CN111974186B - Flue gas SNCR (selective non-catalytic reduction) denitration agent and preparation method thereof - Google Patents

Flue gas SNCR (selective non-catalytic reduction) denitration agent and preparation method thereof Download PDF

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CN111974186B
CN111974186B CN202010712879.8A CN202010712879A CN111974186B CN 111974186 B CN111974186 B CN 111974186B CN 202010712879 A CN202010712879 A CN 202010712879A CN 111974186 B CN111974186 B CN 111974186B
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flue gas
hydrogen storage
storage metal
denitration agent
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CN111974186A (en
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王路路
吴阳杨
邱雪峰
周长宏
王臣
汤凯
邹友国
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Nantong Runqi Environmental Protection Service Co ltd
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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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B01D53/565—Nitrogen oxides by treating the gases with solids
    • 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
    • B01D53/81—Solid phase processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

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  • Environmental & Geological Engineering (AREA)
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Abstract

The invention provides a flue gas SNCR (selective non-catalytic reduction) denitration agent and a preparation method thereof, wherein the flue gas SNCR denitration agent comprises 80-95 parts of reducing agent, 1-5 parts of activated carbon and 0.01-0.2 part of hydrogen storage metal by mass, and the hydrogen storage metal is subjected to hydrogenation treatment in advance. The SNCR denitration agent for flue gas has a wider effective reaction temperature range, generates less solid particles after reaction, has stronger reduction capability on nitrogen oxides, and has a good application prospect.

Description

Flue gas SNCR (selective non-catalytic reduction) denitration agent and preparation method thereof
Technical Field
The invention relates to the technical field of environmental protection, in particular to the technical field of waste gas treatment, and particularly relates to a flue gas SNCR (selective non-catalytic reduction) denitration agent and a preparation method thereof.
Background
In the existing industrial production, the emission of high-temperature flue gas is basically accompanied with the emission of various nitrogen oxides, the nitrogen oxides are harmful to human bodies and can cause acid rain, in order to relieve the pressure of the environment, the national emission requirement on the nitrogen oxides is more and more strict, at present, the control method for the nitrogen oxides mainly comprises two methods, namely a selective catalytic conversion method (SCR) and a selective non-catalytic reduction method (SNCR), wherein the former has mild reaction conditions, the nitrogen oxides in the flue gas react with a reducing agent under the catalytic action of a catalyst to produce harmless nitrogen, and the latter has high reaction temperature, is suitable for the denitration treatment of the high-temperature flue gas, and produces harmless nitrogen emission through the mutual reaction of the nitrogen oxides and the reducing agent under the high-temperature condition.
However, the temperature range of the high-temperature flue gas is unstable, and the reaction temperature of the denitrifier is relatively narrow, so that when the temperature is lower than or higher than the corresponding reaction temperature range, the effect of the denitrifier is poor, or the reduction effect is poor, or the denitrifier is directly over-oxidized, and the generation of pollutants is increased.
In the prior art, the effective reaction temperature range is expanded by adding a synergist or other auxiliary agents, but the synergist and the auxiliary agents can generate products which cannot be eliminated or are not easy to discharge more or less after reaction, the products can be attached to a reactor or directly discharged along with tail gas, other hazardous wastes are easily generated, the service life of equipment is shortened, the maintenance cost is increased, and the environment friendliness is not facilitated.
Disclosure of Invention
In view of the above, the invention provides a flue gas SNCR denitration agent which can react more completely and can expand the effective temperature range of the denitration reaction to a certain extent and a preparation method thereof.
The technical scheme of the invention is realized as follows: the invention provides a flue gas SNCR (selective non-catalytic reduction) denitration agent, which comprises the following components in parts by weight:
80-95 parts of reducing agent
1-5 parts of activated carbon
0.01-0.2 parts of hydrogen storage metal.
On the basis of the technical scheme, preferably, the reducing agent is one or a mixture of more of urea, ammonium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium acetate and melamine, and melamine A and melamine B.
On the basis of the above technical scheme, preferably, the hydrogen storage metal is one of titanium, magnesium, zirconium and iron-titanium alloy.
On the basis of the technical scheme, preferably, the ferrotitanium alloy is Ti-10Cr-18Mn-27V-5 Fe.
Still more preferably, the hydrogen storage metal is a nano metal particle having a particle size of 10 to 100 nm.
On the basis of the above technical solution, preferably, the hydrogen storage metal is subjected to hydrotreating, and the hydrotreating method includes: and (3) placing the hydrogen storage metal in a closed container, filling hydrogen into the closed container, and standing for 10-30min to obtain the hydrogenated hydrogen storage metal.
Based on the above technical solution, preferably, after the closed container is filled with hydrogen, the pressure in the closed container is kept at 100-150 atm.
The invention also discloses a preparation method of the SNCR denitration agent for flue gas, which comprises the following steps:
step one, mixing hydrogen storage metal and activated carbon, slowly stirring and mixing in a stirrer at a stirring speed of 50-100r/min for 5-10min to obtain a first mixture;
and step two, mixing and stirring the first mixture and the reducing agent at the stirring speed of 100-.
Compared with the prior art, the SNCR denitration agent for flue gas has the following beneficial effects:
(1) the SNCR denitration agent for flue gas adopts a conventional ammonium-containing reducing agent as a main raw material, and takes activated carbon and hydrogen storage metal as auxiliary materials, on one hand, the activated carbon has certain reducing capacity and the capacity of combining oxygen atoms at high temperature, so that the reducing agent and oxygen are prevented from violently reacting to generate nitrogen oxide at high temperature, on the other hand, the activated carbon also has good adsorption capacity, can adsorb the hydrogen storage metal, helps the hydrogen storage metal to be better dispersed, and has a certain protection effect, and the hydrogen storage metal reacts at high temperature to produce corresponding oxide, so that the SNCR denitration agent can play a role of a metal catalyst, and reduces the reaction temperature;
(2) the invention also carries out hydrotreatment on the hydrogen storage metal in advance, and hydrogen is released under the high-temperature condition and can be combined with carbon and oxygen to generate carbonyl, so that on one hand, the oxygen content is reduced, and on the other hand, the reduction of nitrogen oxide can be promoted, thereby improving the reduction rate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments of the present invention, belong to the protection scope of the present invention.
Example 1
Preparation of the denitration agent:
respectively weighing 1 part of nano titanium powder with the granularity of 10-100nm, 100 parts of activated carbon and 8000 parts of urea, putting the nano titanium powder into a closed container, filling hydrogen into the closed container, and standing for 10min to obtain hydrogenated hydrogen storage metal;
and mixing and stirring the hydrogenated hydrogen storage metal and the activated carbon powder in a stirrer at the stirring speed of 50r/min for 5min to obtain a first mixture, and then putting the first mixture and urea into the stirrer to be mixed and stirred at the stirring speed of 100r/min for 10min to obtain the flue gas SNCR (selective non-catalytic reduction) denitration agent.
Example 2
Preparation of the denitration agent:
respectively weighing 20 parts of nano magnesium powder with the granularity of 10-100nm, 500 parts of activated carbon and 9500 parts of ammonium carbonate, putting the nano magnesium powder in a closed container, filling hydrogen into the closed container, and standing for 30min to obtain hydrogenated hydrogen storage metal;
and mixing and stirring the hydrogenated hydrogen storage metal and the activated carbon powder in a stirrer at the stirring speed of 100r/min for 10min to obtain a first mixture, putting the first mixture and ammonium carbonate into the stirrer to be mixed and stirred at the stirring speed of 200r/min for 20min to obtain the flue gas SNCR (selective non-catalytic reduction) denitration agent.
Example 3
Preparation of the denitration agent:
respectively weighing 10 parts of nano zirconium powder with the granularity of 10-100nm, 200 parts of activated carbon, 4500 parts of urea and 4500 parts of ammonium bicarbonate, placing the nano zirconium powder in a closed container, filling hydrogen into the closed container, keeping the pressure in the closed container at 100atm, and standing for 10min to obtain hydrogenated hydrogen storage metal;
and mixing and stirring the hydrogenated hydrogen storage metal and the activated carbon powder in a stirrer at a stirring speed of 80r/min for 80min to obtain a first mixture, and then putting the first mixture, urea and ammonium bicarbonate into the stirrer to be mixed and stirred at a stirring speed of 150r/min for 15min to obtain the SNCR (selective non-catalytic reduction) denitration agent for the flue gas.
Example 4
Preparation of the denitration agent:
respectively weighing 5 parts of TiFe with the granularity of 10-100nm0.86Mn0.1Alloy powder, 300 parts of activated carbon, 4500 parts of ammonium sulfate and 4500 parts of ammonium bisulfate, and TiFe0.86Mn0.1Placing the alloy powder in a closed container, filling hydrogen into the closed container, keeping the pressure in the closed container at 150atm, and standing for 30min to obtain hydrogenated hydrogen storage metal;
and mixing and stirring the hydrogenated hydrogen storage metal and the activated carbon powder in a stirrer at the stirring speed of 80r/min for 80min to obtain a first mixture, putting the first mixture, ammonium sulfate and ammonium bisulfate into the stirrer to be mixed and stirred at the stirring speed of 150r/min for 15min to obtain the flue gas SNCR denitration agent.
Example 5
Preparation of the denitration agent:
respectively weighing 15 parts of Ti-10Cr-18Mn-27V-5Fe alloy powder with the granularity of 10-100nm, 400 parts of activated carbon and 9000 parts of melamine, putting the Ti-10Cr-18Mn-27V-5Fe alloy powder into a closed container, filling hydrogen into the closed container, keeping the pressure in the closed container at 120atm, and standing for 30min to obtain hydrogenated hydrogen storage metal;
and mixing and stirring the hydrogenated hydrogen storage metal and the activated carbon powder in a stirrer at a stirring speed of 80r/min for 80min to obtain a first mixture, putting the first mixture and melamine into the stirrer to be mixed and stirred at a stirring speed of 150r/min for 15min to obtain the flue gas SNCR (selective non-catalytic reduction) denitration agent.
Example 6
Preparation of the denitration agent:
respectively weighing 15 parts of Ti-10Cr-18Mn-27V-5Fe alloy powder with the granularity of 10-100nm, 400 parts of activated carbon and 9000 parts of melamine;
mixing and stirring Ti-10Cr-18Mn-27V-5Fe alloy powder and activated carbon powder in a stirrer at a stirring speed of 80r/min for 80min to obtain a first mixture, putting the first mixture and melamine into the stirrer to be mixed and stirred at a stirring speed of 150r/min for 15min to obtain the flue gas SNCR denitration agent.
The SNCR denitration agent for flue gas and the conventional urea denitration agent prepared in the embodiment are respectively used for denitration of flue gas of a garbage incinerator, and under the condition that the SNCR denitration agent and the conventional urea denitration agent are not treated, the concentration of nitrogen oxide in flue gas emission is 400-500 mg/Nm-3Average value of 450mg/Nm3The temperature of the upper part of the furnace chamber is 700-1200 ℃, and the particle concentration at the discharge outlet is generally 80-90mg/Nm3The denitration performance is detected by using the embodiments 1-7 and the conventional urea, the denitration temperature is 700 ℃, 800 ℃, 950 ℃, 1050 ℃ and 1100 ℃ in sequence, and the detection results are as follows:
example 1 results: deviation of reduction at high temperature
Figure BDA0002597220730000061
Example 2 results: deviation of reduction at high temperature
Figure BDA0002597220730000062
Figure BDA0002597220730000071
Example 3 results: are all better
Figure BDA0002597220730000072
Example 4 results: more excellent
Figure BDA0002597220730000073
Example 5 results: the above foundation is more excellent
Figure BDA0002597220730000074
Example 6 results: the above high temperature deviation is similar
Figure BDA0002597220730000075
Comparative example results: are all poor
Figure BDA0002597220730000076
Figure BDA0002597220730000081
The detection results show that the flue gas SNCR denitration agent can greatly reduce the content of nitrogen oxide in flue gas in the flue gas denitration process, and meanwhile, after hydrogen storage metal is subjected to hydrogen storage treatment, the flue gas SNCR denitration agent has a certain effect of reducing the concentration of particulate matters in the flue gas, the denitration capability is greatly improved at lower 700 ℃ and lower 1100 ℃, and particularly, Ti-10Cr-18Mn-27V-5Fe alloy powder is adopted as the hydrogen storage metal, so that the flue gas SNCR denitration agent has better performance in removing the nitrogen oxide and the granularity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.

Claims (5)

1. The SNCR denitration agent for the flue gas is characterized by comprising the following components in parts by weight:
80-95 parts of reducing agent
1-5 parts of activated carbon
0.01-0.2 parts of hydrogen storage metal;
the reducing agent is one or a mixture of more of urea, ammonium carbonate, ammonium bicarbonate and melamine;
the hydrogen storage metal is iron-titanium alloy, and the hydrogen storage metal is subjected to hydrogenation treatment, wherein the hydrogenation treatment method comprises the following steps: and (3) placing the hydrogen storage metal in a closed container, filling hydrogen into the closed container, and standing for 10-30min to obtain the hydrogenated hydrogen storage metal.
2. The SNCR denitration agent for flue gas as recited in claim 1, wherein the hydrogen storage metal is nano metal particles with a particle size of 10-100 nm.
3. The SNCR denitration agent for flue gas as recited in claim 1, wherein the ferrotitanium alloy is Ti-10Cr-18Mn-27V-5 Fe.
4. The SNCR denitration agent for flue gas as recited in claim 1, wherein after the closed container is filled with hydrogen, the pressure in the closed container is maintained at 100-150 atm.
5. The preparation method of the SNCR denitration agent for the flue gas as recited in claim 1, characterized by comprising the following steps:
step one, mixing the hydrogen storage metal after hydrogenation treatment with active carbon, and slowly stirring and mixing in a stirrer at a stirring speed of 50-100r/min for 5-10min to obtain a first mixture;
and step two, mixing and stirring the first mixture and the reducing agent at the stirring speed of 100-.
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