CN106179509A - A kind of catalyst of gas phase acetoxylation synthetic vinegar acid benzyl ester and preparation method thereof - Google Patents
A kind of catalyst of gas phase acetoxylation synthetic vinegar acid benzyl ester and preparation method thereof Download PDFInfo
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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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- 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
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- 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, catalyst of a kind of gas phase acetoxylation synthetic vinegar acid benzyl ester and preparation method thereof.Its raw material toluene, acetic acid and air (oxygen) are in the presence of a catalyst by acetoxylation synthetic vinegar acid benzyl ester, the catalyst used is with palladium as major catalyst, the metal ion such as antimony or copper is promoter, fixing means is infusion process and sol-gal process, and carrier is the complex catalyst system of molecular sieve, silicon oxide.The preparation method of this catalyst has good catalysis activity and selectivity under lower temperature, lower pressure, this catalyst system is heterogeneous catalysis, raw material, product separate with catalyst easily, the advantage such as catalyst choice is good, life-span length, repeatable utilization, have good commercial promise.
Description
Technical field
The invention belongs to catalyst preparation technology and field of chemical technology, be specially a kind of gas phase acetoxyl group chemical combination
Become catalyst of benzyl acetate and preparation method thereof.
Background technology
Benzyl acetate has fruit aroma, is widely used in fragrance formulations preparation perfume fragrance, fruit essence, it is possible to make
Ink, spray paint, the solvent of dyestuff.The benzyl acetate preparation cost of pure natural is high, complex process, in addition it is also necessary to consume substantial amounts of natural
Plant.The most commercial benzyl acetate all belongs to composite.Preparation method typically has two kinds: one is to use benzyl chloride and anhydrous vinegar
Acid sodium reaction prepares, and this method production cost is low, but post processing is difficult, easily causes the problems such as 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 produce benzyl acetate process route typically use after one
Kind, i.e. with toluene as raw material, through chlorination, hydrolyze after benzyl alcohol, then obtain benzyl acetate product with acetic acid esterified.The method is removed
Outside conversion ratio is low, due also to product repeatedly purifies and makes material loss, product yield is low, and production cost is high.It is thus desirable to seek
Ask that a kind of technique is simple, the method for synthetic vinegar acid benzyl ester that low cost, pollution are little.With toluene for raw material at different catalyst and
Can become more meticulous so that synthesizing benzoic alcohol, benzaldehyde, benzoic acid, dimethylbenzene, benzyl acetate, benzyl benzoate etc. are multiple under reaction condition
Chemical product.Acetic acid also causes its price one road to be dropped because of factors such as production capacity surplus and cost of material depressions.By cheap toluene
And acetic acid, under oxygen or air, carry out the benzyl acetate that acetoxyl group is combined to have relatively high added value, be before one has very much
The synthetic route of scape.
In the 1950's, just there is researcher discovery 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 is based on liquid-phase system, and can obtain higher selectivity and yield, but due to
Oxygen or air dissolubility in the solution is less makes reaction rate relatively slow, and side reaction is many, subsequent treatment, purification difficult, thus
Limit its application.Gas phase system synthetic vinegar acid benzyl ester has simple to operate, and reaction condition is gentle, pollutes little, and catalyst can be again
The advantages such as raw recycling, more and more interested to researchers.
Summary of the invention
Present invention aims to above technical problem, it is provided that a kind of gas phase acetoxylation synthetic vinegar acid benzyl ester
Catalyst.This catalyst has good catalysis activity and selectivity under lower temperature, lower pressure, and this catalyst system is
Heterogeneous catalysis, raw material, product separate easily with catalyst, catalyst choice is good, life-span length, repeatable utilization.
Another object of the present invention is to provide the preparation method of more than one described catalyst.
The object of the invention is realized by following technical proposals:
The catalyst of a kind of gas phase acetoxylation synthetic vinegar acid benzyl ester, is with palladium as major catalyst, antimony or copper etc.
Metal ion is promoter and the complex catalyst system of carrier composition；The preparation method of this catalyst mainly uses dipping
Method and sol-gel process；Its reaction is carried out on fixed bed reactors.
