Low-cost cement-clinker-free filling material containing barium slag as well as preparation method and application of low-cost cement-clinker-free filling material

Abstract

The invention belongs to the technical field of mine filling materials, and particularly relates to a low-cost cement-clinker-free filling material containing barium slag and a preparation method and application thereof.The filling material comprises a cementing material, aggregate and water, and the cementing material is prepared from, by weight, 30-78 parts of barium slag, 142-371 parts of slag and 20-50 parts of desulfurized gypsum; the aggregate is prepared from 2000 to 2300 parts of lead and zinc tailings; the preparation method comprises the following steps: weighing a cementing material and an aggregate according to a mass ratio of the cementing material to the aggregate of 1: 4-1: 12, and uniformly mixing the weighed cementing material and aggregate with water according to a slurry concentration of 0.75-0.81; the application is that the filling material is used as a mining filling material; according to the invention, the barium slag, the slag, the desulfurized gypsum and the lead-zinc tailings are doped, and good compressive strength for industrial application can be displayed without adding an activator, an early strength agent and other additives, so that the cement can be used as a mining filling material and is a good substitute of cement.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of mine filling materials, and particularly relates to a low-cost cement clinker-free filling material containing barium residue and a preparation method and application thereof. BACKGROUND

[0002] The barite reserves in Guizhou Province rank first in China, and Guizhou has become the main barium salt production base in China and even in the world. The annual production capacity of barium carbonate is 500-700 thousand tons. According to the data of the Ecological Environment Department of Guizhou Province, 49.82 million tons of barium residue were discharged in the whole province in 2020. Anshun City has become a representative of barium residue production in Guizhou Province. Due to market reasons, the demand for building materials has decreased in recent years, resulting in a decrease in the amount of barium residue disposal. Barium residue is a hazardous waste, and the barium sulfide and acid-soluble barium in it pollute the environment.

[0003] It is predicted that the global urban solid waste production will increase to 2.2 billion tons by 2025, and the waste volume and weight will be reduced by 90% and 70% respectively through incineration power generation technology, which has become an important way for urban solid waste treatment. According to statistics, the total amount of urban solid waste incinerated in China has exceeded 100 million tons per year.

[0004] According to the National Hazardous Waste List, barium residue is a hazardous waste. The harmless disposal and the safety hidden trouble caused to the environment and human health have become a hot topic in the field of solid waste and hazardous waste treatment.

[0005] At present, more researches on green filling materials prepared by barium residue, slag, desulfurization gypsum, lead-zinc tailings alone or in cooperation with other solid wastes or cement provide strong theoretical support for engineering implementation. However, in the above researches, barium residue, slag, desulfurization gypsum and lead-zinc tailings are not disposed cooperatively to prepare ultra-low-cost cement clinker-free filling materials, and the subsequent treatment method of the excessive heavy metals in the leaching solution is not explained. SUMMARY

[0006] In order to solve the problems in the prior art, the application provides a low-cost cement clinker-free filling material containing barium residue and a preparation method and application thereof.

[0007] The technical scheme of the application is as follows: A low-cost cement clinker-free filling material containing barium residue, comprising cementitious material, aggregate and water; The cementitious material consists of the following components in parts by weight: 30-78 parts of barium residue, 142-371 parts of slag and 20-50 parts of desulfurization gypsum; The aggregate is 2000-2300 parts of lead-zinc tailings; The mass ratio of the cementitious material to the aggregate is 1:4-1:12; The slurry concentration of the filling material is 0.75-0.81.

[0008] Further, the barium residue mainly consists of the following components: 30-35 parts by weight of SiO2, 25-30 parts by weight of BaO, 17-22 parts by weight of SO3, 5-10 parts by weight of Fe2O3, 3-4 parts by weight of Na2O, 3-4 parts by weight of Al2O3, and 0-1 parts by weight of MgO.

[0009] Further, the slag mainly consists of the following components: 40-45 parts by weight of CaO, 25-30 parts by weight of SiO2, 13-16 parts by weight of Al2O3, 6-9 parts by weight of MgO, and 1-3 parts by weight of SO3.

[0010] Further, the slag refers to any slag with a 28d activity index of not less than 95%.

[0011] Further, the desulfurization gypsum mainly consists of the following components: 50-55 parts by weight of SO3, 40-45 parts by weight of CaO, 1-2 parts by weight of SiO2, 0-1 parts by weight of Fe2O3, and 0-1 parts by weight of MgO.

