CN108947775A - A method of catalysis dibenzofuran open loop prepares o-phenyl phenol - Google Patents
A method of catalysis dibenzofuran open loop prepares o-phenyl phenol Download PDFInfo
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- CN108947775A CN108947775A CN201810892805.XA CN201810892805A CN108947775A CN 108947775 A CN108947775 A CN 108947775A CN 201810892805 A CN201810892805 A CN 201810892805A CN 108947775 A CN108947775 A CN 108947775A
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- dibenzofuran
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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
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The invention discloses a kind of methods that catalysis dibenzofuran open loop prepares o-phenyl phenol, using industrial dibenzofuran as raw material, use the catalysis of nano-titanium oxide mesoporous composite material supported copper for hydrogenation catalyst, the catalyst is using ordered meso-porous silicon oxide material/nano-titanium oxide mesoporous composite material as carrier, and carried metal copper is come with the carrier, titanium oxide dispersion degree is high, good hydrothermal stability.The catalyst stability is high, catalyst activity component not easily runs off in use, it can repeatedly use, and use the catalyst, can highly selective acquisition o-phenyl phenol product, the yield of o-phenyl phenol is 30% or so, biphenyl 50%, benzene+hexamethylene yield 5% is hereinafter, other are cyclohexylbenzene.
Description
Technical field
The invention belongs to catalyst preparation fields, are related to a kind of side for being catalyzed dibenzofuran open loop and preparing o-phenyl phenol
Method.
Background technique
Biphenyl (BP) is important Organic Ingredients, is widely used in the fields such as medicine, pesticide, dyestuff, liquid crystal material.It can use
It synthesizes plasticizer, preservative, can be also used for manufacture fuel, engineering plastics and high-energy fuel etc..Biphenyl be present in coal tar,
In former oil and gas.The preparation method of biphenyl, which has, is pyrolyzed the chemical synthesis of biphenyl processed etc. by benzene and by various coal tar
The separation and Extraction method of fraction biphenyl.Mass fraction of the biphenyl in coal tar is 0.20%-0.40%, at present coal tar oil extract
Method and chemical synthesis are simultaneously deposited.O-phenyl phenol (OPP) is as a kind of important novel fine chemical product and organic synthesis
Intermediate is widely used in sterilization and anticorrosion, printing and dyeing assistant and surfactant, synthesizing new plastics, resin and macromolecule material
Stabilizer and fire retardant of material etc., and have extremely vast potential for future development.As o-phenyl phenol synthesis technology is continuous
To clean, low cost, high yield direction are developed, domestic and international market is to the demand cumulative year after year of o-phenyl phenol, sale
Market is good, brings opportunity for the development of OPP industry.Dibenzofuran main source is the washing oil by generating during coal tar distillation
It is isolated.Mass fraction of the dibenzofuran in washing oil is about 10%, and mass fraction is up to 30% or more in heavy wash oil.It is close several
Year, it is that the method that raw material prepares o-phenyl phenol has also obtained the concern of people for dibenzofuran, this route is by dibenzofuran and gold
Belong to sodium reaction, then with acid acidification product, obtains o-phenyl phenol.But since technology is not yet mature, this process route is not yet
Realize industrialization.Currently, OPP price also further increases as global consumption demand amount increases year by year.Utilize washing for low value
Oil extract ingredient-dibenzofuran processing OPP has fabulous economic benefit.Can use industrial dibenzofuran hydrofinishing biphenyl and
O-phenyl phenol.But industrial dibenzofuran is because containing the impurity such as dibenzothiophenes, carbazole, fluorenes, acenaphthene, dibenzofuran content 95% or so, oxygen
Fluorenes can direct hydrogenation deoxidation biphenyl, o-phenyl phenol, but dibenzofuran catalytic hydrogenation open loop system can also be prepared with catalytic hydrogenation open loop
O-phenyl phenol is needed using noble metal catalyst.Noble metal catalyst use condition harshness, sulphur and nitrogen content need to be down to several
A ppm level.Therefore directly catalytic hydrogenation open loop OPP cannot be produced by raw material of industrial dibenzofuran, raw material must be refined.Needle
To industrial dibenzofuran property, Hydrobon catalyst is developed, develops industrial dibenzofuran hydrofinishing biphenyl and o-phenyl phenol technique
Technology.With being continuously increased for biphenyl and o-phenyl phenol dosage, development using dibenzofuran be raw material hydrogenation deoxidation prepare biphenyl or plus
Hydrogen open loop is directly prepared in OPP reaction, and catalyst adds hydrogen open loop active, selective most important.Using dibenzofuran as raw material system neighbour
Phenylphenol by the direct deoxidation biphenyl of raw material of dibenzofuran it has been reported that but be really rarely reported.Following known technologies, all exists
Some shortcomings:
Chinese patent, publication number: CN103319313A introduces a kind of method that dibenzofuran open loop prepares o-phenyl phenol, with
Dibenzofuran is raw material, uses glycol dimethyl ether or diethylene glycol dimethyl ether as solvent, metallic sodium is added, under nitrogen protection
It is reacted, reaction mixture is cooled down, and is added ethyl alcohol stirring, is distilled to recover solvent, and water is then added into residue, cold
But to room temperature, unreacting material is recovered by filtration, water phase is added with concentrated hydrochloric acid tune pH less than 3, brown oil is precipitated, with acetic acid second
Ester extraction, anhydrous sodium sulfate is dry, and solvent is sloughed in decompression, recrystallizes to obtain o-phenyl phenol with petroleum ether.Active metal sodium makes
With technique process is more, and comparatively laborious, there are certain risks.
Chinese patent, publication number: CN106495991A discloses a kind of method that dibenzofuran open loop prepares o-phenyl phenol, uses
Solvent dissolves industrial dibenzofuran in dissolution kettle, and solution temperature is 80~100 DEG C, dissolved industry dibenzofuran organic solution injection
Hydrofining reaction is carried out in fixed bed reactors equipped with selection Hydrobon catalyst, product is direct after hydrofining reaction
It into rectifying column rectifying, produces o-phenyl phenol and is directly granulated as product, but the yield of o-phenyl phenol is selected 10% or so
Property is lower.
Summary of the invention
The present invention is to make up the deficiencies in the prior art, provides a kind of method that catalysis dibenzofuran open loop prepares o-phenyl phenol,
O-phenyl phenol, selectivity with higher are prepared using method of the invention, and is post-processed simply, catalyst used may be used also
It recycles and reuses.
A kind of industry dibenzofuran hydrofinishing method for preparing biphenyl and o-phenyl phenol, steps are as follows: by industrial dibenzofuran with
Organic solution injection carries out hydrofining reaction in the hydrofining reaction rectifying column equipped with selection Hydrobon catalyst, adds hydrogen
300~380 DEG C of refining reaction temperature, 1~4MPa of Hydrogen Vapor Pressure, 0.2~1.5h-1 of reaction velocity；Reactive distillation column is filler
Tower, tower pressure are 5-40kPa, and bottom temperature is 280~290 DEG C, and reflux ratio is greater than 0.8, and tower top goes out hexamethylene and benzene, according to boiling point
The o-phenyl phenol of extraction is directly granulated as product, tower bottom extraction purification dibenzofuran, purification dibenzofuran is as raw material for producing
O-phenyl phenol.
The organic solvent is hexamethylene, decahydronaphthalene, one kind of cyclooctane or two kinds of mixing, and the additional amount of solvent is
5~10 times of dibenzofuran weight.
Described selects Hydrobon catalyst for nano-titanium oxide mesoporous composite material copper-loading catalyst, including carrier
And the copper of load on this carrier；The carrier is mesoporous using ordered meso-porous silicon oxide as the nano-titanium oxide of substrate limit threshold assembling
Composite material, the loading of metallic copper are 1~10% weight percent.
Preferably, the average grain diameter of metal copper particle is 5~12nm, Dispersion on surface degree on this carrier is 0.3~
0.5。
The nano-titanium oxide mesoporous composite material copper-loading catalyst is prepared by the following method to obtain: with metatitanic acid
Butyl ester is titanium source, is introduced into the duct of the ordered meso-porous silicon oxide material (SBA-15) by sol-gel method, warp
Nano-titanium oxide mesoporous composite material is obtained after roasting, in this, as carrier；Then, copper chloride is added into the carrier as work
Property component precursor, is prepared catalyst precarsor by infusion process；Then, it is urged in the aqueous solution of sodium formate by above-mentioned after drying
The reduction of agent precursor obtains the catalyst nano medium pore of titania composite material supported copper catalysis after filtration, washing and drying
Agent.
Specific steps include:
S1, a certain amount of ordered meso-porous silicon oxide material SBA-15 powder is added to isopropanol (SBA-15 and isopropanol
Weight ratio be 1:15) in be ultrasonically treated 2h, then by the aqueous isopropanol of butyl titanate (butyl titanate and isopropyl alcohol
Product is slowly added to suitable quantity of water after being thoroughly mixed 1h than being added drop-wise in the mixed system of above-mentioned SBA-15/ isopropanol for 1:10)
(volume ratio of butyl titanate and water is 1:20) is continued to obtain the suspension of white after stirring 2h, be filtered and with largely
Water and ethanol washing, then be dried overnight at 353K, it is mesoporous multiple to obtain final nano-titanium oxide by 623-773K roasting 2h
Condensation material.Different according to titanium oxide content required in composite material, butyl titanate and silica (SBA-15) weight ratio are distinguished
For 0.2288:1；0.4830:1；0.7673:1 and 1.0869:1, finally obtaining weight content is respectively 5%, 10%, 15% and
20% nano-titanium oxide mesoporous composite material；
S2, using nano-titanium oxide mesoporous composite material obtained above as carrier, into carrier be added dropwise copper chloride it is water-soluble
The weight ratio of the ethanol solution of liquid or copper chloride, metallic copper and carrier is 1: 9~99, solvent evaporated after stirring 4~6 hours,
Then nano-titanium oxide mesoporous composite material copper-loading catalyst precursor is obtained within dry 12 hours under 393K in an oven；
S3, above-mentioned catalyst precarsor is flowed back 2 hours in the aqueous sodium formate solution of 368K, the catalysis after being restored
Agent, wherein the molar ratio of sodium formate and copper content in catalyst precarsor is 10:1；
S4, the catalyst after above-mentioned reduction is washed with a large amount of deionized waters after filtering, it is small by under 373K dry 12
When after obtain nano-titanium oxide mesoporous composite material load copper catalyst.
Advantages of the present invention:
The present invention uses the catalysis of nano-titanium oxide mesoporous composite material supported copper for hydrogenation catalyst using industrial dibenzofuran as raw material
Agent, the catalyst be using ordered meso-porous silicon oxide material/nano-titanium oxide mesoporous composite material as carrier, and with the carrier come
Carried metal copper, titanium oxide dispersion degree is high, good hydrothermal stability.The catalyst stability is high, and catalyst is living in use
Property component not easily runs off, and can repeatedly use.And the catalyst is used, it can highly selective acquisition o-phenyl phenol production
Product, the yield of o-phenyl phenol is 30% or so, and biphenyl 50%, benzene+hexamethylene yield 5% is hereinafter, other are phenyl hexamethylene
Alkane.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
[embodiment 1]
S1, a certain amount of ordered meso-porous silicon oxide material SBA-15 powder is added to isopropanol (SBA-15 and isopropanol
Weight ratio be 1:15) in be ultrasonically treated 2h, then by the aqueous isopropanol of butyl titanate (butyl titanate and isopropyl alcohol
Product is slowly added to suitable quantity of water after being thoroughly mixed 1h than being added drop-wise in the mixed system of above-mentioned SBA-15/ isopropanol for 1:10)
(volume ratio of butyl titanate and water is 1:20) is continued to obtain the suspension of white after stirring 2h, be filtered and with largely
Water and ethanol washing, then be dried overnight at 353K, it is mesoporous multiple to obtain final nano-titanium oxide by 623-773K roasting 2h
Condensation material, butyl titanate and silica weight ratio are 0.2288:1, finally obtain the nano-titanium oxide that weight content is 5% and are situated between
Hole composite material；
S2, using nano-titanium oxide mesoporous composite material obtained above as carrier, into carrier be added dropwise copper chloride it is water-soluble
The weight ratio of the ethanol solution of liquid or copper chloride, metallic copper and carrier is 1: 9, then solvent evaporated after stirring 4 hours is being dried
Obtain nano-titanium oxide mesoporous composite material copper-loading catalyst precursor within dry 12 hours under 393K in case；
S3, above-mentioned catalyst precarsor is flowed back 2 hours in the aqueous sodium formate solution of 368K, the catalysis after being restored
Agent, wherein the molar ratio of sodium formate and copper content in catalyst precarsor is 10:1；
S4, the catalyst after above-mentioned reduction is washed with a large amount of deionized waters after filtering, it is small by under 373K dry 12
When after obtain copper nano-titanium oxide mesoporous composite material load copper catalyst, be denoted as C1.
[embodiment 2]
S1, a certain amount of ordered meso-porous silicon oxide material SBA-15 powder is added to isopropanol (SBA-15 and isopropanol
Weight ratio be 1:15) in be ultrasonically treated 2h, then by the aqueous isopropanol of butyl titanate (butyl titanate and isopropyl alcohol
Product is slowly added to suitable quantity of water after being thoroughly mixed 1h than being added drop-wise in the mixed system of above-mentioned SBA-15/ isopropanol for 1:10)
(volume ratio of butyl titanate and water is 1:20) is continued to obtain the suspension of white after stirring 2h, be filtered and with largely
Water and ethanol washing, then be dried overnight at 353K, it is mesoporous multiple to obtain final nano-titanium oxide by 623-773K roasting 2h
Condensation material.Different according to titanium oxide content required in composite material, butyl titanate and silica weight ratio are 0.4830:1, most
The nano-titanium oxide mesoporous composite material that weight content is 10% is obtained afterwards；
S2, using nano-titanium oxide mesoporous composite material obtained above as carrier, into carrier be added dropwise copper chloride it is water-soluble
The weight ratio of the ethanol solution of liquid or copper chloride, metallic copper and carrier is solvent evaporated after 1: 19 stirring 6 hours, is then being dried
Obtain nano-titanium oxide mesoporous composite material copper-loading catalyst precursor within dry 12 hours under 393K in case；
S3, above-mentioned catalyst precarsor is flowed back 2 hours in the aqueous sodium formate solution of 368K, the catalysis after being restored
Agent, wherein the molar ratio of sodium formate and copper content in catalyst precarsor is 10:1；
S4, the catalyst after above-mentioned reduction is washed with a large amount of deionized waters after filtering, it is small by under 373K dry 12
When after obtain nano-titanium oxide mesoporous composite material load copper catalyst be denoted as C2.
[embodiment 3]
S1, a certain amount of ordered meso-porous silicon oxide material SBA-15 powder is added to isopropanol (SBA-15 and isopropanol
Weight ratio be 1:15) in be ultrasonically treated 2h, then by the aqueous isopropanol of butyl titanate (butyl titanate and isopropyl alcohol
Product is slowly added to suitable quantity of water after being thoroughly mixed 1h than being added drop-wise in the mixed system of above-mentioned SBA-15/ isopropanol for 1:10)
(volume ratio of butyl titanate and water is 1:20) is continued to obtain the suspension of white after stirring 2h, be filtered and with largely
Water and ethanol washing, then be dried overnight at 353K, it is mesoporous multiple to obtain final nano-titanium oxide by 623-773K roasting 2h
Condensation material.Different according to titanium oxide content required in composite material, butyl titanate and silica weight ratio are 0.7673:1, most
The nano-titanium oxide mesoporous composite material that weight content is 15% is obtained afterwards；
S2, using nano-titanium oxide mesoporous composite material obtained above as carrier, into carrier be added dropwise copper chloride it is water-soluble
The weight ratio of the ethanol solution of liquid or copper chloride, metallic copper and carrier is 1: 29, then solvent evaporated after stirring 5 hours exists
Obtain nano-titanium oxide mesoporous composite material copper-loading catalyst precursor within dry 12 hours under 393K in baking oven；
S3, above-mentioned catalyst precarsor is flowed back 2 hours in the aqueous sodium formate solution of 368K, the catalysis after being restored
Agent, wherein the molar ratio of sodium formate and copper content in catalyst precarsor is 10:1；
S4, the catalyst after above-mentioned reduction is washed with a large amount of deionized waters after filtering, it is small by under 373K dry 12
When after obtain nano-titanium oxide mesoporous composite material load copper catalyst, be denoted as C3.
[embodiment 4]
S1, a certain amount of ordered meso-porous silicon oxide material SBA-15 powder is added to isopropanol (SBA-15 and isopropanol
Weight ratio be 1:15) in be ultrasonically treated 2h, then by the aqueous isopropanol of butyl titanate (butyl titanate and isopropyl alcohol
Product is slowly added to suitable quantity of water after being thoroughly mixed 1h than being added drop-wise in the mixed system of above-mentioned SBA-15/ isopropanol for 1:10)
(volume ratio of butyl titanate and water is 1:20) is continued to obtain the suspension of white after stirring 2h, be filtered and with largely
Water and ethanol washing, then be dried overnight at 353K, it is mesoporous multiple to obtain final nano-titanium oxide by 623-773K roasting 2h
Condensation material.Different according to titanium oxide content required in composite material, butyl titanate and silica weight ratio are 1.0869:1, most
The nano-titanium oxide mesoporous composite material that weight content is 20% is obtained afterwards；
S2, using nano-titanium oxide mesoporous composite material obtained above as carrier, into carrier be added dropwise copper chloride it is water-soluble
The weight ratio of the ethanol solution of liquid or copper chloride, metallic copper and carrier is 1: 99, then solvent evaporated after stirring 4 hours exists
Obtain nano-titanium oxide mesoporous composite material copper-loading catalyst precursor within dry 12 hours under 393K in baking oven；
S3, above-mentioned catalyst precarsor is flowed back 2 hours in the aqueous sodium formate solution of 368K, the catalysis after being restored
Agent, wherein the molar ratio of sodium formate and copper content in catalyst precarsor is 10:1；
S4, the catalyst after above-mentioned reduction is washed with a large amount of deionized waters after filtering, it is small by under 373K dry 12
When after obtain nano-titanium oxide mesoporous composite material load copper catalyst, be denoted as C4.
[embodiment 5]
Industrial dibenzofuran is respectively provided with selection hydrofinishing prepared by embodiment 1-4 with 3 times of quality decahydronaphthalene injections to urge
Hydrofining reaction, 300 DEG C of hydrofining reaction temperature, hydrogen pressure are carried out in the hydrofining reaction rectifying column of agent C1~C4
Power 1.5MPa, reaction velocity 0.8h-1；Reactive distillation column is packed tower, and tower pressure is 15kPa, and bottom temperature is 280 DEG C, reflux ratio
Greater than 0.8, tower top goes out hexamethylene and benzene, and the o-phenyl phenol of extraction is directly granulated as product according to boiling point, each product
Yield is as shown in table 1.
Table 1
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field
Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (6)
1. a kind of method that catalysis dibenzofuran open loop prepares o-phenyl phenol, steps are as follows:
It will be carried out in industrial dibenzofuran and hydrofining reaction rectifying column of the organic solution injection equipped with selection Hydrobon catalyst
Hydrofining reaction, 300~380 DEG C of hydrofining reaction temperature, 1~4MPa of Hydrogen Vapor Pressure, 0.2~1.5h-1 of reaction velocity；
Reactive distillation column is packed tower, and tower pressure is 5-40kPa, and bottom temperature is 280~290 DEG C, and reflux ratio is greater than 0.8, tower ejection ring
The o-phenyl phenol of extraction is directly granulated as product by hexane and benzene according to boiling point, and tower bottom extraction purification dibenzofuran refines dibenzofuran
As raw material for producing o-phenyl phenol；Described selects Hydrobon catalyst negative for nano-titanium oxide mesoporous composite material
Copper-loaded catalyst.
2. the method that catalysis dibenzofuran open loop according to claim 1 prepares o-phenyl phenol, which is characterized in that described receives
Rice medium pore of titania composite material copper-loading catalyst, the copper including carrier and load on this carrier；The carrier is to have
Sequence mesopore silicon oxide is the nano-titanium oxide mesoporous composite material that substrate limits threshold assembling, and the loading of metallic copper is 1~10% weight
Measure percentage.
3. the method that catalysis dibenzofuran open loop according to claim 2 prepares o-phenyl phenol, which is characterized in that metal copper particle
The average grain diameter of son is 5~12nm, and Dispersion on surface degree on this carrier is 0.3~0.5.
4. the method that catalysis dibenzofuran open loop according to claim 2 prepares o-phenyl phenol, which is characterized in that the nanometer
Medium pore of titania composite material copper-loading catalyst is prepared by the following method to obtain: using butyl titanate as titanium source, passing through
Sol-gel method is introduced into the duct of the ordered meso-porous silicon oxide material (SBA-15), obtains nanometer after being fired
Medium pore of titania composite material, in this, as carrier；Then, copper chloride is added into the carrier as active component precursors, leads to
It crosses infusion process and catalyst precarsor is prepared；Then, above-mentioned catalyst precarsor is restored in the aqueous solution of sodium formate after drying,
The catalyst nano medium pore of titania composite material copper-loading catalyst is obtained after filtration, washing and drying.
5. the method that catalysis dibenzofuran open loop according to claim 3 prepares o-phenyl phenol, it is characterised in that: the preparation
The specific steps of nano-titanium oxide mesoporous composite material copper-loading catalyst include:
S1, it a certain amount of ordered meso-porous silicon oxide material SBA-15 powder is added in isopropanol is ultrasonically treated 2h, then will
The aqueous isopropanol of butyl titanate is added drop-wise in the mixed system of above-mentioned SBA-15/ isopropanol, is delayed after being thoroughly mixed 1h
It is slow that suitable quantity of water is added, continue to obtain the suspension of white after stirring 2h, be filtered and with a large amount of water and ethanol washing, then
It is dried overnight under 353K, obtains final nano-titanium oxide mesoporous composite material by 623-773K roasting 2h；According to composite wood
Required titanium oxide content is different in material, and butyl titanate and silica weight ratio are respectively 0.2288:1；0.4830:1；
0.7673:1 and 1.0869:1, finally obtain weight content be respectively 5%, 10%, 15% and 20% nano-titanium oxide it is mesoporous
Composite material；
S2, using nano-titanium oxide mesoporous composite material obtained above as carrier, into carrier be added dropwise copper chloride aqueous solution or
The weight ratio of the ethanol solution of person's copper chloride, metallic copper and carrier is 1: 9~99, solvent evaporated after stirring 4~6 hours, then
Obtain nano-titanium oxide mesoporous composite material copper-loading catalyst precursor within dry 12 hours under 393K in an oven；
S3, above-mentioned catalyst precarsor is flowed back 2 hours in the aqueous sodium formate solution of 368K, the catalyst after being restored,
The molar ratio of copper content is 10:1 in middle sodium formate and catalyst precarsor；
S4, the catalyst after above-mentioned reduction is washed with a large amount of deionized waters after filtering, after 12 hours dry under 373K
Obtain the copper catalyst of nano-titanium oxide mesoporous composite material load.
6. the method that catalysis dibenzofuran open loop according to claim 1 prepares o-phenyl phenol, it is characterised in that: described has
Solvent is hexamethylene, decahydronaphthalene, one kind of cyclooctane or two kinds of mixing, and the additional amount of solvent is the 5~10 of dibenzofuran weight
Times.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3989761A (en) * | 1975-08-08 | 1976-11-02 | Monsanto Company | Production of orthophenylphenols |
| CN102633581A (en) * | 2012-04-01 | 2012-08-15 | 华东师范大学 | Application of nano titanium oxide mesoporous composite loaded platinum catalyst to catalytic hydrogenation |
| CN106495991A (en) * | 2016-08-31 | 2017-03-15 | 大连理工大学 | A kind of method that industrial dibenzofuran hydrofinishing prepares biphenyl and o-phenyl phenol |
-
2018
- 2018-08-07 CN CN201810892805.XA patent/CN108947775A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3989761A (en) * | 1975-08-08 | 1976-11-02 | Monsanto Company | Production of orthophenylphenols |
| CN102633581A (en) * | 2012-04-01 | 2012-08-15 | 华东师范大学 | Application of nano titanium oxide mesoporous composite loaded platinum catalyst to catalytic hydrogenation |
| CN106495991A (en) * | 2016-08-31 | 2017-03-15 | 大连理工大学 | A kind of method that industrial dibenzofuran hydrofinishing prepares biphenyl and o-phenyl phenol |
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