CN114558587A - Multi-metal composite cerium oxide material, preparation method thereof and application of multi-metal composite cerium oxide material as demercuration catalyst - Google Patents

Multi-metal composite cerium oxide material, preparation method thereof and application of multi-metal composite cerium oxide material as demercuration catalyst Download PDF

Info

Publication number
CN114558587A
CN114558587A CN202210262231.4A CN202210262231A CN114558587A CN 114558587 A CN114558587 A CN 114558587A CN 202210262231 A CN202210262231 A CN 202210262231A CN 114558587 A CN114558587 A CN 114558587A
Authority
CN
China
Prior art keywords
cerium oxide
metal composite
salt
oxide material
composite cerium
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
Application number
CN202210262231.4A
Other languages
Chinese (zh)
Other versions
CN114558587B (en
Inventor
刘恢
李超芳
杨卫春
沈锋华
向开松
袁婧
陈昊
旷蔓祺
李青竹
王海鹰
柴立元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN202210262231.4A priority Critical patent/CN114558587B/en
Publication of CN114558587A publication Critical patent/CN114558587A/en
Application granted granted Critical
Publication of CN114558587B publication Critical patent/CN114558587B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Toxicology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Electromagnetism (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

The invention relates to a multi-metal composite cerium oxide material, a preparation method thereof and application of the multi-metal composite cerium oxide material as a demercuration catalyst. Dispersing cerium salt, cobalt salt, manganese salt, aluminum salt, magnesium salt and surfactant into water by ultrasonic, adding alkaline substance, and mixing uniformly to obtain mixed solution; carrying out hydrothermal reaction on the mixed solution in a microwave heating mode to obtain a hydrothermal reaction product; washing, drying and calcining the hydrothermal reaction product in sequence to obtain the configurationA single, chemically stable, highly disordered distribution of metallic elements, multi-metallic composite cerium oxide material having a multi-metallic synergistically enhanced active center at low temperature and at high SO concentrations2High catalytic activity is maintained under the atmosphere, and the method is particularly suitable for the mercury removal of nonferrous smelting flue gas.

