CN101745309B - Flue gas desulfurization (FGD) and comprehensive utilization method for flyash pudding blast furnace slag - Google Patents
Flue gas desulfurization (FGD) and comprehensive utilization method for flyash pudding blast furnace slag Download PDFInfo
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- CN101745309B CN101745309B CN2010101230464A CN201010123046A CN101745309B CN 101745309 B CN101745309 B CN 101745309B CN 2010101230464 A CN2010101230464 A CN 2010101230464A CN 201010123046 A CN201010123046 A CN 201010123046A CN 101745309 B CN101745309 B CN 101745309B
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- flyash
- furnace slag
- flue gas
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- iron
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Abstract
The invention relates to a method which uses flyash and pudding blast furnace slag for desulfurization in flue gas and comprehensively uses substances after flue gas desulfurization. The flue gas desulfurization (FGD) and comprehensive utilization method comprises the following steps: pre-treating flyash to prepare the flyash into flyash or blast furnace grout; desulfurizing (SO2 absorption), andevacuating the desulfurated flue gas from a chimney after passing through a defroster; filtering and washing; and neutralizing and removing impurities. The required Al compound can be prepared by filtering and separating heavy metal sulfide from solution, and further processing Al2(SO4)3 solution after removal of heavy metal ions. The invention has simple process flow, needs no complex equipment,fully makes use of waste materials such as flyash, pudding blast furnace slag and the like, has low cost and operation cost, saves energy, protects environment, effectively remove SO2 in flue gas andrecoveries valuable metals from the waste materials.
Description
Technical field
The present invention provides how to use flyash, iron-smelting blast-furnace slag desulfurization in a kind of flue gas, and the material comprehensive utilization method after the flue gas desulfurization.
Background technology
Application number is that 200910008934.9 patent application " is the method for absorbing sulfur dioxide in flue gas with flyash " proposes with the coal ash is absorbent, utilizes basic anhydride and the SO in the flue gas in the flyash
2Reaction generates corresponding stable compound, reduces the SO in the flue gas
2, reach the desulfurization purpose.Because the basic anhydride content generally in the flyash is lower, various basic anhydride add and are no more than 10% together.Method with this application proposes uses such flyash to come desulfurization, and its result must be very big as the flyash consumption of absorbent, and 90% inert material is brought desulphurization system into, and power consumption, water consumption increase, and the equipment attrition aggravation finally causes operating cost to increase.Check that the chemical composition of flyash can find to contain in the common flyash Al about 30%
2O
3, Al in some regional flyash
2O
3Content surpass 40%.The method that this patent application proposes, Al
2O
3Do not participate in desulphurization reaction, if can manage to activate these Al
2O
3, making it to participate in desulphurization reaction, the flyash consumption that its result not only is used in desulfurization can greatly reduce, and is merely 1/4 of former consumption, but also very high Al and other metal of recoverable value.
The patent No. is the patent of invention " is the method for absorbing sulfur dioxide in flue gas with the smelting iron and smelting steel slag " of the patent of invention of ZL 200710079615.8, is absorbent with the smelting iron and smelting steel slag, absorbs the SO in the flue gas
2Reaction generates corresponding stable compound, reduces the SO in the flue gas
2, reach the desulfurization purpose.Similar with flyash, iron-smelting blast-furnace slag contains about 15% Al
2O
3, this patent proposes uses blast furnace slag sulfur method, these Al
2O
3Do not participate in desulphurization reaction equally, if can activate these Al
2O
3, make it to participate in desulphurization reaction, can receive equally and reduce the effect that consumes, reclaims valuable metal.
Summary of the invention
The purpose of this invention is to provide the new method that a kind of flyash or iron-smelting blast-furnace slag are used for flue gas desulfurization, with the Al in flyash or the iron-smelting blast-furnace slag
2O
3Activate, make it to participate in desulphurization reaction; And the comprehensive utilization method of the material after a kind of flue gas desulfurization is provided.
Flue gas desulfurization of the present invention and comprehensive utilization method adopt following steps:
(1), flyash preliminary treatment:
1) blending cosolvent in advance in flyash or blast furnace slag;
2) in fermentation vat, add entry, open the flyash or the blast furnace slag of cosolvent that added blending under the situation of mixer, form flyash or blast furnace slag underflow liquid, leave standstill that to soak the back subsequent use.
