CN108435161A - A kind of catalyst and its preparation method and application for flue gas demercuration - Google Patents
A kind of catalyst and its preparation method and application for flue gas demercuration Download PDFInfo
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- CN108435161A CN108435161A CN201810270637.0A CN201810270637A CN108435161A CN 108435161 A CN108435161 A CN 108435161A CN 201810270637 A CN201810270637 A CN 201810270637A CN 108435161 A CN108435161 A CN 108435161A
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- catalyst
- flue gas
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- gas demercuration
- demercuration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- 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
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Abstract
The catalyst and its preparation method and application that the present invention relates to a kind of for flue gas demercuration, the catalyst are made of carrier, active component and auxiliary agent three parts, and the carrier is titanium dioxide, the active component is manganese element, the auxiliary agent is niobium element, wherein manganese element：Niobium element：The molar ratio of titanium elements is 0.13：0.02：1, catalyst preparation uses coprecipitation, last catalyst obtained can be handled mercury element in the exhaust gas of the discharges such as power generation gas turbine and coal-burning boiler, the activity and catalytic capability of low temperature demercuration can be significantly improved, 250 DEG C or more the mercury removal rates that can reach 95% or more, with stronger industrial application value, the catalysis oxidation of mercury can be widely applied to.
Description
Technical field
The present invention relates to a kind of catalyst, more particularly, to a kind of catalyst for flue gas demercuration and preparation method thereof and
Using.
Background technology
Element mercury (Hg0) be pollutant important in coal-burning facility flue gas, to ecological environment and health have compared with
Strong toxic effect.Currently, for Hg0Emission control, activated carbon injection (ACI) technology show optimality in coal-burning power plant
Energy.However, this technology still has some intrinsic defects, such as the high cost of ACI.
Due to Hg2+High-dissolvability, if Hg0It is oxidized to Hg2+, pass through the wet flue gas desulfurization in coal-burning power plant
(WFGD) Hg is absorbed in washer2+An economic removal Hg can be obtained0Process.Research shows that being aoxidized based on certain metals
Object SCR catalyst is by Hg0It is converted into Hg2+Feasibility, if Hg0Conversion ratio is more than 80%, compared with traditional ACI methods,
The combination of SCR and WFGD will more economic remove Hg0。
In denitration and Hg0In the SCR catalyst of oxidation, Mn/TiO2Catalyst is lived because of its environmentally friendly property and low-temperature SCR reaction
Property it is high and become people's focus of attention.In addition to this, MnOxIn with the Mn species of various valence states make Mn/TiO2Catalyst
As the tournament selection of redox reaction, including Hg0Oxidation.However, being used for Hg0The SCR reactors of oxidation are still located at WFGD and wash
Wash the upstream of device, therefore Mn/TiO2Catalyst and SO2Contact be inevitable.However, Mn/TiO2Catalyst is to SO2's
Bad resistance is a well known fact, and catalyst cannot keep high activity, catalytic efficiency during low temperature demercuration
It is low, in addition, there is also water resistant sulfur poisoning-resistant problems.If efficient demercuration catalyst can be developed, can be very good to solve
The above problem.
Invention content
The purpose of the present invention is exactly to provide a kind of catalyst and its system for flue gas demercuration to solve the above-mentioned problems
Preparation Method and application.
The purpose of the present invention is achieved through the following technical solutions：
A kind of catalyst for flue gas demercuration is made of carrier, active component and auxiliary agent three parts, and the carrier is two
Titanium oxide, the active component are manganese element, and the auxiliary agent is niobium element, wherein manganese element：Niobium element：Mole of titanium elements
Than being 0.13：0.02：1.
A kind of preparation method of catalyst for flue gas demercuration, specifically includes following steps：
(1) soluble niobium salt, soluble manganese salt and soluble titanium salt are dissolved in deionized water, stirring is equal at room temperature
It is even, obtain mixed solution；
(2) pH value for ammonium hydroxide being poured into mixed solution, and adjusting mixed solution reaches 10, is formed and is precipitated, and stirring 5~
It is stood after 10min, repeatedly removes supernatant liquor and add new deionized water, until the pH value of solution reaches 7；
(3) will precipitation filtering, Muffle furnace calcining is moved to after drying to get to product.
Preferably, step (1) the soluble niobium salt is (NH4)3[NbO(C2O4)]。
Preferably, step (1) the soluble manganese salt is C4H6MnO4。
Preferably, step (1) the soluble titanium salt is Ti (SO4)2。
Preferably, step (3) drying is dried 24 hours in 100 DEG C of baking ovens.
Preferably, step (3) is when Muffle furnace is calcined, and in air atmosphere, is risen to the heating rate of 2-8 DEG C/min
500 DEG C, calcination time is 4 hours.
Obtained catalyst can be to mercury element in the exhaust gas of the discharges such as power generation gas turbine and coal-burning boiler at
Reason, can significantly improve the activity and catalytic capability of low temperature demercuration.
The present invention uses selective catalytic reduction (SCR) technology, is carrier by active component, titanium dioxide of manganese element,
The method for preparing catalyst uses coprecipitation, and last catalyst obtained can be to rows such as power generation gas turbine and coal-burning boilers
Mercury is handled in the exhaust gas gone out, can significantly improve low temperature demercuration activity and catalytic capability, 250 DEG C or more can reach 95% or more
Hg removal efficiencies, have stronger industrial application value, can be widely used for the catalysis oxidation of mercury.
Compared with prior art, the specific surface of catalyst can be greatly improved using niobium element as catalyst promoter in the present invention
Product, Mn4+, chemically adsorbing oxygen ratio, and then improve catalyst demercuration catalyst activity with water resistant sulfur resistance.In water and
Under the poisoning effect of sulphur, water resistant sulfur resistive poisoning effect is apparent under the conditions of 250 DEG C.In addition, manganese element, niobium in catalyst of the present invention
Element, titanium elements press 0.13：0.02：1 molar ratio compounding, it is to fix to make the mass ratio of provided active component and carrier
Ratio such as changes ratio therein, then can influence the performance of catalyst, to which said effect be not achieved.The present invention passes through coprecipitated
Shallow lake method prepares catalyst, and preparation process is simple, easily operated, raw materials used to be easy to get, thus catalyst preparation is at low cost, just
In industrialization promotion.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail, but should be in no way restrictive.
In the embodiment of the present invention catalytic reactor used use the outer diameter purchased from Zhejiang Fan Tai Instrument Ltd. for 16nm,
The 4100 type fixed bed devices of a length of 480mm, unstripped gas enter reactor by preheating, and reaction temperature is at 150-450 DEG C, flow velocity
For 1000ml/min, space velocity 108000h-1。
Simulated flue gas forms：NO is 500ppm, NH3For 500ppm, O2For 4%, CO2It is 75 μ g/Nm for 12%, Hg3.Its
Residual air body N2As Balance Air, gas flow is by the CS200 type mass flowmenters purchased from Beijing Co., Ltd of Sevenstar Huachuang Electronic
Control.
NO, NH used in the present invention3Molar concentration is 1%, surplus Ar, is purchased from the big limited public affairs of wound calibrating gas in Shanghai
Department.
Drug used is purchased from Aladdin.
Embodiment 1
A kind of catalyst Mn-Nb/TiO for flue gas demercuration2, the molar ratio by contained active component and carrier is
0.13：1, which includes the following steps：
(1) by 0.002mol ammonium niobium oxalates, 0.013mol manganese acetates, 0.1mol phthalic acids dissolve in deionized water,
5~10min is stirred at room temperature, obtains mixed solution；
(2) ammonium hydroxide is poured into after mixed solution until solution pH value reaches 10, formation precipitates, quiet after 5~10min of stirring
It sets, repeatedly removes supernatant liquor and add new deionized water, up to pH value to 7；
(3) precipitation is filtered, moves to Muffle furnace after being dried 24 hours under 100 DEG C of baking ovens, is calcined 4 hours at 500 DEG C
After to obtain black particle be demercuration catalyst.
Comparative example 1
(1) by 0.1mol titanium sulfates, the dissolving of 0.013mol manganese acetates stirs 5~10min, forms mixing in deionized water
Solution；
(2) ammonium hydroxide is poured into after mixed solution until solution pH value reaches 10, formation precipitates, quiet after 5~10min of stirring
It sets, repeatedly removes supernatant liquor and add new deionized water, up to pH value to 7；
(3) precipitation is filtered, moves to Muffle furnace after being dried 24 hours under 100 DEG C of baking ovens, is calcined 4 hours at 500 DEG C
After to obtain black particle be demercuration catalyst.
By the catalyst obtained by embodiment 1, comparative example 1 respectively at 150 DEG C, 175 DEG C, 200 DEG C, 225 DEG C, 250 DEG C,
Demercuration reaction experiment is carried out under 275 DEG C, 300 degrees Celsius.
Laboratory test start before first in simulated flue gas NO and Hg be passed through 0.5~1h of fixed bed, allow improved catalysts
With typical catalyst absorption Hg saturations, the absorption because of catalyst is avoided to cause the reduction of Hg.
(flue gas flow rate 1000ml/min, gas componant are simulated flue gas one：NO is 500ppm, NH3It is for 500ppm, Hg
75 μ g/Nm3, O2For 4%, CO2It is 12%, remaining gas N2) after mixing, be sent into fixed bed device in mixed gas cylinder and improveing
Under the action of catalyst and typical catalyst, Hg is oxidized to Hg2+, the mixed gas after reaction is through phosphoric acid solution absorption unreacted
NH3It is discharged into air by exhaust pipe, the Hg concentration of inlet and outlet is detected using VM3000 mercury vapourmeters, and the result of demercuration see the table below
1。
1 demercuration result of 1 embodiment 1 of table and comparative example
Demercuration efficiency calculation formula is as follows：
Demercuration efficiency=(import Hg concentration-outlet Hg concentration)/import Hg concentration × 100%.
As it can be seen from table 1 using the catalyst that is prepared of the present invention and typical catalyst under the same conditions into
Row flue gas demercuration, more efficient than typical catalyst, at 250-300 DEG C, catalyst demercuration efficiency is up to 97%.
(flue gas flow rate 1000ml/min, gas componant are simulated flue gas two：NO is 500ppm, NH3It is for 500ppm, Hg
75 μ g/Nm3, SO2For 100ppm, O2For 4%, CO2It is 12%, remaining gas N2) after mixing, be sent into and fix in mixed gas cylinder
Bed apparatus is oxidized to Hg under the action of improved catalysts and typical catalyst, by Hg2+, the mixed gas after reaction is molten through phosphoric acid
Liquid absorbs unreacted NH3It is discharged into air by exhaust pipe, the Hg concentration of inlet and outlet is detected using VM3000 mercury vapourmeters, denitration
The result of demercuration see the table below 2.
1 demercuration result of 2 embodiment 1 of table and comparative example
From table 2 it can be seen that the catalyst and typical catalyst that are prepared using the present invention are in identical SO2Poison item
Flue gas demercuration is carried out under part, it is more efficient than typical catalyst.
In conclusion the catalyst for preparing of present invention demercuration efficiency in the case of same gas has than typical catalyst
It is significant to improve, it is more advantageous to the progress of SCR reactions, less residual heat of electric power plant loss improves thermal power plant's performance driving economy.
Above said content is only the basic explanation under present inventive concept, and that is done according to the technique and scheme of the present invention appoints
What equivalent transformation, belongs to the scope of protection of the invention.
Claims (8)
1. a kind of catalyst for flue gas demercuration is made of, which is characterized in that institute carrier, active component and auxiliary agent three parts
It is titanium dioxide to state carrier, and the active component is manganese element, and the auxiliary agent is niobium element, wherein manganese element：Niobium element：Titanium
The molar ratio of element is 0.13：0.02：1.
2. a kind of a kind of preparation method of catalyst for flue gas demercuration as described in claim 1, which is characterized in that specific
Include the following steps：
(1) soluble niobium salt, soluble manganese salt and soluble titanium salt are dissolved in deionized water, are stirred evenly at room temperature,
Obtain mixed solution；
(2) pH value for ammonium hydroxide being poured into mixed solution, and adjusting mixed solution reaches 10, forms precipitation, after stirring 5~10min
It stands, repeatedly removes supernatant liquor and add new deionized water, until the pH value of solution reaches 7；
(3) will precipitation filtering, Muffle furnace calcining is moved to after drying to get to product.
3. a kind of preparation method of catalyst for flue gas demercuration according to claim 2, which is characterized in that step
(1) the soluble niobium salt is (NH4)3[NbO(C2O4)]。
4. a kind of preparation method of catalyst for flue gas demercuration according to claim 2, which is characterized in that step
(1) the soluble manganese salt is C4H6MnO4。
5. a kind of preparation method of catalyst for flue gas demercuration according to claim 2, which is characterized in that step
(1) the soluble titanium salt is Ti (SO4)2。
6. a kind of preparation method of catalyst for flue gas demercuration according to claim 2, which is characterized in that step
(3) drying is dried 24 hours in 100 DEG C of baking ovens.
7. a kind of preparation method of catalyst for flue gas demercuration according to claim 2, which is characterized in that step
(3) when Muffle furnace is calcined, in air atmosphere, 500 DEG C are risen to the heating rate of 2-8 DEG C/min, calcination time is 4 small
When.
8. a kind of a kind of application of catalyst for flue gas demercuration as described in claim 1, which is characterized in that the catalysis
Agent is used for flue gas demercuration.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110548501A (en) * | 2019-07-26 | 2019-12-10 | 天津浩创节能环保设备有限公司 | denitration and demercuration catalyst and preparation method thereof |
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| CN103084165A (en) * | 2013-01-23 | 2013-05-08 | 广东电网公司电力科学研究院 | Demercuration catalyst for elemental mercury in oxidated coal-fired flue gas and preparation method thereof |
| WO2015187550A2 (en) * | 2014-06-04 | 2015-12-10 | Johnson Matthey Public Limited Company | Non-pgm ammonia slip catalyst |
| CN105214679A (en) * | 2015-08-17 | 2016-01-06 | 中国石油大学(北京) | A kind of water resistant sulfur resistive type denitrating flue gas powder catalyst, preparation method and its usage |
| CN105879858A (en) * | 2016-04-15 | 2016-08-24 | 中国建筑材料科学研究总院 | Denitrification catalyst and preparation method thereof |
-
2018
- 2018-03-29 CN CN201810270637.0A patent/CN108435161A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120164047A1 (en) * | 2009-02-16 | 2012-06-28 | Augustine Steven M | Catalyst Promoters In Vanadium-Free Mobile Catalyst |
| CN103084165A (en) * | 2013-01-23 | 2013-05-08 | 广东电网公司电力科学研究院 | Demercuration catalyst for elemental mercury in oxidated coal-fired flue gas and preparation method thereof |
| WO2015187550A2 (en) * | 2014-06-04 | 2015-12-10 | Johnson Matthey Public Limited Company | Non-pgm ammonia slip catalyst |
| CN105214679A (en) * | 2015-08-17 | 2016-01-06 | 中国石油大学(北京) | A kind of water resistant sulfur resistive type denitrating flue gas powder catalyst, preparation method and its usage |
| CN105879858A (en) * | 2016-04-15 | 2016-08-24 | 中国建筑材料科学研究总院 | Denitrification catalyst and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110548501A (en) * | 2019-07-26 | 2019-12-10 | 天津浩创节能环保设备有限公司 | denitration and demercuration catalyst and preparation method thereof |
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Application publication date: 20180824 |