CN104801336A - Zr-Mn-Fe/ZSM-5 composite oxide catalyst for low-temperature NH3 reduction of NOx and preparation method thereof - Google Patents
Zr-Mn-Fe/ZSM-5 composite oxide catalyst for low-temperature NH3 reduction of NOx and preparation method thereof Download PDFInfo
- Publication number
- CN104801336A CN104801336A CN201510168354.1A CN201510168354A CN104801336A CN 104801336 A CN104801336 A CN 104801336A CN 201510168354 A CN201510168354 A CN 201510168354A CN 104801336 A CN104801336 A CN 104801336A
- Authority
- CN
- China
- Prior art keywords
- zsm
- molecular sieve
- composite oxide
- oxide catalyst
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims abstract description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 15
- 238000000746 purification Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 238000010531 catalytic reduction reaction Methods 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000012717 electrostatic precipitator Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 229910016870 Fe(NO3)3-9H2O Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
本发明公开了一种低温NH3还原NOx的Zr-Mn-Fe/ZSM-5复合氧化物催化剂及其制备方法。Zr-Mn-Fe/ZSM-5复合氧化物催化剂由ZrO2、MnO2、Fe2O3和ZSM-5组成，Fe元素质量为原料HZSM-5分子筛质量的5~8%，Mn/Fe摩尔比为1~4/1，Zr/Fe摩尔比为0.3~0.75/1，HZSM-5分子筛中SiO2/Al2O3摩尔比为25~50/1；并以过量溶液的浸渍法负载，搅拌下以90~100℃水浴蒸干，然后于空气气氛下110~125℃干燥2~8小时、500~550℃下焙烧3~4小时。本发明所制备的催化剂具有较佳的低温起燃和稳定转化率反应窗口性能，具有优越的低温催化净化柴油车（机）尾气或固定源尾气中NOx的性能，且生产工艺简单。
The invention discloses a Zr-Mn-Fe/ZSM-5 composite oxide catalyst for reducing NO x with low-temperature NH 3 and a preparation method thereof. Zr-Mn-Fe/ZSM-5 composite oxide catalyst is composed of ZrO 2 , MnO 2 , Fe 2 O 3 and ZSM-5, the mass of Fe element is 5~8% of the mass of raw material HZSM-5 molecular sieve, Mn/Fe mole The ratio is 1~4/1, the Zr/Fe molar ratio is 0.3~0.75/1, and the SiO 2 /Al 2 O 3 molar ratio in HZSM-5 molecular sieve is 25~50/1; and it is loaded by impregnation method of excess solution, Evaporate to dryness in a 90-100°C water bath with stirring, then dry at 110-125°C for 2-8 hours in an air atmosphere, and bake at 500-550°C for 3-4 hours. The catalyst prepared by the invention has better low-temperature light-off and stable conversion rate reaction window performance, excellent low-temperature catalytic performance for purifying NO x in diesel vehicle (machine) exhaust or stationary source exhaust, and simple production process.
Description
技术领域 technical field
本发明涉及一种在低温下以氨（包括尿素等分解的氨基）为还原剂催化净化柴油车（机）尾气或固定源尾气中NOx的ZSM-5基负载型氧化物催化剂及其制备方法。 The invention relates to a ZSM-5-based supported oxide catalyst that uses ammonia (including decomposed amino groups such as urea) as a reducing agent to catalyze and purify NOx in diesel vehicle (machine) exhaust or stationary source exhaust at low temperature and its preparation method .