The main form that Al exists in flyash or iron-smelting blast-furnace slag is the alumina silicate crystal, adds fluoride salt (NH
4F) after, NH
4Pasc reaction in F and the alumina silicate crystal destroys the alumina silicate crystal structure, and the Al in the lattice comes out, and makes it easily and H
2SO
4Reaction, i.e. Al
2O
3By fluoride salt (NH
4F) activate, improved the solubility of vitreum in acid solution in flyash or the iron-smelting blast-furnace slag simultaneously.
3) soaked flyash or blast furnace slag underflow liquid are transferred to surge tank, thin up under condition of stirring adds by MnO again
2The mixed catalyst that the pyrolusite of grade>=35% and ferrous sulfate are formed is modulated into flyash or blast furnace slag slurries.
(2), desulfurization (SO
2Absorb):
Deliver to the flyash that is modulated into or blast furnace slag slurries in the absorption equipment and SO
2Flue gas fully contacts, the SO in the flue gas
2Be dissolved in the slurries, under said mixed catalyst effect, impel to be dissolved in the SO that absorbs in the slurries
2Be oxidized to SO
3, and then generate H
2SO
4, again with the Al that is activated by fluoride salt
2O
3Reaction generates Al
2(SO
4)
3Flyash or blast furnace slag slurries absorb SO
2After become and " absorb SO
2Rear slurry ", when its pH value reaches 4.5～5, it is discharged from absorption equipment.Absorption equipment is mended flyash or the blast furnace slag slurries that are modulated into said method into new again; Flue gas after the desulfurization is through demister, remove wherein after the droplets entrained for clean flue gas by the chimney emptying.
(3), filter, wash:
" absorb SO by what absorption equipment was sent here
2Rear slurry " filter while hot, and use water washing.Filtrating is thick Al
2(SO
4)
3Solution spends after the purification and produces more non-limiting examples of suitable l compound such as Al
2(OH)
3Or active A l
2O
3Deng; Filter cake after the filtration is for containing CaSO
4, SiO
2With the solids of carbon, spend transformation salinity ground as soil conditioner, also can be used as cement producting material; Cleaning solution returns and is used further to modulate pulverized fuel ash slurry.
(4), in and removal of impurities:
Be thick Al by filter process gained filtrating
2(SO
4)
3Solution, using NaOH that solution is neutralized to pH earlier is 7, uses Na again
2S sulfuration makes that heavy metal precipitates with sulphided form in the solution, and when the pH value of solution value rose to 7.5, vulcanization reaction was accomplished, and heavy metal sulfide is filtered to isolate from solution, removes the Al of heavy metal ion
2(SO
4)
3Solution is the available required Al compound that further is processed into.
Remove the Al of heavy metal
2(SO
4)
3Solution promptly can be used to be processed into non-limiting examples of suitable l compound.
Technological process of the present invention is simpler, does not need complex apparatus, makes full use of waste materials such as flyash, iron-smelting blast-furnace slag, and cost and operating cost are lower, energy savings, protection environment, the SO in the effective elimination flue gas
2And reclaimed the valuable metal in the waste material.The present invention has the economic benefit and the social benefit of highly significant.
The specific embodiment
Technical process of the present invention is specific as follows:
(1), flyash preliminary treatment:
1) blending cosolvent in advance in flyash or blast furnace slag, cosolvent is fluoride salt (NH
4F), fluoride salt (NH
4F) addition is 1～10% of flyash or a blast furnace slag quality.
2) in fermentation vat, add entry, open the flyash or the blast furnace slag of fluoride salt that added blending under the situation of mixer, forming liquid-solid ratio is flyash or the blast furnace slag underflow liquid of 2.8-3.2L/kg, leaves standstill to soak 5～20 hours, subsequent use.
3) soaked flyash or blast furnace slag underflow liquid are transferred to surge tank, thin up to liquid-solid ratio is 4～10L/kg under condition of stirring, at this moment adds by MnO
2The mixed catalyst that the pyrolusite of grade>=35% and industrial ferrous sulfate are formed is modulated into flyash or blast furnace slag slurries.The pyrolusite addition is 1～5% of flyash or a blast furnace slag quality, and the ferrous sulfate addition is calculated according to the pyrolusite addition: MnO
2With FeSO
4Molecular proportion is 5～20.To the SO that is modulated into flyash or iron-smelting blast-furnace slag and water
2In the absorption liquid, add SO
2The catalyst pyrolusite and the ferrous sulfate of liquid phase catalytic oxidation can impel in down-stream, to be dissolved in the SO that absorbs in the slurries
2Accelerated oxidation becomes H
2SO
4, H
2SO
4With the Al that is activated
2O
3Reaction generates Al
2(SO
4)
3
(2), desulfurization (SO
2Absorb):
Deliver to the flyash that is modulated into or blast furnace slag slurries in the absorption equipment and SO
2Flue gas fully contacts, control liquid-gas ratio (L/m
3) be 4～10, the SO in the flue gas
2Be dissolved in the slurries, under said mixed catalyst effect, impel to be dissolved in the SO that absorbs in the slurries
2Be oxidized to SO
3, and then generate H
2SO
4, again with the Al that is activated by fluoride salt
2O
3Reaction generates Al
2(SO
4)
3Flyash or blast furnace slag slurries absorb SO
2After become and " absorb SO
2Rear slurry ".When its pH value reaches 4.5～5, it to be discharged from absorption equipment, absorption equipment is mended flyash or the blast furnace slag slurries that are modulated into said method into new again; Flue gas after the desulfurization is through demister, remove wherein after the droplets entrained for clean flue gas by the chimney emptying.
(3), filter, wash:
The absorption SO that sends here by absorption equipment
2Rear slurry filter while hot (if the flue-gas temperature that is processed about 120 ℃, liquid-gas ratio (L/m
3) 6～8 o'clock, absorb SO
2The rear slurry temperature can reach 40～50 ℃), and use water washing.Filtrating is thick Al
2(SO
4)
3Solution spends other more non-limiting examples of suitable l compound such as Al of producing after the purification
2(OH)
3, active A l
2O
3Deng; Filter cake after the filtration is for containing CaSO
4, SiO
2With the solids of carbon, spend transformation salinity ground as soil conditioner, also can be used as cement producting material; Cleaning solution returns and is used further to modulate pulverized fuel ash slurry.
(4), in and removal of impurities:
Filter process gained filtrating is thick Al
2(SO
4)
3Solution, its pH value is 4.5～5, some contained in flyash or blast furnace slag heavy metals also are dissolved in the thick solution.For guaranteeing Al
2(SO
4)
3Purity, these heavy metal ion are essential to be removed, for this reason earlier with NaOH with thick Al
2(SO
4)
3It is 7 that solution is neutralized to pH, uses Na again
2The S sulfuration makes these heavy metals precipitate with sulphided form, and when the pH value of solution value rose to 7.5, vulcanization reaction was accomplished, and heavy metal sulfide is filtered to isolate from solution, promptly becomes the Al that removes heavy metal ion
2(SO
4)
3Solution.Remove the Al of heavy metal ion
2(SO
4)
3Solution is the available required Al compound that further is processed into.These heavy metal sulfides of removing can spend the recovery heavy metal.
Material comprehensive utilization method after the flue gas desulfurization of the present invention, promptly the processing method of Al compound is: the Al that will remove heavy metal
2(SO
4)
3Solution promptly can be used to be processed into non-limiting examples of suitable l compound.
Scheme 1: adopt the method for neutralization to produce Al (OH)
3, and then produce active A l
2O
3That is: remove the Al of heavy metal with NaOH neutralization
2(SO
4)
3Al in the solution
2(SO
4)
3, reaction generates Al (OH)
3And Na
2SO
4, filtering, filter cake is Al (OH)
3Product, and then thermal decomposition can get active A l
2O
3Product, filtrating gets Na through evaporative crystallization
2SO
4And (NH
4)
2SO
4Product.
Scheme 2: direct heat is decomposed Al
2(SO
4)
3Produce active A l
2O
3And H
2SO
4That is: remove the Al of heavy metal
2(SO
4)
3Solution makes Al through pervaporation, crystallization
2(SO
4)
3Crystallization; Filter, filter cake is Al
2(SO
4)
3Crystal is removed the plane of crystal attached water with 100 ℃ of hot-air dried crystals, obtains Al
2(SO
4)
316H
2The O product.Continue to remove 13 crystallizations water wherein remaining 3 crystallization water Al with 100 ℃ of hot air
2(SO
4)
33H
2O, and then thermal decomposition under＞800 ℃ of conditions are with Al
2(SO
4)
33H
2O is decomposed into active A l
2O
3With mole SO such as contain
3And H
2The flue gas of O, flue gas is through (the Al that gathers dust
2O
3) be condensed into H
2SO
4Crystalline mother solution returns evaporation, crystallization, Na in mother liquor
2SO
4And (NH
4)
2SO
4Discharge when enrichment is arrived to a certain degree, reclaim Al (OH) by scheme 1 process route
3And Na
2SO
4And (NH
4)
25O
4
Both compare, and scheme 1 can obtain Al (OH) on demand
3With active A l
2O
3Two products, flow process is simpler, but will consume a large amount of industrial chemicals NaOH; Scheme 2 flow processs are more numerous and diverse, and product removes Al (OH)
3With active A l
2O
3Also can obtain Al outward,
2(SO
4)
316H
2O and H
2SO
4
Claims (7)
1. flyash or iron-smelting blast-furnace slag comprehensive utilization method the steps include:
(1) flyash or iron-smelting blast-furnace slag preliminary treatment:
1) blending cosolvent in advance in flyash or iron-smelting blast-furnace slag, cosolvent is an ammonium fluoride;
2) in fermentation vat, add entry, open the flyash or the iron-smelting blast-furnace slag of cosolvent that added blending under the situation of mixer, form flyash or iron-smelting blast-furnace slag underflow liquid, leave standstill that to soak the back subsequent use;
3) soaked flyash or iron-smelting blast-furnace slag underflow liquid are transferred to surge tank, thin up under condition of stirring adds by MnO again
2The mixed catalyst that the pyrolusite of grade>=35% and ferrous sulfate are formed is modulated into flyash or blast furnace dreg slurry at last;
(2) desulfurization:
Deliver to the flyash that is modulated into or blast furnace dreg slurry in the absorption equipment and SO
2Flue gas fully contacts, the SO in the flue gas
2Be dissolved in the slurries, under said mixed catalyst effect, impel to be dissolved in the SO that absorbs in the slurries
2Be oxidized to SO
3, and then generate H
2SO
4, again with the Al that is activated by said cosolvent
2O
3Reaction generates Al
2(SO
4)
3Flyash or blast furnace dreg slurry absorb SO
2After become and " absorb SO
2Rear slurry ", when its pH value reaches 4.5～5, it is discharged from absorption equipment; Absorption equipment is mended flyash or the blast furnace dreg slurry that is modulated into into the new said method of usefulness step (1) again; Flue gas after the desulfurization is through demister, remove wherein after the droplets entrained for clean flue gas by the chimney emptying;
(3) filter, wash:
" absorb SO by what absorption equipment was sent here
2Rear slurry " filter while hot, and use water washing, filtrating is thick Al
2(SO
4)
3Solution spends after the purification and produces more non-limiting examples of suitable l compd A l (OH)
3Or active A l
2O
3Filter cake after the filtration is for containing CaSO
4, SiO
2With the solids of carbon, spend transformation salinity ground as soil conditioner, or as cement producting material; Cleaning solution returns and is used further to modulate flyash or blast furnace dreg slurry;
(4) in and removal of impurities:
Be thick Al by filter process gained filtrating
2(SO
4)
3Solution, using NaOH that solution is neutralized to pH earlier is 7, uses Na again
2S sulfuration makes that heavy metal precipitates with sulphided form in the solution, and when the pH value of solution value rose to 7.5, vulcanization reaction was accomplished, and heavy metal sulfide is filtered to isolate from solution, removes the Al of heavy metal ion
2(SO
4)
3Solution is the available required Al compound that further is processed into.
2. method according to claim 1 is characterized in that: said step (1) 1) in, the addition of ammonium fluoride is 1～10% of flyash or an iron-smelting blast-furnace slag quality.
3. method according to claim 1 is characterized in that: said step (1) 2) in, flyash that in fermentation vat, forms or iron-smelting blast-furnace slag underflow liquid, its liquid-solid ratio is 2.8-3.2L/kg; Leave standstill soak 5～20 hours subsequent use.
4. method according to claim 1; It is characterized in that: said step (1) 3) in; The liquid-solid ratio of the flyash of thin up or iron-smelting blast-furnace slag is 4～10L/kg in surge tank; In the mixed catalyst that adds again, the pyrolusite addition is 1～5% of flyash or an iron-smelting blast-furnace slag quality, and the ferrous sulfate addition is calculated according to the pyrolusite addition: MnO
2With FeSO
4Molecular proportion is 5～20.
5. method according to claim 1 is characterized in that: in said step (2), and said flyash or blast furnace dreg slurry and SO
2Liquid-gas ratio during the flue gas contact is controlled to be 4～10L/m
3
6. Al who makes with the said method of claim 1
2(SO
4)
3Solution processing becomes the method for Al compound and other products, and step is: with NaOH or Na
2CO
3The said Al that removes heavy metal neutralizes
2(SO
4)
3Al in the solution
2(SO
4)
3, reaction generates Al (OH)
3And Na
2SO
4, filtering, filter cake is Al (OH)
3Product, and then thermal decomposition can get active A l
2O
3Product, filtrating gets Na through evaporative crystallization
2SO
4And (NH
4)
2SO
4Product.
7. Al who makes with the said method of claim 1
2(SO
4)
3Solution processing becomes the method for Al compound and other products, and step is:
Adopt the method for neutralization to produce Al (OH)
3, and then produce active A l
2O
3, that is: remove the Al of heavy metal with NaOH neutralization
2(SO
4)
3Al in the solution
2(SO
4)
3, reaction generates Al (OH)
3And Na
2SO
4, filtering, filter cake is Al (OH)
3Product, and then thermal decomposition can get active A l
2O
3Product, filtrating gets Na through evaporative crystallization
2SO
4And (NH
4)
2SO
4Product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101230464A CN101745309B (en) | 2010-03-12 | 2010-03-12 | Flue gas desulfurization (FGD) and comprehensive utilization method for flyash pudding blast furnace slag |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101230464A CN101745309B (en) | 2010-03-12 | 2010-03-12 | Flue gas desulfurization (FGD) and comprehensive utilization method for flyash pudding blast furnace slag |
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| CN101745309A CN101745309A (en) | 2010-06-23 |
| CN101745309B true CN101745309B (en) | 2012-04-18 |
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ID=42473304
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| CN102153304B (en) * | 2011-05-06 | 2012-10-03 | 史汉祥 | Cement retarder and preparation method thereof |
| CN102688874B (en) * | 2012-04-24 | 2014-07-30 | 中南大学 | Mechanical dry sulfurization processing method for heavy metal waste residue |
| US9550688B2 (en) * | 2013-09-18 | 2017-01-24 | General Electric Technology Gmbh | Method and apparatus for catalyzing seawater aeration basins |
| CN104826481B (en) * | 2015-05-13 | 2017-02-22 | 中国科学院过程工程研究所 | Combined desulfurization and denitrification method implemented by using metallurgical slags |
| CN105340407B (en) * | 2015-09-21 | 2017-09-01 | 史汉祥 | A kind of improved treatment method in salt-soda soil |
| CN105536492B (en) * | 2015-12-25 | 2019-03-08 | 昆明尔康科技有限公司 | A kind of method that ammonium fluoride waste water prepares phosphate ore pulp desulfurizing agent |
| CN108273369A (en) * | 2018-02-08 | 2018-07-13 | 曹子涵 | A method of preparing dry desulfurization block using flyash and chloride waste residue, waste liquid |
| CN110079371B (en) * | 2019-04-30 | 2021-09-14 | 封金财 | Preparation method of purification particles for biomass fuel |
| AU2020317995B2 (en) * | 2019-07-23 | 2023-07-13 | Kleener Power Solutions Oy | Purification composition, method for producing purification composition and method for purifying flue gas by purification composition |
| CN111841295B (en) * | 2020-07-24 | 2021-05-25 | 北京予知环保科技有限公司 | Deacidifying agent, preparation method and application thereof |
| CN117046865B (en) * | 2023-10-11 | 2024-01-23 | 杭州尚善若水环保科技有限公司 | Method for preparing in-furnace desulfurization and denitrification medicament by utilizing waste incineration fly ash |
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| CN1124672A (en) * | 1992-09-16 | 1996-06-19 | 北海道电力株式会社 | Process for treatment of exhaust gas |
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| JPS57184420A (en) * | 1981-05-01 | 1982-11-13 | Nissan Eng Kk | Method for desulfurizing flue gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1124672A (en) * | 1992-09-16 | 1996-06-19 | 北海道电力株式会社 | Process for treatment of exhaust gas |
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| JP昭57-184420A 1982.11.13 |
| 张玉 等.Fe2+液相催化氧化脱除烟气中SO2.《现代化工》.2002,第22卷(第7期),22-26. * |
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Application publication date: 20100623 Assignee: NINGBO TAI CHI ENVIRONMENTAL PROTECTION EQUIPMENT CO., LTD. Assignor: Shi Hanxiang Contract record no.: 2014330000011 Denomination of invention: Flue gas desulfurization (FGD) and comprehensive utilization method for flyash pudding blast furnace slag Granted publication date: 20120418 License type: Exclusive License Record date: 20140126 |