CN111375432A - Nickel monoatomic catalyst loaded by hydroxyapatite and preparation and application thereof - Google Patents
Nickel monoatomic catalyst loaded by hydroxyapatite and preparation and application thereof Download PDFInfo
- Publication number
- CN111375432A CN111375432A CN201811608743.1A CN201811608743A CN111375432A CN 111375432 A CN111375432 A CN 111375432A CN 201811608743 A CN201811608743 A CN 201811608743A CN 111375432 A CN111375432 A CN 111375432A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nickel
- carrier
- reaction
- nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a preparation method of a supported nickel-based monatomic catalyst and application of the supported nickel-based monatomic catalyst in a reaction of generating synthesis gas by dry reforming of methane and carbon dioxide. The carrier is hydroxyapatite doped with one or more than two elements of cerium (Ce), iron (Fe), cobalt (Co) and manganese (Mn), and the mass of the doped elements accounts for 0-20% of the total mass of the catalyst. The nickel is highly dispersed on the carrier mainly in a monoatomic form, and the content of the nickel is 0.005-5 wt% of the total mass of the catalyst. The preparation process has the advantages of simple conditions, good repeatability and easy realization of industrialization. Compared with the traditional nickel-based nanoparticle catalyst, the catalyst prepared by the invention not only enables the atom utilization rate of nickel to reach the maximum value, but also has excellent carbon deposition resistance in the dry reforming reaction of methane, and obviously improves the activity and stability of the reaction.
Description
Technical Field
The invention relates to a preparation method of a nickel monatomic catalyst loaded by hydroxyapatite and application of the nickel monatomic catalyst in dry reforming reaction of methane.
Background
Methane carbon dioxide dry reforming reaction two cheap carbon-containing Compounds (CH) abundantly existing in nature4And CO2) Conversion to synthesis gas (CO and H) of chemical raw material with high added value2) The method is suitable for synthesis of various subsequent chemicals and is an ideal raw material for Fischer-Tropsch synthesis, carbonylation and hydroformylation reactions. Existing studies indicate that group VIII metals, except Os, can catalyze the methane carbon dioxide reforming reaction. Among them, Rh, Ru, Pt, Pd, and other noble metal catalysts show high activity and high stability to the reaction (proceedings of fuel chemistry, 2012,40, 345; chem.soc.rev.,2014,43, 7813.). However, the noble metal is expensive and limited in resources, and is difficult to be used for large-scale industrial production; the non-noble metal catalyst, especially Ni-based catalyst, has good initial reaction activity and selectivity, easily available and cheap raw materials, and strong industrial application potential, such as Ni/Al2O3(CN108273508A and CN105688916A), both of which use nickel as an active component, however, the stability of the catalyst is not ideal, and the activity can only be maintained for about 30 hours. With respect to the deactivation problem of Ni-based catalysts, it is now recognized that the most prominent cause is catalyst coking.
There are two important factors that affect reforming catalyst carbon deposition, one is the size (dispersion) of the active components in the catalyst, and the other is the acidity or basicity of the catalyst (Catal. Rev.,1999, 41, 1; Frontiers in Chemistry,2014, 2, 1; coal conversion, 1997, 20, 32). It is generally believed that the smaller the particle size, the slower the carbon deposition, and below the critical size (2nm), the significantly lower the carbon deposition rate, and thus the better the stability of the catalyst (surf. sci. catal., Elsevier,1996, pp.463). In addition, the adoption of the carrier with Lewis alkalinity can improve the CO pair of the catalyst2The activation capability of the catalyst enhances the oxidability of carbon deposit species, and further improves the carbon deposit resistance of the catalyst. Therefore, constructing the small-size Ni-based catalyst loaded by the alkaline carrier is an effective way for solving the problem of carbon deposition and prolonging the service life of the catalyst. The patent develops a method for preparing a hydroxyapatite-loaded Ni-based monatomic catalyst, and the method is applied to a methane dry reforming reaction to achieve the purposes of high activity and high stability.
The method is characterized in that a nickel precursor is uniformly adsorbed on the surface of a carrier by adjusting the pH value of an impregnation liquid, and the monatomic catalyst with nickel basically dispersed on the carrier in an atomic form is obtained through subsequent drying and reduction. At present, monatomic catalysts show high activity in a series of reactions such as water gas shift (CN201610586356), hydroformylation (CN2016104878090), and the like, but have not been applied to methane reforming reaction. According to the existing reports, the development of a novel nickel-based single-atom catalyst which is efficient, good in carbon deposit resistance and has application prospect on dry reforming reaction of methane is of great significance.
Disclosure of Invention
The invention aims to provide a method for preparing a supported nickel-based single-atom catalyst with simple preparation conditions, good repeatability and easy industrialization, wherein a carrier is hydroxyapatite doped with one or more than two elements of cerium (Ce), iron (Fe), cobalt (Co) and manganese (Mn), and the mass of the doped elements accounts for 0-20% of the total mass of the catalyst. The nickel content is 0.005-5 wt% of the total catalyst mass, more than 50% of nickel is dispersed on the carrier in an atomic form, and the obtained catalyst has high activity and excellent carbon deposition resistance to methane dry reforming reaction.
In order to realize the purpose, the invention firstly uses a coprecipitation method to prepare a metal-doped hydroxyapatite carrier, and then adjusts and controls the pH value of a nickel precursor impregnation liquid to achieve the effect of uniformly dispersing nickel on the carrier, and the specific preparation process is as follows:
1) dissolving calcium nitrate and nitrate of doped metal (M) in water at a mass ratio of M to calcium of 0.1-3, adding ammonia water to adjust pH to 8.5-11.5, controlling heating temperature to 50-90 deg.C, and dropwise adding certain amount of ammonium hydrogen phosphate ((NH) under vigorous stirring4)2HPO4) The solution was stirred for 2-5 hours with the calcium-phosphorus atomic ratio (Ca/P) being 1.67, and the obtained solid was filtered and dried and then calcined at 500 ℃ for 2-5 hours.
2) Dissolving nickel-containing precursor in water, stirring thoroughly, adjusting pH to 8-11 with ammonia water, pouring the carrier into the aqueous solution of metal precursor, stirring vigorously at room temperature for 2-5h to obtain carrier and metal precursorThe mass ratio of the body is 104-10, filtering the catalyst and drying at 60-120 ℃ for 5-20 hours.
3) The catalyst is roasted, the roasting temperature is 400-600 ℃, and the roasting time is 3-5 hours.
4) Reducing the calcined catalyst by hydrogen for 0.5-5 h at 200-600 ℃.
The nickel precursor is one or more than two of nickel chloride, nickel nitrate, nickel acetylacetonate and nickel acetate.
The doped metal nitrate is one or more than two of cerium nitrate, ferric nitrate, cobalt nitrate and manganese nitrate.
The activity test method for the catalyst of the invention is as follows:
preparing synthesis gas by dry reforming of methane and carbon dioxide: CH in raw material gas4And CO2In a ratio of 1, CH4The content of CO is 10-50 vol%2The content is 10-50 vol%, and the volume space velocity is 3000-90000mL gcat –1h-1The reaction pressure is normal pressure, and the reaction temperature is 450-850 ℃.
The preparation method and the application of the catalyst have the following effects:
1. at least 50% of the metallic nickel is dispersed in a monoatomic state on the support, and the rest exists in the form of sub-nanoclusters or nanoparticles.
2. The catalyst prepared by the method has higher catalytic activity and carbon deposit resistance to the reaction of preparing the synthesis gas by dry reforming of methane and carbon dioxide, so the catalyst has excellent stability, and the reduction value of the methane conversion rate is less than 10% within 100 h.
Drawings
FIGS. 1 to 6 are electron micrographs of the catalysts in examples 1 to 5 and comparative example, and FIG. 7 is a photograph after the reaction of the catalyst.
FIG. 1: electron microscopy characterization of the catalyst in example 1, with single atoms circled in the figure. The Ni is completely dispersed on the support in monoatomic form.
FIG. 2: electron microscopy characterization of the catalyst in example 2, with single atoms circled in the figure. The Ni is completely dispersed on the support in monoatomic form.
FIG. 3: electron microscopy characterization of the catalyst in example 3, with single atoms circled in the figure. The Ni is completely dispersed on the support in monoatomic form.
FIG. 4: electron microscopy characterization of the catalyst in example 4, wherein the single atoms are circled in the figure and the clusters are boxed. > 80% of the Ni is present in monoatomic form.
FIG. 5: electron microscopy characterization of the catalyst in example 5, wherein the single atoms are circled in the figure and the clusters are boxed. > 50% of the Ni is present in monoatomic form.
FIG. 6: the electron microscopy characterization of the catalyst in the comparative example, in which the Ni is present in the form of nanoparticles in its entirety, is indicated by a box.
FIG. 7: (a) photograph of the catalyst of comparative example after 10h of reaction. (b) Photograph of the catalyst of example 2 after reaction for 100 h. The catalyst of the comparative example turned dark black, indicating that the Ni nanoparticles were heavily coked up in the reaction and finally deactivated. The catalyst of example 2 appeared light gray after 100h reaction, indicating that the Ni monoatomic species can effectively inhibit the catalyst from carbon deposition.
Detailed Description
To further illustrate the present invention, the following examples are set forth, but the scope of the claims of the present invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied for achieving the purpose.
Example 1
1) Preparing a carrier: dissolving calcium nitrate in 80mL of water, adding ammonia water to adjust pH to 10.5, controlling heating temperature to 90 ℃, and dropwise adding a certain amount of ammonium hydrogen phosphate ((NH) under vigorous stirring4)2HPO4) Adding calcium phosphorus atom ratio (Ca/P) of 1.67, stirring for 2 hr, filtering, drying, and calcining at 400 deg.C for 2 hr to obtain hydroxyapatite as carrier with molecular formula of Ca10(PO4)6(OH)2。
2) Dissolving 1mg of nickel nitrate in 50mL of water, stirring well and adjusting the pH value of the solution to 10 with ammonia water, pouring 5g of HAP, stirring vigorously at room temperature for 3h, filtering the catalyst, drying at 80 ℃ for 12 h, calcining at 500 ℃ for 2 h, and then reducing with hydrogen at 500 ℃ for 0.5 h to obtain the hydroxyapatite-supported 0.006 wt% Ni monatomic catalyst.
3) And (3) reaction test of preparing synthesis gas by dry reforming of methane and carbon dioxide: CH in raw material gas4And CO2In a ratio of 1, CH4Content of 20 vol%, CO2The content is 20 vol%, the balance gas is helium, and the volume space velocity is 60000mL gcat –1h-1The reaction pressure is normal pressure, and the reaction temperature is 750 ℃. The initial conversion of methane was 92% and the conversion of methane after 100h of reaction was 84%.
Example 2
1) Preparing a carrier: dissolving calcium nitrate and cerium nitrate in 80mL of water, wherein the mass ratio of Ce to Ca is 0.125, adding ammonia water to adjust the pH value to 10.5, controlling the heating temperature to 90 ℃, and dropwise adding a certain amount of ammonium hydrogen phosphate ((NH) under vigorous stirring4)2HPO4) The solution was stirred for 2 hours after the completion of the dropwise addition so that the atomic ratio of calcium to phosphorus (Ca/P) was 1.67, and the resulting solid was filtered and dried, and then calcined at 400 ℃ for 2 hours to obtain a hydroxyapatite carrier containing Ce in a mass ratio of Ce to Ca of 0.125.
2) 100mg of nickel nitrate was dissolved in 50mL of water, sufficiently stirred and the pH of the solution was adjusted to 10 with ammonia, 5g of a hydroxyapatite carrier doped with Ce in a mass ratio of Ce to Ca of 0.125 was poured, vigorously stirred at room temperature for 3 hours, the catalyst was filtered, dried at 80 ℃ for 12 hours, calcined at 500 ℃ for 2 hours, and then reduced with hydrogen at 500 ℃ for 0.5 hour to obtain a 0.6 wt% Ni monatomic catalyst supported on hydroxyapatite doped with Ce in a mass ratio of Ce to Ca of 0.125.
3) And (3) reaction test of preparing synthesis gas by dry reforming of methane and carbon dioxide: CH in raw material gas4And CO2In a ratio of 1, CH4Content of 20 vol%, CO2The content is 20 vol%, the balance gas is helium, and the volume space velocity is 60000mL gcat –1h-1The reaction pressure is normal pressure,the reaction temperature was 750 ℃. The initial conversion of methane was 98% and the conversion of methane was 95% after 100h of reaction.
Comparative examples
The nickel content in the catalyst is increased to 10 percent, and the Ni nano-particle catalyst prepared finally has serious carbon deposition and poor stability in the dry reforming reaction of methane. Comparative example is illustrated in conjunction with example 2: the Ni monatomic catalyst is the key of carbon deposit resistance and high stability in the dry reforming reaction of methane.
1) The preparation of the hydroxyapatite with Ce and Ca mixed in the carrier in the mass ratio of 0.125 is the same as that of the hydroxyapatite,
2) dissolving 2g of nickel nitrate in 50mL of water, stirring sufficiently and adjusting the pH value of the solution to 10 with ammonia water, pouring 5g of a hydroxyapatite carrier doped with Ce in a mass ratio of Ce to Ca of 0.125, stirring vigorously at room temperature for 3 hours, filtering the catalyst, drying at 80 ℃ for 12 hours, calcining at 500 ℃ for 2 hours, and then reducing with hydrogen at 500 ℃ for 0.5 hour to obtain a 10 wt% Ni nanoparticle catalyst loaded with hydroxyapatite doped with Ce in a mass ratio of Ce to Ca of 0.125.
3) And (3) reaction test of preparing synthesis gas by dry reforming of methane and carbon dioxide: CH in raw material gas4And CO2In a ratio of 1, CH4Content of 20 vol%, CO2The content is 20 vol%, the balance gas is helium, and the volume space velocity is 60000mL gcat –1h-1The reaction pressure is normal pressure, and the reaction temperature is 750 ℃. The initial conversion of methane was 95% and the conversion of methane after 10h of reaction was 57%.
Example 3
1) Preparing a carrier: dissolving calcium nitrate and ferric nitrate in 80mL of water, wherein the mass ratio of Fe to Ca is 0.5, adding ammonia water to adjust the pH value to 10.5, controlling the heating temperature to 90 ℃, and dropwise adding a certain amount of ammonium hydrogen phosphate ((NH) under vigorous stirring4)2HPO4) The solution was stirred for 2 hours again after the completion of the dropwise addition so that the calcium-phosphorus atomic ratio (Ca/P) was 1.67, and the resulting solid was filtered and dried and then calcined at 300 ℃ for 5 hours to obtain a hydroxyapatite containing Fe in which the mass ratio of Fe to Ca was 0.5.
2) 5.5mg of nickel chloride was dissolved in 50mL of water, sufficiently stirred and the pH of the solution was adjusted to 10 with ammonia, 5g of hydroxyapatite doped with Fe at a Fe to Ca mass ratio of 0.5 was poured, vigorously stirred at room temperature for 3 hours, the catalyst was filtered, dried at 80 ℃ for 12 hours, calcined at 400 ℃ for 5 hours, and then reduced with hydrogen at 200 ℃ for 2 hours to give a 0.05 wt% Ni monatomic catalyst supported on hydroxyapatite doped with Fe at a Fe to Ca mass ratio of 0.5.
3) And (3) reaction test of preparing synthesis gas by dry reforming of methane and carbon dioxide: CH in raw material gas4And CO2In a ratio of 1, CH4Content 50 vol%, CO2The content is 50 vol%, and the volume space velocity is 3000mL gcat –1h-1The reaction pressure is normal pressure, and the reaction temperature is 450 ℃. The initial conversion of methane was 75%, and the conversion of methane after 100h of reaction was 69%.
Example 4
1) Preparing a carrier: dissolving calcium nitrate and manganese nitrate in 80mL of water, wherein the mass ratio of Mn to Ca is 0.25, adding ammonia water to adjust the pH value to 10.5, controlling the heating temperature to be 50 ℃, and dropwise adding a certain amount of ammonium hydrogen phosphate ((NH) under vigorous stirring4)2HPO4) The solution was stirred for 5 hours again after the completion of the dropwise addition so that the calcium-phosphorus atomic ratio (Ca/P) was 1.67, and the resulting solid was filtered and dried and then calcined at 500 ℃ for 3 hours to obtain hydroxyapatite in which Mn was incorporated at a mass ratio of Mn to Ca of 0.25.
2) 300mg of nickel acetate was dissolved in 50mL of water, stirred well and the pH of the solution was adjusted to 10 with ammonia, 5g of hydroxyapatite doped with Mn at a Mn to Ca mass ratio of 0.25 was poured, stirred vigorously at room temperature for 3h, the catalyst was filtered, dried at 80 ℃ for 12 h, calcined at 600 ℃ for 3h, and then reduced with hydrogen at 600 ℃ for 1 h to give a 2 wt% and > 80% Ni in monatomic form supported on hydroxyapatite doped with Mn at a Mn to Ca mass ratio of 0.25.
3) And (3) reaction test of preparing synthesis gas by dry reforming of methane and carbon dioxide: CH in raw material gas4And CO2In a ratio of 1, CH4Content of CO was 10 vol%2The content is 10 vol%, the balance gas is argon, and the volume space velocity is 90000mL gcat –1h-1The reaction pressure is normal pressure, and the reaction temperature is 850 ℃. The initial conversion of methane was 97%, and the conversion of methane was 95% after 100h of reaction.
Example 5
1) Preparing a carrier: dissolving calcium nitrate and cobalt nitrate in 80mL of water, wherein the mass ratio of Co to Ca is 0.025, adding ammonia water to adjust the pH value to 10.5, controlling the heating temperature to 80 ℃, and dropwise adding a certain amount of ammonium hydrogen phosphate ((NH) under vigorous stirring4)2HPO4) The solution was stirred for 5 hours again after the completion of the dropwise addition so that the calcium-phosphorus atomic ratio (Ca/P) was 1.67, and the obtained solid was filtered and dried and then calcined at 500 ℃ for 2 hours to obtain Co-doped hydroxyapatite having a mass ratio of Co to Ca of 0.025.
2) 0.4g of nickel acetylacetonate was dissolved in 50mL of water, stirred well and the pH of the solution was adjusted to 10 with ammonia, 5g of Co-doped hydroxyapatite with a Co to Ca mass ratio of 0.025 was poured, stirred vigorously at room temperature for 3 hours, the catalyst was filtered, dried at 80 ℃ for 12 hours, calcined at 400 ℃ for 3 hours, and then reduced with hydrogen at 300 ℃ for 5 hours to give a catalyst loaded with 1.8 wt% and > 50% Ni in monatomic form of Co-doped hydroxyapatite with a Co to Ca mass ratio of 0.025.
3) And (3) reaction test of preparing synthesis gas by dry reforming of methane and carbon dioxide: CH in raw material gas4And CO2In a ratio of 1, CH4Content of 40 vol%, CO2The content is 40 vol%, the balance gas is argon, and the volume space velocity is 80000mL gcat –1h-1The reaction pressure is normal pressure, and the reaction temperature is 650 ℃. The initial conversion of methane was 51% and the conversion of methane after 100h of reaction was 46%.
Claims (7)
1. A supported nickel-based monatomic catalyst, characterized in that: hydroxyapatite doped with metal elements is taken as a carrier, the doped metal elements are one or more than two of cerium (Ce), iron (Fe), cobalt (Co) and manganese (Mn), and the mass of the doped elements accounts for 0.5-20% of the total mass of the catalyst; the nickel is highly dispersed on the carrier mainly in a monoatomic form, and the content of the nickel is 0.005-5 wt% of the total mass of the catalyst.
2. The catalyst of claim 1, wherein: more than 50% of nickel in the catalyst is dispersed on the carrier in a form of single atom; the doped metal elements are embedded in the crystal lattice of the hydroxyapatite.
3. A method for preparing a supported nickel-based monatomic catalyst according to claim 1 or 2, wherein: firstly, preparing a hydroxyapatite carrier doped with metal elements by a coprecipitation method, and then uniformly dispersing nickel on the surface of the carrier by an adsorption precipitation method, wherein the specific preparation process comprises the following steps:
1) preparing a carrier: dissolving calcium nitrate and nitrate of doped metal (M) in water, wherein the doped metal (M) is one or more of cerium (Ce), iron (Fe), cobalt (Co) and manganese (Mn), the mass ratio of M to calcium is 0.1-3, adding ammonia water to adjust the pH value to 8.5-11.5, controlling the heating temperature to 50-90 ℃, and dropwise adding ammonium hydrogen phosphate ((NH) under stirring4)2HPO4) The solution is added until the calcium-phosphorus atomic ratio (Ca/P) is 1.67, the solution is stirred for 2 to 5 hours after the dripping is finished, and the obtained solid is filtered and dried and then is roasted for 2 to 5 hours at the temperature of 300-;
2) preparing a catalyst: dissolving a nickel-containing precursor in water, fully stirring, adjusting the pH value of the solution to 8-11 by using ammonia water, pouring a carrier into a metal precursor aqueous solution, violently stirring at room temperature for 2-5h, filtering a catalyst, and drying at 60-120 ℃ for 5-20 h;
3) roasting the catalyst at 400-600 deg.c for 3-5 hr;
4) reducing the calcined catalyst by hydrogen for 0.5-5 h at 200-600 ℃.
4. The method for preparing the catalyst according to claim 3, wherein: the nickel precursor is one or more than two of nickel chloride, nickel nitrate, nickel acetylacetonate and nickel acetate.
5. The method for preparing the catalyst according to claim 3, wherein: the doped metal nitrate is one or more than two of cerium nitrate, ferric nitrate, cobalt nitrate and manganese nitrate.
6. A catalyst according to claim 1 or 2 for use in the reaction of methane carbon dioxide dry reforming to synthesis gas.
7. The catalyst of claim 6, used in the reaction of dry reforming of methane and carbon dioxide to produce synthesis gas, characterized in that: CH in raw material gas4And CO2In a volume ratio of 1, CH4The content of CO is 10-50 vol%2The content is 10-50 vol%, nitrogen and/or inert gas is used as balance gas, and the volume space velocity is 3000-cat –1h-1The reaction pressure is normal pressure, and the reaction temperature is 450-850 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811608743.1A CN111375432B (en) | 2018-12-27 | 2018-12-27 | Nickel monoatomic catalyst loaded by hydroxyapatite and preparation and application thereof |
| PCT/CN2019/129225 WO2020135720A1 (en) | 2018-12-27 | 2019-12-27 | Method for forming spherical hydroxyapatite, spherical hydroxyapatite and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811608743.1A CN111375432B (en) | 2018-12-27 | 2018-12-27 | Nickel monoatomic catalyst loaded by hydroxyapatite and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111375432A true CN111375432A (en) | 2020-07-07 |
| CN111375432B CN111375432B (en) | 2023-03-28 |
Family
ID=71128728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811608743.1A Active CN111375432B (en) | 2018-12-27 | 2018-12-27 | Nickel monoatomic catalyst loaded by hydroxyapatite and preparation and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN111375432B (en) |
| WO (1) | WO2020135720A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112121581A (en) * | 2020-09-23 | 2020-12-25 | 苏州云式环境科技有限公司 | Industrial tail gas treatment system |
| CN112403470A (en) * | 2020-11-25 | 2021-02-26 | 榆林学院 | Catalyst for preparing synthesis gas by reforming methane and carbon dioxide and application thereof |
| CN113145176A (en) * | 2021-05-07 | 2021-07-23 | 中国平煤神马能源化工集团有限责任公司 | Cobalt-manganese-based catalyst for hydroformylation of cyclohexene and preparation and application thereof |
| CN113952970A (en) * | 2021-11-10 | 2022-01-21 | 中国科学院山西煤炭化学研究所 | Catalyst with nickel loaded on hydroxyapatite, preparation method and application thereof |
| CN114471636A (en) * | 2022-01-13 | 2022-05-13 | 南京师范大学 | Preparation method and application of supported nickel-based catalyst |
| CN115350718A (en) * | 2022-08-06 | 2022-11-18 | 南京师范大学 | Method for preparing second-generation biodiesel by using Ni-Fe/HAP catalytic grease hydrogenation |
| CN115518652A (en) * | 2022-06-13 | 2022-12-27 | 安徽理工大学 | Silicon-cerium composite microporous material packaged metal catalyst and preparation method and application thereof |
| CN116273090A (en) * | 2022-12-29 | 2023-06-23 | 广西大学 | Preparation method and application of methane dry reforming catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106694015A (en) * | 2016-11-17 | 2017-05-24 | 陕西师范大学 | Simple preparation method of high-dispersion nickel oxide cluster modified carbon nitride photocatalyst for decomposing water to produce hydrogen |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199810A (en) * | 2005-01-20 | 2006-08-03 | Yokohama National Univ | Composite particle and method for producing the same |
| CN102020777B (en) * | 2010-11-29 | 2012-08-22 | 同济大学 | Method for preparing nano hydroxyl apatite calcium alginate injectable hydrogel and application thereof |
| CN102718241B (en) * | 2012-06-28 | 2014-07-02 | 天津大学 | Method for preparing spherical alumina particles by alginic acid auxiliary forming method |
| CN104477953B (en) * | 2014-11-12 | 2016-03-30 | 中国海洋石油总公司 | A kind of forming method of ball-aluminium oxide |
-
2018
- 2018-12-27 CN CN201811608743.1A patent/CN111375432B/en active Active
-
2019
- 2019-12-27 WO PCT/CN2019/129225 patent/WO2020135720A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106694015A (en) * | 2016-11-17 | 2017-05-24 | 陕西师范大学 | Simple preparation method of high-dispersion nickel oxide cluster modified carbon nitride photocatalyst for decomposing water to produce hydrogen |
Non-Patent Citations (2)
| Title |
|---|
| KI HOON KIM ET AL: ""Effects of ceria in CO2 reforming of methane over Ni/calcium hydroxyapatite"", 《KOREAN J. CHEM. ENG，》 * |
| KI HOON KIM ET AL: ""Effects of ceria in CO2 reforming of methane over Ni/calcium hydroxyapatite"", 《KOREAN J. CHEM. ENG》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112121581A (en) * | 2020-09-23 | 2020-12-25 | 苏州云式环境科技有限公司 | Industrial tail gas treatment system |
| CN112403470A (en) * | 2020-11-25 | 2021-02-26 | 榆林学院 | Catalyst for preparing synthesis gas by reforming methane and carbon dioxide and application thereof |
| CN113145176A (en) * | 2021-05-07 | 2021-07-23 | 中国平煤神马能源化工集团有限责任公司 | Cobalt-manganese-based catalyst for hydroformylation of cyclohexene and preparation and application thereof |
| CN113145176B (en) * | 2021-05-07 | 2023-06-30 | 中国平煤神马能源化工集团有限责任公司 | Cobalt-manganese-based catalyst for cyclohexene hydroformylation reaction, and preparation and application thereof |
| CN113952970A (en) * | 2021-11-10 | 2022-01-21 | 中国科学院山西煤炭化学研究所 | Catalyst with nickel loaded on hydroxyapatite, preparation method and application thereof |
| CN114471636A (en) * | 2022-01-13 | 2022-05-13 | 南京师范大学 | Preparation method and application of supported nickel-based catalyst |
