CN106582825B - It is used to prepare the catalyst of allyl acetate - Google Patents
It is used to prepare the catalyst of allyl acetate Download PDFInfo
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- CN106582825B CN106582825B CN201510675517.5A CN201510675517A CN106582825B CN 106582825 B CN106582825 B CN 106582825B CN 201510675517 A CN201510675517 A CN 201510675517A CN 106582825 B CN106582825 B CN 106582825B
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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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
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Abstract
The present invention relates to the catalyst for being used to prepare allyl acetate, mainly solve the problems, such as that catalyst activity and selectivity is not high in the prior art.For the present invention by using the catalyst for being used to prepare allyl acetate, the catalyst includes carrier, active component and co-catalyst；The active component includes metal Pd and Ni metal；The co-catalyst is alkali metal acetate；The carrier includes carrier substrate and surface covering；The substrate is porous silica；The coating is formed by modified metal element and by the silica binder that the modified metal element is bonded in the substrate surface；The modified metal constituent content is 0.10~1.00g/L；The modifying element is selected from the technical solution of at least one of VA metallic element and IVB metallic element, preferably solves the problems, such as this, can be used in the industrial production of allyl acetate.
Description
Technical field
The present invention relates to the synthetic methods of allyl acetate catalyst, the preparation method of catalyst and allyl acetate.
Background technique
Allyl acetate is a kind of colourless flammable liquid, is slightly soluble in water, is soluble in pure and mild ether, can be dissolved in acetone, its conduct
A kind of important industrial chemicals, mainly for the production of propenyl and epoxychloropropane.
In the 1980s, Japanese Showa electrician and the academy of sciences, the former Soviet Union propose in the presence of palladium and co-catalyst, use
Acetoxylation technology, using propylene, oxygen and acetic acid as raw material, Fixed Bed Gas Phase reaction is prepared in the reaction of allyl acetate,
With SiO2、Al2O3Or SiO2And Al2O3The mixture of composition is carrier, and load has Pd, Cu and potassium acetate, and Pd and Cu
It has been well known to those of ordinary skill in the art in the catalyst that eggshell type is distributed.The preparation method of the catalyst via US3,
917,676 (titles are as follows: Process for producing ally acetate) are disclosed, i.e., will be containing precious metals pd and Cu
Mixed liquor is immersed on carrier, after drying process, the Pd of free state and Cu is solidificated in carrier surface and form active metal
Then the Pd and Cu of state obtain the catalyst after co-catalyst KOAc processing is dry.The activity for the catalyst that this method obtains
It is lower with selectivity.
Many scholars study the active component of the noble metal catalyst, co-catalyst.The reaction is thought in research
Main By product is generated by propylene deep oxidation, this was not only related with adsorpting type of the catalyst to reactant, but with catalysis
The Active components distribution of agent is related.Zeng Xianjun etc. then recognizes in " research that propylene aoxidizes acetate propylene ester catalyst processed " text
For propylene is in Pd-K/SiO2On absorption and toluene in Pd-Sn-K/SiO2Oxidation on catalyst is similar, and Shu Qingyu etc.
In " Pd-Sn-K/SiO2Toluene gas phase Acetoxylation reacts on catalyst " reaction of toluene gas phase Acetoxylation is proposed in a text
In Pd-Sn-K/SiO2In activation process on catalyst, methyl c h bond is dissociated into ratedeterming step, and metallic state palladium becomes catalysis
The presence of most important component in agent, KOAc improves the activation of c h bond.