Description

Multi-metal composite cerium oxide material, preparation method thereof and application of multi-metal composite cerium oxide material as demercuration catalyst
Technical Field
The invention relates to a catalytic material, in particular to a multi-metal composite cerium oxide material, and also relates to a preparation method of the multi-metal composite cerium oxide material, and application of the multi-metal composite cerium oxide material as a demercuration catalyst, belonging to the technical field of mercury pollution treatment.
Background
Atmospheric mercury pollution is of widespread concern as a global environmental problem. In the domestic nonferrous smelting industry, the mercury discharge amount accounts for more than 1/4 of the total discharge amount, and the mercury-removing method is of great importance for developing a high-efficiency mercury-removing technology for nonferrous smelting flue gas in order to fulfill the 'water guarantee about mercury' and meet the current domestic mercury discharge standard. The mercury in the nonferrous smelting flue gas is mainly elemental mercury (Hg)0) Mercury (Hg) in its oxidized state2+) Granular mercury (Hg)p) The mercury exists in a form, wherein the ratio of elementary mercury is more than 65%, the treatment difficulty is high, and Hg can be treated by a catalytic method0Conversion to low-toxicity disposable Hg2+The method is not easy to cause secondary pollution, and is a promising atmospheric mercury pollution control technology.
The cerium oxide has excellent propertiesHigher Oxygen Storage Capacity (OSC) and redox performance (Ce)3+/Ce4+) So that the catalyst has better application potential in the field of catalytic demercuration. But the smelting flue gas has lower and unstable oxygen content and has complex atmosphere such as sulfur dioxide with higher concentration. Therefore, the cerium oxide material has the following problems in practical use: (1) the catalytic oxidation capacity is limited, HCl needs to be added, and equipment corrosion is easily caused; (2) the reaction temperature is limited, and a good mercury removal effect can be maintained only at the temperature of more than 250 ℃; (3) easy SO2Poisoning, not being able to treat complex gas components of coloured fumes, in particular SO, in higher concentrations2While maintaining high catalytic activity. The structure of the multi-metal composite cerium oxide material is an effective way for improving the catalytic activity and the sulfur resistance of the demercuration of the cerium oxide, and the research shows that the introduction of transition metals such as Co, Mn and the like which have strong affinity with mercury can improve the defect concentration and the surface active oxygen content, and is beneficial to Hg at medium and low temperature0Capture and catalytic oxidation. However, the components of the multi-metal composite cerium-based material are complex, and a formed heavily doped system is easy to phase separate, so that the distribution of active sites is uneven, and the catalytic performance is influenced. In order to realize high mixing of elements in the multi-metal composite oxide, a high-strength and long-time ball milling method is often adopted in combination with an ultrahigh-temperature calcination synthetic material, so that the synthetic cycle is long, the conditions are harsh, and the exposure of active sites is easily hindered.
Disclosure of Invention
Aiming at the defects in the prior art, the first object of the invention is to provide a multi-metal composite cerium oxide material with a single configuration, good chemical stability and highly disordered distribution of metal elements, the material has an active center reinforced by multi-metal cooperation, the material has high catalytic activity under the condition of lower temperature (100-200 ℃), and the good lattice oxygen fluidity is favorable for surface reconstruction and active site update, SO that the inactivation of a catalyst caused by sulfate deposition is avoided, and the catalyst is further prevented from being deactivated under the condition of high concentration SO2The high catalytic activity is kept under the atmosphere of (500 ppm-1000 ppm), and the method is particularly suitable for the demercuration of nonferrous smelting flue gas.
The second purpose of the invention is to provide a method for preparing the multi-metal composite cerium oxide material, which has simple operation, mild conditions and low cost.
The third purpose of the invention is to provide an application of the multi-metal composite cerium oxide material as a demercuration catalyst, the material has high catalytic activity under a lower temperature condition, and good lattice oxygen fluidity is favorable for surface reconstruction and active site update, the catalyst deactivation caused by sulfate deposition is avoided, and the catalyst is not activated under the condition of high concentration SO2Can keep high catalytic activity under atmosphere, and is particularly suitable for removing mercury from low-temperature high-sulfur nonferrous smelting flue gas.
In order to realize the technical purpose, the invention provides a preparation method of a multi-metal composite cerium oxide material, which comprises the steps of dispersing cerium salt, cobalt salt, manganese salt, aluminum salt, magnesium salt and a surfactant into water by ultrasonic, adding an alkaline substance, and uniformly mixing to obtain a mixed solution; carrying out hydrothermal reaction on the mixed solution in a microwave heating mode to obtain a hydrothermal reaction product; and washing, drying and calcining the hydrothermal reaction product in sequence to obtain the catalyst.
According to the preparation method of the multi-metal composite cerium oxide material, the multi-metal components are introduced, so that the low-temperature catalytic activity and the sulfur resistance of the cerium oxide catalytic material can be improved, meanwhile, the high dispersion of the multi-metal can be enhanced by means of the dispersion effect of the surfactant and the combination of microwave hydrothermal reaction, the defects of uneven distribution of active sites, poor catalytic performance and the like caused by easy phase separation of a heavily doped system are effectively avoided, and the template effect of the surfactant is utilized to form the sheet-shaped structural material with a smooth surface, so that more active sites can be exposed.
As a preferable scheme, the proportion of the cerium salt, the cobalt salt, the manganese salt, the aluminum salt and the magnesium salt is 10-25 percent, 10-25 percent and 10-25 percent according to the mole percentage of the cerium, the cobalt, the manganese, the aluminum and the magnesium. If the content of the single metal element is too low, the catalytic performance is reduced to a certain extent. Cerium, cobalt, manganese, aluminum and magnesium salts are water-soluble salts commonly found in the prior art, such as nitrate, halogen, organic carboxylate, etc. Specifically, cerium acetate, cerium chloride, cobalt acetate, cobalt chloride, manganese acetate, manganese chloride, aluminum acetate, aluminum chloride, magnesium acetate, etc.
Preferably, the concentrations of the cerium salt, the cobalt salt, the manganese salt, the aluminum salt and the magnesium salt in the mixed solution are all in the range of 4mmol/L to 20 mmol/L.
As a preferable scheme, the concentration of the surfactant in the mixed solution is 10-20 g/L; the surfactant is quaternary ammonium salt surfactant and/or polyethylene glycol surfactant. The preferred surfactant not only can play a role in promoting the dispersion of the metal components, but also plays a role in a template, and is beneficial to promoting the growth of the metal oxide into a flaky shape with a smooth surface. Quaternary ammonium salt surfactants are primarily quaternary ammonium salts containing long chain alkyl groups, such as cetyl trimethyl ammonium bromide. Polyethylene glycol type surfactants such as polyethylene glycol 1000.
