CN116947338A - Composite biomass binder modified alkali-activated cementing material and preparation method thereof - Google Patents
Composite biomass binder modified alkali-activated cementing material and preparation method thereof Download PDFInfo
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- CN116947338A CN116947338A CN202310840966.5A CN202310840966A CN116947338A CN 116947338 A CN116947338 A CN 116947338A CN 202310840966 A CN202310840966 A CN 202310840966A CN 116947338 A CN116947338 A CN 116947338A
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- Prior art keywords
- starch
- solid waste
- alkali
- cementing material
- industrial solid
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- 239000000463 material Substances 0.000 title claims abstract description 87
- 239000002028 Biomass Substances 0.000 title claims abstract description 70
- 239000003513 alkali Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000011230 binding agent Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000002910 solid waste Substances 0.000 claims abstract description 89
- 229920002472 Starch Polymers 0.000 claims abstract description 70
- 235000019698 starch Nutrition 0.000 claims abstract description 65
- 239000008107 starch Substances 0.000 claims abstract description 65
- 230000005284 excitation Effects 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims description 54
- 241000196324 Embryophyta Species 0.000 claims description 49
- 239000002245 particle Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002893 slag Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000010902 straw Substances 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 12
- 229920002261 Corn starch Polymers 0.000 claims description 10
- 239000008120 corn starch Substances 0.000 claims description 10
- 244000060011 Cocos nucifera Species 0.000 claims description 9
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 241000209140 Triticum Species 0.000 claims description 8
- 235000021307 Triticum Nutrition 0.000 claims description 8
- 239000004568 cement Substances 0.000 claims description 8
- 239000010881 fly ash Substances 0.000 claims description 8
- 240000007594 Oryza sativa Species 0.000 claims description 7
- 235000007164 Oryza sativa Nutrition 0.000 claims description 7
- 235000009566 rice Nutrition 0.000 claims description 7
- 240000004922 Vigna radiata Species 0.000 claims description 6
- 235000010721 Vigna radiata var radiata Nutrition 0.000 claims description 6
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 6
- 240000003183 Manihot esculenta Species 0.000 claims description 5
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 5
- 240000008042 Zea mays Species 0.000 claims description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 5
- 235000005822 corn Nutrition 0.000 claims description 5
- 229940100445 wheat starch Drugs 0.000 claims description 5
- 229920001592 potato starch Polymers 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 241000609240 Ambelania acida Species 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000010905 bagasse Substances 0.000 claims description 3
- 235000013339 cereals Nutrition 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- 239000010903 husk Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 240000002853 Nelumbo nucifera Species 0.000 claims description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 2
- 235000003283 Pachira macrocarpa Nutrition 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 240000001085 Trapa natans Species 0.000 claims description 2
- 235000014364 Trapa natans Nutrition 0.000 claims description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 235000009165 saligot Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 235000019794 sodium silicate Nutrition 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 9
- 230000007774 longterm Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 238000002156 mixing Methods 0.000 description 8
- 238000005056 compaction Methods 0.000 description 7
- 229920000876 geopolymer Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/1535—Mixtures thereof with other inorganic cementitious materials or other activators with alkali metal containing activators, e.g. sodium hydroxide or waterglass
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the technical field of industrial solid waste resource utilization and building materials, and provides a composite biomass binder modified alkali-activated cementing material and a preparation method thereof. The alkali-activated gelling material comprises the following components: alkali excitant, composite biomass binder and industrial solid waste; the composite biomass binder comprises the following components: plant biomass and starch; the alkali-activated cementing material is prepared by activating and exciting plant biomass in an alkali-activated agent solution at room temperature, and then sequentially adding starch and industrial solid wastes. The invention has the advantages of wide raw material sources, reproducibility, low price and environmental friendliness, wherein the starch provides early strength for the cementing material, and the plant biomass is better dispersed in the cementing material after being subjected to alkaline excitation modification, so that the cementing material with uniformly distributed fiber network is obtained, and meanwhile, the early and long-term strength improvement of the cementing material is realized, so that the invention has wide application.
Description
Technical Field
The invention belongs to the technical field of industrial solid waste resource utilization and building materials, and provides a composite biomass binder modified alkali-activated cementing material and a preparation method thereof.
Background
The alkali-activated cementing material uses solid waste as a raw material, has a simple preparation process, does not need high-temperature calcination, can be used as a new material for replacing Portland cement, can simultaneously reduce carbon emission, reduce energy consumption and realize the recycling of industrial solid waste, but has mechanical strength, long-term stability and other performances which are inferior to those of the conventional Portland cement; in addition, the containing interval of the alkali-activated cementing material for the water-cement ratio is smaller, and when the water-cement ratio is larger, the structure collapse can be caused; the above problems further limit the development of alkali-activated materials and slow down their progress in replacing portland cement.
Chinese patent No. CN101570425B discloses an inorganic geopolymer composite cementing material reinforced by organic fibers, wherein the composite cementing material is prepared by adding organic fibers into an alkali-activated cementing material, the highest flexural strength of the composite cementing material in 28 days is improved by 1.6MPa compared with that of a phosphorus slag geopolymer, and the highest compressive strength in 28 days is increased by 28.4MPa compared with that of the phosphorus slag geopolymer; the reinforcing and toughening effects of the cementing material are realized; however, the added fibers are not easy to uniformly disperse in the slurry, and the addition of the fibers can reduce the fluidity of the slurry, so that the construction difficulty is increased.
At present, the research is carried out on adding a water-soluble polymer material into an inorganic alkali-activated cementing material to obtain an organic/inorganic hybrid composite material, and the mechanical properties of the alkali-activated cementing material can be improved. Chinese patent No. CN109970377B discloses a method for preparing water-soluble organic polymer toughened slag-based geopolymer cementing material, which uses water-soluble polymer organic matter polyvinyl alcohol powder. Chinese patent No. CN111943532B discloses a method for preparing geopolymer-based organic-inorganic composite gel material, in which aqueous epoxy resin emulsion is added during the preparation process. Chinese patent No. CN101560068B discloses a method for preparing composite gel material of composite organic high molecular reinforced kaolin and slag-based geopolymer, which uses binary compound polyvinyl acetate emulsion powder and polyacrylate resin emulsion.
The technical proposal for preparing the alkali-activated cementing material introduces water-soluble polymer materials, and the strength of the alkali-activated cementing material is improved although the types of the organic polymers are different. However, the high molecular polymer used in the prior art is expensive, so that the carbon emission of the full life cycle of the alkali-activated cementing material is increased, and the price advantage of the alkali-activated cementing material over conventional cement is reduced.
The Chinese patent application CN116003002A discloses a multi-solid waste-based inorganic cementing material, which comprises the following components in parts by mass: 40-50 parts of fly ash, 2535 parts of gangue powder, 0.52 part of cementing agent and 12 parts of alkali-exciting agent; the preparation method of the cementing agent comprises the following steps: taking honey, aluminum sulfate, diethanolamine and phosphoric acid as raw materials, and mixing and adding water to generate a cementing agent; the cementing agent and the alkali-exciting agent are utilized to synergistically increase the flowability and strength of the cementing material.
In order to further reduce the preparation cost of the alkali-activated cementing material, improve the performances of compressive strength, flexural strength and the like, the preparation of the cementing material by adopting different cementing agent modified alkali-activated agents is still to be further researched.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of a cementing material using a composite biomass binder to replace organic artificial fibers and a high polymer binder. The used composite biomass binder comprises plant biomass and starch, wherein the plant biomass contains cellulose, hemicellulose and lignin, and the cellulose and the hemicellulose of the biomass are partially decomposed by alkali liquor modified biomass, so that fibers are dissociated from each other and can be well dispersed in the slurry to play a role in reinforcing and toughening. Starch has good viscosity and is a natural adhesive. The composite biomass binder provided by the invention overcomes the problems of high cost, high carbon emission and the like of using synthetic fibers and high molecular polymers, improves the strength of the cementing material, and has a good application prospect.
The invention aims to provide a composite biomass binder modified alkali-activated cementing material; the alkali-activated gelling material comprises the following components: alkali excitant, composite biomass binder and industrial solid waste; the composite biomass binder comprises the following components: plant biomass and starch.
Preferably, the mass ratio of the alkali-activated agent to the industrial solid waste is 0.1-0.25:1.
Preferably, the mass ratio of the plant biomass to the solid waste is 0.005-0.05:1.
Preferably, the mass ratio of the starch to the industrial solid waste is 0.005-0.05:1.
Preferably, the alkali-activator is at least one of sodium hydroxide, sodium silicate, sodium sulfate, sodium phosphate, sodium citrate, sodium bicarbonate, potassium hydroxide, potassium silicate, potassium sulfate, potassium phosphate, potassium citrate, and potassium bicarbonate.
Preferably, the industrial solid waste is mixed industrial solid waste composed of at least three of carbide slag, tailings, metallurgical slag, coal gangue, fly ash, desulfurized gypsum, red mud, phosphogypsum and stone processing bottom mud.
More preferably, the three components of the mixed industrial solid waste comprise at least one of carbide slag, metallurgical slag and red mud.
Preferably, the industrial solid waste particle size is less than or equal to 200 mu m.
More preferably, the industrial solid waste particle size is less than or equal to 100 mu m.
The plant biomass is at least one of bagasse, corn cob, sawdust, rice chaff, coconut husk, straw, wheat straw and corn straw;
preferably, the plant biomass is at least one of coconut shells, rice straws and wheat straws.
More preferably, the plant biomass particle size is less than or equal to 200 μm.
The starch is at least one of wheat starch, corn starch, water chestnut starch, mung bean starch, pea starch, sweet potato starch, tapioca starch, potato starch and lotus root starch.
Preferably, the starch is at least one of wheat starch, corn starch, mung bean starch, tapioca starch and pea starch.
Preferably, the starch has a particle size of 50-300. Mu.m.
More preferably, the starch particle size is 75-150 μm.
Preferably, the cement composition further comprises water.
More preferably, the mass ratio of the water to the industrial solid waste is 0.35-0.6:1.
The second object of the present invention is to provide a method for preparing the above-mentioned cementing material, comprising the following steps:
(1) Dissolving an alkali-activated agent in water, adding plant biomass for alkali activation and excitation to obtain slurry 1;
(2) To the slurry 1 is added starch, stirring and dispersing to obtain slurry 2;
(3) And adding industrial solid waste into the slurry 2, and stirring and dispersing to obtain the cementing material.
Further, in the step (1), the alkali activation excitation temperature is room temperature and the time is 2-24 hours; preferably 12-16h.
Further, in the step (2), stirring and dispersing temperature is room temperature, and the time is 5-30min; preferably 15-30min.
Further, in the step (3), stirring and dispersing temperature is room temperature, and the time is 3-10min; preferably 5-10min.
Further, before the strength of the cementing material is tested, steam curing and room temperature curing are sequentially carried out.
Further, the temperature of the steam curing is 80+/-2 ℃ and the humidity is not less than 95%; the steam curing time is 12-36h; the steam curing time is preferably 24-36 hours.
Further, the room temperature curing temperature is 20+/-2 ℃ and the humidity is not less than 95%; the curing time at room temperature is 1-28d; the curing time at room temperature is preferably 14-28d.
Compared with the prior art, the invention has the beneficial effects that:
(1) The plant biomass used in the invention can be better dispersed in the cementing material after being subjected to alkaline excitation modification, so that the problem of poor dispersibility of common fibers is solved, and the cementing material with uniformly distributed fiber network is obtained; the starch has good cementing effect and can provide early strength for the cementing material;
(2) Plant biomass and starch can improve the short-term strength of the cementing material, but the improvement of the long-term strength of the cementing material mainly depends on the excitation reaction of an alkali excitant and industrial solid wastes; the excessive content of plant biomass and starch occupies most positions of the interfaces of industrial solid waste particles, so that the contact between an alkali excitant and industrial solid waste is influenced, the dissolution reaction is further influenced, and the long-term strength of the cementing material is not facilitated; the early strength and the long-term strength of the cementing material are improved simultaneously by further optimizing the dosage of the plant biomass and the starch;
(3) The invention finally forms the solid waste-based cementing material which is modified by starch bonding, plant biomass toughening and reinforcing and alkali excitation, and the compressive strength of the solid waste-based cementing material is obviously improved by the synergistic effect of the components; meanwhile, the phenomena of low strength of the cementing material, saltpetering and the like are improved by reasonably controlling the dosage proportion of each component.
(4) The invention uses the alkali excitant to excite industrial solid waste into the cementing material, and no additional cementing material is needed, thereby realizing the reutilization of resources and reducing the cost of raw materials; the compressive strength of the product is further improved through the selection of industrial solid wastes; meanwhile, the composite biomass binder is used as plant biomass and starch, so that the method has the advantages of wide sources, reproducibility, low price, environmental friendliness and the like, and solves the problems of high cost, high carbon emission and the like of reinforcing materials and binders in the prior art.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way. The following is merely illustrative of the scope of the invention as it is claimed and many variations and modifications of the invention will be apparent to those skilled in the art in light of the disclosure, which should be construed to fall within the scope of the invention as it is further described in the following detailed description of the invention.
Example 1
The cementing material comprises the following components in percentage by mass: the mass ratio of water to solid waste is 0.4:1, the mass ratio of alkaline excitant to solid waste is 0.15:1, the mass ratio of plant biomass to solid waste is 0.03:1, and the mass ratio of starch to solid waste is 0.02:1;
the preparation process of the cementing material comprises the following steps:
(1) Completely dissolving sodium hydroxide as an alkali-exciting agent in water, adding plant biomass (rice straw, wheat straw and coconut shell according to the mass ratio of 1:1:1; the particle size is less than or equal to 200 mu m), and carrying out alkali-activating excitation for 12 hours at room temperature to obtain slurry 1;
(2) Adding starch (corn starch; particle size of 75 μm) into the slurry 1, stirring and dispersing at room temperature for 15min to obtain slurry 2;
(3) Adding industrial solid wastes (carbide slag, metallurgical slag and red mud with the mass ratio of 1:1:1; the particle size is less than or equal to 100 mu m) into the slurry 2, stirring for 5min at room temperature, and fully and uniformly mixing; obtaining slurry 3;
(4) And finally pouring the slurry 3 into a die, vibrating compaction, steam curing for 24 hours, and curing at room temperature for 28 days to obtain the cementing material product.
Example 2
The cementing material comprises the following components in percentage by mass: the mass ratio of water to solid waste is 0.4:1, the mass ratio of alkaline excitant to solid waste is 0.15:1, the mass ratio of plant biomass to solid waste is 0.05:1, and the mass ratio of starch to solid waste is 0.02:1;
the preparation process of the cementing material comprises the following steps:
(1) Completely dissolving an alkaline excitant potassium hydroxide in water, then adding plant biomass (corn stalk, bagasse, rice chaff and coconut husk with the mass ratio of 1:1:1; the particle size is less than or equal to 200 mu m), and performing alkaline activation excitation for 16 hours at room temperature to obtain slurry 1;
(2) Adding starch (wheat starch and corn starch according to a mass ratio of 1:1; the grain size is 75 mu m) into the slurry 1, and fully stirring and dispersing for 15min at room temperature to obtain slurry 2;
(3) Adding industrial solid waste (carbide slag, coal gangue and fly ash with the mass ratio of 1:1:1, and the particle size of less than or equal to 100 mu m) into the slurry 2, stirring for 5 minutes at room temperature, and fully and uniformly mixing to obtain slurry 3;
(4) And finally pouring the slurry 3 into a die, vibrating compaction, steam curing for 24 hours, and curing at room temperature for 28 days to obtain the cementing material product.
Example 3
The cementing material comprises the following components in percentage by mass: the mass ratio of water to solid waste is 0.4:1, the mass ratio of alkaline excitant to solid waste is 0.15:1, the mass ratio of plant biomass to solid waste is 0.03:1, and the mass ratio of starch to solid waste is 0.05:1;
the preparation process of the cementing material comprises the following steps:
(1) Completely dissolving sodium sulfate as an alkaline activator in water, adding plant biomass (rice straw, wheat straw and coconut shell according to the mass ratio of 1:1:1; the particle size is less than or equal to 200 mu m), and performing alkaline activation and excitation for 12 hours at room temperature to obtain slurry 1.
(2) Adding starch (mung bean starch, tapioca starch and pea starch with the mass ratio of 1:1:1 and the particle size of 200 mu m) into the slurry 1, and fully stirring and dispersing for 15min at room temperature to obtain slurry 2;
(3) Adding industrial solid waste (metallurgical slag, coal gangue and fly ash with the mass ratio of 1:1:1, and particle size of less than or equal to 100 μm) into the slurry 2, stirring for 5min at room temperature, and fully and uniformly mixing to obtain slurry 3;
(4) And finally pouring the slurry 3 into a die, vibrating compaction, steam curing for 24 hours, and curing at room temperature for 28 days to obtain the cementing material product.
Example 4
The cementing material comprises the following components in percentage by mass: the mass ratio of water to solid waste is 0.4:1, the mass ratio of alkaline excitant to solid waste is 0.15:1, the mass ratio of plant biomass to solid waste is 0.03:1, and the mass ratio of starch to solid waste is 0.02:1;
the preparation process of the cementing material comprises the following steps:
(1) Completely dissolving alkaline excitant potassium sulfate in water, then adding plant biomass (straw, wheat straw and coconut shell according to the mass ratio of 1:1:1; the particle size is less than or equal to 200 mu m), and performing alkaline activation excitation for 12 hours at room temperature to obtain slurry 1;
(2) Adding starch (corn starch; particle size of 75 μm) into the slurry 1, stirring and dispersing at room temperature for 15min to obtain slurry 2;
(3) Adding industrial solid waste (red mud, coal gangue and fly ash with the mass ratio of 1:1:1; the particle size is less than or equal to 100 mu m) into the slurry 2, stirring for 5min at room temperature, and fully and uniformly mixing to obtain slurry 3;
(4) And finally pouring the slurry 3 into a die, vibrating compaction, steam curing for 24 hours, and curing at room temperature for 28 days to obtain the cementing material product.
Example 5
The cementing material comprises the following components in percentage by mass: the mass ratio of water to solid waste is 0.4:1, the mass ratio of alkaline excitant to solid waste is 0.2:1, the mass ratio of plant biomass to solid waste is 0.03:1, and the mass ratio of starch to solid waste is 0.02:1;
the preparation process of the cementing material comprises the following steps:
(1) Completely dissolving alkaline excitant sodium hydroxide in water, then adding plant biomass (wheat straw; particle size is less than or equal to 200 mu m), and performing alkaline activation excitation for 12 hours at room temperature to obtain slurry 1;
(2) Adding starch (corn starch and mung bean starch according to a mass ratio of 1:1; the grain size is 75 μm) into the slurry 1, and fully stirring and dispersing for 15min at room temperature to obtain slurry 2;
(3) Adding industrial solid wastes (carbide slag, tailings and metallurgical slag with the mass ratio of 1:1:1; the particle size is less than or equal to 100 mu m) into the slurry 2, stirring for 5min at room temperature, and fully and uniformly mixing to obtain slurry 3;
(4) And finally pouring the slurry 3 into a die, vibrating compaction, steam curing for 24 hours, and curing at room temperature for 28 days to obtain the cementing material product.
Example 6
The cementing material comprises the following components in percentage by mass: the mass ratio of water to solid waste is 0.55:1, the mass ratio of alkaline excitant to solid waste is 0.15:1, the mass ratio of plant biomass to solid waste is 0.03:1, and the mass ratio of starch to solid waste is 0.02:1;
the preparation process of the cementing material comprises the following steps:
(1) Completely dissolving alkaline excitant sodium hydroxide in water, then adding plant biomass (coconut shell; particle size is less than or equal to 200 mu m), and performing alkaline activation excitation for 12 hours at room temperature to obtain slurry 1;
(2) Adding starch (corn starch; particle size of 75 μm) into the slurry 1, stirring and dispersing at room temperature for 15min to obtain slurry 2;
(3) Adding industrial solid wastes (carbide slag, fly ash and desulfurized gypsum according to the mass ratio of 1:1:1; the particle size is less than or equal to 100 mu m) into the slurry 2, stirring for 5min at room temperature, and fully and uniformly mixing to obtain slurry 3;
(4) And finally pouring the slurry 3 into a die, vibrating compaction, steam curing for 24 hours, and curing at room temperature for 28 days to obtain the cementing material product.
Example 7
The cementing material comprises the following components in percentage by mass: the mass ratio of water to solid waste is 0.55:1, the mass ratio of alkaline excitant to solid waste is 0.15:1, the mass ratio of plant biomass to solid waste is 0.03:1, and the mass ratio of starch to solid waste is 0.02:1;
the preparation process of the hair gel material comprises the following steps:
(1) Completely dissolving alkaline excitant sodium hydroxide in water, adding plant biomass (straw; particle size less than or equal to 200 mu m), and performing alkaline activation excitation for 12 hours at room temperature to obtain slurry 1;
(2) Adding starch (corn starch; particle size of 75 μm) into the slurry 1, stirring and dispersing at room temperature for 15min to obtain slurry 2;
(3) Adding industrial solid waste (carbide slag, metallurgical slag, coal gangue and fly ash with the mass ratio of 1:1:1:1; the particle size is less than or equal to 100 mu m) into the slurry 2, stirring for 3-10min at room temperature, and fully and uniformly mixing to obtain slurry 3;
(4) And finally pouring the slurry 3 into a die, vibrating compaction, steam curing for 12 hours, and curing at room temperature for 28 days to obtain the cementing material product.
Comparative example 1
Compared with example 1, the only difference is that: the particle size of the plant biomass and the industrial solid waste is 300-400 mu m, and the rest conditions are the same.
Comparative example 2
Compared with example 1, the only difference is that: the mass ratio of the plant biomass to the industrial solid waste is 0.001:1, and the rest conditions are the same.
Comparative example 3
Compared with example 1, the only difference is that: the mass ratio of the plant biomass to the industrial solid waste is 0.08:1, and the rest conditions are the same.
Comparative example 4
Compared with example 1, the only difference is that: the mass ratio of the alkaline excitant to the industrial solid waste is 0.03:1, and the rest conditions are the same.
Comparative example 5
Compared with example 1, the only difference is that: the mass ratio of water to industrial solid waste is 0.7:1, and the rest conditions are the same.
Comparative example 6
Compared with example 1, the only difference is that: no composite binder of plant biomass and starch is added, and the other conditions are the same.
Comparative example 7
Compared with example 1, the only difference is that: plant biomass is not added, and the mass ratio of starch to industrial solid waste is 0.05:1; the remaining conditions were the same.
Comparative example 8
Compared with example 1, the only difference is that: starch is not added, and the mass ratio of the plant biomass to the industrial solid waste is 0.05:1; the remaining conditions were the same.
Comparative example 9
Compared with example 1, the only difference is that: the mass ratio of the starch to the industrial solid waste is 0.08:1, and the rest conditions are the same.
Comparative example 10
Compared with example 1, the only difference is that: the industrial solid waste is carbide slag and metallurgical slag with the ratio of 1:1, and the rest conditions are the same.
Comparative example 11
Compared with example 1, the only difference is that: the industrial solid waste is carbide slag and red mud in a ratio of 1:1, and the rest conditions are the same.
Comparative example 12
Compared with example 1, the only difference is that: the metallurgical slag and the red mud with the industrial solid waste of 1:1 have the same rest conditions.
Comparative example 13
Compared with example 1, the only difference is that: in the preparation process of the alkali-activated cementing material, the alkali-activated activation temperature of the plant biomass is 80 ℃, and the rest conditions are the same.
The properties of the cement prepared in the above examples and comparative examples were examined, and the results are shown in Table 1.
TABLE 1 detection of the Properties of the cementing Material
As can be seen from table 1:
comparative example 1 has a low gel strength because it is difficult to obtain a dense microstructure because both the particle size of plant biomass and industrial solid wastes are too large compared with example 1;
compared with the embodiment 1, the embodiment 2 has the advantages that the plant biomass is less in amount, a complete enhanced network cannot be generated, the enhancement effect is limited, and the overall strength of the cementing material is low;
compared with the embodiment 1, the comparative example 3 has the advantages that the plant biomass content is high, and the plant biomass content can be widely distributed at the interface of the solid waste particles, so that the dissolution reaction of alkali to the solid waste is affected, and the long-term strength of the cementing material is reduced;
comparative example 4, compared with example 1, has poor excitation effect because the amount of the alkali-activator is too small, and a jelly cannot be formed between particles, and the jelly cannot be combined into a whole, so that sufficient overall strength cannot be provided; in addition, the alkali-exciting agent cannot be excessive, and excessive alkali-exciting agent can generate whiskering;
comparative example 5 compared with example 1, because the mass ratio of water to solid waste is too high, i.e., the water to ash ratio is too large, the spacing of the solid particles in the slurry is large, the colloid produced by hydration cannot fill the gaps between the particles, and in addition, too much water evaporates to leave more water gaps, thereby reducing the strength of the cementitious material;
comparative examples 6, 7 and 8 did not contain biomass and/or starch composite binder, so that the early strength of the samples was lowered and the later strength was raised as alkali excitation proceeded for a long period of time, compared with example 1; as can be seen from the comparison of comparative examples 6 and 7 with example 1, the flexural strength of the samples was drastically reduced in the absence of the plant biomass binder; in addition, the cementing material prepared by the invention achieves better compressive strength and flexural strength under the synergistic effect of plant biomass and starch in the composite binder;
comparative example 9 compared with example 1, the starch content is too high and is widely distributed at the interface of the solid waste particles, so that the dissolution reaction of alkali on the solid waste is affected, and the long-term strength of the cementing material is reduced;
as can be seen from comparison of comparative examples 10, 11 and 12 with example 1, at least three industrial solid wastes exist simultaneously, so that the compressive strength and the flexural strength of the cementing material can be synergistically enhanced;
in comparative example 13, the alkali activation excitation temperature is higher, on the one hand, the plant biomass dissolution reaction is more thoroughly carried out, the residual quantity of the fiber of the early-stage excited plant matter is reduced, and the early strength is reduced; on the other hand, too much alkali is consumed in the early stage, so that the subsequent smooth progress of alkali-activated industrial solid waste is affected, and the long-term strength is also reduced.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The composite biomass binder modified alkali-activated cementing material is characterized in that the cementing material comprises the following components: alkali excitant, composite biomass binder and industrial solid waste; the composite biomass binder comprises the following components: plant biomass and starch.
2. The cementing material according to claim 1, wherein the mass ratio of the alkali-activator to the industrial solid waste is 0.1-0.25:1; the mass ratio of the plant biomass to the industrial solid waste is 0.005-0.05:1; the mass ratio of the starch to the industrial solid waste is 0.005-0.05:1.
3. The cementitious material of claim 1, wherein said alkali-activator is at least one of sodium hydroxide, sodium silicate, sodium sulfate, sodium phosphate, sodium citrate, sodium bicarbonate, potassium hydroxide, potassium silicate, potassium sulfate, potassium phosphate, potassium citrate, and potassium bicarbonate;
the industrial solid waste is mixed industrial solid waste composed of at least three of carbide slag, tailings, metallurgical slag, coal gangue, fly ash, desulfurized gypsum, red mud, phosphogypsum and stone processing bottom mud;
the plant biomass is at least one of bagasse, corn cob, sawdust, rice chaff, coconut husk, straw, wheat straw and corn straw;
the starch is at least one of wheat starch, corn starch, water chestnut starch, mung bean starch, pea starch, sweet potato starch, tapioca starch, potato starch and lotus root starch.
4. A cementitious material in accordance with claim 3, wherein said mixed industrial solid waste comprises at least one of carbide slag, metallurgical slag and red mud;
the plant biomass is at least one of coconut shells, rice straws and wheat straws;
the starch is at least one of wheat starch, corn starch, mung bean starch, tapioca starch and pea starch.
5. The cementitious material of claim 1, wherein said industrial solid waste has a particle size of 200 μm or less; the particle size of the plant biomass is less than or equal to 200 mu m; the grain size of the starch is 50-300 mu m.
6. The cement according to claim 1, wherein the cement composition further comprises water; the mass ratio of water to industrial solid waste is 0.35-0.6:1.
7. The method for preparing a cement according to any one of claims 1 to 6, comprising the steps of:
(1) Dissolving an alkali-activated agent in water, adding plant biomass for alkali activation and excitation to obtain slurry 1;
(2) Adding starch into the slurry 1, stirring and dispersing to obtain slurry 2;
(3) And adding industrial solid waste into the slurry 2, and stirring and dispersing to obtain the cementing material.
8. The method according to claim 7, wherein in the step (1), the alkali activation excitation temperature is room temperature for 2 to 24 hours.
9. The process according to claim 7, wherein in the step (2), the stirring and dispersing temperature is room temperature for 5 to 30 minutes.
10. The process according to claim 7, wherein in the step (3), the stirring and dispersing temperature is room temperature for 3 to 10 minutes.
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| CN117843303A (en) * | 2024-01-09 | 2024-04-09 | 淮阴工学院 | Geopolymer-based composition, composite material and preparation method thereof |
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| CN117843303A (en) * | 2024-01-09 | 2024-04-09 | 淮阴工学院 | Geopolymer-based composition, composite material and preparation method thereof |
| CN117602893A (en) * | 2024-01-24 | 2024-02-27 | 南京工业大学 | High-strength high-durability biomass non-calcium cement, preparation and use methods thereof |
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