[0012] Further, the lead-zinc tailings mainly consist of the following components: 45-50 parts by weight of CaO, 23-28 parts by weight of MgO, 8-13 parts by weight of SiO2, and 3-8 parts by weight of Fe2O3.

[0013] Further, the specific surface area of the barium residue is 400 m 2 / kg or more; The specific surface area of the slag is 500 m 2 / kg or more; The specific surface area of the desulfurization gypsum is 450 m 2 / kg or more.

[0014] The application further provides a preparation method of the low-cost cement clinker-free filling material containing the barium residue, wherein the cementitious material and the aggregate are weighed according to a mass ratio of 1:4-1:12, and the weighed cementitious material and aggregate are uniformly mixed with water at a slurry concentration of 0.75-0.81.

[0015] The application further provides an application of the low-cost cement clinker-free filling material containing the barium residue, and the filling material is used for mining filling material.

[0016] Compared with the prior art, the low-cost cement clinker-free filling material containing the barium residue, and the preparation method and application have the following beneficial effects: 1. The filling material of the present application cooperatively utilizes barium slag, slag, desulfurization gypsum and lead-zinc tailings, has a simpler composition, does not need to add activators, early strength agents and other additives, and does not need to add cement clinker, is composed of barium slag, slag, desulfurization gypsum and lead-zinc tailings, greatly reduces the raw material cost, and has a higher utilization rate of barium slag, slag, desulfurization gypsum and lead-zinc tailings; 2. The cooperative utilization of barium slag, slag, desulfurization gypsum and lead-zinc tailings simplifies the composition and still shows good cementing performance due to the synergistic effect, including the compressive strength and effective solidification of various heavy metals in barium slag and lead-zinc tailings; according to GB17671-1999 "Cement mortar strength test method", the cementing material of the present application is used to prepare filling test blocks with a slurry concentration of 0.75-0.81, the test block size is 40mmx40mmx160mm, the test blocks are cured at a temperature of 22℃ and a humidity of more than 99.5%, and show good compressive strength and leaching safety performance; 3. The super-low-cost cement clinker-free filling material using barium slag, slag, desulfurization gypsum and lead-zinc tailings has good safety, the sulfate ions in the desulfurization gypsum and the ettringite, C-(A)-S-H gel and the like generated through hydration reaction solidify the heavy metal ions (Ba, Cr, Zn and Pb) through precipitation, adsorption and combination reaction, and the leaching concentration of heavy metal ions is all lower than the drinking water standard; 4. The present application controls the chemical composition of the components of barium slag, slag, desulfurization gypsum and lead-zinc tailings, controls the components of barium slag, slag and desulfurization gypsum that constitute the cementing material, and controls the ratio of the cementing material to the lead-zinc tailings as aggregate, thereby effectively improving the performance of the cementing material, ensuring the compressive performance of the filling material, and effectively reducing the industrial application cost; 5. The filling material of the present application is usually mixed with water at a concentration of 0.75-0.81 when used, and the water-cement ratio can be used to replace cement in large scale to provide super-low-cost cement clinker-free cementing material for the preliminary combination cementing filling mining technology or the preparation of concrete for the construction industry; 6. The specific surface area of the raw material is improved by grinding to achieve the optimal specific surface area, which on the one hand stimulates the activity of slag, reduces the hydration difficulty, and on the other hand improves the uniformity of the material; In summary, in summary, the ultra-low-cost filler of the present invention utilizes barium slag, slag, and desulfurized gypsum to replace traditional binder cement, utilizes desulfurized gypsum to fully stimulate the activity of slag, and synergistically utilizes lead-zinc tailings to prepare ultra-low-cost cement-free clinker filler, so that barium slag, slag, desulfurized gypsum and lead-zinc tailings are maximized in resource utilization, and provides the optimal dosage of barium slag, slag, desulfurized gypsum and lead-zinc tailings in the cement-free clinker cementitious system, so that the leaching concentration of heavy metal ions in the system (horizontal oscillation method) is still lower than the drinking water standard, thereby solving the difficult problems of industrial solid waste (slag, desulfurized gypsum and lead-zinc tailings) and industrial solid waste (barium slag) reduction, harmlessness and resource utilization, promoting the coordinated resource utilization and environmental protection of solid waste and hazardous waste, and providing ultra-low-cost cement-free clinker filler for large-scale replacement of cement solidification stabilization safe landfill and preliminary combination of cementitious filling mining technology, laying the foundation for engineering application. DETAILED DESCRIPTION

[0017] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts are within the scope of protection of the present invention.

