CN106582819A - Catalyst for producing allyl acetate - Google Patents
Catalyst for producing allyl acetate Download PDFInfo
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- CN106582819A CN106582819A CN201510674616.1A CN201510674616A CN106582819A CN 106582819 A CN106582819 A CN 106582819A CN 201510674616 A CN201510674616 A CN 201510674616A CN 106582819 A CN106582819 A CN 106582819A
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Abstract
The invention relates to a catalyst for producing allyl acetate, and mainly solves the problem that in the prior art, the catalyst activity and selectivity are low. The catalyst for producing allyl acetate comprises carriers, active constituents and auxiliary catalyst. The active constituents comprise metal Pd and metal Cu. The auxiliary catalyst is base metal acetate. The carriers comprise carrier base material and surface coating. The base material is porous silicon dioxide. The coating comprises modified metal elements and silicon dioxide binder which binds the modified metal elements to the base material surface. The content of the modified metal elements is 0.10-1.00 g/L. The modified elements are selected from either or both of the lanthanide series metal elements or the base metal elements. The catalyst for producing allyl acetate solves the problem that in the prior art, the catalyst activity and selectivity are low, and can be used in the industrial production of allyl acetate.
Description
Technical field
The present invention relates to the synthetic method of the preparation method of allyl acetate catalyst, catalyst and allyl acetate.
Background technology
Allyl acetate is a kind of colourless flammable liquid, is slightly soluble in water, is soluble in alcohol and ether, can be dissolved in acetone, it as a kind of important industrial chemicals, mainly for the production of propenyl and epoxychloropropane.
The eighties in 20th century, Japanese Showa electrician and the academy of sciences of the former Soviet Union propose that, using acetoxylation technology, with propylene, oxygen and acetic acid as raw material, Fixed Bed Gas Phase reaction is prepared in the reaction of allyl acetate, with SiO in the presence of palladium and co-catalyst2、Al2O3Or SiO2And Al2O3The mixture of composition is carrier, is loaded with Pd, Cu and potassium acetate, and catalyst of the Pd and Cu in eggshell type distribution has been well known to those of ordinary skill in the art.The preparation method of the catalyst is via US3, and 917,676 is (entitled：Process for producing ally acetate) it is disclosed, the mixed liquor that precious metals pd and Cu will be contained is immersed on carrier, after dried process, the Pd and Cu of free state are solidificated in into carrier surface and the Pd and Cu of active metallic state is formed, then the catalyst is obtained Jing after co-catalyst KOAc process is dried.The activity and selectivity of the catalyst that the method is obtained is relatively low.
Many scholars are studied the active component of the noble metal catalyst, co-catalyst.Research thinks that the Main By product of the reaction is generated by propylene deep oxidation, and this was both relevant to the adsorpting type of reactant with catalyst, and related to the Active components distribution of catalyst.Zeng Xianjun etc. exists《Propylene aoxidizes the research of acetate propylene ester catalyst processed》Then think in one text, propylene is in Pd-K/SiO2On absorption and toluene in Pd-Sn-K/SiO2Oxidation on catalyst is similar, and Shu Qingyu etc. exists《Pd-Sn-K/SiO2Toluene gas phase Acetoxylation reaction on catalyst》Propose toluene gas phase Acetoxylation in one text to react in Pd-Sn-K/SiO2In activation process on catalyst, methyl c h bond is dissociated into ratedeterming step, and metallic state palladium becomes most important component in catalyst, the presence of KOAc improves the activation of c h bond.
Liang Zhong etc. exists《Adsorb the effect of oxygen and Lattice Oxygen in selective oxidation of n -butane》Think that Lattice Oxygen is conducive to the oxygen of selective oxidation, ADSORPTION STATE to be conducive to deep oxidation, therefore the concentration of catalytic surface Lattice Oxygen should be improved in the reaction of propylene Acetoxylation.Zhao Zhenxing etc. exists《Ethene gas phase Acetoxylation reaction mechanism and dynamics research》In propose ethene gas phase Acetoxylation reaction mechanism, they think the oxygen of absorption most advantageously molecular state of the oxygen on catalyst surface, and the oxygen of molecular state is to participate in acetylizad oxygen source, Pd-SiO2Catalyst activity component Pd, the acetic acid of physical absorption the acetic acid of chemisorbed is changed, so as to the oxygen with molecular state is combined generation allyl acetate.
