CN112742190B - Complexing denitration process capable of recycling - Google Patents
Complexing denitration process capable of recycling Download PDFInfo
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Abstract
The invention provides a complexing denitration process capable of recycling, which is characterized in that a compounding agent, an auxiliary agent, a nano reagent and a dispersing agent are added into a complexing agent mainly containing Fe (II) EDTA, the NO complexing ability of a denitration agent is improved, the oxidation resistance of the denitration agent is improved, the absorption capacity and the use stability of the complexing denitration agent are further improved, then Fe (III) in the invalid complexing denitration agent is precipitated and separated, and then a regenerating agent with reducibility is added to reduce Fe (II) EDTA (NO) into Fe (II) EDTA and N 2 Then the by-product ferrous sulfate heptahydrate in the process of producing titanium dioxide by using sulfuric acid method is used for supplementing Fe 2+ The regeneration method of (1) regenerates the spent complexing denitration agent. Meanwhile, the auxiliary agent and the nano reagent added in the preparation process of the complex denitrifying agent can play a role in catalyzing the regeneration reaction and accelerate the regeneration reaction.
Description
Technical Field
The invention belongs to the technical field of flue gas denitration, and particularly relates to a complexing denitration process capable of cyclic regeneration.
Background
Nitrogen Oxides (NO) as one of the main atmospheric pollutants X ) The discharge of (a) poses a great hazard to humans and the environment. NO X The emission sources of the (B) are mainly fuel combustion process and various industrial processes, mainly including flue gas of coal-fired power plants, industrial boilers (kilns) and automobile exhaust, wherein NO generated by coal combustion X The emission amount of the solid source accounts for about 70 percent of the total emission amount of the solid source in China.
The fields of steel, cement, metallurgy, coking, coal chemical industry, industrial boilers, industrial kilns and the like are the fields with the largest coal consumption except for the electric industry. Under the condition that the atmospheric pollution control in the thermal power industry reaches a certain degree, steel,The order curtain for upgrading and reconstruction is also rapidly opened in non-electric industries such as metallurgy, building materials and the like. In 2019, in 4 months, the ministry of ecological environment of China issued 'opinion on promoting implementation of ultralow emission in the steel industry', and definitely pointed out that NO in the head flue gas of a sintering machine and the pellet roasting flue gas is generated under the condition that the reference oxygen content is 16% X Average hourly discharge concentration of less than 50mg/m 3 . The suggestion points out that the national newly-built (including relocation) steel project is to achieve ultra-low emission in principle, and before the end of 2020, the ultra-low emission modification of steel enterprises in key areas is obviously progressed, and the modification is finished in the strive for about 60% of capacity; by the end of 2025, the ultralow emission modification of iron and steel enterprises in key areas is basically completed, and the national strive for more than 80% of capacity to complete the modification.
Because of the inherent characteristics of low temperature, high humidity, high dust and the like of the sintering flue gas, the selective catalytic reduction denitration technology (SCR) and the selective non-catalytic reduction denitration technology (SNCR) which are applied more in the power industry at present are not suitable for denitration treatment of the sintering flue gas. Fe (II) EDTA complex denitration is used as a low-temperature wet denitration technology, can be well grafted with wet desulphurization equipment, and finally realizes sintering flue gas SO 2 、NO X The discharge reaches the standard. But O in flue gas during denitration 2 Will convert Fe in solution 2+ Is oxidized into Fe 3+ And the addition of EDTA chelating agent can accelerate the oxidation reaction, and Fe (III) EDTA formed after the Fe (II) EDTA is oxidized has NO affinity to NO, so that the complex denitration agent is easy to oxidize, has quick failure and generates precipitate, and the industrial application of the technology is severely restricted.
Van phoenix orchid and the like develop the catalytic reduction regeneration of saturated complex denitration liquid Fe (III) EDTA, study the catalytic performance of the activated carbon loaded copper-based catalyst applied to the removal of nitrogen oxide by Fe (II) EDTA wet method, prepare the loaded copper-based catalyst by the method of equal-volume impregnation, and compare activated carbon, acid-base modified activated carbon and activated carbon loaded Cu and Cu 2 Denitration effect of O. The research shows that: the time and the temperature of the regeneration process are improved, and the regeneration and denitration efficiency of the denitration liquid are facilitated. The activated carbon modified by alkali is beneficial to regeneration of denitration liquid, and the wet-process denitration performance is obviously improved after the copper-based catalyst is loaded. Reduction with sodium borohydride in alkali solutionThe originally prepared activated carbon loaded copper catalyst has stable Fe (II) EDTA complexing denitration performance. (chemical engineering, vol. 48, No. 5, 2020).
Liufu and the like develop researches on synchronous desulfurization and denitrification waste liquid by using Fe regenerated ammonia/Fe (II) EDTA method, and SO in flue gas is synchronously removed by using ammonia/Fe (II) EDTA method 2 And NO X And the denitration efficiency is maintained by Fe (III) in the scrap iron regeneration waste liquid. Experimental results show that the desulfurization efficiency of the ammonia/Fe (II) EDTA method can reach 100%, and the denitration efficiency can reach 68.3%. However, as the experimental time was extended, the denitration efficiency was gradually decreased. After regeneration of fe (iii) -iron by scrap iron, the denitration efficiency increased from 48% to 57.1%. (Industrial safety and environmental protection, vol 43, No. 5, 2017).