[0018] A low-cost, cement-free clinker filler containing barium slag is composed of the following components by mass: 30-78 parts barium slag, 142-371 parts slag, 20-50 parts desulfurized gypsum, 2000-2300 parts lead-zinc tailings, a mortar-sand ratio of 1:4-1:12, and a concentration of 0.75-0.81. Orthogonal experimental design is shown in Table 1. The barium slag, slag, desulfurized gypsum, and lead-zinc tailings used in the present invention can be purchased commercially or prepared in-house, as long as the chemical composition requirements are met.

[0019] The chemical composition of the barium slag, slag, desulfurized gypsum, and lead-zinc tailings described herein refers to the content of various metal or mineral elements as oxides, and does not refer to the content of compounds present as oxides in the barium slag, slag, desulfurized gypsum, or lead-zinc tailings. Furthermore, the above chemical composition results can be obtained using conventional detection methods available in the art, such as typical fluorescence detection methods for post-burnout or pre-burnout measurements.

[0020] The chemical compositions of barium slag, slag powder, desulfurized gypsum and lead-zinc tailings are shown in Table 2. The detection method is: X-ray fluorescence spectrometry (XRF), using an XRF-1800 X-ray fluorescence spectrometer to measure secondary X-rays for material composition analysis.

[0021] After casting and forming, the materials are cured to different ages and then subjected to compressive strength and leaching toxicity tests. The test methods are as follows: The raw materials are weighed in the proportions described in Examples 1-9, respectively, the barium slag is ground to a specific surface of 400 m 2 / kg, the slag is ground to a specific surface of 500 m 2 / kg, the desulfurization gypsum is ground to a specific surface of 450 m 2 / kg, and the lead-zinc tailings are dried and used directly, with a concentration of 0.75-0.81. The sample is prepared according to GB 17671-1999 "Cement mortar strength test method", with a size of 40 mm x 40 mm x 160 mm, and is cured at a temperature of 35°C and a humidity of more than 99.5%.

[0022] The formed test blocks at different curing ages are tested for leaching toxicity and compressive strength according to Chinese Standard (HJ / T 557-2010) "Solid waste leaching toxicity method-horizontal vibration method" and Chinese Standard GB / T 17671-1999 "Cement test method-strength determination" (MTCDS), and the test results are shown in Tables 3 and 4. Example

[0023] The low-cost cement clinker-free filling material containing barium slag of this example comprises cementitious material, aggregate and water, the cementitious material consists of, by weight fraction, 78 parts of barium slag, 371 parts of slag and 50 parts of desulfurization gypsum; the aggregate is lead-zinc tailings, the mass ratio of the cementitious material to the aggregate is 1:4, and the slurry concentration of the filling material is 0.75.

[0024] After casting and forming, the curing is performed to different ages for leaching toxicity and compressive strength testing, and the test methods are as described above, and the test results are shown in Tables 3 and 4. Example

[0025] The low-cost cement clinker-free filling material containing barium slag of this example comprises cementitious material, aggregate and water, the cementitious material consists of, by weight fraction, 78 parts of barium slag, 371 parts of slag and 50 parts of desulfurization gypsum; the aggregate is lead-zinc tailings, the mass ratio of the cementitious material to the aggregate is 1:4, and the slurry concentration of the filling material is 0.78.

[0026] After casting and forming, the curing is performed to different ages for leaching toxicity and compressive strength testing, and the test methods are as described above, and the test results are shown in Tables 3 and 4. Example

[0027] The low-cost cement clinker-free filling material containing barium slag of this example comprises cementitious material, aggregate and water, the cementitious material consists of, by weight fraction, 78 parts of barium slag, 371 parts of slag and 50 parts of desulfurization gypsum; the aggregate is lead-zinc tailings, the mass ratio of the cementitious material to the aggregate is 1:4, and the slurry concentration of the filling material is 0.81.

[0028] After being cast and shaped, the leaching toxicity and compressive strength tests are carried out after curing for different ages, the test method is as described above, and the test results are shown in Tables 3 and 4. Embodiment

[0029] The low-cost cement clinker-free filling material containing barium residue of the embodiment comprises cementitious material, aggregate and water, the cementitious material is composed of the following components in parts by weight: 43 parts of barium residue, 206 parts of slag powder and 28 parts of desulfurization gypsum; the aggregate is lead-zinc tailings, the mass ratio of the cementitious material to the aggregate is 1:8, and the slurry concentration of the filling material is 0.75.

