CN112960922A - Desulfurized fly ash based cementing material and preparation and application thereof - Google Patents
Desulfurized fly ash based cementing material and preparation and application thereof Download PDFInfo
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- CN112960922A CN112960922A CN202110166077.6A CN202110166077A CN112960922A CN 112960922 A CN112960922 A CN 112960922A CN 202110166077 A CN202110166077 A CN 202110166077A CN 112960922 A CN112960922 A CN 112960922A
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- 239000010881 fly ash Substances 0.000 title claims abstract description 104
- 239000000463 material Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002956 ash Substances 0.000 claims abstract description 40
- 239000004094 surface-active agent Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 17
- 239000011707 mineral Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000012360 testing method Methods 0.000 claims description 34
- 238000000465 moulding Methods 0.000 claims description 28
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 21
- 239000004568 cement Substances 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000010440 gypsum Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229910052602 gypsum Inorganic materials 0.000 claims description 13
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- 239000004575 stone Substances 0.000 claims description 8
- 239000011083 cement mortar Substances 0.000 claims description 7
- 239000004567 concrete Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003755 preservative agent Substances 0.000 claims description 7
- 230000002335 preservative effect Effects 0.000 claims description 7
- 239000008247 solid mixture Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 2
- 150000002790 naphthalenes Chemical class 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000002440 industrial waste Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 19
- 239000011449 brick Substances 0.000 description 17
- 238000012423 maintenance Methods 0.000 description 13
- 238000006477 desulfuration reaction Methods 0.000 description 11
- 230000023556 desulfurization Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 6
- 239000002910 solid waste Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 3
- 235000010261 calcium sulphite Nutrition 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 230000003020 moisturizing effect Effects 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910001341 Crude steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- 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
- C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a desulfurized fly ash based cementing material and a preparation method and application thereof. The desulfurized fly ash based cementing material is mainly prepared by doping a certain amount of H in industrial waste residues such as desulfurized fly ash, S95-grade mineral powder, boiler ash, fly ash and the like4000The surfactant is prepared at normal temperature and normal pressure. The preparation method solves the problem that unstable sulfite in the desulfurized fly ash component limits the material application of the desulfurized fly ash component, and has the advantages of simple process, wide raw material source, no addition of corrosive reagents such as strong acid, strong alkali and the like, low energy consumption and small secondary pollution. In addition, the desulfurized ash based cementing material has the characteristics of high early strength, large softening coefficient, continuous increase of later strength and the like, can be used as a wall material and a road bed material, and has wide prospect.
Description
Technical Field
The invention relates to a novel cementing material prepared from circulating fluidized bed semi-dry desulfurized fly ash, a preparation method and application thereof, belonging to the technical field of solid waste recycling.
Background
Iron and steel enterprises can release a large amount of SO in the production process2. In 2019, the yield of crude steel in China is 9.96 hundred million tons, and SO is published by the iron and Steel Association of China2Emission 1.95kg "calculation, SO2The discharge amount of the catalyst can reach 1.94 multiplied by 106t, the yield of the desulfurized ash produced by the flue gas desulfurization process by the circulating fluidized bed semidry method reaches 4.85 multiplied by 106t. At present, the desulfurization ash is mainly stockpiled, and the disposal mode not only occupies a large amount of land resources, but also causes serious pollution to the environment.
How to scientifically treat and utilize the desulfurized fly ash in a high-value manner and realize the harmlessness and reclamation of the desulfurized fly ash is a technical problem to be solved urgently in the steel industry of China and is a gradually severe environmental protection requirement.
The desulfurized fly ash mainly contains calcium hydroxide, calcium oxide, calcium fluoride, calcium carbonate, calcium sulfite, calcium sulfate, fly ash and other components, and has complex composition and difficult utilization. Most of foreign desulfurized fly ash is fully utilized due to less annual output. In the United states, the desulfurized fly ash is mainly applied to producing gypsum wallboards, autoclaved bricks, cement concrete, soil improvement and the like; in Europe, desulfurized fly ash is mainly applied to backfill in the building industry, soil remediation, roadbed materials and cement production; due to the shortage of natural gypsum, japan began to make gypsum boards in the past 50 s by using desulfurization by-products in large quantities, or mixing desulfurized fly ash with fly ash, lime, etc. to produce fly ash materials.
