CN108114596B - A kind of composition for purifying nitrogen oxides and using method thereof - Google Patents
A kind of composition for purifying nitrogen oxides and using method thereof Download PDFInfo
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 40
- 239000000919 ceramic Substances 0.000 claims abstract description 37
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims abstract description 31
- 229960002218 sodium chlorite Drugs 0.000 claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000010431 corundum Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002089 NOx Inorganic materials 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 2
- 235000010261 calcium sulphite Nutrition 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 238000001321 HNCO Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
Classifications
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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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
技术领域technical field
本发明涉及污染气体治理技术领域，更具体地，涉及一种净化氮氧化物的组合物及其使用方法。The invention relates to the technical field of pollution gas treatment, and more particularly, to a composition for purifying nitrogen oxides and a method for using the same.
背景技术Background technique
随着经济的迅猛发展，能源消耗所带来的环境污染问题日益严重。目前，全世界NOx排放总量为达5800万吨/每年。NOx对环境的损害作用极大，它既是形成酸雨的主要物质之一，也是形成大气中光化学烟雾的重要物质和消耗O3的一个重要因子。With the rapid development of economy, the problem of environmental pollution caused by energy consumption is becoming more and more serious. At present, the total amount of NOx emissions in the world is 58 million tons per year. NOx is extremely harmful to the environment. It is not only one of the main substances that form acid rain, but also an important substance that forms photochemical smog in the atmosphere and an important factor that consumes O 3 .
柴油机尾气排放就以PM(颗粒状物质)和NOx为主，柴油机排出的NOx中NO约占90％。目前净化柴油机排出的氮氧化物主要采用选择性催化还原法(SCR)，以NH3为还原剂，在V2O5、Fe分子筛或Cu分子筛等催化剂的作用下，选择性地将富氧尾气中NOx还原为N2。实际应用中，SCR系统多以质量分数为32.5％的尿素水溶液作为NH3源，尿素水溶液以微小液滴形式喷射入SCR转化器前的排气管内，温度在200℃以上时，发生热解反应产生HNCO和NH3。尿素SCR系统存在着管路易腐蚀、喷嘴寿命短、尿素沉积和催化剂易失活等问题，并且该方法消耗大量的氨资源，对农用化肥生产和使用有不利影响。Diesel exhaust emissions are dominated by PM (particulate matter) and NOx, and NOx accounts for about 90% of the NOx emitted by diesel engines. At present, the selective catalytic reduction (SCR ) method is mainly used to purify the nitrogen oxides discharged from diesel engines. NH 3 is used as a reducing agent. NOx is reduced to N 2 in the middle. In practical applications, the SCR system mostly uses urea aqueous solution with a mass fraction of 32.5% as the NH 3 source. The urea aqueous solution is injected into the exhaust pipe before the SCR converter in the form of tiny droplets. When the temperature is above 200 °C, a pyrolysis reaction occurs. HNCO and NH3 are produced. The urea SCR system has problems such as tube corrosion, short nozzle life, urea deposition and catalyst deactivation, and this method consumes a lot of ammonia resources, which has an adverse effect on the production and use of agricultural fertilizers.
因此人们将视线转向湿法排烟脱氮。公开号CN101385942A公开了一种液相氧化-吸收两段式湿法烟气脱硝工艺，采用高锰酸钾、亚氯酸钠、次氯酸钠、次氯酸钙、双氧水、二氧化氯中一种或者几种混合物的溶液作为氧化剂，使烟气中的一氧化氮与氧化剂接触反应，部分氧化成二氧化氮之后，利用碱液吸收经过氧化后烟气中的氮氧化物，生成相应的亚硝酸盐。但该现有技术中，将烟气中的一氧化氮部分氧化成二氧化氮，需要根据烟气量和烟气中氮氧化物的浓度确定液相氧化剂的浓度、pH值、液气比和氧化剂补给量等参数，涉及参数较多，较难准确把控氧化程度，而且最终脱硝效率为80％以上，还有待提高。Therefore, people turn their attention to wet flue gas denitrification. Publication number CN101385942A discloses a liquid-phase oxidation-absorption two-stage wet flue gas denitrification process, which adopts one or more of potassium permanganate, sodium chlorite, sodium hypochlorite, calcium hypochlorite, hydrogen peroxide, and chlorine dioxide. The solution of the mixture is used as an oxidant, and the nitric oxide in the flue gas is contacted and reacted with the oxidant, and after partial oxidation into nitrogen dioxide, the nitrogen oxides in the oxidized flue gas are absorbed by the lye to generate the corresponding nitrite. However, in the prior art, to partially oxidize nitrogen monoxide in the flue gas into nitrogen dioxide, it is necessary to determine the concentration, pH value, liquid-gas ratio, and liquid-gas ratio of the liquid-phase oxidant according to the amount of flue gas and the concentration of nitrogen oxides in the flue gas. The oxidant supply and other parameters involve many parameters, and it is difficult to accurately control the degree of oxidation, and the final denitration efficiency is more than 80%, which needs to be improved.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种克服上述问题的净化氮氧化物的组合物及其使用方法，使用该组合物能深度净化氮氧化物，净化率达88％以上，且所需设备简单成本低，更适用于净化柴油机排放尾气中的NOX。The object of the present invention is to provide a composition for purifying nitrogen oxides that overcomes the above problems and a method of using the same. The composition can deeply purify nitrogen oxides with a purification rate of more than 88%, and the required equipment is simple and low in cost. It is more suitable for purifying NO X in the exhaust gas of diesel engine.
本发明采用的技术方案如下：The technical scheme adopted in the present invention is as follows:
一种净化氮氧化物的组合物，包括亚氯酸钠水溶液、催化陶瓷球和还原剂的水溶液，所述催化陶瓷球由催化剂附着在填料瓷球上形成。A composition for purifying nitrogen oxides comprises an aqueous solution of sodium chlorite, a catalytic ceramic ball and an aqueous solution of a reducing agent, wherein the catalytic ceramic ball is formed by attaching a catalyst to a filler ceramic ball.
上述技术方案采用亚氯酸钠水溶液在催化陶瓷球存在条件下，将氮氧化物中的NO全部氧化成NO2，再利用还原剂的水溶液将NO2还原生成N2，其中亚氯酸钠与NO反应过程如下：The above technical scheme adopts an aqueous solution of sodium chlorite to oxidize all NO in nitrogen oxides into NO 2 in the presence of catalytic ceramic balls, and then uses an aqueous solution of a reducing agent to reduce NO 2 to form N 2 , wherein sodium chlorite and The NO reaction process is as follows:
NaClO2+2NO→2NO2+NaClNaClO 2 +2NO→2NO 2 +NaCl
现有技术中控制一系列参数仅将NO部分氧化，而本发明借助催化陶瓷球将NO全部氧化，使后续反应较单一，易于控制，且反应更充分使净化率更高。In the prior art, a series of parameters are controlled to only partially oxidize NO, but the present invention uses catalytic ceramic balls to completely oxidize NO, so that the subsequent reaction is simpler and easier to control, and the reaction is more sufficient and the purification rate is higher.
优选地，所述亚氯酸钠的质量分数为4％～6％。将亚氯酸钠的质量分数控制在此范围内，净化率更高。Preferably, the mass fraction of the sodium chlorite is 4% to 6%. When the mass fraction of sodium chlorite is controlled within this range, the purification rate is higher.
优选地，所述还原剂为亚硫酸钠，质量分数为20％。产生的副产物具有其他用途，降低造成二次污染的几率。反应式如下：Preferably, the reducing agent is sodium sulfite, and the mass fraction is 20%. The by-products produced have other uses, reducing the chance of secondary pollution. The reaction formula is as follows:
2NO2+4Na2SO3→4Na2SO4+N2↑2NO 2 +4Na 2 SO 3 →4Na 2 SO 4 +N 2 ↑
该反应条件简单，生成的氮气无毒可直接排放到空气中，产生的硫酸钠可用于制造水玻璃、玻璃、瓷釉、纸浆、和干燥剂等。The reaction conditions are simple, the generated nitrogen gas is non-toxic and can be directly discharged into the air, and the generated sodium sulfate can be used to manufacture water glass, glass, enamel, pulp, desiccant and the like.
优选地，所述催化陶瓷球中催化剂为硝酸铜、硝酸铁和硝酸铈中的一种。Preferably, the catalyst in the catalytic ceramic ball is one of copper nitrate, ferric nitrate and cerium nitrate.
优选地，所述填料瓷球为惰性氧化铝瓷球，且在球体表面开设沟槽。惰性氧化铝瓷球耐高温高压，吸水率低，化学性能稳定，能经受酸、碱及其它有机溶剂的腐蚀，并能经受生产过程中出现的温度变化。在球体表面开设沟槽，增加了球体的比表面积，从而进一步增加了物料的分散性，同时也增加了气体或液体分布点，支撑和保护催化剂。但不是比表面积越大越好，所以不宜选用微孔或开孔瓷球，否则通量过大，系统阻力太小，反应会太剧烈，不安全。Preferably, the filler ceramic balls are inert alumina ceramic balls, and grooves are provided on the surface of the balls. Inert alumina ceramic balls are resistant to high temperature and high pressure, low water absorption, stable chemical properties, can withstand the corrosion of acids, alkalis and other organic solvents, and can withstand temperature changes in the production process. Opening grooves on the surface of the sphere increases the specific surface area of the sphere, thereby further increasing the dispersibility of the material, and at the same time increasing the gas or liquid distribution points to support and protect the catalyst. However, the larger the specific surface area, the better, so it is not suitable to use microporous or open-pored ceramic balls, otherwise the flux will be too large, the system resistance will be too small, and the reaction will be too violent and unsafe.
优选地，所述惰性氧化铝瓷球的材质为刚玉质，直径为8-13mm。刚玉质的惰性氧化铝瓷球耐高温和耐腐蚀性能更强，选择直径时，太小抗压强度不够，不利于球磨使催化剂附着，太大不利于催化剂均匀分散，故选择直径为8-13mm。Preferably, the material of the inert alumina ceramic ball is corundum, and the diameter is 8-13mm. Corundum-based inert alumina ceramic balls have stronger high temperature resistance and corrosion resistance. When the diameter is too small, the compressive strength is not enough, which is not conducive to the adhesion of the catalyst by ball milling, and it is not conducive to the uniform dispersion of the catalyst. Therefore, the diameter is 8-13mm. .
上述技术方案中，催化陶瓷球的制备方法包括：将质量比为1:3.5～5的催化剂和惰性氧化铝瓷球置于球磨罐中，加入1/4催化剂重量份的水，球磨5-10min，将催化剂附着于惰性氧化铝瓷球上，然后在400℃下烧结，制得催化陶瓷球。In the above technical scheme, the preparation method of the catalytic ceramic balls includes: placing a catalyst with a mass ratio of 1:3.5-5 and an inert alumina ceramic ball in a ball-milling tank, adding 1/4 of the water by weight of the catalyst, and ball-milling for 5-10min , the catalyst was attached to the inert alumina ceramic ball, and then sintered at 400 ℃ to obtain the catalytic ceramic ball.
上述制备方法简单易操作，催化剂与惰性氧化铝瓷球的适当配比使催化剂较均匀地分布在球体的沟槽内，经过烧结又使催化剂与球体连为一体，增加了催化剂的分散面积。The above preparation method is simple and easy to operate, and the proper ratio of the catalyst and the inert alumina ceramic ball makes the catalyst more evenly distributed in the groove of the sphere, and after sintering, the catalyst and the sphere are connected as a whole, which increases the dispersion area of the catalyst.
优选地，所述亚氯酸钠水溶液、催化陶瓷球和还原剂的水溶液三者的质量比为1:1-1.5:1，优选为1:1.2:1。在此配比范围内，催化效果最好，既能使NO全部氧化，又反应不会过于剧烈而存在安全隐患。Preferably, the mass ratio of the sodium chlorite aqueous solution, the catalytic ceramic ball and the aqueous solution of the reducing agent is 1:1-1.5:1, preferably 1:1.2:1. Within this ratio range, the catalytic effect is the best, which can not only oxidize all the NO, but also the reaction will not be too violent and there is a potential safety hazard.
本发明还提供了上述净化氮氧化物的组合物的使用方法，包括先将亚氯酸钠水溶液雾化成细小液滴覆盖并通过催化陶瓷球，与含氮氧化物的气体形成逆流，亚氯酸钠将含氮氧化物气体中的NO氧化生成NO2，再将氧化后的氮氧化物气体通入还原剂的水溶液中进行反应生成N2，从而实现净化氮氧化物。The present invention also provides a method for using the above-mentioned composition for purifying nitrogen oxides, which comprises firstly atomizing the sodium chlorite aqueous solution into fine droplets to cover and passing through catalytic ceramic balls to form a countercurrent with the nitrogen oxide-containing gas, and the chlorous acid The sodium oxidizes NO in the nitrogen oxide-containing gas to form NO 2 , and then the oxidized nitrogen oxide gas is passed into the aqueous solution of the reducing agent to react to generate N 2 , thereby realizing the purification of nitrogen oxides.
上述技术方案中将亚氯酸钠水溶液雾化成细小液滴覆盖并通过催化陶瓷球和与含氮氧化物的气体形成逆流均为了增加接触反应面积，有利于反应充分。In the above technical scheme, the aqueous solution of sodium chlorite is atomized into fine droplets to cover and pass through the catalytic ceramic ball and form a countercurrent with the nitrogen oxide-containing gas to increase the contact reaction area, which is beneficial to the sufficient reaction.
在具体实施方式中，本发明的含氮氧化物的气体为柴油机排放的尾气。In a specific embodiment, the nitrogen oxide-containing gas of the present invention is exhaust gas emitted by a diesel engine.
本发明相对于现有技术具有的有益效果：The beneficial effects that the present invention has relative to the prior art:
本发明的组合物搭配合理，先用液相氧化剂亚氯酸钠溶液在催化剂存在下，将氮氧化物中的NO全部氧化生成NO2，再利用含还原剂的水溶液将NO2还原生成N2，反应完全易操控，净化率高达88％以上，且所需设备简单成本低，可以替代柴油车上的尿素溶液，适用于深度净化柴油机排放尾气中的NOX。The composition of the invention is reasonably matched. First, the liquid-phase oxidant sodium chlorite solution is used in the presence of a catalyst to oxidize all NO in nitrogen oxides to form NO 2 , and then an aqueous solution containing a reducing agent is used to reduce NO 2 to form N 2 , the reaction is completely easy to control, the purification rate is as high as 88%, and the required equipment is simple and low-cost, which can replace the urea solution on diesel vehicles, and is suitable for deeply purifying NOx in the exhaust gas of diesel engines.
具体实施方式Detailed ways
下面结合具体实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。The specific embodiments of the present invention will be described in further detail below with reference to specific embodiments. The following examples are intended to illustrate the present invention, but not to limit the scope of the present invention.
实施例1Example 1
本实施例提供了一种净化氮氧化物的组合物，包括质量分数为4％的亚氯酸钠水溶液、硝酸铜催化陶瓷球和20％的亚硫酸钠水溶液。其中所述硝酸铜催化陶瓷球由硝酸铜附着在惰性氧化铝瓷球上形成，其制备方法包括：将20重量份的硝酸铜和100重量份的惰性氧化铝瓷球置于球磨罐中，加入5重量份的水，球磨5min，将硝酸铜附着于惰性氧化铝瓷球上，然后在400℃下烧结，制得硝酸铜催化陶瓷球，所述惰性氧化铝瓷球为刚玉质，球体表面开设沟槽，直径为8mm。This embodiment provides a composition for purifying nitrogen oxides, which includes a sodium chlorite aqueous solution with a mass fraction of 4%, a copper nitrate catalytic ceramic ball and a 20% sodium sulfite aqueous solution. The copper nitrate catalytic ceramic ball is formed by attaching copper nitrate to an inert alumina ceramic ball, and the preparation method includes: placing 20 parts by weight of copper nitrate and 100 parts by weight of an inert alumina ceramic ball in a ball mill, adding 5 parts by weight of water, ball-milled for 5 minutes, and the copper nitrate was attached to the inert alumina ceramic ball, and then sintered at 400 ° C to obtain the copper nitrate catalytic ceramic ball. The inert alumina ceramic ball is corundum, and the surface of the Groove, 8mm in diameter.
本实施例还提供了上述组合物的使用方法，包括：先将100重量份亚氯酸钠溶液注入催化氧化装置中；将120重量份硝酸铜催化陶瓷球置于催化氧化装置中亚氯酸钠溶液的上方；将100重量份亚硫酸钠水溶液注入吸收装置中；This embodiment also provides a method for using the above composition, including: firstly injecting 100 parts by weight of sodium chlorite solution into the catalytic oxidation device; placing 120 parts by weight of copper nitrate catalytic ceramic balls in the catalytic oxidation device for sodium chlorite Above the solution; inject 100 parts by weight of sodium sulfite aqueous solution into the absorption device;
再将柴油机排放尾气通入催化氧化装置底部，亚氯酸钠溶液通过喷淋系统雾化成细小液滴覆盖整个催化氧化装置的断面层，通过硝酸铜催化陶瓷球并与尾气形成逆流，充分接触，亚氯酸钠溶液将尾气中的NO催化氧化成NO2，然后再通入吸收装置，与亚硫酸钠溶液反应将NO2还原成N2。经过该方法处理后，柴油机排放尾气中氮氧化物的净化率达91％。Then, the exhaust gas from the diesel engine is passed into the bottom of the catalytic oxidation device, and the sodium chlorite solution is atomized into fine droplets through the spray system to cover the cross-sectional layer of the entire catalytic oxidation device. The sodium chlorite solution catalyzes the oxidation of NO in the exhaust gas into NO 2 , which is then passed into the absorption device to react with the sodium sulfite solution to reduce the NO 2 to N 2 . After the treatment by the method, the purification rate of nitrogen oxides in the exhaust gas of the diesel engine reaches 91%.
以实施例1为基础，就“亚氯酸钠的质量分数”做平行实验，结果如表1所示。Based on Example 1, a parallel experiment was performed on the "mass fraction of sodium chlorite", and the results are shown in Table 1.
表1亚氯酸钠的质量分数对净化率的影响Table 1 Influence of mass fraction of sodium chlorite on purification rate
实施例2Example 2
本实施例提供了一种净化氮氧化物的组合物，包括质量分数为6％的亚氯酸钠水溶液、硝酸铈催化陶瓷球和20％的亚硫酸钙水溶液。其中所述硝酸铈催化陶瓷球由硝酸铈附着在惰性氧化铝瓷球上形成，其制备方法包括：将20重量份的硝酸铈和75重量份的惰性氧化铝瓷球置于球磨罐中，加入5重量份的水，球磨10min，将硝酸铈附着于惰性氧化铝瓷球上，然后在400℃下烧结，制得硝酸铈催化陶瓷球，所述惰性氧化铝瓷球为刚玉质，球体表面开设沟槽，直径为13mm。This embodiment provides a composition for purifying nitrogen oxides, which includes a sodium chlorite aqueous solution with a mass fraction of 6%, a cerium nitrate catalytic ceramic ball and a calcium sulfite aqueous solution with a mass fraction of 20%. The cerium nitrate catalytic ceramic balls are formed by attaching cerium nitrate to inert alumina ceramic balls. The preparation method includes: placing 20 parts by weight of cerium nitrate and 75 parts by weight of inert alumina ceramic balls in a ball mill, adding 5 parts by weight of water, ball milled for 10 minutes, cerium nitrate was attached to the inert alumina ceramic ball, and then sintered at 400 ° C to obtain the cerium nitrate catalytic ceramic ball, the inert alumina ceramic ball is corundum, and the surface of the sphere is open Grooves, 13mm in diameter.
本实施例还提供了上述组合物的使用方法，包括：先将100重量份亚氯酸钠溶液注入催化氧化装置中；将110重量份硝酸铈催化陶瓷球置于催化氧化装置中亚氯酸钠溶液的上方；将100重量份亚硫酸钠水溶液注入吸收装置中；This embodiment also provides a method for using the above composition, which includes: firstly injecting 100 parts by weight of sodium chlorite solution into the catalytic oxidation device; placing 110 parts by weight of cerium nitrate catalytic ceramic balls in the catalytic oxidation device for sodium chlorite Above the solution; inject 100 parts by weight of sodium sulfite aqueous solution into the absorption device;
再将柴油机排放尾气通入催化氧化装置底部，亚氯酸钠溶液通过喷淋系统雾化成细小液滴覆盖整个催化氧化装置的断面层，通过硝酸铈催化陶瓷球并与尾气形成逆流，充分接触，亚氯酸钠溶液将尾气中的NO催化氧化成NO2，然后再通入吸收装置，与亚硫酸钙溶液反应将NO2还原成N2。经过该方法处理后，柴油机排放尾气中氮氧化物的净化率达88％。Then, the exhaust gas from the diesel engine is passed into the bottom of the catalytic oxidation device, and the sodium chlorite solution is atomized into fine droplets through the spray system to cover the cross-sectional layer of the entire catalytic oxidation device. The sodium chlorite solution catalyzes the oxidation of NO in the exhaust gas into NO 2 , which is then passed into the absorption device to react with the calcium sulfite solution to reduce the NO 2 to N 2 . After the treatment by the method, the purification rate of nitrogen oxides in the exhaust gas of the diesel engine reaches 88%.
对比例1Comparative Example 1
其余与实施例1相同，不同的是该对比例的组合物不包括催化陶瓷球。最后柴油机排放尾气中氮氧化物的净化率为78％。The rest is the same as Example 1, except that the composition of this comparative example does not include catalytic ceramic balls. Finally, the purification rate of nitrogen oxides in the exhaust gas of diesel engine is 78%.
对比例2Comparative Example 2
其余与实施例1相同，不同的是该对比例中硝酸铜不制成催化陶瓷球，而是直接置于催化氧化装置的断面层。最后柴油机排放尾气中氮氧化物的净化率为80％。The rest are the same as in Example 1, except that in this comparative example, copper nitrate is not made into catalytic ceramic balls, but is directly placed on the cross-section layer of the catalytic oxidation device. Finally, the purification rate of nitrogen oxides in the exhaust gas of diesel engine is 80%.
对比例3Comparative Example 3
其余与实施例1相同，不同的是亚氯酸钠水溶液、硝酸铜催化陶瓷球和亚硫酸钠水溶液三者的重量份比为1:0.8:1。最后柴油机排放尾气中氮氧化物的净化率为82％。The rest are the same as in Example 1, except that the weight ratio of the sodium chlorite aqueous solution, the copper nitrate catalytic ceramic ball and the sodium sulfite aqueous solution is 1:0.8:1. Finally, the purification rate of nitrogen oxides in the exhaust gas of diesel engine is 82%.
最后，本发明的方法仅为较佳的实施方案，并非用于限定本发明的保护范围。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。Finally, the method of the present invention is only a preferred embodiment, and is not intended to limit the protection scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
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