CN100453148C - Method for absorbing sulfur dioxide in flue gas with smelting iron and smelting steel slag as absorbing agents - Google Patents
Method for absorbing sulfur dioxide in flue gas with smelting iron and smelting steel slag as absorbing agents Download PDFInfo
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- CN100453148C CN100453148C CNB2007100796158A CN200710079615A CN100453148C CN 100453148 C CN100453148 C CN 100453148C CN B2007100796158 A CNB2007100796158 A CN B2007100796158A CN 200710079615 A CN200710079615 A CN 200710079615A CN 100453148 C CN100453148 C CN 100453148C
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Abstract
The invention relates to a wet desulfurization technology field for SO2 flue gas, especially to a technological process for absorbing SO2 in flue gas using iron smelting slag and steel smelting slag as absorbent. The invention uses the seriflux by mixing powder iron smelting slag or steel smelting slag and water together to absorbing SO2 in flue gas. The seriflux after absorbing SO2 is filtrated after counteracted, wherein the filtrate is sent back to the seriflux, and the filter cake can be reused. The flue gas after depriving SO2 reaches the require of environmental protection, and then discharged to the air through chimney.
Description
Technical field
The present invention relates to sulfur dioxide flue gas wet desulphurization technology, being specifically related to a kind of is the process of absorbing sulfur dioxide in flue gas with blast furnace slag, copper smelter slag.
Background technology
Along with rapid development of economy, industries such as electric power, metallurgy, chemical industry and building materials produce the flue gas that contains sulfur dioxide in a large number, enter atmosphere to pollute, and sulfur dioxide becomes one of atmosphere major pollutants.People find the method for a lot of minimizing SO2 emissions through great efforts, and these methods are divided into desulfurization and production back desulfurization in the preceding desulfurization of production, the production, and wherein desulfurization is most economical, effective after the production, occupies leading position.So-called produce the back desulfurization be exactly in process of production the sulphur in raw material and the fuel change sulfur dioxide into, formation contains sulfur dioxide flue gas, and then manages sulfur in smoke to be separated and be fixed up with certain stable, harmless or recycling compound form.Produce the back desulfurization and be commonly referred to " flue gas desulfurization ".
Relevant fume desulphurization method: " flue gas desulfurization " can be divided into wet method, dry method, semidry method again.Wet method is maximum because of its desulfuration efficiency height, technology maturation practical application.
Wet process of FGD is that the absorbent of hygrometric state fully contacts in absorption equipment with flue gas, absorbent and sulfur in smoke reaction, generate stable, harmless or renewable reusable compound, sulfur dioxide is separated from flue gas, reaches the purpose of flue gas desulfurization.
Absorbent: one of essential condition of wet process of FGD be economy will be arranged, conveniently obtain, absorbent that absorbent properties are good.Absorbent commonly used has calcium base, sodium base, amino absorbent, and these absorbents are on the high side comparatively speaking, causes desulphurization cost to raise.If use the trade waste that sulfur dioxide is had absorption, not only can reduce desulphurization cost, and can also in smoke treatment, make discarded object obtain handling as absorbent.In the prior art: ZL00119453.4 " containing the sulfur dioxide flue gas processing method " and ZL01101467.9 " a kind of processing contains the chemosorbent of form waste gas of sulfur dioxide " with the non-ferrous metal smelting furnace slag as absorbent; Application number be 90106120.4 " a kind of dusting and desulfurizing technology for smoke of coal-fired boiler " with boiler blow-off waste water, slag and flue dust as absorbent; Application number is 99121910.4 " a kind of fume desulfurizing agent and fume desulphurization method " with carbide slag or ammonia still process alkaline residue or both mixtures is desulfurizing agent; Application number is that to be primary raw material with pyrite slag and cigarette mud make desulfurizing agent with active carbon or grain flour, ammoniacal liquor as pore creating material to the patent " catalytic desulfurizing agent for flue gas and preparation method thereof " of 85104062A; The granular blast furnace slag that someone proposes with humidity is the sulfur dioxide absorbent, with the form absorption sulfur dioxide of fixed bed.These technology all are that primary raw material is processed into desulfurizing agent and is used for flue gas desulfurization with the trade waste, the present invention is the same with these technology to be as desulfurization absorbent with trade waste, but used discarded object is with above-mentioned different, and formed the complete skill method of a cover practical.
