CN106179509B - A kind of catalyst and preparation method thereof of gas phase acetoxylation synthesis benzyl acetate - Google Patents
A kind of catalyst and preparation method thereof of gas phase acetoxylation synthesis benzyl acetate Download PDFInfo
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- CN106179509B CN106179509B CN201610524560.6A CN201610524560A CN106179509B CN 106179509 B CN106179509 B CN 106179509B CN 201610524560 A CN201610524560 A CN 201610524560A CN 106179509 B CN106179509 B CN 106179509B
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- 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
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract
The invention belongs to catalyst preparation technology and field of chemical technology, specially a kind of catalyst and preparation method thereof of gas phase acetoxylation synthesis benzyl acetate.Its raw material toluene, acetic acid and air(Oxygen)Benzyl acetate is synthesized by acetoxylation in the presence of a catalyst, the catalyst used is using palladium as major catalyst, the metal ions such as antimony or copper are co-catalyst, and fixing means is infusion process and sol-gal process, and carrier is the complex catalyst system of molecular sieve, silica.The preparation method of the catalyst has good catalytic activity and selectivity under lower temperature, lower pressure, the catalyst system is heterogeneous catalysis, raw material, that product is detached with catalyst is easy, catalyst choice is good, long lifespan, repeatable the advantages that utilizing, there is good commercial promise.
Description
Technical field
The invention belongs to catalyst preparation technology and field of chemical technology, specially a kind of gas phase acetoxyl group chemical combination
At the catalyst and preparation method thereof of benzyl acetate.
Background technology
Benzyl acetate has fruit aroma, is widely used in fragrance formulations and prepares perfume fragrance, fruit essence, can also make
Ink, spray painting, dyestuff solvent.Pure natural benzyl acetate manufacturing cost is high, complex process, it is also necessary to which consumption is a large amount of natural
Plant.Commercial benzyl acetate belongs to composite now.There are two types of preparation method is general:One is use benzyl chloride and anhydrous vinegar
The reaction of sour sodium is made, this method production cost is low, but post-processes difficult, the problems such as easily causing environmental pollution;Another kind is with benzene first
Alcohol and glacial acetic acid are raw material, and sulfuric acid catalysis is esterified and obtains.Domestic current produces the process route of benzyl acetate generally using latter
Kind, i.e., using toluene as raw material, through chlorination, hydrolyze after benzyl alcohol, then with acetic acid esterified obtain benzyl acetate product.The method is removed
Conversion ratio is low outer, due also to product repeatedly purification and make material loss, product yield is low, and production cost is high.Therefore it needs to seek
Seek a kind of method of synthesis benzyl acetate simple for process, at low cost, pollution is small.Using toluene as raw material in different catalyst and
It can be with a variety of finings such as synthesizing benzoic alcohol, benzaldehyde, benzoic acid, dimethylbenzene, benzyl acetate, Ergol under reaction condition
Chemical product.Acetic acid is also because the factors such as excess capacity and cost of material depression cause its price to drop all the way.Pass through cheap toluene
And acetic acid, acetoxyl group is carried out under oxygen or air and is combined to the benzyl acetate compared with high added value, is before one kind has very much
The synthetic route of scape.
In the 1950s, just there is researcher to find toluene in acetum, in the effect of some oxidants
Under can generate benzyl acetate (David R.et al.The Journal of organic chemistry.1968, vol33,
No.11:4123-4127;V.Narayana Kalevaru,et al.Catalysis Today.2009,Vol141,317-
324).Until the nineties, researcher can obtain more highly selective and yield based on liquid-phase system, but due to
Oxygen or air in the solution solubility it is smaller so that reaction rate is slower, side reaction is more, subsequent processing, purification difficult, to
Limit its application.Gas phase system synthesize benzyl acetate have it is easy to operate, reaction condition is mild, pollution it is small, catalyst can be again
It is the advantages that raw recycling, more and more interested to researchers.
