CN113856693A - MoSnCo catalyst for catalytic oxidation of CO and preparation method thereof - Google Patents

MoSnCo catalyst for catalytic oxidation of CO and preparation method thereof Download PDF

Info

Publication number
CN113856693A
CN113856693A CN202111167935.5A CN202111167935A CN113856693A CN 113856693 A CN113856693 A CN 113856693A CN 202111167935 A CN202111167935 A CN 202111167935A CN 113856693 A CN113856693 A CN 113856693A
Authority
CN
China
Prior art keywords
catalyst
active component
mosnco
catalytic oxidation
temperature
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.)
Withdrawn
Application number
CN202111167935.5A
Other languages
Chinese (zh)
Inventor
李坚
蔡建宇
樊星
于泽辉
赵靖强
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.)
Beijing University of Technology
Original Assignee
Beijing University of Technology
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 Beijing University of Technology filed Critical Beijing University of Technology
Priority to CN202111167935.5A priority Critical patent/CN113856693A/en
Publication of CN113856693A publication Critical patent/CN113856693A/en
Withdrawn legal-status Critical Current

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
    • B01J23/70—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
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8875—Germanium, tin or lead
    • 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
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • 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
    • B01J23/835—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 germanium, tin or lead
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

A MoSnCo catalyst for catalytic oxidation of CO and a preparation method thereof belong to the field of environmental engineering. The invention adopts a coprecipitation method and an impregnation method to prepare the Co3O4、SnO2、MoO2The composite non-noble metal low-temperature CO catalyst takes one or two or more of W, Ce, Cr, Zr, Fe, Ni, V and Ti as an active component. The precipitant is one or more of alkaline solutions such as sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, ammonium bicarbonate, and ammonia water. The invention has simple preparation process and lower price than that of a noble metal catalyst. The catalyst can realize complete CO conversion at about 120 ℃ and 60 DEG CCan achieve the removal effect of more than 95 percent, and has practical application prospect.

