CN102371110B - Flue gas desulfurization and denitration method - Google Patents

Flue gas desulfurization and denitration method Download PDF

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Publication number
CN102371110B
CN102371110B CN2010102565554A CN201010256555A CN102371110B CN 102371110 B CN102371110 B CN 102371110B CN 2010102565554 A CN2010102565554 A CN 2010102565554A CN 201010256555 A CN201010256555 A CN 201010256555A CN 102371110 B CN102371110 B CN 102371110B
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flue gas
tower
absorbent
ozone
denitration method
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CN102371110A (en
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涂先红
陈卫红
裴旭东
郭荣群
李朝恒
王秀珍
张凡
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China Petroleum and Chemical Corp
Sinopec Luoyang Guangzhou Engineering Co Ltd
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China Petroleum and Chemical Corp
Sinopec Luoyang Petrochemical Engineering Corp
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The present invention discloses a flue gas desulfurization and denitration method. The method comprises the following steps that: ozone is introduced to a flue gas pipeline with a temperature of 50-200 DEG C, wherein a molar ratio of the ozone to the NOx is 1-3:1; the flue gas mixture after the reaction enters a water washing tower, and is subjected to counter current contact with water to carry out quenching, wherein a volume ratio of the water to the flue gas is 0.002-0.003:1; the water-washed flue gas enters a SO2 absorption tower, and contacts with an absorption agent, wherein the temperature of the SO2 absorption tower is 40-65 DEG C, the volume ratio of the absorption agent to the flue gas is 0.25-0.5:1000; the absorption agent absorbing the SO2 enters a regeneration tower to carry out regeneration; the regenerated absorption agent is recycled, and the purified flue gas is discharged to atmosphere by a chimney.

Description

A kind of flue gas desulfurization and denitration method
Technical field:
The present invention relates to separating of sulfur dioxide in flue gas and oxynitrides, particularly from flue gas, removing the method for sulfur dioxide and oxynitrides.
Technical background:
Contain SO 2, NOx waste gas a large amount of discharges caused serious problem of environmental pollution, current control SO 2, the noxious gas emission such as NOx Main Means be that gas cleaning is processed.The flue gas and desulfurizing and denitrifying technology mainly contains oxidation absorption, complexed absorption, Reducing and absorption at present, and the oxidation absorption techniques adopts high energy activation, oxidant oxidation, catalytic oxidation by NOx or simultaneously by SO 2With NOx, be oxidized to high valence state and easily absorb oxide, then adopt absorbent to be absorbed.High energy activation has electron beam irradiation, impulse electric corona plasma, and this method removal efficiency is high, without waste water and waste residue, produce, but the investment operating cost is higher.It is to adopt oxidant such as HClO that oxidation absorbs 3By NOx or simultaneously by SO 2With the NOx oxidation, then with absorption liquid, absorb, this method removal efficiency is high, but adopts strong oxidizer more, and cost is high, and liquid waste processing or byproduct are recycled difficulty.It is to adopt catalyst such as active carbon by SO that catalytic oxidation absorbs 2After with NOx, being oxidized to high valence state, absorb with absorption liquid, this method byproduct recoverable, do not have refuse to produce, easy and simple to handle, but treating capacity is less, it is larger to take up an area, the catalyst regeneration difficulty.Absorption via Chemical Complexation is to adopt iron-retention agent to carry out the complex desorption smoke treatment, but complexing agent regeneration difficulty, secondary wastewater is difficult to process.The Reducing and absorption method is urea and additive method, and NOx is reduced to nitrogen, and reaction generates byproduct of ammonium sulfate, and removal efficiency is not high, amount of reagent large, the high in cost of production shortcoming but this method exists.Also have with this derivative urea seeding agent method, triethylenediamine cobalt urea method, with catalyst by SO 2With the NOx oxidation, then with urea, absorbed to obtain byproduct ammonium nitrate and ammonium sulfate, although these technology removal efficiencies are improved, amount of reagent reduces, and product reclaims and utilization has difficulties, and after adding additive, product quality is vulnerable to impact, increases simultaneously the complex process degree.In summary it can be seen, existing flue gas and desulfurizing and denitrifying technology exists the investment operating cost than high, the problems such as treating capacity is little, floor space is large, complex process, byproduct recycling difficulty, byproduct can not obtain fine utilization, how directly to abandon, and causes the waste of sulfur dioxide resource.
Summary of the invention:
For the deficiencies in the prior art, the present invention provides an efficient desulfurization denitration method for gas cleaning.A kind of flue gas desulfurization and denitration method of the present invention, its step is as follows:
1) at 50~200 ℃ of preferred 100~150 ℃ of flue injection of ozones, ozone and NO xMol ratio be 1~3: 1, the smoke mixture of reaction enters into water scrubber, carries out chilling with the water counter current contacting, water is 0.002~0.003: 1 with the flue gas volume ratio, the flue gas after washing enters into step 2);
2) from 1) flue gas enter SO 2Absorption tower contacts with absorbent, 40~65 ℃ of absorption tower temperature, absorbent with flue gas volume than 0.25~0.5: 1000, absorb SO 2After absorbent enter regenerator and regenerate, the absorbent after regeneration enters absorption tower and recycles, the flue gas after purification enters atmosphere through chimney.
Absorbent absorbs SO 2After enter regenerator and regenerate, the SO parsed 2, can liquefy to do product or enter sulfur recovery facility and produce sulphur.
Described absorbent absorbs SO 2Reaction in absorption tower, carry out, absorbent and SO 2Contact can adopt in the same way, reverse or bubbling mode carries out, preferred reverse contact.
Described flue gas is the gas that contains the sulfur and nitrogen oxides pollutant, particularly the flue gas of petrochemical industry catalytic cracking unit regenerated catalyst generation.
Described ozone is from ozone generator, and the ozone generator raw material is air or oxygen, preferably uses air.
Described absorbent is the disclosed organic amine absorbent of publication number CN101185831.
Described flue-gas temperature after over-quenching between 40~65 ℃, preferably 50~65 ℃.
Any one can be adopted in void tower, packed tower, plate column, valve tower in described absorption tower.
Described regenerator is the absorbent regeneration tower, has absorbed SO 2Rich solution can be by nitrogen or water vapour air lift to separate sucking-off SO 2, preferred water steam air lift.
Described absorbent regeneration tower for in void tower, packed tower, plate column, valve tower any one, the preferred filler tower.
Separate the SO of sucking-off 2Byproduct can be produced liquid SO 2, also can go refinery's sulfur recovery facility to produce sulphur, production sulphur preferably combines with claus process.
In whole absorption-desorption process, due to oxidation, a small amount of SO is arranged 2Be converted into SO 3Thereby, with SO 4 2-Form be present in absorption liquid, this salt can not by the heating mode remove, be called heat stable salt, along with recycling of absorption liquid, heat stable salt is constantly accumulated, and can affect absorptive capacity and the desulfurized effect of absorption liquid, must be removed.The absorption liquid that a part is contained to heat stable salt removes system by heat stable salt, removes heat stable salt, maintains the ionic equilibrium in absorption-regenerative system, to guarantee the desulfuration efficiency of absorption liquid.
A kind of flue gas desulfurization and denitration method of the present invention, can not only remove sulfureous in flue gas oxygen compound and nitrogen oxide, can also remove dust and other highly acid gases in flue gas.