| CN115518652A (en) * | 2022-06-13 | 2022-12-27 | 安徽理工大学 | Silicon-cerium composite microporous material packaged metal catalyst and preparation method and application thereof |
| CN115350718A (en) * | 2022-08-06 | 2022-11-18 | 南京师范大学 | Method for preparing second-generation biodiesel by using Ni-Fe/HAP catalytic grease hydrogenation |
| CN116273090A (en) * | 2022-12-29 | 2023-06-23 | 广西大学 | Preparation method and application of methane dry reforming catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111375432B (en) | 2023-03-28 |
| WO2020135720A1 (en) | 2020-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111375432B (en) | Nickel monoatomic catalyst loaded by hydroxyapatite and preparation and application thereof | |
| CN110252308B (en) | Supported catalyst with active metal dispersed in carrier in atomic level, preparation method and application thereof | |
| CN112871150B (en) | Carbon-supported metal monatomic catalyst prepared based on cyclodextrin supermolecule chemical controllability and preparation method and application method thereof | |
| US20110015062A1 (en) | Cobalt/zirconium-phosphorus/silica catalyst for fischer-tropsch synthesis and method of preparing the same | |
| CN112044462B (en) | Graphene-loaded transition metal nitride nanocomposite and preparation method and application thereof | |
| KR102496214B1 (en) | A loading catalyst in which an active metal is dispersed on an atomic scale in a carrier, and a method for preparing and using the same | |
| CN114210343A (en) | Reduced graphene oxide loaded Ru-Ni bimetallic nanocluster catalytic material | |
| KR100933062B1 (en) | Catalysts for direct production of light olefins from syngas and preparation method there of | |
| CN114733528B (en) | Preparation method and application of nickel/cerium oxide catalyst | |
| CN113351214B (en) | Carbon-doped silicon dioxide-loaded nickel-copper alloy and preparation method and application thereof | |
| CN112844440A (en) | Heavy oil slurry bed hydrogenation carbon-supported molybdenum-cobalt diatomic catalyst and preparation method and application method thereof | |
| CN105582957B (en) | Cobalt-based Fischer-Tropsch synthesis catalyst loaded on spherical carrier and preparation method thereof | |
| CN114950415B (en) | Preparation method of Ru-based catalyst with stable size and application of Ru-based catalyst in ammonia synthesis | |
| CN115138359B (en) | Supported single-atom synergistic nanoparticle bimetallic catalyst and preparation and application thereof | |
| CN114471636A (en) | Preparation method and application of supported nickel-based catalyst | |
| CN112058277B (en) | High-activity catalyst for ammonia synthesis and preparation method thereof | |
| CN114160137A (en) | Cobalt-copper bimetallic catalyst for directly preparing low-carbon alcohol from synthesis gas, and preparation method and use method thereof | |
| KR102311853B1 (en) | A bimetallic catalyst for ammonia dehydrogenation reaction and the method for producing the same | |
| CN114308043A (en) | Preparation method of acidified two-dimensional layered vermiculite supported nickel-based catalyst | |
| Ma et al. | Effect of alkaline-earth metals (Mg, Ca, Sr, and Ba) on precipitated iron-based catalysts for high-temperature Fischer-Tropsch synthesis of light olefins | |
| CN113145127A (en) | Cu catalyst for hydrogen production by methanol steam reforming and preparation method and application thereof | |
| CN108620117B (en) | Low-temperature reduction preparation of high-dispersion load type Ni2Method for preparing P catalyst | |
| CN114308061A (en) | NiAu bimetallic alloy nano catalyst and synthesis and application thereof | |
| CN114471580B (en) | Synthesis and application method of supported nickel-gallium catalyst | |
| CN115212885B (en) | Cobalt silicate derived cobalt-based catalyst for directly preparing low-carbon alcohol from synthesis gas, preparation method and pretreatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |