CN106540525A - A kind of collaboration is using CO in slag and the stable waste gas of waste water2Method and device - Google Patents
A kind of collaboration is using CO in slag and the stable waste gas of waste water2Method and device Download PDFInfo
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- CN106540525A CN106540525A CN201611053253.0A CN201611053253A CN106540525A CN 106540525 A CN106540525 A CN 106540525A CN 201611053253 A CN201611053253 A CN 201611053253A CN 106540525 A CN106540525 A CN 106540525A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/025—Other waste gases from metallurgy plants
Abstract
A kind of collaboration is using CO in slag and the stable waste gas of waste water2Method and device, method is：（1）Metallurgical steel slag is crushed；（2）Prepare alkaline modification agent；（3）Using steel mill's dust waste water as Metallurgical Waste Water；（4）Using metallurgical tail gas as waste gas；（5）Metallurgical steel slag is mixed into loading reactor with alkaline modification agent, Metallurgical Waste Water immersion is added；（6）Waste gas is passed through, CO is carried out2Solidification；（7）After discharging water, waste gas is passed through again；（8）Air-dry and obtain carbonatation steel scoria.Device includes reactor shell and closure, and reactor shell bottom distribution air brick, air brick are connected with air-introduced machine；Multilamellar grate plate is provided with inside reactor shell above air brick.Directly using the pH value and calcium concentration of CaO in metallurgical steel slag and MgO and dust waste water determining the addition of alkaline modification agent, simple production process mitigates environment and social load, is conducive to the sustainable development of society the method for the present invention.
Description
Technical field
The invention belongs to metallurgical technical field of three-waste treatment, more particularly to a kind of collaboration is using slag and the stable waste gas of waste water
Middle CO2Method and device.
Background technology
Since nearly 30 years, China's steel industry has obtained huge development, particularly after 2000, with China
Steel industry high speed development, output of steel is lasting to increase substantially so that metallurgical slag is rapid with the increase of crude steel yield
Increase.Up to the present, although develop the application technology of many kinds of converter slag acidifyings, it is but generally low using added value, and
And the slag after needing to crush is heated again, has thus resulted in equipment investment and operating cost is higher；Therefore, exploitation is with me
The metallurgical slag of state's resource features couples the new technique for utilizing with metallurgical dust waste water collaboration, improves waste residue reuse ratio and product
Added value, to developing a circular economy, sets up resource-conserving and environment-friendly society and is of great significance.
In iron and steel enterprise, the metallurgical three wastes are the main garbages of steel manufacture process.Wherein：The discharge capacity of slag is about
The 12 ~ 15% or so of converter producing crude steel amount；The discharge capacity of waste water is produce crude steel amount more than 2.7 times；Ton steel CO2Discharge
Amount is in more than 1.3t；At present, the secondary approach for utilizing of slag primarily as blast furnace, converter charge in iron and steel enterprise's inner loop
Use, or the raw material as road base material, construction material and slag fertilizer etc., but its utilization rate is not high for a long time, then
It is low using added value.
Application No. 200710038393.5,200710044157.4, patent disclose a kind of carbonatation steel scoria and process
The method of waste water, although refer to slag solidification CO2The method of gas, but special fluidized bed reactor consersion unit is needed,
And whole process needs high temperature；The patent of Application No. 200510030330.6 and 200510093267.0 discloses some will
The method of slag processing waste water, but slag processing waste water as combination formula in one use, not be used alone can
Row, and these processing methods can not process the slag of the first big side-product of steel and iron industry in a large number；So far, both at home and abroad specially
Profit and non-patent literature adopt waste steel slag and waste water directly to cooperate with CO in the stable waste gas of coupling without direct2Application report
Road.
The content of the invention
For the substantial amounts of metallurgical three wastes in existing steel and iron industry（Waste residue, waste water and waste gas）It is upper that process is technically present
Problem is stated, the present invention provides a kind of collaboration using CO in slag and the stable waste gas of waste water2Method and device, with metallurgical steel slag,
Metallurgical Waste Water and emission, add basic matterial as modification agent, carry out CO2Solidification, reach the secondary utilization of slag,
Reduce CO2Discharge capacity, mitigate environment with social load.
The method of the present invention is carried out according to the following steps：
1st, metallurgical steel slag is crushed to into particle diameter≤15mm, wherein particle diameter accounts for gross weight less than or equal to the part of 15mm more than 10mm
Less than 10%, particle diameter accounts for the 13 ~ 35% of gross weight less than or equal to the part of 10mm more than 5mm, and particle diameter is less than or equal to 5mm more than 1mm
Part account for the 30 ~ 60% of gross weight, particle diameter accounts for the 20 ~ 40% of gross weight less than or equal to the part of 1mm more than 0.1, and particle diameter is little
Less than the 8% of gross weight is accounted in the part of 0.1mm；
2nd, alkaline modification agent, Na in alkaline modification agent are prepared+With Ca in metallurgical steel slag2+And Mg2+The mol ratio of sum is（0.2~
1.3）:1；
3rd, using steel mill's dust waste water as Metallurgical Waste Water, pH value is that, between 7.5 ~ 12, calcium concentration is 50 ~ 250 mg/L；
4th, adopt CO2The metallurgical tail gas of content ＞ 15% are used as waste gas, 45 ~ 150 DEG C of temperature；
5th, after be sufficiently mixed metallurgical steel slag with alkaline modification agent, loading bottom is provided with air brick and inside is placed with the anti-of grate plate
Answer in device, metallurgical steel slag is deposited in grate plate with alkaline modification agent；Metallurgical Waste Water is subsequently adding, and metallurgical steel slag is made with alkalescence modification
The mixture of agent soaks more than 12h in Metallurgical Waste Water, and controls temperature more than 30 DEG C；Wherein Metallurgical Waste Water submergence metallurgy steel
Slag is with alkaline modification agent and is higher by metallurgical steel slag and alkalescence more than modification agent upper surface 0.5m；
6th, immersion terminates to be passed through the waste gas that pressure is 0.3 ~ 1MP from the air brick of reactor bottom backward, carries out first CO2Gu
Change, the persistent period is 1 ~ 3h, exhaust gas flow control in 1.0 ~ 5.0L/s, the volume of waste gas intake and the material of inside reactor
Exist than control（15~30）:1；
7th, stop being passed through waste gas, discharge water from the discharging valve of reactor bottom, after water all bleeds off in question response device, again from reaction
The air brick of device bottom is passed through the waste gas that pressure is 0.3 ~ 1MP, carries out secondary CO2Solidification, exhaust gas flow are controlled in 0.5 ~ 6.0L/
S, persistent period are that the volume ratio control of the material of 0.5 ~ 4h, waste gas intake and inside reactor exists（15~30）:1；
8th, the material for completing secondary solidification is air-dried, obtains carbonatation steel scoria.
The composition of the metallurgical steel slag selected in said method contains CaO 35 ~ 60%, SiO by weight percentage2 8 ~ 20%,
Fe2O3 10 ~ 30%, MgO 5 ~ 10%, Al2O31 ~ 3%, P2O5 1.2 ~ 2.8%, MnO 0.1 ~ 2.2%, TiO2 0 ~
1.3%。
The alkaline modification agent selected in said method be soda, sodium bicarbonate and/or Caustic soda, the purity by weight of alkaline modification agent
>=95%, granularity≤30 mesh.
The composition of the carbonatation steel scoria that said method is obtained contains Ca 17.38 ~ 44.67% by weight percentage, and Si 26.89 ~
64.99%, Fe 1.28 ~ 29.18%, Mg 0.02 ~ 0.09%, Al 0.13 ~ 0.79%, P 0.01 ~ 0.10%, Mn 0.14 ~ 2.6%,
Ti 0 ~ 1.2%, C 3.50 ~ 14.57%.
In said method, in metallurgical steel slag, the conversion ratio of CaO is 20 ~ 55%.
In said method, in metallurgical steel slag, the conversion ratio of MgO is 15 ~ 45%.
In said method, metallurgical steel slag per ton is acidified solidify afterwards CO2 0.3 ~ 1.5kg, converts into 0.153 ~ 0.764 m3
CO2。
In said method, in step 5,6,7 acidizations, there is following chemical reaction
(I) dissociation of water：
H2O(l)↔H++OH-（1）
(II) active component CaO and the hydration reaction of MgO in metallurgical steel slag, ionize out Ca2+And Mg2+：
CaO (s)+H2O(l)→ Ca2+ (aq)+2OH- (aq)（2）
MgO (s)+ H2O(l)→ Mg2+ (aq) + 2OH- (aq)（3）
(III) dissociation of alkaline modification agent：
NaHCO3(aq)↔Na+ (aq)+HCO3 - (aq)（4）
HCO3 - (aq) ↔H+ (aq)+CO3 2- (aq)（5）
(Ⅳ) CO2Gas diffusion, dissolving, generation ionization through after gas-liquid interface：
CO2(g)↔ CO2 (aq)（6）
HCO3 - (aq) ↔H+ (aq)+CO3 2- (aq)（7）
CO2 (aq) +OH- (aq)↔HCO3 - (aq)（8）
HCO3 - (aq)+OH- (aq) ↔CO3 2- (aq)+H2O(l)（9）
(Ⅴ) Ca2+And Mg2+With CO3 2-Ion directly reacts, and generates the precipitate of slightly solubility：
Ca2+ (aq)+CO3 2- (aq)→CaCO3(s)（10）
Mg2+ (aq)+CO3 2- (aq)→MgCO3(s)（11）
Ca2+ (aq)+HCO3 - (aq)→CaCO3(s)+H+ (aq)（12）
Mg2+ (aq)+HCO3 - (aq)→MgCO3(s)+H+ (aq)（13）
Ca2+ (aq)+2HCO3 - (aq)→Ca(HCO3)2（14）
Mg2+ (aq)+2HCO3 - (aq)→Mg(HCO3)2（15）
The device of the enforcement said method of the present invention includes the closure at reactor shell and its top, and reactor shell bottom is equal
Even that multiple air bricks for being passed through waste gas are distributed with, air brick is connected with air-introduced machine, wherein air-introduced machine be used for introduce waste gas and
Airing materials, reactor shell bottom are additionally provided with discharging valve, and closure is provided with water intaking valve and diffusion valve；Inside reactor shell
Multilamellar grate plate is provided with above air brick.
In said apparatus, air relief valve on closure, is additionally provided with.
In said apparatus, multilamellar grate plate is uniformly distributed in vertical direction, and the difference in height between two neighboring grate plate is 400
~ 1200mm, is evenly distributed with strip crevice or manhole in grate plate, the width of strip crevice is 0.5 ~ 5mm, manhole
A diameter of 2 ~ 5mm.
In said apparatus, the material of reactor shell is the steel that outside is provided with heat-insulation layer, and air brick is embedded in cylinder
On base plate.
In said apparatus, the material of grate plate is steel, 8 ~ 25mm of thickness.
The using method of said apparatus is：Each layer grate plate is deposited in after metallurgical steel slag is sufficiently mixed with alkaline modification agent
On, will be closed inside reactor shell with closure, waste water is passed through by water intaking valve；After immersion terminates, by reactor cylinder
The air brick of body bottom is passed through waste gas；First CO2After solidification terminates, waste water is discharged by discharging valve, again by reactor
The air brick of cylinder body bottom is passed through waste gas；Secondary CO2After solidification terminates, diffusion valve and air outlet are opened, is made instead by air-introduced machine
Answer device inner barrel to divulge information, material is air-dried.
The method have the characteristics that：Use the metallurgical three wastes（Waste residue, waste water and waste gas）The fixed CO of collaboration coupling2, can be abundant
Side-product and garbage in the utilization steel and iron industry production process of circulation, and preliminary treatment Metallurgical Waste Water, promote China's smelting
The high-efficiency resource recycling of golden slag.The fixed CO of modification agent collaboration is added using the metallurgical three wastes2Technique, with traditional metallurgical slag
Acidification technique is compared, and whole process whole process adopts Metallurgical Waste Water, and can significantly reduce the energy in slag heating process
Consumption, and by solidifying CO2Process preliminary treatment Metallurgical Waste Water.
The method of the present invention can directly utilize metallurgical slag, waste water and waste gas, according to CaO's in metallurgical steel slag and MgO
Amount determines the addition of alkaline modification agent, simple production process with the pH value of dust waste water and calcium concentration；Using metallurgical three
It is useless（Waste residue, waste water and waste gas）CO in the fixed metallurgical industry waste gas of collaboration coupling2, reduce CO2Discharge capacity, mitigate environment with
Social load, is conducive to the sustainable development of society.
Description of the drawings
Fig. 1 is a kind of collaboration of the present invention using CO in slag and the stable waste gas of waste water2Method process flow diagram；
Fig. 2 is the reactor assembly structural representation that adopts in the embodiment of the present invention；
In figure：1st, water intaking valve；2nd, air relief valve；3rd, diffusion valve；4th, grate plate；5th, air-introduced machine；6th, discharging valve；7th, air brick；8th, it is metallurgical
The mixture of slag and alkaline modification agent, 9, closure, 10, reactor shell.
Specific embodiment
The converter steel that slag that the metallurgical steel slag adopted in the embodiment of the present invention is produced for refining plant, converter mill produce
The electric furnace slag that slag or electric furnace shop are produced, composition contain CaO 35 ~ 60%, SiO by weight percentage2 8 ~ 20%, Fe2O3 10
~ 30%, MgO 5 ~ 10%, Al2O31 ~ 3%, P2O5 1.2 ~ 2.8%, MnO 0.1 ~ 2.2%, TiO2 0~1.3%。
The Metallurgical Waste Water adopted in the embodiment of the present invention gives up for converter mill petticoat pipe dust waste water, the dedusting of electric furnace shop petticoat pipe
Water, refining plant dust waste water and mill dephosphorization or cooling waste water.
The waste gas adopted in the embodiment of the present invention does not reach what the process of coal-gas recovering standard Jing was produced to bessemerize early stage
Waste gas, electric furnace Primary period do not reach coal-gas recovering standard Jing and process the waste gas for producing, and sintering generation waste gas, heating furnace produce useless
Gas etc.（CO in waste gas2Effective volume concentration 15 ~ 36%）.
The alkaline modification agent adopted in the embodiment of the present invention adopts soda, sodium bicarbonate and Caustic soda for commercial industrial products.
In the embodiment of the present invention, the using method of device is：It is deposited in after metallurgical steel slag is sufficiently mixed with alkaline modification agent
In each layer grate plate, will be closed inside reactor shell with closure, waste water is passed through by water intaking valve；After immersion terminates, pass through
The air brick of reactor shell bottom is passed through waste gas；First CO2After solidification terminates, waste water is discharged by discharging valve, led to again
The air brick for crossing reactor shell bottom is passed through waste gas；Secondary CO2After solidification terminates, diffusion valve and air outlet are opened, by drawing
Blower fan makes reactor shell inner ventilation, and material is air-dried.
The composition of the carbonatation steel scoria obtained in the embodiment of the present invention contains Ca 17.38 ~ 44.67%, Si by weight percentage
26.89 ~ 64.99%, Fe 1.28 ~ 29.18%, Mg 0.02 ~ 0.09%, Al 0.13 ~ 0.79%, P 0.01 ~ 0.10%, Mn 0.14 ~
2.6%, Ti 0 ~ 1.2%, C 3.50 ~ 14.57%.
Embodiment 1
Metallurgical steel slag is crushed to into particle diameter≤15mm, wherein particle diameter accounts for gross weight less than or equal to the part of 15mm more than 10mm
10%, particle diameter accounts for the 15% of gross weight less than or equal to the part of 10mm more than 5mm, and particle diameter is accounted for less than or equal to the part of 5mm more than 1mm
The 35% of gross weight, part of the particle diameter more than 0.1 less than or equal to 1mm account for the 35% of gross weight, and particle diameter is accounted for always less than the part of 0.1mm
The 5% of weight；
Prepare alkaline modification agent, Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The mol ratio of sum is 0.2:1；Alkali
Property modification agent be soda；
Using steel mill's dust waste water as Metallurgical Waste Water, pH value 7.5, calcium concentration are 50 mg/L；
Using CO2The metallurgical tail gas of content 15% are used as waste gas, temperature 45 C；
After metallurgical steel slag is sufficiently mixed with alkaline modification agent, loading bottom is provided with air brick and inside is placed with the reaction of grate plate
In device, metallurgical steel slag is deposited in grate plate with alkaline modification agent；Metallurgical Waste Water is subsequently adding, and metallurgical steel slag is made with alkaline modification agent
Mixture 12h is soaked in Metallurgical Waste Water, and control temperature at 40 DEG C；Wherein Metallurgical Waste Water submergence metallurgical steel slag and alkalescence change
Matter agent is simultaneously higher by metallurgical steel slag and alkaline modification agent upper surface 0.6m；
6th, immersion terminates to be passed through the waste gas that pressure is 0.3MP from the air brick of reactor bottom backward, carries out first CO2Solidification,
Persistent period is 3h, and exhaust gas flow control is existed with the volume ratio control of the material of inside reactor in 5.0L/s, waste gas intake
30:1；
7th, stop being passed through waste gas, discharge water from the discharging valve of reactor bottom, after water all bleeds off in question response device, again from reaction
The air brick of device bottom is passed through the waste gas that pressure is 0.3MP, carries out secondary CO2Solidification, exhaust gas flow are controlled in 5.0 L/s, are held
The continuous time is that the volume ratio of the material of 3h, waste gas intake and inside reactor is controlled 20:1；
8th, the material for completing secondary solidification is air-dried, obtains carbonatation steel scoria, composition by weight percentage containing Ca 17.38 ~
44.67%, Si 26.89 ~ 64.99%, Fe 1.28 ~ 29.18%, Mg 0.02 ~ 0.09%, Al 0.13 ~ 0.79%, P 0.01 ~
0.10%, Mn 0.14 ~ 2.6%, Ti 0 ~ 1.2%, C 3.50 ~ 14.57%；
In metallurgical steel slag, the conversion ratio of CaO is 38% for the conversion ratio of 20%, MgO；
Apparatus structure is as shown in Fig. 2 including the closure 9 at reactor shell 10 and its top, 10 bottom even of reactor shell
Multiple air bricks 7 for being passed through waste gas are distributed with, air brick 7 is connected with air-introduced machine 6, wherein air-introduced machine 6 is used to introduce waste gas
And airing materials, 10 bottom of reactor shell is additionally provided with discharging valve 6, and closure 9 is provided with water intaking valve 1 and diffusion valve 3；Reactor
The top of 10 inside air brick 7 of cylinder is provided with multilamellar grate plate 4；Air relief valve 2 is additionally provided with closure 9, multilamellar grate plate 4 is in Vertical Square
It is uniformly distributed upwards, the difference in height between two neighboring grate plate 4 is 400mm, and strip crevice, bar shaped are evenly distributed with grate plate 4
The width in gap is 0.5mm；The material of reactor shell 10 is that outside is provided with the steel of heat-insulation layer, and air brick 7 is embedded in reactor
On the base plate of cylinder 10；The material of grate plate 4 be steel, thickness 8mm.
Embodiment 2
Method with embodiment 1, difference is：
（1）The slag that the metallurgical slag for adopting is produced for refining plant, particle diameter are accounted for always less than or equal to the part of 15mm more than 10mm
The 7% of weight, particle diameter account for the 35% of gross weight less than or equal to the part of 10mm more than 5mm, and particle diameter is more than 1mm less than or equal to 5mm's
Part accounts for the 30% of gross weight, and part of the particle diameter more than 0.1 less than or equal to 1mm accounts for the 20% of gross weight, portion of the particle diameter less than 0.1mm
Divide and account for the 8% of gross weight；
（2）Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The mol ratio of sum is 0.4:1；Alkaline modification agent is little
Soda；
（3）Metallurgical Waste Water pH value 12, calcium concentration are 250 mg/L；
（4）90 DEG C of EGT, CO2Content 18%；
（5）Metallurgical steel slag soaks 18h with the mixture of alkaline modification agent, and controls temperature at 30 DEG C；Metallurgical Waste Water is higher by metallurgy
Slag and alkaline modification agent upper surface 0.8m；
（6）Immersion terminates to be passed through the waste gas that pressure is 1MP from the air brick of reactor bottom backward, carries out first CO2Solidification, holds
The continuous time is 1h, and in 1.0L/s, the volume ratio control of waste gas intake and the material of inside reactor is 15 for exhaust gas flow control:
1；
（7）Stopping is passed through waste gas, discharges water from the discharging valve of reactor bottom, after in question response device, water all bleeds off, again from anti-
Answer the air brick of device bottom to be passed through the waste gas that pressure is 1MP, carry out secondary CO2Solidification, exhaust gas flow are controlled in 0.5L/s, are continued
Time is that the volume ratio of the material of 0.5h, waste gas intake and inside reactor is controlled 15:1；
（8）In metallurgical steel slag, the conversion ratio of CaO is 41% for the conversion ratio of 31%, MgO；
Apparatus structure with embodiment 1, difference is：Difference in height between two neighboring grate plate is 1200mm, uniform in grate plate
Strip crevice is distributed with, the width of strip crevice is 2mm；Grate plate thickness 25mm.
Embodiment 3
Method with embodiment 1, difference is：
（1）The slag that the metallurgical slag for adopting is produced for refining plant, particle diameter are accounted for always less than or equal to the part of 15mm more than 10mm
The 1% of weight, particle diameter account for the 13% of gross weight less than or equal to the part of 10mm more than 5mm, and particle diameter is more than 1mm less than or equal to 5mm's
Part accounts for the 60% of gross weight, and part of the particle diameter more than 0.1 less than or equal to 1mm accounts for the 24% of gross weight, portion of the particle diameter less than 0.1mm
Divide and account for the 2% of gross weight；
（2）Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The mol ratio of sum is 1.3:1；Alkaline modification agent is burning
Alkali；
（3）Metallurgical Waste Water pH value 9, calcium concentration are 150 mg/L；
（4）150 DEG C of EGT, CO2Content 36%；
（5）Metallurgical steel slag soaks 15h with the mixture of alkaline modification agent, and controls temperature at 35 DEG C；Metallurgical Waste Water is higher by metallurgy
Slag and alkaline modification agent upper surface 1m；
（6）Immersion terminates to be passed through the waste gas that pressure is 0.5MP from the air brick of reactor bottom backward, carries out first CO2Solidification,
Persistent period is 2h, and exhaust gas flow control is existed with the volume ratio control of the material of inside reactor in 3.0L/s, waste gas intake
20:1；
（7）Stopping is passed through waste gas, discharges water from the discharging valve of reactor bottom, after in question response device, water all bleeds off, again from anti-
Answer the air brick of device bottom to be passed through the waste gas that pressure is 0.3MP, carry out secondary CO2Solidification, exhaust gas flow are controlled in 6.0 L/s,
Persistent period is that the volume ratio of the material of 4h, waste gas intake and inside reactor is controlled 30:1；
（8）In metallurgical steel slag, the conversion ratio of CaO is 29% for the conversion ratio of 55%, MgO；
Apparatus structure with embodiment 1, difference is：Difference in height between two neighboring grate plate is 600mm, is uniformly divided in grate plate
Strip crevice is furnished with, the width of strip crevice is 5mm；Grate plate thickness 10mm.
Embodiment 4
Method with embodiment 1, difference is：
（1）The slag that the metallurgical slag for adopting is produced for refining plant, particle diameter are accounted for always less than or equal to the part of 15mm more than 10mm
The 6% of weight, particle diameter account for the 16% of gross weight less than or equal to the part of 10mm more than 5mm, and particle diameter is more than 1mm less than or equal to 5mm's
Part accounts for the 31% of gross weight, and part of the particle diameter more than 0.1 less than or equal to 1mm accounts for the 40% of gross weight, portion of the particle diameter less than 0.1mm
Divide and account for the 7% of gross weight；
（2）Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The mol ratio of sum is 1.0:1；Alkaline modification agent is little
Soda and Caustic soda；
（3）Metallurgical Waste Water pH value 8, calcium concentration are 70 mg/L；
（4）120 DEG C of EGT, CO2Content 26%；
（5）Metallurgical steel slag soaks 15h with the mixture of alkaline modification agent, and controls temperature at 35 DEG C；Metallurgical Waste Water is higher by metallurgy
Slag and alkaline modification agent upper surface 1m；
（6）Immersion terminates to be passed through the waste gas that pressure is 0.8MP from the air brick of reactor bottom backward, carries out first CO2Solidification,
Persistent period is 2h, and exhaust gas flow control is existed with the volume ratio control of the material of inside reactor in 4.0L/s, waste gas intake
25:1；
（7）Stopping is passed through waste gas, discharges water from the discharging valve of reactor bottom, after in question response device, water all bleeds off, again from anti-
Answer the air brick of device bottom to be passed through the waste gas that pressure is 0.8MP, carry out secondary CO2Solidification, exhaust gas flow are controlled in 1.0 L/s,
Persistent period is that the volume ratio of the material of 1h, waste gas intake and inside reactor is controlled 25:1；
（8）In metallurgical steel slag, the conversion ratio of CaO is 32% for the conversion ratio of 46%, MgO；
Apparatus structure with embodiment 1, difference is：Difference in height between two neighboring grate plate is 800mm, is uniformly divided in grate plate
It is furnished with manhole, a diameter of 5mm of manhole；Grate plate thickness 12mm.
Embodiment 5
Method with embodiment 1, difference is：
（1）The slag that the metallurgical slag for adopting is produced for refining plant, particle diameter are accounted for always less than or equal to the part of 15mm more than 10mm
The 5% of weight, particle diameter account for the 25% of gross weight less than or equal to the part of 10mm more than 5mm, and particle diameter is more than 1mm less than or equal to 5mm's
Part accounts for the 35% of gross weight, and part of the particle diameter more than 0.1 less than or equal to 1mm accounts for the 30% of gross weight, portion of the particle diameter less than 0.1mm
Divide and account for the 5% of gross weight；
（2）Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The mol ratio of sum is 0.9:1；Alkaline modification agent is Soviet Union
Beat and Caustic soda；
（3）Metallurgical Waste Water pH value 10, calcium concentration are 200 mg/L；
（4）90 DEG C of EGT, CO2Content 20%；
（5）Metallurgical steel slag soaks 18h with the mixture of alkaline modification agent, and controls temperature at 30 DEG C；Metallurgical Waste Water is higher by metallurgy
Slag and alkaline modification agent upper surface 0.8m；
（6）Immersion terminates to be passed through the waste gas that pressure is 1MP from the air brick of reactor bottom backward, carries out first CO2Solidification, holds
The continuous time is 2h, and in 2.0L/s, the volume ratio control of waste gas intake and the material of inside reactor is 20 for exhaust gas flow control:
1；
（7）Stopping is passed through waste gas, discharges water from the discharging valve of reactor bottom, after in question response device, water all bleeds off, again from anti-
Answer the air brick of device bottom to be passed through the waste gas that pressure is 1MP, carry out secondary CO2Solidification, exhaust gas flow are controlled in 3.0 L/s, are held
The continuous time is that the volume ratio of the material of 2h, waste gas intake and inside reactor is controlled 20:1；
（8）In metallurgical steel slag, the conversion ratio of CaO is 15% for the conversion ratio of 26%, MgO；
Apparatus structure with embodiment 1, difference is：Difference in height between two neighboring grate plate is 1000mm, uniform in grate plate
Manhole, a diameter of 3mm of manhole is distributed with；Grate plate thickness 20mm.
Embodiment 6
Method with embodiment 1, difference is：
（1）The slag that the metallurgical slag for adopting is produced for refining plant, particle diameter are accounted for always less than or equal to the part of 15mm more than 10mm
The 9% of weight, particle diameter account for the 17% of gross weight less than or equal to the part of 10mm more than 5mm, and particle diameter is more than 1mm less than or equal to 5mm's
Part accounts for the 45% of gross weight, and part of the particle diameter more than 0.1 less than or equal to 1mm accounts for the 22% of gross weight, portion of the particle diameter less than 0.1mm
Divide and account for the 7% of gross weight；
（2）Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The mol ratio of sum is 0.6:1；Alkaline modification agent is little
Soda and Caustic soda；
（3）Metallurgical Waste Water pH value 8, calcium concentration are 80 mg/L；
（4）110 DEG C of EGT, CO2Content 30%；
（5）Metallurgical steel slag soaks 15h with the mixture of alkaline modification agent, and controls temperature at 35 DEG C；Metallurgical Waste Water is higher by metallurgy
Slag and alkaline modification agent upper surface 1m；
（6）Immersion terminates to be passed through the waste gas that pressure is 0.5MP from the air brick of reactor bottom backward, carries out first CO2Solidification,
Persistent period is 3h, and exhaust gas flow control is existed with the volume ratio control of the material of inside reactor in 4.0L/s, waste gas intake
15:1；
（7）Stopping is passed through waste gas, discharges water from the discharging valve of reactor bottom, after in question response device, water all bleeds off, again from anti-
Answer the air brick of device bottom to be passed through the waste gas that pressure is 0.5MP, carry out secondary CO2Solidification, exhaust gas flow are controlled in 5.0 L/s,
Persistent period is that the volume ratio of the material of 3h, waste gas intake and inside reactor is controlled 25:1；
（8）In metallurgical steel slag, the conversion ratio of CaO is 45% for the conversion ratio of 37%, MgO；
Apparatus structure with embodiment 1, difference is：Difference in height between two neighboring grate plate is 500mm, is uniformly divided in grate plate
It is furnished with manhole, a diameter of 2mm of manhole；Grate plate thickness 9mm.
Claims (10)
1. a kind of collaboration is using CO in slag and the stable waste gas of waste water2Method, it is characterised in that carry out according to the following steps：
（1）Metallurgical steel slag is crushed to into particle diameter≤15mm, wherein particle diameter accounts for gross weight less than or equal to the part of 15mm more than 10mm
Less than 10%, particle diameter accounts for the 13 ~ 35% of gross weight less than or equal to the part of 10mm more than 5mm, and particle diameter is less than or equal to more than 1mm
The part of 5mm accounts for the 30 ~ 60% of gross weight, and particle diameter accounts for the 20 ~ 40% of gross weight less than or equal to the part of 1mm more than 0.1, particle diameter
Part less than 0.1mm accounts for less than the 8% of gross weight；
（2）Prepare alkaline modification agent, Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The mol ratio of sum is（0.2~
1.3）:1；
（3）Using steel mill's dust waste water as Metallurgical Waste Water, pH value is that, between 7.5 ~ 12, calcium concentration is 50 ~ 250 mg/L；
（4）Using CO2The metallurgical tail gas of content ＞ 15% are used as waste gas, 45 ~ 150 DEG C of temperature；
（5）After metallurgical steel slag is sufficiently mixed with alkaline modification agent, loading bottom is provided with air brick and inside is placed with the anti-of grate plate
Answer in device, metallurgical steel slag is deposited in grate plate with alkaline modification agent；Metallurgical Waste Water is subsequently adding, and metallurgical steel slag is made with alkalescence modification
The mixture of agent soaks more than 12h in Metallurgical Waste Water, and controls temperature more than 30 DEG C；Wherein Metallurgical Waste Water submergence metallurgy steel
Slag is with alkaline modification agent and is higher by metallurgical steel slag and alkalescence more than modification agent upper surface 0.5m；
（6）Immersion terminates to be passed through the waste gas that pressure is 0.3 ~ 1MP from the air brick of reactor bottom backward, carries out first CO2Gu
Change, the persistent period is 1 ~ 3h, exhaust gas flow control in 1.0 ~ 5.0L/s, the volume of waste gas intake and the material of inside reactor
Exist than control（15~30）:1；
（7）Stopping is passed through waste gas, discharges water from the discharging valve of reactor bottom, after in question response device, water all bleeds off, again from anti-
Answer the air brick of device bottom to be passed through the waste gas that pressure is 0.3 ~ 1MP, carry out secondary CO2Solidification, exhaust gas flow control 0.5 ~
6.0L/s, persistent period are that the volume ratio control of the material of 0.5 ~ 4h, waste gas intake and inside reactor exists（15~30）:1；
（8）The material for completing secondary solidification is air-dried, carbonatation steel scoria is obtained.
2. a kind of collaboration according to claim 1 is using CO in slag and the stable waste gas of waste water2Method, it is characterised in that
The composition of described metallurgical steel slag contains CaO 35 ~ 60%, SiO by weight percentage2 8 ~ 20%, Fe2O3 10 ~ 30%, MgO 5
~ 10%, Al2O31 ~ 3%, P2O5 1.2 ~ 2.8%, MnO 0.1 ~ 2.2%, TiO2 0 ~ 1.3%。
3. a kind of collaboration according to claim 1 is using CO in slag and the stable waste gas of waste water2Method, it is characterised in that
Described alkaline modification agent be soda, sodium bicarbonate and/or Caustic soda, purity by weight >=95% of alkaline modification agent, granularity≤30 mesh.
4. a kind of collaboration according to claim 1 is using CO in slag and the stable waste gas of waste water2Method, it is characterised in that
In metallurgical steel slag, the conversion ratio of CaO is 20 ~ 55%.
5. a kind of collaboration according to claim 1 is using CO in slag and the stable waste gas of waste water2Method, it is characterised in that
In metallurgical steel slag, the conversion ratio of MgO is 15 ~ 45%.
6. a kind of collaboration for implementing the method described in claim 1 utilizes CO in slag and the stable waste gas of waste water2Device, which is special
It is the closure for including reactor shell and its top to levy, and reactor shell bottom even is distributed with multiple for being passed through waste gas
Air brick, air brick connected with air-introduced machine, and wherein air-introduced machine is used to introduce waste gas and airing materials, and reactor shell bottom is also
Discharging valve is provided with, closure is provided with water intaking valve and diffusion valve；Multilamellar grate plate is provided with inside reactor shell above air brick.
7. collaboration according to claim 6 is using CO in slag and the stable waste gas of waste water2Device, it is characterised in that it is described
Closure on be additionally provided with air relief valve.
8. collaboration according to claim 6 is using CO in slag and the stable waste gas of waste water2Device, it is characterised in that it is described
Multilamellar grate plate be uniformly distributed in vertical direction, the difference in height between two neighboring grate plate is 400 ~ 1200mm, in grate plate
Even that strip crevice or manhole is distributed with, the width of strip crevice is 0.5 ~ 5mm, a diameter of 2 ~ 5mm of manhole.
9. collaboration according to claim 6 is using CO in slag and the stable waste gas of waste water2Device, it is characterised in that it is described
The material of reactor shell be that outside is provided with the steel of heat-insulation layer, air brick is embedded on the base plate of cylinder.
10. collaboration according to claim 6 is using CO in slag and the stable waste gas of waste water2Device, it is characterised in that it is described
Grate plate material be steel, 8 ~ 25mm of thickness.
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| CN115446049A (en) * | 2022-08-19 | 2022-12-09 | 宝武环科武汉金属资源有限责任公司 | Economical waste paint bucket cleaning process |
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| CN109160516A (en) * | 2018-08-20 | 2019-01-08 | 中国华能集团清洁能源技术研究院有限公司 | Using the method containing bittern water and solid waste joint trapping mineralization of carbon dioxide |
| CN110950338A (en) * | 2019-12-25 | 2020-04-03 | 江西理工大学 | Method for capturing carbon dioxide and co-producing NPCC (nitrogen phosphorus CC) in converter flue gas by closed cycle of converter steel slag-steelmaking wastewater |
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| CN112791573A (en) * | 2021-01-11 | 2021-05-14 | 东北大学 | Steelmaking waste cooperative treatment system and method based on ball milling reinforcement |
| CN113929334A (en) * | 2021-11-24 | 2022-01-14 | 山东大学 | Acidized and carbonized coupling modified steel slag and preparation process and application thereof |
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| CN115446049A (en) * | 2022-08-19 | 2022-12-09 | 宝武环科武汉金属资源有限责任公司 | Economical waste paint bucket cleaning process |
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