Liang Zhong etc. thinks that Lattice Oxygen is conducive to select " adsorbing the effect of oxygen and Lattice Oxygen in selective oxidation of n -butane "
Property oxidation, the oxygen of ADSORPTION STATE is conducive to deep oxidation, therefore should improve catalytic surface Lattice Oxygen in the reaction of propylene Acetoxylation
Concentration.Zhao Zhenxing etc. proposes ethylene gas phase oxygen acetyl in " ethylene gas phase Acetoxylation reaction mechanism and dynamics research "
Change reaction mechanism, they think that the oxygen that adsorbs most advantageously molecular state of the oxygen on catalyst surface, the oxygen of molecular state are ginsengs
Add the oxygen source of acetylation, Pd-SiO2Catalyst activity component Pd changes the acetic acid of physical absorption the acetic acid of chemisorption, from
And allyl acetate is generated in conjunction with the oxygen of molecular state.
Furthermore many scholars at home and abroad think that the selectivity of allyl acetate catalyst is related with the heat of adsorption of propylene, such as
Han Y F etc. " A kinetic study of acetate synthesis over Pd-based catalysts:
kinetics of vinyl acetate synthesis over Pd-Au/SiO2Catalysts " He Liming when etc. " micro-
Measure adsorption capacity heat technical research Pd-Cu/SiO2Adsorption " in it is also proposed that, introduce metallic copper, tin etc. advantageously reduces Pd table
The oxidation activity of oxygen is adsorbed in face, to improve the selectivity of oxidation.
Summary of the invention
The first technical problem to be solved by the present invention be the allyl acetate catalyst activity that synthesizes in the prior art and
The not high problem of selectivity.Provide it is a kind of for synthesizing the catalyst of allyl acetate, the catalyst have high activity Gao Xuan
The characteristics of selecting property.
The second technical problem to be solved by the present invention is the preparation method of catalyst described in one of technical problem.
The third technical problem to be solved by the present invention is using the synthesis acetic acid allyl of catalyst described in one of technical problem
The method of ester.
One of in order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: being used to prepare allyl acetate
Catalyst, the catalyst include carrier, active component and co-catalyst；The active component includes metal Pd and Ni metal；
The co-catalyst is alkali metal acetate；The carrier includes carrier substrate and surface covering；The substrate is porous dioxy
SiClx；The coating is bonded in the silica of the substrate surface by modified metal element and by the modified metal element
Binder composition；The modified metal constituent content is 0.1~1.00g/L；The modified metal element is selected from VA metallic element
At least one of with IVB metallic element.
In above-mentioned technical proposal, the VA metallic element preferably is selected from least one of Sb and Bi.
In above-mentioned technical proposal, the IVB metallic element preferably is selected from least one of Ti, Zr and Hf.
In above-mentioned technical proposal, as further preferred, the modified metal element includes Bi and Ti, or including Bi and
Zr；The more preferable modified metal includes Bi, Ti and Zr, or including Sb, Ti and Zr；The most preferably described modified metal includes
Bi, Sb, Ti and Zr.There is in terms of catalyst activity and selectivity preferable synergistic effect between above-mentioned modified metal element.
In above-mentioned technical proposal, the alkali metal acetate is preferably potassium acetate.
In above-mentioned technical proposal, the content of Pd is preferably 1.0~10g/L in the catalyst.
In above-mentioned technical proposal, the content of Cu is preferably 0.1~5.0g/L in the catalyst.
In above-mentioned technical proposal, the content of potassium acetate is preferably 10~120g/L in the catalyst.
In above-mentioned technical proposal, the specific surface and Kong Rong of carrier substrate are not particularly limited, and can all obtain certain technology
Effect.But BET specific surface is 100~500m2It is more excellent when 0.85~1.40ml/g of/g, Kong Rongwei.
To solve above-mentioned technical problem two, technical scheme is as follows: the technical side of one of above-mentioned technical problem
Method for preparing catalyst described in case, includes the following steps:
(1) hydroxide of the modified metal element or oxide and silica solution are mixed to get coating liquid；
(2) above-mentioned coating liquid is coated to porous silica silicon face, dry, roasting obtains the catalyst carrier；
(3) maceration extract of the carrier impregnation compound containing Pd and the compound containing Cu is obtained into catalyst precarsor I；
(4) so that compound containing Pd and compound containing Cu is converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；
(5) sedimentation type is reduced to metal Pd and Ni metal obtains catalyst precarsor III；
(6) co-catalyst solution is impregnated, the catalyst is dried to obtain.
