CN117263536A - Preparation method and application of ultrahigh-activity solid waste-based carbon-fixing auxiliary cementing material - Google Patents
Preparation method and application of ultrahigh-activity solid waste-based carbon-fixing auxiliary cementing material Download PDFInfo
- Publication number
- CN117263536A CN117263536A CN202310951277.1A CN202310951277A CN117263536A CN 117263536 A CN117263536 A CN 117263536A CN 202310951277 A CN202310951277 A CN 202310951277A CN 117263536 A CN117263536 A CN 117263536A
- Authority
- CN
- China
- Prior art keywords
- solid waste
- activity
- ultra
- cementing material
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000000694 effects Effects 0.000 title claims abstract description 260
- 239000002910 solid waste Substances 0.000 title claims abstract description 223
- 239000000463 material Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000227 grinding Methods 0.000 claims abstract description 110
- 238000000034 method Methods 0.000 claims abstract description 81
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 54
- 239000000126 substance Substances 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 44
- 230000008569 process Effects 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000002893 slag Substances 0.000 claims description 50
- 239000002131 composite material Substances 0.000 claims description 40
- 239000003469 silicate cement Substances 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- -1 alcohol amine Chemical class 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 239000002956 ash Substances 0.000 claims description 21
- 239000010881 fly ash Substances 0.000 claims description 21
- 239000004567 concrete Substances 0.000 claims description 20
- 239000004615 ingredient Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- 229910000831 Steel Inorganic materials 0.000 claims description 17
- 239000010959 steel Substances 0.000 claims description 17
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 16
- 229920005646 polycarboxylate Polymers 0.000 claims description 16
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 15
- 239000002699 waste material Substances 0.000 claims description 15
- 150000004645 aluminates Chemical class 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000010425 asbestos Substances 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 229910052895 riebeckite Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910000859 α-Fe Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011398 Portland cement Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910021532 Calcite Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 238000007689 inspection Methods 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims description 2
- 230000009919 sequestration Effects 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 2
- 239000004568 cement Substances 0.000 description 59
- 238000006703 hydration reaction Methods 0.000 description 40
- 230000036571 hydration Effects 0.000 description 36
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 26
- 238000005259 measurement Methods 0.000 description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000203 mixture Substances 0.000 description 23
- 239000002440 industrial waste Substances 0.000 description 22
- 238000002474 experimental method Methods 0.000 description 21
- 238000013329 compounding Methods 0.000 description 12
- 239000002585 base Substances 0.000 description 8
- 230000002195 synergetic effect Effects 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- UPKIHOQVIBBESY-UHFFFAOYSA-N magnesium;carbanide Chemical compound [CH3-].[CH3-].[Mg+2] UPKIHOQVIBBESY-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
Classifications
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/17—Mixtures thereof with other inorganic cementitious materials or other activators with calcium oxide containing activators
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material, and belongs to the technical field of building materials. The method comprises the following steps: (1) Pre-grinding the middle-low activity high-alumina volcanic solid waste to a corresponding particle size range to obtain middle-low activity high-alumina volcanic solid waste pre-grinding micro powder, wherein a corresponding compound chemical auxiliary agent is added in the pre-grinding process; (2) The ultra-high activity solid waste based carbon-fixing auxiliary cementing material is obtained by mixing the carbon-fixing solid waste, the low-medium activity high-alumina volcanic ash solid waste pre-grinding micro powder and the calcium-increasing component according to a specific mass ratio and carrying out superfine grinding to reach a corresponding particle size range. The ultra-high activity solid waste base carbon-fixing auxiliary cementing material prepared by the method has the advantages that the 30% doping amount activity index is up to the grade S130-S145, and the 50% doping amount activity index can be up to the grade S120-S130.
Description
Technical Field
The invention belongs to the technical field of building materials, and in particular relates to a method for utilizing carbon-fixing solid waste and medium-low activity high-alumina pozzolanic solid waste according to optimal CO 2 /Al 2 O 3 A process method and application for preparing an ultra-high activity solid waste based carbon-fixing auxiliary cementing material by proportion synergistic compounding.
Background
Cement is an important basic material for supporting national economy construction, and is generally prepared by mixing silicate clinker, auxiliary cementing material and a proper amount of gypsum. The hydration activity of the auxiliary cementing material determines the minimum clinker coefficient (the proportion of the cement clinker to the silicate cement) and the mechanical property of the cement product.
At present, granulated blast furnace slag is an essential component of most of high-activity (28 d activity index is more than 95%) auxiliary cementing materials, and other bulk industrial solid wastes (such as fly ash, furnace bottom slag, steel slag, red mud, coal gangue and the like) cannot completely replace the granulated blast furnace slag to be applied to the preparation of high-activity mineral admixtures due to poor hydration activity or too slow activity exertion. Along with the continuous increase of the productivity of cement and concrete products in China, high-activity auxiliary cementing materials represented by granulated blast furnace slag are also becoming very short. Therefore, how to realize the preparation of the auxiliary cementing material with high activity and even ultra-high activity (28 d activity index is more than 105%) by using only medium-low activity large industrial solid wastes such as fly ash, furnace bottom slag, steel slag, red mud and the like under the condition of no granulating blast furnace slag is a technical means which is urgently needed in the cement and concrete industry, and has remarkable economic benefit and environmental benefit.
Disclosure of Invention
The invention provides a preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material aiming at the technical problems.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the ultra-high activity solid waste based carbon-fixing auxiliary cementing material comprises the following steps:
(1) Pre-grinding the middle-low activity high-alumina volcanic solid waste to obtain middle-low activity high-alumina volcanic solid waste pre-grinding micro powder, and adding corresponding compound chemical auxiliary agents in the pre-grinding process;
(2) Mixing the carbon-fixing solid waste with the low-medium activity high-alumina volcanic ash solid waste pre-grinding micro powder and the calcium-increasing component, and performing superfine grinding to reach a preset particle size range to obtain the ultra-high activity solid waste-based carbon-fixing auxiliary cementing material;
the predetermined particle diameter range is 30 μm with screen residue less than 1%, and specific surface area more than 700m 2 。
The technical scheme of the invention is as follows: the obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing silicate cement clinker in a mass ratio of 30-50% and is applied to the preparation of silicate cement or concrete.
The technical scheme of the invention is as follows: in the step (1), the medium-low activity high-alumina volcanic ash solid waste is one or more of fly ash, coal-fired furnace bottom slag, calcined alumina gangue and calcined clay rock gangue; al of middle-low activity high-alumina pozzolanic solid waste 2 O 3 The content is more than or equal to 25 wt%, and the volcanic quality inspection of the medium-low activity high-aluminum volcanic solid waste is qualified.
The technical scheme of the invention is as follows: the compound chemical auxiliary agent added in the pre-grinding process in the step (1) consists of 40-85 parts by mass of alcohol amine grinding aid, 10-45 parts by mass of polycarboxylate, 0.1-3.5 parts by mass of aluminate or titanate and 4-15 parts by mass of sodium aluminate and/or sodium ferrite; the mixing amount of the composite chemical auxiliary agent is 2-8 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
The technical scheme of the invention is as follows: in the step (1), the specific surface area of the obtained pre-ground micro powder of the medium-low activity high-alumina pozzolanic solid waste is more than 500m 2 Kg and 45 μm screen residue < 3%.
The technical scheme of the invention is as follows: the carbon-fixing solid waste in the step (2) is carbonOne or more of steel slag, carbonized sintering red mud, magnesium carbide slag and carbonized waste concrete micro powder; the carbon-fixing solid waste is prepared from steel slag, red mud from sintering process, magnesium slag, and waste concrete micropowder by dry or wet method 2 Collecting process carbonization, and absorbing weight method CO by using alkali asbestos of solid waste of solid carbon fixation 2 The measured value is more than or equal to 10 wt%, and the carbon component in the carbon-fixing solid waste exists in the form of calcite type or aragonite type calcium carbonate.
The technical scheme of the invention is as follows: the calcium increasing component in the step (2) is one or more of carbide slag and lime.
The technical scheme of the invention is as follows: the mass ratio of the superfine grinding ingredients of the solid waste with carbon fixation to the solid waste with middle-low activity and high aluminum volcanic ash in the step (2) is that CO in the solid waste with carbon fixation 2 And Al in the medium-low activity high-alumina volcanic ash solid waste pre-ground micro powder 2 O 3 The mass ratio of (2) is 0.5-1.5: 1.
in the technical scheme of the invention, the mixing amount of the calcium increasing component in the step (2) is 1-5% of the sum of the mass of the carbon-fixing solid waste and the mass of the pre-ground micro powder of the medium-low activity high-alumina volcanic ash solid waste.
In the technical scheme of the invention, the ultra-high activity solid waste base carbon-fixing auxiliary cementing material in the step (2) is subjected to ultra-fine grinding until the specific surface area is more than 700m 2 Kg and a screen residue of 30 μm < 1%.
According to the technical scheme, the preparation method of the ultra-high activity solid waste base carbon-fixing auxiliary cementing material and the application of the ultra-high activity solid waste base carbon-fixing auxiliary cementing material in preparation of silicate cement or concrete instead of silicate cement clinker are provided.
The beneficial effects are that:
(1) The invention uses specific CO to mix the solid waste of carbon fixation, medium-low activity high alumina volcanic ash and solid waste 2 /Al 2 O 3 The proportion is the compounding principle to carry out cooperative compounding, and different COs are adopted 2 /Al 2 O 3 The calcium-increasing component and the compound chemical auxiliary agent component with proper mixing amount are added in proportion, and the solid waste of carbon fixation, the solid waste of middle-low activity high alumina volcanic ash, the calcium-increasing component and the compound are utilizedThe synergistic activity improving mechanism among the four chemical additives adopts segmented superfine grinding as a production process method, so that the hydration activity of the solid carbon-fixing solid waste and the high-alumina pozzolanic solid waste is obviously improved, the technical aim of '1+1 & gt2' is fulfilled, and the technical effect of preparing the ultra-high activity auxiliary cementing material by using the medium-low activity solid waste is achieved.
(2) The invention takes the medium-low activity solid waste with the activity index lower than S90 (30% doping amount) as the main precursor raw material, prepares the ultra-high activity auxiliary cementing material with the activity index reaching the S130-S145 level at the doping amount of 30% and the activity index higher than the S120-S130 level at the doping amount of 50%, can greatly improve the utilization amount of the solid waste with solid carbon and the medium-low activity high-alumina volcanic ash solid waste in the fields of silicate cement and concrete products, and simultaneously greatly reduces the silicate clinker consumption in the silicate cement and concrete products, thereby having great economic and environmental benefits.
Technical principle:
the invention utilizes synergistic activity lifting mechanism among solid waste of carbon fixation, medium-low activity high-alumina volcanic ash solid waste, calcium-increasing component and composite chemical auxiliary agent, and adopts sectional superfine grinding as production process method, thereby achieving the technical effect of preparing the ultra-high activity auxiliary cementing material by utilizing the medium-low activity solid waste, and the related part of technical principles are as follows:
i. the hydration activity of the solid waste of carbon fixation and the solid waste of middle-low activity high-alumina volcanic ash is synergistically improved, namely, the activity effect of the solid waste of carbon fixation in a silicate cement system is severely limited because a large amount of calcium carbonate contained in the solid waste of carbon fixation is not effectively reacted with calcium silicate ore in silicate cement clinker except for amorphous silicon with potential hydration activity; in silicate cement systems, the low-medium activity high-alumina pozzolanic solid waste can also have limited activity due to the difficulty in rapid and sufficient reaction of the aluminum phase. The invention uses the carbon-fixing solid waste and the medium-low activity high-alumina volcanic ash solid waste as specific CO 2 /Al 2 O 3 Proportional compounding can be doneThe submicron calcium carbonate in the solid waste of the present solid carbon and the aluminum phase in the solid waste of the high-alumina volcanic ash react rapidly in the silicate cement system to form a great amount of hydrated calcium aluminate and other crystalline hydration products, so that the hydration reactivity and the hydration degree of the solid waste of the solid carbon and the solid waste of the high-alumina volcanic ash are improved greatly and the technical effect of 1+1 & gt2 is achieved. In addition, crystalline hydration products such as hydrated calcium carbonate aluminate and the like formed by the rapid reaction of the solid carbon-fixing waste and the medium-low-activity high-alumina volcanic ash solid waste can effectively fill microscopic gaps, improve the compactness of amorphous C-S-H gel formed by hydration of amorphous silicon and the medium-low-activity high-alumina volcanic ash solid waste in cement clinker and the solid carbon-fixing waste, and further improve the activity synergistic lifting effect of the solid carbon-fixing waste and the medium-low-activity high-alumina volcanic ash solid waste.