In addition both at home and abroad many scholars think that the selectivity of allyl acetate catalyst is relevant with the heat of adsorption of propylene, and for example Han Y F etc. exist《A kinetic study of acetate synthesis over Pd-based catalysts:kinetics of vinyl acetate synthesis over Pd-Au/SiO2catalysts》With during Li Ming etc.《Micro-matter tracer technical research Pd-Cu/SiO2Adsorption》In it is also proposed that, the oxidation activity that metallic copper, tin etc. advantageously reduce Pd surface adsorbed oxygens is introduced, so as to improve the selectivity of oxidation.
The content of the invention
One of the technical problem to be solved is the not high problem of the allyl acetate catalyst activity and selectivity synthesized in prior art.There is provided a kind of catalyst for producing allyl acetate, the characteristics of the catalyst has high-activity high-selectivity.
The two of the technical problem to be solved are the preparation methods of one of technical problem catalyst.
The three of the technical problem to be solved are the methods for synthesizing allyl acetate using one of the technical problem catalyst.
In order to solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：For producing allyl acetate catalyst, 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 face coat；The base material is porous silica；The coating is constituted 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 0.1～1.00g/L；At least one of the modified metal element in lanthanide element and alkali earth metal.
In above-mentioned technical proposal, the lanthanide element preferably is selected from least one in La, Ce, Pr, Sm and Eu.
In above-mentioned technical proposal, the alkali earth metal preferably is selected from least one in Be, Mg, Ca, Sr and Ba.
In above-mentioned technical proposal, used as further preferred, the modified metal element includes La and Sr, or including Ce and Sr；More preferably described modified metal includes La, Ce and Sr, or including La, Ce and Be；Most preferably described modified metal includes La, Ce, Sr and Be.Have in terms of catalyst activity and selectivity between above-mentioned modified metal element and preferably act synergistically.
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 pore volume of carrier substrate are not particularly limited, all can obtain can be good technique effect.But BET specific surfaces are 100～500m2/ g, pore volume is more excellent when being 0.85～1.40ml/g.
To solve the two of above-mentioned technical problem, technical scheme is as follows：Method for preparing catalyst described in the technical scheme of one of above-mentioned technical problem, comprises the steps：
(1) hydroxide or oxide of the modified metal element and Ludox are mixed to get into coating liquid；
(2) above-mentioned coating liquid is coated to into porous silica silicon face, dry, roasting obtains the catalyst carrier；
(3) the carrier impregnation compound containing Pd and maceration extract containing Cu compounds are obtained into catalyst precarsor I；
(4) make compound containing Pd and compound containing Cu be converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；
(5) compound state Pd and compound state Cu in the sedimentation type is reduced to into metal Pd and Ni metal obtains catalyst precarsor III；
(6) co-catalyst solution is impregnated, is dried to obtain the catalyst.
In above-mentioned technical proposal, do not specially required based on the roasting of the understanding step (2) of those skilled in the art, sintering temperature is preferably 400～600 DEG C, and roasting time is preferably 1～5 hour.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of allyl acetate, with propylene, acetic acid, oxygen and water as raw material, reaction in the presence of catalyst any one of the technical scheme in one of above-mentioned technical problem obtains allyl acetate.
In above-mentioned technical proposal, the temperature of reaction be preferably 120～150 DEG C, the pressure of reaction be preferably 0.1～1.0MPa, with the preferred propylene of molar ratio computing:Acetic acid:Oxygen:Water=1:(0.1～0.3):(0.1～0.3):(0.2～1), raw material volume air speed is preferably 1500～2500h-1。
Compared with prior art, key problem in technology of the invention be the carrier be that silica its surface lanthanide element and alkali earth metal have carried out modification.Due to replacing conventional carriers using above-mentioned technical proposal, the activity and selectivity of allyl acetate catalyst is improve.For the method for preparing catalyst that the present invention is provided, its key problem in technology is to coat modified metal element in silica surface, and the method for coating has a lot, can spray, it is also possible to which, by colloid roller coating, this is well known for ordinary skill in the art.
