WO2021082307A1 - 一种烟气低温吸附脱硝系统及工艺 - Google Patents

一种烟气低温吸附脱硝系统及工艺 Download PDF

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WO2021082307A1
WO2021082307A1 PCT/CN2020/076850 CN2020076850W WO2021082307A1 WO 2021082307 A1 WO2021082307 A1 WO 2021082307A1 CN 2020076850 W CN2020076850 W CN 2020076850W WO 2021082307 A1 WO2021082307 A1 WO 2021082307A1
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flue gas
denitration
adsorption
adsorption tower
temperature
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PCT/CN2020/076850
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English (en)
French (fr)
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汪世清
樊启祥
许世森
郜时旺
王绍民
赵贺
蒋敏华
肖平
黄斌
牛红伟
王金意
刘练波
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中国华能集团清洁能源技术研究院有限公司
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Priority to JP2021600043U priority Critical patent/JP3241400U/ja
Priority to GB2103479.8A priority patent/GB2595553B/en
Priority to DE112020000100.8T priority patent/DE112020000100B4/de
Priority to AU2020344001A priority patent/AU2020344001A1/en
Priority to DE212020000449.8U priority patent/DE212020000449U1/de
Priority to US17/239,662 priority patent/US20210245096A1/en
Publication of WO2021082307A1 publication Critical patent/WO2021082307A1/zh
Priority to AU2022271506A priority patent/AU2022271506A1/en

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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
    • B01D53/04—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 with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • 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
    • B01D53/002—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 condensation
    • 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
    • B01D53/04—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 with stationary adsorbents
    • B01D53/0462—Temperature swing adsorption
    • 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
    • B01D53/04—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 with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B01D53/0476—Vacuum pressure swing adsorption
    • 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
    • B01D53/26—Drying gases or vapours
    • B01D53/265—Drying gases or vapours by refrigeration (condensation)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • B01D2259/40003—Methods relating to valve switching
    • 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
    • B01D2259/40094—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating by applying microwaves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/65—Employing advanced heat integration, e.g. Pinch technology

Definitions

  • the invention belongs to the technical field of flue gas denitration, and specifically relates to a flue gas low-temperature adsorption denitration system and process.
  • the flue gas produced by burning coal contains a large amount of nitrogen oxides NOx, which is one of the main causes of air pollution.
  • NOx in flue gas is mainly removed by the SCR selective catalytic reduction method.
  • NOx is reduced to harmless N 2 by NH 3 added to the flue gas under the action of a catalyst.
  • the SCR denitration technology is quite mature, there are still many problems.
  • the catalyst only has high activity in a specific temperature range. When the operating load of the power plant is adjusted, the change of the flue gas temperature will seriously affect the SCR denitration efficiency.
  • SCR denitrification has secondary pollution problems such as ammonia escape and solid waste of catalysts, and the denitrification catalyst ages and wears quickly, resulting in high operating costs.
  • SCR selective reduction method there are also wet denitrification technologies, but they all need to first oxidize the insoluble NO gas in NOx into soluble NO 2 acid gas, and then remove it through alkaline liquid absorption.
  • Common pre-oxidation methods include ozone method, hydrogen peroxide method, catalyst oxidation method, low-temperature plasma oxidation method and so on.
  • the ozone method and the hydrogen peroxide method require additional consumption of strong oxidants, high operating costs and easy to cause secondary pollution emissions; the catalyst oxidation method requires practical and expensive precious metal catalysts, and it is difficult to industrially apply; the low-temperature plasma oxidation method consumes high electricity, which also leads to Resulting in higher operating costs.
  • the present invention provides a flue gas low-temperature adsorption denitrification system and process, which can not only adsorb and remove the easily adsorbable component NO 2 in NOx, but also can effectively adsorb the difficult-to-adsorb component NO , To reduce the cost of denitration, and no secondary pollution.
  • the technical solution adopted by the present invention is a flue gas low-temperature adsorption denitration system, including a booster fan, a cold recovery device, a flue gas cooling system, a flue gas switching valve, a first denitration adsorption tower, and a second Denitrification adsorption tower;
  • the inlet of the booster fan is connected with the inlet flue gas pipeline
  • the outlet of the booster fan is connected with the hot side inlet of the cold energy recovery device
  • the hot side outlet of the cold energy recovery device is connected with the inlet of the flue gas cooling system
  • the flue gas outlet of the flue gas cooling system Connected with the inlet of the flue gas switching valve, the outlets of the flue gas switching valve are respectively connected to the flue gas inlets of the first denitrification adsorption tower and the second denitrification adsorption tower, and a flue gas confluence is provided on the flue gas pipeline leading to the cold recovery device.
