CN103084165A - Demercuration catalyst for elemental mercury in oxidated coal-fired flue gas and preparation method thereof - Google Patents
Demercuration catalyst for elemental mercury in oxidated coal-fired flue gas and preparation method thereof Download PDFInfo
- Publication number
- CN103084165A CN103084165A CN2013100237065A CN201310023706A CN103084165A CN 103084165 A CN103084165 A CN 103084165A CN 2013100237065 A CN2013100237065 A CN 2013100237065A CN 201310023706 A CN201310023706 A CN 201310023706A CN 103084165 A CN103084165 A CN 103084165A
- Authority
- CN
- China
- Prior art keywords
- demercuration catalyst
- carrier
- mercury
- active component
- coal
- 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 demercuration catalyst for elemental mercury in oxidated coal-fired flue gas, which comprises titanium dioxide and catalytic active components, wherein the titanium dioxide is used as a carrier, the catalytic active components are loaded on the carrier, and the catalytic active components include a main active component (manganese oxide) and an active additive niobium. The invention also discloses a preparation method of the demercuration catalyst. The demercuration catalyst has a catalytic effect on elemental mercury, especially has a high elemental mercury removal rate under the condition of low-concentration HCl, and can effectively convert elemental mercury which is uneasy to remove in flue gas into bivalent mercury which can be captured by a dust remover and a desulfurization device, and therefore, the demercuration catalyst is applicable to the removal of mercury and compounds of the mercury in coal-fired flue gas.
Description
Technical field
The present invention relates to a kind of demercuration catalyst, be specifically related to a kind of demercuration catalyst for oxidation coal-fired flue-gas nonvalent mercury, the invention still further relates to the preparation method of this catalyst.
Background technology
Along with the development of China's power industry to the atmosphere pollution control technology, the harm that the mercury that discharges in coal-fired flue-gas causes receives publicity day by day.Because the mercury content in China's fire coal is higher, so the mercury pollution problem of coal-burning power plant discharging is serious, and international community's pressure that China faces is also increasing, becomes inevitable to the research of coal-fired flue-gas mercury pollution control technology." fossil-fuel power plant atmospheric pollutant emission standard " of the up-to-date formulation of China (GB 13223-2011) clear, the emission limit of mercury and mercuric compounds is 0.03mg/m
3
In the flue gas that the coal-burning power plant produces, mercury mainly exists with three kinds of forms: particulate form (Hg
p), oxidation state (Hg
2+) and element state (Hg
0).The mercury of front two kinds of forms is easy to be removed by deduster and effective capture of desulfurizer, but the mercury of element state is high because of volatility, water-soluble low being difficult to effectively removed by the existing equipment in coal-burning power plant, therefore to Hg
0The research of control technology become Mercury In Coal Combustion Flue Gas and pollute the key point of controlling, be also the difficulties that needs solve.
Various countries control in the process of studying mercury and find, directly adopt active carbon adsorption with the Hg in flue gas
0Although remove effectively, remove cost very high, be unsuitable for large-scale promotion, if take some measures Hg
0Be oxidized to Hg
2+, then to be removed by deduster and wet desulphurization device be more feasible flue gas demercuration mode.Studies show that, selective catalytic reduction catalysts (Selective Catalytic Reduction, SCR) can promote HCl in flue gas to the oxidation of nonvalent mercury, but the SCR reactor of the actual coal-burning power plant result to the mercury removal performance test is shown, the SCR reactor is difficult to meet the demands to the oxidation effectiveness of nonvalent mercury not good (on average lower than 40%).
Summary of the invention
One of the object of the invention is to provide a kind of demercuration catalyst for oxidation coal-fired flue-gas nonvalent mercury, this demercuration catalyst has catalytic action to the oxidation of nonvalent mercury, especially in the situation that the HCl of low concentration, all has higher nonvalent mercury clearance, can be effectively the Elemental Mercury that is difficult in flue gas removing be converted into the divalence mercury that can be captured by deduster and desulfurizer, be applicable to Mercury In Coal Combustion Flue Gas and compound removes.