背景技术 Background technique
氮氧化物（NOx）是光化学污染和雾霾形成的主要污染物之一，以氨（NH3）或尿素等分解的氨基（－NH2）化合物为还原剂选择性催化净化柴油车（机）尾气或固定源尾气中NOx（NH3-SCR）是最为合适有效的技术。在固定源（如电厂锅炉等）烟尾气的NOx净化应用中，越来越多的用户希望将SCR反应装置安装于电除尘器和脱硫装置之后，以避免催化剂受粉尘和重金属的污染堵塞而使SCR装置提前更换以及减少装置的维护清理工作。但是，烟尾气经电除尘器和脱硫装置之后其温度很低，往往只有80－120℃左右。在移动源的柴油车（机）排放尾气NOx去除的应用实际中，由于柴油车（机）排放尾气中可作为还原剂的CO和CHx浓度较低，催化还原净化NOx的去除效率有限，要满足严格的国ⅳ和国ⅴ排放标准只有采用以尿素分解的氨基（－NH2）化合物为还原剂选择性催化净化柴油车（机）尾气中NOx的催化技术。然而，由于柴油车（机）在启动及低速工况下排气温度较低，到净化器安装位置时排气温度常常只有不到100－150 ℃。在实际应用中，催化剂在排气低温时的起燃性成为柴油车（机）尾气NOx达到日益严格的排放标准的关键应用技术。因此，上述NOx净化应用中，要求催化剂提供的起燃温度（T50）越低越好，并具有较宽的稳定转化率温度窗口，以适应工况的变化。分子筛由于其抗水热稳定性和抗硫毒性好，是柴油车（机）排放尾气或固定源烟气中NOx去除的较为合适的催化剂活性载体。一般地，分子筛基氧化物催化剂通常应用于高温条件，400℃以上NOx净化的NH3-SCR性能较佳，并且活性组分的负载以离子交换法制备。为此，有必要开发一种针对氨（包括尿素等分解的氨基）为还原剂催化净化柴油车（机）尾气或固定源尾气中NOx的以分子筛为载体的低温催化剂，催化剂可在较低的温度下起燃，并具有较宽的稳定转化温度窗口，且生产工艺简便。 Nitrogen oxides (NO x ) are one of the main pollutants of photochemical pollution and smog formation. The decomposed amino (-NH 2 ) compounds such as ammonia (NH 3 ) or urea are used as reducing agents to selectively catalyze and purify diesel vehicles (engines). ) exhaust gas or NO x (NH 3 -SCR) in stationary source exhaust gas is the most suitable and effective technology. In the NO x purification application of flue gas from stationary sources (such as power plant boilers, etc.), more and more users hope to install the SCR reaction device after the electrostatic precipitator and desulfurization device to avoid the catalyst being blocked by dust and heavy metals. The SCR device can be replaced in advance and the maintenance and cleaning work of the device can be reduced. However, the temperature of the flue gas after passing through the electrostatic precipitator and desulfurization device is very low, often only about 80-120°C. In the actual application of mobile source diesel vehicle (engine) exhaust NO x removal, due to the low concentration of CO and CH x that can be used as reductants in diesel vehicle (engine) exhaust exhaust, the removal efficiency of catalytic reduction purification of NO x is limited In order to meet the strict national ⅳ and national Ⅳ emission standards, the only way to use the amino (-NH 2 ) compound decomposed by urea as a reducing agent is to selectively catalyze and purify NO x in the exhaust gas of diesel vehicles (machines). However, due to the low exhaust temperature of diesel vehicles (engines) at start-up and low-speed conditions, the exhaust temperature is often less than 100-150 °C when the purifier is installed. In practical application, the ignitability of catalysts at low temperature exhaust gas has become a key application technology for diesel vehicle (engine) exhaust NO x to meet increasingly stringent emission standards. Therefore, in the above-mentioned NO x purification application, it is required that the catalyst should provide a light-off temperature (T 50 ) as low as possible, and have a wider temperature window for stable conversion rate to adapt to changes in working conditions. Molecular sieve is a more suitable catalyst active carrier for the removal of NOx from diesel vehicle (engine) exhaust or stationary source flue gas due to its good hydrothermal stability and sulfur toxicity resistance. Generally, molecular sieve-based oxide catalysts are usually used in high temperature conditions, and NH 3 -SCR for NO x purification above 400°C has better performance, and the loading of active components is prepared by ion exchange method. For this reason, it is necessary to develop a low-temperature catalyst with molecular sieves as the carrier for ammonia (including decomposed amino groups such as urea) as a reducing agent to catalyze the purification of NOx in diesel vehicle (machine) exhaust or stationary source exhaust. It ignites at a certain temperature, has a wide stable conversion temperature window, and has a simple production process.
发明内容 Contents of the invention
本发明的目的是提供一种在低温下以氨（包括尿素等分解的氨基）为还原剂催化净化柴油车（机）尾气或固定源尾气中NOx的ZSM-5基负载型复合氧化物Zr-Mn-Fe/ZSM-5催化剂及其制备方法，该发明的催化剂可在较低的温度下起燃，并具有较宽的稳定转化率温度窗口，且生产工艺简便。 The object of the present invention is to provide a ZSM -5-based loaded composite oxide Zr that uses ammonia (including decomposed amino groups such as urea) as a reducing agent to catalyze and purify diesel vehicle (engine) exhaust gas or stationary source exhaust gas at low temperatures. -Mn-Fe/ZSM-5 catalyst and its preparation method, the catalyst of the invention can be lighted at a lower temperature, has a wider temperature window for stable conversion rate, and has a simple production process.
本发明涉及的Zr-Mn-Fe/ZSM-5复合氧化物催化剂由ZrO2、MnO2、Fe2O3和ZSM-5组成，其中：Fe元素质量为原料HZSM-5分子筛质量的5~8%，Mn/Fe摩尔比为1~4/1，Zr/Fe摩尔比为0.3~0.75/1，原料HZSM-5分子筛中SiO2/Al2O3摩尔比为25~50/1 The Zr-Mn-Fe/ZSM-5 composite oxide catalyst involved in the present invention is composed of ZrO 2 , MnO 2 , Fe 2 O 3 and ZSM-5, wherein the mass of Fe element is 5-8 of the mass of the raw material HZSM-5 molecular sieve %, the Mn/Fe molar ratio is 1~4/1, the Zr/Fe molar ratio is 0.3~0.75/1, and the SiO 2 /Al 2 O 3 molar ratio in the raw material HZSM-5 molecular sieve is 25~50/1
Zr-Mn-Fe/ZSM-5复合氧化物催化剂的制备方法具体步骤为： The specific steps of the preparation method of Zr-Mn-Fe/ZSM-5 composite oxide catalyst are:
（1）以HZSM-5分子筛（SiO2/Al2O3摩尔比为25~50/1）质量计，Zr-Mn-Fe/ZSM-5复合氧化物催化剂活性组分组成为：Fe元素质量为HZSM-5分子筛质量的5~8%、Mn/Fe摩尔比为1~4/1和Zr/Fe摩尔比为0.3~0.75/1。 (1) Based on the mass of HZSM-5 molecular sieve (SiO 2 /Al 2 O 3 molar ratio is 25~50/1), the active component composition of Zr-Mn-Fe/ZSM-5 composite oxide catalyst is: the mass of Fe element is The mass of HZSM-5 molecular sieve is 5~8%, the molar ratio of Mn/Fe is 1~4/1 and the molar ratio of Zr/Fe is 0.3~0.75/1.
（2）分别称取步骤（1）Fe、Mn和Zr相应质量的硝酸盐或醋酸盐，一并加入到去离子水中搅拌使完全溶解制成盐溶液，溶解过程中加温溶液至50~60℃以促进硝酸盐的溶解，去离子水用量以溶液至少能过量浸没分子筛粉末载体并将各组分盐溶解，最大用量为分子筛质量的4倍。 (2) Weigh nitrates or acetates corresponding to the mass of Fe, Mn and Zr in step (1), add them into deionized water and stir to make a salt solution, and heat the solution to 50~ 60°C to promote the dissolution of nitrate, the amount of deionized water is at least enough to submerge the molecular sieve powder carrier in excess and dissolve the salts of each component, and the maximum amount is 4 times the mass of the molecular sieve.
（3）将HZSM-5分子筛浸没入步骤（2）所得盐溶液中，搅拌下以90~100℃水浴蒸干，然后于空气气氛下110~125℃干燥2小时以上、500~550℃下焙烧3~4小时，得Zr-Mn-Fe/ZSM-5复合氧化物催化剂。 (3) Immerse the HZSM-5 molecular sieve into the salt solution obtained in step (2), evaporate to dryness in a water bath at 90-100°C while stirring, then dry at 110-125°C for more than 2 hours in an air atmosphere, and bake at 500-550°C After 3~4 hours, Zr-Mn-Fe/ZSM-5 composite oxide catalyst was obtained.
制备的Zr-Mn-Fe/ZSM-5复合氧化物催化剂粉末经柠檬酸或醋酸预粘化后加粘结剂制备成浆，涂覆于金属板、金属蜂窝和陶瓷蜂窝上经干燥焙烧制备成可应用的产品。 The prepared Zr-Mn-Fe/ZSM-5 composite oxide catalyst powder is pre-bonded with citric acid or acetic acid and then added with a binder to prepare a slurry, which is coated on a metal plate, a metal honeycomb and a ceramic honeycomb, and is prepared by drying and roasting. Applicable products.
Zr-Mn-Fe/ZSM-5复合氧化物催化剂的NH3选择性催化还原NOx(NH3-SCR)活性评价在模拟的废气净化催化剂评价系统上进行。Zr-Mn-Fe/ZSM-5复合氧化物催化剂粉末评价时需经压片和破碎后取40-60目的颗粒，蜂窝状样品则直接取样评价。反应混合气组成为NO≤0.2 vol.%，NH3/NO摩尔比1.0~1.15，O2 6.0~12.0 vol.%，N2为平衡气，反应空速控制在20000~60000mL/(g.h)范围。采用佛山分析仪有限公司FGA-4100A型烟气分析仪在线分析反应前后的NOx和O2浓度。 The evaluation of NH 3 selective catalytic reduction of NO x (NH 3 -SCR) activity of Zr-Mn-Fe/ZSM-5 composite oxide catalyst was carried out on a simulated exhaust gas purification catalyst evaluation system. The evaluation of Zr-Mn-Fe/ZSM-5 composite oxide catalyst powder needs to be tableted and crushed to take 40-60 mesh particles, and the honeycomb sample is directly sampled for evaluation. The reaction mixture gas composition is NO≤0.2 vol.%, NH 3 /NO molar ratio 1.0~1.15, O 2 6.0~12.0 vol.%, N 2 is the balance gas, and the reaction space velocity is controlled in the range of 20000~60000mL/(gh) . The FGA-4100A flue gas analyzer from Foshan Analyzer Co., Ltd. was used to analyze the NOx and O2 concentrations before and after the reaction.
本发明所得分子筛基Zr-Mn-Fe/ZSM-5复合氧化物催化剂其NH3选择性催化还原NOx(NH3-SCR)起燃温度低，T50可低至138℃；T90窗口宽，可达到160~360℃，稳定最佳转化率窗口可达到180~330℃，具有较佳的低温起燃和稳定转化率反应窗口性能，不仅具有优越的低温催化净化柴油车（机）尾气或固定源尾气中NOx的性能，并且生产工艺简单。 The molecular sieve-based Zr-Mn-Fe/ZSM-5 composite oxide catalyst obtained in the present invention has a low light-off temperature of NH 3 selective catalytic reduction of NO x (NH 3 -SCR), T 50 can be as low as 138 ° C; T 90 window is wide , can reach 160~360°C, and the stable and optimal conversion rate window can reach 180~330°C. It has better low-temperature light-off and stable conversion rate reaction window performance, not only has excellent low-temperature catalytic purification of diesel vehicle (machine) exhaust or The performance of NOx in fixed source exhaust gas, and the production process is simple.
附图说明 Description of drawings
图1为本发明Zr-Mn-Fe/ZSM-5复合氧化物催化剂的NH3选择性催化还原NOx(NH3-SCR)活性图，空速30000mL/(g.h)。 Fig. 1 is the NH 3 selective catalytic reduction NO x (NH 3 -SCR) activity diagram of the Zr-Mn-Fe/ZSM-5 composite oxide catalyst of the present invention, with a space velocity of 30000 mL/(gh).
具体实施方式 Detailed ways
以下通过具体实施例对本发明进行详细说明，但应了解本发明不仅仅限定于所述实施例。 The present invention will be described in detail below through specific examples, but it should be understood that the present invention is not limited to the examples.
实施例： Example:
（1）称取43.4g九水硝酸铁（Fe(NO3)3·9H2O，相当于分子筛质量6.0%的Fe元素）、76.9g质量百分比浓度为50%的硝酸锰水溶液（Mn(NO3)2，相当于Mn/Fe摩尔比2/1或分子筛质量11.8%的Mn元素）和25.3g硝酸锆（Zr(NO3)4，Zr/Fe摩尔比为0.69/1）。 (1) Weigh 43.4g ferric nitrate nonahydrate (Fe(NO 3 ) 3 9H 2 O, equivalent to 6.0% Fe element of molecular sieve mass), 76.9g manganese nitrate aqueous solution (Mn(NO 3 ) 2 , which is equivalent to the Mn element with a molar ratio of Mn/Fe of 2/1 or molecular sieve mass of 11.8%) and 25.3g of zirconium nitrate (Zr(NO 3 ) 4 , with a molar ratio of Zr/Fe of 0.69/1).
（2）将步骤（1）各原料一并加入到150g去离子水中，搅拌并加温溶液至55℃使盐完全溶解。 (2) Add all raw materials in step (1) into 150g of deionized water, stir and heat the solution to 55°C to completely dissolve the salt.
（3）将100g HZSM-5分子筛（SiO2/Al2O3摩尔比为38/1，山东齐鲁华信高科有限公司生产）浸没入步骤（2）所得盐溶液中，搅拌下以100℃水浴蒸干，然后于空气气氛下110℃干燥6小时、550℃下焙烧4小时，得Zr-Mn-Fe/ZSM-5复合氧化物催化剂记为nZr:Mn:Fe=0.69:2:1/ZSM-5。 (3) Immerse 100g of HZSM-5 molecular sieve (SiO 2 /Al 2 O 3 molar ratio is 38/1, produced by Shandong Qilu Huaxin Hi-Tech Co., Ltd.) into the salt solution obtained in step (2), and put it in a 100°C water bath under stirring Evaporate to dryness, then dry at 110°C for 6 hours in an air atmosphere, and bake at 550°C for 4 hours to obtain a Zr-Mn-Fe/ZSM-5 composite oxide catalyst, which is recorded as nZr:Mn:Fe=0.69:2:1/ZSM -5.
Zr-Mn-Fe/ZSM-5复合氧化物催化剂的NH3选择性催化还原NOx(NH3-SCR)活性评价在模拟的废气净化催化剂评价系统(天津大学化学化工学院制造)上进行。Zr-Mn-Fe/ZSM-5复合氧化物催化剂经压片和破碎后取40~60目的颗粒。反应混合气组成为NO 0.1 vol.%，NH3 0.11 vol.%，O2 6.0 vol.%，N2为平衡气，空速30000mL/(g.h)。采用佛山分析仪有限公司FGA-4100A型烟气分析仪在线分析反应前后的NOx和O2浓度。实验测得催化剂起燃温度T50为138℃；T90窗口167~357℃，稳定最佳转化率98%的窗口181~332℃。 The evaluation of the NH 3 selective catalytic reduction of NO x (NH 3 -SCR) activity of the Zr-Mn-Fe/ZSM-5 composite oxide catalyst was carried out on a simulated exhaust gas purification catalyst evaluation system (manufactured by the School of Chemistry and Chemical Engineering, Tianjin University). The Zr-Mn-Fe/ZSM-5 composite oxide catalyst was tableted and crushed to obtain 40-60 mesh particles. The reaction mixture gas composition is NO 0.1 vol.%, NH 3 0.11 vol.%, O 2 6.0 vol.%, N 2 is the balance gas, and the space velocity is 30000mL/(gh). The FGA-4100A flue gas analyzer from Foshan Analyzer Co., Ltd. was used to analyze the NOx and O2 concentrations before and after the reaction. The catalyst light-off temperature T 50 was measured to be 138°C; the T 90 window was 167-357°C, and the window for a stable and optimal conversion rate of 98% was 181-332°C.
本发明实施例制备的Zr-Mn-Fe/ZSM-5复合氧化物催化剂其NH3选择性催化还原NOx(NH3-SCR)活性示于附图1中。可以看到，空速30000mL/(g.h)下，nMn:Fe=2:1/ZSM-5催化剂其起燃温度T50为175℃；T90窗口198~338℃，稳定最佳转化率98%的窗口220~320℃。相比之下，进一步掺入Zr组分后，nZr:Mn:Fe=0.69:2:1/ZSM-5催化剂其起燃温度T50向低温偏移至138℃，降低了37℃；T90窗口向低温偏移至167~357℃，窗口向低温变宽了31℃；稳定最佳转化率98%的窗口181~332℃，窗口向低温变宽了39℃。由此可见，本发明所制备的以ZSM-5分子筛为载体的Zr-Mn-Fe/ZSM-5复合氧化物催化剂，其NH3选择性催化还原NOx(NH3-SCR)起燃温度显著向低温偏移近40℃、T90和稳定最佳转化率窗口向低温显著拓宽近30~40℃，催化剂的低温NH3-SCR性能得到了显著的改善和提高。这表明，本发明所制备的Zr-Mn-Fe/ZSM-5复合氧化物催化剂具有较佳的低温起燃和较宽的稳定转化率反应窗口性能，不仅具有优越的低温催化净化柴油车（机）尾气或固定源尾气中NOx的性能，并且生产工艺简单。 The NH 3 selective catalytic reduction of NO x (NH 3 -SCR) activity of the Zr-Mn-Fe/ZSM-5 composite oxide catalyst prepared in the embodiment of the present invention is shown in Fig. 1 . It can be seen that at a space velocity of 30000mL/(gh), the light-off temperature T 50 of the nMn:Fe=2:1/ZSM-5 catalyst is 175°C; the T 90 window is 198~338°C, and the stable and optimal conversion rate is 98%. The window is 220~320℃. In contrast, after further adding Zr components, the light-off temperature T 50 of nZr:Mn:Fe=0.69:2:1/ZSM-5 catalyst shifted to low temperature to 138°C, which decreased by 37°C; T 90 The window shifted to 167-357°C toward the low temperature, and the window widened by 31°C toward the low temperature; the window for a stable and optimal conversion rate of 98% was 181-332°C, and the window widened by 39°C toward the low temperature. It can be seen that the Zr-Mn-Fe/ZSM-5 composite oxide catalyst prepared by the present invention takes ZSM-5 molecular sieve as a carrier, and its NH Selective catalytic reduction of NO x (NH 3 -SCR) has a significant light-off temperature Shifting to low temperature by nearly 40°C, T 90 and the stable optimum conversion window were significantly widened by nearly 30-40°C toward low temperature, and the low-temperature NH 3 -SCR performance of the catalyst was significantly improved and enhanced. This shows that the Zr-Mn-Fe/ZSM-5 composite oxide catalyst prepared by the present invention has better low-temperature light-off and wider stable conversion reaction window performance, not only has excellent low-temperature catalytic purification of diesel vehicles (engines) ) performance of NO x in tail gas or stationary source tail gas, and the production process is simple.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510168354.1A CN104801336A (en) | 2015-04-11 | 2015-04-11 | Zr-Mn-Fe/ZSM-5 composite oxide catalyst for low-temperature NH3 reduction of NOx and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510168354.1A CN104801336A (en) | 2015-04-11 | 2015-04-11 | Zr-Mn-Fe/ZSM-5 composite oxide catalyst for low-temperature NH3 reduction of NOx and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104801336A true CN104801336A (en) | 2015-07-29 |
Family
ID=53686780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510168354.1A Pending CN104801336A (en) | 2015-04-11 | 2015-04-11 | Zr-Mn-Fe/ZSM-5 composite oxide catalyst for low-temperature NH3 reduction of NOx and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104801336A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105562030A (en) * | 2016-01-06 | 2016-05-11 | 齐鲁工业大学 | Aluminum trioxide sulfur recovery catalyst resistant to sulfation and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101992116A (en) * | 2009-08-10 | 2011-03-30 | 北京石油化工学院 | MnMe/molecular sieve series catalysts and preparation and application thereof |
-
2015
- 2015-04-11 CN CN201510168354.1A patent/CN104801336A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101992116A (en) * | 2009-08-10 | 2011-03-30 | 北京石油化工学院 | MnMe/molecular sieve series catalysts and preparation and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| GUANGYING ZHOU ET AL: ""In situ DRIFTS study of NO reduction by NH3 over Fe–Ce–Mn/ZSM-5 catalysts"", 《CATALYSIS TODAY》 * |
| 王晓波等: ""Zr-Mn-Fe/Al2O3的低温脱硝性能"", 《东南大学学报（自然科学版）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105562030A (en) * | 2016-01-06 | 2016-05-11 | 齐鲁工业大学 | Aluminum trioxide sulfur recovery catalyst resistant to sulfation and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104772162A (en) | Zr-Ce-Mn-Fe/ZSM-5 composite oxide catalyst for low-temperature NH3 reduction of NOx and preparation method thereof | |
| CN103157505B (en) | A kind of Cu-SSZ-13 catalyst, preparation method and its usage | |
| US8975206B2 (en) | Catalyst composition for selective catalytic reduction of exhaust gases | |
| EP2755764B1 (en) | Zeolite promoted v/ti/w catalysts | |
| CN116474763B (en) | SCR Catalyst | |
| CN102166522B (en) | Flue gas denitration catalyst and preparation method and application thereof | |
| JP5987010B2 (en) | Method for treating a gas containing nitric oxide (NOx) using a composition containing zirconium, cerium and niobium as a catalyst | |
| US20150290632A1 (en) | IRON AND COPPER-CONTAINING CHABAZITE ZEOLITE CATALYST FOR USE IN NOx REDUCTION | |
| CN104338545B (en) | A kind of efficient SCR catalyst that is applied to diesel engine vent gas purification of nitrogen oxides | |
| CN105611998A (en) | Zeolite blend catalysts for treating exhaust gases containing NOx | |
| EP2368628A1 (en) | Catalyst for a DeNOx-application and a process for selective catalytic reduction of nitrogen oxides | |
| CN104772163A (en) | Ce-Mn-Fe/ZSM-5 composite oxide catalyst for low-temperature NH3 reduction of NOx and preparation method thereof | |
| CN103769240A (en) | Preparation method of catalyst for selective catalytic reduction denitration reactions | |
| US11492945B2 (en) | SCR catalyst | |
| KR20160136407A (en) | Method and system for treating exhaust gas | |
| CN111437875B (en) | Cerium-iron molecular sieve based catalyst with wide temperature range and preparation method thereof | |
| CN106334577A (en) | Preparation method of Mo modified Cu-SSZ-13 catalyst | |
| CN114057208B (en) | CHA type molecular sieve synthesized by double template agents and method for preparing SCR catalyst by using CHA type molecular sieve | |
| CN104801335A (en) | Zr-Ce-Mn/ZSM-5 composite oxide catalyst for low-temperature NH3 reduction of NOx and preparation method thereof | |
| US20150231620A1 (en) | IRON-ZEOLITE CHABAZITE CATALYST FOR USE IN NOx REDUCTION AND METHOD OF MAKING | |
| CN110947416B (en) | For NH 3 Iron/molecular sieve catalyst of SCR (selective catalytic reduction), and preparation method and application thereof | |
| CN102698736B (en) | A kind of highly thermally stable nitrogen oxide removal catalyst and its preparation method | |
| EP2612705A2 (en) | Catalyst for selective catalytic reduction, with improved durability | |
| KR20080113565A (en) | Method for preparing iron-supported zeolite catalyst for selective catalytic reduction reaction | |
| JP2011509234A (en) | Compositions based on zirconium oxide, yttrium oxide and tungsten oxide, preparation methods and use as catalysts or catalyst supports |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150729 |