In above-mentioned technical proposal, the roasting of the understanding step (2) based on those skilled in the art is not specially required, roasting
Temperature is preferably 400~600 DEG C, and calcining time is preferably 1~5 hour.
To solve above-mentioned technical problem three, technical scheme is as follows: the synthetic method of allyl acetate, with third
Alkene, acetic acid, oxygen and water are raw material, and reaction obtains allyl acetate in the presence of above-mentioned catalyst.
In above-mentioned technical proposal, the temperature of reaction is preferably 120~150 DEG C, the pressure of reaction be preferably 0.1~
1.0MPa, with molar ratio computing propylene: acetic acid: oxygen: water=1:(0.1~0.3): (0.1~0.3): (0.2~1), raw material volume
Air speed is 1500~2500h-1。
Compared with prior art, it is its surface of silica VA metallic element that key problem in technology of the invention, which is the carrier,
Modification has been carried out with IVB metallic element.Due to the adoption of the above technical scheme instead of conventional carriers, allyl acetate is improved
The activity and selectivity of catalyst.For method for preparing catalyst provided by the invention, key problem in technology is in dioxy
The surface coating modified metallic element of SiClx, the method for coating have very much, can spray, can also be by colloid roller coating, this is this
Known to the those of ordinary skill in field.
The catalyst of above method synthesis and comparative catalyst are evaluated and are counted with laboratory microreactor respectively
Calculate the activity and and selectivity of catalyst.Evaluation method is the loading 30ml catalyst in microreactor, using nitrogen leak test,
After ensuring system without leak source, the flow of propylene is adjusted to 0.82mol/h, the flow set of nitrogen is 0.86mol/h, is risen simultaneously
Temperature puts into the acetic acid of 0.20mol/h and the water of 0.42mol/h, starts after twenty minutes when reaction bed temperature reaches 120 DEG C
Oxygen is thrown, sufficient oxygen is thrown after 30 minutes, the amount of oxygen is 0.125mol/h, air speed 2000h-1, reaction temperature is controlled in reaction process
It is 142 DEG C, reaction pressure 0.68MPa.
The content of each component in gas chromatography analysis reaction product, and the activity and choosing of catalyst is calculated according to the following formula
Selecting property:
The experimental results showed that the activity of allyl acetate catalyst prepared by the present invention reaches 373.32g/Lh, select
Selecting property has reached 94.95%, achieves preferable technical effect.Especially catalyst carrier uses VA metallic element and IVB simultaneously
When at least one of metallic element modified metal element, technical effect more outstanding is achieved.Below by embodiment pair
The present invention is further elaborated.
Specific embodiment
The ball SiO used in specific embodiment2BET specific surface be 198m2/ g, Kong Rongwei 0.99ml/g.
[embodiment 1]
The preparation of carrier: by the bismuth oxide (Bi of 0.54g2O3) powder is sufficiently mixed with 1.0g silica solution and coated
Liquid is uniformly sprayed at coating liquid the spherical SiO that 1.0L diameter is 5.6mm2On carrier, 100 DEG C of dryings, in Muffle furnace 500
DEG C roasting after obtain the catalyst carrier.Measuring Bi content in the carrier through ICP is 0.48g/L.
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd's and 0.37gCu
Chlorine palladium acid, copper chloride solution, obtain maceration extract 590ml.It is immersed in the catalyst carrier and is urged in turning pot
Agent precursor I；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and is immersed on precursor II I, it is dry at 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 373.32g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.95%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
[embodiment 2]
The preparation of carrier: by the titanium dioxide (TiO of 0.80g2) powder and 1.0g silica solution be sufficiently mixed to obtain coating liquid,
Coating liquid is uniformly sprayed at the spherical SiO that 1.0L diameter is 5.6mm2On carrier, 100 DEG C of dryings are roasted at 500 DEG C of Muffle furnace
The catalyst carrier is obtained after burning.Measuring Ti content in the carrier through ICP is 0.48g/L.