The contained NO of catalytic cracking flue gas xMiddle NO accounts for more than 90%, and other is NO 2Deng.NO is water insoluble, is one of more unmanageable gaseous contaminant, the NO of high valence state 2, N 2O 3, N 2O 5The Yi Yushui reaction generates HNO 3, in conjunction with the wet scrubbing absorption technique, can reach the denitration rate more than 80%, and can combine with Regeneratable wet catalytic cracking flue gas sulfur removal technology, realize desulphurization denitration simultaneously, device only need add an ozone generator to get final product, without large change, technological process is constant.Ozone is a kind of strong oxidizer, compares with other common oxidant, has strong, selective high, the many merits such as reaction speed is fast, reaction temperature is low, non-secondary pollution of oxidability, thereby enjoys in recent years favor.While utilizing ozone to make oxidant to remove NO, the SO in flue gas 2Also can react and generate SO with ozone 3, but the degree of reaction is lower, can participation and NO and ozone between response competition, accelerate to consume ozone, NO and O 3Between oxidation reaction compare SO 2And O 3Between the oxidation reaction speed of carrying out faster, SO 2Existence very little on the impact of ozone oxidation reaction, in addition ozone in the time of 150 ℃, in 10s ozone without the Catalytic Thermal Decomposition rate below 30%, and with the kinetic reaction time order of magnitude of NO be only 10 -2S, visible ozone self thermal decomposition is very little on the impact of ozone oxidation reaction, in addition, ozone is very strong to the adaptability of NO concentration, be applicable to the not high characteristics of concentration of NO in catalytic cracking flue gas, by 100~150 ℃ of catalytic cracking flue gas pipe temperatures, locating injection of ozone, O 3/ NO amount of substance ratio is 1~3: 1, reaction time 2~10s, NO in flue gas is oxidized to high valence state nitrogen oxide soluble in water, then by water absorption, remove, the denitration rate reaches more than 80%, low-temperature flue gas enters absorption tower and fully reacts with desulfurization absorbent, is that 40~65 ℃, liquid-gas ratio are 0.25~0.5L/m in temperature 3, the time of staying, while being 1.0~1.5s, desulfurization degree reached more than 95%, realized desulphurization denitration simultaneously.
Compared with prior art: a kind of flue gas desulfurization and denitration method of the present invention, have the investment operating cost low, technological process is simple, easy to operate, byproduct SO 2The advantage easily reclaim, removal efficiency is high.Be suitable for processing the flue gas that contains oxygen sulfur compound and nitrogen oxide and dust, be specially adapted to petroleum chemical industry and purify plant catalytic cracking flue gas.
The accompanying drawing explanation
Fig. 1 is a kind of flue gas desulfurization and denitration method of the present invention, and flue gas is catalytic cracking flue gas desulfurization denitration method schematic flow sheet.
1. water scrubber, 2. absorption tower, 3. regenerator, 4. heat stable salt removes device, 5. heat exchanger, 6. ozone generator, 7. fresh water supplements, and SO is 9. reclaimed in 8. purifying smoke emptying 2Device, 10. sewer, 11. high-temperature flue gas, 12. recirculated waters.
The specific embodiment:
Ozone is injected to 50~200 ℃ of preferably 100~150 ℃ of flues, ozone and NO xMol ratio be 1~3: 1, the smoke mixture of reaction enters into water scrubber, carries out chilling with the water counter current contacting, water is 0.002~0.003: 1 with the flue gas volume ratio, the flue gas after washing enters into step 2);
2) from 1) flue gas enter SO 2Absorption tower contacts with absorbent, 40~65 ℃ of absorption tower temperature, absorbent with flue gas volume than 0.25~0.5: 1000, absorb SO 2After absorbent enter regenerator and regenerate, the absorbent after regeneration enters absorption tower and recycles, the flue gas after purification enters atmosphere through chimney.
Embodiment 1
At first the ozone of generation is located to inject the catalytic cracking flue gas pipeline 100~150 ℃ of flue-gas temperatures, ozone in flue with the abundant haptoreaction of nitrogen oxide, exhaust gas volumn is 50m 3/ h, NO, SO 2Content is respectively 400mg/m 3, 2000mg/m 3, according to every cubic metre of flue gas, containing ozone is 1280mg, passes into ozone in flue gas, be 3s time of contact, ozone and NO xThe mol ratio of material is 2: 1, and acid water is reverse fully contacts with 45 ℃ of washings for flue gas, absorbs by the nitrogen oxide of ozone oxidation, remaining oxidation limit, limit absorbs, the cooling of dedusting simultaneously, in water scrubber, spray flux is 120kg/h, is 72mg/m from the content of NO water scrubber flue gas out 3(being converted to NO), the denitration rate is 82%, the flue gas after preliminary treatment enters sulfur dioxide absorbing tower and fully contacts with absorbent is reverse, is that 40 ℃, liquid-gas ratio are 0.25L/m in temperature 3, fully absorb during time of staying 1.2S, the desulfurization degree 96% of the sulfur dioxide in flue gas after purification, the absorbent that goes out absorption tower enters regenerator and carries out heat regeneration, absorbent after parsing enters absorption tower and recycles, the sulfur dioxide parsed can be done product or send into sulfur recovery facility, and the flue gas after purification directly enters atmosphere through chimney.
Embodiment 2
At first the ozone of generation is located to inject the catalytic cracking flue gas pipeline 100~150 ℃ of flue-gas temperatures, ozone in flue with the abundant haptoreaction of nitrogen oxide, exhaust gas volumn is 50m 3/ h, NO x, SO 2Content is respectively 550mg/m 3, 2000mg/m 3, according to every cubic metre of flue gas, containing ozone is 2640mg, passes into ozone in flue gas, be 5s time of contact, ozone and NO xThe mol ratio of material is 3: 1, under adiabatic saturation state, acid water is reverse fully contacts with 60 ℃ of washings for flue gas, absorb by the nitrogen oxide of ozone oxidation, remaining oxidation limit, limit absorbs, the cooling of dedusting simultaneously, in water scrubber, spray flux is 150kg/h, is 77mg/m from the content of NO water scrubber flue gas out 3(being converted to NO), the denitration rate is 86%, the flue gas after preliminary treatment enters sulfur dioxide absorbing tower and fully contacts with absorbent is reverse, is that 60 ℃, liquid-gas ratio are 0.25L/m in temperature 3, the time of staying fully absorbs while being 1.5s, the desulfurization degree of the sulfur dioxide in flue gas after purification is 95%, the absorbent that goes out absorption tower enters regenerator and carries out heat regeneration, absorbent after parsing enters absorption tower and recycles, the sulfur dioxide parsed can be done product or send into sulfur recovery facility, and the flue gas after purification directly enters atmosphere through chimney.

Claims (7)

1. a flue gas desulfurization and denitration method, is characterized in that, concrete steps are:
1) injection of ozone in 50~200 ℃ of flues, ozone and NO xMol ratio be 1~3: 1, after reaction, smoke mixture enters into water scrubber, water scrubber is optional one in void tower, packed tower, plate column and valve tower, with the water counter current contacting, carry out chilling, water is 0.002~0.003: 1 with the flue gas volume ratio, and the rear temperature of washing enters into step 2 at the flue gas of 40~65 ℃);
2) from 1) flue gas enter SO 2Absorption tower contacts with absorbent, absorbent and SO 2Contact in the same way, reverse or bubbling mode, 40~65 ℃ of absorption tower temperature, absorbent with flue gas volume than 0.25~0.5: 1000, absorb SO 2Absorbent enter regenerator and regenerate, the absorbent after regeneration recycles, the flue gas after purification enters atmosphere through chimney.
2. according to a kind of flue gas desulfurization and denitration method claimed in claim 1, it is characterized in that: at 100~150 ℃ of flue injection of ozones.
3. according to a kind of flue gas desulfurization and denitration method claimed in claim 1, it is characterized in that: absorb SO at described absorbent 2In absorption tower, absorbent and SO 2Contact be reverse mode.
4. according to a kind of flue gas desulfurization and denitration method claimed in claim 1, it is characterized in that: described flue gas is the gas that contains oxygen sulfur compound and nitrogen oxides pollution thing.
5. according to a kind of flue gas desulfurization and denitration method claimed in claim 1, it is characterized in that: described flue gas is the flue gas that the catalytic cracking unit regenerated catalyst produces.
6. according to a kind of flue gas desulfurization and denitration method claimed in claim 1, it is characterized in that: described ozone is from ozone generator.
7. according to a kind of flue gas desulfurization and denitration method claimed in claim 1, it is characterized in that: described absorbent regeneration tower is optional one in void tower, packed tower, plate column and valve tower.
CN2010102565554A 2010-08-19 2010-08-19 Flue gas desulfurization and denitration method Active CN102371110B (en)

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Publication number Priority date Publication date Assignee Title
CN103143249B (en) * 2013-03-06 2015-02-18 上海锅炉厂有限公司 Method and device for capturing carbon dioxide in flue gas of power station boiler
CN105318342B (en) * 2014-06-11 2019-05-17 中国石油化工股份有限公司 A kind for the treatment of process of industrial smoke
CN106422722A (en) * 2016-10-12 2017-02-22 广东佳德环保科技有限公司 Sintering flue gas denitration method adopting oxidation method
CN106362587A (en) * 2016-11-07 2017-02-01 上海东化环境工程有限公司 Catalytic cracking smoke gas desulfurization and denitrification process
CN106975346A (en) * 2017-03-31 2017-07-25 盐城工学院 Absorbent solution and preparation method thereof
CN107875838A (en) * 2017-12-15 2018-04-06 马鞍山钢铁股份有限公司 With the production technology and processing system of compound claus oven processing activated coke method coke oven flue gas desulphurization denitration acid vapour

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1923341A (en) * 2006-08-23 2007-03-07 浙江大学 Device and method for coal-burning boiler fume ozone oxidation and simultaneous desulfurization and denitrification
CN101053748A (en) * 2007-04-30 2007-10-17 武汉凯迪电力环保有限公司 Simultaneously removing various pollutant wet ammonia flue gas cleaning technology and system thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1923341A (en) * 2006-08-23 2007-03-07 浙江大学 Device and method for coal-burning boiler fume ozone oxidation and simultaneous desulfurization and denitrification
CN101053748A (en) * 2007-04-30 2007-10-17 武汉凯迪电力环保有限公司 Simultaneously removing various pollutant wet ammonia flue gas cleaning technology and system thereof

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Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No.

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