CN109569240A - NO_x Reduction by Effective ionic liquid and its application method - Google Patents
NO_x Reduction by Effective ionic liquid and its application method Download PDFInfo
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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Abstract
NO_x Reduction by Effective ionic liquid of the present invention, belong to fume treatment technical field, including following component: urea groups is peptide 15-30 parts organic, 60-80 parts of deionized water, 5-10 parts of catalyst, 1-5 parts of stabilizer, 1-5 parts of regulator, high-speed dispersion equipment is added in mentioned component, high speed dispersion is carried out, dispersion reaction forms stable NO_x Reduction by Effective ionic liquid；The application method of the NO_x Reduction by Effective ionic liquid sprays into configured ionic liquid spray gun in Benitration reactor, the use of temperature is 450-1250 DEG C.NO_x Reduction by Effective ionic liquid and its application method of the present invention, high-effect ionic denitration liquid are a kind of colourless, tasteless, non-corrosive liquid, transport and storage safety, and simple and easy to use, this product temperature range of operation without secondary pollution is wide, can run at 450-1250 DEG C；This method operation, does not generate any crystallization and blocking；After this product is put into high-temperature region, flue gas comes into full contact with denitration ionic liquid, increases liquid catalyst and flue gas recovery time, avoids escaping.
Description
Technical field
The invention belongs to fume treatment technical fields, and in particular to a kind of NO_x Reduction by Effective ionic liquid and its application method.
Background technique
The NOx that the combustion of fossil fuel such as coal and petroleum generate is the main source of NO_x in Air Environment.NOx excess emissions
Cause increasingly severe environmental pollution, such as photochemical fog, acid rain, depletion of the ozone layer and greenhouse effects etc..In recent years,
Country performs stringenter limitation standard for NOx emission in power plant's tail flue gas, and power plant also takes many feasible
Measure reduces the generation and discharge of NOx in coal combustion process.
In these technical measures, selective catalytic reduction selectivecatalyticreduction, SCR denitration skill
Art is proved to be to control one of the most mature effective technology of NOx emission in tail flue gas, and is widely applied.Currently,
The SCR catalyst of large-scale industrial application is mainly V2O5-WO3MoO3/TiO2Catalyst.This makes SCR denitration device must cloth
It sets before flue gas desulfurization and dust-extraction unit.This arrangement can service life to catalyst and upstream device generate it is some not
Benefit influences.Such as a large amount of flying dusts present in flue gas will cause the abrasion of catalyst；Alkali-Metal Na, K in flying dust etc. and arsenic, mercury
Equal substances can reduce catalyst life；SO in flue gas2Also it is easy to be oxidized to SO by catalyst3, SO3With the vapor in flue gas
Or the sulfate that NH3 reaction generates can cause to corrode to upstream device.
Non-selective denitration technology (SNCR: a kind of to utilize reducing agent (NH3/ urea is by the chemistry of the NOx removal in flue gas
Process.Usually urea liquid, ammonium hydroxide or gaseous ammonia, are injected directly into the hot fume of boiler and NOx reaction generates nitrogen (N2
With steam (H2O, the reaction do not need catalyst, but need (to run at 850 DEG C -950 DEG C in hot conditions.Flue-gas temperature
To will cause denitration efficiency low the unstable or low time, enter back-end ductwork without reacted ammonia or urea and cause the escaping of ammonia,
Air preheater is blocked, flue is corroded, ammonium sulfate crystallization is formed, cloth bag crystallization is generated in bag filter, influences load, denitration
Efficiency is to reduce.
Ozone method of denitration: having good removal effect to NOx between 90-250 DEG C using ozonation technology,
But the prior art cannot be guaranteed complete reactive absorption, and ozone can almost be reacted with any biological tissue, and that does not react completely is smelly
Oxygen enters atmosphere and causes secondary pollution.
PNCR denitration technology: this process equipment is simple, fixed investment is small, but low efficiency, stability are poor.
Using ammonium hydroxide denitrating technique there are low efficiency, the high situation of operating cost, be partly improved type denitration liquid be mixed with it is outstanding
Floating particles easily cause to gather at spray gun spray nozzle because suspended particulate deposits, and making spray head that blocking occur influences denitration；It needs simultaneously
Spraying process is transformed, boiler improvement is made to have difficulties.
Summary of the invention
The object of the present invention is to provide a kind of NO_x Reduction by Effective ionic liquid and its application methods, to solve the above problems.
To achieve the goals above, the technical solution adopted by the present invention are as follows:
NO_x Reduction by Effective ionic liquid of the present invention, including following component: urea groups is peptide 15-30 parts organic, 60-80 parts of deionized water,
High-speed dispersion equipment is added in 5-10 parts of catalyst, 1-5 parts of stabilizer, 1-5 parts of regulator, mentioned component, carries out high speed dispersion, point
Scattered reaction forms stable NO_x Reduction by Effective ionic liquid；
The preparation step of the organic peptide of urea groups is as follows:
1) amino acid and manganese, vanadium, chromium, cerium nitrate one or more of in 60-80 DEG C of generation amino acids metal
Salt pre-reaction object；
2) reaction kettle is added in urea and the resulting amino acid metal salt pre-reaction object of step 1), then is added into reaction kettle
Ethylene glycol, glycerine are chain extender, and epoxychloropropane is condensing agent, and the urea groups that ring-opening reaction synthesizes under the conditions of 65-80 DEG C has
Machine peptide.
The catalyst is the combination of one or more of oxide of V, Mn, Mo, Ti, Ce.
The regulator is one of ethanol amine, triethanolamine, dodecyl hydramine, ammonium chloride, soda ash, caustic soda or several
The composition of kind.
The stabilizer is one kind or several of polyacrylamide, neopelex, EDTA, tartaric acid, emulsifier
The combination of kind.
The application method of NO_x Reduction by Effective ionic liquid of the present invention, which is characterized in that by configured NO_x Reduction by Effective from
Sub- liquid is sprayed into Benitration reactor with spray gun, the use of temperature is 450-1250 DEG C.
The present invention introduces catalytic metal ions by way of organic peptide, improves the directionality of catalysis, passes through urea groups
The chain structure of organic peptide reduces hydrolysis degree, avoids the escaping of ammonia decomposited, and improve the organic peptide of urea groups utilizes effect
Rate, while the time of contact with nitrogen oxides in effluent is extended, acceleration comes into full contact with the nitrogen oxides in flue gas, improves
The changing effect of nitrogen oxides.
The present invention is base stock by catalyzing and synthesizing the metal salt of novel C HNO- base using the organic peptide of urea groups, metal from
Son is contacted with the oxygen in gas phase, and instantaneous oxidation generates active peptide catalytic body, promotes the rapid decomposition of CHNO- group, is improved
The ability of NOx in gas phase is captured, the NH after decomposing is reduced3Escape probability, improve NOx reduction conversion ratio.
The organic peptide of urea groups effectively slows down the hydrolysis of urea group, increases the residence time in flue gas, improves-CO-
The reducing power of group is conducive to improve denitration efficiency.
The invention has the benefit that NO_x Reduction by Effective ionic liquid of the present invention and its application method, high-effect ionic denitration liquid are
A kind of colourless, tasteless, non-corrosive liquid, transport and storage safety, it is simple and easy to use, it is without secondary pollution；Use process
In it is nontoxic, harmless, no byproduct generates, without subsequent nitrate treatment expense；Product can directly be set using original SNCR denitration
Standby facility, is not necessarily to newly added equipment facility；Using product denitration of the invention, usage amount reduces 70% compared with ammonia or urea, denitration
Rate is up to 95% or more；Operating cost of the present invention is lower than SCR, SNCR denitration operating cost；This product temperature range of operation is wide, can be
450-1250 DEG C of operation；This method operation, does not generate any crystallization and blocking；After this product is put into high-temperature region, flue gas and de-
Nitre ionic liquid comes into full contact with, and increases liquid catalyst and flue gas recovery time, avoids escaping.
Specific embodiment
Embodiment 1
NO_x Reduction by Effective ionic liquid of the present invention, including following component: 15 parts of the organic peptide of urea groups, 60 parts of deionized water, catalyst 5
High-speed dispersion equipment is added in part, 1 part of stabilizer, 1 part of regulator, mentioned component, carries out high speed dispersion, and dispersion reaction, which is formed, stablizes
Ionic liquid；
The preparation step of the organic peptide of urea groups is as follows:
1) amino acid and manganese nitrate are in 60 DEG C of generation amino acid metal salt pre-reaction objects；
2) reaction kettle is added in urea and the resulting amino acid metal salt pre-reaction object of step 1), then is added into reaction kettle
Ethylene glycol, glycerine are chain extender, and epoxychloropropane is condensing agent, and the urea groups that ring-opening reaction synthesizes under the conditions of 65 DEG C is organic
Peptide.
The catalyst is V2O5；The regulator is ethanol amine；The stabilizer is polyacrylamide.
Embodiment 2
NO_x Reduction by Effective ionic liquid of the present invention, including following component: 30 parts of the organic peptide of urea groups, 80 parts of deionized water, catalyst
High-speed dispersion equipment is added in 10 parts, 5 parts of stabilizer, 5 parts of regulator, mentioned component, carries out high speed dispersion, and dispersion reaction forms steady
Fixed ionic liquid；
The preparation step of the organic peptide of urea groups is as follows:
1) amino acid and chromic nitrate are in 80 DEG C of generation amino acid metal salt pre-reaction objects；
2) reaction kettle is added in urea and the resulting amino acid metal salt pre-reaction object of step 1), then is added into reaction kettle
Ethylene glycol, glycerine are chain extender, and epoxychloropropane is condensing agent, and the urea groups that ring-opening reaction synthesizes under the conditions of 80 DEG C is organic
Peptide.
The catalyst is TiO2；The regulator is the composition of triethanolamine and dodecyl hydramine；The stabilizer
For the combination of neopelex and EDTA.
Embodiment 3
NO_x Reduction by Effective ionic liquid of the present invention, including following component: 25 parts of the organic peptide of urea groups, 70 parts of deionized water, catalyst 8
High-speed dispersion equipment is added in part, 3 parts of stabilizer, 3 parts of regulator, mentioned component, carries out high speed dispersion, and dispersion reaction, which is formed, stablizes
Ionic liquid；
The preparation step of the organic peptide of urea groups is as follows:
1) amino acid and manganese, vanadium, chromium, cerium nitrate one or more of in 60-80 DEG C of generation amino acids metal
Salt pre-reaction object；
2) reaction kettle is added in urea and the resulting amino acid metal salt pre-reaction object of step 1), then is added into reaction kettle
Ethylene glycol, glycerine are chain extender, and epoxychloropropane is condensing agent, and the urea groups that ring-opening reaction synthesizes under the conditions of 65-80 DEG C has
Machine peptide.
Application examples 1
It is used by Shandong morning carbonium element group company's carbide furnace, original uses 20% ammonium hydroxide denitration, usage amount 180L/
H, amount of nitrogen oxides is 144mg/m in denitration post analysis gas phase3；
Using the resulting high-effect ionic denitration liquid of embodiment 1, usage amount 105L/h, nitrogen oxidation in denitration post analysis gas phase
Object content is reduced to 29mg/m3, analyze by contrast, usage amount is the 58.3% of former usage amount, and amount of nitrogen oxides is reduced to original
4.96 times come, reduce 79.8%, the requirement lower than discharge standard are fully achieved.
Application examples 2
It is used by 130 tons of fluid bed furnaces of Jining company, original uses 20% ammonium hydroxide denitration, and usage amount 280L/h takes off
Nitrogen oxides is 79mg/m in nitre post analysis gas phase3；
Using the resulting high-effect ionic denitration liquid of embodiment 2, usage amount 95L/h, nitrogen oxidation in denitration post analysis gas phase
Object is 35mg/m3, addition point temperature is 715 DEG C, is analyzed by contrast, and usage amount is the 34% of former usage amount, saves operating cost
Up to 50%.Through continuous operation 90 days, carries out systems inspection nodeless mesh object and be attached on economizer and pipeline, system resistance is without obvious
Increase.
Application examples 3
130 tons of fluid bed furnaces of Jining eastern suburb Thermal Corp use, and original uses fixed-bed catalytic denitration, denitration post analysis gas
Nitrogen oxides is 83mg/m in phase3, often there is inlet ductwork and stopping state occur, system resistance is caused to increase；
Using the resulting high-effect ionic denitration liquid of embodiment 3, usage amount 142L/h, nitrogen oxidation in denitration post analysis gas phase
Object is 4mg/m3, analyze by contrast, reduce former oxynitrides 95.18%, through continuous operation 60 days, dismantle catalytic bed air inlet
Pipeline inspection is held essentially constant without any Crystallization Plugging object, system resistance.Greatly extend fixed-bed catalytic denitrification apparatus
Runing time.
Claims (6)
1. a kind of NO_x Reduction by Effective ionic liquid, which is characterized in that including following component: urea groups is peptide 15-30 parts organic, deionized water
High-speed dispersion equipment is added in 60-80 parts, 5-10 parts of catalyst, 1-5 parts of stabilizer, 1-5 parts of regulator, mentioned component, carries out high
Speed dispersion, dispersion reaction form stable NO_x Reduction by Effective ionic liquid；
The preparation step of the organic peptide of urea groups is as follows:
1) amino acid and manganese, vanadium, chromium, cerium nitrate one or more of it is pre- in 60-80 DEG C of generation amino acid metal salt
Reactant；
2) reaction kettle is added in urea and the resulting amino acid metal salt pre-reaction object of step 1), then second two is added into reaction kettle
Alcohol, glycerine are chain extender, and epoxychloropropane is condensing agent, and the urea groups that ring-opening reaction synthesizes under the conditions of 65-80 DEG C is organic
Peptide.
2. above-mentioned NO_x Reduction by Effective ionic liquid according to claim 1, which is characterized in that the catalyst is V, Mn, Mo, Ti, Ce
One or more of oxide combination.
3. above-mentioned NO_x Reduction by Effective ionic liquid according to claim 1, which is characterized in that the regulator is ethanol amine, three ethyl alcohol
The composition of one or more of amine, dodecyl hydramine, ammonium chloride, soda ash, caustic soda.
4. above-mentioned NO_x Reduction by Effective ionic liquid according to claim 1, which is characterized in that the stabilizer is polyacrylamide, ten
One or more of combinations of dialkyl benzene sulfonic acids sodium, EDTA, tartaric acid, emulsifier.
5. above-mentioned NO_x Reduction by Effective ionic liquid according to claim 1, which is characterized in that the amino acid is glutamic acid or bad ammonia
Acid.
6. a kind of application method of NO_x Reduction by Effective ionic liquid a method as claimed in any one of claims 1 to 5, which is characterized in that will configure
Ionic liquid with spray gun spray into Benitration reactor in, using temperature be 450-1250 DEG C.
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Cited By (4)
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| CN113117475A (en) * | 2021-04-30 | 2021-07-16 | 山东省昔利环境科技有限公司 | Composite fiber denitration agent and preparation method thereof |
| CN113967407A (en) * | 2021-10-18 | 2022-01-25 | 中国人民大学 | SNCR (selective non-catalytic reduction) high-efficiency auxiliary agent as well as preparation method and application thereof |
| CN114717016A (en) * | 2022-03-04 | 2022-07-08 | 苏州仕净科技股份有限公司 | Efficient reburning denitration method |
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