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd's and 0.37gCu
Chlorine palladium acid, copper chloride solution, obtain maceration extract 590ml.It is immersed in the catalyst carrier and is urged in turning pot
Agent precursor I；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and is immersed on precursor II I, it is dry at 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 373.16g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.14%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd's and 0.37gCu
Chlorine palladium acid, copper chloride solution, obtain maceration extract 590ml.The spherical shape that 1.0L diameter is 5.6mm is immersed in turning pot
SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and is immersed on precursor II I, it is dry at 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 364.68g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.08%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
The catalyst used by can be seen that the present invention compared with Examples 1 and 2, carrier are that surface is coated with modification
The silicon dioxide ratio of metallic element Bi or Ti use the catalyst of silica supported preparation, the activity and vinegar of catalyst
The selectivity of allyl propionate increases.
[comparative example 2]
For the comparative example of [embodiment 1].
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd's and 0.37gCu
Chlorine palladium acid, copper chloride solution, obtain maceration extract 590ml.The spherical shape that 1.0L diameter is 5.6mm is immersed in turning pot
SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate and 0.75g bismuth acetate (Bi (OAc) will be contained3) be dissolved in pure water, obtain maceration extract 340ml leaching
Stain, in 100 DEG C of dryings, obtains the catalyst on precursor II I.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L, and Bi contains
Measure 0.48g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 364.55g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.11%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
By compared with Example 1 as can be seen that the present invention is coated with modified metal element Bi using carrier for its surface
Silica preparation catalyst than dipping potassium acetate simultaneously impregnate metal containing Bi made of catalyst, the activity of catalyst and
The selectivity of allyl acetate increases.
[comparative example 3]
For the comparative example of [embodiment 1].
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd, containing 0.37gCu and
Chlorine palladium acid, copper chloride and bismuth acetate (Bi (OAc) containing 0.48gBi3) aqueous solution, obtain maceration extract 590ml.By it in turning pot
It is immersed in the spherical SiO that 1.0L diameter is 5.6mm2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and is immersed on precursor II I, it is dry at 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L, and Bi contains
Measure 0.48g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 363.97g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.15%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
By compared with Example 1 as can be seen that the present invention is coated with modified metal element Bi using carrier for its surface
Catalyst made of dipping metal containing Bi while the catalyst of silica preparation is than dipping noble metal, catalyst it is active with
And the selectivity of allyl acetate increases.From comparative example 2,3 and embodiment 1 as can be seen that only in SiO2Surface applies
Covering containing improving the activity and selectivity of catalyst made of metallic element Bi just has good effect, other the step of or
The activity and selectivity that modified metal element Bi catalyst is added in the process does not obtain good effect.
[embodiment 3]
The preparation of carrier: by the antimony oxide (Sb of 0.59g2O3) powder is sufficiently mixed with 1.0g silica solution and coated
Liquid is uniformly sprayed at coating liquid the spherical SiO that 1.0L diameter is 5.6mm2On carrier, 100 DEG C of dryings, in Muffle furnace 500
DEG C roasting after obtain the catalyst carrier.Measuring Sb content in the carrier through ICP is 0.48g/L.
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd's and 0.37gCu
Chlorine palladium acid, copper chloride solution, obtain maceration extract 590ml.It is immersed in the catalyst carrier and is urged in turning pot
Agent precursor I；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and is immersed on precursor II I, it is dry at 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 373.25g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.97%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
[embodiment 4]
The preparation of carrier: by the zirconium hydroxide (Zr (OH) of 0.18g4) powder is sufficiently mixed with 1.0g silica solution and coated
Liquid is uniformly sprayed at coating liquid the spherical SiO that 1.0L diameter is 5.6mm2On carrier, 100 DEG C of dryings, in Muffle furnace 500
DEG C roasting after obtain the catalyst carrier.Measuring Zr content in the carrier through ICP is 0.10g/L.