A: prepared by infusion process:
(1) with molecular sieve as carrier, through overpickling, wash, be dried etc. and to process, in this, as catalyst carrier；
(2) carrier obtained in step (1) being fixed Sb or Cu metal ion, soak time is 6h, obtains Sb-and divides
Son sieve or Cu-molecular sieve；
(3) on the Sb-molecular sieve after step (2) operation or Cu-molecular sieve, Pd metal ion, soak time are fixed
For 6h；
(4) be dried by above-mentioned metal ion catalyst after fixing, roasting, tabletting or extrusion shape, and can obtain
Present invention catalyst.
Mesopore molecular sieve has uniform pore passage structure, has good sieve effect to molecule, and aperture is adjustable；Its ratio
Surface area and pore volume are very big, in conjunction with the infusion process used, simply, the most controlled, can significantly improve again the activity of catalyst.
B: sol-gel process:
(1) certain density silicate and dispersant solution are added there-necked flask, add acetic acid second under high velocity agitation
Ester and slaine；
(2) with the acetum regulation pH to about 6 that wt% is 15-20%, stirring 50-70min is continued；
(3) vacuum filtration is carried out, and successively with deionized water, ethanol and washing with acetone；
(4) gel after washing is dried, and calcines and i.e. obtain catalyst under conditions of 500 DEG C.
This method can the most uniformly mix, it is possible to equal and quantitative ground mixes trace element, it is achieved molecular level
On Uniform Doped, have in addition uniqueness small-size effect and skin effect, have broad application prospects.
Described molecular sieve is a kind of mesopore molecular sieve.
Described mesopore molecular sieve is silicon oxide mesoporous molecular sieve.
Described silicon oxide mesoporous molecular sieve is that dehydrated alcohol is as helping table using cetyl trimethylammonium bromide as template
Face activating agent, tetraethyl orthosilicate is as silicon source.
Described silicon oxide mesoporous molecular sieve by reaction, centrifugation, wash, be dried, calcining and other processes i.e. obtains.
Described Sb is SbCl3、Sb2(SO4)3Or other antimonous salt, Cu is CuCl2、Cu(NO3)2Or other cupric salt.
Described Pd is PdCl2、Pd(OAc)2、PdNO3, PdO or other palladium double salt, solvent is acetic acid, acetone, dense HCl etc..
Described silicate is soluble silicate, such as: sodium silicate, potassium silicate, ammonium silicate or other salt.
Described slaine is above-mentioned palladium salt and antimonic salt or mantoquita.
The concentration of described acetum is 20% (mass fraction).
Catalyst proportion shared by described catalyst Pd metal ion is 0.1-10%.
Described catalyst Pd metal ion is major catalyst Pd: promoter gold with the mol ratio of promoter metal ion
Belong to ion=0.1-2:1.
Described catalyst is the granule of 20-40 mesh or a diameter of 1.2mm, length 2mm strip solid.
The positive effect of the present invention is:
(1), described method has good catalysis activity and selectivity under lower temperature, lower pressure.
(2), this catalyst system be heterogeneous catalysis, raw material, product separate easily with catalyst.
(3), catalyst there is the advantages such as selectivity is good, life-span length, repeatable utilization, have good commercial promise.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the foregoing invention content of the present invention is described in further detail, but should be by
This is interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment.Without departing from the present invention above-mentioned technological thought situation
Under, according to ordinary skill knowledge and customary means, make various replacement and change, the scope of the present invention all should be included in
In.
Embodiment 1:
Prepared by mesopore molecular sieve: take 1.44g sodium hydroxide, is dissolved in 50mL deionized water；Under agitation it is sequentially added into 5mL
Dehydrated alcohol, 220mL cetyl trimethylammonium bromide solution (mass fraction is 10.8%)；After solution is clarified, slowly drip
Enter 31.2g tetraethyl orthosilicate, at 25 DEG C, stir 6h, then regulate pH to 9-10 with the HCl of 0.3M；It is placed in 110 DEG C of baking ovens quiet
Put 72h；By reactant sucking filtration, it is washed with deionized to neutrality, is dried at room temperature for 10h, obtain carrier molecule sieve.
The concrete preparation process of catalyst is: take 22.5g SbCl3It is dissolved in 150mL deionized water, then by 133.5g warp
Cross pretreated mesopore molecular sieve and be immersed in SbCl3In solution, soak time is 6h, refilters, and dries in baking oven at 120 DEG C
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 fixing Sb is immersed in Pd (OAc)2In solution, soak time is 6h；By gained catalyst mistake
Filter, dries 16h at 120 DEG C；The catalyst solid dried is added 4.5g sesbania powder, 22.5g deionized water, stirs, squeezing
Extrusion molding on bar machine (selects the mould in 1.2mm aperture), obtains the strip solid of 1.2mm, then is cut into the solid of length 2mm,
I.e. obtain the catalyst that component is Pd3%, Sb8% (mass fraction).
