WO2020133574A1 - 一种消除并回收利用燃烧尾气中的氮氧化物的方法 - Google Patents

一种消除并回收利用燃烧尾气中的氮氧化物的方法 Download PDF

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WO2020133574A1
WO2020133574A1 PCT/CN2019/070792 CN2019070792W WO2020133574A1 WO 2020133574 A1 WO2020133574 A1 WO 2020133574A1 CN 2019070792 W CN2019070792 W CN 2019070792W WO 2020133574 A1 WO2020133574 A1 WO 2020133574A1
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adsorbent
combustion exhaust
exhaust gas
combustion
adsorption
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沈美庆
王军
沈谷蓉
王建强
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Tianjin University
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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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • B01D2259/4009—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas

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  • the invention relates to the technical field of pollution control and resource reuse of nitrogen oxides in combustion exhaust gas, in particular to a method for recycling nitrogen oxides in combustion exhaust gas generated in the combustion process of coal combustion/oil/natural gas.
  • NH 3 -SCR ammonia selective catalytic reduction technology
  • NH 3 -SCR technology has the most mature mainstream denitration technology with high denitration efficiency.
  • NH 3 -SCR technology uses NH 3 /urea as reducing material to react with nitrogen oxides to produce nitrogen and water under the action of catalytic materials. Therefore, the core components of NH 3 -SCR technology include catalytic materials, urea injection systems (urea tanks, nozzles, urea metering units, control systems, etc.), nitrogen oxide sensors, etc.; the entire system is complex, the cost of equipment and raw materials is high, and catalysis Materials need higher temperature (greater than 200°C) to work. It is difficult to meet the demand for zero emissions of nitrogen oxides in industries such as motor vehicles, coal/oil/gas power plants, building materials (cement, glass, ceramics, etc.), steel and other industries.
  • NOx is a pollutant, it is also a valuable oxidant resource from another perspective, for example, it can be used as a liquid oxidant for rockets.
  • the large amount of NH 3 consumed in the NH 3 -SCR technology is also a valuable industrial raw material. It is a pity that NOx and NH 3, both of which have valuable value, react and generate nitrogen with no industrial value.
  • the present invention provides a method for eliminating and recycling nitrogen oxides in combustion exhaust gas, which includes the following steps:
  • the combustion exhaust gas containing nitrogen oxides is contacted with an adsorbent at a temperature of less than 150°C to adsorb nitrogen oxides therein; wherein the adsorbent includes an active component supported on a molecular sieve carrier, and the active component is selected From precious metals, rare earth metals or transition metals, and in terms of elemental content, the active component accounts for 0.1-20 wt% of the total mass of the adsorbent; then,
  • the combustion exhaust gas includes various coal-fired/oil/natural gas boilers and engine exhaust gases, such as motor vehicles, coal-fired power plants, gas turbines, cement, glass, ceramics, iron and steel, etc. after dedusting and desulfurization. Exhaust gas.
  • the active component is selected from silver, platinum, rhodium, palladium, yttrium, lanthanum, cerium, praseodymium, neodymium, manganese, iron, cobalt, nickel or copper;
  • the molecular sieve support is selected from BEA, MFI or CHA type Molecular sieve.
  • the molecular sieve has a pore size ranging from 0.1 nm to 1 nm and a specific surface area of 500-1000 m 2 /g.
  • the preparation method of the adsorbent can be prepared by the hydrothermal crystallization method of the active metal source (usually its soluble salts) and the mother liquid of the molecular sieve, or by the method of impregnating the molecular sieve with the active metal source.
  • the specific preparation method can be detailed See the applicant's other patent titled "A Method for Adsorbing Nitrogen Oxides and/or Hydrocarbon Compounds During the Cold Start of Motor Vehicles", which will not be repeated here.
  • the adsorbent also has a certain catalytic effect. For example, it can convert a part of NO to NO 2. Therefore, the adsorbent can also be called a catalyst.
  • the nitrogen oxide is saturated or nearly saturated.
  • the near saturation means that the adsorption capacity reaches more than 70% of its saturation adsorption capacity.
  • the adsorption process of step A is less than 30 seconds.
  • the adsorption temperature in step A is 50-150°C.
  • step A a step of dedusting the combustion exhaust gas is further included.
  • step A a step of desulfurizing the combustion exhaust gas is further included.
  • step A a step of lowering the temperature of the combustion exhaust gas through the waste heat recovery device is further included.
  • the cooling medium in the waste heat recovery device is air, which is used as the high-temperature air in step B after being heated by the waste heat of the combustion exhaust gas.
  • the combustion exhaust gas after heat exchange further radiates to a temperature lower than 150°C along the pipeline, and then enters the adsorption device to contact with the adsorbent.
  • At least two sets of nitrogen oxide adsorption devices are provided, wherein the first set performs step A when the second set performs step B, and the second set performs step A when the first set performs step B, thereby achieving continuous elimination and recycling of combustion Nitrogen oxides in the exhaust.
  • the adsorbent in the present invention can quickly adsorb NOx at a temperature of less than 150°C, and its saturated adsorption capacity can reach 30 mol/g, which can basically completely remove the NOx in the combustion exhaust gas and achieve zero NOx pollution emissions.
  • the present invention completely avoids the shortcomings related to NH 3 -SCR technology, in particular, no need to use expensive NH 3 to reduce NOx, and the cost of raw materials and equipment is greatly reduced. , Greatly reducing equipment investment costs and maintenance costs, and avoid the environmental pressure caused by ammonia leakage and ammonia escape.
  • the waste heat recovery device is used to preheat the ambient air, and the preheated high temperature air desorbs NOx and is supplied to the boiler combustion chamber as combustion air, which not only realizes the recovery of waste heat, but also makes full use of NOx as a strong
  • the characteristics of oxidants have realized the reuse of NOx resources and also eliminated NOx pollution.
  • FIG. 1 is a schematic diagram of the process flow of the method of the present invention.
  • FIG. 2 is an adsorption curve diagram of the adsorbent of the present invention adsorbing NOx in the combustion exhaust gas of the glass industry at 100°C.
  • the abscissa is the contact time, and the ordinate is the NOx concentration in the exhaust gas in volume ppm, the same below.
  • Fig. 3 is a graph of NOx desorption after the adsorbent of the present invention is saturated with exhaust gas from the glass industry and then passed into high-temperature air.
  • FIG. 4 is an adsorption curve diagram of the adsorbent of the present invention adsorbing NOx in combustion exhaust gas of the cement industry at 150°C.
  • Fig. 5 is a graph of the NOx desorption curve after the adsorbent of the present invention is saturated with adsorbed exhaust gas of the cement industry and then passed into high-temperature air.
  • Fig. 6 is an adsorption curve diagram of the adsorbent of the present invention adsorbing NOx in the combustion exhaust gas of a gas boiler at 80°C.
  • Fig. 7 is a graph of NOx desorption after the adsorbent of the present invention is saturated with the exhaust gas of the gas-fired boiler and then passed into high-temperature air.
  • Fig. 8 is an adsorption curve diagram of the adsorbent of the present invention adsorbing NOx in the combustion exhaust gas of a fuel engine at 80°C.
  • FIG. 9 is a graph of NOx desorption after the adsorbent of the present invention is saturated with adsorbed fuel engine exhaust gas and then passed into high-temperature air.
  • FIG. 10 is an adsorption curve diagram of the Pd/Beta adsorbent of the present invention adsorbing NOx in the combustion exhaust gas of the glass industry at 50°C.
  • FIG 11 is a graph of NOx desorption after the Pd/Beta adsorbent of the present invention is saturated with adsorbed glass industry exhaust gas and then passed into high-temperature air.
  • the combustion exhaust gas contains 1500 ppm NOx, 16.5% CO 2 , 8% O 2 , 11.5% H 2 O, and the balance is N 2 .
  • a sample of the combustion exhaust gas was taken for the experiment.
  • the amount of molecular sieve adsorption material was 0.589 g, the total gas flow rate was 900 mL/min, the adsorption temperature was 100° C., and the space velocity was 11,000 h -1 .
  • the adsorbent used is Ce/Beta, which means that Ce is loaded on the Beta molecular sieve, and the composition of the remaining adsorbents is similar to this method), where the percentage content of Ce is 2wt%, and the NOx adsorption results are shown in Figure 2, where After about 41 seconds, the adsorption saturation is reached, and the saturated adsorption amount of NOx reaches 32.8 ⁇ mol/g adsorbent.
  • the combustion exhaust gas contains 1000 ppm NOx, 12.5% CO 2 , 9.2% O 2 , 6% H 2 O, and the balance is N 2 .
  • a sample of the combustion exhaust gas was taken for experiments.
  • the amount of molecular sieve adsorption material was 0.288 g, the total gas flow rate was 1000 mL/min, the adsorption temperature was 150° C., and the space velocity was 25,000 h -1 .
  • the adsorbent used is La/Beta, where the percentage content of La is 5 wt%, and the NOx adsorption result is shown in FIG. 4, wherein the adsorption saturation is reached after about 34 seconds, and the saturated adsorption amount of NOx reaches 33.4 ⁇ mol/g adsorbent.
  • the combustion exhaust gas contains 500 ppm NOx, 5% CO 2 , 8% O 2 , 5% H 2 O, and the balance is N 2 .
  • a sample of the combustion exhaust gas was taken for experiments.
  • the amount of molecular sieve adsorption material was 0.144 g, the total gas flow rate was 1000 mL/min, the adsorption temperature was 80° C., and the space velocity was 50,000 h -1 .
  • the adsorbent used is Cu/ZSM-5, in which the percentage content of Cu is 10wt%, and the NOx adsorption result is shown in FIG. 6, wherein the adsorption saturation is reached after about 47 seconds, and the saturated adsorption amount of NOx reaches 33.6 ⁇ mol/g adsorption Agent.
  • combustion air After desorption, high-temperature air is passed into the combustion chamber of the gas boiler as combustion air, so that the desorbed NOx acts as a combustion aid.
  • the combustion exhaust gas contains 200 ppm NOx, 5% CO 2 , 10% O 2 , 5% H 2 O, and the balance is N 2 .
  • a sample of the combustion exhaust gas was taken for experiments.
  • the amount of molecular sieve adsorption material was 0.144 g, the total gas flow rate was 1000 mL/min, the adsorption temperature was 80° C., and the space velocity was 50,000 h -1 .
  • the adsorbent used is Co/SSZ-13, where the percentage content of Co is 20wt%, and the NOx adsorption result is shown in FIG. 8, wherein the adsorption saturation is reached after 121 seconds, and the saturated adsorption amount of NOx reaches 29.8 ⁇ mol/g adsorption Agent.
  • combustion air after desorption, high-temperature air is passed into the combustion chamber of the fuel engine as combustion air, so that the desorbed NOx acts as a combustion aid.
  • the combustion exhaust gas contains 1500 ppm NOx, 16.5% CO 2 , 8% O 2 , 11.5% H 2 O, and the balance is N 2 .
  • a sample of the combustion exhaust gas was taken for experiment.
  • the amount of molecular sieve adsorption material was 0.589 g, the total gas flow rate was 900 mL/min, the adsorption temperature was 50° C., and the space velocity was 11,000 h -1 .
  • the adsorbent used is PdCe/Beta, which means that Pd and Ce are supported on the Beta molecular sieve, and the composition of the rest of the adsorbents is similar to this method, where the percentage content of Pd is 0.1wt% and the percentage content of Ce is 2wt%
  • the results of NOx adsorption are shown in Fig. 10, where the adsorption saturation is reached after about 42 seconds, and the saturated adsorption amount of NOx reaches 40.4 ⁇ mol/g adsorbent.

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Abstract

提供一种消除并回收利用燃烧尾气中的氮氧化物的方法，包括以下步骤：A、使包含氮氧化物的燃烧尾气与吸附剂在小于150℃的温度下接触以吸附其中的氮氧化物；其中所述吸附剂包括负载在分子筛载体上的活性组分，所述活性组分包括贵金属、稀土金属或过渡金属，以单质含量计，该活性组分占吸附剂总质量的0.1-20wt％；B、向该吸附剂中通入大于250℃的高温空气使所吸附的氮氧化物解吸并随该高温空气送入燃烧室作为助燃空气。适用于各种燃煤、燃气、燃油锅炉和汽车发动机，既消除了NOx污染，又将NOx用作助燃氧化剂，实现了污染物的资源化利用。

Description

一种消除并回收利用燃烧尾气中的氮氧化物的方法 技术领域
本发明涉及燃烧废气中氮氧化物污染治理和资源再利用技术领域，具体涉及一种回收燃煤/石油/天然气等燃烧过程中产生的燃烧废气中的氮氧化物的回收利用方法。
背景技术
工业上存在着大量的以煤炭、石油、天然气为燃料的燃烧装置和动力装置，例如燃煤/石油/天然气电厂、建材(水泥、玻璃、陶瓷等)、钢铁等行业中的锅炉和高炉，以及机动车发动机等。燃烧会排放大量的氮氧化物(NOx)，对生态环境和人类身体健康造成了巨大的威害。如何消除这些NOx污染，是工业脱硝技术的努力方向。
现阶段对氮氧化合物的污染控制一般采用氨选择性催化还原技术(NH 3-SCR)。NH 3-SCR技术具有脱硝效率高，最为成熟的主流脱硝技术。NH 3-SCR技术是在催化材料的作用下，以NH 3/尿素作为还原材料与氮氧化合物反应生成氮气和水。因此，NH 3-SCR技术核心组件包括催化材料、尿素喷射系统(尿素罐、喷嘴、尿素计量单元、控制系统等)、氮氧化物传感器等；整套系统复杂、设备和原料成本较高，且催化材料需要较高温度时(大于200℃)才会起作用。难以满足机动车、燃煤/石油/天然气电厂、建材(水泥、玻璃、陶瓷等)、钢铁等行业氮氧化物零排放的需求。
NOx虽然是污染物，但从另一角度来看其也是宝贵的氧化剂资源，例如可以用作火箭的液体氧化剂。NH 3-SCR技术中大量消耗的NH 3也是有价值的工业原料。NOx和NH 3这两种均有宝贵价值的物质却反应生成了毫无工业价值的氮气而排放，着实令人可惜。
因此，寻求一种工艺简单、低成本、低温(不大于150℃)活性高的燃烧废气中氮氧化物回收利用的方法具有重要的意义。
发明内容
为了解决上述问题，提出本发明。
本发明提供了一种消除并回收利用燃烧尾气中的氮氧化物的方法，其包括以下步骤：
A、使包含氮氧化物的燃烧尾气与吸附剂在小于150℃的温度下接触以吸附其中的氮氧化物；其中所述吸附剂包括负载在分子筛载体上活性组分，所述活性组分选自贵金属、稀土金属或过渡金属，且以单质含量计，该活性组分占吸附剂总质量的0.1-20wt％；然后，
B、向该吸附剂中通入大于250℃的高温空气使所吸附的氮氧化物解吸并随该高温空气送入燃烧室作为助燃空气。
其中所述燃烧尾气包括各种燃煤/石油/天然气锅炉、发动机燃烧废气，例如包括机动车、燃煤电厂、燃气轮机、水泥、玻璃、陶瓷、钢铁等行业经过除尘、脱硫后含氮氧化物的废气。
优选地，所述活性组分选自银、铂、铑、钯、钇、镧、铈、镨、钕、锰、铁、钴、镍或铜；所述分子筛载体选自BEA、MFI或CHA型分子筛。
优选地，所述分子筛孔径范围0.1nm-1nm，比表面积为500-1000m 2/g。
其中所述吸附剂的制备方法可以采用活性金属源(通常为其可溶性盐类)与分子筛母液共同水热晶化法制备，也可以采用活性金属源浸渍分子筛的方法来制备，具体制备方法可详见申请人同时申请的题目为《一种在机动车冷启动过程中吸附氮氧化物和/或烃类化合物的方法》的另一专利，不再赘述。
所述吸附剂也有一定的催化作用，例如它可以将一部分NO转化为NO 2，因此，该吸附剂也可以被称为催化剂。
优选地，步骤A中使氮氧化物达到吸附饱和或近饱和。其中所述近饱和是指吸附容量达到其饱和吸附量的70％以上。
优选地，步骤A的吸附过程小于30秒。
优选地，步骤A中的吸附温度为50-150℃。
优选地，在步骤A之前还包括对燃烧尾气进行除尘的步骤。
优选地，在步骤A之前还包括对燃烧尾气进行脱硫的步骤。
优选地，在步骤A之前还包括使燃烧尾气经过余热回收装置降温的步骤。
更优选地，余热回收装置中的冷却介质为空气，该空气被燃烧尾气的余热加热后被用作步骤B中的高温空气。这种情况下，经过换热的燃烧尾气在沿途 管路进一步散热至温度低于150℃后再进入吸附装置与吸附剂接触。
优选地，设置至少两套氮氧化物吸附装置，其中第一套执行步骤A时第二套执行步骤B，第一套执行步骤B时第二套执行步骤A，从而实现连续消除并回收利用燃烧尾气中的氮氧化物。
本发明的有益效果：
1、本发明中的吸附剂能够在小于150℃的温度下迅速地吸附NOx，其饱和吸附容量可达30mol/g，可将燃烧尾气中的NOx基本完全脱除，实现零NOx污染排放。
2、本发明完全避免了与NH 3-SCR技术有关的缺点，尤其是无需使用昂贵的NH 3来还原NOx，原料及设备成本大大降低，例如燃烧锅炉业主不必再为了脱硝而配建喷氨装置，大大降低设备投资成本和维护成本，且避免了氨泄露及氨逃逸带来的环保压力。
3、利用余热回收装置来预热环境空气，并将该预热后的高温空气去解吸NOx后供应至锅炉燃烧室作为助燃空气，既实现了余热的回收利用，又可充分利用了NOx作为强氧化剂的特点，实现了NOx的资源化再利用，还消除了NOx污染，可谓一举三得。
附图说明
图1是本发明的方法的工艺流程示意图。
图2是本发明的吸附剂在100℃下吸附玻璃行业燃烧尾气中的NOx的吸附曲线图。其中横坐标为接触时间，纵坐标为尾气中的NOx浓度，以体积ppm计，下同。
图3是本发明的吸附剂在吸附玻璃行业尾气饱和后再通入高温空气后的NOx脱附曲线图。
图4是本发明的吸附剂在150℃下吸附水泥行业燃烧尾气中的NOx的吸附曲线图。
图5是本发明的吸附剂在吸附水泥行业尾气饱和后再通入高温空气后的NOx脱附曲线图。
图6是本发明的吸附剂在80℃下吸附燃气锅炉燃烧尾气中的NOx的吸 附曲线图。
图7是本发明的吸附剂在吸附燃气锅炉尾气饱和后再通入高温空气后的NOx脱附曲线图。
图8是本发明的吸附剂在80℃下吸附燃油发动机燃烧尾气中的NOx的吸附曲线图。
图9是本发明的吸附剂在吸附燃油发动机尾气饱和后再通入高温空气后的NOx脱附曲线图。
图10是本发明的Pd/Beta吸附剂在50℃下吸附玻璃行业燃烧尾气中的NOx的吸附曲线图。
图11是本发明的Pd/Beta吸附剂在吸附玻璃行业尾气饱和后再通入高温空气后的NOx脱附曲线图。
具体实施方式
给出以下实施例以举例说明本发明，这些实施例并非限制性的。
实施例1
以某玻璃厂用于冶炼硅石的燃煤锅炉所排出的燃烧尾气为例。
燃烧尾气经过除尘和脱硫处理后，含有1500ppm NOx、16.5％CO 2、8％O 2、11.5％H 2O、余量为N 2。取该燃烧尾气样品进行实验，分子筛吸附材料用量为0.589g、总气体流量900mL/min、吸附温度为100℃，空速11,000h -1。所使用的吸附剂为Ce/Beta表示Ce负载在Beta分子筛上，以下其余各吸附剂的组成表示方法与此类似)，其中Ce的百分比含量为2wt％，NOx吸附结果如图2所示，其中经过41秒左右达到吸附饱和，NOx的饱和吸附量达到32.8μmol/g吸附剂。
吸附饱和后，停止通入该燃烧尾气，并改向吸附剂中通入空气并进行程序升温脱附实验，结果如图3所示，可见当空气温度升高到230℃时，NOx开始从吸附剂上脱附，并在约285℃时脱附的NOx瞬时浓度达到最大。
详细吸附和脱附结果列于下表1中。
工业上，脱附后，将高温空气通入该燃煤锅炉的燃烧室中作为助燃空气，使得所脱附的NOx作为助燃剂。
实施例2
以某水泥厂的燃煤锅炉所排出的燃烧尾气为例。
燃烧尾气经过除尘和脱硫处理后，含有1000ppm NOx、12.5％CO 2、9.2％O 2、6％H 2O、余量为N 2。取该燃烧尾气样品进行实验，分子筛吸附材料用量为0.288g、总气体流量1000mL/min、吸附温度为150℃，空速25,000h -1。所使用的吸附剂为La/Beta，其中La的百分比含量为5wt％，NOx吸附结果如图4所示，其中经过34秒左右达到吸附饱和，NOx的饱和吸附量达到33.4μmol/g吸附剂。
吸附饱和后，停止通入该燃烧尾气，并改向吸附剂中通入空气并进行程序升温脱附实验，结果如图5所示，可见当空气温度升高到220℃时，NOx开始从吸附剂上脱附，并在约280℃时脱附的NOx瞬时浓度达到最大。
详细吸附和脱附结果列于下表1中。
工业上，脱附后，将高温空气通入该燃煤锅炉的燃烧室中作为助燃空气，使得所脱附的NOx作为助燃剂。
实施例3
以某动力电厂的燃气锅炉所排出的燃烧尾气为例。
燃烧尾气经过除尘和脱硫处理后，含有500ppm NOx、5％CO 2、8％O 2、5％H 2O、余量为N 2。取该燃烧尾气样品进行实验，分子筛吸附材料用量为0.144g、总气体流量1000mL/min、吸附温度为80℃，空速50,000h -1。所使用的吸附剂为Cu/ZSM-5，其中Cu的百分比含量为10wt％，NOx吸附结果如图6所示，其中经过47秒左右达到吸附饱和，NOx的饱和吸附量达到33.6μmol/g吸附剂。
吸附饱和后，停止通入该燃烧尾气，并改向吸附剂中通入空气并进行程序升温脱附实验，结果如图7所示，可见当空气温度升高到220℃时，NOx开始从吸附剂上脱附，并在约280℃时脱附的NOx瞬时浓度达到最大。
详细吸附和脱附结果列于下表1中。
工业上，脱附后，将高温空气通入该燃气锅炉的燃烧室中作为助燃空气，使得所脱附的NOx作为助燃剂。
实施例4
以某汽车燃油发动机所排出的燃烧尾气为例。
燃烧尾气经过除尘和脱硫处理后，含有200ppm NOx、5％CO 2、10％O 2、5％H 2O、余量为N 2。取该燃烧尾气样品进行实验，分子筛吸附材料用量为0.144g、总气体流量1000mL/min、吸附温度为80℃，空速50,000h -1。所使用的吸附剂为Co/SSZ-13，其中Co的百分比含量为20wt％，NOx吸附结果如图8所示，其中经过121秒左右达到吸附饱和，NOx的饱和吸附量达到29.8μmol/g吸附剂。
吸附饱和后，停止通入该燃烧尾气，并改向吸附剂中通入空气并进行程序升温脱附实验，结果如图9所示，可见当空气温度升高到230℃时，NOx开始从吸附剂上脱附，并在约283℃时脱附的NOx瞬时浓度达到最大。
详细吸附和脱附结果列于下表1中。
工业上，脱附后，将高温空气通入燃油发动机燃烧室中作为助燃空气，使得所脱附的NOx作为助燃剂。
实施例5
以某玻璃厂用于冶炼硅石的燃煤锅炉所排出的燃烧尾气为例。
燃烧尾气经过除尘和脱硫处理后，含有1500ppm NOx、16.5％CO 2、8％O 2、11.5％H 2O、余量为N 2。取该燃烧尾气样品进行实验，分子筛吸附材料用量为0.589g、总气体流量900mL/min、吸附温度为50℃，空速11,000h -1。所使用的吸附剂为PdCe/Beta表示Pd和Ce负载在Beta分子筛上，以下其余各吸附剂的组成表示方法与此类似)，其中Pd的百分比含量为0.1wt％，Ce的百分比含量为2wt％，NOx吸附结果如图10所示，其中经过42秒左右达到吸附饱和，NOx的饱和吸附量达到40.4μmol/g吸附剂。
吸附饱和后，停止通入该燃烧尾气，并改向吸附剂中通入空气并进行程序升温脱附实验，结果如图11所示，可见当空气温度升高到220℃时，NOx开始从吸附剂上脱附，并在约285℃时脱附的NOx瞬时浓度达到最大。
详细吸附和脱附结果列于下表1中。
工业上，脱附后，将高温空气通入该燃煤锅炉的燃烧室中作为助燃空气，使得所脱附的NOx作为助燃剂。
表1
Figure PCTCN2019070792-appb-000001

Claims (8)

  1. 一种消除并回收利用燃烧尾气中的氮氧化物的方法，其特征在于，包括以下步骤：
    A、使包含氮氧化物的燃烧尾气与吸附剂在小于150℃的温度下接触以吸附其中的氮氧化物；其中所述吸附剂包括负载在分子筛载体上的活性组分，所述活性组分选自贵金属、稀土金属或过渡金属，且以单质含量计，该活性组分占吸附剂总质量的0.1-20wt％；然后，
    B、向该吸附剂中通入大于250℃的高温空气使所吸附的氮氧化物解吸并随该高温空气送入燃烧室作为助燃空气。
  2. 根据权利要求1所述的方法，其特征在于，所述活性组分选自银、铂、铑、钯、钇、镧、铈、镨、钕、锰、铁、钴、镍或铜；所述分子筛载体选自BEA、MFI或CHA型分子筛。
  3. 根据权利要求1所述的方法，其特征在于，步骤A中使氮氧化物达到吸附饱和/或近饱和。
  4. 根据权利要求4所述的方法，其特征在于，步骤A中的吸附温度为50-150℃，吸附过程小于30秒。
  5. 根据权利要求1所述的方法，其特征在于，其特征在于，在步骤A之前还包括使燃烧尾气经过余热回收装置降温的步骤。
  6. 根据权利要求7所述的方法，其特征在于，余热回收装置中的冷却介质为空气，该空气被燃烧尾气的余热加热后被用作步骤B中的高温空气。
  7. 根据权利要求1所述的方法，其特征在于，设置至少两套氮氧化物吸附装置，其中第一套执行步骤A时第二套执行步骤B，第一套执行步骤B时第二套执行步骤A，从而实现连续消除并回收利用燃烧尾气中的氮氧化物。
  8. 根据权利要求1所述的方法，其特征在于，所述分子筛孔径范围0.1nm-1nm，比表面积为500-1000m 2/g。
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