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd's and 0.37gCu
Chlorine palladium acid, copper chloride solution, obtain maceration extract 590ml.It is immersed in the catalyst carrier and is urged in turning pot
Agent precursor I；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and is immersed on precursor II I, it is dry at 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 372.98g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.06%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
[embodiment 5]
The preparation of carrier: by the hafnium oxide (HfO of 1.18g2) powder and 1.0g silica solution be sufficiently mixed to obtain coating liquid,
Coating liquid is uniformly sprayed at the spherical SiO that 1.0L diameter is 5.6mm2On carrier, 100 DEG C of dryings are roasted at 500 DEG C of Muffle furnace
The catalyst carrier is obtained after burning.Measuring Hf content in the carrier through ICP is 1.00g/L.
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd's and 0.37gCu
Chlorine palladium acid, copper chloride solution, obtain maceration extract 590ml.It is immersed in the catalyst carrier and is urged in turning pot
Agent precursor I；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and is immersed on precursor II I, it is dry at 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 373.29g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.18%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
[embodiment 6]
The preparation of carrier: by the bismuth oxide (Bi of 0.27g and 0.40g2O3), titanium dioxide (TiO2) powder with
1.0g silica solution is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO that 1.0L diameter is 5.6mm2It carries
On body, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of Muffle furnace roastings.Bi content in the carrier is measured through ICP
For 0.24g/L, Ti content is 0.24g/L.
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd's and 0.37gCu
Chlorine palladium acid, copper chloride solution, obtain maceration extract 590ml.It is immersed in the catalyst carrier and is urged in turning pot
Agent precursor I；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and is immersed on precursor II I, it is dry at 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 375.36g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.29%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
Found out on year-on-year basis by embodiment 6 and embodiment 1 and embodiment 2, is improving allyl acetate catalyst activity and choosing
In terms of selecting property, the present invention uses the catalysis that carrier is that its surface is coated with modified metal element ti simultaneously, prepared by the silica of Bi
Agent is only coated with modified metal element ti than carrier or is only coated with catalyst made of modified metal element Bi, catalyst activity with
And the selectivity of allyl acetate is high.This has absolutely proved Ti, Bi therebetween in the activity and selectivity for improving catalyst
Aspect has good synergy.
[embodiment 7]
The preparation of carrier: by the bismuth oxide (Bi of 0.27g and 0.42g2O3), zirconium hydroxide (Zr (OH)4) powder with
1.0g silica solution is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO that 1.0L diameter is 5.6mm2It carries
On body, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of Muffle furnace roastings.Bi content in the carrier is measured through ICP
For 0.24g/L, Zr content is 0.24g/L.
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd's and 0.37gCu
Chlorine palladium acid, copper chloride solution, obtain maceration extract 590ml.It is immersed in the catalyst carrier and is urged in turning pot
Agent precursor I；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and is immersed on precursor II I, it is dry at 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 375.47g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.21%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
[embodiment 8]
The preparation of carrier: by the bismuth oxide (Bi of 0.27g, 0.15g and 0.27g2O3), titanium dioxide (TiO2) and hydrogen
Zirconium oxide (Zr (OH)4) powder and 1.0g silica solution be sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at 1.0L
Diameter is the spherical SiO of 5.6mm2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of Muffle furnace roastings.
Measuring Bi content in the carrier through ICP is 0.24g/L, and Ti content is 0.09g/L, and Zr content is 0.15g/L.