Description

MoSnCo catalyst for catalytic oxidation of CO and preparation method thereof
Technical Field
The invention relates to a catalyst for catalytic oxidation of CO and a preparation method thereof, which can be used for removing CO in tail gases of sintering, coking, boilers and the like, simultaneously recovering reaction heat and realizing efficient utilization of resources, and belongs to the field of environmental engineering.
Background
As one of the main atmospheric pollutants, CO is more and more noticed by people, and relevant emission standards of CO are developed in various places. In the CO treatment technology, catalytic oxidation is one of the most effective methods for removing CO, and in the CO catalytic oxidation technology, a catalyst is a key. Therefore, the development of a high-performance CO oxidation catalyst is the key for promoting the application of the CO catalytic oxidation technology.
CN106732601A discloses a cobaltosic oxide nanosheet catalyst for waste gas purification, and preparation and application thereof. CN105268440A discloses a graphene-supported cobalt oxide catalyst and a preparation method thereof, wherein the graphene-supported cobalt oxide catalyst is prepared by taking cobalt acetate and graphene oxide as raw materials and utilizing a precipitation deposition method and a hydrothermal method, and the catalyst can completely convert CO at 100 ℃. CN105233851A discloses a g-C3N4 supported cobalt oxide catalyst and a preparation method thereof, the g-C3N4 supported cobalt oxide catalyst is prepared by taking cobalt acetate and g-C3N4 as raw materials and utilizing a precipitation deposition method and a hydrothermal method, CO can be completely converted by the catalyst at 122 ℃, and the catalytic effect can be maintained at least 2400 min. CN103599698A discloses application of cobalt hydroxide catalyst in catalytic oxidation of carbon monoxide, wherein nano Co (OH)2 is used as a catalyst and applied to CO catalytic oxidation reaction, and the catalytic CO oxidation activity is high. The cobalt hydroxide catalyst has the characteristics of high activity, simple and feasible preparation method, low cost and contribution to large-scale popularization.
The research develops a proper CO catalyst at about 120 ℃ aiming at the sintering flue gas temperature characteristic in the steel industry. The catalyst can realize complete CO conversion at the temperature below 120 ℃ and has obvious heat release.
Disclosure of Invention
Aiming at the temperature characteristic of sintering flue gas in the steel industry at present. The invention provides a MoSnCo catalyst for catalytic oxidation of CO and a preparation method thereof, the catalyst has simple preparation process, is suitable for large-scale production, has excellent catalytic performance, and can realize complete conversion of CO at a temperature below 120 ℃.
The technical scheme of the invention is as follows:
the MoSnCo catalyst for catalytic oxidation of CO is characterized in that Co is used3O4Is a main active component, and is added with a common active component selected from SnO2、MoO2One or two of the components are composite non-noble metal low-temperature CO catalysts which take one or two or more of W, Ce, Cr, Zr, Fe, Ni, V and Ti as auxiliary agents; the catalyst comprises the following components in percentage by weight: main active component content Co3O478-99.9 wt% of common active component SnO2Or/and MoO2The content is 0.1-20 wt%, and the content of the auxiliary agent is 0-2 wt%.
It is further preferred that the co-active component is at least SnO2。
The preparation method adopts a coprecipitation method and an impregnation method which are used together, and the precipitator is one or more than two of alkaline solutions such as sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, ammonium bicarbonate, ammonia water and the like. The preparation method of the MoSnCo catalyst for catalytic oxidation of CO comprises the following steps:
(1) weighing metal salts corresponding to the main active component and the common active component of the catalyst or/and corresponding metal acid substances such as molybdic acid raw materials, and metal salts corresponding to the auxiliary agent or/and corresponding metal acid substances such as titanic acid raw materials;
(2) adding deionized water into part of the raw materials weighed in the step (1) and stirring for dissolving;
(3) putting the solution obtained in the step (2) in a water bath at the temperature of 60-80 ℃, and ultrasonically stirring;
(4) preparing a precipitator, slowly dripping the precipitator into the precursor solution obtained in the step (3), and stopping dripping the precipitator after the precipitation is complete (the pH value is 8-10);
(5) ultrasonically stirring the suspension obtained in the step (4) in a water bath at the temperature of 60-80 ℃ for 2-6 hours;
(6) washing the precipitate obtained in the step (5) to be neutral (pH value is 7) by using a centrifugal or suction filtration mode and the like;
(7) adding water into the paste obtained in the step (6), uniformly stirring, adding an auxiliary agent solution, and ultrasonically stirring for 2-6 hours in a water bath at the temperature of 60-80 ℃;
(8) drying the mixture obtained in the step (7);
(9) roasting the dried catalyst in the step (8) for 1-5 hours at 300-600 ℃ in an air atmosphere;
(10) naturally cooling the catalyst obtained in the step (9), sealing, drying and storing.
The invention has the following advantages:
1. the invention has good CO catalytic performance, and can realize complete conversion of CO at the temperature of below 120 ℃ (especially 60-120 ℃).
2. The catalyst has simple preparation process and is easy for large-scale production and market popularization and application.
Drawings
FIG. 1 is a graph of the CO catalytic performance of the catalysts obtained in examples 1, 2, 3, 4, 5.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
weighing 37g of cobalt acetate, adding 1.8g of stannous chloride and 0.1g of ammonium molybdate, adding deionized water, stirring and dissolving, placing the mixed solution in an ultrasonic cleaning instrument, heating to 75 ℃ in a water bath, and continuing stirring for 30 min. And (3) preparing a sodium carbonate solution, dropwise adding the sodium carbonate solution into the mixed solution, and stopping adding the sodium carbonate solution when the pH value reaches about 10. After stirring for 4 hours, the paste was washed with deionized water to neutrality (pH 7), dried, calcined in a muffle furnace at 400 ℃ for 4 hours, naturally cooled to room temperature, and then sealed and stored, which was designated as sample # 1.
Example 2:
weighing 12g of cobalt acetate, 1.2g of stannous chloride and 0.05g of ammonium molybdate, adding deionized water, stirring and dissolving, placing the mixed solution in an ultrasonic cleaning instrument, heating to 75 ℃ in a water bath, and continuing stirring for 30 min. And (3) preparing a sodium carbonate solution, dropwise adding the sodium carbonate solution into the mixed solution, and stopping adding the sodium carbonate solution when the pH value reaches about 10. After stirring for 3h, the mixture was washed with deionized water to neutral (pH 7), the washed paste was stirred with water, 0.18g of ammonium tungstate was added, and the mixture was stirred at 75 ℃ for 2 h. And drying the uniformly stirred mixture at 110 ℃, roasting the dried mixture in a muffle furnace at 420 ℃ for 3h, naturally cooling the roasted mixture to room temperature, and sealing and storing the cooled mixture to obtain a sample No. 2.
Example 3:
weighing 12g of cobalt acetate, 1.2g of stannous chloride and 0.05g of ammonium molybdate, adding deionized water, stirring and dissolving, placing the mixed solution in an ultrasonic cleaning instrument, heating to 75 ℃ in a water bath, and continuing stirring for 30 min. And (3) preparing a sodium carbonate solution, dropwise adding the sodium carbonate solution into the mixed solution, and stopping adding the sodium carbonate solution when the pH value reaches about 10. After stirring for 3 hours, the mixture was washed with deionized water to neutral (pH 7), the washed paste was stirred with water, 0.27g of ammonium chromate was added, and the mixture was stirred at 75 ℃ for 2 hours. And drying the uniformly stirred mixture at 110 ℃, roasting the dried mixture in a muffle furnace at 400 ℃ for 3h, naturally cooling the roasted mixture to room temperature, and sealing and storing the cooled mixture to obtain a sample No. 3.
Example 4:
weighing 24g of cobalt acetate and 0.24g of stannous chloride, adding deionized water, stirring and dissolving, placing the mixed solution in an ultrasonic cleaning instrument, heating in a water bath to 75 ℃, and continuing stirring for 30 min. And (3) preparing a sodium carbonate solution, dropwise adding the sodium carbonate solution into the mixed solution, and stopping adding the sodium carbonate solution when the pH value reaches about 10. After stirring for 3 hours, the paste was washed with deionized water to neutrality (pH 7), dried, calcined in a muffle furnace at 420 ℃ for 3 hours, naturally cooled to room temperature, and then sealed and stored, which was designated as sample No. 4.
Test example 1:
the CO catalysis experiments were performed using the catalyst # 1 in example 1, the catalyst # 2 in example 2, the catalyst # 3 in example 3, and the catalyst # 4 in example 4, respectively. Testing the components of the smoke: the CO content is 8000ppm, O2Content 16%, N2As balance gas, the space velocity is 30000h-1The CO catalytic efficiency of each catalyst is plotted against temperature in fig. 1. When the temperature of the flue gas reaches 120 ℃, the CO can be completely converted. Wherein the 1# sample and the 4# sample can achieve more than 95% of removal effect at 60 ℃.

