CN107262110B - ternary composite denitration and demercuration catalyst and preparation method thereof - Google Patents

ternary composite denitration and demercuration catalyst and preparation method thereof Download PDF

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CN107262110B
CN107262110B CN201710482491.1A CN201710482491A CN107262110B CN 107262110 B CN107262110 B CN 107262110B CN 201710482491 A CN201710482491 A CN 201710482491A CN 107262110 B CN107262110 B CN 107262110B
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demercuration
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nitrate
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苏胜
刘利军
向军
胡松
汪一
许凯
江龙
卿梦霞
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Huazhong University of Science and Technology
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    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • 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
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Abstract

The invention relates to ternary composite denitration and demercuration catalyst and a preparation method thereof, wherein the ternary composite catalyst consists of 44-68 wt% of a main catalyst, 16-24 wt% of a th auxiliary agent and 8-40 wt% of a second auxiliary agent, the main catalyst is manganese dioxide, the th auxiliary agent is samarium trioxide, and the second auxiliary agent is cobaltosic oxide or molybdenum trioxide.

Description

ternary composite denitration and demercuration catalyst and preparation method thereof
Technical Field
The invention belongs to the field of prevention and control of atmospheric pollutants, relates to removal of nitrogen oxides and mercury in waste gas discharged by industrial furnaces and kilns in thermal power plants, industrial boilers, metallurgy, waste incineration and the like, and particularly relates to ternary composite denitration and demercuration catalyst and a preparation method thereof.
Background
China is the largest coal producing country and consuming country in the world and is also of a few countries with coal-based energy structures in the world, the total coal consumption in the year accounts for more than 50% of the total coal consumption in the world, and the energy structures with coal-based energy structures in China are not expected to be fundamentally changed in a long time of xAnd atmospheric pollutants such as Hg. NOxAnd the discharge of large quantities of Hg can cause significant environmental and human health risks. Countries around the world set strict standards for the emission of pollutants from coal-fired flue gases. In the "thirteen-five" program of our country, the country also targets NOxAnd ultra-low emission of atmospheric pollutants such as Hg. In order to achieve the aims, the development of an efficient, feasible and cheap denitration and demercuration technology is necessary.
At present, the most popular technology for denitration of coal-fired power plants is SCR (Selective Catalytic reduction technology). The catalyst adopted in the technology is a vanadium-titanium-based catalyst, the optimal denitration activity window of the catalyst is 300-420 ℃, and an SCR device is generally arranged between an economizer and an air preheater, the vanadium-titanium-based medium-temperature catalyst has problems in the application of commercial engineering, wherein (1) the catalyst is easily worn and the catalyst performance and service life are reduced because a large amount of fly ash is contained in flue gas before a dust removal device and a desulfurization device, (2) alkali metals (Na, K and the like) in the fly ash, arsenic, mercury and other substances easily cause catalyst poisoning, and the catalyst chemical performance and service life are reduced, and (3) SO in the flue gas2Is easily oxidized into SO under the action of catalyst3Corrosive substances are generated under the action of water vapor in the flue gas, so that downstream equipment such as an air preheater and the like is corroded; (4) SO in flue gas2Is easy to be inIs oxidized into SO under the action of catalyst3Then with NH3And (5) the vanadium component in the vanadium-titanium based catalyst is easy to run off and causes definite damage to human beings and the environment, so if a low-temperature catalyst (100-200 ℃) is developed, and an SCR device is placed behind the air preheater and a dust removal device, even behind a desulfurization device, many technical problems faced by denitration at present are solved.
Aiming at another pollutants Hg in coal-fired flue gas, the most promising removal method is to remove Hg by using an SCR catalyst0Oxidation to Hg2+Then using Hg2+The dissolubility and the subsequent wet desulphurization device realize the Hg pair2+And (4) removing. The technology improves the capability of the environmental protection facility for removing the pollutants in a coordinated manner, avoids the repeated construction of the environmental protection facility and does not need additional investment.
Therefore, the development of an SCR catalyst for simultaneous denitration and demercuration at low temperature becomes a hot spot of research in the field, and the development of the catalyst has an important significance for controlling the emission of flue gas pollutants.
Disclosure of Invention
The invention provides ternary composite denitration and demercuration catalysts and a preparation method thereof, aiming at overcoming the defects in the prior art to a certain extent by and realizing simultaneous denitration and demercuration at low temperature (100-200 ℃).
The technical scheme adopted by the invention for achieving the purpose is that ternary composite denitration and demercuration catalyst is composed of 44-68 wt% of a main catalyst, 16-24 wt% of a th auxiliary agent and 8-40 wt% of a second auxiliary agent, wherein the main catalyst is manganese dioxide, the th auxiliary agent is samarium trioxide, and the second auxiliary agent is cobaltosic oxide or molybdenum trioxide.
The research of the invention finds that the main catalyst manganese dioxide has good NO catalytic reduction at low temperaturexAnd the activity of catalyzing and oxidizing mercury, the addition of the second auxiliary agent cobaltosic oxide or molybdenum trioxide can promote the dispersion of manganese dioxide particles and form stable compounds, and promote mercury oxygenThe addition of the No. auxiliary agent samarium sesquioxide can enlarge the specific surface area of the catalyst and improve the Mn on the surface of the catalyst4+In addition, the addition of the samarium trioxide promotes the interaction among all active components, the synergistic effect improves the low-temperature catalytic activity, and the obtained ternary composite denitration and demercuration catalyst has better denitration and demercuration efficiency at low temperature.
Manganese nitrate, samarium nitrate, cobalt nitrate, ammonium molybdate and the like in the nitrate aqueous solution are converted into corresponding manganese dioxide, samarium trioxide, cobaltosic oxide and molybdenum trioxide through hydrolysis reaction, dehydration reaction and/or oxidation reaction and the like in the processes of reduced pressure rotary distillation and calcination.
The invention also provides a preparation method of the ternary composite denitration and demercuration catalyst, which comprises the following steps:
s1, converting according to the weight percentages of a main catalyst, an th auxiliary agent and a second auxiliary agent, taking manganese nitrate, samarium nitrate and cobalt nitrate or ammonium molybdate in corresponding amounts after conversion, dissolving in deionized water, and uniformly stirring to obtain a nitrate solution (the proportion of the manganese nitrate, the samarium nitrate and the cobalt nitrate or ammonium molybdate can be easily converted by a person skilled in the art according to the weight proportion of the main catalyst, the th auxiliary agent and the second auxiliary agent according to the principle of conservation of mass);
s2, dissolving citric acid which is more than 10 percent more than the total amount of metal ions in the nitrate solution obtained in the step S1 in deionized water to obtain a citric acid solution;
s3, dropwise adding the citric acid solution of S2 into the nitrate solution obtained in S1, uniformly stirring, then adding a dispersing agent, and carrying out decompression rotary evaporation at the temperature of 55-65 ℃ until gel is formed;
and S4, drying the gel obtained in the step S3 in vacuum at the temperature of 70-100 ℃, igniting the dried gel, then calcining, and grinding and screening the calcined product to obtain the ternary composite denitration and demercuration catalyst.
On the basis of the above technical scheme, the invention can also have specific selection of step .
Specifically, the manganese nitrate in the S1 is a 50 wt% manganese nitrate solution.
Specifically, the total concentration of nitrates in the nitrate solution in S1 is 10 to 30 wt%.
Specifically, the concentration of the citric acid solution in the S2 is 20-45 wt%.
Specifically, the reduced pressure rotary evaporation in S3 was carried out in a rotary evaporator under a vacuum of-0.08 MPa.
Specifically, the dispersant in S3 is glycol, and the dosage of the dispersant is 0.25-1% of the mass of the nitrate solution.
Specifically, the vacuum drying time in S4 is more than 24h, and the ignition agent used when the gel is ignited is ethanol.
Specifically, the calcination treatment in S4 is carried out in a muffle furnace, and the calcination treatment specifically comprises the steps of calcining at 400 ℃ for 2h, and then calcining at 650 ℃ for 6 h.
Specifically, the particle size of the ternary composite denitration and demercuration catalyst obtained by grinding and screening in the step S4 is 40-60 meshes.
Compared with the prior art, the invention has the beneficial effects that: the preparation process is simple, the cost is low, the active components in the catalyst are well dispersed, and the high catalytic activity can be obtained by reasonably distributing the content of each component in the catalyst; under the flue gas atmosphere of a typical coal-fired power plant, the denitration efficiency of over 90 percent and the mercury oxidation rate of over 80 percent can be simultaneously obtained by the catalyst at the temperature of 100-200 ℃; the catalyst of the invention has better water resistance and sulfur resistance and has no secondary pollution to the environment.
Detailed Description
The invention is described in further detail in with reference to specific examples, which are provided for purposes of illustration only and are not intended to limit the scope of the invention.
The methods used in the following examples are conventional methods unless otherwise specified, the drugs used are commercially available products, and Mn in the following examplesn1Smn2Con3OxRepresents a ternary complex typeDenitration and demercuration catalyst, wherein n1, n2 and n3 are specific numbers and represent the mass percentage of corresponding metal oxides in the catalyst, such as Mn68Sm16Co16OxThe mass percent of manganese dioxide, samarium trioxide and cobaltosic oxide in the ternary composite denitration and demercuration catalyst is 68%, 16% and 16%.
Example 1
ternary composite denitration and demercuration catalyst Mn68Sm16Co16OxThe preparation method comprises the following steps:
s1, preparing a mixture of manganese dioxide, samarium sesquioxide and cobaltosic oxide according to the weight ratio of 68: 16: converting the weight ratio of 16 into manganese nitrate, samarium nitrate and cobalt nitrate with corresponding weight ratios, taking the manganese nitrate, samarium nitrate and cobalt nitrate with corresponding weights according to the converted weight ratios, dissolving the manganese nitrate, samarium nitrate and cobalt nitrate into deionized water, and magnetically stirring the mixture for 30min at room temperature to obtain a nitrate solution (the total concentration of the nitrate is 20 wt%);
s2, dissolving citric acid which is 10% more than the total amount of metal ions in the nitrate solution in the S1 into the ionized water to obtain a citric acid solution (with the concentration of 20 wt%);
s3, dropwise adding the citric acid solution of S2 into the nitrate solution of S1, then adding a dispersing agent ethylene glycol (accounting for 0.25 percent of the total mass of the solution), magnetically stirring for 1 hour at room temperature, then decompressing to the vacuum degree of-0.08 MPa in a rotary evaporator, and evaporating at 60 ℃ until gel is formed;
s4, drying the gel obtained in the step S3 in a vacuum drying oven at 70 ℃ for 24h, then igniting the gel with ethanol, calcining the gel in a muffle furnace at 400 ℃ for 2h after combustion, calcining the gel at 650 ℃ for 6h, and finally grinding and screening the obtained product to obtain the 40-60-mesh catalyst.
Example 2
ternary composite denitration and demercuration catalyst Mn44Sm24Co32OxThe preparation method comprises the following steps:
s1, preparing a mixture of manganese dioxide, samarium sesquioxide and cobaltosic oxide according to the weight ratio of 44: 24: converting the weight ratio of 32 into manganese nitrate, samarium nitrate and cobalt nitrate with corresponding weight ratios, taking the manganese nitrate, samarium nitrate and cobalt nitrate with corresponding weights according to the converted weight ratios, dissolving the manganese nitrate, samarium nitrate and cobalt nitrate into deionized water, and magnetically stirring the mixture for 30min at room temperature to obtain a nitrate solution (the total concentration of the nitrate is 10 wt%);
s2, dissolving citric acid which is 12% more than the total amount of metal ions in the nitrate solution in the S1 into the ionized water to obtain a citric acid solution (with the concentration of 30 wt%);
s3, dropwise adding the citric acid solution of S2 into the nitrate solution of S1, then adding a dispersing agent ethylene glycol (accounting for 0.5 percent of the total mass of the solution), magnetically stirring for 1 hour at room temperature, then decompressing to the vacuum degree of-0.08 MPa in a rotary evaporator, and evaporating at 60 ℃ until gel is formed;
s4, drying the gel obtained in the step S3 in a vacuum drying oven at 85 ℃ for 24h, then igniting the gel with ethanol, calcining the gel in a muffle furnace at 400 ℃ for 2h after combustion, calcining the gel at 650 ℃ for 6h, and finally grinding and screening the obtained product to obtain the 40-60-mesh catalyst.
Example 3
ternary composite denitration and demercuration catalyst Mn68Sm16Mo16OxThe preparation method comprises the following steps:
s1, preparing a mixture of manganese dioxide, samarium sesquioxide and molybdenum trioxide 68: 16: converting the weight ratio of 16 into manganese nitrate, samarium nitrate and ammonium molybdate in corresponding weight ratio, taking the manganese nitrate, samarium nitrate and cobalt nitrate in corresponding weight ratio according to the converted weight ratio, dissolving in deionized water, and magnetically stirring at room temperature for 30min to obtain nitrate solution (the total concentration of nitrate is 30 wt%);
s2, dissolving citric acid which is 15% more than the total amount of metal ions in the nitrate solution in the S1 in ionized water to obtain a citric acid solution (the concentration is 45 wt%);
s3, dropwise adding the citric acid solution of S2 into the nitrate solution of S1, then adding a dispersing agent ethylene glycol (accounting for 1% of the total mass of the solution), magnetically stirring for 1h at room temperature, then decompressing to the vacuum degree of-0.08 MPa in a rotary evaporator, and evaporating at 60 ℃ until gel is formed;
s4, drying the gel obtained in the step S3 in a vacuum drying oven at 100 ℃ for 24h, then igniting the gel with ethanol, calcining the gel in a muffle furnace at 400 ℃ for 2h after combustion, calcining the gel at 650 ℃ for 6h, and finally grinding and screening the obtained product to obtain the 40-60-mesh catalyst.
Example 4
ternary composite denitration and demercuration catalyst Mn44Sm24Mo32OxThe preparation method comprises the following steps:
s1, preparing a mixture of manganese dioxide, samarium trioxide and molybdenum trioxide 44: 24: converting the weight ratio of 32 into manganese nitrate, samarium nitrate and ammonium molybdate in corresponding weight ratio, taking the manganese nitrate, samarium nitrate and cobalt nitrate in corresponding weight ratio according to the converted weight ratio, dissolving in deionized water, and magnetically stirring at room temperature for 30min to obtain nitrate solution (the total concentration of nitrate is 25 wt%);
s2, dissolving citric acid which is 15% more than the total amount of metal ions in the nitrate solution in the S1 in ionized water to obtain a citric acid solution (the concentration is 40 wt%);
s3, dropwise adding the citric acid solution of S2 into the nitrate solution of S1, then adding a dispersing agent ethylene glycol (accounting for 0.8 percent of the total mass of the solution), magnetically stirring for 1 hour at room temperature, then decompressing to the vacuum degree of-0.08 MPa in a rotary evaporator, and evaporating at 60 ℃ until gel is formed;
s4, drying the gel obtained in the step S3 in a vacuum drying oven at 100 ℃ for 24h, then igniting the gel with ethanol, calcining the gel in a muffle furnace at 400 ℃ for 2h after combustion, calcining the gel at 650 ℃ for 6h, and finally grinding and screening the obtained product to obtain the 40-60-mesh catalyst.
Comparative example 1
composite denitration and demercuration catalyst Mn68Co32OxThe specific steps of the preparation method are basically compared with the preparation method of the embodiment 1, and the difference is that the nitrate solution does not contain samarium nitrate when being prepared.
Comparative example 2
composite denitration and demercuration catalyst Mn68Mo16OxThe specific steps of the preparation method are basically compared with the preparation method of the example 3, and the difference is that the nitrate solution does not contain samarium nitrate when being prepared.
Test example of simultaneous denitration and demercuration activity of obtained catalyst
The catalyst obtained in the above examples and comparative examples was put into a fixed bed reaction system for denitration and demercuration activity test, and the denitration and demercuration activity of the catalyst was evaluated under simulated flue gas conditions. The simulated smoke conditions are as follows: NH (NH)3Concentration 500ppm, NO concentration 500ppm, O2The concentration was 5%, the HCl concentration was 10ppm, the Hg concentration was 70. mu.g/m3，H2O concentration 10%, SO2Concentration 500ppm, N2As carrier gas, the total flow of flue gas is 1L/min, and the space velocity is 60000h-1. Under the above conditions, the reaction temperature was 100 ℃ or 200 ℃, and the simultaneous denitration and demercuration efficiencies of the catalysts according to examples 1 to 4 and comparative examples 1 to 2 are shown in table 1:
Figure BDA0001329716390000071
Figure BDA0001329716390000081
as can be seen from the specific data of the denitration and demercuration efficiency in the table above, the ternary composite denitration and demercuration catalyst provided by the invention has high denitration and demercuration efficiency at a lower temperature (100-; comparing the embodiment with the corresponding comparative example, the addition of the samarium sesquioxide has obvious effect of improving the catalytic efficiency of the three-way composite catalyst; meanwhile, because the simulated flue gas contains water and sulfur dioxide with higher concentration, the test result shows that the catalyst still has higher denitration and demercuration efficiency under the simulated flue gas environment, so that the catalyst provided by the invention has better tolerance to water vapor and sulfur dioxide.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

  1. The ternary composite denitration and demercuration catalyst is characterized by comprising 44-68 wt% of a main catalyst, 16-24 wt% of a th auxiliary agent and 8-40 wt% of a second auxiliary agent, wherein the main catalyst is manganese dioxide, the th auxiliary agent is samarium trioxide, and the second auxiliary agent is cobaltosic oxide or molybdenum trioxide.
  2. 2, A preparation method of the ternary composite denitration and demercuration catalyst of claim 1, comprising the following steps:
    s1, converting according to the weight percentages of a main catalyst, an th auxiliary agent and a second auxiliary agent, taking manganese nitrate, samarium nitrate and cobalt nitrate or ammonium molybdate in corresponding amounts after conversion, dissolving in deionized water, and uniformly stirring to obtain a nitrate solution;
    s2, dissolving citric acid which is more than 10 percent more than the total amount of metal ions in the nitrate solution obtained in the step S1 in deionized water to obtain a citric acid solution;
    s3, dropwise adding all the citric acid solution of S2 into the nitrate solution obtained in S1, uniformly stirring, adding a dispersing agent, and carrying out decompression rotary evaporation at the temperature of 55-65 ℃ until gel is formed;
    and S4, drying the gel obtained in the step S3 in vacuum at the temperature of 70-100 ℃, igniting the dried gel, then calcining, and grinding and screening the calcined product to obtain the ternary composite denitration and demercuration catalyst.
  3. 3. The preparation method of ternary composite denitration and demercuration catalysts according to claim 2, wherein the manganese nitrate in S1 is 50 wt% manganese nitrate solution.
  4. 4. The preparation method of ternary composite denitration and demercuration catalysts according to claim 2, wherein the total concentration of nitrates in the nitrate solution in S1 is 10-30 wt%.
  5. 5. The preparation method of ternary composite denitration and demercuration catalysts according to claim 2, wherein the concentration of the citric acid solution in S2 is 20-45 wt%.
  6. 6. The method for preparing ternary composite denitration and demercuration catalysts according to claim 2, wherein the reduced pressure rotary evaporation in S3 is performed in a rotary evaporator with a vacuum degree of-0.08 MPa.
  7. 7. The preparation method of ternary composite denitration and demercuration catalysts according to claim 2, wherein the dispersant in S3 is ethylene glycol, and the amount of the dispersant is 0.25-1% of the mass of the nitrate solution.
  8. 8. The method for preparing ternary composite denitration and demercuration catalysts according to claim 2, wherein the vacuum drying time in S4 is 24 hours or more, and the ignition agent used when the gel is ignited is ethanol.
  9. 9. The preparation method of the ternary composite denitration and demercuration catalyst of any one of claims 2 to 8 and , wherein the calcination treatment in S4 is performed in a muffle furnace, and the calcination treatment comprises the specific steps of calcination at 400 ℃ for 2h and then at 650 ℃ for 6 h.
  10. 10. The method for preparing ternary composite denitration and demercuration catalysts according to claim 9, wherein the particle size of the ternary composite denitration and demercuration catalyst obtained by grinding and sieving in S4 is 40-60 meshes.
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