CN114149188A - Clinker-free cementing material containing large-mixing-amount wet alkali-removing residues and preparation method and application thereof - Google Patents

Clinker-free cementing material containing large-mixing-amount wet alkali-removing residues and preparation method and application thereof Download PDF

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Publication number
CN114149188A
CN114149188A CN202111364219.6A CN202111364219A CN114149188A CN 114149188 A CN114149188 A CN 114149188A CN 202111364219 A CN202111364219 A CN 202111364219A CN 114149188 A CN114149188 A CN 114149188A
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slag
alkali
clinker
discharging
wet alkali
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Inventor
张兆云
谢闯
桑兆虎
赵庆新
郭维超
杜建军
李德军
李春颖
潘慧敏
齐文跃
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Tangshan Sanyou Chlor Alkali Co ltd
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Tangshan Sanyou Chlor Alkali Co ltd
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Priority to CN202111364219.6A priority Critical patent/CN114149188A/en
Publication of CN114149188A publication Critical patent/CN114149188A/en
Priority to CN202211437289.4A priority patent/CN115745434B/en
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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
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
    • C04B7/1535—Mixtures thereof with other inorganic cementitious materials or other activators with alkali metal containing activators, e.g. sodium hydroxide or waterglass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • 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 clinker-free cementing material containing high-content wet alkali-discharging residue, and a preparation method and application thereof, and relates to the technical field of cementing materials prepared from wet alkali-discharging residue. The clinker-free cementing material containing the high-volume wet alkali-discharging residue consists of a base material and a composite exciting agent, wherein the base material consists of the wet alkali-discharging residue and slag, and the wet alkali-discharging residue accounts for 40-60% and the slag accounts for 40-60% of the dry base by mass percentage; the compound excitant is composed of NaOH and Na2CO3And (4) forming. The material can effectively replace cement, simultaneously reduces the treatment procedures of drying, grinding and the like, can greatly reduce energy consumption and cost, and realizes the resource utilization of the solid waste of the caustic sludge, and the 28d strength can reach more than 30 MPa. The invention uses the wet alkali-discharging residue for preparationA new cementing material is produced, waste is changed into valuable, the environment is protected, and the production cost is reduced.

Description

Clinker-free cementing material containing large-mixing-amount wet alkali-removing residues and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparing a cementing material from wet alkali-discharging residues, in particular to a clinker-free cementing material containing large-content wet alkali-discharging residues and a preparation method and application thereof.
Background
The alkaline residue is alkaline residue produced in the process of producing soda ash by ammonia-soda process, and is usually CaCO3、CaSO4、 CaCl2When the calcium salt component is the main component, about 780 ten thousand tons of solid caustic sludge are discharged every year in China, and the solid caustic sludge is stored in a storage yard after being subjected to filter pressing, so that the resource utilization degree is low. Due to large discharge amount, high transportation cost and few resource utilization ways, a large amount of alkaline residues are treated in an open-air stacking or even in-situ burying mode, so that a large amount of land resources are occupied, and serious pollution is caused to soil and water bodies, so that the environmental problem is increased day by day.
In chlor-alkali enterprises, the caustic sludge is initially white slurry, the water binding capacity is strong, the initial water content can reach more than 90%, and the pH value is about 12-13. In the past, when the caustic sludge is used for preparing the cementing material, the caustic sludge is mostly used as a calcareous component or only used as a filling material, the doping amount is mostly not higher than 30%, and a high-concentration strong base needs to be added for excitation to obtain high strength, so that the cost is high. And the alkaline residue is mostly subjected to treatment procedures of drying, grinding and the like, so that the resource utilization process is complex, the cost is further increased, and the popularization is not facilitated.
Based on this, in the closest prior art, caustic sludge, NaOH, Na have been utilized2CO3The search for alkali activators has not been successful. For example, "preparation of alkali-activated Cement Using alkali dregsIn Soy, NaOH and Na are used2CO3And the sodium silicate is used as an alkali activator to prepare an alkali-activated adhesive material, and the obtained result shows that: with the increase of the water-gel ratio, the compressive strength of the material is reduced; NaOH and Na2CO3Has no excitation effect on the caustic sludge, and the water glass has a certain excitation effect. In the literature, "investigation of polymer materials from caustic sludge-slag" the results obtained show that: with the increase of the water-cement ratio, the strength of the polymer of the alkaline residue slag is continuously reduced; na (Na)2CO3No excitation effect on the reaction, and no strength of the reaction product; when the mixing amount of the alkaline residue is large, the water glass excitation effect is superior to that of NaOH, the early strength of a NaOH excitation product is large, and the later strength of the water glass excitation product is large. The relevant literature is about the utilization of NaOH and Na2CO3The search for alkali activators has not been advanced.