Embodiment 2
Carrier is prepared by embodiment 1.
The concrete preparation process of catalyst is: take 22.5g SbCl3It is dissolved in 150mL deionized water, then by 133.5g warp
Cross pretreated mesopore molecular sieve and be immersed in SbCl3In solution, soak time is 6h, refilters, and dries in baking oven at 120 DEG C
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 fixing Sb is immersed in Pd (OAc)2In solution, soak time is 6h；By gained catalyst mistake
Filter, dries 16h at 120 DEG C；The catalyst solid dried is added 4.5g sesbania powder, 22.5g deionized water, stirs, squeezing
Extrusion molding on bar machine (selects the mould in 2.0mm aperture), obtains the strip solid of 2.0mm, then is cut into the solid of length 2mm,
I.e. obtain the catalyst that component is Pd3%, Sb8% (mass fraction).
Embodiment 3
Carrier is prepared by embodiment 1.
The concrete preparation process of catalyst is: take 22.5g SbCl3It is dissolved in 150mL deionized water, then by 137.9g warp
Cross pretreated mesopore molecular sieve and be immersed in SbCl3In solution, soak time is 6h, refilters, and dries in baking oven at 120 DEG C
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 fixing Sb is immersed in Pd (OAc)2In solution, soak time is 6h；By gained catalyst mistake
Filter, dries 16h at 120 DEG C；The catalyst solid dried is added 4.5g sesbania powder, 22.5g deionized water, stirs, squeezing
Extrusion molding on bar machine (selects the mould in 1.2mm aperture), obtains the strip solid of 1.2mm, then is cut into the solid of length 2mm,
I.e. obtain the catalyst that component is Pd0.1%, Sb8% (mass fraction).
Embodiment 4:
Carrier is prepared by embodiment 1.
The concrete preparation process of catalyst is: take 22.5g SbCl3It is dissolved in 150mL deionized water, then 123g is passed through
Pretreated mesopore molecular sieve is immersed in SbCl3In solution, soak time is 6h, refilters, and dries in baking oven at 120 DEG C
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 fixing Sb is immersed in Pd (OAc)2In solution, soak time is 6h；By gained catalyst mistake
Filter, dries 16h at 120 DEG C；The catalyst solid dried is added 4.5g sesbania powder, 22.5g deionized water, stirs, squeezing
Extrusion molding on bar machine (selects the mould in 1.2mm aperture), obtains the strip solid of 1.2mm, then is cut into the solid of length 2mm,
I.e. obtain the catalyst that component is Pd10%, Sb8% (mass fraction).
Embodiment 5
Carrier is prepared by embodiment 1.
The concrete preparation process of catalyst is: take 22.5g SbCl3It is dissolved in 150mL deionized water, then by 133.5g warp
Cross pretreated mesopore molecular sieve and be immersed in SbCl3In solution, soak time is 6h, refilters, and dries in baking oven at 120 DEG C
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 fixing Sb is immersed in Pd (OAc)2In solution, soak time is 6h；By gained catalyst mistake
Filter, dries 16h at 120 DEG C；The catalyst solid of drying carries out on tablet machine tabletting, and pressure applied is 10Mpa, then will
Tabletting is ground, and gained granule screens with the sieve of 40 mesh and 20 mesh respectively, and i.e. obtaining size is 20-40 mesh granule, component
Catalyst for Pd3%, Sb8% (mass fraction).
Embodiment 6
Carrier is prepared by embodiment 1.
The concrete preparation process of catalyst is: take 32.2g CuCl2 2H2O is dissolved in 150mL deionized water, then will
130.5g is immersed in CuCl through pretreated mesopore molecular sieve2In solution, soak time is 6h, refilters, in baking oven
Dry 16h at 120 DEG C, air is then calcined at 400 DEG C 3h (50ml/min, 3L/h)；By 15.8g Pd (OAc)2It is dissolved in
In 100mL 30% acetum, then the catalyst of fixing Cu is immersed in Pd (OAc)2In solution, soak time is 6h；By institute
Obtain catalyst filtration, dry 16h at 120 DEG C；The catalyst solid of drying carries out on tablet machine tabletting, and pressure applied is
10Mpa, then tabletting is ground, gained granule screens with the sieve of 40 mesh and 20 mesh respectively, and i.e. obtaining size is 20-40 mesh
Granule, component is the catalyst of Pd5%, Cu8% (mass fraction).