  • the flue gas outlets of the first denitrification adsorption tower and the second denitrification adsorption tower are connected with the inlet of the flue gas combiner, and the outlet of the flue gas combiner is connected with the cold side inlet of the cold capacity recovery device.
  • the flue gas cooling system includes a primary cooling system and a secondary cooling system.
  • the primary cooling system adopts air cooling system, heat exchanger cooling system or water cooling system
  • the secondary cooling system adopts compression refrigeration system or absorption refrigeration system, and flue gas cooling
  • the system is provided with a flue gas condensed water outlet, and the flue gas condensed water outlet is connected to the water inlet of the reclaimed water treatment system.
  • the denitrification adsorption tower adopts a fixed-bed adsorption tower, and the fixed bed is filled with NOx adsorption material.
  • the NOx adsorption material uses activated carbon or molecular sieve.
  • the outside of the adsorption tower adopts a cold box structure.
  • the flue gas switching valve adopts an electric or pneumatic switching valve; the input end of the controller of the flue gas switching valve is connected to the output end of the DCS in the factory.
  • the cold recovery device uses a flue gas heat exchanger.
  • a low-temperature flue gas denitrification process After the flue gas for dust removal and desulfurization is pressurized, it is pre-cooled and then cooled to below room temperature.
  • the flue gas with a temperature lower than room temperature enters the denitrification adsorption tower and performs physical adsorption denitrification in the denitrification adsorption tower ,
  • the flue gas after denitration is used to pre-cool the flue gas after dust removal and desulfurization, and the net flue gas that absorbs heat enters the chimney for emission.
  • the system of claim 1 is used for denitration, the flue gas after dust removal and desulfurization enters the fan for pressurization and then enters the cold recovery device and the denitrified low-temperature net flue gas heat exchanges to achieve pre-cooling, and the pre-cooled flue gas enters the flue gas
  • the cooling system performs cooling to obtain cooled flue gas with a temperature lower than room temperature.
  • the cooled flue gas passes through the flue gas switching valve and enters the first denitrification adsorption tower or the second denitrification adsorption tower, the first denitrification adsorption tower or the second denitrification adsorption tower
  • the adsorption tower performs adsorption denitrification and regeneration processes in turn.
  • the net flue gas after adsorption and denitrification enters the flue gas combiner, and then enters the cold recovery device for cold recovery, and the net flue gas after the temperature rises enters the chimney for discharge.
  • the flue gas cooling system adopts circulating cooling water heat exchange cooling or spray cooling to perform primary cooling of the flue gas, and adopts compression refrigeration or absorption refrigeration to perform secondary cooling of the flue gas after the primary cooling.
  • the present invention has at least the following beneficial effects: the low-temperature flue gas adsorption and denitration system of the present invention is equipped with a flue gas cold recovery device, which can use low-temperature clean flue gas to achieve pre-cooling of the flue gas after desulfurization, which can improve The cold capacity of the system is used and it is conducive to the rapid discharge of net flue gas.
  • Two denitrification adsorption towers are set to alternately perform denitration and regeneration processes, which can realize the continuous denitration operation of the system, with high denitrification efficiency, and the adsorption material is recycled after desorption; the denitration system is set up At the back end of the dust removal and desulfurization section, denitrification is performed after the flue gas is reduced to below room temperature.
  • the equipment at the back end of the flue gas cooling system does not need to use high-temperature equipment, which can reduce costs.
  • Figure 1 is a schematic diagram of the process of the present invention.
  • a low-temperature flue gas adsorption denitration system including a booster fan 1, a cold recovery device 2, a flue gas cooling system 3, a flue gas switching valve 4, a first denitration adsorption tower 5, and a second denitration adsorption tower 6 ;
  • the inlet of the booster fan 1 is connected with the inlet flue gas pipeline
  • the outlet of the booster fan 1 is connected with the inlet of the hot side of the cold recovery device 2
  • the outlet of the hot side of the cold recovery device 2 is connected with the inlet of the flue gas cooling system 3, and the flue gas
  • the flue gas outlet of the cooling system 3 is connected to the inlet of the flue gas switching valve 4, and the outlet of the flue gas switching valve 4 is respectively connected to the flue gas inlets of the first denitrification adsorption tower 5 and the second denitrification adsorption tower 6, leading to the cold energy recovery device 2
  • a flue gas combiner 7 is provided on the flue gas pipe of the, the flue
  • the flue gas cooling system 3 includes a primary cooling system and a secondary cooling system.
  • the primary cooling system adopts an air cooling system, a heat exchanger cooling system or a water cooling system
  • the secondary cooling system adopts a compression refrigeration system or an absorption refrigeration system.
  • the cooling system 3 is provided with a flue gas condensed water outlet, and the flue gas condensed water outlet is connected to the water inlet of the reclaimed water treatment system.
  • the denitrification adsorption tower adopts a fixed-bed adsorption tower, and the fixed bed is filled with NOx adsorption material; the NOx adsorption material uses activated carbon or molecular sieve.
  • the outside of the adsorption tower adopts a cold box structure; the cold energy recovery unit 2 adopts a flue gas heat exchanger.
  • the flue gas switching valve 4 adopts an electric or pneumatic switching valve; the input end of the controller of the flue gas switching valve 4 is connected to the output end of the DCS of the factory.
  • a low-temperature flue gas denitrification process After the flue gas for dust removal and desulfurization is pressurized, it is pre-cooled and then cooled to below room temperature.
  • the flue gas with a temperature lower than room temperature enters the denitrification adsorption tower and performs physical adsorption denitrification in the denitrification adsorption tower ,
  • the flue gas after denitration is used to pre-cool the flue gas after dust removal and desulfurization, and the net flue gas that absorbs heat enters the chimney for emission.
  • the system described in claim 1 is used for denitration.
  • the flue gas after dust removal and desulfurization enters the fan 1 after being pressurized and then enters the cold recovery unit 2 to exchange heat with the denitrified low-temperature net flue gas to achieve pre-cooling, and the pre-cooled flue gas enters
  • the flue gas cooling system 3 performs cooling to obtain cooled flue gas with a temperature lower than room temperature.
  • the cooled flue gas passes through the flue gas switching valve 4 and enters the first denitrification adsorption tower 5 or the second denitrification adsorption tower 6, and the first denitrification
  • the adsorption tower 5 or the second denitration adsorption tower 6 performs adsorption denitration and regeneration processes in turn.
  • the net flue gas after adsorption and denitration enters the flue gas combiner 7, and then enters the cold energy recovery unit 2 for cold energy recovery.
  • the flue gas enters the chimney and is discharged.
  • the flue gas cooling system 3 adopts circulating cooling water heat exchange cooling or spray cooling to perform primary cooling of the flue gas, and adopts compression refrigeration or absorption refrigeration to perform secondary cooling of the flue gas after the primary cooling.
  • the adsorption and denitration mechanism of the process of the present invention is as follows:
  • NO 2 is a gas that is easily adsorbed.
  • NO 2 is directly adsorbed and removed.
  • NO is a gas that is extremely difficult to adsorb, and the flue gas is flowing through activated carbon, molecular sieve or other
  • steps (2) and (3) are carried out at the same time, and the overall performance is the low-temperature adsorption and removal of NO.
  • Flue gas cooling step (1) to achieve the necessary enrichment of NO and O 2 oxidation conditions, since O 2 and NO and other difficult-condensable gas only easily adsorbed on the adsorbent enriched surface is formed at a low temperature.
  • Both NO and NO 2 in NOx are adsorbed on the surface of porous materials in the form of NO 2 ; the porous materials desorb the adsorbed NO 2 by heating, depressurizing and microwave regeneration methods to restore the adsorption performance and recycle; The desorbed NO 2 can be recycled to make nitric acid or nitrogen fertilizer.
  • the low-temperature flue gas adsorption denitration system of the present invention includes a booster fan 1, a cold recovery device 2, a flue gas cooling system 3, a flue gas switching valve 4, a first denitration adsorption tower 5 and a second denitration adsorption tower 6;
  • the compressor 1 is used to overcome the flue gas resistance generated by the system and increase the flue gas pressure;
  • the cold energy recovery device 2 includes a gas-air or gas-liquid indirect heat exchanger, and the cold energy recovery device can also use a direct spray packing tower Or a plate tower, used to recover the net flue gas cold after low-temperature denitration, and at the same time to pre-cool the inlet flue gas;
  • the flue gas switching valve 4 automatically switches the flue gas flow to the first denitration adsorption tower 5 or the second denitration adsorption tower 6 according to the set switching conditions.
  • the first denitration adsorption tower 5 and the second denitration adsorption tower 6 are fixed-bed adsorption towers filled with adsorption materials such as activated carbon, molecular sieve, activated coke, silica gel, and activated alumina.
  • the adsorption tower adopts a cold box structure to reduce the heat dissipation loss of low-temperature flue gas.
  • the two adsorption towers are switched periodically to maintain the continuous operation of flue gas adsorption and denitrification.
  • the flue gas confluencer 7 is used to merge the flue gas flowing out of the denitration adsorption tower into the net flue gas pipeline for discharge.
  • the inlet of the booster fan 1 is connected to the inlet flue gas pipeline, the outlet of the booster fan 1 is connected to the hot side inlet of the cold energy recovery device 2, the hot side outlet of the cold energy recovery device 2 is connected to the inlet of the flue gas cooling system 3, the flue gas cooling system 3
  • the flue gas outlet is connected to the inlet of the flue gas switching valve 4, the outlet of the flue gas switching valve 4 is connected to the flue gas inlets of the denitrification adsorption towers 5 and 6 respectively, and the flue gas outlets of the denitrification adsorption towers 5 and 6 are connected to the flue gas manifold 7 inlet ,
  • the outlet of the flue gas confluencer 7 is connected with the cold side inlet of the refrigeration recovery device 2, and the cold side outlet of the refrigeration recovery device 2 is connected with the pipe going to the chimney of the power plant.
  • the boiler flue gas without denitrification undergoes dust removal and desulfurization, and heat recovery through the air preheater, it is introduced into the system of the present invention by the fan 1.
  • the high-temperature flue gas after being pressurized by the fan 1 passes through the cold recovery device 2, and exchanges heat with the low-temperature net flue gas after denitration, and recovers the cold energy of the low-temperature flue gas; the flue gas after being pre-cooled by the cold energy recovery device 2 enters
  • the flue gas cooling system 3 cools the flue gas to below room temperature by circulating cooling water cooling, industrial chiller cooling and other multi-stage cooling methods, and separates the condensed water from the flue gas.
  • the flue gas after cooling and dehumidification passes through the flue gas switching valve 4 and is introduced into the first denitration adsorption tower 5 or the second denitration adsorption tower 6, and the two adsorption towers perform adsorption and regeneration operations in turn to achieve continuous flue gas denitration.
  • the net flue gas after adsorption and denitration passes through the flue gas confluencer 7 and enters the cold recovery unit 2 for cold measurement for cold recovery, and at the same time, the inlet flue gas is pre-cooled.
  • the net flue gas after the cold energy recovery is discharged from the cold energy recovery device 2 and enters the power plant chimney.
  • the flue gas of a 600MW coal-fired or gas-fired unit enters the system of the present invention; after the flue gas is pressurized by the booster fan 1, it enters the cold recovery unit 2, and exchanges heat with the low-temperature net flue gas at 2°C , The temperature is reduced from 50°C to 35°C; the flue gas passes through the flue gas cooling system 3 and is further cooled to 2°C by the low-temperature water chiller, and the flue gas condensate is discharged from the flue gas cooling system; the cooled flue gas passes through the flue gas switching valve 4.
  • the net flue gas after adsorption and denitrification passes through the flue gas combiner 7, and enters the cold recovery unit 2 for cold measurement.
  • the temperature rises to 30°C, and the exhaust Into the chimney; among them, the first denitrification adsorption tower 5 is switched to the second denitrification adsorption tower 6 for adsorption denitrification after 8 hours of adsorption; the first denitrification adsorption tower 5 is switched to the heating regeneration mode to desorb the adsorbed NOx, and the first denitrification
  • the adsorption tower 5 is regenerated for 4 hours, cooled for 4 hours, and then switched to the adsorption mode again.
  • the second denitration adsorption tower 6 is switched to the regeneration mode, and the cycle is like this to realize continuous adsorption and denitration.
  • the first denitration adsorption tower 5 and the second nitrate 6 are each loaded activated carbon adsorption tower 500 tons; desorbed NOx to NO 2 so as to present, can be made by a dilute nitric acid process, or ammonia absorption by recycling production of ammonium nitrate (nitrogen).

Abstract

一种烟气低温吸附脱硝系统，包括增压风机（1）、冷量回收器（2）、烟气冷却系统（3）、烟气切换阀（4）以及脱硝吸附塔（5、6）；其中，增压风机（1）入口与入口烟气管道连通，增压风机（1）、冷量回收器（2）、烟气冷却系统（3）、烟气切换阀（4）以及脱硝吸附塔（5、6）依次连通，烟气切换阀（4）的出口分别连通第一脱硝吸附塔（5）和第二脱硝吸附塔（6），第一脱硝吸附塔（5）和第二脱硝吸附塔（6）的烟气出口与烟气汇流器（7）连通，烟气汇流器（7）连通冷量回收器（2）。一种烟气低温脱硝工艺，经过除尘和脱硫的烟气加压后，进行预冷，再冷却至室温以下，温度低于室温的烟气进入脱硝吸附塔，在脱硝吸附塔中进行物理吸附脱硝，用脱硝后的烟气对经过除尘和脱硫后的烟气进行预冷，吸收热量的净烟气进入烟囱进行排放。

Description

一种烟气低温吸附脱硝系统及工艺 技术领域
本发明属于烟气脱硝技术领域，具体涉及一种烟气低温吸附脱硝系统及工艺。
背景技术
燃煤产生的烟气中含有大量的氮氧化物NOx，是造成大气污染的主要成因之一。目前，烟气中的NOx主要通过SCR选择性催化还原法进行脱除，该方法通过在催化剂的作用下，NOx被加入烟道气的NH 3还原成无害的N 2，进而脱除。SCR脱硝技术虽然目前已相当成熟，但依旧存在诸多问题。例如催化剂只在特定温度区间具备较高活性，当电厂运行负荷调整时，烟气温度的变化会严重影响SCR脱硝效率。另外，SCR脱硝存在氨逃逸、催化剂固废等二次污染问题，而且脱硝催化剂的老化和损耗也很快，造成运行成本居高不下。除了SCR选择性还原法外，也有湿法脱硝技术，但都需要先将NOx中难溶的NO气体氧化成可溶的NO 2酸性气体，然后通过碱性液体吸收脱除。常见的前置氧化法有臭氧法、双氧水法、催化剂氧化法、低温等离子体氧化法等。臭氧法和双氧水法需要额外消耗强氧化剂，运行成本高且容易造成二次污染排放；催化剂氧化法需要实用价格昂贵的贵金属催化剂，也难以工业化应用；低温等离子体氧化法电耗较高，也导致了较高的运行成本。
发明内容
为了解决了现有技术中存在的问题，本发明提一种烟气低温吸附脱硝系统及工艺，不仅能够吸附脱除NOx中易吸附的组分NO 2，也能有效吸附难吸附的组分NO，降低脱硝成本，不带来二次污染。
为了实现上述目的，本发明采用的技术方案是，一种烟气低温吸附脱硝系统，包括增压风机、冷量回收器、烟气冷却系统、烟气切换阀、第一脱硝吸附塔以及第二脱硝吸附塔；
其中，增压风机入口与入口烟气管道连通，增压风机出口与冷量回收器热侧入口连通，冷量回收器热侧出口与烟气冷却系统入口连通，烟气冷却系统的烟气出口与烟气切换阀入口连通，烟气切换阀的出口分别连通第一脱硝吸附塔和第二脱硝吸附塔的烟气入口，通向冷量回收器的烟气管道上设置烟气汇流器，第一脱硝吸附塔和第二脱硝吸附塔的烟气出口与烟气汇流器的入口连通，烟气汇流器的出口连通冷量回收器的冷侧入口。
烟气冷却系统包括一级冷却系统和二级冷却系统，其中一级冷却系统采用空冷系统、换热器冷却系统或水冷系统，二级冷却系统采用压缩制冷系统或吸收式制冷系统，烟气冷却系统设置有烟气冷凝水出口，所述烟气冷凝水出口连通中水处理系统的进水口。
脱硝吸附塔采用固定床式吸附塔，其固定床中填充有NOx吸附材料。
NOx吸附材料采用活性炭或分子筛。
吸附塔外侧采用冷箱结构。
烟气切换阀采用电动或气动切换阀；烟气切换阀的控制器的输入端连接厂区DCS的输出端。
冷量回收器采用烟气换热器。
一种烟气低温脱硝工艺，经过除尘和脱硫的烟气加压后，进行预冷，再冷却至室温以下，温度低于室温的烟气进入脱硝吸附塔，在脱硝吸附塔中进行物理吸附脱硝，用脱硝后的烟气对经过除尘和脱硫后的烟气进行预冷，吸收热量的净烟气进入烟囱进行排放。
采用权利要求1所述系统进行脱硝，经过除尘和脱硫的烟气进入风机增压后进入冷量回收器与脱硝后的低温净烟气换热实现预冷，预冷后的烟气进入烟气冷却系统进行冷却，得到温度低于室温的冷却后烟气，所述冷却后烟气经过烟气切换阀，进入第一脱硝吸附塔或第二脱硝吸附塔，第一脱硝吸附塔或第二脱硝吸附塔轮流进行吸附脱硝和再生流程，经吸附脱硝 后的净烟气进入烟气汇流器，再进入冷量回收器中进行冷量回收，升温后的净烟气进入烟囱排放。
烟气冷却系统中采用循环冷却水换热冷却或喷淋冷却方式对烟气进行一级冷却，采用压缩制冷或吸收式制冷方式对一级冷却后的烟气进行二级冷却。
与现有技术相比，本发明至少具有以下有益效果：本发明的烟气低温吸附脱硝系统设置烟气冷量回收器能采用低温净烟气实现对脱硫后的烟气进行预冷，能提高系统冷量利用，而且有利于净烟气的快速排放，设置两个脱硝吸附塔轮流进行脱硝和再生过程，能实现本系统连续脱硝作业，脱硝效率高，吸附材料解吸后循环利用；脱硝系统设置在除尘和脱硫工段后端，在烟气降低至室温以下后进行脱硝，烟气冷却系统后端的设备无需采用耐高温设备，能降低成本。
采用物理吸附脱硝，同时直接吸附脱除NO 2和NO，不需要前置氧化NO；脱硝效率高，能实现NOx零排放；吸附的NOx以NO 2的形态解吸出来，收集后可以用于制取硝酸或氮肥等高附加值副产品；烟气降温过程中析出大量酸性冷凝水，经中和处理后可供电厂使用，降低电厂耗水量；该工艺采用物理方法脱硝，不需要使用脱硝催化剂、还原剂或氧化剂等化学物品，降低了运行成本，减少了氨逃逸等二次污染排放，而且能实现水资源回收利用。
附图说明
图1为本发明所述工艺示意图。
1-增压风机，2-冷量回收器，3-烟气冷却系统，4-烟气切换阀，5-第一脱硝吸附塔，6-第二脱硝吸附塔，7-烟气汇流器
说明书附图用来提供对本发明的进一步理解，构成本发明的一部分，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。
具体实施方式
为清楚说明本发明，下面结合实施例及附图，对本发明进行进一步详细说明。本领域技术人员了解，下述内容不是对本发明保护范围的限制，任何在本发明基础上做出的改进和变化，都在本发明的保护范围之内。
参考图1，一种烟气低温吸附脱硝系统，包括增压风机1、冷量回收器2、烟气冷却系统3、烟气切换阀4、第一脱硝吸附塔5以及第二脱硝吸附塔6；其中，增压风机1入口与入口烟气管道连通，增压风机1出口与冷量回收器2热侧入口连通，冷量回收器2热侧出口与烟气冷却系统3入口连通，烟气冷却系统3的烟气出口与烟气切换阀4入口连通，烟气切换阀4的出口分别连通第一脱硝吸附塔5和第二脱硝吸附塔6的烟气入口，通向冷量回收器2的烟气管道上设置烟气汇流器7，第一脱硝吸附塔5和第二脱硝吸附塔6的烟气出口与烟气汇流器7的入口连通，烟气汇流器7的出口连通冷量回收器2的冷侧入口。
烟气冷却系统3包括一级冷却系统和二级冷却系统，其中一级冷却系统采用空冷系统、换热器冷却系统或水冷系统，二级冷却系统采用压缩制冷系统或吸收式制冷系统，烟气冷却系统3设置有烟气冷凝水出口，所述烟气冷凝水出口连通中水处理系统的进水口。
脱硝吸附塔采用固定床式吸附塔，其固定床中填充有NOx吸附材料；NOx吸附材料采用活性炭或分子筛。
吸附塔外侧采用冷箱结构；冷量回收器2采用烟气换热器。
烟气切换阀4采用电动或气动切换阀；烟气切换阀4的控制器的输入端连接厂区DCS的输出端。
一种烟气低温脱硝工艺，经过除尘和脱硫的烟气加压后，进行预冷，再冷却至室温以下，温度低于室温的烟气进入脱硝吸附塔，在脱硝吸附塔中进行物理吸附脱硝，用脱硝后的烟气对经过除尘和脱硫后的烟气进行预冷，吸收热量的净烟气进入烟囱进行排放。
采用权利要求1所述系统进行脱硝，经过除尘和脱硫的烟气进入风机1增压后进入冷量回收器2与脱硝后的低温净烟气换热实现预冷，预冷后的烟气进入烟气冷却系统3进行冷却，得到温度低于室温的冷却后烟气，所述冷却后烟气经过烟气切换阀4，进入第一脱硝吸附塔5或第二脱硝吸附塔6，第一脱硝吸附塔5或第二脱硝吸附塔6轮流进行吸附脱硝和再生流程，经吸附脱硝后的净烟气进入烟气汇流器7，再进入冷量回收器2中进行冷量回收，升温后的净烟气进入烟囱排放。
烟气冷却系统3中采用循环冷却水换热冷却或喷淋冷却方式对烟气进行一级冷却，采用压缩制冷或吸收式制冷方式对一级冷却后的烟气进行二级冷却。
本发明所述烟气低温吸附脱硝系统及工艺的具体实施方式如下：
本发明所述工艺吸附脱硝的机理如下：
1、NOx中NO 2的吸附脱除：NO 2是易吸附的气体，烟气在流经活性炭、分子筛或其它多孔吸附材料表面时，NO 2被直接吸附脱除。
2、NOx中NO的吸附脱除：NO是极难吸附的气体，烟气在流经活性炭、分子筛或其它
多孔吸附材料表面时，NO不能被直接吸附脱除，而是通过以下步骤实现的：
(1)烟气通过冷却降温，降至室温以下；
(2)低温烟气中NO的O 2在流经多孔吸附材料表面时富集在表面，大幅度提高NO和O 2的浓度，从而迅速将NO氧化成NO 2；
(3)氧化后的NO 2吸附在多孔材料表面。
其中步骤(2)和(3)是同时进行的，整体表现出来的是NO的低温吸附脱除。烟气降温步骤(1)是实现NO和O 2富集氧化的必要条件，因为NO和O 2等难凝气体只有在低温下才容易在吸附剂表面吸附形成富集。
NOx的再生：NOx中的NO和NO 2均是以NO 2的形态吸附在多孔材料表面的；多孔材料 经升温、降压及微波再生方式解吸出吸附的NO 2，恢复吸附性能，循环使用；解吸出的NO 2则可回收用于制作硝酸或氮肥。
本发明所述烟气低温吸附脱硝系统，包括增压风机1、冷量回收器2、烟气冷却系统3、烟气切换阀4、第一脱硝吸附塔5和第二脱硝吸附塔6；增压风机1用于克服系统产生的烟气阻力，提高烟气压力；冷量回收器2包括气-气或气-液间接式换热器，冷量回收器还可以使用直接喷淋式填料塔或板式塔，用于回收低温脱硝后的净烟气冷量，同时对入口烟气进行预冷；
烟气切换阀4根据设定的切换条件，自动切换烟气流向第一脱硝吸附塔5或第二脱硝吸附塔6。
第一脱硝吸附塔5和第二脱硝吸附塔6为固定床式吸附塔，填充活性炭、分子筛、活性焦、硅胶、活性氧化铝等吸附材料。吸附塔采用冷箱结构，减少低温烟气散热损失。两个吸附塔周期性切换，维持烟气吸附脱硝的连续运行。
烟气汇流器7用于将脱硝吸附塔流出的烟气汇入净烟气管道排出。
增压风机1入口与入口烟气管道相连，增压风机1出口与冷量回收器2热侧入口相连，冷量回收器2热侧出口与烟气冷却系统3入口相连，烟气冷却系统3烟气出口与烟气切换阀4入口相连，烟气切换阀4出口分别与脱硝吸附塔5和6的烟气入口相连，脱硝吸附塔5和6的烟气出口与烟气汇流器7入口相连，烟气汇流器7出口与冷量回收器2冷侧入口相连，冷量回收器2冷侧出口与去电厂烟囱的管道相连。
本发明所述工艺流程如下：
未经脱硝的锅炉烟气经过除尘和脱硫，并经过空预器回收热量后，由风机1引入本发明所述系统。经过风机1增压后的高温烟气流经冷量回收器2，与脱硝后的低温净烟气换热，回收低温烟气冷量；经过冷量回收器2预冷后的烟气进入到烟气冷却系统3，通过循环冷却水冷却、工业冷水机组冷却等多级冷却方式，将烟气冷却至室温以下，并将冷凝水从烟气中分离 出来。经过冷却除湿后的烟气经过烟气切换阀4，导入第一脱硝吸附塔5或第二脱硝吸附塔6，两个吸附塔轮流进行吸附和再生操作，实现烟气连续脱硝。吸附脱硝后的净烟气经过烟气汇流器7进入到冷量回收器2冷测进行冷量回收，同时对入口烟气进行预冷。经冷量回收后的净烟气从冷量回收器2排出，进入到电厂烟囱。
600MW燃煤或燃气机组的烟气经过除尘和脱硫后，进入本发明所述系统；烟气经增压风机1增压后，进入冷量回收器2，与2℃的低温净烟气换热，温度由50℃降至35℃；烟气通过烟气冷却系统3，由低温冷水机组进一步冷却至2℃，烟气冷凝水由烟气冷却系统排出；冷却后的烟气经过烟气切换阀4，进入到脱硝吸附塔5，经过吸附脱硝后的净烟气流经烟气汇流器7，进入到冷量回收器2冷测，与脱硫后烟气换热后温度升至30℃，排入烟囱；其中，第一脱硝吸附塔5吸附8小时候后，切换至第二脱硝吸附塔6进行吸附脱硝；第一脱硝吸附塔5则切换至加热再生模式，解吸出吸附的NOx，第一脱硝吸附塔5进行再生4小时，冷却4小时，然后重新切换至吸附模式，同时，第二脱硝吸附塔6切换至再生模式，如此循环，实现连续吸附脱硝，第一脱硝吸附塔5和第二硝吸附塔6各装填活性炭500吨；解吸出的NOx以NO 2的方式存在，可通过制酸工艺制成稀硝酸，或者通过氨水吸收生产硝酸铵(氮肥)进行回收利用。

Claims (10)

  1. 一种烟气低温吸附脱硝系统，其特征在于，包括增压风机(1)、冷量回收器(2)、烟气冷却系统(3)、烟气切换阀(4)、第一脱硝吸附塔(5)以及第二脱硝吸附塔(6)；
    其中，增压风机(1)入口与入口烟气管道连通，增压风机(1)出口与冷量回收器(2)热侧入口连通，冷量回收器(2)热侧出口与烟气冷却系统(3)入口连通，烟气冷却系统(3)的烟气出口与烟气切换阀(4)入口连通，烟气切换阀(4)的出口分别连通第一脱硝吸附塔(5)和第二脱硝吸附塔(6)的烟气入口，通向冷量回收器(2)的烟气管道上设置烟气汇流器(7)，第一脱硝吸附塔(5)和第二脱硝吸附塔(6)的烟气出口与烟气汇流器(7)的入口连通，烟气汇流器(7)的出口连通冷量回收器(2)的冷侧入口。
  2. 根据权利要求1所述的烟气低温吸附脱硝系统，其特征在于，烟气冷却系统(3)包括一级冷却系统和二级冷却系统，其中一级冷却系统采用空冷系统、换热器冷却系统或水冷系统，二级冷却系统采用压缩制冷系统或吸收式制冷系统，烟气冷却系统(3)设置有烟气冷凝水出口，所述烟气冷凝水出口连通中水处理系统的进水口。
  3. 根据权利要求1所述的烟气低温吸附脱硝系统，其特征在于，脱硝吸附塔采用固定床式吸附塔，其固定床中填充有NOx吸附材料。
  4. 根据权利要求3所述的烟气低温吸附脱硝系统，其特征在于，NOx吸附材料采用活性炭或分子筛。
  5. 根据权利要求1所述的烟气低温吸附脱硝系统，其特征在于，吸附塔外侧采用冷箱结构。
  6. 根据权利要求1所述的烟气低温吸附脱硝系统，其特征在于，烟气切换阀(4)采用电动或气动切换阀；烟气切换阀(4)的控制器的输入端连接厂区DCS的输出端。
  7. 根据权利要求1所述的烟气低温吸附脱硝系统，其特征在于，冷量回收器(2)采用烟气换热器。
  8. 一种烟气低温脱硝工艺，其特征在于，经过除尘和脱硫的烟气加压后，进行预冷，再冷却至室温以下，温度低于室温的烟气进入脱硝吸附塔，在脱硝吸附塔中进行物理吸附脱硝，用脱硝后的烟气对经过除尘和脱硫后的烟气进行预冷，吸收热量的净烟气进入烟囱进行排放。
  9. 根据权利要求8所述的烟气低温脱硝工艺，其特征在于，采用权利要求1所述系统进行脱硝，经过除尘和脱硫的烟气进入风机(1)增压后进入冷量回收器(2)与脱硝后的低温净烟气换热实现预冷，预冷后的烟气进入烟气冷却系统(3)进行冷却，得到温度低于室温的冷却后烟气，所述冷却后烟气经过烟气切换阀(4)，进入第一脱硝吸附塔(5)或第二脱硝吸附塔(6)，第一脱硝吸附塔(5)或第二脱硝吸附塔(6)轮流进行吸附脱硝和再生流程，经吸附脱硝后的净烟气进入烟气汇流器(7)，再进入冷量回收器(2)中进行冷量回收，升温后的净烟气进入烟囱排放。
  10. 根据权利要求9所述的烟气低温脱硝工艺，其特征在于，烟气冷却系统(3)中采用循环冷却水换热冷却或喷淋冷却方式对烟气进行一级冷却，采用压缩制冷或吸收式制冷方式对一级冷却后的烟气进行二级冷却。
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