WO2017096692A1 - Système de lavage par désulfuration et dénitration de gaz combustible, et procédé de désulfuration et de dénitration - Google Patents

Système de lavage par désulfuration et dénitration de gaz combustible, et procédé de désulfuration et de dénitration Download PDF

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Publication number
WO2017096692A1
WO2017096692A1 PCT/CN2016/070847 CN2016070847W WO2017096692A1 WO 2017096692 A1 WO2017096692 A1 WO 2017096692A1 CN 2016070847 W CN2016070847 W CN 2016070847W WO 2017096692 A1 WO2017096692 A1 WO 2017096692A1
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desulfurization
denitration
tower
liquid
pipe
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PCT/CN2016/070847
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English (en)
Chinese (zh)
Inventor
熊靓
朱核光
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深圳广昌达环境科学有限公司
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Publication of WO2017096692A1 publication Critical patent/WO2017096692A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur 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
    • B01D53/34—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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • 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
    • B01D53/96—Regeneration, reactivation or recycling of reactants

Definitions

  • the invention belongs to the field of chemical industry, in particular to a flue gas denitration and desulfurization washing system.
  • SO 2 and NOx are two major gaseous atmospheric pollutants that are produced primarily by combustion or other chemical processes and are emitted to the atmosphere with the flue gases.
  • flue gas desulfurization mainly has two types of wet method and dry method.
  • the dry method uses lime slurry to spray into the desulfurization tower. Under the action of high temperature flue gas, the water in the slurry evaporates quickly, and the lime in the slurry is in the form of solid particles. Precipitation, and the SO 2 in the flue gas is adsorbed on the surface to be removed; the solid lime particles adsorbed with SO 2 are removed together with the dust in the flue gas by a bag filter in the back; the wet desulfurization is used sparsely.
  • the lime liquid elutes SO 2 in the spray tower, and the addition of lime is added according to the control requirements of pH, and the pH is generally controlled to an acidic range of about 6.
  • SO 2 is first absorbed into the aqueous phase, forms sulfurous acid in water and reacts with CaCO 3 (or Ca(OH) 2 ), calcium sulfite and calcium bisulfite and calcium sulfate, used as flue gas in addition to lime or limestone.
  • the desulfurized alkaline material is also NaOH, ammonia water, MgO, and the like.
  • the denitration of flue gas is divided into two types: reduction method and oxidation method.
  • the reduction method uses ammonia or urea as a reducing agent, V 5 O 2 as a catalyst at a temperature of 300-400 ° C, or no catalyst at a temperature of 1000 ° C. under conditions of the NO x in the flue gas is selectively reduced to nitrogen.
  • Selective catalytic reduction method requires the use of a catalyst containing transition metal elements. The catalyst is subject to wear and tear of the flue gas and needs to be replaced frequently. At the same time, there are problems such as ammonia leakage and harsh temperature conditions, and its use is limited. rule catalytic reduction denitration effect can not meet stringent NO x in emission standards, and thus its use is restricted.
  • Oxidation denitration has certain advantages in terms of cost of use and applicability due to its simple process, no need to use a catalyst, and a wide temperature range.
  • Na 2 SO 3 and EDTA are used as absorbents, and also on the gas-liquid surface. It participates in the reaction with NO 2 and affects the absorption of NO 2 , and these basic substances also neutralize the generated nitric acid and nitrous acid.
  • the presence of NaOH has no effect on the absorption rate of NO 2 , but the reaction product Na 2 SO 3 of SO 2 and NaOH absorbs NO 2 , while the use of Na 2 SO 3 as an absorbent, the presence of SO 2 is NO 2 . The absorption is inhibited.
  • the present invention provides a system capable of simultaneous desulfurization and denitrification, which saves cost and protects the environment.
  • the technical scheme adopted by the present invention is as follows:
  • a flue gas denitration desulfurization washing system wherein the washing system comprises a desulfurization tower, a denitration tower, a tower connecting pipe, a desulfurization liquid drainage pipe, a denitration liquid drainage pipe, and a desulfurization tower waste liquid discharge pipe,
  • the desulfurization tower is provided with a flue gas inlet and a desulfurization liquid circulation pipe for circulating the desulfurization liquid in the desulfurization tower, wherein the desulfurization liquid circulation pipe inlet is located at the bottom of the desulfurization tower, and the desulfurization liquid circulation pipe outlet is located at In the upper part of the desulfurization tower, the desulfurization liquid circulation pipe is provided with a desulfurization circulating pump for extracting the desulfurization liquid, and the desulfurization liquid circulation pipe is provided with a desulfurization liquid addition port;
  • the denitration tower is provided with a denitration liquid circulation pipe and a flue gas outlet for circulating the denitration liquid in the denitration tower, wherein the denitration liquid circulation pipe inlet is located at the bottom of the denitration tower, and the denitration liquid circulation pipe outlet is located at the upper part of the denitration pipe
  • the denitration liquid circulation pipe is provided with a denitration circulating pump for extracting the denitration liquid, the denitration liquid circulation pipe is provided with a denitration liquid addition port, and the flue gas outlet is arranged at the top of the denitration tower;
  • a tower connecting pipe is arranged between the desulfurization tower and the denitration tower, the inlet of the tower connecting pipe is located at the top of the desulfurization tower, and the outlet of the tower connecting pipe is located at the bottom of the denitration tower;
  • the desulfurization liquid circulation pipe is further connected to a desulfurization liquid discharge pipe for extracting desulfurization waste liquid from the bottom of the desulfurization tower and sent to the denitration tower, and the desulfurization liquid discharge pipe inlet is located at the bottom of the denitration tower, and the desulfurization liquid discharge pipe is arranged
  • a desulfurization waste liquid control valve for discharging the desulfurization liquid after the reaction to the denitration tube
  • the desulfurization liquid discharge pipe is connected with a desulfurization tower waste liquid discharge pipe for discharging the desulfurization waste liquid, and the desulfurization tower waste liquid discharge pipe is arranged Providing a desulfurization tower waste liquid discharge pipe valve;
  • the denitration liquid circulation pipe is connected with a denitration liquid discharge pipe for discharging the denitration liquid from the denitration tower to the desulfurization tower, and the denitration liquid discharge pipe is provided with a denitration liquid discharge pipe control valve 15.
  • the desulfurization tower is a spray tower or a venturi absorption tower.
  • the denitration tower is a packed tower or a spray tower.
  • the flue gas inlet is located at a lower middle portion of the desulfurization tower.
  • a flue gas denitration desulfurization method comprising the following steps,
  • the flue gas enters the desulfurization tower for desulfurization from the flue gas inlet, and the desulfurization liquid containing NaOH is added to the desulfurization tower from the desulfurization liquid addition port, and the desulfurization circulating pump extracts the desulfurization liquid from the bottom of the desulfurization tower, and the desulfurization liquid flows upward through the desulfurization liquid circulation pipe.
  • the desulfurization liquid further comprises Ca(OH) 2 .
  • the method of controlling the pH is used to control the addition amount of the desulfurization liquid, and the pH of the desulfurization liquid after the sulfur absorption in the tower is controlled to be 6-9.
  • the desulfurization reaction equation is as follows:
  • the exhaust gas containing SO 2 and NO 2 first enters the desulfurization tower, and SO 2 first reacts with NaOH in the desulfurization tower to form Na 2 SO 3 , and part of Na 2 SO 3 can be further used to react with SO 2 to form NaHSO 3 , and the two It will react with oxygen in the flue gas to form Na 2 SO 4 , which is a mixture of the three, wherein Na 2 SO 3 can account for 20-40% of the total salt, due to the residence time of the flue gas of the desulfurization tower Short, the general denitration effect in the desulfurization tower is limited.
  • the liquid contains a relatively high concentration of alkali solution, which is refluxed to the desulfurization tower for use as a supplement to the desulfurization tower alkali liquid NAOH.
  • the denitration liquid when the content of Na 2 SO 3 in the denitration liquid is less than 0.01 mol/L, the denitration liquid may also adopt other alkaline substances, and the desulfurized liquid after the reaction enters the desulfurization along the desulfurization liquid circulation pipe.
  • the liquid discharge pipe enters the denitration tower from the desulfurization liquid discharge pipe.
  • the desulfurization waste liquid control valve is closed.
  • the desulfurization liquid after the reaction is discharged from the desulfurization tower waste liquid discharge pipe, in order to maintain the concentration of the salt in the desulfurization tower, part of The desulfurization liquid or the desulfurization liquid after the reaction is discharged as waste water, and a part is discharged into the subsequent denitration tower, and the desulfurization liquid after the reaction contains Na 2 SO 3 to supplement the denitration liquid and discharge to the denitration tower.
  • the flow rate is determined according to the concentration of Na 2 SO 3 and the NO 2 concentration of the gas entering the denitration column, and is generally 10-50% of the desulfurization column circulating liquid.
  • step 1) the denitration liquid enters the denitration liquid discharge pipe from the denitration liquid circulation pipe from the denitration liquid circulation pipe, and the denitration discharge pipe enters the desulfurization tower to supply NaOH to the desulfurization tower, in order to control the total salt concentration in the denitration liquid, It is also necessary to remove a certain amount of denitration liquid after the reaction, and the denitration liquid after the reaction contains a relatively high concentration of NaOH, which can be discharged into the desulfurization tower through the denitration liquid discharge tube for supplementing the deionization liquid.
  • the invention has the beneficial effects of providing a system capable of simultaneous denitrification and desulfurization, and the desulfurization liquid and the denitration liquid between the two systems can be shared with each other, which greatly saves cost and improves efficiency.
  • Figure 1 is a schematic flow chart of the present invention.
  • a flue gas denitration desulfurization washing system includes a desulfurization tower 2, a denitration tower 4, a tower connection pipe 3, a desulfurization liquid discharge pipe 8, a denitration liquid discharge pipe 14, and a desulfurization tower waste liquid.
  • the discharge pipe 9, the desulfurization tower 2 is provided with a flue gas inlet 1 and a desulfurization liquid circulation pipe 7 for circulating the desulfurization liquid in the desulfurization tower 2, and the inlet of the desulfurization liquid circulation pipe 7 is located at the lower part of the desulfurization tower
  • the outlet of the desulfurization liquid circulation pipe 7 is disposed at the upper portion of the desulfurization tower 2, and the desulfurization liquid circulation pipe 7 is provided with a desulfurization circulation pump 6 for extracting the desulfurization liquid, and the desulfurization liquid circulation pipe 7 is further provided with a desulfurization liquid addition. Mouth 11;
  • the denitration tower 4 is provided with a denitration liquid circulation pipe 13 and a flue gas outlet 5 for circulating the denitration liquid in the denitration tower 4, and the inlet of the denitration liquid circulation pipe 13 is located at the bottom of the denitration tower 4, and the denitration liquid is recycled.
  • the outlet of the tube 13 is located at the upper part of the denitration tube, and the denitration liquid circulation pipe 13 is provided with a denitration circulating pump 12 for extracting the denitration liquid, and the denitration liquid circulation pipe 13 is provided with a denitration liquid addition port 16, the smoke
  • the gas outlet 5 is provided at the top of the denitration column 4;
  • the tower connecting pipe 3 is disposed between the desulfurization tower 2 and the denitration tower 4, the inlet of the tower connecting pipe 3 is located at the top of the desulfurization tower 2, and the outlet of the tower connecting pipe 3 is located at the lower part of the denitration tower 4, above the liquid surface of the denitration liquid;
  • the desulfurization liquid circulation pipe 7 is also connected to the desulfurization liquid discharge pipe 8 for extracting the desulfurization waste liquid from the bottom of the desulfurization tower 2 and feeding it to the denitration tower 4, and the inlet of the desulfurization liquid discharge pipe 8 is located at the lower part of the denitration tower 4,
  • the desulfurization liquid discharge pipe 8 is provided with a desulfurization waste liquid control valve 10 for discharging the desulfurization liquid after the reaction to the denitration pipe, and the desulfurization liquid discharge pipe 8 is connected to the desulfurization tower 2 waste liquid discharge pipe for discharging the desulfurization waste liquid.
  • the desulfurization tower 2 waste liquid discharge pipe is provided with a desulfurization tower waste liquid discharge pipe valve 11;
  • the denitration liquid circulation pipe 13 is connected with a denitration liquid discharge pipe 14 for discharging the denitration liquid from the denitration tower to the desulfurization tower 2, and the denitration liquid discharge pipe 14 is provided with a denitration liquid discharge pipe control valve 15.
  • the desulfurization tower 2 may be a spray tower or a venturi absorption tower.
  • the denitration column 4 can be a packed tower or a spray tower.
  • the flue gas inlet 1 is located at the lower middle portion of the desulfurization tower 2 above the liquid level of the desulfurization liquid.
  • the invention also provides a flue gas denitration and desulfurization method, the method comprising the following steps,
  • the desulfurization liquid circulation pipe 7 flows upward and is dripped from the outlet of the desulfurization liquid circulation pipe 7 to desulfurize; preferably, the desulfurization liquid further includes Ca(OH) 2 ; when the content of the Na 2 SO 3 in the desulfurization liquid after the reaction is too high
  • the desulfurization liquid after the reaction is discharged from the desulfurization tower waste liquid discharge pipe 9, in order to maintain the concentration of the salt in the desulfurization tower, a part of the desulfurization liquid or the desulfurization liquid after the reaction is discharged as waste water, and a part is discharged into the back.
  • the desulfurization liquid after the reaction contains Na 2 SO 3 to supplement the denitration liquid, and the flow rate of the diversion to the denitration tower is determined according to the concentration of Na 2 SO 3 and the NO 2 concentration of the gas entering the denitration tower. Generally speaking, it is 10-50% of the desulfurization tower circulating liquid. It is also necessary to remove a certain amount of denitration liquid after the reaction.
  • the denitration liquid after the reaction contains a relatively high concentration of NaOH, and can be discharged into the desulfurization through the denitration liquid discharge pipe 14. In the tower, it is used to replenish the effluent
  • the method of controlling the pH is used to control the addition amount of the desulfurization liquid, and the pH of the desulfurization liquid after the sulfur absorption in the tower is controlled to be 6-9.
  • the desulfurization reaction equation is as follows:
  • the flue gas after desulfurization enters the denitration tower 4 through the tower connecting pipe 3, and the denitration liquid containing NaOH and Na 2 SO 3 is added to the denitration tower 4 from the denitration liquid addition port 16 , and the NaOH in the denitration tower 2 denitrate liquid
  • the content is 0.1-1 WT%, and the Na 2 SO 3 is 0.01-0.5 mol/L.
  • the denitration circulating pump 12 extracts the denitration liquid from the bottom of the denitration tube, and the denitration liquid flows upward along the denitration liquid circulation pipe 13 and exits from the denitration liquid circulation pipe 13 Drowning, denitrification;
  • the exhaust gas containing SO 2 and NO 2 first enters the desulfurization tower 2, and the SO 2 first reacts with the NaOH in the desulfurization tower to form Na 2 SO 3 , and part of the Na 2 SO 3 can be further used to react with the SO 2 to form NaHSO 3 .
  • Both will react with oxygen in the flue gas to form Na 2 SO 4 , which is a mixture of the three, wherein Na 2 SO 3 can account for 20-40% of the total salt, due to the residence of the flue gas of the desulfurization tower
  • the time is short, the general denitration effect in the desulfurization tower is limited, and the remaining SO 2 and most of the NO 2 enter the subsequent denitration tower with the flue gas, and the denitration of the higher concentration denitration liquid added in the denitration tower, the NO 2 is effective. Remove the ground.
  • the liquid After the reaction of the denitration column, the liquid contains a relatively high concentration of alkali solution, which is refluxed to the desulfurization tower for use as a supplement to the desulfurization tower alkali liquid NAOH; when the content of Na 2 SO 3 in the denitration liquid is less than 0.01 mol/L
  • the denitration liquid can also adopt other alkaline substances.
  • the desulfurized liquid after the reaction enters the desulfurization liquid discharge pipe 8 along the desulfurization liquid circulation pipe 7, and enters the denitration tower from the desulfurization liquid discharge pipe 8, when the content of Na 2 SO 3 is higher than 0.5.
  • the desulfurization waste liquid control valve 10 When mol/L, the desulfurization waste liquid control valve 10 is closed.

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Abstract

L'invention concerne un système de lavage par désulfuration et dénitration de gaz combustible apte à mettre en œuvre une désulfuration et une dénitration de manière synchrone, et comprenant : une tour de désulfuration (2), une tour de dénitration (4), un tuyau de raccordement de tour (3), un tuyau d'évacuation de solution de désulfuration (8), un tuyau d'évacuation de solution de dénitration (14) et un tuyau d'évacuation de liquide résiduaire de tour de désulfuration (9), la solution de désulfuration et la solution de dénitration des systèmes de désulfuration et de dénitration pouvant être partagées.
PCT/CN2016/070847 2015-12-09 2016-01-14 Système de lavage par désulfuration et dénitration de gaz combustible, et procédé de désulfuration et de dénitration WO2017096692A1 (fr)

Applications Claiming Priority (2)

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CN201510900407.4A CN105311946A (zh) 2015-12-09 2015-12-09 一种烟气脱硝脱硫洗涤系统及脱硝脱硫方法
CN201510900407.4 2015-12-09

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CN107754585A (zh) * 2017-10-13 2018-03-06 华电电力科学研究院 一种用于电厂的废气脱硫脱硝净化过滤装置及过滤方法
CN108043204A (zh) * 2017-12-20 2018-05-18 上海电力学院 一种高钙粉煤烟气脱硫系统及其应用
CN108211743A (zh) * 2018-03-09 2018-06-29 无锡雪浪环境科技股份有限公司 一种烟气脱酸脱硝一体化装置及其使用方法
CN109966882A (zh) * 2019-04-26 2019-07-05 山东中玻节能环保发展有限公司 一种湍流混合式烧结机烟气干法脱硫装置
CN112569716A (zh) * 2020-11-06 2021-03-30 中船澄西船舶修造有限公司 一种40000吨自卸船用脱硫装置
CN113117474A (zh) * 2019-12-31 2021-07-16 中晶环境科技股份有限公司 干法烟气脱硫脱硝的一体化方法
CN113648804A (zh) * 2020-05-12 2021-11-16 山东清沂山石化科技有限公司 一种新型炉内脱硫、抑氮的技术方法
CN115634522A (zh) * 2022-10-20 2023-01-24 云南曲靖钢铁集团呈钢钢铁有限公司 一种带式烧结机烟气的环保节能型深度净化系统及方法
CN115646186A (zh) * 2021-12-31 2023-01-31 山东庚辰环保新材料有限公司 循环脱硫装置、工艺及应用

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