Claims (5)

1. The MoSnCo catalyst for catalytic oxidation of CO is characterized in that Co is used3O4Is a main active component, and is added with a common active component selected from SnO2、MoO2One or two of the components are composite non-noble metal low-temperature CO catalysts which take one or two or more of W, Ce, Cr, Zr, Fe, Ni, V and Ti as auxiliary agents; the catalyst comprises the following components in percentage by weight: main active component content Co3O478-99.9 wt% of common active component SnO2Or/and MoO2The content is 0.1-20 wt%, and the content of the auxiliary agent is 0-2 wt%.
2. MoSnCo catalyst for the catalytic oxidation of CO according to claim 1, characterised in that the CO-active component is at least SnO2。
3. Method for preparing a MoSnCo catalyst for the catalytic oxidation of CO according to claim 1 or 2, characterized in that it comprises the following steps:
(1) weighing metal salts corresponding to the main active component and the common active component of the catalyst or/and corresponding metal acid substances such as molybdic acid raw materials, and metal salts corresponding to the auxiliary agent or/and corresponding metal acid substances such as titanic acid raw materials;
(2) adding deionized water into part of the raw materials weighed in the step (1) and stirring for dissolving;
(3) putting the solution obtained in the step (2) in a water bath at the temperature of 60-80 ℃, and ultrasonically stirring;
(4) preparing a precipitator, slowly dripping the precipitator into the precursor solution obtained in the step (3), and stopping dripping the precipitator after the precipitation is completed;
(5) ultrasonically stirring the suspension obtained in the step (4) in a water bath at the temperature of 60-80 ℃ for 2-6 hours;
(6) washing the precipitate obtained in the step (5) to be neutral (pH value is 7) by using a centrifugal or suction filtration mode and the like;
(7) adding water into the paste obtained in the step (6), uniformly stirring, adding an auxiliary agent solution, and ultrasonically stirring for 2-6 hours in a water bath at the temperature of 60-80 ℃;
(8) drying the mixture obtained in the step (7);
(9) roasting the dried catalyst in the step (8) for 1-5 hours at 300-600 ℃ in an air atmosphere;
(10) naturally cooling the catalyst obtained in the step (9), sealing, drying and storing.
4. Use of a MoSnCo catalyst according to claim 1 or 2 for the catalytic oxidation of CO at temperatures below 120 ℃ for complete oxidative conversion of CO.
5. Use according to claim 4 for the complete oxidative conversion of CO in the window of 60-120 ℃.
CN202111167935.5A 2021-09-29 2021-09-29 MoSnCo catalyst for catalytic oxidation of CO and preparation method thereof Withdrawn CN113856693A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111167935.5A CN113856693A (en) 2021-09-29 2021-09-29 MoSnCo catalyst for catalytic oxidation of CO and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111167935.5A CN113856693A (en) 2021-09-29 2021-09-29 MoSnCo catalyst for catalytic oxidation of CO and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113856693A true CN113856693A (en) 2021-12-31

