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CN102350194A - Regenerative amine desulphurization technology for iron ore pellet roasting tail gas - Google Patents

Regenerative amine desulphurization technology for iron ore pellet roasting tail gas Download PDF

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CN102350194A
CN102350194A CN2011101796128A CN201110179612A CN102350194A CN 102350194 A CN102350194 A CN 102350194A CN 2011101796128 A CN2011101796128 A CN 2011101796128A CN 201110179612 A CN201110179612 A CN 201110179612A CN 102350194 A CN102350194 A CN 102350194A
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organic amine
gas
amine liquid
liquid
flue gas
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朱德庆
徐五七
李启厚
左永伟
潘建
徐光泽
唐达高
吴炳智
杨庄
王天保
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Tongling Nonferrous Metals Group Holdings Co.,Ltd. Tongguan Metallurgical Chemical Industry Branch
Central South University
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TONGLING NONFERROUS METALS GROUP HOLDINGS CO LTD TONGGUAN METALLURGICAL CHEMICAL INDUSTRY BRANCH
Central South University
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Priority to CN2011101796128A priority Critical patent/CN102350194A/en
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Abstract

The invention discloses a regenerative amine desulphurization technology for iron ore pellet roasting tail gas. The process flow comprises steps of: (1) electrostatic precipitation of flue gas; (2) prewashing and SO2 absorption; (3) SO2 desorption; (4) organic amine liquid filtering and purifying. The regenerative amine desulphurization technology for iron ore pellet roasting tail gas of the invention utilizes resource efficiently and effectively protects the environment.

