CN117463325A - Alkyne selective hydrogenation catalyst and preparation method thereof - Google Patents

Alkyne selective hydrogenation catalyst and preparation method thereof Download PDF

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CN117463325A
CN117463325A CN202210847575.1A CN202210847575A CN117463325A CN 117463325 A CN117463325 A CN 117463325A CN 202210847575 A CN202210847575 A CN 202210847575A CN 117463325 A CN117463325 A CN 117463325A
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catalyst
solution
semi
palladium
finished catalyst
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谭都平
向永生
张峰
谢元
车春霞
韩伟
温翯
韩迎红
杨博
边虎
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Petrochina Co Ltd
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Priority to PCT/CN2022/139263 priority patent/WO2024016576A1/en
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Abstract

The invention provides an alkyne selective hydrogenation catalyst and a preparation method thereof. The active component of the catalyst at least contains Pd and Ag, the content of Pd is 0.045-0.075% and the content of Ag is 0.06-0.12% based on 100% of the mass of the carrier; the catalyst comprises an organic cage, wherein the organic cage is positioned on the outer surface of the catalyst, the size of the organic cage is 2.7-3.6nm, pd is loaded in the organic cage, and Ag is positioned in the middle or at the bottom of a Pd active center. The catalyst of the invention is applied to the selective hydrogenation process of the carbon two fractions, the yield of butene can be reduced to less than 1/2 of that of the traditional catalyst, and the yield of oxygenated compounds such as aldehyde and the like is also greatly reduced.

Description

Alkyne selective hydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to an alkyne selective hydrogenation catalyst and a preparation method thereof, and belongs to the technical field of catalyst preparation.
Background
Ethylene obtained by steam cracking petroleum hydrocarbon (such as ethane, naphtha, diesel oil, hydrogenated tail oil, etc.) contains 0.2-2.5% of acetylene by mass. When used in polymerization, acetylene in ethylene reduces the activity of the polymerization catalyst and affects the physical properties of the polymer, and must therefore be removed. At present, a selective hydrogenation method is generally adopted in industry to remove acetylene in ethylene, and the adopted catalyst is mainly noble metal catalyst such as Pd, pt, au and the like. In order to ensure that ethylene generated by acetylene hydrogenation and original ethylene in raw materials are not continuously hydrogenated to generate ethane, so that ethylene loss is caused, the higher hydrogenation selectivity of the catalyst is ensured, and better economic benefit can be obtained.
The second-carbon hydrogenation is to calculate the needed hydrogen according to the content of acetylene and match the hydrogen with hydrogenation materials, the mole ratio of the hydrogen to the acetylene is generally not more than 2, and the hydrogen is less, so that the dimerization reaction of the acetylene is easy to occur, the fourth-carbon fraction is generated, and the fourth-carbon fraction is further polymerized to generate an oligomer with wider molecular weight, commonly called as green oil. Green oil adsorbs on the catalyst surface and further forms coke, blocking catalyst pore channels, preventing the reactant from diffusing to the surface of the active center of the catalyst, thereby causing the activity of the catalyst to be reduced.
The noble metal catalyst has higher activity, but green oil is easy to generate in the use process, so that the catalyst is coked and deactivated, and the stability and the service life of the catalyst are affected. CN200810119385.8 discloses a non-noble metal supported selective hydrogenation catalyst, a preparation method and application thereof, comprising a carrier, and a main active component and a co-active component supported on the carrier, wherein the main active component is Ni, the co-active component is selected from at least one of Mo, la, ag, bi, cu, nd, cs, ce, zn and Zr, the main active component and the co-active component are both in amorphous form, the average particle size is less than 10nm, and the carrier is a porous material without oxidizing property; and the catalyst is prepared by a micro-emulsification method.
CN200810114744.0 discloses an unsaturated hydrocarbon selective hydrogenation catalyst and a preparation method thereof. The catalyst takes alumina as a carrier and palladium as an active component, and the rare earth, alkaline earth metal and fluorine are added to improve the impurity resistance and coking resistance of the catalyst, but the selectivity of the catalyst is not ideal.
The catalyst prepared by the method adopts the catalyst with single pore diameter distribution, and the catalyst selectivity is poor under the influence of internal diffusion in the fixed bed reaction process. The carrier with double-peak pore distribution ensures high activity of the catalyst, and the existence of macropores can reduce the influence of internal diffusion and improve the selectivity of the catalyst. CN101433842a discloses a hydrogenation catalyst, which is characterized in that the catalyst has a bimodal pore distribution, the most probable radius of the small pore portion is 2-50nm, the most probable radius of the large pore portion is 100-500nm, and the catalyst has good hydrogenation activity and good selectivity and large ethylene increment at the same time of the bimodal pore distribution.
In the carbon di-hydrogenation reaction, green oil generation and catalyst coking are important factors affecting catalyst service life. The activity, selectivity and service life of the catalyst form the overall performance of the catalyst, and the methods listed above either provide a better approach to improving the activity and selectivity of the catalyst, but do not solve the problem that the catalyst is easy to coke, or solve the problem that the catalyst is easy to generate green oil and coke, but do not solve the problem of selectivity. The carrier with a macroporous structure can improve the selectivity, but larger molecules generated by polymerization and chain growth reaction are easy to accumulate in macropores of the carrier, so that the catalyst is coked and deactivated, and the service life of the catalyst is influenced.
In the carbon two selective hydrogenation reaction, pd is used as the main active component, and Pd is used as Pd in the traditional impregnation preparation process of the catalyst 2+ Or [ PdCl ] 4 ] 2- The ionic species is bound to the support and during activation Pd aggregates to become active sites. Due to the aggregation of Pd during activation, it is a kinetic-governed random process, that is, the size of each active center is difficult to control in advance.
Previous studies have found a selective hydrogenation process for acetylene which is: first one acetylene molecule is combined with 1 hydrogen atom to form vinyl, which is then combined with a hydrogen atom to form ethylene, or 2 vinyl groups are coupled to form butadiene. Since butadiene can undergo a series of polymerization reactions to form green oil and then coke, inhibition of butadiene formation becomes a key to preventing coking of the carbon two selective hydrogenation catalyst.
It is apparent that if 2 vinyl groups are formed simultaneously at 1 catalyst activity center, the probability of butadiene formation increases greatly. It was also found that the large size of the active center increases the yield of butadiene. To prevent large active center sizes, there are generally 2 approaches: one is to reduce the amount of active ingredient and the other is to enlarge the dispersion area of the active ingredient. However, the load of the active components is reduced, the number of active centers is possibly insufficient, the hydrogenation activity is insufficient, acetylene cannot be completely removed, the hydrogenation product is unqualified, and the economic loss is extremely large.
The expansion of the active component loading area, the active center with part not located near the catalyst surface, results in poor catalyst selectivity and great ethylene loss in the hydrogenation process.
In order to prepare catalysts with narrow particle size distribution, some researchers have synthesized a series of organic cages with three-dimensional structures, which have fixed sizes and can be used for fixing metals, thereby preparing catalysts with highly dispersed metal clusters. At present, the three-dimensional organic cages are used for full hydrogenation or homogeneous hydrogenation after being loaded with active components and uniformly distributed on a carrier in a solution. In the case of selective hydrogenation, not only the size of the active center affects the reaction, but also the distribution of the active components in the catalyst has a great influence on the reaction result, and the catalyst with uniformly distributed active components is not suitable for selective hydrogenation reaction.
There are many studies on the hydrogenation of noble metal monoatomic catalysts, but for the hydrogenation of alkynes, there is a considerable distance between the catalyst and the practical application. The reason for this is: in the active center of hydrogenation reaction, 2 processes need to be completed, wherein 1 is the activation of alkyne molecules, namely electron pairs of alkyne molecules double bonds enter into empty orbitals of active center atoms, and the active center atoms feed back the electron pairs to the opposite bond orbitals of alkyne molecules, so that double bond energy is reduced, double bonds are activated, and breakage occurs; at the same time, the same process is required for hydrogen molecules to activate hydrogen into hydrogen atoms. For a single-atom active center, the physical size of a single atom is limited, and meanwhile, the 2 processes are difficult to finish, so that the reaction process is slower, and the requirements of practical application are difficult to meet. Therefore, it is a natural matter that the activity neutrality needs to have a certain physical size, and in fact, for the palladium catalyst, since a large amount of hydrogen can be absorbed inside the stacked structure, the activation of hydrogen and the transfer of hydrogen atoms are completed inside the stacked structure of palladium, and thus the activity is higher than that of the active component capable of adsorbing hydrogen only on the surface.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an alkyne selective hydrogenation catalyst and a preparation method thereof, wherein the catalyst is suitable for an acetylene selective hydrogenation process involving CO.
In order to achieve the aim, the invention provides a selective hydrogenation catalyst, wherein the active component of the catalyst contains Pd and Ag, the content of Pd is 0.045-0.075 percent and the content of Ag is 0.06-0.12 percent based on 100 percent of the mass of a carrier;
the catalyst comprises an organic cage, wherein the organic cage is positioned on the outer surface of the catalyst, the size of the organic cage is 2.7-3.6nm, pd is loaded in the organic cage, and Ag is positioned in the middle or at the bottom of a Pd active center.
The catalyst of the invention synthesizes organic cages with regular structures on the outer surface of the carrier in situ, the size of the cages is 2.7-3.6nm, and active components are loaded in the organic cages. The size of the active center is uniform and uniform due to the limitation of the size of the organic cage, so that the activity requirement can be met, and the probability of simultaneously adsorbing olefin and CO in the acetylene hydrogenation process is greatly reduced without an oversized active center.
In the catalyst of the invention, ag can form an alloy with Pd to improve selectivity of acetylene hydrogenation, and in particular, the role of Ag has two roles: firstly, silver atoms separate palladium atoms, so that the space distance of adsorbed acetylene molecules is increased, the mutual distance between corresponding reaction intermediates after acetylene hydrogenation is larger, strong adsorption species of acetylene are not formed, and intermediate-vinyl coupling is not easy to occur, so that the formation of green oil is reduced, and the method is called geometric action; and the second is that electrons of the outer layer S of silver enter the empty track of palladium, and reduce the adsorption effect of palladium on ethylene, which is called electron effect.
If the reaction mass contains CO, the probability of formation of strong adsorption of acetylene can be reduced and the above-mentioned geometrical effect can be achieved because of its competitive adsorption relationship with acetylene, so that Ag may not be exposed to the outer surface of the catalyst, but the electronic effect of silver is still required for improving the selectivity of the catalyst, so that silver may be present in the interior or bottom of the active center of the catalyst.
According to a specific embodiment of the present invention, preferably, the specific surface area of the catalyst is 15 to 30m 2 /g。
According to a particular embodiment of the invention, preferably the support of the catalyst is alumina or mainly alumina.
According to particular embodiments of the present invention, preferably, the alumina in the support may be in the form of theta, alpha or a mixture thereof; the alumina content in the catalyst carrier is more than 80%.
According to a specific embodiment of the present invention, preferably, the support also contains other metal oxides, such as magnesium oxide and/or titanium oxide.
The invention also provides a preparation method of the catalyst, which mainly comprises the following steps:
(1) Forming a polar polymer within the support, the polymer occupying 80-95% of the pore volume of the support;
(2) In-situ synthesizing an organic cage in the residual outer holes of the carrier;
(3) Loading palladium active components in an organic cage, drying and roasting; decomposing the polar polymer formed in step (1);
(4) Loading auxiliary active component silver;
(5) The palladium active component is loaded in the organic cage.
According to a specific embodiment of the present invention, preferably, the above preparation method comprises the following specific steps:
(1) Mixing hydrophilic polymerizable monomer with a roasted carrier, and polymerizing at a certain temperature to obtain a first semi-finished catalyst, wherein the volume of a polymer synthesized by the hydrophilic monomer is 80-95% (preferably 85-95%) of the pore volume of the carrier;
(2) Mixing tri (4-formylphenyl) amine and halogenated acetic acid, dissolving in halogenated acetic acid, then mixing with a first semi-finished catalyst, stirring, dropwise adding a mixed solution of aromatic diamine compounds and halogenated acetic acid, standing the mixture, pouring out residual liquid after the reaction is completed, washing with alcohol and deionized water respectively, and drying to obtain a second semi-finished catalyst;
wherein, the mol ratio of the aromatic diamine compound to the tri (4-formylphenyl) amine is 1.2-2.5:1, the mass ratio of the tri (4-formylphenyl) amine to the halogenated acetic acid is 2000-6000:1;
(3) Dissolving organic palladium salt in an organic solvent to obtain a first solution of a palladium precursor;
immersing the second semi-finished catalyst into an alcohol solution, dropwise adding a first solution of a palladium precursor into a mixture of the second semi-finished catalyst and alcohol, stirring at the same time, dropwise adding a reducing agent, heating and stirring until the surface of the second semi-finished catalyst is not discolored, pouring out the solution, washing with deionized water, drying, and roasting at a temperature at which the polymer formed in the step (1) can be decomposed to obtain a third semi-finished catalyst;
(4) Dissolving soluble silver salt in deionized water or an organic solvent to obtain a silver-containing impregnating solution, immersing a third semi-finished catalyst in the silver-containing impregnating solution, standing after the third semi-finished catalyst is completely absorbed, dropwise adding a reducing agent to reduce silver, pouring the solution, washing with deionized water, and drying to obtain a fourth semi-finished catalyst;
(5) Dissolving organic palladium salt in an organic solvent to obtain a second solution of a palladium precursor, immersing a fourth semi-finished catalyst in an alcohol solution, dropwise adding the second solution of the palladium precursor into a mixture of the fourth semi-finished catalyst and alcohol, and stirring at the same time;
and (3) dropwise adding a reducing agent into the solution, heating and stirring until the surface of the fourth semi-finished catalyst is not discolored, pouring the solution, washing and drying to obtain the catalyst, or pouring the solution, washing with deionized water, drying and roasting to obtain the catalyst without reduction.
According to a specific embodiment of the present invention, preferably, the mass ratio of the total mass of the organic palladium salt to the tris (4-formylphenyl) amine in the above-mentioned preparation method, step (3) and step (5) is 2 to 14:1.
According to a specific embodiment of the present invention, preferably, the above preparation method, step (4) is performed prior to step (3), and step (3) is performed in combination with step (5).
According to the specific embodiment of the invention, in order to obtain the catalyst with uniform active center scale, an organic cage is firstly prepared, and then the active component palladium is loaded in the organic cage, so that the active center scale of the prepared catalyst is also in the range of 2.7-3.6nm, and the formation of 2 vinyl groups on one active center or the simultaneous adsorption of CO and ethylene in hydrogenation reaction can be avoided.
If the synthesis process of the organic cage is carried out in the carrier, the synthesized organic cage is uniformly distributed on the carrier, and the loaded catalyst active components are uniformly distributed on all parts of the catalyst, so that the catalyst can only be used for full hydrogenation without considering selectivity or for homogeneous hydrogenation without diffusion limitation, and cannot be used for gas phase selective hydrogenation. In order to ensure that the organic cage is positioned on the outer surface of the carrier, other mediums occupy the pore canal inside the carrier in advance, so that the organic cage is synthesized in the pore close to the outer surface, in the obtained catalyst, the active component Pd is distributed in the organic cage, and the dimension of the active center is also in the proper range of 2.7-3.6nm, thus being applicable to gas phase selective hydrogenation reaction, in particular to the selective hydrogenation process of the carbon two fractions.
According to a specific embodiment of the present invention, the present invention is not limited to the specific kind of monomer used for synthesizing the organic cage, as long as the synthesized organic cage has a size of between 2.7 and 3.6 nm. Preferably, in step (1), the hydrophilic polymerizable monomer is a monomer containing a carbonyl group and/or a carboxyl group and capable of undergoing polymerization or condensation reaction, more preferably comprising lactic acid, acrylic acid or formaldehyde.
According to a specific embodiment of the present invention, the certain temperature in step (1) means the temperature at which the thermal condensation reaction or bulk polymerization of the monomer occurs, and is generally 80 to 200℃depending on the monomers.
