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CN114682283B - Carbon-nitrogen coated supported metal monoatomic catalyst, preparation method and application thereof - Google Patents

Carbon-nitrogen coated supported metal monoatomic catalyst, preparation method and application thereof Download PDF

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CN114682283B
CN114682283B CN202011637270.5A CN202011637270A CN114682283B CN 114682283 B CN114682283 B CN 114682283B CN 202011637270 A CN202011637270 A CN 202011637270A CN 114682283 B CN114682283 B CN 114682283B
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catalyst
metal
carrier
zif
precursor
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CN114682283A (en
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李杨
连超
邓明亮
王梦云
杨洪衬
王敏朵
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Beijing Single Atom Catalysis Technology Co ltd
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Beijing Single Atom Catalysis Technology Co ltd
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • 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
    • 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
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds
    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention protects a novel chip with CN@M 1 A catalyst with a carrier structure, a preparation method, a regeneration method and application thereof, wherein M is noble metal and transition metal, and at least part of M metal in the catalyst is dispersed on a carrier in a single atom site state. Compared with the traditional catalyst, the catalyst has lower active metal consumption and higher catalytic conversion rate and selectivity.

Description

Carbon-nitrogen coated supported metal monoatomic catalyst, preparation method and application thereof
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to an alkane dehydrogenation catalyst.
Background
The low-carbon olefin comprises isobutene, 1-butene, 2-butene, 1, 3-butadiene, propylene, ethylene and the like, is a basic raw material for petrochemical industry, and is widely used for producing organic chemical raw materials, resin rubber plastics, synthetic gasoline and the like. A large amount of lower alkanes are produced in the petrochemical industry in the form of byproducts, and the corresponding lower olefins can be obtained by dehydrogenating the lower alkanes, so that the lower alkanes are gradually paid attention to the academia and industry.
The catalytic system for the dehydrogenation of the lower alkane, which has been successfully applied to industrialization, is mainly a supported metal nanoparticle catalytic system taking an oxide as a carrier, and active metal elements can be platinum, chromium, vanadium, molybdenum, gallium and the like, but since the eighties of the last century, the two types of platinum series and chromium series are only successfully applied to the industrialization, and a great deal of researches are only carried out on the basis of the two types of platinum series and chromium series, and a plurality of auxiliary agents such as lithium, potassium, magnesium, calcium, lanthanum, zinc, tin and the like are added for modification, so as to try to utilize the interaction of the metal elements with active components in the catalyst and the carrier to regulate and optimize the catalytic performance.
However, both types of catalysts have significant drawbacks: the platinum exists in the form of nano particles on the platinum-based catalyst, precious metals are not fully exposed on the surface of the catalyst, the loading capacity is high, and the utilization rate is low; chromium compounds have high toxicity, are easy to cause environmental pollution, have short continuous reaction time in alkane dehydrogenation reaction, and rapidly accumulate carbon on the surface of a catalyst in the reaction process, and need to frequently switch and regenerate and catalyze two processes.
The active metal exists in the form of single atom on the single atom catalyst, and the application of the active metal to the dehydrogenation reaction of lower alkane can effectively avoid the problems: firstly, the metal element has the highest atomic utilization rate when existing in a single-atom form, so that the metal consumption can be reduced, and non-toxic metal elements are selected to reduce the cost and pollution; and secondly, the monodisperse atomic active sites are single, no adjacent active sites exist, the activation of C-H bonds can be catalyzed with high selectivity without damaging the C-C bonds, the generation of byproducts is avoided, the generation of carbon deposit is effectively inhibited, and the service life of the catalyst is effectively prolonged.
Patent CN107626294a discloses a method of preparing a noble metal monoatomic catalyst using in situ synthesis to form a noble metal monoatomic catalyst on a carbon nitrogen (N-C) based support. Patent CN109225306a discloses the use of noble metal monoatomic catalysts in the dehydrogenation of lower alkanes. The preparation of the monoatomic catalysts in both patents requires a considerable preparation time, and in situ preparation requires a stirring time of 24 hours and a drying time of more than 24 hours, which greatly limits the productivity for industrial production. In addition, the catalyst disclosed in the above patent has a structure of M/N-C in most cases, although some of the catalyst has a structure of M/N-C-Al 2 O 3 But its catalytic performance is significantly lower than that of the M/N-C catalyst. In addition, in this patent, considering the mixing problem with the organic ligand, the metal precursor should be selected as much as possible from organic salts such as acetylacetonate, resulting in high production costs and difficulty in controlling the actual load of the metal. More importantly, the catalysts of the patents are all powder, and are produced in actual industryThe molded catalyst is needed in the production process, otherwise, the problems of coking, blocking and the like are easy to occur. The monoatomic catalyst of this patent is used in industry, and has the following problems: 1. a method for preparing a monoatomic catalyst rapidly and efficiently; 2. a method for rapid regeneration of a catalyst.
There is an urgent need for a shaped catalyst which meets the needs of industrial production, is simple in raw materials, simple in preparation, and can be rapidly regenerated after the catalytic performance is reduced.
Disclosure of Invention
The invention protects a novel chip with CN@M 1 Catalyst of support structure, wherein M is selected from one or more of noble metal atoms or transition metals, wherein the noble metal atoms are selected from Pt, au, ru, rh, pd, ir or Ag and the transition metals are selected from Fe, co, mn, ni or Cu, M 1 Indicating that the metal is present in a single atomic site state. Preferably the M metal is selected from Pt, ru, pd, ir, rh or Co. The M content of the catalyst is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 1% by weight, based on the weight of the catalyst.
The carrier is a carrier commonly used in industry and comprises alumina, molecular sieve, silica-alumina, titanium oxide or a mixture of any two or more of the above; the catalyst carrier plays a role of loading, and the form of the carrier is selected from non-formed powder or formed structure. The molded structures include spheres, strips, cylinders, multi-void channels, honeycombs, and the like. As an example, the present invention implements alumina, molecular sieves, titania supports.
CN represents nitrogen doped carbon, also labeled C-N or N-C, or carbon nitrogen, and in the present invention, these terms are synonymous. The @ symbol means the meaning of cladding, "CN @ M 1 The carrier means CN coated on M 1 Surface of the carrier.
The catalyst further comprises Zn, wherein the Zn is derived from a precursor ZIF-8 coating of CN formed in the preparation process of the catalyst. The Zn content is from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, particularly preferably from 0.1 to 5% by weight, based on the weight of the catalyst.
The invention further provides a novel catalyst having CN@M 1 -Zn/carrier structured catalyst whereinThe M content is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 1% by weight, the Zn content is from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, particularly preferably from 0.1 to 5% by weight, based on the weight of the catalyst, the M metal and the catalyst being as defined above. Preferably, the M metal is Pt, ru, pd, ir or Rh.
The invention discloses a method for quickly preparing a catalyst with CN@M 1 A method of supporting a structured monoatomic catalyst, the method comprising:
step one: the metal active component is loaded on a carrier and marked as a catalyst precursor;
step two: coating the catalyst precursor with ZIF-8;
step three: in vacuum, inert gas or H 2 Pyrolysis is carried out in the atmosphere, and the pyrolysis temperature is 400-1000 ℃.
The carrier is a carrier commonly used in industry and comprises alumina, molecular sieve, silicon dioxide-alumina, titanium oxide or a mixture of any two or more of the alumina, the molecular sieve and the titanium oxide, and the invention is exemplified by the alumina, the molecular sieve and the titanium oxide carrier; the carrier serves as a support.
In the first step, the M metal active component is supported on the carrier in a metal precursor manner, and any means known in the art may be used for supporting, including impregnation, spin evaporation, adsorption, ion exchange, incipient wetness impregnation, precipitation, spray drying, grinding, and the like, and the impregnation method and the spin evaporation method are used for supporting in the embodiment of the present invention. The M metal precursor may be an inorganic metal salt, an organic metal salt or a metal complex, preferably the metal precursor is a nitrate, chloride, sulfate, acetate, oxalate, acetylacetonate or a chlorine complex, the active metal is selected from one or more of noble metal atoms or transition metals, wherein the noble metal atoms are selected from Pt, au, ru, rh, pd, ir or Ag, and the transition metals are selected from Fe, co, mn, ni or Cu. Preferably M is Pt, ru, pd, ir, rh or Co. The M content is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 1% by weight, based on the weight of the catalyst.
In the second step, the ZIF-8 material is prepared according to the prior art method or purchased commercially.
The coating process comprises the step of retaining the ZIF-8-containing suspension, emulsion or powder, etc., as uniformly as possible on the surface of the article to be coated, using existing conventional means. Methods that may be used include dipping, spin steaming, and the like. ZIF-8 and Al 2 O 3 The theoretical mass ratio of (2) is 0.005-0.50:1, the actual addition values in the embodiment of the present invention are within this range.
The inventor finds that the previously prepared ZIF-8 coated active metal-loaded catalyst carrier can avoid the problem that in the prior art (CN 109225306A), only a powder catalyst taking an N-C component as a carrier can be manufactured, and a granular catalyst can be obtained, so that the industrial production efficiency is improved, and the catalyst can be directly applied to industrial devices. Meanwhile, only active metal is loaded on the carrier, so that the raw material range of the active metal salt is enlarged, expensive acetylacetonate is avoided, and the preparation cost of the catalyst is greatly reduced. The method also solves the problem that noble metal cannot be quantitatively added in the prior art, and avoids the problem that the actual load capacity is reduced and the load cannot be quantitatively carried out due to the fact that liquid-phase active metal remains in the solid-liquid separation process in the prior art. In addition, the catalysts formed in the present invention also have a new structure different from the catalysts formed in situ in the prior art (CN 109225306 a), but also have similar catalytic activity.
Step three, pyrolysis temperatures of 450-800℃are preferred.
Further, the invention protects a CN@M 1 A method for regenerating a single-atom catalyst having a support structure, the method comprising:
step A: removal results in CN@M 1 A catalyst-poisoning or deactivating substance of the support structure to form a catalyst-containing precursor;
and (B) step (B): coating the catalyst precursor to be regenerated with ZIF-8;
step C: in vacuum, inert gas or H 2 Pyrolysis is carried out in the atmosphere, and the pyrolysis temperature is 400-1000 ℃.
Wherein, the step A can remove the inactivating substance by the conventional method, the inactivating substance comprises carbon deposit, sulfur and the like, and the removing method comprises the following steps of using O 2 Empty spaceRemoval by oxidation of gases, or by use of H 2 And (5) reduction and removal.
The carrier is a carrier commonly used in industry and comprises alumina, molecular sieve, silicon dioxide-alumina, titanium oxide or a mixture of any two or more of the alumina, the molecular sieve and the titanium oxide, and the invention is exemplified by the alumina, the molecular sieve and the titanium oxide carrier; the carrier serves as a support.
The M metal active component is supported on the carrier in the form of a metal precursor, and can be carried out by any means known in the art, including impregnation, rotary evaporation, adsorption, ion exchange, incipient wetness, precipitation, spray drying, ball milling and the like. The M metal salt is an inorganic metal salt, an organic metal salt or a complex, preferably the metal salt is a nitrate, chloride, sulfate, acetate, oxalate, acetylacetonate or a chloride complex. The active metal is selected from one or more of noble metal atoms selected from Pt, au, ru, rh, pd, ir, ag or transition metals selected from Fe, co, mn, ni or Cu, preferably M is Pt, ru, pd, ir, rh or Co. M is M 1 Indicating that the metal is present in a single atomic site state. The M content is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 1% by weight, based on the weight of the catalyst.
In step C, the pyrolysis temperature is preferably 450-800 ℃.
Further, the invention protects the CN@M 1 Use of a single-atom catalyst of a support structure for catalyzing the dehydrogenation of alkanes, C, to form olefins 2-6 Alkane, dehydrogenation to obtain C 2-6 An olefin.
The invention also discloses a method for preparing lower olefin by dehydrogenating lower alkane, which comprises the following steps of using the CN@M 1 Mono-atom catalyst of carrier structure for catalyzing dehydrogenation of lower alkane to form lower alkene, wherein the alkane is C 2-6 Alkane, dehydrogenation to obtain C 2-6 An olefin.
Definition and interpretation
The term "dispersed state in a single-atom site state, single-atom distribution, single-atom morphology or single-atom level" as used herein refers to a state in which the active metal elements are separated from each other in a state in which metal atoms (ions) are independent of each other, and the active metal atoms do not form a metal-metal bond directly connected to each other, and are dispersed in an atomic scale or in a single-atom site state. The metal dispersed in the single atomic site state may exist in an atomic state or in an ionic state, and more likely is between an atomic and an ionic state (the valence state is between two valence states). In the metal state nano-particles, metal atoms in the same particle are mutually bonded, and obviously, the metal atoms do not belong to a monoatomic state or a monoatomic dispersion state defined by the invention; for compound or mixture nanoparticles formed by metal and other elements (such as O, S or even other metals), although the metal is separated by the other elements, the compound or mixture nanoparticles tend to be easily converted into metallic nanoparticles (such as oxide nanoparticles which are converted through reduction), and the compound or mixture nanoparticles also do not belong to a single-atom site state or a single-atom separation state defined by the invention. The metals in the single atomic site state protected by the present invention are theoretically completely independent of each other. However, random deviations in the control of the operating conditions of the different batch preparations do not exclude the presence of small amounts of agglomerated metal species, such as clusters containing a number of atoms or ions; nor does it exclude that part of the metal assumes a nanoparticle state. In other words, it is possible that the active metal in the catalyst of the present invention exists in a single-atom site dispersed state, while a cluster state containing aggregation of metal atoms exists partially, and/or a part of the metal exhibits a nanocrystalline state. And the monoatomic state transitions to a cluster and/or nanostate as the external environment changes. The monoatomic state as claimed in the present application requires a certain proportion of monoatomic noble metal in the different forms of monoatomic noble metal monoatoms, noble metal clusters, noble metal nanocrystals, etc., for example, above 10%, preferably above 20%, particularly preferably above 50%. But is limited to the current technical means, the method can only analyze and characterize a large number of different local areas randomly selected in a catalyst test sample through a relatively rough statistical means by a high-resolution spherical aberration electron microscope, randomly select various noble metal existence states for statistical analysis, or analyze the catalyst sample through an X-ray absorption fine structure spectrum (EXAFS) capable of characterizing the whole information of the sample, obtain the ratio of metal and other atomic bonding signals to metal-metal bonding signals, and determine the approximate ratio of monoatomic states. It is noted that essentially, the catalyst product is obtained with even a partial monoatomic state as long as the technique of the invention is used in the product, which product shows an improvement in performance. Therefore, if only the product is prepared by the method provided by the invention, the three-way catalyst with single atom characteristics is prepared, and the three-way catalyst is considered to be within the scope of protection of the application.
CN represents nitrogen doped carbon, also labeled C-N or N-C, or carbon nitrogen, and in the present invention, these terms have the same meaning.
Complexes are also referred to as complexes, including complexes of noble or transition metals with ligands, common ligands including halogens (fluorine, chlorine, bromine, iodine), nitro, nitroso, cyano, ammonia, water molecules or organic groups, and are typically chloro complexes, ammine complexes, cyano complexes, and the like, including chloroplatinic acid, chloroplatinate, chloroplatinic acid hydrate. See "handbook (essence) of noble metal Compound and Complex Synthesis" (Yu Jianmin, 2009, chemical industry Press).
The beneficial effects are that:
1. the invention obtains a catalyst with CN@M 1 New monoatomic catalysts of support structure in which the metal is present in a monoatomic grade of separation.
2. According to the invention, the active metal is directly loaded on the carrier, and the ZIF-8 is coated with the noble metal, so that the single-atom catalyst is formed by pyrolysis, and compared with the single-atom catalyst synthesis method in the prior art, the preparation time is saved, the preparation efficiency is greatly improved, the raw material cost is reduced, and the preparation method is suitable for the preparation and application of industrial catalysts. In addition, the problem of quantitative loading of active metals is solved.
3. A simple method for regenerating a monoatomic catalyst is provided.
4. The catalyst has higher catalytic alkane dehydrogenation activity.
Drawings
FIG. 1 shows the change in appearance of the alumina pellets, coated with ZIF-8 (at different levels), pyrolyzed to CN coated alumina pellets, where B1-B5 show the appearance of alumina pellets of different coating concentrations (essentially white) and C1-C5 show the appearance of alumina pyrolyzed to CN coated (C1 yellow, C2 brown, C3 dark brown, C4 black, C5 black, respectively).
FIG. 2 is an appearance of different carriers and different shaped carriers at different stages, including carriers (A1-A4) -ZIF-8 coated (B1-B4) -pyrolysis to form CN coated carriers (C1-C4). Wherein (A1) is a small spherical Al 2 O 3 White, (A2) five-tooth spherical Al 2 O 3 White, (A3) small sphere NaY molecular sieve light yellow, (A4) short rod-shaped TiO 2 White; coated (B1) globular ZIF-8@Al 2 O 3 White, (B2) five-tooth spherical ZIF-8@Al 2 O 3 White, (B3) small sphere ZIF-8@NaY molecular sieve light yellow, (B4) short rod-shaped ZIF-8@TiO 2 Pale yellow; pellets CN@Al after pyrolysis (C1) 2 O 3 Black, (C2) pentadentate sphere cn@al 2 O 3 Grey, (C3) globular CN@NaY molecular sieve black, (C4) CN@ short bar-shaped TiO 2 Grey.
FIG. 3 is a graph showing the change in appearance of catalysts before and after loading with different active metals, respectively (A) Al 2 O 3 White; after loading metal, (B1) Ir/Al is obtained 2 O 3 Pale yellow, (B2) Rh/Al 2 O 3 Yellow, (B3) Ru/Al 2 O 3 Light brown, (B4) Co/Al 2 O 3 Light pink; after coating, (C1) ZIF-8@Ir/Al is obtained 2 O 3 Pale yellow, (C2) ZIF-8@Rh/Al 2 O 3 Pale yellow; (C3) ZIF-8@Ru/Al 2 O 3 Off-white, (C4) ZIF-8@Co/Al 2 O 3 Purple powder; after pyrolysis, black (D1) CN@Ir/Al is obtained 2 O 3 ，(D2)CN@Rh/Al 2 O 3 ，(D3)CN@Ru/Al 2 O 3 ，(D4)CN@Co/Al 2 O 3 。
FIG. 4 shows the microstructure of the raw materials and products at different stages dynamically, A-C shows the surface morphology of alumina, D-F shows the crystal configuration of ZIF-8 formed on the surface of alumina after coating ZIF-8, and G-I shows the microstructure of the catalyst surface after pyrolysis.
Detailed Description
Terms and explanations used in the examples:
concentration of metal precursor: calculated by the mass of metal elements, for example, pd in 0.02g/g concentration is expressed as the content of Pd element in each gram of solution is 0.02g
Micro-reflection device: fixed bed microreactor or microreactor device
Micro-reverse tail gas: tail gas produced after reaction in microreactor or microreactor device
min: minute (min)
h: hours of
wt%: mass percent
TEM: transmission electron microscope (Transmission Electron Microscope)
HR-TEM: high resolution transmission electron microscope (High Resolution Transmission Electron Microscope)
AC-STEM: spherical aberration correction transmission electron microscope (Spherical Aberration-Corrected Scanning Transmission Electron Microscopy)
General procedure or raw materials preparation method
1. ZIF-8 preparation:
preparation of ZIF-8 methanol dispersion, 40mmol of zinc nitrate and 240mmol of 2-methylimidazole were dissolved in 400mL of methanol, respectively, and after the above raw materials were sufficiently dissolved, the 2-methylimidazole solution was added to the zinc nitrate solution, and stirred at room temperature for 24 hours to obtain a methanol dispersion of ZIF-8, which was labeled ZIF-8 (MeOH). The methanol dispersions of ZIF-8 used in the examples herein were prepared according to this method (same ratio).
2. The application test method comprises the following steps: alkane dehydrogenation experiments (propane dehydrogenation to propylene is taken as an example)
The catalytic performance of the catalyst was evaluated by using a fixed bed continuous flow reaction apparatus, 1.0g of the catalyst was loaded in an 8mm inner diameter straight quartz reaction tube, the reaction temperature was controlled at 600℃by a tube type resistance furnace, the flow rate of pure propane was controlled at 26.2mL/min by a mass flow meter, and purging was performed before and after the reaction using nitrogen or other inert gases.
Assembly of HP-PLOTAl using a gas chromatograph of Shimadzu 2 O 3 The reaction product was analyzed by S capillary chromatography column to sample after 5 minutes of reaction gas was introduced as initial catalytic performance, followed by sampling every 15 minutes.
3. Catalysts with different metals and different loading amounts are prepared.
Comparative example 1, 0.2wt% Iridium-supported Al 2 O 3 Is a catalyst (201019 b)
An aqueous solution of Ir was prepared in advance with Ir chloride and sodium chloride at a concentration of 0.02g/g, 10.0g was taken into a round-bottomed flask and diluted with ethanol to 84.8g, followed by addition of 99.8g of globular Al 2 O 3 Then spin-evaporating treatment is carried out, and the iridium species are fully loaded on Al after the solvent is completely evaporated 2 O 3 The surface can be prepared into the iridium-loaded Al 2 O 3 Catalyst, labeled Ir (0.2wt％) /Al 2 O 3 。
Comparative example 2, 0.2wt% ruthenium supported Al 2 O 3 Is a catalyst (201019 c)
An aqueous solution of Ru was prepared beforehand with a concentration of 0.02g/g of ruthenium chloride, 10.0g was taken into a round-bottomed flask and diluted with ethanol to 84.8g, followed by addition of 99.8g of globular Al 2 O 3 Then spin-evaporating treatment is carried out until the solvent is completely evaporated and the ruthenium species is fully supported on Al 2 O 3 The surface can be prepared into the ruthenium-loaded Al 2 O 3 Catalyst, labeled Ru (0.2wt％) /Al 2 O 3 。
Comparative example 3, 0.2wt% rhodium-supported Al 2 O 3 Is a catalyst (201019 d)
An aqueous solution of Rh was prepared in advance as a rhodium nitrate solution at a concentration of 0.02g/g, 10.0g was taken into a round-bottomed flask and diluted with ethanol to 84.8g, followed by addition of 99.8g of globular Al 2 O 3 Then spin-evaporating treatment is carried out, and rhodium species are fully loaded on Al after the solvent is completely evaporated 2 O 3 The surface can be prepared into rhodium-loaded Al 2 O 3 Catalyst, labeled Rh (0.2wt％) /Al 2 O 3 。
Comparative example 4, 0.2wt% platinum-supported Al 2 O 3 Is a catalyst (201022 a)
An aqueous solution of Pt was prepared beforehand at a concentration of 0.02g/g with chloroplatinic acid, 10.0g was taken into a round-bottomed flask and diluted with ethanol to 84.8g, followed by addition of 99.8g of globular Al 2 O 3 Then spin-evaporating treatment is carried out, and the platinum species are fully loaded on Al after the solvent is completely evaporated 2 O 3 The surface can be prepared into the platinum-loaded Al 2 O 3 Catalyst, labeled Pt (0.2wt％) /Al 2 O 3 。
Comparative example 5, 0.2wt% palladium on Al 2 O 3 Is a catalyst (201022 b)
An aqueous solution of Pd was prepared in advance in a concentration of 0.02g/g with a palladium nitrate solution, 10.0g was taken into a round-bottomed flask and diluted with ethanol to 84.8g, followed by addition of 99.8g of globular Al 2 O 3 Then spin-evaporating treatment is carried out until the solvent is completely evaporated and palladium species are fully loaded on Al 2 O 3 The surface can be prepared into palladium-loaded Al 2 O 3 Catalyst, labeled Pd (0.2wt％) /Al 2 O 3 。
Comparative example 6, 0.5wt% cobalt supported Al 2 O 3 Is a catalyst (200928 g)
Into a round bottom flask was taken 2.47g of cobalt nitrate hexahydrate and dissolved with ethanol, diluted to 84.6g, followed by 99.5g of globular Al 2 O 3 Then spin-evaporating treatment is carried out until the solvent is completely evaporated and cobalt species are fully loaded on Al 2 O 3 The surface can be prepared into cobalt-loaded Al 2 O 3 Catalyst, labeled Co (0.5wt％) /Al 2 O 3 。
Comparative example 7, 0.5wt% iron-supported Al 2 O 3 Catalyst (d 201002 a)
Into a round bottom flask was taken 3.62g of ferric nitrate nonahydrate and dissolved with ethanol, diluted to 84.6g, followed by addition of 99.5g of globular Al 2 O 3 Then spin-steaming treatment is carried out, and when the solvent is completely evaporated and the iron species is fully loaded in Al 2 O 3 The surface can be prepared into the iron-loaded Al 2 O 3 Catalyst, marked Fe (0.5wt％) /Al 2 O 3 。
Comparative example 8, 0.5wt% Nickel-supported Al 2 O 3 Catalyst (d 201002 b)
Into a round bottom flask was taken 2.48g of nickel nitrate hexahydrate and dissolved with ethanol, diluted to 84.6g, followed by 99.5g of globular Al 2 O 3 Then spin-evaporating treatment is carried out, and the nickel species are fully loaded on Al after the solvent is completely evaporated 2 O 3 The surface of the alloy is provided with nickel-loaded Al 2 O 3 Catalyst, labeled Ni (0.5wt％) /Al 2 O 3 。
Comparative example 9, 0.5wt% copper-supported Al 2 O 3 Catalyst (d 201003)
Into a round bottom flask was taken 1.90g of chromium nitrate trihydrate and dissolved in ethanol, diluted to 84.6g, followed by addition of 99.5g of globular Al 2 O 3 Then spin-evaporating treatment is carried out, and the copper species are fully loaded on Al after the solvent is completely evaporated 2 O 3 The surface of the copper-loaded Al alloy is prepared 2 O 3 Catalyst, marked Cu (0.5wt％) /Al 2 O 3 。
Example 1: CN coated 0.2wt% Iridium supported Al 2 O 3 201020 d)
Into a round bottom flask were charged 60g and 15g of a methanol dispersion of ZIF-8, spherical Ir (0.2wt％) /Al 2 O 3 Subsequently, spin-steaming treatment is carried out until the solvent is completely evaporated, so that ZIF-8 is fully coated on Ir (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Ir (0.2wt％) /Al 2 O 3 Marked as CN@Ir (0.2wt％) /Al 2 O 3 。
Example 2: CN coated 0.2wt% ruthenium supported Al 2 O 3 201020 e)
Into a round bottom flask was added a methanol dispersion of ZIF-860g and 15g of small spherical Ru (0.2wt％) /Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that the ZIF-8 is fully coated on Ru (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolysis is carried out for 3 hours under the protective atmosphere, thus obtaining the Ru coated by CN (0.2wt％) /Al 2 O 3 Marked as CN@Ru (0.2wt％) /Al 2 O 3 。
EXAMPLE 3 CN coated 0.2wt% rhodium-supported Al 2 O 3 201020 f)
Into a round bottom flask was charged 60g and 15g of spherical Rh as a methanol dispersion of ZIF-8 (0.2wt％) /Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated to fully coat the ZIF-8 on Rh (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Rh (0.2wt％) /Al 2 O 3 Marked as CN@Rh (0.2wt％) /Al 2 O 3 。
EXAMPLE 4 CN coated 0.2wt% platinum-supported Al 2 O 3 Is a catalyst (201023 d)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, spherical Pt (0.2wt％) /Al 2 O 3 Then spin-steaming treatment is carried out until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Pt (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolysis is carried out for 3 hours under the protective atmosphere, thus obtaining the Pt coated by the CN (0.2wt％) /Al 2 O 3 Marked as CN@Pt (0.2wt％) /Al 2 O 3 。
EXAMPLE 5 CN coated 0.2wt% Palladium-supported Al 2 O 3 Is a catalyst (201210 g)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, spherical Pd (0.2wt％) /Al 2 O 3 Then spin-steaming treatment is carried out until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Pd (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the Pd coated by the CN (0.2wt％) /Al 2 O 3 Marked as CN@Pd (0.2wt％) /Al 2 O 3 。
EXAMPLE 6 CN coated 0.5wt% cobalt-supported Al 2 O 3 Is a catalyst (201210 d)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, globular Co (0.2wt％) /Al 2 O 3 Then spin-steaming treatment is carried out until the solvent is completely evaporated, so that the ZIF-8 is fully coated on Co (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolysis is carried out for 3 hours under the protective atmosphere, thus obtaining the Co coated by CN (0.2wt％) /Al 2 O 3 Marked as CN@Co (0.2wt％) /Al 2 O 3 。
EXAMPLE 7 CN coated 0.5wt% iron-supported Al 2 O 3 Is a catalyst (201210 e)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, spherical Fe (0.2wt％) /Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that ZIF-8 is fully coated on Fe (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the Fe coated with CN (0.2wt％) /Al 2 O 3 Marked as CN@Fe (0.2wt％) /Al 2 O 3 。
EXAMPLE 8 CN coated 0.5wt% Nickel-supported Al 2 O 3 Is a catalyst (201210 f)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, spherical Ni (0.2wt％) /Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that ZIF-8 is fully coated on Ni (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolysis is carried out for 3 hours under the protective atmosphere, thus obtaining the Ni coated by CN (0.2wt％) /Al 2 O 3 Marked as CN@Ni (0.2wt％) /Al 2 O 3 。
EXAMPLE 9 CN coated 0.5wt% copper loaded Al 2 O 3 Is a catalyst (201211 e)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, spherical Cu (0.2wt％) /Al 2 O 3 Then spin-steaming treatment is carried out until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Cu (0.2wt％) /Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain CN coated Cu (0.2wt％) /Al 2 O 3 Marked as CN@Cu (0.2wt％) /Al 2 O 3 。
PREPARATION EXAMPLE 1 CN coated Al 2 O 3 Catalyst (201124 k)
Into a round bottom flask were charged 5g of a methanol dispersion of ZIF-8, 5g of methanol and 10g of globular Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Al 2 O 3 Marked as CN@Al 2 O 3 (0.5)。
Preparation example 2, CN coated Al 2 O 3 Catalyst (201120 c)
Into a round bottom flask were charged 15g of a methanol dispersion of ZIF-8 and 15g of globular Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Al 2 O 3 Marked as CN@Al 2 O 3 (1)。
PREPARATION EXAMPLE 3 CN coated Al 2 O 3 Catalyst (201120 b)
Into a round bottom flask was charged 30g of a methanol dispersion of ZIF-8 and 15g of globular Al 2 O 3 Then spin-steaming treatment is carried out until the solvent is completely evaporated, so that ZIF-8 is fully coatedAl 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Al 2 O 3 Marked as CN@Al 2 O 3 (2)。
PREPARATION EXAMPLE 4 CN coated Al 2 O 3 Catalyst (201015 e)
Into a round bottom flask was charged 60g and 15g of a methanol dispersion of ZIF-8, globular Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Al 2 O 3 Marked as CN@Al 2 O 3 (4)。
PREPARATION EXAMPLE 5 CN coated Al 2 O 3 Catalyst (201124 l)
Into a round bottom flask was charged 200g of a methanol dispersion of ZIF-8 and 10g of globular Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Al 2 O 3 Marked as CN@Al 2 O 3 (20)。
Preparation example 6, CN coated Al 2 O 3 Catalyst (201211 a)
Into a round bottom flask were charged 60g and 15g of a methanol dispersion of ZIF-8 as pentadentate spherical Al 2 O 3 Then spin-evaporating until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the Al 2 O 3 Surface, then at 600 ℃, N 2 Pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated Al 2 O 3 Marked as CN@Al 2 O 3 。
PREPARATION EXAMPLE 7 CN coated NaY catalyst (201211 c)
Adding 60g and 15g of small spherical NaY molecular sieve of ZIF-8 methanol dispersion into a round bottom flask, and then performing rotary evaporation treatment until the solvent is completely evaporated to ensure that the ZIF-8 is fully coated on the NaY surface, and then performing N at 600 DEG C 2 And pyrolyzing for 3 hours in a protective atmosphere to obtain the CN coated NaY, wherein the CN coated NaY is marked as CN@NaY.
Preparation example 8 CN coated TiO 2 Catalyst (201211 d)
Into a round bottom flask was charged 60g and 15g of short bar-shaped TiO as a methanol dispersion of ZIF-8 2 Then spin-steaming treatment is carried out until the solvent is completely evaporated, so that the ZIF-8 is fully coated on the TiO 2 Surface, then at 600 ℃, N 2 Pyrolysis is carried out for 3 hours under the protective atmosphere, thus obtaining the TiO coated by CN 2 Marked as CN@TiO 2 。
Application test embodiment and results
1. The activity test was performed in the manner of the preparation example, differing from the test of CN109225306a in that pure propane alkane gas was used, and CN109225306a was 5% propane gas (see patent example 24, tables 5 and 0065). The test results were as follows:
Figure BDA0002878848910000111
Figure BDA0002878848910000121
Figure BDA0002878848910000131
table 1 propane dehydrogenation application test experimental and comparative data
From table 1, it can be concluded that the catalyst of the present invention significantly improves the catalytic activity, and that even the catalyst containing Fe, pt and Pd, which has poor catalytic activity, has significantly improved conversion and selectivity, compared to the catalyst not coated with CN.
2. Product structure characterization
The prepared examples, intermediates and raw material products are characterized, the photographs of fig. 1-4 are prepared, and the photographs can show that the surface color of the catalyst is changed and the coating effect is displayed after ZIF coatings with different coating amounts and pyrolysis.
FIG. 1 shows the change in appearance of the alumina pellets, coated with ZIF-8 (at different levels), pyrolyzed to CN coated alumina pellets, where B1-B5 show the appearance of alumina pellets of different coating concentrations (essentially white) and C1-C5 show the appearance of alumina pyrolyzed to CN coated (C1 yellow, C2 brown, C3 dark brown, C4 black, C5 black, respectively).
FIG. 2 is an appearance of different carriers and different shaped carriers at different stages, including carriers (A1-A4) -ZIF-8 coated (B1-B4) -pyrolysis to form CN coated carriers (C1-C4). Wherein (A1) is a small spherical Al 2 O 3 White, (A2) five-tooth spherical Al 2 O 3 White, (A3) small sphere NaY molecular sieve light yellow, (A4) short rod-shaped TiO 2 White; coated (B1) globular ZIF-8@Al 2 O 3 White, (B2) five-tooth spherical ZIF-8@Al 2 O 3 White, (B3) small sphere ZIF-8@NaY molecular sieve light yellow, (B4) short rod-shaped ZIF-8@TiO 2 Pale yellow; pellets CN@Al after pyrolysis (C1) 2 O 3 Black, (C2) pentadentate sphere cn@al 2 O 3 Grey, (C3) globular CN@NaY molecular sieve black, (C4) CN@ short bar-shaped TiO 2 Grey.
FIG. 3 is a graph showing the change in appearance of catalysts before and after loading with different active metals, respectively (A) Al 2 O 3 White; after loading metal, (B1) Ir/Al is obtained 2 O 3 Pale yellow, (B2) Rh/Al 2 O 3 Yellow, (B3) Ru/Al 2 O 3 Light brown, (B4) Co/Al 2 O 3 Light pink; after coating, (C1) ZIF-8@Ir/Al is obtained 2 O 3 Pale yellow, (C2) ZIF-8@Rh/Al 2 O 3 Pale yellow; (C3) ZIF-8@Ru/Al 2 O 3 Off-white, (C4) ZIF-8@Co/Al 2 O 3 Purple powder; after pyrolysis, black (D1) CN@Ir/Al is obtained 2 O 3 ，(D2)CN@Rh/Al 2 O 3 ，(D3)CN@Ru/Al 2 O 3 ，(D4)CN@Co/Al 2 O 3 。
FIG. 4 shows the microstructure of the feedstock and product at different stages dynamically, A-C shows the surface morphology of alumina, D-F shows the surface visible as ZIF-8 after coating with ZIF-8, and G-I shows the microstructure of the catalyst surface after pyrolysis.
The foregoing examples of the present invention are provided for the purpose of clearly illustrating the present invention and are not to be construed as limiting the embodiments of the present invention, and other and different forms of variation or modification may be made by those skilled in the art based on the foregoing description, and it is not intended to be exhaustive of all the embodiments, and all obvious variations or modifications which come within the scope of the invention are defined by the appended claims.

Claims (15)

1. Have CN@M 1 A catalyst of Zn/carrier structure, wherein M metal is selected from one or more of noble metal atoms selected from Pt, au, ru, rh, pd, ir or Ag or transition metals selected from Fe, co, mn, ni or Cu, M 1 Indicating that the metal exists in a single atom site state, the M content in the catalyst is 0.01-10wt% based on the weight of the catalyst,
zn content is 0.01-20wt% based on the weight of the catalyst;
the carrier is a carrier commonly used in industry and comprises alumina, molecular sieve, silica-alumina, titanium oxide or a mixture of any two or more of the above; the carrier is shaped into a molded structure, and the molded structure comprises a sphere, a strip, a cylinder, a multi-hollow channel and a honeycomb body;
CN@ the carbon nitrogen layer wrap;
the catalyst is prepared by the following method, which comprises the following steps:
step one: m metal active components are loaded on a carrier to form a catalyst precursor;
step two: coating the catalyst precursor with ZIF-8;
step three: in vacuum, inert gas or H 2 Pyrolyzing in atmosphere at 400-800 ℃;
the M metal active component is loaded on the carrier in a metal precursor mode, and the M metal precursor is inorganic metal salt, organic metal salt or complex.
2. The catalyst of claim 1, wherein the M metal content in the catalyst is 0.05-5wt% based on the weight of the catalyst; zn content is 0.05-10wt% based on the weight of the catalyst.
3. The catalyst of claim 1 wherein the M metal content in the catalyst is from 0.1 to 1wt% based on the weight of the catalyst; zn content is 0.1-5wt% based on the weight of the catalyst.
4. A catalyst as claimed in any one of claims 1 to 3 wherein the M metal is Pt, ru, pd, ir or Rh.
5. The catalyst of claim 4 wherein the support is an alumina, molecular sieve or titania support.
6. A method of preparing the catalyst of any one of claims 1-5, comprising:
step one: m metal active components are loaded on a carrier to form a catalyst precursor;
step two: coating the catalyst precursor with ZIF-8;
step three: in vacuum, inert gas or H 2 Pyrolysis is carried out in the atmosphere, and the pyrolysis temperature is 400-800 ℃.
7. The method of claim 6, wherein in step one, the M metal active component is supported on a carrier in the form of a metal precursor, and the M metal precursor is an inorganic metal salt, an organic metal salt or a complex.
8. The method of claim 6, wherein in the second step, the ZIF-8 is coated on the surface of the precursor by using a dipping and spin-steaming mode.
9. The process of claim 6, wherein in step three, the pyrolysis temperature is 450-800 ℃.
10. The method of claim 7, wherein the M metal precursor is a nitrate, chloride, sulfate, acetate, oxalate, acetylacetonate, or chloride complex of M metal.
11. Have CN@M 1- A method for regenerating a Zn/support structured monoatomic catalyst, the method comprising:
step A: removal results in a device having a cn@m as claimed in claim 1 1- A Zn/support structure catalyst poisoned or deactivated species forming a catalyst containing precursor;
and (B) step (B): coating a catalyst precursor to be regenerated by ZIF-8, and coating by a dipping or rotary steaming mode;
step C: in vacuum, inert gas or H 2 Pyrolyzing in atmosphere at 400-800 ℃;
wherein step A removes the inactivating substance by a conventional method comprising using O 2 Removal by air oxidation, or by use of H 2 、CO 2 Removing water vapor and inactivating substances through reaction;
m metal is selected from one or more of noble metal atoms or transition metals, wherein the noble metal atoms are selected from Pt, au, ru, rh, pd, ir or Ag and the transition metals are selected from Fe, co, mn, ni or Cu; the carrier is a carrier commonly used in industry and comprises alumina, molecular sieve, silica-alumina, titanium oxide or a mixture of any two or more of the above;
the M metal active component is loaded on a carrier in the form of a metal precursor, and the M metal precursor is nitrate, chloride, sulfate, acetate, oxalate, acetylacetonate or chlorine complex of M metal.
12. The regeneration method of claim 11, wherein step a uses air oxidation to remove the deactivating species.
13. The regeneration method according to claim 11, wherein the carrier is alumina, molecular sieve, titanium oxide carrier.
14. Use of the catalyst of any one of claims 1-5 or the catalyst prepared by the method of any one of claims 6-10 for catalyzing the dehydrogenation of an alkane to form an alkene, the alkane being C 2-6 Alkane, dehydrogenation to obtain C 2-6 An olefin.
15. A process for the preparation of olefins by dehydrogenation of alkanes comprising preparing cn@m using the catalyst of any of claims 1-5 or the process of any of claims 6-10 1- Zn/carrier structure catalyst for catalyzing alkane dehydrogenation to form alkene, wherein the alkane is C 2-6 Alkanes, the olefins being C 2-6 An olefin.
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