CN112624640A - Full-solid waste sulphoaluminate cement clinker for prefabricated parts and preparation method thereof - Google Patents

Abstract

The invention relates to a full solid waste sulphoaluminate cement clinker for prefabricated parts and a preparation method thereof, wherein the clinker comprises 5-20% of siliceous raw materials, 5-12% of SO 3-containing raw materials, 5-30% of aluminum raw materials and 50-60% of calcareous raw materials by mass percent. Compared with the prior art, the cement prepared by the method can be prepared by cooperatively blending various solid wastes according to the component characteristics of the industrial solid wastes, reasonably matching and optimizing the proportion, and the influence factors of the mineral sintering and hydration performances of the cement clinker are analyzed by testing means such as XRD, lithofacies analysis and SEM and the like, so that the proper mineral composition and the optimal calcining process condition of the cement clinker are determined, the industrial solid wastes are 100 percent utilized to produce the high belite sulphoaluminate cement clinker, the maximum utilization of the industrial waste residues is realized, the production cost is reduced, and the waste of natural resources is reduced.

Description

Full-solid waste sulphoaluminate cement clinker for prefabricated parts and preparation method thereof

Technical Field

The invention relates to the technical field of production of cement-based blending materials for concrete, in particular to a full-solid waste sulphoaluminate cement clinker for prefabricated parts and a preparation method thereof.

Background

The mineral composition of the high belite sulphoaluminate cement clinker is basically the same as that of the common sulphoaluminate cement clinker, but C₂The content of S is higher than that of C₄A₃-

The raw materials used for preparation are basically the same, and generally limestone, bauxite and natural gypsum are taken as main raw materials. However, with the long-term mass exploitation of natural resources, cement production raw materials are increasingly scarce, and the replacement of materials such as limestone, bauxite and natural gypsum by various industrial solid wastes becomes a focus of attention of researchers. With the acceleration of industrialization and urbanization, most industrial solid wastes are simply buried or stockpiled in the open without any treatment, which wastes land and pollutes environment.

Chinese patent CN109133684A discloses a high-iron belite sulphoaluminate cement clinker and a preparation method thereof, wherein the cement clinker is prepared by using low-grade bauxite, low-grade limestone, sandstone and shale as raw materials; chinese patent CN108793785A discloses a low-temperature preparation method of a sulfosilicate-belite-sulphoaluminate cement, which also selects bauxite, limestone and high-alumina cement as raw materials to prepare cement clinker; chinese patent CN106966617A discloses a belite-sulphoaluminate-ferro-aluminate cement, which also uses bauxite as raw material to prepare cement clinker; chinese patent CN105060745A discloses a method for firing belite-sulphoaluminate-sulphoferro-aluminate-calcium sulphosilicate cement clinker, which also uses bauxite as raw material to prepare cement clinker; chinese patent CN105314902A discloses a method for calcining belite sulphoaluminate cement clinker by using industrial waste residues completely, which is characterized in that although the cement clinker is prepared by using the industrial waste residues as raw materials, industrial mineral borax is added to regulate the calcining performance of the cement clinker; the methods for calcining belite sulphoaluminate cement clinker all use at least one natural mineral or all use industrial waste residue plus industrial mineral raw materials. The partial substitution of natural raw materials causes the utilization of industrial waste residues to have a certain limit, the utilization rate of the industrial solid waste reaches 70-90 percent at present, and the 100 percent utilization rate of the industrial solid waste cannot be completely realized to produce the high belite sulphoaluminate cement.

The key problem to be solved is how to invent the all-solid-waste sulphoaluminate cement clinker for the prefabricated part and the preparation method thereof, wherein the all-solid-waste sulphoaluminate cement clinker can reduce the emission of carbon dioxide during cement production, promote the resource utilization of solid wastes, utilize various solid wastes to prepare the high belite sulphoaluminate cement cooperatively, can exert the complementary advantages of different types of raw material components, widen the resource utilization way of the solid wastes and give consideration to social benefits.

Disclosure of Invention

In order to solve the technical problems that the utilization of industrial waste residues is limited due to partial replacement of natural raw materials, the utilization rate of the existing industrial solid waste reaches 70% -90%, the high belite sulphoaluminate cement can not be produced by completely realizing the utilization rate of 100% of the industrial solid waste, the maximized utilization of the industrial waste residues can not be realized, the production cost is increased, the natural resources are wasted and the like in the conventional method for calcining the belite sulphoaluminate cement clinker, the invention provides the full-solid waste sulphoaluminate cement clinker for the prefabricated member, the preparation method and the preparation method thereof, which can reduce the emission of carbon dioxide during the cement production and promote the resource utilization of the solid waste, the high belite sulphoaluminate cement can be prepared by using various solid wastes in a synergistic manner, the complementary advantages of different types of raw material components can be exerted, and the utilization ways of the solid waste can be widened at the same time, the social benefit is also considered.

The technical scheme of the invention is as follows: the full-solid waste sulphoaluminate cement clinker for prefabricated parts and the preparation method thereof comprise the following raw materials, 5-20% of siliceous raw material and SO-containing raw material by mass percentage₃5 to 12 percent of raw materials, 5 to 30 percent of aluminum raw materials and 50 to 60 percent of calcium raw materials.

The siliceous raw material comprises at least one of tailings such as molybdenum tailings, gold tailings and the like, and SiO in the tailings such as the molybdenum tailings, the gold tailings and the like₂The mass fraction is more than or equal to 60.0 percent.

Said SO-containing₃The raw materials include citric acid residue, lactic acid residue, titanium white residue, fluorine gypsum, etc. containing SO₃At least one of the raw materials.

The aluminum raw material comprises at least one of aluminum profile factory industrial waste residue, aluminum sulfate residue, aluminum silicate roller bar waste material and aluminum refractory material waste material, and Al in the aluminum profile factory industrial waste residue, aluminum sulfate residue and ceramic ore dressing waste residue₂O₃The mass fraction of the component (a) is more than or equal to 17.0 percent.

The calcareous raw material comprises at least one of marble tailings, construction waste, lime slag and dicyandiamide slag, and CaO in the marble tailings, the construction waste, the lime slag and the dicyandiamide slag is more than or equal to 45.0%.

The preparation method of the full-solid waste sulphoaluminate cement clinker for the prefabricated part comprises the following steps:

firstly, a calcium raw material, a silicon raw material, an aluminum raw material and SO₃After the raw materials are measured according to the proportion, the raw materials are ground to be below 80 mu m by an experimental ball mill, and the raw materials are put into a special forming die to be pressed into a cylindrical test block after being uniformly mixed;

step two, during calcination, firstly placing the mixture in a drying box which is kept at the constant temperature of 105 +/-5 ℃ for drying for 1 hour, then placing the mixture in a high-temperature furnace which is kept at the constant temperature of 900-1000 ℃ for presintering for 30 minutes, then quickly moving the mixture into the high-temperature furnace which is kept at the constant temperature of 1220-1300 ℃ for calcination for 30 minutes, and quickly cooling to obtain the full-solid waste high belite sulphoaluminate cement clinker for UHPC, wherein the full-solid waste high belite sulphoaluminate cement clinker is used for UHThe mineral composition of the clinker is C₄A₃S:20%～30%，C₂S:50%～55%，C₄AF:12%～30%。

The invention has the following beneficial effects: 1) compared with the prior art, according to the component characteristics of the industrial solid waste, the method has the advantages that the influence factors of the mineral firing and hydration performance of the cement clinker are analyzed by the test means such as XRD, lithofacies analysis and SEM, the proper mineral composition and the optimal calcination process condition of the cement clinker are determined, the industrial solid waste is 100% utilized to produce the high belite sulphoaluminate cement clinker, the maximum utilization of industrial waste residues is realized, the production cost is reduced, and the waste of natural resources is reduced;

2) the technology adopts an ion doping calcination technology, and fully utilizes Cu rich in industrial metal tailings²⁺、P²⁺And Zn²⁺Plasma, after high temperature calcination of the raw material, Cu²⁺、P²⁺And Zn²⁺Plasma into clinker minerals

-C₂S crystal lattices cause the reduction of the symmetry of a crystal structure, cause lattice distortion, contribute to the reduction of the melting temperature of the crystal, improve the crystallinity and the reaction degree, increase the hydration reaction activity of the crystal, improve the burnability of clinker, improve the strength of the clinker, realize the preparation of the high belite sulphoaluminate cement clinker at the low temperature of 1300 ℃, achieve the aims of low coal consumption, good grindability, low grinding energy consumption and low production cost, and have the excellent characteristics of low hydration heat, high fluidity, high durability, high later strength, freezing resistance, impermeability, erosion resistance, low water consumption for standard consistency, long condensation time, small linear expansion rate, small mortar dry shrinkage rate and the like.

Drawings

FIG. 1 shows XRD spectrum of clinker calcined at 1280 ℃ for 30 min;

FIG. 2 shows a TG-DSC curve of the fired clinker.

Detailed Description

The present invention will be described in further detail with reference to specific examples.

Examples

The full-solid waste sulphoaluminate cement clinker for prefabricated parts comprises, by mass, 5-20% of siliceous raw materials and SO₃5 to 12 percent of raw materials, 5 to 30 percent of aluminum raw materials and 50 to 60 percent of calcium raw materials.

The siliceous raw material comprises at least one of tailings such as molybdenum tailings, gold tailings and the like, and SiO in the tailings such as the molybdenum tailings, the gold tailings and the like₂The mass fraction is more than or equal to 60.0 percent.

Said SO-containing₃The raw materials include citric acid residue, lactic acid residue, titanium white residue, fluorine gypsum, etc. containing SO₃At least one of the raw materials.

The aluminum raw material comprises at least one of aluminum profile factory industrial waste residue, aluminum sulfate residue, aluminum silicate roller bar waste material and aluminum refractory material waste material, and Al in the aluminum profile factory industrial waste residue, aluminum sulfate residue and ceramic ore dressing waste residue₂O₃The mass fraction of the component (a) is more than or equal to 17.0 percent.

The calcareous raw material comprises at least one of marble tailings, construction waste, lime slag and dicyandiamide slag, and CaO in the marble tailings, the construction waste, the lime slag and the dicyandiamide slag is more than or equal to 45.0%.

The preparation method of the full-solid waste sulphoaluminate cement clinker for the prefabricated part comprises the following steps:

firstly, a calcium raw material, a silicon raw material, an aluminum raw material and SO₃After the raw materials are measured according to the proportion, the raw materials are ground to be below 80 mu m by an experimental ball mill, and the raw materials are put into a special forming die to be pressed into a cylindrical test block after being uniformly mixed;

step two, during calcination, firstly placing the mixture in a drying box which is kept at the constant temperature of 105 +/-5 ℃ for drying for 1 hour, then placing the mixture in a high-temperature furnace which is kept at the constant temperature of 900-1000 ℃ for presintering for 30 minutes, then quickly moving the mixture into the high-temperature furnace which is kept at the constant temperature of 1220-1300 ℃ for calcination for 30 minutes, and quickly cooling to obtain the full-solid waste high belite sulphoaluminate cement clinker for UHPC, wherein the mineral composition of the clinker is C₄A₃S:20%～30%，C₂S:50%～55%，C₄AF:12%～30%。

In the invention, more types of industrial solid waste raw materials are applied, and in order to make the purposes, technical schemes and advantages of the invention more clear, the industrial solid waste is selected from one of the four raw materials and is subjected to burdening and calcination in the example, so that the invention is further described in detail. It is to be understood that the specific examples of the use of the materials described herein are merely illustrative of the invention and are not intended to limit all other materials used in the invention.

In order to ensure the formation of 4 minerals in the clinker, a proportioning calculation method needs to be designed, the proportioning of the raw materials is calculated according to the designed mineral composition of the clinker and the chemical components of the raw materials, and the following steps can be taken:

in the production of high belite sulphoaluminate cement clinker, the alkalinity coefficient (C) is introduced_m) The concept of three values of Al-Si ratio (n) and Al-S ratio (P) which are mainly used for adjusting the raw material proportion and controlling the clinker components.

1) Coefficient of basicity (C)_m）：

C_m=

2) Aluminum-silicon ratio (n):

=

3) sulfur to aluminum ratio (P):

=

the mineral composition of the clinker is designed.

ω（C₂S）=2.87ω（SiO₂）

ω（C₄A₃

）=3.04ω（Fe₂O₃）

ω（C₄A₃

）=0.99[ω（Al₂O₃）-0.64ω（Fe₂O₃）]

The chemical composition of the clinker is calculated from the mineral composition according to the following formula:

ω（CaO）=0.6512ω（C₂S）+0.3672ω（C₄A₃

）+0.4616ω（C₄AF）

ω（SiO₂）=0.3488ω（C₂S）

ω（Al₂O₃）=0.5016ω（C₄A₃

）+0.2098ω（C₄AF）

ω（Fe₂O₃）=0.33ω（C₄AF）

ω（SO₃）=0.1311ω（C₄A₃

）

and establishing a relational expression according to the principle that the chemical components of the clinker are equal to the sum of the corresponding chemical components of the raw materials in each proportion, and calculating the proportion of each raw material by solving to obtain the proportion of the raw materials.

The raw material ratio obtained by calculation can be used for calculating the raw material ratio, and determining whether the analysis value meets the design requirement, if not, the raw material ratio can be properly adjusted on the basis until the design requirement is met. Under the general condition, if the selection of raw materials meets the design of the composition of a plurality of groups of minerals, the raw material proportion can be accurately calculated according to the calculation steps; if the raw material selection does not fully satisfy the design requirements, further steps may be taken to make the adjustments.

The mineral composition of the clinker is as follows: c₄A₃

:20%～30%， C₂S:50%～55%，C₄AF:12%～30%，

The clinker comprises the following oxides in percentage by mass:

Ca0:48.0%～53.0%、SiO₂:15.0%～18.0%、Fe₂O₃:2.0%～3.0%、Al₂O₃:19.0%～25.0%、S O₃:6.0%～8.5%。

the raw materials used for preparing the high belite sulphoaluminate cement clinker comprise calcium raw materials, silicon raw materials, aluminum raw materials, iron raw materials and CaSO-containing raw materials₄Raw material components.

One industrial solid waste is selected from four raw materials, and the mixture is calcined in the example; the siliceous raw material is molybdenum tailings, and SiO in the molybdenum tailings₂More than or equal to 60.0 percent; the aluminum raw material is industrial waste residue of an aluminum section bar factory, and Al in the industrial waste residue of the aluminum section bar factory₂O₃More than or equal to 17.0 percent; the calcareous raw material selects marble tailings, and CaO in the marble tailings is more than or equal to 45.0 percent; containing SO₃The raw material is titanium white slag and SO₃≥35.0%。

TABLE 1 chemical composition of four industrial residues

The present invention will be described in further detail with reference to specific examples below:

examples 1-4 various industrial residues and their chemical compositions are shown in table 1:

examples 1-4 examples industrial residue ratios are shown in table 2:

examples 1-example 4 clinker preparation method:

drying four kinds of industrial waste residues in the table 1 in a drying box at 100 ℃, respectively weighing according to the proportioning requirements of the industrial waste residues in each example in the table 2, weighing 3Kg of mixed materials after weighing, uniformly mixing, grinding in a test ball mill until the screen residue of a square-hole sieve with the particle size of 80 mu m is less than or equal to 10.0 percent, and then putting in a special forming die to press into a cylindrical test block; during calcination, the mixture is firstly placed in a drying box which is kept at the constant temperature of (105 +/-5) DEG C for drying for 1h, then is put in a high-temperature furnace which is kept at the constant temperature of 950 ℃ for presintering for 30min, then is quickly moved into the high-temperature furnace which is kept at the constant temperature of 1280 ℃ for calcination for 30min, and then is taken out and is quenched in the air to the room temperature until all material columns are completely calcined. Then crushing the calcined and cooled clinker, and grinding the crushed clinker by using an experimental ball mill until the specific surface area is 375 m3/kg (set according to industrial actual production control indexes).

The XRD spectrum of clinker is calcined at 1280 ℃ for 30min, as shown in figure 1;

a TG-DSC curve of the calcined clinker as shown in figure 2;

the results of measuring the physical properties of the cement clinker such as strength, consistency, water consumption, setting time, etc. according to the national standard method are shown in Table 3.

TABLE 3 physical Properties of Cement Clinker

It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or some technical features can be replaced. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. The utility model provides a prefabricated component is with useless sulphoaluminate cement clinker admittedly entirely, its characterized in that: comprises the following raw materials, 5-20% of siliceous raw material and SO₃5 to 12 percent of raw materials, 5 to 30 percent of aluminum raw materials and 50 to 60 percent of calcium raw materials.

2. The full solid waste sulphoaluminate cement clinker for prefabricated parts according to claim 1, wherein: the siliceous raw material comprises at least one of tailings such as molybdenum tailings, gold tailings and the like, and SiO in the tailings such as the molybdenum tailings, the gold tailings and the like₂The mass fraction is more than or equal to 60.0 percent.

3. The full solid waste sulphoaluminate cement clinker for prefabricated parts according to claim 1, wherein: said SO-containing₃The raw materials include citric acid residue, lactic acid residue, titanium white residue, fluorine gypsum, etc. containing SO₃At least one of the raw materials.

4. The full solid waste sulphoaluminate cement clinker for prefabricated parts according to claim 1, wherein: the aluminum raw material comprises at least one of aluminum profile factory industrial waste residue, aluminum sulfate residue, aluminum silicate roller bar waste material and aluminum refractory material waste material, and Al in the aluminum profile factory industrial waste residue, aluminum sulfate residue and ceramic ore dressing waste residue₂O₃The mass fraction of the component (a) is more than or equal to 17.0 percent.

5. The full solid waste sulphoaluminate cement clinker for prefabricated parts according to claim 1, wherein: the calcareous raw material comprises at least one of marble tailings, construction waste, lime slag and dicyandiamide slag, and CaO in the marble tailings, the construction waste, the lime slag and the dicyandiamide slag is more than or equal to 45.0%.

6. The method for preparing the full solid waste sulphoaluminate cement clinker for prefabricated parts, as claimed in any one of claims 1 to 5, comprising the following steps:

firstly, a calcium raw material, a silicon raw material, an aluminum raw material and SO₃After the raw materials are measured according to the proportion, the raw materials are ground to be below 80 mu m by an experimental ball mill, and the raw materials are put into a special forming die to be pressed into a cylindrical test block after being uniformly mixed;

step two, during calcination, firstly placing the mixture in a drying box which is kept at the constant temperature of 105 +/-5 ℃ for drying for 1 hour, then placing the mixture in a high-temperature furnace which is kept at the constant temperature of 900-1000 ℃ for presintering for 30 minutes, then quickly moving the mixture into the high-temperature furnace which is kept at the constant temperature of 1220-1300 ℃ for calcination for 30 minutes, and quickly cooling to obtain the full-solid waste high belite sulphoaluminate cement clinker for UHPC, wherein the mineral composition of the clinker is C₄A₃S:20%～30%，C₂S:50%～55%，C₄AF:12%～30%。

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