CN106582855B - Catalyst for preparing allyl acetate - Google Patents

Catalyst for preparing allyl acetate Download PDF

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CN106582855B
CN106582855B CN201510675576.2A CN201510675576A CN106582855B CN 106582855 B CN106582855 B CN 106582855B CN 201510675576 A CN201510675576 A CN 201510675576A CN 106582855 B CN106582855 B CN 106582855B
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acetate
metal element
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CN106582855A (en
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查晓钟
杨运信
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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China Petrochemical Corp
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Abstract

The invention relates to a catalyst for preparing allyl acetate, which mainly solves the problem that the catalyst in the prior art is low in activity and selectivity. The catalyst for preparing allyl acetate is adopted, and comprises a carrier, an active component and a cocatalyst; the active component comprises metal Pd and metal Cu; the cocatalyst is alkali metal acetate; the carrier comprises a carrier substrate and a surface coating; the substrate is porous silicon dioxide; the coating consists of a modified metal element and a silicon dioxide binder for binding the modified metal element on the surface of the base material; the content of the modified metal element is 0.10-1.00 g/L; the technical scheme that the modification element is at least one of IIIB metal element and IIIA metal element better solves the problem and can be used for industrial production of allyl acetate.

Description

Catalyst for preparing allyl acetate
Technical Field
The invention relates to an allyl acetate catalyst, a preparation method of the catalyst and a synthesis method of allyl acetate.
Background
Allyl acetate is a colorless flammable liquid, is slightly soluble in water, is easily soluble in alcohol and ether, can be dissolved in acetone, is used as an important chemical raw material, and is mainly used for producing allyl alcohol and epoxy chloropropane.
In the 80 s of the 20 th century, the institute of Showa electrician and the former Soviet Union, proposed the preparation of allyl acetate by the fixed bed gas phase reaction of propylene, oxygen and acetic acid as raw materials using the technique of acetyl oxidation in the presence of palladium and a promoter2、Al2O3Or SiO2And Al2O3The catalyst of which the mixture is a carrier and is loaded with Pd, Cu and potassium acetate, and the Pd and Cu are distributed in an eggshell shape is well known to those skilled in the art. The preparation method of the catalyst is disclosed in US3, 917, 676 (titled: Process for producing all acetate), namely, a mixed solution containing noble metals Pd and Cu is soaked on a carrier, after drying treatment, free Pd and Cu are solidified on the surface of the carrier to form active metal Pd and Cu, and then the active metal Pd and Cu are treated by a promoter KOAc and dried to obtain the catalyst. The catalyst obtained by the method has low activity and selectivity.
Activity of the noble metal catalyst by many scholarsThe components and the cocatalyst were studied. It is believed that the main by-product of the reaction is formed by the deep oxidation of propylene, which is related to both the type of adsorption of the reactants by the catalyst and the distribution of the active components of the catalyst. Zengxianjun et al in the article of research on catalyst for preparing propylene acetate by propylene oxidation2Adsorption on toluene on Pd-Sn-K/SiO2The oxidation phase on the catalyst is similar, while Tuqingyu et al are in Pd-Sn-K/SiO2The toluene gas phase oxyacetylation reaction on the catalyst is proposed in the text of Pd-Sn-K/SiO2During the activation process on the catalyst, the dissociation of methyl C-H bond is a speed control step, the metallic palladium becomes the most important component in the catalyst, and the existence of KOAc improves the activation of the C-H bond.
The role of adsorbing oxygen and lattice oxygen in n-butane selective oxidation, according to Nissan faith et al, suggests that lattice oxygen favors selective oxidation and that adsorbed oxygen favors deep oxidation, so that the concentration of lattice oxygen on the catalytic surface should be increased in the propylene oxyacetylation reaction. The ethylene vapor phase oxyacetylation reaction mechanism is proposed by Zhao Zheng et al in "research on ethylene vapor phase oxyacetylation reaction mechanism and kinetics", who believe that adsorption of oxygen on the surface of the catalyst is most advantageous for molecular oxygen, which is an oxygen source participating in acetylation, Pd-SiO2The catalyst active component Pd converts the physically adsorbed acetic acid into the chemically adsorbed acetic acid, so that the physically adsorbed acetic acid is combined with molecular oxygen to generate allyl acetate.