Embodiment 7
The concrete preparation process of catalyst is: in 50 DEG C of waters bath with thermostatic control, by 41.2gNa2SiO3 9H2O joins a certain amount of
In deionized water, it is made into the aqueous solution of 100mL, then is transferred in there-necked flask, add 100g dispersant PEG12000, at a high speed
Stirring is lower adds 50mL ethyl acetate, 10mL SbCl3(weigh 1.5SbCl3) and 10mLPd (OAc)2(weigh 1.1gPd
(OAc)2) solution, react 6h；Then with 20% acetum regulation pH to about 6, stirring 1h is continued；Carry out vacuum filtration, and
Successively with deionized water, ethanol and washing with acetone；Gel after washing is dried 5h at 100 DEG C, 500 DEG C of calcining 2h；To forge
The catalyst solid burnt carries out tabletting on tablet machine, and pressure applied is 10Mpa, then is ground by tabletting, gained
Granule screens with the sieve of 40 mesh and 20 mesh respectively, and i.e. obtaining size is 20-40 mesh granule, and component is Pd5%, Sb 8% (matter
Amount mark) catalyst.
Embodiment 8
The concrete preparation process of catalyst is: in 50 DEG C of waters bath with thermostatic control, by 41.2gNa2SiO3 9H2O joins a certain amount of
In deionized water, it is made into the aqueous solution of 100mL, then is transferred in there-necked flask, add 100g dispersant PEG12000, at a high speed
Stirring is lower adds 50mL ethyl acetate, 10mL CuCl2(weigh 2.1g CuCl2 2H2And 10mLPd (OAc) O)2(weigh
1.1gPd(OAc)2) solution, react 6h；Then with 20% acetum regulation pH to about 6, stirring 1h is continued；Carry out vacuum
Sucking filtration, and successively with deionized water, ethanol and washing with acetone；Gel after washing is dried 5h at 100 DEG C, 500 DEG C of calcinings
2h；Burnt catalyst solid carries out on tablet machine tabletting, and pressure applied is 10Mpa, then is ground by tabletting
Mill, gained granule screens with the sieve of 40 mesh and 20 mesh respectively, and i.e. obtaining size is 20-40 mesh granule, and component is Pd5%,
The catalyst of Cu8% (mass fraction).
Embodiment 9:
In order to verify that catalyst of the present invention has good catalytic performance, it is possible to significantly improve toluene gas phase acetoxylation
The yield of synthetic vinegar acid benzyl ester, prepares embodiment 1 to embodiment 8 and sends out a catalyst and be applied to toluene gas phase acetoxyl group and be combined to
Benzyl acetate, and detect the yield of synthetic vinegar acid benzyl ester under different catalysts.Catalyst of the present invention is applied to toluene gas phase acetyl
The detailed process that epoxide is combined to benzyl acetate is as follows:
Toluene gas phase acetoxylation reaction is carried out in the stainless steel tube that internal diameter is 9mm.Reaction temperature is by being placed in reaction
Interlayer inner tube interior-heat galvanic couple in pipe measures, and is located proximate in the middle part of catalyst layer；Reaction pressure and control are respectively by the pressure of system
Power table and counterbalance valve measure and regulation.For ensureing that gaseous mixture is evenly distributed, catalyst upper and lower side fills the stone of 20 high for 50mm mesh
Sand.Before the reaction, need to activate catalyst, activation temperature is 300 DEG C, and is passed through air, and flow velocity is 27mL/min
(1.62L/h).Toluene is mixed homogeneously according to fixed proportion with acetic acid, squeezes into pre-heating system by constant-flux pump and vaporizes, then with O2-N2
Entering reaction system after mixing and carry out acetoxylation reaction, reactant liquor is condensed obtains reactor product.The ratio of the most each material
Example: toluene: acetic acid: oxygen: noble gas=1:3:2:8, reaction temperature is 200 DEG C, and pressure is 0.15MPa, Liquid sample introduction speed
Rate is 0.2mL/min, and catalyst amount is 10mL, reacts 8h, the yield of benzyl acetate in terms of toluene.
The yield of embodiment 1 to embodiment 8 synthetic vinegar acid benzyl ester is as shown in table 1 below:
The yield of table 1 embodiment 1 to embodiment 8 synthetic vinegar acid benzyl ester
Claims (8)
1. the catalyst of a gas phase acetoxylation synthetic vinegar acid benzyl ester, it is characterised in that: described catalyst includes with acetic acid
Palladium be major catalyst, antimony or copper metal ion be promoter and carrier composition complex catalyst system, in this catalyst, palladium
Metal ion is the 0.1%～10% of catalyst quality, antimony or copper metal ion and the mol ratio of palladium metal ion is 1:0.1～2,
Gross mass percentage composition sum is 100%.
The preparation method of the catalyst of gas phase acetoxylation synthetic vinegar acid benzyl ester the most according to claim 1, its feature
It is that this preparation method uses infusion process, specifically includes following steps:
(1) with molecular sieve as carrier, through overpickling, washing and dried, the material obtained is as catalyst carrier；
(2) using the catalyst carrier obtained in step (1) to fix Sb or Cu, soak time is 6h, obtain Sb-molecular sieve or
Cu-molecular sieve；
(3) fixing Pd on Sb-molecular sieve or Cu-molecular sieve, soak time is 6h；
(4) be dried by the catalyst crude product obtained in step (3), roasting, tabletting or extrusion shape, and obtain this catalyst
Product.
The preparation method of the catalyst of gas phase acetoxylation synthetic vinegar acid benzyl ester the most according to claim 1, its feature
It is that this preparation method uses sol-gel process, specifically includes following steps:
(1') certain density silicate and dispersant solution are added there-necked flask, add under high velocity agitation ethyl acetate and
Slaine；
(2') regulate pH to about 6 with acetum, continue stirring 1h；
(3') carry out vacuum filtration, and successively with deionized water, ethanol and washing with acetone；
(4') the gel after washing is dried, and 500 DEG C of calcinings i.e. obtain catalyst.
The preparation method of the catalyst of gas phase acetoxylation synthetic vinegar acid benzyl ester the most according to claim 2, its feature
Be: described molecular sieve is a kind of mesopore molecular sieve, the most silicon oxide mesoporous molecular sieve, this silicon oxide mesoporous molecular sieve be with
Cetyl trimethylammonium bromide is as template, and dehydrated alcohol is as cosurfactant, and tetraethyl orthosilicate is as silicon source.
The preparation method of the catalyst of gas phase acetoxylation synthetic vinegar acid benzyl ester the most according to claim 4, its feature
The preparation method being this silicon oxide mesoporous molecular sieve is: takes appropriate sodium hydroxide and is dissolved in deionized water, in stirring
Add dehydrated alcohol and cetyl trimethylammonium bromide solution under state, after solution is clarified, be slowly dropped into tetraethyl orthosilicate,
And stir 6h at 25 DEG C, then be 9-10 with HCl regulation pH value, it is placed in the baking oven of 110 DEG C standing 72h, by reactant sucking filtration, uses
Deionized water wash, to neutral, obtains carrier molecule sieve after drying at room temperature 10h.
The catalyst of gas phase acetoxylation synthetic vinegar acid benzyl ester the most according to claim 1, it is characterised in that: described Sb
For SbCl3、Sb2(SO4)3Or other antimonous salt, Cu is CuCl2 、Cu(NO3)2Or cupric salt.
The catalyst of gas phase acetoxylation synthetic vinegar acid benzyl ester the most according to claim 1, it is characterised in that: described Pd
For PdCl2、Pd(OAc)2、PdNO3, PdO or other palladium double salt.
8. according to the catalysis of the gas phase acetoxylation synthetic vinegar acid benzyl ester described in any one claim in claim 2-7
The preparation method of agent, it is characterised in that: use the granule that catalyst is 20-40 mesh or a diameter of that above method prepares
1.2mm, length 2mm strip solid.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| A. BENHMID等: ""Highly Active and Selective Pd–Cu–TiO2 Catalyst for the Direct Synthesis of Benzyl Acetate by Gas Phase Acetoxylation of Toluene"", 《CHEMISTRY LETTERS》 * |
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