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd's and 0.37gCu
Chlorine palladium acid, copper chloride solution, obtain maceration extract 590ml.It is immersed in the catalyst carrier and is urged in turning pot
Agent precursor I；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and is immersed on precursor II I, it is dry at 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 376.86g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.57%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
Found out on year-on-year basis by embodiment 8 and embodiment 6 and embodiment 7, is improving allyl acetate catalyst activity and choosing
In terms of selecting property, the present invention uses the silica that carrier metal element is that its surface is coated with modified metal element Bi, Ti, Zr simultaneously
The catalyst of preparation is only coated with modified Bi, Ti than carrier or is only coated with catalyst made of modified metal element Bi, Zr, catalyst
Activity and allyl acetate selectivity it is high.This absolutely proved Bi, Ti, Zr three improve catalyst activity and
Selectivity aspect has good synergy.
[embodiment 9]
The preparation of carrier: by the antimony oxide (Sb of 0.30g, 0.15g and 0.27g2O3), titanium dioxide (TiO2) and hydrogen
Zirconium oxide (Zr (OH)4) powder and 1.0g silica solution be sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at 1.0L
Diameter is the spherical SiO of 5.6mm2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of Muffle furnace roastings.
Measuring Sb content in the carrier through ICP is 0.24g/L, and Ti content is 0.09g/L, and Zr content is 0.15g/L.
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd's and 0.37gCu
Chlorine palladium acid, copper chloride solution, obtain maceration extract 590ml.It is immersed in the catalyst carrier and is urged in turning pot
Agent precursor I；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and is immersed on precursor II I, it is dry at 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 376.75g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.68%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
[embodiment 10]
The preparation of carrier: successively by the bismuth oxide (Bi of 0.14g, 0.15g, 0.15g and 0.27g2O3), three oxidation two
Antimony (Sb2O3), titanium dioxide (TiO2) and zirconium hydroxide (Zr (OH)4) powder be sufficiently mixed and coated with 1.0g silica solution
Liquid is uniformly sprayed at coating liquid the spherical SiO that 1.0L diameter is 5.6mm2On carrier, 100 DEG C of dryings, in Muffle furnace 500
DEG C roasting after obtain the catalyst carrier.Measuring Bi content in the carrier through ICP is 0.12g/L, and Sb content is 0.12g/L,
Ti content is 0.09g/L, and Zr content is 0.15g/L.
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.06, containing 3.18gPd's and 0.37gCu
Chlorine palladium acid, copper chloride solution, obtain maceration extract 590ml.It is immersed in the catalyst carrier and is urged in turning pot
Agent precursor I；
After (2) 80 DEG C of dryings, contain 21.5g Na with 105ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing for 24 hours, obtains
To catalyst precarsor II；
It (3) is 10% (with N with solubility2H4·H2O weight ratio meter) it is that 550ml hydrazine hydrate is restored, through washing, 90 DEG C
It is dried to obtain catalyst precarsor III；
(4) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and is immersed on precursor II I, it is dry at 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.18g/L, Cu content 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate:
By 30ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2System is sufficiently purged, system liter
Wen Hou cuts a certain amount of propylene and N2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, investment acetic acid and
Water continues to heat up, and carries out throwing oxygen, and control reaction temperature is 142 DEG C, reaction pressure 0.68MPa；Raw material volume air speed:
2000h-1；Raw material forms: propylene/acetic acid/oxygen/water (molar ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops
Reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 378.93g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.84%.In order to
Convenient for comparing, the main preparation condition of support modification condition, catalyst is listed in table 1, physical property and the catalytic performance column of catalyst
In table 2.
Found out on year-on-year basis by embodiment 10 and embodiment 8 and embodiment 9, is improving allyl acetate catalyst activity and choosing
In terms of selecting property, the present invention uses the dioxy that carrier metal element is that its surface is coated with modified metal element Bi, Sb, Ti, Zr simultaneously
The catalyst of SiClx preparation is only coated with modified Bi, Ti, Zr or is only coated with made of modified metal element sb, Ti, Zr than carrier urges
Agent, the activity of catalyst and the selectivity of allyl acetate are high.This has absolutely proved that Bi, Sb, Ti, Zr are being improved
There is good synergy in terms of the activity and selectivity of catalyst.