The calcium-increasing component continuously improves the long-term hydration activity of the solid waste and the middle-low-activity high-alumina pozzolanic solid waste, namely, the process of forming the product hydrated calcium carbonate aluminate through the synergistic reaction of the solid waste and the middle-low-activity high-alumina pozzolanic solid waste can obviously improve the consumption of calcium hydroxide of a silicate clinker-solid waste-middle-low-activity high-alumina pozzolanic solid waste system, further, the relatively insufficient content of calcium hydroxide in the system is caused in the long-term, and finally, the full play of the long-term hydration activity of the ultra-high-activity solid waste-based solid carbon-assisted cementing material is obviously restricted; the invention adopts the calcium increasing component with proper mixing amount and different CO 2 /Al 2 O 3 The optimal compounding of the carbon-fixing solid waste and the high-alumina pozzolanic solid waste in proportion promotes the full and efficient exertion of the hydration activity of the ultra-high activity solid waste-based carbon-fixing auxiliary cementing material under different age conditions.
And the synergistic improvement effect of the composite chemical auxiliary agent on the hydration activity of the ultrahigh-activity solid waste-based solid carbon auxiliary cementing material, namely the ultrahigh-hydration activity of the solid waste-based solid carbon auxiliary cementing material is closely related to the improvement of the hydration activity of the composite chemical auxiliary agent, the promotion of the hydration reaction process and the improvement of the stability of hydration products. Aiming at the material characteristics and the hydration principle of the ultra-high activity solid waste based carbon-fixing auxiliary cementing material system, the invention further introduces specific chemical components based on the traditional alcohol amine auxiliary agent, and further promotes the ultra-high hydration activity exertion of the solid waste based carbon-fixing auxiliary cementing material according to the principle effects of different specific chemical components in the aspects of accelerating the generation of the hydration calcium carbonate aluminate product, improving the stability of the hydration calcium aluminate product, improving the dissolution of the active components of the solid waste based carbon-fixing auxiliary cementing material, reducing the potential negative influence of the solid waste based carbon-fixing auxiliary cementing material on the workability and the like.
The invention uses the sectional superfine grinding technology to not only improve the superfine grinding efficiency, but also fully peel and disperse the calcium carbonate product layer and the amorphous silicon product layer in the solid waste, and improve the reaction contact area of the calcium carbonate component in the solid waste and the middle-low activity high alumina solid waste micropowder, thereby further improving the activity synergistic effect of the solid waste and the high alumina pozzolanic solid waste.
Drawings
Fig. 1 is a process flow diagram of preparing an ultra-high activity solid waste based carbon-fixing auxiliary cementing material by utilizing carbon-fixing solid waste and medium-low activity high-alumina pozzolanic solid waste in a synergic manner.
FIG. 2X-ray diffraction patterns of the reference cements, comparative example 1, comparative example 4, comparative example 9, and the composite Portland cements obtained in example 4 after hydration for 28 days.
FIG. 3 is a back-scattered electron image of the hydration 28d of the ultra-high activity solid waste based carbon fixing supplementary cementitious material obtained in example 1.
FIG. 4 is a back-scattered electron image of the hydration 28d of the ultra-high activity solid waste based carbon fixing supplementary cementitious material obtained in example 1.
FIG. 5 is a back-scattered electron image of hydration 28d of the ultra-high activity solid waste based carbon fixing supplementary cementitious material obtained in example 6.
Fig. 6 a secondary electron image of the hydration 28d of the ultra-high activity solid waste based carbon fixing supplementary cementitious material obtained in example 6.
Detailed Description
The invention is further illustrated below with reference to examples, but the scope of the invention is not limited thereto:
the key chemical composition parameters of the carbon-fixing solid waste, the high alumina pozzolanic solid waste and the composite chemical auxiliary agent used in each example and comparative example are listed here:
the carbon-fixing wastes used include: (1) carbonizing converter steel slag, preparing by dry carbonizing process, and absorbing CO by alkali asbestos by gravimetric method 2 The content measurement value was 11.4%; (2) carbonization sintering method red mud and wet carbonization process, and alkali asbestos absorbs CO by weight method 2 The content measurement value was 15.7%; (3) carbonized waste concrete micropowder, wet carbonization process, and alkali asbestos for absorbing CO by weight method 2 The content measurement value was 13.1%; (4) magnesium carbide slag, dry carbonization preparation and alkali asbestos absorption weight method CO thereof 2 The content was found to be 10.1%.
The medium-low activity high-alumina pozzolanic solid waste comprises: (1) fly ash, commercially available grade II, al 2 O 3 Content 28.9wt.%; (2) calcining aluminum gangue, self-making, al 2 O 3 Content 32.7wt.%; (3) slag of coal furnace bottom, al 2 O 3 Content 27.5wt.%. The volcanic property test of the high-alumina volcanic solid waste is qualified.
In the used composite chemical auxiliary agent, the alcohol amine grinding aid is formed by compounding triisopropanolamine (Macklin, AR) and diethanol monoisopropanolamine (Macklin, AR) in a mass ratio of 1:1, and polycarboxylate (Sika, 225P) is prepared from aluminate, titanate, sodium aluminate and sodium ferrite which are all commercially available chemical pure products of Yonghua chemical Co.
Example 1
A preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material comprise the following steps:
(1) Pre-grinding calcined aluminum gangue to a specific surface area=504 m 2 Kg and 45 μm screen residue = 2.7% to obtain calcined alumina gangue pre-ground micropowder; in the grinding process, a composite chemical auxiliary agent is added, wherein the auxiliary agent consists of 80 parts by mass of alcohol amine grinding aid, 15 parts by mass of polycarboxylate, 0.5 part by mass of aluminate and 4.5 parts by mass of sodium aluminate, and the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) The carbonized converter steel slag and the calcined aluminum gangue are pre-ground into micro powder and are treated by CO 2 /Al 2 O 3 Mass ratio ingredients=0.5; meanwhile, 1wt.% of carbide slag is added as a calcium-increasing component (the addition amount of the calcium-increasing component is 1% of the sum of the mass of the carbon-fixing solid waste and the mass of the pre-ground micro powder of the medium-low activity high-alumina pozzolanic solid waste, and the definitions of examples 2 to 11 are the same), superfine grinding is carried out, and the specific surface area=714 m is obtained 2 And 30 μm screen residue = 0.8% of ultra-high activity solid waste based carbon-fixing auxiliary cementing material.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Example 2
A preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material comprise the following steps:
(1) Pre-grinding calcined aluminum gangue to a specific surface area=504 m 2 Kg and 45 μm screen residue = 2.7% to obtain calcined alumina gangue pre-ground micropowder; the composite chemical auxiliary agent is added in the grinding process, and consists of 70 parts by mass of alcohol amine grinding aid, 18 parts by mass of polycarboxylate, 3 parts by mass of aluminate, 6 parts by mass of sodium aluminate and 3 parts by mass of sodium ferrite, wherein the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) Pre-powder of red mud and calcined aluminum gangue by carbonization sintering methodGrinding the fine powder into CO 2 /Al 2 O 3 Mass ratio ingredients=0.5; at the same time, 1.5wt.% lime was added as a calcium-increasing component, and superfine grinding was performed to obtain a specific surface area=723 m 2 And 30 μm screen residue = 0.8% of ultra-high activity solid waste based carbon-fixing auxiliary cementing material.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Example 3
A preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material comprise the following steps:
(1) Pre-grinding calcined aluminum gangue to a specific surface area=504 m 2 Kg and 45 μm screen residue = 2.7% to obtain calcined alumina gangue pre-ground micropowder; in the grinding process, a composite chemical auxiliary agent is added, wherein the auxiliary agent consists of 65 parts by mass of alcohol amine grinding aid, 25.5 parts by mass of polycarboxylate, 1.5 parts by mass of titanate and 8 parts by mass of sodium aluminate, and the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) The magnesium carbide slag and the calcined aluminum gangue are pre-ground into micro powder and CO is used for preparing the micro powder 2 /Al 2 O 3 Mass ratio ingredients of =1; at the same time, 3wt.% lime was added as a calcium-increasing component, and superfine grinding was performed to obtain a specific surface area=721 m 2 And/kg, and the screen residue of 30 mu m is less than 0.8 percent.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Example 4
A preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material comprise the following steps:
(1) Pre-grinding fly ash to specific surface area =516m 2 Kg and 45 μm screen residue = 2.6%, obtaining fly ash pre-ground micropowder; in the grinding process, a composite chemical auxiliary agent is added, wherein the auxiliary agent consists of 70 parts by mass of an alcohol amine grinding aid, 20 parts by mass of polycarboxylate, 1.5 parts by mass of aluminate and 8.5 parts by mass of sodium aluminate, and the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) The carbonized converter steel slag and fly ash are pre-ground into micro powder by CO 2 /Al 2 O 3 Mass ratio ingredients of =1; meanwhile, 2wt.% of carbide slag is added as a calcium increasing component, and superfine grinding is carried out to obtain the calcium increasing component with specific surface area more than 714m 2 And/kg, and the screen residue of 30 mu m is less than 0.9 percent.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Example 5
A preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material comprise the following steps:
(1) Pre-grinding calcined aluminum gangue to a specific surface area=504 m 2 Kg and 45 μm screen residue = 2.7% to obtain calcined alumina gangue pre-ground micropowder; in the grinding process, a composite chemical auxiliary agent is added, wherein the auxiliary agent consists of 52.5 parts by mass of alcohol amine grinding aid, 35 parts by mass of polycarboxylate, 2.5 parts by mass of titanate and 10 parts by mass of sodium aluminate, and the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) The carbonized waste concrete micro powder and calcined aluminum gangue pre-ground micro powder are prepared by using CO 2 /Al 2 O 3 Mass ratio ingredients of =1; at the same time, 3.5wt.% of carbide slag is added as a calcium-increasing component, and superfine grinding is carried out to obtain a specific surface area=734 m 2 And 30 μm screen residue = 0.8% of ultra-high activity solid waste based carbon-fixing auxiliary cementing material.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Example 6
A preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material comprise the following steps:
(1) Pre-grinding calcined aluminum gangue to a specific surface area=504 m 2 Kg and 45 μm screen residue = 2.7% to obtain calcined alumina gangue pre-ground micropowder; in the grinding process, a composite chemical auxiliary agent is added, wherein the auxiliary agent consists of 55 parts by mass of alcohol amine grinding aid, 30 parts by mass of polycarboxylate, 3 parts by mass of aluminate and 12 parts by mass of sodium ferrite, and the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) The carbonized converter steel slag and the calcined aluminum gangue are pre-ground into micro powder and are treated by CO 2 /Al 2 O 3 Mass ratio ingredients=1.5; at the same time, 4.5wt.% of carbide slag is added as a calcium-increasing component, and superfine grinding is carried out to obtain a specific surface area=749m 2 And 30 μm screen residue = 0.7% of ultra-high activity solid waste based carbon-fixing auxiliary cementing material.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Example 7
A preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material comprise the following steps:
(1) Pre-grinding the bottom slag of the coal-fired furnace to a specific surface area=511 m 2 Kg and 45 μm screen residue = 2.6%, obtaining fly ash pre-ground micropowder; in the grinding process, a composite chemical auxiliary agent is added, wherein the auxiliary agent consists of 60 parts by mass of an alcohol amine grinding aid, 22 parts by mass of polycarboxylate, 3 parts by mass of aluminate and 15 parts by mass of sodium aluminate, and the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) The red mud and the coal-fired furnace bottom slag of the carbonization sintering method are pre-ground into micro powder and are treated with CO 2 /Al 2 O 3 Mass ratio ingredients=1.5; at the same time, 4wt.% of carbide slag is added as a calcium-increasing component, and superfine grinding is carried out to obtain specific surface area=733m 2 And 30 μm screen residue = 0.8% of ultra-high activity solid waste based carbon-fixing auxiliary cementing material.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Example 8
A preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material comprise the following steps:
(1) Pre-grinding calcined aluminum gangue to a specific surface area=504 m 2 Kg and 45 μm screen residue = 2.7% to obtain calcined alumina gangue pre-ground micropowder; the composite chemical auxiliary agent is added in the grinding process, and consists of 40 parts by mass of alcohol amine grinding aid, 42 parts by mass of polycarboxylate, 3.5 parts by mass of aluminate, 10 parts by mass of sodium aluminate and 4.5 parts by mass of sodium ferrite, wherein the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) The carbonized waste concrete micro powder and calcined aluminum gangue pre-ground micro powder are prepared by using CO 2 /Al 2 O 3 Mass ratio ingredients=1.5; at the same time, 5wt.% lime was added as a calcium-increasing component, and superfine grinding was performed to obtain a specific surface area=728 m 2 And 30 μm screen residue = 0.8% of ultra-high activity solid waste based carbon-fixing auxiliary cementing material.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Example 9
A preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material comprise the following steps:
(1) Pre-grinding calcined aluminum gangue to a specific surface area=504 m 2 Kg and 45 μm screen residue = 2.7% to obtain calcined alumina gangue pre-ground micropowder; in the grinding process, a composite chemical auxiliary agent is added, wherein the auxiliary agent consists of 65 parts by mass of alcohol amine grinding aid, 25.5 parts by mass of polycarboxylate, 1.5 parts by mass of aluminate and 8 parts by mass of sodium aluminate, and the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) The carbonized converter steel slag and the calcined aluminum gangue are pre-ground into micro powder and are treated by CO 2 /Al 2 O 3 Mass ratio ingredients of =1; at the same time, 3wt.% lime was added as a calcium-increasing component, and superfine grinding was performed to obtain a specific surface area=740 m 2 And 30 μm screen residue = 0.7% of ultra-high activity solid waste based carbon-fixing auxiliary cementing material.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 50 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Example 10
A preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material comprise the following steps:
(1) Pre-grinding fly ash to specific surface area=516 m 2 Kg and 45 μm screen residue = 2.6%, obtaining fly ash pre-ground micropowder; in the grinding process, a composite chemical auxiliary agent is added, wherein the auxiliary agent consists of 70 parts by mass of an alcohol amine grinding aid, 20 parts by mass of polycarboxylate, 1.5 parts by mass of aluminate and 8.5 parts by mass of sodium aluminate, and the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) The red mud and fly ash of carbonization sintering method are pre-ground into micro powder and CO is used for preparing the micro powder 2 /Al 2 O 3 Mass ratio ingredients of =1; at the same time, 2wt.% of carbide slag is added as a calcium-increasing component, and superfine grinding is carried out to obtain the specific surface area=768 m 2 And 30 μm screen residue = 0.5% of ultra-high activity solid waste based carbon-fixing auxiliary cementing material.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 50 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Example 11
A preparation method and application of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material comprise the following steps:
(1) Pre-grinding calcined aluminum gangue to a specific surface area=504 m 2 Kg and 45 μm screen residue = 2.7% to obtain calcined alumina gangue pre-ground micropowder; in the grinding process, a composite chemical auxiliary agent is added, wherein the auxiliary agent consists of 52.5 parts by mass of alcohol amine grinding aid, 35 parts by mass of polycarboxylate, 2.5 parts by mass of aluminate and 10 parts by mass of sodium aluminate, and the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) The red mud of carbonization sintering method and the pre-ground micro powder of calcined aluminum gangue are treated by CO 2 /Al 2 O 3 Mass ratio ingredients of =1; at the same time, 3.5wt.% of carbide slag is added as a calcium-increasing component, and superfine grinding is carried out to obtain a specific surface area=752 m 2 And 30 μm screen residue = 0.6% of ultra-high activity solid waste based carbon-fixing auxiliary cementing material.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 50 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Comparative example 1
Grinding the carbon-fixing solid waste-carbonized converter steel slag to the specific surface area=743m 2 3, preparing carbonized steel slag micropowder by adopting the method of/kg and 30 mu m screen residue=0.6%; the obtained carbonized steel slag micropowder is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Comparative example 2
Will solid carbonWaste-carbonized sintering red mud, grinding to specific surface area=725 m 2 3, preparing carbonized sintering red mud micropowder with 30 μm screen residue=0.8%; the obtained carbonized sintering method red mud micropowder is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experimental method for cement mixture of GB/T12957-2005.
Comparative example 3
Grinding the carbonized waste concrete which is the solid waste with carbon fixation to the specific surface area=733m 2 3, preparing carbonized waste concrete micro powder by adopting the method of/kg and 30 mu m screen residue=0.6%; the obtained carbonized waste concrete micro powder is used for replacing cement clinker by 30 percent to prepare silicate cement, and the silicate cement is prepared by referring to GB/T12957-2005 industrial waste residue activity experiment method for cement mixture
An activity index measurement of 28d was performed.
Comparative example 4
The silicate cement is prepared by replacing cement clinker with 30% of fly ash (grade II), which is a solid waste of middle-low activity high-alumina volcanic ash, and the industrial waste residue activity experimental method for cement mixture is referred to GB/T12957-2005
An activity index measurement of 28d was performed.
Comparative example 5
Grinding the coal-fired furnace bottom slag which is the medium-low activity high-alumina pozzolanic solid waste to the specific surface area of 704m 2 Silicate cement was prepared by replacing cement clinker with 30% and with 30% of 30 μm screen residue=1.0%, and was prepared by referring to GB/T
12957-2005 was used for 28d activity index measurement in industrial residue activity test method of cement admixture.
Comparative example 6
Grinding the calcined aluminum gangue, which is the medium-low activity high-aluminum volcanic solid waste, to the specific surface area=715 m 2 Silicate cement is prepared by replacing cement clinker with 30% of 30% and 30 μm screen residue=0.8%, and is referred to GB/T
12957-2005 was used for 28d activity index measurement in industrial residue activity test method of cement admixture.
Comparative example 7
(1) Pre-grinding calcined aluminum gangue to a specific surface area=504 m 2 Kg and 45 μm screen residue = 2.7% to obtain calcined alumina gangue pre-ground micropowder; only an alcohol amine grinding aid is added in the grinding process, and the mixing amount of the alcohol amine grinding aid is 4 per mill.
(2) The carbonized converter steel slag and the calcined aluminum gangue are pre-ground into micro powder and are treated by CO 2 /Al 2 O 3 Mass ratio ingredients=0.5; at the same time, no calcium-increasing component is added, and superfine grinding is carried out to obtain the specific surface area=706 m 2 Per kg and 30 μm screen residue = 0.9% of solid waste based carbon-fixing supplementary cementitious material.
(3) The obtained solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experimental method for cement mixture of GB/T12957-2005.
Comparative example 8
(1) Pre-grinding fly ash to specific surface area=516 m 2 Kg and 45 μm screen residue = 2.6%, obtaining fly ash pre-ground micropowder; only an alcohol amine grinding aid is added in the grinding process, and the mixing amount of the alcohol amine grinding aid is 4 per mill.
(2) The red mud and fly ash of carbonization sintering method are pre-ground into micro powder and CO is used for preparing the micro powder 2 /Al 2 O 3 Mass ratio ingredients=0.5; at the same time, no calcium-increasing component is added, and superfine grinding is carried out to obtain specific surface area=722 m 2 And 30 μm screen residue = 0.9% of ultra-high activity solid waste based carbon-fixing auxiliary cementing material.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
Comparative example 9
(1) Pre-grinding fly ash to specific surface area=516 m 2 Kg and 45 μm screen residue = 2.6%, obtaining calcined alumina gangue pre-ground micropowder; powderOnly an alcohol amine grinding aid is added in the grinding process, and the mixing amount of the alcohol amine grinding aid is 4 per mill.
(2) The carbonized converter steel slag and fly ash are pre-ground into micro powder by CO 2 /Al 2 O 3 Mass ratio ingredients of =1; at the same time, no calcium-increasing component is added, and superfine grinding is carried out to obtain specific surface area=728 m 2 Per kg and 30 μm screen residue = 0.8% of solid waste based carbon-fixing supplementary cementitious material.
(3) The obtained solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experimental method for cement mixture of GB/T12957-2005.
Comparative example 10
(1) Pre-grinding the bottom slag of the coal-fired furnace to a specific surface area=511 m 2 Kg and 45 μm screen residue = 2.6%, obtaining coal-fired furnace bottom slag pre-ground micro powder; only an alcohol amine grinding aid is added in the grinding process, and the mixing amount of the alcohol amine grinding aid is 4 per mill.
(2) The red mud and the coal-fired furnace bottom slag of the carbonization sintering method are pre-ground into micro powder and are treated with CO 2 /Al 2 O 3 Mass ratio ingredients=1.5; at the same time, no calcium-increasing component is added, and superfine grinding is carried out to obtain the specific surface area=715 m 2 Per kg and 30 μm screen residue = 0.8% of solid waste based carbon-fixing supplementary cementitious material.
(3) The obtained solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experimental method for cement mixture of GB/T12957-2005.
Comparative example 11
(1) Pre-grinding calcined aluminum gangue to specific surface area=362 m 2 Kg and 45 μm screen residue = 6.6%, obtaining calcined alumina gangue pre-ground coarse powder; in the grinding process, a composite chemical auxiliary agent is added, wherein the auxiliary agent consists of 80 parts by mass of alcohol amine grinding aid, 15 parts by mass of polycarboxylate, 0.5 part by mass of aluminate and 4.5 parts by mass of sodium aluminate, and the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) Will bePre-grinding coarse powder of carbonized converter steel slag and calcined aluminum gangue by CO 2 /Al 2 O 3 Mass ratio ingredients=0.5; at the same time, 1wt.% of carbide slag was added as a calcium-increasing component, and a specific surface area=544 m was further obtained 2 Kg and 30 μm screen residue
=9.6% of solid waste based carbon fixation auxiliary cementing material.
(3) The obtained solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 30 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experimental method for cement mixture of GB/T12957-2005.
Comparative example 12
(1) Pre-grinding fly ash to specific surface area=371 m 2 Kg and 45 μm screen residue = 5.2% to give fly ash pre-ground coarse powder; in the grinding process, a composite chemical auxiliary agent is added, wherein the auxiliary agent consists of 70 parts by mass of an alcohol amine grinding aid, 20 parts by mass of polycarboxylate, 1.5 parts by mass of aluminate and 8.5 parts by mass of sodium aluminate, and the mixing amount of the composite chemical auxiliary agent is 4 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
(2) Pre-grinding red mud and fly ash of carbonization sintering method into coarse powder by CO 2 /Al 2 O 3 Mass ratio ingredients of =1; at the same time, 2wt.% of carbide slag is added as a calcium-increasing component, and superfine grinding is carried out to obtain the specific surface area=526 m 2 Kg and 30 μm screen residue
=9.7% of solid waste based carbon fixation auxiliary cementing material.
(3) The obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing cement clinker by 50 percent to prepare silicate cement, and 28d activity index measurement is carried out by referring to industrial waste residue activity experiment method for cement mixture of GB/T12957-2005.
The supplementary cementitious materials prepared in examples 1 to 27 and comparative examples 1 to 6 were subjected to 28d activity index test, and the corresponding material ratios and activity index test results are shown in Table 1, with reference to "GB/T12957-2005 Industrial waste residue Activity test method for Cement Admixture".
TABLE 1
/>
As can be seen from the experimental results of each example and comparative example in Table 1, the technique of the present invention was adopted to optimize the blending ratio (CO 2 /Al 2 O 3 ) The ultra-high activity solid waste based carbon-fixing auxiliary cementing material with the activity index far higher than that of a single solid carbon-fixing solid waste component or a single high-alumina pozzolanic solid waste component can be prepared by the technological means of externally doping a calcium-increasing component, compounding a composite chemical auxiliary agent, sectionally superfine grinding and the like. By adopting the optimal technical scheme, the cement clinker is replaced by 30 percent, and the 28d activity index of the ultra-high activity solid waste based carbon-fixing auxiliary cementing material can reach S140 grade (examples 2-5); the 28d activity index of the ultra-high activity solid waste base carbon-fixing auxiliary cementing material can reach S120-S130 (examples 9-11) by replacing cement clinker in a proportion of 50%, and the hydration activity of the ultra-high activity solid waste base carbon-fixing auxiliary cementing material is far higher than the highest activity index grade in the current national standard (S105 grade, GB/T18046-2017 is used for granulating blast furnace slag powder in cement, mortar and concrete).
It is also clear from a comparison of the examples in Table 1 with the comparative examples: (1) compounding ratio (CO) of solid waste of carbon fixation and solid waste of high-alumina volcanic ash 2 /Al 2 O 3 ) Has obvious influence on the hydration activity of the ultra-high activity solid waste based carbon-fixing auxiliary cementing material, and the optimal compounding proportion is CO 2 /Al 2 O 3 =1; (2) compared with the traditional alcohol amine grinding aid, the compound chemical auxiliary agent adopted by the invention can further promote the solid waste obtained by compounding by promoting the formation of hydration of hydrated calcium carbonate aluminate, improving the stability of the hydrated calcium carbonate aluminate product and the likeHydration activity of the base carbon-fixing auxiliary cementing material; (3) the calcium increasing component has obvious positive influence on the improvement of the 28d activity index of the ultra-high activity solid waste based carbon fixing auxiliary cementing material; (4) grinding to the specific particle specific surface area and the particle size range defined by the technical proposal are the necessary conditions for realizing the ultra-high activity solid waste based carbon-fixing auxiliary cementing material. Therefore, in the technical scheme of the invention, the material mixing ratio (CO 2 /Al 2 O 3 ) The technical means such as the external doping of calcium-increasing components, the compounding of composite chemical additives, the optimal specific surface area of particles, the particle size range and the like are all necessary technical means for preparing the ultra-high activity solid waste based carbon-fixing auxiliary cementing material.
In addition, in order to verify the activity promoting mechanism of the ultra-high activity solid waste base carbon-fixing mineral admixture, the inventor also performs analysis and characterization on the hydration reaction mineral phase composition and microstructure morphology of the ultra-high activity solid waste base carbon-fixing mineral admixture according to some embodiments. FIG. 2 shows X-ray diffraction patterns of the composite Portland cements obtained in comparative examples 1, 4, 9 and 4 after hydration for 28 days. As can be seen from fig. 2, compared with comparative examples 1 and 4, the hydration reaction of the ultra-high activity solid waste carbon-fixing auxiliary cementing material (example 4) in the cement system forms a large amount of hydrated calcium carbonate (MC), and the active effect of the calcium Carbonate Component (CC) is fully exerted, so that the hydration activity of the ultra-high activity solid waste carbon-fixing auxiliary cementing material is effectively improved. As is evident from a comparison of comparative example 9 with example 4, the addition of the composite chemical auxiliary further promotes the formation of hydrated calcium carbonate (MC) and increases the content of hydrated calcium carbonate (MC). In addition, as can be seen from the comparison of the example 4 and the comparative example 9, the introduction of the calcium increasing component effectively increases the calcium hydroxide content in the long-term cementing material system, which can effectively avoid influencing the continuous exertion of the hydration activity of the ultra-high activity solid waste based carbon-fixing auxiliary cementing material due to the relatively insufficient alkalinity of the cementing material system. The samples of the ultra-high activity solid waste based carbon fixing auxiliary cementing material obtained in the examples 1 and 6 were subjected to back scattering electron image or secondary electron image observation, and the results are shown in fig. 3 to 6. Wherein, FIG. 3 is a back-scattered electron image (3000 times) of the hydration 28d of the ultra-high activity solid waste based carbon-fixing auxiliary gel material obtained in example 1, and FIG. 4 is a back-scattered electron image (20000 times) of the hydration 28d of the ultra-high activity solid waste based carbon-fixing auxiliary gel material obtained in example 1. Fig. 5 is a back-scattered electron image (20000 times) of the hydration 28d of the ultra-high activity solid waste based carbon-fixing auxiliary binder obtained in example 6, and fig. 6 is a secondary electron image (100000 times) and EDS spectrum of the hydration 28d of the ultra-high activity solid waste based carbon-fixing auxiliary binder obtained in example 6. As is apparent from fig. 3 to 6, the reaction of the ultra-high activity solid waste based carbon-fixing auxiliary cementing material forms a large amount of hydrated calcium carbonate products, which is one of the important reasons for the ultra-high activity of the ultra-high activity solid waste based carbon-fixing auxiliary cementing material according to the technical scheme of the invention.
The above examples show that by using the technical scheme of the invention, the optimized proportioning ratio (CO 2 /Al2O 3 ) The hydration activity of the medium-low activity solid waste and the high-alumina pozzolanic solid waste can be effectively improved by the technological means of externally doping calcium-increasing components, compounding composite chemical auxiliary agents, sectionally superfine grinding and the like, and the ultra-high activity solid waste-based solid carbon auxiliary cementing material with the activity index reaching the grade S130-S145 (30% doping amount) is prepared. The technical scheme of the invention can greatly improve the application value of the medium-low activity solid carbon waste and the high-alumina pozzolanic solid waste in cement and concrete materials.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (11)
1. A preparation method of an ultra-high activity solid waste based carbon-fixing auxiliary cementing material is characterized by comprising the following steps: the method comprises the following steps:
(1) Pre-grinding the middle-low activity high-alumina volcanic solid waste to obtain middle-low activity high-alumina volcanic solid waste pre-grinding micro powder, and adding corresponding compound chemical auxiliary agents in the pre-grinding process;
(2) Mixing the carbon-fixing solid waste with the low-medium activity high-alumina volcanic ash solid waste pre-grinding micro powder and the calcium-increasing component, and performing superfine grinding to reach a preset particle size range to obtain the ultra-high activity solid waste-based carbon-fixing auxiliary cementing material;
the predetermined particle diameter range is 30 μm with screen residue less than 1%, and specific surface area more than 700m 2 。
2. The method for preparing the ultra-high activity solid waste based carbon-fixing auxiliary cementing material according to claim 1, which is characterized in that: the obtained ultra-high activity solid waste based carbon-fixing auxiliary cementing material is used for replacing silicate cement clinker in a mass ratio of 30-50% and is applied to the preparation of silicate cement or concrete.
3. The method for preparing the ultra-high activity solid waste based carbon-fixing auxiliary cementing material and the application thereof according to claim 1, wherein in the step (1), the medium-low activity high-alumina pozzolanic solid waste is one or more of fly ash, coal-fired furnace bottom slag, calcined alumina gangue and calcined clay rock gangue; al of middle-low activity high-alumina pozzolanic solid waste 2 O 3 The content is more than or equal to 25 wt%, and the volcanic quality inspection of the medium-low activity high-aluminum volcanic solid waste is qualified.
4. The preparation method and the application of the ultra-high activity solid waste carbon-fixing auxiliary cementing material are characterized in that the composite chemical auxiliary agent added in the pre-grinding process in the step (1) consists of 40-85 parts by mass of alcohol amine grinding aid, 10-45 parts by mass of polycarboxylate, 0.1-3.5 parts by mass of aluminate or titanate and 4-15 parts by mass of sodium aluminate and/or sodium ferrite; the mixing amount of the composite chemical auxiliary agent is 2-8 per mill of the mass of the medium-low activity high-alumina pozzolanic solid waste.
5. The ultra-high activity solid waste based carbon sequestration co-product of claim 1The preparation method and the application of the auxiliary cementing material are characterized in that in the step (1), the specific surface area of the obtained medium-low activity high-alumina volcanic ash solid waste pre-ground micro powder is more than 500m 2 Kg and 45 μm screen residue < 3%.
6. The method for preparing the ultra-high activity solid waste based carbon-fixing auxiliary cementing material and the application thereof according to claim 1, wherein the solid waste carbon-fixing in the step (2) is one or more of carbonized steel slag, carbonized sintering red mud, carbonized magnesium slag and carbonized waste concrete micro powder; the carbon-fixing solid waste is prepared from steel slag, red mud from sintering process, magnesium slag, and waste concrete micropowder by dry or wet method 2 Collecting process carbonization, and absorbing weight method CO by using alkali asbestos of solid waste of solid carbon fixation 2 The measured value is more than or equal to 10 wt%, and the carbon component in the carbon-fixing solid waste exists in the form of calcite type or aragonite type calcium carbonate.
7. The method for preparing the ultra-high activity solid waste based carbon-fixing auxiliary cementing material and the application thereof according to claim 1, wherein the calcium-increasing component in the step (2) is one or more of carbide slag and lime.
8. The method for preparing the ultra-high activity solid waste based carbon-fixing auxiliary cementing material and the application thereof according to claim 1, wherein the mass ratio of the ultra-fine grinding ingredients of the solid waste of carbon-fixing to the solid waste of middle-low activity high-alumina pozzolan in the step (2) is characterized in that the solid waste of carbon-fixing contains CO 2 And Al in the medium-low activity high-alumina volcanic ash solid waste pre-ground micro powder 2 O 3 The mass ratio of (2) is 0.5-1.5: 1.
9. the preparation method and application of the ultra-high activity solid waste based carbon-fixing auxiliary cementing material disclosed in claim 1 are characterized in that the doping amount of the calcium-adding component in the step (2) is 1-5% of the sum of the mass of the carbon-fixing solid waste and the mass of the pre-ground micro powder of the medium-low activity high-alumina pozzolanic solid waste.
10. The method for preparing the ultra-high activity solid waste based carbon-fixing auxiliary cementing material and the application thereof according to claim 1, wherein the ultra-high activity solid waste based carbon-fixing auxiliary cementing material in the step (2) is subjected to ultra-fine grinding until the specific surface area is more than 700m 2 Kg and a screen residue of 30 μm < 1%.
11. The method for preparing the ultra-high activity solid waste based carbon-fixing auxiliary cementing material according to any one of claims 1-10 and application of the ultra-high activity solid waste based carbon-fixing auxiliary cementing material in preparation of Portland cement or concrete instead of Portland cement clinker.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310951277.1A CN117263536A (en) | 2023-07-31 | 2023-07-31 | Preparation method and application of ultrahigh-activity solid waste-based carbon-fixing auxiliary cementing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310951277.1A CN117263536A (en) | 2023-07-31 | 2023-07-31 | Preparation method and application of ultrahigh-activity solid waste-based carbon-fixing auxiliary cementing material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117263536A true CN117263536A (en) | 2023-12-22 |
Family
ID=89213203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310951277.1A Pending CN117263536A (en) | 2023-07-31 | 2023-07-31 | Preparation method and application of ultrahigh-activity solid waste-based carbon-fixing auxiliary cementing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117263536A (en) |
-
2023
- 2023-07-31 CN CN202310951277.1A patent/CN117263536A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yao et al. | Activation of hydration properties of iron ore tailings and their application as supplementary cementitious materials in cement | |
| EP2801559B1 (en) | Method of enhancing the latent hydraulic and/or pozzolanic reactivity of materials | |
| CN110041028A (en) | A kind of regeneration concrete and preparation method thereof using building waste | |
| CN111847921B (en) | Low clinker cement and preparation method and application thereof | |
| He et al. | Effect of lime mud under wet grinding on the compressive strength and hydration of cement mortar | |
| Danner et al. | Calcined marl as a pozzolan for sustainable development of the cement and concrete industry | |
| Shi et al. | Co-utilization of reactivated cement pastes with coal gangue | |
| CN111302677A (en) | Super-sulfate cement and preparation method thereof | |
| Shen et al. | Hydration-hardening properties of low-clinker composite cement incorporating carbonated waste sintering red mud and metakaolin | |
| Liang et al. | Preparation and phase characteristics of autoclaved aerated concrete using iron ore tailings | |
| Liang et al. | Study on preparation of eco-friendly autoclaved aerated concrete from low silicon and high iron ore tailings | |
| Chen et al. | Pre-carbonation of calcium carbide slag for the preparation of eco-friendly mortars | |
| CN117263536A (en) | Preparation method and application of ultrahigh-activity solid waste-based carbon-fixing auxiliary cementing material | |
| JP2019011235A (en) | Hydration accelerator, manufacturing method therefor, and liquid hydration accelerator | |
| Yang et al. | Preparation of micro-iron ore tailings by wet-grinding and its application in sulphoaluminate cement | |
| CN114315195A (en) | Preparation method of single-component early-strength rapid-setting geopolymer | |
| CN116409948A (en) | Low-carbon composite cementing material based on regenerated micro powder, and preparation method and application thereof | |
| CN113880486A (en) | Composite admixture utilizing solid waste of iron and steel plant and preparation method thereof | |
| Khalil et al. | Environmental and economical aspects of partial replacement of ordinary Portland cement with Saudi raw minerals | |
| Feng et al. | Shale ash concrete | |
| JP7062225B2 (en) | Strength-enhancing agent, its manufacturing method, and Portland cement strength-enhancing method | |
| CN104513034A (en) | Binder material useful for forming concrete type material | |
| TWI796036B (en) | Concrete composition and concrete block thereof | |
| Jiao et al. | Influence of Fineness Levels and Dosages of Light-Burned Dolomite on Portland Cement Performance. Materials 2022, 15, 5798 | |
| Kazlauskaitė et al. | Influence of KOH and Granite Cutting Waste on the Formation of Calcium Silicate Hydrates under Hydrothermal Conditions at 200° C |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |