CN103537273A - Denitration catalyst for collaborative mercury removal and preparation method thereof - Google Patents
Denitration catalyst for collaborative mercury removal and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a denitration catalyst for collaborative mercury removal. The denitration catalyst comprises the following components in percentage by mass: 5-10% of vanadium pentoxide, 5-10% of molybdenum trioxide and the balance of titanium dioxide. The preparation method of the catalyst comprises the following steps: mixing tetra-n-butyl titanate, absolute ethyl alcohol, ammonia water and a citric acid solution, and shaking to obtain a titanium-containing sol; respectively dissolving metavanadic ammonia acid and molybdenum trioxide into the ammonia water to obtain a mixed solution, then leading the mixed solution into the sol, shaking and drying to obtain a gel; calcining and grinding the gel to obtain the denitration catalyst. The denitration catalyst for collaborative mercury removal can be used for significantly improving the efficiency of catalyzing and oxidizing mercury and controlling the ratio of oxidizing SO2 into SO3, and the catalyst is simple in component, reasonable in proportion and low in cost. The components in the catalyst prepared by the sol-gel method provided by the invention for preparing the catalyst have good dispersity, so that uniform doping of all active components at the molecular level is well realized.
Description
Technical field
The present invention relates to denitrating catalyst of a kind of collaborative demercuration and preparation method thereof, belong to atmosphere pollution purification techniques field.
Background technology
Coal is the abundantest a kind of fossil fuel resource of content, and China is maximum in the world coal production and country of consumption, and since the nineties in last century, the coal production of China and consumption figure are just sure to occupy No. 1 in the world for a long time.And the particularly operation of coal-burning power plant of coal burning can bring serious problem of environmental pollution, mercury and the nitrogen oxide of coal-burning power plant's discharge are that human activity is discharged into main source in atmosphere.Due to the mercury of discharging into the atmosphere enters behind biosphere can enrichment in human body, the nervous system of human body is damaged to serious harm health.And nitrogen oxide (NO
x) can cause the local environment problems such as acid rain and photochemical fog, bring serious threat to the mankind's existence.Based on this, country has stipulated first the discharge standard of mercury and nitrogen oxide in thermal power plant's pollutant emission standard of promulgating for 2011, and wherein the discharge standard of mercury is 0.03mg/Nm
3, the discharge standard of nitrogen oxide is 100mg/Nm
3.
Mercury is mainly present in coal-fired flue-gas with three kinds of forms: Elemental Mercury (Hg
0), particle mercury (Hg
p) and divalence mercury (Hg
2+).Wherein, particle mercury (Hg
p) be easy to be removed by electrostatic precipitator or sack cleaner with particle divalence mercury (Hg
2+) because of soluble in water, easily by wet desulphurization device (FGD), removed, only have Elemental Mercury (Hg
0) due to its strong volatility and be insoluble to water-based, existing smoke eliminator is difficult to be removed.Therefore, the technical barrier removing of Mercury In Coal Combustion Flue Gas, mainly concentrates on removing Elemental Mercury in flue gas.The removal methods of controlling at present coal-burning power plant's Elemental Mercury mainly contains two kinds: absorption method and oxidizing process.It is that a kind of effect is adsorbed demercuration method preferably that active carbon sprays into, but it is expensive, and the flying dust that is mixed with higher carbon content is difficult to be used effectively.Oxidizing process demercuration is first to utilize catalyst that Elemental Mercury Catalytic Oxygen is changed into divalence mercury, then uses wet desulphurization device (WFGD) to remove divalence mercury.Oxidizing process demercuration is the main method that current coal-fired flue-gas Elemental Mercury removes.
NO in coal-fired flue-gas
xremoval methods generally adopt selective catalytic reduction, for improving reaction efficiency, general auxiliary with denitrating catalyst (take vanadic anhydride as main active, titanium dioxide are matrix, claim again SCR catalyst).Denitrating catalyst is at reductive NO
xtime have the performance of capable of oxidizing simple substance mercury concurrently, still, under typical SCR temperature window (350 ℃-400 ℃), the NO of denitrating catalyst
xalthough percent reduction can reach more than 80%, but can only reach 20%-50% to the oxidation efficiency of Elemental Mercury, its main cause be the optimum temperature of denitrating catalyst mercury oxide lower than 300 ℃, thereby can not be at reductive NO
xsuitable operating temperature (350 ℃-400 ℃) be issued to desirable mercury oxidation efficiency.
In addition, due in denitrating catalyst, if the content of main active vanadic anhydride is higher, the SO in coal-fired flue-gas
2be oxidized to SO
3ratio can obviously increase, and SO
3can make the reactive metal oxide on denitrating catalyst surface generate sulfate, thereby make catalyst poisoning, so in traditional SCR denitrating catalyst, the content of vanadium is generally all lower than 3%.Because the content of active material vanadic anhydride in denitrating catalyst is less, the oxidation activity site that can offer Elemental Mercury is seldom corresponding, causes the oxidation efficiency of Elemental Mercury further to reduce.Thereby, use the smoke eliminator of existing coal-burning power plant and traditional denitrating catalyst, be difficult to make Elemental Mercury in flue gas to reach the discharge standard of national regulation.
Application for a patent for invention " a kind of denitrating catalyst of double demercuration ", date of publication: 2012.3.7, publication No.: CN102366722A, discloses a kind of denitrating catalyst of double demercuration, and chemical general formula is: MX
n-V
2o
5-Y/TiO
2, wherein, M is selected from metal unit Fe, Cu, Mn or Co; X is halogen Cl or Br; Y is WO
3or MoO
3, n=2～4; Weight proportion is: M1～10, V1～1.5, W or Mo7.5～8.5, TiO
275～100.This catalyst MCl
nor MBr
ndipping V
2o
5-WO
3/ TiO
2or V
2o
5-MoO
3/ TiO
2, drying, roasting are made.This catalyst, owing to having added transition metal halide, can utilize wherein Cl or the strong oxidizing property of Br and the redox property of transition metal, by nonvalent mercury Hg
0be oxidized to Hg
2+overcome the impact on SCR catalyst acid active site of halide with traditional K, Na, guaranteed catalytic activity, thereby make catalyst under the flue gas of 300～450 ℃, keep higher denitration efficiency, make again the oxygenation efficiency of Hg below 30%, bring up to 85.1%～93.8% by traditional simultaneously, greatly promoted catalytic efficiency, the SCR denitrating catalyst that transition metal halide is processed simultaneously can not increase SO
2/ SO
3conversion ratio, has avoided catalyst poisoning and secondary pollution.
But also there are obvious shortcomings and deficiencies in above-mentioned catalyst: the one, add transition metal halide as oxidant, greatly increased catalyst cost; The 2nd, main active V
2o
5content lower (1～1.5%), V
2o
5the oxidation efficiency of capable of oxidizing simple substance mercury is lower; The 3rd, although added WO in catalyst
3or MoO
3, but fail clear and definite its at reductive NO
x, capable of oxidizing simple substance mercury reaction in the catalytic action and the Catalysis Principles that play, thereby also fail to provide the rational proportion of above-mentioned substance in catalyst.
Summary of the invention
Technical purpose of the present invention is intended to solve existing denitrating catalyst and adopts the shortcomings and deficiencies such as the cost that transition metal halide exists for capable of oxidizing simple substance mercury as oxidant is higher, active component proportioning is unreasonable, denitrating catalyst of a kind of collaborative demercuration and preparation method thereof is provided, the active component of this catalyst is comprised of vanadic anhydride and molybdenum trioxide, by interpolation and the rational proportion of molybdenum trioxide, make catalyst in the good catalytic denitration performance of maintenance, to significantly improve the efficiency of catalytic oxidation mercury, and can effectively control SO
2be oxidized to SO
3ratio, and the component of catalyst is simple, reasonable mixture ratio, with low cost.
The present invention is that the technical scheme that realizes technical purpose employing is: a kind of denitrating catalyst of collaborative demercuration, it is characterized in that: described catalyst comprises that mass percent is 5%～10% vanadic anhydride, mass percent is 5%～10% molybdenum trioxide, and all the other compositions in described catalyst are titanium dioxide.
A denitrating catalyst for collaborative demercuration, described catalyst is ground into 100～325 orders.
A method for the denitrating catalyst of collaborative demercuration, comprises the following steps:
(1) positive four butyl esters of the metatitanic acid of quantitative volume are evenly mixed under 40 ℃ of conditions with isopyknic absolute ethyl alcohol, obtain mixed liquor;
(2) according to ammoniacal liquor and positive four butyl esters of metatitanic acid, take the ratio that volume ratio is 1:3, ammoniacal liquor is imported to step (1) and obtain in mixed liquor, in 40 ℃ of environment, shake 1h, obtain the Sol A of titaniferous;
(3) citric acid solution that configuration quality concentration is 10%, gets and the middle isopyknic citric acid solution of ammoniacal liquor of step (2), imports in Sol A, under 40 ℃ of conditions, shakes 10min, obtains sol B;
(4) take the inclined to one side vanadium propylhomoserin solid that v element content is 5～10 weight portions, be dissolved in step (2) in the isopyknic salpeter solution of ammoniacal liquor in, obtain solution A, take the molybdenum trioxide of 5～10 weight portions, be dissolved in the isopyknic ammoniacal liquor of ammoniacal liquor in step (2), obtain solution B;
(5) solution A step (4) being obtained, B successively import in the sol B that titanium elements content is 80～90 weight portions, then add red fuming nitric acid (RFNA) will regulate pH value to 1, and under 40 ℃ of conditions, shake 5h, be then warming up to 70 ℃ and under 70 ℃ of conditions dry 48h, obtain gel;
(6) gel step (5) being obtained is placed in Muffle furnace, is warming up to 400 ℃, and calcining 5h, grinds, and obtains this catalyst.
A method for the denitrating catalyst of collaborative demercuration, in described step (5), gel heats up according to the heating rate of 6 ℃/min.
Although application to some extent of titanium vanadium-molybdenum catalyst in prior art, but prior art was not carried out correlation theory research on the interpolation of molybdenum for the impact of mercury oxidation, thereby also fail to obtain Catalysis Principles and the catalytic effect of molybdenum in vanadium titanium catalyst, naturally also fail to obtain the rational proportion of molybdenum in catalyst.
Applicant of the present invention finds through research, after adding molybdenum trioxide, be conducive to improve the architectural characteristic of catalyst in traditional titanium vanadium catalyst, has increased catalyst surface
acid site, in titanium vanadium catalyst, main active substances that can mercury oxide is vanadic anhydride, and in titanium vanadium-molybdenum catalyst, except vanadic anhydride generation effect, molybdenum trioxide and vanadium molybdenum complex all can be beneficial to the oxidation of mercury, thereby can significantly promote the oxidation efficiency of Elemental Mercury.The more important thing is, molybdenum not only can not participate in SO
2oxidation, and the interpolation of molybdenum causes the improvement of catalyst structure, is unfavorable for SO
2in catalyst surface absorption, thereby stoped SO
2further to SO
3transformation, thereby the interpolation of molybdenum not only can not increase, can reduce SO on the contrary
2to SO
3level of conversion.So, adding under the prerequisite of molybdenum, can also further improve the content of main active vanadic anhydride, thereby realize SO simultaneously
2be oxidized to SO
3ratio maintain under the prerequisite of reduced levels, significantly improve the oxidation efficiency of Elemental Mercury.
Applicant of the present invention is by great many of experiments, studied in titanium vanadium-molybdenum catalyst, add molybdenum after to catalyst at the high SO of high temperature
2the impact of mercury oxide under condition.Experimental result shows, after the molybdenum of interpolation 5%～10%, even if the content of vanadic anhydride reaches in 5%～10%(prior art, is generally no more than 3%), SO
2be oxidized to SO
3ratio still maintain 2% with interior low-level, and simultaneously, NO
xpercent reduction can reach 85～90%, and mercury oxidation rate can reach 75～82%.Experimental result also shows, when the content of molybdenum is 5%～10%, the oxidation efficiency of mercury kept to higher and similar level roughly; When molybdenum content is lower than 5% time or higher than 10% time, mercury oxidation efficiency is all lower.Therefore the best proportioning of molybdenum in catalyst is 5%～10%.
With prior art titanium vanadium-molybdenum catalyst, compare, catalyst provided by the invention is without adding transition metal halide, only by the content of rational proportion molybdenum trioxide, improve the content of vanadic anhydride simultaneously, just can make active component molybdenum trioxide and vanadic anhydride reach best catalytic effect, thereby solve under hot conditions the too low and oxygenate content of mercury oxidation rate SO when higher
2be oxidized to SO3 ratio compared with high-technology problem, and obviously reduced the product cost of catalyst.
In the present invention, the preparation method of catalyst is sol-gel process, then to catalyst sample calcining moulding, and prior art SCR method for preparing catalyst is generally infusion process, sol-gel process is the good dispersion of each component in the catalyst of preparation with respect to the advantage of infusion process, realized well the Uniform Doped of each active component in catalyst on molecular level.
The specific embodiment
Embodiment 1 catalyst (TV of the present invention
5m
5) preparation
According to the following steps:
(1) positive four butyl esters of the metatitanic acid of quantitative volume are evenly mixed under 40 ℃ of conditions with isopyknic absolute ethyl alcohol, obtain mixed liquor;
(2) according to ammoniacal liquor and positive four butyl esters of metatitanic acid, take the ratio that volume ratio is 1:3, ammoniacal liquor is imported to step (1) and obtain in mixed liquor, in 40 ℃ of environment, shake 1h, obtain the Sol A of titaniferous;
(3) citric acid solution that configuration quality concentration is 10%, gets and the middle isopyknic citric acid solution of ammoniacal liquor of step (2), imports in Sol A, under 40 ℃ of conditions, shakes 10min, obtains sol B;
(4) take the inclined to one side vanadium propylhomoserin solid that v element content is 5 weight portions, be dissolved in step (2) in the isopyknic salpeter solution of ammoniacal liquor in, obtain solution A, take the molybdenum trioxide of 5 weight portions, be dissolved in the isopyknic ammoniacal liquor of ammoniacal liquor in step (2), obtain solution B;
(5) solution A step (4) being obtained, B successively import in the sol B that titanium elements content is 90 weight portions, then add red fuming nitric acid (RFNA) and regulate pH value to 1, and shake 5h under 40 ℃ of conditions, be then warming up to 70 ℃ and under 70 ℃ of conditions dry 48h, obtain gel;
(6) gel step (5) being obtained is placed in Muffle furnace, with the heating rate of 6 ℃/min, is warming up to 400 ℃, and calcining 5h, grinds, and then the product after calcining is milled to 100～325 orders, obtains catalyst TV
5m
5.
Embodiment 2 catalyst (TV of the present invention
5m
10) preparation
According to the following steps:
Step (1)～(3) are with embodiment 1;
(4) take the inclined to one side vanadium propylhomoserin solid that v element content is 5 weight portions, be dissolved in step (2) in the isopyknic salpeter solution of ammoniacal liquor in, obtain solution A, take the molybdenum trioxide of 10 weight portions, be dissolved in the isopyknic ammoniacal liquor of ammoniacal liquor in step (2), obtain solution B;
(5) it is in 85 weight portion sol B that solution A step (4) being obtained, B successively import titanium elements content, then with red fuming nitric acid (RFNA), will regulate ph value of mixture to 1, and under 40 ℃ of conditions, shake 5h, be then warming up to 70 ℃ and under 70 ℃ of conditions dry 48h, obtain gel;
(6) gel step (5) being obtained is placed in Muffle furnace, with the heating rate of 6 ℃/min, is warming up to 400 ℃, and calcining 5h, grinds, and then the product after calcining is milled to 100～325 orders, obtains catalyst TV
5m
10.
Embodiment 3 catalyst (TV of the present invention
10m
5) preparation
According to the following steps:
Step (1)～(3) are with embodiment 1;
(4) take the inclined to one side vanadium propylhomoserin solid that v element content is 10 weight portions, be dissolved in step (2) in the isopyknic salpeter solution of ammoniacal liquor in, obtain solution A, take the molybdenum trioxide of 5 weight portions, be dissolved in the isopyknic ammoniacal liquor of ammoniacal liquor in step (2), obtain solution B;
(5) it is in 85 weight portion sol B that solution A step (4) being obtained, B successively import titanium elements content, then with red fuming nitric acid (RFNA), will regulate ph value of mixture to 1, and under 40 ℃ of conditions, shake 5h, be then warming up to 70 ℃ and under 70 ℃ of conditions dry 48h, obtain gel;
(6) gel step (5) being obtained is placed in Muffle furnace, with the heating rate of 6 ℃/min, is warming up to 400 ℃, and calcining 5h, grinds, and then the product after calcining is milled to 100～325 orders, obtains catalyst TV
10m
5.
Embodiment 4 catalyst (TV of the present invention
10m
10) preparation
According to the following steps:
Step (1)～(3) are with embodiment 1;
(4) take the inclined to one side vanadium propylhomoserin solid that v element content is 10 weight portions, be dissolved in step (2) in the isopyknic salpeter solution of ammoniacal liquor in, obtain solution A, take the molybdenum trioxide of 10 weight portions, be dissolved in the isopyknic ammoniacal liquor of ammoniacal liquor in step (2), obtain solution B;
(5) it is in 80 weight portion sol B that solution A step (4) being obtained, B successively import titanium elements content, then with red fuming nitric acid (RFNA), will regulate ph value of mixture to 1, and under 40 ℃ of conditions, shake 5h, be then warming up to 70 ℃ and under 70 ℃ of conditions dry 48h, obtain gel;
(6) gel step (5) being obtained is placed in Muffle furnace, with the heating rate of 6 ℃/min, is warming up to 400 ℃, and calcining 5h, grinds, and then the product after calcining is milled to 100～325 orders, obtains catalyst TV
10m
10.
Comparative example 1 catalyst (TV
5) preparation
According to the following steps:
Step (1)～(3) are with embodiment 1;
(4) take the inclined to one side vanadium propylhomoserin solid that v element content is 5 weight portions, be dissolved in step (2) in the isopyknic salpeter solution of ammoniacal liquor in, obtain solution A;
(5) it is in 95 weight portion sol B that the solution A that step (4) obtained imports titanium elements content, then with red fuming nitric acid (RFNA), will regulate ph value of mixture to 1, and shake 5h under 40 ℃ of conditions, is then warming up to 70 ℃ and under 70 ℃ of conditions, be dried 48h, obtains gel;
(6) gel step (5) being obtained is placed in Muffle furnace, with the heating rate of 6 ℃/min, is warming up to 400 ℃, and calcining 5h, grinds, and then the product after calcining is milled to 100～325 orders, obtains catalyst TV
5.
Comparative example 2 catalyst (TV
10) preparation
According to the following steps:
Step (1)～(3) are with embodiment 1;
(4) take the inclined to one side vanadium propylhomoserin solid that v element content is 10 weight portions, be dissolved in step (2) in the isopyknic salpeter solution of ammoniacal liquor in, obtain solution A;
(5) it is in 90 weight portion sol B that the solution A that step (4) obtained imports titanium elements content, then with red fuming nitric acid (RFNA), will regulate ph value of mixture to 1, and shake 5h under 40 ℃ of conditions, is then warming up to 70 ℃ and under 70 ℃ of conditions, be dried 48h, obtains gel;
(6) gel step (5) being obtained is placed in Muffle furnace, with the heating rate of 6 ℃/min, is warming up to 400 ℃, and calcining 5h, grinds, and then the product after calcining is milled to 100～325 orders, obtains catalyst TV
10.
Catalyst activity test experiments
The activity of testing respectively six catalyst prepared by four embodiment of the present invention and two comparative examples on fixed bed reactors, test event comprises: mercury oxidation rate, NO
xpercent reduction and SO
2be oxidized to SO
3ratio.Test condition is: simulated flue gas flow is 0.9Nm
3/ h; Simulated flue gas composition is 0.04%NO, 0.04%NH
3, 6%O
2, 13%CO
2, 8%H
2o, 0.08%SO
2, 0.002%HCl, 55 μ g/Nm
3; Reaction temperature is 350 ℃; The catalyst amount of single test is 0.3g.Test result is as shown in the table:
| Embodiment | Contrast is real | Embodiment | Embodiment 2 | Contrast is real | Embodiment 1 | Embodiment 2 |
| ? | Execute example 1 | 1 | ? | Execute example 2 | ? | ? |
| Catalyst | TV 5 | TV 5M 5 | TV 5M 10 | TV 10 | TV 10M 5 | TV 10M 10 |
| Mercury oxidation rate | 53% | 81% | 75% | 49% | 82% | 78% |
| NO xPercent reduction | 89% | 90% | 85% | 91% | 86% | 88% |
| SO 2Oxygenation efficiency | 3% | 2% | 1.5% | 6% | 1.5% | 1.8% |
As can be seen from the above table: do not adding under the prerequisite of molybdenum, when improving content to 5～10% of vanadium, although NO
xpercent reduction can reach the higher level of 90% left and right, but the oxygenation efficiency of mercury can only reach 50% left and right, and SO
2oxygenation efficiency reaches 3%～6%, far beyond required standard; After adding 5～10% molybdenums and improve content of vanadium and being increased to 5～10%, titanium vanadium catalyst is (350 ℃～400 ℃) under typical SCR temperature window, NO
xpercent reduction can keep 85～91% higher level, and the efficiency of simultaneous oxidation mercury is significantly increased to 75～82%, and SO
2oxygenation efficiency maintains 2% with interior low-level, and the property indices of obvious vanadium titanium molybdenum catalyst provided by the invention has all reached very satisfied level.
Claims (4)
1. a denitrating catalyst for collaborative demercuration, is characterized in that: described catalyst comprises that mass percent is 5%～10% vanadic anhydride, the molybdenum trioxide that mass percent is 5%～10%, and all the other compositions in described catalyst are titanium dioxide.
2. the denitrating catalyst of a kind of collaborative demercuration according to claim 1, is characterized in that: described catalyst is ground into 100～325 orders.
3. for the preparation of a method for the denitrating catalyst of collaborative demercuration claimed in claim 1, it is characterized in that comprising the following steps:
(1) positive four butyl esters of the metatitanic acid of quantitative volume are evenly mixed under 40 ℃ of conditions with isopyknic absolute ethyl alcohol, obtain mixed liquor;
(2) according to ammoniacal liquor and positive four butyl esters of metatitanic acid, take the ratio that volume ratio is 1:3, ammoniacal liquor is imported to step (1) and obtain in mixed liquor, in 40 ℃ of environment, shake 1h, obtain the Sol A of titaniferous;
(3) citric acid solution that configuration quality concentration is 10%, gets and the middle isopyknic citric acid solution of ammoniacal liquor of step (2), imports in Sol A, under 40 ℃ of conditions, shakes 10min, obtains sol B;
(4) take the inclined to one side vanadium propylhomoserin solid that v element content is 5～10 weight portions, be dissolved in step (2) in the isopyknic salpeter solution of ammoniacal liquor in, obtain solution A, take the molybdenum trioxide of 5～10 weight portions, be dissolved in the isopyknic ammoniacal liquor of ammoniacal liquor in step (2), obtain solution B;
(5) solution A step (4) being obtained, B successively import in the sol B that titanium elements content is 80～90 weight portions, then add red fuming nitric acid (RFNA) will regulate pH value to 1, and under 40 ℃ of conditions, shake 5h, be then warming up to 70 ℃ and under 70 ℃ of conditions dry 48h, obtain gel;
(6) gel step (5) being obtained is placed in Muffle furnace, is warming up to 400 ℃, and calcining 5h, grinds, and obtains this catalyst.
4. the method for a kind of denitrating catalyst for the preparation of collaborative demercuration according to claim 3, is characterized in that: in described step (5), gel heats up according to the heating rate of 6 ℃/min.
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| CN108686651A (en) * | 2018-05-30 | 2018-10-23 | 临沂大学 | A kind of catalyst and its preparation method and application of flue gas denitration demercuration simultaneously |
| CN110433837A (en) * | 2019-06-06 | 2019-11-12 | 大唐南京环保科技有限责任公司 | A kind of denitration demercuration catalyst and preparation method thereof for flue gas |
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| CN106362732A (en) * | 2016-08-30 | 2017-02-01 | 山东海润环保科技有限公司 | Denitration and demercuration catalyst |
| CN106362732B (en) * | 2016-08-30 | 2019-08-16 | 山东海润环保科技有限公司 | Denitration demercuration catalyst |
| CN108686651A (en) * | 2018-05-30 | 2018-10-23 | 临沂大学 | A kind of catalyst and its preparation method and application of flue gas denitration demercuration simultaneously |
| CN108686651B (en) * | 2018-05-30 | 2020-10-23 | 临沂大学 | Catalyst for simultaneously denitrifying and removing mercury from flue gas, and preparation method and application thereof |
| CN110433837A (en) * | 2019-06-06 | 2019-11-12 | 大唐南京环保科技有限责任公司 | A kind of denitration demercuration catalyst and preparation method thereof for flue gas |
| CN110433837B (en) * | 2019-06-06 | 2022-04-12 | 大唐南京环保科技有限责任公司 | Denitration and demercuration catalyst for flue gas and preparation method thereof |
| CN114308010A (en) * | 2021-12-23 | 2022-04-12 | 江苏金聚合金材料有限公司 | Preparation and application of titanium dioxide loaded molybdenum trioxide and vanadium pentoxide catalyst |
| CN114308010B (en) * | 2021-12-23 | 2023-11-03 | 江苏金聚合金材料有限公司 | Preparation and application of titanium dioxide loaded molybdenum trioxide and vanadium pentoxide catalyst |
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