CN105032404A - Calcination-free MnO2/CNTs low-temperature denitration catalyst and preparation method thereof - Google Patents
Calcination-free MnO2/CNTs low-temperature denitration catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN105032404A CN105032404A CN201510450777.2A CN201510450777A CN105032404A CN 105032404 A CN105032404 A CN 105032404A CN 201510450777 A CN201510450777 A CN 201510450777A CN 105032404 A CN105032404 A CN 105032404A
- Authority
- CN
- China
- Prior art keywords
- low
- cnts
- catalyst
- preparation
- temperature denitration
- 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.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a calcination-free MnO2/CNTs low-temperature denitration catalyst and a preparation method thereof. The calcination-free MnO2/CNTs low-temperature denitration catalyst is composed of a carrier carbon nano tube and a single active component MnO2; through a low-temperature co-precipitation method, manganese dioxide is generated through redox reaction of potassium permanganate and hydrogen peroxide and precipitated on the carbon nano tube, so that the calcination-free MnO2/CNTs low-temperature denitration catalyst is prepared without a calcination process. MnO2 is used as a main single active component, and an auxiliary catalyst is not required to be used, so that higher catalytic performance at the low temperature is realized. The catalyst has the advantages that excellent activity at the low temperature (80-180 DEG C) is realized, the preparation process is simple and calcination is not required.
Description
Technical field
The invention belongs to field of catalyst preparation, be specifically related to one and exempt from calcinated type MnO
2/ CNTs low-temperature denitration catalyst and preparation method thereof.
Background technology
The NO of coal burning and motor vehicle emission
xa kind of common atmosphere pollution, severe contamination environment.Each state has all formulated strict NO
xdischarge standard.The denitration technology of flue gas and tail gas also becomes the emphasis of people's research.Wherein, ammonia Selective Catalytic Reduction of NO (NH
3-SCR) be a kind of maturation and effective tail gas denitration technology.
The method, when not using catalyst, needs could effectively carry out under the condition of 800 DEG C.At present, the use of business-like vanadium titanium catalyst system has made the effective running temperature window of denitration be down to 350-400 DEG C, but after flue gas desulfurization and electrostatic dust collection equipment, the temperature of tail gas is usually less than 200 DEG C.Moreover the preparation process of existing denitrating catalyst mainly comprises: high-temperature calcination and high pressure hydro-thermal.Certain deficiency is there is in these class methods in security and operability.Therefore, the emphasis of present stage research is exploitation low temperature (<200 DEG C) excellent catalytic effect and the simple NH of preparation technology
3-SCR catalyst.Mn oxide active constituent is loaded on carrier carbon nanotube by low temperature liquid polymerization process by the present invention, obtains the simple and MnO that low temperature active is excellent of technique
2/ CNTs catalyst.
Summary of the invention
The object of the invention is to problem that is not high in low-temperature region activity for existing denitrating catalyst and preparation method's complexity, provide one to exempt from calcinated type MnO
2/ CNTs low-temperature denitration catalyst and preparation method thereof.It is simple and without the need to advantages such as calcinings that this catalyst has low temperature (80 ~ 180 DEG C) superior activity, preparation technology.
For achieving the above object, the present invention adopts following technical scheme:
One exempts from calcinated type MnO
2the preparation method of/CNTs low-temperature denitration catalyst, comprises the following steps:
1) with red fuming nitric acid (RFNA) process CNT 4h, the CNT of functionalization is obtained;
2) CNT that step 1) is obtained is added in liquor potassic permanganate, stirs 10h;
3) by H
2o
2dropwise is added to step 2) in the mixed solution that obtains, be warming up to 40 DEG C, stir 14h, filter, washing, 105 DEG C of oven dry obtain MnO
2/ CNTs catalyst;
Red fuming nitric acid (RFNA) concentration described in step 1) is 65 ~ 68wt%;
The caliber of the CNT described in step 1) is 60 ~ 100nm;
Step 2) described in liquor potassic permanganate concentration be 0.02mol/L, the consumption of potassium permanganate and CNT is that 2 ~ 6:100 calculates according to Mn/C mol ratio;
H in step 3)
2o
2the concentration of solution is 30wt%;
What a kind of preparation method as above obtained exempts from calcinated type MnO
2the application of/CNTs low-temperature denitration catalyst, for 80 ~ 180 DEG C of low-temperature denitration of flue gas.