According to a specific embodiment of the present invention, the carrier in step (1) may be spherical, cylindrical, clover, and the like.
According to a specific embodiment of the present invention, preferably the hydrophilic polymerizable monomer forms a polymer having a decomposition temperature of less than 450 ℃, more preferably less than 420 ℃.
According to a specific embodiment of the present invention, preferably, in step (2), the aromatic diamine is a tetraphenylenediamine or a derivative thereof having a substituent on a benzene ring, preferably a para-tetraphenylenediamine or a derivative thereof having a substituent on a benzene ring, and the substituent is preferably halogen or an alkyl group.
According to a specific embodiment of the present invention, preferably, the halogenated acetic acid is a catalyst for the reaction of tris (4-formylphenyl) amine with aromatic diamine-based compound, and in step (2), the halogenated acetic acid is a fluoroacetic acid or chloroacetic acid, preferably trifluoroacetic acid or dichloroacetic acid.
According to a specific embodiment of the present invention, preferably, the haloalkane is a solvent required for the reaction, and in step (2), the haloalkane comprises a fluoroalkyl, a chloroalkane or a bromoalkane, more preferably a halomethane or a haloethane, further preferably dichloroethane or trichloromethane.
According to a specific embodiment of the present invention, preferably, in step (3) and step (5), the organic palladium salt comprises palladium acetate or palladium acetylacetonate;
when the organic palladium salt is palladium acetylacetonate, the organic solvent is chloroform; when the organic palladium salt is palladium acetate, the organic solvent is one or a combination of more than two of chloroform, dichloromethane and glacial acetic acid.
According to a specific embodiment of the present invention, preferably, in step (3) and step (5), the alcohol comprises ethanol or methanol, more preferably ethanol.
According to a specific embodiment of the present invention, preferably, in step (3), step (4) and step (5), the reducing agent is a reducing compound, more preferably one or a combination of two or more of methanol, formaldehyde, formic acid, ethanol, acetaldehyde, hydrazine hydrate.
According to a specific embodiment of the present invention, preferably, in the step (4), the soluble silver salt is a silver salt soluble in water or an organic solvent, more preferably, silver nitrate soluble in water and/or silver acetylacetonate soluble in an organic solvent, or the like. Ag is supported by a solution method such as a saturation impregnation method.
According to an embodiment of the present invention, after Ag is supported in step (4), pd is supported in step (5), and then the catalyst may be calcined to form an oxidized catalyst or directly reduced to form a reduced catalyst.
The invention also provides a carbon two-fraction selective hydrogenation process taking crude hydrogen as a hydrogen source, which is carried out by adopting the catalyst.
The catalyst provided by the invention has the following characteristics: the palladium is loaded in the organic cage, and the active center formed by the palladium is limited by the physical size of the cage, the maximum size of the active center is the size of the cage, and the active center with the aggregation size of more than 3.0nm is reduced. The size meets the requirement of activity in the selectivity of acetylene, but the probability of simultaneously forming 2 vinyl groups or simultaneously adsorbing CO and olefin in one active center is greatly reduced, the probability of hydroformylation reaction is reduced, the deactivation rate of the catalyst is delayed, the yield of butene can be reduced to less than 1/2 of that of the traditional catalyst, and the generation amount of oxygen-containing compound aldehyde and the like is also greatly reduced. Moreover, the organic cage is positioned on the outer surface of the catalyst, so that the influence of inner diffusion limitation on catalytic reaction is avoided, and the selectivity of the catalyst is good. The catalyst of the invention can reduce the production of carbon four-side products, and the carbonyl hydrogenation of the oxygen-containing compound reduces the production of macromolecular oxygen-containing compound.
The catalyst prepared by the method can not even need regeneration because of the great reduction of byproducts. Even if regenerated, the catalyst can be regenerated at the temperature lower than 450 ℃, so that the organic cage structure is not damaged, the good performance of the hydrogenation process is ensured, and the service life of the catalyst is greatly prolonged.
Drawings
FIG. 1 is a plot of pore size of the synthetic organic cage of example 1 as determined by the BET method.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
The catalyst of the invention adopts the following characterization method in the preparation process: BET testers, in the united states of america, measure specific surface area and pore size distribution. The Pd and Ag contents in the catalyst were measured on an A240FS atomic absorption spectrometer.
Agilent 7890A gas chromatograph measures reactor outlet, inlet hydrogen, acetylene content and butene content.
The catalyst weight was measured with a 0.1mg electronic balance.
Raw materials: tris (4-formylphenyl) amine, dichloroacetic acid, dichloroethane, biphenyldiamine, hydrazine hydrate, ethanol, methanol, acetic acid, formic acid, formaldehyde, lactic acid, acrylic acid, palladium acetate, palladium acetylacetonate, silver nitrate, analytically pure, shanghai national pharmaceutical group company; alumina, shandong aluminum products group Co.
Example 1
The present embodiment provides a catalyst wherein:
catalyst carrier: a commercially available spherical alumina carrier was used, 4mm in diameter. After being roasted for 4 hours at 1080 ℃, the pore volume is 0.55m 3 Per gram, specific surface area of 30m 2 And/g. 100g of the carrier was weighed.
And (3) preparing a catalyst:
(1) Weighing 65.31g of lactic acid, mixing with 100g of roasted carrier, and keeping the temperature at 160 ℃ for 10 hours to obtain a semi-finished catalyst A;
(2) Mixing 22.79mg of tris (4-formylphenyl) amine with 0.00379mg of dichloroacetic acid, dissolving in 60ml of dichloroethane, then mixing with a semi-finished catalyst A1, stirring and dropwise adding a mixed solution of 27.54mg of tetraphenylenediamine and 10ml of dichloroethane, standing the mixture at room temperature for 200 hours, pouring out residual liquid, washing with ethanol and deionized water respectively, and drying to obtain a semi-finished catalyst B;
(3) And (3) dissolving 38mg of palladium acetate in 50mL of glacial acetic acid, obtaining a palladium acetate solution after palladium acetate is completely dissolved, immersing a semi-finished catalyst B in 50mL of ethanol solution, dropwise adding the palladium acetate solution into a mixture of the semi-finished catalyst B and ethanol while stirring, dropwise adding about 20mL of 40% formaldehyde solution into the mixture while stirring, stirring at 70 ℃ for 1 hour, pouring out the solution, washing with deionized water, drying at 120 ℃, and roasting at 260 ℃ for 8 hours to obtain a semi-finished catalyst C.
(4) Weighing 0.11g of silver nitrate, dissolving the silver nitrate into 52.3g of deionized water, immersing the semi-finished catalyst C into the prepared silver nitrate solution, standing for 4 hours after the solution is completely absorbed, then dropwise adding 5ml of hydrazine hydrate solution with the concentration of 5% into the solution, stirring for 1 hour at room temperature, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the semi-finished catalyst D.
(5) Palladium acetate 56.96mg is dissolved in 50mL glacial acetic acid, palladium acetate solution is obtained after palladium acetate is completely dissolved, semi-finished catalyst D is immersed in 50mL ethanol solution, palladium acetate solution is added dropwise into a mixture of semi-finished catalyst D and ethanol while stirring, then about 20mL formaldehyde solution with concentration of 40% is added dropwise into the mixture while stirring, stirring is carried out for 1 hour at 70 ℃, solution is poured off, washing is carried out with deionized water, and drying is carried out at 120 ℃ to obtain the required catalyst.
The pore size results of the synthetic organic cage of example 1, as determined by the BET method, are shown in FIG. 1. As can be seen from FIG. 1, the maximum pore diameter is 3.53nm, and the minimum pore diameter is 2.91nm.
The catalyst prepared in example 1 had a Pd content of 0.045% and an Ag content of 0.07% as measured by atomic absorption spectrometry.
Comparative example 1
This comparative example provides a catalyst wherein:
Catalyst carrier: the carrier used in example 1 was used.
And (3) preparing a catalyst: the process conditions were the same as in example 1, except that silver was not supported;
(1) Weighing 65.30g of lactic acid, mixing with 100g of roasted carrier, and keeping the temperature at 160 ℃ for 10 hours to obtain a semi-finished catalyst A1;
(2) Mixing 22.79mg of tris (4-formylphenyl) amine with 0.00379mg of dichloroacetic acid, dissolving in 60ml of dichloroethane, then mixing with a semi-finished catalyst A1, stirring and dropwise adding a mixed solution of 27.54mg of tetraphenylenediamine and 10ml of dichloroethane, standing the mixture at room temperature for 200 hours, pouring out residual liquid, washing with ethanol and deionized water respectively, and drying to obtain a semi-finished catalyst B1;
(3) And (3) dissolving 38mg of palladium acetate in 50mL of glacial acetic acid, completely dissolving palladium acetate to obtain a palladium acetate solution, immersing the semi-finished catalyst B1 in 50mL of ethanol solution, dropwise adding the palladium acetate solution into a mixture of the semi-finished catalyst B1 and ethanol, stirring, dropwise adding about 20mL of 40% formaldehyde solution into the mixture, stirring at 70 ℃ for 1 hour, pouring out the solution, washing with deionized water, drying at 120 ℃, and roasting at 260 ℃ for 8 hours to obtain the semi-finished catalyst C1.
(4) Palladium acetate 56.96mg is dissolved in 50mL glacial acetic acid, palladium acetate solution is obtained after palladium acetate is completely dissolved, semi-finished catalyst C1 is immersed in 50mL ethanol solution, palladium acetate solution is added dropwise into a mixture of semi-finished catalyst C1 and ethanol while stirring, then about 20mL formaldehyde solution with concentration of 40% is added dropwise into the mixture while stirring for 1 hour at 70 ℃, solution is poured off, washed with deionized water, and dried at 120 ℃ to obtain the required catalyst.
The Pd content in the catalyst prepared in comparative example 1 was 0.045% as measured by atomic absorption spectrometry.
Example 2
The present embodiment provides a catalyst wherein:
and (3) a carrier: a commercially available spherical alumina carrier was used, 3mm in diameter. After baking for 4 hours at 1150 ℃, the water absorption pore volume is 0.65m 3 Per gram, specific surface area of 15.07m 2 And/g. 100g of the carrier was weighed.
And (3) preparing a catalyst:
(1) Weighing 73.7g of lactic acid, mixing with 100g of roasted carrier, and keeping the temperature at 200 ℃ for 10 hours to obtain a semi-finished catalyst E;
(2) Mixing 3.57mg of tri (4-formylphenyl) amine with 0.0017mg of dichloroacetic acid, dissolving in 60ml of dichloroethane, then mixing with a semi-finished catalyst E, stirring and dropwise adding a mixed solution of 8.89mg of tetraphenylenediamine and 10ml of trichloroethane, standing the mixture at room temperature for 200 hours, pouring out residual liquid, washing with ethanol and deionized water respectively, and drying to obtain a semi-finished catalyst F;
(3) 28.6mg of palladium acetylacetonate is dissolved in 50mL of chloroform, palladium acetylacetonate is completely dissolved to obtain palladium acetylacetonate solution, semi-finished catalyst F is immersed in 50mL of ethanol solution, palladium acetylacetonate solution is dropwise added into a mixture of semi-finished catalyst F and ethanol while stirring, 20mL of 40% formaldehyde solution is dropwise added into the mixture while stirring for 1 hour at 70 ℃, the solution is poured off, washed with deionized water, dried at 120 ℃, and baked at 300 ℃ for 8 hours to obtain semi-finished catalyst G.
(4) Weighing 0.094G of silver nitrate, dissolving the silver nitrate into 65G of deionized water, immersing the semi-finished catalyst G into the prepared silver nitrate solution, standing for 4 hours after the solution is completely absorbed, then dropwise adding 5ml of hydrazine hydrate solution with the concentration of 5% into the solution, stirring for 1 hour at room temperature, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the required catalyst. Semi-finished catalyst H is obtained.
(5) Palladium acetylacetonate 114.58mg is dissolved in 50mL of chloroform, after palladium acetylacetonate is completely dissolved, semi-finished catalyst H is immersed in 50mL of ethanol solution, palladium acetylacetonate solution is added dropwise to a mixture of semi-finished catalyst H and ethanol while stirring, then about 20mL of 40% formaldehyde solution is added dropwise to the mixture, stirring is carried out at 70 ℃ for 1 hour, the solution is poured off, washing is carried out with deionized water, and drying is carried out at 120 ℃ to obtain the required catalyst.
The catalyst prepared in example 2 had a Pd content of 0.05% and an Ag content of 0.06% as measured by atomic absorption spectrometry.
Comparative example 2
This comparative example provides a catalyst wherein:
and (3) a carrier: the same carrier as in example 2 was used.
And (3) preparing a catalyst: the preparation conditions were the same as in example 2, except that palladium was all supported in step (3);
(1) Weighing 73.7g of lactic acid, mixing with 100g of roasted carrier, and keeping the temperature at 200 ℃ for 10 hours to obtain a semi-finished catalyst E1;
(2) Mixing 3.57mg of tri (4-formylphenyl) amine with 0.0017mg of dichloroacetic acid, dissolving in 60ml of dichloroethane, then mixing with a semi-finished catalyst E, stirring and dropwise adding a mixed solution of 8.89mg of tetraphenylenediamine and 10ml of trichloroethane, standing the mixture at room temperature for 200 hours, pouring out residual liquid, washing with ethanol and deionized water respectively, and drying to obtain a semi-finished catalyst F1;
(3) Palladium acetylacetonate 143.18mg is dissolved in 50mL of chloroform, palladium acetylacetonate is completely dissolved to obtain palladium acetylacetonate solution, semi-finished catalyst F1 is immersed in 50mL of ethanol solution, palladium acetylacetonate solution is added dropwise to a mixture of semi-finished catalyst F1 and ethanol while stirring, 20mL of 40% formaldehyde solution is added dropwise to the mixture while stirring for 1 hour at 70 ℃, the solution is poured off, washed with deionized water, dried at 120 ℃, and baked at 300 ℃ for 8 hours to obtain semi-finished catalyst G1.
(4) Weighing 0.094G of silver nitrate, dissolving the silver nitrate into 65G of deionized water, immersing the semi-finished catalyst G1 into the prepared silver nitrate solution, standing for 4 hours after the solution is completely absorbed, then dropwise adding 5ml of hydrazine hydrate solution with the concentration of 5% into the solution, stirring for 1 hour at room temperature, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the required catalyst.
The catalyst prepared in comparative example 2 had a Pd content of 0.05% and an Ag content of 0.06% as measured by atomic absorption spectrometry.
Example 3
The present embodiment provides a catalyst wherein:
and (3) a carrier: adopts a commercially available spherical alumina-titania carrier, and the content of titania is 20%The diameter was 4mm. After being roasted for 4 hours at 1105 ℃, the pore volume is 0.50m 3 Per gram, specific surface area 25.14m 2 And/g. 100g of the carrier was weighed.
And (3) preparing a catalyst:
(1) Weighing 18.9g of acrylic acid, 26g of water, 0.01g of potassium hypophosphite monohydrate, 0.023g of copper acetate monohydrate and 0.16ml of 35% hydrogen peroxide as an initiator, uniformly mixing, adding 100g of calcined carrier, transferring the solution into a reflux bottle after the solution is completely absorbed, heating to 80 ℃ under stirring, and keeping the temperature for 1 hour to obtain a semi-finished catalyst I;
(2) Mixing 16.25mg of tri (4-formylphenyl) amine with 0.00325mg of trichloroacetic acid, dissolving in 50ml of dichloroethane, then mixing with a semi-finished catalyst I, stirring and dropwise adding a mixed solution of 33.15mg of tetraphenylenediamine and 10ml of trichloroethane, standing the mixture at room temperature for 150 hours, pouring out residual liquid, washing with ethanol and deionized water respectively, and drying to obtain a semi-finished catalyst J;
(3) 29.13mg of palladium acetylacetonate is dissolved in 50ml of chloroform, palladium acetylacetonate is completely dissolved to obtain palladium acetylacetonate solution, semi-finished catalyst J is immersed in 50ml of ethanol solution, palladium acetylacetonate solution is dropwise added into a mixture of semi-finished catalyst J and ethanol while stirring, 10ml of 50% formic acid solution is dropwise added into the mixture while stirring, heating and stirring are carried out for 2 hours at 70 ℃, solution is poured off, deionized water is used for washing, drying is carried out at 120 ℃, and roasting is carried out at 400 ℃ for 2 hours, thus obtaining semi-finished catalyst K.
