CN106693637A - Wet desulfurization method in metallurgy of iron and steel - Google Patents

Wet desulfurization method in metallurgy of iron and steel Download PDF

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Publication number
CN106693637A
CN106693637A CN201611218496.5A CN201611218496A CN106693637A CN 106693637 A CN106693637 A CN 106693637A CN 201611218496 A CN201611218496 A CN 201611218496A CN 106693637 A CN106693637 A CN 106693637A
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cooling
desulfurization
metallurgical
dehalogenation
metallurgical gas
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CN201611218496.5A
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Chinese (zh)
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周玉祥
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合肥天翔环境工程有限公司
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Publication of CN106693637A publication Critical patent/CN106693637A/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D47/00Separating dispersed particles from gases, air or vapours by liquid as separating agent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/007Separation 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 irradiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/50Sulfur oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/64Heavy metals or compounds thereof, e.g. mercury
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/68Halogens or halogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75Multi-step processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/80Semi-solid phase processes, i.e. by using slurries
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/10Oxidants
    • B01D2251/108Halogens or halogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/20Reductants
    • B01D2251/206Ammonium compounds
    • B01D2251/2067Urea
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/40Alkaline earth metal or magnesium compounds
    • B01D2251/404Alkaline earth metal or magnesium compounds of calcium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/20Halogens or halogen compounds
    • B01D2257/204Inorganic halogen compounds
    • B01D2257/2045Hydrochloric acid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/20Halogens or halogen compounds
    • B01D2257/204Inorganic halogen compounds
    • B01D2257/2047Hydrofluoric acid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/60Heavy metals or heavy metal compounds
    • B01D2257/602Mercury or mercury compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/80Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/804UV light

Abstract

The invention provides a wet desulfurization method in metallurgy of iron and steel. The method comprises the following steps: (1) firstly, cooling and carrying out dehalogenation after metallurgical flue gases are boosted by a booster fan, and further cooling the gases to be 100 DEG C or below 100 DEG C through evaporation of alkali liquor and process water, wherein the alkali liquor is boiler ash flushing water; 2) then introducing the metallurgical flue gases which are subjected to dehalogenation and cooling in the step 1) to a desulfurization device, firstly carrying out primary spraying on the metallurgical flue gases by using a spraying way in the desulfurization device, then enabling the metallurgical flue gases to rise to a turbulent ball section directly in the desulfurization device, wherein the turbulent ball section comprises two layers of structures, namely a foam granular packing layer and an ultraviolet light irradiation layer, and demisting and then discharging the metallurgical flue gases. The method is high in desulfurization efficiency, has no scale formation and clogging, and further can effectively remove hydrogen halide in the flue gases to improve the desulfurization efficiency of a desulfurization tower and prolong the service life of the desulfurization tower.

Description

Wet desulphurization method in Ferrous Metallurgy

Technical field

The invention belongs to technical field of desulfurization, and in particular to wet desulphurization method in a kind of Ferrous Metallurgy.

Background technology

Existing flue gas desulfurization device can be divided into two major classes, and a class is packed tower, and packed tower air resistance is big, easy fouling: Class is separately appointed to be plate column, plate column desulfuration efficiency is low.The harmful substances such as flue dust, SOx, NOx in boiler produced by fuel combustion Air is received serious pollution, and injure the health of the mankind.With development and energy development, the utilization of national economy Increase, State of Air pollution also sharply increasing.For environmental protection, make air more pure and fresh, it is necessary to the row of pollutant High-volume it is any limitation as, especially the discharge capacity to the harmful substance produced by fuel combustion in boiler is controlled by.

Current sintering flue gas desulfurization just starts starting, and referring especially to the wet fuel gas desulfurizing technology flow such as power station, its is main Sweetening process is all carried out in the desulfurizers such as spray column, grid tower, bubble tower, wherein it is spray column to run most, its suction It is that absorbent slurry is atomized in absorption tower through sprinkling to receive principle, from the top down sprinkling with from the upward flue gas mixed process of bottom of towe In, absorb the SO in flue gas2, its major defect be flue gas mix with absorbent slurry be difficult to fully, cause desulfuration efficiency relatively low, Especially sintering amount of sulfur contenting in smoke is low, and desulfuration efficiency is more difficult to ensure;Meanwhile, the flow velocity of spray column is low, and equipment is big, therefore takes up an area Area is big;For bubble tower, its technological process is that flue gas is to absorb and crystallize all to exist by being sent directly into absorbing liquid, major defect Occur in solution pool, the pH value for absorbing requirement is high, and crystallization requires that pH value is low, this contradiction causes to absorb and crystallize not thorough Bottom, additionally, due to the alveolate generation of bubble cleaning, causes desulfuration efficiency very low.

