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CN114054040A - High-efficiency CO oxidation catalyst meeting high space velocity - Google Patents

High-efficiency CO oxidation catalyst meeting high space velocity Download PDF

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Publication number
CN114054040A
CN114054040A CN202010785515.2A CN202010785515A CN114054040A CN 114054040 A CN114054040 A CN 114054040A CN 202010785515 A CN202010785515 A CN 202010785515A CN 114054040 A CN114054040 A CN 114054040A
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weight
parts
space velocity
catalyst
nitrate solution
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CN202010785515.2A
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毛忠辉
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Ecocat Catalyst Danyang Co ltd
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Ecocat Catalyst Danyang Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00—Specific waste
    • F23G2209/14—Gaseous waste or fumes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a high-efficiency CO oxidation catalyst meeting the requirement of high airspeed, which is used for coating a metal or ceramic honeycomb carrier and comprises coating slurry mixed with 30% of metal powder matrix and 70% of noble metal solution; the metal powder matrix comprises 6 parts by weight of alumina, 8 parts by weight of cerium-modified alumina, 2 parts by weight of copper oxide, 2 parts by weight of zirconia, 3 parts by weight of titania, and 20 parts by weight of alkaline earth; the noble metal solution has an active precursor with the thickness of 2 nm-3 nm, wherein the active precursor contains Pt and Pd, and the ratio of the Pt to the Pd is 2: 1. According to the invention, the catalyst coating slurry is mixed by the active precursor of 2-3 nm and the metal powder matrix, so that the trouble of poor CO oxidation catalytic activity of the conventional catalyst at high airspeed is avoided.