Description

Iron ore pellet roasting tail gas regenerated amine sulfur removal technology
Affiliated field
The present invention relates to a kind of sulfur removal technology, particularly relate to a kind of iron ore pellet roasting tail gas regenerated amine sulfur removal technology.
Background technology
SO 2Bringing the most serious problem to the mankind is acid rain, and the pollution of acid rain and the harm that causes thereof have become one of global environment problem of paying close attention to countries in the world.The destruction of Acidic Precipitation on Aquatic Ecosystems system; Being to reduce through lake water pH value to cause fish kills on the one hand, is that acid rain has flooded soil on the other hand, has corroded mineral; Make Al element and heavy metal element flow near water body along the basement rock crack, influence the aquatile growth or make its death.Acid rain has also quickened many corrosion that are used for materials such as building structure, bridge, dam, industrial equipment, water supply network, sunken tank, hydraulic generator unit, power and communication apparatus.Acid rain also produces indirect influence to health in addition, and acid rain makes the surface water become acid, and the tenor in the underground water also increases, and the fish of drinking in this water or the edible acid river can produce harm to health.
Sulfur dioxide mainly is to get into human body through respiratory system to the influence of human body, with the respiratory apparatus effect, causes or increase the weight of the disease of respiratory apparatus.Research shows, the annual 10ug/m that increases of the concentration of sulfur dioxide in the atmosphere 3, the death toll of respiratory disease will increase by 5%.Often by floating dust absorption, the cooperative effect of sulfur dioxide and floating dust makes its harm to human body bigger to sulfur dioxide.The floating dust of absorption sulfur dioxide can be brought sulfur dioxide into people's lung, makes the toxicity of sulfur dioxide increase by 3~4 times.
Because SO 2Be one of major pollutants that cause ecological deterioration, the enormous economic loss of having given natural environment, economic construction band has also been brought serious harm to human beings'health.In order to protect environment, make the mankind and accomplish sustainable development naturally, countries in the world are to SO 2The improvement of pollution put into effect relevant policy, to SO 2Discharge capacity also made strict regulation.China has just made " atmosphere pollution comprehensive regulation discharge standard " (GB16297-1996) the nineties in last century, has strengthened environmental monitoring and environmental improvement to " two control districts ", and each department, all departments have also strengthened the improvement to sulfur dioxide.
SO in the atmosphere 2,, be mainly derived from the utilization and the metallurgical process of fossil fuel, such as industries such as thermal power generation, cement, Ferrous Metallurgy, non-ferrous metal metallurgies except natural phenomena such as the volcanic eruption.The method of administering sulfur dioxide pollution in the industry is a lot, comprises charcoal absorption, lime stone/cream method, ammoniacal liquor absorption process etc.Abandon method but mostly a lot of industrialized units are to adopt, do not accomplish that the sulphur resource reclaims.Because China's sulphur shortage of resources; Some need lean on external import the required sulphur of chemical industry, so if can reclaim the mode of the sulfur dioxide in the flue gas during smelting through enrichment, not only alleviated the pollution of environment; Can also reclaim the sulphur resource, have certain economic benefits.
Tongling copper colored hat smelting is divided 1,200,000 t/a ferric oxide pellet factories of company and is adopted grate kiln-central cooler technology.The SO of discharging 2Mainly come from pellet roasting waste gas, i.e. the SO that in roasting process, produces of sulphur in raw material, the fuel 2, concentration of emission is about 2400ppmv (maximum emission concentration 2650ppmv), this part low concentration SO 2Flue gas had not both reached the requirement of direct relieving haperacidity, again far above discharging standards, but will guarantee to produce, and tail gas must be handled.
Summary of the invention
Technical problem to be solved by this invention provides a kind of resource of both efficiently having utilized, and has effectively protected the iron ore pellet roasting tail gas regenerated amine sulfur removal technology of environment again.
In order to solve the problems of the technologies described above, iron ore pellet roasting tail gas regenerated amine sulfur removal technology provided by the invention, technological process is:
(1), flue gas electrostatic precipitation:
The pellet roasting flue gas gets into electrostatic precipitator and carries out dedusting, removes coarse dust, makes flue gas obtain preliminary purification;
(2), pre-wash and SO 2Absorb:
Pelletizing tail gas through electrostatic precipitator is introduced the wet cleaning system in desulfurization zone by main exhauster, carries out gas-liquid two-phase mass exchange and exchange heat with cleaning solution; Flue gas after dedusting cooling demist gets into SO 2The absorption tower; Poor regeneration organic amine liquid is sent into SO by poor regeneration organic amine liquid drawing pump 2Absorption reaction is carried out with the flue gas of reverse entering in the absorption tower, and its technical standard is: organic amine concentration 20~25wt%, moisture 80~85wt%, thermal-stable salt 1.1~1.4eq/mol, pH value 4.5~5.5; Removed SO 2Be SO 2Content 400mg/Nm 3Flue gas get into desulfidation tail gas chimney qualified discharge;
(3), SO 2The desorb part:
At SO 2Absorbed SO in the absorption tower 2Rich organic amine liquid through delivery pump, send into rich or poor organic amine liquid heat exchanger earlier, with SO 2The poor organic amine liquid of the high temperature that desorber effluxes carries out heat exchange, rich organic amine liquid temp is elevated to 92 ℃~95 ℃ gets into SO 2Desorber; Rich organic amine liquid is at SO 2From top to down through packing layer, contact with the steam that rises from tower bottom in the desorber, the heat that steam provides makes the absorption reaction reverse and with SO 2Change back to gas phase, the SO of gaseous state 2By steam zone and together to rise to cat head and at last at SO 2Discharge at the desorber top; SO 2The SO that comes out in the desorber top 2The saturated vapor water that in condenser, is cooled is cooled to 45 ℃~48.9 ℃ indirectly, gets into the phegma separating tank then and carries out gas-liquid separation, and phegma is most of from flowing back to SO 2Desorber, a part are delivered to spray column as supplementing water, high-purity SO 2Gas is sent to acid accumulator plant and is used for relieving haperacidity.
(4) organic amine liquid filtration, purification:
Poor organic amine liquid at first gets into amine liquid filter remove dust after, part gets into organic amine liquid purifier and removes thermal-stable salt; Poor organic amine liquid after the processing returns basin and recycles.
Described SO 2The absorption tower is a packed tower.
Adopt the iron ore pellet roasting tail gas regenerated amine sulfur removal technology of technique scheme; From high sulfide pyrite pellet roasting flue gas, reclaim desulfurization; Produce high concentration SO 2, more high-purity SO2 is sent to the acid plant, constitute pyrite burning relieving haperacidity, burning slag system pelletizing and pellet roasting smoke SO 2 and reclaim the circulation industrial chain of sending the acid plant; Promptly efficiently utilize resource, effectively protected environment again.It is absorbent that the present invention adopts the regeneration organic amine, develops regenerated amine liquid absorption-desorption method flue gas desulfurization technique, and desulfuration byproduct is pure sulfur dioxide flue gas.Organic amine can be recycled, the loss of active carbon when having avoided active carbon adsorption.
Regeneration organic amine absorbent is to SO 2The selection absorbability to far be better than other kind absorption liquid, make regenerated amine absorb desorption technique and the internal circulating load of absorption liquid required lower, greatly reduce system's operation energy consumption.
In the regeneration organic amine absorption liquid strong acid radical ion being absorbed the salt that produces is a kind of thermal-stable salt, non-volatile, can not thermal regeneration.Reduce the energy of desorption consumption on the one hand, guaranteed SO on the other hand 2The high-purity of byproduct.
Regeneration organic amine absorption liquid purification process is that purifier through a band ion exchange column is with the part that produces in the absorption process " thermal-stable salt " discharge system; Be the important technical that guarantees system balancing, this device utilizes sulphite or bisulfites to replace non-renewable strong acid root anion.
With respect to other technology; Regenerated amine absorbs desorption method and has nontoxic, harmless, non-corrosiveness, advantage such as non-volatility at normal temperatures; Simultaneously through improving and improve absorbent properties; Solved the absorbent problem of oxidation preferably, more outstanding than other absorption desorption techniques such as natrium citricum absorption desorption method and basic aluminium sulphate absorption desorption methods on absorbability and desorb energy consumption and performance.Amine liquid as raw material only needs once perfusion (annual small amount of supplemental) simultaneously, can be recycled; Byproduct is highly purified SO 2, can directly be used for relieving haperacidity or process liquid SO 2, avoided adopting tradition such as lime-gypsum method to abandon raw material that method brings to enterprise and a large amount of contingency questions of after-treatments such as Product transport, storage and landfill, antiseepage.
Desulfuration efficiency is high, and is insensitive to the air inlet sulfur content, and the concentration range of apparatus processes is at 800ppm~14% at present; Technological process is simple, and cleaning solution does not have the highly acid corrosion; System is reliable, operation is easy, easy maintenance.Non-hazardous chemicals or produce system's non-secondary pollution problem less than the particle of DN2.5; Renewable amine adsorption liquid can be recycled and reaches 50,000 absorption cycles, about seven to ten years; Reduce operating cost, realize recycling economy.
The exhaust gas volumn 270454-351590Nm of pelletizing plant 3/ h, SO in the flue gas 2Content 2400-2650ppmv.Flue-gas temperature 160-220 ℃.The high-purity SO of byproduct 2Gas butt purity 99.99%, output 42.3t/d, through realizing qualified discharge fully after the desulphurization system, the SO2 content that effluxes tail gas is 50ppmv only, far below the requirement of 400ppmv, system's desulfuration efficiency>=95.0%.
Description of drawings
Fig. 1 flue gas desulfurization technique flow chart.
The specific embodiment
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is described further.
Referring to Fig. 1, iron ore pellet roasting tail gas regenerated amine sulfur removal technology, technological process is:
(1), flue gas electrostatic precipitation
Pellet roasting flue gas (temperature is about 180 ℃) gets into electrostatic precipitator and carries out dedusting, removes coarse dust, makes flue gas obtain preliminary purification.
(2), pre-wash and SO 2Absorb
Pelletizing tail gas (temperature is about 160 ℃) from pelletizing plant's electrostatic precipitator is introduced the wet cleaning system in desulfurization zone by main exhauster, carries out gas-liquid two-phase mass exchange and exchange heat with cleaning solution.Microfine flue dust in the flue gas is washed liquid and takes away, a spot of SO in the flue gas 3Also be dissolved in the cleaning solution.Owing to exchange heat, the moisture content in the cleaning solution is by adiabatic evaporation simultaneously, and flue gas reaches capacity, and temperature drops to below 65 ℃.Flue gas after dedusting cooling demist gets into SO 2The absorption tower.
Wash cycle liquid effluxes owing to containing the solid grit and be acid, need being drawn on a small quantity by the spent acid drawing pump, is sent to sewage plant and handles.
SO 2The absorption tower is a packed tower, has higher gas liquid contacting efficiency and antiseptic effect, and can adapt to exhaust gas volumn and SO 2The fluctuation of concentration, but long-term safety operation.Poor regeneration organic amine liquid (does not absorb SO 2Amine liquid) send into SO by poor regeneration organic amine liquid drawing pump 2Absorption reaction is carried out with the flue gas of reverse entering in the absorption tower.Removed SO 2Flue gas (SO 2Content≤400mg/Nm 3) entering desulfidation tail gas chimney qualified discharge.Absorbed SO 2Rich organic amine liquid from SO 2Send to SO through delivery pump at the bottom of the absorption tower 2Desorber.
Regeneration organic amine absorption liquid performance just has decisive influence to SO2 absorption efficiency in the flue gas, and its technical standard is: organic amine concentration 20~25wt%, moisture 80~85wt%, thermal-stable salt 1.1~1.4eq/mol, pH value 4.5~5.5;
(3) SO 2The desorb part
At SO 2Absorbed SO in the absorption tower 2Rich organic amine liquid through delivery pump, send into rich or poor organic amine liquid heat exchanger earlier, with SO 2The poor organic amine liquid of the high temperature that desorber effluxes carries out heat exchange, rich organic amine liquid temp is elevated to 92 ℃~95 ℃ gets into SO 2Desorber has made full use of system's waste heat and has reduced the consumption of living steam.
From top to down through packing layer, it contacts with the steam that rises from tower bottom rich organic amine liquid in desorber.The heat that steam provides reverses absorption reaction and with SO 2Change back to gas phase.The SO of gaseous state 2By steam zone and together to rise to cat head and at last at SO 2Discharge at the desorber top.
SO 2The SO that comes out in the desorber top 2Saturated vapor (temperature is 110~120 ℃) water that in condenser, is cooled is cooled to 45~48.9 ℃ indirectly, gets into the phegma separating tank then and carries out gas-liquid separation, and phegma is most of from flowing back to SO 2Desorber, a part are delivered to spray column as supplementing water.High-purity SO 2Gas is sent to acid accumulator plant and is used for relieving haperacidity.
(4) organic amine liquid filtration, purification
The main purpose that organic amine liquid filters is to remove the ultrafine dust of enrichment in the amine liquid, makes SO 2Absorption tower and desorber can not stop up packing layer because of the dust enrichment of amine liquid, cause the packed tower running resistance to rise and influence the normal operation of system.The main purpose that organic amine liquid purifies is the thermal-stable salt that displaces enrichment in the organic amine liquid through ion exchange resin with sodium hydroxide solution.The thermal-stable salt that displaces is sent to sewage plant and handles.
Poor organic amine liquid at first gets into amine liquid filter remove dust after, part gets into organic amine liquid purifier and removes thermal-stable salt.Poor organic amine liquid after the processing returns basin and recycles.
The flue gas desulfurization technique relevant parameter is seen shown in the table 1.
Table 1 flue gas desulfurization technique relevant parameter
Figure BDA0000072259080000051
Embodiment 1:
The exhaust gas volumn 270460Nm of pelletizing plant 3/ h, SO in the flue gas 2Content 2410ppm, 165 ℃ of flue-gas temperatures.The high-purity SO of byproduct 2Gas butt purity 99.99% can realize qualified discharge fully through after the desulphurization system, effluxes the SO of tail gas 2Content is 40ppmv, system's desulfuration efficiency 97.0%.
Embodiment 2:
The exhaust gas volumn 283500Nm of pelletizing plant 3/ h, SO in the flue gas 2Content 2520ppm, 170 ℃ of flue-gas temperatures.The high-purity SO of byproduct 2Gas butt purity 99.99% can realize qualified discharge fully through after the desulphurization system, effluxes the SO of tail gas 2Content is 43ppmv only, system's desulfuration efficiency 96.6%.
Embodiment 3:
The exhaust gas volumn 298600Nm of pelletizing plant 3/ h, SO in the flue gas 2Content 2580ppm, 190 ℃ of flue-gas temperatures.The high-purity SO of byproduct 2Gas butt purity 99.99% can realize qualified discharge fully through after the desulphurization system, effluxes the SO of tail gas 2Content is 46ppmv only, system's desulfuration efficiency 97.2%.
Embodiment 4:
The exhaust gas volumn 303500Nm of pelletizing plant 3/ h, SO in the flue gas 2Content 2650ppm, 200 ℃ of flue-gas temperatures.The high-purity SO of byproduct 2Gas butt purity 99.99% can realize qualified discharge fully through after the desulphurization system, effluxes the SO of tail gas 2Content is 48ppmv only, system's desulfuration efficiency 96.4%.
Embodiment 5:
The exhaust gas volumn 351590Nm of pelletizing plant 3/ h, SO in the flue gas 2Content 2520ppm, 220 ℃ of flue-gas temperatures.The high-purity SO of byproduct 2Gas butt purity 99.99% can realize qualified discharge fully through after the desulphurization system, effluxes the SO of tail gas 2Content is 50ppmv, system's desulfuration efficiency 95.3%.

Claims (3)

1. iron ore pellet roasting tail gas regenerated amine sulfur removal technology, it is characterized in that: technological process is:
(1), flue gas electrostatic precipitation:
The pellet roasting flue gas gets into electrostatic precipitator and carries out dedusting, removes coarse dust, makes flue gas obtain preliminary purification;
(2), pre-wash and SO 2Absorb:
Pelletizing tail gas through electrostatic precipitator is introduced the wet cleaning system in desulfurization zone by main exhauster, carries out gas-liquid two-phase mass exchange and exchange heat with cleaning solution; Flue gas after dedusting cooling demist gets into SO 2The absorption tower; Poor regeneration organic amine liquid is sent into SO by poor regeneration organic amine liquid drawing pump 2Absorption reaction is carried out with the flue gas of reverse entering in the absorption tower, and its technical standard is: organic amine concentration 20~25wt%, moisture 80~85wt%, thermal-stable salt 1.1~1.4eq/mol, pH value 4.5~5.5; Removed SO 2Be SO 2Content 400mg/Nm 3Flue gas get into desulfidation tail gas chimney qualified discharge;
(3), SO 2The desorb part:
At SO 2Absorbed SO in the absorption tower 2Rich organic amine liquid through delivery pump, send into rich or poor organic amine liquid heat exchanger earlier, with SO 2The poor organic amine liquid of the high temperature that desorber effluxes carries out heat exchange, rich organic amine liquid temp is elevated to 92~95 ℃ gets into SO 2Desorber; Rich organic amine liquid is at SO 2From top to bottom through packing layer, contact with the steam that rises from tower bottom in the desorber, the heat that steam provides makes the absorption reaction reverse and with SO 2Change back to gas phase, the SO of gaseous state 2By steam zone and together to rise to cat head and at last at SO 2Discharge at the desorber top; SO 2The SO that comes out in the desorber top 2The saturated vapor water that in condenser, is cooled is cooled to 45~48.9 ℃ indirectly, gets into the phegma separating tank then and carries out gas-liquid separation, and phegma is most of from flowing back to SO 2Desorber, a part are delivered to spray column as supplementing water, high-purity SO 2Gas is sent to acid accumulator plant and is used for relieving haperacidity.
2. iron ore pellet roasting tail gas regenerated amine sulfur removal technology according to claim 1 is characterized in that: also comprise step (4), organic amine liquid filtration, purification:
Poor organic amine liquid at first gets into amine liquid filter remove dust after, part gets into organic amine liquid purifier and removes thermal-stable salt; Poor organic amine liquid after the processing returns basin and recycles.
3. iron ore pellet roasting tail gas regenerated amine sulfur removal technology according to claim 1 and 2 is characterized in that: described SO 2The absorption tower is a packed tower.
CN2011101796128A 2011-06-29 2011-06-29 Regenerative amine desulphurization technology for iron ore pellet roasting tail gas Pending CN102350194A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102849814A (en) * 2011-06-28 2013-01-02 湖南合磷化工有限公司 Treatment method for purifying sewage and tail gas from furnace gas in acid production from gypsum
CN103285712A (en) * 2012-03-02 2013-09-11 克莱斯克(北京)环境工程有限公司 Method for circularly absorbing SO2 in RFCC (Residue Fluid Catalytic Cracking) regenerative flue gas by utilizing ionic liquid
CN106800278A (en) * 2015-11-25 2017-06-06 湖南恒光化工有限公司 A kind of control system for smelting production sulfuric acid
CN112933767A (en) * 2021-02-03 2021-06-11 吉林吉恩镍业股份有限公司 Organic amine method blowing ring collection flue gas desulfurization process for nickel smelting
CN113082946A (en) * 2021-04-08 2021-07-09 成都达奇环境科技有限公司 Method for treating waste gas from non-ferrous metal smelting

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1362277A (en) * 2001-01-08 2002-08-07 陈鸣楼 Electrosatic wet desulfurizing and dust collecting system
CN101185838A (en) * 2007-08-24 2008-05-28 中国石油化工集团公司 Regeneratable wet fuel gas desulfurizing technology
CN101422691A (en) * 2008-11-20 2009-05-06 武汉凯迪电力环保有限公司 Multi-pollutant removing technique and device of fuel coal smoke

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1362277A (en) * 2001-01-08 2002-08-07 陈鸣楼 Electrosatic wet desulfurizing and dust collecting system
CN101185838A (en) * 2007-08-24 2008-05-28 中国石油化工集团公司 Regeneratable wet fuel gas desulfurizing technology
CN101422691A (en) * 2008-11-20 2009-05-06 武汉凯迪电力环保有限公司 Multi-pollutant removing technique and device of fuel coal smoke

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102849814A (en) * 2011-06-28 2013-01-02 湖南合磷化工有限公司 Treatment method for purifying sewage and tail gas from furnace gas in acid production from gypsum
CN102849814B (en) * 2011-06-28 2014-09-03 湖南合磷化工有限公司 Treatment method for purifying sewage and tail gas from furnace gas in acid production from gypsum
CN103285712A (en) * 2012-03-02 2013-09-11 克莱斯克(北京)环境工程有限公司 Method for circularly absorbing SO2 in RFCC (Residue Fluid Catalytic Cracking) regenerative flue gas by utilizing ionic liquid
CN106800278A (en) * 2015-11-25 2017-06-06 湖南恒光化工有限公司 A kind of control system for smelting production sulfuric acid
CN112933767A (en) * 2021-02-03 2021-06-11 吉林吉恩镍业股份有限公司 Organic amine method blowing ring collection flue gas desulfurization process for nickel smelting
CN113082946A (en) * 2021-04-08 2021-07-09 成都达奇环境科技有限公司 Method for treating waste gas from non-ferrous metal smelting

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Co-applicant after: Central South University

Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932

Applicant before: Central South University

Co-applicant before: Tongling Nonferrous Metals Group Holdings Co.,Ltd. Tongguan Metallurgical Chemical Industry Branch

C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20120215