Metallurgical gas feature is that flue-gas temperature is high, dustiness big, and fluctuation range is big, and some flue gases also have humidity very high, And containing mordant gas (SO2、SO3, HF) toxic gas (As2O3, mercury, Pb steam).At present, metallurgical gas desulfuration can not The gases such as the poisonous corrosivity such as HF and mercury are removed well.

The content of the invention

The present invention proposes wet desulphurization method in a kind of Ferrous Metallurgy, and the method desulfuration efficiency is high, and non-scaling is blocked, and Can effectively remove except the hydrogen halides in flue gas, improve desulfurizing tower desulfuration efficiency, extend the service life of desulfurizing tower.

The technical proposal of the invention is realized in this way:

Wet desulphurization method in a kind of Ferrous Metallurgy, comprises the following steps:

1) after metallurgical gas are boosted through booster fan, cooling dehalogenation is carried out first, while by alkali lye and process water By cigarette temperature drop to less than 100 DEG C, the alkali lye is boiler ash wash slag water for evaporation;

2) and then by step 1) metallurgical gas after dehalogenation cooling are passed through desulfurizer, first using spray in desulfurizer Spill mode carries out one-level sprinkling to metallurgical gas, and then metallurgical gas directly rise to rapid ball section, the rapids in desulfurizer Ball section is made up of double-layer structure, i.e. foam beads packing layer and ultra violet lamp layer, will be discharged after metallurgical gas demisting.

Further, step 2 described in some embodiments of the invention) the used flushing liquor of sprinkling be by lime stone slurry, The slurries that urea is configured to chloric strong oxidant, improve desulfurizing tower denitrification efficiency.

Further, weight of urea percentage is the 10~20% of lime stone slurry, chloride Strong oxdiative in described absorbent Agent percetage by weight is the 0.2~1.2% of lime stone slurry.

Further, the chloric strong oxidant is sodium chlorite, sodium hypochlorite, calcium chlorite, calcium hypochlorite and bleaching One or more in powder.

Further, the step 1) in cooling dehalogenation process one cooling defluorinate device in carry out.

Beneficial effects of the present invention:

1st, the HF gases containing tens or even hundreds of milligrams in metallurgical gas.HF gas attacks are extremely strong, are dissolved in life after water Into hydrofluoric acid can produce serious corrosion to desulfurizing tower inner member and anti-corrosion material, to glass-reinforced plastic material it is destructive especially Greatly, alkali lye needed for using boiler ash wash slag water solution as dehalogenation, can effectively remove HF.Because the HCl gases in flue gas also have There is high solubility, therefore most HCl is removed when defluorinate is cooled down, while removing the flue dust of bulky grain.

2nd, pretreated flue gas carries out reinforcing desulfuration into the rapid ball section in desulfurizer, is to increase the characteristics of rapid ball section Air-flow, makes the filler in tower be kept in motion, ultraviolet irradiation (photocatalyst of oxidation), is given off by spray process Flue gas, in making flue gas there is sufficient oxidation reaction in most Elemental Mercury Hg0 with sulfur dioxide, oxygen, generate solid phase mercuration Compound mereurous sulfate and mercury oxide.

Specific embodiment

Embodiment 1

The technical proposal of the invention is realized in this way:

Wet desulphurization method in a kind of Ferrous Metallurgy, comprises the following steps:

1) after metallurgical gas are boosted through booster fan, cooling dehalogenation is carried out in defluorinate device is cooled down first, while passing through By cigarette temperature drop to less than 100 DEG C, the alkali lye is boiler ash wash slag water for the evaporation of alkali lye and process water;

2) and then by step 1) metallurgical gas after dehalogenation cooling are passed through desulfurizer, first using spray in desulfurizer Spill mode carries out one-level sprinkling to metallurgical gas, and then metallurgical gas directly rise to rapid ball section, the rapids in desulfurizer Ball section is made up of double-layer structure, i.e., foam beads packing layer is located at ultraviolet with ultra violet lamp layer, wherein foam beads packing layer Light irradiation layer lower section, will discharge after metallurgical gas demisting.The used flushing liquor of sprinkling is by lime stone slurry, urea and bleaching The slurries that powder is configured to, improve desulfurizing tower denitrification efficiency.Weight of urea percentage is lime stone slurry in absorbent 16%, bleaching powder percetage by weight is the 0.7% of lime stone slurry.

Embodiment 2

Wet desulphurization method in a kind of Ferrous Metallurgy, comprises the following steps:

1) after metallurgical gas are boosted through booster fan, cooling dehalogenation is carried out in defluorinate device is cooled down first, while passing through By cigarette temperature drop to less than 100 DEG C, the alkali lye is boiler ash wash slag water for the evaporation of alkali lye and process water;

2) and then by step 1) metallurgical gas after dehalogenation cooling are passed through desulfurizer, first using spray in desulfurizer Spill mode carries out one-level sprinkling to metallurgical gas, and then metallurgical gas directly rise to rapid ball section, the rapids in desulfurizer Ball section is made up of double-layer structure, i.e., foam beads packing layer is located at ultraviolet with ultra violet lamp layer, wherein foam beads packing layer Light irradiation layer lower section, will discharge after metallurgical gas demisting.The used flushing liquor of sprinkling is by lime stone slurry, urea and secondary chlorine The slurries that sour sodium is configured to, improve desulfurizing tower denitrification efficiency.Weight of urea percentage is lime stone slurry in absorbent 10%, sodium hypochlorite percetage by weight for lime stone slurry 0.4%.

Embodiment 3

Wet desulphurization method in a kind of Ferrous Metallurgy, comprises the following steps:

1) after metallurgical gas are boosted through booster fan, cooling dehalogenation is carried out in defluorinate device is cooled down first, while passing through By cigarette temperature drop to less than 100 DEG C, the alkali lye is boiler ash wash slag water for the evaporation of alkali lye and process water;

2) and then by step 1) metallurgical gas after dehalogenation cooling are passed through desulfurizer, first using spray in desulfurizer Spill mode carries out one-level sprinkling to metallurgical gas, and then metallurgical gas directly rise to rapid ball section, the rapids in desulfurizer Ball section is made up of double-layer structure, i.e., foam beads packing layer is located at ultraviolet with ultra violet lamp layer, wherein foam beads packing layer Light irradiation layer lower section, will discharge after metallurgical gas demisting.The used flushing liquor of sprinkling is by lime stone slurry, urea and secondary chlorine The slurries that sour sodium is configured to, improve desulfurizing tower denitrification efficiency.Weight of urea percentage is lime stone slurry in absorbent 12%, sodium hypochlorite percetage by weight for lime stone slurry 0.2%.

Embodiment 4

Wet desulphurization method in a kind of Ferrous Metallurgy, comprises the following steps:

1) after metallurgical gas are boosted through booster fan, cooling dehalogenation is carried out in defluorinate device is cooled down first, while passing through By cigarette temperature drop to less than 100 DEG C, the alkali lye is boiler ash wash slag water for the evaporation of alkali lye and process water;

2) and then by step 1) metallurgical gas after dehalogenation cooling are passed through desulfurizer, first using spray in desulfurizer Spill mode carries out one-level sprinkling to metallurgical gas, and then metallurgical gas directly rise to rapid ball section, the rapids in desulfurizer Ball section is made up of double-layer structure, i.e., foam beads packing layer is located at ultraviolet with ultra violet lamp layer, wherein foam beads packing layer Light irradiation layer lower section, will discharge after metallurgical gas demisting.The used flushing liquor of sprinkling is by lime stone slurry, urea and secondary chlorine The slurries that sour calcium is configured to, improve desulfurizing tower denitrification efficiency.Weight of urea percentage is lime stone slurry in absorbent 15%, calcium hypochlorite percetage by weight for lime stone slurry 1.2%.

Embodiment 5

Wet desulphurization method in a kind of Ferrous Metallurgy, comprises the following steps:

1) after metallurgical gas are boosted through booster fan, cooling dehalogenation is carried out in defluorinate device is cooled down first, while passing through By cigarette temperature drop to less than 100 DEG C, the alkali lye is boiler ash wash slag water for the evaporation of alkali lye and process water;

2) and then by step 1) metallurgical gas after dehalogenation cooling are passed through desulfurizer, first using spray in desulfurizer Spill mode carries out one-level sprinkling to metallurgical gas, and then metallurgical gas directly rise to rapid ball section, the rapids in desulfurizer Ball section is made up of double-layer structure, i.e., foam beads packing layer is located at ultraviolet with ultra violet lamp layer, wherein foam beads packing layer Light irradiation layer lower section, will discharge after metallurgical gas demisting.The used flushing liquor of sprinkling is by lime stone slurry, urea and sub- chlorine The slurries that sour calcium is configured to, improve desulfurizing tower denitrification efficiency.Weight of urea percentage is lime stone slurry in absorbent 20%, calcium chlorite's percetage by weight for lime stone slurry 0.6%.

Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.

Claims (5)

1. wet desulphurization method in a kind of Ferrous Metallurgy, it is characterised in that comprise the following steps:
1) after metallurgical gas are boosted through booster fan, cooling dehalogenation is carried out first, while by the evaporation of alkali lye and process water By cigarette temperature drop to less than 100 DEG C, the alkali lye is boiler ash wash slag water;
2) and then by step 1) metallurgical gas after dehalogenation cooling are passed through desulfurizer, use sprinkling side first in desulfurizer Formula carries out one-level sprinkling to metallurgical gas, and then metallurgical gas directly rise to rapid ball section, the rapid ball section in desulfurizer It is made up of double-layer structure, i.e. foam beads packing layer and ultra violet lamp layer, will be discharged after metallurgical gas demisting.
2. wet desulphurization method in Ferrous Metallurgy according to claim 1, it is characterised in that the step 2) sprinkling adopted Flushing liquor is the slurries being configured to by lime stone slurry, urea and chloric strong oxidant.
3. wet desulphurization method in Ferrous Metallurgy according to claim 2, it is characterised in that urea in described absorbent Percetage by weight for lime stone slurry 10~20%, chloric strong oxidant percetage by weight for lime stone slurry 0.2~ 1.2%.
4. wet desulphurization method in the Ferrous Metallurgy according to Claims 2 or 3, it is characterised in that the chloride Strong oxdiative Agent be sodium chlorite, sodium hypochlorite, calcium chlorite, calcium hypochlorite and bleaching powder in one or more.
5. wet desulphurization method in Ferrous Metallurgy according to claim 1, it is characterised in that the step 1) in cooling Dehalogenation process is carried out in a cooling defluorinate device.
CN201611218496.5A 2016-12-26 2016-12-26 Wet desulfurization method in metallurgy of iron and steel CN106693637A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101168118A (en) * 2006-10-25 2008-04-30 宝山钢铁股份有限公司 Sintering smoke wet method sulphur removing and dust removing technology
CN101279849A (en) * 2008-05-26 2008-10-08 广东欧文莱陶瓷有限公司 Energy-saving emission reduction process for ceramic production
CN101352647A (en) * 2008-09-08 2009-01-28 环境保护部华南环境科学研究所 Simultaneous desulfuration and denitration technique by wet flue gas method
CN101940871A (en) * 2010-09-29 2011-01-12 东南大学 Photochemical advanced oxygenation-based simultaneous desulfuration and denitration system
CN203108418U (en) * 2013-01-30 2013-08-07 北京中科创新园环境技术有限公司 Wet process flue gas desulfurization and denitrification integrated device
CN104307323A (en) * 2014-11-05 2015-01-28 华玉叶 Wet desulphurization method in ferrous metallurgy
CN104785081A (en) * 2015-04-21 2015-07-22 南京朗洁环保科技有限公司 Method for realizing desulfuration, denitration and demercuration through combination of ozone and radiated peroxides
CN105498480A (en) * 2015-11-30 2016-04-20 大连海事大学 Ultraviolet radiation enhancement based method and device for simultaneous desulfurization, denitrification and particulate removal of pypocholoride

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101168118A (en) * 2006-10-25 2008-04-30 宝山钢铁股份有限公司 Sintering smoke wet method sulphur removing and dust removing technology
CN101279849A (en) * 2008-05-26 2008-10-08 广东欧文莱陶瓷有限公司 Energy-saving emission reduction process for ceramic production
CN101352647A (en) * 2008-09-08 2009-01-28 环境保护部华南环境科学研究所 Simultaneous desulfuration and denitration technique by wet flue gas method
CN101940871A (en) * 2010-09-29 2011-01-12 东南大学 Photochemical advanced oxygenation-based simultaneous desulfuration and denitration system
CN203108418U (en) * 2013-01-30 2013-08-07 北京中科创新园环境技术有限公司 Wet process flue gas desulfurization and denitrification integrated device
CN104307323A (en) * 2014-11-05 2015-01-28 华玉叶 Wet desulphurization method in ferrous metallurgy
CN104785081A (en) * 2015-04-21 2015-07-22 南京朗洁环保科技有限公司 Method for realizing desulfuration, denitration and demercuration through combination of ozone and radiated peroxides
CN105498480A (en) * 2015-11-30 2016-04-20 大连海事大学 Ultraviolet radiation enhancement based method and device for simultaneous desulfurization, denitrification and particulate removal of pypocholoride

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Application publication date: 20170524