CN106540525B - A kind of cooperate with stablizes CO in exhaust gas using clinker and waste water2Method and device - Google Patents
A kind of cooperate with stablizes CO in exhaust gas using clinker and waste water2Method and device Download PDFInfo
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- CN106540525B CN106540525B CN201611053253.0A CN201611053253A CN106540525B CN 106540525 B CN106540525 B CN 106540525B CN 201611053253 A CN201611053253 A CN 201611053253A CN 106540525 B CN106540525 B CN 106540525B
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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 cooperate with stablizes CO in exhaust gas using clinker and waste water2Method and device, method are as follows: (1) be crushed metallurgical steel slag；(2) prepare alkaline modification agent；(3) using steel mill's dust waste water as Metallurgical Waste Water；(4) using metallurgical tail gas as exhaust gas；(5) metallurgical steel slag is mixed with alkaline modification agent and is packed into reactor, Metallurgical Waste Water is added and impregnates；(6) it is passed through exhaust gas, carries out CO2Solidification；(7) after discharging water, it is passed through exhaust gas again；(8) it air-dries and obtains carbonatation steel scoria.Device includes reactor shell and sealing cover, and reactor shell bottom is distributed air brick, and air brick is connected to air-introduced machine；The top of air brick is equipped with multilayer grate plate inside reactor shell.Method of the invention directly determines that the additional amount of alkaline modification agent, simple production process mitigate environment and social load, be conducive to the sustainable development of society using the pH value and calcium concentration of CaO in metallurgical steel slag and MgO and dust waste water.
Description
Technical field
The invention belongs to metallurgical technical field of three-waste treatment, in particular to a kind of collaboration stablizes exhaust gas using clinker and waste water
Middle CO2Method and device.
Background technique
Since nearly 30 years, China's steel industry has obtained huge development, especially 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, generally low using added value although developing the application technology of many kinds of converter slags acidification, and
And it needs again to heat broken clinker, thus result in equipment investment and operating cost is higher；Therefore, exploitation has me
The new technology that the metallurgical slag of state's resource features cooperates with coupling to utilize with metallurgical dust waste water, improves waste residue reuse ratio and product
Added value is established resource-conserving and environment-friendly society and is of great significance to developing a circular economy.
In iron and steel enterprise, the metallurgical three wastes are the main wastes of steel manufacture process.Wherein: the discharge amount of clinker is about
12 ~ 15% or so of converter producing crude steel amount；The discharge amount of waste water is 2.7 times or more for producing crude steel amount；Ton steel CO2Discharge
Amount is in 1.3t or more；Currently, the approach of clinker secondary use recycles inside iron and steel enterprise primarily as blast furnace, converter charge
It uses, or its utilization rate is not high as road substrate, construction material and raw material of steel slag fertilizer etc., but for a long time, then
It is relatively low using added value.
Application No. is 200710038393.5,200710044157.4, patents to disclose a kind of carbonatation steel scoria processing
The method of waste water, although referring to steel slag solidification CO2The method of gas, but dedicated fluidized bed reactor consersion unit is needed,
And whole process needs high temperature；Application No. is 200510030330.6 and 200510093267.0 patents to disclose some incite somebody to action
The method of slag processing waste water, but slag processing waste water is as one in combination formula use, without exclusive use can
Row, and these processing methods cannot largely handle the steel slag of the big byproduct of steel and iron industry first；So far, both at home and abroad specially
Benefit and non-patent literature nothing directly adopt waste steel slag and waste water and coupling are directly cooperateed with to stablize CO in exhaust gas2Application report
Road.
Summary of the invention
On existing for the metallurgy three wastes (waste residue, waste water and exhaust gas) processing technically a large amount of in existing steel and iron industry
Problem is stated, the present invention provides a kind of cooperate with and stablizes CO in exhaust gas using clinker and waste water2Method and device, with metallurgical steel slag,
Metallurgical Waste Water and emission are added basic matterial as modification agent, carry out CO2Solidification, reach the secondary use of steel slag,
Reduce CO2Discharge amount, mitigate environment and social load.
