CN114988735B - Method for preparing phosphate-based geopolymer by using low-activity solid waste - Google Patents
Method for preparing phosphate-based geopolymer by using low-activity solid waste Download PDFInfo
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- 230000000694 effects Effects 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 24
- 239000010452 phosphate Substances 0.000 title claims abstract description 24
- 239000002910 solid waste Substances 0.000 title claims abstract description 24
- 229920000876 geopolymer Polymers 0.000 title description 9
- 239000000843 powder Substances 0.000 claims abstract description 83
- 239000000463 material Substances 0.000 claims abstract description 57
- 239000010438 granite Substances 0.000 claims abstract description 46
- 239000003245 coal Substances 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 239000003818 cinder Substances 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012190 activator Substances 0.000 claims abstract description 31
- 239000000292 calcium oxide Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 30
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 30
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims abstract description 30
- 235000019801 trisodium phosphate Nutrition 0.000 claims abstract description 30
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000227 grinding Methods 0.000 claims abstract description 25
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 22
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000465 moulding Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 15
- 238000004137 mechanical activation Methods 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- 239000013043 chemical agent Substances 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 21
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000004090 dissolution Methods 0.000 abstract description 6
- 230000005284 excitation Effects 0.000 abstract description 5
- 230000002308 calcification Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006703 hydration reaction Methods 0.000 description 10
- 230000036571 hydration Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- -1 silicon-oxygen-aluminum Chemical compound 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 description 1
- BXYHXVIURNMBJM-UHFFFAOYSA-N [P].[Si].[Ca] Chemical compound [P].[Si].[Ca] BXYHXVIURNMBJM-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 210000003000 inclusion body Anatomy 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 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
- 238000002386 leaching Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000007847 structural defect Effects 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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
-
- 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
- C04B12/027—Phosphate cements mixtures thereof with other inorganic cementitious materials
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a method for preparing a phosphate group polymer by using low-activity solid waste, which comprises the following steps: uniformly mixing the coal cinder and granite powder to obtain a mixture A; uniformly mixing calcium oxide and trisodium phosphate to prepare a composite excitant B; mixing the mixture A and the composite activator B, and grinding to obtain cementing material precursor powder; and uniformly mixing the cementing material precursor powder with water glass and water, and then molding and curing to obtain the cured and molded phosphate-based polymer cementing material. According to the invention, the mixture A is calcified to accelerate the dissolution and polycondensation of the soluble silicon-aluminum component; through the synergistic excitation of trisodium phosphate, the quantity and the types of gel phases are enriched, and negative effects caused by calcification are inhibited; the particle characteristics of granite powder enable the granite powder to play a role of a grinding medium in grinding, and economic cost can be reduced while grinding efficiency and early strength are remarkably improved.
Description
Technical Field
The invention relates to the technical field of preparation of cementing materials, in particular to a method for preparing a phosphate-based polymer by using low-activity solid waste.
Background
The geopolymer gel material is an alkali excitation material, and can better excite the activity of raw materials in alkali solution, so that a series of reactions occur to form gel phases with silicon-oxygen-aluminum three-dimensional network structures in space. Compared with the process of preparing the ordinary Portland cement, the method for processing the raw materials of the alkali-activated cementing material is simple, and the preparation process has the characteristics of low energy consumption, low emission and low cost. At present, polymers based on phosphorus acid groups have been further developed on the basis of conventional polymers, charge compensation cations in conventional polymers being unnecessary in phosphorus acid group polymers, since this task can be carried out by [ PO 4 ] 3- Tetrahedra. Thus, charge balance within the molecular structure can be achieved without the participation of other cations. The formation mechanism ensures that the geopolymer containing phosphate has the characteristics of smoother and denser gel structure, low frosting and low dielectric loss, and the application performance of the geopolymer is obviously improved. However, the application of the polymer with phosphate groups at present has great limitation, and most of the polymer is applied to the acidic condition of phosphoric acid and the strong base system shared by phosphate and sodium hydroxide and acts on high-activity metakaolin, fly ash, silica fume and the like, and the phosphoric acidThe principle of action of the base polymer is to be explored under mild environment and application of the base polymer to low-activity solid waste.
The coal cinder is the residue of coal in the industrial coal-fired boiler industry after being burnt in the coal-fired boiler. Because of limited access, many unused coal-fired slag is stacked in the open. If the recycling treatment is not carried out, a large amount of land is occupied, even fire disaster is caused, and the environmental hazard and the potential safety hazard are brought to the surrounding. Granite powder is powder waste generated in the process of industrial utilization of granite stone, and is discharged at will without collection and treatment, so that the growth of crops can be inhibited, farmlands are hardened, respiratory diseases are generated by people and animals, and the harm is extremely large. Therefore, how to consume a great deal of accumulated coal cinder and granite powder becomes a serious difficulty in the research of the current solid waste recycling field.
The coal cinder and granite powder contain higher silicon-aluminum components, but most of the silicon-aluminum components are stably in the lattice structure of quartz, mullite or feldspar, and only part of the silicon-aluminum components are in the glass phase, so that the dissolution speed of the silicon-aluminum components is slow, less gel components can be provided in a short time, the prepared gel material has poor strength, and the utilization of the coal cinder and the granite powder is greatly limited. Chinese patents CN202110974024.7 and CN202110974810.7 disclose two methods for mass utilization of coal cinder and granite powder and preparation of cement. However, the two utilization modes still adopt an activation means of high-temperature roasting, the leaching of the active silicon aluminum in the raw materials can be realized under the strong alkali system of calcium oxide and sodium hydroxide, and the cementing material with excellent performance can be obtained by utilizing the combined enhancement of a plurality of complex medicaments, so that the industrialized popularization of the technology is limited to a great extent.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a method for preparing a phosphate group polymer by using low-activity solid waste, which solves the technical problems of high energy consumption and complex preparation flow of coal slag or granite powder in the prior art.
In a first aspect, the present invention provides a method for preparing a phosphate-based polymer using low-activity solid waste, comprising the steps of:
preparing raw materials: uniformly mixing the coal cinder and granite powder to obtain a mixture A;
preparing chemical agents: uniformly mixing calcium oxide and trisodium phosphate to prepare a composite excitant B;
mechanical activation: mixing the mixture A and the composite activator B, and grinding to obtain cementing material precursor powder;
preparing a clean slurry: uniformly mixing the cementing material precursor powder with water glass and water to obtain clean slurry;
and (5) molding and curing: and (3) carrying out molding maintenance on the clean slurry to obtain the cured and molded phosphate group polymer gel material.
In a second aspect, the present invention provides a phosphate-based polymer obtained by the method for producing a phosphate-based polymer using low-activity solid waste provided in the first aspect of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through the co-mechanical activation of coal cinder and granite powder, under a low-alkalinity calcium-silicon-phosphorus ternary system, the dissolution and polycondensation of soluble silicon-aluminum components are accelerated through calcification of the mixture A, and through the synergistic excitation of trisodium phosphate, the quantity and the variety of gel phases are enriched, and the negative effect caused by calcification is inhibited; the method not only realizes the cooperative utilization of multiple solid wastes, but also uses granite powder to replace grinding media, establishes a self-grinding system during raw material grinding, and can obviously improve grinding efficiency and early strength and reduce economic cost; the method has the characteristics of simplicity, convenience, safety, low cost, low energy consumption, high solid waste utilization rate, environmental friendliness and high economic benefit; the cementing material prepared by the invention has high early compressive strength and better freezing resistance.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In a first aspect, the present invention provides a method for preparing a phosphate-based polymer using low-activity solid waste, comprising the steps of:
s1, preparing raw materials: uniformly mixing the coal cinder and granite powder to obtain a mixture A;
s2, preparing chemical agents: uniformly mixing calcium oxide and trisodium phosphate to prepare a composite excitant B;
s3, mechanical activation: mixing the mixture A and the composite activator B, and grinding to obtain cementing material precursor powder;
s4, preparing clean slurry: uniformly mixing the cementing material precursor powder with water glass and water to obtain clean slurry;
s5, molding and curing: and (3) carrying out molding maintenance on the clean slurry to obtain the cured and molded phosphate group polymer gel material.
The components in the chemical agent used in the invention act as follows:
calcium oxide: the calcium oxide emits heat in the hydration process, a self-heating reaction system is formed in the die cavity, and meanwhile, ca (OH) is formed 2 The aqueous solution is made alkaline during dissolution, which provides a favorable environment for the dissolution of the soluble silicon-aluminum components; ca can be introduced early in the process of [ PO 4 ] 3- Immobilized in the form of calcium phosphate series compounds, which simultaneously form A cement-like hydration product (C-S-H or C- (A) -S-H gel) and provide nucleation sites for the formation of A higher polymerization degree geopolymerization product (N-A-S-H gel) and convert [ PO ] 4 ] 3- The novel gel structure of Si-Al-P is formed in the network structure of the geopolymer, the gel phase is further complicated, and the polymerization degree of the gel is improved, so that all performances of the cementing material are improved.
Trisodium phosphate: hydrolysis of trisodium phosphate can make the solution more alkaline, providing a favorable environment for dissolution of soluble silica-alumina components. With the introduction of a calcium source, the workability of the slurry is obviously reduced, and the hydration rate of the C-S-H gel is out of control, so that a large number of inclusion bodies are generatedPreventing the polymerization reaction from proceeding in a late stage. In addition, excess Ca (OH) 2 The likelihood of dry shrinkage and cracking may increase, disrupting the formation of the three-dimensional polymer network. Trisodium phosphate is thus introduced in order to promote the progress of the polymerization and to reduce Ca (OH) which does not participate in the polymerization 2 Preventing premature hardening, swelling and cracking. Meanwhile, under the action of trisodium phosphate, the aluminosilicate precursor can be polymerized to form Si-Al-P gel. Unlike conventional geopolymerization products, the charge compensating cation of the gel is not necessary, since charge balancing can be achieved by [ PO 4 ] 3- Tetrahedral completion, a mechanism of formation that allows for incorporation of [ PO ] 4 ] 3- The geopolymer has the characteristics of smoother and denser gel structure, low frosting and low dielectric loss, and the application performance of the cementing material is obviously improved.
Water glass: the water glass is mainly used as an adjusting component of active silicon and is used for directly adjusting the active silicon content of raw materials, so that the final product has enough silicon unit structure; in addition, the water glass has viscosity, can fill gaps among particles in the early stage, plays a role of adhesion and further improves the compactness of early samples.
In the invention, the coal cinder and granite powder are respectively powder waste materials generated in the processes of mining, processing, utilizing and the like of granite stone in stone industry, wherein the powder waste materials are residual waste residues generated after coal is combusted in a coal-fired boiler in the industrial coal-fired boiler industry.
In some embodiments of the invention, the primary chemical components of the coal cinder are: CO 2 The loss on ignition is 4 to 10 weight percent, siO 2 The content is 43 to 64 weight percent, al 2 O 3 The content is 20 to 40 weight percent, fe 2 O 3 The content is 2 to 6 weight percent, and the CaO content is 1 to 3 weight percent; the primary particle size of the coal cinder is below 5 meshes.
In some embodiments of the present invention, the granite powder comprises the following main chemical components: CO 2 The loss on ignition is 0 to 2 weight percent, siO 2 The content is 60 to 80 weight percent, al 2 O 3 The content is 10 to 25 weight percentwt％，Na 2 The O content is 2 to 6 weight percent, K 2 The O content is 2 to 6 weight percent, and Fe 2 O 3 The content is 1 to 3 weight percent, and the CaO content is 1 to 3 weight percent; the initial particle size of granite powder is 50 meshes or less.
In the present invention, the mass ratio of the coal cinder to the granite powder in the mixture A is (5-20): 1, preferably (5-15): 1, more preferably (8-9): 1.
In the composite activator B of the present invention, the mass ratio of calcium oxide to trisodium phosphate is (1 to 5): 1, preferably (1.5 to 4.5): 1, and more preferably (2 to 4): 1.
In the cementing material precursor powder, the mass ratio of the mixture A to the composite exciting agent B is 1: (0.2 to 0.5), preferably 1: (0.3 to 0.4), more preferably 1: (0.3-0.35).
In some embodiments of the invention, the milling time is 4-6 minutes.
In some embodiments of the present invention, the mixture a and the composite activator B are mixed and then ground to a D90 particle size of 400 mesh or less.
In the invention, the content of the water glass is 30-50%, further 42wt%, and the modulus is 2-3.3, further 2.31; the liquid-solid ratio of the water glass to the cementing material precursor powder is 0.05-0.20 (mL/g), and further 0.1-0.15 (mL/g).
In the present invention, the liquid-solid ratio of water to the cement precursor powder is 0.26 to 0.42 (mL/g), preferably 0.30 to 0.34 (mL/g).
In the invention, the molding mode is as follows: and (5) introducing the clean slurry into a mould for vibration molding.
In the invention, the maintenance mode is as follows: sealing the die with the paste cast, curing for 12-24 hours at the temperature of 40-80 ℃, demoulding, and curing at the room temperature until the specified period of time is reached after demoulding, thus obtaining the cured and formed phosphate group polymer gel material.
In some preferred embodiments of the invention, the specified period is 3 to 28 days old. For example, 3 days, 7 days, 21 days, 28 days, etc., and those skilled in the art can choose the method according to the actual situation.
In a second aspect, the present invention provides a phosphate-based polymer obtained by the method for producing a phosphate-based polymer using low-activity solid waste provided in the first aspect of the present invention.
In order to avoid redundancy, the following examples and comparative examples of the present invention will now be described in detail with reference to the following examples, in which the following examples are set forth in detail:
the coal cinder refers to residual waste cinder after coal is combusted in a coal-fired boiler in the industry of industrial coal-fired boilers, and the main chemical components are as follows: CO 2 Loss on ignition of 6.68wt%, siO 2 The content of Al is 53.98wt% 2 O 3 The content is 30.31wt percent, fe 2 O 3 The content was 4.20wt% and the CaO content was 1.77wt%.
Granite powder refers to powder waste generated in the process of industrial utilization of granite stone, and the main chemical components are as follows: CO 2 Loss on ignition of 0.98wt%, siO 2 The content of Al is 70.01wt% 2 O 3 The content of Na is 16.32wt percent 2 O content of 4.19wt%, K 2 O content of 4.28wt%, fe 2 O 3 The content was 1.78wt% and the CaO content was 1.27wt%.
Parameters of water glass: 42wt% and modulus 2.31.
Example 1
Example 1 provides a method for preparing a phosphate-based polymer using low activity solid waste, comprising the steps of:
(1) Preparing raw materials: granite powder (with the initial particle size below 50 meshes) and coal cinder (with the initial particle size below 5 meshes) are placed in an oven, and are baked until the quality is no longer changed, and are cooled to room temperature and then are pressed according to m (coal cinder): m (granite powder) =9:1, and uniformly mixing to obtain a mixture A;
(2) Preparing chemical agents: according to m (calcium oxide): m (trisodium phosphate) =2:1, and uniformly mixing to prepare a compound excitant B;
(3) Mechanical activation: according to m (mixture A): m (composite activator B) =1: 0.35 is mixed and then is put into a vibration mill for grinding for 4min until the D90 particle size is 400 meshes, so as to obtain cementing material precursor powder;
(4) Preparing a clean slurry: adding water glass and water into the cementing material precursor powder, and uniformly stirring to obtain clean slurry; wherein the ratio of the volume (mL) of the water glass to the mass (g) of the cementing material precursor powder is 0.10; the ratio of the volume of water (mL) to the mass (g) of the cementing material precursor powder is 0.30;
(5) And (5) molding and curing: pouring the clean slurry into a mould for vibration molding to obtain a sample, sealing the sample after vibration molding by using a self-sealing bag, curing for 24 hours in a curing box at 60 ℃, demoulding, sealing the sample by using the self-sealing bag, and continuously curing at room temperature until the 7 th day to obtain the cured phosphate-based polymer cementing material.
Example 2
Example 2 provides a method for preparing a phosphate-based polymer using low activity solid waste, comprising the steps of:
(1) Preparing raw materials: granite powder (with the initial particle size below 50 meshes) and coal cinder (with the initial particle size below 5 meshes) are placed in an oven, and are baked until the quality is no longer changed, and are cooled to room temperature and then are pressed according to m (coal cinder): m (granite powder) =9:1, and uniformly mixing to obtain a mixture A;
(2) Preparing chemical agents: according to m (calcium oxide): m (trisodium phosphate) =2:1, and uniformly mixing to prepare a compound excitant B;
(3) Mechanical activation: according to m (mixture A): m (composite activator B) =1: 0.30 is mixed and then is put into a vibration mill for grinding for 4min until the D90 particle size is 400 meshes, so as to obtain cementing material precursor powder;
(4) Preparing a clean slurry: adding water glass and water into the cementing material precursor powder, and uniformly stirring to obtain clean slurry; wherein the ratio of the volume (mL) of the water glass to the mass (g) of the cementing material precursor powder is 0.15; the ratio of the volume of water (mL) to the mass (g) of the cementing material precursor powder is 0.34;
(5) And (5) molding and curing: pouring the clean slurry into a mould for vibration molding to obtain a sample, sealing the sample after vibration molding by using a self-sealing bag, curing the sample in a curing box at 80 ℃ for 12 hours, demolding, sealing the sample by using the self-sealing bag, and continuously curing the sample at room temperature until the 7 th day, thus obtaining the cured phosphate-based polymer cementing material.
Example 3
Example 3 provides a method for preparing a phosphate-based polymer using low activity solid waste, comprising the steps of:
(1) Preparing raw materials: granite powder (with the initial particle size below 50 meshes) and coal cinder (with the initial particle size below 5 meshes) are placed in an oven, and are baked until the quality is no longer changed, and are cooled to room temperature and then are pressed according to m (coal cinder): m (granite powder) =8:1, and uniformly mixing to obtain a mixture A;
(2) Preparing chemical agents: according to m (calcium oxide): m (trisodium phosphate) =1:1, and uniformly mixing to prepare a compound excitant B;
(3) Mechanical activation: according to m (mixture A): m (composite activator B) =1: 0.35 is mixed and then is put into a vibration mill for grinding for 4min until the D90 particle size is 400 meshes, so as to obtain cementing material precursor powder;
(4) Preparing a clean slurry: adding water glass and water into the cementing material precursor powder, and uniformly stirring to obtain clean slurry; wherein the ratio of the volume (mL) of the water glass to the mass (g) of the cementing material precursor powder is 0.15; the ratio of the volume of water (mL) to the mass (g) of the cementing material precursor powder is 0.32;
(5) And (5) molding and curing: pouring the clean slurry into a mould for vibration molding to obtain a sample, sealing the sample after vibration molding by using a self-sealing bag, curing for 24 hours in a curing box at 60 ℃, demoulding, sealing the sample by using the self-sealing bag, and continuously curing at room temperature until the 7 th day to obtain the cured phosphate-based polymer cementing material.
Comparative example 1
Comparative example 1 differs from example 1 only in that the content of each component in the mixture a is not uniform, specifically as follows:
preparing raw materials: granite powder (with the initial particle size below 50 meshes) and coal cinder (with the initial particle size below 5 meshes) are placed in an oven, and are baked until the quality is no longer changed, and are cooled to room temperature and then are pressed according to m (coal cinder): m (granite powder) =10:0, and mixing uniformly to obtain a mixture A.
Comparative example 2
Comparative example 2 differs from example 1 only in that the content of each component in the mixture a is not uniform, specifically as follows:
preparing raw materials: granite powder (with the initial particle size below 50 meshes) and coal cinder (with the initial particle size below 5 meshes) are placed in an oven, and are baked until the quality is no longer changed, and are cooled to room temperature and then are pressed according to m (coal cinder): m (granite powder) =0:10, and mixing uniformly to obtain a mixture A.
Comparative example 3
Comparative example 3 differs from example 1 only in that the contents of the components in the composite activator B are not uniform, specifically as follows:
preparing chemical agents: according to m (calcium oxide): m (trisodium phosphate) =1:0, and the mixture is uniformly mixed to prepare the composite activator B.
Comparative example 4
Comparative example 4 differs from example 1 only in that the contents of the respective components in the composite activator B are not uniform, specifically as follows:
preparing chemical agents: according to m (calcium oxide): m (trisodium phosphate) =0:1, and the mixture is uniformly mixed to prepare the composite activator B.
Comparative example 5
Comparative example 5 differs from example 1 only in that the content of each component in the cement precursor powder is not uniform, specifically as follows:
mechanical activation: according to m (mixture A): m (composite activator B) =1: and (3) mixing 0.10, and then grinding in a vibration mill for 4min until the D90 particle size is 400 meshes to obtain the cementing material precursor powder.
Comparative example 6
Comparative example 6 differs from example 1 only in that the content of each component in the cement precursor powder is not uniform, specifically as follows:
mechanical activation: according to m (mixture A): m (composite activator B) =1: mixing 0.60, and grinding in a vibration mill for 4min until the D90 particle size is 400 meshes to obtain the cementing material precursor powder.
Comparative example 7
Comparative example 7 differs from example 1 only in the components of the composite activator B, specifically as follows:
preparing chemical agents: according to m (sodium hydroxide): m (trisodium phosphate) =2:1, and the mixture is uniformly mixed to prepare the composite activator B.
Comparative example 8
Comparative example 8 differs from example 1 only in the components of the composite activator B, specifically as follows:
preparing chemical agents: according to m (calcium hydroxide): m (trisodium phosphate) =2:1, and the mixture is uniformly mixed to prepare the composite activator B.
Comparative example 9
Comparative example 9 differs from example 1 only in the components of the composite activator B, specifically as follows:
preparing chemical agents: according to m (phosphoric acid): m (trisodium phosphate) =2:1, and the mixture is uniformly mixed to prepare the composite activator B.
Comparative example 10
Comparative example 10 differs from example 1 only in the manner of adding the composite activator B, specifically as follows:
mechanical activation: mixing the mixture A and calcium oxide, and then putting the mixture A and the calcium oxide into a vibration mill for grinding for 4min until the particle size of D90 is 400 meshes, so as to obtain cementing material precursor powder;
preparing a clean slurry: and uniformly mixing the cementing material precursor powder with trisodium phosphate, water glass and water to obtain the clean slurry.
Comparative example 11
Comparative example 11 differs from example 1 only in the manner of adding the composite activator B, specifically as follows:
mechanical activation: mixing the mixture A and trisodium phosphate, and then putting the mixture A and trisodium phosphate into a vibration mill for grinding for 4min until the particle size of D90 is 400 meshes, so as to obtain cementing material precursor powder;
preparing a clean slurry: and uniformly mixing the cementing material precursor powder with calcium oxide, water glass and water to obtain the clean slurry.
Comparative example 12
Comparative example 12 differs from example 1 only in that no water glass was added, specifically as follows:
preparing a clean slurry: and adding water into the cementing material precursor powder, and uniformly stirring to obtain clean slurry.
Test group
The gelled materials obtained in examples 1 to 3 and comparative examples 1 to 12 were subjected to performance tests using the test criteria specified in GB 175-2007 general Portland Cement and GB/T41060-2021 method for testing the frost resistance of cement mortar, the samples were circulated 25 times in a freeze thawing cycle at-20℃to 5℃and the loss rate of compressive strength was measured after returning to room temperature to determine the frost resistance, and the results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the method in examples 1 to 3 of the present invention can prepare a cementing material with high early strength and good freezing resistance from low-activity solid waste coal cinder and granite powder.
Compared with the example 1, the sample without granite powder in the comparative example 1 is reduced in the aspects of early compressive strength and freezing resistance, because the grinding efficiency cannot be improved by the action of the micro-particle steel balls of the granite powder after the granite powder is absent, the active silicon content is reduced, and holes cannot be filled by the micro-filler effect of the granite powder, so that the pore structure of the sample is enlarged; the sample of comparative example 2, which was not blended with the coal cinder, lost almost all compressive strength because the coal cinder, which was more inactive in the system, resulted in a decrease in cement, and the sample had almost no compressive resistance, and after being pressed, significant compression deformation rather than cracking occurred.
Compared with the example 1, the compressive strength of the sample 7d is obviously reduced after only calcium oxide is added in the comparative example 3, and the exothermic effect is obvious due to the increase of the dosage of the calcium oxide, so that the hydration speed is out of control, and the severe reaction causes harmful phenomena such as swelling, cracking and the like of the product; comparative example 4 lacks the trisodium phosphate aloneThe hydration product of calcium oxide accelerates and induces the progress of polymerization reaction, resulting in a remarkable decrease in compressive strength of sample 7d while introducing excessive Na + Resulting in significant blooming.
Compared with the example 1, the addition amount of the composite activator B in the comparative example 5 is lower, the strength of the sample is obviously reduced, the excitation is not thorough enough, the generated gel phase is less, and a uniform and compact gel phase matrix is difficult to form; the addition amount of the composite activator B in the comparative example 6 is higher, and the sample simultaneously shows the negative effects (out of control of hydration speed and excessive residual metal cations) caused by the two medicaments, so that the compressive strength of the composite activator B is obviously reduced.
Compared with the example 1, the compound excitant B in the comparative example 7 consists of a strong alkaline compound excitant of sodium hydroxide and trisodium phosphate, the excitation effect of a sample is poor, and meanwhile, excessive metal cations which do not participate in the reaction are introduced to cause a frosting phenomenon to be obvious, so that the compressive strength of the obtained product is extremely low; when the composite activator B in the comparative example 8 consists of calcium hydroxide and other alkaline calcium compound composite activators of trisodium phosphate, the early strength of the sample is obviously reduced due to the hydration and heat release effects of the calcium oxide, but the compressive strength of the sample is also increased to a certain extent along with the extension of the curing time, which indicates that the rate of the polymerization reaction is obviously delayed; when the composite activator B of comparative example 9 consisted of an acidic composite activator of phosphoric acid and trisodium phosphate, the compressive strength of the sample was also extremely low, which means that the method did not have the effect of improving the compressive strength of the sample.
In comparison with example 1, in comparative example 10, [ PO ] was produced because trisodium phosphate was not added during mechanical activation 4 ] 3- Is difficult to be fixed by calcium without mechanical force, thus affecting [ PO ] 4 ] 3- The final compressive strength of the sample is reduced by incorporating into the network structure of the geopolymer and cannot reach the 42.5R standard; comparative example 11, in which calcium oxide was not added during mechanical activation, the calcium oxide was present as a single compound, and thus, it was impossible to form various complex calcium-phosphorus minerals like during mechanical grinding, and the negative effect of calcium oxide in a single compound form was observedThe effect is clearly manifested, so that the compressive strength of the test specimen is significantly reduced and the freezing resistance is also reduced due to the expansion of the volume of the test specimen.
Comparative example 12, without the addition of water glass, reduced the active silicon forming the polymer network structure compared to example 1, thereby significantly reducing the final compressive strength of the test specimen.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention takes the coal cinder and the granite powder as raw materials for preparing the cementing material, so that the low-activity coal cinder and the granite powder which are difficult to utilize can be utilized in a large scale with high benefit, and simultaneously, a new direction is provided for researching the comprehensive utilization of less coal cinder and granite powder solid wastes.
(2) According to the invention, after granite powder is added into coal cinder, the compressive strength and the freezing resistance of the prepared cementing material can be obviously improved, the compressive strength reaches 42.5R grade specified in GB 175-2007 general Portland Cement, and the strength loss rate of a sample under the action of 25 freeze thawing cycles is lower than 5%; the granite powder has high density and does not change due to the change of temperature and air components, so that the granite powder which does not participate in the reaction is used as fine aggregate in the cementing material to fill holes, has stable property, and can effectively weaken the negative influence of the external environment on the inside.
(3) According to the invention, the high-hardness granite powder is mixed in the mechanical activation process, so that the effect of micro-particle steel balls is realized during grinding, the structural damage of coal cinder caused by grinding and extrusion is more obvious, the grinding efficiency is obviously improved, and the grinding cost is reduced; the structural defects of the crystal lattice are obviously increased in the same grinding time, namely the content of soluble active silicon aluminum is increased.
(4) The compound excitant B prepared by the invention can produce a synergistic effect with remarkable effect. The alkaline environment after the composite excitant B is dissolved is favorable for dissolving silicon-aluminum components in the precursor powder of the cementing material, raw materials are provided for generating more hydration products, the hydration reaction of calcium oxide is accelerated, other gel phases are induced to form, the trisodium phosphate prevents the hydration rate from being out of control, the gel structure (Si-Al-P) of the geopolymer is optimized and complicated, so that a large amount of complicated gel phases coexist in early stages of the cementing material sample, and the early strength is greatly improved.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (6)
1. A method for preparing a phosphate-based polymer by using low-activity solid waste, which is characterized by comprising the following steps:
preparing raw materials: uniformly mixing the coal cinder and granite powder to obtain a mixture A;
preparing chemical agents: uniformly mixing calcium oxide and trisodium phosphate to prepare a composite excitant B;
mechanical activation: mixing and grinding the mixture A and the composite activator B to obtain cementing material precursor powder;
preparing a clean slurry: uniformly mixing the cementing material precursor powder with water glass and water to obtain clean slurry;
and (5) molding and curing: shaping and curing the clean slurry to obtain a cured and molded phosphate-based polymer gel material;
in the mixture A, the mass ratio of the coal cinder to the granite powder is (5-20): 1; in the composite excitant B, the mass ratio of the calcium oxide to the trisodium phosphate is (1-5): 1; in the cementing material precursor powder, the mass ratio of the mixture A to the composite exciting agent B is 1: (0.2 to 0.5); the liquid-solid ratio of the water glass to the cementing material precursor powder is 0.05-0.20 (mL/g); the liquid-solid ratio of the water to the cementing material precursor powder is 0.26-0.42 (mL/g).
2. The method for preparing the phosphate-based polymer by using the low-activity solid waste according to claim 1, wherein the mass ratio of the coal cinder to the granite powder in the mixture A is (5-15): 1.
3. The method for preparing a phosphate group polymer by using low-activity solid waste according to claim 1, wherein the mass ratio of calcium oxide to trisodium phosphate in the composite activator B is (1.5-4.5): 1.
4. The method for preparing a phosphate-based polymer by using low-activity solid waste according to claim 1, wherein the content of the water glass is 30% -50% and the modulus is 2-3.3.
5. The method for preparing a phosphate-based polymer by using low-activity solid waste according to claim 1, wherein the curing is performed by: sealing the die with the paste cast, curing for 12-24 hours at the temperature of 40-80 ℃, demolding, and curing at the room temperature until the specified period of time is reached after demolding, so as to obtain the cured and molded phosphate-based polymer cementing material.
6. A phosphoric acid-based polymer, which is obtained by the method for producing a phosphoric acid-based polymer using the low-activity solid waste according to any one of claims 1 to 5.
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