Table 1
2 catalyst physical property of table and evaluation data
Claims (10)
1. being used to prepare the catalyst of allyl acetate, the catalyst includes carrier, active component and co-catalyst；The work
Property component includes metal Pd and Ni metal；The co-catalyst is alkali metal acetate；The carrier includes carrier substrate and table
Finishing coat；The substrate is porous silica；The coating is glued by modified metal element and by the modified metal element
The silica binder tied in the substrate surface forms；The modified metal constituent content is 0.10~1.00g/L；It is described
Modifying element is selected from least one of VA metallic element and IVB metallic element.
2. catalyst according to claim 1, it is characterised in that the VA metallic element in Sb and Bi at least one
Kind.
3. catalyst according to claim 1, it is characterised in that the IVB metallic element in Ti, Zr and Hf extremely
Few one kind.
4. catalyst according to claim 1, it is characterised in that the alkali metal acetate is potassium acetate.
5. catalyst according to claim 1, it is characterised in that the content of Pd is 1.0~10.0g/L in catalyst.
6. catalyst according to claim 1, it is characterised in that the content of Cu is 0.1~5.0g/L in catalyst.
7. catalyst according to claim 1, it is characterised in that in the catalyst content of potassium acetate be 10.0~
120.0g/L。
8. being included the following steps: by the preparation method of catalyst described in claim 1
(1) hydroxide of the modified metal element or oxide and silica solution are mixed to get coating liquid；
(2) above-mentioned coating liquid is coated to porous silica silicon face, dry, roasting obtains the catalyst carrier；
(3) maceration extract of the carrier impregnation compound containing Pd and the compound containing Cu is obtained into catalyst precarsor I；
(4) so that compound containing Pd and compound containing Cu is converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；
(5) sedimentation type is reduced to metal Pd and Ni metal obtains catalyst precarsor III；
(6) co-catalyst solution is impregnated, the catalyst is dried to obtain.
9. the synthetic method of allyl acetate, using propylene, acetic acid, oxygen and water as raw material, in claim 1~7 Arbitrary Term institute
Reaction obtains allyl acetate in the presence of stating catalyst.
10. synthetic method according to claim 9, it is characterized in that the temperature of reaction is the pressure of 120~150 DEG C, reaction
For 0.1~1MPa, with molar ratio computing propylene: acetic acid: oxygen: water=1:(0.1~0.3): (0.1~0.3): (0.2~1), it is former
Material volume space velocity is 1500~2500h-1。
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|---|---|---|---|---|
| WO2005066107A1 (en) * | 2004-01-09 | 2005-07-21 | INSTITUT FüR ANGEWANDTE CHEMIE BERLIN-ADLERSHOF E.V. | Solid phase catalyst, associated production method and use in the production of aryl esters |
| CN103055941A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Allyl acetate catalyst and preparation method thereof |
| CN103121955A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing allyl acetate |
| CN103120961A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Propenyl ethanoate catalyst and preparation method thereof |
| CN103121954A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing allyl acetate |
| CN104437670A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of propenyl ethanoate catalyst and synthesis method of propenyl ethanoate |
| CN104549517A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005066107A1 (en) * | 2004-01-09 | 2005-07-21 | INSTITUT FüR ANGEWANDTE CHEMIE BERLIN-ADLERSHOF E.V. | Solid phase catalyst, associated production method and use in the production of aryl esters |
| CN103055941A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Allyl acetate catalyst and preparation method thereof |
| CN103121955A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing allyl acetate |
| CN103120961A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Propenyl ethanoate catalyst and preparation method thereof |
| CN103121954A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing allyl acetate |
| CN104437670A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of propenyl ethanoate catalyst and synthesis method of propenyl ethanoate |
| CN104549517A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and application thereof |
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