CN109365006A - M-Ce-TiO2USY molecular sieve catalyst and the method for generating o-cresol - Google Patents
M-Ce-TiO2USY molecular sieve catalyst and the method for generating o-cresol Download PDFInfo
- Publication number
- CN109365006A CN109365006A CN201811397061.0A CN201811397061A CN109365006A CN 109365006 A CN109365006 A CN 109365006A CN 201811397061 A CN201811397061 A CN 201811397061A CN 109365006 A CN109365006 A CN 109365006A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- tio
- cresol
- surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- 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
Abstract
The present invention provides a kind of M-Ce-TiO2The features such as USY molecular sieve catalyst and the method for generating o-cresol, the catalyst component is simple, while especially suitable for catalysis of phenol and dimethyl carbonate synthesis o-cresol, and active high and o-cresol is selectively high.The M-Ce-TiO2The preparation method of USY molecular sieve catalyst includes the following steps: 1) to load TiO in USY molecular sieve2And CeO2；2) carrier surface activating agent M on the molecular sieve obtained by step 1), obtains the catalyst, is denoted as M-Ce-TiO2USY molecular sieve catalyst；Wherein, the surfactant M is preferably Cetyltrimethylammonium bromide, cetyl trimethylammonium bromide and/or cetyl pyridinium.
Description
Technical field
The present invention relates to the synthetic method of o-cresol, in particular to the catalyst of a kind of synthesizing o-cresol and its preparation side
Method, and the method using the catalyst synthesizing o-cresol.
Background technique
O-cresol is a kind of important chemical intermediate, is widely used in pesticide, medicine, antioxidant, fragrance, epoxy novolac
The fields such as resin.O-cresol be earliest it is isolated from coal tar, the complex process, product purity is low, much can not meet
Demand.O-cresol then is produced using chemically synthesized method, using ortho-aminotoluene diazotising Hydrolyze method and adjacent chloromethane
The shortcomings that benzene Hydrolyze method synthesizing o-cresol, the technique is pollution environment, corrosion equipment and higher cost.Currently used technique is
Phenol methanol alkylation method carrys out synthesizing o-cresol, and this method is divided into two methods of liquid and gas, and liquid phase method process conditions are harsh,
High temperature and pressure impurity is more, does not use this method.Vapor-phase alkylation selectivity is higher, and technical process is simple, the earliest U.S.
General Electric using MgO as catalyst synthesizing o-cresol, but this method there are the shortcomings that for temperature it is higher (about 550 DEG C), catalyst
Service life is short.Japanese Asahi Kasei Corporation develops V2O5-Fe2O3Catalyst synthesizing o-cresol, and started Fe2O3Series catalysts synthesis
O-cresol.CN201310355671 use new catalyst synthesizing o-cresol, the catalyst synthesis it is more complex, reaction temperature compared with
Height, and the reactivity of methanol is lower, has toxicity, does not meet the concept of Green Chemistry.
Summary of the invention
In view of this, the present invention provides a kind of M-Ce-TiO2USY molecular sieve catalyst and preparation method thereof, the catalyst
Ingredient is simple, easily prepared, while especially suitable for catalysis of phenol and dimethyl carbonate synthesis o-cresol, and it is active high and
The features such as o-cresol is selectively high.
The present invention be reach its purpose, the technical solution adopted is as follows:
One aspect of the present invention provides a kind of M-Ce-TiO2The preparation method of USY molecular sieve catalyst, includes the following steps:
1) TiO is loaded in USY molecular sieve2And CeO2；
2) carrier surface activating agent M on the molecular sieve obtained by step 1), obtains the catalyst, is denoted as M-Ce-TiO2-
USY molecular sieve catalyst；Wherein, the surfactant M is preferably Cetyltrimethylammonium bromide, cetyl trimethyl
The combination of one or more of ammonium bromide and cetyl pyridinium.
