CN109529948A - A method of improving manganese-based low-temperature SCR denitration water resistant, resistance to SO_2 - Google Patents
A method of improving manganese-based low-temperature SCR denitration water resistant, resistance to SO_2 Download PDFInfo
- Publication number
- CN109529948A CN109529948A CN201811441127.1A CN201811441127A CN109529948A CN 109529948 A CN109529948 A CN 109529948A CN 201811441127 A CN201811441127 A CN 201811441127A CN 109529948 A CN109529948 A CN 109529948A
- Authority
- CN
- China
- Prior art keywords
- temperature scr
- resistance
- water resistant
- catalyst
- scr 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
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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
Abstract
A method of manganese-based low-temperature SCR denitration water resistant, resistance to SO_2 are improved, preparation water resistant, resistance to SO_2 catalyst technical field are belonged to.Use hydrophobic PTFE for cladding or dopant, by simple dispersion and manganese-based catalyst by being mixed in the reaction vessel equipped with dehydrated alcohol, filtering, drying, calcining, can prepare with excellent water resistant, the manganese-based low-temperature SCR denitration of sulfur resistance.The method of the present invention process is simple, at low cost, non-toxic, pollution-free, can prepare with excellent water resistant, the manganese-based low-temperature SCR catalyst of sulfur resistance.
Description
Technical field
A method of manganese-based low-temperature SCR denitration water resistant, resistance to SO_2 are improved, is had particularly suitable for preparation excellent
Water resistant, the manganese-based low-temperature SCR denitration of sulfur resistance belong to preparation water resistant, resistance to SO_2 catalyst technical field.
Background technique
Currently, selective catalytic reduction (SCR) is the main stream approach of denitrification, denitration efficiency up to 90% with
On, application is relatively broad, and technology is also more mature.V2O5–WO3(MoO3)/TiO2Catalyst is catalyzed as typical business SCR
Agent has been widely used in power plant, steel mill, the fields such as glass furnace.But since the operating temperature of traditional SCR is generally
300-400 DEG C even higher, and SO can occur in flue gas at this temperature2Oxidation, NH3The reaction such as oxidation, and be chronically in addition
So high reaction temperature, V-based catalyst are easy to inactivate.
Low-temperature SCR technology catalyst operating temperature, hereinafter, after reactor can be placed in desulfurization and dedusting, is avoided at 250 DEG C
SO2, flue dust and high temperature adverse effect, for relatively-high temperature SCR, there is higher economic and practical, more efficiently and easily
In popularization.Catalyst is the core of low temperature SCR denitration technology, is the research emphasis in current low temperature SCR denitration field both at home and abroad.But
It is from the point of view of report both domestic and external, SCR denitration has the shortcomings that not resistant to sulfur and non-water resistant in low-temperature range, greatly limits
The application of SCR denitration is made.Currently, low-temperature SCR reactor is placed in after desulfurating dust-removing equipment mostly, desulfurization and dedusting work
Skill comparative maturity, can be by SO in the flue gas for entering SCR reaction2Content is down to 10-30mg/Nm3, it is largely avoided
NH4HSO4Generation and the problem of catalyst chemistry sulfur poisoning.Therefore the water resistance of low temperature SCR denitration catalyst is poor becomes
The problem of urgent need to resolve.Low-temperature SCR catalyst poor water resistance significantly limits SCR denitration in waste incineration, natural
The engineer application in the gas burning fields such as (boiler) and biomass power generation is ground both at home and abroad in order to solve the resistance to water problems of low temperature catalyst
The person of studying carefully has carried out a large amount of work, and important opinion is proposed to catalyst water intoxication, while many water resistances have also been developed
Strong low-temperature SCR catalyst.For example, Cao etc. has developed Fe-Mn-Ce/Al2O3Low-temperature SCR catalyst, at 250 DEG C, 10%
H2In the presence of O, the working time of nearly 1000h, NOxConversion ratio only drops to 88% or so (Fuel, 2015,139,232-239).
