CN116099569A - Catalyst for purification of ammonia internal combustion engine tail gas, preparation method and application thereof - Google Patents
Catalyst for purification of ammonia internal combustion engine tail gas, preparation method and application thereofDownload PDFInfo
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- B01J29/76—Iron group metals or copper
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- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
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Abstract
Translated fromChinese
Description
Translated fromChinese技术领域technical field
本发明涉及尾气净化领域，具体涉及一种氨内燃机尾气净化用催化剂及其制备方法和用途。The invention relates to the field of tail gas purification, in particular to a catalyst for purifying the tail gas of an ammonia internal combustion engine, a preparation method and application thereof.
背景技术Background technique
目前，氨气作为一种理想的储能物质，其分子中不含有碳元素，完全燃烧产物仅包括水和氮气，且其相较于大多数气体燃料具有易被压缩为液态的特点，使其便于储运，使得氨气具有成为内燃机替代燃料的潜力。At present, ammonia is an ideal energy storage substance, its molecules do not contain carbon elements, and the complete combustion products only include water and nitrogen, and compared with most gaseous fuels, it is easy to be compressed into a liquid state, making it It is convenient for storage and transportation, making ammonia have the potential to become an alternative fuel for internal combustion engines.
如CN115095455A公开了氨燃烧内燃机，通过设置内燃机、进气管、滤网、转动环、清理板、一号槽、一号弹簧、导柱、延伸盒、二号弹簧、配重棒，通过在进气管内设置滤网，以此来隔绝杂质，防止杂质通过进气管进入到内燃机的燃烧室内部，并通过进气管自身晃动的能量为清理板提供动能，清理板对滤网的网眼进行分段清理，在清理的同时又保证不会堵塞滤网，以此来降低堵塞的滤网导致空气无法及时的从内燃机的进气管进入到内燃机的燃烧室内，从而造成内燃机的动力下降这一问题发生的概率。Disclosed ammonia burning internal combustion engine as CN115095455A, by arranging internal combustion engine, intake pipe, filter screen, rotating ring, cleaning plate, No. 1 groove, No. 1 spring, guide post, extension box, No. 2 spring, counterweight rod, A filter screen is set in the pipe to isolate impurities and prevent impurities from entering the combustion chamber of the internal combustion engine through the intake pipe, and provides kinetic energy for the cleaning plate through the sloshing energy of the intake pipe itself, and the cleaning plate cleans the mesh of the filter screen in sections. While cleaning, it is guaranteed that the filter screen will not be blocked, so as to reduce the probability that the clogged filter screen will cause air to fail to enter the combustion chamber of the internal combustion engine from the intake pipe of the internal combustion engine in time, thereby causing the power of the internal combustion engine to drop.
CN115234391A公开了一种氨内燃机定压燃烧控制方法及装置和内燃机，涉及动力与能源工程领域。针对现有技术中存在的由于氨燃料的辛烷值高，氨燃料缸内直喷压燃时存在严重的高爆发压力问题，对于内燃机的机械强度和热负荷都有很大的要求，影响内燃机的效率和可靠性得问题，提出了一种控制氨燃烧爆发压力，进行氨内燃机缸内直喷定压燃烧氨脉冲喷射的方法，具体的：内燃机定压燃烧控制方法，方法包括：步骤1：根据内燃机的特性，确定所述内燃机的最高工作压力；步骤2：根据最高工作压力，确定第一次燃料喷射参数和最佳喷射次数；步骤3：当内燃机内部压力下降后，进行燃料喷射；步骤4，重复步骤3，直到达到最佳喷射次数。适合在氨燃料压燃研究和实施中应用。CN115234391A discloses a constant-pressure combustion control method and device of an ammonia internal combustion engine and an internal combustion engine, which relate to the field of power and energy engineering. Due to the high octane number of ammonia fuel in the prior art, there is a serious problem of high burst pressure during direct injection and compression ignition of ammonia fuel, which has great requirements for the mechanical strength and thermal load of the internal combustion engine, which affects the internal combustion engine. In view of the problems of efficiency and reliability, a method of controlling the explosion pressure of ammonia combustion and performing ammonia pulse injection with direct injection and constant pressure combustion in cylinders of ammonia internal combustion engines is proposed. Specifically: the method of constant pressure combustion control of internal combustion engines, the method includes: Step 1: According to the characteristics of the internal combustion engine, determine the maximum working pressure of the internal combustion engine; Step 2: Determine the first fuel injection parameters and the best injection times according to the maximum working pressure; Step 3: After the internal combustion engine internal pressure drops, perform fuel injection; Step 4. Repeat step 3 until the optimal number of injections is reached. It is suitable for application in research and implementation of compression ignition of ammonia fuel.
然而，氨内燃机在燃烧过程中仍会有部分燃料氨气未进行充分燃烧，同时氨气在燃烧过程中会形成氮氧化物和水汽，而燃烧过程中形成的氮氧化物会导致现有的氨分解催化剂在实际环境下性能降低且容易产生二次污染物二氧化氮和氧化亚氮，导致尾气无法被有效的净化。However, in the combustion process of the ammonia internal combustion engine, there will still be part of the fuel ammonia that is not fully combusted. At the same time, the ammonia gas will form nitrogen oxides and water vapor during the combustion process, and the nitrogen oxides formed during the combustion process will lead to the existing ammonia. The performance of the decomposition catalyst is reduced in the actual environment and it is easy to produce secondary pollutants nitrogen dioxide and nitrous oxide, resulting in the inability to effectively purify the exhaust gas.
发明内容Contents of the invention
鉴于现有技术中存在的问题，本发明的目的在于提供一种氨内燃机尾气净化用催化剂及其制备方法和用途，以解决氨内燃机尾气中少量氮氧化物存在时尾气净化效果差的问题。In view of the problems existing in the prior art, the purpose of the present invention is to provide a catalyst for purifying ammonia internal combustion engine tail gas and its preparation method and application, so as to solve the problem of poor tail gas purification effect when a small amount of nitrogen oxide exists in ammonia internal combustion engine tail gas.
为达此目的，本发明采用以下技术方案：For reaching this purpose, the present invention adopts following technical scheme:
第一方面，本发明提供了一种氨内燃机尾气净化用催化剂的制备方法，所述制备方法包括：In a first aspect, the present invention provides a method for preparing a catalyst for purifying ammonia internal combustion engine tail gas, the preparation method comprising:
S1、将氨型分子筛和铜盐溶液经混合、固液分离和第一焙烧后，得到载铜分子筛；S1. After mixing ammonia-type molecular sieve and copper salt solution, solid-liquid separation and first roasting, copper-loaded molecular sieve is obtained;
S2、将S1所得载铜分子筛和溶剂混合后，依次经钌盐处理、蒸发和第二焙烧得到氨内燃机尾气净化用催化剂。S2. After mixing the copper-loaded molecular sieve obtained in S1 with a solvent, sequentially undergoing ruthenium salt treatment, evaporation and second roasting to obtain a catalyst for purifying ammonia internal combustion engine exhaust gas.