How strong and the like develop Fe (II) EDTA complexing wet denitration and regeneration researches, Fe (III) EDTA is reduced by adopting iron powder at room temperature under the aerobic condition, the influence of oxygen content, initial molar ratio of the iron powder to the Fe (III) EDTA, initial concentration of the Fe (III) EDTA and pH value on the reduction of the Fe powder to the Fe (III) EDTA is researched, and the result shows that the reduction of the Fe (III) EDTA by the iron powder under the aerobic condition can be divided into two stages: an Fe (II) concentration increasing stage and an Fe (II) concentration decreasing stage. In the Fe (II) concentration increasing stage, the rate of reducing Fe (III) EDTA by iron powder is reduced along with the increase of the oxygen content or the pH value in the solution, and the concentration of the Fe (II) EDTA generated by reduction is increased along with the increase of the initial Fe (III) EDTA concentration or the initial molar ratio of the iron powder to the Fe (III) EDTA; in the second stage, the concentration of Fe (II) EDTA is reduced due to the existence of oxygen, and reddish brown gamma-FeOOH precipitation occurs, and finally, a kinetic model of reducing Fe (III) EDTA by iron powder in an anaerobic environment and an aerobic environment is deduced. The NO removal is carried out by combining metal powder with Fe (II) EDTA, and the effect of combining iron powder and zinc powder with Fe (II) EDTA in a permeable reaction device is examined. As a result, in the permeable reaction device, the removal rate of NO can be kept above 90% within 90 minutes by combining iron powder with Fe (II) EDTA absorption liquid, and the removal rate of NO can be kept above 80% within 130 minutes. When the zinc powder is used for replacing iron powder, the absorption effect is obviously enhanced, the NO removal rate can reach 90% within 15 hours, and a more efficient denitration technology can be provided for industrial denitration. (doctor academic paper of university of southern China, 6 months in 2017)
The male invar has developed the experimental research of Fe (II) EDTA removal of NO, and the preparation of the complexing solution is only Fe 2+ Mutual solubility with EDTA, and Fe 2+ The mol ratio of EDTA is 3:2, other substances are not added and other treatments are not carried out, and the complexing solution has the problems of low absorption capacity, quick failure and the like (industrial safety and environmental protection, vol.43, No. 10 in 2017).
In conclusion, on one hand, the research on the optimization and improvement of the solution itself is less for Fe (II) EDTA complexation denitration, and the problems of low absorption capacity, slow mass transfer, easy oxidation, fast failure and the like of the Fe (II) EDTA solution are not fundamentally solved. On the other hand, the treatment of the ineffective complex denitration agent generally adopts a method of adding a reducing agent or microorganism to reduce Fe (III) EDTA and Fe (II) EDTA (NO) to generate Fe (II) EDTA, but the problems of large consumption of the reducing agent, low efficiency, high operation cost and the like exist in the whole reduction method, and the engineering application of complex denitration is severely restricted.
Disclosure of Invention
The invention aims to provide a complexing denitration process capable of being regenerated circularly, the complexing denitration process has high denitration efficiency, a denitration agent can be regenerated circularly, and the operation cost is low.
The invention provides a complexing denitration process capable of recycling, which comprises the following steps:
A) contacting a complex denitration agent with low-temperature flue gas to perform denitration until the complex denitration agent fails;
the denitration agent comprises disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent, a dispersing agent and a solvent;
the compounding agent is one or more of cysteine, linnoroline, methyl cyclopentenolone, ethylenediamine, triethanolamine, piperazine, hydroquinone and dibutyl hydroxy toluene;
the auxiliary agent is one or more of sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, sodium sulfide, ascorbic acid and carbohydrazide;
the nano reagent is one or more of nano titanium dioxide, nano nickel oxide, nano ferroferric oxide, nano iron powder and nano silicon dioxide;
B) adjusting the pH value of the complex denitration agent which is out of work in the step A) to 8.5-9.0, and removing precipitates;
C) adjusting the pH value of the filtrate obtained by removing the precipitate in the step B) to 5.5-6, adding a regenerant, and carrying out a reduction reaction to obtain a reduced denitration agent;
D) adding a ferrous iron supplement into the reduced denitration agent to enable Fe in the denitration agent 2+ With EDTA 2 + The mole number of the catalyst is equivalent to obtain a regenerated complex denitration agent;
the ferrous iron supplement is a byproduct FeSO generated in the production of titanium dioxide by a sulfuric acid method 4 7H 2 O。
Preferably, the ferrous salt is ferrous sulfate; the dispersing agent is one or more of sodium citrate, sodium pyrophosphate, trihexyl hexyl phosphoric acid, sodium dodecyl benzene sulfonate, polyacrylamide and triton.
Preferably, the concentration of the ferrous salt is 25-50 mmol/L; the concentration of the disodium ethylene diamine tetraacetate is 120-150% of that of the ferrous salt; the concentration of the compounding agent is 30-50% of that of the ferrous salt; the concentration of the auxiliary agent is 50-70% of that of the ferrous salt; the concentration of the nano reagent is 0.1-0.2% of that of the ferrous salt; the concentration of the dispersing agent is 1-5% of that of the ferrous salt.
