WO2023124787A1 - Catalyseur à base de pt et son application - Google Patents

Catalyseur à base de pt et son application Download PDF

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WO2023124787A1
WO2023124787A1 PCT/CN2022/136433 CN2022136433W WO2023124787A1 WO 2023124787 A1 WO2023124787 A1 WO 2023124787A1 CN 2022136433 W CN2022136433 W CN 2022136433W WO 2023124787 A1 WO2023124787 A1 WO 2023124787A1
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catalyst
platinum
dehydrogenation
shell
spherical
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PCT/CN2022/136433
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English (en)
Chinese (zh)
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张鹏
韩晓琳
吕雉
鲁玉莹
王宗宝
肖海成
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中国石油天然气股份有限公司
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Priority claimed from CN202111671539.6A external-priority patent/CN116408075A/zh
Priority claimed from CN202111675656.XA external-priority patent/CN116408076A/zh
Application filed by 中国石油天然气股份有限公司 filed Critical 中国石油天然气股份有限公司
Publication of WO2023124787A1 publication Critical patent/WO2023124787A1/fr

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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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • 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
    • 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

Definitions

  • the invention relates to the field of chemical industry, in particular, the invention relates to a Pt-based catalyst and its application.
  • Propane catalytic dehydrogenation catalysts are divided into platinum-based catalysts and chromium-based catalysts.
  • the Oleflex process uses platinum-based catalysts
  • the Catofin process uses chromium-based catalysts. Since the catalysts of each process involve confidential information, the information about the catalysts found is not comprehensive, but the service life of the catalysts of each process is mostly about two years, but the operation cycle is different.
  • Platinum catalysts have the remarkable characteristics of high activity, high selectivity, and low wear rate, but they are expensive, and it is difficult to stabilize their performance by the traditional method of preparation of supported catalysts.
  • Chromium-based catalysts have good activity for the dehydrogenation of low-carbon alkanes and have relatively low requirements for impurities in raw materials.
  • Pt-based catalysts for propane dehydrogenation Pt atoms are dispersed on the catalyst from the inside to the outside, from the inner core to the outer surface.
  • the carbon deposit is also dispersed on the catalyst from the inside to the outside, from the inner core to the outer surface.
  • the catalyst is burnt and regenerated, the carbon deposits in the center of the catalyst or on the inner core are not easy to completely burn out, the catalyst is damaged and the dust is serious, which will lead to the reduction of the strength of the regenerated catalyst, the blockage of the screen, the increase of pressure drop, the decrease of the reaction performance and the shortening of the start-up period and other issues, affecting production efficiency and safe operation.
  • An object of the present invention is to provide a Pt-based dehydrogenation catalyst
  • Another object of the present invention is to provide the application of the Pt-based dehydrogenation catalyst.
  • the present invention provides a Pt-based dehydrogenation catalyst, wherein the Pt-based dehydrogenation catalyst is a spherical ⁇ -alumina as a carrier, and the active component Pt is all dispersed in the outer layer of the catalyst and Spherical catalyst particles are formed, and the active component Pt forms a shell layer whose thickness is 10-90% of the radius of the spherical catalyst particle.
  • the active component of the catalyst Pt atoms or Pt clusters
  • the active component of the catalyst is highly dispersed and distributed on the outer layer of the catalyst, and does not exist in the inner core of the catalyst, so that the coke after the reaction is only produced on the outer layer of the catalyst and no carbon deposit is formed in the inner core. Since the mass and heat transfer efficiency of the outer layer of the catalyst is much higher than that of the inner core, the coke deposits on the catalyst are easier to be completely burned, which ensures that the reaction performance of the regenerated catalyst is fully restored, especially the advantages of no coke in the catalyst core of the present invention and the resulting The advantage of lower coking temperature can greatly reduce the probability of catalyst rupture, and effectively solve the problems of large dust, large pressure drop and short operation period during the operation of the device.
  • the Pt content is 0.1-1.0 wt%.
  • the Pt content is 0.2-0.4 wt%.
  • the Pt-based dehydrogenation catalyst also contains the following percentage components: 0.05-2.0wt% Sn, 0-0.8wt% % Cl, 0.3-3.0 wt% of at least one alkali metal and/or alkaline earth metal.
  • the present invention has no requirements on the distribution of the above-mentioned components (Sn, Cl, alkali metal and/or alkaline earth metal), and the inner and outer shells can be uniform, or only in the outer layer (shell layer) together with Pt.
  • the catalyst in the present invention does not contain Cl or only contains a small amount of Cl.
  • the content of Cl is 0.1-0.8wt%.
  • the alkali metal is selected from one or more combinations of lithium, sodium and potassium.
  • the alkaline earth metal is selected from magnesium or calcium.