(4) Dissolving 0.16g of silver nitrate into 45g of deionized water, immersing a semi-finished catalyst K into the prepared silver nitrate solution, standing for 4 hours after the solution is fully absorbed, adding 5ml of 10% hydrazine hydrate solution dropwise into the solution, stirring for 1 hour at room temperature, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the semi-finished catalyst M.
(5) Palladium acetylacetonate 156.84mg is dissolved in 50ml of chloroform, and after palladium acetylacetonate is completely dissolved, semi-finished catalyst M is immersed in 50ml of ethanol solution, the prepared palladium acetylacetonate solution is added dropwise to a mixture of semi-finished catalyst M and ethanol while stirring, 10ml of a 50% formic acid solution is added dropwise to the mixture while stirring, heating and stirring are performed at 70 ℃ for 2 hours, the solution is poured off, washed with deionized water, dried at 120 ℃, and baked at 400 ℃ for 2 hours, thereby obtaining the desired catalyst.
The catalyst prepared in example 3 had a Pd content of 0.065% and an Ag content of 0.1% as measured by atomic absorption spectrometry.
Comparative example 3
This comparative example provides a catalyst wherein:
and (3) a carrier: the same carrier as in example 3 was used.
And (3) preparing a catalyst: the catalyst preparation conditions were the same as in example 3, except that the tris (4-formylphenyl) amine in comparative example 3 was 4-fold higher than in example 3;
(1) Weighing 18.9g of acrylic acid, 26g of water, 0.01g of potassium hypophosphite monohydrate, 0.023g of copper acetate monohydrate and 0.16ml of 35% hydrogen peroxide as an initiator, uniformly mixing, adding 100g of calcined carrier, transferring the solution into a reflux bottle after the solution is completely absorbed, heating to 80 ℃ under stirring, and keeping the temperature for 1 hour to obtain a semi-finished catalyst I1;
(2) Mixing 65mg of tris (4-formylphenyl) amine with 0.00325mg of trichloroacetic acid, dissolving in 50ml of dichloroethane, then mixing with a semi-finished catalyst I1, stirring and dropwise adding a mixed solution of 33.15mg of tetraphenylenediamine and 10ml of trichloroethane, standing the mixture at room temperature for 150 hours, pouring out residual liquid, washing with ethanol and deionized water respectively, and drying to obtain a semi-finished catalyst J1;
(3) 29.13mg of palladium acetylacetonate is dissolved in 50ml of chloroform, palladium acetylacetonate is completely dissolved to obtain palladium acetylacetonate solution, a semi-finished catalyst J1 is immersed in 50ml of ethanol solution, palladium acetylacetonate solution is dropwise added into a mixture of the semi-finished catalyst J1 and ethanol while stirring, 10ml of 50% formic acid solution is dropwise added into the mixture while stirring, heating and stirring are carried out for 2 hours at 70 ℃, the solution is poured off, deionized water is used for washing, drying is carried out at 120 ℃, and roasting is carried out for 2 hours at 400 ℃, thus obtaining the semi-finished catalyst K1.
(4) Dissolving 0.16g of silver nitrate into 45g of deionized water, immersing a semi-finished catalyst K1 into the prepared silver nitrate solution, standing for 4 hours after the solution is fully absorbed, adding 5ml of 10% hydrazine hydrate solution into the solution, stirring for 1 hour at room temperature, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the semi-finished catalyst M1.
(5) Palladium acetylacetonate 156.84mg is dissolved in 50ml of chloroform, and after palladium acetylacetonate is completely dissolved, semi-finished catalyst M1 is immersed in 50ml of ethanol solution, the prepared palladium acetylacetonate solution is added dropwise to a mixture of semi-finished catalyst M1 and ethanol while stirring, 10ml of a 50% formic acid solution is added dropwise to the above mixture while stirring, heating and stirring are performed at 70 ℃ for 2 hours, the solution is poured off, washed with deionized water, dried at 120 ℃, and baked at 400 ℃ for 2 hours, thereby obtaining the desired catalyst.
The catalyst prepared in comparative example 3 had a Pd content of 0.065% and an Ag content of 0.1% as measured by atomic absorption spectrometry.
Example 4
The present embodiment provides a catalyst wherein:
and (3) a carrier: the commercial tooth-ball type alumina-magnesia carrier is adopted, the magnesia content is 5 percent, and the diameter is 3mm. Roasting for 4 hours at 1135 ℃ and then obtaining the pore volume of 0.55m 3 Per gram, specific surface area of 22.39m 2 And/g. 100g of the carrier was weighed.
And (3) preparing a catalyst:
(1) Weighing 58.43g of lactic acid, mixing with 100g of roasted carrier, and adding the mixture to keep the temperature at 190 ℃ for 2 hours to obtain a semi-finished catalyst N;
(2) 10.7mg of tri (4-formylphenyl) amine and 0.0018mg of trifluoroacetic acid are taken and mixed, dissolved in 50ml of dichloroethane, then mixed with a semi-finished catalyst N, stirred and dropwise added with a mixed solution of 14.9mg of tetraphenylenediamine and 10ml of dichloroethane, the mixture is kept stand at room temperature for 180 hours, residual liquid is poured out, and the residual liquid is washed with ethanol and deionized water respectively and dried to obtain a semi-finished catalyst O;
(3) 94.95mg of palladium acetate was dissolved in 50ml of chloroform, and the solution was prepared after the palladium acetate was completely dissolved. Immersing the semi-finished catalyst O in 50ml of ethanol solution, dripping the prepared palladium acetate solution into a mixture of the semi-finished catalyst O and ethanol, stirring, dripping more than 20ml of 80% methanol solution into the mixture, stirring for 1 hour at 80 ℃, pouring out the solution, washing with deionized water, drying at 120 ℃, and roasting at 420 ℃ for 1 hour to obtain the semi-finished catalyst P.
(4) Dissolving 0.189g of silver nitrate into 53g of deionized water, immersing a semi-finished catalyst P into the prepared silver nitrate solution, standing for 4 hours after the solution is fully absorbed, dripping 5ml of hydrazine hydrate solution with the concentration of 5% into the solution, stirring for 1 hour at room temperature, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the semi-finished catalyst Q.
(5) 63.31mg of palladium acetate was dissolved in 50ml of chloroform, and the solution was prepared after the palladium acetate was completely dissolved. Immersing the semi-finished catalyst Q in 50ml of ethanol solution, dripping the prepared palladium acetate solution into a mixture of the semi-finished catalyst Q and ethanol, stirring, dripping more than 20ml of 80% methanol solution into the mixture, stirring for 1 hour at 80 ℃, pouring out the solution, washing with deionized water, drying at 120 ℃, and roasting at 400 ℃ for 1 hour to obtain the required catalyst.
The catalyst prepared in example 4 had a Pd content of 0.075% and an Ag content of 0.12% as measured by atomic absorption spectrometry.
Comparative example 4
This comparative example provides a catalyst wherein:
and (3) a carrier: the catalyst carrier was the same as in example 4.
And (3) preparing a catalyst: the difference between this comparative example and example 4 is that there is no step (1).
(1) Mixing 10.7mg of tri (4-formylphenyl) amine with 0.0018mg of trifluoroacetic acid, dissolving in 50ml of dichloroethane, then mixing with a carrier, stirring and dropwise adding a mixed solution of 14.9mg of tetraphenylenediamine and 10ml of dichloroethane, standing the mixture at room temperature for 180 hours, pouring out residual liquid, washing with ethanol and deionized water respectively, and drying to obtain a semi-finished catalyst O1;
(2) 94.95mg of palladium acetate was dissolved in 50ml of chloroform, and the solution was prepared after the palladium acetate was completely dissolved. Immersing the semi-finished catalyst O1 in 50ml of ethanol solution, dripping the prepared palladium acetate solution into a mixture of the semi-finished catalyst O1 and ethanol, stirring, dripping more than 20ml of 80% methanol solution into the mixture, stirring at 80 ℃ for 1 hour, pouring out the solution, washing with deionized water, drying at 120 ℃, and roasting at 420 ℃ for 1 hour to obtain the semi-finished catalyst P1.
(3) Dissolving 0.189g of silver nitrate into 53g of deionized water, immersing a semi-finished catalyst P1 into the prepared silver nitrate solution, standing for 4 hours after the solution is fully absorbed, dripping 5ml of hydrazine hydrate solution with the concentration of 5% into the solution, stirring for 1 hour at room temperature, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the semi-finished catalyst Q1.
(4) 63.31mg of palladium acetate was dissolved in 50ml of chloroform, and the solution was prepared after the palladium acetate was completely dissolved. Immersing the semi-finished catalyst Q1 in 50ml of ethanol solution, dripping the prepared palladium acetate solution into a mixture of the semi-finished catalyst Q1 and ethanol, stirring, dripping more than 20ml of 80% methanol solution into the mixture, stirring for 1 hour at 80 ℃, pouring out the solution, washing with deionized water, drying at 120 ℃, and roasting at 400 ℃ for 1 hour to obtain the required catalyst.
The catalyst prepared in comparative example 4 had a Pd content of 0.075% and an Ag content of 0.12% as measured by atomic absorption spectrometry.
Example 5
The present embodiment provides a catalyst wherein:
and (3) a carrier: spherical alumina-magnesia carrier is adopted, the magnesia content is 10 percent, and the diameter is 3mm. After roasting for 4 hours at 1100 ℃, the pore volume is 0.53m 3 Per gram, specific surface area 28.68m 2 And/g. 100g of the carrier was weighed.
And (3) preparing a catalyst:
(1) Weighing 63.90g of lactic acid, mixing with 100g of roasted carrier, and adding the mixture to keep the temperature at 180 ℃ for 2 hours to obtain a semi-finished catalyst R;
(2) Mixing 11.67mg of tri (4-formylphenyl) amine with 0.0047mg of dichloroacetic acid, dissolving in 50ml of dichloroethane, then mixing with a semi-finished catalyst R, stirring and dropwise adding a mixed solution of 26.19mg of tetraphenylenediamine and 10ml of dichloroethane, standing the mixture at room temperature for 190 hours, pouring out residual liquid, washing with ethanol and deionized water respectively, and drying to obtain a semi-finished catalyst S;
(3) 100mg of palladium acetylacetonate was dissolved in 50ml of benzene, and the solution was prepared until palladium acetylacetonate was completely dissolved. Immersing the semi-finished catalyst S in 50ml of 80% methanol solution, dripping the prepared palladium acetylacetonate solution into a mixture of the semi-finished catalyst S and methanol, stirring, dripping about 10ml of 40% formaldehyde solution into the mixture, stirring at 50 ℃ for 1 hour, pouring out the solution, washing with deionized water, drying at 120 ℃, and roasting at 380 ℃ for 1 hour to obtain the semi-finished catalyst T.
(4) Dissolving 0.141g of silver nitrate into 53g of deionized water, immersing the semi-finished catalyst T into the prepared silver nitrate solution, standing for 4 hours after the solution is fully absorbed, dripping 20ml of 50% formic acid solution into the solution, stirring for 1 hour at 50 ℃, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the semi-finished catalyst U.
(5) 100mg of palladium acetylacetonate was dissolved in 50ml of benzene, and the solution was prepared until palladium acetylacetonate was completely dissolved. Immersing the semi-finished catalyst U in 50ml of methanol solution, dripping the prepared palladium acetylacetonate solution into a mixture of the semi-finished catalyst U and methanol, stirring, dripping about 10ml of 40% formaldehyde solution into the mixture, stirring for 1 hour at 50 ℃, pouring out the solution, washing with deionized water, drying at 120 ℃, and roasting at 380 ℃ for 1 hour to obtain the desired catalyst.
The catalyst prepared in example 5 had a Pd content of 0.07% and an Ag content of 0.09% as measured by atomic absorption spectrometry.
Comparative example 5
This comparative example provides a catalyst in which the catalyst support is the same as example 5, except that the catalyst is prepared using a conventional method.
(1) Weighing 116.67mg of palladium chloride, dissolving in 80ml of deionized water, regulating the pH to 2.5, immersing 100g of the roasted carrier in the solution for 30min, drying at 120 ℃, and roasting at 500 to obtain a semi-finished catalyst T1;
(2) 142.16mg of silver nitrate is weighed and dissolved in 52.25g of deionized water to obtain a silver nitrate solution, the semi-finished catalyst T1 is immersed in the prepared silver nitrate solution, and after the solution is completely absorbed, the catalyst is dried at 100 ℃ and baked at 550 ℃ to obtain the required catalyst.
The catalyst prepared in comparative example 5 had a Pd content of 0.07% and an Ag content of 0.09% as measured by atomic absorption spectrometry.
Example 6
The present embodiment provides a catalyst wherein:
and (3) a carrier: the spherical carrier is commercially available, the alumina content is 95%, the titanium oxide content is 5%, and the diameter is 3mm. Roasting for 4 hours at 1090 ℃ and then obtaining the porous ceramic with the pore volume of 0.48m 3 Per gram, specific surface area of 30.13m 2 And/g. 100g of the carrier was weighed.
And (3) preparing a catalyst:
(1) Weighing 57.14g of lactic acid, mixing with 100g of roasted carrier, and keeping the temperature at 190 ℃ for 1 hour to obtain a semi-finished catalyst V;
(2) Mixing 8.13mg of tris (4-formylphenyl) amine with 0.0023mg of trifluoroacetic acid, dissolving in 50ml of dichloroethane, then mixing with a semi-finished catalyst V, stirring, dropwise adding a mixed solution of 15.46mg of 3-methyltetrabiphenyldiamine and 10ml of dichloroethane, standing the mixture at room temperature for 100 hours, pouring out residual liquid, washing with ethanol and deionized water respectively, and drying to obtain a semi-finished catalyst W;
(3) Weighing 173.23mg of silver nitrate, dissolving the silver nitrate into 48g of deionized water, immersing the semi-finished catalyst W into the prepared solution, standing for 4 hours after the solution is fully absorbed, then dripping 50ml of an acetaldehyde solution with concentration of more than 50% into the solution, stirring for 1 hour at 60 ℃, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the semi-finished catalyst Y.
(4) Palladium acetate 137.16mg was dissolved in 50ml of dichloroethane, and the resulting solution was prepared for use after the palladium acetate was completely dissolved. Immersing the semi-finished catalyst Y in 50ml of ethanol solution, dripping the prepared palladium acetate solution into a mixture of the semi-finished catalyst Y and ethanol, stirring, dripping 30ml of an acetaldehyde solution with concentration of more than 50% into the mixture, stirring for 1 hour at 60 ℃, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the required catalyst.
The catalyst prepared in example 6 had a Pd content of 0.065% and an Ag content of 0.11% as measured by atomic absorption spectrometry.
Comparative example 6
This comparative example provides a catalyst wherein:
and (3) a carrier: the same carrier as in example 6 was used, except that the same molar amount of phenylenediamine as 3-methyltetrabiphenyldiamine was used, and tris (4-formylphenyl) amine was used to prepare the organic cage as in example 6.
And (3) preparing a catalyst:
(1) Weighing 57.14g of lactic acid, mixing with 100g of roasted carrier, and keeping the temperature at 190 ℃ for 1 hour to obtain a semi-finished catalyst V1;
(2) Mixing 8.13mg of tri (4-formylphenyl) amine with 0.0023mg of trifluoroacetic acid, dissolving in 50ml of dichloroethane, then mixing with a semi-finished catalyst V1, stirring and dropwise adding a mixed solution of 4.80mg of phenylenediamine and 10ml of dichloroethane, standing the mixture at room temperature for 100 hours, pouring out residual liquid, washing with ethanol and deionized water respectively, and drying to obtain a semi-finished catalyst W1;
(3) Weighing 173.23mg of silver nitrate, dissolving the silver nitrate into 48g of deionized water, immersing the semi-finished catalyst W1 into the prepared solution, standing for 4 hours after the solution is fully absorbed, then dripping 50ml of an acetaldehyde solution with concentration of more than 50% into the solution, stirring for 1 hour at 60 ℃, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the semi-finished catalyst Y1.
