CN114988735A - Method for preparing phosphoric acid-based polymer by using low-activity solid waste - Google Patents
Method for preparing phosphoric acid-based polymer by using low-activity solid waste Download PDFInfo
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- CN114988735A CN114988735A CN202210737429.3A CN202210737429A CN114988735A CN 114988735 A CN114988735 A CN 114988735A CN 202210737429 A CN202210737429 A CN 202210737429A CN 114988735 A CN114988735 A CN 114988735A
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- 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
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- 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
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- 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
Abstract
The invention discloses a method for preparing a phosphoric acid-based polymer by using low-activity solid waste, which comprises the following steps: uniformly mixing the coal slag and granite powder to obtain a mixture A; mixing calcium oxide and trisodium phosphate uniformly to prepare a compound excitant B; mixing the mixture A and the composite activator B, and then grinding to obtain a cementing material precursor powder; uniformly mixing the cementing material precursor powder with water glass and water, and then molding and maintaining to obtain the cured and molded phosphoric acid-based polymer cementing material. According to the invention, the dissolution and polycondensation of soluble silicon-aluminum components are accelerated by calcification of the mixture A; the quantity and the variety of gel phases are enriched by synergistic excitation of trisodium phosphate, and the negative effect generated by calcification is inhibited; the particle characteristics of the granite powder enable the granite powder to play a role of an ore grinding medium in grinding, so that the grinding efficiency and the early strength are obviously improved, and the economic cost can be reduced.
Description
Technical Field
The invention relates to the technical field of preparation of cementing materials, in particular to a method for preparing a phosphoric acid-based polymer by using low-activity solid waste.
Background
The geopolymer gelled material is an alkali-activated material, and can well activate the activity of raw materials in an alkali solution, so that the raw materials are subjected to a series of reactions to form a gel phase with a silicon-oxygen-aluminum three-dimensional network structure in space. Compared with the process of preparing ordinary Portland cement, the raw material treatment method of the alkali-activated cementing material is simple, and the preparation method is simpleThe preparation process has the characteristics of low energy consumption, low emission and low cost. At present, the phospho-based polymers are further developed on the basis of conventional polymers in which charge compensating cations are not necessary, since this task can be represented by [ PO ] 4 ] 3- Tetrahedrally. Thus, charge balance within the molecular structure can be achieved without the involvement of other cations. The formation mechanism enables the phosphate-containing geopolymer to have the characteristics of smoother and denser gel structure, low blooming and low dielectric loss, and the application performance of the geopolymer is obviously improved. However, the application of the existing phosphate-based polymer has great limitation, most of the phosphate-based polymer is applied to the acidic condition of phosphoric acid and the strong base system shared by phosphate and sodium hydroxide and acts on metakaolin, fly ash, silica fume and the like with high activity, and the application of the action principle of the phosphate-based polymer in the mild environment and on low-activity solid waste needs to be explored urgently.
Coal-fired slag is the residual slag after coal is burned in a coal-fired boiler in the industry of industrial coal-fired boilers. Due to the limited availability, a lot of unutilized coal slag is stockpiled in the open air. If the resource treatment is not carried out, not only a large amount of land is occupied, but also fire disasters can be caused, and harm and potential safety hazards are brought to the surrounding environment. Granite stone powder is powder waste generated in the industrial utilization process of granite stone, and if the powder waste is randomly discharged without collection and treatment, the powder waste can inhibit the growth of crops, harden farmlands, cause respiratory diseases to people and animals, and is extremely harmful. Therefore, how to consume a large amount of accumulated coal slag and granite stone powder becomes a significant difficulty in the research of the field of resource utilization of the current solid wastes.
The coal-fired slag and granite powder contain higher silicon-aluminum components, but most of the silicon-aluminum components exist in the crystal lattice structure of quartz, mullite or feldspar stably, and only part of the silicon-aluminum components exist in the glass phase, so that the silicon-aluminum components are slow in dissolution speed, less gel components can be provided in a short time, the strength of the prepared gel material is poor, and the utilization of the coal-fired slag and granite powder is limited to a great extent. Chinese patents CN202110974024.7 and CN202110974810.7 disclose two methods for large-scale utilization and preparation of cementitious materials for coal slag and granite stone powder. However, the two utilization modes still use an activation means of high-temperature roasting, leaching of active silicon-aluminum in the raw materials can be realized under a strong alkali system of calcium oxide and sodium hydroxide, and a cementing material with excellent performance is obtained by joint reinforcement of a plurality of complex medicaments, so that the industrial popularization of the technology is limited to a great extent.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a method for preparing a phosphoric acid-based polymer by using low-activity solid waste, and solves the technical problems of high energy consumption and complex preparation process of coal slag or granite stone powder in the prior art.
The first aspect of the invention provides a method for preparing a phosphate-based polymer by using low-activity solid waste, which comprises the following steps:
preparing raw materials: uniformly mixing the coal slag and granite powder to obtain a mixture A;
preparing a chemical agent: mixing calcium oxide and trisodium phosphate uniformly to prepare a compound excitant B;
mechanical activation: mixing the mixture A and the composite activator B, and then grinding to obtain a cementing material precursor powder;
preparing a neat paste: uniformly mixing the cementing material precursor powder with water glass and water to obtain a neat paste;
forming and maintaining: and (4) carrying out forming maintenance on the clear slurry to obtain the cured and formed phosphoric acid-based polymer cementing material.
In a second aspect of the present invention, there is provided a phosphoric acid-based polymer obtained by the method for producing a phosphoric acid-based polymer using low-activity solid waste according to the first aspect of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the coal slag and granite stone powder are mechanically activated together, the dissolution and polycondensation of soluble silicon-aluminum components are accelerated by calcification of the mixture A under a low-alkalinity calcium-silicon-phosphorus ternary system, and the quantity and variety of gel phases are enriched by synergistic excitation of trisodium phosphate, and the negative effect generated by calcification is inhibited; the method not only realizes the cooperative utilization of multiple solid wastes, but also replaces grinding media with granite powder, establishes an autogenous grinding system for grinding raw materials, and can reduce economic cost while remarkably improving grinding efficiency and early strength; 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
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The first aspect of 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 slag and granite powder to obtain a mixture A;
s2, preparing a chemical agent: mixing calcium oxide and trisodium phosphate uniformly to prepare a compound excitant B;
s3, mechanical activation: mixing the mixture A and the composite activator B, and then grinding to obtain a cementing material precursor powder;
s4, preparing neat paste: uniformly mixing the cementing material precursor powder with water glass and water to obtain a neat paste;
s5, forming and maintaining: and (4) carrying out forming maintenance on the clear slurry to obtain the cured and formed phosphoric acid-based polymer cementing material.
The chemical agent used in the invention has the following functions in the system:
calcium oxide: the calcium oxide can emit heat in the hydration process, a self-heating reaction system is formed in the die cavity, and Ca (OH) is formed at the same time 2 Making the aqueous solution dissolveThe alkalinity is formed, which provides favorable environment for the dissolution of soluble silicon-aluminum components; the introduction of Ca can lead [ PO ] to be converted in an early stage 4 ] 3- Fixing in the form of calcium phosphate series compound, providing nucleation sites for the formation of polymerization reaction product with higher polymerization degree (N-A-S-H gel) while generating cement hydration product (C-S-H or C- (A) -S-H gel), and adding [ PO ] into the cement hydration product 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 properties of the gel material are improved.
Trisodium phosphate: hydrolysis of trisodium phosphate makes the solution more alkaline, providing a favourable environment for the dissolution of the soluble silicoaluminophosphate component. With the introduction of the 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 amount of inclusion bodies are generated to prevent the later polymerization reaction from proceeding. In addition, excess Ca (OH) 2 It may increase the likelihood of dry shrinkage and cracking, disrupting the formation of a three-dimensional polymer network. The trisodium phosphate is therefore introduced in order to accelerate the polymerization and to reduce the Ca (OH) which is not involved in the polymerization 2 Preventing premature hardening, bulging, cracking and the like. Meanwhile, under the action of trisodium phosphate, the aluminosilicate precursor can be polymerized to generate Si-Al-P gel. Unlike conventional geopolymerized reaction products, the charge compensating cation of the gel is not necessary, since the charge balance can be built up from [ PO ] 4 ] 3- Tetrahedra are completed, the mechanism of formation being the introduction of [ PO ] 4 ] 3- The geopolymer has the characteristics of smoother and denser gel structure, low blooming and low dielectric loss, and the application performance of the gel material is obviously improved.
Water glass: the water glass is mainly used as a regulating component of active silicon and is used for directly regulating the active silicon content of the raw materials so that the final product has a sufficient silicon unit structure; in addition, the water glass has viscosity, so that gaps among particles can be filled in the early stage, the effect of bonding is achieved, and the compactness of an early sample is improved.
In the invention, the coal slag and the granite stone powder are respectively residual slag generated after coal is combusted in a coal-fired boiler in the industrial coal-fired boiler industry and powder waste generated in the processes of mining, processing, utilizing and the like of granite stone in the stone industry.
In some embodiments of the invention, the main chemical components of the coal-fired slag are: CO 2 2 The ignition loss is 4 wt% -10 wt%, SiO 2 43 to 64 weight percent of Al 2 O 3 20 to 40 weight percent of Fe 2 O 3 The content is 2 to 6 weight percent, and the content of CaO is 1 to 3 weight percent; the primary particle size of the coal-fired slag is 5 mesh or less.
In some embodiments of the present invention, the main chemical components of the granite stone powder are: CO 2 2 The loss on ignition is 0 to 2 weight percent, and SiO 2 60 to 80 weight percent of Al 2 O 3 10 to 25 weight percent of Na 2 O content of 2-6 wt%, K 2 2 to 6 weight percent of O, and Fe 2 O 3 The content is 1 to 3 weight percent, and the content of CaO is 1 to 3 weight percent; the initial particle size of the granite powder is 50 meshes or less.
In the invention, the mass ratio of the coal slag to the granite stone powder in the mixture A is (5-20): 1, preferably (5-15): 1, and more preferably (8-9): 1.
In the composite exciting agent B, the mass ratio of calcium oxide to trisodium phosphate is (1-5): 1, preferably (1.5-4.5): 1, and more preferably (2-4): 1.
In the invention, in the precursor powder of the cementing material, the mass ratio of the mixture A to the composite excitant 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 present invention, the grinding time is 4-6 min.
In some embodiments of the invention, the mixture A and the composite exciting agent B are mixed and ground into D90 with the grain size of 400 meshes or below.
In the invention, the content of the water glass is 30-50%, further 42 wt%, and the modulus is 2-3.3, further 2.31; the liquid-solid ratio of the water glass to the precursor powder of the binding material is 0.05-0.20 (mL/g), and further 0.1-0.15 (mL/g).
In the invention, the liquid-solid ratio of water to the precursor powder of the gel material is 0.26-0.42 (mL/g), preferably 0.30-0.34 (mL/g).
In the invention, the forming mode is as follows: and guiding the clean slurry into a mould for vibration molding.
In the invention, the maintenance mode is as follows: and (3) curing the mold poured with the neat paste at the temperature of 40-80 ℃ for 12-24 h after sealing, demolding, and continuously curing at the sealed room temperature to the specified age after demolding to obtain the cured and molded phosphoric acid-based polymer cementing material.
In some preferred embodiments of the invention, the defined age is 3 to 28 days. For example, the number of days may be 3, 7, 21, 28, etc., and those skilled in the art may select the number according to the actual situation.
In a second aspect of the present invention, there is provided a phosphoric acid based polymer obtained by the method for producing a phosphoric acid based polymer using a low-activity solid waste according to the first aspect of the present invention.
In order to avoid redundancy, the following raw materials and process parameters in the following examples and comparative examples of the present invention are described in a unified manner as follows:
the coal-fired slag refers to the residual slag of coal in the industrial coal-fired boiler industry after the coal is combusted in the coal-fired boiler, and the main chemical components are as follows: CO 2 2 The loss on ignition is 6.68 wt% SiO 2 53.98 wt% of Al 2 O 3 30.31 wt% of Fe 2 O 3 The content was 4.20% by weight, and the content of CaO was 1.77% by weight.
The granite powder refers to powder waste generated in the industrial utilization process of granite, and comprises the following main chemical components: CO 2 2 The ignition loss was 0.98 wt% and SiO 2 70.01 wt% of Al 2 O 3 16.32 wt% of Na 2 O content 4.19 wt%, K 2 O content 4.28 wt%, Fe 2 O 3 The content was 1.78 wt%, and the CaO content was 1.27 wt%.
Parameters of the water glass: content 42 wt% 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: placing granite powder (with primary particle size below 50 meshes) and coal slag (with primary particle size below 5 meshes) in an oven, baking until the mass is not changed, cooling to room temperature, and mixing according to m (coal slag): uniformly mixing m (granite stone powder) 9:1 to obtain a mixture A;
(2) preparing a chemical agent: as m (calcium oxide): mixing m (trisodium phosphate) 2:1 uniformly to prepare a compound excitant B;
(3) mechanical activation: m (mixture A): m (composite activator B) ═ 1: 0.35, mixing, and then placing into a vibration mill to grind for 4min until the grain diameter of D90 is 400 meshes, so as to obtain the precursor powder of the cementing material;
(4) preparing a neat paste: adding water glass and water into the cementing material precursor powder, and uniformly stirring to obtain a neat paste; 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 (mL) of water to the mass (g) of the precursor powder of the cementing material is 0.30;
(5) forming and maintaining: and pouring the clean slurry into a mold for vibration molding to obtain a sample, then sealing the vibration molded sample by using a self-sealing bag, curing for 24 hours in a curing box at 60 ℃, demolding, placing the sample in the self-sealing bag for sealing, and continuing curing at room temperature for 7 days to obtain the cured phosphate-based polymer cementing material.
Example 2
Embodiment 2 provides a method for preparing a phosphate-based polymer using low-activity solid waste, comprising the steps of:
(1) preparing raw materials: putting granite powder (with the initial particle size of below 50 meshes) and coal slag (with the initial particle size of below 5 meshes) into an oven, baking until the mass of the granite powder is not changed, cooling to room temperature, and mixing the granite powder and the coal slag according to the mass m (coal slag): uniformly mixing m (granite stone powder) 9:1 to obtain a mixture A;
(2) preparing a chemical agent: as m (calcium oxide): mixing m (trisodium phosphate) 2:1 uniformly to prepare a compound excitant B;
(3) mechanical activation: m (mixture A): m (composite activator B) ═ 1: 0.30, and then placing the mixture into a vibration mill to be ground for 4min until the grain diameter of D90 is 400 meshes, so as to obtain the precursor powder of the cementing material;
(4) preparing a neat paste: adding water glass and water into the cementing material precursor powder, and uniformly stirring to obtain a neat paste; wherein the ratio of the volume (mL) of the water glass to the mass (g) of the precursor powder of the cementing material is 0.15; the ratio of the volume (mL) of water to the mass (g) of the precursor powder of the cementing material is 0.34;
(5) forming and maintaining: and pouring the clean slurry into a mold for vibration molding to obtain a sample, then sealing the vibration molded sample by using a self-sealing bag, curing for 12 hours in a curing box at the temperature of 80 ℃, demolding, placing the sample in the self-sealing bag for sealing, and continuing curing at room temperature for 7 days to obtain the cured phosphate-based polymer cementing material.
Example 3
Embodiment 3 provides a method for preparing a phosphate-based polymer using low-activity solid waste, comprising the steps of:
(1) preparing raw materials: placing granite powder (with primary particle size below 50 meshes) and coal slag (with primary particle size below 5 meshes) in an oven, baking until the mass is not changed, cooling to room temperature, and mixing according to m (coal slag): uniformly mixing m (granite stone powder) 8:1 to obtain a mixture A;
(2) preparing a chemical agent: as m (calcium oxide): mixing m (trisodium phosphate) 1:1 uniformly to prepare a compound excitant B;
(3) mechanical activation: m (mixture A): m (composite activator B) ═ 1: 0.35, mixing, and then placing into a vibration mill to grind for 4min until the grain diameter of D90 is 400 meshes, so as to obtain the precursor powder of the cementing material;
(4) preparing a neat paste: adding water glass and water into the cementing material precursor powder, and uniformly stirring to obtain a neat paste; 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 (mL) of water to the mass (g) of the precursor powder of the cementing material is 0.32;
(5) forming and maintaining: and pouring the clean slurry into a mold for vibration molding to obtain a sample, then sealing the vibration molded sample by using a self-sealing bag, curing for 24 hours in a curing box at 60 ℃, demolding, placing the sample in the self-sealing bag for sealing, and continuing curing at room temperature for 7 days to obtain the cured phosphate-based polymer cementing material.
Comparative example 1
Compared with example 1, the difference of comparative example 1 is only that the contents of the components in the mixture A are different, and the specific contents are as follows:
preparing raw materials: placing granite powder (with primary particle size below 50 meshes) and coal slag (with primary particle size below 5 meshes) in an oven, baking until the mass is not changed, cooling to room temperature, and mixing according to m (coal slag): and (3) uniformly mixing m (granite stone powder) 10:0 to obtain a mixture A.
Comparative example 2
Compared with example 1, the difference of the comparative example 2 is only that the contents of the components in the mixture A are different, and the specific contents are as follows:
preparing raw materials: putting granite powder (with the initial particle size of below 50 meshes) and coal slag (with the initial particle size of below 5 meshes) into an oven, baking until the mass of the granite powder is not changed, cooling to room temperature, and mixing the granite powder and the coal slag according to the mass m (coal slag): and (3) uniformly mixing m (granite stone powder) 0:10 to obtain a mixture A.
Comparative example 3
Compared with example 1, comparative example 3 is different from example 1 only in that the contents of the components in the compound exciting agent B are different, and the specific contents are as follows:
preparing a chemical agent: as m (calcium oxide): m (trisodium phosphate) is 1:0, and the compound excitant B is prepared.
Comparative example 4
Compared with example 1, comparative example 4 is different from example 1 only in that the contents of the components in the compound exciting agent B are different, and the specific contents are as follows:
preparing a chemical agent: as m (calcium oxide): m (trisodium phosphate) ═ 0:1, and mixing uniformly to prepare the compound excitant B.
Comparative example 5
Compared with the example 1, the difference of the comparative example 5 is that the contents of the components in the precursor powder of the cementing material are not consistent, and the specific difference is as follows:
mechanical activation: m (mixture A): m (composite activator B) ═ 1: 0.10, and then placing the mixture into a vibration mill to grind for 4min until the grain diameter of D90 is 400 meshes, thus obtaining the precursor powder of the cementing material.
Comparative example 6
Compared with the example 1, the difference of the comparative example 6 is that the contents of the components in the precursor powder of the cementing material are different, and the specific difference is as follows:
mechanical activation: m (mixture A): m (composite activator B) ═ 1: 0.60 of the mixture is put into a vibration mill to be ground for 4min until the grain diameter of D90 is 400 meshes, and the precursor powder of the cementing material is obtained.
Comparative example 7
Comparative example 7 is different from example 1 only in that the components in the compound activator B are different, specifically as follows:
preparing a chemical agent: as m (sodium hydroxide): m (trisodium phosphate) ═ 2:1 is mixed uniformly to prepare the compound excitant B.
Comparative example 8
Comparative example 8 is different from example 1 only in the difference of each component in the compound activator B, and the specific difference is as follows:
preparing a chemical agent: as m (calcium hydroxide): m (trisodium phosphate) ═ 2:1 is mixed uniformly to prepare the compound excitant B.
Comparative example 9
Comparative example 9 is different from example 1 only in the difference of each component in the compound activator B, and is specifically as follows:
preparing a chemical agent: according to m (phosphoric acid): mixing m (trisodium phosphate) 2:1 uniformly to prepare the compound excitant B.
Comparative example 10
Compared with example 1, the comparative example 10 is different from the example 1 only in the addition mode of the compound exciting agent B, and specifically comprises the following steps:
mechanical activation: mixing the mixture A and calcium oxide, and then placing the mixture A and calcium oxide into a vibration mill for grinding for 4min until the particle size of D90 is 400 meshes, so as to obtain a cementing material precursor powder;
preparing a neat paste: and uniformly mixing the cementing material precursor powder with trisodium phosphate, water glass and water to obtain a neat paste.
Comparative example 11
Compared with example 1, comparative example 11 is different from example 1 only in the addition mode of the composite exciting agent B, and the specific steps are as follows:
mechanical activation: mixing the mixture A and trisodium phosphate, and then placing 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 a precursor powder of the cementing material;
preparing a neat paste: and uniformly mixing the precursor powder of the cementing material with calcium oxide, water glass and water to obtain the neat paste.
Comparative example 12
Comparative example 12 differs from example 1 only in that no water glass is added, as follows:
preparing a neat paste: and adding water into the cementing material precursor powder, and uniformly stirring to obtain a neat paste.
Test group
The performance of the gelled materials obtained in the above examples 1-3 and comparative examples 1-12 is tested by adopting the test standards specified in GB 175-2007 general portland cement and GB/T41060-2021 cement mortar frost resistance test method, the samples are circulated for 25 times in a freeze-thaw cycle at-20 ℃ to 5 ℃, and the frost resistance of the samples is judged by measuring the loss rate of the compressive strength after the samples are recovered to the room temperature, and the results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the method in the embodiments 1-3 of the present invention can prepare the cementitious material with high early strength and good frost resistance from the low-activity solid waste coal slag and granite stone powder.
Compared with the embodiment 1, the sample which is not doped with the granite powder in the comparative example 1 has reduced early compressive strength and frost resistance, because the grinding efficiency cannot be improved by the action of the micro-fine steel balls of the granite powder after the granite powder is lacked, the content of active silicon is reduced, and the holes cannot be filled by the micro-fine filling effect of the granite powder, so that the pore structure of the sample is enlarged; the sample without coal slag in comparative example 2 lost almost all of its compressive strength, because the more inactive coal slag in the system resulted in a reduced cement, the sample had almost no compressive strength, and significant compression deformation rather than cracking occurred after compression.
Compared with the embodiment 1, after only calcium oxide is added in the comparative example 3, the compressive strength of the sample 7d is obviously reduced, because the heat release effect is obvious due to the increase of the using amount of the calcium oxide, the hydration speed is out of control, and the severe reaction causes the harmful phenomena of swelling, cracking and the like of the product; in comparative example 4, the hydration product lacking calcium oxide accelerated and induced the polymerization reaction to proceed after only trisodium phosphate was added, resulting in a significant decrease in the compressive strength of sample 7d, while introducing excessive Na + Leading to significant blooming.
Compared with the example 1, the compound exciting agent B in the comparative example 5 has lower addition amount, obviously reduces the strength of the sample, and has incomplete excitation, and the generated gel phase is less, so that a uniform and compact gel phase matrix is difficult to form; in the comparative example 6, the addition amount of the composite exciting agent B is higher, and the sample shows negative effects (the hydration speed is out of control and the metal cation residue is too much) brought by the two agents at the same time, so that the compressive strength of the sample is obviously reduced.
Compared with the example 1, the compound excitant B in the comparative example 7 consists of the strong alkaline compound excitant of sodium hydroxide and trisodium phosphate, the excitation effect of the sample is very poor, excessive metal cations which do not participate in the reaction are introduced to cause the phenomenon of blooming to be very obvious, and the compressive strength of the obtained product is extremely low; when the composite exciting agent B in the comparative example 8 consists of other basic calcium compound composite exciting agents of calcium hydroxide and trisodium phosphate, the early strength of the sample is obviously reduced due to the hydration heat release effect without 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 shows that the rate of the polymerization reaction is obviously delayed; in comparative example 9, when the composite activator B consists of an acidic composite activator of phosphoric acid and trisodium phosphate, the compressive strength of the sample is also extremely low, which indicates that the method does not have the function of improving the compressive strength of the sample.
In comparison with example 1, in comparative example 10, [ PO ] due to the absence of trisodium phosphate during the mechanical activation 4 ] 3- Is difficult to be fixed by calcium without mechanical force, thus affecting [ PO ] 4 ] 3- The network structure of the geopolymer is incorporated, so that the final compressive strength of the sample is reduced and cannot reach the standard of 42.5R; in comparative example 11, since calcium oxide is not added during the mechanical activation process, calcium oxide exists in the form of a single compound, and the negative effects of calcium oxide in the form of a single compound are remarkably shown, unlike the formation of various complex calcium-phosphorus series minerals during the mechanical grinding process, so that the compressive strength of the sample is remarkably reduced and the freezing resistance of the sample is also deteriorated due to the expansion of the volume of the sample.
Comparative example 12, in comparison to example 1, without the addition of water glass, reduces the active silicon forming the polymer network structure, thereby significantly reducing the ultimate compressive strength of the sample.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention takes the coal-fired slag and the granite powder as the raw materials for preparing the cementing material, so that the coal-fired slag with low activity and the granite powder which are difficult to utilize can be utilized in a large scale and in high benefit, and a new direction is provided for researching the comprehensive utilization of less solid wastes of the coal-fired slag and the granite powder.
(2) According to the invention, after granite powder is added into the coal-fired slag, the compressive strength and the frost 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 the sample is lower than 5% under the action of 25 times of freeze-thaw cycles; the granite powder has high density and can not change due to the change of temperature and air components, so the unreacted granite powder serving as fine aggregate has stable property after being used for filling holes in a cementing material, and the negative influence of the external environment on the inside can be effectively weakened.
(3) The high-hardness granite powder is mixed in the mechanical activation process, the function of the micro-fine steel balls is realized during grinding, the grinding and extrusion effects are more obvious to damage the structure of the coal cinder, the grinding efficiency is obviously improved, and the grinding cost is reduced; the structural defects of crystal lattices are obviously increased in the same grinding time, namely the content of soluble active silicon-aluminum is increased.
(4) The composite excitant B prepared by the invention can generate a synergistic effect with a remarkable effect. The alkaline environment of the composite exciting agent B after dissolution is beneficial to the dissolution of the silicon-aluminum component in the cementing material precursor powder, provides raw materials for generating more hydration products, accelerates the hydration reaction of calcium oxide and induces the formation of other gel phases, and the trisodium phosphate prevents the hydration rate from being out of control, optimizes and complicates the gel structure (Si-Al-P) of the polymer, so that a large amount of complex gel phases are formed in the early stage of a cementing material sample to coexist, and the early strength is greatly improved.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A method for preparing a phosphate-based polymer by using low-activity solid waste is characterized by comprising the following steps:
preparing raw materials: uniformly mixing the coal slag and granite powder to obtain a mixture A;
preparing a chemical agent: mixing calcium oxide and trisodium phosphate uniformly to prepare a compound excitant B;
mechanical activation: mixing the mixture A and the composite exciting agent B and then grinding to obtain a cementing material precursor powder;
preparing a neat paste: uniformly mixing the cementing material precursor powder with water glass and water to obtain a neat paste;
forming and maintaining: and carrying out forming maintenance on the clean slurry to obtain the cured and formed phosphoric acid-based polymer cementing material.
2. The method for preparing the phosphate-based polymer by using the low-activity solid waste as claimed in claim 1, wherein the mass ratio of the coal-fired slag to the granite powder in the mixed material A is (5-20): 1.
3. The method for preparing the phosphate-based polymer by using the low-activity solid waste as claimed in claim 1, wherein the mass ratio of the coal-fired slag to the granite powder in the mixed material A is (5-15): 1.
4. The method for preparing a phosphate-based polymer from low-activity solid waste as claimed in claim 1, wherein the mass ratio of calcium oxide to trisodium phosphate in the composite activator B is (1-5): 1.
5. The method for preparing a phosphate-based polymer from low-activity solid waste as claimed in claim 1, wherein the mass ratio of calcium oxide to trisodium phosphate in the composite activator B is (1.5-4.5): 1.
6. The method for preparing a phosphate-based polymer by using the low-activity solid waste as claimed in claim 1, wherein the mass ratio of the mixture A to the composite activator B in the precursor powder of the cementing material is 1: (0.2-0.5).
7. The method for preparing a phosphate-based polymer by using low-activity solid waste as claimed in claim 1, wherein the content of the water glass is 30-50%, and the modulus is 2-3.3; the liquid-solid ratio of the water glass to the cementing material precursor powder is 0.05-0.20 (mL/g).
8. The method for preparing a phosphate-based polymer by using low-activity solid waste as claimed in claim 1, wherein the liquid-solid ratio of the water to the precursor powder of the gelling material is 0.26-0.42 (mL/g).
9. The method for preparing a phosphate-based polymer using low-activity solid waste as claimed in claim 1, wherein the curing is performed by: and (3) curing the mold poured with the neat paste at the temperature of 40-80 ℃ for 12-24 h after sealing, demolding, and continuously curing at the sealed room temperature to the specified age after demolding to obtain the cured and molded phosphoric acid-based polymer cementing material.
10. A phosphate-based polymer obtained by the method for producing a phosphate-based polymer from a low-activity solid waste as set forth in any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115849781A (en) * | 2022-12-05 | 2023-03-28 | 武汉理工大学 | Geopolymer gelled material based on multiple solid wastes and preparation method thereof |
| CN115947568A (en) * | 2022-12-05 | 2023-04-11 | 武汉理工大学 | Method for preparing phosphoric acid-based polymer by roasting granite powder at low temperature |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04285083A (en) * | 1991-03-12 | 1992-10-09 | Nippon Kayaku Co Ltd | Clad material |
| WO2003035576A1 (en) * | 2001-10-21 | 2003-05-01 | National Institute Of Advanced Industrial Science And Technology | Porous article of sintered calcium phosphate, process for producing the same and artificial bone and histomorphological scaffold using the same |
| CN107746212A (en) * | 2017-10-18 | 2018-03-02 | 浙江大学 | Modified enhanced ground oligomer gel material of one kind and preparation method thereof |
| CN110627470A (en) * | 2019-11-01 | 2019-12-31 | 新化县天马建筑新材料科技有限公司 | Double-network reinforced composite quick-drying gel cement material and preparation method thereof |
| CN112125586A (en) * | 2020-09-23 | 2020-12-25 | 常熟理工学院 | Preparation method and application of sulfhydryl modified graphene oxide nanosheet/geopolymer composite material |
| CN113620618A (en) * | 2021-08-24 | 2021-11-09 | 武汉理工大学 | Method for preparing integrated cementing material by utilizing granite powder and coal slag |
| CN113716908A (en) * | 2021-10-14 | 2021-11-30 | 盐城工学院 | Modified calcium sulfate whisker reinforced geopolymer and preparation method thereof |
-
2022
- 2022-06-27 CN CN202210737429.3A patent/CN114988735B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04285083A (en) * | 1991-03-12 | 1992-10-09 | Nippon Kayaku Co Ltd | Clad material |
| WO2003035576A1 (en) * | 2001-10-21 | 2003-05-01 | National Institute Of Advanced Industrial Science And Technology | Porous article of sintered calcium phosphate, process for producing the same and artificial bone and histomorphological scaffold using the same |
| CN107746212A (en) * | 2017-10-18 | 2018-03-02 | 浙江大学 | Modified enhanced ground oligomer gel material of one kind and preparation method thereof |
| CN110627470A (en) * | 2019-11-01 | 2019-12-31 | 新化县天马建筑新材料科技有限公司 | Double-network reinforced composite quick-drying gel cement material and preparation method thereof |
| CN112125586A (en) * | 2020-09-23 | 2020-12-25 | 常熟理工学院 | Preparation method and application of sulfhydryl modified graphene oxide nanosheet/geopolymer composite material |
| CN113620618A (en) * | 2021-08-24 | 2021-11-09 | 武汉理工大学 | Method for preparing integrated cementing material by utilizing granite powder and coal slag |
| CN113716908A (en) * | 2021-10-14 | 2021-11-30 | 盐城工学院 | Modified calcium sulfate whisker reinforced geopolymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 袁宇兴;汤裕;郑章宏;卢安贤;: "粉煤灰-水泥基地质聚合物复合泡沫材料的研制" * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115849781A (en) * | 2022-12-05 | 2023-03-28 | 武汉理工大学 | Geopolymer gelled material based on multiple solid wastes and preparation method thereof |
| CN115947568A (en) * | 2022-12-05 | 2023-04-11 | 武汉理工大学 | Method for preparing phosphoric acid-based polymer by roasting granite powder at low temperature |
| CN115849781B (en) * | 2022-12-05 | 2024-02-23 | 武汉理工大学 | Geopolymer cementing material based on multiple solid wastes and preparation method thereof |
| CN115947568B (en) * | 2022-12-05 | 2024-02-23 | 武汉理工大学 | Method for preparing phosphate-based polymer by low-temperature roasting of granite powder |
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