  • the Pt dispersed on the outer layer of the catalyst is Pt atoms or nano-scale Pt atom clusters.
  • the particle size of the nanoscale Pt atomic clusters is larger than 2 nm.
  • the Pt dispersion value measured by the hydrogen-oxygen titration method is not less than 85%.
  • the Pt dispersion value measured by the hydrogen-oxygen titration method is 85-100%.
  • the thickness of the shell layer is 30-70% of the radius of the spherical catalyst particle.
  • the spherical ⁇ -alumina has a radius of 0.5-1.2 mm, a specific surface area of 50-160 m 2 /g, and a bulk density of 0.5-0.8 g/cm 3 .
  • the Pt-based dehydrogenation catalyst is prepared by a method comprising the following steps: loading Sn and alkali metal and/or alkaline earth metal components on the carrier by impregnation method, drying and then roasting, Then, the Pt component is supported by an impregnation method, and then dried and calcined to obtain the Pt-based dehydrogenation catalyst.
  • loading Sn and alkali metal and/or alkaline earth metal components on the carrier by the impregnation method comprises using an aqueous solution of a water-soluble salt of Sn and a water-soluble salt of alkali metal and/or alkaline earth metal to impregnated carrier.
  • the water-soluble salts of Sn and the water-soluble salts of alkali metals and/or alkaline earth metals each independently include nitrates, sulfates and hydrochlorides thereof.
  • the temperature for calcination after loading Sn and alkali metal and/or alkaline earth metal components is 400-800°C; preferably 400-600°C; more preferably 500°C.
  • the time for firing after loading Sn and alkali metal and/or alkaline earth metal components is 1-10 h; preferably 2-5 h.
  • the loading of the Pt component includes using an aqueous solution of chloroplatinic acid as an impregnating solution, and loading at a pH value of 1-4 (preferably 1-2).
  • the temperature of the calcination after loading the Pt component is 400-800°C; preferably 400-600°C; more preferably 500°C.
  • the calcination time after loading the Pt component is 1-10 h; preferably 2-5 h.
  • the drying temperature after loading the Pt component is 100-300°C; preferably 120-200°C.
  • the present invention also provides the application of the Pt-based dehydrogenation catalyst described in any one of the present invention in the dehydrogenation of low-carbon saturated hydrocarbons to produce low-carbon olefins.
  • the low-carbon saturated hydrocarbon is ethane, propane, butane or pentane.
  • the present invention also provides a platinum-based catalyst, which includes: a carrier, an active component and an auxiliary element;
  • the carrier is a spherical shell made of ⁇ -alumina
  • the active component is platinum, dispersed in the outer layer of the spherical shell to form a platinum-containing layer, the thickness of the platinum-containing layer is 10% to 90% of the radius of the platinum-based catalyst, the active component
  • the content in the platinum-based catalyst is 0.1-1.0wt%;
  • the additive elements include: 0.05-2.0 wt% Sn, 0-0.8 wt% Cl, and 0.3-3.0 wt% alkali metal and/or alkaline earth metal.
  • the invention provides a platinum-based catalyst, comprising: a carrier, an active component and an auxiliary element.
  • the carrier is a spherical shell made of ⁇ -alumina, and the center of the sphere is a hollow part, which can be filled with other substances or not filled with any substance.
  • the active component is platinum, specifically nanoscale platinum atoms or atomic clusters. Platinum is dispersed in the outer layer of the spherical shell to form a platinum-containing layer, and platinum does not exist at the center or inner core of the spherical shell, so the macroscopic appearance is a shell-like shape with a certain thickness.
  • the thickness of the platinum-containing layer is 10-90% of the radius of the platinum-based catalyst, preferably 30-70% of the radius of the platinum-based catalyst.
  • the content of the active component in the platinum-based catalyst is 0.1-1.0 wt%, preferably 0.2-0.4 wt%. In the platinum-based catalyst, the degree of dispersion of platinum measured by the hydrogen-oxygen titration method is not less than 85%.
  • the auxiliary elements include: 0.05-2.0 wt% of Sn, 0-0.8 wt% of Cl, and 0.3-3.0 wt% of alkali metal and/or alkaline earth metal.
  • the position of the promoter element in the platinum-based catalyst is not limited, it can be located in the outer layer of the spherical shell of the carrier, or in the hollow part of the spherical shell.
  • the platinum-based catalyst has the characteristics of high activity, easy burning, and low chlorine.
  • the active component of the catalyst Pt atoms or Pt clusters, on the outer layer of the catalyst and not in the inner core of the catalyst, the coke after the reaction is only produced on the outer layer of the catalyst without carbon deposits in the inner core.
  • the coke deposits on the catalyst are easier to be completely burned, which ensures that the reaction performance of the regenerated catalyst is fully restored, especially the advantages of no coke in the catalyst core of the present invention and the resulting
  • the advantage of lower coking temperature can greatly reduce the probability of catalyst rupture, and effectively solve the problems of large dust, large pressure drop and short operation period during the operation of the device.
  • the invention solves the problems that the carbon deposits in the center of the catalyst or on the inner core are not easy to be completely burnt out, the catalyst is damaged and the dust is relatively serious when the conventional propane dehydrogenation to propylene noble metal catalyst is scorched and regenerated. Alleviate the phenomenon of reduced strength of the regenerated catalyst, blockage of the screen, increased pressure drop, and decreased reaction performance, thereby enhancing safe operation, improving the start-up cycle, and increasing production efficiency. It solves the phenomenon of Cl loss on the traditional propane dehydrogenation catalyst and avoids the problem of Cl corrosion of equipment. At the same time, in order to solve the phenomenon of Cl loss on the traditional propane dehydrogenation catalyst, eliminate the corrosion problem and reduce the acidity of the catalyst, the catalyst in the embodiment of the present invention does not contain Cl or only contains a small amount of Cl.
  • Another aspect of the present invention provides a method for dehydrogenating low-carbon saturated hydrocarbons, wherein the above-mentioned platinum-based catalyst is used.
  • Yet another aspect of the present invention provides a method for producing propylene by dehydrogenating propane, wherein the above-mentioned platinum-based catalyst is used.
  • Chinese patent 1 discloses an egg yolk-eggshell type SiO 2 -Al 2 O 3 noble metal propane dehydrogenation catalyst and its preparation method.
  • the catalyst uses solid SiO 2 -Al 2 O 3 microspheres as egg yolk , using porous SiO 2 -Al 2 O 3 hollow spheres as egg shells, and the egg yolk and egg shell layers are respectively loaded with effective catalytically active components with different functions.
  • Cida patent 2 discloses a catalyst for catalytic propane dehydrogenation reaction, the carrier of which is an eggshell-like mesoporous material obtained by crystallization of a template, trimethylpentane and tetramethoxysilane , Mesoporous materials are micron-scale shell-shaped hollow small grains.
  • Citone 3 discloses a catalyst for selective oxidation of hydrogen, comprising an inner core of an inert carrier and a layered composite carrier composed of an outer layer of a porous coating material bonded to the inner core, the carrier The inner and outer layers are different substances combined by coating.
  • Chinese patent 4 discloses a thin-shell catalyst for the dehydrogenation of low-carbon alkanes to prepare low-carbon olefins.
  • the slurry of the coated porous material is coated on the inner core of the inert carrier, and then dried for 700 Calcining at -1000° C. for 1 to 9 hours obtains a layered composite carrier, and the coated porous material is in the shape of a shell macroscopically.
  • Chinese patent 5 (CN202010427158.2) discloses a core-shell structured alumina carrier.
  • the carrier uses alumina or silicon oxide as the seed crystal of the core material, and an alumina precursor is first grown on the surface of the seed crystal of the core material, and then After firing, activated alumina is obtained as the shell.
  • the carrier of the platinum-based catalyst in the embodiment of the present invention uses a single ⁇ -alumina, which has low cost and is easier to manufacture.
  • Chinese patent 6 discloses a core-shell catalyst for propane dehydrogenation to propylene.
  • the shell layer of the catalyst is the Fe component, while other components are buried in the core layer of the catalyst, which can block the inner layer The opportunity for the active components of the catalyst to come into contact with the reactor wall.
  • the difference from this patent is that the platinum-based catalyst described in the examples of the present invention firstly does not contain Fe component, and secondly, the active component Pt is not located in the inner core but in the shell layer. There is a significant difference.
  • Chinese patent 7 discloses a supported core-shell structure ZnO catalyst, with Al 2 O 3 as the carrier, loaded with active components of NiZn@ZnO core-shell morphology, in which NiZn alloy is the core, ZnO for the shell.
  • Chinese patent 8 (CN201810400639.7 ) discloses a supported nano-Pt catalyst , which uses metal Pt as the active component. structure, with CeO2 as the core.
  • the inventors found that the core-shell structures disclosed in the above Chinese patents 7-8 refer to core-shell structures with microscopic morphology composed of an active metal and another metal oxide. It is substantially different from the platinum-based catalyst described in the examples of the present invention.
  • Cia patent 9 discloses a platinum-based catalyst with a core-shell structure as a carrier.
  • the metal is coated in SiO2 by the stober method, and then it is coated twice by the glucose hydrothermal method.
  • solidify the carbon material by high-temperature calcination under inert gas, etch the SiO 2 with a strong base to form a core-shell structure carrier with an inner metal outer carbon layer, and then use a platinum-containing precursor solution to carry out platinum loading on it.
  • the core-shell structure of this patent means that the inner core is metal and the outer shell is carbon, which is significantly different from the platinum-based catalyst described in the examples of the present invention.
  • Chinese patent 10 (CN201180066672.7) discloses a method for manufacturing catalyst particles used for fuel cell electrode materials. The diameter is 4-40nm, the palladium-containing electrode is immersed in the platinum solution, and the ionization tendency is different, and the copper and the platinum are subjected to displacement plating, and finally the platinum single-atom layer catalyst particles are formed.
  • the Chinese patent 10 belongs to the preparation method of electrode materials in the field of fuel cells, which is obviously different from the field of application of the present invention; Pb, and the size of the catalyst and the core is at the millimeter level, which is much larger than the nanometer level; the Pt of the monoatomic layer film in Chinese Patent 10 is coated on the outer layer of Pb by displacement plating, and the Pt of the present invention is not a monoatomic layer film.
  • Chinese patent 11 discloses a thin-shell catalyst in which the active components are unevenly distributed in the shell, comprising an inert carrier core, a porous material shell bonded to the core, and on the shell At least one platinum group metal active component is loaded, and the content of the platinum group metal active component on the surface of the shell is lower than that inside the shell.
  • the inventor found that: the Chinese patent 11 requires that the inner core is an inert substance, the outer shell is an active porous material, platinum is loaded on the outer shell, and the platinum content in the outer shell is higher than that on the outer surface; this is the same as the inner core and the outer shell in the present invention.
  • the characteristics of uniform and high dispersion of Pt in the carrier and the shell are obviously different.
  • Chinese patent 12 (CN201711019192.0) discloses a carbon tetrachloride gas-phase hydrodechlorination catalyst for the preparation of chloroform, the main feature of which is to use an organic acid competitive adsorbent to pretreat the carrier, so that the active component platinum is on the carrier.
  • the upper distribution is in the form of thick shell penetration.
  • U.S. Patent 1 discloses a core-shell structure propane dehydrogenation catalyst based on SBA-15, which contains two elemental components, one of which is Pt , the other is Fe, Co, Ni as coagents, Pt and Fe, Co, Ni form a core-shell structure in the form of an alloy at the microscopic scale, the catalyst has a propylene selectivity of 85%.
  • the carrier of this patent is completely different from the platinum-based catalyst of the embodiment of the present invention.
  • Pt, Fe, Co, and Ni are necessary, and the selectivity of propylene is relatively low.
  • U.S. Patent 2 discloses a dehydrogenation catalyst containing a Group VIII noble metal component supported on an alumina carrier, a co-formed Group IVA metal component and an alkali
  • the surface area of the alumina carrier is that the precious metal is evenly distributed inside and outside the carrier, and the reaction raw material in this patent is liquid n-alkane with a large molecular weight above C9.
  • this article mainly discusses the influence of several organic acids on the formation of Pt uniformity or protein morphology, and the single Pt catalyst in the article is very poor for propane dehydrogenation reaction, which is different from the platinum-based catalyst described in the embodiments of the present invention. Significantly different.
  • the platinum-based catalyst described in the embodiment of the present invention can be used for propane whose raw material is far less than naphtha in molecular weight, and the product is olefin.
  • the shell catalyst of the present invention still possesses a very high degree of dispersion.
  • the catalyst of the present invention Because it also contains other auxiliary elements other than Pt and Sn, it has significantly higher activity and selectivity for propane dehydrogenation reaction.
  • the present invention provides a Pt-based catalyst and its application.
  • the invention solves the problems that the carbon deposits in the center of the catalyst or on the inner core are not easy to be completely burnt out, the catalyst is damaged and the dust is relatively serious when the conventional propane dehydrogenation to propylene noble metal catalyst is scorched and regenerated.
  • the catalyst of the invention is easy to burn and regenerate, and has the advantages of low burn regeneration temperature and low catalyst damage rate.
  • the active component Pt atoms or Pt clusters of the catalyst are highly dispersed and distributed on the outer layer of the catalyst, but not in the inner core of the catalyst, so that the coke after reaction is only produced on the outer layer of the catalyst and no carbon deposit is formed in the inner core.
  • the invention alleviates the phenomenon of reduced strength of the regenerated catalyst, blockage of the screen, increased pressure drop, and decreased reaction performance, thereby enhancing safe operation, improving the start-up period, and increasing production efficiency.
  • the invention solves the phenomenon of Cl loss on the traditional propane dehydrogenation catalyst and avoids the problem of Cl corrosion of equipment.
  • the catalyst of the invention is suitable for the reaction of propane dehydrogenation to produce propylene, and has excellent propane conversion rate and propylene yield.
  • the catalyst carrier of the invention is simple, low in cost and easy to prepare.
  • Fig. 1 is a shell-like topography diagram showing a certain thickness of Pt uniformly and highly dispersed on the outer layer of the catalyst in Examples 1-4, 6-9.
  • Fig. 2 is the XRD diffraction peak spectrum of the catalyst carrier in Examples 1-4 according to ⁇ -alumina.
  • Figure 3 is a cross-sectional view of the catalysts in Comparative Examples 1, 2, and 4; wherein Pt is uniformly distributed from the outer surface to the inner core.
  • Fig. 4 is a typical STEM electron micrograph of the catalyst of the present invention in Examples 1-4, 6-10.
  • Fig. 5 is the XRD diffraction peak spectrum of the catalyst carrier in Examples 5-10 conforming to ⁇ -alumina.
  • the shell-type propane dehydrogenation catalyst of this example is referred to as catalyst A.
  • catalyst A First, purchase or customize a commercial carrier, which is spherical ⁇ -alumina with a radius of 0.5 mm, a specific surface area of 50 m 2 /g, and a bulk density of 0.5 g/cm 3 .
  • the catalyst metal is in an oxidized state, and if necessary, it can be further reduced in hydrogen to become a reduced state.
  • Pt is evenly loaded on the outer layer of the catalyst, the thickness of Pt accounts for 10% of the radius, and there is no Pt distribution at the center or inner core of the catalyst (proof method: after the catalyst is reduced by hydrogen at 500°C for 2 hours, the inner core is white or light-colored, and the The outer layer of Pt is gray or dark).
  • the content of Pt on the catalyst is 0.1%, the content of Sn is 0.05%, the content of Cl is 0%, and the content of Na is 0.3%.
  • the Pt dispersion value was determined to be 91% by the hydrogen-oxygen titration method.
  • the microscopic morphology of Pt presents single atoms, diatoms or atomic clusters, as shown in the STEM scanning transmission electron microscope photo of Figure 4, which is in a highly dispersed state.
  • the shell-type propane dehydrogenation catalyst of this example is referred to as catalyst B.
  • catalyst B The shell-type propane dehydrogenation catalyst of this example, as shown in FIG. 1 , is referred to as catalyst B.
  • a commercial carrier which is spherical ⁇ -alumina with a radius of 0.8 mm, a specific surface area of 80 m 2 /g, and a bulk density of 0.6 g/cm 3 .
  • the shell-type propane dehydrogenation catalyst of this embodiment is referred to as catalyst C.
  • a commercial carrier which is spherical ⁇ -alumina with a radius of 1.0 mm, a specific surface area of 120 m 2 /g, and a bulk density of 0.7 g/cm 3 . Its diffraction peaks are in line with the XRD spectrum shown in Figure 2; then the impregnation method is used to load 0.6wt% Sn and 1.2wt% Ca, the solvent is deionized water, and the solutes are Sn(NO 3 ) 2 and Ca(NO 3 ) 2.
  • the content of Pt on the catalyst is 0.4%, the content of Sn is 0.6%, the content of Cl is 0.4%, and the content of Ca is 1.2%.
  • the Pt dispersion value was determined to be 91% by the hydrogen-oxygen titration method.
  • the STEM scanning transmission electron micrograph of Pt is similar to Fig. 4.
  • the shell-type propane dehydrogenation catalyst of this example is referred to as catalyst D.
  • catalyst D The shell-type propane dehydrogenation catalyst of this example, as shown in FIG. 1 , is referred to as catalyst D.
  • a commercial carrier which is spherical ⁇ -alumina with a radius of 1.2 mm, a specific surface area of 160 m 2 /g, and a bulk density of 0.8 g/cm 3 .
  • the carrier is spherical ⁇ -alumina with a radius of 1.2 mm, a specific surface area of 160 m 2 /g, and a bulk density of 0.8 g/cm 3 . Its diffraction peaks conform to the XRD spectrum shown in Figure 2. Pt is uniformly loaded on the outer layer of the catalyst (the inner core is white or light-colored after the catalyst is reduced by hydrogen at 500°C for 2 hours), the morphology of Pt is thick shell, and the thickness accounts for 90% of the radius, and there is no Pt distribution at the center or inner core of the catalyst ,As shown in Figure 1.
  • the content of Pt on the catalyst is 1.0%, the content of Sn is 2.0%, the content of Cl is 0.8%, the content of Li is 2.0%, the content of Mg is 1.0%, and the total content of Li and Mg is 3.0wt%.
  • the Pt dispersion value determined by the hydrogen-oxygen titration method was 90%.
  • the STEM scanning transmission electron micrograph of Pt is similar to Fig. 4.
  • the carrier involved in the present invention is a shell-type propane dehydrogenation catalyst of gamma-alumina, and its carrier diffraction peak conforms to the X-ray diffraction (X-ray diffraction, XRD) spectrum as shown in Figure 5.
  • the representative physical properties of the catalyst spherical carrier ⁇ -alumina of the present invention are: radius 0.5-1.2 mm, specific surface area 160-220 m 2 /g, bulk density 0.5-0.8 g/cm 3 .
  • the calcination temperature of ⁇ -alumina is only 500-650°C, and the production cost and energy consumption of ⁇ -alumina are lower. Low.
  • the carrier of this example is a shell-type propane dehydrogenation catalyst of ⁇ -alumina, which is referred to as catalyst E.
  • catalyst E a shell-type propane dehydrogenation catalyst of ⁇ -alumina, which is referred to as catalyst E.
  • the carrier is spherical ⁇ -alumina with a radius of 0.5mm; then use the impregnation method to load 0.05wt% Sn and 0.3wt% Na, the solvent is deionized water, and the solute is Sn(NO 3 ) 2 and NaNO 3 , baked at 500°C after drying; after roasting, the sample continued to load 0.1wt% Pt by impregnation method, the solvent was deionized water, the solute was chloroplatinic acid, and nitric acid was added to adjust the pH value of the solution to 2, and stirred at room temperature Immerse for 0.2h, then dry at 200°C and bake at 500°C; at this time, the catalyst metal is in an oxidized state,
  • Pt is evenly loaded on the outer layer of the catalyst, the thickness of Pt accounts for 10% of the radius, and there is no Pt distribution at the center or inner core of the catalyst (proof method: after the catalyst is reduced by hydrogen at 500°C for 2 hours, the inner core is white or light-colored, and the The outer layer of Pt is gray or dark), as shown in Figure 1.
  • the content of Pt on the catalyst is 0.1wt%, the content of Sn is 0.05wt%, the content of Cl is 0%, and the content of Na is 0.3wt%.
  • the value of the Pt dispersion measured by the hydrogen-oxygen titration method was 92%.
  • the shell-type propane dehydrogenation catalyst whose carrier is ⁇ -alumina in this example is called catalyst F.
  • the carrier is spherical ⁇ -alumina with a radius of 0.8mm; then use the impregnation method to load 0.3wt% Sn and 1.0wt% K, the solvent is deionized water, and the solute is Sn(NO 3 ) 2 and KNO 3 , baked at 500°C after drying; after roasting, the sample continued to load 0.2wt% Pt by impregnation method, the solvent was deionized water, the solute was chloroplatinic acid, and hydrochloric acid was added to adjust the pH value of the solution to 1.5, and stirred at room temperature Immerse under water for 0.4h, then dry at 200°C and bake at 500°C; at this time, the catalyst metal is in an oxidized state, and if necessary, it can be further reduced in hydrogen to become a reduced state.
  • Pt is uniformly loaded on the outer layer of the catalyst, the thickness of Pt accounts for 30% of the radius, and there is no Pt distribution at the center or inner core of the catalyst, as shown in Figure 1.
  • the content of Pt on the catalyst is 0.2%, the content of Sn is 0.3%, the content of Cl is 0.1wt%, and the content of K is 1.0wt%.
  • the Pt dispersion value determined by the hydrogen-oxygen titration method was 95%.
  • the shell-type propane dehydrogenation catalyst whose carrier is ⁇ -alumina in this example is called catalyst G.
  • the carrier is spherical ⁇ -alumina with a radius of 1.0mm; then use the impregnation method to load 0.6wt% Sn and 1.2wt% Ca, the solvent is deionized water, and the solute is Sn(NO 3 ) 2 and Ca(NO 3 ) 2 , and roasted at 500°C after drying; after roasting, the sample was loaded with 0.4wt% Pt by impregnation method, the solvent was deionized water, the solute was chloroplatinic acid, and the pH value of the solution was adjusted to 1.2.
  • the catalyst metal is in an oxidized state, and if necessary, it can be further reduced in hydrogen to become a reduced state.
  • Pt is evenly loaded on the outer layer of the catalyst, the thickness of Pt accounts for 70% of the radius, and there is no Pt distribution at the center or inner core of the catalyst, as shown in Fig. 1.
  • the content of Pt on the catalyst is 0.4wt%, the content of Sn is 0.6wt%, the content of Cl is 0.4wt%, and the content of Ca is 1.2wt%.
  • the Pt dispersion value determined by the hydrogen-oxygen titration method was 95%.
  • the carrier of this example is a shell-type propane dehydrogenation catalyst of ⁇ -alumina, which is referred to as catalyst H.
  • catalyst H a shell-type propane dehydrogenation catalyst of ⁇ -alumina, which is referred to as catalyst H.
  • the carrier is spherical ⁇ -alumina with a radius of 1.2mm; then use the impregnation method to load 2.0wt% of Sn, 2.0wt% of Li and 1.0wt% of Mg, the solvent is deionized water, and the solute Sn(NO 3 ) 2 , LiNO 3 , and Mg(NO 3 ) 2 , respectively, and baked at 500°C after drying; after roasting, the samples were loaded with 1.0wt% Pt by impregnation method, the solvent was deionized water, and the solute was platinum chloride acid, add hydrochloric acid to adjust the pH value of the solution to 1, impregnate for 0.8h under stirring at room temperature, then dry at 120°C and
  • Pt is evenly loaded on the outer layer of the catalyst, the morphology of Pt is thick shell, the thickness accounts for 90% of the radius, and there is no Pt distribution at the center or core of the catalyst, as shown in Figure 1.
  • the content of Pt on the catalyst is 1.0wt%, the content of Sn is 2.0wt%, the content of Cl is 0.8wt%, the content of Li is 2.0wt%, the content of Mg is 1.0wt%, and the total content of Li and Mg is 3.0wt%.
  • the value of the Pt dispersion measured by the hydrogen-oxygen titration method was 92%.
  • the carrier involved in the present invention is a shell-type propane dehydrogenation catalyst of spherical gamma-alumina, such as the catalysts of Examples 6 to 9, whose Pt microscopic appearance presents single atoms, diatoms or atomic clusters, and STEM (scanning transmission electron Microscope (Scanning Transmission Electron Microscopy) scanning transmission electron microscope photograph is close to Fig. 4, and the white spot in the figure is Pt atom, and the shell type propane dehydrogenation catalyst involved in the present invention, the microscopic morphology of its Pt presents single atom, double atom or The atomic clusters are in a highly dispersed state at the nanometer level, and coincide with the Pt dispersion data of more than 85% in the examples.
  • a shell-type propane dehydrogenation catalyst of spherical gamma-alumina such as the catalysts of Examples 6 to 9, whose Pt microscopic appearance presents single atoms, diatoms or atomic clusters, and STEM (scanning transmission electron
  • a typical commercial propane dehydrogenation catalyst referred to as Comparative 1.
  • Pt is evenly distributed inside and outside on the alumina, and the topography of Pt on the catalyst is shown in Figure 3, which is uniform inside and outside.
  • the catalyst has a radius of 0.9mm, a Pt content of 0.4%, a Sn content of 0.4%, and a certain amount of Cl and auxiliary metals.
  • the Pt dispersion value determined by the hydrogen-oxygen titration method was 90%.
  • a propane dehydrogenation catalyst was prepared according to the Chinese journal article "Effect of Solvent and Competitive Adsorbents on the Performance of PtSnK/ ⁇ -Al 2 O 3 Isobutane Dehydrogenation Catalyst", which is called contrast agent 2.
  • Pt is evenly dispersed inside and outside the catalyst, and the topography of Pt on the catalyst is also shown in Figure 3, which is uniform inside and outside.
  • the catalyst carrier is ⁇ -alumina, and the equal volume co-impregnation method is used to support the metal, wherein the content of Pt is 0.5%, the content of Sn is 0.6%, the content of Cl is 0.1%, and the content of K is 0.8%.
  • the Pt dispersion value was determined to be 65% by the hydrogen-oxygen titration method.
  • a single metal Pt/Al 2 O 3 thin-shell catalyst was prepared, called contrast agent 3.
  • Pt is supported only on the extremely thin outer surface of the catalyst, with a shell thickness of about 15 ⁇ m, accounting for 0.3% of the catalyst radius.
  • the catalyst carrier is ⁇ -alumina, and the equal-volume co-impregnation method is adopted, ethanol is used as the impregnation solution, and the Pt content of the catalyst is 0.29%.
  • the value of the Pt dispersion measured by the hydrogen-oxygen titration method was 30%.
  • a monometallic Pt/Al 2 O 3 catalyst, called contrast agent 4, was prepared according to the Chinese journal article "Study on Preparation of Pt/Al 2 O 3 Catalyst by Impregnation Method——Influence of Competitive Adsorbents on Pt Distribution”.
  • the catalyst carrier is ⁇ -alumina, and citric acid is used as a competitive adsorbent.
  • Pt is uniformly dispersed inside and outside the catalyst.
  • the topography of Pt on the catalyst is also shown in Figure 3, which is uniform inside and outside.
  • the Pt content of the catalyst is 0.3%, and the Pt dispersion value measured by the hydrogen-oxygen titration method is 60%.
  • a bimetallic Pt-Sn/Al 2 O 3 catalyst was prepared, called contrast agent 5.
  • the catalyst carrier is ⁇ -alumina, which is prepared as an eggshell catalyst with a competitive adsorbent.
  • the Pt content of the catalyst is 0.3%, and the Pt dispersion value measured by the hydrogen-oxygen titration method is 80%.
  • a single Pt thick-shell catalyst called contrast agent 6, was prepared.
  • the Pt content of the catalyst is 0.7wt%, and the Pt dispersion value measured by the hydrogen-oxygen titration method is 50%.
  • the reaction performance evaluation of each catalyst for propane dehydrogenation to propylene was carried out.
  • the raw material is pure propane
  • the reaction evaluation device is a 20mL fixed-bed evaluation device
  • the reaction temperature is 580°C
  • normal pressure The reaction results of each catalyst are shown in Table 1 below.
  • the shell catalyst of the present invention has higher propane conversion rate, propylene selectivity and propylene yield at the same time.
  • the inner core has carbon deposits that have not been burned clean, and 0.2-1% of the catalyst is broken contrast agent 2
  • the inner core has carbon deposits that have not been burned clean, and 0.2-1% of the catalyst is broken Contrast agent 3 All burned clean, no catalyst cracked contrast agent 4
  • the inner core has carbon deposits that have not been burned clean, and 0.2-1% of the catalyst is broken Contrast agent 5 All burned clean, no catalyst cracked Contrast agent 6 All burned clean, no catalyst cracked Catalyst A All burned clean, no catalyst cracked
  • Catalyst B All burned clean, no catalyst cracked Catalyst C All burned clean, no catalyst cracked Catalyst D All burned clean, no catalyst cracked Catalyst E All burned clean, no catalyst cracked Catalyst F All burned clean, no catalyst cracked Catalyst G All burned clean, no catalyst cracked Catalyst H All burned clean, no catalyst cracked
  • Criteria for judging whether the carbon on the catalyst is burnt clean After the catalyst is cut open, if the color of the inner core or the center is obviously darker than that of the surrounding area, it means that the carbon is not completely burned out;
  • the coke produced by the shell-type catalyst of the present invention is more likely to be burnt, and all the coke is burned off cleanly, and there is no catalyst cracking phenomenon, so there will be no Visible dust generation.
  • the catalyst prepared by the present invention is easier to burn, which not only makes the burn temperature lower, thereby reducing catalyst wear and device energy consumption, but also It fully guarantees that the catalyst burnt regeneration is more thorough, so as to ensure the best recovery of catalyst activity.

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Abstract

La présente invention concerne un catalyseur de déshydrogénation à base de Pt et son application. Le catalyseur de déshydrogénation à base de Pt prend l' θ-alumine sphérique en tant que support, le composant actif Pt est complètement dispersé sur la couche externe du catalyseur et des particules de catalyseur sphériques sont formées, le composant actif Pt forme une couche d'enveloppe, et l'épaisseur de la couche d'enveloppe est de 10 à 90 % du rayon des particules de catalyseur sphériques. Selon la présente invention, les problèmes selon lesquels le dépôt de carbone sur le centre ou le noyau interne du catalyseur n'est pas facile à brûler complètement, et le catalyseur se rompt et la poussière est importante pendant la régénération par combustion de coke d'un catalyseur de métal noble pour préparer du propylène au moyen d'une déshydrogénation de propane classique sont résolus. La présente invention présente les avantages du catalyseur qui est sujet à la régénération par combustion du coke, et d'une faible température de régénération par combustion du coke, et d'un faible taux de rupture de catalyseur.
PCT/CN2022/136433 2021-12-31 2022-12-05 Catalyseur à base de pt et son application WO2023124787A1 (fr)

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CN202111671539.6A CN116408075A (zh) 2021-12-31 2021-12-31 一种铂基催化剂及其制备方法和应用
CN202111675656.XA CN116408076A (zh) 2021-12-31 2021-12-31 Pt基脱氢催化剂及其应用
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150158024A1 (en) * 2012-08-13 2015-06-11 Reliance Industries Limited Dehydrogenation catalyst for hydrocarbons and method of preparation thereof
CN111097457A (zh) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 一种低碳烷烃脱氢催化剂及其制备方法
CN111989156A (zh) * 2018-04-18 2020-11-24 科莱恩国际有限公司 基于铂-硫的壳催化剂、其生产和在烃脱氢中的用途

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150158024A1 (en) * 2012-08-13 2015-06-11 Reliance Industries Limited Dehydrogenation catalyst for hydrocarbons and method of preparation thereof
CN111989156A (zh) * 2018-04-18 2020-11-24 科莱恩国际有限公司 基于铂-硫的壳催化剂、其生产和在烃脱氢中的用途
CN111097457A (zh) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 一种低碳烷烃脱氢催化剂及其制备方法

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