations, the precipitation method or hydrothermal synthesis method preparation；
The CeO2Catalyst is using one-step calcinations, the precipitation method or hydrothermal synthesis method preparation.
The one-step calcinations are to weigh a certain amount of cerium salt in air atmosphere, roast 5h at 450 DEG C~700 DEG C,
Up to ceria；
The precipitation method are as follows: weigh a certain amount of soluble cerium salt and be dissolved in water, using precipitating reagent, regulation system pH
=9~12, by gained precipitation and centrifugal separation, dry, 450 DEG C~700 DEG C roasting 3h~10h are to get ceria；
The hydrothermal synthesis method is to weigh a certain amount of cerous nitrate respectively and cetyl trimethylammonium bromide is dissolved in
In water, stirring, until being completely dissolved.Using precipitating reagent, above-mentioned system is added dropwise, until pH=9~12.The mixture is put
Enter in 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 roasting 3h~
10h is to get ceria.
The tube inner diameter are as follows: 5mm~9mm；Loading catalyst bed height is 5cm~30cm, reaction temperature 300
DEG C~550 DEG C；
The preferable tube inner diameter are as follows: 6mm~8mm；Loading catalyst bed is preferably highly 8cm in reaction tube
~12cm, preferable reaction temperature are 350 DEG C~450 DEG C；
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 is by second
When acid, formaldehyde and methanol form, the molar ratio of acetic acid and formaldehyde is 1:1~1:10, and the ingredient molar ratio of formaldehyde and methanol is
5:1~1:1.Reaction solution charging rate is 0.01mLmin-1~0.1mLmin-1；Nitrogen is carrier gas, flow velocity 20mL
min-1~80mLmin-1.When the raw material is made of acetic acid and formaldehyde, acetic acid and the preferable molar ratio of formaldehyde are 1:1~1:
5；When the raw material is made of acetic acid, formaldehyde and methanol, acetic acid and the preferable molar ratio of formaldehyde are 1:1~1:5, and formaldehyde and first
The preferable ingredient molar ratio of alcohol is 5:1~1:1.Preferable reaction solution charging rate is 0.01mLmin-1~0.05mL
min-1；Nitrogen is carrier gas, and preferable flow velocity is 30mLmin-1~50mLmin-1；
By roasting regeneration, maturing temperature is 500 DEG C~600 DEG C for catalyst after the reaction, calcining time be 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.
CeO as catalyst2Surface has Acid-Base pair, and its acid-base property is adjustable.With acetic acid, formaldehyde or acetic acid, first
Aldehyde and methanol are as reactant, in CeO2Catalytic action under, generate phenolic compound.Speculate that catalytic pathway substantially includes following
Several processes: acetic acid reacts on ceria acid-base catalysis center, generates acetone, carbon dioxide and water；Acetone and first
Aldehyde 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 cyclic 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 the acetone of the generation of base catalysis and other ketone compounds that 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, and using acetic acid and acetone cheap and easy to get as raw material, reaction conversion ratio is high, the highest of reaction
Conversion ratio reaches 100%, and the overall selectivity of phenolic compound reaches 85%.
(3) China has rare earth resources abundant, and this process is with CeO2For catalyst, catalyst is cheap, preparation is simple
And it is high-efficient, it can be by being regenerated after roasting carbon remover.
Detailed description of the invention
Fig. 1 is the gas chromatograph results that embodiment 4 reacts collection liquid, in product each substance be identified through mass spectrum (MS,
Agilent 5975C) it realizes.
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
Weigh 200g ammonium ceric nitrate in air atmosphere, 500 DEG C of roasting 5h are to get ceria.Ceria is formed
In the reaction tube that it is 7mm to internal diameter that sieve, which takes 14-25 mesh catalyst to fill, fill 15cm bed, under normal pressure, by acetic acid, formaldehyde and
Ethyl alcohol is raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:5:1 is prepared-1, nitrogen is carrier gas, stream
Speed is 30mLmin-1, 12h is reacted at 350 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil
Analysis.Acetic acid conversion is 70%, and the overall selectivity of phenolic compound is 75%.
Embodiment 2
Weigh 200g ammonium ceric nitrate in air atmosphere, 500 DEG C of roasting 5h are to get ceria.Ceria is formed
In the reaction tube that it is 8mm to internal diameter that sieve, which takes 14-25 mesh catalyst to fill, 25cm bed is filled, under normal pressure, acetic acid and formaldehyde are pressed
It is raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:5 is prepared-1, nitrogen is carrier gas, and flow velocity is
30mL·min-1, 12h is reacted at 350 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.
Acetic acid conversion is 80%, and the overall selectivity of phenolic compound is 73%.
Embodiment 3
It weighs 50g cerous nitrate to be dissolved in 4L water, using the ammonium hydroxide of 25wt% as precipitating reagent, regulation system pH=9 will
Gained precipitation and centrifugal separation, dry, 500 DEG C of roasting 3h are to get ceria.14-25 mesh is taken to be catalyzed ceria molding sieve
In the reaction tube that it is 7mm to internal diameter that agent, which is filled, 9cm bed is filled, under normal pressure, by acetic acid, formaldehyde and methanol according to molar ratio 1:
The reaction solution that 5:1 is prepared is raw material, charging rate 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1,
12h is reacted at 350 DEG C, after reaction through liquid separation, chromatography is respectively adopted in obtained oil phase and water phase.Acetic acid conversion
It is 100%, the overall selectivity of phenolic compound is 85%.
Embodiment 4
It weighs 50g cerous nitrate to be dissolved in 4L water, using the sodium hydroxide solution of 10wt% as precipitating reagent, regulation system
Gained precipitation and centrifugal separation is washed till neutrality by pH=11.5, and dry, 500 DEG C of roasting 3h are to get ceria.By ceria
It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 6mm to internal diameter, filling 25cm bed, under normal pressure, by acetic acid, first
Aldehyde and methanol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:5:1 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 77%.
Embodiment 5
It weighs 50g ammonium ceric nitrate to be dissolved in 4L water, using the aqueous sodium carbonate of 25wt% as precipitating reagent, adjusts body
It is pH=10, by gained precipitation and centrifugal separation, is washed till neutrality, dry, 500 DEG C of roasting 3h is to get ceria.By ceria
It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 7mm to internal diameter, filling 15cm bed, under normal pressure, by acetic acid, first
Aldehyde and methanol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:5:1 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 82%.
Embodiment 6
50g cerous nitrate is weighed respectively and 36g cetyl trimethylammonium bromide is dissolved in 5L water, is stirred, until completely
Dissolution.Using the ammonium hydroxide of 25wt% as precipitating reagent, above-mentioned system is added dropwise, until pH=10.0.The mixture is put into
In synthesis reactor, crystallization 3d at 100 DEG C after crystallization, is centrifuged, washs, dry, and 3h is roasted at 500 DEG C to get ceria.By two
In the reaction tube that it is 8mm to internal diameter that cerium oxide molding sieve, which takes 14-25 mesh catalyst to fill, 25cm bed is filled, 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 350 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 72%.
Embodiment 7
It weighs 50g cerous nitrate to be dissolved in 4L water, using the potassium hydroxide aqueous solution of 15wt% as precipitating reagent, adjusts body
It is pH=11, by gained precipitation and centrifugal separation, is washed till neutrality, dry, 500 DEG C of roasting 3h is to get ceria.By ceria
It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 10mm to internal diameter, filling 30cm bed, under normal pressure, by acetic acid, first
Aldehyde and methanol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:5:1 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 73%.
Embodiment 8
It weighs 50g ammonium ceric nitrate to be dissolved in 5L water, using the wet chemical of 25wt% as precipitating reagent, adjusts body
It is pH=10, by gained precipitation and centrifugal separation, is washed till neutrality, dry, 500 DEG C of roasting 3h is to get ceria.By ceria
It forms sieve 14-25 mesh catalyst is taken to fill in the reaction tube for being 12mm to internal diameter, filling 25cm bed, under normal pressure, by acetic acid, first
Aldehyde and methanol are raw material, charging rate 0.03mLmin according to the reaction solution that molar ratio 1:5:1 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 78%.
Embodiment 9
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 8mm to internal diameter that agent, which is filled, 25cm bed is filled, under normal pressure, by acetic acid, formaldehyde and ethyl alcohol according to molar ratio
The reaction solution that 1:1:1 is prepared is raw material, charging rate 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid conversion
Rate is 100%, and the overall selectivity of phenolic compound is 78%.
Embodiment 10
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 8mm to internal diameter that agent, which is filled, 20cm bed is filled, under normal pressure, by acetic acid, formaldehyde and methanol according to molar ratio
The reaction solution that 1:2:1 is prepared is raw material, charging rate 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid conversion
Rate is 100%, and the overall selectivity of phenolic compound is 80%.
Embodiment 11
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 8mm to internal diameter that agent, which is filled, 25cm bed is filled, under normal pressure, by acetic acid, formaldehyde and methanol according to molar ratio
The reaction solution that 1:3:1 is prepared is raw material, charging rate 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid conversion
Rate is 100%, and the overall selectivity of phenolic compound is 82%.
Embodiment 12
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 10mm to internal diameter that agent, which is filled, fill 10cm bed, under normal pressure, by acetic acid, formaldehyde and methanol according to mole
It is raw material, charging rate 0.03mLmin than the reaction solution that 1:2:2 is prepared-1, nitrogen is carrier gas, flow velocity 30mL
min-1, 12h is reacted at 350 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid turns
Rate is 100%, and the overall selectivity of phenolic compound is 81%.
Embodiment 13
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 6mm 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 1:5:5 is prepared is raw material, charging rate 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid conversion
Rate is 100%, and the overall selectivity of phenolic compound is 84%.
Embodiment 14
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 11mm to internal diameter that agent, which is filled, fill 25cm bed, under normal pressure, by acetic acid, formaldehyde and methanol according to mole
It is raw material, charging rate 0.03mLmin than the reaction solution that 1:5:1 is prepared-1, nitrogen is carrier gas, flow velocity 30mL
min-1, 12h is reacted at 450 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid turns
Rate is 100%, and the overall selectivity of phenolic compound is 72%.
Embodiment 15
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 8mm to internal diameter that agent, which is filled, 25cm 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 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 400 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid conversion
Rate is 100%, and the overall selectivity of phenolic compound is 79%.
Embodiment 16
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 8mm to internal diameter that agent, which is filled, 20cm 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 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 300 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid conversion
Rate is 78%, and the overall selectivity of phenolic compound is 77%.
Embodiment 17
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, 25cm 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 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid conversion
Rate is 52%, and the overall selectivity of phenolic compound is 82%.
Embodiment 18
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 8mm to internal diameter that agent, which is filled, 25cm 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 0.03mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 350 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid conversion
Rate is 100%, and the overall selectivity of phenolic compound is 72%.
Embodiment 19
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 10mm to internal diameter that agent, which is filled, fill 25cm bed, under normal pressure, by acetic acid, formaldehyde and methanol according to mole
It is raw material, charging rate 0.08mLmin than the reaction solution that 1:5:1 is prepared-1, nitrogen is carrier gas, flow velocity 30mL
min-1, 12h is reacted at 400 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid turns
Rate is 93%, and the overall selectivity of phenolic compound is 80%.
Embodiment 20
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 8mm to internal diameter that agent, which is filled, 12cm 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 0.05mLmin-1, nitrogen is carrier gas, flow velocity 30mLmin-1, 12h is reacted at 400 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid conversion
Rate is 100%, and the overall selectivity of phenolic compound is 82%.
Embodiment 21
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 22
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, 9cm 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 80mLmin-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 72%, the overall selectivity of phenolic compound is 81%.
Embodiment 23
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 8mm 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 50mLmin-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 79%, the overall selectivity of phenolic compound is 81%.
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 10mm to internal diameter that agent, which is filled, fill 25cm bed, under normal pressure, by acetic acid, formaldehyde and methanol according to mole
It is raw material, charging rate 0.04mLmin than the reaction solution that 1:5:1 is prepared-1, nitrogen is carrier gas, flow velocity 60mL
min-1, 12h is reacted at 350 DEG C, and after reaction through liquid separation, mutually and water phase, chromatography is respectively adopted in obtained oil.Acetic acid turns
Rate is 100%, and the overall selectivity of phenolic compound is 78%.
Embodiment 25
Ceria after embodiment 3 to be reacted to 12h, is passed through air, flow velocity 50mLmin-1, 4h is roasted at 550 DEG C,
Catalyst after being regenerated.According to specific operation process described in embodiment 4, the sample after reusing regeneration be catalyzed anti-
12h, acetic acid conversion 100% are answered, selectivity is 83%.
Embodiment 26
Ceria after embodiment 25 to be reacted to 12h, is passed through air, flow velocity 50mLmin-1, roast at 550 DEG C
4h, the catalyst after being regenerated.According to specific operation process described in embodiment 4, the sample after reusing regeneration is urged
Change reaction 12h, acetic acid conversion 100%, selectivity is 84%.
Embodiment 27
Ceria after embodiment 26 to be reacted to 12h, is passed through air, flow velocity 50mLmin-1, roast at 550 DEG C
4h, the catalyst after being regenerated.According to specific operation process described in embodiment 4, the sample after reusing regeneration is urged
Change reaction 12h, acetic acid conversion 100%, selectivity is 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, reaction condition is modified or equivalent replacement of some of the technical features, all at this
Within the spirit and principle of invention, any modification, equivalent replacement, improvement and so on should be included in protection model of the invention
Within enclosing.
Claims (8)
1. a kind of method for preparing phenolic compound, it is characterised in that:
The catalyst filling CeO in reaction tube2Reaction tube is placed in fixed bed reactors afterwards, is reacted under normal pressure, is reacted
Temperature is 300 DEG C~550 DEG C；
Reaction raw materials are acetic acid, the formaldehyde of the acetic acid of certain mol proportion example, the reaction solution that formaldehyde is prepared or certain mol proportion example
The reaction solution prepared with methanol；
When the raw material is made of acetic acid and formaldehyde, the molar ratio of acetic acid and formaldehyde 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 formaldehyde and first
The molar ratio of alcohol is 5:1~1:1；
The CeO2Catalyst is using one-step calcinations, the precipitation method or hydrothermal synthesis method preparation.
2. according to the method for claim 1, it is characterised in that:
The one-step calcinations be weigh a certain amount of cerium salt in air atmosphere, at 450 DEG C~700 DEG C roast 5h to get
Ceria；
The precipitation method are as follows: weigh a certain amount of soluble cerium salt and be dissolved in water, using precipitating reagent, regulation system pH=9
~12, by gained precipitation and centrifugal separation, dry, 450 DEG C~700 DEG C roasting 3h~10h are to get ceria；
The hydrothermal synthesis method is to weigh a certain amount of cerous nitrate respectively and cetyl trimethylammonium bromide is dissolved in water,
Until being completely dissolved, using precipitating reagent, above-mentioned system is added dropwise in stirring, until pH=9~12, are put into conjunction for the mixture
At in kettle, 1~3d of crystallization at 80 DEG C~150 DEG C after crystallization, is centrifuged, washs, dry, 450 DEG C~700 DEG C roasting 3h~10h,
Up to ceria.
3. 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.
4. 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.
5. 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。
6. according to the method for claim 1, it is characterised in that:
When the raw material is made of acetic acid and formaldehyde, the molar ratio of acetic acid and formaldehyde is 1:1~1:5；The raw material is by acetic acid, first
When aldehyde and methanol form, the molar ratio of acetic acid and formaldehyde is 1:1~1:5, and the molar ratio of formaldehyde and methanol is 5:1~1:1；
Reaction solution charging rate is 0.01mLmin-1~0.05mLmin-1；Nitrogen is carrier gas, flow velocity 30mLmin-1
~50mLmin-1。
7. according to the method for claim 1, it is characterised in that:
Catalyst after the reaction can pass through roasting regeneration.
8. 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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Citations (2)
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|---|---|---|---|---|
| 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
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| 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 |
|---|
| Formation of Aromatic Compounds from Condensation Reactions of Cellulose Degradation Products;J. A. Russell等;《Biomass》;19831231;第3卷(第1期);第43-57页 * |
| 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 * |
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