Family

ID=79001729

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111167935.5A Withdrawn CN113856693A (en) 2021-09-29 2021-09-29 MoSnCo catalyst for catalytic oxidation of CO and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113856693A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1660491A (en) * 2004-02-26 2005-08-31 中国科学院大连化学物理研究所 Catalyst of composite oxides of copper and manganese and application
CN101143321A (en) * 2006-09-15 2008-03-19 中国人民解放军63971部队 Low-temperature CO oxidation non-noble metal catalyst
CN102059127A (en) * 2010-11-09 2011-05-18 华东理工大学 Catalyst for CO normal temperature catalytic oxidation and preparation method thereof
US20150375207A1 (en) * 2013-02-14 2015-12-31 Haldor Topsoe A/S Method and catalyst for the simultaneous removal of carbon monoxide and nitrogen oxides from flue or exhaust gas
CN106807392A (en) * 2017-03-07 2017-06-09 北京工业大学 A kind of MoCeCoO for low temperature CO catalysisXThe preparation and application of catalyst
CN113117693A (en) * 2021-04-13 2021-07-16 浙江工业大学 Pd-Cu/TiO for catalytic oxidation of CO2Bimetallic catalyst and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1660491A (en) * 2004-02-26 2005-08-31 中国科学院大连化学物理研究所 Catalyst of composite oxides of copper and manganese and application
CN101143321A (en) * 2006-09-15 2008-03-19 中国人民解放军63971部队 Low-temperature CO oxidation non-noble metal catalyst
CN102059127A (en) * 2010-11-09 2011-05-18 华东理工大学 Catalyst for CO normal temperature catalytic oxidation and preparation method thereof
US20150375207A1 (en) * 2013-02-14 2015-12-31 Haldor Topsoe A/S Method and catalyst for the simultaneous removal of carbon monoxide and nitrogen oxides from flue or exhaust gas
CN106807392A (en) * 2017-03-07 2017-06-09 北京工业大学 A kind of MoCeCoO for low temperature CO catalysisXThe preparation and application of catalyst
CN113117693A (en) * 2021-04-13 2021-07-16 浙江工业大学 Pd-Cu/TiO for catalytic oxidation of CO2Bimetallic catalyst and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DANTING LU ET AL. *

Similar Documents

Publication Publication Date Title
WO2021088277A1 (en) Hydrogenated tio2 denitration catalyst, preparation method therefor and application thereof
CN110102290B (en) K-doped alpha-MnO2/Mn3O4High-efficiency photo-thermal catalyst, preparation method and application
CN102500358B (en) Denitration catalyst with excellent alkali metal and alkaline-earth metal poisoning resistance
CN108940304A (en) A kind of Mn/Ce/Cu base low-temperature plasma body catalyst and preparation and application
CN107983338B (en) Method for improving catalytic performance of perovskite type composite metal oxide
CN110947394A (en) ZIF-67-Mn/Co-based low-temperature NO oxidation catalyst, and preparation method and application thereof
CN114768794B (en) Composite manganese oxide catalyst for synchronously removing VOCs and NOx in medium-low temperature flue gas, and preparation method and application thereof
CN106345523A (en) Low-temperature denitrification catalyst based on carbonized MOFs (metal organic frameworks) and preparation method thereof
CN105797714B (en) A kind of manganese titanium composite oxide low-temperature denitration catalyst and preparation method thereof that holmium is modified
CN110372875A (en) A kind of application of the more metal-organic framework materials of heteronuclear and preparation and denitration demercuration
CN107282068A (en) Pillared layered manganese oxide catalyst of Cu oxide and preparation method and application
WO2022233340A1 (en) Vocs combustion catalyst prepared from recycled waste ternary lithium-ion batteries, and preparation method therefor
CN107008327A (en) A kind of low temperature sulfuric-resisting hydrogen ammonium SCR denitration and its preparation method and application
CN112337460A (en) Method for preparing Mn-based spinel low-temperature denitration catalyst by using complex acid solution
CN106669672B (en) Activated carbon catalyst for sulfur dioxide recovery and preparation method thereof
CN108940302A (en) A kind of O composite metallic oxide catalyst and its preparation method and application
CN113751024B (en) Catalyst for catalytic oxidation of CO and preparation method thereof
CN113877638B (en) Preparation method for preparing denitration and dioxin removal VOCs integrated catalyst by fractional precipitation method and prepared catalyst
CN113856693A (en) MoSnCo catalyst for catalytic oxidation of CO and preparation method thereof
CN103007980A (en) Metal doped type visible light denitrification photocatalyst and preparation method and application thereof
CN108262049B (en) Modified low-temperature SCO denitration catalyst and preparation method thereof
CN114849789B (en) Preparation method and application of MIL-125 supported 1T-phase molybdenum sulfide composite photocatalyst
CN115245820A (en) Spinel catalyst, preparation method and application thereof
CN110975873B (en) Simultaneously removing NO in sintering flue gasxCO-and-carbon-based catalyst, and preparation method and application thereof
CN114160161A (en) Pt-Fe bimetallic catalyst for CO and NO oxidation and preparation method and application 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
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20211231