CN115893958A - High-strength cement mortar based on iron ore waste residues and preparation process thereof - Google Patents
High-strength cement mortar based on iron ore waste residues and preparation process thereof Download PDFInfo
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- CN115893958A CN115893958A CN202310055959.4A CN202310055959A CN115893958A CN 115893958 A CN115893958 A CN 115893958A CN 202310055959 A CN202310055959 A CN 202310055959A CN 115893958 A CN115893958 A CN 115893958A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000011083 cement mortar Substances 0.000 title claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 41
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 239000003822 epoxy resin Substances 0.000 claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 40
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 23
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 23
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 23
- 229940033123 tannic acid Drugs 0.000 claims abstract description 23
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 23
- 229920002258 tannic acid Polymers 0.000 claims abstract description 23
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 239000004576 sand Substances 0.000 claims abstract description 18
- 239000010881 fly ash Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000000887 hydrating effect Effects 0.000 claims abstract description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 27
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 27
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 19
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 19
- 229920001223 polyethylene glycol Polymers 0.000 claims description 19
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 15
- 230000036571 hydration Effects 0.000 claims description 13
- 238000006703 hydration reaction Methods 0.000 claims description 13
- XTOQOJJNGPEPMM-UHFFFAOYSA-N o-(2-oxo-1,3,2$l^{5}-dioxaphosphinan-2-yl)hydroxylamine Chemical compound NOP1(=O)OCCCO1 XTOQOJJNGPEPMM-UHFFFAOYSA-N 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000011398 Portland cement Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 4
- -1 amidine hydrochloride Chemical class 0.000 claims description 4
- 150000001409 amidines Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000000052 comparative effect Effects 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000004568 cement Substances 0.000 description 7
- 239000013530 defoamer Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229920001864 tannin Polymers 0.000 description 4
- 235000018553 tannin Nutrition 0.000 description 4
- 239000001648 tannin Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical group OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- 230000003487 anti-permeability effect Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008030 superplasticizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to the technical field of cement mortar, and discloses high-strength cement mortar based on iron ore waste residues and a preparation process thereof. The method comprises the following steps: step 1: uniformly mixing silicate, fly ash, river sand and iron ore waste residues to obtain an inorganic mixture; step 2: adding 0.25-0.35 wt% of inorganic mixture into deionized water, adding tannic acid, and hydrating for 5-6 hours at 400-600 rpm; adding modified biochar, and uniformly dispersing to obtain a mixed solution; and step 3: adding the rest inorganic mixture into the mixed solution, and stirring and mixing; adding a water reducing agent and a defoaming agent, stirring and mixing; and adding the waterborne epoxy resin, and uniformly stirring to obtain the high-strength cement mortar. The cement mortar prepared by the scheme has excellent compressive strength and impermeability.
Description
Technical Field
The invention relates to the technical field of cement mortar, in particular to high-strength cement mortar based on iron ore waste residues and a preparation process thereof.
Background
Cement mortar is a building material formed by mixing cement, gravel and water, is widely used for building walls, channels, floor tiles and the like, and plays a role in stabilization. With the rapid development of the infrastructure of China, the demand of cement mortar is increased, and gravels which are one of main substances are also excessively exploited, so that the ecological environment is damaged. Meanwhile, the waste iron ore and waste slag generated every year in China also threatens the environment. Therefore, research is gradually tending to use iron ore waste residues instead of sand stones to prepare cement mortar, thereby utilizing wastes, reducing cost and reducing environmental hazards.
In the prior art, iron ore waste residues are used for replacing gravels, so that the defects of slow setting and hardening, large drying shrinkage, poor compression resistance, poor freezing resistance, poor impermeability and the like of cement products formed by cement mortar exist. And the polymer binder is used for increasing the crosslinking density of the cement product, so that the internal pores are effectively reduced, the impermeability is improved, and the fracture resistance is improved. Epoxy resin is widely used for modifying cement mortar due to the advantages of good chemical resistance, frost resistance, high adhesiveness, low curing shrinkage and the like, so that the frost resistance and the impermeability are enhanced. However, the chelating property of the existing epoxy resin crosslinking agent and cement mortar is not high, the plasticity of the cement paste is not high, and the enhancement of the compression resistance is limited. In addition, a curing agent is generally required to be additionally introduced for crosslinking and curing, and a diluent is introduced to increase compatibility; however, the introduction of multiple substances has complexity, and the problems of low crosslinking uniformity and high curing stress exist, so that curing cracks can be generated, and the pressure resistance and the anti-permeability performance are reduced.
In conclusion, the preparation of the high-strength cement mortar based on the iron ore waste residue has important application value in solving the problems.
Disclosure of Invention
The invention aims to provide high-strength cement mortar based on iron ore waste residues and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation process of high-strength cement mortar based on iron ore waste residues comprises the following steps:
step 1: uniformly mixing silicate, fly ash, river sand and iron ore waste residues to obtain an inorganic mixture;
and 2, step: adding 0.25-0.35 wt% of inorganic mixture into deionized water, adding tannic acid, and hydrating for 5-6 hours at 400-600 rpm to obtain a hydration product solution; adding modified biochar, and uniformly dispersing to obtain a mixed solution;
and step 3: adding the rest inorganic mixture into the mixed solution, and stirring and mixing; adding a water reducing agent and a defoaming agent, stirring and mixing; and adding the waterborne epoxy resin, and uniformly stirring to obtain the high-strength cement mortar.
Preferably, the high-strength cement mortar comprises the following raw materials: 95-105 parts of inorganic mixture, 0.5-0.7 part of tannic acid, 0.8-1 part of modified biochar, 12-15 parts of deionized water, 5-6 parts of aqueous epoxy resin, 0.1-0.2 part of water reducing agent and 0.1-0.15 part of defoaming agent; the water reducing agent is one of a polycarboxylic acid water reducing agent and a sulfonic water reducing agent; the defoaming agent is a polyether defoaming agent.
Preferably, the inorganic mixture comprises: 32 to 36 portions of Portland cement, 6 to 9 portions of fly ash, 43 to 50 portions of river sand and 10 to 14 portions of iron ore waste residue.
Preferably, the density of the portland cement is 3.0-3.2 g/cm 3 (ii) a The density of the river sand is 2.5-2.7 g/cm 3 The fineness modulus is 2.5-2.8; the density of the iron ore waste residue is 2.8-3.0 g/cm 3 。
Preferably, the preparation process of the modified biochar comprises the following steps: adding nano biochar into deionized water, dispersing uniformly, adding triethylene diamine, adding the mixture to the temperature of 40-80 ℃, reacting for 12-14 hours, cooling, filtering and drying to obtain the modified biochar.
Preferably, the mass ratio of the triethylene diamine to the nano biochar is 1 (3-4).
Preferably, the preparation process of the water-based epoxy resin comprises the following steps:
(1) Adding 2-aminoethylsulfonic acid and aminotrimethylene phosphoric acid into the medium hydrochloric acid solution, and adjusting the pH =8.5 +/-0.2 by using sodium hydroxide to obtain a modified solution;
(2) Adding epoxy resin E54 into a reaction bottle, adding tetrabutyl ammonium bromide aqueous solution, setting the temperature to be 90-98 ℃ under the nitrogen atmosphere, and stirring for 30-40 minutes; dropping the modified solution for 20-30 min to react for 4-5 hr; cooling to 60-70 ℃, adding aqueous solution of azodiisobutyramidine hydrochloride, uniformly stirring, heating to 90-98 ℃, adding mixed aqueous solution of methoxy polyethylene glycol acrylamide and acrylamide, reacting for 4-5 hours, performing rotary evaporation, washing with ethyl acetate, and drying to obtain the waterborne epoxy resin.
Preferably, the aqueous epoxy resin comprises the following raw materials: according to the weight portion, 100 portions of epoxy resin E54, 18 to 20 portions of 2-aminoethylsulfonic acid, 8 to 10 portions of amino trimethylene phosphoric acid, 30 to 34 portions of methoxy polyethylene glycol acrylamide, 8 to 12 portions of acrylamide and 3 to 4 portions of azo diisobutyl amidine hydrochloride.
Preferably, the concentration of the hydrochloric acid solution is 1-1.2 mol/L; the concentration of the tetrabutylammonium bromide aqueous solution is 15-20 wt%; the concentration of the azodiisobutyl amidine hydrochloride aqueous solution is 10-12 wt%; the concentration of the mixed aqueous solution is 15-20 wt%.
The cement mortar prepared by the preparation process of the high-strength cement mortar based on the iron ore waste residue is more optimized.
The technical scheme of the application has the beneficial effects that:
(1) In the scheme, an inorganic mixture (main raw material of cement mortar) with extremely low content is taken in advance and dispersed in deionized water, tannic acid is added, the mixture is stirred and hydrated to generate a hydration product solution, then modified nano biomass carbon is introduced, and the mixture is uniformly mixed to obtain a mixed solution.
The method is characterized in that the strong chelation of tannic acid is utilized to chelate calcium ions, iron ions and the like in an inorganic mixture in a hydration product solution, nanoparticles such as C-S-H, CH and the like are induced in situ on the surface of the hydration product due to the specificity of the tannic acid, and the nanoparticles generated in situ can be well dispersed in slurry due to hydrophobic interaction generated by pi-pi accumulation. The formed nano particles can be used as nucleation sites for C-S-H growth in the subsequent hydration process of the residual inorganic mixture, and the hydration process of the cement in the later period is promoted. On the other hand, the in-situ growth of the porous silicon dioxide is in the structure of cement mortar, so that the pore structure is effectively refined, the strength and the impermeability are improved, and the durability is improved.
On the other hand, too high content of tannic acid is not preferable, and thus the plasticity of the mortar is lowered and the stability of the cement mortar is lowered. Therefore, in order to cooperate with the hydration product and further improve the strength and the impermeability, the modified nano biomass charcoal is further introduced. The amino biochar is obtained by modifying biochar with triethylene diamine. Wherein, the nano biochar can also improve and promote the refinement of the pore structure. The modified triethylene diamine is a metal chelating agent, compared with tannin, the metal chelating agent has a basic functional group and an acidic functional group, and the metal chelating types and the chelating sequence are different; in addition, the loss of tannin in the pre-hydration process can be reduced by introducing triethylene diamine, so that the triethylene diamine and the tannin have a synergistic effect by introducing the triethylene diamine and the tannin, and the impermeability and the compressive strength are synergistically improved. Similarly, the introduction amount of the modified nano biomass charcoal needs to be limited, and the compressive strength is increased and then reduced along with the introduction of the modified nano biomass charcoal.
(2) In the scheme, the waterborne epoxy resin is introduced to promote the formation of a cross-linked network, so that the strength and the mechanical property are improved. Because the existing epoxy resin has the problems of compatibility, dispersibility and curing brittleness, in the scheme, a double modification means is used to increase the dispersibility of the epoxy resin in cement mortar, and meanwhile, the modified epoxy resin can be self-crosslinked, so that the introduction of redundant substances is reduced, and the generation of cracks caused by curing stress is inhibited.
The waterborne epoxy resin is based on epoxy resin E54, the amino ring-opening grafting of 2-aminoethylsulfonic acid and amino trimethylene phosphoric acid is carried out in the presence of a tetrabutylammonium bromide catalyst, and the hydrophilic side chain is effectively increased by grafting, so that the dispersibility is improved, the toughness and the heat resistance are improved by introducing the side chain, and the grafting of the side chain and the hydrophilic side chain does not influence the hydration of cement. Because the binding capacity of the phosphate group and calcium is higher than that of the sulfonate ion, when the grafting amount of the 2-aminoethylsulfonic acid and the amino trimethylene phosphoric acid with quantitative ratio is higher, the introduction of the water-based epoxy resin has good plasticity, and the fluidity of cement mortar can be improved. Further, in the scheme, the graft is carried out on a beta-carbon adjacent to a hydroxyl group of the beta-carbon through a free radical reaction. By introducing long-chain methoxy polyethylene glycol acrylamide and short-chain acrylamide, the toughness is effectively enhanced, and the self-crosslinking performance is improved. The long-chain methoxy polyethylene glycol acrylamide effectively enhances the hydrogen bond effect inside pores, thereby improving the anti-permeability performance. The long-chain methoxy polyethylene glycol acrylamide and the short-chain acrylamide effectively form a cross-linking network in the long-chain methoxy polyethylene glycol acrylamide and combine with the hydrogen bond effect of the long-chain methoxy polyethylene glycol acrylamide to effectively form a stress dispersion effect, so that when external stress impacts, the effect of the effective dispersion force is realized, the concentration is inhibited, and the cracking of a cement sheath is reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the following examples, the iron ore slag is a slag from a mixing plant and mainly contains 30.2wt% CaO and 33.5wt% SiO 2 12.0wt% of Al 2 O 3 5.37wt% Fe 2 O 3 And 2.84wt% of MgO. Silicate cement (PI: 42.5) having a density of 3.18g/cm 3 (ii) a The density of the river sand is 2.56g/cm 3 The fineness modulus is 2.6; the density of the iron ore waste residue is 2.83/cm 3 (ii) a The density of the fly ash is 2.03g/cm 3 . The molecular weight of the methoxypolyethylene glycol acrylamide is 350; the model of the polycarboxylate superplasticizer is SPC-100, and the model of the polyether defoamer is KX-306.
Example 1:
step 1: uniformly mixing silicate, fly ash, river sand and iron ore waste residues to obtain an inorganic mixture;
step 2: (1) Weighing triethylene diamine and nano biochar in a mass ratio of 1;
(2) Adding 19 parts by weight of 2-aminoethylsulfonic acid and 9 parts by weight of aminotrimethylene phosphoric acid into 1mol/L hydrochloric acid solution, and adjusting the pH value to be =8.6 by using sodium hydroxide to obtain a modified solution; adding 100 parts of epoxy resin E54 into a reaction bottle, adding 15wt% of tetrabutylammonium bromide aqueous solution (containing 6 parts of tetrabutylammonium bromide), setting the temperature at 95 ℃ under the nitrogen atmosphere, and stirring for 30 minutes; dropwise adding the modified solution for 30 minutes, and reacting for 5 hours; and (2) cooling to 65 ℃, adding 3 parts of azo-diisobutyramidine hydrochloride aqueous solution (containing 12wt% of azo-diisobutyramidine hydrochloride), uniformly stirring, heating to 95 ℃, adding 20wt% of mixed aqueous solution (containing 32 parts of methoxy polyethylene glycol acrylamide and 10 parts of acrylamide) containing methoxy polyethylene glycol acrylamide and acrylamide, reacting for 5 hours, and carrying out rotary evaporation, ethyl acetate washing and drying to obtain the water-based epoxy resin.
(3) Adding 0.3wt% of inorganic mixture into deionized water, adding tannic acid, and stirring and hydrating for 6 hours at 500rpm to obtain a hydration product solution; adding modified biochar, and uniformly dispersing to obtain a mixed solution;
and 3, step 3: adding the rest inorganic mixture into the mixed solution, and stirring and mixing; adding a polycarboxylic acid water reducing agent and a polyether defoaming agent, stirring and mixing; and adding the waterborne epoxy resin, and uniformly stirring to obtain the high-strength cement mortar.
In the technical scheme, the high-strength cement mortar comprises the following raw materials: 100 parts of inorganic mixture, 0.6 part of tannic acid, 0.9 part of modified biochar, 15 parts of deionized water, 5.5 parts of waterborne epoxy resin, 0.15 part of polycarboxylic acid water reducer and 0.12 part of polyether defoamer; the inorganic mixture includes: 35 parts of portland cement, 7 parts of fly ash, 46 parts of river sand and 12 parts of iron ore waste residues.
Example 2:
step 1: uniformly mixing silicate, fly ash, river sand and iron ore waste residues to obtain an inorganic mixture;
step 2: (1) Weighing triethylene diamine and nano biochar in a mass ratio of 1;
(2) Adding 18 parts by weight of 2-aminoethylsulfonic acid and 10 parts by weight of aminotrimethylene phosphoric acid into 1mol/L hydrochloric acid solution, and adjusting the pH value to be =8.6 by using sodium hydroxide to obtain a modified solution; adding 100 parts of epoxy resin E54 into a reaction bottle, adding 15wt% of tetrabutylammonium bromide aqueous solution (containing 6 parts of tetrabutylammonium bromide), setting the temperature at 95 ℃ under the nitrogen atmosphere, and stirring for 30 minutes; dropwise adding the modified solution for 30 minutes, and reacting for 5 hours; and (2) cooling to 65 ℃, adding 3 parts of azo-diisobutymidine hydrochloride aqueous solution (containing 12wt% of azo-diisobutymidine hydrochloride), uniformly stirring, heating to 95 ℃, adding 20wt% of mixed aqueous solution (containing 30 parts of methoxy polyethylene glycol acrylamide and 12 parts of acrylamide) containing methoxy polyethylene glycol acrylamide and acrylamide, reacting for 5 hours, and carrying out rotary evaporation, ethyl acetate washing and drying to obtain the water-based epoxy resin.
(3) Adding 0.25wt% of inorganic mixture into deionized water, adding tannic acid, and stirring and hydrating for 6 hours at 500rpm to obtain a hydration product solution; adding modified biochar, and dispersing uniformly to obtain a mixed solution;
and 3, step 3: adding the rest inorganic mixture into the mixed solution, and stirring and mixing; adding a polycarboxylic acid water reducing agent and a polyether defoaming agent, stirring and mixing; and adding the waterborne epoxy resin, and uniformly stirring to obtain the high-strength cement mortar.
In the technical scheme, the high-strength cement mortar comprises the following raw materials: 105 parts of inorganic mixture, 0.5 part of tannic acid, 1 part of modified biochar, 15 parts of deionized water, 5 parts of waterborne epoxy resin, 0.2 part of polycarboxylic acid water reducer and 0.15 part of polyether defoamer; the inorganic mixture includes: 32 parts of portland cement, 9 parts of fly ash, 50 parts of river sand and 14 parts of iron ore waste residue.
Example 3:
step 1: uniformly mixing silicate, fly ash, river sand and iron ore waste residues to obtain an inorganic mixture;
step 2: (1) Weighing triethylene diamine and nano biochar in a mass ratio of 1;
(2) Adding 20 parts by weight of 2-aminoethylsulfonic acid and 8 parts by weight of aminotrimethylene phosphoric acid into 1mol/L hydrochloric acid solution, and adjusting the pH value to be =8.5 by using sodium hydroxide to obtain a modified solution; adding 100 parts of epoxy resin E54 into a reaction bottle, adding 15wt% of tetrabutylammonium bromide aqueous solution (containing 6 parts of tetrabutylammonium bromide), setting the temperature at 95 ℃ under the nitrogen atmosphere, and stirring for 30 minutes; dropwise adding the modified solution for 30 minutes, and reacting for 5 hours; and (2) cooling to 65 ℃, adding 3 parts of azo-diisobutymidine hydrochloride aqueous solution (containing 12wt% of azo-diisobutymidine hydrochloride), uniformly stirring, heating to 95 ℃, adding 20wt% of mixed aqueous solution (containing 34 parts of methoxy polyethylene glycol acrylamide and 8 parts of acrylamide) containing methoxy polyethylene glycol acrylamide and acrylamide, reacting for 5 hours, and carrying out rotary evaporation, ethyl acetate washing and drying to obtain the water-based epoxy resin.
(3) Adding 0.35wt% of inorganic mixture into deionized water, adding tannic acid, and stirring and hydrating for 6 hours at 500rpm to obtain a hydration product solution; adding modified biochar, and uniformly dispersing to obtain a mixed solution;
and 3, step 3: adding the rest inorganic mixture into the mixed solution, and stirring and mixing; adding a polycarboxylic acid water reducing agent and a polyether defoaming agent, stirring and mixing; and adding the waterborne epoxy resin, and uniformly stirring to obtain the high-strength cement mortar.
In the technical scheme, the high-strength cement mortar comprises the following raw materials: according to the weight parts, 95 parts of inorganic mixture, 0.7 part of tannic acid, 0.8 part of modified biochar, 12 parts of deionized water, 6 parts of waterborne epoxy resin, 0.1 part of polycarboxylic acid water reducer and 0.1 part of polyether defoamer; the inorganic mixture includes: 36 parts of portland cement, 6 parts of fly ash, 43 parts of river sand and 10 parts of iron ore waste residues.
Comparative example 1: the same procedure as in example 1 was repeated except that the tannic acid was not previously hydrated in part of the inorganic mixture;
step 1: uniformly mixing silicate, fly ash, river sand and iron ore waste residues to obtain an inorganic mixture;
and 2, step: (1) Weighing triethylene diamine and nano biochar in a mass ratio of 1;
(2) Adding 19 parts by weight of 2-aminoethylsulfonic acid and 9 parts by weight of aminotrimethylene phosphoric acid into 1mol/L hydrochloric acid solution, and adjusting the pH value to be =8.6 by using sodium hydroxide to obtain a modified solution; adding 100 parts of epoxy resin E54 into a reaction bottle, adding 15wt% of tetrabutylammonium bromide aqueous solution (containing 6 parts of tetrabutylammonium bromide), setting the temperature at 95 ℃ under the nitrogen atmosphere, and stirring for 30 minutes; dropwise adding the modified solution for 30 minutes, and reacting for 5 hours; and (2) cooling to 65 ℃, adding 3 parts of azo-diisobutymidine hydrochloride aqueous solution (containing 12wt% of azo-diisobutymidine hydrochloride), uniformly stirring, heating to 95 ℃, adding 20wt% of mixed aqueous solution (containing 32 parts of methoxy polyethylene glycol acrylamide and 10 parts of acrylamide) containing methoxy polyethylene glycol acrylamide and acrylamide, reacting for 5 hours, and carrying out rotary evaporation, ethyl acetate washing and drying to obtain the water-based epoxy resin.
And step 3: sequentially adding tannic acid and modified biochar into deionized water, and uniformly stirring; adding the inorganic mixture, and stirring and mixing; adding a polycarboxylic acid water reducing agent and a polyether defoaming agent, stirring and mixing; and adding the waterborne epoxy resin, and uniformly stirring to obtain the high-strength cement mortar.
In the technical scheme, the high-strength cement mortar comprises the following raw materials: 100 parts of inorganic mixture, 0.6 part of tannic acid, 0.9 part of modified biochar, 15 parts of deionized water, 5.5 parts of waterborne epoxy resin, 0.15 part of polycarboxylic acid water reducer and 0.12 part of polyether defoamer; the inorganic mixture includes: 35 parts of portland cement, 7 parts of fly ash, 46 parts of river sand and 12 parts of iron ore waste residues.
Comparative example 2: the introduced amount of tannic acid is increased, and the rest is the same as that of the example 1;
the difference lies in that: in the technical scheme, the high-strength cement mortar comprises the following raw materials: 100 parts of inorganic mixture, 1.2 parts of tannic acid, 0.9 part of modified biochar, 15 parts of deionized water, 5.5 parts of waterborne epoxy resin, 0.15 part of polycarboxylic acid water reducer and 0.12 part of polyether defoamer; the inorganic mixture includes: 35 parts of portland cement, 7 parts of fly ash, 46 parts of river sand and 12 parts of iron ore waste residues.
Comparative example 3: the charcoal was not modified with triethylene diamine, and the rest was the same as in example 1;
the difference lies in that: in the step (3) of the step 2, 0.3wt% of inorganic mixture is added into deionized water, tannic acid is added, and the mixture is stirred and hydrated for 6 hours at 500rpm to obtain a hydrated product solution; adding the nano biochar, and dispersing uniformly to obtain a mixed solution.
Comparative example 4: the contents of 2-aminoethylsulfonic acid and aminotrimethylene phosphoric acid were changed, and the same procedures as in example 1 were repeated;
the difference lies in that: in the step 2 (2), 9 parts of 2-aminoethylsulfonic acid and 19 parts of aminotrimethylene phosphoric acid are added into 1mol/L hydrochloric acid solution in parts by weight, and sodium hydroxide is used for adjusting the pH value to be =8.6, so as to obtain a modified solution; adding 100 parts of epoxy resin E54 into a reaction bottle, adding 15wt% of tetrabutylammonium bromide aqueous solution (containing 6 parts of tetrabutylammonium bromide), setting the temperature at 95 ℃ under the nitrogen atmosphere, and stirring for 30 minutes; dropwise adding the modified solution for 30 minutes, and reacting for 5 hours; and (2) cooling to 65 ℃, adding 3 parts of azo-diisobutyramidine hydrochloride aqueous solution (containing 12wt% of azo-diisobutyramidine hydrochloride), uniformly stirring, heating to 95 ℃, adding 20wt% of mixed aqueous solution (containing 32 parts of methoxy polyethylene glycol acrylamide and 10 parts of acrylamide) containing methoxy polyethylene glycol acrylamide and acrylamide, reacting for 5 hours, and carrying out rotary evaporation, ethyl acetate washing and drying to obtain the water-based epoxy resin.
Comparative example 5: the methoxypolyethylene glycol acrylamide was replaced with 2-acrylamido-2-methylpropanesulfonic acid, and the rest was the same as in example 1.
Experiment: detecting the high-strength cement mortar prepared in the examples and the comparative examples, stirring the cement mortar, standing for 20 minutes, and detecting the fluidity before and after detection; then, the cement mortar was cured at 85 ℃ for 5 hours, cured at 25 ℃ and 60% relative humidity for 28 days, and then subjected to a test of compressive strength at 28 days under a load of 0.25MPa/s using a 40mm X160 mm sample according to JC/T985-2017 standard. And the sample is subjected to an impervious pressure test, the sample with the thickness of 70mm multiplied by 80mm multiplied by 30mm is cured for 5 hours at the temperature of 85 ℃, and is tested by a mortar digital display impervious instrument according to the standard of JGJ/T70-2009 after being maintained for 14 days under the conditions that the temperature is 25 ℃ and the relative humidity is 60 percent, and the obtained data are shown in the following table:
| sample (I) | Initial fluidity mm | Fluidity mm in 20 minutes | Compressive strength Mpa | Resistance to osmotic pressure Mpa |
| Example 1 | 152 | 151 | 73.1 | 2.28 |
| Example 2 | 151 | 149 | 72.0 | 2.23 |
| Example 3 | 153 | 151 | 72.3 | 2.24 |
| Comparative example 1 | 151 | 145 | 61.0 | 1.98 |
| Comparative example 2 | 146 | 131 | 71.6 | 2.20 |
| Comparative example 3 | 152 | 148 | 68.7 | 2.05 |
| Comparative example 4 | 145 | 129 | 65.0 | 2.00 |
| Comparative example 5 | 150 | 146 | 67.3 | 2.07 |
And (4) conclusion: as can be seen from the data of the examples, the cement mortar prepared by the scheme has excellent compressive strength and impermeability. As can be seen from the data of comparative example, in comparative example 1, since the inorganic substance was not previously hydrated by tannic acid, the hydrate containing the nanoparticles was not generated, so that the performance degradation was remarkable. In comparative example 2, since the introduced amount of tannic acid was increased, the plasticity was reduced so that the fluidity was remarkably decreased at 20 minutes. In comparative example 3, since the biochar was not modified, the compressive strength was reduced. In comparative example 4, the chelating property was changed due to the change in the graft content of 2-aminoethylsulfonic acid and 8 parts of aminotrimethylenephosphoric acid, so that the plasticity was decreased and the fluidity was decreased for 20 minutes, and in comparative example 5, the hydrogen bonding effect was decreased due to the replacement of methoxypolyethyleneglycol acrylamide with 2-acrylamido-2-methylpropanesulfonic acid, so that the compressive strength and the barrier property were decreased.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation process of high-strength cement mortar based on iron ore waste residues is characterized by comprising the following steps: the method comprises the following steps:
step 1: uniformly mixing silicate, fly ash, river sand and iron ore waste residues to obtain an inorganic mixture;
step 2: adding 0.25-0.35 wt% of inorganic mixture into deionized water, adding tannic acid, and hydrating for 5-6 hours at 400-600 rpm to obtain a hydration product solution; adding modified biochar, and uniformly dispersing to obtain a mixed solution;
and step 3: adding the rest inorganic mixture into the mixed solution, and stirring and mixing; adding a water reducing agent and a defoaming agent, stirring and mixing; and adding the waterborne epoxy resin, and uniformly stirring to obtain the high-strength cement mortar.
2. The preparation process of the high-strength cement mortar based on the iron ore waste residue as claimed in claim 1, which is characterized in that: the high-strength cement mortar comprises the following raw materials: according to the weight portion, 95 to 105 portions of inorganic mixture, 0.5 to 0.7 portion of tannic acid, 0.8 to 1 portion of modified biochar, 12 to 15 portions of deionized water, 5 to 6 portions of aqueous epoxy resin, 0.1 to 0.2 portion of water reducing agent and 0.1 to 0.15 portion of defoaming agent; the water reducing agent is one of a polycarboxylic acid water reducing agent and a sulfowater reducing agent; the defoaming agent is a polyether defoaming agent.
3. The preparation process of the high-strength cement mortar based on the iron ore waste residue as claimed in claim 1, which is characterized in that: the inorganic mixture includes: 32 to 36 portions of Portland cement, 6 to 9 portions of fly ash, 43 to 50 portions of river sand and 10 to 14 portions of iron ore waste residue.
4. The preparation process of the high-strength cement mortar based on the iron ore waste residue as claimed in claim 1, which is characterized in that: the density of the portland cement is 3.0-3.2 g/cm 3 (ii) a The density of the river sand is 2.5-2.7 g/cm 3 The fineness modulus is 2.5-2.8; the density of the iron ore waste residue is 2.8-3.0 g/cm 3 。
5. The preparation process of the high-strength cement mortar based on the iron ore waste residue as claimed in claim 1, which is characterized in that: the preparation process of the modified biochar comprises the following steps: adding the nano biochar into deionized water, uniformly dispersing, adding triethylene diamine, adding the mixture to the temperature of 40-80 ℃, reacting for 12-14 hours, cooling, filtering and drying to obtain the modified biochar.
6. The process for preparing high-strength cement mortar based on iron ore waste residues as claimed in claim 5, wherein the process comprises the following steps: the mass ratio of the triethylene diamine to the nano biochar is 1 (3-4).
7. The preparation process of high-strength cement mortar based on iron ore waste residues as claimed in claim 1, which is characterized in that: the preparation process of the waterborne epoxy resin comprises the following steps:
(1) Adding 2-aminoethylsulfonic acid and aminotrimethylene phosphoric acid into the medium hydrochloric acid solution, and adjusting the pH =8.5 +/-0.2 by using sodium hydroxide to obtain a modified solution;
(2) Adding epoxy resin E54 into a reaction bottle, adding tetrabutylammonium bromide aqueous solution, setting the temperature at 90-98 ℃ under the nitrogen atmosphere, and stirring for 30-40 minutes; dropwise adding the modified solution for 20-30 minutes, and reacting for 4-5 hours; cooling to 60-70 ℃, adding aqueous solution of azodiisobutyl amidine hydrochloride, uniformly stirring, heating to 90-98 ℃, adding mixed aqueous solution of methoxy polyethylene glycol acrylamide and acrylamide, reacting for 4-5 hours, performing rotary evaporation, washing with ethyl acetate, and drying to obtain the waterborne epoxy resin.
8. The process for preparing high-strength cement mortar based on iron ore waste residues as claimed in claim 7, wherein the process comprises the following steps: the water-based epoxy resin comprises the following raw materials: according to the weight portion, 100 portions of epoxy resin E54, 18 to 20 portions of 2-aminoethylsulfonic acid, 8 to 10 portions of amino trimethylene phosphoric acid, 30 to 34 portions of methoxy polyethylene glycol acrylamide, 8 to 12 portions of acrylamide and 3 to 4 portions of azo diisobutyl amidine hydrochloride.
9. The process for preparing high-strength cement mortar based on iron ore waste residues as claimed in claim 7, wherein the process comprises the following steps: the concentration of the hydrochloric acid solution is 1-1.2 mol/L; the concentration of the tetrabutylammonium bromide aqueous solution is 15-20 wt%; the concentration of the azodiisobutyramidine hydrochloride aqueous solution is 10 to 12 weight percent; the concentration of the mixed aqueous solution is 15-20 wt%.
10. The cement mortar prepared by the process for preparing high-strength cement mortar based on iron ore waste residues according to any one of claims 1 to 9.
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