CN117285325B - A preparation process of highly water-resistant magnesium-phosphate cement-based material - Google Patents
A preparation process of highly water-resistant magnesium-phosphate cement-based material Download PDFInfo
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- CN117285325B CN117285325B CN202311332500.0A CN202311332500A CN117285325B CN 117285325 B CN117285325 B CN 117285325B CN 202311332500 A CN202311332500 A CN 202311332500A CN 117285325 B CN117285325 B CN 117285325B
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- 239000004568 cement Substances 0.000 title claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 title claims abstract 16
- 239000004137 magnesium phosphate Substances 0.000 title claims abstract 16
- 229960002261 magnesium phosphate Drugs 0.000 title claims abstract 16
- 229910000157 magnesium phosphate Inorganic materials 0.000 title claims abstract 16
- 235000010994 magnesium phosphates Nutrition 0.000 title claims abstract 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 239000010881 fly ash Substances 0.000 claims abstract description 19
- 229910021487 silica fume Inorganic materials 0.000 claims abstract description 19
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims abstract description 18
- 235000019796 monopotassium phosphate Nutrition 0.000 claims abstract description 18
- 230000003068 static effect Effects 0.000 claims abstract description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 16
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 238000000197 pyrolysis Methods 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 10
- 229910021538 borax Inorganic materials 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 10
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 10
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 10
- 239000002028 Biomass Substances 0.000 claims abstract description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000010902 straw Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000005554 pickling Methods 0.000 claims description 7
- 244000025254 Cannabis sativa Species 0.000 claims description 6
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 6
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 6
- 235000009120 camo Nutrition 0.000 claims description 6
- 235000005607 chanvre indien Nutrition 0.000 claims description 6
- 239000011487 hemp Substances 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019820 disodium diphosphate Nutrition 0.000 claims description 3
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims description 3
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 3
- 241000209140 Triticum Species 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- FLFJVPPJGJSHMF-UHFFFAOYSA-L manganese hypophosphite Chemical compound [Mn+2].[O-]P=O.[O-]P=O FLFJVPPJGJSHMF-UHFFFAOYSA-L 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 22
- 238000004090 dissolution Methods 0.000 abstract description 5
- 235000012245 magnesium oxide Nutrition 0.000 abstract description 2
- 238000005562 fading Methods 0.000 abstract 1
- LWNCNSOPVUCKJL-UHFFFAOYSA-N [Mg].[P] Chemical compound [Mg].[P] LWNCNSOPVUCKJL-UHFFFAOYSA-N 0.000 description 50
- 239000000047 product Substances 0.000 description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 15
- 239000012265 solid product Substances 0.000 description 13
- 239000002002 slurry Substances 0.000 description 8
- 238000006703 hydration reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 6
- 238000007580 dry-mixing Methods 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000004575 stone Substances 0.000 description 6
- 229910052567 struvite Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 230000005469 synchrotron radiation Effects 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 239000006012 monoammonium phosphate Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/02—Phosphate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/022—Carbon
- C04B14/026—Carbon of particular shape, e.g. nanotubes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Civil Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明涉及磷镁水泥技术领域，具体公开一种高耐水性磷镁水泥基材料的制备工艺。该制备工艺包括如下步骤：(1)将生物质碳源置于加热炉中密闭后在静态空气状态下进行热解碳化处理。完成后冷却至室温，将得到的碳化产物与磷源混合研磨成粉体，然后将该粉体置于加热炉中密闭后在静态空气状态下进行热处理。完成后冷却至室温，将得到的产物酸洗后水洗、干燥，即得改性多孔碳材料。(2)将所述改性多孔碳材料与重烧氧化镁、磷酸二氢铵或磷酸二氢钾、硼砂、粉煤灰、硅灰、细骨料、粗骨料、水复配，即得高耐水性磷镁水泥。本发明通过能够特异性吸附磷酸根离子的多孔碳材料，有效改善了磷镁水泥因磷酸根离子的溶出而造成的强度损失和泛碱的问题。
The present invention relates to the technical field of magnesium phosphate cement, and specifically discloses a preparation process of a magnesium phosphate cement-based material with high water resistance. The preparation process comprises the following steps: (1) placing a biomass carbon source in a sealed heating furnace and then performing pyrolysis and carbonization treatment under a static air state. After completion, the biomass carbon source is cooled to room temperature, the obtained carbonized product is mixed with a phosphorus source and ground into a powder, and then the powder is placed in a sealed heating furnace and then heat-treated under a static air state. After completion, the biomass carbon source is cooled to room temperature, and then the obtained product is acid-washed, washed with water, and dried to obtain a modified porous carbon material. (2) The modified porous carbon material is compounded with dead-burned magnesium oxide, ammonium dihydrogen phosphate or potassium dihydrogen phosphate, borax, fly ash, silica fume, fine aggregate, coarse aggregate, and water to obtain a magnesium phosphate cement with high water resistance. The present invention effectively improves the strength loss and alkali-fading problems of magnesium phosphate cement caused by the dissolution of phosphate ions by using a porous carbon material that can specifically adsorb phosphate ions.
Description
Technical Field
The invention relates to the technical field of phosphorus-magnesium cement-based materials, in particular to a preparation process of a high-water-resistance phosphorus-magnesium cement-based material.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The phosphorus-magnesium cement is a new type special cement, which has quick setting and hardening, high early strength and good compatibility with common silicate cement, so that the phosphorus-magnesium cement is often used for quick rush repair engineering. However, the hydration product of the phosphorus-magnesium cement, namely struvite (Struvite, mgNH 4PO4·6H2 O), has weaker water stability, and after being corroded by water, the struvite is often corroded into phosphate ions, ammonium ions and magnesium ions, migrates to the outside from pores inside the phosphorus-magnesium cement, and is recrystallized on the surface of the phosphorus-magnesium cement to generate struvite crystals again, so that the phosphorus-magnesium cement has serious strength loss and has a large-area 'whiskering' phenomenon. Therefore, improving the water resistance of phosphorus magnesium cements has been a challenging task.
Because of the specificity of the composition of the phosphorus-magnesium cement, the consumption of magnesium raw materials is often far more than that of the phosphorus raw materials, the rest magnesium serves as a framework structure to play a supporting role in the cement, hydration products begin to nucleate and grow by taking magnesium as a framework, and gradually crosslink into a reticular structure, and finally the cement body is formed. Since phosphorus is indispensable and the content is far lower than that of magnesium, reducing the dissolution of phosphorus is a fundamental measure for solving the water resistance of phosphorus-magnesium cement. The main method at present is to add mineral admixture and superfine powder into phosphorus-magnesium cement. The purpose of this method is to allow finer mineral particles to fill the pores of the cement, thereby reducing the ingress of water into the cement matrix in the external environment. However, the method does not fundamentally improve the water resistance of the phosphorus-magnesium cement, and the prepared phosphorus-magnesium cement still has the problem of insufficient water resistance.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation process of a high-water-resistance phosphorus-magnesium cement-based material, and the problems of strength loss and whiskering of phosphorus-magnesium cement caused by dissolution of phosphate ions are effectively solved by the porous carbon material capable of specifically adsorbing the phosphate ions. In order to achieve the above purpose, the present invention discloses the following technical solutions.
A preparation process of a high-water-resistance phosphorus-magnesium cement-based material comprises the following steps:
(1) And (3) placing the biomass carbon source into a heating furnace, sealing, and performing pyrolysis carbonization treatment in a static air state. Cooling to room temperature after completion, mixing and grinding the obtained carbonized product and a phosphorus source into powder, and then placing the powder into a heating furnace for sealing and then carrying out heat treatment in a static air state. And cooling to room temperature after the completion, washing the obtained product with acid, and drying to obtain the modified porous carbon material.
(2) And (3) compounding the modified porous carbon material with the re-burned magnesium oxide, ammonium dihydrogen phosphate or potassium dihydrogen phosphate, borax, fly ash, silica fume, fine aggregate, coarse aggregate and water to obtain the high-water-resistance phosphorus-magnesium cement-based material.
Further, in step (1), the biomass carbon source includes, but is not limited to: at least one of chitosan, wheat straw, wood, rice straw, hemp stalk, etc.
In the invention, the static air state refers to that air in a heating environment is not circulated or external air is introduced in the heating process, and the atmosphere environment in the initial heating state is taken as a process environment until the pyrolysis carbonization treatment or the heat treatment is finished, and the product obtained by the treatment is continuously naturally cooled to the room temperature in the environment.
Further, in the step (1), the temperature of the pyrolysis carbonization treatment is 200-700 ℃ and the time is 2-8 h.
Further, in the step (1), the mass ratio of the carbonized product to the phosphorus source is 1-3: 1. preferably, the phosphorus source includes at least one of monopotassium phosphate, sodium acid pyrophosphate, sodium metaphosphate, manganese hypophosphite, metaphosphoric acid, and the like.
Further, in the step (1), the heat treatment temperature is 200-500 ℃ and the time is 2-8 h. And introducing a phosphorus source into the carbonized product, and then performing heat treatment again in a static air state to regulate and control the carbonized product so as to form positively charged oxygen vacancies and form the porous carbon material rich in the special oxygen vacancies.
Further, in the step (1), the pickling process comprises the following steps: and (3) placing the product into citric acid or acetic acid and stirring for 10-30 min to finish the pickling process. Optionally, the mass fraction of the citric acid or the acetic acid is 5-20%. The acid washing is used for removing superfluous functional groups on the surface of the product, so that the reaction with a cement matrix is avoided, and the adsorption effect is reduced.
Further, in the step (1), the water washing process is as follows: and washing the acid-washed product with clear water until the washing liquid is neutral, thereby completing the water washing process.
Further, in the step (1), the drying temperature is 30-70 ℃ and the drying time is 12-24 h.
Further, in the step (2), the proportion of each raw material is as follows: 5 to 30 parts of modified porous carbon material, 200 to 400 parts of burned magnesia, 80 to 120 parts of ammonium dihydrogen phosphate or potassium dihydrogen phosphate, 70 to 130 parts of borax, 20 to 90 parts of fly ash, 20 to 90 parts of silica fume, 500 to 700 parts of fine aggregate, 800 to 1600 parts of coarse aggregate and 150 to 300 parts of water.
Optionally, the fineness of the monoammonium phosphate or potassium dihydrogen phosphate, the fly ash and the silica fume is 100-300 meshes.
Compared with the prior art, the technical scheme of the invention has at least the following beneficial effects:
Aiming at the problems of strength loss and alkali efflorescence caused by the dissolution of phosphate ions of the phosphorus-magnesium cement, the invention prepares the porous carbon material capable of specifically adsorbing the phosphate ions, and the porous carbon material is matched with the phosphorus-magnesium cement to radically improve the water resistance of the phosphorus-magnesium cement. The porous carbon material prepared by adopting the special process has rich oxygen vacancies and obvious electropositivity, can specifically adsorb phosphate ions in cement paste, is chemically inert, and can adsorb and release the phosphate ions according to the concentration difference of the phosphate ions in the internal environment of the phosphorus-magnesium cement. Thereby: when the phosphate cement is corroded by water, the hydration product, namely bird droppings Dan Rongshi, is phosphate ions and the like, the concentration of the phosphate ions in the phosphate cement is increased, and the excessive phosphate ions are adsorbed and stored in the porous carbon material and cannot be lost to the outside of the phosphate cement. And after the normal environment without rain wash is restored, ammonium ions and magnesium ions formed by the struvite corrosion react with phosphate ions from new water to form struvite crystals. As the cement hydration proceeds, the phosphate ions in the phosphorus-magnesium cement are gradually consumed, when the phosphate ion concentration is lower than that in the porous carbon material, the phosphate ions stored in the carbon material are released into the cement body continuously to participate in the hydration reaction, new hydration products are continuously generated until the hydration is complete, and the problems of phosphorus-magnesium cement strength loss and alkali efflorescence caused by the loss of the phosphate ions with lower content but indispensable content due to dissolution are well avoided, so that the water resistance of the phosphorus-magnesium cement is fundamentally improved.
In addition, in order to achieve the above object, the present invention proposes a process capable of preparing a porous carbon material having abundant positively charged oxygen vacancies, and first, the present invention subjects a biomass carbon source to pyrolysis carbonization treatment in a static air state, thereby being capable of forming a carbonized product while also being capable of introducing a special site of oxygen vacancies therein. Furthermore, the invention also utilizes a phosphorus source to regulate oxygen vacancies in the carbonized product, and the existence of phosphorus is used for balancing charges, increasing vacancies and increasing the adsorption quantity of phosphate ions. This is because phosphorus is less electronegative than oxygen and carbon, and therefore has less ability to attract electrons than carbon and oxygen, and has weaker adsorption ability to electrons when oxygen vacancies are formed. Oxygen atoms are less limited as they become superoxide radicals and electrons leave the matrix, thereby making it easier to create more oxygen vacancies in the carbon material.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a graph showing the effect of the modified porous carbon material prepared in example 1 of the present invention.
FIG. 2 is a graph showing the curing effect in water of the test block prepared in example 1 of the present invention.
FIG. 3 is a graph showing the compressive strength test of the test block prepared in example 1 of the present invention.
Fig. 4 is an effect diagram of the modified porous carbon material prepared in example 4 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The reagents or materials used in the present invention may be purchased in conventional manners, and unless otherwise indicated, they may be used in conventional manners in the art or according to the product specifications.
In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The technical scheme of the invention is further described with reference to the specification, the drawings and the specific embodiments.
Example 1
A preparation process of a high-water-resistance phosphorus-magnesium cement-based material comprises the following steps:
(1) Placing chitosan into a tubular furnace, heating the tubular furnace to 400 ℃ at a heating rate of 10 ℃/min in a static air state, and preserving the temperature for 5 hours to carry out pyrolysis carbonization treatment on the chitosan. And naturally cooling to room temperature after the completion of the process to obtain a carbonized product for standby.
(2) Mixing the carbonized product with sodium metaphosphate according to the following 2:1, grinding the mixture into 200-mesh powder after mixing, then placing the powder into a tube furnace, heating the tube furnace to 400 ℃ at a heating rate of 10 ℃/min in a static air state after sealing the tube furnace, and carrying out heat treatment by preserving heat for 3 hours. After completion, cooling to room temperature, adding the obtained solid product into 5% citric acid solution by mass fraction, stirring for 30min, and pickling. After completion, the solid product was separated by centrifugation and washed with clean water until the wash liquor was neutral. And then placing the solid product in an oven and drying at 70 ℃ for 12 hours to obtain the modified porous carbon material (shown in figure 1) for standby.
(3) The following raw materials are taken: 10 parts of modified porous carbon material, 300 parts of burned magnesia, 100 parts of ammonium dihydrogen phosphate, 105 parts of borax, 75 parts of fly ash, 60 parts of silica fume, 650 parts of river sand fine aggregate, 1300 parts of crushed stone coarse aggregate and 260 parts of water. Wherein: the fineness of the monoammonium phosphate, the fly ash and the silica fume is 300 meshes. And adding the solid components in the raw materials into a stirrer, dry mixing for 2min, and then adding the water, and rapidly stirring for 3min to obtain the phosphorus-magnesium cement slurry.
1. The X-ray absorption fine structure spectrum test and Zeta potential test of the modified porous carbon material synchrotron radiation prepared in the embodiment show that: oxygen vacancy content=2.57%, zeta potential=3.65 mV. It can be seen that: the modified porous carbon material has rich oxygen vacancies and obvious electropositive characteristic.
2. Mass loss rate test: the phosphorus magnesium cement slurry prepared in this example was poured into a mold having a size of 40 x 40mm, and demolding after six hours. And then curing (shown in figure 2) in water for 28 days to obtain the test block. The concrete calculation method of the mass loss rate comprises the following steps: the mass of the test block before entering water is recorded as A1, after curing in water for 28 days, the test block is taken out from the water, the water on the surface of the test block is wiped off, the mass of the test block is measured as A2, and the mass loss rate is the ratio of (A1-A2)/A1.
3. Intensity loss rate test: the phosphorus magnesium cement slurry prepared in this example was poured into a mold having a size of 40 x 40mm, and demolding after six hours. And curing in the air for 28 days to obtain the test block. Test pieces were prepared by the same method, and after demolding, were left in water for curing for 28 days. The specific calculation method of the intensity loss rate comprises the following steps: the compressive strength of the block obtained by curing in air for 28 days was denoted as B1 (see FIG. 3), the compressive strength of the block obtained by curing in water for 28 days was denoted as B2, and (B1-B2)/B1 was denoted as strength loss.
The phosphorus-magnesium cement prepared by the invention can be characterized in terms of water resistance through the mass loss rate and the strength loss rate, and the test results are as follows: mass loss rate=0.77%, strength loss rate=20.04%.
Example 2
A preparation process of a high-water-resistance phosphorus-magnesium cement-based material comprises the following steps:
(1) Placing crushed straw into a tube furnace, sealing the tube furnace, heating to 700 ℃ at a heating rate of 10 ℃/min in a static air state, and preserving heat for 2 hours to carry out pyrolysis carbonization treatment on the straw. And naturally cooling to room temperature after the completion of the process to obtain a carbonized product for standby.
(2) Mixing the carbonized product with potassium dihydrogen phosphate according to the weight ratio of 1.5:1, grinding the mixture into 200-mesh powder after mixing, then placing the powder into a tube furnace, heating the tube furnace to 500 ℃ in a static air state at a heating rate of 10 ℃/min, and preserving heat for 2 hours for heat treatment. After completion, cooling to room temperature, adding the obtained solid product into a citric acid solution with the mass fraction of 10%, stirring for 20min, and carrying out acid washing. After completion, the solid product was separated by centrifugation and washed with clean water until the wash liquor was neutral. And then placing the solid product in an oven and drying at 30 ℃ for 24 hours to obtain the modified porous carbon material (shown in figure 4) for standby.
(3) The following raw materials are taken: 30 parts of modified porous carbon material, 400 parts of burned magnesia, 120 parts of monopotassium phosphate, 130 parts of borax, 90 parts of fly ash, 90 parts of silica fume, 700 parts of river sand fine aggregate, 1600 parts of crushed stone coarse aggregate and 300 parts of water. Wherein: the fineness of the potassium dihydrogen phosphate, the fly ash and the silica fume is 100 meshes. And adding the solid components in the raw materials into a stirrer, dry mixing for 2min, and then adding the water, and rapidly stirring for 3min to obtain the phosphorus-magnesium cement slurry.
1. And carrying out spectrum test on the X-ray absorption fine structure of the synchrotron radiation of the modified porous carbon material prepared in the embodiment. The results show that: oxygen vacancy content=2.68%, zeta potential=3.89 mV. It can be seen that: the modified porous carbon material has rich oxygen vacancies and obvious electropositive characteristic.
2. The mass loss rate and the strength loss rate of the phosphorus-magnesium cement test block prepared in this example were tested by the same method as in example 1, and the test results were: mass loss rate=0.72%, strength loss rate=17.54%.
Example 3
A preparation process of a high-water-resistance phosphorus-magnesium cement-based material comprises the following steps:
(1) Placing the crushed hemp stems into a tubular furnace, heating the tubular furnace to 200 ℃ at a heating rate of 10 ℃/min in a static air state, and preserving the heat for 8 hours to carry out pyrolysis carbonization treatment on the hemp stems. And naturally cooling to room temperature after the completion of the process to obtain a carbonized product for standby.
(2) Mixing the carbonized product with sodium acid pyrophosphate according to a ratio of 3:1, grinding the mixture into 300 meshes of powder after mixing, then placing the powder into a tube furnace, heating the tube furnace to 200 ℃ at a heating rate of 10 ℃/min in a static air state after sealing the tube furnace, and carrying out heat treatment by preserving heat for 8 hours. After completion, cooling to room temperature, adding the obtained solid product into a citric acid solution with the mass fraction of 20%, stirring for 10min, and carrying out acid washing. After completion, the solid product was separated by centrifugation and washed with clean water until the wash liquor was neutral. And then placing the solid product in an oven and drying at 40 ℃ for 18 hours to obtain the modified porous carbon material for later use.
(3) The following raw materials are taken: the modified porous carbon material prepared in the embodiment comprises 5 parts by weight of burned magnesium oxide 200 parts by weight, potassium dihydrogen phosphate 80 parts by weight, borax 70 parts by weight, fly ash 20 parts by weight, silica fume 20 parts by weight, river sand fine aggregate 500 parts by weight, crushed stone coarse aggregate 800 parts by weight and water 150 parts by weight. Wherein: the fineness of the potassium dihydrogen phosphate, the fly ash and the silica fume is 200 meshes. And adding the solid components in the raw materials into a stirrer, dry mixing for 2min, and then adding the water, and rapidly stirring for 3min to obtain the phosphorus-magnesium cement slurry.
The spectrum test of the X-ray absorption fine structure of the synchrotron radiation of the modified porous carbon material prepared in the embodiment shows that: oxygen vacancy content=2.44%, zeta potential=3.51 mV. It can be seen that: the modified porous carbon material has rich oxygen vacancies and obvious electropositive characteristic.
2. The mass loss rate and the strength loss rate of the phosphorus-magnesium cement test block prepared in this example were tested by the same method as in example 1, and the test results were: mass loss rate=0.86%, strength loss rate=21.60%.
Example 4
A preparation process of a high-water-resistance phosphorus-magnesium cement-based material comprises the following steps: the following raw materials are taken: 300 parts of burned magnesia, 100 parts of ammonium dihydrogen phosphate, 105 parts of borax, 75 parts of fly ash, 60 parts of silica fume, 650 parts of river sand fine aggregate, 1300 parts of crushed stone coarse aggregate and 260 parts of water. Wherein: the fineness of the monoammonium phosphate, the fly ash and the silica fume is 300 meshes. And adding the solid components in the raw materials into a stirrer, dry mixing for 2min, and then adding the water, and rapidly stirring for 3min to obtain the phosphorus-magnesium cement slurry.
The mass loss rate and the strength loss rate of the phosphorus-magnesium cement test block prepared in this example were tested by the same method as in example 1, and the test results were: mass loss rate=1.79%, strength loss rate=52.14%.
Example 5
A preparation process of a high-water-resistance phosphorus-magnesium cement-based material comprises the following steps:
The following raw materials are taken: 30 parts of mineral particles (fly ash with 300 meshes), 400 parts of burned magnesia, 120 parts of monopotassium phosphate, 130 parts of borax, 90 parts of fly ash, 90 parts of silica fume, 700 parts of river sand fine aggregate, 1600 parts of crushed stone coarse aggregate and 300 parts of water. Wherein: the fineness of the potassium dihydrogen phosphate, the fly ash and the silica fume is 100 meshes. And adding the solid components in the raw materials into a stirrer, dry mixing for 2min, and then adding the water, and rapidly stirring for 3min to obtain the phosphorus-magnesium cement slurry.
The mass loss rate and the strength loss rate of the phosphorus-magnesium cement test block prepared in this example were tested by the same method as in example 1, and the test results were: mass loss rate=1.64%, intensity loss rate= 47.58%.
Example 6
A preparation process of a high-water-resistance phosphorus-magnesium cement-based material comprises the following steps:
The following raw materials are taken: 30 parts of mineral particles (silica fume with fineness of 400 meshes), 400 parts of burned magnesia, 120 parts of monopotassium phosphate, 130 parts of borax, 90 parts of fly ash, 90 parts of silica fume, 700 parts of river sand fine aggregate, 1600 parts of crushed stone coarse aggregate and 300 parts of water. Wherein: the fineness of the potassium dihydrogen phosphate, the fly ash and the silica fume is 100 meshes. And adding the solid components in the raw materials into a stirrer, dry mixing for 2min, and then adding the water, and rapidly stirring for 3min to obtain the phosphorus-magnesium cement slurry.
The mass loss rate and the strength loss rate of the phosphorus-magnesium cement test block prepared in this example were tested by the same method as in example 1, and the test results were: mass loss rate=1.68% and strength loss rate= 46.27%.
Example 7
The preparation process of the high-water-resistance phosphorus-magnesium cement-based material is the same as that of the above example 3, except that the modified porous carbon material of this example is prepared by the following method:
(1) Placing the crushed hemp stems into a tubular furnace, heating the tubular furnace to 200 ℃ at a heating rate of 10 ℃/min in a static air state, and preserving the heat for 8 hours to carry out pyrolysis carbonization treatment on the hemp stems. And naturally cooling to room temperature after the completion of the process to obtain a carbonized product for standby.
(2) And adding the carbonized product into a citric acid solution with the mass fraction of 20%, and stirring for 10min for pickling. After completion, the solid product was separated by centrifugation and washed with clean water until the wash liquor was neutral. And then placing the solid product in an oven and drying at 40 ℃ for 12 hours to obtain the modified porous carbon material.
1. And carrying out spectrum test on the X-ray absorption fine structure of the synchrotron radiation of the modified porous carbon material prepared in the embodiment. The results show that: oxygen vacancy content=2.08%, zeta potential=2.95 mV. It can be seen that: the modified porous carbon material has low oxygen vacancy content and obviously weakened electropositive characteristic.
2. The mass loss rate and the strength loss rate of the phosphorus-magnesium cement test block prepared in this example were tested by the same method as in example 1, and the test results were: mass loss rate=1.26%, strength loss rate=36.5%.
Example 8
The preparation process of the high-water-resistance phosphorus-magnesium cement-based material is the same as that of the above example 2, except that the modified porous carbon material of this example is prepared by the following method:
(1) Crushed straw was mixed with potassium dihydrogen phosphate according to 1.5:1, placing the rice straw into a tubular furnace, heating the rice straw to 700 ℃ at a heating rate of 10 ℃/min in a static air state after sealing the tubular furnace, and preserving the heat for 2 hours to carry out pyrolysis carbonization treatment on the rice straw. And naturally cooling to room temperature after the completion of the process to obtain a carbonized product for standby.
(2) The carbonized product is ground into 200-mesh powder, and then added into 10% citric acid solution by mass fraction, and stirred for 20min for pickling. After completion, the solid product was separated by centrifugation and washed with clean water until the wash liquor was neutral. And then placing the solid product in an oven and drying at 30 ℃ for 24 hours to obtain the modified porous carbon material for later use.
1. And carrying out spectrum test on the X-ray absorption fine structure of the synchrotron radiation of the modified porous carbon material prepared in the embodiment. The results show that: oxygen vacancy content=2.17%, zeta potential=3.03 mV. It can be seen that: the modified porous carbon material has relatively low oxygen vacancy content and obviously weakened electropositive characteristic.
2. The mass loss rate and the strength loss rate of the phosphorus-magnesium cement test block prepared in this example were tested by the same method as in example 1, and the test results were: mass loss = 1.07%, strength loss = 25.33%.
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.
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| CN101058213A (en) * | 2007-06-01 | 2007-10-24 | 济南大学 | Method for preparing building material with carbonization maintenance waste |
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