Method of the invention sequentially includes the following steps:
1, metallurgical steel slag is crushed to partial size≤15mm, wherein part of the partial size greater than 10mm less than or equal to 15mm accounts for gross weight
The 10% of amount accounts for the 13 ~ 35% of total weight hereinafter, partial size is greater than part of the 5mm less than or equal to 10mm, and partial size is less than or equal to greater than 1mm
The part of 5mm accounts for the 30 ~ 60% of total weight, and partial size is greater than 0.1 part less than or equal to 1mm and accounts for the 20 ~ 40% of total weight, partial size
Part less than 0.1mm accounts for 8% or less total weight；
2, prepare alkaline modification agent, Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The sum of molar ratio be
(0.2 ~ 1.3): 1；
3, using steel mill's dust waste water as Metallurgical Waste Water, pH value is between 7.5 ~ 12, and calcium concentration is 50 ~ 250 mg/L；
4, using CO2The metallurgical tail gas of content > 15% is as exhaust gas, and 45 ~ 150 DEG C of temperature；
5, bottom is packed into equipped with air brick after being sufficiently mixed metallurgical steel slag and alkaline modification agent and inside is placed with grate plate
Reactor in, metallurgical steel slag and alkaline modification agent are deposited in grate plate；Then Metallurgical Waste Water is added, makes metallurgical steel slag and alkalinity
The mixture of modification agent impregnates 12h or more in Metallurgical Waste Water, and controls temperature at 30 DEG C or more；Wherein Metallurgical Waste Water submerges smelting
Golden steel slag and alkaline modification agent are simultaneously higher by metallurgical steel slag and alkalinity modification agent upper surface 0.5m or more；
6, impregnating terminates to be passed through the exhaust gas that pressure is 0.3 ~ 1MP from the air brick of reactor bottom backward, carries out first CO2
Solidification, duration are 1 ~ 3h, and exhaust gas flow control is in 1.0 ~ 5.0L/s, the body of the material of exhaust gas intake and inside reactor
Product is than control in (15 ~ 30): 1；
7, stop be passed through exhaust gas, discharge water from the discharging valve of reactor bottom, after water is all bled off in reactor, again from
The air brick of reactor bottom is passed through the exhaust gas that pressure is 0.3 ~ 1MP, carries out secondary CO2Solidification, exhaust gas flow control 0.5 ~
6.0L/s, duration are 0.5 ~ 4h, and the volume ratio of the material of exhaust gas intake and inside reactor is controlled in (15 ~ 30): 1；
8, the material for completing secondary curing is air-dried, obtains carbonatation steel scoria.
The ingredient for the metallurgical steel slag selected in the above 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 the above method is soda, sodium bicarbonate and/or caustic soda, the purity by weight of alkaline modification agent
>=95%, granularity≤30 mesh.
The ingredient for the carbonatation steel scoria that the above method obtains 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%.
The conversion ratio of CaO is 20 ~ 55% in metallurgical steel slag in the above method.
The conversion ratio of MgO is 15 ~ 45% in metallurgical steel slag in the above method.
Solidify CO after metallurgical steel slag per ton acidification in the above method2 0.3 ~ 1.5kg converts into 0.153 ~ 0.764 m3
CO2。
Following chemical reaction occurs in the above method, in step 5,6,7 acidizations
(I) dissociation of water:
H2O(l)↔H++OH- (1)
(II) in metallurgical steel slag active component CaO and MgO hydration reaction, 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 spreads after passing through gas-liquid interface, dissolution, ionizes:
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 sediment 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 implementation above method of the invention includes the sealing cover at reactor shell and its top, reactor shell bottom
Portion is evenly distributed with multiple air bricks for being used to be passed through exhaust gas, and air brick is connected to air-introduced machine, and wherein air-introduced machine is useless for introducing
Gas and airing materials, reactor shell bottom are additionally provided with discharging valve, and sealing cover is equipped with inlet valve and diffusion valve；Reactor shell
The top of internal air brick is equipped with multilayer grate plate.
In above-mentioned apparatus, pressure reducing valve is additionally provided on sealing cover.
In above-mentioned apparatus, multilayer 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 circular through hole in grate plate, and the width of strip crevice is 0.5 ~ 5mm, circular through hole
Diameter is 2 ~ 5mm.
In above-mentioned apparatus, the material of reactor shell is the external steel for being equipped with insulating layer, and air brick is embedded in cylinder
On bottom plate.
In above-mentioned apparatus, the material of grate plate is steel, 8 ~ 25mm of thickness.
The application method of above-mentioned apparatus are as follows: be deposited in each layer grate plate after being sufficiently mixed metallurgical steel slag and alkaline modification agent
On, it will be closed inside reactor shell with sealing cover, waste water be passed through by inlet valve；After impregnating, pass through reactor cylinder
The air brick of body bottom is passed through exhaust gas；First CO2After solidification, waste water is discharged by discharging valve, again by reactor
The air brick of cylinder body bottom is passed through exhaust gas；Secondary CO2After solidification, diffusion valve and air outlet are opened, is made instead by air-introduced machine
It answers device inner barrel to divulge information, material is carried out air-dried.
Fixed CO is coupled present invention is characterized in that being cooperateed with the metallurgical three wastes (waste residue, waste water and exhaust gas)2, can be abundant
Byproduct and waste 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 clinker.Modification agent is added using the metallurgical three wastes and cooperates with fixed CO2Technique, with traditional metallurgical slag
Acidification technique is compared, and whole process whole process uses Metallurgical Waste Water, and can significantly reduce the energy in steel slag heating process
Consumption, and pass through solidification CO2Process preliminary treatment Metallurgical Waste Water.
Method of the invention can directly utilize metallurgical slag, waste water and exhaust gas, according to CaO's in metallurgical steel slag and MgO
It measures with the pH value of dust waste water and calcium concentration and determines the additional amount of alkaline modification agent, simple production process；Utilize metallurgy three
Useless (waste residue, waste water and exhaust gas) collaboration couples the CO in fixed metallurgical industry exhaust gas2, reduce CO2Discharge amount, mitigate environment with
Social load is conducive to the sustainable development of society.
Detailed description of the invention
Fig. 1 is that a kind of collaboration of the invention utilizes CO in clinker and the stable exhaust gas of waste water2Method and process flow diagram；
Fig. 2 is the reactor assembly structural schematic diagram used in the embodiment of the present invention；
In figure: 1, inlet valve；2, pressure reducing valve；3, diffusion valve；4, grate plate；5, air-introduced machine；6, discharging valve；7, air brick；8,
The mixture of metallurgical steel slag and alkaline modification agent, 9, sealing cover, 10, reactor shell.
Specific embodiment
The converter steel of steel slag, converter mill generation that the metallurgical steel slag used in the embodiment of the present invention generates for refining plant
The electric furnace slag that slag or electric furnace shop generate, ingredient 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 used in the embodiment of the present invention is useless for converter mill petticoat pipe dust waste water, electric furnace shop petticoat pipe dedusting
Water, refining plant dust waste water and mill dephosphorization or cooling waste water.
The exhaust gas used in the embodiment of the present invention is not achieved what coal-gas recovering standard was generated through processing early period to bessemerize
The exhaust gas that coal-gas recovering standard is generated through processing is not achieved in exhaust gas, electric furnace Primary period, and sintering generation exhaust gas, heating furnace generate useless
(the CO in exhaust gas such as gas2Effective volume concentration 15 ~ 36%).
The alkaline modification agent used in the embodiment of the present invention uses soda, sodium bicarbonate and caustic soda for commercially available industrial products.
The application method of device in the embodiment of the present invention are as follows: be deposited in after being sufficiently mixed metallurgical steel slag with alkaline modification agent
In each layer grate plate, it will be closed inside reactor shell with sealing cover, waste water be passed through by inlet valve；After impregnating, pass through
The air brick of reactor shell bottom is passed through exhaust gas；First CO2After solidification, waste water is discharged by discharging valve, is led to again
The air brick for crossing reactor shell bottom is passed through exhaust gas；Secondary CO2After solidification, diffusion valve and air outlet are opened, by drawing
Blower makes reactor shell inner ventilation, carries out to material air-dried.
The ingredient 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 partial size≤15mm, wherein part of the partial size greater than 10mm less than or equal to 15mm accounts for total weight
10%, partial size is greater than part of the 5mm less than or equal to 10mm and accounts for the 15% of total weight, and partial size is greater than the part that 1mm is less than or equal to 5mm
The 35% of total weight is accounted for, partial size is greater than 0.1 part less than or equal to 1mm and accounts for the 35% of total weight, and part of the partial size less than 0.1mm accounts for
The 5% of total weight；
Prepare alkaline modification agent, Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The sum of molar ratio be 0.2:
1；Alkaline modification agent is soda；
Using steel mill's dust waste water as Metallurgical Waste Water, pH value 7.5, calcium concentration is 50 mg/L；
Using CO2The metallurgical tail gas of content 15% is as exhaust gas, temperature 45 C；
It is packed into bottom after metallurgical steel slag and alkaline modification agent are sufficiently mixed equipped with air brick and inside is placed with grate plate
In reactor, metallurgical steel slag and alkaline modification agent are deposited in grate plate；Then Metallurgical Waste Water is added, changes metallurgical steel slag with alkalinity
The mixture of matter agent impregnates 12h in Metallurgical Waste Water, and controls temperature at 40 DEG C；Wherein Metallurgical Waste Water submergence metallurgical steel slag and alkali
Property modification agent and be higher by metallurgical steel slag and alkaline modification agent upper surface 0.6m；
6, impregnating terminates to be passed through the exhaust gas that pressure is 0.3MP from the air brick of reactor bottom backward, carries out first CO2Gu
Change, duration 3h, in 5.0L/s, the volume ratio of the material of exhaust gas intake and inside reactor is controlled for exhaust gas flow control
In 30:1；
7, stop be passed through exhaust gas, discharge water from the discharging valve of reactor bottom, after water is all bled off in reactor, again from
The air brick of reactor bottom is passed through the exhaust gas that pressure is 0.3MP, carries out secondary CO2Solidification, exhaust gas flow are controlled in 5.0 L/
The volume ratio of the material of s, duration 3h, exhaust gas intake and inside reactor is controlled in 20:1；
8, the material for completing secondary curing is air-dried, obtains carbonatation steel scoria, ingredient contain by weight percentage 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%；
The conversion ratio that the conversion ratio of CaO is 20%, MgO in metallurgical steel slag is 38%；
Apparatus structure is as shown in Fig. 2, include the sealing cover 9 at reactor shell 10 and its top, 10 bottom of reactor shell
Multiple air bricks 7 for being used to be passed through exhaust gas are evenly distributed with, air brick 7 is connected to air-introduced machine 6, and wherein air-introduced machine 6 is for introducing
Exhaust gas and airing materials, 10 bottom of reactor shell are additionally provided with discharging valve 6, and sealing cover 9 is equipped with inlet valve 1 and diffusion valve 3；Instead
The top of 10 inside air brick 7 of device cylinder is answered to be equipped with multilayer grate plate 4；Pressure reducing valve 2 is additionally provided on sealing cover 9, multilayer grate plate 4 is being hung down
Histogram is uniformly distributed upwards, and the difference in height between two neighboring grate plate 4 is 400mm, is evenly distributed with strip crevice in grate plate 4,
The width of strip crevice is 0.5mm；The material of reactor shell 10 is the external steel for being equipped with insulating layer, and air brick 7 is embedded in instead
On the bottom plate for answering device cylinder 10；The material of grate plate 4 is steel, thickness 8mm.
Embodiment 2
With embodiment 1, difference is method:
(1) steel slag that the metallurgical slag used generates for refining plant, partial size are greater than the part that 10mm is less than or equal to 15mm
The 7% of total weight is accounted for, partial size is greater than part of the 5mm less than or equal to 10mm and accounts for the 35% of total weight, and partial size is less than or equal to greater than 1mm
The part of 5mm accounts for the 30% of total weight, and partial size is greater than 0.1 part less than or equal to 1mm and accounts for the 20% of total weight, and partial size is less than
The part of 0.1mm accounts for the 8% of total weight；
(2) Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The sum of molar ratio be 0.4:1；Alkaline modification agent
For sodium bicarbonate；
(3) Metallurgical Waste Water pH value 12, calcium concentration are 250 mg/L；
(4) 90 DEG C of exhaust gas temperature, CO2Content 18%；
(5) mixture of metallurgical steel slag and alkaline modification agent impregnates 18h, and controls temperature at 30 DEG C；Metallurgical Waste Water is higher by
Metallurgical steel slag and alkaline modification agent upper surface 0.8m；
(6) impregnating terminates to be passed through the exhaust gas that pressure is 1MP from the air brick of reactor bottom backward, carries out first CO2Gu
Change, duration 1h, in 1.0L/s, the volume ratio of the material of exhaust gas intake and inside reactor is controlled for exhaust gas flow control
In 15:1；
(7) stop being passed through exhaust gas, discharge water from the discharging valve of reactor bottom, after water is all bled off in reactor, again
It is passed through the exhaust gas that pressure is 1MP from the air brick of reactor bottom, carries out secondary CO2Solidification, exhaust gas flow are controlled in 0.5L/s,
Duration is 0.5h, and the volume ratio of the material of exhaust gas intake and inside reactor is controlled in 15:1；
(8) conversion ratio that the conversion ratio of CaO is 31%, MgO in metallurgical steel slag is 41%；
With embodiment 1, difference is apparatus structure: difference in height between two neighboring grate plate is 1200mm, in grate plate
It is evenly distributed with strip crevice, the width of strip crevice is 2mm；Grate plate thickness 25mm.
Embodiment 3
With embodiment 1, difference is method:
(1) steel slag that the metallurgical slag used generates for refining plant, partial size are greater than the part that 10mm is less than or equal to 15mm
The 1% of total weight is accounted for, partial size is greater than part of the 5mm less than or equal to 10mm and accounts for the 13% of total weight, and partial size is less than or equal to greater than 1mm
The part of 5mm accounts for the 60% of total weight, and partial size is greater than 0.1 part less than or equal to 1mm and accounts for the 24% of total weight, and partial size is less than
The part of 0.1mm accounts for the 2% of total weight；
(2) Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The sum of molar ratio be 1.3:1；Alkaline modification agent
For caustic soda；
(3) Metallurgical Waste Water pH value 9, calcium concentration are 150 mg/L；
(4) 150 DEG C of exhaust gas temperature, CO2Content 36%；
(5) mixture of metallurgical steel slag and alkaline modification agent impregnates 15h, and controls temperature at 35 DEG C；Metallurgical Waste Water is higher by
Metallurgical steel slag and alkaline modification agent upper surface 1m；
(6) impregnating terminates to be passed through the exhaust gas that pressure is 0.5MP from the air brick of reactor bottom backward, carries out first CO2
Solidification, duration 2h, exhaust gas flow control is in 3.0L/s, the volume ratio control of the material of exhaust gas intake and inside reactor
System is in 20:1；
(7) stop being passed through exhaust gas, discharge water from the discharging valve of reactor bottom, after water is all bled off in reactor, again
It is passed through the exhaust gas that pressure is 0.3MP from the air brick of reactor bottom, carries out secondary CO2Solidification, exhaust gas flow are controlled 6.0
The volume ratio of the material of L/s, duration 4h, exhaust gas intake and inside reactor is controlled in 30:1；
(8) conversion ratio that the conversion ratio of CaO is 55%, MgO in metallurgical steel slag is 29%；
With embodiment 1, difference is apparatus structure: difference in height between two neighboring grate plate is 600mm, in grate plate
Even that strip crevice is distributed with, the width of strip crevice is 5mm；Grate plate thickness 10mm.
Embodiment 4
With embodiment 1, difference is method:
(1) steel slag that the metallurgical slag used generates for refining plant, partial size are greater than the part that 10mm is less than or equal to 15mm
The 6% of total weight is accounted for, partial size is greater than part of the 5mm less than or equal to 10mm and accounts for the 16% of total weight, and partial size is less than or equal to greater than 1mm
The part of 5mm accounts for the 31% of total weight, and partial size is greater than 0.1 part less than or equal to 1mm and accounts for the 40% of total weight, and partial size is less than
The part of 0.1mm accounts for the 7% of total weight；
(2) Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The sum of molar ratio be 1.0:1；Alkaline modification agent
For sodium bicarbonate and caustic soda；
(3) Metallurgical Waste Water pH value 8, calcium concentration are 70 mg/L；
(4) 120 DEG C of exhaust gas temperature, CO2Content 26%；
(5) mixture of metallurgical steel slag and alkaline modification agent impregnates 15h, and controls temperature at 35 DEG C；Metallurgical Waste Water is higher by
Metallurgical steel slag and alkaline modification agent upper surface 1m；
(6) impregnating terminates to be passed through the exhaust gas that pressure is 0.8MP from the air brick of reactor bottom backward, carries out first CO2
Solidification, duration 2h, exhaust gas flow control is in 4.0L/s, the volume ratio control of the material of exhaust gas intake and inside reactor
System is in 25:1；
(7) stop being passed through exhaust gas, discharge water from the discharging valve of reactor bottom, after water is all bled off in reactor, again
It is passed through the exhaust gas that pressure is 0.8MP from the air brick of reactor bottom, carries out secondary CO2Solidification, exhaust gas flow are controlled 1.0
The volume ratio of the material of L/s, duration 1h, exhaust gas intake and inside reactor is controlled in 25:1；
(8) conversion ratio that the conversion ratio of CaO is 46%, MgO in metallurgical steel slag is 32%；
With embodiment 1, difference is apparatus structure: difference in height between two neighboring grate plate is 800mm, in grate plate
Even that circular through hole is distributed with, the diameter of circular through hole is 5mm；Grate plate thickness 12mm.
Embodiment 5
With embodiment 1, difference is method:
(1) steel slag that the metallurgical slag used generates for refining plant, partial size are greater than the part that 10mm is less than or equal to 15mm
The 5% of total weight is accounted for, partial size is greater than part of the 5mm less than or equal to 10mm and accounts for the 25% of total weight, and partial size is less than or equal to greater than 1mm
The part of 5mm accounts for the 35% of total weight, and partial size is greater than 0.1 part less than or equal to 1mm and accounts for the 30% of total weight, and partial size is less than
The part of 0.1mm accounts for the 5% of total weight；
(2) Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The sum of molar ratio be 0.9:1；Alkaline modification agent
For soda and caustic soda；
(3) Metallurgical Waste Water pH value 10, calcium concentration are 200 mg/L；
(4) 90 DEG C of exhaust gas temperature, CO2Content 20%；
(5) mixture of metallurgical steel slag and alkaline modification agent impregnates 18h, and controls temperature at 30 DEG C；Metallurgical Waste Water is higher by
Metallurgical steel slag and alkaline modification agent upper surface 0.8m；
(6) impregnating terminates to be passed through the exhaust gas that pressure is 1MP from the air brick of reactor bottom backward, carries out first CO2Gu
Change, duration 2h, in 2.0L/s, the volume ratio of the material of exhaust gas intake and inside reactor is controlled for exhaust gas flow control
In 20:1；
(7) stop being passed through exhaust gas, discharge water from the discharging valve of reactor bottom, after water is all bled off in reactor, again
It is passed through the exhaust gas that pressure is 1MP from the air brick of reactor bottom, carries out secondary CO2Solidification, exhaust gas flow are controlled in 3.0 L/
The volume ratio of the material of s, duration 2h, exhaust gas intake and inside reactor is controlled in 20:1；
(8) conversion ratio that the conversion ratio of CaO is 26%, MgO in metallurgical steel slag is 15%；
With embodiment 1, difference is apparatus structure: difference in height between two neighboring grate plate is 1000mm, in grate plate
It is evenly distributed with circular through hole, the diameter of circular through hole is 3mm；Grate plate thickness 20mm.
Embodiment 6
With embodiment 1, difference is method:
(1) steel slag that the metallurgical slag used generates for refining plant, partial size are greater than the part that 10mm is less than or equal to 15mm
The 9% of total weight is accounted for, partial size is greater than part of the 5mm less than or equal to 10mm and accounts for the 17% of total weight, and partial size is less than or equal to greater than 1mm
The part of 5mm accounts for the 45% of total weight, and partial size is greater than 0.1 part less than or equal to 1mm and accounts for the 22% of total weight, and partial size is less than
The part of 0.1mm accounts for the 7% of total weight；
(2) Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The sum of molar ratio be 0.6:1；Alkaline modification agent
For sodium bicarbonate and caustic soda；
(3) Metallurgical Waste Water pH value 8, calcium concentration are 80 mg/L；
(4) 110 DEG C of exhaust gas temperature, CO2Content 30%；
(5) mixture of metallurgical steel slag and alkaline modification agent impregnates 15h, and controls temperature at 35 DEG C；Metallurgical Waste Water is higher by
Metallurgical steel slag and alkaline modification agent upper surface 1m；
(6) impregnating terminates to be passed through the exhaust gas that pressure is 0.5MP from the air brick of reactor bottom backward, carries out first CO2
Solidification, duration 3h, exhaust gas flow control is in 4.0L/s, the volume ratio control of the material of exhaust gas intake and inside reactor
System is in 15:1；
(7) stop being passed through exhaust gas, discharge water from the discharging valve of reactor bottom, after water is all bled off in reactor, again
It is passed through the exhaust gas that pressure is 0.5MP from the air brick of reactor bottom, carries out secondary CO2Solidification, exhaust gas flow are controlled 5.0
The volume ratio of the material of L/s, duration 3h, exhaust gas intake and inside reactor is controlled in 25:1；
(8) conversion ratio that the conversion ratio of CaO is 37%, MgO in metallurgical steel slag is 45%；
With embodiment 1, difference is apparatus structure: difference in height between two neighboring grate plate is 500mm, in grate plate
Even that circular through hole is distributed with, the diameter of circular through hole is 2mm；Grate plate thickness 9mm.
Claims (10)
1. a kind of collaboration stablizes CO in exhaust gas using clinker and waste water2Method, it is characterised in that sequentially include the following steps:
(1) metallurgical steel slag is crushed to partial size≤15mm, wherein part of the partial size greater than 10mm less than or equal to 15mm accounts for total weight
10% account for the 13 ~ 35% of total weight less than or equal to the part of 10mm hereinafter, partial size is greater than 5mm, partial size is less than or equal to greater than 1mm
The part of 5mm accounts for the 30 ~ 60% of total weight, and partial size is greater than 0.1 part less than or equal to 1mm and accounts for the 20 ~ 40% of total weight, partial size
Part less than 0.1mm accounts for 8% or less total weight；
(2) prepare alkaline modification agent, Na in alkaline modification agent+With Ca in metallurgical steel slag2+And Mg2+The sum of molar ratio be (0.2 ~
1.3): 1；
(3) using steel mill's dust waste water as Metallurgical Waste Water, pH value is between 7.5 ~ 12, and calcium concentration is 50 ~ 250 mg/L；
(4) CO is used2The metallurgical tail gas of content > 15% is as exhaust gas, and 45 ~ 150 DEG C of temperature；
(5) CO in exhaust gas is stablized using clinker and waste water using collaboration2Device, which includes reactor shell and its top
Sealing cover, reactor shell bottom is evenly distributed with multiple for being passed through the air bricks of exhaust gas, and air brick is connected to air-introduced machine,
Wherein air-introduced machine is additionally provided with discharging valve for introducing exhaust gas and airing materials, reactor shell bottom, and sealing cover is equipped with water inlet
Valve and diffusion valve；The top of air brick is equipped with multilayer grate plate inside reactor shell；Metallurgical steel slag and alkaline modification agent is abundant
It is packed into bottom after mixing equipped with air brick and inside is placed in the reactor cylinder body of grate plate, metallurgical steel slag and alkaline modification agent heap
It is placed in grate plate；Then Metallurgical Waste Water is added, metallurgical steel slag and the mixture of alkaline modification agent is made to impregnate 12h in Metallurgical Waste Water
More than, and temperature is controlled at 30 DEG C or more；Wherein Metallurgical Waste Water submerges metallurgical steel slag and alkaline modification agent and is higher by metallurgical steel slag
With alkaline modification agent upper surface 0.5m or more；
(6) impregnating terminates to be passed through the exhaust gas that pressure is 0.3 ~ 1MP from the air brick of reactor shell bottom backward, carries out first CO2
Solidification, duration are 1 ~ 3h, and exhaust gas flow controls the material inside 1.0 ~ 5.0L/s, exhaust gas intake and reactor shell
Volume ratio control in (15 ~ 30): 1；
(7) stop being passed through exhaust gas, discharge water from the discharging valve of reactor shell bottom, after water is all bled off in reactor cylinder body,
It is passed through the exhaust gas that pressure is 0.3 ~ 1MP from the air brick of reactor shell bottom again, carries out secondary CO2Solidification, exhaust gas flow
In 0.5 ~ 6.0L/s, the duration is 0.5 ~ 4h, the volume ratio control of the material inside exhaust gas intake and reactor shell for control
System is in (15 ~ 30): 1；
(8) material for completing secondary curing is air-dried, obtains carbonatation steel scoria.
2. a kind of collaboration according to claim 1 stablizes CO in exhaust gas using clinker and waste water2Method, it is characterised in that
The ingredient of the 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 stablizes CO in exhaust gas using clinker and waste water2Method, it is characterised in that
The alkaline modification agent is 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 stablizes CO in exhaust gas using clinker and waste water2Method, it is characterised in that
The conversion ratio of CaO is 20 ~ 55% in metallurgical steel slag.
5. a kind of collaboration according to claim 1 stablizes CO in exhaust gas using clinker and waste water2Method, it is characterised in that
The conversion ratio of MgO is 15 ~ 45% in metallurgical steel slag.
6. a kind of collaboration for implementing method described in claim 1 stablizes CO in exhaust gas using clinker and waste water2Device, it is special
Sign be include reactor shell and its top sealing cover, reactor shell bottom be evenly distributed with it is multiple be used for be passed through exhaust gas
Air brick, air brick is connected to air-introduced machine, and wherein air-introduced machine is for introducing exhaust gas and airing materials, and reactor shell bottom is also
Equipped with discharging valve, sealing cover is equipped with inlet valve and diffusion valve；The top of air brick is equipped with multilayer grate plate inside reactor shell.
7. collaboration according to claim 6 stablizes CO in exhaust gas using clinker and waste water2Device, it is characterised in that it is described
Sealing cover on be additionally provided with pressure reducing valve.
8. collaboration according to claim 6 stablizes CO in exhaust gas using clinker and waste water2Device, it is characterised in that it is described
Multilayer 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 circular through hole is distributed with, the width of strip crevice is 0.5 ~ 5mm, and the diameter of circular through hole is 2 ~ 5mm.
9. collaboration according to claim 6 stablizes CO in exhaust gas using clinker and waste water2Device, it is characterised in that it is described
The material of reactor shell be the external steel for being equipped with insulating layer, air brick is embedded on the bottom plate of cylinder.
10. collaboration according to claim 6 stablizes CO in exhaust gas using clinker and waste water2Device, it is characterised in that it is described
Grate plate material be steel, 8 ~ 25mm of thickness.
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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 |
| CN110950338B (en) * | 2019-12-25 | 2023-05-16 | 江西理工大学 | Method for capturing carbon dioxide in converter flue gas and coproducing NPCC (neutral carbon dioxide) by closed cycle of converter steel slag and steelmaking wastewater |
| CN112791573B (en) * | 2021-01-11 | 2022-03-25 | 东北大学 | Steelmaking waste cooperative treatment system and method based on ball milling reinforcement |
| CN115626788B (en) * | 2021-11-24 | 2023-11-14 | 山东大学 | Device for modifying steel slag through acidification and carbonization coupling |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323240A (en) * | 1998-10-29 | 2001-11-21 | 日本钢管株式会社 | Method of reducing discharged carbon dioxide |
| CN103111186A (en) * | 2013-02-22 | 2013-05-22 | 中国科学院过程工程研究所 | Method for mineralizing and fixing carbon dioxide by using strengthened steel slag |
-
2016
- 2016-11-25 CN CN201611053253.0A patent/CN106540525B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323240A (en) * | 1998-10-29 | 2001-11-21 | 日本钢管株式会社 | Method of reducing discharged carbon dioxide |
| CN103111186A (en) * | 2013-02-22 | 2013-05-22 | 中国科学院过程工程研究所 | Method for mineralizing and fixing carbon dioxide by using strengthened steel slag |
Non-Patent Citations (1)
| Title |
|---|
| 利用转炉石与钢铁废水在浆体反应槽中进行碳酸化反应;邱安家;《台湾大学机构典藏》;20160823;中文摘要部分，第4-7页第2段，第3-9页 |
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