Two of the object of the invention is to provide the preparation method of above-mentioned demercuration catalyst.
First purpose of the present invention is achieved through the following technical solutions: a kind of demercuration catalyst for oxidation coal-fired flue-gas nonvalent mercury, comprise as the titanium dioxide of carrier and load on catalytic active component on carrier, described catalytic active component comprises main active component manganese oxide (MnO
2) and coagent niobium (Nb).
Main active component manganese oxide (MnO of the present invention
2) load capacity be 3 ~ 10wt%, the load capacity of described coagent niobium (Nb) is with niobium pentaoxide (Nb
2O
5) count 1 ~ 5wt%.
In the present invention, active component MnO
2Catalytic oxidation to Elemental Mercury has higher activity, after adding auxiliary agent Nb, Nb is carried on titanium dioxide, can effectively strengthen the acidity of catalyst, manganese in winner's active component is increased at the avtive spot of carrier titanium dioxide, thereby strengthen the activity of catalyst.Simultaneously, Nb can keep catalyst high-specific surface area at high temperature, improves the heat endurance of catalyst.
Second purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of the demercuration catalyst for oxidation coal-fired flue-gas nonvalent mercury, and with main active component manganese oxide (MnO
2) the presoma manganese nitrate add the water stirring and dissolving after, add niobium pentaoxide (Nb
2O
5) presoma nitric acid niobium stir, make compound dipping solution, the carrier titania powder is immersed in compound dipping solution, mix, at 60 ℃ of lower heating water baths and constantly stir, make manganese oxide (MnO
2), niobium pentaoxide (Nb
2O
5) and the abundant hybrid reaction 4～6h of carrier, 110 ℃ of drying 10～12h grind, and are warming up to 350～500 ℃ of roasting 4～6h at the Muffle furnace Program, then naturally cool to room temperature, make the demercuration catalyst.
MnO in described compound maceration extract
2With Nb
2O
5Mass ratio be 1 ﹕ 1～10 ﹕ 1.
Compared with prior art, the present invention has following beneficial effect:
Catalyst of the present invention has catalytic action preferably to nonvalent mercury, preparation technology is simple, need not to increase special-purpose demercuration equipment, through after machine-shaping, can be positioned over the lower floor of denitrating catalyst in the SCR reactor, realize the efficient oxidation of nonvalent mercury, and then captured by the wet method fume desulfurizing system in downstream and remove, be very suitable for the application that removes of mercury in coal-fired plant flue gas.
The specific embodiment
Embodiment 1
With main active component MnO
2The presoma manganese nitrate add after the water stirring and dissolving to get dipping solution, the carrier titania powder is immersed in dipping solution, mix, in 60 ℃ of heating water baths and constantly stirring, make the abundant hybrid reaction 5h of active component and carrier, 110 ℃ of dry 10h, grind, be warming up to 400 ℃ of roasting 4～6h at the Muffle furnace Program, then naturally cool to room temperature, make the demercuration catalyst, MnO
2Load capacity is 5wt%.
Embodiment 2
With main active component MnO
2The presoma manganese nitrate add the water stirring and dissolving after, add Nb
2O
5Presoma nitric acid niobium stir, make compound dipping solution, MnO in compound maceration extract
2With Nb
2O
5Mass ratio be 3:1, the carrier titania powder is immersed in compound dipping solution, mix, at 60 ℃ of heating water baths and constantly stir, make MnO
2, Nb
2O
5And the abundant hybrid reaction 5h of carrier, 110 ℃ of dry 10h grind, and are warming up to 400 ℃ of roasting 4～6h at the Muffle furnace Program, then naturally cool to room temperature, make the demercuration catalyst, MnO
2Load capacity is 3wt%, Nb
2O
5Load capacity be 1wt%.
Embodiment 3
With main active component MnO
2The presoma manganese nitrate add the water stirring and dissolving after, add Nb
2O
5Presoma nitric acid niobium stir, make compound dipping solution, MnO in compound maceration extract
2With Nb
2O
5Mass ratio be 5:1, the carrier titania powder is immersed in compound dipping solution, mix, at 60 ℃ of heating water baths and constantly stir, make MnO
2, Nb
2O
5And the abundant hybrid reaction 5h of carrier, 110 ℃ of dry 10h grind, and at Muffle furnace Program intensification roasting 4～6h, then naturally cool to room temperature, make the demercuration catalyst, MnO
2Load capacity is 5wt%, Nb
2O
5Load capacity be 1wt%.
Embodiment 4
With main active component MnO
2The presoma manganese nitrate add the water stirring and dissolving after, add Nb
2O
5Presoma nitric acid niobium stir, make compound dipping solution, MnO in compound maceration extract
2With Nb
2O
5Mass ratio be 7 ﹕ 1, the carrier titania powder is immersed in compound dipping solution, mix, at 60 ℃ of heating water baths and constantly stir, make MnO
2, Nb
2O
5And the abundant hybrid reaction 5h of carrier, 110 ℃ of dry 10h grind, and are warming up to 400 ℃ of roasting 4～6h at the Muffle furnace Program, then naturally cool to room temperature, make the demercuration catalyst, MnO
2Load capacity is 7wt%, Nb
2O
5Load capacity be 1wt%.
Embodiment 5
With main active component MnO
2The presoma manganese nitrate add the water stirring and dissolving after, add Nb
2O
5Presoma nitric acid niobium stir, make compound dipping solution, MnO in compound maceration extract
2With Nb
2O
5Mass ratio be 10 ﹕ 1, the carrier titania powder is immersed in compound dipping solution, mix, at 60 ℃ of heating water baths and constantly stir, make MnO
2, Nb
2O
5And the abundant hybrid reaction 5h of carrier, 110 ℃ of dry 10h grind, and are warming up to 400 ℃ of roasting 4～6h at the Muffle furnace Program, then naturally cool to room temperature, make the demercuration catalyst, MnO
2Load capacity is 10wt%, Nb
2O
5Load capacity be 1wt%.
Embodiment 6
With main active component MnO
2The presoma manganese nitrate add the water stirring and dissolving after, add Nb
2O
5Presoma nitric acid niobium stir, make compound dipping solution, MnO in compound maceration extract
2With Nb
2O
5Mass ratio be 5 ﹕ 2, the carrier titania powder is immersed in compound dipping solution, mix, at 60 ℃ of heating water baths and constantly stir, make MnO
2, Nb
2O
5And the abundant hybrid reaction 5h of carrier, 110 ℃ of dry 10h grind, and are warming up to 400 ℃ of roasting 4～6h at the Muffle furnace Program, then naturally cool to room temperature, make the demercuration catalyst, MnO
2Load capacity is 5wt%, Nb
2O
5Load capacity be 2wt%.
Embodiment 7
With main active component MnO
2The presoma manganese nitrate add the water stirring and dissolving after, add Nb
2O
5Presoma nitric acid niobium stir, make compound dipping solution, MnO in compound maceration extract
2With Nb
2O
5Mass ratio be 5 ﹕ 3, the carrier titania powder is immersed in compound dipping solution, mix, at 60 ℃ of heating water baths and constantly stir, make MnO
2, Nb
2O
5And the abundant hybrid reaction 5h of carrier, 110 ℃ of dry 10h grind, and are warming up to 400 ℃ of roasting 4～6h at the Muffle furnace Program, then naturally cool to room temperature, make the demercuration catalyst, MnO
2Load capacity is 5wt%, Nb
2O
5Load capacity be 3wt%.
Embodiment 8
With main active component MnO
2The presoma manganese nitrate add the water stirring and dissolving after, add Nb
2O
5Presoma nitric acid niobium stir, make compound dipping solution, MnO in compound maceration extract
2With Nb
2O
5Mass ratio be 1 ﹕ 1, the carrier titania powder is immersed in compound dipping solution, mix, at 60 ℃ of heating water baths and constantly stir, make MnO
2, Nb
2O
5And the abundant hybrid reaction 5h of carrier, 110 ℃ of dry 10h grind, and are warming up to 400 ℃ of roasting 4～6h at the Muffle furnace Program, then naturally cool to room temperature, make the demercuration catalyst, MnO
2Load capacity is 5wt%, Nb
2O
5Load capacity be 5wt%.
Experimental example:
The demercuration catalyst 10g that makes with embodiment 1 to 8 packs in tubular fixed-bed quartz reactor (φ 9mm), passes into simulated flue gas, and concrete composition is O
2Be 3%, Hg
0Be 0.3mg/m
3, HCl is 5ppm, NO 300ppm, NH
3300ppm, all the other are N
2, temperature is 350 ℃, the control gas space velocity is 40000h
-1Investigate catalyst under condition to Hg
0Oxidation activity.The results are shown in Table 1.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention or principal character.Above-mentioned embodiment of the present invention all can only be thought explanation of the present invention rather than restriction, therefore every foundation essence technology of the present invention to any trickle modification, equivalent variations and modification that above embodiment does, all belongs in the scope of technical solution of the present invention.
Claims (4)
1. a demercuration catalyst that is used for oxidation coal-fired flue-gas nonvalent mercury, is characterized in that, comprises as the titanium dioxide of carrier and load on catalytic active component on carrier, and described catalytic active component comprises main active component manganese oxide and coagent niobium.
2. the demercuration catalyst for oxidation coal-fired flue-gas nonvalent mercury according to claim 1, is characterized in that, the load capacity of described main active component manganese oxide is 3 ~ 10wt%, and the load capacity of described coagent niobium is counted 1 ~ 5wt% with niobium pentaoxide.
3. the preparation method of the described demercuration catalyst for oxidation coal-fired flue-gas nonvalent mercury of a claim 1 or 2, it is characterized in that, after the presoma manganese nitrate of main active component manganese oxide is added the water stirring and dissolving, add the presoma nitric acid niobium of niobium pentaoxide to stir, make compound dipping solution, the carrier titania powder is immersed in compound dipping solution, mix, in 60 ℃ of lower heating water baths and constantly stirring, make manganese oxide, the abundant hybrid reaction 4～6h of niobium pentaoxide and carrier, 110 ℃ of drying 10～12h, grind, be warming up to 350～500 ℃ of roasting 4～6h at the Muffle furnace Program, then naturally cool to room temperature, make the demercuration catalyst.
4. the preparation method of the demercuration catalyst for oxidation coal-fired flue-gas nonvalent mercury according to claim 3, is characterized in that, in described compound maceration extract, the mass ratio of manganese oxide and niobium pentaoxide is 1 ﹕ 1～10 ﹕ 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100237065A CN103084165A (en) | 2013-01-23 | 2013-01-23 | Demercuration catalyst for elemental mercury in oxidated coal-fired flue gas and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100237065A CN103084165A (en) | 2013-01-23 | 2013-01-23 | Demercuration catalyst for elemental mercury in oxidated coal-fired flue gas and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103084165A true CN103084165A (en) | 2013-05-08 |
Family
ID=48197594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100237065A Pending CN103084165A (en) | 2013-01-23 | 2013-01-23 | Demercuration catalyst for elemental mercury in oxidated coal-fired flue gas and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103084165A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105263617A (en) * | 2013-12-11 | 2016-01-20 | 浙江大学 | Catalyst for synergistic control of oxynitride and mercury and method for preparing same |
| CN105561917A (en) * | 2015-12-22 | 2016-05-11 | 盐城工学院 | Dye wastewater decoloring agent and preparation method and application thereof |
| CN105688931A (en) * | 2016-03-09 | 2016-06-22 | 铜仁学院 | Novel method for preparing coal-fired flue gas mercury-removal catalyst from rhodochrosite |
| CN106975331A (en) * | 2017-04-27 | 2017-07-25 | 北京清新环境技术股份有限公司 | A kind of smoke catalytic absorbing synergic mercury removal device and its method |
| CN108435161A (en) * | 2018-03-29 | 2018-08-24 | 上海电力学院 | A kind of catalyst and its preparation method and application for flue gas demercuration |
| CN108579730A (en) * | 2018-03-29 | 2018-09-28 | 上海电力学院 | A kind of catalyst and its preparation method and application for flue gas demercuration |
| CN110523419A (en) * | 2019-08-09 | 2019-12-03 | 上海电力大学 | Catalyst for flue gas demercuration and preparation method thereof |
| CN110575739A (en) * | 2019-09-30 | 2019-12-17 | 大唐郓城发电有限公司 | Method for removing metallic mercury in flue gas |
| CN112444595A (en) * | 2019-08-29 | 2021-03-05 | 国家能源投资集团有限责任公司 | Device and method for jointly evaluating activity of denitration and demercuration catalyst |
| CN114164004A (en) * | 2021-11-26 | 2022-03-11 | 北京市生态环境保护科学研究院 | Soil zero-valent mercury composite oxidant and method for repairing soil by using same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008093137A1 (en) * | 2007-01-29 | 2008-08-07 | The University Of Nottingham | A sorbent composition |
| CN101574660A (en) * | 2009-06-11 | 2009-11-11 | 上海交通大学 | Method for preparing mixed compound catalyst used for catalyzing null-valence mercury in flue-gas to be oxidized |
| CN102698753A (en) * | 2012-05-15 | 2012-10-03 | 中国科学院过程工程研究所 | Catalyst for mercury oxidation and preparation method and purpose thereof |
| CN103182312A (en) * | 2011-12-31 | 2013-07-03 | 上海钒铖环保科技有限公司 | Low temperature NH3-SCR denitration catalyst for flue gas with low water vapor content, and preparation method thereof |
-
2013
- 2013-01-23 CN CN2013100237065A patent/CN103084165A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008093137A1 (en) * | 2007-01-29 | 2008-08-07 | The University Of Nottingham | A sorbent composition |
| CN101574660A (en) * | 2009-06-11 | 2009-11-11 | 上海交通大学 | Method for preparing mixed compound catalyst used for catalyzing null-valence mercury in flue-gas to be oxidized |
| CN103182312A (en) * | 2011-12-31 | 2013-07-03 | 上海钒铖环保科技有限公司 | Low temperature NH3-SCR denitration catalyst for flue gas with low water vapor content, and preparation method thereof |
| CN102698753A (en) * | 2012-05-15 | 2012-10-03 | 中国科学院过程工程研究所 | Catalyst for mercury oxidation and preparation method and purpose thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李应成等: "铌酸/氧化铌在多相催化反应中的应用", 《化学通报》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105263617A (en) * | 2013-12-11 | 2016-01-20 | 浙江大学 | Catalyst for synergistic control of oxynitride and mercury and method for preparing same |
| CN105263617B (en) * | 2013-12-11 | 2017-06-06 | 浙江大学 | For the catalyst and preparation method of nitre mercury Collaborative Control |
| CN105561917A (en) * | 2015-12-22 | 2016-05-11 | 盐城工学院 | Dye wastewater decoloring agent and preparation method and application thereof |
| CN105688931A (en) * | 2016-03-09 | 2016-06-22 | 铜仁学院 | Novel method for preparing coal-fired flue gas mercury-removal catalyst from rhodochrosite |
| CN105688931B (en) * | 2016-03-09 | 2017-11-28 | 铜仁学院 | A kind of new method that coal-fired flue gas mercury removal catalyst is prepared using manganese spar |
| CN106975331A (en) * | 2017-04-27 | 2017-07-25 | 北京清新环境技术股份有限公司 | A kind of smoke catalytic absorbing synergic mercury removal device and its method |
| CN108435161A (en) * | 2018-03-29 | 2018-08-24 | 上海电力学院 | A kind of catalyst and its preparation method and application for flue gas demercuration |
| CN108579730A (en) * | 2018-03-29 | 2018-09-28 | 上海电力学院 | A kind of catalyst and its preparation method and application for flue gas demercuration |
| CN110523419A (en) * | 2019-08-09 | 2019-12-03 | 上海电力大学 | Catalyst for flue gas demercuration and preparation method thereof |
| CN112444595A (en) * | 2019-08-29 | 2021-03-05 | 国家能源投资集团有限责任公司 | Device and method for jointly evaluating activity of denitration and demercuration catalyst |
| CN110575739A (en) * | 2019-09-30 | 2019-12-17 | 大唐郓城发电有限公司 | Method for removing metallic mercury in flue gas |
| CN114164004A (en) * | 2021-11-26 | 2022-03-11 | 北京市生态环境保护科学研究院 | Soil zero-valent mercury composite oxidant and method for repairing soil by using same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103084165A (en) | Demercuration catalyst for elemental mercury in oxidated coal-fired flue gas and preparation method thereof | |
| CN102974367B (en) | Method for regenerating inactivation SCR denitration catalyst by using antitoxic renewable liquid | |
| CN102350340B (en) | Composite smoke denitration catalyst capable of oxidizing zero-valence mercury | |
| CN104162349B (en) | A kind of low-temperature denitration catalyst SO that suppresses2Poisoning method | |
| CN103143345B (en) | Composite catalyst for catalytically oxidizing nitrogen oxide and preparation method of composite catalyst | |
| CN101602018B (en) | Method for preparing rare-earth element doped composite metal oxide mercury removal catalyst | |
| CN101590369B (en) | Mercury removal process based on lime-gypsum method desulphurization system and mercury removal absorption liquid | |
| CN101474581B (en) | Catalyst module edge hardening liquid with activity | |
| CN103111128A (en) | Dust-removal mercury-removal filter bag for bag-type dust remover and preparation method of filter bag | |
| CN103203176B (en) | Method for flue gas desulfurization, denitrification and demercuration by semidry method | |
| CN101391178B (en) | Method for removing mercury in flue gas using V2O5/carbon material catalyst | |
| CN111097442B (en) | Flue gas synergistic denitration and demercuration catalyst and preparation method thereof | |
| CN101972652A (en) | Preparation method of compound SCR catalyst with zero-valent mercury conversion function | |
| CN105597732A (en) | Composite carrier type SCR denitration catalyst capable of simultaneously removing nitrate and mercury, and preparation method thereof | |
| CN202860378U (en) | Smoke forced oxidation desulfurization and denitrification integrated device | |
| CN102101007B (en) | Method for removing mercury from smoke in coal fired power plant and mercury removing agent used by same | |
| CN105195013A (en) | Denitration and demercuration apparatus and method with CFB (circulating fluidized bed) boiler | |
| CN103537273B (en) | Denitrating catalyst of a kind of collaborative demercuration and preparation method thereof | |
| CN110605092B (en) | Iron-based rare earth oxygen storage type composite solid solution adsorbent and application thereof in flue gas dearsenification and demercuration | |
| CN109174097B (en) | Catalyst for desulfurization and denitrification of metallurgical sintering flue gas and preparation method thereof | |
| CN109201041A (en) | A kind of flue gas demercuration catalyst and preparation method thereof of Mn doping cerium zirconium sosoloid | |
| CN210171198U (en) | Flue gas wet denitration system based on physical adsorption pre-oxidation | |
| CN102764655A (en) | Novel demercuration catalyst | |
| CN105057008A (en) | Regeneration liquid used in regeneration method for inactivated SCR denitration catalyst | |
| CN103990487A (en) | Denitration and demercuration catalyst 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 | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130508 |