In addition, many scholars at home and abroad believe that the selectivity of allyl acetate catalysts is related to the heat of adsorption of propylene, such as Han Y F et al, A kinetic study of acetate synthesis over Pd-based catalysts, kinetics of vinyl acetate synthesis over Pd-Au/SiO2Researches on Pd-Cu/SiO by micro adsorption calorimetry from catalysts and Li Ming Shi2The introduction of copper, tin and the like is also proposed to be beneficial to reducing the oxidation activity of Pd surface adsorbed oxygen, thereby improving the oxidation selectivity.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem that the allyl acetate catalyst synthesized in the prior art is low in activity and selectivity. Provides a catalyst for preparing allyl acetate, which has the characteristics of high activity and high selectivity.
The second technical problem to be solved by the present invention is a method for preparing the catalyst.
The invention also provides a method for synthesizing allyl acetate by using the catalyst.
In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: a catalyst for preparing allyl acetate, which comprises a carrier, an active component and a cocatalyst; the active component comprises metal Pd and metal Cu; the cocatalyst is alkali metal acetate; the carrier comprises a carrier substrate and a surface coating; the substrate is porous silicon dioxide; the coating consists of a modified metal element and a silicon dioxide binder for binding the modified metal element on the surface of the base material; the content of the modified metal element is 0.1-1.00 g/L; the modified metal element is at least one selected from IIIB metal element and IIIA metal element.
In the above technical solution, the IIIB metal element is preferably at least one selected from Sc, Y, La, Pr, and Ce.
In the above technical solution, the IIIA metal element is preferably at least one selected from Al, Ga, and In.
In the above technical solution, as a further preferred aspect, the modified metal element includes Sc and Ga, or includes Y and Ga; more preferably, the modified metal comprises Sc, Y and Ga, or comprises Sc, Y and In; most preferably, the modifying metals include Sc, Y, Ga and In. The modified metal elements have better synergistic effect on the aspects of catalyst activity and selectivity.
In the above technical solution, the alkali metal acetate is preferably potassium acetate.
In the technical scheme, the content of Pd in the catalyst is preferably 1.0-10 g/L.
In the technical scheme, the content of Cu in the catalyst is preferably 0.1-5.0 g/L.
In the technical scheme, the content of potassium acetate in the catalyst is preferably 10-120 g/L.
In the above-mentioned technical means, the specific surface and pore volume of the carrier base material are not particularly limited, and excellent technical effects can be obtained. But has a BET specific surface area of 100 to 500m2The pore volume is preferably 0.85 to 1.40 ml/g.
To solve the second technical problem, the technical solution of the present invention is as follows: the preparation method of the catalyst in the technical scheme of one of the technical problems comprises the following steps:
(1) mixing the hydroxide or oxide of the modified metal element with silica sol to obtain coating liquid;
(2) coating the coating liquid on the surface of porous silicon dioxide, drying and roasting to obtain the catalyst carrier;
(3) impregnating the carrier with impregnation liquid containing a Pd compound and a Cu compound to obtain a catalyst precursor I;
(4) converting a Pd-containing compound and a Cu-containing compound into a precipitate type by using an alkaline solution to obtain a catalyst precursor II;
(5) reducing the combined Pd and the combined Cu in the precipitation type into metal Pd and metal Cu to obtain a catalyst precursor III;
(6) dipping a cocatalyst solution, and drying to obtain the catalyst.
In the above technical scheme, the roasting in step (2) is not particularly required based on the understanding of the skilled person, the roasting temperature is preferably 400 to 600 ℃, and the roasting time is preferably 1 to 5 hours.
To solve the third technical problem, the technical scheme of the invention is as follows: the synthesis method of allyl acetate takes propylene, acetic acid, oxygen and water as raw materials, and allyl acetate is obtained by reaction in the presence of any one of the catalysts in the technical scheme of one of the technical problems.
In the above technical scheme, the reaction temperature is preferably 120 to 150 ℃, the reaction pressure is preferably 0.1 to 1.0MPa, the molar ratio of propylene, acetic acid, oxygen, water is preferably (0.1 to 0.3), (0.2 to 1),the preferred volume space velocity of the raw material is 1500-2500 h-1。
Compared with the prior art, the technical key point of the invention is that the carrier is silicon dioxide, and the surface of the carrier is modified by IIIB metal elements and IIIA metal elements. Due to the adoption of the technical scheme to replace the traditional carrier, the activity and the selectivity of the allyl acetate catalyst are improved. The technical key to the preparation method of the catalyst provided by the invention is to coat the modified metal element on the surface of the silica, and the coating methods are various and can be spray coating or colloid roll coating, which is well known to those skilled in the art.
The catalysts synthesized by the above-described method and the comparative catalysts were evaluated with a laboratory microreactor and the activity and selectivity of the catalysts were calculated, respectively. The evaluation method comprises the steps of filling 30ml of catalyst into a micro-reactor, adopting nitrogen to test leakage, adjusting the flow rate of propylene to 0.82mol/h after ensuring that a system has no leakage point, setting the flow rate of nitrogen to 0.86mol/h, simultaneously raising the temperature, adding 0.20mol/h of acetic acid and 0.42mol/h of water when the temperature of a catalyst bed layer reaches 120 □, starting oxygen adding after 20 minutes, adding enough oxygen after 30 minutes, wherein the amount of oxygen is 0.125mol/h, and the space velocity is 2000h-1The reaction temperature is controlled to be 142 □ and the reaction pressure is controlled to be 0.68MPa in the reaction process.
The contents of the components in the reaction product were analyzed by gas chromatography, and the activity and selectivity of the catalyst were calculated according to the following formulas:
Figure BDA0000824285130000041
Figure BDA0000824285130000042
experimental results show that the activity of the allyl acetate catalyst prepared by the invention reaches 373.37 g/L.h, the selectivity reaches 94.96%, and a good technical effect is achieved. Particularly, when the catalyst carrier simultaneously uses at least one modified metal element of IIIB metal element and IIIA metal element, more outstanding technical effect is obtained. The invention is further illustrated by the following examples.
Detailed Description
Spherical SiO used in the detailed description2BET specific surface area of 198m2The pore volume is 0.99 ml/g.
[ example 1 ]
Preparation of the carrier: 0.77g of dicris (Sc) oxide2O3) Mixing the powder with 1.0g silica sol to obtain coating solution, and uniformly spraying the coating solution on 1.0L spherical SiO with diameter of 5.6mm2Drying the carrier at 100 ℃, and roasting the carrier in a muffle furnace at 500 ℃ to obtain the catalyst carrier. The Sc content of the carrier was determined by ICP to be 0.50 g/L.
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the catalyst precursor I on the catalyst carrier in a rotary pot to obtain a catalyst precursor I;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating to catalyst bed temperature of 120 □, adding acetic acid and water, heating, adding oxygen, and controlling reactionThe reaction temperature is 142 □, and the reaction pressure is 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 373.37 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 94.96%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
[ example 2 ]
Preparation of the carrier: 0.68g of gallium sesquioxide (Ga)2O3) Mixing the powder with 1.0g silica sol to obtain coating solution, and uniformly spraying the coating solution on 1.0L spherical SiO with diameter of 5.6mm2Drying the carrier at 100 ℃, and roasting the carrier in a muffle furnace at 500 ℃ to obtain the catalyst carrier. The Ga content of the carrier was determined by ICP to be 0.50 g/L.
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the catalyst precursor I on the catalyst carrier in a rotary pot to obtain a catalyst precursor I;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 □, adding acetic acid and water, continuously heating, adding oxygen, and controlling the reaction temperature to be 142 □ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 373.21 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.22%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
[ COMPARATIVE EXAMPLE 1 ]
Are comparative examples of [ example 1 ] and [ example 2 ].
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the mixture in 1.0L of spherical SiO with the diameter of 5.6mm in a rotary pot2Obtaining a catalyst precursor I on the carrier;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 □, adding acetic acid and water, continuously heating, adding oxygen, and controlling the reaction temperature to be 142 □ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 364.61 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 94.10%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
As can be seen from comparison with examples 1 and 2, the catalyst used in the present invention has a carrier of silica coated with a modified metal element Sc or Ga, and the catalyst activity and allyl acetate selectivity are improved as compared with the catalyst prepared by using silica as a carrier.
[ COMPARATIVE EXAMPLE 2 ]
Is a comparative example of [ example 1 ].
