CN115069362B - Method for carbon fixation and emission reduction of wet-milling steel slag in steel plant and application of method - Google Patents

Method for carbon fixation and emission reduction of wet-milling steel slag in steel plant and application of method Download PDF

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CN115069362B
CN115069362B CN202210599827.3A CN202210599827A CN115069362B CN 115069362 B CN115069362 B CN 115069362B CN 202210599827 A CN202210599827 A CN 202210599827A CN 115069362 B CN115069362 B CN 115069362B
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steel slag
grinding
steel
wet
mass
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CN115069362A (en
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苏英
李承昊
贺行洋
郑正旗
杨进
王迎斌
谭洪波
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Hubei University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
    • 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
    • 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
    • B01D53/82—Solid phase processes with stationary reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/06—Selection or use of additives to aid disintegrating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C2201/00—Codes relating to disintegrating devices adapted for specific materials
    • B02C2201/06—Codes relating to disintegrating devices adapted for specific materials for garbage, waste or sewage

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Food Science & Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crushing And Grinding (AREA)

Abstract

The invention discloses a method for carbon fixation and emission reduction of wet-milling steel slag in a steel plant, which comprises the following steps: (1) Quenching molten steel slag produced by a steel plant by water quenching, and then crushing, deironing and dry grinding in sequence to obtain steel slag powder with the median particle size of 20-500 mu m; (2) mixing steel slag powder and water according to a mass ratio of 1: (1-4) mixing and stirring to obtain steel slag slurry; (3) CO-containing effluent from steel plants 2 The flue gas is collected in a gas collecting bottle; (4) Introducing 100 parts by mass of steel slag slurry and 5-18 parts by mass of flue gas into a horizontal stirred ball mill, adding grinding media and a stabilizer accounting for 1-5% of the mass of steel slag powder for wet grinding, and carrying out carbon fixation by utilizing the steel slag slurry; (5) Drying the wet ground slurry to obtain CO 2 And curing the material. The invention has the advantages of high carbon fixation rate, low cost, environmental protection and suitability for popularization and production.

Description

Method for carbon fixation and emission reduction of wet-milling steel slag in steel plant and application of method
Technical Field
The invention belongs to the technical field of industrial solid waste treatment and environmental protection, and particularly relates to a method for carbon fixation and emission reduction of wet-grinding steel slag in a steel plant and application thereof.
Background
Since the industrial revolution, energy consumption and CO have been expanding with the expansion of various industrial scales 2 Is increasingly dischargedMany. Since 1960 CO 2 The emissions of (2) have risen year by year, so far global CO 2 The annual emission of (2) reaches 322.8 hundred million tons, compared with the CO in 1960 2 The annual discharge amount is 90 hundred million tons, and the rise amplitude is up to 258.6 percent. And CO 2 The concentration level in the atmosphere also maintains a faster growth rate, and the CO in the atmosphere has been 1860 2 The concentration has increased from 288ppm to 411ppm, and the rise is as high as 42.7%. CO in greenhouse gases 2 The contribution ratio to the greenhouse effect is up to 50%, the accumulation of greenhouse gases in the atmosphere directly leads to the generation of the greenhouse effect, and the greenhouse effect leads to the frequent occurrence of natural disasters such as forest fires, floods, drought and the like.
Through the rapid development of the steel industry, china has become the largest steel production and consumption country in the world, and the steel yield accounts for about one fifth of the steel yield worldwide. The iron and steel industry brings great economic benefit and simultaneously generates a plurality of problems. On the one hand, a large amount of CO is generated during steelmaking 2 Emissions, about two tons of CO are produced per ton of crude iron produced 2 Emissions, 2019, global coarse steel yield of 19 hundred million tons, CO in the annual steel industry 2 About 38 hundred million tons of global artificial CO are discharged 2 7% of the emissions. On the other hand, steel slag is produced in the steelmaking process, the discharge amount of the steel slag is about 15% -20% of the steel yield, a large amount of steel slag occupies more and more land, the land is alkalized by the alkalinity of the steel slag, the ecological environment is polluted and destroyed, and a method is found to reasonably use the steel slag. Taking into account CO 2 The solidification reaction occurs in an alkaline environment, and a large amount of alkaline steel slag generated by a steel plant is used for CO 2 Has great potential and prospect in curing and sealing, but the prior method for fixing carbon by utilizing steel slag has the difficult problem which is partially difficult to solve.
In the chinese patent publication No. CN 102240501A, a method for carbon sequestration and emission reduction is disclosed, which includes: A. absorbing the discharged carbon dioxide by an absorption tower; B. calcining a carbon-fixing raw material and ammonium salt together, and reacting to generate ammonia gas and a salt solid product, wherein the carbon-fixing raw material contains metal elements capable of forming a precipitate with carbonate; C. introducing the produced ammonia gas into an absorption tower to react with carbon dioxide, and adding water to obtain an ammonium bicarbonate solution; D. b, placing the salt solid product obtained in the step B into water for leaching; E. and C, introducing the ammonium bicarbonate solution obtained in the step D into the liquid obtained by leaching in the step D to react to produce carbonate. The method has complex process, high cost caused by high-temperature calcination and waste gas and waste liquid generated in the carbon fixing process, and is not beneficial to environmental protection.
In the Chinese patent publication No. CN 104860474A, a method for fixing carbon and biologically treating sulfur-containing waste lye is disclosed, which uses biotechnology, needs to culture anaerobic bacteria special for fixing carbon, and needs to use strong alkali sodium hydroxide in a plurality of procedures, and has the advantages of complex process, difficult control, high cost and low carbon fixing rate.
In the Chinese patent publication No. CN 108246090A, a process method for wet decarburization by utilizing steel slag slurry is disclosed, and comprises the following steps: preparing the steel slag into steel slag slurry, wherein the steel slag slurry enters from the upper part of an absorption tower, and carbon dioxide-containing flue gas enters from the lower part of the absorption tower, and the steel slag slurry is fully contacted with the flue gas, so that decarburization is realized. However, the reaction efficiency and the carbon fixation rate of the method are low, and the method needs to be further improved.
In summary, the existing carbon fixing method generally has the problem that the carbon fixing rate and the cost are difficult to be compatible, and the waste gas and the waste liquid of most carbon fixing methods are not beneficial to environmental protection.
Disclosure of Invention
The invention aims to provide a method for carbon sequestration and emission reduction of wet-milled steel slag in a steel plant and application thereof, wherein the method has obviously higher reaction efficiency and carbon sequestration rate.
The invention takes materials locally, utilizes a large amount of steel slag waste solids produced by the steel plant, and utilizes the steel slag to discharge CO containing gas discharged by the steel plant 2 The flue gas is used for carbon fixation, the cost is low, the reaction efficiency is high, the carbon fixation rate is high, the carbon emission of a steel plant can be obviously reduced, and the obtained steel slag carbon fixation product can be also used for concrete production.
The technical scheme of the invention is as follows:
a method for carbon fixation and emission reduction of wet-milling steel slag in a steel plant comprises the following steps:
(1) Quenching molten steel slag produced by a steel plant by water quenching, and then crushing, deironing and dry grinding in sequence to obtain steel slag powder with the median particle size of 20-500 mu m;
(2) The steel slag powder and water are mixed according to the mass ratio of 1: (1-4) mixing and stirring to obtain steel slag slurry;
(3) CO-containing effluent from steel plants 2 The flue gas is collected in a gas collecting bottle;
(4) Introducing 100 parts by mass of steel slag slurry and 5-18 parts by mass of flue gas into a horizontal stirred ball mill, adding grinding media and a stabilizer accounting for 1-5% of the mass of steel slag powder for wet grinding, and carrying out carbon fixation by utilizing the steel slag slurry;
(5) Drying the wet ground slurry to obtain CO 2 And curing the material.
In some embodiments, CO in the flue gas 2 The mass concentration of (2) is 10-15%.
In some embodiments, the stabilizer is one or more of sucrose, sodium gluconate, sodium citrate, sodium metaphosphate.
In some embodiments, the milling media are zirconia balls and/or agate balls.
Further, the grinding medium is graded by grinding balls with the ball diameter of 3-5 mm, grinding balls with the ball diameter of 20-30 mm and grinding balls with the ball diameter of 80-90 mm, wherein the mass ratio of the grinding balls with the ball diameter of 3-5 mm, the grinding balls with the ball diameter of 20-30 mm and the grinding balls with the ball diameter of 80-90 mm is (1-3): 2: (3-1).
In some embodiments, the grinding media is used in an amount of 50 to 10 parts by mass.
In some embodiments, the rotational speed of the horizontal stirred ball mill is set to 20-50 r/s.
In some embodiments, step (4) is specifically:
adding 100 parts by mass of steel slag slurry, a stabilizer accounting for 1-5% of the mass of steel slag powder and a grinding medium into a horizontal stirring ball mill, starting wet grinding and simultaneously introducing 5-18 parts by mass of flue gas; meanwhile, monitoring the pH value of overflowed gas of the horizontal stirring ball mill, and if the pH value of the overflowed gas is less than 7 when the fume is started to be introduced, reducing the fume introduction speed until the pH value of the overflowed gas reaches 7; and (3) detecting the pH value of the wet-grinding slurry at regular time in the wet-grinding process, and stopping wet-grinding when the pH value of the slurry is less than 7. Since the original steel slag slurry is alkaline, when the pH value of the original steel slag slurry is less than 7, the steel slag slurry and the flue gas are completely reacted.
In some embodiments, the pH value of the overflow gas is monitored by arranging a pH detector at the air outlet of the horizontal stirring ball mill.
The agglomeration phenomenon of steel slag particles easily occurs when steel slag is pulped, and the coated steel slag particles are difficult to contact CO 2 The method comprises the steps of carrying out a first treatment on the surface of the In the carbon fixation reaction process, calcium and magnesium ions in the steel slag particles can slowly dissolve out, and in the calcium and magnesium ion dissolution process, siliceous film structures can be generated in the steel slag particles to prevent the calcium and magnesium ions from continuously dissolving out. Dissolved calcium and magnesium ions and CO dissolved in water 2 The reaction forms a layer of compact carbonate film structure on the surface of the steel slag particles to prevent CO 2 And continuously contacting with the steel slag. And the produced calcium carbonate precipitate is precipitated towards the bottom of the ball mill, the newly generated carbonate covers the steel slag slurry, and more steel slag particles are wrapped and covered. The above reasons lead to low utilization rate, low reaction efficiency and low carbon fixation rate of the existing steel slag carbon fixation.
The invention solves the problems by utilizing wet grinding and steel slag carbon fixation. The molten steel slag is quenched and fixed by water when the internal crystal structure of the steel slag is not stable, and compared with the common air-cooled steel slag, the steel slag has higher activity. The wet grinding is carried out by utilizing the grinding medium to impact the particles in the steel slag slurry at a high speed under the drive of the stirring shaft so as to reduce the particle size of the particles.
The agglomerated particles can be further opened in the wet grinding process, so that the steel slag particles in the slurry are more uniformly dispersed. While introducing CO 2 Wet grinding is carried out at the same time in the solidification reaction stage, and the grinding medium not only can grind the grain diameter of the steel slag particles to be less than 20 mu m, but also can obviously increase the specific surface area of the steel slag; the coating lamellar structure outside the free calcium oxide and the free magnesium oxide can be destroyed, and the active ingredients are released; can also destroy siliceous inner membranes formed in the interior of steel slag particlesThe structure of the steel slag is that calcium and magnesium ions in the steel slag particles are further dissolved out.
In addition, the quenched steel slag can generate hydration reaction in the wet grinding process, and the generated calcium hydroxide is used for generating CO 2 Can play a certain promoting role, thereby greatly improving the carbon fixation rate of the steel slag slurry. And the grinding medium is hit during wet grinding to collide with the steel slag particles, and the process can lead the steel slag particles to collide with CO 2 The calcium carbonate carbonized film generated on the surface of the steel slag particles is broken during the reaction, and the dense carbonized film can expose fresh surface after being broken, thus the steel slag particles can continue to react with CO 2 Contact and reaction. The addition of the stabilizer can prevent the agglomeration of the steel slag during wet grinding, so that the steel slag particles are dispersed more uniformly in the solution, and the carbonization rate of the steel slag is improved.
The invention has the following characteristics and beneficial effects:
(1) The carbon fixation rate of the steel slag can be remarkably improved:
the wet grinding technology is utilized to refine the grain diameter of the steel slag, increase the specific surface area of the steel slag and facilitate the carbon fixation reaction; the siliceous inner membrane in the steel slag can be destroyed by wet grinding, and the continuous dissolution of calcium and magnesium ions is promoted; the addition of the stabilizer can prevent the agglomeration of the steel slag in the grinding process, so that the steel slag particles can be uniformly dispersed in the slurry; the grinding and carbon fixation reactions are carried out simultaneously, and the grinding medium continuously impacts the steel slag particles to break down compact carbonized layers on the surfaces of the steel slag particles and expose fresh surfaces and CO 2 Fully contacts, thereby greatly improving the utilization rate, the reaction efficiency and the carbon fixation rate of the steel slag.
(2) The cost can be obviously reduced:
the steel slag is waste solid in the steel plant, can be obtained locally in the steel plant, can obtain water-cooled slag in the process of refining steel, avoids energy consumption and transportation cost for heating the steel slag to a molten state in other application scenes, and can also avoid CO 2 Is not limited by the cost of transportation.
(3) The reaction environment is warmed;
the invention can realize high-efficiency CO without high-temperature and high-pressure environment assistance 2 Solidifying and sealing.
(4) Is favorable for environmental protection:
the flue gas and the steel slag discharged in the production process of the steel plant are utilized to carry out carbon fixation reaction, so that the waste in the steel plant is consumed in situ, the nature of the carbon fixation reaction is acid-base neutralization, and the alkalinity of the steel slag slurry is eliminated when the carbon fixation reaction is finally completed; in addition, in the carbon fixing process, not only calcium ions and magnesium ions play a role in carbon fixing, but also other metal ions in the steel slag slurry play a role in carbon fixing, so that the harm of heavy metals contained in the steel slag slurry is eliminated after the carbon fixing reaction is completed. When the solid carbon steel slag slurry is piled up and treated later, the alkaline pollution and heavy metal pollution of the steel slag to the environment can be avoided.
In summary, the method provided by the invention has the advantages of high carbon fixation rate, low cost and environmental friendliness, and is suitable for popularization and production.
Detailed Description
The invention will be further explained with reference to examples. The examples are given for illustrative purposes only and are not intended to limit the scope of the present invention.
In the wet grinding process, steel slag slurry is discharged into a horizontal stirring ball mill, a gas collecting cylinder is connected with a gas inlet of the horizontal stirring ball mill through a gas inlet valve, and pH value at a gas overflow port of the horizontal stirring ball mill is monitored by pH detection equipment. The flow of the flue gas entering the horizontal stirring ball mill is regulated and controlled by adjusting an air inlet valve of the gas collecting bottle.
Example 1
Quenching molten steel slag produced by a certain steel plant by water quenching, and then crushing, deironing and dry grinding in sequence to obtain steel slag powder with the median particle size of 500 mu m; collecting the flue gas (CO in the flue gas) in the flue of a certain steel plant 2 About 10% of the mass content) in the gas collection bottle for standby; and (3) taking 100 parts by mass of steel slag powder and 100 parts by mass of water, fully mixing and stirring to obtain steel slag slurry. Pouring the steel slag slurry into a horizontal stirring ball mill, adding 1 part by mass of sodium gluconate and 50 parts by mass of grinding media (in the embodiment, the grinding media are compounded by grinding balls with the ball diameter of 3-5 mm, grinding balls with the ball diameter of 20-30 mm and grinding balls with the ball diameter of 80-90 mm according to the mass ratio of 1:2:1), and performing airtight horizontal stirring ball millingAnd a feed inlet of the machine. And then connecting an air inlet of the horizontal stirring ball mill with an air collecting bottle, arranging a pH detector at an air outlet, starting the horizontal stirring ball mill at a rotating speed of 20r/s for wet grinding, and simultaneously introducing flue gas into the horizontal stirring ball mill at a flow rate of 5 parts by mass/h. After one hour, wet milling and aeration were stopped, at which time the slurry was not fully reacted, and the pH of the slurry in the horizontal stirred ball mill was measured to be 10.5 using a pH measuring instrument.
Freeze drying the sampled slurry, grinding and sieving, taking 10g of dried sample for thermogravimetric analysis and test, obtaining thermogravimetric analysis data for analysis, and obtaining mass loss of the sample at 500-900 ℃ which is CO generated after carbonate decomposition 2 The mass loss of the calculated sample at the temperature of 500-900 ℃ is 0.87g, so that the carbon fixation rate of the steel slag slurry in one hour is 8.7%.
Example 2
Quenching molten steel slag produced by a certain steel plant by water quenching, and then crushing, deironing and dry grinding in sequence to obtain steel slag powder with the median particle size of 100 mu m; collecting flue gas (CO) in a flue of a steel plant 2 About 10% of the content) is stored in a gas collecting bottle for standby; and (3) taking 100 parts by mass of steel slag powder and 100 parts by mass of water, fully mixing and stirring to obtain steel slag slurry. Pouring the steel slag slurry into a horizontal stirred ball mill, adding 1 part by mass of sodium gluconate and 50 parts by mass of grinding media (in the embodiment, the grinding media are compounded by grinding balls with the ball diameter of 3-5 mm, grinding balls with the ball diameter of 20-30 mm and grinding balls with the ball diameter of 80-90 mm according to the mass ratio of 1:2:1), and sealing a feed inlet of the horizontal stirred ball mill. And then connecting an air inlet of the horizontal stirring ball mill with an air collecting bottle, arranging a pH detection instrument at an air outlet, starting the horizontal stirring ball mill at a rotating speed of 30r/s for wet grinding, and simultaneously introducing flue gas into the horizontal stirring ball mill at a flow rate of 9 parts by mass/h. After one hour, wet milling and aeration were stopped, at which time the slurry was not fully reacted, and the pH of the slurry in the horizontal stirred ball mill was measured to be 9.3 using a pH tester.
Freeze drying the sampled slurry, grinding and sieving, taking 10g of dried sample for thermogravimetric analysis and test, obtaining thermogravimetric analysis data for analysis, and obtaining the mass loss of the sample at 500-900 ℃ which is the product after carbonate decompositionRaw CO 2 The mass loss of the calculated sample at the temperature of 500-900 ℃ is 0.94g, so that the carbon fixation rate of the steel slag slurry in one hour is 9.4%.
Example 3
Quenching molten steel slag produced by a certain steel plant by water quenching, and then crushing, deironing and dry grinding in sequence to obtain steel slag powder with a median particle size of 20 mu m; collecting flue gas (CO) in a flue of a steel plant 2 About 10% of the content) is stored in a gas collecting bottle for standby; and (3) fully mixing and stirring 100 parts by mass of steel slag powder and 200 parts by mass of water to obtain steel slag slurry. Pouring the steel slag slurry into a horizontal stirred ball mill, adding 2 parts by mass of sodium gluconate and 50 parts by mass of grinding media (in the embodiment, the grinding media are prepared by mixing grinding balls with the ball diameter of 3-5 mm, grinding balls with the ball diameter of 20-30 mm and grinding balls with the ball diameter of 80-90 mm according to the mass ratio of 1:2:2), and sealing a feed inlet of the horizontal stirred ball mill. And then connecting an air inlet of the horizontal stirring ball mill with an air collecting bottle, arranging a pH detection instrument at an air outlet, starting the horizontal stirring ball mill at a rotating speed of 40r/s for wet grinding, and simultaneously introducing smoke into the horizontal stirring ball mill at a flow rate of 12 parts by mass/h. After one hour, wet milling and aeration were stopped, at which time the slurry was not fully reacted, and the pH of the slurry in the horizontal stirred ball mill was measured to be 8.1 using a pH tester.
Freeze drying the sampled slurry, grinding and sieving, taking 10g of dried sample for thermogravimetric analysis and test, obtaining thermogravimetric analysis data for analysis, and obtaining mass loss of the sample at 500-900 ℃ which is CO generated after carbonate decomposition 2 The mass loss of the sample at the temperature of 500-900 ℃ is 1.12g, so the carbon fixation rate of the slurry in one hour is about 11.2%.
Example 4
Quenching molten steel slag produced by a certain steel plant by water quenching, and then crushing, deironing and dry grinding in sequence to obtain steel slag powder with a median particle size of 20 mu m; collecting flue gas (CO) in a flue of a steel plant 2 About 10% of the content) is stored in a gas collecting bottle for standby; and (3) fully mixing and stirring 100 parts by mass of steel slag powder and 300 parts by mass of water to obtain steel slag slurry. The steel slag slurry was poured into a horizontal stirred ball mill, and 3 parts by mass of sodium gluconate and 50 parts by mass of a grinding medium (this solidIn the embodiment, the grinding medium consists of grinding balls with the ball diameter of 3-5 mm, grinding balls with the ball diameter of 20-30 mm and grinding balls with the ball diameter of 80-90 mm according to the weight ratio of 1:1:1 mass ratio), and sealing the feed inlet of the horizontal stirred ball mill. And then connecting an air inlet of the horizontal stirring ball mill with an air collecting bottle, arranging a pH detection instrument at an air outlet, starting the horizontal stirring ball mill at a rotating speed of 40r/s for wet grinding, and simultaneously introducing smoke into the horizontal stirring ball mill at a flow rate of 15 parts by mass/h. After one hour, wet milling and aeration were stopped, at which time the slurry was not fully reacted, and the pH of the slurry in the horizontal stirred ball mill was measured to be 8.7 using a pH tester.
Freeze drying the sampled slurry, grinding and sieving, taking 10g of dried sample for thermogravimetric analysis and test, obtaining thermogravimetric analysis data for analysis, and obtaining mass loss of the sample at 500-900 ℃ which is CO generated after carbonate decomposition 2 The mass loss of the calculated sample at the temperature of 500-900 ℃ is 1.02g, so that the carbon fixation rate of the steel slag slurry in one hour is 10.2%, and the slurry is not fully reacted.
Example 5
Quenching molten steel slag produced by a certain steel plant by water quenching, and then crushing, deironing and dry grinding in sequence to obtain steel slag powder with a median particle size of 20 mu m; collecting flue gas (CO) in a flue of a steel plant 2 About 10% of the content) is stored in a gas collecting bottle for standby; and (3) fully mixing and stirring 100 parts by mass of steel slag powder and 400 parts by mass of water to obtain steel slag slurry. Pouring the steel slag slurry into a horizontal stirring ball mill, adding 5 parts by mass of sodium gluconate to obtain the steel slag slurry and 100 parts by mass of grinding media (in the embodiment, the grinding media are compounded by grinding balls with the ball diameter of 3-5 mm, grinding balls with the ball diameter of 20-30 mm and grinding balls with the ball diameter of 80-90 mm according to the mass ratio of 3:2:3), and sealing a feed inlet of the horizontal stirring ball mill. And then connecting an air inlet of the horizontal stirring ball mill with an air collecting bottle, arranging a pH detection instrument at an air outlet, starting the horizontal stirring ball mill at a rotating speed of 50r/s for wet grinding, and simultaneously introducing flue gas into the horizontal stirring ball mill at a flow rate of 18 parts by mass/h. After one hour, wet milling and aeration were stopped, at which time the slurry was completely reacted, and the pH of the slurry in the horizontal stirred ball mill was measured to be 6.8 using a pH tester.
Freeze drying the sampled slurry, grinding and sieving, taking 10g of dried sample for thermogravimetric analysis and test, obtaining thermogravimetric analysis data for analysis, and obtaining mass loss of the sample at 500-900 ℃ which is CO generated after carbonate decomposition 2 The mass loss of the calculated sample at the temperature of 500-900 ℃ is 1.25g, so the carbon fixation rate of the steel slag slurry in one hour is about 12.5%.
Comparative example
Collecting flue gas (CO) in a flue of a steel plant 2 The content is about 10%) is stored in a gas collecting bottle for standby, 100 parts by mass of steel slag powder with the median particle size of 100 mu m and 100 parts by mass of water are fully mixed and stirred to obtain steel slag slurry, 200 parts by mass of steel slag slurry is poured into a horizontal stirring ball mill, a feed inlet is sealed, then a gas inlet is connected with the gas collecting bottle, and a pH detecting instrument is arranged at a gas outlet. The pH of the slurry measured by a pH tester after one hour is 11.3, the sampled slurry is freeze-dried, ground and sieved, 10g of dried sample is obtained for thermogravimetric analysis and test, thermogravimetric analysis data are obtained for analysis, and the mass loss of the sample at 500-900 ℃ is the mass of carbon dioxide generated after the decomposition of carbonate, and the mass loss of the sample is 0.33g, so that the carbon fixation rate of the steel slag slurry in one hour is 3.3%.
The carbon fixation rate data of examples 1 to 5 and comparative example are shown in Table 1, and it is clear from Table 1 that the steel slag slurry of the present invention has significantly higher carbon fixation rate than the comparative example in which the steel slag slurry is directly used for carbon fixation, and can significantly improve the utilization rate of the steel slag slurry as a carbon fixation material, thereby greatly reducing CO in steel plants 2 Discharge amount.
Table 1 carbon fixation data for examples 1-5 and comparative examples
Numbering device Rotational speed Median particle diameter of steel slag Slurry pH after wet milling for 1h Carbon fixation rate
Example 1 20r/min 500μm 9.7 8.7％
Example 2 30r/min 100μm 9.3 9.4％
Example 3 40r/min 20μm 8.1 11.2％
Example 4 40r/min 20μm 8.7 10.2％
Example 5 50r/min 20μm 6.8 12.5％
Comparative example 1 0 100μm 11.9 3.3％
The foregoing is merely exemplary of the present invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (5)

1. A method for carbon fixation and emission reduction of wet-milling steel slag in a steel plant is characterized by comprising the following steps:
(1) Quenching molten steel slag produced by a steel plant in a water quenching way, and then crushing, deironing and dry grinding in sequence to obtain steel slag powder with a median particle size of 20-500 mu m;
(2) The steel slag powder and water are mixed according to the mass ratio of 1: (1-4) mixing and stirring to obtain steel slag slurry;
(3) CO-containing effluent from steel plants 2 The flue gas is collected in a gas collecting bottle;
(4) Introducing 100 parts by mass of steel slag slurry and 5-18 parts by mass of flue gas into a horizontal stirred ball mill, adding grinding media and a stabilizer accounting for 1-5% of the mass of steel slag powder for wet grinding, and carrying out carbon fixation by utilizing the steel slag slurry;
(5) Drying the wet ground slurry to obtain CO 2 Solidifying the material;
the stabilizer adopts one or a combination of more of sucrose, sodium gluconate, sodium citrate and sodium metaphosphate; the grinding medium is used in an amount of 50-100 parts by mass.
2. The method for carbon sequestration and emission reduction of wet-milled steel slag in steel works according to claim 1, which is characterized in that:
CO in the flue gas 2 The mass concentration of (2) is 10-15%.
3. The method for carbon sequestration and emission reduction of wet-milled steel slag in steel works according to claim 1, which is characterized in that:
the grinding medium is zirconia balls and/or agate balls.
4. The method for carbon sequestration and emission reduction of wet-milled steel slag in steel works according to claim 1, which is characterized in that:
the grinding medium is prepared from grinding balls with the spherical diameters of 3-5 mm, grinding balls with the spherical diameters of 20-30 mm and grinding balls with the spherical diameters of 80-90 mm, wherein the mass ratio of the grinding balls with the spherical diameters of 3-5 mm, the grinding balls with the spherical diameters of 20-30 mm and the grinding balls with the spherical diameters of 80-90 mm is (1-3): 2: (3-1).
5. The method for carbon sequestration and emission reduction of wet-milled steel slag in steel works according to claim 1, which is characterized in that:
the step (4) is specifically as follows:
adding 100 parts by mass of steel slag slurry, a stabilizer accounting for 1-5% of the mass of steel slag powder and a grinding medium into a horizontal stirring ball mill, starting wet grinding and simultaneously introducing 5-18 parts by mass of flue gas; meanwhile, monitoring the pH value of overflowed gas of the horizontal stirring ball mill, and if the pH value of the overflowed gas is less than 7 when the fume is started to be introduced, reducing the fume introduction speed until the pH value of the overflowed gas reaches 7; and (3) detecting the pH value of the wet-grinding slurry at regular time in the wet-grinding process, and stopping wet-grinding when the pH value of the slurry is less than 7.
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