Disclosure of Invention
The invention provides a clinker-free cementing material containing large-volume wet alkali-discharging residue and a preparation method and application thereof, wherein cement is not used, the alkali residue is utilized without drying, grinding and other processes, a certain amount of waste alkali contained in wet alkali-discharging residue slurry is utilized, and a small amount of compound alkaline activator is doped in the wet alkali-discharging residue slurry to synergistically excite slag to form the cementing material, so that the cement can be effectively replaced, and the resource utilization of the solid waste of the alkali residue is realized.
In order to realize the technical purpose, the invention adopts the following scheme:
the clinker-free cementing material containing the high-volume wet alkali-discharging residue consists of a base material and a composite exciting agent, wherein the base material consists of the wet alkali-discharging residue and slag, and the wet alkali-discharging residue accounts for 40-60% and the slag accounts for 40-60% of the dry base by mass percentage; the compound excitant is composed of NaOH and Na2CO3And (4) forming.
Further, the mass of the composite exciting agent is 3-5% of the total mass of dry basis and slag in the wet alkali-removing slag.
Further, NaOH and Na in the compound excitant2CO3The mass ratio of (A) to (B) is 4: 1.
Further, NaOH, Na2CO3Respectively, the particles were analyzed.
The preparation method of the clinker-free cementing material containing the high-doping-amount wet alkali-discharging residue comprises the following steps:
s1, taking the wet alkali-discharging residues, standing for 5-7 days, pumping out supernatant liquid every day, uniformly stirring, obtaining alkali residue slurry when the water content of the wet alkali-discharging residues is 40-50%, and taking out for later use;
s2, uniformly stirring the caustic sludge slurry obtained in the step S1, determining solid content-density data of the caustic sludge slurry through experiments, fitting a solid content-density function curve and determining a relational expression;
s3, according to the relation obtained in S2, when the caustic sludge slurry is used, the solid content is obtained by directly testing the density of the caustic sludge slurry, and then the required wet basis weight is calculated inversely according to the solid content and the dry basis weight in the mixing proportion; simultaneously calculating the moisture content in the slurry;
s4, taking NaOH and Na2CO3Respectively dissolving in water to obtain NaOH solution and Na2CO3Standing the solution for 2-4 h for later use;
s5, mixing the caustic sludge slurry, NaOH solution and Na2CO3Adding the solution into a stirrer, stirring for 60-90 s at a rotating speed of 135-145 r/min, adding slag into the stirrer to obtain a mixture, stirring for 30-60 s at a rotating speed of 135-145 r/min, stirring for 60-90 s at a rotating speed of 275-295 r/min, scraping the mixture on the blades and the pot wall into the middle of the pot, and stirring for 90-120 s at a rotating speed of 275-295 r/min to obtain the clinker-free cementing material.
Further, the amount of water contained in the caustic sludge slurry in S3 and NaOH and Na in S42CO3The ratio of the total amount of water for dissolution (i.e., the amount of added water) to the total mass of the dry basis and the slag in the alkaline residue slurry is 0.45-0.55, preferably 0.5.
The slag in the S5 is S95 level ground slag.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention optimizes the proportion of the alkali residue, the slag and the externally doped excitant to ensure that a certain amount of waste alkali and NaOH-Na with a specific proportion are contained in the wet alkali-removing residue2CO3Forming a synergistic excitation effect, and exciting the slag to form a gelled material to obtain the optimal strength. Simultaneously realizes the full utilization of the waste alkaliBy utilizing the method, the mixing amount of the alkaline residue is effectively increased, the use amount of the strong base is reduced, and the production cost of the alkali-activated cementing material is effectively reduced.
(2) The invention changes the drying and milling mode of the prior caustic sludge for preparing the cementing material, directly uses the wet base caustic sludge discharged by a factory, saves the drying and milling process with high energy consumption, and further reduces the cost.
(3) The invention is helpful to solve various environmental pollution problems caused by the stockpiling of the solid waste of the alkaline residue; the cementing material replaces cement to produce a non-reinforced product in partial fields, and the problems of high energy consumption and high pollution caused by the production of portland cement are reduced to a certain extent.
The clinker-free cementing material containing a large amount of wet alkali-discharging residues is applied to building materials.
According to GB/T17671-1999 method for testing cement mortar strength (ISO method), the strength of the cement is evaluated by using a mortar test piece, so that additional components are required: sand, tap water.
Preferably, the sand is natural river sand, the particle size is 0.16 mm-2.36 mm, and the mud content is less than 0.5%.
Preferably, the mass ratio of the sand to the sum of the dry basis mass + the slag mass in the wet alkali-discharging slag is 3.0.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention, but the present invention is not limited thereto.
The composition of the wet alkali-discharging residue is shown in the following table 1:
TABLE 1 alkaline residue composition (wt/%)
Figure BDA0003360014070000031
Note: LOI-loss on ignition
Considering that the wet alkali discharging residue slurry is alkaline and contains calcium, silicon and aluminum components, if the wet alkali discharging residue can be directly used in a wet base state, the waste alkali contained in the slurry is used to cooperate with a small amount of alkaline exciting agent to form a precursor with a synergistic excitation effect to excite slag and the like, and the calcium, silicon and aluminum components contained in the alkali residue are used as the supplement of the precursor to further prepare the cementing material meeting the strength requirement, so that the using amount of strong base can be greatly reduced, the mixing amount of the alkali residue can be increased, the alkali residue does not need the procedures of drying, grinding and the like, and the energy consumption and the cost can be greatly reduced.
The principle of the invention is as follows: wet alkali-removing slag and small amount of NaOH-Na with specific proportion2CO3The composite excitant has stronger synergistic excitation effect, which is discovered and proposed for the first time. The invention discloses the reason for the generation of the synergistic excitation effect as follows: the wet alkali-discharging residue contains a certain amount of waste alkali and OH in the contained water-The ion concentration is higher, about 0.032-0.063 mol/L, and the pH value is about 12.5-12.8, which is the excitation source 1. NaOH-Na with specific ratio2CO3The solution contains OH-And CO3 2-This is an excitation source 2. CaCl contained in caustic sludge2、CaSO4Etc. may also excite slag, which is the excitation source 3. Among the three types of excitation sources, OH-、CO3 2-The slag is synergistically excited to generate calcium silicate hydrate (C-S-H), calcium aluminate hydrate (C-A-H) gel and calcium aluminate hydrate (7CaO 2 Al)2O3·CaCO3·24H2O), hydrotalcite and the like crystal-type product, CaCl2、CaSO4The slag is excited to generate hydrated calcium chloroaluminate (3 CaO. Al)2O3·CaCl2·10H2O), hydrated calcium sulfoaluminate (3 CaO. Al)2O3·3CaSO4·30H2O) and the like. When the ratio of the three types of excitation sources is appropriate, OH is particularly preferred-With CO3 2-When the proportion of the C-S-H, C-A-H gel is proper, the C-S-H, C-A-H gel can be generated more and faster, and crystal type hydration products are richer and are filled in the surface and the internal microcracks of the gel, so that the strength is effectively improved, and a better excitation effect is shown; when the ratio of the excitation source is not proper, particularly OH-When the amount is too large or too small, the above-mentioned excitation effect cannot be achieved, and the intensity is low.
The invention provides a clinker-free cementing material containing large-content wet alkali-discharging residue, which comprises the following components: the base material consists of wet alkali-discharging slag and slag, wherein the sum of the dry basis weight of the wet alkali-discharging slag and the total weight of the slag is 100%, the dry basis weight of the wet alkali-discharging slag accounts for 40-60% of the total weight, and the slag accounts for 40-60% of the total weight.
The mass of the composite excitant is 3-5% of the sum of the dry basis mass and the slag mass in the wet alkali-discharging slag, and the composite excitant is composed of NaOH (granular) and Na2CO3(granular) composition of NaOH and Na2CO3The mass ratio of (A) to (B) is 4: 1.
The caustic sludge used in the scheme is a wet basis, but the metering proportion is calculated according to a dry basis contained in the slurry. And inversely calculating the required wet basis mass according to the solid content-density function relation, and simultaneously calculating the moisture contained in the slurry.
Example 1
A preparation method of a clinker-free cementing material containing a large amount of wet alkali-removing residues comprises the following steps:
s1, placing the wet alkali-removing residues in a sedimentation tank, standing for 5-7 days, pumping out supernate every day, uniformly stirring, obtaining alkali residue slurry when the water content of a sedimentary layer (namely slurry) is 40-50% (mass percentage), and taking out for later use.
S2, uniformly stirring the caustic sludge slurry, and determining the solid content (Y) of the caustic sludge slurry through testss) -density (p)s) Data, fitting a solid content-density function curve and determining a relation, see the following formula:
Ys＝37.920ρs–22.777。
in order to determine the quantitative relationship of solid content-density of caustic sludge slurry. Firstly, taking a plurality of groups of samples, respectively stirring uniformly, determining the density of the slurry by using an electronic scale and a measuring cylinder, then drying the slurry at high temperature, testing the dried mass, and dividing the mass by the mass of the slurry to obtain the solid content. According to the data of a plurality of groups of samples, the solid contents at different densities are obtained, and a wet base is directly used as a basis for the following.
S3, directly testing the density of the alkaline residue slurry to obtain solid content when in use according to the mixing proportion, and then inversely calculating the required wet basis mass according to the dry basis mass in the mixing proportion; and calculating the water content in the slurry.
S4, mixing NaOH 14.40g and Na2CO33.60g of the extract is respectively dissolved in a proper amount of tap water and stands for 2 hours for standby.
S5, mixing the needed caustic sludge slurry containing 180g of dry basis, NaOH solution and Na2CO3Adding the solution into a stirrer, and stirring at the rotating speed of 135-145 r/min for 60s to obtain a uniform mixture as a composite exciting agent. And adding 270g of slag into a stirrer, stirring for 30s at the rotating speed of 135-145 r/min, stirring for 60s at the rotating speed of 275-295 r/min, scraping the mixture on the blades and the pot wall into the middle of the pot, and stirring for 90s at the rotating speed of 275-295 r/min to obtain a clinker-free cementing material sample 1. Wherein, the water content in the alkaline residue slurry containing 180g of dry basis and NaOH and Na2CO3The ratio of the total amount of water used for dissolution to the sum of the dry basis weight and the slag weight in the alkaline residue slurry is 0.5. The slag is ground slag of grade S95. The blending ratio of each raw material is shown in table 2.
A method for detecting the strength of a clinker-free cementing material containing large-amount wet alkali-discharging residues is characterized in that a mortar test piece is used for evaluating the strength of the cementing material, and the method needs additional components: and (4) sand. Wherein the total mass ratio of the dry base and the slag in the sand and the wet alkali-discharging slag is 3.0, the sand is natural river sand, the particle size is 0.16 mm-2.36 mm, and the mud content is less than 0.5%.
The method comprises the following specific steps: 1350g of sand is added into the stirrer containing the sample 1, the mixture is stirred at a high speed for 60s, then the mortar on the blades and the pot wall is scraped into the middle of the pot, the mixture is stirred at a high speed for 90s, and the mortar is obtained and subjected to strength test, wherein the compressive strength results are shown in Table 3.
Example 2, example 3, example 4 and example 5 the procedure was the same as in example 1, wherein NaOH and Na2CO3The amounts of wet soda ash and slag were added in the amounts shown in Table 1 to obtain sample 2, sample 3, sample 4 and sample 5, respectively, and the same strength test method was used, and the results are shown in Table 2.
Comparative example 1
A preparation method of a clinker-free cementing material containing a large amount of wet alkali-removing residues comprises the following steps:
s1, placing the wet alkali-removing residues in a sedimentation tank, standing for 5-7 days, pumping out supernate every day, uniformly stirring, and taking out for later use when the water content of a sedimentary layer is 40-50%.
S2, uniformly stirring the caustic sludge slurry, determining solid content-density data of the caustic sludge slurry and the caustic sludge slurry through tests, fitting a solid content-density function curve and determining a relational expression, Ys＝37.920ρs–22.777。
S3, according to the mixing proportion, the solid content can be obtained by directly testing the density of the alkaline residue slurry when in use, and then the required wet basis weight is calculated by the reverse calculation of the dry basis weight in the mixing proportion; and calculating the water content in the slurry.
S4, dissolving 18.00g of NaOH in a proper amount of tap water, and standing for 2 hours for later use.
S5, adding the required caustic sludge slurry containing 180g of dry basis and NaOH solution into a stirrer, and quickly stirring for 60S to obtain a uniform mixture as an excitant. And adding 270g of slag into a stirrer, stirring at a low speed for 30s, then stirring at a high speed for 60s, scraping the mixture of the blades and the wall of the pot into the middle of the pot, and then stirring at a high speed for 90s to obtain a clinker-free cementing material comparative sample 1. Wherein the ratio of the total amount of water contained in the caustic sludge slurry containing 180g of dry basis and the amount of NaOH dissolved water to the total mass of dry basis and slag in the caustic sludge slurry is 0.5. The slag is ground slag of grade S95. The blending ratio of each raw material is shown in table 2.
The strength test method was the same as in example 1, and the results of the compressive strength were shown in Table 3.
Comparative example 2
A preparation method of a clinker-free cementing material containing a large amount of wet alkali-removing residues comprises the following steps:
s1, placing the wet alkali-removing residues in a sedimentation tank, standing for 5-7 days, pumping out supernate every day, uniformly stirring, and taking out for later use when the water content of a sedimentary layer is 40-50%.
S2, uniformly stirring the caustic sludge slurry, determining solid content-density data of the caustic sludge slurry and the caustic sludge slurry through tests, fitting a solid content-density function curve and determining a relational expression, Ys＝37.920ρs–22.777。
S3, according to the mixing proportion, the solid content can be obtained by directly testing the density of the alkaline residue slurry when in use, and then the required wet basis weight is calculated by the reverse calculation of the dry basis weight in the mixing proportion; and calculating the water content in the slurry.
S4, mixing Na2CO3Dissolving 18.00g of the extract in a proper amount of tap water, and standing for 2 hours for later use.
S5, adding the required caustic sludge slurry containing 180g of dry basis and Na2CO3Adding the solution into a stirrer, and rapidly stirring for 60s to obtain a uniform mixture as a joint stimulant. And adding 270g of slag into a stirrer, stirring at a low speed for 30s, then stirring at a high speed for 60s, scraping the mixture of the blades and the pot wall into the middle of the pot, and then stirring at a high speed for 90s to obtain a clinker-free cementing material comparative sample 2. Wherein the caustic sludge slurry containing 180g of dry basis contains Na and water2CO3The ratio of the total amount of water used for dissolution to the total mass of dry basis and slag in the alkaline residue slurry is 0.5. The slag is ground slag of grade S95. The blending ratio of each raw material is shown in table 2.
The strength test method was the same as in example 1, and the results of the compressive strength were shown in Table 3.
Comparative example 3
A preparation method of a clinker-free cementing material containing a large amount of wet alkali-removing residues comprises the following steps:
s1, placing the wet alkali-removing residues in a sedimentation tank, standing for 5-7 days, pumping out supernate every day, uniformly stirring, and taking out for later use when the water content of a sedimentary layer is 40-50%.
S2, uniformly stirring the caustic sludge slurry, determining solid content-density data of the caustic sludge slurry and the caustic sludge slurry through tests, fitting a solid content-density function curve and determining a relational expression, Ys＝37.920ρs–22.777。
S3, according to the mixing proportion, the solid content can be obtained by directly testing the density of the alkaline residue slurry when in use, and then the required wet basis weight is calculated by the reverse calculation of the dry basis weight in the mixing proportion; meanwhile, calculating the moisture content in the slurry;
s4, mixing NaOH 10.8g and Na2CO37.2g of the mixture is respectively dissolved in a proper amount of tap water and stands for 2 hours for standby.
S5, mixing the needed caustic sludge slurry containing 180g of dry basis, NaOH solution and Na2CO3Solutions ofAdding into a stirrer, and rapidly stirring for 60s to obtain a uniform mixture as a composite excitant. And adding 270g of slag into a stirrer, stirring at a low speed for 30s, then stirring at a high speed for 60s, scraping the mixture of the blades and the pot wall into the middle of the pot, and then stirring at a high speed for 90s to obtain a clinker-free cementing material comparative sample 3. Wherein, the water content in the alkaline residue slurry containing 180g of dry basis and NaOH and Na2CO3The ratio of the total amount of dissolved water to the total mass of dry basis and slag in the caustic sludge slurry was 0.5. The slag is ground slag of grade S95. The blending ratio of each raw material is shown in table 2.
The strength test method was the same as in example 1, and the results of the compressive strength were shown in Table 3.
TABLE 2 test mix proportions
Figure BDA0003360014070000081
TABLE 3 test results
Sample numbering 3d compressive Strength (MPa) 7d compressive Strength (MPa) 28d compressive Strength (MPa)
Sample 1 12.5 18.2 34.7
Comparative sample 1 8.1 14.9 26.2
Comparative sample 2 2.6 5.4 9.1
Comparative sample 3 7.8 12.2 22.7
Sample 2 10.9 16.7 31.9
Sample 3 10.1 15.5 30.1
Sample No. 4 11.2 16.9 32.4
Sample No. 5 10.7 15.8 31.2
As shown in tables 2 and 3, the 28d compressive strengths of samples 1, 2, 3, 4 and 5 were all 30MPa or more, and the differences in overall properties were small, but the compressive strength of sample 1 wasIs relatively high. The 28d compressive strength of comparative samples 1, 2, 3 were all below 30MPa and the strength at each age was lower than samples 1, 2, 3, 4, 5. Therefore, the wet alkali-discharging residue and NaOH-Na with a specific proportion can be seen2CO3The synergistic excitation effect is formed, the cementing material obtains higher compressive strength, and NaOH or Na is used alone2CO3Or NaOH and Na2CO3When the ratio of (a) to (b) is other than 4:1, the excitation effect is remarkably deteriorated. In conclusion, the invention utilizes the wet alkali-removing residue to cooperate with NaOH-Na2CO3The slag is excited to prepare the cementing material with the compressive strength of more than 30MPa, so that the treatment processes of drying, grinding and the like are reduced, the resource utilization process is simplified, the alkali slag mixing amount is increased, considerable strength is obtained, and the method has obvious economic and technical benefits and huge industrial popularization prospects.
Finally, it is noted that: the above-mentioned list is only the preferred embodiment of the present invention, and naturally those skilled in the art can make modifications and variations to the present invention, which should be considered as the protection scope of the present invention provided they are within the scope of the claims of the present invention and their equivalents.

Claims (8)

1. The clinker-free cementing material containing the high-content wet alkali-discharging residue is characterized by comprising a base material and a composite excitant, wherein the base material comprises the wet alkali-discharging residue and slag, and the wet alkali-discharging residue accounts for 40-60% and the slag accounts for 40-60% of the dry base by mass percentage; the compound excitant is composed of NaOH and Na2CO3And (4) forming.
2. The clinker-free cementing material containing the high-content wet alkali-discharging slag according to claim 1, characterized in that the mass of the composite excitant is 3-5% of the total mass of dry basis and slag in the wet alkali-discharging slag.
3. The clinker-free cementing material containing high-content wet alkali-discharging residues as claimed in claim 1, wherein NaOH and Na in the composite excitant2CO3The mass ratio of (A) to (B) is 4: 1.
4. The clinker-free cementitious material containing high-content wet alkali-discharging residue as claimed in claim 1, characterized in that NaOH and Na2CO3Respectively, the particles were analyzed.
5. A method for preparing a clinker-free cementitious material containing a large amount of wet alkali-discharging residues according to any one of claims 1 to 4, which is characterized by comprising the following steps:
s1, taking the wet alkali-removing residues, standing for 5-7 days, pumping out supernatant liquid every day, uniformly stirring, obtaining alkali residue slurry when the water content of a deposition layer is 40-50%, and taking out for later use;
s2, uniformly stirring the caustic sludge slurry obtained in the step S1, determining solid content-density data of the caustic sludge slurry through experiments, fitting a solid content-density function curve and determining a relational expression;
s3, according to the relation obtained in S2, when the caustic sludge slurry is used, the solid content is obtained by directly testing the density of the caustic sludge slurry, and then the required wet basis weight is calculated inversely according to the solid content and the dry basis weight in the mixing proportion; simultaneously calculating the moisture content in the slurry;
s4, taking NaOH and Na2CO3Respectively dissolving in water to obtain NaOH solution and Na2CO3Standing the solution for 2-4 h for later use;
s5, mixing the caustic sludge slurry, NaOH solution and Na2CO3Adding the solution into a stirrer, stirring for 60-90 s at a rotating speed of 135-145 r/min, adding slag into the stirrer to obtain a mixture, stirring for 30-60 s at a rotating speed of 135-145 r/min, stirring for 60-90 s at a rotating speed of 275-295 r/min, scraping the mixture on the blades and the pot wall into the middle of the pot, and stirring for 90-120 s at a rotating speed of 275-295 r/min to obtain the clinker-free cementing material.
6. The method for preparing clinker-free cementitious material containing heavily doped wet alkali-discharging residue as claimed in claim 5, wherein the water content in the slurry of the alkali residue in S3 and NaOH and Na in S42CO3The ratio of the total amount of water used for dissolving to the total mass of the dry basis and the slag in the alkaline residue slurry is 0.45-0.55.
7. The method for preparing a clinker-free cementitious material containing a large amount of wet alkali-discharging slag according to claim 5, wherein the slag in S5 is ground slag grade S95.
8. Use of a clinker-free cementitious material containing a high loading of wet alkali-drainage residues according to any one of claims 1 to 4 on construction materials.
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