Remarkable advantage of the present invention is:
(1) active component of catalyst loads on CNT by low-temperature co-precipitation method by the present invention, facilitates the dispersion of active component, adds avtive spot; And can obtain without the need to calcining in preparation process, greatly simplify preparation technology, improve the security of preparation process;
(2) MnO
2as the main single-activity composition of catalyst, without the need to using co-catalyst, there is higher catalytic performance at low temperatures; And CNT has the tunnel conduction characteristic of the large π key of high specific area, chemical inertness and delocalization, material catalytic performance at low temperatures can be improved, 80 ~ 180 DEG C of superior activity.
Accompanying drawing explanation
Fig. 1 is catalyst prepared by the present invention, as MnO in catalyst
2when the content of active component is different, it is to the conversion ratio variation diagram of NO;
Fig. 2 is the XRD collection of illustrative plates of catalyst prepared by the present invention: the CNTs that (a) nitric acid treatment is crossed; (b) 2%MnO
2/ CNTs; (c) 4%MnO
2/ CNTs; (d) 6%MnO
2/ CNTs; (e) MnO
x/ CNTs;
Fig. 3 is the SEM collection of illustrative plates of catalyst prepared by the present invention: (A) acid-treated CNTs; (B) 4%MnO
2/ CNTs and (C) Mn; (D) C; (E) distribution diagram of element of O;
Fig. 4 is the TEM collection of illustrative plates of catalyst prepared by the present invention: (A) 4%MnO
2/ CNTs; (B) MnO
x/ CNTs; (C) the EDS spectrogram of red circle in figure A;
Fig. 5 is the XPS collection of illustrative plates of catalyst prepared by the present invention: (A) composes entirely; (B) Mn2p; (C) O1s.
Detailed description of the invention
The present invention's the following example further illustrates the present invention, but protection scope of the present invention is not limited to the following example.
embodiment 1
1) process CNT 6h with nitric acid (65wt.%), post processing obtains the CNT of functionalization;
2) CNT that 0.3g step 1) obtains is added to 25mL, in 0.02mol/L liquor potassic permanganate, stirs 10h; Wherein the consumption of potassium permanganate calculates according to mol ratio=2% of Mn/C;
3) by 0.14mL30wt%H
2o
2dropwise is added to step 2) in the mixed solution that obtains, be warming up to 40 DEG C, stir 14h, filter, washing, 105 DEG C of oven dry obtain 2%MnO
2/ CNTs catalyst;
The catalyst that the present embodiment is obtained carries out denitration efficiency test:
Test condition is: [NO]=[NH
3]=400ppm, [O
2]=5%, N
2for Balance Air, air speed is WHSV=108000mlg
cat -1h
-1, 0.2g catalyst;
Result is: the denitration efficiency of 80 DEG C is that the denitration efficiency of 41.8%, 180 DEG C is greater than 86%.
embodiment 2
1) process CNT 6h with nitric acid (68wt.%), post processing obtains the CNT of functionalization;
2) CNT that 0.3g step 1) obtains is added to 50mL, in 0.02mol/L liquor potassic permanganate, stirs 10h; Wherein the consumption of potassium permanganate calculates according to mol ratio=4% of Mn/C;
3) by the H of 0.28mL30wt%
2o
2dropwise is added to step 2) in the mixed solution that obtains, be warming up to 40 DEG C, stir 14h, filter, washing, 105 DEG C of oven dry obtain 4%MnO
2/ CNTs catalyst;
The catalyst that the present embodiment is obtained carries out denitration efficiency test:
Test condition is: [NO]=[NH
3]=400ppm, [O
2]=5%, N
2for Balance Air, air speed is WHSV=108000mlg
cat -1h
-1, 0.2g catalyst;
Result is: the denitration efficiency of 80 DEG C is that the denitration efficiency of 51.8%, 180 DEG C is greater than 89%.