As a preferable scheme, the concentration of the alkaline substances in the mixed solution is 40-60 g/L; the alkaline substance is at least one of urea, sodium bicarbonate and sodium carbonate. Preferably urea, which decomposes under hydrothermal conditions to release ammonia to facilitate the co-precipitation process of the metal ions.
Preferably, the power of the microwave heating is 100-600W. Hydrothermal reaction is carried out in a microwave heating mode, the method has the characteristics of short synthesis time, high yield and the like, the synthesis efficiency is greatly improved, and meanwhile, high-energy microwaves are utilized to drive elements to be premixed, so that highly disordered distribution of the elements under a relatively mild condition is realized. The power of the microwave heating is preferably 300-500W.
As a preferred embodiment, the hydrothermal reaction conditions are: the temperature is 150-180 ℃, the reaction time is 2-3 h, and the reaction pressure is 0.5-4 MPa.
As a preferred embodiment, the calcination conditions are: the temperature is 400-800 ℃, and the time is 3-6 h. If the temperature is too low, the metal oxide cannot be formed, and if the temperature is too high, the effect is greatly reduced. The more preferable calcination temperature is 500 to 600 ℃.
The invention also provides a multi-metal composite cerium oxide material, which is prepared by the preparation method.
The multi-metal composite of the inventionThe cerium oxide-containing material takes cerium oxide as a basic component, and the cerium oxide has excellent Oxygen Storage Capacity (OSC) and redox performance (Ce)3+/Ce4+) Co and Mn metal elements are introduced as mercury affinity active components, the Co and Mn metal elements have good affinity effect on mercury, Al metal is used as a sulfur-resistant component, and the introduction of the Al metal element can enhance the surface acidity of the material and reduce SO2The Mg metal element is introduced as an entropy driving component, the structure and the phase change of the material are related to the enthalpy change and the entropy change in the synthesis process, the entropy change is used as a leading factor in the synthesis process to increase the dispersion degree of the metal element of the material, a proper amount of magnesium element is introduced to achieve the best effect, the atomic radiuses of the four elements of Co, Mn, Al and Mg are all smaller than that of cerium atoms, and compared with elements with larger radiuses of nickel, zinc and the like, the Mg metal element is more beneficial to stably existing in cerium oxide lattices, and the high lattice distortion is caused by the diversification of the atomic radiuses and valence states of the metal to influence the Ce lattice distortion3+/Ce4 +The valence state is balanced, the defect structure with rich structure is formed, the oxygen storage capacity and the oxygen transmission performance under the medium and low temperature conditions are effectively improved, and Hg is promoted0And (4) oxidizing.
The multi-metal composite material has a sheet-like structure, a smooth surface and a single fluorite-structured cerium oxide phase.
The invention also provides application of the multi-metal composite cerium oxide material as a demercuration catalyst, which is applied to catalytic oxidation of elemental mercury.
The multi-metal composite cerium oxide material is used for the flue gas demercuration process: the applicable flue gas temperature range is 50-200 ℃, and the gas Hg is0Has a concentration of 75 μ g m-3～250μg m-3，O2Concentration of 4% -6%, SO2The concentration is 500ppm to 1000 ppm.
The mechanism of the high sulfur resistance and high catalytic activity of the multi-metal composite cerium oxide material is as follows: the multi-metal composite cerium oxide material introduces elements Co and Mn as mercury-philic active components, element Al as a sulfur-resistant component and element Mg as an entropy driving component. The active component and the sulfur-resistant component are highly dispersed and strong in the crystal structureRealization of Hg under synergistic effect0Quickly capture and prevent surface sulfation, and high lattice distortion caused by the diversification of the radius and valence of metal elements to influence Ce3+/Ce4+The valence state is balanced, the defect structure with rich structure is formed, the oxygen storage capacity and the oxygen transmission performance under the medium and low temperature conditions are effectively improved, and Hg is promoted0And (4) oxidizing.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
(1) compared with the common hydrothermal method, the ball milling method, the precipitation method and the like, the microwave hydrothermal method has the advantages of short synthesis time, high yield and greatly improved synthesis efficiency, and the microwave hydrothermal reaction can strengthen the high dispersion of the multi-metal, thereby effectively avoiding the defects of uneven distribution of active sites and poor catalytic performance caused by easy phase separation of a heavy doping system.
(2) The multi-metal composite material provided by the invention is in a sheet shape with a smooth surface, has a single fluorite-structured cerium oxide phase, is highly dispersed by multiple metals, enhances the site activity by strong synergistic effect, constructs rich defect structures by multiple metals, and enhances the oxygen storage capacity and the catalytic performance.
(3) The multi-metal composite cerium oxide material has high and low temperature activity and good sulfur resistance, and the treatment concentration is 150 mu g m-3Hg of0At a temperature of 100 ℃ in N2+4％O2+1000ppm SO2The demercuration reaction is carried out under the condition, the efficiency reaches more than 95 percent, and the low-temperature activity and the sulfur resistance are superior to those of the prior cerium-based composite metal oxide materials.
Drawings
Fig. 1 is SEM images of the multi-metal composite cerium oxide materials of examples 1 and 9; it can be seen from fig. 1 that the multi-metal composite cerium oxide is in the form of a nano-flake with a smooth surface.
FIG. 2 is an XRD pattern of the multi-metal composite cerium oxide material of example 1 and example 9; it can be seen from fig. 2 that the phase of the multi-metal composite material is single fluorite structured cerium oxide.
FIG. 3 is the EDS-mapping chart of the multi-metal composite cerium oxide material of example 1; it can be seen from fig. 3 that each metal element in the multi-metal composite cerium oxide is highly uniformly dispersed.
FIG. 4 is a Raman diagram of the multi-metal composite cerium oxide material of example 1; it can be seen from fig. 4 that the multi-metal composite cerium oxide has a high concentration of defects.
FIG. 5 is an SEM photograph of materials prepared in examples 5, 6, 7 and 8; it can be seen from fig. 5 that none of the materials lacking one of Mg, Al, Mn, and Co can be formed into a nano-flake shape with a smooth surface.
FIG. 6 is an EDS-mapping chart of materials prepared in examples 5, 6, 7, 8; it can be seen from FIG. 6 that the uniformity of the distribution of the metal elements in the material lacking one of Mg, Al, Mn and Co is somewhat reduced.
FIG. 7 is a graph showing the mercury removal effect of the multi-metal composite cerium oxide materials of examples 1 and 9 at different temperatures; a is 100 ℃, B is 200 ℃; from fig. 7, it can be seen that the mercury removal efficiency of the multi-metal composite cerium oxide can reach more than 95% under the low-temperature condition.
FIG. 8 shows the multi-metal composite cerium oxide material SO of examples 1 and 92A demercuration effect graph under the atmosphere; from FIG. 8, it can be seen that the multi-metal composite cerium oxide has SO at low temperature2The mercury removal efficiency is still higher than 95% when the concentration is 500ppm and 1000ppm, and the sulfur resistance is good.
FIG. 9 is a graph showing the mercury removal effect of the multi-metal composite cerium oxide material of example 2; it can be seen from fig. 9 that when the cobalt addition ratio in the multi-metal composite cerium oxide is 0.5mmol, the demercuration efficiency is still stabilized at 90% or more at 100 ℃.
FIG. 10 is a graph showing the mercury removal effect of the multi-metal composite cerium oxide material of example 3; from fig. 9, it can be seen that the catalytic performance of the material with too high calcination temperature is greatly reduced, and the mercury removal efficiency is only about 50% under the condition of 100 ℃.
FIG. 11 is a graph showing the demercuration effect of the multi-metallic composite material prepared by a general hydrothermal method according to example 4; from fig. 9, it can be seen that the effect of the multi-metal composite material synthesized by the ordinary hydrothermal method is far inferior to that of the multi-metal composite material synthesized by the microwave hydrothermal method, for example, the mercury removal efficiency is only about 60% at 100 ℃.
FIG. 12 is a graph showing the effect of mercury removal on the materials prepared in examples 5, 6, 7 and 8; from fig. 10, it can be seen that the absence of one of Mg, Al, Mn and Co leads to a certain reduction in the mercury removal performance of the material at 100 ℃, wherein the absence of Co, Al and Mn has a more significant effect, which indicates that the superior low-temperature mercury removal performance is caused by the synergistic effect of the metal elements.
FIG. 13 shows SO of the materials prepared in examples 5, 6, 7 and 82A mercury removal effect graph under the atmosphere; from FIG. 11 it can be seen that the material lacking one of the elements Mg, Al, Mn and Co is 1000ppm SO at 100 deg.C2Under the condition, the demercuration performance is greatly reduced, wherein the sulfur resistance is most obviously influenced by the lack of Co, Al and Mn.
FIG. 14 is a graph showing the mercury removal effect of the multi-metal composite cerium oxide material of example 10; from fig. 14, it can be seen that the multi-metal composite cerium oxide material prepared under the conditions of microwave hydrothermal reaction for 2 hours and calcination temperature of 600 ℃ and calcination time of 4 hours has the mercury removal efficiency of about 95% under the condition of 100 ℃.
FIG. 15 is a graph showing the mercury removal effect of the multi-metal composite cerium oxide material of example 11; from fig. 15, it can be seen that the mercury removal efficiency of the multi-metal composite cerium oxide material prepared under the conditions of microwave power of 300W, pressure of 3MPa, constant temperature reaction at 180 ℃ for 3h, calcination temperature of 500 ℃ and calcination time of 4h is higher than 90% at 100 ℃.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be merely illustrative of the principles of the present invention and are not to be construed as limiting the invention.
In the following examples, all the starting materials are commercially available starting materials unless otherwise specified.
Example 1
0.317g of Ce (Ac)3·xH2O，0.249g Co(Ac)2·4H2O g，0.245g Mn(Ac)2·4H2O，0.214g Mg(Ac)2·4H2O，0.204g C9H21AlO3And 0.5g of hexadecyl trimethyl ammonium bromide is added into 50mL of deionized water, ultrasonic reaction is carried out for 10min until the mixture is uniformly mixed, 2g of urea is added, stirring reaction is carried out for 30min, the mixture is transferred into a special microwave hydrothermal reaction kettle, a temperature probe and a pressure probe in the microwave hydrothermal reactor are connected, the microwave power is set to be 500W, the pressure is set to be 1MPa, and the constant temperature reaction is carried out for 3h at the temperature of 150 ℃. Washing the obtained precipitate with deionized water for three times, washing with ethanol for three times, drying in an oven at 80 ℃, and finally calcining in a tube furnace at 500 ℃ for 4 hours to obtain the five-metal mixed multi-metal composite cerium oxide material ((MgAlMnCo) CeO2-x-Ac)。
Example 2
0.317g of Ce (Ac)3·xH2O，0.125g Co(Ac)2·4H2O g，0.245g Mn(Ac)2·4H2O，0.214g Mg(Ac)2·4H2O，0.204g C9H21AlO3And 0.5g of hexadecyl trimethyl ammonium bromide is added into 50mL of deionized water, ultrasonic reaction is carried out for 10min until the mixture is uniformly mixed, 2g of urea is added, stirring reaction is carried out for 30min, the mixture is transferred into a special microwave hydrothermal reaction kettle, a temperature probe and a pressure probe in the microwave hydrothermal reactor are connected, the microwave power is set to be 500W, the pressure is set to be 1MPa, and the constant temperature reaction is carried out for 3h at the temperature of 150 ℃. Washing the obtained precipitate with deionized water for three times, washing with ethanol for three times, drying in an oven at 80 ℃, and finally calcining in a tube furnace at 500 ℃ for 4 hours to obtain the five-metal mixed multi-metal composite cerium oxide material ((MgAlMnCo)0.5)CeO2-x-Ac)。
Example 3 (comparative example)
0.317g of Ce (Ac)3·xH2O，0.249g Co(Ac)2·4H2O g，0.245g Mn(Ac)2·4H2O 0.214g Mg(Ac)2·4H2O，0.204g C9H21AlO3Adding 0.5g of hexadecyl trimethyl ammonium bromide into 50mL of deionized water, carrying out ultrasonic reaction for 10min until the ammonium bromide is uniformly mixed, adding 2g of urea, stirring and reacting for 30min, transferring the mixture into a special microwave hydrothermal reaction kettle, connecting a temperature probe and a pressure probe in the microwave hydrothermal reactor, setting the microwave power to be 500W and the pressure to be 1MPa,reacting for 3 hours at constant temperature of 150 ℃. Washing the obtained precipitate with deionized water for three times, washing with ethanol for three times, drying in an oven at 80 ℃, and finally calcining in a tubular furnace at 900 ℃ for 4 hours to obtain the multi-metal composite material mixed with five metals.
Example 4 (comparative example)
0.317g of Ce (Ac)3·xH2O，0.249g Co(Ac)2·4H2O g，0.245g Mn(Ac)2·4H2O，0.214g Mg(Ac)2·4H2O，0.204g C9H21AlO3And 0.5g of hexadecyl trimethyl ammonium bromide is added into 50mL of deionized water, ultrasonic reaction is carried out for 10min until the mixture is uniformly mixed, 2g of urea is added, stirring reaction is carried out for 30min, the mixture is transferred into a hydrothermal reaction kettle, and constant temperature reaction is carried out for 12h in an oven at the temperature of 200 ℃. Washing the obtained precipitate with deionized water for three times, washing with ethanol for three times, drying in an oven at 80 ℃, and finally calcining in a tubular furnace at 500 ℃ for 4 hours to obtain the polymetallic composite cerium oxide material synthesized by the Prastine hydrothermal method.
Example 5 (comparative example)
0.317g of Ce (Ac)3·xH2O，0.249g Co(Ac)2·4H2O g，0.245g Mn(Ac)2·4H2O，0.204g C9H21AlO3And 0.5g of hexadecyl trimethyl ammonium bromide are added into 50mL of deionized water, ultrasonic reaction is carried out for 10min until uniform mixing is achieved, 2g of urea is added, stirring reaction is carried out for 30min, the mixture is transferred into a special microwave hydrothermal reaction kettle, a temperature probe and a pressure probe in the microwave hydrothermal reactor are connected, the microwave power is 500W, the pressure is 1MPa, and constant temperature reaction is carried out for 3h at the temperature of 150 ℃. Washing the obtained precipitate with deionized water for three times, washing with ethanol for three times, drying in an oven at 80 ℃, and finally calcining in a tube furnace at 500 ℃ for 4 hours to obtain the multi-metal composite cerium oxide material ((AlMnCo) CeO) mixed with four metals2-x)。
Example 6 (comparative example)
0.317g of Ce (Ac)3·xH2O，0.249g Co(Ac)2·4H2O g，0.245g Mn(Ac)2·4H2O，0.214g Mg(Ac)2·4H2Adding O and 0.5g of hexadecyl trimethyl ammonium bromide into 50mL of deionized water, carrying out ultrasonic reaction for 10min until the O and the hexadecyl trimethyl ammonium bromide are uniformly mixed, adding 2g of urea, stirring and reacting for 30min, transferring the mixture into a special microwave hydrothermal reaction kettle, connecting a temperature probe and a pressure probe in the microwave hydrothermal reactor, setting the microwave power to be 500W, setting the pressure to be 1MPa, and carrying out thermostatic reaction for 3h at 150 ℃. Washing the obtained precipitate with deionized water for three times, washing with ethanol for three times, drying in an oven at 80 ℃, and finally calcining in a tube furnace at 500 ℃ for 4 hours to obtain the multi-metal composite cerium oxide material ((MgMnCo) CeO) mixed with four metals2-x)。
Example 7 (comparative example)
0.317g of Ce (Ac)3·xH2O，0.249g Co(Ac)2·4H2O g，0.214g Mg(Ac)2·4H2O，0.204g C9H21AlO3And 0.5g of hexadecyl trimethyl ammonium bromide is added into 50mL of deionized water, ultrasonic reaction is carried out for 10min until the mixture is uniformly mixed, 2g of urea is added, stirring reaction is carried out for 30min, the mixture is transferred into a special microwave hydrothermal reaction kettle, a temperature probe and a pressure probe in the microwave hydrothermal reactor are connected, the microwave power is set to be 500W, the pressure is set to be 1MPa, and the constant temperature reaction is carried out for 3h at the temperature of 150 ℃. Washing the obtained precipitate with deionized water for three times, washing with ethanol for three times, drying in an oven at 80 ℃, and finally calcining in a tube furnace at 500 ℃ for 4 hours to obtain the multi-metal composite cerium oxide material ((MgAlCo) CeO) mixed with four metals2-x)。
Example 8 (comparative example)
0.317g of Ce (Ac)3·xH2O，0.245g Mn(Ac)2·4H2O，0.214g Mg(Ac)2·4H2O，0.204g C9H21AlO3And 0.5g of hexadecyl trimethyl ammonium bromide is added into 50mL of deionized water, ultrasonic reaction is carried out for 10min until the mixture is uniformly mixed, 2g of urea is added, stirring reaction is carried out for 30min, the mixture is transferred into a special microwave hydrothermal reaction kettle, a temperature probe and a pressure probe in the microwave hydrothermal reactor are connected, the microwave power is set to be 500W, the pressure is set to be 1MPa, and the constant temperature reaction is carried out for 3h at the temperature of 150 ℃. Washing the obtained precipitate with deionized water for three times, and washing with waterWashing with alcohol for three times, drying in an oven at 80 deg.C, and calcining in a tube furnace at 500 deg.C for 4 hr to obtain four-metal mixed multi-metal composite cerium oxide ((MgAlMn) CeO2-x)。
Example 9
0.246g of CeCl3·6H2O，0.237g CoCl2·6H2O，0.162g MnCl2·2H2O，0.203g MgCl2·6H2O，0.171g AlCl3·6H2Adding O and 0.5g of hexadecyl trimethyl ammonium bromide into 50mL of deionized water, carrying out ultrasonic reaction for 10min until the O and the hexadecyl trimethyl ammonium bromide are uniformly mixed, adding 2g of urea, stirring and reacting for 30min, transferring the mixture into a special microwave hydrothermal reaction kettle, connecting a temperature probe and a pressure probe in the microwave hydrothermal reactor, setting the microwave power to be 500W, setting the pressure to be 1MPa, and carrying out constant-temperature reaction for 3h at the temperature of 150 ℃. Washing the obtained precipitate with deionized water for three times, washing with ethanol for three times, drying in an oven at 80 ℃, and finally calcining in a tube furnace at 500 ℃ for 4 hours to obtain the five-metal mixed multi-metal composite cerium oxide material ((MgAlMnCo) CeO2-x-Cl。
Example 10
0.246g of CeCl3·6H2O，0.237g CoCl2·6H2O，0.162g MnCl2·2H2O，0.203g MgCl2·6H2O，0.171g AlCl3·6H2Adding 50mL of O and 0.5g of hexadecyl trimethyl ammonium bromide into 50mL of deionized water, carrying out ultrasonic reaction for 10min until the mixture is uniformly mixed, adding 2g of urea, stirring and reacting for 30min, transferring the mixture into a special microwave hydrothermal reaction kettle, connecting a temperature probe and a pressure probe in the microwave hydrothermal reactor, setting the microwave power of 500W, the pressure of 1MPa, and carrying out constant-temperature reaction for 2h at 150 ℃. Washing the obtained precipitate with deionized water for three times, washing with ethanol for three times, drying in an oven at 80 ℃, and finally calcining in a tubular furnace at 600 ℃ for 4 hours to obtain the multi-metal composite cerium oxide material mixed with five metals.
Example 11
0.246g of CeCl3·6H2O，0.237g CoCl2·6H2O，0.162g MnCl2·2H2O，0.203g MgCl2·6H2O，0.171g AlCl3·6H2Adding 50mL of O and 0.5g of hexadecyl trimethyl ammonium bromide into 50mL of deionized water, carrying out ultrasonic reaction for 10min until the O and the hexadecyl trimethyl ammonium bromide are uniformly mixed, adding 2g of urea, stirring and reacting for 30min, transferring the mixture into a special microwave hydrothermal reaction kettle, connecting a temperature probe and a pressure probe in the microwave hydrothermal reactor, setting the microwave power of 300W, the pressure of 3MPa, and carrying out constant-temperature reaction for 3h at 180 ℃. Washing the obtained precipitate with deionized water for three times, washing with ethanol for three times, drying in an oven at 80 ℃, and finally calcining in a tubular furnace at 500 ℃ for 4 hours to obtain the multi-metal composite cerium oxide material mixed with five metals.
Example 12
The material prepared in examples 1 and 9 was treated with a catalyst at 100 ℃ and 200 ℃ respectively at a treatment concentration of 150. mu. g m-3Hg of0Steam with space velocity of 120000h-1In N at2+4％O2The mercury removal effect of the materials of the embodiment 1 and the embodiment 9 can reach more than 95 percent.
Example 13
The catalyst treatment concentration of the materials prepared in examples 1 and 9 was 150. mu. g m at 100 ℃-3Hg of0Steam with space velocity of 120000h-1By N2As carrier gas, 4% O2Under the condition, the SO of 500ppm and 1000ppm is introduced2The mercury removal effect of the materials of the embodiment 1 and the embodiment 9 is always kept above 95%.
Example 14
The material prepared in example 2 was used as a catalyst at a treatment concentration of 150 μ gm at 100 deg.C-3Hg of0Steam with space velocity of 120000h-1By N2As carrier gas, 4% O2Under the condition, the mercury removal effect of the material of the embodiment 2 is always kept above 90%.
Example 15
The material prepared in example 3 was used as a catalyst at a treatment concentration of 150 μ gm at 100 deg.C-3Hg of0Steam generationSpace velocity of 120000h-1By N2As carrier gas, 4% O2Under the condition, the mercury removal effect of the material of the embodiment 3 is only about 50%.
Example 16
The material prepared in example 4 was used as a catalyst at a treatment concentration of 150 μ gm at 100 deg.C-3Hg of0Steam with space velocity of 120000h-1By N2As carrier gas, 4% O2Under the condition, the mercury removal effect of the material of the embodiment 4 is only about 60%.
Example 17
The materials prepared in the examples 5, 6, 7 and 8 are used as catalysts at 100 ℃ and the treatment concentration is 150 mu g m-3Hg of0Steam with space velocity of 120000h-1By N2As carrier gas, 4% of O2Under the condition, the demercuration efficiency is 85 percent, 78 percent, 70 percent and 62 percent in sequence.
Example 18
The materials prepared in the examples 5, 6, 7 and 8 are used as catalysts at 100 ℃ and the treatment concentration is 150 mu g m-3Hg of0Steam with space velocity of 120000h-1By N2As carrier gas, 4% O2Under the condition, 1000ppm SO is introduced2The mercury removal effect of the materials of the embodiment 5, 6, 7 and 8 is respectively 80 percent, 62 percent, 65 percent and 50 percent.
Example 19
The material prepared in example 10 was treated with a catalyst at 100 ℃ to a concentration of 150. mu. g m-3Hg of0Steam with space velocity of 120000h-1By N2As carrier gas, 4% of O2Under the condition, the mercury removal effect of the material of the embodiment 10 is kept above 95%.
Example 20
The material prepared in example 11 was treated with a catalyst at 100 ℃ to a concentration of 150. mu. g m-3Hg of0Steam with space velocity of 120000h-1By N2As carrier gas, 4% O2Under the condition, the mercury removal effect of the material of the embodiment 10 is kept above 90%.

Claims (10)

1. A preparation method of a multi-metal composite cerium oxide material is characterized by comprising the following steps: dispersing cerium salt, cobalt salt, manganese salt, aluminum salt, magnesium salt and surfactant into water by ultrasonic, adding alkaline substance, and mixing uniformly to obtain mixed solution; carrying out hydrothermal reaction on the mixed solution in a microwave heating mode to obtain a hydrothermal reaction product; and washing, drying and calcining the hydrothermal reaction product in sequence to obtain the catalyst.
2. The method for preparing a multi-metal composite cerium oxide material according to claim 1, wherein: the proportion of the cerium salt, the cobalt salt, the manganese salt, the aluminum salt and the magnesium salt is 10-25 percent, 10-25 percent and 10-25 percent according to the mole percentage of the cerium, the cobalt, the manganese, the aluminum and the magnesium.
3. The method for preparing a multi-metal composite cerium oxide material according to claim 1, wherein: the concentration of cerium salt, cobalt salt, manganese salt, aluminum salt and magnesium salt in the mixed solution is in the range of 4 mmol/L-20 mmol/L.
4. The method for preparing a multi-metal composite cerium oxide material according to claim 1, wherein: the concentration of the surfactant in the mixed solution is 10-20 g/L; the surfactant is quaternary ammonium salt surfactant and/or polyethylene glycol surfactant.
5. The method for preparing a multi-metal composite cerium oxide material according to claim 1, wherein: the concentration of alkaline substances in the mixed solution is 40-60 g/L; the alkaline substance is at least one of urea, sodium bicarbonate and sodium carbonate.
6. The method for preparing a multi-metal composite cerium oxide material according to claim 1, wherein: the microwave heating power is 100-600W.
7. The method for preparing a multi-metal composite cerium oxide material according to claim 1, wherein: the conditions of the hydrothermal reaction are as follows: the temperature is 150-180 ℃, the reaction time is 2-3 h, and the reaction pressure is 0.5-4 MPa.
8. The method for preparing a multi-metal composite cerium oxide material according to claim 1, wherein: the calcining conditions are as follows: the temperature is 400-800 ℃, and the time is 3-6 h.
9. A multi-metal composite cerium oxide material is characterized in that: the preparation method of any one of claims 1 to 8.
10. The use of the multi-metal composite cerium oxide material as claimed in claim 9 as a demercuration catalyst, wherein: the method is applied to the catalytic oxidation of elemental mercury.
CN202210262231.4A 2022-03-17 2022-03-17 Multi-metal composite cerium oxide material, preparation method thereof and application thereof as mercury removal catalyst Active CN114558587B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210262231.4A CN114558587B (en) 2022-03-17 2022-03-17 Multi-metal composite cerium oxide material, preparation method thereof and application thereof as mercury removal catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210262231.4A CN114558587B (en) 2022-03-17 2022-03-17 Multi-metal composite cerium oxide material, preparation method thereof and application thereof as mercury removal catalyst