Resource utilization research of the desulfurization ash in China starts late, in recent years, researchers mainly concentrate on partially replacing cement to serve as concrete admixture, steam-pressed brick production, floor rotating and other wall materials, the desulfurization ash can be partially absorbed, but the resource products contain calcium sulfite to cause unstable product performance, such as low mechanical strength, heavy metal and chloride ion corrosion, and the energy consumption of the production process is very large. Therefore, it is necessary to develop a desulfurized fly ash-based gelled material which can be prepared at normal temperature and pressure, has high performance and low cost, and solves the problem of the discharge of desulfurized fly ash.
Aiming at the current disposal situation of the desulfurized fly ash and the problems of the main resource utilization technology, from the aspects of solid waste reduction, resource utilization and harmlessness, the invention fully utilizes the desulfurized fly ash generated by high-content semi-dry flue gas desulfurization, and combines the desulfurized fly ash with other solid waste by H4000The master batch surfactant is chemically modified, and the novel efficient low-cost cementing material is prepared based on synergistic effect principles of physical adsorption, chemical consolidation, isomorphous replacement and the like. Achieves the aim of material utilization while realizing the harmlessness of the desulfurized fly ash.
Disclosure of Invention
Aiming at the problems of the current treatment situation and the resource utilization technology of the existing desulfurized fly ash, the invention aims to provide a novel desulfurized fly ash-based cementing material with high efficiency and low cost, and realize the material utilization of the desulfurized fly ash and other industrial solid wastes. The cementing material can oxidize unstable sulfite in the desulfurized fly ash into sulfate without high-temperature catalysis, and lays a foundation for preparing a stable cementing material.
The second purpose of the invention is to provide a preparation method of the desulfurized fly ash based cementing material, which is carried out at normal temperature and normal pressure, has simple process and low cost and is beneficial to large-scale industrial production.
The third purpose of the invention is to provide the application of the desulfurized fly ash based cementing material, the cementing material has excellent mechanical property, can be used for producing wall materials such as non-steamed baking-free bricks, floor bricks, square bricks and the like and roadbed materials, further expands the application field of desulfurized fly ash, can absorb a large amount of desulfurized fly ash, realizes resource utilization, and has environmental benefit, economic benefit and social benefit.
The invention provides a desulfurized fly ash based cementing material which comprises the following components in parts by weight: 10-30 parts of desulfurized ash, 50-70 parts of S95-grade mineral powder, 3-5 parts of boiler ash, 10-20 parts of cement clinker, 5-10 parts of fly ash and H40003-5 parts of a master batch surfactant.
Preferably, said H4000The master batch surfactant comprises the following raw materials in parts by weight: 70-90 parts of desulfurized gypsum, 1-3 parts of naphthalene water reducing agent, 3-5 parts of sodium carbonate, 3-5 parts of sodium silicate, 1-5 parts of polymeric polyol and 1-5 parts of triethanolamine.
The invention also provides a preparation method of the desulfurized fly ash based cementing material, which comprises the following specific steps:
(1) crushing the blocky fly ash;
(2) respectively drying the fly ash, the desulfurized ash, the boiler ash and the S95-grade mineral powder for later use;
(3)H4000preparation of master batch surfactant: respectively weighing and mixing desulfurized gypsum, sodium carbonate, sodium silicate and naphthalene water reducing agent in proportion to prepare a solid mixture, respectively weighing and spraying liquid triethanolamine and polymeric polyol in proportion into the solid mixture, and finally uniformly mixing to prepare the H4000 master batch surfactant;
(4) drying the fly ash, the desulfurized ash, the boiler ash, S95-grade mineral powder, cement clinker and H4000And (3) respectively metering and mixing the master batch surfactant according to the mixing proportion, mechanically ball-milling and sieving to obtain the desulfurized fly ash gel material.
Preferably, the blocky fly ash in the desulfurized fly ash-based cementing material is crushed to have the particle size of less than 5 mm.
Preferably, the fly ash, the desulfurized ash, the boiler ash and the S95-grade mineral powder in the desulfurized ash-based cementing material are respectively dried until the moisture content is not more than 1%.
Preferably, H in the desulfurized fly ash-based cementing material4000The preparation of the master batch surfactant adopts a planetary ball mill to carry out blending mechanical force activation for 30-35min at the rotating speed of 250-350r/min, and the screen allowance is not more than 10% after the master batch surfactant passes through a 45 mu m square hole sieve.
The invention also provides application of the desulfurized fly ash based cementing material in a cementing material for buildings.
Preferably, the desulfurized fly ash cementing material is applied to wall materials or road foundation materials.
Preferably, the concrete preparation steps of the wall material comprise:
(1) the desulfurized fly ash cementing material, the desulfurized fly ash, the pebbles and the stone powder are mixed according to the proportion of (8-15): (20-25): (28-33) and (30-35), sequentially putting the mixture into a cement mortar stirrer, dry-stirring for 1-2 min, adding 10-12 parts of water, and wet-stirring for 3-5 min to obtain a mixture;
(2) adding the mixture into a mold, demolding after molding on a press, keeping the speed at 2-3 kN/s by using the molding pressure of 130-160KN, avoiding the press from running too fast in the molding process, and simultaneously, after the molding is finished, not immediately opening an oil return valve of the press, standing for at least 1min, and then opening the oil return valve to return oil to the press;
(3) and (3) packaging the pressed test block with a preservative film, putting the test block into a curing box, curing at the temperature of 20 +/-2 ℃ and the relative humidity of more than 90 percent under the standard curing condition, and detecting the performance when the test block reaches the curing age without moving.
Preferably, the concrete preparation steps of the road base material comprise:
(1) and (3) mixing the desulfurized fly ash cementing material, desulfurized fly ash, pebbles and stone powder according to the ratio of (3-5): (30-45): (30-45): (23-28), sequentially putting the mixture into a cement mortar stirrer in sequence, carrying out dry stirring for 1-2 min, adding 5-10 parts of water, and carrying out wet stirring for 3-5 min to obtain a mixture;
(2) adding the mixture into a mold, demolding after molding on a press, keeping the speed at 2-3 kN/s by using the molding pressure of 130-160KN, avoiding the press from running too fast in the molding process, and simultaneously, after the molding is finished, not immediately opening an oil return valve of the press, standing for at least 1min, and then opening the oil return valve to return oil to the press;
(3) and (3) packaging the pressed test block with a preservative film, putting the test block into a curing box, curing at the temperature of 20 +/-2 ℃ and the relative humidity of more than 90 percent under the standard curing condition, and detecting the performance when the test block reaches the curing age without moving.
The performance of the material provided by the invention meets the standard requirement of slag portland cement 42.5 in GB 175-2007 Standard for general portland cement.
The invention fully utilizes the bulk industrial waste residues such as semi-dry desulfurized fly ash, desulfurized gypsum, slag, fly ash and the like of the circulating fluidized bed to prepare the desulfurized fly ash-based cementing material, and provides a new idea for the safe disposal and resource utilization of the desulfurized fly ash. And certain environmental benefit, economic benefit and social benefit can be realized. The production process of the desulfurized ash based cementing material is low-carbon and environment-friendly, the traditional cement is upgraded from 'two-grinding and one-burning' to 'one-grinding and one-drying', the carbon emission is radically reduced, the energy consumption and the secondary pollution to the environment are greatly reduced, meanwhile, the raw materials are wide in source and low in price, the performance of the prepared material can reach the standard of 42.5 of common portland cement, and the desulfurized ash based cementing material has a wide application prospect.
In the invention, mineral components in S95-grade mineral powder and fly ash are mainly silicon dioxide and aluminum oxide, belonging to artificial pozzolanic materials; the industrial solid wastes such as desulfurized fly ash, mineral powder and the like have potential activity and are activated by mechanical force and H4000The chemical modification of the master batch surfactant further promotes the hydration reaction of the system to form a zeolite-like hydraulic product, and the product has good mechanical strength and stability of heavy metals and chloride ions.
In view of the fact that the content of calcium in the waste brick powder is low, a certain amount of slag is added into the cementing material system, and the dicalcium silicate in the slag can adjust hydration products and hydration speed of the system and improve the setting and hardening performance of the cementing material.
For further exciting desulfurized fly ash and other industriesThe activity of solid wastes promotes the material system to quickly and efficiently grind, develops H mainly based on desulfurized gypsum4000Master batch surfactant, the4000The master batch surfactant can play the following three roles; firstly, calcium sulfite in desulfurized fly ash is efficiently stabilized; secondly, the components such as desulfurized fly ash and fly ash are ensured to be activated by full mechanical force, the ball milling efficiency is improved, and the energy consumption is reduced; ③ H4000The alkaline component in the master batch surfactant can effectively excite the activity of the volcanic ash material; and fourthly, the early strength of the cementing material is enhanced.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that: the invention mainly aims at the problems of influence of sulfite in the desulfurized fly ash on the strength of a cementing body and corrosion of heavy metal and chloride ions caused by the sulfite, improves the contact interface of the desulfurized fly ash and other reactants by doping the surfactant, and can convert sulfite in a system into stable sulfate and simultaneously convert H into H at normal temperature4000The master batch surfactant can realize the quick and efficient excitation of the volcanic ash activity of the silicon-aluminum based materials such as desulfurized ash, fly ash and the like, promote the silicon-oxygen bonds and the aluminum-oxygen bonds of different material particles to be broken, form a new space network structure consisting of silicon-oxygen tetrahedrons and aluminum-oxygen tetrahedrons, and realize the long-acting stabilization of heavy metals and chloride ions through the actions of isomorphous displacement, physical adsorption, chemical bonding and the like.
The gel material is prepared by fully utilizing other industrial waste residues such as circulating fluidized bed semidry desulfurization ash, fly ash, desulfurization gypsum, mineral powder and the like, doping certain master batch and surfactant and performing a one-grinding one-baking process, has the advantages of cheap and easily-obtained raw materials, low energy consumption, small environmental pollution, easy production process and stable and reliable product quality compared with the traditional two-grinding one-baking process of cement, further widens the material utilization channel of the desulfurization ash, and can create huge economic benefit, environmental benefit and social benefit for enterprises and society.
Drawings
FIG. 1 is a photograph showing the fracture resistance test of the desulfurized fly ash based cementitious material of the present invention;
FIG. 2 is a photograph showing the compression resistance test of the desulfurized fly ash based cementitious material of the present invention;
FIG. 3 is a photograph showing a test of the setting properties of the desulfurized fly ash based gelling material of the present invention;
FIG. 4 shows a standard desulfurized fly ash-based brick prepared by the present invention.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present invention, and the present invention shall be covered thereby. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
The preparation process of the novel desulfurized fly ash-based cementing material comprises the following steps: firstly, crushing the blocky fly ash to the particle size of less than 5 mm; then respectively drying the fly ash, the desulfurized ash, the boiler ash and the S95-grade mineral powder until the water content is not more than 1%; mixing the dried fly ash, desulfurized ash, boiler ash, S95-grade mineral powder, cement clinker and H4000The master batch surfactant is respectively metered according to the mixing proportion, and is activated for 30-35min by adopting a planetary ball mill under the rotating speed of 250-350r/min and the screen allowance is not more than 10 percent after passing through a square hole screen with the size of 45 mu m.
Wherein H4000The preparation method of the master batch surfactant comprises the following steps: mixing desulfurized gypsum, sodium carbonate, sodium silicate and naphthalene series water reducing agent according to a certain proportion respectively to prepare a solid mixture, spraying liquid triethanolamine and polymeric polyol into the solid mixture according to a certain proportion respectively, and finally mixing uniformly by using a mixer to prepare the composite excitant.
The first embodiment is as follows:
the cementing materials are mixed according to the mass part ratio shown in table 1, wherein H4000The proportion of the master batch surfactant is 82 parts of desulfurized gypsum, 2 parts of naphthalene water reducer, 5 parts of sodium carbonate, 5 parts of sodium silicate, 3 parts of polymeric polyol and 3 parts of triethanolamine.
The materials are measured and ground to prepare the gelled material, a gelled sand strength experiment is carried out according to a cement gelled sand strength test method (GB177-5), the initial setting time and the final setting time of each mixture ratio are respectively tested, and the compressive strength and the flexural strength of the gelled material are tested at 3d, 28d and 120d after standard maintenance.
TABLE 1 blend ratio of desulfurized fly ash based cementitious materials
TABLE 2 desulfurized fly ash based cementitious Material Properties
Example two:
(1) the cementing material is prepared from the following components in parts by weight: 15 parts of desulfurized ash, 56 parts of S95-grade mineral powder, 7 parts of fly ash, 4 parts of boiler ash, 15 parts of 42.5 cement clinker, and H4000And 3 parts of a master batch surfactant. Wherein H4000The proportion of the master batch surfactant is 82 parts of desulfurized gypsum, 2 parts of naphthalene water reducer, 5 parts of sodium carbonate, 5 parts of sodium silicate, 3 parts of polymeric polyol and 3 parts of triethanolamine.
(2) Mixing the cementing material, the desulfurized fly ash, the cobblestone and the stone powder according to a certain proportion, sequentially putting the materials into a cement mortar stirrer, dry-stirring for 1-2 min, adding external water (calculated on a dry basis), and wet-stirring for 3-5 min to obtain a mixture.
(3) Adding the mixture into a mold with the diameter of 10 multiplied by 5cm, demolding after molding on a press, wherein the molding pressure is 160KN, attention needs to be paid to avoid the press from going too fast during molding in the molding process, the speed is kept at 2-3 kN/s, meanwhile, after the molding is finished, an oil return valve of the press is not required to be opened immediately, the press should be kept still for about 1min, and then the oil return valve is opened to return oil to the press, so that the aim of the process is that the pressed brick has restoring force at the initial molding stage, if the oil return valve is opened immediately, the test block can rebound to damage the structure of the test block, and the strength is influenced.
(4) And (3) adopting a normal-temperature natural moisturizing maintenance process, covering the pressed test block with a preservative film, putting the test block into a maintenance box, maintaining the test block under standard maintenance conditions (the temperature is 20 +/-2 ℃, and the relative humidity is more than 90 percent) without moving, and detecting the performance when the test block reaches the maintenance age.
(5) Under a proper proportion, the performance of the prepared standard desulfurization ash brick meets the requirements of ' concrete solid brick ' GB/T21144-2007 ', namely the 28d compressive strength is not lower than 15MPa, and the softening coefficient is not lower than 0.8.
TABLE 3 blend ratio of desulfurized fly ash based standard brick
TABLE 4 desulfurized fly ash based Standard brick Properties
Remarking; wherein (27+1) d represents unconfined compressive strength of the test block after being maintained for 27 days under standard conditions and soaked in water for 1 day,
example three:
(1) the cementing material is prepared from the following components in parts by weight: 15 parts of desulfurized ash, 56 parts of S95-grade mineral powder, 7 parts of fly ash, 4 parts of boiler ash, 15 parts of 42.5 cement clinker, and H4000And 3 parts of a master batch surfactant. Wherein H4000The proportion of the master batch surfactant is 82 parts of desulfurized gypsum, 2 parts of naphthalene water reducer, 5 parts of sodium carbonate, 5 parts of sodium silicate, 3 parts of polymeric polyol and 3 parts of triethanolamine.
(2) Mixing the cementing material, the desulfurized fly ash, the cobblestone and the stone powder according to a certain proportion, sequentially putting the materials into a cement mortar stirrer, dry-stirring for 1-2 min, adding external water (calculated on a dry basis), and wet-stirring for 3-5 min to obtain a mixture.
(3) Adding the mixture into a mold with the diameter of 10 multiplied by 5cm, demoulding after forming on a press, wherein the forming pressure is 130 plus 160KN, and in the forming process, attention needs to be paid to avoid the press from going too fast during forming, the speed is kept at 2-3 kN/s, meanwhile, after the forming is finished, an oil return valve of the press is not opened immediately, the press is kept still for about 1min, and then the oil return valve is opened to return oil of the press, so that the aim of returning oil of the press is that the pressed brick has restoring force in the early forming stage, and if the oil return valve is opened immediately, a test block can rebound to damage the structure of the test block, and the strength is influenced.
(4) A normal-temperature natural moisturizing maintenance process is adopted, the pressed test block is wrapped by a preservative film and is placed in a maintenance box to be maintained under standard maintenance conditions (the temperature is 20 +/-2 ℃, and the relative humidity is more than 90 percent) without moving, and performance detection is carried out when the test block reaches the maintenance age;
(5) under a proper proportion, the performance of the prepared roadbed material meets the requirement of performance indexes of a cement stabilized soil base layer in urban road engineering construction and quality acceptance criteria (CJJ1-2008), namely the 7d water-soaked unconfined compressive strength is not less than 3 MPa.
TABLE 5 blend ratio of desulfurized fly ash based roadbed materials
| Serial number | Cementitious material | Stone | Stone powder | Desulfurized fly ash | Adding water to the outside |
| 1 | 3 | 36 | 36 | 25 | 8 |
| 2 | 3 | 42 | 30 | 25 | 8 |
| 3 | 3 | 30 | 42 | 25 | 8 |
| 4 | 5 | 35 | 35 | 25 | 8 |
| 5 | 5 | 40 | 30 | 25 | 8 |
| 6 | 5 | 30 | 40 | 25 | 8 |
TABLE 6 desulfurized fly ash based roadbed material Properties
Remarking; wherein (6+1) d represents the unconfined compressive strength of the test block after being cured for 6 days under standard conditions and soaked in water for 1 day.
Comparative example 4
(1) 42.5 cement is used as a cementing material to replace a desulfurized fly ash cementing material, and the desulfurized fly ash is solidified to prepare the standard brick.
(2) Mixing the cementing material (same as the second embodiment), the desulfurized fly ash, the stones and the stone powder according to a certain proportion, sequentially putting the mixture into a cement mortar stirrer, dry-stirring the mixture for 1 to 2min, adding external water (calculated on a dry basis), and wet-stirring the mixture for 3 to 5min to obtain a mixture.
(3) Adding the mixture into a mold with the diameter of 10 multiplied by 5cm, demolding after molding on a press, wherein the molding pressure is 160KN, attention needs to be paid to avoid the press from going too fast during molding in the molding process, the speed is kept at 2-3 kN/s, meanwhile, after the molding is finished, an oil return valve of the press is not required to be opened immediately, the press should be kept still for about 1min, and then the oil return valve is opened to return oil to the press, so that the aim of the process is that the pressed brick has restoring force at the initial molding stage, if the oil return valve is opened immediately, the test block can rebound to damage the structure of the test block, and the strength is influenced.
(4) And (3) adopting a normal-temperature natural moisturizing maintenance process, covering the pressed test block with a preservative film, putting the test block into a maintenance box, maintaining the test block under standard maintenance conditions (the temperature is 20 +/-2 ℃, and the relative humidity is more than 90 percent) without moving, and detecting the performance when the test block reaches the maintenance age.
(5) Under a proper proportion, the performance of the prepared standard desulfurization ash brick meets the requirements of ' concrete solid brick ' GB/T21144-2007 ', namely the 28d compressive strength is not lower than 15MPa, and the softening coefficient is not lower than 0.8.
TABLE 7 Cement/desulfurized fly ash cementitious mixture ratios
| Serial number | 42.5 Cement | Cementitious material | Stone | Stone powder | Desulfurized fly ash | Adding water to the outside |
| 1 | 11 | 30 | 34 | 25 | 11 | |
| 2 | 11 | 30 | 34 | 25 | 11 | |
| 3 | 11 | 64 | 0 | 25 | 11 | |
| 4 | 11 | 64 | 0 | 26 | 11 | |
| 5 | 11 | 0 | 64 | 26 | 11 | |
| 6 | 11 | 0 | 64 | 26 | 11 |
TABLE 8 Cement/desulfurized fly ash cementitious Material Properties
Remarking; wherein (27+1) d represents the unconfined compressive strength of the test block after being cured for 27 days under standard conditions and soaked in water for 1 day.
Claims (7)
1. A desulfurized fly ash cementing material is characterized in that: comprises the following components in parts by weight: 10-30 parts of desulfurized ash, 50-70 parts of S95-grade mineral powder, 3-5 parts of boiler ash, 10-20 parts of cement clinker, 5-10 parts of fly ash and H40003-5 parts of a master batch surfactant;
said H4000The master batch surfactant comprises the following raw materials in parts by weight: 70-90 parts of desulfurized gypsum; 1-3 parts of a naphthalene water reducer; 3-5 parts of sodium carbonate; 3-5 parts of sodium silicate; 1-5 parts of polymeric polyol; and 1-5 parts of triethanolamine.
2. The method for preparing the desulfurized fly ash gelling material of claim 1, comprising the steps of:
(1) crushing the blocky fly ash;
(2) respectively drying the fly ash, the desulfurized ash, the boiler ash and the S95-grade mineral powder for later use;
(3)H4000preparation of master batch surfactant: the desulfurized gypsum, sodium carbonate, sodium silicate and naphthalene series water reducing agent are respectively proportioned and mixed to prepare a solid mixture, liquid triethanolamine and polymeric polyol are respectively proportioned and sprayed into the solid mixture, and finally the solid mixture is uniformly mixed to prepare H4000A masterbatch surfactant;
(4) mixing the dried fly ash, desulfurized ash, boiler ash, S95-grade mineral powder, cement clinker and H4000And (3) respectively metering and mixing the master batch surfactant according to the mixing proportion, mechanically ball-milling and sieving to obtain the desulfurized fly ash gel material.
3. The production method according to claim 2,
crushing the blocky fly ash to a particle size of less than 5 mm;
respectively drying the fly ash, the desulfurized ash, the boiler ash and S95-grade mineral powder until the water content is not more than 1%;
and (3) activating by adopting a planetary ball mill at the rotating speed of 250-350r/min for 30-35min through blending mechanical force, and sieving the mixture by a square-hole sieve with the particle size of 45 mu m to obtain the residue of not more than 10%.
4. Use of the desulfurized fly ash cement according to claim 1 in construction cements.
5. The use according to claim 4, wherein the desulfurized fly ash is used for preparing wall materials or roadbed materials.
6. The application of claim 5, wherein the wall material is prepared by the following specific steps:
(1) the desulfurized fly ash cementing material, the desulfurized fly ash, the pebbles and the stone powder are mixed according to the proportion of (8-15): (20-25): (28-33) mixing the components in parts by mass (30-35), sequentially putting the components into a cement mortar stirrer, dry-stirring for 1-2 min, adding 10-12 parts of water, and wet-stirring for 3-5 min to obtain a mixture;
(2) adding the mixture into a mold, demolding after molding on a press, keeping the molding pressure of 130-160KN, avoiding the press from going too fast in the molding process, keeping the speed at 2-3 kN/s, simultaneously, not immediately opening an oil return valve of the press after the molding is finished, standing for at least 1min, then opening the oil return valve to return oil to the press,
(3) and (3) packaging the pressed test block with a preservative film, putting the test block into a curing box, curing at the temperature of 20 +/-2 ℃ and the relative humidity of more than 90 percent under the standard curing condition, and detecting the performance when the test block reaches the curing age without moving.
7. The use according to claim 5, characterized in that the concrete steps of preparation of the road-base material comprise:
(1) and (3) mixing the desulfurized fly ash cementing material, desulfurized fly ash, pebbles and stone powder according to the ratio of (3-5): (30-45): (30-45): (23-28) mixing in parts by mass, sequentially putting the materials into a cement mortar stirrer, dry-stirring for 1-2 min, adding 5-10 parts of water, and wet-stirring for 3-5 min to obtain a mixture;
(2) adding the mixture into a mold, demolding after molding on a press, keeping the molding pressure of 130-160KN, avoiding the press from going too fast in the molding process, keeping the speed at 2-3 kN/s, simultaneously, not immediately opening an oil return valve of the press after the molding is finished, standing for at least 1min, then opening the oil return valve to return oil to the press,
(3) and (3) packaging the pressed test block with a preservative film, putting the test block into a curing box, curing at the temperature of 20 +/-2 ℃ and the relative humidity of more than 90 percent under the standard curing condition, and detecting the performance when the test block reaches the curing age without moving.
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| CN114455862A (en) * | 2021-12-29 | 2022-05-10 | 武汉大学(肇庆)资源与环境技术研究院 | Desulfurization ash-based cementing material and preparation method and application thereof |
| CN116986829A (en) * | 2023-06-13 | 2023-11-03 | 中国地质大学（武汉） | Semi-dry desulfurization ash-fly ash-slag composite cementing material and preparation method thereof |
| CN117865626A (en) * | 2024-01-23 | 2024-04-12 | 唐山学院 | Iron alloy slag-based filling material for iron ore and preparation method thereof |
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