CN101851071A - Method for fixing carbon dioxide and digesting free calcium oxide in slag micro powder - Google Patents
Method for fixing carbon dioxide and digesting free calcium oxide in slag micro powder Download PDFInfo
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- CN101851071A CN101851071A CN201010160637A CN201010160637A CN101851071A CN 101851071 A CN101851071 A CN 101851071A CN 201010160637 A CN201010160637 A CN 201010160637A CN 201010160637 A CN201010160637 A CN 201010160637A CN 101851071 A CN101851071 A CN 101851071A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention relates to a method for fixing carbon dioxide and digesting free calcium oxide in slag micro powder, which belongs to the technical field of the carbon dioxide reduction and the industrial solid waste resource utilization. Converter steel slag is soaked in water, then the steel slag after being soaked in the water is added into a grinding machine, at the same time, waste heat smoke gas containing carbon dioxide is introduced into the grinding machine with the steel slag to carry out the stabilization reaction, and the steel slag is ground and dried; the waste heat smoke gas brings out the steel slag micro powder after being ground and dried from the tail section of the grinding machine to enter a power collection device, and the steel slag micro powder is discharged from the bottom part of the powder collection device; and the temperature of the waste heat smoke gas is 150 to 180 DEG C. The method has the advantages that: carbon dioxide in the waste smoke gas is used for chemically modifying the steel slag micro powder, so the content of the f-CaO is reduced, the chemical stability of the steel slag micro powder is improved, and technical requirements of the national standard GB/T 20491 - 2006 of steel slag powder for cement and concrete can be reached. The carbon dioxide also can be cured, so the exhaustion of the greenhouse gas can be reduced, and the environment-friendly carbon cycling mode can be realized.
Description
Technical field
The invention belongs to carbon dioxide discharge-reduction and industrial solid castoff application technology as the second resource field, the method that free calcium oxide is cleared up in a kind of carbon dioxide fixation and the slag micro powder particularly is provided, slag is carried out stabilization treatment, and the carbonic acid gas that fixedly discharges in the Industrial processes, reduce the method for free calcium oxide (f-CaO) content in the slag micro powder fast.
Technical background
Bessemer furnace slag is the solid waste that produces in the steelmaking process, and generation is at 100～150kg/ ton steel.China is Iron and Steel Production big country, and the about 500,000,000 tons of steel of annual production produce bessemer furnace slag and reach 5,000 ten thousand tons.Slag after present most of magnetic separation uses mainly as material of construction.Free calcium oxide in the slag (f-CaO) is to influence the critical limitation condition of slag as material of construction, and free calcium oxide (f-CaO) content is between 5～10% in bessemer furnace slag.F-CaO in the slag is mainly from the calcined lime of crossing that produces in the steelmaking process.At 1650 ℃, these free calcium oxides can form fine and close crystal, the active reduction.The f-CaO aquation is very slow, because the Effect of Electric Double Layer around crystal growth pressure, oxyhydroxide dissolution of crystals and the hydrated product causes slag to expand, even produces differential expansion in hydration process, causes slag hotchpotch cracking even collapses.F-CaO aquation molecular volume increases 96% in theory, and the f-CaO in the slag is state of aggregation, and it is very inhomogeneous to distribute, and this must cause local cracking.Therefore, the f-CaO in the slag can produce volumetric expansion in the slag use, endanger huge.The Ministry of Construction just must not use separately at slag swelling property regulation pre-slag as far back as nineteen ninety, should adopt the old slag of piling up more than 1 year; It is to handle stable slag through ageing or other method that Ministry of Metallurgical Industry builds the road with slag in regulation in 1991, and the fluctuation upper limit of its Pulverization ratio measured value should be no more than 5%.Contrasting these regulations can find, even granularity is the converter slag of 1～5mm after ageing in 60 days, fragmentation, its cubical expansivity still surpasses 5%, and is defective.
Slag micro powder is the important means of slag high value added utilization, and it is mainly used in cement and the concrete and substitutes part cement as Additive.The utilization of slag micro powder can reduce the use of cement, reduces the Carbon emission that manufacture of cement produced, and helps recycling of solid wastes utilization and energy-saving and emission-reduction.The f-CaO content of slag micro powder is one of important indicator that restricts at present the slag micro powder use.The slag micro powder f-CaO content of regulation must be lower than 3% in the national standard (GB/T20491-2006) " slag micro powder that is used for cement and coagulation ".At present also there is not suitable process for treating steel slag that the f-CaO content in the slag tailings is reduced to below 3% fully.Therefore, although bessemer furnace slag has the potential activity, f-CaO content is higher to have limited its preparation slag micro powder promoting the use of at building field to a great extent.
At present,, adopt slag to place in the open, need just can be used more than 2 years for the slag stabilization treatment.Slag adopts hot water to soak ageing and then needs 7 day time, adopts open-air steam ageing then to need 48 hours.Japan minority steel mill adopts adding pressure type steam aging tank that slag is carried out stabilization treatment, and water vapor is 0.6MPa, and the treatment time is 2 hours, and this method facilities and equipments complexity is invested greatlyyer, and treatment capacity is less.The at present main mode that adopts is that the hot water that utilizes the slag waste heat to produce soaks the mode in a vexed week and handles slag, this mode can realize most slag stabilization treatment, but some slag can't reach requirement, this method causes that evaporation of water is serious in addition, cause water loss bigger, be difficult in the place of shortage of water resources realize.
Patent of invention " the carbonating bessemer furnace slag is in the application that promotes on the carbonic anhydride absorption of ocean " (CN101269998A) be with 20 orders～80 purpose waste steel slags under 350～800 ℃, 0.1～3.6 normal atmosphere, 5～25% content water vapor conditions; in the ebullated bed treatment unit that bessemer furnace slag is housed, feed industrial gaseous waste or flue gas; in 2～5 hours reaction times, then the bessemer furnace slag after the carbonating is dropped into the ocean with particle or fragment of brick form.This patent mainly is to utilize the little metal iron in the bessemer furnace slag to promote the marine alga growth, utilizes marine alga to absorb carbon dioxide in air, and need be heated to 350～800 ℃ to slag and formed new energy consumption.Patent of invention " carbonatation processing method of steel scoria " (CN101269998A), the slag that makes particle diameter≤15mm under 350～800 ℃ of conditions with CO
2Gas reaction 2-12 hour.This invention uses the industrial smoke that contains certain water vapour as source of the gas, has reduced discharge of carbon dioxide greenhouse gas when finishing the slag carbonating.The slag particle diameter that this method is used is bigger, need give time enough and temperature condition absorbing carbon dioxide to greatest extent, simultaneously most of free calcium oxide of steel slag particle inside can't contact with carbonic acid gas and not have an effect of absorbing carbon dioxide.At present also do not utilize industrial smoke to clear up the processing method of f-CaO in the slag micro powder fast, make the slag micro powder specific surface area reach 400m
2More than/the kg, can be directly as cement or concrete admixture.
The process that slag micro powder is produced in domestic and international at present utilization is come absorbing carbon dioxide and is cleared up the processing method of free calcium oxide in the slag micro powder.
Summary of the invention
The object of the present invention is to provide the method that free calcium oxide is cleared up in a kind of carbon dioxide fixation and the slag micro powder, realized CO
2Free calcium oxide is cleared up fast in fixing and the slag micro powder.
Know-why of the present invention is: the free calcium oxide in carbonic acid gas, water and the slag is issued biochemical reaction being lower than 80 ℃, generate the lime carbonate material, reach stabilizing carbon dioxide simultaneously and clear up the purpose of the calcium oxide that dissociates in the slag fast.
Implementation procedure of the present invention is: earlier bessemer furnace slag is soaked in the water, then water logging bubble back slag is added in the pulverizing mill, will contain CO simultaneously
2Waste heat flue gas (general temperature at 150～180 ℃) feed in the pulverizing mill that slag is housed stabilization reactions take place, simultaneously the slag pulverized powder is carried out drying; Waste heat flue gas is taken the dried slag micro powder of grinding out of from the pulverizing mill rear, and enters in the powder collector, and slag micro powder is discharged from the powder collector bottom, can directly be used as cement building material raw material, the direct qualified discharge of useless flue gas after the dedusting; Contain CO
2Waste heat flue gas is opposite with the flow direction of slag in pulverizing mill.
Bessemer furnace slag of the present invention is for having selected the tailings behind the metallic iron, and particle scale is less than 10mm.
Slag and water logging bubble 0.5～2 hour soak back slag water ratio 10%～20%.
The CO that contains of the present invention
2Waste heat flue gas can be the boiler waste heat flue gas that any combustion carbon boiler emission comes out, comprise coal furnace, oil oven or gas furnace discharge tail gas.
The CO that contains of the present invention
2Opposite exhanst gas outlet and the slag inlet of being meant with the flow direction of slag in pulverizing mill of waste heat flue gas is at same end, and smoke inlet and slag outlet are at same end.
In free 1～3 hour stable calcium oxide reaction times in carbonic acid gas and the slag in the interior flue gas of pulverizing mill, temperature of reaction is at 60～80 ℃.
The present invention utilizes the CO in the useless flue gas
2Slag micro powder is carried out chemical modification, reduce f-CaO content, improve the chemical stability of slag micro powder, reach GB/T 20491-2006 " steel-making slag powder that is used for cement and concrete " national standard technical requirements.The slag micro powder useful as concrete fine mineral admixture of producing substitutes part cement, improves workability of concrete energy and endurance quality, becomes the requisite Additive of preparation high performance concrete.The present invention not only can improve the stability of slag micro powder, but also can solidify CO
2, reduce greenhouse gas emission, realize eco-friendly carbon cycle model.
Advantage of the present invention:
1) stabilization treatment of realization slag micro powder in the preparation process of slag micro powder is not carried out heat treated with slag in addition, the f-CaO content in the slag can be reduced to 1%～2%, and requirement is up to state standards.
2) utilize Industrial Boiler to produce and contain CO
2Waste heat flue gas to the drying and the stabilization of slag micro powder, realize the UTILIZATION OF VESIDUAL HEAT IN and the CO of flue gas
2Reduce discharging.
3) the slag stabilization effect is obvious, just can realize the stabilization of slag in 1～3 hour, and traditional hot vexed ageing process needs 7 day treatment time just can reach.
Description of drawings
Fig. 1 clears up schema for free calcium oxide in carbon dioxide fixation of the present invention and the slag micro powder.
Embodiment
Specify technological process of the present invention in conjunction with Fig. 1.Particle diameter enters the pond less than the slag of 10mm, makes the slag adsorption moisture, is convenient to the hydration reaction in later stage.Adopt grab bucket that the slag after the aquation is sent in the pulverizing mill, contain CO
2Waste heat flue gas by blower fan with hot flue gas from the reverse introducing pulverizing mill of the logistics of pulverizing mill, make the CO in the flue gas
2With water and the free calcium oxide in the slag in the slag stabilization reactions takes place simultaneously, the lime carbonate that reaction is produced is ground again and material surface friction disengaging steel slag particle surface simultaneously, and the free calcium oxide of steel slag particle inside is come out, and with the CO of periphery
2With water in conjunction with generating new lime carbonate, so repeatedly, finally reach free stable calcium oxide and CO in the slag
2The fixed effect.
Finish the flue gas behind stabilization reactions and the heat exchange function, carry slag micro powder secretly, come out from the upper end exhanst gas outlet at the opening for feed position of pulverizing mill, and enter in the fly-ash separator, behind the flue gas ash removal by the chimney qualified discharge.The slag micro powder of discharging from the fly-ash separator end opening enters the slag micro powder storage bin by packing auger.
Embodiment 1: with free calcium oxide content is that 6.26% slag tailings 5kg adds in the ball mill, adds water 5kg, and feeds CO
2Content is 800mg/Nm
3, flow is 1.8Nm
3The CO of/h
2With Air mixing gas, the treatment time is 1 hour.Slag micro powder free calcium oxide content after the processing is 1.62%, and free calcium oxide is cleared up rate and reached 74.1%.Adopt fixedly 36.5kg carbonic acid gas of this method slag per ton.
Embodiment 2: with free calcium oxide content is that 6.26% slag tailings 5kg adds in the ball mill, adds water 5kg, and feeds CO
2Content is 800mg/Nm
3, flow is 1.8Nm
3The CO of/h
2With Air mixing gas, the treatment time is 3 hours.Slag micro powder free calcium oxide content after the processing is 0.10%, and free calcium oxide is cleared up rate and reached 98.4%.Adopt fixedly 48.4kg carbonic acid gas of this method slag per ton.
Claims (6)
1. the method that free calcium oxide is cleared up in carbon dioxide fixation and the slag micro powder is characterized in that: earlier bessemer furnace slag is soaked in the water, then water logging bubble back slag is added in the pulverizing mill, will contain CO simultaneously
2Waste heat flue gas feed in the pulverizing mill that slag is housed stabilization reactions take place, the slag pulverized powder is carried out drying; Waste heat flue gas is taken the dried slag micro powder of grinding out of from the pulverizing mill rear, and enters in the powder collector, and slag micro powder is discharged from the powder collector bottom; Contain CO
2Waste heat flue gas is opposite with the flow direction of slag in pulverizing mill, and the temperature of waste heat flue gas is 150～180 ℃.
2. method according to claim 1 is characterized in that: described bessemer furnace slag is for having selected the tailings behind the metallic iron, and particle scale is less than 10mm.
3. method according to claim 1 is characterized in that, slag and water logging bubble 0.5～2 hour soak back slag water ratio 10%～20%.
4. method according to claim 1 is characterized in that, the described CO that contains
2Waste heat flue gas be coal furnace, oil oven or gas furnace discharge tail gas.
5. method according to claim 1 is characterized in that, described opposite exhanst gas outlet and the slag inlet of being meant with the flow direction of slag in pulverizing mill of carbonic acid gas waste heat flue gas that contain is at same end, and smoke inlet and slag outlet are at same end.
6. method according to claim 1 is characterized in that, in free 1～3 hour stable calcium oxide reaction times in carbonic acid gas and the slag in the interior flue gas of pulverizing mill, temperature of reaction is at 60～80 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010160637A CN101851071A (en) | 2010-04-26 | 2010-04-26 | Method for fixing carbon dioxide and digesting free calcium oxide in slag micro powder |
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| CN201010160637A CN101851071A (en) | 2010-04-26 | 2010-04-26 | Method for fixing carbon dioxide and digesting free calcium oxide in slag micro powder |
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Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249566A (en) * | 2011-07-04 | 2011-11-23 | 武汉钢铁(集团)公司 | Process for carbonating active lime with rotary kiln tail gas |
| CN102671519A (en) * | 2012-05-29 | 2012-09-19 | 中国科学院过程工程研究所 | Method for fixing CO2 (carbon dioxide) by steel slag recycling |
| CN102875038A (en) * | 2012-10-22 | 2013-01-16 | 辽宁科技大学 | Method for removing free calcium oxide and magnesium oxide in converter steel making slag |
| 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 |
| CN103691283A (en) * | 2013-12-24 | 2014-04-02 | 中南大学 | Method for fixing carbon dioxide in industrial smoke |
| CN104961495A (en) * | 2015-07-01 | 2015-10-07 | 盐城工学院 | Comprehensive utilization method of coal-fired flue gas |
| CN106854407A (en) * | 2017-01-09 | 2017-06-16 | 娄底市湖泉亿达工贸有限公司 | A kind of method of comprehensive utilization of converter slag |
| CN108246090A (en) * | 2018-03-21 | 2018-07-06 | 宁波大学 | A kind of process using slag slurries wet method decarburization |
| CN108640542A (en) * | 2018-06-11 | 2018-10-12 | 福州大学 | A kind of curing heavy metal seals CO up for safekeeping2Ground polymers cement and preparation method thereof |
| CN109081309A (en) * | 2018-08-01 | 2018-12-25 | 江苏焕鑫新材料股份有限公司 | A method of improving the quality of the technical hydrochloric acid containing polyphenol mixture and sulfurous acid |
| CN109320290A (en) * | 2018-11-02 | 2019-02-12 | 山西大学 | A kind of processing method of concrete prefabricated product enhancing carbon sequestration |
| CN109368643A (en) * | 2018-11-30 | 2019-02-22 | 华北理工大学 | A method of utilizing AOD slag carbon sequestration |
| CN110128037A (en) * | 2019-05-14 | 2019-08-16 | 中冶节能环保有限责任公司 | A kind of steel slag tailings prepare the processing unit and method of sandstone |
| CN110698087A (en) * | 2019-11-05 | 2020-01-17 | 中国科学院过程工程研究所 | Device and method for comprehensively utilizing thermal-state steel slag |
| CN111041134A (en) * | 2019-07-10 | 2020-04-21 | 江苏富凯重工机械有限公司 | Method for carrying out hot stuffy treatment on steel slag by using steel slag stuffy pot |
| CN111777352A (en) * | 2020-07-07 | 2020-10-16 | 马鞍山马钢嘉华商品混凝土有限公司 | Steel wind-quenching solid waste composite micro-powder superfine aggregate and application thereof in concrete |
| CN111847941A (en) * | 2020-08-12 | 2020-10-30 | 河北蓝海智投环保科技有限公司 | Method for digesting free calcium oxide in steelmaking fly ash |
| CN113650143A (en) * | 2021-07-26 | 2021-11-16 | 霖和气候科技(北京)有限公司 | Utilize flue gas CO2Reaction device and method for improving stability of steel slag building material |
| CN114212811A (en) * | 2014-04-28 | 2022-03-22 | 理科思维亚公司 | Process for producing alkaline earth carbonate |
| CN114315301A (en) * | 2022-01-25 | 2022-04-12 | 华泰恒生科技发展（北京）有限公司 | Large-mixing-amount steel slag foam concrete foamed by taking industrial waste gas as gas and preparation method thereof |
| CN114367179A (en) * | 2021-12-03 | 2022-04-19 | 首钢集团有限公司 | Denitration carbon-fixing agent taking steel slag as raw material and preparation method and application thereof |
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| CN115069362A (en) * | 2022-05-30 | 2022-09-20 | 湖北工业大学 | Carbon fixation and emission reduction method for steel plant wet-grinding steel slag and application |
| CN115365274A (en) * | 2022-09-20 | 2022-11-22 | 中南大学 | Method for improving steel slag grinding efficiency and iron resource recovery rate |
| CN115872637A (en) * | 2023-01-03 | 2023-03-31 | 山西太钢不锈钢股份有限公司 | Method for reducing free calcium oxide in steel slag |
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|---|---|---|---|---|
| CN102249566B (en) * | 2011-07-04 | 2013-01-02 | 武汉钢铁(集团)公司 | Process for carbonating active lime with rotary kiln tail gas |
| CN102249566A (en) * | 2011-07-04 | 2011-11-23 | 武汉钢铁(集团)公司 | Process for carbonating active lime with rotary kiln tail gas |
| CN102671519A (en) * | 2012-05-29 | 2012-09-19 | 中国科学院过程工程研究所 | Method for fixing CO2 (carbon dioxide) by steel slag recycling |
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| CN104961495A (en) * | 2015-07-01 | 2015-10-07 | 盐城工学院 | Comprehensive utilization method of coal-fired flue gas |
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| CN108640542A (en) * | 2018-06-11 | 2018-10-12 | 福州大学 | A kind of curing heavy metal seals CO up for safekeeping2Ground polymers cement and preparation method thereof |
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| CN109368643A (en) * | 2018-11-30 | 2019-02-22 | 华北理工大学 | A method of utilizing AOD slag carbon sequestration |
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| CN111041134A (en) * | 2019-07-10 | 2020-04-21 | 江苏富凯重工机械有限公司 | Method for carrying out hot stuffy treatment on steel slag by using steel slag stuffy pot |
| CN111041134B (en) * | 2019-07-10 | 2021-11-26 | 江苏富凯重工机械有限公司 | Method for carrying out hot stuffy treatment on steel slag by using steel slag stuffy pot |
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