Summary of the invention
Purpose of the present invention provides a kind of slurries that are modulated into powdery iron-smelting blast-furnace slag and copper smelter slag and water as the sulfur dioxide absorbent, absorbs the method for sulfur in smoke, belongs to wet desulphurization.
Technical scheme summary of the present invention is: with blast furnace slag, copper smelter slag is the process of absorbing sulfur dioxide in flue gas, be that the slurries that are modulated into powdery blast furnace slag or copper smelter slag and water are absorbent, absorb sulfur in smoke, slurries behind the absorption sulfur dioxide filter after neutralizing, filtrate returning spends sizes mixing, and filter cake is recycling.The flue gas that removes behind the sulfur dioxide reaches environmental requirement, enters atmosphere through chimney.
Specifically: the slurries that are modulated into powdery blast furnace slag or copper smelter slag and water are absorbent, in absorption equipment, react with sulfur in smoke, after oxidation, generate the sulfate of calcium, iron, magnesium and alundum (Al, silica, neutralize with lime again, make soluble-salt be transformed into precipitation of hydroxide, after filtration, filtrate returning spends sizes mixing, and filter cake is recycling.Flue gas behind the separating SO 2 enters atmosphere through chimney.The granularity of this powdery blast furnace slag or copper smelter slag :-250 orders account for more than 85%.With the slurries that powdery blast furnace slag or copper smelter slag and water are modulated into, concentration of slurry is 5～20%.With the lime neutralization, make soluble-salt be transformed into precipitation of hydroxide, the final pH value of slurries is 10.6.
Absorption reaction is extremely relevant with the mineral composition and the chemical composition of absorbent.
Description of drawings
Accompanying drawing is a process flow diagram of the present invention.
The specific embodiment
Iron-smelting blast-furnace slag and copper smelter slag mineral composition and chemical composition: the essential mineral of iron-smelting blast-furnace slag is formed melilite, and it is by cacoclasite (2CaOAl
2O
3SiO
2), akermanite (2CaOMgOSiO
2) the complicated solid solution formed; Dicalcium silicate (2CaOSiO
2) content be only second to melilite; Contained other mineral are followed successively by: pseudowollastonite (CaOSiO
2), anorthite (CaOAl
2O
32SiO
2), monticellite (CaOMgOSiO
2), manganolite (3CaOMgO2SiO
2) and magnesium scapolite (2CaOMgO2SiO
2) etc.High-temperature slag granulates (being Water Quenching Slag) with a large amount of water quick coolings, and wherein each kind of compound has little time to form crystalline mineral, forms the vitreum state.
The chemical composition of iron-smelting blast-furnace slag mainly is the oxide of Ca, Mg, Al, Si, Mn etc., contains the CaO height, about 40%; It is very low to contain FeO, less than 1%; Contain very important MgO and Al, reach 4～12% and 7～9.4% respectively.
Slag can be divided into vessel slag, open hearth slag, electroslag, is subdivided into initial stage slag, the latter stage slag of open hearth again, the oxidizing slag of electric furnace, reducing slag.No matter different process, slag that different times produces all are by metal oxide and nonmetal oxide CaO, FeO, SiO
2, Al
2O
3, the mineral that constitute such as MgO soluble solids, only mutual quantity is different.Be that with the blast furnace slag difference oxide of forming slag removes CaO, SiO
2Outside very important MgO, the content of FeO is not low, reaches 4～22%, even also has Fe
3O
4Exist, and Al
2O
3Content is on the low side.The essential mineral that they constitute has monticellite (CaOMgOSiO
2), manganolite (3CaOMgO2SiO
2), tricalcium silicate (3CaOSiO
2), dicalcium silicate (2CaOSiO
2).
Its chemical composition is depended in the mineral composition of converter slag, as the basicity (CaO/ (SiO of slag
2+ P
2O
5)) be 0.75～1.8 o'clock, essential mineral is monticellite (CaOMgOSiO
2), manganolite (3CaOMgO2SiO
2); Basicity is 1.8～2.5 o'clock, and essential mineral is dicalcium silicate (2CaOSiO
2) and bivalent metal oxide solid solution; Basicity is 2.5 when above, and essential mineral is tricalcium silicate (3CaOSiO
2), dicalcium silicate (2CaOSiO
2) and bivalent metal oxide solid solution.
Smelting iron and smelting steel slag is the chemical equation of absorbing sulfur dioxide in flue gas:
The response class of the reaction of sulfur dioxide and blast furnace slag, copper smelter slag and general wet desulphurization seemingly, in two steps.The first step is SO
2Dissolving in water, absorption, oxidation, second step was decomposition, the oxidation of blast furnace slag, copper smelter slag.
SO
2The reaction equation of the dissolving in water, absorption, oxidation is as follows:
SO
2+H
2O＝H
2SO
3＝HSO
3 -+H
+------------------(1)
HSO
3 -＝SO
3 2-+H
+---------------------------(2)
SO
2+1/2O
2+H
2O＝H
2SO
4----------------------(3)
SO
3 2-+1/2O
2＝SO
4 2-------------------------(4)
Gaseous state SO
2Direct oxidation generates SO
3Reaction carry out very slowly, need come accelerated reaction with catalyst.The SO that is dissolved in the water
2Oxidation and gaseous state SO
2Oxidation is different.In aqueous medium, the metal ion with catalytic action participates in SO down
2Can be oxidized to SO
3, directly generate dilute sulfuric acid.Studies show that manganese, copper, iron and other metal oxides can play catalytic action, promote SO
2Oxidation in aqueous medium, smelting iron and smelting steel slag just provides the metal oxide with catalytic action as absorbent, reaction equation (3), fine the carrying out of (4) energy.。
The decomposition of blast furnace slag, oxidation reaction formula are as follows:
(2CaO·Al
2O
3·SiO
2)+2SO
3 2-＝2CaSO
3+Al
2O
3+Si
2---------------------(5)
(2CaO·MgO·SiO
2)+3SO
3 2-＝2CaSO
3+MgSO
3+SiO
2----------------------(6)
CaSO
3+1/2O
2＝CaSO
4-----------------------------------------------(7)
MgSO
3+1/2O
2＝MgSO
4-----------------------------------------------(8)
(2CaO·Al
2O
3·SiO
2)+2SO
4 2-＝2CaSO
4+Al
2O
3+SiO
2--------------------(9)
(2CaO·MgO·SiO
2)+3SO
4 2-＝2CaSO
4+MgSO
4+SiO
2----------------------(10)
The decomposition of copper smelter slag, oxidation reaction formula are as follows:
(3CaO·MgO·2SiO
2)+4SO
3 2-＝3CaSO
3+MgSO
3+2SiO
2--------------------(11)
(3CaO·SiO
2)+3SO
3 2-＝3CaSO
3+SiO
2---------------------------------(12)
Fe
3O
4+4SO
3 2-＝Fe
2(SO
3)
3+FeSO
3------------------------------------(13)
CaSO
3+1/2O
2＝CaSO
4-----------------------------------------------(7)
MgSO
3+1/2O
2＝MgSO
4-----------------------------------------------(8)
(3CaO·MgO·2SiO
2)+4SO
4 2-＝3CaSO
4+MgSO
4+2Si
2---------------------(14)
(3CaO·SiO
2)+3SO
4 2-＝3CaSO
4+SiO
2---------------------------------(15)
Fe
3O
4+4SO
4 2-＝Fe
2(SO
4)
3+FeSO
4------------------------------------(16)
By above-mentioned reaction equation as can be seen, it is solubility sulphite and sulfate that some reactions generate, separate from water in order to make these salt, spending again after the separation sized mixing, need in absorbing the sulfur dioxide rear slurry, add lime and neutralize, adjust pH value and make salt change into precipitation of hydroxide to be convenient to filtration.Neutralization reaction is as follows:
MeSO
3+CaO+H
2O＝Me(OH)
2+CaSO
3---------------------------------(17)
MeSO
4+CaO+H
2O＝Me(OH)
2+CaSO
4---------------------------------(18)
Smelting iron and smelting steel slag is the technological process of absorbing sulfur dioxide in flue gas: with the smelting iron and smelting steel slag be absorbing sulfur dioxide in flue gas the process flow process as shown in drawings.
Be milled to-250 orders through abrasive dust equipment and account for blast furnace slag or copper smelter slag more than 85%, join in the pulping tank, it is 5～20% slurries that water and the filtrate of returning are modulated into concentration, deliver in the absorption equipment, disperse slurries by its on-board components, fully contact with the flue gas that flows through, sulfur dioxide is separated, is absorbed by water-soluble, the flue gas that removes behind the sulfur dioxide enters atmosphere through chimney, slurries behind dissolving, the absorption sulfur dioxide flow into the circulating slot of absorption equipment bottom, finish decomposition, the oxidation reaction of slag under the condition of stirring and bubbling air.Slurries circulate in absorption equipment and carry out absorption reaction repeatedly, finish the slurries that absorb the sulfur dioxide reaction and flow in the neutralization chamber, progressively add lime and neutralize under condition of stirring, the pH value of adjusting slurries by about 5 to 10.6.Slurries after the neutralization are delivered to filter and are filtered, and filtrate returning spends sizes mixing, and filter cake is then sent to and utilized.
The major technique condition:
Blast furnace slag, copper smelter slag granularity :-250 orders account for more than 85%
Concentration of slurry: 5～20%
In and the final pH value: 10.6
Difference with other sulfur method in aforementioned relevant patent or the patent application:
The slag that patent ZL00119453.4 " containing the sulfur dioxide flue gas processing method " is adopted specially refers to reduce the slag that copper metallurgy produces, and all different with ironmaking, copper smelter slag chemical composition and mineral composition that the present invention adopts, difference is bigger.Referring to following table 1, table 2.
Three kinds of slag chemical compositions of table 1 difference table
Three kinds of slag mineral compositions of table 2 difference table
| The reduction copper slag | Blast furnace slag | Copper smelter slag (converter) |
| (CaO·FeO)·SiO 2 CaO·SiO 2 FeO·SiO 2 | 2CaO·Al 2O 3·SiO 2 2CaO·MgO·SiO 2 2CaO·SiO 2 | CaO·MgO·SiO 2 3CaO·MgO·2SiO 2 2CaO·SiO 2 3CaO·SiO 2 |
Technical process of the present invention has N-process, and reaches 10.6 with pH in requiring, and the water of the usefulness of sizing mixing is reused, and reaches no waste water and discharges; And do not have N-process in patent ZL00119453.4 " the containing the sulfur dioxide flue gas processing method " technology, and cause soluble metal salt accumulation in the water, be an impediment to water reuse, there is waste water to discharge unavoidably.
The present invention requires slag granularity-250 order to account for more than 85%, and slag reacts, the utilization rate height; And patent ZL00119453.4 " containing the sulfur dioxide flue gas processing method " requires slag granularity 40-250 order, reacts relatively poor, and the slag utilization rate is lower.
Application number be 90106120.4 patent " a kind of dusting and desulfurizing technology for smoke of coal-fired boiler " with boiler blow-off waste water, slag and flue dust as absorbent; Application number is 99121910.4 patent " a kind of fume desulfurizing agent and fume desulphurization method " with carbide slag or ammonia still process alkaline residue or both mixtures is desulfurizing agent; Application number is that the patent " catalytic desulfurizing agent for flue gas and preparation method thereof " of 85104062A is a primary raw material with pyrite slag and cigarette mud, makes desulfurizing agent with active carbon or grain flour, ammoniacal liquor as pore creating material.Used absorbent of these patents and the used blast furnace slag of the present invention, copper smelter slag are different.Be pointed out that especially application number is that the patent indication pyrite slag of 85104062A is with Fe
2O
3, Fe
3O
4Be main, with ironmaking, copper smelter slag with CaO, FeO, SiO
2And MgO, Al
2O
3The double salt that constitutes is different fully.
With granular blast furnace slag be the difference of absorbent:
With the granular blast furnace slag of humidity be that absorbent absorbs sulfur dioxide, the problem that exists some to solve.The first, the water that so-called " humidity " comprised seldom is difficult to satisfy the requirement of sulfur dioxide dissolving, absorption, even is not enough to offset the moisture content that flue gas is taken away.The second, granular slag can only be with the form and the gas reaction of fixed bed or moving bed, and not only resistance is very big, equipment is huge, and reaction is influenced by DIFFUSION CONTROLLED to carry out very slow very not thoroughly.Three, do not form complete, maturation process capable of being industrialized, only rest on the lab scale stage, also have a lot of roads to walk.
This slurries that adopt Powdered slag to be modulated into are that absorbent absorbs sulfur dioxide, not only very big limit has overcome the influence of DIFFUSION CONTROLLED, the enough required moisture content of reaction is provided, and multiple absorption equipment can be for selecting for use, and these absorption equipments comprise spray column, grid tower, tubulent contact tower, liquid column tower, large aperture percolation tower, the described heterophase reactor of patent ZL01126707.0, bubble tower etc.
The present invention has formed complete, maturation process capable of being industrialized.
Claims (4)
1, a kind of is the process of absorbing sulfur dioxide in flue gas with blast furnace slag, copper smelter slag, it is characterized in that: be that the slurries that are modulated into powdery blast furnace slag or copper smelter slag and water are absorbent, in absorption equipment, react with sulfur in smoke, after oxidation, generate sulfate and the alundum (Al and the silica of calcium, iron and magnesium, with the lime neutralization, make soluble-salt be transformed into precipitation of hydroxide, after filtration again, filtrate returning spends sizes mixing, and filter cake is recycling; Flue gas behind the separating SO 2 enters atmosphere through chimney.
2, process as claimed in claim 1 is characterized in that: described powdery blast furnace slag or copper smelter slag, its granularity accounts for more than 85% for-250 purposes.
3, process as claimed in claim 1 is characterized in that: the described slurries that are modulated into powdery blast furnace slag or copper smelter slag and water, the concentration of slurries is 5～20%.
4, process as claimed in claim 1 is characterized in that: describedly make soluble-salt be transformed into precipitation of hydroxide with lime neutralization, the final pH value of its slurries is 10.6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100796158A CN100453148C (en) | 2007-02-28 | 2007-02-28 | Method for absorbing sulfur dioxide in flue gas with smelting iron and smelting steel slag as absorbing agents |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100796158A CN100453148C (en) | 2007-02-28 | 2007-02-28 | Method for absorbing sulfur dioxide in flue gas with smelting iron and smelting steel slag as absorbing agents |
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| CN101053761A CN101053761A (en) | 2007-10-17 |
| CN100453148C true CN100453148C (en) | 2009-01-21 |
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| CN101053761A (en) | 2007-10-17 |
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Assignee: NINGBO TAI CHI ENVIRONMENTAL PROTECTION EQUIPMENT CO., LTD. Assignor: Shi Hanxiang Contract record no.: 2011330000728 Denomination of invention: Method for absorbing sulfur dioxide in flue gas with smelting iron and smelting steel slag as absorbing agents Granted publication date: 20090121 License type: Exclusive License Open date: 20071017 Record date: 20110614 |