本发明提供的制备方法，通过采用特定的制备过程引入活性组分钌和铜，利用金属的协同作用提高催化剂氨氧化反应的低温活性和氮气选择性。所得催化剂中的钌主要以氧化态存在，铜主要以离子态存在，从而利用氧化态的钌和离子态的铜配合实现了氮氧化物和水汽等气体存在环境下氨氧化反应的高效进行，达到实际情况下氨内燃机尾气的净化需求。In the preparation method provided by the invention, the active components ruthenium and copper are introduced through a specific preparation process, and the synergistic effect of metals is used to improve the low-temperature activity and nitrogen selectivity of the ammoxidation reaction of the catalyst. The ruthenium in the obtained catalyst mainly exists in the oxidized state, and the copper mainly exists in the ionic state, so that the combination of the oxidized ruthenium and the ionic copper realizes the efficient ammoxidation reaction in the presence of gases such as nitrogen oxides and water vapor, and achieves Purification requirements of ammonia internal combustion engine exhaust in actual conditions.
本发明中，为了保证催化剂中活性物质的负载量，步骤S1和步骤S2可以进行多次。In the present invention, in order to ensure the loading capacity of active substances in the catalyst, step S1 and step S2 can be performed multiple times.
本发明中，固液分离和第一焙烧之间，蒸发和第二焙烧之间，可以增设有有干燥过程以充分去除残余的溶剂或水分等物料。In the present invention, between the solid-liquid separation and the first calcination, between the evaporation and the second calcination, a drying process may be added to fully remove residual solvent or water and other materials.
作为本发明优选的技术方案，所述氨型分子筛包括ZSM-5分子筛、SSZ-13分子筛或Y分子筛中的1种或至少2种的组合。As a preferred technical solution of the present invention, the ammonia-type molecular sieve includes one or a combination of at least two of ZSM-5 molecular sieve, SSZ-13 molecular sieve or Y molecular sieve.
优选地，配置步骤(1)所述铜盐溶液所用铜盐包括氯化铜、硫酸铜、硝酸铜或醋酸铜中的1种或至少2种的组合，优选为硝酸铜。Preferably, the copper salt used in the copper salt solution in the configuration step (1) includes one or a combination of at least two of copper chloride, copper sulfate, copper nitrate or copper acetate, preferably copper nitrate.
优选地，所述铜盐溶液中铜元素的浓度为3.2-128g/L，例如可以是3.2g/L、4g/L、5g/L、6g/L、7g/L、8g/L、9g/L、10g/L、12g/L、14g/L、16g/L、18g/L、20g/L、22g/L、24g/L、26g/L、28g/L、30g/L、32g/L、34g/L、36g/L、38g/L、40g/L、42g/L、44g/L、46g/L、48g/L、50g/L、52g/L、54g/L、56g/L、58g/L、60g/L、62g/L、64g/L、66g/L、68g/L、70/L、72g/L、74g/L、76g/L、78g/L、80g/L、82g/L、84g/L、86g/L、88g/L、90g/L、92g/L、94g/L、96g/L、98g/L、100g/L、102g/L、104g/L、106g/L、108g/L、110g/L、112g/L、114g/L、116g/L、118g/L、120g/L、122g/L、124g/L、126g/L或128g/L等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。Preferably, the concentration of copper element in the copper salt solution is 3.2-128g/L, such as 3.2g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L L, 10g/L, 12g/L, 14g/L, 16g/L, 18g/L, 20g/L, 22g/L, 24g/L, 26g/L, 28g/L, 30g/L, 32g/L, 34g/L, 36g/L, 38g/L, 40g/L, 42g/L, 44g/L, 46g/L, 48g/L, 50g/L, 52g/L, 54g/L, 56g/L, 58g/L L, 60g/L, 62g/L, 64g/L, 66g/L, 68g/L, 70/L, 72g/L, 74g/L, 76g/L, 78g/L, 80g/L, 82g/L, 84g/L, 86g/L, 88g/L, 90g/L, 92g/L, 94g/L, 96g/L, 98g/L, 100g/L, 102g/L, 104g/L, 106g/L, 108g/L L, 110g/L, 112g/L, 114g/L, 116g/L, 118g/L, 120g/L, 122g/L, 124g/L, 126g/L or 128g/L, etc., but not limited to the listed values , other unlisted values within this range are also applicable.
优选地，所述氨型分子筛和铜盐溶液的固液比g/mL为1:(10-150)，例如可以是1:10、1:15、1:20、1:25、1:30、1:35、1:40、1:45、1:50、1:55、1:60、1:65、1:70、1:75、1:80、1:85、1:90、1:95、1:100、1:105、1:110、1:115、1:120、1:125、1:130、1:135、1:140、1:145或1:150等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。Preferably, the solid-to-liquid ratio g/mL of the ammonia-type molecular sieve and the copper salt solution is 1:(10-150), such as 1:10, 1:15, 1:20, 1:25, 1:30 , 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90, 1 :95, 1:100, 1:105, 1:110, 1:115, 1:120, 1:125, 1:130, 1:135, 1:140, 1:145 or 1:150, etc., but not Limited to the listed values, other unlisted values within this range are also applicable.
作为本发明优选的技术方案，所述氨型分子筛和铜盐溶液的混合时间为5-8h，例如可以是5h、5.1h、5.2h、5.3h、5.4h、5.5h、5.6h、5.7h、5.8h、5.9h、6h、6.1h、6.2h、6.3h、6.4h、6.5h、6.6h、6.7h、6.8h、6.9h、7h、7.1h、7.2h、7.3h、7.4h、7.5h、7.6h、7.7h、7.8h、7.9h或8h等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。As a preferred technical solution of the present invention, the mixing time of the ammonia-type molecular sieve and copper salt solution is 5-8h, for example, it can be 5h, 5.1h, 5.2h, 5.3h, 5.4h, 5.5h, 5.6h, 5.7h , 5.8h, 5.9h, 6h, 6.1h, 6.2h, 6.3h, 6.4h, 6.5h, 6.6h, 6.7h, 6.8h, 6.9h, 7h, 7.1h, 7.2h, 7.3h, 7.4h, 7.5h, 7.6h, 7.7h, 7.8h, 7.9h or 8h, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
作为本发明优选的技术方案，所述第一焙烧的温度为500-700℃，例如可以是500℃、510℃、520℃、530℃、540℃、550℃、560℃、570℃、580℃、590℃、600℃、610℃、620℃、630℃、640℃、650℃、660℃、670℃、680℃、690℃或700℃等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。As a preferred technical solution of the present invention, the temperature of the first calcination is 500-700°C, such as 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C , 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, 690°C or 700°C, etc., but not limited to the listed values, other Values not listed also apply.
