CN109569240B - Efficient denitration ionic liquid and use method thereof - Google Patents
Efficient denitration ionic liquid and use method thereof Download PDFInfo
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- CN109569240B CN109569240B CN201811532636.5A CN201811532636A CN109569240B CN 109569240 B CN109569240 B CN 109569240B CN 201811532636 A CN201811532636 A CN 201811532636A CN 109569240 B CN109569240 B CN 109569240B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/12—Methods and means for introducing reactants
- B01D2259/124—Liquid reactants
Abstract
The invention relates to a high-efficiency denitration ionic liquid, belonging to the technical field of flue gas treatment, and comprising the following components: 15-30 parts of carbamido organic peptide, 60-80 parts of deionized water, 5-10 parts of catalyst, 1-5 parts of stabilizer and 1-5 parts of regulator, wherein the components are added into high-speed dispersion equipment for high-speed dispersion, and the dispersion reaction is carried out to form stable high-efficiency denitration ionic liquid; the using method of the high-efficiency denitration ionic liquid comprises the step of spraying the prepared ionic liquid into a denitration reactor by using a spray gun, wherein the using temperature is 450-. The high-efficiency ionic denitration liquid is colorless, tasteless and non-corrosive liquid, is safe to transport and store, is convenient and simple to use, has no secondary pollution, has a wide operation temperature range, and can operate at 1250 ℃; the method is operated, and no crystallization and blockage are generated; after the product is put into a high-temperature area, the flue gas is fully contacted with the denitration ionic liquid, so that the reduction time of the liquid catalyst and the flue gas is prolonged, and the escape is avoided.
Description
Technical Field
The invention belongs to the technical field of flue gas treatment, and particularly relates to a high-efficiency denitration ionic liquid and a using method thereof.
Background
NOx produced by the combustion of fossil fuels such as coal and petroleum is a major source of atmospheric nitrogen oxides. Excessive NOx emissions cause increasingly severe environmental pollution such as photochemical smog, acid rain, ozone layer depletion, greenhouse effect, and the like. In recent years, countries have implemented stricter limiting standards for NOx emission in tail flue gas of power plants, and power plants have also adopted many feasible measures to reduce the generation and emission of NOx in coal combustion processes.
Among these technical measures, selective catalytic reduction, SCR denitration, has proven to be one of the most mature and effective technologies for controlling NOx emissions in tail flue gas, and is widely used. At present, the SCR catalyst for large-scale industrial application is mainly V2O5-WO3MoO3/TiO2A catalyst. This necessitates the arrangement of the SCR denitration device in front of the flue gas desulfurization and dust removal device. This arrangement can have some detrimental effects on catalyst life and downstream equipment. For example, the large amount of fly ash present in flue gas can cause catalyst attrition; the alkali metals Na, K and the like in the fly ash and the substances such as arsenic, mercury and the like can reduce the catalystThe service life; SO in flue gas2Is also easily oxidized to SO by the catalyst3，SO3The sulfates produced by reaction with water vapor or NH3 in the flue gas can cause corrosion of downstream equipment.
Non-selective denitration technique (SNCR: a method of using a reducing agent (NH)3Urea chemical process for removing NOx from flue gases. Usually urea solution, ammonia water or gaseous ammonia, is directly injected into the hot flue gases of the boiler and reacts with NOx to form nitrogen (N)2And steam (H)2And O, the reaction does not need a catalyst, but needs to be operated under a high-temperature condition (850-950 ℃, the denitration efficiency is low due to unstable or low flue gas temperature, and the unreacted ammonia or urea enters a tail flue to cause ammonia escape, so that an air preheater is blocked, the flue is corroded to form ammonium sulfate crystals, bag crystals are generated in a bag-type dust collector, the load is influenced, and the denitration efficiency is reduced.
The ozone denitration method comprises the following steps: the ozone oxidation technology has good removal effect on NOx at 90-250 ℃, but the prior art can not ensure complete reaction and absorption, the ozone can almost react with any biological tissue, and the incompletely reacted ozone enters the atmosphere to cause secondary pollution.