embodiment 3
1) process CNT 6h with nitric acid (66wt.%), post processing obtains the CNT of functionalization;
2) CNT that 0.3g step 1) obtains is added to 75mL, in 0.02mol/L liquor potassic permanganate, stirs 10h; Wherein the consumption of potassium permanganate calculates according to mol ratio=6% of Mn/C;
3) by the H of 0.42mL30wt%
2o
2dropwise is added to step 2) in the mixed solution that obtains, be warming up to 40 DEG C, stir 14h, filter, washing, 105 DEG C of oven dry obtain 6%MnO
2/ CNTs catalyst;
The catalyst that the present embodiment is obtained carries out denitration efficiency test condition:
Test condition is: [NO]=[NH
3]=400ppm, [O
2]=5%, N
2for Balance Air, air speed is WHSV=108000mlg
cat -1h
-1, 0.2g catalyst;
Result is: the denitration efficiency of 80 DEG C is that the denitration efficiency of 36.2%, 180 DEG C is greater than 78%.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. exempt from calcinated type MnO for one kind
2the preparation method of/CNTs low-temperature denitration catalyst, is characterized in that: comprise the following steps:
1) with red fuming nitric acid (RFNA) process CNT 4h, the CNT of functionalization is obtained;
2) CNT that step 1) is obtained is added in liquor potassic permanganate, stirs 10h;
3) by H
2o
2dropwise is added to step 2) in the mixed solution that obtains, be warming up to 40 DEG C, stir 14h, filter, washing, 105 DEG C of oven dry obtain MnO
2/ CNTs catalyst.
2. according to claim 1ly exempt from calcinated type MnO
2the preparation method of/CNTs low-temperature denitration catalyst, is characterized in that: the caliber of the CNT described in step 1) is 60 ~ 100nm.
3. according to claim 1ly exempt from calcinated type MnO
2the preparation method of/CNTs low-temperature denitration catalyst, is characterized in that: step 2) described in liquor potassic permanganate concentration be 0.02mol/L, the consumption of potassium permanganate and CNT is that 2 ~ 6:100 calculates according to Mn/C mol ratio.
4. according to claim 1ly exempt from calcinated type MnO
2the preparation method of/CNTs low-temperature denitration catalyst, is characterized in that: H in step 3)
2o
2the concentration of solution is 30wt%.
5. what a preparation method as claimed in claim 1 obtained exempts from calcinated type MnO
2the application of/CNTs low-temperature denitration catalyst, is characterized in that: described catalyst is used for 80 ~ 180 DEG C of low-temperature denitration of flue gas.
6. according to claim 5ly exempt from calcinated type MnO
2the application of/CNTs low-temperature denitration catalyst, is characterized in that: described catalyst is used for 80 DEG C of low-temperature denitration of flue gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510450777.2A CN105032404A (en) | 2015-07-28 | 2015-07-28 | Calcination-free MnO2/CNTs low-temperature denitration catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510450777.2A CN105032404A (en) | 2015-07-28 | 2015-07-28 | Calcination-free MnO2/CNTs low-temperature denitration catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105032404A true CN105032404A (en) | 2015-11-11 |
Family
ID=54439720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510450777.2A Pending CN105032404A (en) | 2015-07-28 | 2015-07-28 | Calcination-free MnO2/CNTs low-temperature denitration catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105032404A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289640A (en) * | 2015-10-27 | 2016-02-03 | 福州大学 | Ternary Mn-Cu-FeOx/CNTs denitration catalyst and preparation |
| CN105854785A (en) * | 2016-04-21 | 2016-08-17 | 南京大学 | Method for adsorption-removing lead pollution in water body by utilizing magnetic loading manganese dioxide composite material |
| CN105854802A (en) * | 2016-05-17 | 2016-08-17 | 遵义师范学院 | Cadmium-containing sewage treatment nano-composite material and preparing method thereof |
| CN106495227A (en) * | 2016-11-23 | 2017-03-15 | 黑龙江工程学院 | A kind of preparation method of oil-soluble dispersed nano manganese dioxide powder |
| CN106881080A (en) * | 2017-01-11 | 2017-06-23 | 重庆大学 | A kind of preparation method of nano bar-shape cerium manganese composite catalyst |
| CN109158111A (en) * | 2018-10-03 | 2019-01-08 | 佛山霖诺环保科技有限公司 | A kind of preparation method of nano carbon-base Supported Manganese cobalt dual-metal formaldehyde catalyst |
| CN110368900A (en) * | 2019-08-20 | 2019-10-25 | 厦门理工学院 | A kind of bamboo charcoal modified material and its preparation method and application |
| CN111610071A (en) * | 2020-04-28 | 2020-09-01 | 重庆大学 | Method for characterizing strength of denitration catalyst carrier titanium dioxide powder |
| CN112604694A (en) * | 2020-12-16 | 2021-04-06 | 辽宁科技大学 | Novel low-temperature water-resistant sulfur-resistant NH taking low-cost fly ash as carrier3-SCR catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071484A (en) * | 2013-01-10 | 2013-05-01 | 上海大学 | Preparation method of manganese dioxide nanosheet/CNT (carbon nano tube) denitration catalyst with core-shell structure |
| CN103896260A (en) * | 2012-12-28 | 2014-07-02 | 新昌县冠阳技术开发有限公司 | Preparation method of graphene based lithium ion battery composite negative electrode material |
-
2015
- 2015-07-28 CN CN201510450777.2A patent/CN105032404A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896260A (en) * | 2012-12-28 | 2014-07-02 | 新昌县冠阳技术开发有限公司 | Preparation method of graphene based lithium ion battery composite negative electrode material |
| CN103071484A (en) * | 2013-01-10 | 2013-05-01 | 上海大学 | Preparation method of manganese dioxide nanosheet/CNT (carbon nano tube) denitration catalyst with core-shell structure |
Non-Patent Citations (2)
| Title |
|---|
| MENG XU ET AL.: "Removal of Pb(II) from aqueous solution by hydrous manganese dioxide:Adsorption behavior and mechanism", 《JOURNAL OF ENVIRONMENTAL SCIENCES》 * |
| YANBING ZHANG ET AL.: "Preparation of Mn-FeOx/CNT catalysts by redox co-precipitation and application in low temperature NO reduction with NH3", 《CATALYSIS COMMUNICATIONS》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289640A (en) * | 2015-10-27 | 2016-02-03 | 福州大学 | Ternary Mn-Cu-FeOx/CNTs denitration catalyst and preparation |
| CN105854785A (en) * | 2016-04-21 | 2016-08-17 | 南京大学 | Method for adsorption-removing lead pollution in water body by utilizing magnetic loading manganese dioxide composite material |
| CN105854802A (en) * | 2016-05-17 | 2016-08-17 | 遵义师范学院 | Cadmium-containing sewage treatment nano-composite material and preparing method thereof |
| CN106495227A (en) * | 2016-11-23 | 2017-03-15 | 黑龙江工程学院 | A kind of preparation method of oil-soluble dispersed nano manganese dioxide powder |
| CN106495227B (en) * | 2016-11-23 | 2018-01-19 | 黑龙江工程学院 | A kind of preparation method of oil-soluble dispersed nano manganese dioxide powder |
| CN106881080A (en) * | 2017-01-11 | 2017-06-23 | 重庆大学 | A kind of preparation method of nano bar-shape cerium manganese composite catalyst |
| CN109158111A (en) * | 2018-10-03 | 2019-01-08 | 佛山霖诺环保科技有限公司 | A kind of preparation method of nano carbon-base Supported Manganese cobalt dual-metal formaldehyde catalyst |
| CN110368900A (en) * | 2019-08-20 | 2019-10-25 | 厦门理工学院 | A kind of bamboo charcoal modified material and its preparation method and application |
| CN111610071A (en) * | 2020-04-28 | 2020-09-01 | 重庆大学 | Method for characterizing strength of denitration catalyst carrier titanium dioxide powder |
| CN112604694A (en) * | 2020-12-16 | 2021-04-06 | 辽宁科技大学 | Novel low-temperature water-resistant sulfur-resistant NH taking low-cost fly ash as carrier3-SCR catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105032404A (en) | Calcination-free MnO2/CNTs low-temperature denitration catalyst and preparation method thereof | |
| CN104923249B (en) | One kind exempts from calcinated type MnO2‑Fe2O3‑Ce2O3‑CeO2/ CNTs low-temperature denitration catalysts | |
| CN102335604B (en) | SCR (selective catalyctic reduction) low-temperature denitrification catalyst with nano core-shell structure and preparation method thereof | |
| CN103071484B (en) | Preparation method of manganese dioxide nanosheet/CNT (carbon nano tube) denitration catalyst with core-shell structure | |
| CN106582606B (en) | Non-vanadium low-temperature denitration catalyst and preparation method thereof | |
| CN103785409B (en) | A kind of ultrasonic method preparing low-temperature denitration composite catalyst with step impregnation method | |
| CN105327698B (en) | Using titanium-containing blast furnace slag as the preparation method of the Novel SCR catalyst for denitrating flue gas of carrier | |
| CN104971764A (en) | Low-temperature efficient denitration catalyst and preparation method thereof | |
| CN105727936A (en) | Low-temperature sulfur-resistant denitration catalyst and preparation method thereof | |
| CN104014331A (en) | Preparation method of mesoporous titanium dioxide ball supported Mn-Ce-W compound oxide denitration catalyst | |
| CN101972661B (en) | Sulfur-resisting and nitrogen-removed oxide compound metallic oxide SCR (Selective Catalytic Reduction) catalyst and preparation method thereof | |
| CN104971736A (en) | Natural Fe-Mn bimetal oxide SCR denitration catalyst and method utilizing denitration catalyst to denitrate smoke | |
| CN104437540A (en) | Phosphorus-resistant low-temperature SCR denitration catalyst and preparation method thereof | |
| CN102716753A (en) | Catalyst for low-temperature selective catalytic reduction of nitric oxide and preparation method of catalyst | |
| CN109433254A (en) | A kind of confinement molecular sieve denitrating catalyst and preparation method thereof | |
| CN103801288B (en) | For the composite oxide catalysts and preparation method thereof of oxidation of nitric oxide | |
| CN103191603A (en) | Catalytic filtration material with denitration and dust removal functions and preparation method of catalytic filtration material | |
| CN105597732A (en) | Composite carrier type SCR denitration catalyst capable of simultaneously removing nitrate and mercury, and preparation method thereof | |
| CN107185523B (en) | Preparation method of holmium modified denitration catalyst and product thereof | |
| CN104971716A (en) | Multi-walled carbon nano-tube supported manganese oxide-based catalyst preparation method | |
| CN108671946A (en) | Phosphorus doping cerium titanium catalyst, preparation and its application in selective-catalytic-reduction denitrified | |
| CN104971722A (en) | Magnetically separable and recyclable iron oxide SCR denitration catalyst and application method thereof | |
| CN104128188A (en) | Denitration catalyst used in waste incineration power plant and preparation method thereof | |
| CN106215949A (en) | A kind of low-temperature selective catalytic reduction denitration catalyst and preparation method thereof | |
| CN103506121A (en) | Low-temperature denitration catalyst with iron loaded on carbon nanotube and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151111 |