Publications (2)

Publication Number Publication Date
CN114558587A true CN114558587A (en) 2022-05-31
CN114558587B CN114558587B (en) 2023-05-30

Family

ID=81719623

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210262231.4A Active CN114558587B (en) 2022-03-17 2022-03-17 Multi-metal composite cerium oxide material, preparation method thereof and application thereof as mercury removal catalyst

Country Status (1)

Country Link
CN (1) CN114558587B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115970670A (en) * 2022-11-30 2023-04-18 中南大学 Carbon-based supported alumina, preparation method thereof and application thereof in degrading CF (carbon fluoride) 4 In (1)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1705637A (en) * 2002-10-17 2005-12-07 巴斯福股份公司 Method for the production of a multi-metal oxide material
CN105080573A (en) * 2015-08-13 2015-11-25 陕西科技大学 Method for preparing SnS/SnO2 nano-photocatalysis composite material through microwave hydrothermal method
CN105289513A (en) * 2015-12-01 2016-02-03 济南大学 Magnetic graphene oxide adsorbent modified by citric acid for removing Hg<2+> ions and preparation method of magnetic graphene oxide adsorbent
US20160243531A1 (en) * 2015-02-24 2016-08-25 California Institute Of Technology Processes for preparing zincoaluminosilicates with aei, cha, and gme topologies and compositions derived therefrom
CN105964266A (en) * 2016-07-08 2016-09-28 南京工程学院 Catalyst for synthesizing nonanal by high-selectivity catalytic oxidation of oleic acid
WO2017216012A1 (en) * 2016-06-13 2017-12-21 Basf Se CATALYST COMPOSITE AND USE THEREOF IN THE SELECTIVE CATALYTIC REDUCTION OF NOx
CN108926911A (en) * 2018-06-26 2018-12-04 清华大学盐城环境工程技术研发中心 A kind of preparation method of denitration demercuration monoblock type filtrate

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1705637A (en) * 2002-10-17 2005-12-07 巴斯福股份公司 Method for the production of a multi-metal oxide material
US20160243531A1 (en) * 2015-02-24 2016-08-25 California Institute Of Technology Processes for preparing zincoaluminosilicates with aei, cha, and gme topologies and compositions derived therefrom
CN105080573A (en) * 2015-08-13 2015-11-25 陕西科技大学 Method for preparing SnS/SnO2 nano-photocatalysis composite material through microwave hydrothermal method
CN105289513A (en) * 2015-12-01 2016-02-03 济南大学 Magnetic graphene oxide adsorbent modified by citric acid for removing Hg<2+> ions and preparation method of magnetic graphene oxide adsorbent
WO2017216012A1 (en) * 2016-06-13 2017-12-21 Basf Se CATALYST COMPOSITE AND USE THEREOF IN THE SELECTIVE CATALYTIC REDUCTION OF NOx
CN105964266A (en) * 2016-07-08 2016-09-28 南京工程学院 Catalyst for synthesizing nonanal by high-selectivity catalytic oxidation of oleic acid
CN108926911A (en) * 2018-06-26 2018-12-04 清华大学盐城环境工程技术研发中心 A kind of preparation method of denitration demercuration monoblock type filtrate

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DONG YE: "Effects of synthesis methods on the physicochemical properties and Hg0 capture capability of MnO2-CeO2 mixed oxides", 《APPLIED SURFACE SCIENCE》 *
HASSAN ALIJANI: "Synthesis of high growth rate SWCNTs and their magnetite cobalt sulfide nanohybrid as super-adsorbent for mercury removal", 《CHEMICAL ENGINEERING RESEARCH AND DESIGN》 *
张志会: "制备方法对MnOx-TiO2吸附剂脱汞性能的影响", 《洁净煤技术》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115970670A (en) * 2022-11-30 2023-04-18 中南大学 Carbon-based supported alumina, preparation method thereof and application thereof in degrading CF (carbon fluoride) 4 In (1)

Also Published As

Publication number Publication date
CN114558587B (en) 2023-05-30

Similar Documents

Publication Publication Date Title
Shan et al. A review on application of cerium-based oxides in gaseous pollutant purification
Bi et al. Research progress on photocatalytic reduction of CO 2 based on LDH materials
CN102574108A (en) Mixed metal oxide catalyst for decomposition of nitrogen oxides
CN112551590B (en) Synthesis of porous manganese dioxide and desulfurization application thereof
CA3132392C (en) Rare-earth-manganese/cerium-zirconium-based composite compound, method for preparing same and use thereof
CN105056955A (en) Oxygen carrier for chemical cycle dry gas reforming, and preparation method and application of oxygen carrier
CN114618503B (en) High-entropy oxide oxygen storage material and preparation method and application thereof
CN113262801A (en) Ce-Mn-based solid solution catalyst and preparation method and application thereof
CN105597769A (en) Preparing method for flake-feature nano-composite metal oxide catalyst CeO2-Co3O4
CN114558587B (en) Multi-metal composite cerium oxide material, preparation method thereof and application thereof as mercury removal catalyst
CN112275290B (en) Copper-based oxygen carrier with lattice oxygen participating in methanol autothermal reforming hydrogen production and preparation and application thereof
Chen et al. In situ deposition of 0D CeO2 quantum dots on Fe2O3-containing solid waste NH3-SCR catalyst: Enhancing redox and NH3 adsorption ability
CN104936692B (en) The ammoxidation catalyst based on the sour yttrium of metal-doped positive cobalt for producing nitric acid
CN107983354B (en) Preparation method of alkali poisoning resistant copper-based spinel low-temperature denitration catalyst
CN115646500B (en) Catalyst for producing hydrogen by ammonia decomposition and preparation method and application thereof
CN115888725B (en) C (C)2+Catalyst for conversion reaction of alkane and carbon dioxide to synthesis gas and preparation thereof
JP2002079101A (en) Catalyst precursor for methanol steam reforming, catalyst for methanol steam reforming and its manufacturing method
CN115999543A (en) Multi-shell structure CO-SCR denitration catalyst and preparation method thereof
CN109647504A (en) A kind of Mn for cement kiln containing tourmaline, Fe, Ce/Cu-SAPO-34 low-temperature denitration catalyst
CN113546636B (en) Catalyst for preparing methylacrolein from isobutene or tertiary butanol and preparation method thereof
CN114870859A (en) Copper-based catalyst for hydrogen production by methanol steam reforming and preparation method thereof
CN114950457B (en) Preparation method of iron-doped cerium vanadate-based solid solution flue gas denitration catalyst
CN112871177B (en) Application of hexaaluminate high-temperature resistant catalytic material in ammonolysis reaction
CN114558566B (en) Hydrogen sulfide selective oxidation catalyst and preparation method and application thereof
CN116832811B (en) Low-crystalline iron-based SCR catalyst and preparation method thereof

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