The present invention is by by TiO2It is carried in USY molecular sieve, the acid site L of catalyst surface can be optimized, utilized simultaneously
The modified USY molecular sieve of Ce can significantly improve the acid site catalyst surface B, promote the conversion of phenol, Ti and Ce bimetallic-modified,
The acids type of synergistic effect regulating catalyst, improves the acid site L content, to improve the selectivity of o-cresol；In addition, surface is living
Property agent load promote the better adsorbing phenol of molecular sieve, and the introducing of Ce element can also preferably promote TiO2On the surface USY
Dispersion；Present inventor's discovery introduces Ti, Ce bimetallic and surfactant using USY molecular sieve as carrier to be modified,
Traditional alkylating reagent methanol can be replaced with high activity Green Chemistry reagent carbonic acid two by triple combination, obtained catalyst
Methyl esters, with phenol synthesis o-cresol, dimethyl carbonate has higher active and nontoxic compared to methanol.
In the preparation method, step 1) can be carried out according to following scheme one or scheme two；Wherein, the scheme one is specific
Include the following steps:
1.1a) USY molecular sieve and organic titanium solution are mixed, dipping, preferably dip time are 12-36 hours (examples
Such as 12,15,20,25,30,35h), solvent is removed later；In a specific embodiment, it is dry can to carry out grinding in advance for USY molecular sieve
Dry processing；
1.2a) by step 1.1a) products therefrom and Ce (NO3)3·6H2O aqueous solution is mixed, dipping, when preferably impregnating
Between be 12-36h (such as 12,15,20,25,30,35h), remove solvent and roast later；
The scheme two specifically comprises the following steps:
1.1b) by USY molecular sieve and Ce (NO3)3·6H2O aqueous solution is mixed, and dipping, preferably dip time are 12-
36h (such as 12,15,20,25,30,35h), removes solvent later；In a specific embodiment, USY molecular sieve can carry out in advance
Mill-drying processing；
1.2b) step 1.1b) products therefrom and organic titanium solution are mixed, dipping, preferably dip time are 12-36
Hour (such as 12,15,20,25,30,35h) removes solvent later and roasts.
Wherein, in step 1), organic titanium used is preferably selected from butyl titanate, isopropyl titanate and tetraethyl titanate
A combination of one or more；Solvent in organic titanium solution used is preferably in benzene, toluene, hexamethylene and n-hexane
A combination of one or more.
In some preferred embodiments, CeO2Load capacity in the catalyst is preferably 2-5wt%.Some implementations
In mode, the Ce (NO3)3·6H2O dosage be the USY molecular sieve quality 5-12%, such as 5%, 7%, 9%, 10%,
12% etc..In some preferred embodiments, TiO in the obtained catalyst2Load capacity be 5-15wt% (based on urging
Agent gross mass), such as 5%, 7%, 9%, 13%, 15% etc., the dosage of the organic titanium used in step 1) is with catalyst
Middle TiO2Load capacity subject to determine.Using the preferred Ce (NO3)3·6H2O dosage and TiO2Load capacity, what is obtained urges
In agent, Ce and Ti are combined in specific proportions, can preferably be acted synergistically, and catalyst activity is high, and catalyst phenol obtained turns
Rate is high, and target product selectivity is high.
In some embodiments, dipping involved in each concrete operation step of step 1) is in room temperature (such as 20-
30 DEG C) under closed dipping；Removing solvent described in each concrete operation step of step 1) can be by way of drying with water bath
Solvent is steamed；Roasting involved in each concrete operation step of step 1) is to roast at 450-540 DEG C.
In preferable some embodiments, the step 2) includes: by molecular sieve obtained by step 1) and surfactant water
Solution is mixed at 50-70 DEG C (such as 50 DEG C, 60 DEG C, 70 DEG C), and preferably mixing time is 20-50min, is washed later
Wash, dry, forming, the molding specific molding mode is not particularly limited, for example, by with binder (such as inertia oxygen
Change aluminium and silica etc.) mixing is to form, such as is shaped to the particle of 20-40 mesh.
By introducing surfactant, especially Cetyltrimethylammonium bromide, cetyl front three in the catalyst
Base ammonium bromide and/or cetyl pyridinium can be such that molecular sieve Pyrogentisinic Acid preferably adsorbs, and improve the conversion of phenol in the reaction
Rate improves catalytic effect；In preferred some embodiments, the concentration of the aqueous surfactant solution be 1-5wt% (such as
1wt%, 2wt%, 4wt%, 5wt% etc.), the dosage of the surfactant be USY molecular sieve quality 10-50% (such as
10%, 20%, 30%, 40%, 50%), using the surfactant of preferable amount, obtained molecular sieve Pyrogentisinic Acid adsorbs effect
Fruit is more preferable.
Another aspect of the present invention also provides a kind of M-Ce-TiO2USY molecular sieve catalyst, the catalyst is with USY molecular sieve
For carrier, the supported on carriers has surfactant, TiO2And CeO2, wherein the TiO of the catalyst2Load capacity it is preferred
For 5-15wt% (such as 5wt%, 8wt%, 10wt%, 13wt%, 15wt% etc.), the CeO2Load capacity be preferably 2-
5wt% (such as 2wt%, 3wt%, 4wt%, 5wt% etc.)；The load capacity of the surfactant M is preferably 0.1-0.5wt%
(such as 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt% etc.)；The surfactant M is preferably selected from octadecane
The combination of one or more of base trimethylammonium bromide, cetyl trimethylammonium bromide and cetyl pyridinium.It should
Catalyst specifically can preparation method as described above be made.
Catalyst provided by the present invention is alkylated synthesizing o-cresol, tool especially suitable for catalysis of phenol and dimethyl carbonate
There are higher o-cresol selectivity and stability.Based on this, the present invention also provides a kind of method for generating o-cresol, phenol and carbon
Dimethyl phthalate reacts under catalyst generates the o-cresol, wherein the catalyst is preparation method system described above
Or catalyst described above.Dimethyl carbonate can be used and replace when being used for synthesizing o-cresol using catalyst of the invention
For traditional methanol as alkylating reagent, dimethyl carbonate is a kind of high activity green containing methyl, methoxyl group and carbonyl
Chemical reagent, activity are apparently higher than methanol and nontoxic.
In some preferred embodiments, the reaction carries out in fixed bed, reaction temperature be 250-500 DEG C (such as
250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 500 DEG C etc.), preferably 300-400 DEG C, gauge pressure be 0.05-0.5MPa (such as
0.05MPa, 0.1MPa, 0.3MPa, 0.5MPa etc.), mass space velocity 1-5h-1, the molar ratio of phenol and dimethyl carbonate is 1:
(0.5-2).Using catalyst of the invention, the reaction of catalysis of phenol and dimethyl carbonate synthesis o-cresol is preferably in fixed bed
It carries out, used fixed-bed process does not have three wastes generation, and the renewable recycling of molecular sieve meets modern " green chemical industry "
It is required that.Fixed bed is specifically, for example, cast electrothermal reactor etc..
Technical solution provided by the invention has the following beneficial effects:
New catalyst provided by the invention, which has high activity and o-cresol highly selective, in some implementations
In mode, o-cresol selection performance reaches 70% or more, and the prior art is only capable of reaching 50% or so, and the catalyst is renewable,
With environment friendly.
Catalyst of the invention, when being used for synthesizing o-cresol, the raw material of use is phenol and dimethyl carbonate, the alkylation
Reagent safety environmental protection, low toxicity, meet the concept of Green Chemistry.
Specific embodiment
For a better understanding of the technical solution of the present invention, below with reference to the embodiment content that the present invention is further explained,
But the contents of the present invention are not limited only to following embodiment.
The test equipment that following embodiment uses includes: that gas phase uses Shimadzu Angilent 7820A type gas chromatograph
(hydrogen flame detector, nitrogen is as carrier gas) is analyzed, and DB-5 type capillary chromatographic column (5%Phenyl Methyl is used
Siloxan, 30m × 0.32mm × 0.25 μm), hydrogen flame detector (FID).Sample injector and detector temperature are 280 DEG C；Column
Temperature is controlled using temperature programming: initial 100 DEG C of column temperature are kept for 0.5 minute, and 15 DEG C/min is warming up to 260 DEG C, is kept for 5 minutes.Column
Pressure 8.5868psi, flow velocity 1.5mL/min.Sample volume: 0.2 μ L.Conversion ratio and selectivity are counted using area normalization method
It calculates.
The test equipment that the chemical composition of catalyst uses is Agilent ICP-OES720.
Raw material used in testing below is marketable material, is carried out below to part material as described below:
Embodiment 1
42.5g, 85g, 127.5g butyl titanate are weighed respectively, is dissolved in the toluene of 200g respectively, then respectively by 20g
USY is dissolved in above-mentioned solution, after being sufficiently stirred for 24 hours in the closed dipping of room temperature, is most afterwards steamed toluene through water-bath, drying, product
It is denoted as TiO2USY molecular sieve,
Then by 1.0g Ce (NO3)3·6H2O is dissolved in 50ml distilled water, is separately added into 10g, 12.5g, 16g
TiO23h is stirred at room temperature in the closed dipping of room temperature for 24 hours in USY molecular sieve, and 80 DEG C of stirring in water bath are evaporated, move into baking oven 110 DEG C it is dry
Dry 12h, 450 DEG C of Muffle kiln roasting 5h, obtains load C eO2Ce-TiO2USY molecular sieve.
The Cetyltrimethylammonium bromide of the 2g stirring and dissolving in 200g distilled water is weighed, 4g Ce-TiO is taken2- USY points
In above-mentioned solution, 60 DEG C of stirring 30min are washed after terminating through distilled water, 100 DEG C of dry 6h, are obtained M-Ce-TiO sieve2-
USY molecular sieve.This three sections of molecular sieve surface activating agent load capacity are 0.2%, are denoted as catalyst A1, A2, A3, TiO respectively2's
Load capacity respectively is 5%, 10%, 15%, CeO2Load capacity respectively be 3.0%, 2.5%, 2.0%.
Catalyst A1, A2, A3 are separately formed the particle packing for 20 mesh in the cast electrothermal reactor placed vertically, dress
Matrix amount be 2g, 350 DEG C of temperature, pressure 0.5MPa, mass space velocity 2h-1, the molar ratio 1:1 of phenol and dimethyl carbonate into
Row reaction, the conversion ratio of phenol is respectively 45%, 75%, 85%, the selectivity of o-cresol is respectively 72.1%, 70.2%,
68.6%.
Embodiment 2
71g isopropyl titanate is weighed respectively and 57g tetraethyl titanate is dissolved in respectively in the toluene of 200g, then respectively will
20gUSY is dissolved in above-mentioned solution, after being sufficiently stirred for 24 hours in the closed dipping of room temperature, is most afterwards steamed toluene through water-bath, drying, is produced
Object is denoted as TiO2USY molecular sieve.Then by 1g Ce (NO3)3·6H2O is dissolved in 50ml distilled water, and 10g TiO is added2-USY
Molecular sieve, be stirred at room temperature 3h in room temperature it is closed dipping for 24 hours, 80 DEG C of stirring in water bath are evaporated, move into baking oven in 110 DEG C of dry 12h,
450 DEG C of Muffle kiln roasting 5h, have been loaded CeO2Ce-TiO2USY molecular sieve.
The Cetyltrimethylammonium bromide of the 2g stirring and dissolving in 200g distilled water is weighed, 4g Ce-TiO is taken2- USY points
Son sieve is in above-mentioned solution, 60 DEG C of stirring 30min, through distilled water washing, 100 DEG C of dry 6h after terminating, obtains surfactant
Load capacity is 0.2% M-Ce-TiO2USY molecular sieve is successively denoted as catalyst A4, A5, TiO respectively2Load capacity difference
For 10%, CeO2Load capacity be respectively 3.0%.
Catalyst A4, A5 are separately formed the particle packing for 30 mesh in the cast electrothermal reactor placed vertically, filling
Quality is 2g, 350 DEG C of temperature, pressure 0.5MPa, mass space velocity 2h-1, the molar ratio 1:1 progress of phenol and dimethyl carbonate
Reaction, the conversion ratio of phenol is respectively 77.4%, 75.6%, and the selectivity of o-cresol is respectively 71.2%, 70.7%.
Embodiment 3
It weighs 71g isopropyl titanate to be dissolved in the toluene of 200g, then 20g USY is dissolved in above-mentioned solution, is sufficiently stirred
After mixing for 24 hours in the closed dipping of room temperature, most toluene is steamed through water-bath, drying afterwards, product is denoted as TiO2Then USY molecular sieve will
1g Ce(NO3)3·6H2O is dissolved in 50ml distilled water, and 10g TiO is added2It is close in room temperature that 3h is stirred at room temperature in USY molecular sieve
Close dipping for 24 hours, 80 DEG C of stirring in water bath are evaporated, and move into 110 DEG C of dry 12h in baking oven, and 450 DEG C of Muffle kiln roasting 5h are born
Carry CeO2Ce-TiO2USY molecular sieve.
The Cetyltrimethylammonium bromide of 2g, 3g, 5g stirring and dissolving in 200g distilled water is weighed, 4g Ce- is taken
TiO2USY molecular sieve is in above-mentioned solution, 60 DEG C of stirring 30min, through distilled water washing, 100 DEG C of dry 6h after terminating, obtains
Surfactant loadings respectively are 0.2%, 0.3%, 0.5% M-Ce-TiO2USY molecular sieve is successively denoted as respectively
Catalyst A6, A7, A8, TiO2Load capacity be respectively 10%, CeO2Load capacity be respectively 3.0%.
Catalyst A6, A7, A8 are separately formed the particle packing for 30 mesh in the cast electrothermal reactor placed vertically, dress
Matrix amount be 2g, 350 DEG C of temperature, pressure 0.5MPa, mass space velocity 2h-1, the molar ratio 1:1 of phenol and dimethyl carbonate into
Row reaction, the conversion ratio of phenol is respectively 70.6%, 77.4%, 73.3%, the selectivity of o-cresol is respectively 67.7%,
71.2%, 68.3%.
It will be understood by those skilled in the art that under the introduction of this specification, the present invention can be made some modifications or
Adjustment.These modifications or adjustment should also be as within the scope of the claims in the present invention.
Claims (10)
1. a kind of M-Ce-TiO2The preparation method of USY molecular sieve catalyst, which comprises the steps of:
1) TiO is loaded in USY molecular sieve2And CeO2；
2) carrier surface activating agent M on the molecular sieve obtained by step 1), obtains the catalyst；Wherein, the surfactant M
Preferably one or both of Cetyltrimethylammonium bromide, cetyl trimethylammonium bromide and cetyl pyridinium with
On combination.
2. preparation method according to claim 1, which is characterized in that the step 1) is according to following scheme one or scheme two
It carries out；
Wherein, the scheme one includes the following steps:
1.1a) USY molecular sieve and organic titanium solution are mixed, dipping, preferably dip time are 12-36 hours, are removed later
Remove solvent；
1.2a) by step 1.1a) products therefrom and Ce (NO3)3·6H2O aqueous solution is mixed, and dipping, preferably dip time is
12-36h removes solvent later and roasts；
The scheme two includes the following steps:
1.1b) by USY molecular sieve and Ce (NO3)3·6H2O aqueous solution is mixed, and dipping, preferably dip time are 12-36h,
Solvent is removed later；
1.2b) step 1.1b) products therefrom and organic titanium solution are mixed, dipping, preferably dip time are that 12-36 is small
When, solvent is removed later and is roasted.
3. preparation method according to claim 2, which is characterized in that the organic titanium is selected from butyl titanate, metatitanic acid isopropyl
The combination of one or more of ester and tetraethyl titanate；
Solvent in organic titanium solution is preferably the group of one or more of benzene, toluene, hexamethylene and n-hexane
It closes.
4. preparation method according to claim 2 or 3, which is characterized in that the Ce (NO3)3·6H2O dosage is described
The 5-12% of USY molecular sieve quality.
5. the preparation method according to claim 4, which is characterized in that in the obtained catalyst, TiO2Load capacity
For 5-15wt%.
6. according to the described in any item preparation methods of claim 2-5, which is characterized in that dipping described in each step be
Closed dipping at room temperature；Removing solvent described in each step is to be steamed solvent by drying with water bath；
Roasting described in each step is to roast at 450-540 DEG C.
7. preparation method according to claim 1-6, which is characterized in that the step 2) includes: by step 1)
Gained molecular sieve and aqueous surfactant solution are mixed at 50-70 DEG C, and preferably mixing time is 20-50min, carry out later
The step of washing, drying, it is also preferable to include moldings；
Preferably, the concentration of the aqueous surfactant solution is 1-5wt%, and the dosage of the surfactant M is USY molecule
Sieve the 10-50% of quality.
8. a kind of M-Ce-TiO2USY molecular sieve catalyst, which is characterized in that using USY molecular sieve as carrier, born on the carrier
It is loaded with surfactant M, TiO2And CeO2, the TiO2Load capacity in the catalyst is preferably 5-15wt%, described
CeO2Load capacity in the catalyst is preferably 2-5wt%；The load capacity of the surfactant M is preferably 0.1-
0.5wt%；The surfactant M is preferably selected from Cetyltrimethylammonium bromide, cetyl trimethylammonium bromide and ten
The combination of one or more of six alkyl pyridines；
Preferably, the catalyst is made according to the described in any item preparation methods of claim 1-7.
9. a kind of method for generating o-cresol, which is characterized in that phenol and dimethyl carbonate react generation under catalyst
The o-cresol, wherein the catalyst be the described in any item preparation methods of claim 1-7 be made or claim 8 described in
Catalyst.
10. according to the method described in claim 9, reaction temperature is it is characterized in that, the reaction carries out in fixed bed
250-500 DEG C, pressure 0.05-0.5MPa, mass space velocity 1-5h-1, the molar ratio of phenol and dimethyl carbonate is 1:(0.5-
2)。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811397061.0A CN109365006B (en) | 2018-11-22 | 2018-11-22 | M-Ce-TiO2-USY molecular sieve catalyst and method for generating o-cresol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811397061.0A CN109365006B (en) | 2018-11-22 | 2018-11-22 | M-Ce-TiO2-USY molecular sieve catalyst and method for generating o-cresol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109365006A true CN109365006A (en) | 2019-02-22 |
| CN109365006B CN109365006B (en) | 2021-04-20 |
Family
ID=65383085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811397061.0A Active CN109365006B (en) | 2018-11-22 | 2018-11-22 | M-Ce-TiO2-USY molecular sieve catalyst and method for generating o-cresol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109365006B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3857899A (en) * | 1968-10-05 | 1974-12-31 | Sumitomo Chemical Co | Process for selective methylation of phenols |
| CN101811938A (en) * | 2010-04-30 | 2010-08-25 | 常州大学 | Method for catalytically synthesizing p-methylphenol |
| CN103254039A (en) * | 2013-06-08 | 2013-08-21 | 济南卡博唐生物科技有限公司 | Preparation method of orthocresol |
-
2018
- 2018-11-22 CN CN201811397061.0A patent/CN109365006B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3857899A (en) * | 1968-10-05 | 1974-12-31 | Sumitomo Chemical Co | Process for selective methylation of phenols |
| CN101811938A (en) * | 2010-04-30 | 2010-08-25 | 常州大学 | Method for catalytically synthesizing p-methylphenol |
| CN103254039A (en) * | 2013-06-08 | 2013-08-21 | 济南卡博唐生物科技有限公司 | Preparation method of orthocresol |
Non-Patent Citations (3)
| Title |
|---|
| 明阳等: "Mg/Ce-USY分子筛催化苯酚甲醇烷基化 ", 《分子催化》 * |
| 李艳歌等: "Ce/USY分子筛催化苯酚甲醇烷基化 ", 《精细石油化工》 * |
| 郑国才: "TiO2/MCM-41催化苯酚与碳酸二甲酯邻位烷基化研究", 《化学研究与应用》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109365006B (en) | 2021-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106824259B (en) | The molecular sieve catalyst of yttrium containing zinc, preparation method and the application method of 1,3- butadiene are prepared for ethyl alcohol conversion | |
| CN105498839B (en) | A kind of heterogeneous catalysis and preparation method thereof of catalysis asymmetric Aldol reaction | |
| EP2990103A1 (en) | Fischer-tropsch synthesis catalyst for syngas to low carbon olefins, modified molecular sieve carrier and preparation method thereof | |
| CN101347744A (en) | Catalyst for synthesizing pyridine using microsphere type high-silicon ZSM-5 molecular sieve as carrier and preparation method thereof | |
| CN110961110A (en) | Catalyst and application thereof in hydrodechlorination of 2,3, 6-trichloropyridine | |
| CN110801841A (en) | Catalyst for preparing 2, 2' -bipyridine by coupling synthesis of pyridine and preparation method and application thereof | |
| CN109485621A (en) | A method of producing gamma valerolactone | |
| CN104549254B (en) | Catalyst for preparing 1,6-hexanediol through direct reduction of adipic acid | |
| CN104785298B (en) | A kind of solid base catalyst, preparation method and applications with metal-organic framework materials as carrier | |
| CN109365006A (en) | M-Ce-TiO2USY molecular sieve catalyst and the method for generating o-cresol | |
| CN111097446A (en) | Catalyst for preparing furfuryl alcohol by furfural liquid phase hydrogenation, preparation method and application thereof, and method for preparing furfuryl alcohol by furfural liquid phase hydrogenation | |
| CN107970928B (en) | A kind of preparing furan through decarbonylation of furfural catalyst, preparation method and application | |
| CN105967981B (en) | A kind of method that solid base catalyst [Smim] X/SBA 15 catalyzes and synthesizes propylene glycol monomethyl ether | |
| CN105944719B (en) | It is a kind of for catalyst of crotonaldehyde selective hydrogenation crotyl alcohol preparation and preparation method thereof | |
| CN106890669B (en) | A kind of catalyst producing methyl acetate, preparation method and application | |
| CN115672399A (en) | Organic amine catalyst, preparation method thereof and preparation method of diquat dichloride | |
| KR20180090001A (en) | Method for heterogeneous catalyst and method for the synthesis of compounds using the same | |
| CN112387268B (en) | Solid base catalyst for preparing 3-hydroxybutyraldehyde and preparation method thereof | |
| CN112441922B (en) | Method for preparing oxalate through CO oxidative coupling, catalyst and preparation method thereof | |
| CN102627558A (en) | Preparation method of vinyl carboxylate | |
| CN106518602B (en) | The method that hydroalkylation prepares cyclohexyl benzene | |
| CN111482178A (en) | Supported nano nickel-based catalyst and preparation method and application thereof | |
| CN104801291B (en) | Zn/ gold/mesoporous carbon catalysts for producing chloroethanes and preparation method thereof | |
| CN109529936A (en) | MOPs loads application of the bidentate chelating type metallic catalyst in suzuki reaction | |
| CN107790153B (en) | Silicon modified Fischer-Tropsch synthesis catalyst and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |