CN106582821B - Catalyst for preparing allyl acetate - Google Patents
Catalyst for preparing allyl acetate Download PDFInfo
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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 modified element is at least one of lanthanide series metal elements and IIIA metal elements better solves the problem and can be used for industrial production of allyl acetate.
Description
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 electric and former Soviet Union, proposed the use of acetyl oxidation technology in the presence of palladium and a promoter, in the reaction of allyl acetate production by fixed bed gas phase reaction using propylene, oxygen and acetic acid as raw materials, catalysts in which Pd, Cu and potassium acetate are supported on a carrier of SiO 2, Al 2 O 3 or a mixture of SiO 2 and Al 2 O 3 in an eggshell distribution have been known to those skilled in the art, and the catalysts are produced by the processes of U.S. Pat. Nos. 3, 917, 676 (Process for producing alloy acetate), in which a mixture containing noble metals Pd and Cu is impregnated on a carrier, dried, then the free Pd and Cu are solidified on the surface of the carrier to form active metallic Pd and Cu, and then dried by the promoter KOAc.
The main by-product of the reaction is generated by deep oxidation of propylene, which is related to the adsorption type of the catalyst to reactants and the distribution of active components of the catalyst, Zengxianjun et al in the research on the catalyst for preparing acetate propylene ester by propylene oxidation consider that the adsorption of propylene on Pd-K/SiO 2 is similar to the oxidation of toluene on Pd-Sn-K/SiO 2 catalyst, while Boqing et al in the research on the toluene gas phase oxygen acetylation on Pd-Sn-K/SiO 2 catalyst propose that the toluene gas phase oxygen acetylation is on the Pd-Sn-K/SiO 2 catalyst, the dissociation of methyl C-H bond is the rate control step, the metallic palladium becomes the most important component in the catalyst, and the existence of KOAc improves the activation of C-H bond.
zhaosheng et al have proposed a mechanism of ethylene vapor phase oxyacetylation in research on mechanism and kinetics of ethylene vapor phase oxyacetylation reaction, and they have considered that adsorption of oxygen on the surface of a catalyst is most advantageous for molecular oxygen, which is an oxygen source participating in acetylation, and Pd-SiO 2 catalyst active component Pd converts physically adsorbed acetic acid into chemically adsorbed acetic acid, thereby combining with molecular oxygen to produce allyl acetate.
In addition, many scholars at home and abroad think that the selectivity of allyl acetate catalyst is related to the adsorption heat of propylene, for example, Han Y F et al in A kinetic study of acetate synthesis over Pd-based catalysts, kinetics of vinyl acetate synthesis over Pd-Au/SiO 2 catalysts and Li Ming et al in the research of surface adsorption of Pd-Cu/SiO 2 by micro adsorption calorimetry technology also propose that the introduction of metallic copper, tin and the like is beneficial to reducing the oxidation activity of Pd surface adsorption 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, wherein the catalyst 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 lanthanide metal elements and IIIA metal elements.
in the above technical solution, the lanthanide metal element is preferably at least one of La, Ce, Pr, Sm, Eu and Lu.
in the above technical solution, the IIIA metal element is preferably at least one selected from Al, Ga, In and Tl.
in the above technical solution, as a further preferred, the modified metal element includes Sm and In, or includes Lu and In; more preferably, the modifying metal comprises Sm, Lu and In, or Sm, Lu and Al; most preferably, the modifying metals include Sm, Lu, In and Al. 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 technical solutions, the specific surface and pore volume of the carrier substrate are not particularly limited, and the excellent technical effects can be obtained, but the BET specific surface is preferably 100 to 500m 2/g, and the 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 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 obtains the allyl acetate by reaction in the presence of the catalyst.
In the technical scheme, the reaction temperature is preferably 120-150 ℃, the reaction pressure is preferably 0.1-1.0 MPa, the molar ratio of propylene, acetic acid, oxygen and water is (0.1-0.3), (0.2-1), and the 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 lanthanide series 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 evaluation method comprises the steps of filling 30ml of catalyst into the 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 heating, when the temperature of a catalyst bed layer reaches 120 ℃, adding 0.20mol/h of acetic acid and 0.42mol/h of water, starting oxygen feeding after 20 minutes, adding enough oxygen after 30 minutes, wherein the amount of oxygen is 0.125mol/h, the space velocity is 2000h -1, and controlling the reaction temperature to 142 ℃ and the reaction pressure to 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:
experimental results show that the activity of the allyl acetate catalyst prepared by the invention reaches 373.49 g/L.h, the selectivity reaches 94.98%, and a good technical effect is achieved. Particularly, when the catalyst carrier simultaneously uses at least one modified metal element of lanthanide series metal element and IIIA metal element, more outstanding technical effects are obtained. The invention is further illustrated by the following examples.
Detailed Description
The BET specific surface area of the spherical SiO 2 used in the specific embodiment was 198m 2/g, and the pore volume was 0.99 ml/g.
[ example 1 ]
the preparation of the carrier comprises the steps of fully mixing 0.63g of samarium trioxide (Sm 2 O 3) powder with 1.0g of silica sol to obtain coating liquid, uniformly spraying the coating liquid on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm, drying at 100 ℃, roasting at 500 ℃ in a muffle furnace to obtain the catalyst carrier, and measuring the Sm content in the carrier to be 0.54g/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) Drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 373.49 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 94.98%. 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 ]
The preparation of the carrier is carried out by mixing 0.66g of indium oxide (In 2 O 3) powder with 1.0g of silica sol to obtain a coating liquid, uniformly spraying the coating liquid on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm, drying at 100 ℃, roasting at 500 ℃ In a muffle furnace to obtain the catalyst carrier, and measuring the In content In the carrier to be 0.54g/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) Drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
Filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 373.25 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.23%. 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) Preparing an aqueous solution of chloropalladate and copper chloride with the pH value of 1.06 and the content of 3.18g Pd and 0.37g Cu by using a sodium bicarbonate pH value regulator and water as solvents to obtain 590ml of impregnation liquid, and impregnating the impregnation liquid in a rotary pot on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm to obtain a catalyst precursor I;
(2) drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 364.66 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 94.14%. 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.
compared with the examples 1 and 2, the catalyst used In the invention has the advantages that the catalyst activity and allyl acetate selectivity are improved compared with the catalyst prepared by using silica as the carrier, wherein the silica is used as the carrier and the surface of the silica is coated with the modified metal element Sm or In.
[ COMPARATIVE EXAMPLE 2 ]
is a comparative example of [ example 1 ].
preparation of the catalyst:
(1) Preparing an aqueous solution of chloropalladate and copper chloride with the pH value of 1.06 and the content of 3.18g Pd and 0.37g Cu by using a sodium bicarbonate pH value regulator and water as solvents to obtain 590ml of impregnation liquid, and impregnating the impregnation liquid in a rotary pot on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm to obtain a catalyst precursor I;
(2) Drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(4) The catalyst was obtained by dissolving 33g of potassium acetate and 1.7g of samarium acetate (Sm (OAc) 3 & 6H 2 O) in pure water to give 340ml of an impregnation solution, impregnating the precursor III with the solution, and drying the impregnated solution at 100 ℃.
The catalyst has Pd content of 3.18g/L, Cu content of 0.37g/L, potassium acetate content of 33g/L and Sm content of 0.54g/L determined by ICP.
synthesis of allyl acetate:
Filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 94.06%. 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.
Compared with the example 1, the catalyst prepared by using the silicon dioxide with the carrier coated with the modified metal element Sm has higher activity and allyl acetate selectivity than the catalyst prepared by dipping the compound containing the Sm metal element while dipping the potassium acetate.
[ COMPARATIVE EXAMPLE 3 ]
Is a comparative example of [ example 1 ].
preparation of the catalyst:
(1) Preparing an aqueous solution of chloropalladic acid, copper chloride and samarium acetate (Sm (OAc) 3.6H 2 O) with the pH value of 1.06, the pH value of 3.18g Pd, 0.37g Cu and 0.54gSm by using a sodium bicarbonate pH value regulator and water as solvents to obtain 590ml of impregnation liquid, and impregnating the impregnation liquid on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm in a rotary pot to obtain a catalyst precursor I;
(2) drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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 Pd content of 3.18g/L, Cu content of 0.37g/L, potassium acetate content of 33g/L and Sm content of 0.54g/L determined by ICP.
Synthesis of allyl acetate:
filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 364.58 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 94.08%. 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 comparison with example 1 that the catalyst prepared by using silica having a carrier coated with the modified metal element Sm on the surface thereof according to the present invention has improved activity and allyl acetate selectivity as compared with the catalyst prepared by impregnating a compound containing the modified metal element Sm with a noble metal, and also as compared with the catalyst prepared by impregnating a compound containing the modified metal element Sm with the noble metal, it can be seen from comparative examples 2, 3 and example 1 that the catalyst prepared by coating the modified metal element Sm on the surface of SiO 2 has excellent activity and selectivity, and the catalyst prepared by adding the modified metal element Sm in other steps or processes has no excellent activity and selectivity.
[ example 3 ]
The preparation of the carrier is that 0.74g of lanthanum hydroxide (La (OH) 3) powder and 1.0g of silica sol are fully mixed to obtain coating liquid, the coating liquid is uniformly sprayed on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm, the carrier is dried at 100 ℃, and the carrier is obtained after being roasted at 500 ℃ in a muffle furnace, and the La content in the carrier is 0.54g/L through ICP measurement.
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) Drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 373.43 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 ]
The preparation of the carrier is that 0.81g of cerium hydroxide (Ce (OH) 4) powder and 1.0g of silica sol are fully mixed to obtain coating liquid, the coating liquid is uniformly sprayed on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm, the carrier is dried at 100 ℃, and the catalyst carrier is obtained after the carrier is roasted at 500 ℃ in a muffle furnace, and the content of Ce in the carrier is 0.54g/L through ICP measurement.
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) drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
Filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 5 ]
The preparation of the carrier comprises the steps of fully mixing 0.62g of lutetium oxide (Lu 2 O 3) powder and 1.0g of silica sol to obtain coating liquid, uniformly spraying the coating liquid on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm, drying at 100 ℃, roasting at 500 ℃ in a muffle furnace to obtain the catalyst carrier, and measuring the Lu content in the carrier to be 0.54g/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) Drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
Filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 373.48 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.20%. 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 ]
the preparation of the carrier is carried out by mixing 0.29g of aluminum hydroxide (Al (OH) 3) powder with 1.0g of silica sol to obtain coating liquid, spraying the coating liquid on 1.0L of 5.6mm diameter spherical SiO 2 carrier, drying at 100 deg.C, calcining at 500 deg.C in muffle furnace to obtain the catalyst carrier, and measuring Al content in the carrier to be 0.10g/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) drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
Filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 372.79 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.25%. 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 ]
The preparation of the carrier comprises the steps of fully mixing 1.35g of gallium oxide (Ga 2 O 3) powder and 1.0g of silica sol to obtain a coating solution, uniformly spraying the coating solution on 1.0L of a spherical SiO 2 carrier with the diameter of 5.6mm, drying at 100 ℃, roasting at 500 ℃ in a muffle furnace to obtain the catalyst carrier, and measuring the Ga content in the carrier to be 1.00g/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) Drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
Filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 373.18 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.27%. 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 ]
the preparation of the carrier comprises the steps of fully mixing 0.32g and 0.33g of samarium oxide (Sm 2 O 3) and indium oxide (In 2 O 3) powder with 1.0g of silica sol to obtain a coating solution, uniformly spraying the coating solution on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm, drying at 100 ℃, and roasting at 500 ℃ In a muffle furnace to obtain the catalyst carrier, wherein the content of Sm In the carrier is 0.27g/L and the content of In the carrier is 0.27g/L through ICP measurement.
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) Drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
Filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 375.41 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.59%. 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 the allyl acetate catalyst, the catalyst prepared by using silica having a carrier whose surface is simultaneously coated with the modified metal elements Sm and In has higher activity and selectivity of allyl acetate than the catalyst prepared by coating the carrier with only the modified metal elements Sm or only the modified metal elements In. This fully demonstrates the good synergistic effect between Sm and In improving the activity and selectivity of the catalyst.
[ example 9 ]
The preparation of the carrier comprises the steps of fully mixing 0.31g and 0.33g of powder of lutetium oxide (Lu 2 O 3) and indium oxide (In 2 O 3) with 1.0g of silica sol to obtain a coating solution, uniformly spraying the coating solution on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm, drying at 100 ℃, and roasting at 500 ℃ In a muffle furnace to obtain the catalyst carrier, wherein the Lu content and the In content In the carrier are respectively 0.27g/L and 0.27g/L respectively through ICP measurement.
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) Drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 375.53 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.43%. 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 ]
The preparation of the carrier comprises the steps of fully mixing 0.22g, 0.10g and 0.33g of samarium trioxide (Sm 2 O 3), lutetium oxide (Lu 2 O 3) and indium oxide (In 2 O 3) powder with 1.0g of silica sol to obtain a coating solution, uniformly spraying the coating solution on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm, drying at 100 ℃, roasting at 500 ℃ In a muffle furnace to obtain the catalyst carrier, and measuring the content of Sm In the carrier to be 0.18g/L, the content of Lu to be 0.09g/L and the content of In to be 0.27g/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) Drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
Filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 95.88%. 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 the comparison between example 10 and examples 8 and 9, it is seen that, In the present invention, In terms of improving the activity and selectivity of the allyl acetate catalyst, the catalyst prepared by using the silica having the surface coated with the modified metal elements Sm, Lu and In as the carrier metal element is higher than the catalyst prepared by coating the carrier with only the modified metal elements Sm and In or coating the carrier with only the modified metal elements Lu and In as the catalyst, the activity of the catalyst and the selectivity of allyl acetate are higher. The good synergistic effect of Sm, Lu and In on improving the activity and selectivity of the catalyst is fully demonstrated.
[ example 11 ]
the preparation of the carrier comprises the steps of fully mixing 0.22g, 0.10g and 0.79g of samarium trioxide (Sm 2 O 3), lutetium oxide (Lu 2 O 3) and aluminum hydroxide (Al (OH) 3) powder with 1.0g of silica sol to obtain coating liquid, uniformly spraying the coating liquid on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm, drying at 100 ℃, roasting at 500 ℃ in a muffle furnace to obtain the catalyst carrier, and measuring the content of Sm in the carrier to be 0.18g/L, the content of Lu to be 0.09g/L and the content of Al to be 0.27g/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) drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 377.02 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 95.71%. 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 ]
The preparation of the carrier comprises the steps of fully mixing 0.22g, 0.10g, 0.27g and 0.15g of samarium trioxide (Sm 2 O 3), lutetium oxide (Lu 2 O 3), indium oxide (In 2 O 3) and aluminum hydroxide (Al (OH) 3) powder with 1.0g of silica sol to obtain a coating liquid, uniformly spraying the coating liquid on 1.0L of spherical SiO 2 carrier with the diameter of 5.6mm, drying at 100 ℃, roasting at 500 ℃ In a muffle furnace to obtain the catalyst carrier, and measuring the content of Sm In the carrier to be 0.18g/L, the content of Lu to be 0.09g/L, the content of In to be 0.22g/L and the content of Al to be 0.05g/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) drying at 80 ℃, then fully mixing with 105ml of a solution containing 21.5g of Na 2 SiO 3.9H 2 O, and aging for 24H to obtain a catalyst precursor II;
(3) Reducing with hydrazine hydrate with the solubility of 10 percent (calculated by the weight ratio of N 2 H 4. H 2 O) of 550ml, washing with water, and drying at 90 ℃ to obtain a catalyst precursor III;
(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:
Filling 30ml of catalyst in a fixed bed reactor, after leakage testing by using N 2, fully purging the system by using N 2, after the system is heated, cutting in a certain amount of mixture of propylene and N 2, heating until the temperature of a catalyst bed reaches 120 ℃, adding acetic acid and water, continuously heating, adding oxygen, controlling the reaction temperature to be 142 ℃, the reaction pressure to be 0.68MPa, the volume space velocity of raw materials to be 2000h -1, wherein the raw materials comprise propylene/acetic acid/oxygen/water (molar ratio) of 1/0.18/0.2/0.3, and stopping the reaction after the reaction is continuously carried out for 100 h.