Invention content
It is an object of the invention to be directed to the above technical problem, a kind of gas phase acetoxylation synthesis benzyl acetate is provided
Catalyst.There is the catalyst good catalytic activity and selectivity, the catalyst system to be under lower temperature, lower pressure
Heterogeneous catalysis, raw material, that product is detached with catalyst is easy, and catalyst choice is good, long lifespan, repeatable utilizes.
Another object of the present invention is to provide the preparation method of more than one catalyst.
The object of the invention is realized by following technical proposals:
A kind of catalyst of gas phase acetoxylation synthesis benzyl acetate, is antimony or copper etc. using palladium as major catalyst
Metal ion is the complex catalyst system that co-catalyst and carrier form;The preparation method of the catalyst is mainly using dipping
Method and sol-gel method;Its reaction carries out on fixed bed reactors.
A:It is prepared by infusion process:
(1) using molecular sieve as carrier, through processing such as overpickling, washing, dryings, in this, as catalyst carrier;
(2) carrier obtained in step (1) will be passed through and fix Sb or Cu metal ions, soaking time 6h obtains Sb- points
Son sieve or Cu- molecular sieves;
(3) by step (2) operation after Sb- molecular sieves or Cu- molecular sieves on fix Pd metal ions, soaking time
For 6h;
(4) catalyst after fixing above-mentioned metal ion is dried, roasts, tabletting or extrusion shape, you can obtains
Present invention catalyst.
Mesopore molecular sieve has uniform pore passage structure, has good sieve effect to molecule, and aperture is adjustable;It compares
Surface area and pore volume are very big, in conjunction with used infusion process, both simply, controllably, and can significantly improve the activity of catalyst.
B:Sol-gel method:
(1) three-necked flask is added in certain density silicate and dispersant solution, acetic acid second is added under high velocity agitation
Ester and metal salt;
(2) pH to 6 or so is adjusted with the wt% acetums for being 15-20%, continues to stir 50-70min;
(3) it is filtered by vacuum, and is washed successively with deionized water, ethyl alcohol and acetone;
(4) gel after washing is dried, and calcining is to obtain catalyst under conditions of 500 DEG C.
This method can be mixed uniformly on a molecular scale, also can mix to equal and quantitative trace element, realize molecular level
On Uniform Doped, in addition have unique small-size effect and skin effect, have broad application prospects.
The molecular sieve is a kind of mesopore molecular sieve.
The mesopore molecular sieve is silicon oxide mesoporous molecular sieve.
The silicon oxide mesoporous molecular sieve is using cetyl trimethylammonium bromide as template, and absolute ethyl alcohol is used as and helps table
Face activating agent, ethyl orthosilicate is as silicon source.
The silicon oxide mesoporous molecular sieve is obtained by reaction, centrifugation, washing, drying, calcining and other processes.
The Sb is SbCl3、Sb2(SO4)3Or other antimonous salts, Cu CuCl2、Cu(NO3)2Or other cupric salts.
The Pd is PdCl2、Pd(OAc)2、PdNO3, PdO or other palladium double salt, solvent is acetic acid, acetone, dense HCl etc..
The silicate is soluble silicate, such as:Sodium metasilicate, potassium silicate, ammonium silicate or other salt.
The metal salt is above-mentioned palladium salt and antimonic salt or mantoquita.
A concentration of 20% (mass fraction) of the acetum.
Catalyst proportion shared by the catalyst Pd metal ions is 0.1-10%.
The molar ratio of the catalyst Pd metal ions and promoter metal ion is major catalyst Pd:Co-catalyst gold
Belong to ion=0.1-2:1.
The catalyst is the particle of 20-40 mesh or a diameter of 1.2mm, length 2mm strip solids.
The positive effect of the present invention is:
(1), the method has good catalytic activity and selectivity under lower temperature, lower pressure.
(2), the catalyst system is heterogeneous catalysis, and raw material, that product is detached with catalyst is easy.
(3), catalyst has many advantages, such as good selectivity, long lifespan, repeatable utilization, there is good commercial promise.
