CN116621487A - Method for eliminating steel slag stability and preparing carbon sequestration recycled aggregate by utilizing CO 2-containing tail gas based on acetic acid circulation - Google Patents
Method for eliminating steel slag stability and preparing carbon sequestration recycled aggregate by utilizing CO 2-containing tail gas based on acetic acid circulation Download PDFInfo
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- CN116621487A CN116621487A CN202310682092.5A CN202310682092A CN116621487A CN 116621487 A CN116621487 A CN 116621487A CN 202310682092 A CN202310682092 A CN 202310682092A CN 116621487 A CN116621487 A CN 116621487A
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- steel slag
- acetic acid
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 240
- 239000002893 slag Substances 0.000 title claims abstract description 189
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 149
- 239000010959 steel Substances 0.000 title claims abstract description 149
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 12
- 230000009919 sequestration Effects 0.000 title description 2
- 239000000243 solution Substances 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims abstract description 43
- 239000001639 calcium acetate Substances 0.000 claims abstract description 43
- 235000011092 calcium acetate Nutrition 0.000 claims abstract description 43
- 229960005147 calcium acetate Drugs 0.000 claims abstract description 43
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims abstract description 41
- 239000011654 magnesium acetate Substances 0.000 claims abstract description 41
- 235000011285 magnesium acetate Nutrition 0.000 claims abstract description 41
- 229940069446 magnesium acetate Drugs 0.000 claims abstract description 41
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 13
- 230000007704 transition Effects 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 5
- 238000012216 screening Methods 0.000 claims abstract description 5
- 238000005260 corrosion Methods 0.000 claims abstract description 3
- 230000007797 corrosion Effects 0.000 claims abstract description 3
- 230000008021 deposition Effects 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 36
- 239000000292 calcium oxide Substances 0.000 claims description 22
- 239000000395 magnesium oxide Substances 0.000 claims description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 238000010891 electric arc Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 18
- 238000007789 sealing Methods 0.000 abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 21
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 21
- 230000035425 carbon utilization Effects 0.000 description 20
- 239000004567 concrete Substances 0.000 description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000013112 stability test Methods 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000004566 building material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009847 ladle furnace Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000000399 orthopedic effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
- C04B20/107—Acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
- C04B18/142—Steelmaking slags, converter slags
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/16—Waste materials; Refuse from building or ceramic industry
- C04B18/167—Recycled materials, i.e. waste materials reused in the production of the same materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Civil Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Furnace Details (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
Abstract
The application relates to a method for recycling CO based on acetic acid 2 The method for eliminating the stability of steel slag by tail gas and preparing the carbon-sealed recycled aggregate comprises the following steps: crushing and screening, corrosion of steel slag by acetic acid, carbonization and deposition of mixed solution of calcium acetate and magnesium acetate, and recycling of acetic acid solution. According to the application, differentiated treatment processes are adopted for different types of steel slag, the volume stability of the steel slag is eliminated by utilizing acetic acid to corrode the steel slag, and carbon sealing recycled aggregate is prepared by utilizing corrosive liquid and carbon dioxide tail gas; the application effectively aims at different types of steel slag particles, obtains the steel slag particles with stable volume by processing in a low energy consumption mode, and utilizes the dioxygen in the industrial tail gasThe carbon is converted, the interface transition area of the recycled aggregate is improved, and the whole production process has the advantages of low carbon, environmental protection, recycling, high reaction efficiency and the like.
Description
Technical Field
The application relates to the technical field of green low-carbon building materials, in particular to a method for eliminating steel slag stability and preparing carbon sealing recycled aggregate by utilizing tail gas containing CO2 based on acetic acid circulation.
Background
Steel slag is a solid waste produced in industrial steelmaking process, and the yield of the steel slag is 12% -20% of the yield of coarse steel. However, the current utilization rate of the steel slag is lower, the comprehensive utilization rate is only 30%, and the accumulation amount of part of steel slag in large steel and iron works exceeds 10 hundred million tons. The low utilization rate of steel slag is the volume stability problem which is most difficult to treat besides the poor self-hydration activity. The steel slag contains a large amount of free calcium oxide and free magnesium oxide (f-CaO and f-MgO) and is easy to be converted into Ca (OH) in the hydration process 2 And Mg (OH) 2 The expansion amounts are 98% and 148%, respectively, and the incorporation into concrete will cause local expansion and even cracking of the concrete, and a certain amount of MgO, mnO, feO in solid solution (RO) in steel slag will also cause poor volume stability problems. The traditional steel slag stability treatment method such as a hot disintegrating method, a water quenching method, a high-temperature aging method and the like has a series of problems of incomplete stability elimination, complex process, high energy consumption and the like although the application is common.
CO 2 The trapping, utilizing and sealing (CCUS) technology is an effective measure for reducing carbon emissions in the building material industry, such as utilizing carbon dioxide tail gas generated in the process of high carbon emission industry (cement, steel, electric power industry), injecting the carbon dioxide tail gas into concrete to improve strength, or manufacturing synthetic aggregate or mineralized concrete blocks, etc. Studies have shown that minerals rich in alkaline earth metals (Ca, mg) can be combined with dissolved CO 2 And reacting to form a carbonate product. In the process, CO 2 Is trapped and converted into carbonate, and through solidification, fills the matrix voids, a dense and stable structure can be formed. At present, chinese steel slagThe average chemical composition is CaO (40-50%), siO 2 (10-15％)，Fe 2 O 3 (3.14％)，Al 2 O 3 (1-5%), mgO (12%), the higher content of free calcium oxide/magnesium (f-CaO/f-MgO) determines itself to have higher carbonization reactivity. Therefore, based on CC US technology, CO is carried out on steel slag 2 Mineralizing and curing, and eliminating f-CaO/f-MgO which causes the problem of volume stability of the steel slag, thereby obtaining the steel slag with stable performance. Laboratory stage common pure CO 2 The gas is used for preparing various steel slag building material products, and the actual industrial production is difficult to obtain pure CO at low cost 2 Gas, lack of CO to non-purity 2 Application of industrial tail gas. In addition, some CO 2 The mineralization maintenance production process also adopts the direct reaction of solid-phase steel slag and gas phase, and has the problem of low reaction efficiency.
Because of the difference of the physical and chemical property compositions of steel slag produced by different steelmaking processes, for example, the CaO (MgO) content of Ladle Furnace Slag (LFS) is 65-75%, the CaO (MgO) (MgO) content of Basic Oxygen Furnace Slag (BOFS) is 45-65%, the CaO (MgO) content of Electric Arc Furnace Reducing Slag (EAFRS) is 45-65%, and the CaO (MgO) content of Electric Arc Furnace Oxidizing Slag (EAFOS) is 30-45%. While a high CaO (MgO) content generally means a higher carbonization reactivity, theoretically without excessive mechanical activation for the production of building material products, the energy consumption required is lower. However, the current industrial production homogenization preparation process does not effectively utilize the element composition characteristics of the steel slag, so that unnecessary energy consumption and lower production efficiency are caused in the actual production process.
Disclosure of Invention
The application aims to solve the technical problems that: in order to overcome the defects in the prior art, the utility CO-containing catalyst based on acetic acid circulation is provided 2 The tail gas eliminates the stability of steel slag and prepares carbon sealing recycled aggregate.
The technical scheme adopted by the application is as follows: utilization CO-containing based on acetic acid circulation 2 The method for eliminating the stability of steel slag by tail gas and preparing the carbon-sealed recycled aggregate is characterized by comprising the following steps of:
step 1, crushing and screening: crushing different types of steel slag raw slag to different particle sizes, and screening to obtain steel slag particles;
step 2, corrosion of steel slag by acetic acid: soaking the steel slag particles obtained in the step 1 in acetic acid solution, reacting f-CaO and f-MgO in the steel slag particles with acetic acid to generate calcium acetate, magnesium acetate and water, wherein the reaction time is 1-3 hours, and simultaneously obtaining corroded porous steel slag particles;
step 3, carbonization deposition of calcium acetate and magnesium acetate mixed solution:
taking out part of the calcium acetate and magnesium acetate mixed solution obtained in the step 2, immersing the recycled aggregate obtained in the building dismantling process in the solution, and then introducing CO-containing material 2 The industrial tail gas is accumulated in the transition zone of the recycled aggregate interface to enhance the surface compactness, thereby improving the workability and the hardening physical properties of the recycled aggregate-made mortar concrete mixture;
introducing CO into the residual mixed solution 2 The industrial tail gas reacts with calcium acetate and magnesium acetate to generate carbonate which is accumulated on the surfaces of steel slag particles to seal CO 2 And preparing the steel slag carbon utilization aggregate,
according to the Gibbs free energy theory calculation, the Gibbs free energy of the calcium acetate and the carbon dioxide in the liquid phase environment for producing the calcium carbonate and the acetic acid is-2.75 kJ/mol, namely the reaction can be carried out spontaneously;
step 4, recycling acetic acid solution: calcium acetate and magnesium acetate solution and CO in step 3 2 The products after complete reaction are carbonate precipitation and acetic acid, solid particles after reaction or modified steel slag particles and recycled aggregate are filtered out, so that an acetic acid solution can be obtained, and the acetic acid solution is recycled for corroding steel slag in the step 2, thereby recycling the steel slag.
The application adopts differential treatment technology aiming at different types of steel slag, eliminates the volume stability of the steel slag by utilizing acetic acid to corrode the steel slag, and prepares carbon sealing recycled aggregate by utilizing corrosive liquid and carbon dioxide tail gas. According to the type of steel slag, crushing the steel slag into different particle sizes, soaking the steel slag in acetic acid water solutions with different concentrations, and dissolving f-CaO/f-MgO which causes the problem of steel slag stability to form a soluble calcium acetate and magnesium acetate mixed solution. According to the Gibbs free energy theory calculation, the Gibbs free energy of the calcium acetate and the carbon dioxide in the liquid phase environment for producing the calcium carbonate and the acetic acid is-2.75 kJ/mol, namely the reaction can be carried out spontaneously. Therefore, the recycled aggregate is soaked in the acetate solution in advance, and then the industrial tail gas containing carbon dioxide is introduced, so that calcium carbonate precipitate can be formed by coating the porous recycled aggregate and cement slurry interface, the surface porosity and the water absorption rate of the recycled aggregate are reduced, and the workability and the strength of a hardened body of the recycled aggregate-made mortar concrete mixture are enhanced; in addition, acetic acid is generated by the reaction, and the obtained acetic acid solution can be further used for corroding steel slag and is continuously recycled. The application effectively aims at different types of steel slag particles, obtains the steel slag particles with stable volume by processing in a low energy consumption mode, utilizes the carbon dioxide in the industrial tail gas, improves the interface transition zone of recycled aggregate, and has a series of advantages of low carbon, environmental protection, recycling, high reaction efficiency and the like.
Further, in the step 1, the grain sizes of the broken steel slag raw slag of different types are as follows:
the fineness of the oxidizing slag of the electric arc furnace is less than 1.18mm,
the fineness of the basic oxygen converter slag and the arc furnace reducing slag is 1.18-2.36mm,
the fineness of the ladle slag is 2.36mm-4.75mm.
Considering the influence of the steel slag type, the volume stability of the steel slag is eliminated. Aiming at the differences of chemical elements, hardness and porosity of steel slag, the application adjusts the steel slag crushing process to minimize energy consumption, and utilizes acetic acid to corrode the steel slag, so as to dissolve f-CaO/f-MgO in the steel slag to form a soluble calcium acetate and magnesium acetate mixed solution, thereby eliminating the problem of steel slag stability and obtaining stable steel slag particles.
Sealing CO in industrial tail gas 2 To reduce carbon emissions. Introducing industrial tail gas into the calcium acetate/magnesium acetate mixed solution obtained by dissolving solid waste through acetic acid treatment, so as to obtain CO 2 The gas is converted into carbonate solid, namely CO 2 Sealing and storing, reducing CO in the environment 2 Exhaust emissions.
And preparing the steel slag carbon utilization aggregate. Directly introducing CO into the steel slag particles corroded by acetic acid 2 Calcium acetate/magnesium acetate and CO can be used 2 The carbonate generated by the reaction is accumulated on the surfaces of the steel slag particles, thereby sealing a certain amount of CO 2 And (5) preparing the steel slag carbon utilization aggregate.
And the interface transition area of recycled aggregate is enhanced, and the performance of the prepared mortar concrete is improved. The interface transition area between the cement paste on the surface of the recycled aggregate and the aggregate has the problems of loose, porous and easy water absorption, and the mixed solution of calcium acetate and magnesium acetate is used for soaking and introducing CO 2 The calcium carbonate coating can be generated to be filled in the pores of the interface transition zone, so that the compactness of the recovered aggregate interface transition zone is enhanced, and the workability and the hardening physical properties of the recycled aggregate-made mortar concrete mixture are improved.
The whole production process is low-carbon and recyclable, and acetic acid is recycled. Introducing CO into the calcium acetate/magnesium acetate mixed solution formed by corroding steel slag by acetic acid 2 A calcium/magnesium carbonate precipitate may then be formed, as well as acetic acid. Thus, the whole production process is low-carbon and recyclable, and acetic acid can be recycled in the process.
Further, in the step 3, CO is contained 2 CO in industrial tail gas 2 The concentration is 15-45vol% and the temperature is 40-150 ℃.
Further, in the step 4, the carbonate precipitate includes calcium carbonate and magnesium carbonate.
Compared with the prior art, the application has the following advantages:
1. under the condition of high-efficiency chemical reaction of solid and liquid phases, the acetic acid is utilized to corrode the steel slag, and f-CaO/f-MgO in the steel slag particles is eliminated, so as to obtain steel slag particles with good volume stability;
2. in the process of corroding the steel slag by acetic acid, the differences of chemical elements, hardness and porosity of different types of steel slag are considered, and different crushing systems are adopted for the different types of steel slag so as to save the energy consumption of production;
3. calcium acetate/magnesium acetate solution obtained by corroding steel slag by acetic acid is introduced with CO 2 Industrial tail gas spontaneously reacts to form carbonate precipitate, and a certain amount of CO can be stored 2 . When the sediment is accumulated on the surfaces of the steel slag particles, the steel slag carbon utilization aggregate can be prepared; when the precipitate is coated on the recycled aggregateWhen the surface is provided, the interface transition area can be improved to enhance the workability and the hardening physical properties of the recycled aggregate-made mortar concrete mixture;
4. CO in industrial tail gas 2 Acetic acid can be regenerated in the reaction process of the calcium acetate/magnesium acetate mixed solution, and an acetic acid solution obtained by filtering solids can be reused for corroding steel slag, and the whole process has no wastewater discharge, and is low-carbon, environment-friendly and renewable.
Drawings
Fig. 1 is a process flow diagram of the present application.
The chemical reactions involved in the process flow are as follows:
reaction I:
reaction II: ca (CH) 3 COO) 2 /Mg(CH 3 COO) 2 +CO 2 +H 2 O→CaCO 3 /MgCO 3 +2CH 3 COOH
Detailed Description
The following describes the embodiments of the present application in detail, and the embodiments and specific operation procedures are given on the premise of the technical solution of the present application, but the scope of protection of the present application is not limited to the following embodiments.
Example 1
Crushing 100kg/min Ladle Furnace Slag (LFS) by a crusher, and sieving to obtain steel slag particles with the diameter of 2.36-4.75 mm. The steel slag particles are soaked in an acetic acid solution reaction tank with the concentration of 3-5mol/L, and the introducing rate of the acetic acid solution is 50L/min. Soaking the steel slag particles in acetic acid solution for 1-2 hours to dissolve and decompose the free calcium oxide and the free magnesium oxide in the steel slag into the acetic acid solution to form a calcium acetate and magnesium acetate mixed solution. Will contain CO 2 Industrial tail gas (CO) 2 The concentration is 15-25vol%, the temperature is 40-80 ℃ and the concentration is 100m 3 /min) introducing into a reaction tank, calcium acetate, magnesium acetate and dissolved CO 2 The reaction generates calcium acetate and magnesium acetate which are piled up on the surface of steel slag particles to prepare 115kg/min steel slag carbon utilization aggregate (ladle slag). Filtering and fishing aggregate in a reaction tankAnd 3-5mol/L of acetic acid solution is used as the residual liquid, so that the acetic acid solution is reused.
3kg of aggregate is randomly taken out from 115kg/min of steel slag carbon utilization aggregate (ladle slag), and the volume stability detection method of the steel slag carbon utilization aggregate (ladle slag) is referred to GB/T24175-2009 Steel slag stability test method: adding 1200ml of distilled water into the autoclave, putting aggregate into the autoclave, sealing, steaming for 3 hours under saturated steam pressure of 2.0MPa, starting timing from the pressure of 2MPa, automatically stopping heating the autoclave after 3 hours, and opening an exhaust fan for cooling. After the autoclave is automatically stopped, taking out the aggregate to observe pulverization, and finding that the aggregate is not cracked after being autoclaved for 3 hours.
Example 2
Crushing 100kg/min Ladle Furnace Slag (LFS) by a crusher, and sieving to obtain 4.75-9.5mm steel slag particles. The steel slag particles are soaked in an acetic acid solution reaction tank with the concentration of 3-5mol/L, and the introducing rate of the acetic acid solution is 50L/min. Soaking the steel slag particles in acetic acid solution for 1-2 hours to dissolve and decompose the free calcium oxide and the free magnesium oxide in the steel slag into the acetic acid solution to form a calcium acetate and magnesium acetate mixed solution. Will contain CO 2 Industrial tail gas (CO) 2 The concentration is 15-25vol%, the temperature is 40-80 ℃ and the concentration is 100m 3 /min) introducing into a reaction tank, calcium acetate, magnesium acetate and dissolved CO 2 The reaction generates calcium acetate and magnesium acetate which are piled up on the surface of steel slag particles to prepare 115kg/min steel slag carbon utilization aggregate (ladle slag). Filtering and fishing out the aggregate in the reaction tank, wherein the residual liquid is acetic acid solution with the concentration of 3-5mol/L, so that the acetic acid solution is reused.
3kg of aggregate is randomly taken out from 115kg/min of steel slag carbon utilization aggregate (ladle slag), and the volume stability detection method of the steel slag carbon utilization aggregate (ladle slag) is referred to GB/T24175-2009 Steel slag stability test method: adding 1200ml of distilled water into the autoclave, putting aggregate into the autoclave, sealing, steaming for 3 hours under saturated steam pressure of 2.0MPa, starting timing from the pressure of 2MPa, automatically stopping heating the autoclave after 3 hours, and opening an exhaust fan for cooling. After the autoclave is automatically stopped, the aggregate is taken out to observe pulverization, and the result shows that the aggregate is expanded after being autoclaved for 3 hours.
TABLE 1LFS slag volume stability versus reaction time
TABLE 2 relationship between LFS slag volume stability and aggregate fineness
TABLE 3LFS slag volume stability versus acetic acid concentration
Example 3
Crushing 100kg/min of Basic Oxygen Furnace Slag (BOFS) by a crusher, and sieving to obtain 1.18-2.36mm steel slag particles. The steel slag particles are soaked in an acetic acid solution reaction tank with the concentration of 5-8mol/L, and the introducing rate of the acetic acid solution is 50L/min. Soaking the steel slag particles in acetic acid solution for 2-3 hours to dissolve and decompose the free calcium oxide and the free magnesium oxide in the steel slag into the acetic acid solution to form a calcium acetate and magnesium acetate mixed solution. Will contain CO 2 Industrial tail gas (CO) 2 The concentration is 25-35vol%, the temperature is 80-120 ℃ and the concentration is 100m 3 /min) introducing into a reaction tank, calcium acetate, magnesium acetate and dissolved CO 2 The reaction is carried out to generate calcium acetate and magnesium acetate which are piled up on the surfaces of the steel slag particles to prepare 110kg/min of steel slag carbon utilization aggregate (basic oxygen converter slag). Filtering and fishing out the aggregate in the reaction tank, wherein the residual liquid is 5-8mol/L acetic acid solution, so that the acetic acid solution is reused.
3kg of aggregate is randomly taken out from 110kg/min of steel slag carbon utilization aggregate (basic oxygen furnace slag), and the volume stability detection method of 110kg/min of steel slag carbon utilization aggregate (basic oxygen furnace slag) is referred to GB/T24175-2009 Steel slag stability test method: adding 1200ml of distilled water into the autoclave, putting aggregate into the autoclave, sealing, steaming for 3 hours under saturated steam pressure of 2.0MPa, starting timing from the pressure of 2MPa, automatically stopping heating the autoclave after 3 hours, and opening an exhaust fan for cooling. After the autoclave is automatically stopped, taking out the aggregate to observe pulverization, and finding that the aggregate is not cracked after being autoclaved for 3 hours.
Example 4
Crushing 100kg/min of Basic Oxygen Furnace Slag (BOFS) by a crusher, and sieving to obtain 1.18-2.36mm steel slag particles. The steel slag particles are soaked in an acetic acid solution reaction tank with the concentration of 2-3mol/L, and the introducing rate of the acetic acid solution is 50L/min. Soaking the steel slag particles in acetic acid solution for 2-3 hours to dissolve and decompose the free calcium oxide and the free magnesium oxide in the steel slag into the acetic acid solution to form a calcium acetate and magnesium acetate mixed solution. Will contain CO 2 Industrial tail gas (CO) 2 The concentration is 25-35vol%, the temperature is 80-120 ℃ and the concentration is 100m 3 /min) introducing into a reaction tank, calcium acetate, magnesium acetate and dissolved CO 2 The reaction is carried out to generate calcium acetate and magnesium acetate which are piled up on the surfaces of the steel slag particles to prepare 110kg/min of steel slag carbon utilization aggregate (basic oxygen converter slag). Filtering and fishing out the aggregate in the reaction tank, wherein the residual liquid is 5-8mol/L acetic acid solution, so that the acetic acid solution is reused.
3kg of aggregate is randomly taken out from 110kg/min of steel slag carbon utilization aggregate (basic oxygen furnace slag), and the volume stability detection method of 110kg/min of steel slag carbon utilization aggregate (basic oxygen furnace slag) is referred to GB/T24175-2009 Steel slag stability test method: adding 1200ml of distilled water into the autoclave, putting aggregate into the autoclave, sealing, steaming for 3 hours under saturated steam pressure of 2.0MPa, starting timing from the pressure of 2MPa, automatically stopping heating the autoclave after 3 hours, and opening an exhaust fan for cooling. After the autoclave is automatically stopped, the aggregate is taken out to observe pulverization, and the result shows that the aggregate is expanded after being autoclaved for 3 hours.
TABLE 4 relationship between BOFS steel slag volume stability and reaction time
TABLE 5 relationship between volume stability of BOFS slag and fineness of aggregate
TABLE 6 relationship between BOFS steel slag volume stability and acetic acid concentration
Example 5
100kg/min of arc furnace oxide slag (EAFOS) is crushed by a crusher and sieved to obtain steel slag particles smaller than 1.18 mm. The steel slag particles are soaked in an acetic acid solution reaction tank with the concentration of 8-10mol/L, and the introducing rate of the acetic acid solution is 50L/min. Soaking the steel slag particles in acetic acid solution for 2-3 hours to dissolve and decompose the free calcium oxide and the free magnesium oxide in the steel slag into the acetic acid solution to form a calcium acetate and magnesium acetate mixed solution. Will contain CO 2 Industrial tail gas (CO) 2 The concentration is 35-45vol%, the temperature is 120-150 ℃ and the concentration is 100m 3 /min) introducing into a reaction tank, calcium acetate, magnesium acetate and dissolved CO 2 The reaction generates calcium acetate and magnesium acetate which are accumulated on the surfaces of steel slag particles to prepare 105kg/min of steel slag carbon utilization aggregate (arc furnace oxidizing slag). Or the corroded oxidizing slag of the electric arc furnace is fished out in the reaction tank, and then 100kg/min of recycled aggregate obtained by dismantling the building is added into the reaction tank. Soaking orthopedics department in the solution for 1 hr, and adding CO 2 Industrial tail gas (CO) 2 The concentration is 35-45vol%, the temperature is 120-150 ℃ and the concentration is 100m 3 /min) introducing into a reaction tank, calcium acetate, magnesium acetate and dissolved CO 2 The reaction generates calcium acetate and magnesium acetate which are coated on the surface of the recycled aggregate, the coating thickness is 5-10% of the particle size of the aggregate, and the prepared 120kg/min coated recycled aggregate is coated. Filtering and taking out the coated recycled aggregate in a reaction tank, wherein the residual liquid is acetic acid solution with the concentration of 8-10mol/L,can be further used for corroding steel slag.
3kg of aggregate is randomly taken out from 105kg/min of steel slag carbon utilization aggregate (arc furnace oxidizing slag), and the volume stability detection method of the coating recycled aggregate is referred to GB/T24175-2009 steel slag stability test method: adding 1200ml of distilled water into the autoclave, putting aggregate into the autoclave, sealing, steaming for 3 hours under saturated steam pressure of 2.0MPa, starting timing from the pressure of 2MPa, automatically stopping heating the autoclave after 3 hours, and opening an exhaust fan for cooling. After the autoclave is automatically stopped, taking out the aggregate to observe pulverization, and finding that the aggregate is not cracked after being autoclaved for 3 hours.
Example 6
100kg/min of arc furnace oxide slag (EAFOS) is crushed by a crusher and sieved to obtain steel slag particles smaller than 1.18 mm. The steel slag particles are soaked in an acetic acid solution reaction tank with the concentration of 8-10mol/L, and the introducing rate of the acetic acid solution is 50L/min. Soaking the steel slag particles in acetic acid solution for 0.5-1 hour to dissolve and decompose the free calcium oxide and the free magnesium oxide in the steel slag into the acetic acid solution to form a calcium acetate and magnesium acetate mixed solution. Will contain CO 2 Industrial tail gas (CO) 2 The concentration is 35-45vol%, the temperature is 120-150 ℃ and the concentration is 100m 3 /min) introducing into a reaction tank, calcium acetate, magnesium acetate and dissolved CO 2 The reaction generates calcium acetate and magnesium acetate which are accumulated on the surfaces of steel slag particles to prepare 105kg/min of steel slag carbon utilization aggregate (arc furnace oxidizing slag). Or the corroded oxidizing slag of the electric arc furnace is fished out in the reaction tank, and then 100kg/min of recycled aggregate obtained by dismantling the building is added into the reaction tank. Soaking orthopedics department in the solution for 1 hr, and adding CO 2 Industrial tail gas (CO) 2 The concentration is 35-45vol%, the temperature is 120-150 ℃ and the concentration is 100m 3 /min) introducing into a reaction tank, calcium acetate, magnesium acetate and dissolved CO 2 The reaction generates calcium acetate and magnesium acetate which are coated on the surface of the recycled aggregate, the coating thickness is 5-10% of the particle size of the aggregate, and the prepared 115kg/min coated recycled aggregate is prepared. Filtering and taking out the coated recycled aggregate in a reaction tank, wherein the residual liquid is acetic acid solution with the concentration of 8-10mol/L, and the method can be further used for corroding steel slag.
3kg of aggregate is randomly taken out from 105kg/min of steel slag carbon utilization aggregate (arc furnace oxidizing slag), and the volume stability detection method of the coating recycled aggregate is referred to GB/T24175-2009 steel slag stability test method: adding 1200ml of distilled water into the autoclave, putting aggregate into the autoclave, sealing, steaming for 3 hours under saturated steam pressure of 2.0MPa, starting timing from the pressure of 2MPa, automatically stopping heating the autoclave after 3 hours, and opening an exhaust fan for cooling. After the autoclave is automatically stopped, the aggregate is taken out to observe pulverization, and as a result, slight expansion of the aggregate is found after the autoclave is autoclaved for 3 hours.
TABLE 7 relationship between EAFOS steel slag volume stability and reaction time
TABLE 8 relationship between EAFOS steel slag volume stability and aggregate fineness
TABLE 9 relationship between EAFOS steel slag volume stability and acetic acid concentration
Claims (4)
1. Utilization CO-containing based on acetic acid circulation 2 The method for eliminating the stability of steel slag by tail gas and preparing the carbon-sealed recycled aggregate is characterized by comprising the following steps of:
step 1, crushing and screening: crushing different types of steel slag raw slag to different particle sizes, and screening to obtain steel slag particles;
step 2, corrosion of steel slag by acetic acid: soaking the steel slag particles obtained in the step 1 in acetic acid solution, reacting f-CaO and f-MgO in the steel slag particles with acetic acid to generate calcium acetate, magnesium acetate and water, wherein the reaction time is 1-3 hours, and simultaneously obtaining corroded porous steel slag particles;
step 3, carbonization deposition of calcium acetate and magnesium acetate mixed solution:
taking out part of the calcium acetate and magnesium acetate mixed solution obtained in the step 2, immersing the recycled aggregate obtained in the building dismantling process in the solution, and then introducing CO-containing material 2 The industrial tail gas generates carbonate which is accumulated in the interface transition zone of the recycled aggregate;
introducing CO into the residual mixed solution 2 Reacting industrial tail gas with calcium acetate and magnesium acetate to generate carbonate which is accumulated on the surfaces of steel slag particles;
step 4, recycling acetic acid solution: calcium acetate and magnesium acetate solution and CO in step 3 2 The products after complete reaction are carbonate precipitation and acetic acid, solid particles after reaction or modified steel slag particles and recycled aggregate are filtered out, so that an acetic acid solution can be obtained, and the acetic acid solution is recycled for corroding the steel slag in the step 2.
2. Utilization of CO-containing based on acetic acid recycle according to claim 1 2 The method for eliminating the stability of the steel slag by the tail gas and preparing the carbon-sealed recycled aggregate is characterized in that in the step 1, the crushed grain sizes of the steel slag raw slag of different types are as follows:
the fineness of the oxidizing slag of the electric arc furnace is less than 1.18mm,
the fineness of the basic oxygen converter slag and the arc furnace reducing slag is 1.18-2.36mm,
the fineness of the ladle slag is 2.36mm-4.75mm.
3. Utilization of CO-containing based on acetic acid recycle according to claim 1 2 The method for eliminating the stability of the steel slag by tail gas and preparing the carbon-sealed recycled aggregate is characterized in that in the step 3, the carbon-sealed recycled aggregate contains CO 2 CO in industrial tail gas 2 The concentration is 15-45vol% and the temperature is 40-150 ℃.
4. Utilization of CO-containing based on acetic acid recycle according to claim 1 2 The method for eliminating the stability of steel slag by tail gas and preparing the carbon-sealed recycled aggregate is characterized in that in the step 4, carbonate precipitation comprises calcium carbonate and magnesium carbonate.
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