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 380.05 g/L.multidot.h, and the selectivity to allyl acetate was calculated to be 96.04%. 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 the comparison between example 12 and examples 10 and 11, 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 coated with modified metal elements Sm, Lu, In and Al simultaneously as the carrier metal element is higher than the catalyst prepared by coating the carrier with modified metal elements Sm, Lu and In alone or modified metal elements Sm, Lu and Al alone, and the activity of catalyst and the selectivity of allyl acetate are higher. The good synergistic effect of Sm, Lu, In and Al on improving the activity and selectivity of the catalyst is fully demonstrated.
TABLE 1
TABLE 2 catalyst Properties and evaluation data
Claims (10)
1. A catalyst for preparing allyl acetate, wherein the catalyst 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 g/L; the modifying metal element is selected from at least one of lanthanide series metal elements and at least one of group IIIA metal elements.
2. The catalyst according to claim 1, characterized in that the lanthanide metal element is selected from at least one of La, Ce, Pr, Sm, Eu and Lu.
3. The catalyst according to claim 1, characterized In that the group IIIA metal element is selected from at least one of Al, Ga, In and Tl.
4. The catalyst of claim 1, wherein the alkali metal acetate is potassium acetate.
5. The catalyst according to claim 1, wherein the Pd content in the catalyst is 1.0-10.0 g/L.
6. The catalyst according to claim 1, wherein the Cu content in the catalyst is 0.1 to 5.0 g/L.
7. The catalyst according to claim 4, wherein the content of potassium acetate in the catalyst is 10.0-120.0 g/L.
8. the method for preparing the catalyst according to 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.
9. a 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 the catalyst of any one of claims 1-7.
10. The synthesis method of claim 9, wherein the reaction temperature is 120-150 ℃, the reaction pressure is 0.1-1 MPa, the molar ratio of propylene, acetic acid, oxygen, water is 1 (0.1-0.3) (0.2-1), and the volume space velocity of the raw material is 1500-2500 h -1.
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| CN1295878A (en) * | 1999-11-10 | 2001-05-23 | 大连化学工业股份有限公司 | Catalyst for acylation and preparation process and use thereof |
| CN1340378A (en) * | 2000-08-30 | 2002-03-20 | 上海石油化工股份有限公司 | High-activity catalyst for preparing vinyl acetate by ethylene method |
| CN101722043A (en) * | 2008-10-15 | 2010-06-09 | 赢创德固赛有限责任公司 | Catalyst, preparation method thereof and application thereof for producing vinyl acetate monomer |
| CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| 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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| CN1295878A (en) * | 1999-11-10 | 2001-05-23 | 大连化学工业股份有限公司 | Catalyst for acylation and preparation process and use thereof |
| CN1340378A (en) * | 2000-08-30 | 2002-03-20 | 上海石油化工股份有限公司 | High-activity catalyst for preparing vinyl acetate by ethylene method |
| CN101722043A (en) * | 2008-10-15 | 2010-06-09 | 赢创德固赛有限责任公司 | Catalyst, preparation method thereof and application thereof for producing vinyl acetate monomer |
| CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
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