CN116730638B - Alkali-resistant iron-rich sulphoaluminate cement composite cementing material and preparation process thereof - Google Patents
Alkali-resistant iron-rich sulphoaluminate cement composite cementing material and preparation process thereof Download PDFInfo
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- CN116730638B CN116730638B CN202310710205.8A CN202310710205A CN116730638B CN 116730638 B CN116730638 B CN 116730638B CN 202310710205 A CN202310710205 A CN 202310710205A CN 116730638 B CN116730638 B CN 116730638B
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- iron
- alkali
- sulphoaluminate cement
- red mud
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 239000004568 cement Substances 0.000 title claims abstract description 124
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 101
- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000003513 alkali Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000002156 mixing Methods 0.000 claims abstract description 55
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000012750 alkali resistant agent Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000007790 solid phase Substances 0.000 claims description 43
- 239000010451 perlite Substances 0.000 claims description 31
- 235000019362 perlite Nutrition 0.000 claims description 31
- 239000002893 slag Substances 0.000 claims description 29
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 22
- 239000012071 phase Substances 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 241001122767 Theaceae Species 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 15
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 15
- 235000013824 polyphenols Nutrition 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000010440 gypsum Substances 0.000 claims description 10
- 229910052602 gypsum Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000010881 fly ash Substances 0.000 claims description 5
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 4
- 235000019738 Limestone Nutrition 0.000 claims description 4
- 229910001570 bauxite Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000006028 limestone Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 4
- 239000000176 sodium gluconate Substances 0.000 claims description 4
- 235000012207 sodium gluconate Nutrition 0.000 claims description 4
- 229940005574 sodium gluconate Drugs 0.000 claims description 4
- 239000001433 sodium tartrate Substances 0.000 claims description 4
- 229960002167 sodium tartrate Drugs 0.000 claims description 4
- 235000011004 sodium tartrates Nutrition 0.000 claims description 4
- 239000002956 ash Substances 0.000 claims description 3
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229960004599 sodium borate Drugs 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 27
- 238000006253 efflorescence Methods 0.000 abstract description 11
- 206010037844 rash Diseases 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 9
- 239000000047 product Substances 0.000 description 46
- 238000012360 testing method Methods 0.000 description 29
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 26
- 239000011734 sodium Substances 0.000 description 25
- 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 description 24
- 229910001414 potassium ion Inorganic materials 0.000 description 20
- 229910001415 sodium ion Inorganic materials 0.000 description 19
- 229910000019 calcium carbonate Inorganic materials 0.000 description 13
- 238000001914 filtration Methods 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 239000004567 concrete Substances 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- 238000002386 leaching Methods 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 238000006703 hydration reaction Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004131 Bayer process Methods 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 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
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 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
- C04B7/32—Aluminous cements
- C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
-
- 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
-
- 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
- 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
-
- 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
Abstract
The invention relates to the technical field of sulphoaluminate cement, in particular to an alkali-resistant iron-rich sulphoaluminate cement composite cementing material and a preparation process thereof. The composite cementing material comprises the following components: 120-145 parts of iron-rich sulphoaluminate cement clinker, 30-42 parts of modified alkali resistance agent, 48-61 parts of active mixing water and 0.22-0.3 part of retarder. Wherein: the iron-rich sulphoaluminate cement clinker is prepared by taking modified red mud as one of the raw materials. The process comprises the following steps: and uniformly mixing the iron-rich sulphoaluminate cement clinker and the modified alkali resistant agent, and then adding the active mixing water and the retarder and uniformly stirring to obtain the composite material. According to the invention, the red mud is pretreated and the alkali resistance agent is added, so that the alkali efflorescence resistance of the iron-rich sulphoaluminate cement prepared by taking the red mud as a raw material is effectively improved.
Description
Technical Field
The invention relates to the technical field of sulphoaluminate cement, in particular to an alkali-resistant iron-rich sulphoaluminate cement composite cementing material and a preparation process thereof.
Background
The sulphoaluminate cement is a cement cementing material prepared from clinker which is obtained by calcining raw materials formed by limestone, bauxite, gypsum and the like and takes anhydrous calcium sulphoaluminate and dicalcium silicate as main mineral components. Sulphoaluminate cement was developed by the institute of construction materials in the twentieth 70 th century, and it and silicate cement, aluminate cement, are the three largest types of cement currently used. The sulphoaluminate cement has the characteristics of quick hardening, early strength, high impermeability, high freezing resistance, corrosion resistance and the like, so that the sulphoaluminate cement is more suitable for the construction of rush repair and rush construction engineering, seawater corrosion resistance engineering and the like. The iron-rich sulphoaluminate cement is a derivative product of the sulphoaluminate cement, and compared with the common sulphoaluminate cement, the mineral component of the iron-rich sulphoaluminate cement clinker contains calcium ferroaluminate, and correspondingly, the iron content of the iron-rich sulphoaluminate cement raw material is higher, so that the calcination temperature is reduced during calcination, and the energy consumption of cement production is reduced. In addition, the substitution of a portion of the alumina by an iron source is also beneficial in reducing the reliance on non-renewable sources of such aluminum sources.
At present, a great deal of researches on preparing iron-rich sulphoaluminate cement clinker by various industrial solid wastes (such as red mud, steel slag, aluminum-containing fly ash, carbide slag, desulfurized gypsum and the like) have been carried out so as to realize the recycling utilization of large amounts of industrial solid wastes and reduce the dependence on non-renewable raw materials. Wherein, the red mud is a potential raw material for preparing the iron-rich sulphoaluminate cement clinker due to the fact that the red mud contains silicon dioxide, aluminum oxide, calcium oxide, ferric oxide and the like. However, the inventor discovers that the red mud is solid waste with higher content of alkali metal elements such as sodium and potassium, and the sodium and potassium elements form concrete with the iron-rich sulphoaluminate cement clinker and other components, and the sodium and potassium ions have high solubility and weaker combination with a concrete matrix, so that the concrete is difficult to solidify. In addition, a large number of pores are usually formed in the concrete, so that sodium ions and potassium ions are easy to migrate to the surface of the concrete by taking water as a carrier to cause the phenomenon of whiskering, the appearance of the concrete is not only influenced, but also the problems of powder falling, falling off and the like of a paint layer on the surface of the concrete are easy to cause.
Disclosure of Invention
Aiming at the problems, the invention provides the alkali-resistant iron-rich sulfoaluminate cement composite cementing material and the preparation process thereof. Specifically, the technical scheme of the invention is as follows.
Firstly, the invention discloses an alkali-resistant iron-rich sulphoaluminate cement composite cementing material, which comprises the following components in parts by weight: 120-145 parts of iron-rich sulphoaluminate cement clinker, 30-42 parts of modified alkali resistance agent, 48-61 parts of active mixing water and 0.22-0.3 part of retarder. Wherein: the iron-rich sulphoaluminate cement clinker is prepared by taking modified red mud as one of the raw materials.
The preparation process of the modified red mud, the modified alkali resistant agent and the active mixing water comprises the following steps:
(1) Uniformly mixing red mud and clear water, standing, carrying out solid-liquid separation, respectively collecting the obtained red mud slurry and alkaline water phase, drying the red mud slurry, and grinding to obtain the modified red mud.
(2) And uniformly mixing the alkaline aqueous phase with perlite powder, performing heating and heat preservation reaction, performing solid-liquid separation after the reaction is completed, respectively collecting the obtained solid phase product and liquid phase, washing the solid phase product to remove residual alkaline aqueous phase, and drying to obtain the powdery modified alkali resistant agent.
(3) And adding carbide slag into the liquid phase, stirring until the carbide slag is not dissolved, cooling to room temperature, and separating undissolved carbide slag to obtain saturated lime water solution. Then adding tea polyphenol into the saturated lime water solution and uniformly mixing to obtain the modified saturated lime water solution.
(4) And introducing carbon dioxide into the modified saturated lime water solution until solid-phase products are not generated any more, separating the solid-phase products, washing the solid-phase products, and dispersing the washed solid-phase products in water to obtain the active mixing water.
Further, in the step (1), the ratio of the red mud to the clear water is 1g: 30-50 ml, so as to utilize clear water to elute the red mud and reduce the alkali content in the red mud. Optionally, the red mud comprises any one of bayer process red mud, sintering process red mud, combined process red mud and the like.
In the step (1), the red mud slurry is dried at 80-130 ℃ until the water content is not higher than 3%.
Further, in the step (2), the proportion of the alkaline aqueous phase to the perlite powder is 1g: 15-30 ml. Optionally, the particle size of the perlite powder is 200-300 meshes. In the step, the alkaline water is utilized to carry out surface modification on the perlite powder, so that the surface activity of the perlite powder is improved, and the reaction between the alkaline water and the perlite powder is utilized to modify micropores in the perlite.
Further, in the step (2), the heating temperature is 50-70 ℃ and the reaction time is 40-60 min. And after the completion, separating out the solid phase product, cleaning the solid phase product by using clear water until the pH value of the cleaning solution is=7.0-7.2, and drying the obtained solid phase product at 70-90 ℃ for 1-1.5 hours after the completion, thus obtaining the modified alkali resistant agent.
Further, in the step (3), the mass fraction of tea polyphenol in the modified saturated lime water solution is 0.2-0.5%. The benzene ring of the tea polyphenol contains a large number of hydroxyl groups, and the tea polyphenol easily loses electrons and shows good ion complexing capacity, so that the active mixing water containing active calcium carbonate can be prepared in subsequent reactions. In addition, the undissolved carbide slag separated in the step can be reused and can also be used as a calcareous raw material for preparing the iron-enriched sulphoaluminate cement clinker.
Further, in the step (4), the carbon dioxide is introduced at a rate of 2-4.5L/min, and in the process, the tea polyphenol is complexed on the surface of the formed metastable phase calcium carbonate to prevent the calcium carbonate from being further converted into stable phase calcium carbonate, so that the high-activity calcium carbonate is obtained, and the mechanical property and alkali resistance of the concrete are improved.
Further, in the step (4), the content of the solid-phase product in the active mixing water is 5-8 g/L. The invention disperses the solid-phase product/active calcium carbonate in the water phase, which is not only helpful for dispersing the solid-phase product/active calcium carbonate in the composite cementing material, but also can be used as mixing water of the composite cementing material for hydration reaction.
Further, the retarder includes, but is not limited to, any of sodium tartrate, sodium citrate, sodium gluconate, sodium borate, and the like. The retarder is utilized to enable perlite in the modified alkali resistant agent to fully absorb sodium and potassium ions in the composite cementing material, so that the alkali resistant effect is improved.
Further, the preparation of the iron-rich sulphoaluminate cement clinker comprises the following steps:
(i) The preparation method comprises the following steps of: 51-54% of calcareous material, 28-35% of aluminum material, 8-12% of gypsum material and 6-10% of modified red mud.
(ii) The raw materials are mixed to form raw materials, the raw materials are heated to 850-950 ℃ to be preheated for 10-20 min, and then the raw materials are transferred to 1230-1300 ℃ to be calcined for 40-60 min. Quenching to room temperature after completion, crushing and grinding the obtained product to obtain the iron-enriched sulphoaluminate cement clinker.
Further, the calcareous material includes, but is not limited to, at least one of limestone, carbide slag, and the like.
Further, the aluminum material includes, but is not limited to, at least one of aluminum ash, bauxite, aluminum tailings, fly ash, and the like.
Further, the gypsum-based material includes, but is not limited to, at least one of desulfurized gypsum, phosphogypsum, fluorgypsum, and the like.
Secondly, the invention discloses a preparation process of the alkali-resistant iron-rich sulphoaluminate cement composite cementing material, which comprises the following steps: and uniformly mixing the iron-rich sulphoaluminate cement clinker and the modified alkali resistant agent, and then adding the active mixing water and the retarder and uniformly stirring to obtain the composite material.
Compared with the prior art, the invention has at least the following beneficial technical effects: when the red mud is directly used as a raw material for preparing the iron-rich sulphoaluminate cement clinker, sodium carbonate, potassium carbonate and the like formed by high-content alkali metal elements such as sodium and potassium can cause serious alkali efflorescence in the later period. Therefore, the invention firstly reduces alkali in clear water for the red mud, so that sodium and potassium in the red mud are quickly dissolved out, and the content of sodium and potassium elements in the red mud is reduced. The method is simple and convenient to operate, but the obtained modified red mud still contains partial sodium and potassium elements, and the partial sodium and potassium elements finally enter the iron-rich sulphoaluminate cement clinker, so that the phenomenon of later-stage alkali efflorescence of a concrete body manufactured by the cement clinker is easily caused. For this purpose, the invention further prepares the modified alkali resistant agent by means of the alkaline liquid phase obtained by washing the red mud and perlite. In the process, on one hand, the characteristic that perlite contains alumina is utilized, alumina is dissolved under the action of alkaline liquid phase to further modify porous perlite, sodium and potassium ions introduced by red mud and the like in the clinker are quickly absorbed by the rich pores of the perlite after the perlite is mixed with the iron-rich sulphoaluminate cement clinker, so that the sodium and potassium ion content in a cement matrix is reduced, and meanwhile, the sodium and potassium ions are sealed in the pores of the perlite by gel generated by hydration of the cement matrix, so that the dissolving difficulty of the sodium and potassium ions is reduced, the solidifying capacity of the sodium and potassium ions is improved, and the whiskering phenomenon is inhibited. On the other hand, because the main component of the perlite is silicon dioxide and contains partial aluminum oxide, the reactivity of the perlite at normal temperature is very low, after the perlite is modified by the characteristics of the alkaline liquid phase, the silicon oxygen bonds and the aluminum oxygen bonds on the surface of the perlite are broken, so that a large number of active bonds are formed on the surface of the perlite, and when the iron-rich sulphoaluminate cement clinker enters a hydration stage, the generated hydration product calcium hydroxide reacts with the active bonds on the surface of the perlite to form gel phases such as calcium silicate hydrate, calcium aluminate hydrate (C- (A) -S-H) and the like, and the gel phases not only can further improve the tightness of the pores of the perlite and increase the dissolution difficulty of sodium and potassium ions, but also can help to lighten the phenomenon of whiskering by consuming the hydration product calcium hydroxide. Meanwhile, the binding between the perlite particles and the cement matrix is tighter by the gel phases, so that the porosity in the cement matrix is reduced, channels for migration of sodium and potassium ions are reduced, and the whiskering phenomenon is inhibited; and the more compact combination between the perlite particles and the cement matrix is helpful for improving the strength of the cement matrix. In addition, the sealing is beneficial to overcoming the problem that the blocking effect is weakened due to the conduction effect of pores when the perlite particles play a role in filling and blocking the pore channels in the cement matrix, and increasing the difficulty of sodium-potassium ion migration, thereby inhibiting the whiskering phenomenon. In addition, as the alkaline water phase after washing the red mud contains a large amount of calcium ions, the calcium ions in the alkaline water phase are further converted into active calcium carbonate by using carbide slag and tea polyphenol and are compounded with water to form mixing water, and waste liquid generated by washing the red mud is fully utilized to recycle the mixing water. In the process, the method firstly adds the solid waste raw material of the carbide slag for preparing the sulphoaluminate cement to convert the alkaline water phase/liquid phase into the saturated lime water solution so as to improve the preparation efficiency of the active calcium carbonate and effectively utilize the carbide slag. Furthermore, the invention utilizes the characteristic that the benzene ring of the tea polyphenol contains a large number of hydroxyl volatile electrons and then is adsorbed on the surface of the formed metastable intermediate phase calcium carbonate to inhibit the transition of the intermediate phase calcium carbonate to the stable state calcium carbonate. The intermediate phase calcium carbonate is dissolved and recrystallized in the hydration stage of the iron-rich sulphoaluminate cement clinker to form a composite cementing product together with the cement clinker, which is beneficial to improving the strength of a cement matrix and reducing a channel for sodium and potassium ion migration, thereby inhibiting the phenomenon of whiskering.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is an SEM image of the iron-enriched sulfoaluminate cement clinker of the following example 1.
Fig. 2 is an XRD test pattern of the iron-enriched sulfoaluminate cement clinker of the following example 1.
Fig. 3 is an XRD test pattern of the iron-enriched sulfoaluminate cement clinker of the following example 2.
Fig. 4 is an XRD test pattern of the iron-enriched sulfoaluminate cement clinker of the following example 3.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer. The invention will now be further described with reference to specific embodiments.
In the following embodiments, the main components of the sintering red mud are: siO (SiO) 2 22.7％、CaO 48.3％、Al 2 O 3 5.4％、Fe 2 O 3 9.8％、Na 2 O 3.7％、K 2 O 0.6％、MgO 1.4％、TiO 2 2.8% and the balance of other unavoidable impurities.
Example 1
1. The preparation of the iron-rich sulphoaluminate cement clinker, the modified red mud, the modified alkali resistance agent and the active mixing water comprises the following steps of
(1) Mixing 1g of sintered red mud and 1g of clear water: mixing 40ml, stirring for 15min, and standing for 30min to dissolve alkaline substances in red mud. And then filtering the obtained slurry, and respectively collecting the obtained red mud slurry and the alkaline water phase. And (3) drying the red mud slurry at 110 ℃ until the water content is lower than 3%, grinding, and sieving with a 300-mesh sieve (the screen residue is 2%) to obtain modified red mud for later use.
(2) The alkaline aqueous phase and perlite powder with the particle size of 300 meshes are mixed according to 1g: mixing at a ratio of 25ml, stirring, heating to 65deg.C, and maintaining for 50min. And after the completion, filtering, respectively collecting the obtained solid phase product and the liquid phase, washing the solid phase product to the pH=7.1 of a washing liquid by using clear water, and drying the obtained solid phase product for 1.5 hours at the temperature of 80 ℃ after the completion, thereby obtaining the modified alkali resistant agent.
(3) And (3) adding carbide slag into the liquid phase in the step (2), stirring until the carbide slag is not dissolved, cooling to room temperature, and filtering undissolved carbide slag to obtain a saturated lime water solution. Then adding tea polyphenol into the saturated lime water solution and stirring uniformly to obtain a modified saturated lime water solution with the mass fraction of tea polyphenol of 0.4%.
(4) Carbon dioxide was introduced into the modified saturated lime water solution at a rate of 3L/min until solid phase products were no longer produced, and then the solid phase products were filtered off and washed 3 times with clean water. Finally, the solid phase product is dispersed in water according to the proportion of 7g/L, and the active mixing water is obtained.
(5) The preparation method comprises the following steps of: 52% of carbide slag, 28.5% of bauxite, 12% of desulfurized gypsum and 7.5% of modified red mud.
(6) The raw materials are mixed to form raw materials, the raw materials are heated to 920 ℃ to be preheated for 15min, and then calcined for 50min at 1280 ℃. After the completion, the obtained calcined product is quenched to room temperature by blowing air, and the obtained product is crushed and ground into powder with the surface area of 400m 2 And (3) per kg of powder to obtain the iron-enriched sulphoaluminate cement clinker (refer to figure 1).
2. The preparation of the alkali-resistant iron-rich sulphoaluminate cement composite cementing material comprises the following steps:
(1) The following raw materials were prepared: 130 parts of the iron-rich sulphoaluminate cement clinker prepared in the embodiment, 36 parts of the modified alkali resistance agent, 55 parts of active mixing water and 0.27 part of sodium tartrate retarder.
(2) And mixing the iron-rich sulphoaluminate cement clinker and the modified alkali-resistant agent, mechanically stirring for 10min, adding the active mixing water and the retarder, and continuously stirring for 5min to obtain the alkali-resistant iron-rich sulphoaluminate cement composite cementing material.
1. The percentage content of each component in the iron-enriched sulphoaluminate cement clinker (refer to figure 2) is tested and is respectively C 4 A 3 S：53.9％、C 2 S：20.8％、C 6 AF 2 :21.4% and the other 3.9%.
2. Various performance indexes of the iron-rich sulphoaluminate cement composite cementing material of the embodiment are tested: and pouring the iron-rich sulphoaluminate cement composite cementing material into a mould to prepare a standard test piece, and then testing the 28d compressive strength of the standard test piece, wherein the result is 71.46MPa.
3. In the embodiment, the method of ion leaching concentration is adopted to quantitatively characterize the degree of the saltpetering. The greater the ion concentration measured, the more severe the degree of efflorescence. The specific method comprises the following steps: immersing a test piece prepared from the iron-rich sulphoaluminate cement composite cementing material in the embodiment in distilled water, standing for 30min, then applying ultrasonic vibration for 15min, taking a water sample after completion, and testing the total concentration of sodium ions and potassium ions in the water sample to obtain a result of 7.418ppm.
Example 2
1. The preparation of the iron-rich sulphoaluminate cement clinker, the modified red mud, the modified alkali resistance agent and the active mixing water comprises the following steps of
(1) Mixing 1g of sintered red mud and 1g of clear water: mixing the materials in a proportion of 30ml, stirring for 10min, and standing for 25min to fully dissolve alkaline substances in the red mud. And then filtering the obtained slurry, and respectively collecting the obtained red mud slurry and the alkaline water phase. And (3) drying the red mud slurry at 130 ℃ until the water content is lower than 3%, grinding, and sieving with a 350-mesh sieve (screen residue is 3%), thus obtaining modified red mud for later use.
(2) The alkaline aqueous phase and perlite powder with the grain size of 200 meshes are mixed according to 1g: mixing at a ratio of 30ml, stirring, heating to 50deg.C, and maintaining for 60min. And after the completion, filtering, respectively collecting the obtained solid phase product and the liquid phase, washing the solid phase product to the pH=7.0 of a washing liquid by using clear water, and drying the obtained solid phase product for 1.0 hour at the temperature of between 90 ℃ after the completion, thereby obtaining the modified alkali resistant agent.
(3) And (3) adding carbide slag into the liquid phase in the step (2), stirring until the carbide slag is not dissolved, cooling to room temperature, and filtering undissolved carbide slag to obtain a saturated lime water solution. Then adding tea polyphenol into the saturated lime water solution and stirring uniformly to obtain a modified saturated lime water solution with the mass fraction of tea polyphenol of 0.2%.
(4) Carbon dioxide was introduced into the modified saturated lime water solution at a rate of 2L/min until solid phase products were no longer produced, and then the solid phase products were filtered off and washed with clear water 4 times. Finally, the solid phase product is dispersed in water according to the proportion of 5g/L, and the active mixing water is obtained.
(5) The preparation method comprises the following steps of: 51% of limestone, 35% of aluminum ash, 8% of phosphogypsum and 6% of modified red mud.
(6) The raw materials are mixed to form raw materials, the raw materials are heated to 850 ℃ to be preheated for 20min, and then calcined for 40min at 1300 ℃. After the completion, the obtained calcined product is quenched to room temperature by blowing air, and the obtained product is crushed and ground into powder with the surface area of 400m 2 And (3) per kg of powder to obtain the iron-rich sulphoaluminate cement clinker.
2. The preparation of the alkali-resistant iron-rich sulphoaluminate cement composite cementing material comprises the following steps:
(1) The following raw materials were prepared: 145 parts of iron-rich sulphoaluminate cement clinker, 42 parts of modified alkali resistance agent, 61 parts of active mixing water and 0.3 part of sodium gluconate retarder.
(2) And mixing the iron-rich sulphoaluminate cement clinker and the modified alkali-resistant agent, mechanically stirring for 10min, adding the active mixing water and the retarder, and continuously stirring for 5min to obtain the alkali-resistant iron-rich sulphoaluminate cement composite cementing material.
1. The percentage content of each component in the iron-enriched sulphoaluminate cement clinker was tested (see figure 3), C respectively 4 A 3 S：51.6％、C 2 S：23.3％、C 6 AF 2 :20.9% and the other 4.2%.
2. Various performance indexes of the iron-rich sulphoaluminate cement composite cementing material of the embodiment are tested: and pouring the iron-rich sulphoaluminate cement composite cementing material into a mould to prepare a standard test piece, and testing the 28d compressive strength of the standard test piece, wherein the result is 74.21MPa.
3. In this example, the extent of the efflorescence was quantitatively characterized by using the method of ion leaching concentration, and the specific method was the same as in example 1 above. The total concentration of sodium and potassium ions in the water sample was measured and found to be 7.246ppm.
Example 3
1. The preparation of the iron-rich sulphoaluminate cement clinker, the modified red mud, the modified alkali resistance agent and the active mixing water comprises the following steps of
(1) Mixing 1g of sintered red mud and 1g of clear water: 50ml of the red mud is mixed and stirred for 15min, and then the mixture is kept stand for 25min, so that alkaline substances in the red mud are fully dissolved. And then filtering the obtained slurry, and respectively collecting the obtained red mud slurry and the alkaline water phase. And (3) drying the red mud slurry at 80 ℃ until the water content is lower than 3%, grinding, and sieving with a 300-mesh sieve (the screen residue is 2%) to obtain modified red mud for later use.
(2) The alkaline aqueous phase and perlite powder with the particle size of 300 meshes are mixed according to 1g: mixing at a ratio of 15ml, stirring, heating to 70deg.C, and maintaining the temperature for 40min. And after the completion, filtering, respectively collecting the obtained solid phase product and the liquid phase, washing the solid phase product to the pH=7.2 of a washing liquid by using clear water, and drying the obtained solid phase product for 1.5 hours at the temperature of between 70 ℃ after the completion, thereby obtaining the modified alkali resistant agent.
(3) And (3) adding carbide slag into the liquid phase in the step (2), stirring until the carbide slag is not dissolved, cooling to room temperature, and filtering undissolved carbide slag to obtain a saturated lime water solution. Then adding tea polyphenol into the saturated lime water solution and stirring uniformly to obtain a modified saturated lime water solution with the mass fraction of tea polyphenol of 0.5%.
(4) Carbon dioxide was introduced into the modified saturated lime water solution at a rate of 4.5L/min until solid phase products were no longer produced, and then the solid phase products were filtered off and washed 3 times with clean water. Finally, the solid phase product is dispersed in water according to the proportion of 8g/L, and the active mixing water is obtained.
(5) The preparation method comprises the following steps of: 54% of carbide slag, 28% of fly ash and 8% of fluorogypsum, wherein the modified red mud is 10%.
(6) The raw materials are mixed to form raw materials, the raw materials are heated to 950 ℃ to be preheated for 10min, and then calcined at 1230 ℃ for 60min. After the completion, the obtained calcined product is quenched to room temperature by blowing air, and the obtained product is crushed and ground into powder with the surface area of 400m 2 And (3) per kg of powder to obtain the iron-rich sulphoaluminate cement clinker.
2. The preparation of the alkali-resistant iron-rich sulphoaluminate cement composite cementing material comprises the following steps:
(1) The following raw materials were prepared: 120 parts of the iron-rich sulphoaluminate cement clinker prepared in the embodiment, 30 parts of the modified alkali resistance agent, 48 parts of the active mixing water and 0.22 part of the sodium citrate retarder.
(2) And mixing the iron-rich sulphoaluminate cement clinker and the modified alkali-resistant agent, mechanically stirring for 10min, adding the active mixing water and the retarder, and continuously stirring for 5min to obtain the alkali-resistant iron-rich sulphoaluminate cement composite cementing material.
1. The percentage content of each component in the iron-enriched sulphoaluminate cement clinker was tested (see figure 4), C respectively 4 A 3 S：56.2％、C 2 S：20.7％、C 6 AF 2 :19.4%, the other 3.7%.
2. Various performance indexes of the iron-rich sulphoaluminate cement composite cementing material of the embodiment are tested: and pouring the iron-rich sulphoaluminate cement composite cementing material into a mould to prepare a standard test piece, and then testing the 28d compressive strength of the standard test piece, wherein the result is 69.63MPa.
3. In this example, the extent of the efflorescence was quantitatively characterized by using the method of ion leaching concentration, and the specific method was the same as in example 1 above. The total concentration of sodium and potassium ions in the water sample was measured and found to be 7.522ppm.
Example 4
The preparation of the alkali-resistant iron-rich sulphoaluminate cement composite cementing material is the same as that of the above example 1, except that the preparation of the material adopts the following steps:
(1) The following raw materials were prepared: 130 parts by weight of the iron-rich sulphoaluminate cement clinker prepared in the above example 1, 55 parts by weight of active mixing water and 0.27 part by weight of sodium tartrate retarder.
(2) And (3) continuously stirring the iron-rich sulphoaluminate cement clinker, the active mixing water and the retarder for 5min to obtain the alkali-resistant iron-rich sulphoaluminate cement composite cementing material.
Various performance indexes of the iron-rich sulphoaluminate cement composite cementing material of the embodiment are tested: and pouring the iron-rich sulphoaluminate cement composite cementing material into a mould to prepare a standard test piece, and then testing the 28d compressive strength of the standard test piece, wherein the result is 53.87MPa.
In this example, the extent of the efflorescence was quantitatively characterized by using the method of ion leaching concentration, and the specific method was the same as in example 1 above. The total concentration of sodium and potassium ions in the water sample was measured and found to be 28.536ppm.
Example 5
The preparation of the alkali-resistant iron-rich sulphoaluminate cement composite cementing material is similar to the preparation of the example 1, and the difference is that: the preparation of the modified alkali resistant agent adopts the following process: mixing clear water with perlite powder with the particle size of 300 meshes according to 1g: mixing at a ratio of 25ml, stirring, heating to 65deg.C, and maintaining for 50min. Filtering out a solid phase product after completion, and drying the solid phase product at the temperature of 80 ℃ for 1.5 hours to obtain the modified alkali resistant agent.
Various performance indexes of the iron-rich sulphoaluminate cement composite cementing material of the embodiment are tested: and pouring the iron-rich sulphoaluminate cement composite cementing material into a mould to prepare a standard test piece, and testing the 28d compressive strength of the standard test piece, wherein the result is 60.32MPa.
In this example, the extent of the efflorescence was quantitatively characterized by using the method of ion leaching concentration, and the specific method was the same as in example 1 above. The total concentration of sodium and potassium ions in the water sample was measured and found to be 32.741ppm.
Example 6
The preparation of the alkali-resistant iron-rich sulphoaluminate cement composite cementing material is similar to the preparation of the above example 2, and the difference is that the preparation of the active mixing water adopts the following process:
(3) Adding carbide slag into the liquid phase in the step (2), stirring until the carbide slag is not dissolved, cooling to room temperature, and filtering undissolved carbide slag to obtain saturated lime water solution for later use.
(4) Carbon dioxide was introduced into the saturated aqueous lime solution at a rate of 2L/min until no more precipitate was produced, and the precipitate was filtered off and washed with clear water 4 times. Finally, the solid phase product is dispersed in water according to the proportion of 5g/L, and the active mixing water is obtained.
Various performance indexes of the iron-rich sulphoaluminate cement composite cementing material of the embodiment are tested: and pouring the iron-rich sulphoaluminate cement composite cementing material into a mould to prepare a standard test piece, and then testing the 28d compressive strength of the standard test piece, wherein the result is 66.84MPa.
In this example, the extent of the efflorescence was quantitatively characterized by using the method of ion leaching concentration, and the specific method was the same as in example 1 above. The total concentration of sodium and potassium ions in the water sample was measured and found to be 30.603ppm.
Example 7
The preparation of the alkali-resistant iron-rich sulphoaluminate cement composite cementing material is similar to that of the example 2, and the difference is that:
(1) The following raw materials were prepared: 145 parts of the iron-rich sulphoaluminate cement clinker prepared in the above example 2, 42 parts of modified alkali resistance agent, 61 parts of deionized water and 0.3 part of sodium gluconate retarder.
(2) And mixing the iron-rich sulphoaluminate cement clinker and the modified alkali-resistant agent, mechanically stirring for 10min, adding the deionized water and the retarder, and continuously stirring for 5min to obtain the alkali-resistant iron-rich sulphoaluminate cement composite cementing material.
Various performance indexes of the iron-rich sulphoaluminate cement composite cementing material of the embodiment are tested: and pouring the iron-rich sulphoaluminate cement composite cementing material into a mould to prepare a standard test piece, and then testing the 28d compressive strength of the standard test piece, wherein the result is 62.45MPa.
In this example, the extent of the efflorescence was quantitatively characterized by using the method of ion leaching concentration, and the specific method was the same as in example 1 above. The total concentration of sodium and potassium ions in the water sample was measured and found to be 25.187ppm.
Example 8
The preparation of the alkali-resistant iron-rich sulphoaluminate cement composite cementing material is the same as that of the embodiment 3, and the difference is that the preparation of the iron-rich sulphoaluminate cement clinker adopts the following process: the preparation method comprises the following steps of: 54% of carbide slag, 28% of fly ash, 8% of fluorogypsum and 10% of sintering red mud which is not subjected to water washing treatment. The raw materials are mixed to form raw materials, the raw materials are heated to 950 ℃ to be preheated for 10min, and then calcined at 1230 ℃ for 60min. After the completion, the obtained calcined product is quenched to room temperature by blowing air, and the obtained product is crushed and ground into powder with the surface area of 400m 2 And (3) per kg of powder to obtain the iron-rich sulphoaluminate cement clinker.
Various performance indexes of the iron-rich sulphoaluminate cement composite cementing material of the embodiment are tested: and pouring the iron-rich sulphoaluminate cement composite cementing material into a mould to prepare a standard test piece, and testing the 28d compressive strength of the standard test piece, wherein the result is 68.08MPa.
In this example, the extent of the efflorescence was quantitatively characterized by using the method of ion leaching concentration, and the specific method was the same as in example 1 above. The total concentration of sodium and potassium ions in the water sample was measured and found to be 49.635ppm.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The alkali-resistant iron-rich sulphoaluminate cement composite cementing material is characterized by comprising the following components in parts by weight: 120-145 parts of iron-rich sulphoaluminate cement clinker, 30-42 parts of modified alkali resistance agent, 48-61 parts of active mixing water and 0.22-0.3 part of retarder; wherein:
the iron-rich sulphoaluminate cement clinker is prepared by taking modified red mud as one of the raw materials;
the preparation process of the modified red mud, the modified alkali resistant agent and the active mixing water comprises the following steps:
(1) Uniformly mixing red mud and clear water, standing, performing solid-liquid separation, respectively collecting the obtained red mud slurry and alkaline water phase, drying the red mud slurry, and grinding to obtain modified red mud;
(2) Uniformly mixing the alkaline aqueous phase with perlite powder, then carrying out heating and heat preservation reaction, carrying out solid-liquid separation after completion, respectively collecting the obtained solid phase product and liquid phase, washing the solid phase product, and drying to obtain the powdery modified alkali resistant agent;
(3) Adding carbide slag into the liquid phase, stirring until the carbide slag is no longer dissolved, cooling to room temperature, and separating undissolved carbide slag to obtain saturated lime water solution; then adding tea polyphenol into the saturated lime water solution and uniformly mixing to obtain a modified saturated lime water solution;
(4) And introducing carbon dioxide into the modified saturated lime water solution until solid-phase products are not generated any more, separating the solid-phase products, washing the solid-phase products, and dispersing the washed solid-phase products in water to obtain the active mixing water.
2. The alkali-resistant iron-rich sulfoaluminate cement composite cementing material according to claim 1, wherein in the step (1), the ratio of the red mud to the clean water is 1g: 30-50 ml;
optionally, in the step (1), the red mud slurry is dried at 80-130 ℃ until the water content is not higher than 3%.
3. The alkali-resistant iron-rich sulfoaluminate cement composite cement according to claim 1, wherein in the step (2), the ratio of the alkali aqueous phase to the perlite powder is 1g: 15-30 ml;
optionally, in the step (2), the particle size of the perlite powder is 200-300 meshes.
4. The alkali-resistant iron-rich sulphoaluminate cement composite cementing material according to claim 1, wherein in the step (2), the heating temperature is 50-70 ℃ and the reaction time is 40-60 min; and after the completion, separating out the solid phase product, cleaning the solid phase product by using clear water until the pH value of the cleaning solution is=7.0-7.2, and drying the obtained solid phase product at 70-90 ℃ for 1-1.5 hours after the completion, thus obtaining the modified alkali resistant agent.
5. The alkali-resistant iron-rich sulphoaluminate cement composite cementing material of claim 1, wherein in the step (3), the mass fraction of tea polyphenol in the modified saturated lime water solution is 0.2-0.5%.
6. The alkali-resistant iron-rich sulfoaluminate cement composite cementing material according to claim 1, wherein in the step (4), the carbon dioxide is introduced at a rate of 2-4.5L/min.
7. The alkali-resistant iron-rich sulfoaluminate cement composite cementing material according to claim 1, wherein in the step (4), the content of solid phase products in the active mixing water is 5-8 g/L.
8. The alkali-resistant iron-rich sulfoaluminate cement composite cement clinker according to any one of claims 1 to 7, wherein the preparation of the iron-rich sulfoaluminate cement clinker comprises the following steps:
(i) The preparation method comprises the following steps of: 51-54% of calcareous material, 28-35% of aluminum material, 8-12% of gypsum material and 6-10% of modified red mud;
(ii) Heating the raw materials to 850-950 ℃ to preheat for 10-20 min, and then transferring the raw materials to 1230-1300 ℃ to calcine for 40-60 min; quenching to room temperature after completion, crushing and grinding the obtained product to obtain the iron-enriched sulphoaluminate cement clinker.
9. The alkali-resistant iron-rich sulfoaluminate cement composite cement material according to claim 8, wherein the calcareous material comprises at least one of limestone and carbide slag;
optionally, the aluminum material comprises at least one of aluminum ash, bauxite, aluminum tailings and fly ash;
optionally, the gypsum-based material comprises at least one of desulfurized gypsum, phosphogypsum and fluorine gypsum;
optionally, the retarder comprises any one of sodium tartrate, sodium citrate, sodium gluconate and sodium borate.
10. The process for preparing the alkali-resistant iron-rich sulphoaluminate cement composite cementing material according to any one of claims 1 to 9, which is characterized by comprising the following steps: and uniformly mixing the iron-rich sulphoaluminate cement clinker and the modified alkali resistant agent, and then adding the active mixing water and the retarder and uniformly stirring to obtain the composite material.
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