优选地，所述第一焙烧的时间为5-9h，例如可以是5h、5.1h、5.2h、5.3h、5.4h、5.5h、5.6h、5.7h、5.8h、5.9h、6h、6.1h、6.2h、6.3h、6.4h、6.5h、6.6h、6.7h、6.8h、6.9h、7h、7.1h、7.2h、7.3h、7.4h、7.5h、7.6h、7.7h、7.8h、7.9h、8h、8.1h、8.2h、8.3h、8.4h、8.5h、8.6h、8.7h、8.8h、8.9h或9h等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。Preferably, the first roasting time is 5-9h, for example, it can be 5h, 5.1h, 5.2h, 5.3h, 5.4h, 5.5h, 5.6h, 5.7h, 5.8h, 5.9h, 6h, 6.1h h, 6.2h, 6.3h, 6.4h, 6.5h, 6.6h, 6.7h, 6.8h, 6.9h, 7h, 7.1h, 7.2h, 7.3h, 7.4h, 7.5h, 7.6h, 7.7h, 7.8 h, 7.9h, 8h, 8.1h, 8.2h, 8.3h, 8.4h, 8.5h, 8.6h, 8.7h, 8.8h, 8.9h or 9h, etc., but not limited to the listed values, other not within this range The listed values also apply.
作为本发明优选的技术方案，所述溶剂包括水和/或乙醇。As a preferred technical solution of the present invention, the solvent includes water and/or ethanol.
优选地，所述载铜分子筛和溶剂混合的时间为1-4h，例如可以是1h、1.1h、1.2h、1.3h、1.4h、1.5h、1.6h、1.7h、1.8h、1.9h、2h、2.1h、2.2h、2.3h、2.4h、2.5h、2.6h、2.7h、2.8h、2.9h、3h、3.1h、3.2h、3.3h、3.4h、3.5h、3.6h、3.7h、3.8h、3.9h或4h等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。Preferably, the time for mixing the copper-loaded molecular sieve and the solvent is 1-4h, for example, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h, 3h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7 h, 3.8h, 3.9h or 4h, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
作为本发明优选的技术方案，所述钌盐处理为向载铜分子筛和溶剂混合后所得物料中加入钌盐。As a preferred technical solution of the present invention, the treatment of the ruthenium salt is to add the ruthenium salt to the material obtained after mixing the copper-loaded molecular sieve and the solvent.
优选地，所述钌盐处理中所用钌盐包括三氯化钌、三硝基亚硝酰钌或醋酸钌中的1种或至少2种的组合，优选为三硝基亚硝酰钌。Preferably, the ruthenium salt used in the ruthenium salt treatment includes one or a combination of at least two of ruthenium trichloride, ruthenium trinitrosyl or ruthenium acetate, preferably ruthenium trinitrosyl.
优选地，所述钌盐处理中载铜分子筛与所用钌盐中钌元素的质量比为1:(0.005-0.05)，例如可以是1:0.005、1:0.006、1:0.007、1:0.008、1:0.009、1:0.01、1:0.012、1:0.014、1:0.016、1:0.018、1:0.02、1:0.022、1:0.024、1:0.026、1:0.028、1:0.03、1:0.032、1:0.034、1:0.036、1:0.038、1:0.04、1:0.042、1:0.044、1:0.046、1:0.048或1:0.05等，但不限于所列举的数值，该范围内其它未列举的数值同样适用Preferably, the mass ratio of the copper-loaded molecular sieve to the ruthenium element in the ruthenium salt used in the ruthenium salt treatment is 1:(0.005-0.05), such as 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.01, 1:0.012, 1:0.014, 1:0.016, 1:0.018, 1:0.02, 1:0.022, 1:0.024, 1:0.026, 1:0.028, 1:0.03, 1:0.028 0.032, 1:0.034, 1:0.036, 1:0.038, 1:0.04, 1:0.042, 1:0.044, 1:0.046, 1:0.048 or 1:0.05, etc., but not limited to the listed values, within this range Other values not listed also apply
作为本发明优选的技术方案，所述蒸发包括水浴旋转蒸发；As a preferred technical solution of the present invention, the evaporation comprises water bath rotary evaporation;
优选地，所述蒸发的温度为50-80℃，例如可以是50℃、51℃、52℃、53℃、54℃、55℃、56℃、57℃、58℃、59℃、60℃、61℃、62℃、63℃、64℃、65℃、66℃、67℃、68℃、69℃、70℃、71℃、72℃、73℃、74℃、75℃、76℃、77℃、78℃、79℃或80℃等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。Preferably, the evaporation temperature is 50-80°C, such as 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C , 78°C, 79°C or 80°C, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
优选地，所述第二焙烧的温度为400-700℃，例如可以是400℃、410℃、420℃、430℃、440℃、450℃、460℃、470℃、480℃、490℃、500℃、510℃、520℃、530℃、540℃、550℃、560℃、570℃、580℃、590℃、600℃、610℃、620℃、630℃、640℃、650℃、660℃、670℃、680℃、690℃或700℃等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。Preferably, the temperature of the second calcination is 400-700°C, such as 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C, 500°C ℃, 510℃, 520℃, 530℃, 540℃, 550℃, 560℃, 570℃, 580℃, 590℃, 600℃, 610℃, 620℃, 630℃, 640℃, 650℃, 660℃, 670°C, 680°C, 690°C, or 700°C, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
优选地，所述第二焙烧的时间为4-8h，例如可以是4h、4.1h、4.2h、4.3h、4.4h、4.5h、4.6h、4.7h、4.8h、4.9h、5h、5.1h、5.2h、5.3h、5.4h、5.5h、5.6h、5.7h、5.8h、5.9h、6h、6.1h、6.2h、6.3h、6.4h、6.5h、6.6h、6.7h、6.8h、6.9h、7h、7.1h、7.2h、7.3h、7.4h、7.5h、7.6h、7.7h、7.8h、7.9h或8h等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。Preferably, the second roasting time is 4-8h, for example, it can be 4h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h, 5h, 5.1h h, 5.2h, 5.3h, 5.4h, 5.5h, 5.6h, 5.7h, 5.8h, 5.9h, 6h, 6.1h, 6.2h, 6.3h, 6.4h, 6.5h, 6.6h, 6.7h, 6.8 h, 6.9h, 7h, 7.1h, 7.2h, 7.3h, 7.4h, 7.5h, 7.6h, 7.7h, 7.8h, 7.9h or 8h, etc., but not limited to the listed values, other not within this range The listed values also apply.
作为本发明优选的技术方案，所述制备方法包括：As a preferred technical solution of the present invention, the preparation method comprises:
S1、将氨型分子筛和铜盐溶液经混合、固液分离和第一焙烧后，得到载铜分子筛；S1. After mixing ammonia-type molecular sieve and copper salt solution, solid-liquid separation and first roasting, copper-loaded molecular sieve is obtained;
S2、将S1所得载铜分子筛和溶剂混合后，依次经钌盐处理、蒸发和第二焙烧得到氨内燃机尾气净化用催化剂；S2, after mixing the copper-loaded molecular sieve obtained in S1 with a solvent, successively undergo ruthenium salt treatment, evaporation and second roasting to obtain a catalyst for purifying ammonia internal combustion engine tail gas;
S1中所述氨型分子筛包括ZSM-5分子筛、SSZ-13分子筛或Y分子筛中的1种或至少2种的组合；所述铜盐溶液所用铜盐包括氯化铜、硫酸铜、硝酸铜或醋酸铜中的1种或至少2种的组合；所述铜盐溶液中铜元素的浓度为3.2-128g/L；所述氨型分子筛和铜盐溶液的固液比g/mL为1:(10-150)；所述氨型分子筛和铜盐溶液的混合时间为5-8h；所述第一焙烧的温度为500-700℃；所述第一焙烧的时间为5-9h；The ammonia-type molecular sieve described in S1 includes ZSM-5 molecular sieve, SSZ-13 molecular sieve or Y molecular sieve or a combination of at least 2 kinds; the copper salt used in the copper salt solution includes copper chloride, copper sulfate, copper nitrate or One or at least two combinations of copper acetate; the concentration of copper in the copper salt solution is 3.2-128g/L; the solid-to-liquid ratio g/mL of the ammonia-type molecular sieve and copper salt solution is 1:( 10-150); the mixing time of the ammonia-type molecular sieve and the copper salt solution is 5-8h; the temperature of the first roasting is 500-700°C; the time of the first roasting is 5-9h;
S2中所述溶剂包括水和/或乙醇；所述载铜分子筛和溶剂混合的时间为1-4h；所述钌盐处理为向载铜分子筛和溶剂混合后所得物料中加入钌盐；所述钌盐处理中所用钌盐包括三氯化钌、三硝基亚硝酰钌或醋酸钌中的1种或至少2种的组合；所述钌盐处理中载铜分子筛与所用钌盐中钌元素的质量比为1:(0.005-0.05)；所述蒸发包括水浴旋转蒸发；所述蒸发的温度为50-80℃；所述第二焙烧的温度为400-700℃；所述第二焙烧的时间为4-8h。The solvent in S2 includes water and/or ethanol; the mixing time of the copper-loaded molecular sieve and the solvent is 1-4h; the ruthenium salt treatment is to add ruthenium salt to the material obtained after the copper-loaded molecular sieve is mixed with the solvent; the The ruthenium salt used in the ruthenium salt treatment includes ruthenium trichloride, ruthenium trinitrosylruthenium or ruthenium acetate or a combination of at least two kinds; The mass ratio is 1:(0.005-0.05); the evaporation comprises a water bath rotary evaporation; the evaporation temperature is 50-80°C; the second roasting temperature is 400-700°C; the second roasting The time is 4-8h.
本发明中，配置所用溶液时所用溶剂为本领域中常用溶剂，具体可以是水和/或乙醇等。In the present invention, the solvent used when configuring the solution used is a common solvent in the art, specifically water and/or ethanol, etc.
第二方面，本发明提供了如第一方面所述制备方法所得氨内燃机尾气净化用催化剂，所述氨内燃机尾气净化用催化剂以质量百分含量计包括活性组分：钌0.5-5％和铜2-5％，余量为分子筛载体。In a second aspect, the present invention provides a catalyst for purifying ammonia internal combustion engine tail gas obtained by the preparation method described in the first aspect. The catalyst for purifying ammonia internal combustion engine tail gas includes active components in terms of mass percentage: ruthenium 0.5-5% and copper 2-5%, the rest is molecular sieve carrier.
本发明中，氨内燃机尾气净化用催化剂活性组分钌以质量百分含量计为0.5-5％，例如可以是0.5％、0.6％、0.8％、1％、1.2％、1.4％、1.6％、1.8％、2％、2.2％、2.4％、2.6％、2.8％、3％、3.2％、3.4％、3.6％、3.8％、4％、4.2％、4.4％、4.6％、4.8％或5％等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。In the present invention, the catalyst active component ruthenium used for purification of ammonia internal combustion engine tail gas is 0.5-5% in mass percent, such as 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, or 5% etc., but not limited to the listed values, other unlisted values within this range are also applicable.
本发明中，氨内燃机尾气净化用催化剂活性组分铜以质量百分含量计为2-5％，例如可以是2％、2.1％、2.2％、2.3％、2.4％、2.5％、2.6％、2.7％、2.8％、2.9％、3％、3.1％、3.2％、3.3％、3.4％、3.5％、3.6％、3.7％、3.8％、3.9％、4％、4.1％、4.2％、4.3％、4.4％、4.5％、4.6％、4.7％、4.8％、4.9％或5％等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。In the present invention, the catalyst active component copper for ammonia internal combustion engine tail gas purification is 2-5% in mass percentage, for example, it can be 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3% , 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9% or 5%, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
第三方面，本发明提供了如第一方面所述制备方法所得氨内燃机尾气净化用催化剂的用途，所述用途包括采用所述分子筛催化剂对氨内燃机运行中形成的尾气进行催化净化。In the third aspect, the present invention provides the use of the catalyst for purifying ammonia internal combustion engine tail gas obtained by the preparation method described in the first aspect, and the use includes using the molecular sieve catalyst to catalytically purify the tail gas formed during the operation of the ammonia internal combustion engine.
所述催化净化的温度为200-500℃，例如可以是200℃、210℃、220℃、230℃、240℃、250℃、260℃、270℃、280℃、290℃、300℃、310℃、320℃、330℃、340℃、350℃、360℃、370℃、380℃、390℃、400℃、410℃、420℃、430℃、440℃、450℃、460℃、470℃、480℃、490℃或500℃等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。The temperature of the catalytic purification is 200-500°C, such as 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C , 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C °C, 490 °C or 500 °C, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
所述氨内燃机尾气中的含水量以体积百分含量计为5-15％，例如可以是5％、5.5％、6％、6.5％、7％、7.5％、8％、8.5％、9％、9.5％、10％、10.5％、11％、11.5％、12％、12.5％、13％、13.5％、14％、14.5％或15％等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。The water content in the exhaust gas of the ammonia internal combustion engine is 5-15% by volume, for example, it can be 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9% , 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% or 15%, but not limited to the listed values, other Values not listed also apply.
所述氨内燃机形成的尾气中氨气的浓度为500-2000ppm，例如可以是500ppm、550ppm、600ppm、650ppm、700ppm、750ppm、800ppm、850ppm、900ppm、950ppm、1000ppm、1050ppm、1100ppm、1150ppm、1200ppm、1250ppm、1300ppm、1350ppm、1400ppm、1450ppm、1500ppm、1550ppm、1600ppm、1650ppm、1700ppm、1750ppm、1800ppm、1850ppm、1900ppm、1950ppm或2000ppm等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。The concentration of ammonia in the tail gas formed by the ammonia internal combustion engine is 500-2000ppm, such as 500ppm, 550ppm, 600ppm, 650ppm, 700ppm, 750ppm, 800ppm, 850ppm, 900ppm, 950ppm, 1000ppm, 1050ppm, 1100ppm, 1150ppm, 1200ppm ppm, 1250ppm, 1300ppm, 1350ppm, 1400ppm, 1450ppm, 1500ppm, 1550ppm, 1600ppm, 1650ppm, 1700ppm, 1750ppm, 1800ppm, 1850ppm, 1900ppm, 1950ppm or 2000ppm, etc., but not limited to the listed values, Other values not listed in this range are also Be applicable.
所述氨内燃机形成的尾气中一氧化氮的浓度为100-500ppm，例如可以是100ppm、120ppm、140ppm、160ppm、180ppm、200ppm、220ppm、240ppm、260ppm、280ppm、300ppm、320ppm、340ppm、360ppm、380ppm、400ppm、420ppm、440ppm、460ppm、480ppm或500ppm等，但不限于所列举的数值，该范围内其它未列举的数值同样适用。The concentration of nitric oxide in the tail gas formed by the ammonia internal combustion engine is 100-500ppm, such as 100ppm, 120ppm, 140ppm, 160ppm, 180ppm, 200ppm, 220ppm, 240ppm, 260ppm, 280ppm, 300ppm, 320ppm, 340ppm, 360ppm, 380ppm , 400ppm, 420ppm, 440ppm, 460ppm, 480ppm or 500ppm, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
本发明中，本发明中，净化中气体的总流量可以是400-600mL/min，空速为100000-300000h-1。In the present invention, in the present invention, the total flow rate of gas during purification may be 400-600mL/min, and the space velocity may be 100000-300000h-1 .
与现有技术方案相比，本发明具有以下有益效果：Compared with the prior art solutions, the present invention has the following beneficial effects:
(1)本发明氨氧化催化剂在200-500℃范围内和5-15％的水蒸气存在下具有较高的活性，能够满足氨内燃机在少量氮氧化物和水汽条件下对催化剂尾气净化的要求。贵金属钌具有优异的氧化能力，以小纳米颗粒的形态分布于分子筛载体上配合离子态的铜，使氨气在氮氧化物存在的情况下能够完全被氧化。(1) The ammonia oxidation catalyst of the present invention has relatively high activity in the range of 200-500°C and the presence of 5-15% water vapor, and can meet the requirements of the ammonia internal combustion engine for catalyst tail gas purification under the condition of a small amount of nitrogen oxides and water vapor . The precious metal ruthenium has excellent oxidation ability. It is distributed on the molecular sieve carrier in the form of small nanoparticles and combined with ionic copper, so that ammonia can be completely oxidized in the presence of nitrogen oxides.
(2)本发明氨氧化催化剂在尾气中存在氮氧化物的条件下，200-500℃范围内仍具有较高的氮气选择性(91-99％)，达到了氨内燃机中净化气体的要求，活性金属铜是以高度分散的离子形式存在于催化剂中与氧化态的钌配合，选择性地将副产物氮氧化物和尾气中的一氧化氮还原为氮气，提高氮气选择性。(2) The ammonia oxidation catalyst of the present invention still has higher nitrogen selectivity (91-99%) in the range of 200-500°C under the condition of nitrogen oxides in the tail gas, which meets the requirements of purifying gas in ammonia internal combustion engines, The active metal copper exists in the catalyst in the form of highly dispersed ions and cooperates with the oxidized ruthenium to selectively reduce the by-product nitrogen oxides and nitrogen monoxide in the tail gas to nitrogen, improving the selectivity of nitrogen.
附图说明Description of drawings
图1是本发明应用例1中氨氧化反应的氨气转化率和氮气选择性图。Fig. 1 is the ammonia conversion rate and the nitrogen selectivity diagram of the ammoxidation reaction in the application example 1 of the present invention.
下面对本发明进一步详细说明。但下述的实例仅仅是本发明的简易例子，并不代表或限制本发明的权利保护范围，本发明的保护范围以权利要求书为准。The present invention will be further described in detail below. However, the following examples are only simple examples of the present invention, and do not represent or limit the protection scope of the present invention, and the protection scope of the present invention shall be determined by the claims.
具体实施方式Detailed ways
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：For better illustrating the present invention, facilitate understanding technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
实施例1Example 1
本实施例提供一种氨内燃机尾气净化用催化剂，所述分子筛催化剂以质量百分含量计包括活性组分：钌2％和铜4％，余量为分子筛载体。This embodiment provides a catalyst for purifying exhaust gas of an ammonia internal combustion engine. The molecular sieve catalyst includes active components in terms of mass percentage: 2% ruthenium and 4% copper, and the balance is molecular sieve carrier.
制备方法具体如下：The preparation method is as follows:
S1、将氨型分子筛和铜盐溶液进行混合，之后经依次进行的固液分离、干燥和第一焙烧，得到载铜分子筛；S1. Mixing the ammonia-type molecular sieve and the copper salt solution, followed by sequential solid-liquid separation, drying and first roasting, to obtain the copper-loaded molecular sieve;
配置S1所述铜盐溶液所用铜盐为硝酸铜；所述氨型分子筛为SSZ-13分子筛；所述铜盐溶液中铜元素的摩尔浓度为6.4g/L；所述氨型分子筛和铜盐溶液的固液比g/mL为1:100；所述搅拌的温度为60℃，时间为6h；所述第一焙烧的温度为600℃，时间为6h；The copper salt used in configuring the copper salt solution described in S1 is copper nitrate; the ammonia molecular sieve is SSZ-13 molecular sieve; the molar concentration of copper element in the copper salt solution is 6.4g/L; the ammonia molecular sieve and copper salt The solid-to-liquid ratio g/mL of the solution is 1:100; the temperature of the stirring is 60°C, and the time is 6h; the temperature of the first roasting is 600°C, and the time is 6h;
本实施例中S1进行2次以确保铜的负载量可以达到4％。In this embodiment, S1 is performed twice to ensure that the copper loading can reach 4%.
S2、将S1得到的所述载铜分子筛和溶剂进行混合，之后经依次进行的钌盐处理、蒸发、干燥和第二焙烧，得到氨内燃机尾气净化用催化剂；S2. The copper-loaded molecular sieve obtained in S1 is mixed with a solvent, followed by sequential ruthenium salt treatment, evaporation, drying and second roasting to obtain a catalyst for purifying ammonia internal combustion engine tail gas;
S2中所述溶剂为去离子水；所述混合的温度为25℃，时间为0.5h；所述钌盐处理为向混合所得物料中加入钌盐，所述钌盐处理中所用钌盐为三硝基亚硝酰，所述钌盐处理中载铜分子筛与所用钌盐中钌元素的质量比为1:0.02；所述蒸发包括水浴旋转蒸发，温度为60℃；所述第二焙烧的温度为550℃，时间为4h。The solvent described in S2 is deionized water; the temperature of the mixing is 25° C., and the time is 0.5 h; the ruthenium salt treatment is to add ruthenium salt to the mixed material, and the ruthenium salt used in the ruthenium salt treatment is three Nitronitrosyl, the mass ratio of the copper-loaded molecular sieve to the ruthenium element in the ruthenium salt used in the ruthenium salt treatment is 1:0.02; the evaporation includes a water bath rotary evaporation, and the temperature is 60 ° C; the temperature of the second roasting It is 550°C and the time is 4h.
实施例2Example 2
本实施例提供一种氨内燃机尾气净化用催化剂，所述分子筛催化剂以质量百分含量计包括活性组分：钌2.5％和铜4％，余量为分子筛载体。This embodiment provides a catalyst for purifying exhaust gas of an ammonia internal combustion engine. The molecular sieve catalyst includes active components by mass percentage: 2.5% ruthenium and 4% copper, and the balance is molecular sieve carrier.
制备方法具体如下：The preparation method is as follows:
S1、将氨型分子筛和铜盐溶液进行混合，之后经依次进行的固液分离、干燥和第一焙烧，得到载铜分子筛；S1. Mixing the ammonia-type molecular sieve and the copper salt solution, followed by sequential solid-liquid separation, drying and first roasting, to obtain the copper-loaded molecular sieve;
配置步骤S1所述铜盐溶液所用铜盐为硝酸铜；所述氨型分子筛为SSZ-13分子筛；所述铜盐溶液中铜元素的摩尔浓度为3.2g/L；所述氨型分子筛和铜盐溶液的固液比g/mL为1:100；所述第一混合搅拌的温度为60℃，时间为6h；所述第一焙烧的温度为600℃，时间为5h；The copper salt used in the copper salt solution in configuration step S1 is copper nitrate; the ammonia molecular sieve is SSZ-13 molecular sieve; the molar concentration of copper in the copper salt solution is 3.2g/L; the ammonia molecular sieve and copper The solid-to-liquid ratio g/mL of the salt solution is 1:100; the temperature of the first mixing and stirring is 60°C, and the time is 6h; the temperature of the first roasting is 600°C, and the time is 5h;
S2、将S1得到的所述载铜分子筛和溶剂进行混合，之后经依次进行的钌盐处理、蒸发、干燥和第二焙烧，得到氨内燃机尾气净化用催化剂；S2. The copper-loaded molecular sieve obtained in S1 is mixed with a solvent, followed by sequential ruthenium salt treatment, evaporation, drying and second roasting to obtain a catalyst for purifying ammonia internal combustion engine tail gas;
S2中所述溶剂为去离子水；所述第二混合搅拌的温度为25℃，时间为0.5h；所述钌盐处理为向混合所得物料中加入钌盐，所述钌盐处理中所用钌盐为三硝基亚硝酰钌，所述钌盐处理中载铜分子筛与所用钌盐中钌元素的质量比为1:0.025；所述蒸发为水浴旋转蒸发，温度为60℃；所述第二焙烧的温度为550℃，时间为4h。The solvent described in S2 is deionized water; the temperature of the second mixing and stirring is 25° C., and the time is 0.5 h; The salt is trinitronitrosyl ruthenium, and the mass ratio of the copper-loaded molecular sieve to the ruthenium element in the ruthenium salt used in the ruthenium salt treatment is 1:0.025; the evaporation is a water bath rotary evaporation, and the temperature is 60 ° C; the first The temperature of the second calcination is 550°C, and the time is 4h.
实施例3Example 3
本实施例提供一种氨内燃机尾气净化用催化剂，所述分子筛催化剂以质量百分含量计包括活性组分：钌1.0％和铜4％，余量为分子筛载体。This embodiment provides a catalyst for purifying exhaust gas of an ammonia internal combustion engine. The molecular sieve catalyst includes active components by mass percentage: 1.0% ruthenium and 4% copper, and the balance is molecular sieve carrier.
制备方法具体如下：The preparation method is as follows:
S1、将氨型分子筛和铜盐溶液进行混合，之后经依次进行的固液分离、干燥和第一焙烧，得到负载铜分子筛；S1. Mixing the ammonia-type molecular sieve and the copper salt solution, followed by sequential solid-liquid separation, drying and first roasting, to obtain the supported copper molecular sieve;
配置S1所述铜盐溶液所用铜盐为硝酸铜；所述氨型分子筛为SSZ-13分子筛；所述铜盐溶液中铜元素的浓度为6.4/L；所述氨型分子筛和铜盐溶液的固液比g/mL为1:100；所述混合的温度为60℃，时间为6h；所述第一焙烧的温度为600℃，时间为5h；The copper salt used in configuring the copper salt solution described in S1 is copper nitrate; the ammonia molecular sieve is SSZ-13 molecular sieve; the concentration of copper element in the copper salt solution is 6.4/L; the ammonia molecular sieve and copper salt solution The solid-to-liquid ratio g/mL is 1:100; the temperature of the mixing is 60°C, and the time is 6h; the temperature of the first roasting is 600°C, and the time is 5h;
S2、将步骤S1得到的所述载铜分子筛和溶剂进行混合，之后经依次进行的钌盐处理、蒸发、干燥和第二焙烧，得到氨内燃机尾气净化用催化剂；S2. Mix the copper-loaded molecular sieve obtained in step S1 with a solvent, and then undergo sequential ruthenium salt treatment, evaporation, drying and second roasting to obtain a catalyst for purifying ammonia internal combustion engine exhaust;
S2中所述溶剂为去离子水；所述混合的温度为25℃，时间为0.5h；所述钌盐处理为向混合所得物料中加入钌盐，所述钌盐处理中所用钌盐为三硝基亚硝酰钌，所述钌盐处理中负载铜分子筛与所用钌盐中钌元素的质量比为1:0.010；所述蒸发为水浴旋转蒸发，温度为60℃；所述第二焙烧的温度为550℃，时间为8h。The solvent described in S2 is deionized water; the temperature of the mixing is 25° C., and the time is 0.5 h; the ruthenium salt treatment is to add ruthenium salt to the mixed material, and the ruthenium salt used in the ruthenium salt treatment is three Nitronitrosyl ruthenium, the mass ratio of the copper molecular sieve loaded in the ruthenium salt treatment to the ruthenium element in the ruthenium salt used is 1:0.010; the evaporation is a water bath rotary evaporation, and the temperature is 60 ° C; the second roasted The temperature is 550°C and the time is 8h.
实施例4Example 4
本实施例提供一种氨内燃机氨净化的分子筛催化剂，所述分子筛催化剂以质量百分含量计包括活性组分：钌2％和铜2％，余量为分子筛载体。This embodiment provides a molecular sieve catalyst for ammonia purification of an ammonia internal combustion engine. The molecular sieve catalyst includes active components by mass percentage: 2% ruthenium and 2% copper, and the balance is a molecular sieve carrier.
制备方法具体如下：The preparation method is as follows:
S1、将氨型分子筛和铜盐溶液进行混合，之后经依次进行的固液分离、干燥和第一焙烧，得到载铜分子筛；S1. Mixing the ammonia-type molecular sieve and the copper salt solution, followed by sequential solid-liquid separation, drying and first roasting, to obtain the copper-loaded molecular sieve;
配置S1所述铜盐溶液所用铜盐为硝酸铜；所述氨型分子筛为SSZ-13分子筛；所述铜盐溶液中铜元素的摩尔浓度为64g/L；所述氨型分子筛和铜盐溶液的固液比g/mL为1:100；所述混合的温度为60℃，时间为6h；所述第一焙烧的温度为600℃，时间为7h；The copper salt used in configuring the copper salt solution described in S1 is copper nitrate; the ammonia molecular sieve is SSZ-13 molecular sieve; the molar concentration of copper element in the copper salt solution is 64g/L; the ammonia molecular sieve and copper salt solution The solid-to-liquid ratio g/mL is 1:100; the temperature of the mixing is 60°C, and the time is 6h; the temperature of the first roasting is 600°C, and the time is 7h;
S2、将S1得到的所述载铜分子筛和溶剂进行混合，之后经依次进行的钌盐处理、蒸发、干燥和第二焙烧，得到所述分子筛催化剂；S2. Mix the copper-loaded molecular sieve obtained in S1 with a solvent, and then undergo sequential ruthenium salt treatment, evaporation, drying and second calcination to obtain the molecular sieve catalyst;
S2中所述溶剂为去离子水；所述混合的温度为25℃，时间为0.5h；所述钌盐处理为向混合所得物料中加入钌盐，所述钌盐处理中所用钌盐为三硝基亚硝酰钌，所述钌盐处理中负载铜分子筛与所用钌盐中钌元素的质量比为1:0.020；所述蒸发为水浴旋转蒸发，温度为60℃；所述第二焙烧的温度为550℃，时间为5h。The solvent described in S2 is deionized water; the temperature of the mixing is 25° C., and the time is 0.5 h; the ruthenium salt treatment is to add ruthenium salt to the mixed material, and the ruthenium salt used in the ruthenium salt treatment is three Nitronitrosyl ruthenium, the mass ratio of the copper molecular sieve loaded in the ruthenium salt treatment to the ruthenium element in the ruthenium salt used is 1:0.020; the evaporation is a water bath rotary evaporation, and the temperature is 60 ° C; the second roasted The temperature is 550°C and the time is 5h.
实施例5Example 5
与实施例1的区别仅在于将钌盐替换为等量的氯铂酸。The difference from Example 1 is only that the ruthenium salt is replaced by an equivalent amount of chloroplatinic acid.
应用例1Application example 1
采用实施例1对模拟氨内燃机出现的尾气进行催化净化，对催化净化的温度进行梯度温度试验，温度为150℃、175℃、200℃、225℃、250℃、275℃、300℃、325℃、350℃、375℃和400℃；Adopt embodiment 1 to carry out catalytic purification to the tail gas that simulates ammonia internal combustion engine to appear, carry out gradient temperature test to the temperature of catalytic purification, the temperature is 150 ℃, 175 ℃, 200 ℃, 225 ℃, 250 ℃, 275 ℃, 300 ℃, 325 ℃ , 350°C, 375°C and 400°C;
所述氨内燃机尾气中的含水量以体积百分含量计为5％；The water content in the exhaust gas of the ammonia internal combustion engine is 5% by volume percentage;
所述氨内燃机尾气中的气体总流量为500mL/min，空速为200000h-1。The total gas flow rate in the exhaust gas of the ammonia internal combustion engine is 500mL/min, and the space velocity is 200000h-1 .
所述氨内燃机运行中形成的氨气的浓度为1000ppm。The concentration of ammonia gas formed during the operation of the ammonia internal combustion engine is 1000 ppm.
所述氨内燃机运行中形成的一氧化氮的浓度为200ppmThe concentration of nitric oxide formed in the operation of the ammonia internal combustion engine is 200ppm
300℃净化后气体的指标详见表1，其他温度条件下详见图1。See Table 1 for the indicators of the purified gas at 300°C, and see Figure 1 for details at other temperature conditions.
应用例2Application example 2
采用实施例1对模拟氨内燃机出现的尾气进行催化净化，所述催化净化的温度为300℃；Adopt embodiment 1 to carry out catalytic purification to the tail gas that simulates ammonia internal combustion engine to appear, the temperature of described catalytic purification is 300 ℃;
所述氨内燃机尾气中的含水量以体积百分含量计为5％；The water content in the exhaust gas of the ammonia internal combustion engine is 5% by volume percentage;
所述氨内燃机尾气中的气体总流量为500mL/min，空速为200000h-1。The total gas flow rate in the exhaust gas of the ammonia internal combustion engine is 500mL/min, and the space velocity is 200000h-1 .
所述氨内燃机运行中形成的氨气的浓度为1000ppm。The concentration of ammonia gas formed during the operation of the ammonia internal combustion engine is 1000 ppm.
所述氨内燃机运行中形成的一氧化氮的浓度为100ppm。The concentration of nitric oxide formed during the operation of the ammonia internal combustion engine is 100 ppm.
净化后气体的指标详见表1。The indicators of the purified gas are shown in Table 1.
应用例3Application example 3
采用实施例1对模拟氨内燃机出现的尾气进行催化净化，所述催化净化的温度为300℃；Adopt embodiment 1 to carry out catalytic purification to the tail gas that simulates ammonia internal combustion engine to appear, the temperature of described catalytic purification is 300 ℃;
所述氨内燃机尾气中的含水量以体积百分含量计为5％；The water content in the exhaust gas of the ammonia internal combustion engine is 5% by volume percentage;
所述氨内燃机尾气中的气体总流量为500mL/min，空速为200000h-1。The total gas flow rate in the exhaust gas of the ammonia internal combustion engine is 500mL/min, and the space velocity is 200000h-1 .
所述氨内燃机运行中形成的氨气的浓度为200ppm。The concentration of ammonia gas formed during the operation of the ammonia internal combustion engine is 200 ppm.
所述氨内燃机运行中形成的一氧化氮的浓度为500ppm。The concentration of nitric oxide formed during the operation of the ammonia internal combustion engine is 500 ppm.
净化后气体的指标详见表1。The indicators of the purified gas are shown in Table 1.
应用例4Application example 4
采用实施例2对模拟氨内燃机出现的尾气进行催化净化，所述催化净化的温度为300℃；Adopt embodiment 2 to carry out catalytic purification to the tail gas that simulates ammonia internal combustion engine to appear, the temperature of described catalytic purification is 300 ℃;
所述氨内燃机尾气中的含水量以体积百分含量计为5％；The water content in the exhaust gas of the ammonia internal combustion engine is 5% by volume percentage;
所述氨内燃机尾气中的气体总流量为500mL/min，空速为200000h-1。The total gas flow rate in the exhaust gas of the ammonia internal combustion engine is 500mL/min, and the space velocity is 200000h-1 .
所述氨内燃机运行中形成的氨气的浓度为1000ppm。The concentration of ammonia gas formed during the operation of the ammonia internal combustion engine is 1000 ppm.
所述氨内燃机运行中形成的一氧化氮的浓度为200ppm。The concentration of nitric oxide formed during the operation of the ammonia internal combustion engine is 200 ppm.
净化后气体的指标详见表1。The indicators of the purified gas are shown in Table 1.
应用例5Application example 5
采用实施例3对模拟氨内燃机出现的尾气进行催化净化，所述催化净化的温度为300℃；Adopt embodiment 3 to carry out catalytic purification to the tail gas that simulates ammonia internal combustion engine to appear, the temperature of described catalytic purification is 300 ℃;
所述氨内燃机尾气中的含水量以体积百分含量计为5％；The water content in the exhaust gas of the ammonia internal combustion engine is 5% by volume percentage;
所述氨内燃机尾气中的气体总流量为500mL/min，空速为200000h-1。The total gas flow rate in the exhaust gas of the ammonia internal combustion engine is 500mL/min, and the space velocity is 200000h-1 .
所述氨内燃机运行中形成的氨气的浓度为1000ppm。The concentration of ammonia gas formed during the operation of the ammonia internal combustion engine is 1000 ppm.
所述氨内燃机运行中形成的一氧化氮的浓度为200ppm。The concentration of nitric oxide formed during the operation of the ammonia internal combustion engine is 200 ppm.
净化后气体的指标详见表1。The indicators of the purified gas are shown in Table 1.
应用例6Application example 6
采用实施例4对模拟氨内燃机出现的尾气进行催化净化，所述催化净化的温度为300℃；Adopt embodiment 4 to carry out catalytic purification to the tail gas that simulates ammonia internal combustion engine to appear, the temperature of described catalytic purification is 300 ℃;
所述氨内燃机尾气中的含水量以体积百分含量计为5％；The water content in the exhaust gas of the ammonia internal combustion engine is 5% by volume percentage;
所述氨内燃机尾气中的气体总流量为500mL/min，空速为200000h-1。The total gas flow rate in the exhaust gas of the ammonia internal combustion engine is 500mL/min, and the space velocity is 200000h-1 .
所述氨内燃机运行中形成的氨气的浓度为1000ppm。The concentration of ammonia gas formed during the operation of the ammonia internal combustion engine is 1000 ppm.
所述氨内燃机运行中形成的一氧化氮的浓度为200ppm。The concentration of nitric oxide formed during the operation of the ammonia internal combustion engine is 200 ppm.
净化后气体的指标详见表1。The indicators of the purified gas are shown in Table 1.
应用例7Application example 7
与应用例2的区别仅在于采用实施例5的催化剂。The difference from Application Example 2 is only that the catalyst of Example 5 is used.
净化后气体的指标详见表1。对比表1数据可知，当将活性物质替换为铂和铜的组合时，催化剂性能在有氮氧化物存在的情况下出现明显的降低，在以贵金属铂和铜为活性组分制备的催化剂中，由于氧气在贵金属铂表面解离为活性氧，活性氧进一步诱导氨气脱氢为氮原子产生氮气。同时活性氧和氮原子结合产生一氧化氮，一氧化氮和氨气在贵金属铂上会生成氧化亚氮副产物，从而导致其氮气选择性较低。而以钌和铜为活性组分的催化剂在一氧化氮存在时，一氧化氮和氨气在活性组分钌上不会或极少量生成氧化亚氮副产物，因此能够更好的去除氨气，以解决实际情况中氨内燃机尾气净化的问题。The indicators of the purified gas are shown in Table 1. Comparing the data in Table 1, it can be seen that when the active material is replaced by a combination of platinum and copper, the catalyst performance is significantly reduced in the presence of nitrogen oxides. In the catalyst prepared with the noble metal platinum and copper as active components, Oxygen dissociates into active oxygen on the surface of noble metal platinum, which further induces the dehydrogenation of ammonia to nitrogen atoms to generate nitrogen. At the same time, reactive oxygen and nitrogen atoms are combined to produce nitric oxide, and nitric oxide and ammonia will generate nitrous oxide by-products on the noble metal platinum, resulting in low nitrogen selectivity. When the catalyst with ruthenium and copper as active components exists in the presence of nitric oxide, nitric oxide and ammonia will not or a very small amount of nitrous oxide by-products will be generated on the active component ruthenium, so ammonia can be removed better , to solve the problem of ammonia internal combustion engine tail gas purification in actual conditions.
表1Table 1
通过上述应用例的结果可知，通过引入活性组分钌和铜，利用金属的协同作用提高催化剂氨氧化反应的低温活性和氮气选择性。贵金属钌具有较高活性，可以保证氨氧化反应的顺利进行。活性组分铜具有还原氮氧化物的能力，可以将尾气中的氮氧化物有效还原，解决了当前氨内燃机尾气中少量氮氧化物存在时尾气净化的问题。According to the results of the above application examples, it can be seen that by introducing the active components ruthenium and copper, the synergistic effect of the metals can be used to improve the low-temperature activity and nitrogen selectivity of the ammoxidation reaction of the catalyst. The noble metal ruthenium has high activity, which can ensure the smooth progress of the ammoxidation reaction. The active component copper has the ability to reduce nitrogen oxides, and can effectively reduce the nitrogen oxides in the exhaust gas, which solves the current problem of exhaust gas purification when there is a small amount of nitrogen oxides in the exhaust gas of ammonia internal combustion engines.
声明，本发明通过上述实施例来说明本发明的详细结构特征，但本发明并不局限于上述详细结构特征，即不意味着本发明必须依赖上述详细结构特征才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用部件的等效替换以及辅助部件的增加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。It is stated that the present invention illustrates the detailed structural features of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed structural features, that is, it does not mean that the present invention must rely on the above-mentioned detailed structural features to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of selected components in the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.
Claims (10)
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