Description

High-efficiency CO oxidation catalyst meeting high space velocity
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a high-efficiency CO oxidation catalyst meeting the requirement of high space velocity.
Background
Due to the continuous development of transportation business, industrial and mining enterprises of all countries in the world, the consumption of fuels such as coal, petroleum and the like is continuously increased, and the emission of carbon monoxide is increased. CO is colorless and odorless gas, is formed by incomplete and insufficient combustion of fuel, is toxic gas capable of suffocating people, and has an affinity 200 times stronger than oxygen with hemoglobin with oxygen delivery capacity in blood, so that after a human body inhales CO, the oxygen delivery capacity of the blood is greatly reduced, important organs of the heart, brain and the like of the human body are seriously anoxic, and light people have dizziness and nausea according to different concentrations and time of the CO inhaled by the human body. Headache, etc., and even serious ones, they may have difficulty in moving and coma until death. The CO treatment mainly comprises two modes of recovery and destruction. Here, the catalytic combustion is to completely oxidize carbon monoxide in the exhaust gas into a non-polluting substance such as carbon dioxide with the cooperation of a catalyst. The catalytic combustion method has the characteristics of good safety, low combustion temperature, low requirements on the concentration and heat value of combustible components of CO, and the like, and is an effective method for purifying waste gas (CO is a main component). However, conventional catalytic combustion is biased toward low space velocity (within 80000 h-1), and relatively few reports have been made on the development of carbon monoxide treated catalysts at high space velocity.
The technical development and application of metal oxide to mesoporous coating of ultra-small platinum group metal nanoparticles. The traditional technical process of dipping platinum metal salt solution by metal oxide and high-temperature roasting is changed, the platinum nano particles with uniform size and ultra-small size (average particle size is less than 2-3 nm) are prepared by reduction and template agent protection preparation process, the in-situ loading of Al2O 3-based oxides and the like on the surface of the platinum group metal nano particles with ultra-small size is realized, the problem that noble metal catalyst particles are easy to coarsen is effectively solved, and the service life of the catalyst reaches or is superior to that of similar products in the market.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a high-efficiency CO oxidation catalyst meeting the requirement at a high airspeed, and the trouble of poor CO oxidation catalytic activity of the conventional catalyst at the high airspeed is avoided by mixing a catalyst coating slurry with an active precursor of 2 nm-3 nm and a metal powder substrate.
In order to solve the technical problem, the invention discloses a high-efficiency CO oxidation catalyst meeting the requirement at high airspeed, which is used for coating a metal or ceramic honeycomb carrier and comprises coating slurry mixed with 30% of metal powder matrix and 70% of noble metal solution; the metal powder matrix comprises 6 parts by weight of alumina, 8 parts by weight of cerium-modified alumina, 2 parts by weight of copper oxide, 2 parts by weight of zirconia, 3 parts by weight of titania, and 20 parts by weight of alkaline earth; the noble metal solution has an active precursor with the thickness of 2 nm-3 nm, wherein the active precursor contains Pt and Pd, and the ratio of the Pt to the Pd is 2: 1.
According to an embodiment of the present invention, the noble metal solution further comprises 20% of copper salt, 10% of manganese salt, 11% of tin salt, and 100ml of precipitant.
According to an embodiment of the present invention, the precipitating agent is ammonia.
According to an embodiment of the present invention, the noble metal solution is a mixture of a platinum nitrate solution and a palladium nitrate solution, wherein the mixing ratio is 2:1, the platinum nitrate solution is prepared by dissolving 4g of triacetic acid and 5g of PVP in 2L of distilled water, adding a platinum nitrate solution with a concentration of 11% and a weight of 15 g, and adjusting the pH value to 7-10 with ammonia water; the palladium nitrate solution was prepared by adding 2g of copper salt, 1g of manganese salt and 1.1g of tin salt to 2L of distilled water, dissolving them sufficiently, and adding 11% by weight of 7.5 g of palladium nitrate solution.
According to an embodiment of the present invention, 80g of the metal powder substrate is weighed, and 100g of deionized water is added to mix uniformly and poured into the noble metal solution.
According to an embodiment of the present invention, the ionic suspension of the noble metal is obtained by ultrasonic dispersion during the mixing of the platinum nitrate solution and the palladium nitrate solution.
Compared with the prior art, the invention can obtain the following technical effects:
the catalyst coating slurry is mixed by the active precursor with the particle size of 2 nm-3 nm and the metal powder matrix, so that the trouble of poor CO oxidation catalytic activity of the conventional catalyst at high space velocity is avoided.
Of course, it is not necessary for any one product in which the invention is practiced to achieve all of the above-described technical effects simultaneously.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a graph of a nanoparticle distribution for a high efficiency CO oxidation catalyst meeting high space velocity for an embodiment of the present invention;
FIG. 2 is a graph showing the reaction effect of different precursors of a high-efficiency CO oxidation catalyst satisfying a high space velocity at a space velocity of 80000h < -1 > according to an embodiment of the present invention;
FIG. 3 is a graph showing the reaction effect of different precursors of the high efficiency CO oxidation catalyst satisfying high space velocity at 160000 h-1.
Detailed Description
The embodiments of the present invention will be described in detail with reference to the accompanying drawings and examples, so that how to implement the technical means for solving the technical problems and achieving the technical effects of the present invention can be fully understood and implemented.
Referring to fig. 1 to 3 together, fig. 1 is a distribution diagram of nanoparticles of a high efficiency CO oxidation catalyst satisfying high space velocity according to an embodiment of the present invention; FIG. 2 is a graph showing the reaction effect of different precursors of a high-efficiency CO oxidation catalyst satisfying a high space velocity at a space velocity of 80000h < -1 > according to an embodiment of the present invention; FIG. 3 is a graph showing the reaction effect of different precursors of the high efficiency CO oxidation catalyst satisfying high space velocity at 160000 h-1. As shown in the figure, the high-efficiency CO oxidation catalyst meeting the high space velocity is used for coating a metal or ceramic honeycomb carrier and comprises coating slurry mixed with 30% of metal powder matrix and 70% of noble metal solution.
Specifically, the metal powder matrix contains 6 parts by weight of alumina, 8 parts by weight of cerium-modified alumina, 2 parts by weight of copper oxide, 2 parts by weight of zirconia, 3 parts by weight of titania, and 20 parts by weight of alkaline earth; the noble metal solution has an active precursor with the thickness of 2 nm-3 nm, wherein the active precursor contains Pt and Pd, and the ratio of the Pt to the Pd is 2: 1. In the embodiment of the invention, the alumina, the cerium modified alumina, the copper oxide, the zirconium oxide and the titanium oxide are metal oxides, and when the metal oxides are mixed and configured, the metal oxides need to be subjected to ball milling by a ball mill or a sand mill, the degree of the metal oxides is ensured to be between 3 and 6 mu m, the metal oxides are uniformly stirred, and the viscosity is controlled to be in a range suitable for coating, preferably between 50 and 150 cp. The alkaline earth contains various metal oxides, which can further improve the activity of the catalyst in the oxidation catalytic reaction.
The noble metal solution also comprises 20% of copper salt, 10% of manganese salt, 11% of tin salt and 100ml of precipitator.
Preferably, the precipitator is ammonia water for adjust the pH value in the noble metal solution, guarantee that the pH value can reach 6~10, borrow this to improve the activity.
The noble metal solution is formed by mixing a platinum nitrate solution and a palladium nitrate solution, and the mixing ratio is 2:1, so that high catalytic oxidation activity on CO is realized.
The platinum nitrate solution is prepared by fully dissolving 4g of triacetic acid and 5g of PVP in 2L of distilled water, adding 11% platinum nitrate solution with the weight of 15 g, and adjusting the pH value to about 7-10 by using ammonia water.
The palladium nitrate solution was prepared by adding 2g of copper salt, 1g of manganese salt and 1.1g of tin salt to 2L of distilled water, dissolving them sufficiently, and adding 11% by weight of 7.5 g of palladium nitrate solution. Wherein, the copper salt is one of copper nitrate and copper chloride sulfate; the manganese salt is manganese nitrate; the tin salt is one of stannic chloride, stannous chloride, sodium stannate and potassium stannate; the tin oxide modified copper-manganese composite oxide is beneficial to the increase and stability of the specific surface area of the catalyst.
It is worth mentioning that the precious metal ion suspension is obtained by ultrasonic dispersion in the mixing process of the platinum nitrate solution and the palladium nitrate solution, and the precious metal ion suspension is fully precipitated, so that the subsequent waste is conveniently discharged and effectively filtered.
When mixing the noble metal solution and the metal powder substrate, preferably 80g of the metal powder substrate is weighed, 100g of deionized water is added, mixed uniformly and poured into the noble metal solution.
Referring to fig. 2 and 3, it can be seen that the catalyst prepared by the present invention has better catalytic activity, especially better CO oxidation performance under high space velocity condition than the catalyst prepared by the conventional method, and is suitable for being used as the main component of the catalyst coating for catalytic combustion of carbon monoxide in industrial exhaust gas.
The foregoing description shows and describes several preferred embodiments of the invention, but as aforementioned, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (6)

1. A high-efficiency CO oxidation catalyst meeting the high space velocity is used for coating a metal or ceramic honeycomb carrier and is characterized by comprising coating slurry mixed with 30 percent of metal powder matrix and 70 percent of noble metal solution;
the metal powder matrix comprises 6 parts by weight of alumina, 8 parts by weight of cerium-modified alumina, 2 parts by weight of copper oxide, 2 parts by weight of zirconia, 3 parts by weight of titania, and 20 parts by weight of alkaline earth;
the noble metal solution is provided with an active precursor with the thickness of 2 nm-3 nm, wherein the active precursor contains Pt and Pd, and the ratio of the Pt to the Pd is 2: 1.
2. The catalyst for high efficiency CO oxidation at high space velocity according to claim 1, wherein the noble metal solution further comprises 20% copper salt, 10% manganese salt, 11% tin salt, and 100ml of precipitant.
3. The catalyst for high efficiency CO oxidation at high space velocity of claim 2 wherein the precipitant is ammonia.
4. The catalyst for efficient CO oxidation at high space velocity according to claim 1, wherein the noble metal solution is prepared by mixing a platinum nitrate solution and a palladium nitrate solution at a mixing ratio of 2:1, wherein the platinum nitrate solution is prepared by fully dissolving 4g of triacetic acid and 5g of PVP in 2L of distilled water, adding a platinum nitrate solution with a concentration of 11% and a weight of 15 g, and adjusting the pH value to 7-10 by using ammonia water; the palladium nitrate solution is prepared by weighing 2g of copper salt, 1g of manganese salt and 1.1g of tin salt, adding into 2L of distilled water, fully dissolving, and adding 7.5 g of palladium nitrate solution with the concentration of 11%.
5. The catalyst for high efficiency CO oxidation at high space velocity as claimed in claim 1, wherein the metal powder base is prepared by weighing 80g of the metal powder base, adding 100g of deionized water, mixing uniformly, and pouring into the noble metal solution.
6. The catalyst for high efficiency CO oxidation at high space velocity according to claim 4 wherein the ionic suspension of noble metal is obtained by ultrasonic dispersion during the mixing of the platinum nitrate solution and the palladium nitrate solution.
CN202010785515.2A 2020-08-05 2020-08-05 High-efficiency CO oxidation catalyst meeting high space velocity Pending CN114054040A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116237060A (en) * 2023-03-27 2023-06-09 吉林大学 Wide-temperature sulfur-resistant CO oxidation catalyst and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116237060A (en) * 2023-03-27 2023-06-09 吉林大学 Wide-temperature sulfur-resistant CO oxidation catalyst and preparation method and application thereof
CN116237060B (en) * 2023-03-27 2024-08-20 吉林大学 Wide-temperature sulfur-resistant CO oxidation catalyst and preparation method and application thereof

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