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the mixture in 1.0L of spherical SiO with the diameter of 5.6mm in a rotary pot2Obtaining a catalyst precursor I on the carrier;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2The solution of O is fullMixing and aging for 24h to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) a mixture of 33g of potassium acetate and 3.67g of scandium acetate (Sc (OAc))3·6H2O) was dissolved in pure water to obtain 340ml of an impregnation solution, which was then impregnated into the precursor III and dried at 100 ℃.
The Pd content of the catalyst is 3.18g/L, the Cu content is 0.37g/L, the potassium acetate content is 33g/L and the Sc content is 0.50g/L through ICP determination.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 □, adding acetic acid and water, continuously heating, adding oxygen, and controlling the reaction temperature to be 142 □ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 364.56 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 94.03%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
It can be seen from the comparison with example 1 that the catalyst prepared by using silica having a carrier coated with a modified metallic element Sc on the surface thereof has improved activity and allyl acetate selectivity compared with the catalyst prepared by impregnating a compound containing a Sc metallic element with potassium acetate.
[ COMPARATIVE EXAMPLE 3 ]
Is a comparative example of [ example 1 ].
Preparation of the catalyst:
(1) sodium bicarbonate pH adjuster and water as solvent to make pH 1.06, 3.18gPd, 0.37gCu, 0.50gSc chloropalladic acid, cupric chloride and scandium acetate (Sc (OAc)3·6H2O) aqueous solution to obtain 590ml of an impregnation solution. Dipping the mixture in 1.0L of spherical SiO with the diameter of 5.6mm in a rotary pot2Obtaining a catalyst precursor I on the carrier;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The Pd content of the catalyst is 3.18g/L, the Cu content is 0.37g/L, the potassium acetate content is 33g/L and the Sc content is 0.50g/L through ICP determination.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 □, adding acetic acid and water, continuously heating, adding oxygen, and controlling the reaction temperature to be 142 □ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 364.69 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 94.02%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
It can be seen from the comparison with example 1 that the catalyst prepared by using silica having a modified metal element Sc coated on the surface thereof as a carrier according to the present invention has improved activity of the catalyst and allyl acetate selectivity as compared with the catalyst prepared by impregnating a Sc-containing metal element compound with a noble metal. As can be seen from comparative examples 2 and 3 and example 1, only in SiO2The surface coating of the catalyst containing the modified metal element Sc has good effects on improving the activity and selectivity of the catalyst, and the activity and selectivity of the catalyst containing the modified metal element Sc in other steps or processes do not have good effects.
[ example 3 ]
Preparation of the carrier: 0.64g of yttrium oxide (Y)2O3) Mixing the powder with 1.0g silica sol to obtain coating solution, and uniformly spraying the coating solution on 1.0L spherical SiO with diameter of 5.6mm2Drying the carrier at 100 ℃, and roasting the carrier in a muffle furnace at 500 ℃ to obtain the catalyst carrier. The Y content of the carrier was determined to be 0.50g/L by ICP.
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the catalyst precursor I on the catalyst carrier in a rotary pot to obtain a catalyst precursor I;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 □, adding acetic acid and water, continuously heating, adding oxygen, and controlling the reaction temperature to be 142 □ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 373.42 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 94.99%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
[ example 4 ]
Preparation of the carrier: 0.69g of lanthanum hydroxide (La (OH)3) Mixing the powder with 1.0g silica sol to obtain coating solution, and uniformly spraying the coating solution on 1.0L spherical SiO with diameter of 5.6mm2Drying the carrier at 100 ℃, and roasting the carrier in a muffle furnace at 500 ℃ to obtain the catalyst carrier. The La content in the carrier was determined by ICP to be 0.50 g/L.
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the catalyst precursor I on the catalyst carrier in a rotary pot to obtain a catalyst precursor I;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (or less)N2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 □, adding acetic acid and water, continuously heating, adding oxygen, and controlling the reaction temperature to be 142 □ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 373.40 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.01%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
[ example 5 ]
Preparation of the carrier: 0.59g of praseodymium oxide (Pr)2O3) Mixing the powder with 1.0g silica sol to obtain coating solution, and uniformly spraying the coating solution on 1.0L spherical SiO with diameter of 5.6mm2Drying the carrier at 100 ℃, and roasting the carrier in a muffle furnace at 500 ℃ to obtain the catalyst carrier. The Pr content of the carrier was determined by ICP to be 0.50 g/L.
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the catalyst precursor I on the catalyst carrier in a rotary pot to obtain a catalyst precursor I;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, adding acetic acid and water, continuing heating, adding oxygen, controlling the reaction temperature to be 142 ℃ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 373.44 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.03%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
[ example 6 ]
Preparation of the carrier: 0.29g of aluminum hydroxide (Al (OH))3) Mixing the powder with 1.0g of silica sol to obtain a coating solution, and mixing the coating solutionUniformly spraying on 1.0L of spherical SiO with diameter of 5.6mm2Drying the carrier at 100 ℃, and roasting the carrier in a muffle furnace at 500 ℃ to obtain the catalyst carrier. The Al content of the carrier was determined by ICP to be 0.10 g/L.
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the catalyst precursor I on the catalyst carrier in a rotary pot to obtain a catalyst precursor I;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, adding acetic acid and water, continuing heating, adding oxygen, controlling the reaction temperature to be 142 ℃ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 372.78 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 94.86%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
[ example 7 ]
Preparation of the carrier: 1.21g of indium sesquioxide (In)2O3) Mixing the powder with 1.0g silica sol to obtain coating solution, and uniformly spraying the coating solution on 1.0L spherical SiO with diameter of 5.6mm2Drying the carrier at 100 ℃, and roasting the carrier in a muffle furnace at 500 ℃ to obtain the catalyst carrier. The In content of the carrier was 1.00g/L as determined by ICP.
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the catalyst precursor I on the catalyst carrier in a rotary pot to obtain a catalyst precursor I;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 ℃, adding acetic acid and water, continuing heating, adding oxygen, controlling the reaction temperature to be 142 ℃ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a Raw material groupThe composition is as follows: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 373.15 g/L.h, and the selectivity to allyl acetate was calculated to be 95.30%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
[ example 8 ]
Preparation of the carrier: 0.42g and 0.23g of dicris (Sc) trioxide2O3) Gallium sesquioxide (Ga)2O3) The powder of (2) was thoroughly mixed with 1.0g of silica sol to obtain a coating solution, and the coating solution was uniformly sprayed on 1.0L of spherical SiO having a diameter of 5.6mm2Drying the carrier at 100 ℃, and roasting the carrier in a muffle furnace at 500 ℃ to obtain the catalyst carrier. The carrier had a Sc content of 0.27g/L and a Ga content of 0.23g/L as determined by ICP.
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the catalyst precursor I on the catalyst carrier in a rotary pot to obtain a catalyst precursor I;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 □, adding acetic acid and water, continuously heating, adding oxygen, and controlling the reaction temperature to be 142 □ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 375.50 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.62%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
As can be seen from example 8 in comparison with examples 1 and 2, in the present invention, in terms of improving the activity and selectivity of allyl acetate catalyst, the catalyst prepared by using silica having a carrier whose surface is simultaneously coated with the modified metal elements Sc and Ga is higher in both the activity of catalyst and the selectivity of allyl acetate than the catalyst prepared by coating a carrier with only the modified metal element Sc or only the modified metal element Ga. This fully demonstrates the good synergistic effect between Sc and Ga in improving the activity and selectivity of the catalyst.
[ example 9 ]
Preparation of the carrier: 0.35g and 0.23g of yttrium oxide (Y)2O3) Gallium sesquioxide (Ga)2O3) The powder of (2) was thoroughly mixed with 1.0g of silica sol to obtain a coating solution, and the coating solution was uniformly sprayed on 1.0L of spherical SiO having a diameter of 5.6mm2Drying the carrier at 100 ℃, and roasting the carrier in a muffle furnace at 500 ℃ to obtain the catalyst carrier. The carrier had a Y content of 0.27g/L and a Ga content of 0.23g/L as determined by ICP.
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the catalyst precursor I on the catalyst carrier in a rotary pot to obtain a catalyst precursor I;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 □, adding acetic acid and water, continuously heating, adding oxygen, and controlling the reaction temperature to be 142 □ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 375.61 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.54%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
[ example 10 ]
Preparation of the carrier: 0.23g, 0.16g and 0.31g of dicris (Sc) trioxide2O3) Yttrium oxide (Y)2O3) And gallium sesquioxide (Ga)2O3) The powder of (2) was thoroughly mixed with 1.0g of silica sol to obtain a coating solution, and the coating solution was uniformly sprayed on 1.0L of spherical SiO having a diameter of 5.6mm2Drying the carrier at 100 ℃, and roasting the carrier in a muffle furnace at 500 ℃ to obtain the catalyst carrier. The carrier was found by ICP to have a Sc content of 0.15g/L, a Y content of 0.12g/L and a Ga content of 0.23 g/L.
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the catalyst precursor I on the catalyst carrier in a rotary pot to obtain a catalyst precursor I;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 □, adding acetic acid and water, continuously heating, adding oxygen, and controlling the reaction temperature to be 142 □ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: propylene/acetic acid/oxygen/water (molar ratio) ═ 1/0.18/0.2/0.3, after 100h of reactionThe reaction was stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 376.89 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.89%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
From example 10, which is compared with examples 8 and 9, it can be seen that, in the present invention, in terms of improving the activity and selectivity of allyl acetate catalyst, the catalyst prepared by using silica whose surface is simultaneously coated with the modified metal elements Sc, Y and Ga as the carrier metal element has higher activity and allyl acetate selectivity than the catalyst prepared by coating the carrier with only the modified metal elements Sc, Ga or only the modified metal element Y, Ga. The Sc, the Y and the Ga have good synergistic effect on the aspect of improving the activity and the selectivity of the catalyst.
[ example 11 ]
Preparation of the carrier: 0.23g, 0.16g and 0.28g of dicris (Sc) trioxide2O3) Yttrium oxide (Y)2O3) And indium oxide (In)2O3) The powder of (2) was thoroughly mixed with 1.0g of silica sol to obtain a coating solution, and the coating solution was uniformly sprayed on 1.0L of spherical SiO having a diameter of 5.6mm2Drying the carrier at 100 ℃, and roasting the carrier in a muffle furnace at 500 ℃ to obtain the catalyst carrier. The carrier was found by ICP to have a Sc content of 0.15g/L, a Y content of 0.12g/L and an In content of 0.23 g/L.
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the catalyst precursor I on the catalyst carrier in a rotary pot to obtain a catalyst precursor I;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24h to obtain a catalyst precursorII；
(3) With a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 □, adding acetic acid and water, continuously heating, adding oxygen, and controlling the reaction temperature to be 142 □ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 376.94 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.73%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
[ example 12 ]
Preparation of the carrier: 0.23g, 0.16g, 0.18 g and 0.12g of scandium oxide (Sc)2O3) Yttrium oxide (Y)2O3) Gallium sesquioxide (Ga)2O3) And indium oxide (In)2O3) The powder of (2) was thoroughly mixed with 1.0g of silica sol to obtain a coating solution, and the coating solution was uniformly sprayed on 1.0L of spherical SiO having a diameter of 5.6mm2Drying the carrier at 100 ℃, and roasting the carrier in a muffle furnace at 500 ℃ to obtain the catalyst carrierAnd (3) a body. The carrier was found by ICP to have a Sc content of 0.15g/L, a Y content of 0.12g/L, a Ga content of 0.13g/L and an In content of 0.10 g/L.
Preparation of the catalyst:
(1) an aqueous solution of chloropalladate and copper chloride having a pH of 1.06 and containing 3.18g of Pd and 0.37g of Cu was prepared using a sodium hydrogencarbonate pH adjuster and water as solvents to obtain 590ml of an impregnation solution. Dipping the catalyst precursor I on the catalyst carrier in a rotary pot to obtain a catalyst precursor I;
(2) dried at 80 ℃ and mixed with 105ml of a solution containing 21.5g of Na2SiO3·9H2Fully mixing the solution of O, and aging for 24 hours to obtain a catalyst precursor II;
(3) with a solubility of 10% (in N)2H4·H2O weight ratio) is 550ml hydrazine hydrate, and the catalyst precursor III is obtained after washing and drying at 90 ℃;
(4) the catalyst was obtained by dissolving 33g of potassium acetate in pure water to obtain 340ml of an impregnation solution, impregnating the impregnation solution on the precursor III, and drying the impregnation solution at 100 ℃.
The catalyst has a Pd content of 3.18g/L, a Cu content of 0.37g/L and a potassium acetate content of 33g/L as determined by ICP.
Synthesis of allyl acetate:
30ml of catalyst are charged in a fixed bed reactor, N is used2After leakage testing, use N2Fully purging the system, and cutting in a certain amount of propylene and N after the system is heated2Heating the mixture until the temperature of the catalyst bed reaches 120 □, adding acetic acid and water, continuously heating, adding oxygen, and controlling the reaction temperature to be 142 □ and the reaction pressure to be 0.68 MPa; volume space velocity of raw materials: 2000h-1(ii) a The raw materials comprise: the reaction was continued for 100 hours with a molar ratio of propylene/acetic acid/oxygen/water of 1/0.18/0.2/0.3 and then stopped.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The activity of the catalyst was calculated to be 380.12 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 96.02%. For the sake of comparison, the conditions for modifying the support and the main conditions for preparing the catalyst are shown in Table 1, and the physical properties and catalytic performance of the catalyst are shown in Table 2.
As can be seen from the comparison between example 12 and examples 10 and 11, In the present invention, In terms of improving the activity and selectivity of allyl acetate catalyst, the catalyst prepared by using the silica having the modified metal elements Sc, Y, Ga and In simultaneously coated on the surface thereof as the carrier metal element is higher In both activity of catalyst and selectivity of allyl acetate than the catalyst prepared by coating the carrier with only the modified metal elements Sc, Y and Ga or only the modified metal elements Sc, Y and In. This fully demonstrates that Sc, Y, Ga, and In have good synergistic effects In improving the activity and selectivity of the catalyst.
TABLE 1
Figure BDA0000824285130000201
TABLE 2 catalyst Properties and evaluation data
Figure BDA0000824285130000211

Claims (9)

1. A catalyst for preparing allyl acetate, which comprises a carrier, an active component and a cocatalyst; the active component comprises metal Pd and metal Cu; the cocatalyst is alkali metal acetate; the carrier comprises a carrier substrate and a surface coating; the substrate is porous silicon dioxide; the coating consists of a modified metal element and a silicon dioxide binder for binding the modified metal element on the surface of the base material; the content of the modified metal element is 0.10-1.00 g/L; the modifying element is simultaneously selected from at least one of IIIB group metal elements and at least one of IIIA group metal elements; the group IIIA metal element is at least one selected from Al, Ga and In.
2. The catalyst according to claim 1, characterized in that the IIIB metal element is selected from at least one of Sc, Y, La, Pr and Ce.
3. The catalyst of claim 1, wherein the alkali metal acetate is potassium acetate.
4. The catalyst according to claim 1, wherein the Pd content in the catalyst is 1.0-10.0 g/L.
5. The catalyst according to claim 1, wherein the Cu content in the catalyst is 0.1 to 5.0 g/L.
6. The catalyst according to claim 1, wherein the content of potassium acetate in the catalyst is 10.0-120.0 g/L.
7. A method of preparing the catalyst of claim 1, comprising the steps of:
(1) mixing the hydroxide or oxide of the modified metal element with silica sol to obtain coating liquid;
(2) coating the coating liquid on the surface of porous silicon dioxide, drying and roasting to obtain the catalyst carrier;
(3) impregnating the carrier with impregnation liquid containing a Pd compound and a Cu compound to obtain a catalyst precursor I;
(4) converting a Pd-containing compound and a Cu-containing compound into a precipitate type by using an alkaline solution to obtain a catalyst precursor II;
(5) reducing the combined Pd and the combined Cu in the precipitation type into metal Pd and metal Cu to obtain a catalyst precursor III;
(6) dipping a cocatalyst solution, and drying to obtain the catalyst.
8. A synthesis method of allyl acetate, which takes propylene, acetic acid, oxygen and water as raw materials and reacts in the presence of the catalyst of any one of claims 1-6 to obtain the allyl acetate.
9. A process according to claim 8, wherein the reaction temperature is 120E to EThe reaction pressure is 0.1-1 MPa at 150 ℃, the molar ratio of propylene, acetic acid, oxygen and water is 1 (0.1-0.3), 0.1-0.3, 0.2-1, and the volume space velocity of the raw materials is 1500-2500 h-1。
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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
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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