[0030] After being cast and shaped, the leaching toxicity and compressive strength tests are carried out after curing for different ages, the test method is as described above, and the test results are shown in Tables 3 and 4. Embodiment

[0031] The low-cost cement clinker-free filling material containing barium residue of the embodiment comprises cementitious material, aggregate and water, the cementitious material is composed of the following components in parts by weight: 43 parts of barium residue, 206 parts of slag powder and 28 parts of desulfurization gypsum; the aggregate is lead-zinc tailings, the mass ratio of the cementitious material to the aggregate is 1:8, and the slurry concentration of the filling material is 0.75.

[0032] After being cast and shaped, the leaching toxicity and compressive strength tests are carried out after curing for different ages, the test method is as described above, and the test results are shown in Tables 3 and 4. Embodiment

[0033] The low-cost cement clinker-free filling material containing barium residue of the embodiment comprises cementitious material, aggregate and water, the cementitious material is composed of the following components in parts by weight: 43 parts of barium residue, 206 parts of slag powder and 28 parts of desulfurization gypsum; the aggregate is lead-zinc tailings, the mass ratio of the cementitious material to the aggregate is 1:8, and the slurry concentration of the filling material is 0.75.

[0034] After being cast and shaped, the leaching toxicity and compressive strength tests are carried out after curing for different ages, the test method is as described above, and the test results are shown in Tables 3 and 4. Embodiment

[0035] The low-cost cement clinker-free filling material containing barium residue of the embodiment comprises cementitious material, aggregate and water, the cementitious material is composed of the following components in parts by weight: 43 parts of barium residue, 206 parts of slag powder and 28 parts of desulfurization gypsum; the aggregate is lead-zinc tailings, the mass ratio of the cementitious material to the aggregate is 1:8, and the slurry concentration of the filling material is 0.75.

[0036] After being cast into shape, the leaching toxicity and compressive strength tests were carried out after curing for different ages, the test method was as described above, and the test results were as shown in Tables 3 and 4. Embodiment

[0037] The low-cost cement clinker-free filling material containing barium residue of the embodiment comprises cementitious material, aggregate and water, the cementitious material is composed of the following components in parts by weight: 30 parts of barium residue, 142 parts of slag powder and 20 parts of desulfurization gypsum; the aggregate is lead-zinc tailings, the mass ratio of the cementitious material to the aggregate is 1:12, and the slurry concentration of the filling material is 0.78.

[0038] After being cast into shape, the leaching toxicity and compressive strength tests were carried out after curing for different ages, the test method was as described above, and the test results were as shown in Tables 3 and 4. Embodiment

[0039] The low-cost cement clinker-free filling material containing barium residue of the embodiment comprises cementitious material, aggregate and water, the cementitious material is composed of the following components in parts by weight: 30 parts of barium residue, 142 parts of slag powder and 20 parts of desulfurization gypsum; the aggregate is lead-zinc tailings, the mass ratio of the cementitious material to the aggregate is 1:12, and the slurry concentration of the filling material is 0.78.

[0040] After being cast into shape, the leaching toxicity and compressive strength tests were carried out after curing for different ages, the test method was as described above, and the test results were as shown in Tables 3 and 4.

[0041] Comparative Example 1 As a comparative example of the embodiments 1-9, the embodiment provides a low-cost cement clinker-free filling material containing barium residue, which comprises cementitious material, aggregate and water, the cementitious material is composed of the following components in parts by weight: 250 parts of barium residue, 200 parts of slag powder and 50 parts of desulfurization gypsum; the aggregate is lead-zinc tailings, the mass ratio of the cementitious material to the aggregate is 1:4, and the slurry concentration of the filling material is 0.81.

[0042] After being cast into shape, the leaching toxicity and compressive strength tests were carried out after curing for different ages, the test method was as described above, and the test results were as shown in Tables 3 and 4.

[0043] Comparative Example 2 As a comparative example of the embodiments 1-9, the embodiment provides a low-cost cement clinker-free filling material containing barium residue, which comprises cementitious material, aggregate and water, the cementitious material is composed of the following components in parts by weight: 250 parts of barium residue, 200 parts of slag powder and 50 parts of desulfurization gypsum; the aggregate is lead-zinc tailings, the mass ratio of the cementitious material to the aggregate is 1:4, and the slurry concentration of the filling material is 0.81.

[0044] After being cast into shape, the samples are cured to different ages for leaching toxicity and compressive strength tests, the test methods are as described above, and the test results are shown in Table 3 and Table 4.

[0045] Table 1 horizontal test in examples

[0046] Table 2 chemical composition analysis of raw materials

[0047] Table 3 heavy metal leaching concentration (μg / L) of barium residue, lead-zinc tailings and filling material test blocks with different ages used in examples

[0048] Table 4 compressive strength of filling material test blocks

[0049] As shown in Table 4, the low-cost cement clinker-free filling material containing barium residue provided by the present application has a mortar ratio of 1:4-1:12 and a concentration of 0.75-0.81, and the early compressive strength thereof is greater than 1 MPa (satisfying the requirement that the compressive strength of the stope filling body should be no less than 0.8 MPa), the compressive strength after 28 days is greater than 3 MPa, and even greater than 7 MPa; and as shown in Comparative Example 1 and Comparative Example, and Table 3 and Table 4, too high content of barium residue not only leads to high leaching concentration of barium ions, but also results in that the early compressive strength and the compressive strength after 28 days of the filling material are both lower than the compressive strength requirement of the stope filling body; therefore, the filling material provided by the present application can be used as a mining filling material, thereby improving the recycling rate of barium residue and lead-zinc tailings.

[0050] The above shows and describes the basic principles and main features of the present application and the advantages of the present application, and it is obvious for those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and the present application can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application; therefore, no matter from which point of view, the embodiments should be regarded as exemplary and non-limiting, and the scope of the present application is defined by the appended claims rather than the above description, and therefore all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present application.

[0051] In addition, it should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent technical solution, and the description manner of the specification is only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be properly combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A low-cost cement-free clinker filler containing barium slag, comprising a cementitious material, aggregate and water, characterized in that: The gelling material is composed of the following components by weight: 30-78 parts of barium slag, 142-371 parts of slag, and 20-50 parts of desulfurized gypsum; The aggregate is 2000-2300 parts of lead-zinc tailings; The mass ratio of the cementitious material to the aggregate is 1:4-1:12; The slurry concentration of the filler is 0.75-0.

81.

2. The low-cost cement-free clinker filler containing barium slag according to claim 1, characterized in that: The barium slag mainly consists of the following components: by weight: 30-35 parts of SiO2, 25-30 parts of BaO, 17-22 parts of SO3, 5-10 parts of Fe2O3, 3-4 parts of Na2O, 3-4 parts of Al2O3, and 0-1 part of MgO.

3. The low-cost cement-free clinker filler containing barium slag according to claim 1, characterized in that: The slag mainly consists of the following components: by weight, 40-45 parts of CaO, 25-30 parts of SiO2, 13-16 parts of Al2O3, 6-9 parts of MgO, and 1-3 parts of SO3.

4. The low-cost cement-free clinker filler containing barium slag according to claim 1, characterized in that: The desulfurization gypsum mainly consists of the following components: by weight, 50-55 parts of SO3, 40-45 parts of CaO, 1-2 parts of SiO2, 0-1 part of Fe2O3, and 0-1 part of MgO.

5. The low-cost cement-free clinker filler containing barium slag according to claim 1, characterized in that: The lead-zinc tailings are mainly composed of the following components: by weight, 45-50 parts of CaO, 23-28 parts of MgO, 8-13 parts of SiO2, and 3-8 parts of Fe2O3.

6. The low-cost cement-free clinker filler containing barium slag according to claim 1, characterized in that: The specific surface area of ​​the barium slag is 400m 2 / kg or more; The specific surface area of ​​slag is 500m 2 / kg or more; The specific surface area of ​​the desulfurized gypsum is 450m 2 / kg or more.

7. The method for preparing a low-cost cement-free clinker filler containing barium slag according to any one of claims 1 to 6, characterized in that: The cementitious material and aggregate are weighed at a mass ratio of 1:4-1:12, and the weighed cementitious material and aggregate are uniformly mixed with water at a slurry concentration of 0.75-0.

81.

8. Use of the low-cost cement-free clinker filler containing barium slag according to any one of claims 1 to 6, characterized in that: The filler material is used as mining filler material.

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