CN112023921B - Preparation method of Pt-based catalyst with high dispersion of active component - Google Patents

Preparation method of Pt-based catalyst with high dispersion of active component Download PDF

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CN112023921B
CN112023921B CN202010902576.2A CN202010902576A CN112023921B CN 112023921 B CN112023921 B CN 112023921B CN 202010902576 A CN202010902576 A CN 202010902576A CN 112023921 B CN112023921 B CN 112023921B
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CN112023921A (en
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张海娟
张向月
李承泽
万海
王卫强
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Liaoning Shihua University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B01J35/396—
    • B01J35/40—
    • B01J35/615—
    • B01J35/635—
    • B01J35/657—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/322—Catalytic processes with metal oxides or metal sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/324—Catalytic processes with metals
    • C07C5/325—Catalytic processes with metals of the platinum group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a preparation method of a Pt-based catalyst with a high dispersion active component, which comprises the following steps: (1) Taking Sn-containing alumina as a carrier, adding an ethylenediamine tetraacetic acid potassium solution, and carrying out suction filtration to obtain an alumina carrier sample containing Sn and K; (2) After the obtained product is vacuumized, adding an ethanol solution containing porphyrin Pt, heating and refluxing under a vacuum state, stopping refluxing, and continuously evaporating the solvent; (3) Heating the obtained product in nitrogen atmosphere, cutting into nitrogen mixed gas containing HCl and water vapor, treating for a certain time, and then introducing nitrogen for cooling; (4) And (3) dipping the obtained product into an alkali metal auxiliary agent K, and drying and roasting to obtain the Pt-based catalyst with high dispersion of the active components of the target product. The invention can realize high dispersion of Pt, reduce the Pt consumption, has stable active phase structure, good activity, high propylene selectivity and strong stability, and is beneficial to the industrial production of the catalyst.

Description

Preparation method of Pt-based catalyst with high dispersion of active component
Technical Field
The invention relates to a preparation method of a high-dispersion dehydrogenation catalyst, in particular to a preparation method of a Pt-based catalyst with a high-dispersion active component.
Background
Propylene is one of the most important basic raw materials in the chemical industry. The annual average rate of increase was 1.8 times that of GDP over the past 5 years. The propylene productivity of the traditional process is seriously insufficient, and an alternative process for propylene production must be sought. Propane dehydrogenation propylene production technology (PDH) is the most competitive route and will be one of the key technologies for ensuring core competitiveness in global competition of petrochemical industry in various countries.
The propane dehydrogenation technology commonly uses supported Pt-based catalysts, and the main problems currently faced are: the active component Pt has high heat sensitivity and is extremely easy to migrate, agglomerate and even sinter at high temperature, so that the active component Pt is difficult to keep highly dispersed, the catalytic efficiency of the Pt active phase is rapidly reduced, the carbon deposition amount is rapidly increased, and even the Pt active phase is permanently deactivated due to sintering. The process strategies such as adding dilution gas hydrogen, negative pressure operation and the like are adopted internationally to achieve the purposes of improving the selectivity and the stability of the catalyst and delay the deactivation of the catalyst. However, the problems of poor high-temperature stability and rapid carbon deposit deactivation of the catalyst are not essentially solved. Therefore, how to realize the controllable preparation of the active phase, construct the Pt active phase with a high-temperature stable structure, improve the catalytic efficiency and prolong the service life of the Pt active phase, and is a main challenge faced by the development of a Pt-based propane dehydrogenation catalyst.
CN1579616 patent provides a gamma-Al with a double pore structure with large pore, low bulk ratio 2 O 3 The pellets are used as carriers for the catalyst of the dehydrogenation of the linear alkane, and the reaction performance of the dehydrogenation of the low-carbon alkane can be improved through the modulation of the catalyst. USP4,914,075 discloses Pt-based catalysts supported on propane and other lower alkane dealuminated hydroxides, with high alkane conversion and alkene selectivity. CN1201715 discloses Pt-Sn-K/Al for dehydrogenating light alkane 2 O 3 A method for preparing the catalyst. USP4,914,075, USP4,353,815, EP98,622, etc., all report a Pt-based catalyst for the dehydrogenation of propane and other lower alkanes with high alkane conversion and olefin selectivity. Although these catalysts have high alkane conversion and olefin selectivity under certain reaction conditions, the catalyst is easy to accumulate carbon and deactivate under high temperature conditions, so that the stability of the catalytic reaction is poor, and the service life of the catalyst is short. Propane dehydrogenation research of Pt-Sn catalysts taking alumina as a carrier at home and abroad is widely reported, but the catalyst activity, stability, product selectivity, preparation economy and the like cannot be considered. The traditional Pt-based propane dehydrogenation catalyst takes alumina as a carrier, and when Pt is introduced by adopting an impregnation method, the alumina carrier has strong adsorption effect on a Pt precursor, but the Pt cannot be dispersed highly although a competitive adsorbent is adopted, so that the dosage of Pt cannot be reduced, and the Pt is easy to gather and grow up in the reaction process, so that the propane conversion rate and the propylene selectivity are reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a Pt-based catalyst with high dispersion of active components, and the catalyst prepared by the method can realize high dispersion of Pt, has stable active phase structure, better activity, selectivity and stability and lower raw material coking rate.
In order to solve the technical problems, the invention is realized as follows:
a preparation method of a Pt-based catalyst with a high dispersion of an active component comprises the following steps:
(1) Taking Sn-containing alumina as a carrier, adding an ethylenediamine tetraacetic acid potassium solution, and carrying out suction filtration to obtain an alumina carrier sample containing Sn and K;
(2) After vacuumizing the product obtained in the step (1), adding an ethanol solution containing porphyrin Pt, heating and refluxing in a vacuum state, stopping refluxing, and continuously evaporating the solvent;
(3) Heating the product obtained in the step (2) in a nitrogen atmosphere, cutting into a nitrogen mixed gas containing HCl and water vapor, treating for a certain time, and then introducing nitrogen for cooling;
(4) And (3) dipping the product obtained in the step (3) into an alkali metal auxiliary agent K, and drying and roasting to obtain the Pt-based catalyst with high dispersion of the active component of the target product.
As a preferable scheme, in the step (1), the Sn-containing alumina carrier is spherical, bar-shaped, microsphere or special-shaped; the specific surface of the Sn-containing alumina carrier is 170-260 m 2 Per gram, the pore volume is 0.40-0.90 cm 3 /g。
The Sn in the Sn-containing alumina carrier can be introduced in the alumina gel forming process, can be introduced in a loading manner, and can be introduced by kneading in the alumina forming process.
Further, in the step (1), the potassium ethylenediamine tetraacetate solution is prepared by mixing ethylenediamine tetraacetic acid, potassium hydroxide and water.
Further, the molar ratio of the ethylenediamine tetraacetic acid to the potassium hydroxide is 1:4 to 10, preferably 1:6 to 8; the concentration of the potassium ethylenediamine tetraacetate solution is 0.01-0.3 mol/L, preferably 0.05-0.2 mol/L based on the mass of the ethylenediamine tetraacetic acid.
Further, in the step (1), the addition amount of the Sn-containing alumina is 50-300 g, preferably 100-200 g, calculated by 1L of the potassium ethylenediamine tetraacetate solution; stirring is carried out for 1 to 24 hours, preferably 4 to 8 hours.
Further, in the step (2), the product obtained in the step (1) is vacuumized for 0.3 to 2 hours, preferably 0.5 to 1.2 hours, an ethanol solution containing porphyrin Pt is added, and the mixture is heated to 40 to 80 ℃, preferably 50 to 70 ℃ in a vacuum state, and is kept under reflux for 1 to 6 hours, preferably 2 to 4 hours; the ratio of the volume of the ethanol solution containing porphyrin Pt to the volume of the product obtained in the step (1) is 4-6: 1.
further, in the step (3), the nitrogen mixed gas containing HCl and water vapor is cut into at the temperature of 120-240 ℃, preferably 160-200 ℃ for 1-8 hours, preferably 2-4 hours; the volume airspeed is 200-2000 h -1 Preferably 500h -1 -1000h -1 The method comprises the steps of carrying out a first treatment on the surface of the In the nitrogen mixed gas, the volume content of HCl is 1-10%; preferably 2 to 4%; the volume content of the water vapor is 5 to 30%, preferably 10 to 20%.
Further, in the step (4), the product obtained in the step (3) is further impregnated with an alkali metal additive K, aged for 2 to 16 hours, preferably 4 to 8 hours at room temperature, dried for 2 to 16 hours at 40 to 160 ℃, preferably dried for 4 to 8 hours at 80 to 120 ℃, and baked for 2 to 20 hours at 400 to 800 ℃, preferably baked for 4 to 8 hours at 500 to 700 ℃, preferably baked for 6 to 18 hours at 450 to 600 ℃.
Further, in the Pt-based catalyst with the highly dispersed active component, the weight percentage of Pt is 0.1 to 1.0 percent, preferably 0.2 to 0.5 percent; 0.2 to 10 percent of Sn in terms of element weight percent; preferably 0.5 to 5%; the content of K is 0.3-4% by weight of the element, preferably 0.3-3%.
Further, in the step (2), porphyrin Pt is octaethylporphyrin platinum; the alkali metal auxiliary K is potassium nitrate. The alkali metal auxiliary K is soluble K-containing salt, can be inorganic salt or organic salt, and is preferably potassium nitrate.
According to the preparation method, potassium ethylenediamine tetraacetate is pre-dispersed on the surface of Sn-containing alumina, porphyrin platinum with larger kinetic diameter is loaded, under the combined action of HCl and water vapor, under the existence of hydroxyl free radicals, the large pi ring of porphyrin is destroyed, conjugation is lost, the stability of porphyrin platinum is reduced, chloride ions and platinum in the porphyrin platinum have stronger affinity, the platinum is eluted from a coordination structure and then migrates to the vicinity of ethylenediamine tetraacetic acid, potassium combined with the ethylenediamine tetraacetic acid is replaced, so that a complex of ethylenediamine tetraacetic acid and Pt is formed, and after drying and roasting, the highly dispersed Pt-containing catalyst is obtained. The preparation method can realize high dispersion of Pt, reduce the dosage of Pt, and has the advantages of stable active phase structure, good activity, high propylene selectivity and strong stability. The preparation method of the catalyst is simple, the process technology is mature, and the industrial production of the catalyst is facilitated.
Drawings
The invention is further described below with reference to the drawings and the detailed description. The scope of the present invention is not limited to the following description.
FIG. 1 is a transmission electron microscope image of the catalyst obtained in example 2.
Detailed Description
Example 1
Respectively weighing a certain amount of ethylenediamine tetraacetic acid powder and solid potassium hydroxide with the molar ratio of 1:7, adding the ethylenediamine tetraacetic acid powder and the solid potassium hydroxide into deionized water, and fully stirring to prepare a mixed solution containing ethylenediamine tetraacetic acid potassium and potassium hydroxide with the molar concentration of 0.15mol/L calculated by ethylenediamine tetraacetic acid.
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm) 3 Per gram, specific surface area 224m 2 Per gram, the following examples all used the carrier) 75g, was added to 500mL of potassium ethylenediamine tetraacetate solution, stirred well for 6 hours, and then suction filtered. Placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 1h, adding 375mL ethanol solution containing a certain amount of octaethylporphyrin platinum, heating at 60 ℃ in a vacuum state, treating for 3h, stopping refluxing, continuously evaporating the solvent, cooling and taking out the solid. The obtained solid was placed in a fixed bed reactor, heated to 180℃under nitrogen atmosphere, and then cut into HCl-containing volume concentrateNitrogen with 3% degree and 15% water vapor volume concentration, and a volume space velocity of 750h -1 After 3h of treatment, switching to nitrogen and cooling. 75mL of potassium nitrate solution with a certain concentration is prepared and added into 50g of solid treated by nitrogen containing HCl and water vapor, the solid is aged for 10 hours, dried for 6 hours at 100 ℃, and baked for 10 hours at 500 ℃ to obtain a catalyst C-1, wherein the contents of components in the catalyst are as follows: pt 0.3wt%, sn 1wt% and K2 wt%. The particle size distribution of Pt grains in the range of 1nm to 3nm was 93%. Evaluation conditions: at 600 ℃, the mass airspeed of propane is 2h -1 The propane dehydrogenation reaction was carried out under normal pressure, and 3g of catalyst was used. The evaluation results are shown in Table 1.
Example 2
Respectively weighing a certain amount of the components according to the molar ratio of 1:6, adding the ethylenediamine tetraacetic acid powder and solid potassium hydroxide into deionized water, and fully stirring to prepare a mixed solution containing the potassium ethylenediamine tetraacetate and the potassium hydroxide, wherein the molar concentration of the mixed solution is 0.2mol/L calculated by the ethylenediamine tetraacetic acid.
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm) 3 Per gram, specific surface area 224m 2 Per g, the following examples all used the carrier) 100g, was added to 500mL of a potassium ethylenediamine tetraacetate-containing solution, stirred well for 4 hours, and then suction filtered. Placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 1.2 hours, adding 400mL of ethanol solution containing a certain amount of octaethylporphyrin platinum, heating at 50 ℃ in a vacuum state, treating for 4 hours, stopping refluxing, continuously evaporating the solvent, cooling and taking out the solid. The solid obtained was placed in a fixed bed reactor, heated to 160℃under nitrogen atmosphere, and then nitrogen gas having a HCl volume concentration of 4% and a water vapor volume concentration of 20% was fed in at a volume space velocity of 500h -1 After 4h of treatment, switching to nitrogen and cooling. 75mL of potassium nitrate solution with a certain concentration is prepared and added into 50g of solid treated by nitrogen containing HCl and water vapor, the solid is aged for 16h, dried for 4h at 80 ℃, and baked for 18h at 450 ℃ to obtain a catalyst C-2, wherein the contents of components in the catalyst are as follows: pt 0.5wt%, sn 5wt% and K3 wt%. The particle size distribution of Pt grains in the range of 1nm to 3nm was 96%. Evaluation conditions: at 600 ℃, the mass airspeed of propane is 2h -1 Under normal pressureThe dehydrogenation reaction of propane, the catalyst use amount is 3g. The evaluation results are shown in Table 1.
Example 3
Respectively weighing a certain amount of ethylenediamine tetraacetic acid powder and solid potassium hydroxide with the molar ratio of 1:8, adding the ethylenediamine tetraacetic acid powder and the solid potassium hydroxide into deionized water, and fully stirring to prepare a mixed solution containing ethylenediamine tetraacetic acid potassium and potassium hydroxide with the molar concentration of 0.05mol/L calculated by ethylenediamine tetraacetic acid.
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm) 3 Per gram, specific surface area 224m 2 Per g, the carrier is used in the examples below) 50g, is added to 500mL of a potassium ethylenediamine tetraacetate-containing solution, stirred well for 4 hours, and then suction filtered. Placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 0.5h, adding 300mL of ethanol solution containing a certain amount of octaethylporphyrin platinum, heating at 70 ℃ in a vacuum state, treating for 2h, stopping refluxing, continuously evaporating the solvent, cooling and taking out the solid. The solid obtained was placed in a fixed bed reactor, heated to 160℃under nitrogen atmosphere, and then nitrogen gas containing 2% by volume of HCl and 10% by volume of water vapor was fed in at a volume space velocity of 1000h -1 After 2h of treatment, switching to nitrogen and cooling. 75mL of potassium nitrate solution with a certain concentration is prepared and added into 50g of solid treated by nitrogen containing HCl and water vapor, the mixture is aged for 10 hours, dried for 4 hours at 120 ℃, and roasted for 6 hours at 600 ℃ to obtain a catalyst C-3, wherein the contents of components in the catalyst are as follows: pt 0.2%, sn 0.5%, K1.0% by weight. The particle size distribution of Pt grains in the range of 1nm to 3nm was 92%. Evaluation conditions: at 600 ℃, the mass airspeed of propane is 2h -1 The propane dehydrogenation reaction was carried out under normal pressure, and 3g of catalyst was used. The evaluation results are shown in Table 1.
Example 4
Respectively weighing a certain amount of ethylenediamine tetraacetic acid powder and solid potassium hydroxide with the molar ratio of 1:7, adding the ethylenediamine tetraacetic acid powder and the solid potassium hydroxide into deionized water, and fully stirring to prepare a mixed solution containing ethylenediamine tetraacetic acid potassium and potassium hydroxide with the molar concentration of 0.15mol/L calculated by ethylenediamine tetraacetic acid.
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm) 3 Per gram, specific surface area 224m 2 Per g, the following examples all used the carrier) 100g, was added to 500mL of a potassium ethylenediamine tetraacetate-containing solution, stirred well for 4 hours, and then suction filtered. Placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 0.8h, adding 500mL of ethanol solution containing a certain amount of octaethylporphyrin platinum, heating at 60 ℃ in a vacuum state, treating for 3h, stopping refluxing, continuously evaporating the solvent, cooling and taking out the solid. The obtained solid was placed in a fixed bed reactor, heated to 160℃under nitrogen atmosphere, and then nitrogen gas containing 3% by volume of HCl and 15% by volume of water vapor was fed in at a volume space velocity of 900h -1 After 4h of treatment, switching to nitrogen and cooling. 75mL of potassium nitrate solution with a certain concentration is prepared and added into 50g of solid treated by nitrogen containing HCl and water vapor, the mixture is aged for 4 hours, dried for 6 hours at 100 ℃, and roasted for 8 hours at 500 ℃ to obtain a catalyst C-4, wherein the contents of components in the catalyst are as follows: pt 0.3wt%, sn 2wt% and K1 wt%. The particle size distribution of Pt grains in the range of 1nm to 3nm was 95%. Evaluation conditions: at 600 ℃, the mass airspeed of propane is 2h -1 The propane dehydrogenation reaction was carried out under normal pressure, and 3g of catalyst was used. The evaluation results are shown in Table 1.
Example 5
Respectively weighing a certain amount of ethylenediamine tetraacetic acid powder and solid potassium hydroxide with the molar ratio of 1:7, adding the ethylenediamine tetraacetic acid powder and the solid potassium hydroxide into deionized water, and fully stirring to prepare a mixed solution containing ethylenediamine tetraacetic acid potassium and potassium hydroxide with the molar concentration of 0.15mol/L calculated by ethylenediamine tetraacetic acid.
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm) 3 Per gram, specific surface area 224m 2 Per gram, the following examples all used the carrier) 75g, was added to 500mL of potassium ethylenediamine tetraacetate solution, stirred well for 6 hours, and then suction filtered. Placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 0.7h, adding 300mL of ethanol solution containing a certain amount of octaethylporphyrin platinum, heating at 60 ℃ in a vacuum state, treating for 3h, stopping refluxing, continuously evaporating the solvent, cooling and taking out the solid. Placing the obtained solid in a fixed bed reactor, heating to 180deg.C under nitrogen atmosphere, cutting into the solid containing HCl with volume concentration of 3%, and steamingAnd (3) nitrogen with the gas volume concentration of 15% and the volume space velocity of 800h, and after 3h of treatment, switching to nitrogen and cooling. 75mL of potassium nitrate solution with a certain concentration is prepared and added into 50g of solid treated by nitrogen containing HCl and water vapor, the mixture is aged for 4 hours, dried for 6 hours at 100 ℃, and roasted for 8 hours at 500 ℃ to obtain a catalyst C-4, wherein the contents of components in the catalyst are as follows: pt 0.4wt%, sn 3.0 wt%, K2.0 wt%. The particle size distribution of Pt grains in the range of 1nm to 3nm was 94%. Evaluation conditions: at 600 ℃, the mass airspeed of propane is 2h -1 The propane dehydrogenation reaction was carried out under normal pressure, and 3g of catalyst was used. The evaluation results are shown in Table 1.
Comparative example 1
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm) 3 Per gram, specific surface area 224m 2 Per gram, the carrier is used in the following examples), 75g of the carrier is placed in a rotary evaporator, after vacuuming treatment for 1h, 375mL of ethanol solution containing a certain amount of octaethylporphyrin platinum is added, heating is carried out at 60 ℃ in a vacuum state, treatment is carried out for 3h, reflux is stopped, solvent is continuously evaporated, and the solid is taken out after cooling. The solid obtained was placed in a fixed bed reactor, heated to 180℃under nitrogen atmosphere, and then nitrogen gas containing 3% by volume of HCl and 15% by volume of water vapor was fed in, with a volume space velocity of 750h -1 After 3h of treatment, switching to nitrogen and cooling. 75mL of potassium nitrate solution with a certain concentration is prepared and added into 50g of solid treated by nitrogen containing HCl and water vapor, the mixture is aged for 10 hours, dried for 6 hours at 100 ℃, and baked for 10 hours at 500 ℃ to obtain a catalyst D-1, wherein the contents of components in the catalyst are as follows: pt 0.3wt%, sn 1wt% and K2 wt%. The particle size distribution of Pt grains in the range of 1nm to 3nm was 52%. Evaluation conditions: at 600 ℃, the mass airspeed of propane is 2h -1 The propane dehydrogenation reaction was carried out under normal pressure, and 3g of catalyst was used. The evaluation results are shown in Table 1.
Comparative example 2
Respectively weighing a certain amount of the components according to the molar ratio of 1:7, adding the ethylenediamine tetraacetic acid powder and solid potassium hydroxide into deionized water, and fully stirring to prepare a solution containing potassium ethylenediamine tetraacetate with the molar concentration of 0.15mol/L calculated by ethylenediamine tetraacetic acid and the molar concentration calculated by ethylenediamine tetraacetic acid.
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm) 3 Per gram, specific surface area 224m 2 Per gram, the following examples all used the carrier) 75g, was added to 500mL of potassium ethylenediamine tetraacetate solution, stirred well for 6 hours, and then suction filtered. Placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 1h, adding 375mL of aqueous solution containing a certain amount of chloroplatinic acid, heating at 60 ℃ in a vacuum state, treating for 3h, stopping refluxing, continuously evaporating the solvent, cooling and taking out the solid. The solid obtained was placed in a fixed bed reactor, heated to 180℃under nitrogen atmosphere, and then nitrogen gas containing 3% by volume of HCl and 15% by volume of water vapor was fed in, with a volume space velocity of 750h -1 After 3h of treatment, switching to nitrogen and cooling. 75mL of potassium nitrate solution with a certain concentration is prepared and added into 50g of solid treated by nitrogen containing HCl and water vapor, the solid is aged for 10 hours, dried for 6 hours at 100 ℃, and baked for 10 hours at 500 ℃ to obtain a catalyst D-2, wherein the contents of components in the catalyst are as follows: pt 0.3wt%, sn 1wt% and K2 wt%. The particle size distribution of Pt grains in the range of 1nm to 3nm was 72%. Evaluation conditions: at 600 ℃, the mass airspeed of propane is 2h -1 The propane dehydrogenation reaction was carried out under normal pressure, and 3g of catalyst was used. The evaluation results are shown in Table 1.
TABLE 1 reactivity of catalysts
The description of the present invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Claims (5)

1. The preparation method of the Pt-based catalyst with the highly dispersed active component is characterized by comprising the following steps: respectively weighing a certain amount of the components according to the molar ratio of 1:7, adding the ethylenediamine tetraacetic acid powder and solid potassium hydroxide into deionized water, and fully stirring to prepare a mixed solution containing the potassium ethylenediamine tetraacetate and the potassium hydroxide, wherein the molar concentration of the mixed solution is 0.15mol/L calculated by the ethylenediamine tetraacetic acid; weighing 75g of dried Sn-containing alumina carrier, and obtaining a spherical shape with a diameter of 1.6mm and a pore volume of 0.56cm 3 Per gram, specific surface area 224m 2 Adding the mixture to 500mL of potassium ethylenediamine tetraacetate solution, fully stirring for 6h, and then carrying out suction filtration; placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 1h, adding 375mL ethanol solution containing a certain amount of octaethylporphyrin platinum, heating at 60 ℃ in a vacuum state, treating for 3h, stopping refluxing, continuously evaporating the solvent, cooling and taking out the solid; the solid obtained was placed in a fixed bed reactor, heated to 180℃under nitrogen atmosphere, and then nitrogen gas containing 3% by volume of HCl and 15% by volume of water vapor was fed in, with a volume space velocity of 750h -1 After 3 hours of treatment, switching to nitrogen and cooling; 75mL of potassium nitrate solution with a certain concentration is prepared and added into 50g of solid treated by nitrogen containing HCl and water vapor, the solid is aged for 10 hours, dried for 6 hours at 100 ℃, and baked for 10 hours at 500 ℃ to obtain a catalyst C-1, wherein the contents of components in the catalyst are as follows: 0.3wt% of Pt, 1wt% of Sn and 2wt% of K; the particle size distribution of Pt grains in the range of 1nm to 3nm was 93%.
2. The preparation method of the Pt-based catalyst with the highly dispersed active component is characterized by comprising the following steps: respectively weighing a certain amount of the components according to the molar ratio of 1:6 adding the ethylenediamine tetraacetic acid powder and solid potassium hydroxide into deionized water, fully stirring to prepare the mixed solution of the potassium ethylenediamine tetraacetate and potassium hydroxide with the molar concentration of 0.2mol/L calculated by ethylenediamine tetraacetic acidA liquid; weighing 100g of dried Sn-containing alumina carrier, and obtaining a spherical shape with a diameter of 1.6mm and a pore volume of 0.56cm 3 Per gram, specific surface area 224m 2 Adding 100g of the solution into 500mL of potassium ethylenediamine tetraacetate solution, fully stirring for 4h, and then carrying out suction filtration; placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 1.2h, adding 400mL ethanol solution containing a certain amount of octaethylporphyrin platinum, heating at 50deg.C under vacuum state for 4h, stopping refluxing, continuously evaporating the solvent, cooling, taking out the solid, placing the obtained solid in a fixed bed reactor, heating to 160deg.C under nitrogen atmosphere, cutting into nitrogen gas containing 4% of HCl volume concentration and 20% of water vapor volume concentration, and controlling volume space velocity to 500h -1 After 4 hours of treatment, switching to nitrogen, cooling, preparing 75mL of potassium nitrate solution with a certain concentration, adding the solution into 50g of solid treated by nitrogen containing HCl and water vapor, aging for 16 hours, drying at 80 ℃ for 4 hours, and roasting at 450 ℃ for 18 hours to obtain a catalyst C-2, wherein the content of each component in the catalyst is as follows: 0.5wt% of Pt, 5wt% of Sn and 3wt% of K; the grain size distribution of Pt grains in the range of 1nm to 3nm was 96%.
3. The preparation method of the Pt-based catalyst with the highly dispersed active component is characterized by comprising the following steps: respectively weighing a certain amount of the components according to the molar ratio of 1:8, adding the ethylenediamine tetraacetic acid powder and solid potassium hydroxide into deionized water, and fully stirring to prepare a mixed solution containing the potassium ethylenediamine tetraacetate and the potassium hydroxide, wherein the molar concentration of the mixed solution is 0.05mol/L calculated by the ethylenediamine tetraacetic acid; weighing 50g of dried Sn-containing alumina carrier, and obtaining a spherical shape with a diameter of 1.6mm and a pore volume of 0.56cm 3 Per gram, specific surface area 224m 2 Adding 500mL of solution containing potassium ethylenediamine tetraacetate, stirring for 4h, filtering, vacuum-treating the obtained solid in a rotary evaporator for 0.5h, adding 300mL ethanol solution containing a certain amount of platinum octaethylporphyrin, heating at 70deg.C under vacuum for 2h, stopping refluxing, evaporating solvent continuously, cooling, taking out the solid, placing the obtained solid in a fixed bed reactor, heating to 160deg.C under nitrogen atmosphere, cutting into nitrogen gas containing 2% of HCl volume concentration and 10% of water vapor volume concentration, and controlling the volume space velocity to 1000h -1 After 2 hours of treatment, switching to nitrogen and cooling; 75mL of potassium nitrate solution with a certain concentration is prepared and added into 50g of solid treated by nitrogen containing HCl and water vapor, the mixture is aged for 10 hours, dried for 4 hours at 120 ℃, and roasted for 6 hours at 600 ℃ to obtain a catalyst C-3, wherein the contents of components in the catalyst are as follows: pt 0.2wt%, sn 0.5wt%, K1.0 wt%, pt grains in the range of 1nm to 3nm have a particle size distribution of 92%.
4. The preparation method of the Pt-based catalyst with the highly dispersed active component is characterized by comprising the following steps: respectively weighing a certain amount of the components according to the molar ratio of 1:7, adding the ethylenediamine tetraacetic acid powder and solid potassium hydroxide into deionized water, and fully stirring to prepare a mixed solution containing the potassium ethylenediamine tetraacetate and the potassium hydroxide, wherein the molar concentration of the mixed solution is 0.15mol/L calculated by the ethylenediamine tetraacetic acid; weighing 100g of dried Sn-containing alumina carrier, and obtaining a spherical shape with a diameter of 1.6mm and a pore volume of 0.56cm 3 Per gram, specific surface area 224m 2 Adding the mixture to 500mL of potassium ethylenediamine tetraacetate solution, fully stirring for 4 hours, and then carrying out suction filtration; placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 0.8h, adding 500mL ethanol solution containing a certain amount of octaethylporphyrin platinum, heating at 60 ℃ in a vacuum state, treating for 3h, stopping refluxing, continuously evaporating the solvent, cooling and taking out the solid; the obtained solid was placed in a fixed bed reactor, heated to 160℃under nitrogen atmosphere, and then nitrogen gas containing 3% by volume of HCl and 15% by volume of water vapor was fed in at a volume space velocity of 900h -1 After 4h of treatment, switching to nitrogen, cooling, preparing 75mL of potassium nitrate solution with a certain concentration, adding the solution into 50g of solid treated by nitrogen containing HCl and water vapor, aging for 4h, drying at 100 ℃ for 6h, and roasting at 500 ℃ for 8h to obtain a catalyst C-4, wherein the content of each component in the catalyst is as follows: 0.3wt% of Pt, 2wt% of Sn and 1wt% of K; the grain size distribution of Pt grains in the range of 1nm to 3nm was 95%.
5. The preparation method of the Pt-based catalyst with the highly dispersed active component is characterized by comprising the following steps: respectively weighing a certain amount of the components according to the molar ratio of 1:7 ethylenediamine tetraacetic acid powder and solid potassium hydroxide, adding into deionized waterFully stirring to prepare a mixed solution containing potassium ethylenediamine tetraacetate and potassium hydroxide, wherein the molar concentration of the mixed solution is 0.15mol/L calculated by ethylenediamine tetraacetic acid; weighing 75g of dried Sn-containing alumina carrier, and obtaining a spherical shape with a diameter of 1.6mm and a pore volume of 0.56cm 3 Per gram, specific surface area 224m 2 Adding 500mL of potassium ethylenediamine tetraacetate solution, stirring for 6h, filtering, placing the solid obtained after filtering in a rotary evaporator, vacuumizing for 0.7h, adding 300mL ethanol solution containing a certain amount of octaethylporphyrin platinum, heating at 60 ℃ in a vacuum state, treating for 3h, stopping refluxing, continuously evaporating the solvent, cooling, and taking out the solid; the obtained solid was placed in a fixed bed reactor, heated to 180℃under nitrogen atmosphere, and then nitrogen gas containing 3% by volume of HCl and 15% by volume of water vapor was fed in at a volume space velocity of 800h -1 After 3h of treatment, switching to nitrogen, cooling, preparing 75mL of potassium nitrate solution with a certain concentration, adding the solution into 50g of solid treated by nitrogen containing HCl and water vapor, aging for 4h, drying at 100 ℃ for 6h, and roasting at 500 ℃ for 8h to obtain a catalyst C-4, wherein the content of each component in the catalyst is as follows: pt 0.4wt%, sn 3.0 wt%, K2.0 wt%, and Pt grains in the range of 1nm to 3nm have a grain size distribution of 94%.
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