CN115819008A - High-activity and low-shrinkage composite mineral admixture and preparation method thereof - Google Patents
High-activity and low-shrinkage composite mineral admixture and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-activity low-shrinkage composite mineral admixture and a preparation method thereof, and relates to the technical field of concrete mineral admixtures. The composite mineral admixture comprises the following raw material components in percentage by weight: 15-25% of lithium slag, 30-50% of granulated electric furnace phosphorus slag, 10-20% of ferrovanadium slag, 10-15% of nickel slag, 5-10% of sulphoaluminate cement clinker, 0.5-1.0% of superplasticizer and 0.3-0.5% of early strength grinding aid. The admixture of the invention fully exerts the synergistic and complementary effects of different types of smelting slag and raw materials, and realizes the anti-shrinkage capability and higher activity of the composite mineral admixture from early stage to later stage.
Description
Technical Field
The invention relates to the technical field of concrete mineral admixtures, in particular to a high-activity and low-shrinkage composite mineral admixture and a preparation method thereof.
Background
The shrinkage cracking of concrete in building engineering is a common problem, which not only reduces the bearing capacity of the concrete structure, but also affects the safety and durability of the main body of the structure. The aggregate volume stability in concrete is excellent, and the main cause of shrinkage cracking is the matrix part. This is not only related to shrinkage of the cement-based material due to moisture migration, but also to cement hydration. After the silicate cement is hydrated, the sum of the volume of a reaction product and the residual free volume is smaller than the volume before reaction, so that shrinkage is caused, the volume shrinkage is usually between 2.3% and 5.1%, and the shrinkage is one of main reasons for causing shrinkage and shrinkage cracks of a cement-based material. The mineral admixture is an auxiliary cementing material capable of partially replacing cement, and when the mineral admixture is mixed with cement, the mineral admixture can react with the cement and cement hydration products to influence the cement-based material on different levels, so that the shrinkage and other properties of the cement-based material can be regulated and controlled.
Meanwhile, in the southwest region of China, due to natural resources and geographical factors, the mixing amount of the traditional mineral admixtures such as the fly ash is small, but due to the abundant resources of phosphorus, lithium, vanadium, titanium and the like in the region, related resource industries are formed, and industrial smelting slag such as lithium slag, granulated electric furnace phosphorus slag, ferrovanadium slag and the like are byproducts. The bulk industrial smelting slag is prepared into mineral admixture, so that the problem of insufficient granulated blast furnace slag powder and fly ash can be effectively solved. However, because of unique phase and chemical composition, the industrial smelting slag has special properties of powder formed by processing, partial physical and chemical properties are not good, and although the industrial smelting slag has certain hydration activity, the industrial smelting slag is difficult to be directly used as a mineral admixture.
Therefore, the resource utilization of the industrial smelting slag in the southwest region and the regulation and control of the shrinkage of the cement-based material are realized, the invention aims to adopt the industrial smelting slag such as lithium slag, granulated electric furnace phosphorus slag, ferrovanadium slag, nickel slag and the like and other materials to prepare the composite mineral admixture, and the synergistic and complementary effects of different types of materials are fully exerted, so that the formula and the preparation method of the composite mineral admixture with high activity and low shrinkage are formed.
In view of this, the present application is specifically made.
Disclosure of Invention
The invention aims to provide a high-activity low-shrinkage composite mineral admixture, which is prepared from industrial smelting slag such as lithium slag, granulated electric furnace phosphorus slag, ferrovanadium slag, nickel slag and the like, and fully exerts the synergistic and complementary action of different types of smelting slag to form the high-activity low-shrinkage composite mineral admixture.
The invention is realized by the following technical scheme:
a high-activity low-shrinkage complex mineral admixture comprises the following raw material components: lithium slag, granulated electric furnace phosphorus slag, nickel slag, ferrovanadium slag, sulphoaluminate cement clinker, grinding aid and superplasticizer.
According to the invention, the lithium slag, the nickel slag, the phosphorus slag of the granulating electric furnace, the ferrovanadium slag and the sulphoaluminate cement clinker are compounded to be used as the mineral admixture, so that the synergistic complementary action of different types of smelting slag and clinker is fully exerted, the performance defect of single use of the smelting slag can be overcome, the activity of the mineral admixture can be improved, and the shrinkage rate can be reduced.
Furthermore, the chemical composition P in the phosphorus slag of the granulating electric furnace adopted by the invention 2 O 5 Not more than 3.5 percent, the mass coefficient K not less than 1.0, the content of glass phase in the phosphorus slag of the granulating electric furnace not less than 80 percent, and the internal illumination index I of the phosphorus slag of the granulating electric furnace Ra Not more than 1.5, and external illumination index I γ ≤1.5。
The invention limits the P of the phosphorus slag of the used granulating electric furnace 2 O 5 Less than or equal to 3.5 percent, the soluble phosphorus in the phosphorus slag can greatly prolong the setting time of the cement-based material slurry, and can prolong the time of the mixture slurry in the plasticity stage to cause the plastic shrinkage to increase, so that the P is limited 2 O 5 Can effectively reduce the influence of soluble phosphorus on the setting time. As the radioactivity of the raw material phosphate rock used by the phosphorus slag in the southwest area is generally higher, the radioactivity of the phosphorus slag is higher. Therefore, the invention limits the internal illumination index I of the phosphorous slag Ra Less than or equal to 1.5, and external illumination index I γ Less than or equal to 1.5, and the radioactivity of other raw materials used in the invention is low, so the above limitation is satisfiedThe radioactivity of the performance of the composite mineral admixture meets the requirement of building material radionuclide limitation GB6566-2010, and the phosphorus slag range capable of being recycled is enlarged.
Further, the lithium slag is a lithium slag by-product of lithium smelting by a sulfuric acid method, and SiO of the lithium slag 2 +Al 2 O 3 Content is not less than 65%, SO 3 The content is more than or equal to 5 percent and less than or equal to 10.0 percent, the water demand ratio is less than or equal to 115 percent, and the internal illumination index I Ra Not more than 0.6, and external illumination index I γ ≤0.6。
The lithium slag used in the invention is limited to be the lithium slag which is a byproduct of lithium smelting by a sulfuric acid method, and the lithium slag has better activity compared with the lithium slag which is obtained by a byproduct of an alkali method. SO of the invention 3 The calcium aluminate cement is one of the main reactants of the ettringite which is an early expansion source of a cementing material system, the tricalcium aluminate cement mineral can react to generate the ettringite under the condition of sufficient gypsum, and the volume expansion of about 125 percent can be generated in the process, so that the shrinkage of the system can be reduced. For SO in lithium slag 3 The restriction is made, and the anti-shrinkage capability of the composite mineral admixture can be effectively guaranteed. The invention also limits the water demand ratio of the lithium slag to be less than or equal to 115 percent, and can reduce the negative effect of the lithium slag on the fluidity of the composite mineral admixture. The invention limits the internal illumination index I of the lithium slag Ra Not more than 0.6, and external illumination index I γ Less than or equal to 0.6, and provides conditions for qualified radioactivity of the composite mineral admixture.
Further, the ferrovanadium slag is ferrovanadium slag which is a byproduct in producing vanadium-titanium alloy by an aluminothermic method, the content of calcium oxide is more than or equal to 50%, the content of magnesium oxide is 5-15.0%, and the internal irradiation index I is Ra Less than or equal to 0.6, and external illumination index I γ ≤0.6。
The method limits the used ferrovanadium slag to be ferrovanadium slag which is a byproduct in producing vanadium-titanium alloy by an aluminothermic method, free calcium oxide and magnesium oxide components exist in the ferrovanadium slag, and simultaneously limits the content of calcium oxide in the used ferrovanadium slag to be more than or equal to 50 percent and the content of magnesium oxide to be 5-15 percent, because the free calcium oxide component and the magnesium oxide component can expand in a hydration process, the volume shrinkage of a cement-based material in a middle period and a later period can be partially counteracted. The invention limits the internal illumination index I of the ferrovanadium slag Ra Not more than 0.6, and external illumination index I γ Less than or equal to 0.6, and provides conditions for qualified radioactivity of the composite mineral admixture.
Furthermore, the nickel slag is waste slag discharged in the production of nonferrous metal nickel, the content of magnesium oxide is more than or equal to 30 percent and less than or equal to 50 percent, and the internal illumination index I Ra Not more than 0.6, and external illumination index I γ ≤0.6。
The nickel slag used in the invention is waste slag discharged in the production of nonferrous metal nickel, the content of magnesium oxide is limited to be more than or equal to 30 percent and less than or equal to 50 percent, and the characteristic that the magnesium oxide in the nickel slag slowly expands in the later period can be fully utilized, so that the prepared composite mineral admixture has better later-period expansion capability. The invention limits the internal illumination index I of the nickel slag Ra Not more than 0.6, and external illumination index I γ Less than or equal to 0.6, and provides conditions for qualified radioactivity of the composite mineral admixture.
Furthermore, the admixture also comprises a grinding aid, wherein the grinding aid is an early strength grinding aid, the superplasticizer is high-performance polycarboxylic acid solid powder, the water content of the high-performance polycarboxylic acid solid powder is less than or equal to 5%, and the water reducing rate of the high-performance polycarboxylic acid solid powder is more than or equal to 35%.
Further, the invention relates to a high-activity and low-shrinkage composite mineral admixture which comprises the following raw material components in percentage by weight: 15-25% of lithium slag, 30-50% of granulated electric furnace phosphorus slag, 10-20% of ferrovanadium slag, 10-15% of nickel slag, 5-10% of sulphoaluminate cement clinker, 0.5-1.0% of superplasticizer and 0.3-0.5% of early strength grinding aid.
The content of the lithium slag in the composite mineral admixture is 15-25%, namely the lithium slag powder is 15-25% of the secondary component of the composite mineral admixture. On one hand, the lithium slag has high activity, and on the other hand, the high-content gypsum phase in the lithium slag not only can play a role of exciting phosphorous slag powder by sulfate and excite the activity of the phosphorous slag powder, but also can react with sulphoaluminate cement clinker and cement to form ettringite, and the reaction occurs at the early hardening stage of cement slurry and is accompanied with volume expansion, so that the early volume shrinkage of the early cement slurry can be effectively reduced. Meanwhile, the lithium slag is used as a silicon-aluminum mineral admixture, the phosphorus slag and the ferrovanadium slag are calcium-silicon mineral admixtures, and the doping of the lithium slag can effectively make up the defects of silicon-aluminum components in a system and can fully play the synergistic and complementary roles of different smelting slags.
The content of the ferrovanadium slag in the composite mineral admixture is 10-20%. According to the invention, 10% -20% of ferrovanadium slag is adopted, the ferrovanadium slag contains expansion components of free calcium oxide and magnesium oxide, the free calcium oxide can react with water to generate calcium hydroxide after being hardened with cement, and the calcium hydroxide expands along with the volume, so that the effect of reducing shrinkage in the middle stage of the system can be realized. The magnesium oxide in the ferrovanadium slag also has the characteristic of delaying hydration reaction in the hardened cement paste, and can play a role in resisting shrinkage in the later stage of the hardened cement paste. In addition, from the activity perspective, the content of the vanadium iron slag is limited to be related to the lower activity index of the vanadium iron slag, and the activity of the complex mineral admixture is obviously reduced by excessively high mixing amount. Meanwhile, the hydration mechanism of the ferrovanadium slag is different from that of the lithium slag and the phosphorus slag, the hydration activity of the ferrovanadium slag is mainly derived from the hydration reaction of mineral phases such as dicalcium silicate, and the lithium slag and the phosphorus slag in the composite mineral admixture react with calcium hydroxide to obtain the hydration activity, so the two sides cannot form a competitive relationship.
The content of the nickel slag in the composite mineral admixture is 10-15%. The invention adopts 10-15% of nickel slag, because magnesium oxide is an anti-shrinkage component in the later stage of the system, the content of magnesium oxide in ferrovanadium slag is about 10%, the content of magnesium oxide is lower, the anti-shrinkage capability provided for the later stage of the system is limited, the content of magnesium oxide in nickel slag is about 30-40%, the content of magnesium oxide in the system can be compensated, the magnesium oxide can be combined with water to form magnesium hydroxide in the later stage of hydration, the volume expansion of 2.48 times exists, and the system shrinkage can be effectively reduced.
The content of the phosphorus slag of the granulating electric furnace in the composite mineral admixture is limited to be 30-50%, because the 28d activity index of the phosphorus slag can be more than or equal to 90% after the phosphorus slag is processed into powder, and the fluidity ratio is more than or equal to 100%. As the radioactivity of the phosphorus slag of the granulating electric furnace in the southwest region is generally higher, the basic mechanics and working performance of the composite mineral admixture are ensured under the doping amount, and unqualified radioactivity of the composite mineral admixture caused by higher radioactivity of the phosphorus slag can be avoided.
According to the invention, the content of the sulphoaluminate cement clinker is limited to be 5-10%, and the sulphoaluminate cement clinker can provide aluminate ions, calcium ions and sulfate ions in the hydrolysis process, and can generate ettringite with calcium sulfate in the lithium slag and calcium hydroxide hydrated by cement, so that the effect of compensating shrinkage is achieved.
The content of the superplasticizer in the composite mineral admixture is 0.5-1.0 thousandth, so that the fluidity of the composite mineral admixture can be effectively improved, and the fluidity ratio of the composite mineral admixture is ensured to be more than or equal to 105%. On the other hand, the superplasticizer has obvious surfactant property, can reduce the surface tension of aqueous solution in the pores of the gelled material slurry after being doped, and reduces the shrinkage caused by capillary action, thereby being beneficial to improving the shrinkage performance of a system.
The content of the early-strength grinding aid in the composite mineral admixture is 0.3 to 0.5 thousandth, so that the grinding efficiency of each raw material can be effectively improved, and the production cost is saved.
The invention also provides a preparation method of the high-activity low-shrinkage composite mineral admixture, which comprises the following steps:
s1: drying the lithium slag, the ferrovanadium slag, the nickel slag and the granulated electric furnace phosphorus slag until the water content is less than or equal to 1 percent;
s2: grinding the dried granulated electric furnace phosphorus slag and 0.3 to 0.5 thousandth of early strength grinding aid by using vertical grinding equipment until the specific surface area is 450 to 600m 2 /kg；
S3: mixing and grinding the dried lithium slag powder, ferrovanadium slag and nickel slag and 0.3 to 0.5 per mill of early strength grinding aid until the specific surface area is 450 to 650m 2 /kg；
S4: grinding the sulphoaluminate cement clinker until the specific surface area is 350 to 600m 2 /kg；
S5: weighing 15-25% of lithium slag, 30-50% of granulated electric furnace phosphorous slag, 10-20% of ferrovanadium slag, 10-15% of nickel slag, 5-10% of sulphoaluminate cement clinker and 0.5-1.0% of superplasticizer according to the proportion of the powder processed by S2-S4 and other raw materials;
s6: and (3) uniformly mixing the weighed raw materials in a dry mode to obtain the high-activity low-shrinkage composite mineral admixture.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the high-activity low-shrinkage composite mineral admixture and the preparation method thereof provided by the embodiment of the invention, the lithium slag, the ferrovanadium slag, the phosphorus slag of the granulating electric furnace, the nickel slag and the sulphoaluminate cement clinker are compounded to be used as the mineral admixture, so that the synergistic and complementary effects of different types of smelting slag and raw materials are fully exerted, and the anti-shrinkage capability of the composite mineral admixture from the early stage to the later stage is realized;
2. according to the high-activity low-shrinkage composite mineral admixture and the preparation method thereof provided by the embodiment of the invention, the prepared mineral composite mineral admixture has the 7d activity index of more than or equal to 70%, the 28d activity index of more than or equal to 90%, the fluidity ratio of more than or equal to 100%, and is qualified in radioactivity, so that the problem that a single industrial smelting slag powder body cannot meet the application requirement easily is solved.
Description of the preferred embodiment
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one of ordinary skill in the art that: it is not necessary to employ these specific details to practice the present invention. In other instances, well-known materials or methods have not been described in detail in order to avoid obscuring the present invention.
Throughout the specification, reference to "one embodiment," "an embodiment," "one example," or "an example" means: the particular features, structures, or characteristics described in connection with the embodiment or example are included in at least one embodiment of the invention. Thus, the appearances of the phrase "one embodiment," "an embodiment," "one example" or "an example" in various places throughout this specification are not necessarily all referring to the same embodiment or example. Furthermore, the particular features, structures, or characteristics may be combined in any suitable combination and/or sub-combination in one or more embodiments or examples. Further, as used herein, the term "and/or" will be understood by those of ordinary skill in the art to include any and all combinations of one or more of the associated listed items.
Example 1
The embodiment of the invention provides a preparation method of a high-activity and low-shrinkage composite mineral admixture, which comprises the following steps:
s1: drying the lithium slag, the ferrovanadium slag, the nickel slag and the granulated electric furnace phosphorus slag until the water content is less than or equal to 1 percent;
s2: grinding the dried granulated electric furnace phosphorus slag and 0.4 per mill of early strength grinding aid by adopting vertical grinding equipment until the specific surface area is 500m 2 /kg；
S3: mixing and grinding the dried lithium slag powder, ferrovanadium slag and nickel slag and 0.4 per mill of early strength grinding aid to 600m of specific surface area 2 /kg；
S4: grinding the sulphoaluminate cement clinker to 400m of specific surface area 2 /kg；
S5: weighing the powder processed by the S2-S4 and other raw materials according to the following proportion, wherein the proportion of the lithium slag is 20%, the proportion of the granulated electric furnace phosphorus slag is 43%, the proportion of the ferrovanadium slag is 17%, the proportion of the nickel slag is 12%, the proportion of the sulphoaluminate cement clinker is 8%, and the proportion of the superplasticizer is 0.60 per mill;
s6: and (3) mixing the weighed raw materials uniformly in a dry mode.
According to appendix A of JG/T486-2015 composite admixture for concrete, the 7d activity index, the 28d activity index and the fluidity ratio of the composite mineral admixture are tested according to the mass ratio of cement to the high-performance composite mineral admixture of the embodiment of 7.
According to GB/T17671-2021, molding cement and the high-performance composite mineral admixture according to the mass ratio of 7 to 3, filling a dry-shrinkage mortar test piece into the mold by adopting a triple steel die with the length of 40mm multiplied by 160mm, wherein two end plates of the mold are respectively provided with 3 blind holes with the length of 6mm, placing a round-head copper rod measuring head with the length of 2.5cm and the diameter of 6mm before molding, covering a layer of preservative film on the surface after molding, and curing at the relative humidity of more than 90% in a standard curing chamber at the curing temperature (20 +/-3) DEG C for 1d and removing the mold; the initial value of the specimen length is determined with a screw micrometer (unit: mm to 0 \ 8729001 mm); and (4) moving the sample into a constant temperature and humidity chamber (curing temperature (20 +/-2) DEG C, relative humidity 60% +/-5%), testing the length of the sample at the initial curing time and 28d respectively, and testing the shrinkage rate of the sample.
The radioactive index of the embodiment is judged according to building material radionuclide limitation GB 6566-2010.
Example 2
The embodiment of the invention provides a preparation method of a high-activity and low-shrinkage composite mineral admixture, which comprises the following steps:
s1: drying the lithium slag, the ferrovanadium slag, the nickel slag and the granulated electric furnace phosphorus slag until the water content is less than or equal to 1 percent;
s2: grinding the dried granulated electric furnace phosphorus slag and 0.4 per mill of early strength grinding aid by adopting vertical grinding equipment until the specific surface area is 500m 2 /kg；
S3: mixing and grinding the dried lithium slag powder, ferrovanadium slag and nickel slag and 0.4 per mill of early strength grinding aid to 600m of specific surface area 2 /kg；
S4: grinding the sulphoaluminate cement clinker to 400m of specific surface area 2 /kg；
S5: weighing the powder processed by the S2-S4 and other raw materials according to the following proportion, wherein the proportion of the lithium slag is 20%, the proportion of the granulated electric furnace phosphorus slag is 47%, the proportion of the ferrovanadium slag is 15%, the proportion of the nickel slag is 10%, the proportion of the sulphoaluminate cement clinker is 8%, and the proportion of the superplasticizer is 0.60 per mill;
s6: and (3) mixing the weighed raw materials uniformly in a dry mode.
The performance of the high-performance composite mineral admixture of the embodiment was tested by mixing with cement in the same manner as in embodiment 1.
Example 3
The embodiment of the invention provides a preparation method of a high-activity and low-shrinkage composite mineral admixture, which comprises the following steps:
s1: drying the lithium slag, the ferrovanadium slag, the nickel slag and the granulated electric furnace phosphorus slag until the water content is less than or equal to 1 percent;
s2: grinding the dried granulated electric furnace phosphorus slag and 0.4 per mill of early strength grinding aid by adopting vertical grinding equipment until the specific surface area is 500m 2 /kg；
S3: mixing and grinding the dried lithium slag powder, ferrovanadium slag and nickel slag with 0.4 per mill of early strength grinding aid to 600m of specific surface area 2 /kg；
S4: grinding the sulphoaluminate cement clinker to 400m of specific surface area 2 /kg；
S5: weighing the powder processed by the S2-S4 and other raw materials according to the following proportion, namely 18% of lithium slag, 44% of granulated electric furnace phosphorus slag, 18% of ferrovanadium slag, 13% of nickel slag, 7% of sulphoaluminate cement clinker and 0.60% of superplasticizer;
s6: and (3) mixing the weighed raw materials uniformly in a dry mode.
The performance of the high-performance composite mineral admixture of the embodiment was tested by mixing with cement in the same manner as in embodiment 1.
Comparative example 1
Blank comparison, cement alone, without the mineral admixture according to the invention, was tested in the same manner as in example 1.
Comparative example 2
The comparative example uses granulated electric furnace phosphorous slag powder to prepare mineral admixture, and the steps are as follows:
s1: drying the granulated electric furnace phosphorus slag until the water content is less than or equal to 1 percent;
s2: mixing the dried granulated electric furnace phosphorus slag with 0.4 per mill of early strength grinding aid, and grinding the mixture by a ball mill until the specific surface is 500m 2 /kg；
The maximum size of the phosphorus slag of the granulating electric furnace is not more than 50 mm, and the granules with the maximum size more than 10mm are not more than 5%. The chemical composition P 2 O 5 1.8 percent, the mass coefficient K is 1.3, and the content of the glass phase is 87 percent. Internal illumination index I Ra Is 1.1, and has an external illumination index I γ Is 1.0.
The comparative example mineral admixture was mixed with cement to conduct performance testing in the same manner as in example 1.
Comparative example 3
The comparative example uses lithium slag powder to prepare mineral admixture, and comprises the following steps:
s1: drying the lithium slag until the water content is less than or equal to 1%;
s2: grinding the dried lithium slag to 550m of specific surface area 2 Per kg, forming a mineral admixture.
The lithium slag is the byproduct of lithium smelting by a sulfuric acid method, namely SiO 2 +Al 2 O 3 70% of SO 3 The content is 6.5 percent, the water demand ratio is 113 percent, and the internal illumination index I Ra Is 0.3, and has an external illumination index I γ Is 0.3.
The comparative example mineral admixture was mixed with cement to conduct performance testing in the same manner as in example 1.
Comparative example 4
The mineral admixture is prepared from the ferrovanadium slag according to the comparative example, and the steps are as follows:
s1: drying the ferrovanadium slag until the water content is less than or equal to 1 percent;
s2: mixing the dried ferrovanadium slag with 0.4 per mill of early strength grinding aid, and grinding to a specific surface area of 650m 2 Per kg, forming a mineral admixture.
The ferrovanadium slag is a byproduct ferrovanadium slag produced in the production of vanadium-titanium alloy by an aluminothermic method, and has the calcium oxide content of 57 percent, the magnesium oxide content of 9.7 percent, the ignition loss of 2.2 percent and the internal illumination index I Ra Is 0.2, and has an external illumination index I γ Is 0.2.
The performance test was carried out by mixing the mineral admixture of this comparative example with cement in the same manner as in example 1.
Comparative example 5
The comparative example adopts nickel slag to prepare mineral admixture, and comprises the following steps:
s1: drying the nickel slag until the water content is less than or equal to 1%;
s2: mixing the dried nickel slag with 0.4 per mill of early strength grinding aid, and grinding to specific surface area of 600m 2 Per kg, mineral admixtures are formed.
The comparative example mineral admixture was mixed with cement to conduct performance testing in the same manner as in example 1.
Comparative example 6
This comparative example prepared a complex mineral admixture on the basis of example 1 using raw materials whose processes were outside the scope of the invention, the steps of which were as follows:
s1: drying the lithium slag, the ferrovanadium slag, the nickel slag and the granulated electric furnace phosphorus slag until the water content is less than or equal to 1 percent;
s2: grinding the dried granulated electric furnace phosphorus slag and 0.4 per mill of early strength grinding aid by adopting a vertical grinding device to a specific surface area of 300m 2 /kg；
S3: mixing and grinding the dried lithium slag powder, ferrovanadium slag and nickel slag and 0.4 per mill of early strength grinding aid to 400m of specific surface area 2 /kg；
S4: grinding the sulphoaluminate cement clinker to the specific surface area of 300m 2 /kg；
S5: weighing the powder processed by the S2-S4 and other raw materials according to the following proportion, wherein the proportion of the lithium slag is 20%, the proportion of the granulated electric furnace phosphorus slag is 43%, the proportion of the ferrovanadium slag is 17%, the proportion of the nickel slag is 12%, the proportion of the sulphoaluminate cement clinker is 8%, and the proportion of the superplasticizer is 0.60 per mill;
s6: and (3) mixing the weighed raw materials uniformly in a dry mode.
The preparation method and the detection method of the composite mineral admixture of the comparative example are the same as those of the example 1.
Comparative example 7
The comparative example prepares a complex mineral admixture by using raw materials with a mixture ratio which is not within the scope of the invention on the basis of the example 1, and comprises the following steps:
s1: drying the lithium slag, the ferrovanadium slag, the nickel slag and the granulated electric furnace phosphorus slag until the water content is less than or equal to 1 percent;
s2: grinding the dried granulated electric furnace phosphorus slag and 0.4 per mill of early strength grinding aid by adopting vertical grinding equipment until the specific surface area is 500m 2 /kg；
S3: mixing and grinding the dried lithium slag powder, ferrovanadium slag and nickel slag and 0.4 per mill of early strength grinding aid to 600m of specific surface area 2 /kg；
S4: grinding the sulphoaluminate cement clinker to 400m of specific surface area 2 /kg；
S5: weighing 20% of lithium slag, 70% of granulated electric furnace phosphorus slag, 5% of ferrovanadium slag, 5% of nickel slag, 0% of sulphoaluminate cement clinker and 0.60% of superplasticizer according to the proportion of the powder processed by S2-S4 and other raw materials;
s6: and (3) mixing the weighed raw materials uniformly in a dry mode.
The composite mineral admixture of the comparative example was mixed with cement to conduct performance testing, the testing method was the same as that of example 1.
Comparative example 8
The comparative example prepares the complex mineral admixture by adopting the raw materials with the mixture ratio which is not in the scope of the invention on the basis of the example 1, and comprises the following steps:
s1: drying the lithium slag, the ferrovanadium slag, the nickel slag and the granulated electric furnace phosphorus slag until the water content is less than or equal to 1 percent;
s2: grinding the dried granulated electric furnace phosphorus slag and 0.4 per mill of early strength grinding aid by adopting vertical grinding equipment until the specific surface area is 500m 2 /kg；
S3: mixing and grinding the dried lithium slag powder, ferrovanadium slag and nickel slag and 0.4 per mill of early strength grinding aid to 600m of specific surface area 2 /kg；
S4: grinding the sulphoaluminate cement clinker to 400m of specific surface area 2 /kg；
S5: weighing 50% of lithium slag, 20% of granulated electric furnace phosphorus slag, 20% of ferrovanadium slag, 10% of nickel slag and 0% of sulphoaluminate cement clinker;
s6: and (3) mixing the weighed raw materials uniformly in a dry mode.
The composite mineral admixture of the comparative example is mixed with cement for performance detection, and the detection method is the same as that of the example 1.
TABLE 1 performance of the mortar test blocks obtained in the examples and comparative examples
| Numbering | 7d Activity index/%) | 28d Activity index/%) | Fluidity ratio/%) | Radioactivity | 28d shrinkage/10 -6 |
| Example 1 | 76 | 92 | 102 | Qualified | 95 |
| Example 2 | 78 | 94 | 102 | Qualified | 93 |
| Example 3 | 75 | 91 | 103 | Qualified | 82 |
| Comparative example 1 | -- | -- | -- | Qualified | 406 |
| Comparative example 2 | 72 | 94 | 101 | Fail to be qualified | 275 |
| Comparative example 3 | 76 | 106 | 88 | Qualified | 251 |
| Comparative example 4 | 69 | 81 | 96 | Qualified | 23 |
| Comparative example 5 | 64 | 77 | 97 | Qualified | 42 |
| Comparative example 6 | 66 | 85 | 98 | Qualified | 164 |
| Comparative example 7 | 74 | 97 | 102 | Qualified | 233 |
| Comparative example 8 | 71 | 94 | 85 | Qualified | 115 |
The results of the tests of the examples and comparative examples are shown in Table 1. As can be seen from Table 1, by comparing example 1 with comparative examples 2 to 4, the single phosphorus slag powder, lithium slag powder, ferrovanadium slag powder and nickel slag powder have one or more problems of low activity index, poor fluidity, unqualified radioactivity and the like.
As can be seen by comparing example 1 with comparative example 5, the combination of properties of the composite mineral admixtures prepared without the requirement of the present invention is inferior.
It can be seen from the comparison between example 1 and comparative examples 6 to 7 that the composite mineral admixture not formulated according to the formulation of the present invention has the problems of low activity index and low fluidity.
In conclusion, the mineral composite mineral admixture prepared according to the invention can meet the requirements that the activity index of 7d is more than or equal to 70%, the activity index of 28d is more than or equal to 90%, the fluidity ratio is more than or equal to 95% and the radioactivity is qualified, and meanwhile, the 28d shrinkage rate of the mineral composite mineral admixture is reduced by more than 50% compared with that of a sample (not doped with the mineral admixture) in a comparative example 1, so that the shrinkage of a base material can be effectively reduced, and the shrinkage cracking resistance of a cement-based material can be improved.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (3)
1. The high-activity low-shrinkage composite mineral admixture is characterized by comprising the following raw material components in percentage by weight: 15-25% of lithium slag, 30-50% of granulated electric furnace phosphorus slag, 10-20% of ferrovanadium slag, 10-15% of nickel slag, 5-10% of sulphoaluminate cement clinker, 0.5-1.0% of superplasticizer and 0.3-0.5% of early strength grinding aid.
2. The high activity, low shrinkage complex mineral admixture as defined in claim 1,
the lithium slag is the lithium slag which is the byproduct of lithium smelting by a sulfuric acid method and is SiO 2 +Al 2 O 3 Content is not less than 65%, SO 3 The content is more than or equal to 5 percent and less than or equal to 10.0 percent, the water demand ratio is less than or equal to 115 percent, and the internal illumination index I Ra Less than or equal to 0.6, and external illumination index I γ ≤0.6；
The chemical composition P in the phosphorus slag of the granulating electric furnace 2 O 5 Not more than 3.5 percent, the mass coefficient K not less than 1.0, the content of glass phase in the phosphorus slag of the granulating electric furnace not less than 80 percent, and the internal illumination index I of the phosphorus slag of the granulating electric furnace Ra Not more than 1.5, and external illumination index I γ ≤1.5；
The nickel slag is waste slag discharged in the production of nonferrous metal nickel, the content of magnesium oxide is more than or equal to 30 percent and less than or equal to 50 percent, and the internal illumination index I Ra Not more than 0.6, and external illumination index I γ ≤0.6；
The ferrovanadium slag is ferrovanadium slag which is a byproduct in producing vanadium-titanium alloy by an aluminothermic method, the content of calcium oxide is more than or equal to 50 percent, the content of magnesium oxide is 5-15.0 percent, and the internal irradiation index I is Ra Not more than 0.6, and external illumination index I γ ≤0.6。
3. The method of claim 1 wherein the step of preparing a high activity, low shrinkage complex mineral admixture comprises the steps of:
s1: drying the lithium slag, the ferrovanadium slag, the nickel slag and the granulated electric furnace phosphorus slag until the water content is less than or equal to 1 percent;
s2: grinding the dried granulated electric furnace phosphorus slag and 0.3 to 0.5 thousandth of early strength grinding aid by using vertical grinding equipment until the specific surface area is 450 to 600m 2 /kg；
S3: mixing and grinding the dried lithium slag powder, ferrovanadium slag and nickel slag and 0.3 to 0.5 per mill of early strength grinding aid until the specific surface area is 450 to 650m 2 /kg；
S4: grinding the sulphoaluminate cement clinker until the specific surface area is 350 to 600m 2 /kg；
S5: weighing 15-25% of lithium slag, 30-50% of granulated electric furnace phosphorus slag, 10-20% of ferrovanadium slag, 10-15% of nickel slag, 5-10% of sulphoaluminate cement clinker and 0.5-1.0% of superplasticizer according to the following proportion;
s6: and (3) uniformly mixing the weighed raw materials in a dry mode to obtain the high-activity low-shrinkage composite mineral admixture.
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