(4) Palladium acetate 137.16mg is dissolved in 50ml dichloroethane, and the prepared solution is reserved after the palladium acetate is completely dissolved; immersing the semi-finished catalyst Y1 in 50ml of ethanol solution, dripping the prepared palladium acetate solution into a mixture of the semi-finished catalyst Y1 and ethanol, stirring, dripping 30ml of an acetaldehyde solution with concentration of more than 50% into the mixture, stirring at 60 ℃ for 1 hour, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the required catalyst.
The catalyst prepared in comparative example 6 had a Pd content of 0.065% and an Ag content of 0.11% as measured by atomic absorption spectrometry.
Example 7
The present embodiment provides a catalyst wherein:
and (3) a carrier: a commercially available spherical alumina carrier was used, 4mm in diameter. Roasting for 4 hours at 1135 ℃, and the water absorption pore volume is 0.60m 3 Per gram, specific surface area of 21.75m 2 And/g. 100g of the carrier was weighed.
And (3) preparing a catalyst:
(1) Weighing 67.5g of lactic acid, mixing with 100g of roasted carrier, and adding the mixture into the carrier to keep the temperature at 210 ℃ for 2 hours to obtain a semi-finished catalyst AA;
(2) Mixing 17.14mg of tris (4-formylphenyl) amine with 0.0057mg of difluoroacetic acid, dissolving in 50ml of dichloroethane, then mixing with a semi-finished catalyst AA, stirring and dripping a mixed solution of 42.40mg of 2-chloro-tetraphenylenediamine and 10ml of dichloroethane, standing the mixture at room temperature for 120 hours, pouring out residual liquid, washing with ethanol and deionized water respectively, and drying to obtain a semi-finished catalyst BB;
(3) Palladium acetate 51.53mg was weighed and dissolved in 50ml of dichloroethane, and palladium acetate solution was obtained after palladium acetate was completely dissolved.
Immersing a semi-finished catalyst BB in 50ml of ethanol solution, dripping the prepared palladium acetate solution into a mixture of the semi-finished catalyst BB and methanol, stirring, dripping 3ml of hydrazine hydrate solution with the concentration of 5% into the mixture, stirring for 1 hour at room temperature, pouring out the solution, washing with deionized water, drying at 120 ℃, and roasting at 300 ℃ for 2 hours to obtain the semi-finished catalyst CC.
(4) Weighing 0.23g of silver acetylacetonate, dissolving the silver acetylacetonate into 60ml of toluene, immersing a semi-finished catalyst CC into the prepared silver acetylacetonate solution, standing for 4 hours after the solution is completely absorbed, then dropwise adding 3ml of hydrazine hydrate solution with the concentration of 5% into the solution, stirring for 1 hour at room temperature, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the semi-finished catalyst DD.
(5) 73.47mg of palladium acetate was weighed and dissolved in 50ml of dichloroethane, and a palladium acetate solution was obtained after the palladium acetate was completely dissolved.
Immersing the semi-finished catalyst DD in 50ml of ethanol solution, dripping the prepared palladium acetate solution into a mixture of the semi-finished catalyst DD and methanol, stirring, dripping 3ml of hydrazine hydrate solution with the concentration of 5% into the mixture, stirring for 1 hour at room temperature, pouring out the solution, washing with deionized water, drying at 120 ℃, and roasting at 300 ℃ for 2 hours to obtain the required catalyst.
The catalyst prepared in example 7 had a Pd content of 0.06% and an Ag content of 0.12% as measured by atomic absorption spectrometry.
Comparative example 7
This comparative example provides a catalyst wherein:
and (3) a carrier: the same carrier as in example 7 was used.
And (3) preparing a catalyst: the preparation conditions were the same as in example 7, except that the firing temperature in step (3) was 600 ℃.
(1) Weighing 67.5g of lactic acid, mixing with 100g of roasted carrier, and adding the mixture into the carrier to keep the temperature at 210 ℃ for 2 hours to obtain a semi-finished catalyst AA1;
(2) Mixing 17.14mg of tris (4-formylphenyl) amine with 0.0057mg of difluoroacetic acid, dissolving in 50ml of dichloroethane, then mixing with a semi-finished catalyst AA1, stirring and dropwise adding a mixed solution of 42.40mg of 2-chloro-tetraphenylenediamine and 10ml of dichloroethane, standing the mixture at room temperature for 120 hours, pouring out residual liquid, washing with ethanol and deionized water respectively, and drying to obtain a semi-finished catalyst BB1;
(3) Palladium acetate 51.53mg was weighed and dissolved in 50ml of dichloroethane, and palladium acetate solution was obtained after palladium acetate was completely dissolved.
Immersing the semi-finished catalyst BB1 in 50ml of ethanol solution, dripping the prepared palladium acetate solution into a mixture of the semi-finished catalyst BB1 and methanol, stirring, dripping 3ml of hydrazine hydrate solution with the concentration of 5% into the mixture, stirring at room temperature for 1 hour, pouring out the solution, washing with deionized water, drying at 120 ℃, and roasting at 600 ℃ for 2 hours to obtain the semi-finished catalyst CC1.
(4) Weighing 0.23g of silver acetylacetonate, dissolving the silver acetylacetonate into 60ml of toluene, immersing a semi-finished catalyst CC1 into the prepared silver acetylacetonate solution, standing for 4 hours after the solution is fully absorbed, then dropwise adding 3ml of hydrazine hydrate solution with the concentration of 5% into the solution, stirring for 1 hour at room temperature, pouring out the solution, washing with deionized water, and drying at 120 ℃ to obtain the semi-finished catalyst DD1.
(5) 73.47mg of palladium acetate was weighed and dissolved in 50ml of dichloroethane, and a palladium acetate solution was obtained after the palladium acetate was completely dissolved.
Immersing the semi-finished catalyst DD1 in 50ml of ethanol solution, dripping the prepared palladium acetate solution into a mixture of the semi-finished catalyst DD1 and methanol, stirring, dripping 3ml of hydrazine hydrate solution with the concentration of 5% into the mixture, stirring at room temperature for 1 hour, pouring out the solution, washing with deionized water, drying at 120 ℃, and roasting at 300 ℃ for 2 hours to obtain the desired catalyst.
The catalyst prepared in comparative example 7 had a Pd content of 0.06% and an Ag content of 0.12% as measured by atomic absorption spectrometry.
Performance of catalyst for hydrogenation reaction after two carbon atoms
Evaluation mode:
the catalyst loading in the fixed bed reactor was 100mL (recording weight), packing 50mL, space velocity of reaction mass: 4000/h, operating pressure 2.5MPa, hydrogen-alkyne ratio 1.5, reactor inlet temperature 75 ℃.
And (3) reduction of a catalyst: the hydrogen flow is 10 liters/hour, and the temperature is kept constant at 130 ℃ for 4 hours.
The evaluation results were calculated as shown in Table 1.
Table 1 evaluation results calculation method
The initial selectivity was the selectivity measured 24 hours from the start of the reactor charge.
The initial activity was the activity (acetylene conversion) measured 24 hours from the start of the reactor charge.
The reaction mass composition was as follows:
acetylene 0.9% (mol/mol), ethylene 82% (mol/mol), ethane 17% (mol/mol), CO 200ppm, and carbon three content 0.5% (mol/mol).
The evaluation results of the catalyst are shown in Table 2.
Table 2 results of catalyst evaluation
The comparison of the results of the catalyst evaluation in Table 2 can be seen:
compared to example 1, the selectivity was at least 5 percent lower in comparative example 1 due to the absence of silver loading.
In comparative example 2, since all palladium was supported first and silver was supported later, the active site of the active center surface portion was occupied by silver, the ability to adsorb alkyne was lowered, and the catalytic activity was greatly lowered as compared with example 2.
In comparative example 3, the amount of tris (4-formylphenyl) amine was greatly increased, the number of organic cages formed at the initial stage of synthesis was increased, the number of corresponding active centers was excessive, and the size of palladium active center supported by a single organic cage was decreased, resulting in insufficient catalyst activity.
In comparative example 4, the synthesis reaction of the organic cage was carried out at all sites inside the carrier without synthesizing the polar polymer in advance, and the active center of the supported palladium was also located at all sites inside the carrier, and the activity selectivity was inferior to that of example 4 due to the influence of the diffusion limitation of the reactive molecule.
Comparative example 5 the catalyst was prepared by conventional methods, resulting in reduced catalyst activity due to silver occupying part of the outer surface of the active sites. Similar to the case of comparative example 2.
In comparative example 6, phenylenediamine is used to replace terphenylenediamine, the synthesized organic cage is obviously smaller, the active center size is smaller, and the activity of the catalyst is insufficient in the carbon dioxide hydrogenation reaction in which CO participates.
In comparative example 7, during the calcination in step (3), the temperature was higher than the decomposition temperature of the organic cage, resulting in disintegration of the organic cage, and when palladium was supported in step (5), part of the palladium could not be supported in the organic cage, but could be dispersed in other parts of the carrier, and the catalyst activity was significantly lower.
Under the condition of the participation of CO in the reaction, CO can be adsorbed on palladium atoms to form competitive adsorption with acetylene, so that the probability of simultaneously forming a plurality of vinyl groups in the same active center is reduced, and the effects of reducing the green oil production and improving the selectivity are objectively achieved. However, CO may still form strong adsorption and formylation reactions occur. In order to reduce the formylation reaction, the adsorption strength of CO on the active center needs to be reduced, and the electronic effect of silver after forming an alloy with palladium can be utilized, namely S electrons of silver enter the outer empty orbitals of palladium first, and then the silver is not required to be exposed outside the active center. Silver does not occupy the position of the outer layer, so that the reduction of the activity of the catalyst is not significant. Compared with the traditional method, the catalyst provided by the invention has the advantages that the loading of noble metal palladium is greatly reduced, the green oil generation is also reduced, and the operation period of the catalyst is prolonged.

Claims (13)

1. An alkyne selective hydrogenation catalyst, wherein the active component of the catalyst contains Pd and Ag, the content of Pd is 0.045-0.075% and the content of Ag is 0.06-0.12% based on 100% of the mass of the carrier;
the catalyst comprises an organic cage, wherein the organic cage is positioned on the outer surface of the catalyst, the size of the organic cage is 2.7-3.6nm, pd is loaded in the organic cage, and Ag is positioned in the middle or at the bottom of a Pd active center.
2. The catalyst according to claim 1, wherein the specific surface area of the catalyst is 15-30m 2 /g。
3. A catalyst according to claim 1 or 2, wherein the support of the catalyst is alumina or predominantly alumina;
preferably, the alumina in the carrier is in a theta, alpha or mixed crystal form thereof; alumina in the catalyst carrier is more than 80%; more preferably, the support further comprises magnesium oxide and/or titanium oxide.
4. A process for the preparation of a catalyst as claimed in any one of claims 1 to 3 comprising the steps of:
(1) Mixing a hydrophilic polymerizable monomer with a roasted carrier, and polymerizing at a certain temperature to obtain a first semi-finished catalyst, wherein the volume of a polymer synthesized by the hydrophilic polymerizable monomer is 80-95%, preferably 85-95%, of the pore volume of the carrier;
(2) Mixing tri (4-formylphenyl) amine and halogenated acetic acid, dissolving in halogenated acetic acid, then mixing with a first semi-finished catalyst, stirring, dropwise adding a mixed solution of aromatic diamine compounds and halogenated acetic acid, standing the mixture, pouring out residual liquid after the reaction is completed, washing with alcohol and deionized water respectively, and drying to obtain a second semi-finished catalyst;
wherein, the mol ratio of the aromatic diamine compound to the tri (4-formylphenyl) amine is 1.2-2.5:1, the mass ratio of the tri (4-formylphenyl) amine to the halogenated acetic acid is 2000-6000:1;
(3) Dissolving organic palladium salt in an organic solvent to obtain a first solution of a palladium precursor;
immersing the second semi-finished catalyst into an alcohol solution, dropwise adding a first solution of a palladium precursor into a mixture of the second semi-finished catalyst and alcohol, stirring at the same time, dropwise adding a reducing agent, heating and stirring until the surface of the second semi-finished catalyst is not discolored, pouring out the solution, washing with deionized water, drying, and roasting at a temperature at which the polymer formed in the step (1) can be decomposed to obtain a third semi-finished catalyst;
(4) Dissolving soluble silver salt in deionized water or an organic solvent to obtain a silver-containing impregnating solution, immersing a third semi-finished catalyst in the silver-containing impregnating solution, standing after the third semi-finished catalyst is completely absorbed, dropwise adding a reducing agent to reduce silver, pouring the solution, washing with deionized water, and drying to obtain a fourth semi-finished catalyst;
(5) Dissolving organic palladium salt in an organic solvent to obtain a second solution of a palladium precursor, immersing a fourth semi-finished catalyst in an alcohol solution, dropwise adding the second solution of the palladium precursor into a mixture of the fourth semi-finished catalyst and alcohol, and stirring at the same time;
dropwise adding a reducing agent into the solution, heating and stirring until the surface of the fourth semi-finished catalyst is not discolored any more, pouring the solution, washing and drying to obtain the catalyst, or pouring the solution, washing with deionized water, drying and roasting to obtain the catalyst without reduction;
preferably, the ratio of the total mass of palladium in the organic palladium salt in step (3) and step (5) to the mass of tris (4-formylphenyl) amine is 2-14:1.
5. The production method according to claim 4, wherein in the step (1), the hydrophilic polymerizable monomer is a monomer containing a carbonyl group and/or a carboxyl group and capable of undergoing polymerization or condensation reaction, preferably comprising lactic acid, acrylic acid or formaldehyde;
preferably, the hydrophilic polymerizable monomer forms a polymer having a decomposition temperature of less than 450 ℃, more preferably less than 420 ℃.
6. The production process according to claim 4, wherein in the step (2), the aromatic diamine is a tetraphenylenediamine or a derivative having a substituent on a benzene ring thereof, preferably a para-tetraphenylenediamine or a derivative having a substituent on a benzene ring thereof, and the substituent is preferably a halogen or an alkyl group.
7. The production process according to claim 4, wherein in step (2), the halogenated acetic acid is a fluorinated acetic acid or a chloroacetic acid, preferably a trifluoroacetic acid or a dichloroacetic acid.
8. The process according to claim 4, wherein in step (2), the haloalkane comprises a fluoroalkyl, chloroalkane or bromoalkane, preferably a halomethane or a haloethane, more preferably dichloroethane or trichloromethane.
9. The production method according to claim 4, wherein in step (3) and step (5), the organic palladium salt comprises palladium acetate or palladium acetylacetonate;
when the organic palladium salt is palladium acetylacetonate, the organic solvent is chloroform; when the organic palladium salt is palladium acetate, the organic solvent is one or a combination of more than two of chloroform, dichloromethane and glacial acetic acid.
10. The production method according to claim 4, wherein in step (3) and step (5), the alcohol comprises ethanol or methanol.
11. The process according to claim 4, wherein in the steps (3), (4) and (5), the reducing agent is a reducing compound, preferably one or a combination of two or more of methanol, formaldehyde, formic acid, ethanol, acetaldehyde and hydrazine hydrate.
12. The preparation method according to claim 4, wherein in step (4), the soluble silver salt is a silver salt soluble in water or an organic solvent, preferably silver nitrate and/or silver acetylacetonate.
13. The preparation method according to claim 4, wherein step (4) is performed prior to step (3), and step (3) and step (5) are performed in combination.
CN202210847575.1A 2022-07-19 2022-07-19 Alkyne selective hydrogenation catalyst and preparation method thereof Pending CN117463325A (en)

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