CN117843325A - Cement mortar doped with iron tailing sand and preparation method thereof - Google Patents
Cement mortar doped with iron tailing sand and preparation method thereof Download PDFInfo
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- CN117843325A CN117843325A CN202410264368.2A CN202410264368A CN117843325A CN 117843325 A CN117843325 A CN 117843325A CN 202410264368 A CN202410264368 A CN 202410264368A CN 117843325 A CN117843325 A CN 117843325A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000004576 sand Substances 0.000 title claims abstract description 84
- 239000011083 cement mortar Substances 0.000 title claims abstract description 61
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920001661 Chitosan Polymers 0.000 claims abstract description 100
- 239000010881 fly ash Substances 0.000 claims abstract description 76
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001994 activation Methods 0.000 claims abstract description 28
- 230000004913 activation Effects 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- 238000011282 treatment Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 150000002505 iron Chemical class 0.000 claims abstract description 15
- 239000004568 cement Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 62
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 150000001263 acyl chlorides Chemical class 0.000 claims description 16
- DZAUWHJDUNRCTF-UHFFFAOYSA-N 3-(3,4-dihydroxyphenyl)propanoic acid Chemical compound OC(=O)CCC1=CC=C(O)C(O)=C1 DZAUWHJDUNRCTF-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 14
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 13
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 12
- 150000001540 azides Chemical class 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 58
- 230000000052 comparative effect Effects 0.000 description 10
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the field of cement mortar, and in particular discloses cement mortar doped with iron tailing sand and a preparation method thereof. Step 1: (1) Adding iron tailing sand into hydrochloric acid solution for primary activation treatment; transferring into sodium hydroxide solution, performing secondary activation treatment, filtering, and drying to obtain activated iron tailing sand; (2) Uniformly mixing activated iron tailing sand and standard sand to obtain a sand material composition; step 2: uniformly mixing the fly ash, the modified fly ash by a hydrothermal method and the chitosan derivative to obtain a fly ash composition; step 3: and uniformly mixing the fly ash composition with magnetized water, adding the sand material composition, stirring and mixing, adding cement, and homogenizing to obtain the cement mortar. In the application, the compressive strength and the impermeability of the cement ore sand are effectively improved by activating the iron tailing sand and introducing the fly ash composition with a specific proportion.
Description
Technical Field
The invention relates to the field of cement mortar, and in particular discloses cement mortar doped with iron tailing sand and a preparation method thereof.
Background
Cement mortar is one of the materials commonly used in construction engineering such as pavement, wall, floor and the like. The traditional cement mortar is prepared from cement, sand and water. In recent years, with the importance of society on resource reuse and environmental protection, the conventional cement mortar needs to further optimize components and reduce excessive consumption of raw materials. Iron tailings, on the other hand, are the main solid waste in the traditional metallurgical industry, and there are large resource waste and environmental damage. Therefore, in the prior art, the iron tailing sand is introduced into the cement mortar, so that waste resources are effectively utilized, and the effects of pollution reduction and emission reduction are achieved for the environment.
However, the iron tailings contain some impurities, and the impurities are doped in the cement mortar, so that the fluidity of the cement mortar is reduced, and the stability and the coagulability are reduced; resulting in larger voids in the cement mortar and thus lower compression and permeability resistance of the cement mortar incorporating the iron tailings sand.
In summary, solving the problems described above, it is of great importance to prepare a cement mortar incorporating iron tailings sand.
Disclosure of Invention
The invention aims to provide cement mortar doped with iron tailing sand and a preparation method 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:
the preparation method of the cement mortar doped with the iron tailing sand comprises the following steps:
step 1: (1) Adding iron tailing sand into hydrochloric acid solution for primary activation treatment; transferring into sodium hydroxide solution, performing secondary activation treatment, filtering, and drying to obtain activated iron tailing sand; (2) Uniformly mixing activated iron tailing sand and standard sand to obtain a sand material composition;
step 2: (1) Adding chitosan into deionized water, stirring and dissolving, and adjusting the pH to be 5.5+/-0.2; simultaneously dropwise adding a solution A containing 3, 4-dihydroxyphenylpropionic acid and 4-pentenoic acid, adding a solution B containing 1-ethyl- (3-dimethylaminopropyl) carbodiimide, stirring at room temperature for 12-15 hours, and purifying to obtain modified chitosan, wherein the modified chitosan is used as a chitosan derivative; (2) Uniformly mixing the fly ash, the modified fly ash by a hydrothermal method and the chitosan derivative to obtain a fly ash composition;
step 3: and uniformly mixing the fly ash composition with magnetized water, adding the sand material composition, stirring and mixing, adding cement, and homogenizing to obtain the cement mortar.
In a further aspect of the embodiments of the present application, the cement mortar raw materials include the following materials: 100 parts of sand material composition, 20-25 parts of fly ash composition, 25-30 parts of cement and 20-25 parts of magnetized water.
In a further aspect of embodiments of the present application, the sand composition comprises the following materials: 20-25 parts of activated iron tailing sand and 75-80 parts of standard sand in parts by weight; the fly ash composition comprises the following materials: 7-10 parts of fly ash, 3-5 parts of modified fly ash by a hydrothermal method and 9-12 parts of chitosan derivative.
In the further scheme of the embodiment of the application, in the step 1, the solid-liquid ratio of the iron tailing sand to the hydrochloric acid solution or the sodium hydroxide solution is 1 (5-10); the content of the hydrochloric acid in the hydrochloric acid solution is 4.8-5wt%; the content of sodium hydroxide in the sodium hydroxide solution is 3-3.2wt%; the temperature of the primary activation treatment is 70-80 ℃ and the time is 3-4 hours; the temperature of the secondary activation treatment is 80-90 ℃ and the time is 4-6 hours.
In a further scheme of the embodiment of the application, the preparation method of the modified fly ash by the hydrothermal method comprises the following steps: adding the fly ash into the disodium hydrogen phosphate solution, and uniformly dispersing by ultrasonic waves to obtain a mixed solution; and carrying out microwave hydrothermal reaction on the mixed solution for 30-60 minutes at the power of 1500-1800W and the temperature of 180-200 ℃, and filtering and drying to obtain the modified fly ash by a hydrothermal method.
In a further scheme of the embodiment of the application, the concentration of the disodium hydrogen phosphate solution is 0.25-1 mol/L; the solid-to-liquid ratio of the fly ash to the disodium hydrogen phosphate solution is 1g (3-5) mL.
In a further aspect of the embodiments of the present application, the raw materials of the modified chitosan include the following materials: 10 parts of chitosan, 5-7 parts of 3, 4-dihydroxyphenylpropionic acid, 3-4 parts of 4-pentenoic acid and 0.1-0.12 part of 1-ethyl- (3-dimethylaminopropyl) carbodiimide.
In a further aspect of the embodiments of the present application, the preparation method of the chitosan derivative is:
(1) Adding modified chitosan into N, N-dimethylformamide, adding thioglycollic acid and a photoinitiator, stirring at room temperature, and carrying out ultraviolet irradiation reaction for 1-2 hours; dropwise adding thionyl chloride at the temperature of 0-5 ℃; reacting for 3-4 hours at 60-65 ℃, thermally filtering, washing the precipitate with carbon tetrachloride, and drying to obtain acyl chloride chitosan;
(2) Adding acyl chloride chitosan into acetone, and stirring uniformly; and (3) dropwise adding a sodium azide solution with the concentration of 6-8wt% at the temperature of 0-5 ℃, continuously stirring for 3-5 hours, and purifying to obtain chitosan azide, wherein the chitosan azide is used as a chitosan derivative.
In a further scheme of the embodiment of the application, the ratio of the modified chitosan to the thioglycollic acid to the thionyl chloride is 10g (2-3 g) (12-15 mL); the mass ratio of the chitosan chloride to the sodium azide in the sodium azide solution is 10 (2-3).
Compared with the prior art, the invention has the following beneficial effects:
(1) In the invention, in order to reduce the influence of the iron tailing sand on the performance of the cement mortar, the impurities of the iron tailing sand are reduced and the activity of the iron tailing sand is increased by further activating the iron tailing sand, so that the performance of the cement mortar is improved.
The method comprises the steps of carrying out an activation treatment on iron tailing sand twice by using a hydrochloric acid solution and a sodium hydroxide solution to form a composite activation process, wherein compared with single hydrochloric acid solution activation or sodium hydroxide solution activation, the composite activation can promote alkali activation reaction of the iron tailing sand to form silicate with gelation performance, and meanwhile, hydrochloric acid can eliminate impurities in the iron tailing sand and reduce the generation of gelation reaction, so that the compression resistance and the impermeability of cement mortar are synergistically improved. It should be noted that: the activation effect on the iron tailings is different by solution treatment with different sequences and different concentrations, and the optimized scheme is as follows: firstly, 4.8-5 wt% hydrochloric acid solution is treated, and then 3-3.2 wt% sodium hydroxide solution is treated.
(2) In the invention, the fly ash composition comprising fly ash, modified fly ash by a hydrothermal method and chitosan derivative is introduced and used for partially replacing cement, so that the processability and strength are improved.
The fly ash is used for partially replacing cement, so that the resource utilization of waste can be increased, and the environmental pollution is reduced; secondly, the fly ash has smaller size, and can be filled in the cement mortar to improve the density of the cement mortar, thereby reducing the cracking property and increasing the durability. In the scheme, in order to maximize the performance of the fly ash, the dispersibility of the fly ash in the cement mortar is improved by carrying out hydrothermal modification treatment on part of the fly ash and introducing chitosan, and the hydration is promoted, so that the performance of the cement mortar is improved.
The modified fly ash is prepared by microwave hydrothermal reaction, and under the action of microwaves, the dissolution and crystallization of the fly ash are accelerated, so that nano zeolite and phosphate products are generated, the introduction of the modified fly ash by the hydrothermal method can increase nucleation sites of hydration reaction, promote later hydration, and can be embedded in pores, so that the overall strength of the hydrated cement mortar is increased.
The chitosan derivative is introduced, and the hydroxyl and amino groups of the chitosan derivative are utilized to be coordinated with hydrogen bonds, metals and crosslinking properties generated in the cement mortar, so that the interface effect between the cementing material and the aggregate is improved, the compressive property of the cement mortar is improved, and meanwhile, the chitosan derivative is introduced to have good ductility and flexibility, so that the stress concentration is reduced, the cracking resistance probability is reduced, and the impermeability of the cement mortar is improved. The modified derivative obtained by modifying chitosan by using 3, 4-dihydroxyphenyl propionic acid and 4-pentenoic acid increases the solubility of the chitosan derivative in water after modification and increases the abundance of oxygen-containing groups, thereby further promoting gelation.
Meanwhile, in a further scheme, thioglycollic acid is utilized to graft and modify chitosan, and then acyl chlorination and azide are sequentially carried out to form chitosan derivatives, and as the azide groups can generate stable crystalline substances with calcium ions in cement, the cohesive force of cement mortar is increased; meanwhile, the cement mortar is filled in the gaps of the cement mortar, so that the penetration channels are reduced. In addition, the grafting of the azide groups ensures that the chitosan derivative has higher dispersibility and surface activity, thereby ensuring the fluidity of the cement mortar, enabling the cement mortar particles to form a more stable dispersion system, improving the stability of the cement mortar, and further increasing the compression resistance and the impermeability of the cement mortar. It should be noted that: the addition amount of the chitosan derivative needs to be limited, and too high of the chitosan derivative can affect the fluidity of the cement mortar, thereby causing the quality performance of the hardened cement mortar to be reduced.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: the preparation method of the cement mortar doped with the iron tailing sand comprises the following steps:
step 1: (1) Adding iron tailing sand into 5wt% hydrochloric acid solution, wherein the solid-liquid mass is 1:8, and performing primary activation treatment for 4 hours at 75 ℃; transferring into 3wt% sodium hydroxide solution with solid-liquid mass of 1:8, and performing secondary activation treatment at 85 ℃ for 6 hours; filtering and drying to obtain activated iron tailing sand; (2) Uniformly mixing 20 parts of activated iron tailing sand and 80 parts of standard sand to obtain a sand material composition;
step 2: (1) S1: adding 10 parts of chitosan into 60 parts of deionized water, stirring for dissolution, and adjusting the pH to be 5.6; simultaneously dropwise adding a solution A (7 parts of 3, 4-dihydroxyphenylpropionic acid, 3.2 parts of 4-pentenoic acid and 30 parts of deionized water) containing 3, 4-dihydroxyphenylpropionic acid and 4-pentenoic acid, adding a solution B (0.1 part of 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 10 parts of deionized water) containing 1-ethyl- (3-dimethylaminopropyl) carbodiimide, stirring at room temperature for 12 hours, and purifying to obtain modified chitosan; s2: adding modified chitosan into N, N-dimethylformamide (the mass of the N, N-dimethylformamide is 10 times of that of the modified chitosan), adding thioglycollic acid and azodiisobutyronitrile, stirring at room temperature, and carrying out illumination reaction for 2 hours under the irradiation of an ultraviolet lamp; dropwise adding thionyl chloride under ice bath; reacting for 4 hours at 65 ℃, thermally filtering, washing the precipitate with carbon tetrachloride, and drying to obtain the acyl chloride chitosan; wherein, the ratio of the modified chitosan, the thioglycollic acid and the thionyl chloride is 10g:2.5g:15mL; the addition amount of the azodiisobutyronitrile accounts for 0.1wt% of the modified chitosan) S3: adding acyl chloride chitosan into acetone (the mass of the acetone is 15 times of that of the acyl chloride chitosan), and uniformly stirring; dropwise adding a 6wt% sodium azide solution (the mass ratio of chitosan acyl chloride to sodium azide in the sodium azide solution is 10:2.5) in an ice bath, continuously stirring at room temperature for 3 hours after the dropwise adding is finished, and purifying to obtain chitosan azide, wherein the chitosan azide is taken as a chitosan derivative;
adding the fly ash into 0.5mol/L disodium hydrogen phosphate solution, and uniformly dispersing the fly ash by ultrasonic, wherein the solid-liquid ratio of the fly ash to the disodium hydrogen phosphate solution is 1g to 5mL to obtain a mixed solution; carrying out microwave hydrothermal reaction on the mixed solution for 30 minutes at the power of 1800W and the temperature of 180 ℃, filtering and drying to obtain modified fly ash by a hydrothermal method;
uniformly mixing 7 parts of fly ash, 5 parts of modified fly ash by a hydrothermal method and 12 parts of chitosan derivative to obtain a fly ash composition;
step 3: uniformly mixing 24 parts of fly ash composition with 25 parts of magnetized water, adding 100 parts of sand material composition, stirring and mixing, adding 25 parts of cement, and homogenizing to obtain cement mortar.
Example 2: the preparation method of the cement mortar doped with the iron tailing sand comprises the following steps:
step 1: (1) Adding iron tailing sand into 5wt% hydrochloric acid solution, wherein the solid-liquid mass is 1:8, and performing primary activation treatment for 4 hours at 75 ℃; transferring into 3wt% sodium hydroxide solution with solid-liquid mass of 1:8, and performing secondary activation treatment at 85 ℃ for 6 hours; filtering and drying to obtain activated iron tailing sand; (2) Uniformly mixing 20 parts of activated iron tailing sand and 80 parts of standard sand to obtain a sand material composition;
step 2: (1) S1: adding 10 parts of chitosan into 60 parts of deionized water, stirring for dissolution, and adjusting the pH to be 5.6; simultaneously dropwise adding a solution A (7 parts of 3, 4-dihydroxyphenylpropionic acid, 3.2 parts of 4-pentenoic acid and 30 parts of deionized water) containing 3, 4-dihydroxyphenylpropionic acid and 4-pentenoic acid, adding a solution B (0.1 part of 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 10 parts of deionized water) containing 1-ethyl- (3-dimethylaminopropyl) carbodiimide, stirring at room temperature for 12 hours, and purifying to obtain modified chitosan; s2: adding modified chitosan into N, N-dimethylformamide (the mass of the N, N-dimethylformamide is 10 times of that of the modified chitosan), adding thioglycollic acid and azodiisobutyronitrile, stirring at room temperature, and carrying out illumination reaction for 2 hours under the irradiation of an ultraviolet lamp; dropwise adding thionyl chloride under ice bath; reacting for 4 hours at 65 ℃, thermally filtering, washing the precipitate with carbon tetrachloride, and drying to obtain the acyl chloride chitosan; wherein, the ratio of the modified chitosan, the thioglycollic acid and the thionyl chloride is 10g:2.5g:15mL; the addition amount of the azodiisobutyronitrile accounts for 0.1wt% of the modified chitosan) S3: adding acyl chloride chitosan into acetone (the mass of the acetone is 15 times of that of the acyl chloride chitosan), and uniformly stirring; dropwise adding a 6wt% sodium azide solution (the mass ratio of chitosan acyl chloride to sodium azide in the sodium azide solution is 10:2.5) in an ice bath, continuously stirring at room temperature for 3 hours after the dropwise adding is finished, and purifying to obtain chitosan azide, wherein the chitosan azide is taken as a chitosan derivative;
(2) Adding the fly ash into 0.5mol/L disodium hydrogen phosphate solution, and uniformly dispersing the fly ash by ultrasonic, wherein the solid-liquid ratio of the fly ash to the disodium hydrogen phosphate solution is 1g to 5mL to obtain a mixed solution; carrying out microwave hydrothermal reaction on the mixed solution for 30 minutes at the power of 1800W and the temperature of 180 ℃, filtering and drying to obtain modified fly ash by a hydrothermal method;
(3) Uniformly mixing 10 parts of fly ash, 3 parts of modified fly ash by a hydrothermal method and 9 parts of chitosan derivative to obtain a fly ash composition;
step 3: and uniformly mixing 21 parts of the fly ash composition with 20 parts of magnetized water, adding 100 parts of the sand material composition, stirring and mixing, adding 30 parts of cement, and homogenizing to obtain the cement mortar.
Example 3: the preparation method of the cement mortar doped with the iron tailing sand comprises the following steps:
step 1: (1) Adding iron tailing sand into 5wt% hydrochloric acid solution, wherein the solid-liquid mass is 1:8, and performing primary activation treatment for 4 hours at 75 ℃; transferring into 3wt% sodium hydroxide solution with solid-liquid mass of 1:8, and performing secondary activation treatment at 85 ℃ for 6 hours; filtering and drying to obtain activated iron tailing sand; (2) Uniformly mixing 20 parts of activated iron tailing sand and 80 parts of standard sand to obtain a sand material composition;
step 2: (1) S1: adding 10 parts of chitosan into 60 parts of deionized water, stirring for dissolution, and adjusting the pH to be 5.6; simultaneously dropwise adding a solution A (7 parts of 3, 4-dihydroxyphenylpropionic acid, 3.2 parts of 4-pentenoic acid and 30 parts of deionized water) containing 3, 4-dihydroxyphenylpropionic acid and 4-pentenoic acid, adding a solution B (0.1 part of 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 10 parts of deionized water) containing 1-ethyl- (3-dimethylaminopropyl) carbodiimide, stirring at room temperature for 12 hours, and purifying to obtain modified chitosan; s2: adding modified chitosan into N, N-dimethylformamide (the mass of the N, N-dimethylformamide is 10 times of that of the modified chitosan), adding thioglycollic acid and azodiisobutyronitrile, stirring at room temperature, and carrying out illumination reaction for 2 hours under the irradiation of an ultraviolet lamp; dropwise adding thionyl chloride under ice bath; reacting for 4 hours at 65 ℃, thermally filtering, washing the precipitate with carbon tetrachloride, and drying to obtain the acyl chloride chitosan; wherein, the ratio of the modified chitosan, the thioglycollic acid and the thionyl chloride is 10g:2.5g:15mL; the addition amount of the azodiisobutyronitrile accounts for 0.1wt% of the modified chitosan) S3: adding acyl chloride chitosan into acetone (the mass of the acetone is 15 times of that of the acyl chloride chitosan), and uniformly stirring; dropwise adding a 6wt% sodium azide solution (the mass ratio of chitosan acyl chloride to sodium azide in the sodium azide solution is 10:2.5) in an ice bath, continuously stirring at room temperature for 3 hours after the dropwise adding is finished, and purifying to obtain chitosan azide, wherein the chitosan azide is taken as a chitosan derivative;
(2) Adding the fly ash into 0.5mol/L disodium hydrogen phosphate solution, and uniformly dispersing the fly ash by ultrasonic, wherein the solid-liquid ratio of the fly ash to the disodium hydrogen phosphate solution is 1g to 5mL to obtain a mixed solution; carrying out microwave hydrothermal reaction on the mixed solution for 30 minutes at the power of 1800W and the temperature of 180 ℃, filtering and drying to obtain modified fly ash by a hydrothermal method;
(3) Uniformly mixing 8 parts of fly ash, 5 parts of modified fly ash by a hydrothermal method and 10 parts of chitosan derivative to obtain a fly ash composition;
step 3: and uniformly mixing 23 parts of the fly ash composition with 25 parts of magnetized water, adding 100 parts of the sand material composition, stirring and mixing, adding 27 parts of cement, and homogenizing to obtain the cement mortar.
Comparative example 1: based on example 3, the chitosan derivative was replaced in the fly ash composition, and the rest was the same as in example 3, with the following specific modification steps: in the step (1) of the step 2, 10 parts of chitosan is added into 60 parts of deionized water, stirred and dissolved, and the pH=5.6 is adjusted; simultaneously dropwise adding a solution A (7 parts of 3, 4-dihydroxyphenylpropionic acid, 3.2 parts of 4-pentenoic acid and 30 parts of deionized water) containing 3, 4-dihydroxyphenylpropionic acid and 4-pentenoic acid, adding a solution B (0.1 part of 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 10 parts of deionized water) containing 1-ethyl- (3-dimethylaminopropyl) carbodiimide, stirring at room temperature for 12 hours, and purifying to obtain modified chitosan; this was used as a chitosan derivative.
Comparative example 2: based on example 3, the chitosan derivative content was increased in the fly ash composition, and the rest was the same as in example 3, with the following specific modification steps: in the step (3) of the step 2, 5 parts of fly ash, 3 parts of modified fly ash by a hydrothermal method and 15 parts of chitosan derivative are uniformly mixed to obtain a fly ash composition.
Comparative example 3: based on example 3, the fly ash composition was modified without introducing a hydrothermal method, and the rest was the same as in example 3, with the following specific modification steps: in the step (3) of the step 2, 13 parts of fly ash and 10 parts of chitosan derivative are uniformly mixed to obtain the fly ash composition.
Comparative example 4: based on example 3, the concentration of sodium hydroxide solution during the activation treatment was modified, and the rest was the same as in example 3, with the following modification steps: in the step (1), iron tailing sand is added into 5wt% hydrochloric acid solution, the solid-liquid mass is 1:8, and the primary activation treatment is carried out for 4 hours at 75 ℃; transferring into 5wt% sodium hydroxide solution with solid-liquid mass of 1:8, and performing secondary activation treatment at 85 ℃ for 6 hours; filtering and drying to obtain the activated iron tailing sand.
Detection experiment 1: the cement mortars prepared in examples and comparative examples were put into a test mold, and cured at 23℃under 60% relative humidity for 7 days to form 40X 160mm after molding 3 Is loaded at a constant speed at a speed of 2500N/S, and the compressive strength is tested; the test is carried out by referring to the process of 15 impervious performance test in JGJ/T-2009 building mortar basic performance test method Standard, wherein the curing time after demolding is 14 days, and the maximum pressure during water seepage is obtained; the specific data are shown in the following table:
conclusion: from the data in the table above, it can be seen that: according to the cement mortar, the iron tailing sand is subjected to composite activation, and meanwhile, the defect of the iron tailing sand is effectively improved through the fly ash composition with a specific proportion, so that the cement mortar with excellent compression resistance and impermeability is obtained. Comparing the data of example 3 with the data of comparative examples 1-5, the data change indicates: in comparative example 1, the chitosan derivative was not diazotized, so that the performance was lowered; in comparative example 2, fluidity was changed due to the change in the content of chitosan derivative in the fly ash composition, resulting in a decrease in the overall properties; in comparative example 3, since the hydrothermal method modified fly ash was not introduced into the fly ash composition, the compression resistance and the permeation resistance were lowered; in comparative example 4, the surface activity of the iron tailings was changed due to the change in the concentration of sodium hydroxide in the activation treatment, resulting in a decrease in performance.
In the above embodiment, it should be noted that: the parts are calculated according to parts by weight; all raw material buyers involved are not limited in any way and include, illustratively: hydrochloric acid is commercially available, with a mass fraction of about 37; the brand of the chitosan is sigma, and the product number is the molecular weight 448877 in the chitosan; thionyl chloride having a purity of 99%, 3, 4-dihydroxyphenylpropionic acid having a CAS number of 1078-61-1, 4-pentenoic acid having a CAS number of 591-80-0, 1-ethyl- (3-dimethylaminopropyl) carbodiimide having a CAS number of 25952-53-8, thioglycollic acidThe CAS number is 68-11-1, the CAS number of sodium azide is 26628-22-8, and the CAS number of disodium hydrogen phosphate is 7558-79-4, all of which are commercially available; the main component of the iron tailing sand is silicon dioxide, and then aluminum oxide, and the specific surface area is about 400m 2 Kg, average particle size about 35 microns; the standard sand is ISO standard sand; the cement is Portland cement with PI42.5 and density of 3.0g/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The density of the fly ash is 2.03g/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The magnetized water is prepared by circulating 80 times under the magnetic field intensity of 1.4T and the single circulation time is 36 seconds.
Finally, it should be noted that: 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 (9)
1. A preparation method of cement mortar doped with iron tailing sand is characterized by comprising the following steps: the method comprises the following steps:
step 1: (1) Adding iron tailing sand into hydrochloric acid solution for primary activation treatment; transferring into sodium hydroxide solution, performing secondary activation treatment, filtering, and drying to obtain activated iron tailing sand; (2) Uniformly mixing activated iron tailing sand and standard sand to obtain a sand material composition;
step 2: (1) Adding chitosan into deionized water, stirring and dissolving, and adjusting the pH to be 5.5+/-0.2; simultaneously dropwise adding a solution A containing 3, 4-dihydroxyphenylpropionic acid and 4-pentenoic acid, adding a solution B containing 1-ethyl- (3-dimethylaminopropyl) carbodiimide, stirring at room temperature for 12-15 hours, and purifying to obtain modified chitosan, wherein the modified chitosan is used as a chitosan derivative; (2) Adding the fly ash into the disodium hydrogen phosphate solution, and uniformly dispersing by ultrasonic waves to obtain a mixed solution; carrying out microwave hydrothermal reaction on the mixed solution for 30-60 minutes at the power of 1500-1800W and the temperature of 180-200 ℃, and filtering and drying to obtain modified fly ash by a hydrothermal method; (3) Uniformly mixing the fly ash, the modified fly ash by a hydrothermal method and the chitosan derivative to obtain a fly ash composition;
step 3: and uniformly mixing the fly ash composition with magnetized water, adding the sand material composition, stirring and mixing, adding cement, and homogenizing to obtain the cement mortar.
2. The method for preparing the cement mortar doped with the iron tailing sand according to claim 1, wherein the method comprises the following steps: the cement mortar comprises the following raw materials: 100 parts of sand material composition, 20-25 parts of fly ash composition, 25-30 parts of cement and 20-25 parts of magnetized water.
3. The method for preparing the cement mortar doped with the iron tailing sand according to claim 1, wherein the method comprises the following steps: the sand material composition comprises the following materials: 20-25 parts of activated iron tailing sand and 75-80 parts of standard sand in parts by weight; the fly ash composition comprises the following materials: 7-10 parts of fly ash, 3-5 parts of modified fly ash by a hydrothermal method and 9-12 parts of chitosan derivative.
4. The method for preparing the cement mortar doped with the iron tailing sand according to claim 1, wherein the method comprises the following steps: in the step 1, the solid-liquid ratio of the iron tailing sand to the hydrochloric acid solution or the sodium hydroxide solution is 1 (5-10); the content of the hydrochloric acid in the hydrochloric acid solution is 4.8-5wt%; the content of sodium hydroxide in the sodium hydroxide solution is 3-3.2wt%; the temperature of the primary activation treatment is 70-80 ℃ and the time is 3-4 hours; the temperature of the secondary activation treatment is 80-90 ℃ and the time is 4-6 hours.
5. The method for preparing the cement mortar doped with the iron tailing sand according to claim 1, wherein the method comprises the following steps: the concentration of the disodium hydrogen phosphate solution is 0.25-1 mol/L; the solid-to-liquid ratio of the fly ash to the disodium hydrogen phosphate solution is 1g (3-5) mL.
6. The method for preparing the cement mortar doped with the iron tailing sand according to claim 1, wherein the method comprises the following steps: the raw materials of the modified chitosan comprise the following materials: 10 parts of chitosan, 5-7 parts of 3, 4-dihydroxyphenylpropionic acid, 3-4 parts of 4-pentenoic acid and 0.1-0.12 part of 1-ethyl- (3-dimethylaminopropyl) carbodiimide.
7. The method for preparing the cement mortar doped with the iron tailing sand according to claim 1, wherein the method comprises the following steps: the preparation method of the chitosan derivative comprises the following steps:
(1) Adding modified chitosan into N, N-dimethylformamide, adding thioglycollic acid and a photoinitiator, stirring at room temperature, and carrying out ultraviolet irradiation reaction for 1-2 hours; dropwise adding thionyl chloride at the temperature of 0-5 ℃; reacting for 3-4 hours at 60-65 ℃, thermally filtering, washing the precipitate with carbon tetrachloride, and drying to obtain acyl chloride chitosan;
(2) Adding acyl chloride chitosan into acetone, and stirring uniformly; and (3) dropwise adding a sodium azide solution with the concentration of 6-8wt% at the temperature of 0-5 ℃, continuously stirring for 3-5 hours, and purifying to obtain chitosan azide, wherein the chitosan azide is used as a chitosan derivative.
8. The method for preparing the cement mortar doped with the iron tailing sand according to claim 7, wherein the method comprises the following steps: the ratio of the modified chitosan to the thioglycollic acid to the thionyl chloride is 10g (2-3 g) (12-15 mL); the mass ratio of the chitosan chloride to the sodium azide in the sodium azide solution is 10 (2-3).
9. The cement mortar prepared by the preparation method of the cement mortar doped with iron tailing sand according to any one of claims 1 to 8.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105884281A (en) * | 2016-04-19 | 2016-08-24 | 东南大学 | High-ductility fiber cement impervious wall prepared from tailing sand and preparation method of high-ductility fiber cement impervious wall |
| CN109665754A (en) * | 2019-02-26 | 2019-04-23 | 焦作大学 | A kind of energy conservation and environmental protection green construction material and preparation method thereof |
| CN112897940A (en) * | 2021-02-04 | 2021-06-04 | 天津住建混凝土有限公司 | Wet-mixed mortar and preparation method thereof |
| KR20230135720A (en) * | 2022-03-16 | 2023-09-26 | 원광대학교산학협력단 | Cement mortar composition comprising chitosan-based polymer and steel slag fine aggregate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105884281A (en) * | 2016-04-19 | 2016-08-24 | 东南大学 | High-ductility fiber cement impervious wall prepared from tailing sand and preparation method of high-ductility fiber cement impervious wall |
| CN109665754A (en) * | 2019-02-26 | 2019-04-23 | 焦作大学 | A kind of energy conservation and environmental protection green construction material and preparation method thereof |
| CN112897940A (en) * | 2021-02-04 | 2021-06-04 | 天津住建混凝土有限公司 | Wet-mixed mortar and preparation method thereof |
| KR20230135720A (en) * | 2022-03-16 | 2023-09-26 | 원광대학교산학협력단 | Cement mortar composition comprising chitosan-based polymer and steel slag fine aggregate |
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