Specific implementation mode
The foregoing invention content of the present invention is described in further detail With reference to embodiment, but should not be incited somebody to action
This range for being interpreted as the above-mentioned theme of the present invention is only limitted to following embodiments.The above-mentioned technological thought situation of the present invention is not being departed from
Under, according to ordinary skill knowledge and customary means, various replacements and change are made, the scope of the present invention should all be included in
It is interior.
Embodiment 1:
It is prepared by mesopore molecular sieve:1.44g sodium hydroxides are taken, 50mL deionized waters are dissolved in;5mL is sequentially added under stiring
Absolute ethyl alcohol, 220mL cetyl trimethylammonium bromide solutions (mass fraction 10.8%);After solution clarification, slowly drip
Enter 31.2g ethyl orthosilicates, 6h is stirred at 25 DEG C, then pH to 9-10 is adjusted with the HCl of 0.3M;It is placed in quiet in 110 DEG C of baking ovens
Set 72h;Reactant is filtered, is washed with deionized to neutrality, is dried at room temperature for 10h, obtains carrier molecule sieve.
The specific preparation process of catalyst is:Take 22.5g SbCl3It is dissolved in 150mL deionized waters, then 133.5g is passed through
It crosses pretreated mesopore molecular sieve and is immersed in SbCl3In solution, soaking time 6h is refiltered, and is dried at 120 DEG C in baking oven
16h then calcines 3h (50ml/min, 3L/h) at 400 DEG C in air;By 9.5g Pd (OAc)2It is dissolved in 100mL 30%
In acetum, then the catalyst of fixed Sb is immersed in Pd (OAc)2In solution, soaking time 6h;By gained catalyst mistake
16h is dried in filter at 120 DEG C;4.5g sesbania powders are added in the catalyst solid of drying, 22.5g deionized waters stir evenly, and are squeezing
Extrusion molding (mold for selecting the apertures 1.2mm), obtains the strip solid of 1.2mm, then be cut into the solid of length 2mm on machine,
It is Pd3%, the catalyst of Sb8% (mass fraction) to obtain component.
Embodiment 2
Carrier is prepared by embodiment 1.
The specific preparation process of catalyst is:Take 22.5g SbCl3It is dissolved in 150mL deionized waters, then 133.5g is passed through
It crosses pretreated mesopore molecular sieve and is immersed in SbCl3In solution, soaking time 6h is refiltered, and is dried at 120 DEG C in baking oven
16h then calcines 3h (50ml/min, 3L/h) at 400 DEG C in air;By 9.5g Pd (OAc)2It is dissolved in 100mL 30%
In acetum, then the catalyst of fixed Sb is immersed in Pd (OAc)2In solution, soaking time 6h;By gained catalyst mistake
16h is dried in filter at 120 DEG C;4.5g sesbania powders are added in the catalyst solid of drying, 22.5g deionized waters stir evenly, and are squeezing
Extrusion molding (mold for selecting the apertures 2.0mm), obtains the strip solid of 2.0mm, then be cut into the solid of length 2mm on machine,
It is Pd3%, the catalyst of Sb8% (mass fraction) to obtain component.
Embodiment 3
Carrier is prepared by embodiment 1.
The specific preparation process of catalyst is:Take 22.5g SbCl3It is dissolved in 150mL deionized waters, then 137.9g is passed through
It crosses pretreated mesopore molecular sieve and is immersed in SbCl3In solution, soaking time 6h is refiltered, and is dried at 120 DEG C in baking oven
16h then calcines 3h (50ml/min, 3L/h) at 400 DEG C in air;By 0.3g Pd (OAc)2It is dissolved in 100mL 30%
In acetum, then the catalyst of fixed Sb is immersed in Pd (OAc)2In solution, soaking time 6h;By gained catalyst mistake
16h is dried in filter at 120 DEG C;4.5g sesbania powders are added in the catalyst solid of drying, 22.5g deionized waters stir evenly, and are squeezing
Extrusion molding (mold for selecting the apertures 1.2mm), obtains the strip solid of 1.2mm, then be cut into the solid of length 2mm on machine,
It is Pd0.1%, the catalyst of Sb8% (mass fraction) to obtain component.
Embodiment 4:
Carrier is prepared by embodiment 1.
The specific preparation process of catalyst is:Take 22.5g SbCl3It is dissolved in 150mL deionized waters, then 123g is passed through
Pretreated mesopore molecular sieve is immersed in SbCl3In solution, soaking time 6h is refiltered, and is dried at 120 DEG C in baking oven
16h then calcines 3h (50ml/min, 3L/h) at 400 DEG C in air;By 31.7g Pd (OAc)2It is dissolved in 100mL 30%
In acetum, then the catalyst of fixed Sb is immersed in Pd (OAc)2In solution, soaking time 6h;By gained catalyst mistake
16h is dried in filter at 120 DEG C;4.5g sesbania powders are added in the catalyst solid of drying, 22.5g deionized waters stir evenly, and are squeezing
Extrusion molding (mold for selecting the apertures 1.2mm), obtains the strip solid of 1.2mm, then be cut into the solid of length 2mm on machine,
It is Pd10%, the catalyst of Sb8% (mass fraction) to obtain component.
Embodiment 5
Carrier is prepared by embodiment 1.
The specific preparation process of catalyst is:Take 22.5g SbCl3It is dissolved in 150mL deionized waters, then 133.5g is passed through
It crosses pretreated mesopore molecular sieve and is immersed in SbCl3In solution, soaking time 6h is refiltered, and is dried at 120 DEG C in baking oven
16h then calcines 3h (50ml/min, 3L/h) at 400 DEG C in air;By 9.5g Pd (OAc)2It is dissolved in 100mL 30%
In acetum, then the catalyst of fixed Sb is immersed in Pd (OAc)2In solution, soaking time 6h;By gained catalyst mistake
16h is dried in filter at 120 DEG C;The catalyst solid of drying is subjected to tabletting, pressure applied 10Mpa on tablet press machine, then is incited somebody to action
Tabletting is ground, and gained particle is screened respectively with the sieve of 40 mesh and 20 mesh to get being 20-40 mesh particles, component to size
For Pd3%, the catalyst of Sb8% (mass fraction).
Embodiment 6
Carrier is prepared by embodiment 1.
The specific preparation process of catalyst is:Take 32.2g CuCl2 2H2O is dissolved in 150mL deionized waters, then will
130.5g is immersed in CuCl by pretreated mesopore molecular sieve2In solution, soaking time 6h is refiltered, in baking oven
16h is dried at 120 DEG C, then calcines 3h (50ml/min, 3L/h) in air at 400 DEG C;By 15.8g Pd (OAc)2It is dissolved in
In 30% acetums of 100mL, then the catalyst of fixed Cu is immersed in Pd (OAc)2In solution, soaking time 6h;By institute
Catalyst filtration is obtained, 16h is dried at 120 DEG C;The catalyst solid of drying is subjected to tabletting on tablet press machine, pressure applied is
10Mpa, then tabletting is ground, gained particle is screened respectively with the sieve of 40 mesh and 20 mesh to get being 20-40 mesh to size
Particle, group are divided into Pd5%, the catalyst of Cu8% (mass fraction).
Embodiment 7
The specific preparation process of catalyst is:In 50 DEG C of waters bath with thermostatic control, by 41.2gNa2SiO3 9H2O is added to a certain amount of
In deionized water, it is made into the aqueous solution of 100mL, then is transferred in three-necked flask, 100g dispersant PEG12000 are added, in high speed
It is added with stirring 50mL ethyl acetate, 10mL SbCl3(weigh 1.5SbCl3) and 10mLPd (OAc)2(weigh 1.1gPd
(OAc)2) solution, react 6h;Then pH to 6 or so is adjusted with 20% acetum, continues to stir 1h;It is filtered by vacuum, and
It is washed successively with deionized water, ethyl alcohol and acetone;5h, 500 DEG C of calcining 2h are dried at 100 DEG C for gel after washing;It will forge
The catalyst solid burnt carries out tabletting, pressure applied 10Mpa on tablet press machine, then tabletting is ground, gained
Particle is screened with the sieve of 40 mesh and 20 mesh to get being 20-40 mesh particles to size respectively, and group is divided into Pd5%, 8% (matter of Sb
Measure score) catalyst.
Embodiment 8
The specific preparation process of catalyst is:In 50 DEG C of waters bath with thermostatic control, by 41.2gNa2SiO3 9H2O is added to a certain amount of
In deionized water, it is made into the aqueous solution of 100mL, then is transferred in three-necked flask, 100g dispersant PEG12000 are added, in high speed
It is added with stirring 50mL ethyl acetate, 10mL CuCl2(weigh 2.1g CuCl2 2H2) and 10mLPd (OAc) O2It (weighs
1.1gPd(OAc)2) solution, react 6h;Then pH to 6 or so is adjusted with 20% acetum, continues to stir 1h;Carry out vacuum
It filters, and is washed successively with deionized water, ethyl alcohol and acetone;5h, 500 DEG C of calcinings are dried at 100 DEG C for gel after washing
2h;Burnt catalyst solid is subjected to tabletting, pressure applied 10Mpa on tablet press machine, then tabletting is ground
Mill, gained particle are screened with the sieve of 40 mesh and 20 mesh to get being 20-40 mesh particles to size respectively, and group is divided into Pd5%,
The catalyst of Cu8% (mass fraction).
Embodiment 9:
There is good catalytic performance in order to verify catalyst of the present invention, toluene gas phase acetoxylation can be significantly improved
Embodiment 1 to embodiment 8 is prepared hair catalyst and is combined to applied to toluene gas phase acetoxyl group by the yield for synthesizing benzyl acetate
Benzyl acetate, and detect the yield that benzyl acetate is synthesized under different catalysts.Catalyst of the present invention is applied to toluene gas phase acetyl
The detailed process that oxygroup is combined to benzyl acetate is as follows:
Toluene gas phase acetoxylation reaction carries out in the stainless steel tube that internal diameter is 9mm.Reaction temperature is by being placed in reaction
Thermocouple measures in interlayer inner tube in pipe, is located proximate in the middle part of catalyst layer;Reaction pressure is with control respectively by the pressure of system
Power table and counterbalance valve are measured and are adjusted.To ensure that gaseous mixture is evenly distributed, catalyst upper and lower side fills the stone of 20 mesh of 50mm high
Sand.Before the reaction, catalyst need to be activated, activation temperature is 300 DEG C, and is passed through air, flow velocity 27mL/min
(1.62L/h).Toluene is uniformly mixed with acetic acid according to fixed proportion, squeezes into pre-heating system vaporization by constant-flux pump, then with O2-N2
Enter reaction system after mixing and carry out acetoxylation reaction, reaction solution is condensed to obtain reactor product.The ratio of wherein each material
Example:Toluene:Acetic acid:Oxygen:Inert gas=1:3:2:8, reaction temperature is 200 DEG C, pressure 0.15MPa, Liquid sample introduction speed
Rate is 0.2mL/min, catalyst amount 10mL, reacts 8h, the yield of benzyl acetate in terms of toluene.
The yield that embodiment 1 synthesizes benzyl acetate to embodiment 8 is as shown in table 1 below:
1 embodiment 1 of table synthesizes the yield of benzyl acetate to embodiment 8
Claims (6)
1. gas phase acetoxylation synthesize benzyl acetate catalyst preparation method, it is characterised in that the catalyst include with
Palladium is major catalyst, and antimony or copper metal ion are the complex catalyst system that co-catalyst and carrier form, the catalyst
In, palladium metal ion is the 0.1%~10% of catalyst quality, and antimony or the molar ratio of copper metal ion and palladium metal ion are 1:
0.1~2, the sum of gross mass percentage composition is 100%;
The preparation method uses infusion process, specifically includes following steps:
(1)Using molecular sieve as carrier, through overpickling, washing and drying process, obtained substance is as catalyst carrier;Described point
Son sieve is a kind of mesopore molecular sieve, and specially silicon oxide mesoporous molecular sieve, which is with cetyl three
Methyl bromide ammonium is as template, and absolute ethyl alcohol is as cosurfactant, and ethyl orthosilicate is as silicon source;
(2)Using step(1)In obtained catalyst carrier fix Sb or Cu, soaking time 6h, obtain Sb- molecular sieves or
Cu- molecular sieves;
(3)Pd, soaking time 6h are fixed on Sb- molecular sieves or Cu- molecular sieves;
(4)By step(3)In obtained catalyst crude product be dried, roast, the forming of tabletting or extrusion to get this catalyst at
Product.
2. gas phase acetoxylation synthesize benzyl acetate catalyst preparation method, it is characterised in that the catalyst include with
Palladium is major catalyst, and antimony or copper metal ion are the complex catalyst system that co-catalyst and carrier form, the catalyst
In, palladium metal ion is the 0.1%~10% of catalyst quality, and antimony or the molar ratio of copper metal ion and palladium metal ion are 1:
0.1~2, the sum of gross mass percentage composition is 100%;
The preparation method uses sol-gel method, specifically includes following steps:
(1')Three-necked flask is added in certain density silicate and dispersant solution, be added under high velocity agitation ethyl acetate and
Metal salt;
(2')PH to 6 or so is adjusted with acetum, continues to stir 1h;
(3')It is filtered by vacuum, and is washed successively with deionized water, ethyl alcohol and acetone;
(4')Gel after washing is dried, and 500 DEG C of calcinings obtain catalyst.
3. the preparation method of the catalyst of gas phase acetoxylation synthesis benzyl acetate according to claim 1, feature
It is that the preparation method of the silicon oxide mesoporous molecular sieve is:Suitable sodium hydroxide is taken to be dissolved in deionized water, in stirring
Absolute ethyl alcohol and cetyl trimethylammonium bromide solution are added under state, ethyl orthosilicate is slowly dropped into after solution clarification,
And 6h is stirred at 25 DEG C, then it is 9-10 to adjust pH value with HCl, is placed in 110 DEG C of baking oven and stands 72h, reactant is filtered, and is used
Deionized water is washed to neutrality, and carrier molecule sieve is obtained after drying at room temperature 10h.
4. the preparation of the catalyst of the gas phase acetoxylation synthesis benzyl acetate according to claim 1 or claim 2
Method, it is characterised in that:The Sb is SbCl3、Sb2(SO4)3Or other antimonous salts, Cu CuCl2 、Cu(NO3)2Or divalent
Mantoquita.
5. the preparation of the catalyst of the gas phase acetoxylation synthesis benzyl acetate according to claim 1 or claim 2
Method, it is characterised in that:The Pd is PdCl2、Pd(OAc)2、PdNO3, PdO or other palladium double salt.
6. the catalysis of the gas phase acetoxylation synthesis benzyl acetate according to any one of claim 1-3 claims
The preparation method of agent, it is characterised in that:Use the catalyst that above method is prepared for the particle of 20-40 mesh or a diameter of
1.2mm, length 2mm strip solids.
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Citations (2)
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CN102371180A (en) * | 2011-11-17 | 2012-03-14 | 江南大学 | Catalyst for use in gas-phase synthesis of diethyl carbonate and preparation method thereof |
CN104275195A (en) * | 2014-10-11 | 2015-01-14 | 江苏常州酞青新材料科技有限公司 | Preparation method of benzyl acetate catalyst |
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CN102371180A (en) * | 2011-11-17 | 2012-03-14 | 江南大学 | Catalyst for use in gas-phase synthesis of diethyl carbonate and preparation method thereof |
CN104275195A (en) * | 2014-10-11 | 2015-01-14 | 江苏常州酞青新材料科技有限公司 | Preparation method of benzyl acetate catalyst |
Non-Patent Citations (1)
Title |
---|
"Highly Active and Selective Pd–Cu–TiO2 Catalyst for the Direct Synthesis of Benzyl Acetate by Gas Phase Acetoxylation of Toluene";A. Benhmid等;《Chemistry Letters》;20041231;第33卷(第10期);第1238页左栏3段 * |
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