PNCR denitration technique: the process has simple equipment, small fixed investment, low efficiency and poor stability.
The ammonia water denitration process has the problems of low efficiency and high operation cost, and the denitration is influenced by blockage of a spray head due to the fact that suspended particles are easily deposited and gathered at the spray head of the spray gun when part of improved denitration liquid is mixed with the suspended particles; meanwhile, the spraying flow needs to be modified, so that the boiler is difficult to modify.
Disclosure of Invention
The invention aims to provide an efficient denitration ionic liquid and a using method thereof, and aims to solve the problems.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention relates to a high-efficiency denitration ionic liquid, which comprises the following components: 15-30 parts of carbamido organic peptide, 60-80 parts of deionized water, 5-10 parts of catalyst, 1-5 parts of stabilizer and 1-5 parts of regulator, wherein the components are added into high-speed dispersion equipment for high-speed dispersion, and the dispersion reaction is carried out to form stable high-efficiency denitration ionic liquid;
the preparation steps of the ureido organic peptide are as follows:
1) amino acid and one or more nitrates of manganese, vanadium, chromium and cerium generate amino acid metal salt pre-reactant at 60-80 ℃;
2) adding urea and the amino acid metal salt pre-reactant obtained in the step 1) into a reaction kettle, adding ethylene glycol and glycerol into the reaction kettle as chain extenders and epichlorohydrin as a condensing agent, and opening ring reaction at 65-80 ℃ to synthesize the ureido organic peptide.
The catalyst is one or a combination of several of oxides of V, Mn, Mo, Ti and Ce.
The regulator is one or more of ethanolamine, triethanolamine, dodecylamine, ammonium chloride, soda ash and caustic soda.
The stabilizer is one or a combination of more of polyacrylamide, sodium dodecyl benzene sulfonate, EDTA, tartaric acid and an emulsifier.
The application method of the high-efficiency denitration ionic liquid is characterized in that the prepared high-efficiency denitration ionic liquid is sprayed into a denitration reactor by a spray gun, and the application temperature is 450-.
The catalytic metal ions are introduced in the organic peptide mode, so that the catalytic directionality is improved, the hydrolysis degree is reduced through the chain structure of the carbamido organic peptide, the decomposed ammonia is prevented from escaping, the utilization efficiency of the carbamido organic peptide is improved, the contact time of the carbamido organic peptide with nitrogen oxides in smoke is prolonged, the full contact of the carbamido organic peptide with the nitrogen oxides in the smoke is accelerated, and the conversion effect of the nitrogen oxides is improved.
The invention uses carbamido organic peptide as basic raw material to synthesize novel CHNO-based metal salt through catalysis, and metal ions are contacted with oxygen in gas phase to be instantly oxidized to generate active peptide catalyst body, thereby promoting the rapid decomposition of CHNO-group, improving the capability of capturing NOx in gas phase and reducing decomposed NH3The escape probability of the NOx reduction catalyst is improved.
The carbamido organic peptide effectively slows down the hydrolysis of urea groups, increases the retention time in flue gas, improves the reducing capability of-CO-groups and is beneficial to improving the denitration efficiency.
The invention has the beneficial effects that: the high-efficiency ionic denitration liquid is colorless, tasteless and non-corrosive, is safe to transport and store, is convenient and simple to use, and does not cause secondary pollution; the use process is nontoxic and harmless, no by-product is generated, and no subsequent nitrate treatment cost exists; the product can directly use the original SNCR denitration equipment and facilities without adding new equipment and facilities; compared with ammonia gas or urea, the denitration rate of the product is more than 95 percent; the operation cost of the invention is lower than that of SCR and SNCR denitration; the product has wide operation temperature range and can operate at 450-1250 ℃; the method is operated, and no crystallization and blockage are generated; after the product is put into a high-temperature area, the flue gas is fully contacted with the denitration ionic liquid, so that the reduction time of the liquid catalyst and the flue gas is prolonged, and the escape is avoided.
Detailed Description
Example 1
The invention relates to a high-efficiency denitration ionic liquid, which comprises the following components: 15 parts of carbamido organic peptide, 60 parts of deionized water, 5 parts of catalyst, 1 part of stabilizer and 1 part of regulator, wherein the components are added into high-speed dispersion equipment for high-speed dispersion, and the dispersion reaction is carried out to form stable ionic liquid;
the preparation steps of the ureido organic peptide are as follows:
1) amino acid and manganese nitrate generate an amino acid metal salt pre-reactant at 60 ℃;
2) adding urea and the amino acid metal salt pre-reactant obtained in the step 1) into a reaction kettle, adding ethylene glycol and glycerol into the reaction kettle as chain extenders and epoxy chloropropane as condensing agents, and opening ring reaction at 65 ℃ to synthesize the ureido organic peptide.
The catalyst is V2O5(ii) a The regulator is ethanolamine; the stabilizer is polyacrylamide.
Example 2
The invention relates to a high-efficiency denitration ionic liquid, which comprises the following components: 30 parts of carbamido organic peptide, 80 parts of deionized water, 10 parts of catalyst, 5 parts of stabilizer and 5 parts of regulator, wherein the components are added into high-speed dispersion equipment for high-speed dispersion, and the dispersion reaction is carried out to form stable ionic liquid;
the preparation steps of the ureido organic peptide are as follows:
1) amino acid and chromium nitrate generate amino acid metal salt pre-reactant at 80 ℃;
2) adding urea and the amino acid metal salt pre-reactant obtained in the step 1) into a reaction kettle, adding ethylene glycol and glycerol into the reaction kettle as chain extenders and epoxy chloropropane as condensing agents, and opening ring reaction at 80 ℃ to synthesize the ureido organic peptide.
The catalyst is TiO2(ii) a The regulator consists of triethanolamine and dodecylamine; the stabilizer is the combination of sodium dodecyl benzene sulfonate and EDTA.
Example 3
The invention relates to a high-efficiency denitration ionic liquid, which comprises the following components: 25 parts of carbamido organic peptide, 70 parts of deionized water, 8 parts of catalyst, 3 parts of stabilizer and 3 parts of regulator, wherein the components are added into high-speed dispersion equipment for high-speed dispersion, and the dispersion reaction is carried out to form stable ionic liquid;
the preparation steps of the ureido organic peptide are as follows:
1) amino acid and one or more nitrates of manganese, vanadium, chromium and cerium generate amino acid metal salt pre-reactant at 60-80 ℃;
2) adding urea and the amino acid metal salt pre-reactant obtained in the step 1) into a reaction kettle, adding ethylene glycol and glycerol into the reaction kettle as chain extenders and epichlorohydrin as a condensing agent, and opening ring reaction at 65-80 ℃ to synthesize the ureido organic peptide.
Application example 1
The method is used by a carbonization furnace of Yangcarbon group company in certain morning of Shandong, 20% ammonia water is originally adopted for denitration, the using amount is 180L/h, and the content of nitrogen oxide in gas phase is analyzed to be 144mg/m after denitration3；
The high efficiency obtained in example 1 was usedThe using amount of the ionic denitration liquid is 105L/h, and the content of nitrogen oxides in the analyzed gas phase after denitration is reduced to 29mg/m3Through comparative analysis, the use amount is 58.3 percent of the original use amount, the content of nitrogen oxides is reduced to 4.96 times of the original use amount, the content is reduced by 79.8 percent, and the requirement of being lower than the emission standard is completely met.
Application example 2
The method is used by 130 tons of fluidized bed furnaces of Jining company, 20 percent ammonia water is originally adopted for denitration, the using amount is 280L/h, and the content of nitrogen oxide in gas phase after denitration analysis is 79mg/m3；
The high-efficiency ionic denitration liquid obtained in example 2 is used in an amount of 95L/h, and nitrogen oxides in a gas phase after denitration analysis are 35mg/m3The temperature of the addition point is 715 ℃, the usage amount is 34 percent of the original usage amount through comparative analysis, and the operation cost is saved by 50 percent. After the system is continuously operated for 90 days, no crystal is attached to the economizer and the pipeline in the system check, and the system resistance is not obviously increased.
Application example 3
130 ton fluidized bed furnace of Dingning suburb thermodynamic company, originally fixed bed catalytic denitration is adopted, and the nitrogen oxide in the gas phase is analyzed to be 83mg/m after denitration3The inlet pipeline is blocked frequently, so that the system resistance is increased;
the high-efficiency ionic denitration liquid obtained in example 3 is used in an amount of 142L/h, and nitrogen oxides in a gas phase after denitration analysis are 4mg/m3According to comparative analysis, the original oxynitride 95.18% is reduced, and after continuous operation for 60 days, the gas inlet pipeline of the catalytic bed is disassembled to check that no crystal blockage exists, and the system resistance is basically kept unchanged. The operation time of the fixed bed catalytic denitration device is greatly prolonged.
Claims (6)
1. The efficient denitration ionic liquid is characterized by comprising the following components: 15-30 parts of carbamido organic peptide, 60-80 parts of deionized water, 5-10 parts of catalyst, 1-5 parts of stabilizer and 1-5 parts of regulator, wherein the components are added into high-speed dispersion equipment for high-speed dispersion, and the dispersion reaction is carried out to form stable high-efficiency denitration ionic liquid;
the preparation steps of the ureido organic peptide are as follows:
1) amino acid and one or more nitrates of manganese, vanadium, chromium and cerium generate amino acid metal salt pre-reactant at 60-80 ℃;
2) adding urea and the amino acid metal salt pre-reactant obtained in the step 1) into a reaction kettle, adding ethylene glycol and glycerol into the reaction kettle as chain extenders and epichlorohydrin as a condensing agent, and opening ring reaction at 65-80 ℃ to synthesize the ureido organic peptide.
2. The ionic liquid for high efficiency denitration according to claim 1, wherein the catalyst is one or more of oxides of V, Mn, Mo, Ti and Ce.
3. The ionic liquid for high efficiency denitration according to claim 1, wherein the modifier is one or more of ethanolamine, triethanolamine, dodecylolamine, ammonium chloride, soda ash and caustic soda.
4. The ionic liquid for denitration according to claim 1, wherein the stabilizer is one or more selected from polyacrylamide, sodium dodecylbenzenesulfonate, EDTA, and tartaric acid.
5. The ionic liquid for denitration according to claim 1, wherein the amino acid is glutamic acid or lysine.
6. A method for using the high-efficiency denitration ionic liquid as claimed in any one of claims 1 to 5, wherein the prepared ionic liquid is sprayed into the denitration reactor by a spray gun, and the use temperature is 715 ℃.
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| CN110102179A (en) * | 2019-05-06 | 2019-08-09 | 苏州仕净环保科技股份有限公司 | LCR liquid catalyst denitrating technique |
| CN113117475B (en) * | 2021-04-30 | 2021-11-19 | 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 |
| CN114717016B (en) * | 2022-03-04 | 2023-07-25 | 苏州仕净科技股份有限公司 | Efficient reburning denitration method |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101406793A (en) * | 2008-11-13 | 2009-04-15 | 上海交通大学 | Bromine chloride mercury-removing compositional liquor and method for removing mercury in flue gas using the same |
| CN101775312A (en) * | 2010-03-25 | 2010-07-14 | 武汉聚隆功能塑料有限公司 | Oil-denitrifying finishing agent |
| CN103113157A (en) * | 2013-02-01 | 2013-05-22 | 兰州熙瑞化工科技有限公司 | Slow-release water-retaining compound fertilizer composition |
| CN103239978A (en) * | 2013-05-14 | 2013-08-14 | 成都信息工程学院 | Amino acid nickel complex wet flue gas denitration method |
| WO2018036417A1 (en) * | 2016-08-23 | 2018-03-01 | Airborne China Limited | Flue gas clean up method using a multiple system approach |
| CN107987223A (en) * | 2017-11-30 | 2018-05-04 | 湖北工业大学 | A kind of ester modified high-adaptability polycarboxylate water-reducer of alkyl acrylic and preparation method |
| WO2018104169A1 (en) * | 2016-12-05 | 2018-06-14 | Sms Group Gmbh | Method and device for reducing nox in exhaust gas flows of metallurgical vessels and furnaces |
| WO2018124418A1 (en) * | 2016-12-27 | 2018-07-05 | ㈜파나시아 | Flue gas denitrogenization system for ship |
| CN108310943A (en) * | 2018-03-06 | 2018-07-24 | 北京建筑大学 | A kind of ozone oxidation type embrane method flue gas waste heat recovery and purification system |
| CN108929387A (en) * | 2018-08-08 | 2018-12-04 | 烟台浩忆生物科技有限公司 | A kind of preparation method of chitosan-g- antibacterial peptide polymer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8318116B2 (en) * | 2006-04-07 | 2012-11-27 | Liang Hu | Methods for deacidizing gaseous mixtures by phase enhanced absorption |
| CN102526923A (en) * | 2010-12-21 | 2012-07-04 | 精祎科技有限公司 | Formaldehyde scavenger |
| CN103055837B (en) * | 2013-01-14 | 2015-05-20 | 中国科学院生态环境研究中心 | Titanium dioxide catalyst for photo-catalytic oxidation NOx (nitric oxide) in visible light, and preparation method as well as application of titanium dioxide |
| AU2015219586A1 (en) * | 2014-02-19 | 2016-08-18 | Instytut Biochemii I Biofizyki Polskiej Akademii Nauk | Method for synthesis of a biopolymer derivative, a biopolymer derivative and its use |
-
2018
- 2018-12-14 CN CN201811532636.5A patent/CN109569240B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101406793A (en) * | 2008-11-13 | 2009-04-15 | 上海交通大学 | Bromine chloride mercury-removing compositional liquor and method for removing mercury in flue gas using the same |
| CN101775312A (en) * | 2010-03-25 | 2010-07-14 | 武汉聚隆功能塑料有限公司 | Oil-denitrifying finishing agent |
| CN103113157A (en) * | 2013-02-01 | 2013-05-22 | 兰州熙瑞化工科技有限公司 | Slow-release water-retaining compound fertilizer composition |
| CN103239978A (en) * | 2013-05-14 | 2013-08-14 | 成都信息工程学院 | Amino acid nickel complex wet flue gas denitration method |
| WO2018036417A1 (en) * | 2016-08-23 | 2018-03-01 | Airborne China Limited | Flue gas clean up method using a multiple system approach |
| WO2018104169A1 (en) * | 2016-12-05 | 2018-06-14 | Sms Group Gmbh | Method and device for reducing nox in exhaust gas flows of metallurgical vessels and furnaces |
| WO2018124418A1 (en) * | 2016-12-27 | 2018-07-05 | ㈜파나시아 | Flue gas denitrogenization system for ship |
| CN107987223A (en) * | 2017-11-30 | 2018-05-04 | 湖北工业大学 | A kind of ester modified high-adaptability polycarboxylate water-reducer of alkyl acrylic and preparation method |
| CN108310943A (en) * | 2018-03-06 | 2018-07-24 | 北京建筑大学 | A kind of ozone oxidation type embrane method flue gas waste heat recovery and purification system |
| CN108929387A (en) * | 2018-08-08 | 2018-12-04 | 烟台浩忆生物科技有限公司 | A kind of preparation method of chitosan-g- antibacterial peptide polymer |
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