The catalyst of said method synthesis and comparative catalyst are evaluated respectively and are calculated activity and and the selectivity of catalyst with laboratory microreactor.Evaluation method is the loading 30ml catalyst in microreactor, using nitrogen leak test, it is ensured that after system is without leak source, the flow of propylene is adjusted to into 0.82mol/h, the flow set of nitrogen is 0.86mol/h, heat up simultaneously, when reaction bed temperature reaches 120 DEG C, put into the acetic acid of 0.20mol/h and the water of 0.42mol/h, start to throw oxygen after 20 minutes, sufficient oxygen is thrown after 30 minutes, the amount of oxygen is 0.125mol/h, and air speed is 2000h-1, controlling reaction temperature is 142 DEG C in course of reaction, reaction pressure 0.68MPa.
The content of each component in gas chromatography analysis product, and calculate the activity and selectivity of catalyst by following equation：
Test result indicate that, the activity of the allyl acetate catalyst prepared by the present invention reaches 373.45g/Lh, has selectively reached 94.97%, achieves preferable technique effect.Especially catalyst carrier uses at least one modified metal element in lanthanide element and alkali earth metal simultaneously when, more prominent technique effect is achieved.Below by embodiment, the present invention is further elaborated.
Specific embodiment
The ball SiO adopted in specific embodiment2BET specific surfaces be 198m2/ g, pore volume is 0.99ml/g.
【Embodiment 1】
The preparation of carrier：By the lanthanum hydroxide (La (OH) of 0.70g3) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, and coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.51g/L that Jing ICP determine La contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.45g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.97%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 2】
The preparation of carrier：Strontium oxide strontia (SrO) powder of 0.61g and 1.0g Ludox are sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.51g/L that Jing ICP determine Sr contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.28g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.20%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.The spherical SiO of a diameter of 5.6mm of 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas-chromatography-GC-MS (GC-MASS).
The activity for being computed the catalyst is 364.64g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.12%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Can be seen that by comparing with 2 with embodiment 1, the catalyst that the present invention is used, its carrier uses the catalyst of silica supported preparation, the activity of catalyst and the selectivity of allyl acetate to increase for the silicon dioxide ratio that surface scribbles modified metal element La or Sr.
【Comparative example 2】
For【Embodiment 1】Comparative example.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.The spherical SiO of a diameter of 5.6mm of 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates and 1.49g lanthanum acetates (La (OAc) will be contained3·5H2O) it is dissolved in pure water, obtains maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtains the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L, La contents 0.51g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas-chromatography-GC-MS (GC-MASS).
The activity for being computed the catalyst is 364.67g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.09%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
By can be seen that compared with Example 1, the present invention impregnates catalyst made by metallic element compound containing La simultaneously using the catalyst that carrier is the silica preparation that its surface scribbles modified metal element La than dipping potassium acetate, and the selectivity of the active and allyl acetate of catalyst increases.
【Comparative example 3】
For【Embodiment 1】Comparative example.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, containing 3.18gPd, the chlorine palladium acid containing 0.37gCu and containing 0.51gLa, copper chloride and lanthanum acetate (La (OAc)3·5H2O) the aqueous solution, obtains maceration extract 590ml.The spherical SiO of a diameter of 5.6mm of 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L, La contents 0.51g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas-chromatography-GC-MS (GC-MASS).
The activity for being computed the catalyst is 364.60g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.15%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
By can be seen that compared with Example 1, the present invention is increased using the catalyst that carrier is the silica preparation that its surface scribbles modified metal element La than catalyst made by dipping metallic element compound containing La while dipping noble metal, the activity of catalyst and the selectivity of allyl acetate.From comparative example 2,3 and embodiment 1 as can be seen that only in SiO2Surface coating just has good effect containing the activity and selectivity of catalyst made by improving metallic element La, the step of other or during add the activity and selectivity of modified metal element La catalyst and obtain good effect.
【Embodiment 3】
The preparation of carrier：By the cerium hydroxide (Ce (OH) of 0.76g4) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, and coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.51g/L that Jing ICP determine Ce contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.47g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.96%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 4】
The preparation of carrier：By the samarium sesquioxide (Sm of 0.60g2O3) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, and coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.51g/L that Jing ICP determine Sm contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.41g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.08%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 5】
The preparation of carrier：Beryllium oxide (BeO) powder of 1.42g and 1.0g Ludox are sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.51g/L that Jing ICP determine Be contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas-chromatography-GC-MS (GC-MASS).
The activity for being computed the catalyst is 373.23g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.22%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 6】
The preparation of carrier：Magnesia (MgO) powder of 0.85g and 1.0g Ludox are sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.51g/L that Jing ICP determine Mg contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.19g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.24%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 7】
The preparation of carrier：By the calcium hydroxide (Ca (OH) of 0.19g2) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, and coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.10g/L that Jing ICP determine Ca contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 372.86g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 94.95%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 8】
The preparation of carrier：By the barium hydroxide (Ba (OH) of 2.30g2) powder and 1.0g Ludox be sufficiently mixed and obtain coating liquid, and coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 1.00g/L that Jing ICP determine Ba contents in the carrier.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 373.27g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.26%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 9】
The preparation of carrier：By the lanthanum hydroxide (La (OH) of 0.42g and 0.25g3), the powder of strontium oxide strontia (SrO) and 1.0g Ludox be sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.30g/L that Jing ICP determine La contents in the carrier, and Sr contents are 0.21g/L.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.38g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.56%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis with embodiment 1 and embodiment 2 by embodiment 9, in terms of allyl acetate catalyst activity and selectivity is improved, the present invention is its surface at the use of carrier while catalyst prepared by the silica for scribbling modified metal element La, Sr only scribbles modified metal element La or only scribbles catalyst made by modified metal elements Sr than carrier, and the selectivity of the active and allyl acetate of catalyst is high.This has absolutely proved that La, Sr have therebetween good synergy in terms of the activity and selectivity of catalyst is improved.
【Embodiment 10】
The preparation of carrier：By the cerium hydroxide (Ce (OH) of 0.42g and 0.25g4), the powder of strontium oxide strontia (SrO) and 1.0g Ludox be sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.30g/L that Jing ICP determine Ce contents in the carrier, and Sr contents are 0.21g/L.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.51g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.48%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 11】
The preparation of carrier：By the lanthanum hydroxide (La (OH) of 0.21g, 0.23g, 0.25g3), cerium hydroxide (Ce (OH)4), the powder of strontium oxide strontia (SrO) and 1.0g Ludox be sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.15g/L that Jing ICP determine La contents in the carrier, and Ce contents are 0.15g/L, and Sr contents are 0.21g/L.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 376.93g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.84%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis with embodiment 9 and embodiment 10 by embodiment 11, in terms of allyl acetate catalyst activity and selectivity is improved, the present invention is its surface at the use of carrier metal element while the catalyst for scribbling the silica preparation of modified metal element La, Ce, Sr only scribbles modified La, Sr or only scribbles catalyst made by modified metal Elements C e, Sr than carrier, and the selectivity of the active and allyl acetate of catalyst is high.This has absolutely proved that La, Ce, Sr three has good synergy in terms of the activity and selectivity of catalyst is improved.
【Embodiment 12】
The preparation of carrier：By the lanthanum hydroxide (La (OH) of 0.21g, 0.23g, 0.70g3), cerium hydroxide (Ce (OH)4), the powder of beryllium oxide (BeO) and 1.0g Ludox be sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.15g/L that Jing ICP determine La contents in the carrier, and Ce contents are 0.15g/L, and Be contents are 0.21g/L.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas-chromatography-GC-MS (GC-MASS).
The activity for being computed the catalyst is 376.98g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 95.73%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 13】
The preparation of carrier：By the lanthanum hydroxide (La (OH) of 0.21g, 0.23g, 0.16g, 0.23g3), cerium hydroxide (Ce (OH)4), strontium oxide strontia (SrO), the powder of beryllium oxide (BeO) and 1.0g Ludox be sufficiently mixed and obtain coating liquid, coating liquid is uniformly sprayed at the spherical SiO of a diameter of 5.6mm of 1.0L2On carrier, 100 DEG C of dryings obtain the catalyst carrier after 500 DEG C of roastings of Muffle furnace.It is 0.15g/L that Jing ICP determine La contents in the carrier, and Ce contents are 0.15g/L, and Sr contents are 0.13g/L, and Be contents are 0.08g/L.
The preparation of catalyst：
(1) it is 1.06 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.18gPd and 0.37gCu, copper chloride solution obtain maceration extract 590ml.It is immersed in pot is turned in the catalyst carrier and obtains catalyst precarsor I；
After (2) 80 DEG C of dryings, with 105ml 21.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and is aged 24h, obtains catalyst precarsor II；
(3) it is 10% (with N with solubility2H4·H2O weight ratio meters) reduced for 550ml hydrazine hydrates, Jing washing, 90 DEG C be dried to obtain catalyst precarsor III；
(4) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 340ml and be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.18g/L, Cu contents 0.37g/L, acetic acid potassium content 33g/L.
The synthesis of allyl acetate：
By 30ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, a certain amount of propylene and N is cut2Mixture, and be warming up to reaction bed temperature up to after 120 DEG C, input acetic acid and water, continue to heat up, carry out throwing oxygen, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.68MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Propylene/acetic acid/oxygen/water (mol ratio)=1/0.18/0.2/0.3, after sustained response 100h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas-chromatography-GC-MS (GC-MASS).
The activity for being computed the catalyst is 380.04g/Lh, and the selectivity of Dichlorodiphenyl Acetate allyl ester is 96.02%.For the ease of comparing, the main preparation condition of support modification condition, catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis with embodiment 11 and embodiment 12 by embodiment 13, in terms of allyl acetate catalyst activity and selectivity is improved, the present invention is its surface at the use of carrier metal element while the catalyst for scribbling the silica preparation of modified metal element La, Ce, Sr, Be only scribbles modified La, Ce, Sr or only scribbles catalyst made by modified metal element La, Ce, Be than carrier, and the selectivity of the active and allyl acetate of catalyst is high.This has absolutely proved that La, Ce, Sr, Be have good synergy in terms of the activity and selectivity of catalyst is improved.
Table 1
The catalyst physical property of table 2 and evaluating data
Claims (10)
1. it is used to produce the catalyst of allyl acetate, the catalyst includes carrier, active component and co-catalyst；It is described
Active component includes metal Pd and Ni metal；The co-catalyst is alkali metal acetate；The carrier includes carrier substrate
And face coat；The base material is porous silica；The coating is by modified metal element and by the modified metal
Element is bonded in the silica binder composition of the substrate surface；The modified metal constituent content be 0.10～
1.00g/L；At least one of the modifying element in lanthanide element and alkali earth metal.
2. catalyst according to claim 1, it is characterised in that the lanthanide element is selected from La, Ce, Pr, Sm
With at least one in Eu.
3. catalyst according to claim 1, it is characterised in that the alkali earth metal is selected from Be, Mg, Ca, Sr
With at least one in Ba.
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 the content of potassium acetate is 10.0～120.0 in the catalyst
g/L。
8., by the preparation method of the catalyst described in claim 1, comprise the steps：
(1) hydroxide or oxide of the modified metal element and Ludox are mixed to get into coating liquid；
(2) above-mentioned coating liquid is coated to into porous silica silicon face, dry, roasting obtains the catalyst carrier；
(3) the carrier impregnation compound containing Pd and maceration extract containing Cu compounds are obtained into catalyst precarsor I；
(4) make compound containing Pd and compound containing Cu be converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；
(5) compound state Pd and compound state Cu in the sedimentation type is reduced to into metal Pd and Ni metal obtains catalyst precarsor
III；
(6) co-catalyst solution is impregnated, is dried to obtain the catalyst.
9. the synthetic method of allyl acetate, with propylene, acetic acid, oxygen and water as raw material, in claim 1～7 Arbitrary Term institute
State reaction in the presence of catalyst and obtain allyl acetate.
10. synthetic method according to claim 9, it is characterized in that the temperature reacted be 120～150 DEG C, the pressure of reaction be
0.1～1MPa, with molar ratio computing propylene:Acetic acid:Oxygen:Water=1:(0.1～0.3):(0.1～0.3):(0.2～1), raw material
Volume space velocity is 1500～2500h-1。
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| 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 |
| CN104437622A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Allyl acetate catalyst and preparation method of allyl acetate catalyst |
| 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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