Wang etc. is prepared for Fe-Ce oxide catalyst, at 250 DEG C, 5%H2In the presence of O, by 10h reaction time, NOxConversion ratio according to
So maintain 95% (J.Hazard.Mater., 2016,301,512-521).Shen etc. is prepared for MnOx/TiO2Catalyst leads to
It crosses and is passed through the comparative experiments of water at 160 DEG C and 200 DEG C and points out that temperature is lower, influence of the water for catalyst is bigger, is being lower than
At 200 DEG C, the influence of water is more obvious (Chin.J.Catal., 2011,32,1803-1811).Although some catalyst systems
With preferable water resistance, still, still it is difficult to apply to the water content such as waste incineration and combustion of natural gas and is up to 20-30%
(v/v) denitrating flue gas is administered, and especially when catalyst running temperature is lower than 200 DEG C, water resistance is even more important.
Describing one kind in the technical scheme only needs simple process, that is, manganese-based low-temperature SCR catalyst water resistant can be improved, resist
Sulphur performance, while keeping excellent denitration activity.
Summary of the invention
The technical problem to be solved in the present invention is that providing a kind of process simple, at low cost, non-toxic, pollution-free raising
SCR denitration water resistant, the method for resistance to SO_2.
A kind of raising manganese-based low-temperature SCR denitration water resistant of technical solution of the present invention, the method for resistance to SO_2, feature
It is, comprising the following steps: disperse the polytetrafluoroethylene PTFE of 1-4 mass parts in the container equipped with dehydrated alcohol, stir
Disperse 2-5h, the low-temperature SCR catalyst particle of 16 mass parts is added in said vesse, stir 10-20h, filters, in baking oven
In 120 DEG C drying, be placed in 200 DEG C of calcining 1-2h in Muffle furnace.
The invention is characterized in that the mass ratio of control PTFE and catalyst is (1-4): 16, it is 1- that PTFE, which disperses mixing time,
5h, mixing time is 1-20h after catalyst is added.
The invention is characterized in that PTFE is distributed in dehydrated alcohol, PTFE dispersion liquid is formed.
Low-temperature SCR catalyst system is to contain one of low temperature SCR denitration catalyst in the present invention；PTFE molecular weight is
One or more of 3000-5000,5000-15000,10000-30000.
The mass ratio range that feeds intake of PTFE and catalyst is (1-4) in the present invention: 16, it is preferably in a proportion of (3-4): 16.
The invention has the advantages that the method for the present invention directlys adopt PTFE cheap and easy to get for doping or covering material, using simple liquid
Mutually dispersing, liquid phase package/doping can be obtained with excellent water resistant, the manganese-based low-temperature SCR denitration of sulfur resistance, this
Method has many advantages, such as simple, nontoxic, pollution-free.
Detailed description of the invention
Fig. 1 is that embodiment 1-4 coats rear catalyst catalytically active assessment curve.
Fig. 2 is that the catalyst after embodiment 1-4 preparation is passed through 5%H at 160 DEG C of temperature2O, 180 DEG C are passed through 20%H2When O
NOxThe curve that conversion ratio changes over time.
Fig. 3 is that the catalyst after embodiment 3-4 preparation is passed through 5%H at 160 DEG C of temperature2O、50ppm SO2, 180 DEG C are passed through
20%H2O、50ppm SO2When NOxThe curve that conversion ratio changes over time.
Specific embodiment
The present invention is explained below with reference to embodiment, but the present invention is not limited to following embodiments.
PTFE used in following embodiment is bought in the auspicious micropowder material factory in the Shenyang City sky, model nanoscale N06.
Embodiment 1: dispersing 0.25g PTFE in the container equipped with 200ml dehydrated alcohol, stirs 2h, and 4g is added
MnO2, 10h is stirred at room temperature, filtering is dried in 120 DEG C of baking ovens, is placed in 200 DEG C of Muffle furnaces and is calcined 2h, it is resistance to can to prepare SCR
Water, sulfur-tolerant type catalyst.
Embodiment 2: by the preparation method of embodiment 1, the container equipped with 200ml dehydrated alcohol is dispersed by 0.5g PTFE
In, 2h is stirred, 4g MnO is added2, 10h is stirred at room temperature, filtering is dried in 120 DEG C of baking ovens, is placed in 200 DEG C of Muffle furnaces and is forged
2h is burnt, can prepare that SCR is water-fast, sulfur-tolerant type catalyst.
Embodiment 3: by the preparation method of embodiment 1, the container equipped with 200ml dehydrated alcohol is dispersed by 0.75g PTFE
In, 2h is stirred, 4g MnO is added2, 10h is stirred at room temperature, filtering is dried in 120 DEG C of baking ovens, is placed in 200 DEG C of Muffle furnaces and is forged
2h is burnt, can prepare that SCR is water-fast, sulfur-tolerant type catalyst.
Embodiment 4: by the preparation method of embodiment 1, dispersing 1g PTFE in the container equipped with 200ml dehydrated alcohol,
2h is stirred, 4g MnO is added2, 10h is stirred at room temperature, filtering is dried in 120 DEG C of baking ovens, is placed in 200 DEG C of Muffle furnaces and is calcined
2h, can prepare that SCR is water-fast, sulfur-tolerant type catalyst.
It is urged according to a kind of raising SCR denitration water resistant, the method for resistance to SO_2, preparation described in above technical scheme
Agent can be used for that flue-gas temperature is low, high-moisture NH3SCR denitration occasion.Involved evaluating catalyst item in above example
Part: 1000ppm NH3, 1000ppm NO, 6%O2, 5%H2O,N2For Balance Air, air speed 30000h-1.Aqueous conditions: 5% or
20%H2O；Sulfur-bearing condition: 50ppmSO2。
Claims (5)
1. a kind of raising manganese-based low-temperature SCR denitration water resistant, the method for resistance to SO_2, which comprises the following steps:
It disperses the polytetrafluoroethylene PTFE of 1-4 mass parts in the container equipped with dehydrated alcohol, is dispersed with stirring 2-5h, by 16 mass parts
Low-temperature SCR catalyst particle be added in said vesse, stir 10-20h, filtering, in an oven 120 DEG C drying, be placed in horse
Not 200 DEG C of calcining 1-2h in furnace.
2. a kind of raising manganese-based low-temperature SCR denitration water resistant described in accordance with the claim 1, the method for resistance to SO_2, special
Sign is that the mass ratio of PTFE and catalyst is that ratio is (3-4): 16.
3. a kind of raising manganese-based low-temperature SCR denitration water resistant described in accordance with the claim 1, the method for resistance to SO_2, special
Sign is that low-temperature SCR catalyst system is to contain at least one of low temperature SCR denitration catalyst.
4. a kind of raising manganese-based low-temperature SCR denitration water resistant described in accordance with the claim 1, the method for resistance to SO_2, special
Sign is that PTFE molecular weight is 3000-5000,5000-15000, one or more of 10000-30000.
5. the manganese-based low-temperature SCR denitration being prepared according to the described in any item methods of claim 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811441127.1A CN109529948A (en) | 2018-11-29 | 2018-11-29 | A method of improving manganese-based low-temperature SCR denitration water resistant, resistance to SO_2 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811441127.1A CN109529948A (en) | 2018-11-29 | 2018-11-29 | A method of improving manganese-based low-temperature SCR denitration water resistant, resistance to SO_2 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109529948A true CN109529948A (en) | 2019-03-29 |
Family
ID=65851007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811441127.1A Pending CN109529948A (en) | 2018-11-29 | 2018-11-29 | A method of improving manganese-based low-temperature SCR denitration water resistant, resistance to SO_2 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109529948A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110280315A (en) * | 2019-07-16 | 2019-09-27 | 中国科学院兰州化学物理研究所 | The method of low-temperature SCR catalyst anti-ABS and water resistant anti-dust performance in a kind of raising |
| CN110280314A (en) * | 2019-07-16 | 2019-09-27 | 中国科学院兰州化学物理研究所 | A method of improving manganese-based low-temperature SCR catalyst water resistant and anti-dust performance |
| CN111659364A (en) * | 2020-05-06 | 2020-09-15 | 江苏龙净科杰环保技术有限公司 | Sulfur-resistant and water-resistant manganese-based low-temperature denitration catalyst and preparation method thereof |
| CN111672542A (en) * | 2020-05-18 | 2020-09-18 | 上海大学 | Method for organizing inorganic solid waste and catalytic membrane material prepared by method |
| CN111715216A (en) * | 2020-06-08 | 2020-09-29 | 上海大学 | Catalyst composite material prepared by recycling inorganic solid waste and preparation method thereof |
| CN111939977A (en) * | 2020-08-12 | 2020-11-17 | 无锡威孚环保催化剂有限公司 | Fluoropolymer-modified denitration catalyst and preparation method thereof |
| CN113952982A (en) * | 2021-11-05 | 2022-01-21 | 安徽元琛环保科技股份有限公司 | Manganese-based ultralow-temperature denitration catalyst and preparation method thereof |
| CN114682297A (en) * | 2020-12-30 | 2022-07-01 | 中国石油大学(北京) | Low-temperature denitration catalyst and preparation method and application thereof |
| CN115212890A (en) * | 2022-07-28 | 2022-10-21 | 辽宁科隆精细化工股份有限公司 | High-water-resistance modified microporous layer modified low-temperature SCR denitration catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226311A (en) * | 2014-08-21 | 2014-12-24 | 中国工程物理研究院核物理与化学研究所 | Preparation method of neat hydrophobic catalyst |
| CN107694564A (en) * | 2017-11-23 | 2018-02-16 | 苏州祥派智能科技有限公司 | A kind of catalyst of decomposing formaldehyde and preparation method thereof |
-
2018
- 2018-11-29 CN CN201811441127.1A patent/CN109529948A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226311A (en) * | 2014-08-21 | 2014-12-24 | 中国工程物理研究院核物理与化学研究所 | Preparation method of neat hydrophobic catalyst |
| CN107694564A (en) * | 2017-11-23 | 2018-02-16 | 苏州祥派智能科技有限公司 | A kind of catalyst of decomposing formaldehyde and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈建军: "锰基催化剂研制及其低温选择性催化还原NOX机理研究", 《清华大学硕士论文》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110280315A (en) * | 2019-07-16 | 2019-09-27 | 中国科学院兰州化学物理研究所 | The method of low-temperature SCR catalyst anti-ABS and water resistant anti-dust performance in a kind of raising |
| CN110280314A (en) * | 2019-07-16 | 2019-09-27 | 中国科学院兰州化学物理研究所 | A method of improving manganese-based low-temperature SCR catalyst water resistant and anti-dust performance |
| CN111659364A (en) * | 2020-05-06 | 2020-09-15 | 江苏龙净科杰环保技术有限公司 | Sulfur-resistant and water-resistant manganese-based low-temperature denitration catalyst and preparation method thereof |
| CN111672542B (en) * | 2020-05-18 | 2023-05-16 | 上海大学 | Method for organizing inorganic solid waste and catalytic membrane material prepared by same |
| CN111672542A (en) * | 2020-05-18 | 2020-09-18 | 上海大学 | Method for organizing inorganic solid waste and catalytic membrane material prepared by method |
| CN111715216A (en) * | 2020-06-08 | 2020-09-29 | 上海大学 | Catalyst composite material prepared by recycling inorganic solid waste and preparation method thereof |
| CN111715216B (en) * | 2020-06-08 | 2023-06-09 | 上海大学 | Catalyst composite material prepared by recycling inorganic solid wastes and preparation method thereof |
| CN111939977A (en) * | 2020-08-12 | 2020-11-17 | 无锡威孚环保催化剂有限公司 | Fluoropolymer-modified denitration catalyst and preparation method thereof |
| CN114682297A (en) * | 2020-12-30 | 2022-07-01 | 中国石油大学(北京) | Low-temperature denitration catalyst and preparation method and application thereof |
| CN114682297B (en) * | 2020-12-30 | 2023-09-08 | 中国石油大学(北京) | Low-temperature denitration catalyst and preparation method and application thereof |
| CN113952982A (en) * | 2021-11-05 | 2022-01-21 | 安徽元琛环保科技股份有限公司 | Manganese-based ultralow-temperature denitration catalyst and preparation method thereof |
| CN113952982B (en) * | 2021-11-05 | 2024-01-19 | 安徽元琛环保科技股份有限公司 | Manganese-based ultralow-temperature denitration catalyst and preparation method thereof |
| CN115212890A (en) * | 2022-07-28 | 2022-10-21 | 辽宁科隆精细化工股份有限公司 | High-water-resistance modified microporous layer modified low-temperature SCR denitration catalyst and preparation method and application thereof |
| CN115212890B (en) * | 2022-07-28 | 2023-12-05 | 辽宁科隆精细化工股份有限公司 | High-water-resistance modified microporous layer modified low-temperature SCR denitration catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109529948A (en) | A method of improving manganese-based low-temperature SCR denitration water resistant, resistance to SO_2 | |
| CN104525216B (en) | Denitrating catalyst under the conditions of wide temperature window high-sulfur and preparation method thereof | |
| CN101284238B (en) | Catalysts for stationary source ammine selective catalytic reduction for nitrous oxides | |
| WO2018233129A1 (en) | Wide-temperature range flue gas denitrification catalyst preparation method and application thereof | |
| CN105727936A (en) | Low-temperature sulfur-resistant denitration catalyst and preparation method thereof | |
| CN107649116A (en) | Cerium tin composite oxides denitrating catalyst and its preparation method and application | |
| CN105289644B (en) | A kind of flat sulfur resistive low temperature SCR denitration catalyst and preparation method thereof | |
| CN109999829A (en) | A kind of bimetallic manganese iron low temperature SCR denitration catalyst, preparation method and applications | |
| CN106731226B (en) | The method that one step in-situ synthesis prepares binary denitration sulfur resistant catalyst load filtrate | |
| CN105833901B (en) | A kind of PrOx-MnOx/ SAPO-34 low-temperature SCR catalyst for denitrating flue gas and the preparation method and application thereof | |
| CN204865783U (en) | Low temperature flue gas denitration catalytic reaction device | |
| CN105879879A (en) | High-sulfur-resistant ultralow-temperature SCR (Selective Catalytic Reduction) denitration catalyst and preparation method thereof | |
| CN105363434A (en) | Manganese based SCR catalyst for low temperature denitration and preparation method thereof | |
| CN101433855B (en) | Process for preparing SCR denitration catalyst and SCR denitration catalyst prepared by the method | |
| CN101869833B (en) | Catalyst for SCR denitration of furnace middle temperature fume and preparation method thereof | |
| CN109482194A (en) | A kind of collaboration denitration and the catalyst of mercury oxidation and preparation method thereof | |
| CN108939918B (en) | Low-temperature SCR denitration treatment method and device | |
| CN110404553A (en) | Low temperature SCR denitration catalyst and preparation method thereof with water resistant resistance to SO_2 | |
| CN106362733A (en) | High-temperature resistant manganite catalyst and preparation method thereof | |
| CN112718018B (en) | Lanthanum cobaltite perovskite catalyst treated by acetic acid and preparation method thereof | |
| CN112295555B (en) | Cerium-titanium composite nanorod catalyst for fixed source flue gas denitration reaction and preparation method thereof | |
| CN106622273A (en) | Denitration catalyst and preparation method thereof | |
| CN106732547B (en) | Demercuration catalyst for low-temperature oxidation of zero-valent mercury in coal-fired flue gas and preparation method thereof | |
| CN111068709A (en) | Preparation method of ferro-manganese catalyst | |
| CN103537273B (en) | Denitrating catalyst of a kind of collaborative demercuration 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 |