CN115430423B - Rare earth doped spherical alumina-based PtSn catalyst, and preparation method and application thereof - Google Patents

Rare earth doped spherical alumina-based PtSn catalyst, and preparation method and application thereof Download PDF

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CN115430423B
CN115430423B CN202211151663.4A CN202211151663A CN115430423B CN 115430423 B CN115430423 B CN 115430423B CN 202211151663 A CN202211151663 A CN 202211151663A CN 115430423 B CN115430423 B CN 115430423B
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rare earth
catalyst
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ptsn
spherical alumina
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CN115430423A (en
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贺宇飞
李家乐
李殿卿
刘雅楠
冯俊婷
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Beijing University of Chemical Technology
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    • 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
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B01J35/23—
    • B01J35/394—
    • B01J35/40—
    • B01J35/50—
    • B01J35/51—
    • B01J35/647—
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/63—Platinum group metals with rare earths or actinides
    • 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 discloses a rare earth doped spherical alumina-based PtSn catalyst, a preparation method and application thereof, wherein the adopted preparation method is to uniformly dope rare earth elements into aluminum sol, prepare a spherical alumina carrier with uniformly dispersed rare earth elements by an oil column forming method, and utilize hydroxymethyl functional groups of the spherical alumina carrier to form S-Al with uniformly communicated pore channels by in-situ addition condensation of formaldehyde decomposed in the reaction process by adding a crosslinking agent containing hydroxymethyl functional groups 2 O 3 A carrier having a bulk density of 0.4 to 0.8g/cm 3 The crushing strength is 30-60N, the pore volume is 0.4-1.0 cm 3 The average pore diameter is 18-50 nm. Then, the active components are immersed on the surface of the carrier by adopting a vacuum-spraying method, so that the Pt and Sn active components are immersed in the pore canal of the carrier deeply; then Pt is obtained by gas phase reduction x Sn y /S‑Al 2 O 3 A catalyst. The size of Pt nano particles of the active component of the catalyst is between 1 and 3nm. The active nano particles are uniformly dispersed and have smaller size. The catalyst shows excellent catalytic activity and selectivity when applied to the propane dehydrogenation reaction.

Description

Rare earth doped spherical alumina-based PtSn catalyst, and preparation method and application thereof
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to a rare earth doped spherical alumina Pt-based catalyst and a preparation method thereof.
Background
Propylene is an important chemical raw material for producing chemicals such as polypropylene, acrylonitrile and the like, and along with the continuous increase of the demand of downstream chemical products, the propylene produced by the traditional method is difficult to meet the market demand. In recent years, shale gas is largely exploited and utilized as an independent and considerable energy source, expanding the propylene source by the dehydrogenation of propane to produce propylene exclusively. The method for preparing propylene by dehydrogenating propane has the advantages of high yield, low equipment cost, simple process flow and the like, and is an important way for expanding the source of propylene. Propane dehydrogenation is a reversible reaction with strong endothermic reaction and increased molecular volume, and high temperature is advantageous for the main reaction, so that the reaction temperature of industrially used Pt-based catalysts is usually 550-650 ℃. Under the high temperature condition, the C-C bond is easier to break than the C-H bond, and propane molecules are easy to crack in the catalysis process, so that byproducts such as ethylene, methane, ethane and the like are generated. High temperatures also tend to cause sintering of the catalyst, resulting in reduced stability of the reaction.
At present, the research of the propane dehydrogenation catalyst mainly focuses on the active metal site sintering and carbon deposition inhibition under the high-temperature condition, and the introduction of additives (Sn, ga, nb and the like) can improve the energy barrier of C-C bond fracture so as to reduce the carbon deposition generation rate and promote the separation of active metals, thereby inhibiting the agglomeration and carbon deposition behavior of the active metal Pt under the high-temperature reaction condition. The literature ACS Catalysis,2021,11,4401-4410 reports that the impregnation of Pt and Sn on the SAB-15 surface forms a Pt-Sn alloy structure, and that the introduction of Sn increases the energy barrier for cleavage of the C-C bond of propane on the catalyst surface from 2.40eV to 2.64eV, inhibiting the formation of carbon deposition, compared to the single metal Pt/SAB-15 catalyst. At the reaction temperature of 600 ℃, the selectivity of Pt/SAB-15 catalyst for carbon deposition propylene is less than 65 percent, and the deactivation constant is 0.17h -1 While the Pt-Sn/SAB-15 catalyst had a propylene selectivity of 92% and a deactivation constant of only 0.09h -1 . Document Catal. Sci. Technology, 2020,10,5973-5982 reports Pt-Ti/SiO 2 And Pt-Nb/SiO 2 Catalyst, pt was found to be anchored to TiO with strong metal interactions 2 And Nb (Nb) 2 O 5 On the above, by dividing Pt active sites and enhancing electron transfer, pt anti-sintering capability is obviously enhanced, 2Pt-8Nb/SiO 2 And 2Pt-6Ti/SiO 2 The catalyst conversion rates were 0.19 and 0.22s, respectively -1 While Pt/SiO 2 Is converted into 0.17s -1 . 2Pt-8Nb/SiO at a reaction temperature of 550 DEG C 2 Achieves 30 percent of propane conversion rate and 87 percent of propylene selectivity, 2Pt-6Ti/SiO 2 Has 25% propane conversion and 90% propylene selectivity, and Pt/SiO under the same conditions 2 The catalyst had a propane conversion of only 10% and a propylene selectivity of 70%. In view of the problems occurring at high temperatures, there has been increasing attention to develop a low Wen Bingwan dehydrogenation catalyst having the ability to inhibit sintering and reduce cracking side reactions. Applied Catalysis B Environmental,2022,300,120731 reports 2.5% Si@PtGa/Al 2 O 3 The catalyst utilizes the auxiliary gallium to divide active metal sites, so that the energy barrier for C-C bond rupture on the surface of the catalyst is improved, and C-H bonds are easier to be ruptured in thermodynamics than C-C bonds. Introduction of Ga and at PtGa/Al 2 O 3 The silicon dioxide layer coated on the surface of the catalyst can adjust Pt and Al 2 O 3 The metal-carrier interaction between the matrixes ensures that Pt active sites on the surface of the carrier are not easy to sinter and agglomerate, thereby improving the propane dehydrogenation activity of the catalyst at low reaction temperature. The catalyst had an initial propane conversion of 21.8% and an initial propylene selectivity of 90.7% at a reaction temperature of 450 ℃ and a deactivation constant of 0.007h -1 。
In conclusion, the carbon deposition and sintering phenomena of active metal sites can be effectively inhibited by introducing the auxiliary agent under the high-temperature reaction condition, and the reaction activity and selectivity of the catalyst are improved. From the thermodynamic point of view, the problem of active metal site sintering and carbon deposition can be essentially solved by reducing the reaction temperature of propane dehydrogenation reaction, but the currently reported catalyst has lower reaction activity under the low-temperature condition and has a larger distance from industrial application. Therefore, the invention aims to develop a propane dehydrogenation catalyst with high activity and low temperature and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a rare earth doped spherical alumina-based PtSn catalyst and a preparation method thereof, wherein the catalyst is suitable for low Wen Bingwan dehydrogenation reaction.
The rare earth doped spherical alumina-based PtSn catalyst provided by the invention is expressed as PtSn/S-Al 2 O 3 PtSn is an active component, the load of Pt is 0.15-1.2 wt%, and the load of Sn is 0.05-1.5 wt%; S-Al 2 O 3 The rare earth doped spherical alumina carrier, wherein S represents rare earth element, which is one of yttrium (Y), lanthanum (La) and europium (Eu), and the doping amount is 3-10wt%; the catalyst is spherical with the whole diameter of 1.2-2.5 mm and the bulk density of 0.4-0.8 g/cm 3 The crushing strength is 30-60N, and the pore diameter is 18-50 nm.
The preparation technology scheme adopted by the invention is that rare earth elements are evenly doped into aluminum sol, spherical alumina carrier with evenly dispersed rare earth elements is prepared by an oil column forming method, and a hydroxymethyl functional group-containing cross-linking agent is added, and S-Al with evenly communicated pore channels is formed by in-situ addition condensation of the hydroxymethyl functional group and formaldehyde decomposed in the reaction process 2 O 3 A carrier. Then, the active components are immersed on the surface of the carrier by adopting a vacuum-spraying method, so that the Pt and Sn active components are immersed in the pore canal of the carrier deeply; the catalyst is then obtained by a gas phase reduction process. The catalyst prepared by the method has excellent low Wen Bingwan dehydrogenation reaction catalytic performance.
The preparation method of the rare earth doped spherical alumina-based PtSn catalyst provided by the invention comprises the following specific steps:
A. preparation of rare earth doped aluminum sol
Dissolving aluminum powder into dilute hydrochloric acid to prepare aluminum sol, wherein the aluminum content is 15-20wt%, the mass ratio of Al/Cl is 0.5-2.5, and the pH is 2-4; adding 3-10wt% of rare earth source into the mixture, fully mixing the mixture, adding 1-10wt% of cross-linking agent into the mixture, and uniformly stirring the mixture to obtain rare earth doped aluminum sol.
The rare earth source is one of nitrate, chloride, sulfate and hydroxide of yttrium, lanthanum and europium. Preferably Y (OH) 3 、LaCl 3 ·7H 2 O or Eu (NO) 3 ) 3 ·6H 2 O。
The cross-linking agent is an organic matter containing hydroxymethyl functional groups and is N-methylolacrylamide (C) 4 H 7 NO 2 ) 5-hydroxymethylfurfural (C) 6 H 6 O 3 ) Or ethanol (C) 2 H 5 OH), one or both of which.
B. Rare earth doped spherical alumina carrier S-Al 2 O 3 Is prepared from
Fully and uniformly mixing organic amine and the rare earth doped aluminum sol at the temperature of between 0 and 10 ℃ to obtain forming liquid, wherein NH + ：Al 3+ The molar ratio of (2) is 0.2-0.5; dropwise adding the molding liquid into a reactor filled with molding oil at 80-100 ℃, curing at high temperature for 2-3 hours, filtering out sol pellets, and then transferring into an aging kettle to age for 6-10 hours at 150-170 ℃; washing the aged pellets with hot water at 60-90 ℃ until no chloride ions and no greasy dirt exist in the washing water, and drying the pellets in a baking oven at 100-120 ℃ for 12-16 hours; roasting in a muffle furnace at 900-1000 deg.C for 4-8 hr to obtain rare earth doped spherical alumina expressed as S-Al 2 O 3 Wherein rare earth elements are highly dispersed in alumina.
The organic amine is hexamethylenetetramine (C) 6 H 12 N 4 ) Urea (CO (NH)), wherein the molding oil is one of vacuum pump oil, simethicone, and paraffin oil.
C.PtSn/S-Al 2 O 3 Preparation of the catalyst
Will H 2 PtCl 6 ·xH 2 O is dissolved in deionized water to prepare a chloroplatinic acid solution with the concentration of 180-420 mmol/L; and then dissolving the soluble Sn salt in 8-12% hydrochloric acid solution by mass fraction for full ultrasonic dissolution to prepare Sn hydrochloric acid solution with the concentration of 0.85-7.69 mmol/L.
Mixing a chloroplatinic acid solution and a Sn hydrochloric acid solution to prepare an impregnating solution, wherein the concentration and the addition amount of the solution are determined according to the set Pt and Sn loading amounts of a target catalyst, and the amount and the water absorption rate of a used carrier; wherein the volume of the impregnating solution is such that the carrier is saturated with water.
The soluble Sn salt is SnCl 4 Or SnCl 2 ·2H 2 O, pt/Sn molar ratio is 3:1-1:3;
vacuum spraying methodSpraying the impregnating solution onto S-Al 2 O 3 The carrier is saturated by water absorption; taking out, and drying at 80-120 ℃ for 16-20 hours; then reducing for 3-6 hours in a reducing atmosphere in a tubular atmosphere furnace at a heating rate of 2-10 ℃/min to 550-650 ℃ to obtain PtSn/S-Al 2 O 3 A catalyst; the flow rate of the reducing atmosphere is 20-40 mL/min; the reducing atmosphere is 5-10% H 2 /N 2 And (3) mixing gas.
The prepared samples were characterized and the results were as follows:
FIG. 1 shows Eu-Al prepared in step B of example 1 2 O 3 X-ray diffraction pattern (XRD) of the carrier. The peak positions in the figure correspond to the characteristic diffraction peaks of theta alumina and no peaks of rare earth oxides, indicating that the rare earth elements are highly dispersed in the alumina support.
FIG. 2 shows Eu-Al prepared in step B of example 1 2 O 3 Low temperature nitrogen adsorption and desorption curve and pore size distribution diagram of carrier. The graph a shows a low-temperature nitrogen adsorption and desorption curve, which is of type IV, and shows that the carrier has a good mesoporous structure. FIG. b is a pore size distribution plot showing that the pore size of the support is between 18 and 50nm, with a most probable pore size of about 43nm.
FIG. 3 shows PtSn/Eu-Al prepared in step C of example 1 2 O 3 HRTEM dark field plot and particle size distribution of the catalyst. Fig. a is HRTEM dark field plot, the bright spots on the carrier are Pt nanoparticles, and fig. b is particle size distribution plot. The result shows that Pt nano particles are uniformly dispersed on the surface of alumina, and the average particle size is 2.17nm.
FIG. 4 is a Y-Al prepared in step B of example 3 2 O 3 X-ray diffraction pattern (XRD) of (a). The peak positions in the figure correspond to the characteristic diffraction peaks of theta alumina and no peaks of rare earth oxides, indicating that the rare earth elements are highly dispersed in the alumina support.
FIG. 5 is a Y-Al prepared in step B of example 3 2 O 3 Low temperature nitrogen adsorption and desorption curve and pore size distribution diagram of carrier. The graph a shows a low-temperature nitrogen adsorption and desorption curve, which is of type IV, and shows that the carrier has a good mesoporous structure. Panel b is a pore size distribution plot showing that the pore size of the support is between 22-40nm,the most probable pore size is about 35nm.
FIG. 6 shows PtSn/Y-Al prepared in step C of example 3 2 O 3 HRTEM dark field plot and particle distribution of the catalyst. Fig. a is HRTEM dark field plot, the bright spots on the carrier are Pt nanoparticles, and fig. b is particle size distribution plot. The result shows that Pt nano particles are uniformly dispersed on the surface of alumina, and the average particle size is 1.37nm.
FIG. 7 shows the curves of propane conversion (a) and propylene selectivity (b) over time at 450℃in the propane dehydrogenation reactions for the catalysts prepared in example 1 and example 3, respectively. PtSn/Eu-Al prepared in example 1 2 O 3 The catalyst achieved 29.4% propane conversion and 97.9% propylene selectivity, ptSn/Y-Al prepared in example 3 2 O 3 The catalyst achieved 28.2% propane conversion and 99.2% propylene selectivity. The catalyst showed good propane conversion (a) and propylene selectivity (b) at a reaction temperature of 450 ℃.
FIG. 8 shows the curves of propane conversion (a) and propylene selectivity (b) over time at 500℃in the propane dehydrogenation reactions for the catalysts prepared in example 1 and example 3, respectively. PtSn/Eu-Al prepared in example 1 2 O 3 The catalyst achieved 42.9% propane conversion and 95.8% propylene selectivity, ptSn/Y-Al prepared in example 3 2 O 3 The catalyst achieved a propane conversion of 33.4% and a propylene selectivity of 98.5%. The catalyst showed good propane conversion (a) and propylene selectivity (b) at a reaction temperature of 500 ℃.
The invention has the beneficial effects that:
the invention prepares the rare earth doped alumina carrier by introducing rare earth sources into the alumina sol in the process of preparing the forming liquid, thereby promoting the uniform dispersion of rare earth elements in the carrier. And utilizes the side chain functional group (-CH) of cross-linking template agent 2 OH) and formaldehyde are subjected to nucleophilic addition and condensation reaction in situ to construct a cage-type acetal structure with a three-dimensional cross-linked network, so that hydrated alumina microcrystals can grow controllably in a limited space, and optimization of an alumina pore channel structure is realized. Compared with the traditional method of introducing rare earth source by impregnation method, the rare earth doped alumina prepared by the invention is dopedThe element dispersion is more uniform, and the pore canal structure is excellent. And then dipping the active components on the surface of the carrier by adopting a one-step vacuum-spraying method, so that the Pt and Sn active components can be deeply dipped into the pore channels of the carrier. Then PtSn/S-Al is obtained through a gas phase reduction process 2 O 3 A catalyst. The size of Pt nano particles of the active component of the catalyst is between 1 and 3nm. The conversion rate of propane can reach 29% at the reaction temperature of 450 ℃, and the propylene selectivity is higher than 97%; the conversion rate of propane can reach 42% at 500 ℃ and the propylene selectivity is higher than 95%.
Description of the drawings:
FIG. 1 shows Eu-Al prepared in step B of example 1 2 O 3 X-ray diffraction analysis pattern (XRD) of the carrier.
FIG. 2 shows Eu-Al prepared in step B of example 1 2 O 3 A low-temperature nitrogen adsorption-desorption curve (a) and a pore size distribution diagram (b) of the carrier.
FIG. 3 shows PtSn/Eu-Al prepared in step C of example 1 2 O 3 High Resolution Transmission Electron Microscope (HRTEM) dark field plot (a) and particle size distribution plot (b) of the catalyst.
FIG. 4 is a Y-Al prepared in step B of example 3 2 O 3 X-ray diffraction pattern (XRD) of the carrier.
FIG. 5 is a Y-Al prepared in step B of example 3 2 O 3 A low-temperature nitrogen adsorption-desorption curve (a) and a pore size distribution diagram (b) of the carrier.
FIG. 6 shows PtSn/Y-Al prepared in step C of example 3 2 O 3 High resolution transmission electron microscope dark field graph (a) and particle size distribution graph (b) of the catalyst.
FIG. 7 shows PtSn/Eu-Al in example 1, respectively 2 O 3 Catalyst (Curve 1) and PtSn/Y-Al in example 3 2 O 3 The catalyst (curve 2) shows the propane conversion and the propylene selectivity over time at 450℃in the propane dehydrogenation reaction.
FIG. 8 shows PtSn/Eu-Al in example 1, respectively 2 O 3 Catalyst (Curve 1) and PtSn/Y-Al in example 3 2 O 3 Catalyst (Curve 2) propane conversion and propylene selectivity over time at 500 ℃ in propane dehydrogenationA change curve.
The specific embodiment is as follows:
example 1
The target catalyst is PtSn/Eu-Al with Pt loading of 0.5wt%, sn loading of 0.16wt% and Eu doping amount of 5wt% 2 O 3 A catalyst.
Preparation of Eu doped aluminium sol
100g of aluminum powder with the grain size of 100-200 mu m is weighed, 350mL of 10wt% hydrochloric acid solution is slowly added, and 20wt% aluminum sol is prepared while stirring, wherein the mass ratio of Al/Cl is 1.5, and the pH is approximately equal to 3. 166.5g of europium nitrate hexahydrate is weighed and added into 400g of aluminum sol, then 10g of methylol acrylamide cross-linking agent is added, and the Eu doped aluminum sol is obtained by uniform mixing.
B. Spherical alumina carrier Eu-Al 2 O 3 Is prepared from
Fully mixing Eu doped aluminum sol obtained in the step A with 52g of hexamethylenetetramine in ice water bath to prepare a forming liquid; dropwise adding the molding liquid into a round-bottom flask filled with 90 ℃ vacuum pump oil, solidifying, filtering out pellets, and aging for 7 hours in an aging kettle at 150 ℃; taking out the aged pellets, putting the pellets into a beaker, repeatedly cleaning surface oil stains by using hot water at 60 ℃, detecting no chloride ions and obvious greasy dirt in the waste water after washing, putting the pellets into a baking oven for drying at 120 ℃ for 16 hours, and roasting the pellets in a muffle furnace at 960 ℃ for 8 hours to obtain theta-type spherical Eu-Al 2 O 3 A carrier.
C.Pt 3 Sn 1 /Eu-Al 2 O 3 Preparation of the catalyst
0.0133g of H was weighed out 2 PtCl 6 ·xH 2 Dissolving O solid with 200 mu L deionized water to prepare chloroplatinic acid solution; 1.93mg of SnCl 2 ·2H 2 O is dissolved in 1mL hydrochloric acid solution with mass fraction of 10%; mixing the two solutions, and fully dissolving by ultrasonic to obtain the impregnating solution.
And B, adopting a vacuum-spraying method to obtain 1g of spherical Eu-Al prepared in the step B 2 O 3 Placing the carrier into a suction filter flask, vacuumizing with a vacuum pump, loading the above impregnating solution into a separating funnel, and dropwise adding into spherical shapeDropwise adding and stirring the carrier until the impregnating solution is completely dripped; drying in an oven at 90 ℃ for 20 hours; then the mixture is placed in a tubular atmosphere furnace, and 10% H with the gas flow rate of 40mL/min is added 2 /N 2 In the mixed gas atmosphere, the temperature is increased to 600 ℃ at the heating rate of 10 ℃/min for reduction for 4 hours, and PtSn/Eu-Al is obtained 2 O 3 A catalyst. Wherein the Pt loading is 0.5wt%, the Sn loading is 0.16wt%, and the Pt/Sn molar ratio is 3:1, wherein the Eu doping amount relative to the carrier is 5wt%.
Example 2
The target catalyst is PtSn/La-Al with Pt loading of 1.0wt%, sn loading of 0.33wt% and La doping amount of 5wt% 2 O 3 A catalyst.
Preparation of La-doped aluminum sol
100g of aluminum powder with the grain size of 100-200 mu m is weighed, 350mL of 10wt% hydrochloric acid solution is slowly added, and 16wt% aluminum sol is prepared while stirring, wherein the mass ratio of Al/Cl is 1.2, and the pH is approximately equal to 4. 117.8g of lanthanum chloride heptahydrate is weighed and added into 400g of aluminum sol, then 10g of methylol acrylamide cross-linking agent is added, and La doped aluminum sol is obtained by uniform mixing.
B. Spherical alumina carrier La-Al 2 O 3 Is prepared from
Fully mixing La-doped aluminum sol obtained in the step A with 52g of hexamethylenetetramine in ice water bath to prepare a forming liquid, dropwise dripping the forming liquid into a round-bottom flask filled with 90 ℃ vacuum pump oil, filtering out pellets after solidification, and aging in an aging kettle at 170 ℃ for 10 hours; taking out the aged pellets, putting the pellets into a beaker, repeatedly cleaning surface oil stains by using hot water at 60 ℃, detecting no chloride ions and obvious greasy dirt in the waste water after washing, putting the pellets into a baking oven for drying at 120 ℃ for 16 hours, and roasting the pellets in a muffle furnace at 960 ℃ for 8 hours to obtain theta-type spherical La-Al 2 O 3 A carrier.
C.PtSn/La-Al 2 O 3 Preparation of the catalyst
0.0266g of H was weighed out 2 PtCl 6 ·xH 2 Dissolving O solid with 200 mu L deionized water to prepare chloroplatinic acid solution; 3.86mg of SnCl 2 ·2H 2 O is dissolved in 1mLHydrochloric acid solution with the mass fraction of 10%; mixing the two solutions, and fully dissolving by ultrasonic to obtain the impregnating solution.
And C, adopting a vacuum-spraying method to obtain 1g of spherical La-Al prepared in the step B 2 O 3 Placing the carrier into a suction filtration bottle, vacuumizing the pressure by a vacuum pump, filling all the impregnating solution into a separating funnel, dropwise adding the impregnating solution into the spherical carrier, and stirring the impregnating solution while dropwise adding until the impregnating solution is completely dripped; drying in an oven at 110 ℃ for 16 hours; then the mixture is placed in a tubular atmosphere furnace, and 10% H with the gas flow rate of 40mL/min is added 2 /N 2 In the mixed gas atmosphere, the temperature is increased to 600 ℃ at the heating rate of 10 ℃/min for reduction for 4 hours, and PtSn/La-Al is obtained 2 O 3 A catalyst. Wherein the loading of Pt is 1.0wt%, the loading of Sn is 0.33wt%, and the Pt/Sn molar ratio is 3:1, wherein the doping amount of La relative to the carrier is 5wt%.
Example 3
The target catalyst is PtSn/Y-Al with Pt loading of 0.5wt%, sn loading of 0.16wt% and Y doping amount of 5wt% 2 O 3 A catalyst.
Preparation of A.Y doped aluminum sol
100g of aluminum powder with the grain size of 100-200 mu m is weighed, 350mL of 10wt% hydrochloric acid solution is slowly added, and 20wt% aluminum sol is prepared while stirring, wherein the mass ratio of Al/Cl is 1.5, and the pH is approximately equal to 3. 44.6g of yttrium hydroxide is weighed and added into 400g of aluminum sol, then 5g of methylol acrylamide cross-linking agent is added, and the mixture is uniformly mixed to obtain the Y-doped aluminum sol.
B. Spherical alumina carrier Y-Al 2 O 3 Is prepared from
Fully mixing the Y-doped aluminum sol obtained in the step A with 31.2g of hexamethylenetetramine in an ice water bath to prepare a forming liquid, dropwise dripping the forming liquid into a round-bottom flask filled with 90 ℃ vacuum pump oil, filtering out pellets after solidification, and aging for 7 hours in an aging kettle at 150 ℃; taking out the aged pellets, putting the pellets into a beaker, repeatedly cleaning surface oil stains by using hot water at 70 ℃, detecting no chloride ions and obvious greasy dirt in the washed wastewater, putting the pellets into a baking oven for drying at 120 ℃ for 16 hours, and roasting the pellets in a muffle furnace at 960 ℃ for 8 hours to obtain theta-type pelletsForm Y-Al 2 O 3 A carrier.
C.PtSn/Y-Al 2 O 3 Preparation of the catalyst
0.0133g of H was weighed out 2 PtCl 6 ·xH 2 Dissolving O solid with 200 mu L deionized water to prepare chloroplatinic acid solution; 1.93mg of SnCl 2 ·2H 2 O is dissolved in 1mL hydrochloric acid solution with mass fraction of 10%; mixing the two solutions, and fully dissolving by ultrasonic to obtain the impregnating solution.
And C, adopting a vacuum-spraying method to obtain 1g of spherical Y-Al prepared in the step B 2 O 3 Placing the carrier into a suction filtration bottle, vacuumizing the pressure by a vacuum pump, filling all the impregnating solution into a separating funnel, dropwise adding the impregnating solution into the spherical carrier, and stirring the impregnating solution while dropwise adding until the impregnating solution is completely dripped; drying in an oven at 90 ℃ for 20 hours; then the mixture is placed in a tubular atmosphere furnace, and 10% H with the gas flow rate of 30mL/min is added 2 /N 2 In the mixed gas atmosphere, the temperature is increased to 600 ℃ at the heating rate of 10 ℃/min for reduction for 4 hours, and PtSn/Y-Al is obtained 2 O 3 A catalyst. Wherein the loading of Pt is 0.5wt%, the loading of Sn is 0.16wt%, and the Pt/Sn molar ratio is 3:1, wherein the doping amount of Y relative to the carrier is 5wt%.
Example 4
The target catalyst is PtSn/Y-Al with Pt loading of 0.8wt%, sn loading of 0.8wt% and Y doping amount of 5wt% 2 O 3 A catalyst.
Preparation of A.Y doped aluminum sol
100g of aluminum powder with the grain size of 100-200 mu m is weighed, 350mL of 10wt% hydrochloric acid solution is slowly added, and 16wt% aluminum sol is prepared while stirring, wherein the mass ratio of Al/Cl is 1.2, and the pH is approximately equal to 4. 44.6g of yttrium hydroxide is weighed and added into 400g of aluminum sol, then 5g of methylol acrylamide cross-linking agent is added, and the mixture is uniformly mixed to obtain the Y-doped aluminum sol.
B. Spherical alumina carrier Y-Al 2 O 3 Is prepared from
Fully mixing the Y-doped aluminum sol obtained in the step A with 52g of hexamethylenetetramine in an ice water bath to prepare a forming liquid, and dropwise adding the forming liquid into the ice water bathFiltering out pellets after solidification in a round-bottom flask with 90 ℃ vacuum pumping oil, and then placing the pellets in an aging kettle with 150 ℃ for aging for 7 hours; taking out the aged pellets, putting the pellets into a beaker, repeatedly cleaning surface oil stains with hot water at 70 ℃, detecting no chloride ions and obvious greasy dirt in the washed wastewater, putting the pellets into a baking oven for drying at 100 ℃ for 12 hours, and roasting the pellets in a muffle furnace at 900 ℃ for 6 hours to obtain theta-type spherical Y-Al 2 O 3 A carrier.
C.PtSn/Y-Al 2 O 3 Preparation of the catalyst
0.0213g of H is weighed 2 PtCl 6 ·xH 2 Dissolving O solid with 200 mu L deionized water to prepare chloroplatinic acid solution; 9.25mg of SnCl 2 ·2H 2 O is dissolved in 1mL hydrochloric acid solution with mass fraction of 10%; mixing the two solutions, and fully dissolving by ultrasonic to obtain the impregnating solution.
And C, adopting a vacuum-spraying method to obtain 1g of spherical Y-Al prepared in the step B 2 O 3 Placing the carrier into a suction filtration bottle, vacuumizing the pressure by a vacuum pump, filling all the impregnating solution into a separating funnel, dropwise adding the impregnating solution into the spherical carrier, and stirring the impregnating solution while dropwise adding until the impregnating solution is completely dripped; drying in an oven at 90 ℃ for 20 hours; then the mixture is placed in a tubular atmosphere furnace, and 10% H with the gas flow rate of 30mL/min is added 2 /N 2 In the mixed gas atmosphere, the temperature is increased to 600 ℃ at a heating rate of 5 ℃/min for reduction for 4 hours, and PtSn/Y-Al is obtained 2 O 3 A catalyst. Wherein the loading of Pt is 0.8wt%, the loading of Sn is 0.8wt%, and the Pt/Sn molar ratio is 1:1, wherein the doping amount of Y relative to the carrier is 5wt%.
Example 5
The target catalyst is PtSn/Y-Al with Pt loading of 0.5wt%, sn loading of 1.5wt% and Y doping amount of 3wt% 2 O 3 A catalyst.
Preparation of A.Y doped aluminum sol
100g of aluminum powder with the grain size of 100-200 mu m is weighed, 350mL of 10wt% hydrochloric acid solution is slowly added, and 20wt% aluminum sol is prepared while stirring, wherein the mass ratio of Al/Cl is 1.5, and the pH is approximately equal to 3. 26.76g of yttrium hydroxide is weighed and added into 400g of aluminum sol, then 5g of methylol acrylamide cross-linking agent is added, and the mixture is uniformly mixed to obtain the Y-doped aluminum sol.
B. Spherical alumina carrier Y-Al 2 O 3 Is prepared from
Fully mixing the Y-doped aluminum sol obtained in the step A with 31.2g of hexamethylenetetramine in an ice water bath to prepare a forming liquid, dropwise dripping the forming liquid into a round-bottom flask filled with 90 ℃ vacuum pump oil, filtering out pellets after solidification, and aging for 7 hours in an aging kettle at 150 ℃; taking out the aged pellets, putting the pellets into a beaker, repeatedly cleaning surface oil stains by using hot water at the temperature of 60 ℃, detecting no chloride ions and obvious greasy dirt in the waste water after washing, putting the pellets into a baking oven for drying at the temperature of 100 ℃ for 12 hours, and roasting the pellets in a muffle furnace at the temperature of 900 ℃ for 6 hours to obtain theta-type spherical Y-Al 2 O 3 A carrier.
C.PtSn/Y-Al 2 O 3 Preparation of the catalyst
0.0133g of H was weighed out 2 PtCl 6 ·xH 2 Dissolving O solid with 200 mu L deionized water to prepare chloroplatinic acid solution; 17.34mg of SnCl 2 ·2H 2 O is dissolved in 1mL hydrochloric acid solution with mass fraction of 10%; mixing the two solutions, and fully dissolving by ultrasonic to obtain the impregnating solution.
And C, adopting a vacuum-spraying method to obtain 1g of spherical Y-Al prepared in the step B 2 O 3 Placing the carrier into a suction filtration bottle, vacuumizing the pressure by a vacuum pump, filling all the impregnating solution into a separating funnel, dropwise adding the impregnating solution into the spherical carrier, and stirring the impregnating solution while dropwise adding until the impregnating solution is completely dripped; drying in an oven at 110 ℃ for 16 hours; then the mixture is placed in a tubular atmosphere furnace, and 10% H with the gas flow rate of 30mL/min is added 2 /N 2 In the atmosphere of the mixed gas, the temperature is increased to 650 ℃ at a heating rate of 5 ℃/min for reduction for 2 hours, and PtSn/Y-Al is obtained 2 O 3 A catalyst. Wherein the loading of Pt is 0.5wt%, the loading of Sn is 1.5wt%, and the Pt/Sn molar ratio is 1:3, wherein the doping amount of Y relative to the carrier is 3wt%.
Application example:
the catalysts prepared in examples 1 and 3 and comparative examples were subjected to propane dehydrogenation performance evaluation, wherein the evaluation device is a fixed bed microreactor, and the specific steps are as follows:
each of the catalyst of examples 1 and 3 and the comparative sample was weighed out at 0.5g, and the reaction system was placed in a quartz tube having an outer diameter of 9mm at a relative pressure of 5psi. Before the reaction starts, the catalyst is pretreated, and is heated to 600 ℃ at a speed of 10 ℃/min under the protection of nitrogen with a gas flow rate of 50mL/min, and then 10% H is opened 2 /N 2 The gas flow rate was adjusted to 60mL/min, the nitrogen was turned off, and the reaction was allowed to proceed at 600℃for 60min. Then the reaction temperature is reduced to (450 ℃ and 500 ℃ respectively), and the reaction gas, namely the mixed gas of propane, hydrogen and balance gas nitrogen, is introduced, wherein the total gas flow rate is 50mL/min, N 2 、5％C 3 H 8 /N 2 With 10% H 2 /N 2 The flow rates are respectively 12.5mL/min, 25mL/min and 12.5mL/min, C 3 H 8 、H 2 、N 2 The contents were 2.5%, 2.5% and 95%, respectively, and the reaction was carried out under the reaction conditions for 1 hour. The concentration of the reactants and products was analyzed by on-line gas chromatography (Agilent 6890), the detector was a hydrogen flame ionization detector, and the capillary column model was Restek Rt-aluminum BOND/Na 2 SO 4 (inner diameter 0.32mm, length 30m, film thickness 0.5 μm). The average propane conversion, propylene selectivity and propylene yield results of the catalyst at 450 ℃ and 500 ℃ for one hour are shown in table 1;
TABLE 1
Note that: comparative example is PtSn/Al reported in literature Science,2021,373,217-222 2 O 3 A catalyst.
As can be seen from Table 1, compared with the comparative example, the catalyst prepared by the present invention has better catalyst activity and propylene yield in the propane dehydrogenation reaction at the reaction temperature of 450 and 500 ℃.

Claims (6)

1. The preparation method of the rare earth doped spherical alumina-based PtSn catalyst for the propane dehydrogenation reaction is characterized by comprising the following steps:
A. preparation of rare earth doped aluminum sol
Dissolving aluminum powder into dilute hydrochloric acid to prepare aluminum sol, wherein the aluminum content is 15-20wt%, the mass ratio of Al/Cl is 0.5-2.5, and the pH is 2-4; adding 3-10wt% of rare earth source into the mixture, fully mixing the mixture, adding 1-10wt% of cross-linking agent into the mixture, and uniformly stirring the mixture to obtain rare earth doped aluminum sol;
the rare earth source is one of nitrate, chloride, sulfate and hydroxide of yttrium, lanthanum and europium;
the cross-linking agent is an organic matter containing hydroxymethyl functional groups and is one or two of N-methylolacrylamide and 5-methylol furfural;
B. rare earth doped spherical alumina carrier S-Al 2 O 3 Is prepared from
Fully and uniformly mixing organic amine and the rare earth doped aluminum sol at 0-10 ℃ to obtain forming liquid, wherein NH + ：Al 3+ The molar ratio of (2) is 0.2-0.5; dropwise adding the molding liquid into a reactor filled with molding oil at 80-100 ℃, curing at a high temperature for 2-3 hours, filtering out sol pellets, and then transferring the sol pellets into an aging kettle to age for 6-10 hours at 150-170 ℃; the aged pellets are used for 60 to 90 percent o C, washing with hot water until no chloride ions or greasy dirt exist in the washing water, and drying in a drying oven at 100-120 ℃ for 12-16 hours; roasting in a muffle furnace at 900-1000 ℃ for 4-8 hours to obtain rare earth doped spherical alumina expressed as S-Al 2 O 3 Wherein the rare earth element is highly dispersed in the alumina;
the organic amine is hexamethylenetetramine, and the forming oil is one of vacuum pump oil, dimethyl silicone oil and paraffin oil;
C.PtSn/S-Al 2 O 3 preparation of the catalyst
Will H 2 PtCl 6 ·xH 2 Dissolving O in deionized water to prepare a chloroplatinic acid solution with the concentration of 180-420 mmol/L; and then dissolving the soluble Sn salt in 8-12% hydrochloric acid solution by mass fraction, and fully dissolving by ultrasonic to prepare 0.85-7.69 mmol/L Sn hydrochloric acid solution.
2. Mixing a chloroplatinic acid solution and a Sn hydrochloric acid solution to prepare an impregnating solution, wherein the concentration and the addition amount of the solution are determined according to the set Pt and Sn loading amounts of a target catalyst, and the amount and the water absorption rate of a used carrier; wherein the volume of the impregnating solution is such that the carrier is saturated with water;
the soluble Sn salt is SnCl 4 Or SnCl 2 ·2H 2 O, pt/Sn molar ratio is 3:1-1:3;
spraying the impregnating solution onto S-Al by vacuum-spraying 2 O 3 The carrier is saturated by water absorption; taking out from 80 to 120 o C, drying for 16-20 hours; then in a reducing atmosphere in a tube atmosphere furnace, the reaction temperature is 2-10 o C/min heating rate is increased to 550-650 o C is reduced for 3 to 6 hours to obtain PtSn/S-Al 2 O 3 A catalyst; the flow rate of the reducing atmosphere is 20-40 mL/min; the reducing atmosphere is 5-10% H 2 /N 2 And (3) mixing gas.
3. The method for producing a rare earth doped spherical alumina-based PtSn catalyst according to claim 1, wherein the rare earth source is Y (OH) 3 、LaCl 3 •7H 2 O or Eu (NO) 3 ) 3 •6H 2 O。
4. A rare earth doped spherical alumina-based PtSn catalyst for propane dehydrogenation prepared by the process according to claim 1 or 2, characterized in that the catalyst is represented by PtSn/S-Al 2 O 3 Wherein PtSn is an active component, the loading amount of Pt is 0.15-1.2 wt% and the loading amount of Sn is 0.05-1.5 wt%; S-Al 2 O 3 The rare earth doped spherical alumina carrier is characterized in that S represents a rare earth element and is one of yttrium, lanthanum and europium; the doping amount is 3-10wt%; S-Al 2 O 3 Is spherical with the thickness of 1.2-2.5 mm and the bulk density of 0.4-0.8 g/cm 3 The crushing strength is 30-60N, and the pore diameter is 18-50 nm.
5. A rare earth doped spherical alumina-based PtSn catalyst according to claim 3, characterized in that S represents a rare earth element, yttrium or europium.
6. Use of a rare earth doped spherical alumina-based PtSn catalyst for propane dehydrogenation according to claim 3, in a propane dehydrogenation process.
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