Preferably, the complex denitration agent is prepared according to the following steps:
1) mixing disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent and a dispersing agent in a solvent under the condition of introducing protective gas to obtain a mixed solution;
2) and carrying out ultrasonic oscillation on the mixed solution to obtain the complex denitration agent.
Preferably, the residence time of the denitration is 5-7 s, and the liquid-gas ratio is 3-5L/m 2 The flow rate of the empty tower is 2-2.5 m/s, and the denitration temperature is 45-50 ℃.
Preferably, an alkaline substance is added in the step B) to adjust the pH value of the spent complexing denitration agent;
the alkaline substance is Na 2 CO 3 One or more of NaOH and ammonia water.
Preferably, an acidic substance is added in the step C) to adjust the pH value of the filtrate to 5.5-6;
the acidic substance is one or more of sulfuric acid, phosphoric acid and citric acid.
Preferably, the regenerant is one or more of sodium sulfite, sodium metabisulfite, sodium sulfide, urea, ascorbic acid, carbohydrazide and hydrazine hydrate;
the regenerant and EDTA 2+ The molar ratio of (0.5-1): 1.
preferably, the temperature of the reduction reaction in the step B) is 40-55 ℃; the time of the reduction reaction in the step B) is 10-15 min.
The invention provides a complexing denitration process capable of recycling, which comprises the following steps: A) contacting a complex denitration agent with low-temperature flue gas to perform denitration until the complex denitration agent fails; the denitration agent comprises disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent, a dispersing agent and a solvent; the compounding agent is one or more of cysteine, linnoroline, methyl cyclopentenolone, ethylenediamine, triethanolamine, piperazine, hydroquinone and dibutyl hydroxy toluene; the auxiliary agent is one or more of sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, sodium sulfide, ascorbic acid and carbohydrazide; the nano reagent is one or more of nano titanium dioxide, nano nickel oxide, nano ferroferric oxide, nano iron powder and nano silicon dioxide; B) adjusting the pH value of the complex denitration agent which is out of work in the step A) to 8.5-9.0, and removing precipitates; C) adjusting the pH value of the filtrate obtained by removing the precipitate in the step B) to 5.5-6, adding a regenerant, and carrying out a reduction reaction to obtain a reduced denitration agent; D) adding a ferrous iron supplement into the reduced denitration agent to enable Fe in the denitration agent 2+ With EDTA 2+ Is equivalent to obtain regenerationThe complex denitrifying agent; the ferrous iron supplement is a byproduct FeSO generated in the production of titanium dioxide by a sulfuric acid method 4 7H 2 And O. According to the invention, a compounding agent, an auxiliary agent, a nano reagent and a dispersing agent are added into a complexing agent mainly containing Fe (II) EDTA, so that the NO complexing ability of the denitrifying agent is improved, the oxidation resistance of the denitrifying agent is improved, the absorption capacity and the use stability of the complexing denitrifying agent are further improved, then Fe (III) in the ineffective complexing denitrifying agent is precipitated and separated, then a regenerating agent with reducibility is added, and Fe (II) EDTA (NO) is reduced to generate Fe (II) EDTA and N 2 Then the by-product ferrous sulfate heptahydrate in the process of producing titanium dioxide by using sulfuric acid method is used for supplementing Fe 2+ The regeneration method of (1) regenerates the spent complexing denitration agent. Meanwhile, the auxiliary agent and the nano reagent added in the preparation process of the complex denitration agent can play a role in catalyzing the regeneration reaction and accelerate the regeneration reaction.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a flow diagram of a complex denitration process with cyclic regeneration according to the present invention;
FIG. 2 shows NO at the flue gas outlet in the process of example 1 of the present invention X The concentration change curve of (1);
FIG. 3 shows NO at the flue gas outlet in the process of example 2 of the present invention X The concentration change curve of (1);
FIG. 4 shows NO at the flue gas outlet in the process of example 3 of the present invention X The concentration change curve of (1).
Detailed Description
The invention provides a complexing denitration process capable of recycling, which comprises the following steps:
A) contacting a complex denitration agent with low-temperature flue gas to perform denitration until the complex denitration agent fails;
the denitration agent comprises disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent, a dispersing agent and a solvent;
the compounding agent is one or more of cysteine, linnoroline, methyl cyclopentenolone, ethylenediamine, triethanolamine, piperazine, hydroquinone and dibutyl hydroxy toluene;
the auxiliary agent is one or more of sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, sodium sulfide, ascorbic acid and carbohydrazide;
the nano reagent is one or more of nano titanium dioxide, nano nickel oxide, nano ferroferric oxide, nano iron powder and nano silicon dioxide;
B) adjusting the pH value of the complex denitration agent which is out of work in the step A) to 8.5-9.0, and removing precipitates;
C) adjusting the pH value of the filtrate obtained by removing the precipitate in the step B) to 5.5-6, adding a regenerant, and carrying out a reduction reaction to obtain a reduced denitration agent;
D) adding a ferrous iron supplement into the reduced denitration agent to enable Fe in the denitration agent 2+ With EDTA 2 + The mole number of the catalyst is equivalent to obtain a regenerated complex denitration agent;
the ferrous iron supplement is a byproduct FeSO generated in the production of titanium dioxide by a sulfuric acid method 4 7H 2 O。
The complex denitration process comprises a denitration section and a regeneration section, wherein the denitration section carries out denitration reaction in a denitration system, and the regeneration section regenerates an ineffective complex denitration agent in the regeneration system.
In the invention, the denitration agent comprises disodium ethylene diamine tetraacetate, ferrous salt, a preparation agent, an auxiliary agent, a nano reagent, a dispersing agent and a solvent;
the concentration of the ferrous salt is preferably 25-50 mmol/L, more preferably 30-45 mmol/L, and most preferably 35-40 mmol/L, and specifically, in the embodiment of the present invention, it may be 25mmol/L or 40 mmol/L.
In the present invention, the concentration of the disodium ethylenediaminetetraacetate (EDTA-2Na) is preferably 120 to 150%, more preferably 130 to 140% of the concentration of the divalent iron salt, that is, the concentration of the disodium ethylenediaminetetraacetate is preferably 30 to 75mmol/L, more preferably 30 to 60mmol/L, and specifically, in an embodiment of the present invention, may be 30mmol/L or 52 mmol/L.
In the invention, the preparation agent is mainly used for improving the capability of the denitration liquid for complexing NO and accelerating the reaction, and comprises one or more of cysteine, linnorphine, methyl cyclopentenolone, ethylenediamine, triethanolamine, piperazine, hydroquinone and dibutyl hydroxy toluene.
The concentration of the preparation is preferably 30 to 50%, more preferably 35 to 45% of the concentration of the divalent iron salt, that is, the concentration of the preparation is preferably 7.5 to 25mmol/L, more preferably 10 to 20mmol/L, most preferably 12 to 15mmol/L, and specifically, in the embodiment of the present invention, 12.5mmol/L or 12mmol/L may be used. More specifically, in one embodiment of the invention, the formulation is 10mmol/L cysteine +2mmol/L piperazine, and in another embodiment of the invention, the formulation is 5mmol/L cysteine +5mmol/L methylcyclopentenolone +2.5mmol/L dibutylhydroxytoluene.
In the invention, the auxiliary agent is mainly used for improving the oxidation resistance of the denitration liquid, and comprises one or more of sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, sodium sulfide, ascorbic acid and carbohydrazide, specifically, in the embodiment of the invention, sodium carbonate + disodium hydrogen phosphate + sodium sulfite + carbohydrazide, or sodium dihydrogen phosphate + sodium sulfite + ascorbic acid.
The concentration of the auxiliary agent is preferably 50-70%, more preferably 55-65% of the concentration of the ferrous salt, that is, the concentration of the auxiliary agent is preferably 12.5-35 mol/L, more preferably 12.5-30 mol/L, specifically, in an embodiment of the present invention, 12.5mol/L or 28mol/L, more specifically, in an embodiment of the present invention, the auxiliary agent is 4mmol/L sodium carbonate +4mmol/L disodium hydrogen phosphate +2.5mmol/L sodium sulfite +2mmol/L carbohydrazide, and in another embodiment of the present invention, the auxiliary agent is 10mmol/L sodium dihydrogen phosphate +10mmol/L sodium sulfite +8mmol/L ascorbic acid.
In the invention, the nano-reagent is mainly used for the antioxidation of the catalytic assistant, and comprises one or more of nano titanium dioxide, nano nickel oxide, nano ferroferric oxide, nano ferric oxide, nano iron powder and nano silicon dioxide, and specifically, in the embodiment of the invention, the nano-reagent can be nickel oxide and ferroferric oxide, or nano titanium dioxide and nano silicon dioxide.
In the invention, the concentration of the nano reagent is preferably 0.1-0.2% of the concentration of the ferrous salt, that is, the concentration of the nano reagent is preferably 0.025-0.1 mmol/L, more preferably 0.03-0.08 mmol/L, most preferably 0.04-0.05 mmol/L, specifically, in an embodiment of the invention, 0.04mmol/L or 0.05mmol/L, more specifically, in an embodiment of the invention, the nano reagent is 0.02mmol/L nickel oxide +0.02mmol/L nano ferroferric oxide, and in another embodiment of the invention, the nano reagent is 0.025mmol/L nano titanium dioxide +0.025mmol/L nano silicon dioxide.
In the invention, the dispersant mainly enables the nano reagent to be well dispersed in the denitration liquid, and the dispersant comprises one or more of sodium citrate, sodium pyrophosphate, trihexyl hexyl phosphoric acid, sodium dodecyl benzene sulfonate, polyacrylamide and triton, and specifically, in the embodiment of the invention, the dispersant can be sodium pyrophosphate + polyacrylamide or sodium dodecyl benzene sulfonate.
The concentration of the dispersant is preferably 1-5%, more preferably 2-4%, and most preferably 3-4% of the concentration of the ferrous salt, that is, the concentration of the dispersant is preferably 0.25-2.5 mmol/L, more preferably 0.5-2 mmol/L, and most preferably 1-1.5 mmol/L, specifically, in an embodiment of the present invention, 1mmol/L, more specifically, in an embodiment of the present invention, 1mmol/L sodium dodecylbenzenesulfonate, and in another embodiment of the present invention, 0.5mmol/L sodium pyrophosphate +0.5mmol/L polyacrylamide
In the present invention, the solvent is preferably water, and may be distilled water or deionized water.
Based on the formula of the complex denitration agent, a person skilled in the art can add other functional additives according to the conventional knowledge in the field on the premise of not influencing the absorption capacity and stability of the complex denitration agent in the scheme so as to meet the use requirements of various working conditions.
The complex denitration agent is preferably prepared according to the following preparation method:
A) mixing disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent and a dispersing agent in a solvent under the condition of introducing protective gas to obtain a mixed solution;
B) and carrying out ultrasonic oscillation on the mixed solution to obtain the complex denitration agent.
In the present invention, the types and amounts of the disodium edta, the ferrous salt, the compounding agent, the auxiliary agent, the nano reagent, the dispersing agent and the solvent are the same as those of the disodium edta, the ferrous salt, the compounding agent, the auxiliary agent, the nano reagent, the dispersing agent and the solvent, and thus, the description thereof is omitted.
The solvent is preferably first freed from oxygen by methods commonly used by those skilled in the art, such as boiling distilled water, introducing protective gas under sealed conditions to remove dissolved oxygen and isolate oxidation of air, and mixing with disodium edetate.
In the invention, the protective gas is preferably nitrogen, helium or argon, and the flow rate of the protective gas is preferably 0.5-3L/min, and more preferably 1-2L/min.
Adding raw materials such as disodium ethylene diamine tetraacetate, continuously introducing protective gas for 60min, and mixing uniformly to obtain a mixed solution.
The invention preferably seals the mixed solution liquid and then puts the mixed solution liquid into an ultrasonic cell disruption instrument for ultrasonic oscillation to obtain the complex denitration agent.
The method utilizes the cavitation effect generated by the ultrasonic cell disruptor in the liquid to treat the solution, can obviously improve the stability and the dispersibility of the solution, and has the ultrasonic oscillation frequency of 20-25 KHz, stops for 15-20min after oscillation for 25-30 min, then carries out ultrasonic oscillation again, and repeats for 4-6 times.
After ultrasonic oscillation, the pH value of the complexing denitration agent is adjusted to 6.5-7.5 by using acid or alkali, such as sulfuric acid, sodium hydroxide and the like.
In the invention, the denitration reaction is a gas-liquid contact reaction, the residence time of the denitration reaction is preferably 5-7 s, and the liquid-gas ratio of the denitration reaction is preferably 3-5L/m 2 The flow rate of the empty tower is 2-2.5 m/s, and the denitration temperature is 45-50 ℃.
The complex denitration agent is efficient and stable, the failure time is 270min, and after the complex denitration agent fails, the complex denitration agent is conveyed to a regeneration system through a booster pump to regenerate the complex denitration agent.
In the invention, the regeneration system comprises a modulation tank, a filter, a regeneration reactor and a Fe supplement which are sequentially communicated 2+ The 'communication' can be direct communication or indirect communication.
Firstly, conveying the complex denitration liquid which is invalid after reaction to a tempering tank by a booster pump, adjusting the pH to 8.5-9.0, standing for 15-20min, filtering and precipitating, and removing oxidized Fe in the denitration liquid 3+ 。
According to the invention, preferably, an alkaline substance is added into the spent complexing denitration agent, the pH value of the spent complexing denitration agent is adjusted to 8.5-9.0, and through a large number of experimental researches, Fe in the solution within the range of pH8.5-9.0 is found 3+ Just right with (OH) -1 Combined (in this case Fe) 3+ And (OH) -1 Just stronger than with EDTA 2- Complex of (b) to form Fe (OH) 3 Precipitation of Fe 2+ Then can remain with EDTA 2- No precipitate is formed by complexation of the complex; and in this pH range Fe (OH) 3 The filtration and separation of the precipitate are easier. In the present invention, the alkaline substance is preferably Na 2 CO 3 One or more of NaOH and ammonia water.
Filtering the filtrate, conveying the filtrate to a regeneration reactor, adding an acidic substance into the filtered filtrate, adjusting the pH value to 5.5-6, adding a regenerating agent, performing a reduction reaction, and reducing Fe (II) EDTA (NO) to generate Fe (II) EDTA and N 2 And obtaining the reduced denitration agent.
In the invention, the acidic substance is preferably one or more of sulfuric acid, phosphoric acid and citric acid, and through a great deal of experimental research in the application, the pH range can accelerate the regeneration reduction reaction and ensure that the subsequent step is supplemented with Fe 2+ The pH of the post-complexing denitration solution is maintained at 7-7.5 (the pH denitration reaction proceeds most rapidly).
In the present invention, the regenerant mainly plays a reducing role, and is preferably one or more of sodium sulfite, sodium metabisulfite, sodium sulfide, urea, ascorbic acid, carbohydrazide and hydrazine hydrate, and specifically, in the embodiment of the present invention, the regenerant can be a combination of sodium sulfite and urea, a combination of sodium sulfite and carbohydrazide, and a combination of sodium sulfide and hydrazine hydrate; more specifically, the regenerant may be a combination of the above several in certain molar ratios, for example, sodium sulfite: urea 4:1, sodium sulfite: carbohydrazide 1:1, sodium sulfide: hydrazine hydrate 1: 2.
In the present invention, the regenerant is mixed with EDTA 2+ The molar ratio of (0.5-1): 1, preferably (0.6-0.9): 1, more preferably (0.7 to 0.8): 1; specifically, in the embodiment of the present invention, it may be 0.48:1 or 0.83: 1.
And after the regenerant is added, heating the solution to raise the temperature, and carrying out reduction reaction to obtain the reduced complex denitration agent.
In the invention, the temperature of the reduction reaction is preferably 40-55 ℃, and more preferably 45-50 ℃; the time of the reduction reaction is preferably 10-15 min.
After the reduction regeneration is finished, the invention conveys the reduced complex denitration agent to the Fe supplement 2+ The groove is provided with a plurality of grooves,adding ferrous salt supplement to make the denitration agent contain Fe 2+ With EDTA 2+ The molar number of the Fe is equivalent, and the Fe is completely precipitated 3+ And the loss of iron element.
In the invention, the byproduct FeSO generated in the production of titanium dioxide by a sulfuric acid method 4 7H 2 O, in the production process of titanium dioxide by a sulfuric acid method, ilmenite reacts with sulfuric acid to prepare Ti (SO) 4 ) 2 And TiOSO 4 With concurrent production of FeSO 4 And Fe 2 (SO 4 ) 3 The reaction is as follows:
TiO 2 +H 2 SO 4 →TiOS 4 +H 2 O
FeO 2 +H 2 SO 4 →FeSO 4 +H 2 O
FeO 2 +3H 2 SO 4 →Fe 2 (SO 4 ) 3 +3H 2 O
TiOSO produced by acidolysis 4 And FeSO 4 Leaching and settling the mixture to remove about 20% of insoluble impurities, adding waste iron sheet into the solution after removing impurities, and reducing to obtain Fe 3+ With Fe 2+ In the form of TiOSO 4 With Ti 2 (SO 4 ) 3 The form exists. The titanium liquid after purification and reduction treatment is concentrated and cooled in vacuum to lead ferrous sulfate to be FeSO 4 7H 2 And crystallizing the O form, drying by a centrifugal machine, taking out, and producing 3-4 t of ferrous sulfate every 1t of titanium white, wherein the treatment of the ferrous sulfate is always a difficult problem in the titanium white industry of the sulfuric acid process due to the large yield of the ferrous sulfate.
After the treatment by the process, Fe (III) EDTA and Fe (II) EDTA (NO) in the ineffective complexing denitration agent are treated, the complexing denitration liquid recovers the denitration performance, and the complexing denitration liquid is pumped into a denitration tower by a circulating pump to be continuously denitrated.
According to the invention, the compounding agent, the auxiliary agent, the nano reagent and the dispersing agent are added into the complexing agent mainly containing Fe (II) (EDTA), so that the NO complexing capability of the denitration agent is improved, the oxidation resistance of the denitration agent is improved, the absorption capacity and the use stability of the complexing denitration agent are further improved, and the method is favorable for improving the absorption capacity and the use stability of the complexing denitration agentFe (II) EDTA (NO) is reduced into Fe (II) EDTA and N by precipitating and separating Fe (III) in the spent complexing denitration agent and then adding a regenerating agent with reducibility 2 Then the by-product ferrous sulfate heptahydrate in the process of producing titanium dioxide by using sulfuric acid method is used for supplementing Fe 2+ The regeneration method of (1) regenerates the spent complexing denitration agent. Meanwhile, the auxiliary agent and the nano reagent added in the preparation process of the complex denitration agent can play a role in catalyzing the regeneration reaction and accelerate the regeneration reaction.
In order to further illustrate the present invention, the following detailed description of a complex denitration process capable of recycling regeneration provided by the present invention is provided with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Firstly, preparing 1000L of complex denitration liquid: then, 25mmol/L ferrous sulfate, 30mmol/L disodium ethylenediaminetetraacetate, 12.5mmol/L of a preparation (5mmol/L cysteine +5mmol/L methylcyclopentadienolone +2.5mmol/L dibutylhydroxytoluene), 12.5mmol/L of an auxiliary agent (4mmol/L sodium carbonate +4mmol/L disodium hydrogenphosphate +2.5mmol/L sodium sulfite +2mmol/L carbohydrazide), 0.05mmol/L of a nano-reagent (0.025mmol/L nano-titanium dioxide +0.025mmol/L nano-silicon dioxide), and 1mmol/L of a dispersant (1mmol/L sodium dodecylbenzenesulfonate) were added to 1000L of distilled water. After the solution is uniformly mixed, the solution is sealed and then placed into an ultrasonic cell disruption instrument for ultrasonic oscillation, the frequency of the ultrasonic oscillation is 20KHz, the ultrasonic oscillation is stopped for 20min after 30min, then the ultrasonic oscillation is carried out again, the steps are repeated for 6 times, and the pH value of the prepared complex denitration liquid is adjusted to be 7.
The prepared complex denitration liquid and low-temperature flue gas are subjected to gas-liquid contact reaction, and the gas flow is 500m 3 /h，NO X Concentration of 280-300mg/m 3 ，O 2 The concentration is 15-15.5%, the residence time of gas-liquid contact reaction is 5s, and the liquid-gas ratio is 3L/m 3 The empty column flow rate was 2m/s and the reaction temperature was 50 ℃. Conveying the invalid complex denitration liquid to a tempering tank by a booster pump, adding NaOH to adjust the pH to 8.5, standing for 15min, filtering and precipitating to remove oxidized Fe in the denitration liquid 3+ . Adjusting pH of the filtrate to 5.5 with sulfuric acid, adding sodium sulfite and carbonyl as regenerantHydrazine (the total concentration of the two is 25mmol/L, the ratio is 1:1), heating to 45 ℃, reacting for 10min under the condition of stirring, and supplementing Fe 2+ Adding a byproduct FeSO generated in the production of titanium dioxide by a sulfuric acid method into the complex denitration liquid in the tank 4 7H 2 O (25mmol/L) is uniformly mixed, Fe (III) EDTA and Fe (II) EDTA (NO) in the spent complex denitration liquid are treated by the step, the complex denitration liquid recovers the denitration performance, and the complex denitration liquid is pumped into a denitration tower by a circulating pump to be continuously denitrated.
FIG. 2 shows that the outlet NO X The concentration is stably maintained to be less than 50mg/m within 12h of test time 3 。
Example 2
Firstly, preparing 1000L of complex denitration liquid: 40mmol/L ferrous sulfate, 52mmol/L disodium ethylene diamine tetraacetate, 12mmol/L preparation agent (10mmol/L cysteine +2mmol/L piperazine), 28mmol/L auxiliary agent (10mmol/L sodium dihydrogen phosphate +10mmol/L sodium sulfite +8mmol/L ascorbic acid), 0.04mmol/L nano reagent (0.02mmol/L nickel oxide +0.02mmol/L nano ferroferric oxide), and 1mmol/L dispersing agent (0.5mmol/L sodium pyrophosphate +0.5mmol/L polyacrylamide) are added into 1000L distilled water. And sealing the solution, placing the solution into an ultrasonic cell disruption instrument for ultrasonic oscillation, wherein the frequency of the ultrasonic oscillation is 20KHz, stopping the ultrasonic oscillation for 15min after 25min, then repeating the ultrasonic oscillation for 4 times, and adjusting the pH value of the prepared complex denitration liquid to 6.5.
The prepared complex denitration liquid and low-temperature flue gas are subjected to gas-liquid contact reaction, and the gas flow is 500m 3 /h，NO X Concentration of 280-300mg/m 3 ，O 2 The concentration is 15-15.5%, the residence time of gas-liquid contact reaction is 5s, and the liquid-gas ratio is 3L/m 3 The empty column flow rate was 2m/s and the reaction temperature was 50 ℃. Conveying the invalid complex denitration liquid to a tempering tank by a booster pump, adding NaOH to adjust the pH to 8.5, standing for 15min, filtering and precipitating to remove oxidized Fe in the denitration liquid 3+ . Adjusting pH of the filtrate to 5.5 with sulfuric acid, adding sodium sulfite and carbohydrazide (total concentration of 25mmol/L and ratio of 1:1), heating to 45 deg.C, reacting under stirring for 10min, and supplementing Fe 2+ Adding the side product generated in the production of titanium dioxide by sulfuric acid process into the complex denitration liquid in the tankProduct FeSO 4 7H 2 O (25mmol/L) is uniformly mixed, Fe (III) EDTA and Fe (II) EDTA (NO) in the spent complex denitration liquid are treated by the step, the complex denitration liquid recovers the denitration performance, and the complex denitration liquid is pumped into a denitration tower by a circulating pump to be continuously denitrated.
FIG. 3 shows that the NO is exported by optimizing and improving the formula of the denitrifier X The concentration is stably maintained to be less than 40mg/m within 12h of test time 3 。
Example 3
Firstly, preparing 1000L of complex denitration liquid: 40mmol/L ferrous sulfate, 52mmol/L disodium ethylene diamine tetraacetate, 12mmol/L preparation agent (10mmol/L cysteine +2mmol/L piperazine), 28mmol/L auxiliary agent (10mmol/L sodium dihydrogen phosphate +10mmol/L sodium sulfite +8mmol/L ascorbic acid), 0.04mmol/L nano reagent (0.02mmol/L nickel oxide +0.02mmol/L nano ferroferric oxide), and 1mmol/L dispersing agent (0.5mmol/L sodium pyrophosphate +0.5mmol/L polyacrylamide) are added into 1000L distilled water. And sealing the solution, placing the solution into an ultrasonic cell disruption instrument for ultrasonic oscillation, wherein the frequency of the ultrasonic oscillation is 20KHz, stopping the ultrasonic oscillation for 15min after 25min, then repeating the ultrasonic oscillation for 4 times, and adjusting the pH value of the prepared complex denitration liquid to 6.5.
The prepared complex denitration liquid and low-temperature flue gas are subjected to gas-liquid contact reaction, and the gas flow is 500m 3 /h，NO X Concentration of 280-300mg/m 3 ，O 2 The concentration is 15-15.5%, the residence time of gas-liquid contact reaction is 7s, and the liquid-gas ratio is 5L/m 3 The empty column flow rate was 2m/s and the reaction temperature was 50 ℃. Conveying the invalid complex denitration liquid after reaction to a tempering tank by a booster pump, adding NaOH to adjust the pH to 9, standing for 15min, filtering and precipitating to remove oxidized Fe in the denitration liquid 3+ . Adjusting pH of the filtrate to 6 with sulfuric acid, adding sodium sulfide and hydrazine hydrate (total concentration of 25mmol/L and ratio of 1:2), heating to 50 deg.C, reacting under stirring for 10min, and supplementing Fe 2+ Adding a byproduct FeSO generated in the production of titanium dioxide by a sulfuric acid method into the complex denitration liquid in the tank 4 7H 2 O (25mmol/L) is uniformly mixed, and Fe (III) EDTA and Fe (II) EDTA (NO) in the spent complex denitration liquid are treated by the stepAnd recovering the denitration performance of the complex denitration liquid, and pumping the complex denitration liquid into a denitration tower through a circulating pump to continuously carry out denitration.
FIG. 4 shows that the outlet NO is optimized and improved by the formula of the denitrifier, the gas-liquid reaction parameters and the regeneration parameters X The concentration is stably maintained to be less than 25mg/m within 12h of test time 3 。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A complexing denitration process capable of cyclic regeneration comprises the following steps:
A) contacting a complex denitration agent with low-temperature flue gas to perform denitration until the complex denitration agent fails;
the denitration agent comprises disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent, a dispersing agent and a solvent;
the compounding agent is one or more of cysteine, linnoroline, methyl cyclopentenolone, ethylenediamine, triethanolamine, piperazine, hydroquinone and dibutyl hydroxy toluene;
the auxiliary agent is one or more of sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, sodium sulfide, ascorbic acid and carbohydrazide;
the nano reagent is one or more of nano titanium dioxide, nano nickel oxide, nano ferroferric oxide, nano iron powder and nano silicon dioxide;
B) adjusting the pH value of the complex denitration agent which is out of work in the step A) to 8.5-9.0 to ensure that Fe 3+ And (OH) -1 Combine to form Fe (OH) 3 Precipitation of Fe 2+ Retention with EDTA 2- No precipitate is formed and the precipitate is removed;
C) adjusting the pH value of the filtrate obtained by removing the precipitate in the step B) to 5.5-6, adding a regenerant, and carrying out a reduction reaction to obtain a reduced denitration agent;
D) adding a ferrous iron supplement into the reduced denitration agent to enable Fe in the denitration agent 2+ With EDTA 2+ The mole number of the catalyst is equivalent to obtain a regenerated complex denitration agent;
the ferrous iron supplement is a byproduct FeSO generated in the production of titanium dioxide by a sulfuric acid method 4 7H 2 O。
2. The complex denitration process of claim 1, wherein the ferrous salt is ferrous sulfate; the dispersing agent is one or more of sodium citrate, sodium pyrophosphate, trihexyl hexyl phosphoric acid, sodium dodecyl benzene sulfonate, polyacrylamide and triton.
3. The complex denitration process of claim 1, wherein the concentration of the ferrous salt is 25-50 mmol/L; the concentration of the disodium ethylene diamine tetraacetate is 120-150% of that of the ferrous salt; the concentration of the compounding agent is 30-50% of that of the ferrous salt; the concentration of the auxiliary agent is 50-70% of that of the ferrous salt; the concentration of the nano reagent is 0.1-0.2% of that of the ferrous salt; the concentration of the dispersing agent is 1-5% of that of the ferrous salt.
4. The complex denitration process according to any one of claims 1 to 3, wherein the complex denitration agent is prepared by the following steps:
1) mixing disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent and a dispersing agent in a solvent under the condition of introducing protective gas to obtain a mixed solution;
2) and carrying out ultrasonic oscillation on the mixed solution to obtain the complex denitration agent.
5. The complex denitration process of claim 4, wherein the denitration residence time is 5-7 s, and the liquid-gas ratio is 3-5L/m 2 The flow rate of the empty tower is 2-2.5 m/s, and the denitration temperature is 45-50 ℃.
6. The complex denitration process according to claim 1, wherein an alkaline substance is added in the step B) to adjust the pH value of the spent complex denitration agent;
the alkaline substance is Na 2 CO 3 One or more of NaOH and ammonia water.
7. The complex denitration process according to claim 1, wherein an acidic substance is added in the step C) to adjust the pH value of the filtrate to 5.5-6;
the acidic substance is one or more of sulfuric acid, phosphoric acid and citric acid.
8. The complex denitration process of claim 1, wherein the regenerant is one or more of sodium sulfite, sodium metabisulfite, sodium sulfide, urea, ascorbic acid, carbohydrazide and hydrazine hydrate;
the regenerant and EDTA 2+ The molar ratio of (0.5-1): 1.
9. the complex denitration process according to claim 1, wherein the temperature of the reduction reaction in the step B) is 40-55 ℃; the time of the reduction reaction in the step B) is 10-15 min.
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| CN115400757B (en) * | 2022-09-22 | 2023-05-26 | 东华理工大学 | Iron oxide@FeEDTA complexing wet denitration absorbent and preparation method thereof |
| CN115738632B (en) * | 2022-11-23 | 2024-08-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Complexation denitration technology |
| CN115738599B (en) * | 2022-11-23 | 2024-06-04 | 攀钢集团攀枝花钢铁研究院有限公司 | At the same time absorb NOxPreparation method of complexing denitration liquid of CO |
| CN115722054B (en) * | 2022-11-23 | 2024-08-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for regenerating failure complexation denitration liquid by using carbon monoxide in flue gas |
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