阅读说明：本技术 复合激发多固废制备低成本充填胶凝材料的制备方法 (Preparation method for preparing low-cost filling cementing material by composite excitation multi-solid waste ) 是由 吴凡 温震江 杨晓炳 翟淑花 李胜辉 高谦 尹升华 巴蕾 韦寒波 胡亚军 郭斌 于 2020-04-08 设计创作，主要内容包括：本发明公开了一种复合激发多固废制备低成本充填胶凝材料的制备方法,属于充填采矿技术领域。包括：选择盐基激发剂和碱基激发剂及相应的配方范围,并分别快速优化,得到盐基激发剂和碱基激发剂的优化配方；根据优化配方得到复合激发剂配比,分别建立充填胶凝材料充填体强度、体积膨胀率以及充填胶凝材料成本与复合激发剂配比的关系模型；基于关系模型建立复合激发剂配比优化模型并求解,获得复合激发剂优化配方；根据复合激发剂优化配方制备低成本胶凝材料。该方法能够针对复杂多固废资源,快速获取复合激发剂最优配方,由此制备低成本充填胶凝材料在充填采矿中利用,可以获得显著的经济效益和环保效益。(The invention discloses a preparation method for preparing a low-cost filling cementing material by compounding and exciting multiple solid wastes, and belongs to the technical field of filling mining. The method comprises the following steps: selecting a base activator, a base activator and a corresponding formula range, and respectively and quickly optimizing to obtain optimized formulas of the base activator and the base activator; obtaining the proportion of the composite exciting agent according to the optimized formula, and respectively establishing a relation model of the filling body strength and the volume expansion rate of the filled cementing material, the cost of the filled cementing material and the proportion of the composite exciting agent; establishing a compound excitant ratio optimization model based on the relation model and solving to obtain a compound excitant optimization formula; and preparing the low-cost cementing material according to the optimized formula of the composite excitant. The method can quickly obtain the optimal formula of the composite exciting agent aiming at complex multi-solid waste resources, so that the prepared low-cost filling cementing material is utilized in filling mining, and remarkable economic benefit and environmental protection benefit can be obtained.)

1. The preparation method for preparing the low-cost filling cementing material by compounding and exciting multiple solid wastes is characterized by comprising the following steps:

step 1: selecting a base activator, a base activator and a corresponding formula range, and respectively and quickly optimizing to obtain optimized formulas of the base activator and the base activator;

step 2: obtaining the proportion of the composite exciting agent according to the optimized formula of the base exciting agent and the base exciting agent, and respectively establishing a relation model of the filling body strength and the volume expansion rate of the filled cementing material, the cost of the filled cementing material and the proportion of the composite exciting agent;

and step 3: establishing a compound activator proportioning optimization model based on the relation model and solving to obtain a compound activator optimized formula which meets the requirements of filling body strength and expansion rate of a filling mine and has the lowest cost of a low-cost filling cementing material;

and 4, step 4: and preparing the low-cost cementing material according to the obtained compound excitant optimized formula.

2. The preparation method according to claim 1, wherein the step 1 specifically comprises:

selecting a base exciting agent aiming at the available solid waste resources, developing a base exciting agent orthogonal test under the high-temperature curing condition of high temperature of 40 ℃ and humidity of more than or equal to 95%, and optimizing the formula of the base exciting agent by adopting range analysis;

selecting a basic group excitant aiming at the solid waste resource which can be utilized, carrying out a basic group excitant orthogonal test under the high-temperature curing condition that the high temperature is 40 ℃ and the humidity is more than or equal to 95 percent, and optimizing the basic group excitant formula by adopting range analysis.

3. The production method according to claim 1, wherein the salt-based activator is mainly a sulfate activator, and a small amount of an alkali activator is added.

4. The preparation method of claim 1, wherein the basic group activator takes a basic solid waste mixture as a main activator, and a small amount of sulfate activator is added.

5. The preparation method according to claim 1, wherein the step 2 specifically comprises:

step 21: obtaining the proportion of the composite excitant according to the optimized formula of the base excitant and the base excitant;

step 22: performing orthogonal design on the composite excited cementing material, performing an orthogonal test on the strength of a cementing body of the low-cost filled cementing material, and obtaining an orthogonal test result on the strength of the cementing body;

step 23: calculating the cost of the filling cementing material according to the composite excitant material and the solid waste utilization cost;

step 24: and (3) performing stepwise regression analysis by using a quadratic polynomial, and respectively establishing a relation model of the filling body strength and the volume expansion rate of the filled cementing material, the cost of the filled cementing material and the proportion of the composite exciting agent.

6. The preparation method according to claim 5, wherein the relationship models of the filling body strength, the volume expansion rate and the filling cementing material cost of the filling cementing material and the proportion of the composite activator are respectively as follows:

R_7d＝F₁(Y)、R_7drepresents the strength of the filling body 7 d; r_28dRepresenting a filling body28d strength; f₁(Y) represents the strength model of the pack 7 d; f₂(Y) represents the strength model of the pack 28 d;

V_28d＝F₃(Y)，V_28drepresenting the filling body expansion coefficient, F₃(Y) represents a filling body expansion rate model;

C_F＝F₄(Y)，C_Trepresents the cost of the filled cementitious material; f₄(Y) represents a filled cementitious material cost model; y ═ Y₁，y₂}^TRepresenting the proportion variable of the composite exciting agent of the filling cementing material in percentage.

7. The method of claim 6, wherein F is₁(Y) to F₄The concrete model (Y) is as follows:

F₁(Y)＝a₁+b₁y₁+c₁y₂+d₁y₁y₁+e₁y₂y₂+f₁y₁y₂；

F₂(Y)＝a₂+b₂y₁+c₂y₂+d₂y₁y₁+e₂y₂y₂+f₂y₁y₂；

F₃(Y)＝a₃+b₃y₁+c₃y₂+d₃y₁y₁+e₃y₂y₂+f₃y₁y₂；

F₄(Y)＝a₄+b₄y₁+c₄y₂+d₄y₁y₁+e₄y₂y₂+f₄y₁y₂，

wherein, a_n、b_n、c_n、d_n、e_n、f_n(n-1, 2, 3, 4) represents constant terms after quadratic polynomial stepwise regression analysis, respectively.

8. The method according to claim 1, wherein the step 3 comprises:

step 31: determining the strength indexes [ R ] of 7d and 28d of filling cementing material filling bodies produced safely in mines_7d]、[R_28d]And a permissible value [ V ] of the expansion coefficient of the filler_28d]；

Step 32: establishing a low-cost filling cementing material composite exciting agent proportioning optimization model by taking the cost of the low-cost filling cementing material as an optimization target and taking the filling body strength and the volume expansion rate of the filling cementing material as constraint conditions;

step 33: and solving to obtain the optimized formula of the composite exciting agent which meets the requirements of filling body strength and expansion rate of the filled mine and has the lowest cost of the low-cost filling cementing material.

9. The preparation method according to claim 8, wherein the optimization model of the proportioning of the low-cost filling cementing material and the compound activator in the step 32 is as follows:

optimizing the target: MinC_T＝MinF₄(Y)；

Constraint conditions are as follows: r_7d＝F₁(Y)≥[R_7d]；

R_28d＝F₂(Y)≥[R_28d]；

V_28d＝F₃(Y)≤[Y_28d]。

10. The composite excitation multi-solid waste prepared low-cost filling cementing material is characterized by being prepared by the preparation method according to any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of filling mining of various solid waste resources, in particular to a preparation method for preparing a low-cost filling cementing material by compounding and exciting multiple solid wastes.

Background

With the rapid development of national economy and the continuous development of resources, resources with high grade and good conditions are gradually exhausted, and more deep-buried, high ground stress and large water difficult-to-mine deposits are being developed. For safe, environment-friendly and green mining and clean production, the filling mining method is the primary choice. The stoping process of the filling mining method is complex, the production capacity is low, and the mining cost is high. Therefore, the development and utilization of the low-cost and high-performance filling cementing material are the necessary way for improving the economic benefit and the environmental protection benefit of filling mining.

For over 10 years, people are always exploring and utilizing various industrial solid wastes such as slag, steel slag, desulfurized gypsum and the like to invent a novel filling cementing material with low cost and high strength and a preparation method thereof. The research result shows that: the smelting industrial waste residue after high-temperature calcination and water quenching has potentially different degrees of water hardening activity. The activity of the slag is closely related to the type of metallurgical slag, mineral composition and the treatment process of the discharge process. Therefore, the potential activity of the waste residues of different types of solid wastes and different treatment processes of the same solid wastes has great difference and uncertainty, thereby bringing technical problems to the resource utilization of industrial solid wastes. The filling cementing material developed by utilizing industrial solid wastes at present is mainly prepared by mechanical grinding (force excitation) and a chemical excitant. Therefore, the grinding fineness of the solid waste materials, the exciting agent and the formula not only influence the performance of the cementing material (the strength of a filling body and the fluidity of slurry), but also determine the cost of the filling cementing material. Obviously, the finer the solid waste powder, the higher the activity. But the grinding cost is improved along with the increase of the grinding fineness. The chemical activator mainly comprises a salt-based activator mainly comprising sulfate, a base activator mainly comprising calcium oxide and a composite activator prepared from alkali salt. Undoubtedly, the activator material and the formula not only affect the performance of the filled cementing material, but also relate to the cost of the filled cementing material, and are key technologies for preparing low-cost filled cementing materials based on multiple solid wastes.

Chinese invention patents CN103613294A, CN104609749A and CN103787601A disclose a formula of a composite excitation material mainly developed by slag and filled with a gelled material and a preparation method thereof; CN102249611A, CN102633448A, CN103043975A, CN103102089A, CN106565187B and CN107352825A invent a formula and a preparation method of a filling cementing material for metal mine beneficiation tailing aggregate; for rod sanding and mixing aggregates, CN103803826A, CN103803928A and CN103803929A disclose formulations of consolidated powder filled cementitious materials; CN107540302A discloses a formula for preparing a filling cementing material by using low-quality solid wastes such as steel slag, loess and phosphogypsum; CN102234191A, CN108178597A and CN110054423A invent early strength filling cementitious material formulas suitable for mining by a downward stratified filling method; CN102924005A and CN108439910A disclose filled cementitious formulations with micro-expansion; CN108240233A invents the proportion of the filling cementing material prepared by the cement synergist; for coal gangue mixed coarse aggregate and filling coal mining technology, CN105152601A, CN105753418A, CN107619249A, CN107805023A and CN108083701A provide a filling cementing material proportioning and preparation method; CN110218010A also discloses a method for preparing the filling cementing material by calcining the mixture of steel slag, ash and the like.

In conclusion, the characteristics of the invention are as follows: discloses a formula of a filling cementing material and a preparation method thereof aiming at specific solid wastes. The disclosed exciting agent material and the proportion are only limited to specific purposes and specific conditions, the development of multi-solid waste filling cementing materials is not suitable, and the optimized formula of the composite exciting agent for mine tailings with different fillings is difficult to obtain.

Different from building gelled materials, the filling gelled materials are developed based on metallurgical slag, various complex and variable solid waste resources with uncertain factors are involved, and filling gelled materials with excellent performance and low cost can be obtained only through optimization decision by using a filling gelled material excitant and a formula. More importantly, the filling mine mining method, the filling aggregate and the filling system influence the performance requirements and the proportion of the filling cementing material. It is clear that by combining the mining method, the stoping process and the filling system to prepare a low-cost filled cementitious material, it is possible to obtain a filled cementitious material with the lowest filling material cost and good performance.

Aiming at the current development situation and the existing problems of the filling cementing material, the invention discloses a method for rapidly optimizing the preparation of a low-cost filling cementing material by compounding and exciting multiple solid wastes, which is characterized by comprising the following steps: adopting high-temperature maintenance to quickly obtain a base and a basic group excitant optimized formula; then, under the standard nutrient condition, carrying out orthogonal design of the proportion of the composite exciting agent and a strength test of the cemented filling body; on the basis, establishing a compound excitant optimization model for proportioning optimization; and carrying out economic analysis on the filled cementing material through a strength verification test of the cemented filling body.

Disclosure of Invention

In order to realize the purpose, the invention provides a quick optimization method for preparing a low-cost filling cementing material by compounding and exciting multiple solid wastes, wherein a high-temperature curing is adopted to quickly obtain a base and a basic activator formula; carrying out a compound excitant proportioning orthogonal test under a standard curing condition; establishing and solving a compound excitant ratio optimization model; economic analysis was performed by a pack strength validation test.

According to the first aspect of the invention, the preparation method for preparing the low-cost filling cementing material by compounding and exciting multiple solid wastes comprises the following steps:

step 1: selecting a base activator, a base activator and a corresponding formula range, and respectively and quickly optimizing to obtain optimized formulas of the base activator and the base activator;

step 2: obtaining the proportion of the composite exciting agent according to the optimized formula of the base exciting agent and the base exciting agent, and respectively establishing a relation model of the filling body strength and the volume expansion rate of the filled cementing material, the cost of the filled cementing material and the proportion of the composite exciting agent;

and step 3: establishing a compound activator proportioning optimization model based on the relation model and solving to obtain a compound activator optimized formula which meets the requirements of filling body strength and expansion rate of a filling mine and has the lowest cost of a low-cost filling cementing material;

and 4, step 4: and preparing the low-cost cementing material according to the obtained compound excitant optimized formula.

Further, the step 1 specifically includes:

selecting a base exciting agent aiming at the available solid waste resources, developing a base exciting agent orthogonal test under the high-temperature curing condition of high temperature of 40 ℃ and humidity of more than or equal to 95%, and optimizing the formula of the base exciting agent by adopting range analysis;

selecting a basic group excitant aiming at the solid waste resource which can be utilized, carrying out a basic group excitant orthogonal test under the high-temperature curing condition that the high temperature is 40 ℃ and the humidity is more than or equal to 95 percent, and optimizing the basic group excitant formula by adopting range analysis.

Furthermore, the salt-based activator takes a sulfate activator as a main component, and a small amount of alkali activator is added.

Furthermore, the basic group excitant takes an alkaline solid waste mixture as a main excitant and a small amount of sulfate excitant is added.

Further, the step 2 specifically includes:

step 21: obtaining the proportion of the composite excitant according to the optimized formula of the base excitant and the base excitant;

step 22: performing orthogonal design on the composite excited cementing material, performing an orthogonal test on the strength of a cementing body of the low-cost filled cementing material, and obtaining an orthogonal test result on the strength of the cementing body;

step 23: calculating the cost of the filling cementing material according to the composite excitant material and the solid waste utilization cost;

step 24: and (3) performing stepwise regression analysis by using a quadratic polynomial, and respectively establishing a relation model of the filling body strength and the volume expansion rate of the filled cementing material, the cost of the filled cementing material and the proportion of the composite exciting agent.

Furthermore, the relation models of the filling body strength, the volume expansion rate, the filling cementing material cost and the compound activator ratio of the filling cementing material are respectively as follows:

R_7d＝F₁(Y)、R_7drepresents the strength of the filling body 7 d; r_28dRepresents the strength of the pack 28 d; f₁(Y) represents the strength model of the pack 7 d; f₂(Y) represents the strength model of the pack 28 d;

V_28d＝F₃(Y)，V_28drepresenting the filling body expansion coefficient, F₃(Y) represents a filling body expansion rate model;

C_T＝F₄(Y)，C_Trepresents the cost of the filled cementitious material; f₄(Y) represents a filled cementitious material cost model; y ═ Y₁，y₂}^TRepresenting the mixing ratio variable of the filling cementing material and the exciting agentAnd (4) calculating the percentage.

Further, said F₁(Y) to F₄The concrete model (Y) is as follows:

F₁(Y)＝a₁+b₁y₁+c₁y₂+d₁y₁y₁+e₁y₂y₂+f₁y₁y₂

F₂(Y)＝a₂+b₂y₁+c₂y₂+d₂y₁y₁+e₂y₂y₂+f₂y₁y₂

F₃(Y)＝a₃+b₃y₁+c₃y₂+d₃y₁y₁+e₃y₂y₂+f₃y₁y₂

F₄(Y)＝a₄+b₄y₁+c₄y₂+d₄y₁y₁+e₄y₂y₂+f₄y₁y₂

wherein, a_n、b_n、c_n、d_n、e_n、f_n(n-1, 2, 3, 4) represents constant terms after quadratic polynomial stepwise regression analysis, respectively.

Further, the step 3 specifically includes:

step 31: determining the strength indexes [ R ] of 7d and 28d of filling cementing material filling bodies produced safely in mines_7d]、[R_28d]And a permissible value [ V ] of the expansion coefficient of the filler_28d]；

Step 32: establishing a low-cost filling cementing material composite exciting agent proportioning optimization model by taking the cost of the low-cost filling cementing material as an optimization target and taking the filling body strength and the volume expansion rate of the filling cementing material as constraint conditions;

step 33: and solving to obtain the optimized formula of the composite exciting agent which meets the requirements of filling body strength and expansion rate of the filled mine and has the lowest cost of the low-cost filling cementing material.

Further, the optimization model of the low-cost filling cementing material composite exciting agent ratio in the step 32 is as follows:

optimizing the target: MinC_T＝MinF₄(Y)；

Constraint conditions are as follows: r_7d＝F₁(Y)≥[R_7d]；

R_28d＝F₂(Y)≥[R_28d]；

V_28d＝F₃(Y)≤[V_28d]。

According to a second aspect of the invention, a composite excitation multi-solid waste prepared low-cost filling cementing material is provided, and the filling cementing material is prepared by the preparation method according to any one of the above aspects.

The invention has the beneficial effects that:

1. aiming at available solid waste resources, a base and base exciting agent orthogonal test is carried out under the high-temperature curing condition that the temperature is high at 40 ℃ and the humidity is more than or equal to 95 percent, the base and base exciting agent formula is optimized by adopting range analysis, and the technical problem brought by the utilization of industrial solid waste resources can be effectively solved by utilizing various industrial solid wastes.

2. The base and base exciting agent are used for optimizing the formula, the orthogonal design of the composite excited cementing material and the orthogonal test of the cementing body strength are carried out, the orthogonal test result and the cementing material cost are obtained, a relation model of the filling body strength, the volume expansion rate, the cementing material cost and the exciting agent is established, the method is applicable to the development of the filling cementing material with multiple solid wastes, and the technical problem of the difference of the composite exciting agent caused by different mine tailings is effectively solved.

3. The low-cost filling cementing material cost is taken as an optimization target, the strength and the volume expansion rate of a cemented filling body are taken as constraint conditions, a low-cost filling cementing material proportion optimization model is established, a composite excitant optimization formula with the lowest filling cementing material cost and meeting the strength and the volume expansion rate of the cemented filling body required by the safe production of a filling mine is obtained, and the low-cost and high-performance filling cementing material is developed and utilized, so that the economic and social benefits of filling mining can be effectively improved.

Drawings

FIG. 1 is a flow chart of a method for preparing a low-cost filling cementing material by using composite excitation multi-solid wastes according to the invention;

FIG. 2 is a particle size distribution curve of Handsteel slag micropowder according to an embodiment of the present invention;

FIG. 3 is a graph showing the particle size distribution of desulfurized gypsum according to an embodiment of the invention;

FIG. 4 is a particle size distribution curve of cement clinker powder according to an embodiment of the present invention;

FIG. 5 is a plot of the distribution of the particle size of the ultra-fine full-sized iron ore of interest in the example of the present invention;

FIG. 6 is a particle size distribution curve of the fine slag powder of Benxi iron and steel company in the embodiment of the present invention;

FIG. 7 is a graph showing a distribution curve of the particle size of desulfurized gypsum from Steel company in the example of the present invention;

FIG. 8 is a particle size distribution curve of cement clinker powder in an embodiment of the present invention;

FIG. 9 is a plot of the size distribution of the whole tailing of the Seshan mountain iron ore in the example of the present invention.

Detailed Description

In order to more clearly illustrate the method for rapidly optimizing the composite-excited multi-solid waste preparation of the low-cost cementing material disclosed by the invention and the related key technology and implementation steps, the following detailed description is provided with reference to the accompanying drawings and specific implementation examples.

As shown in FIG. 1, the preparation method for preparing the low-cost filling cementing material by using the composite excitation multi-solid waste comprises the following steps:

step 101: selecting a base activator, a base activator and a corresponding formula range, and respectively and rapidly optimizing to obtain an optimized formula of the base activator and the base activator.

Aiming at available solid waste resources, a salt-based exciting agent is selected by virtue of engineering experience, an orthogonal test of the salt-based exciting agent is carried out under the high-temperature curing condition that the temperature is 40 ℃ and the humidity is more than or equal to 95%, and the formula of the salt-based exciting agent is optimized by adopting range analysis.

The salt-based activator mainly comprises a sulfate activator, and a small amount of alkali activator is added. The sulfate excitant comprises industrial by-product gypsum, such as desulfurized gypsum, fluorgypsum, phosphogypsum, desulfurized ash and the like.

Aiming at available solid waste resources, a base exciting agent is selected by virtue of engineering experience, a base exciting agent orthogonal test is carried out under the high-temperature curing condition that the temperature is 40 ℃ and the humidity is more than or equal to 95%, and base exciting agent formula optimization is carried out by adopting range analysis.

The basic activator takes cement clinker, quicklime, NaOH and the like or basic solid waste mixture of steel slag, magnesium slag, carbide slag and the like as the main activator, and a small amount of sulfate activator is added.

Step 102: obtaining the proportion of the composite exciting agent according to the optimized formula of the base exciting agent and the base exciting agent, and respectively establishing a relation model of the filling body strength and the volume expansion rate of the filled cementing material, the cost of the filled cementing material and the proportion of the composite exciting agent.

Optimizing a formula by using a base and a basic exciting agent, performing composite excited cementing material orthogonal design, and performing a low-cost cementing material filling cementing body strength orthogonal test according to a cement mortar strength test method B/T17671-1999 to obtain a cementing body strength orthogonal test result; and calculating the cost of the filling cementing material according to the utilization cost of the exciting agent material and the solid wastes.

And (3) performing stepwise regression analysis by using a quadratic polynomial to establish a relation model of the strength and the volume expansion rate of the low-cost filling cementing material filling body and the cost of the filling cementing material and the composite exciting agent.

The method specifically comprises the following steps: r_7d＝F₁(Y)、R_28d＝F₂(Y)，R_7dRepresents the strength of the filling body 7 d; r_28dRepresents the strength of the pack 28 d; f₁(Y) represents the strength model of the pack 7 d; f₂(Y) represents the strength model of the pack 28 d; v_28d＝F₃(Y)，V_28dRepresenting the filling body expansion coefficient, F₃(Y) represents a filling body expansion rate model; c_T＝F₄(Y)，C_TRepresents the cost of the filled cementitious material; f₄(Y) represents a filled cementitious material cost model; y ═ Y₁，y₂，…，y_n}^TRepresenting the filling cement composite excitant variable.

Step 103: and establishing a compound activator proportioning optimization model based on the relation model and solving to obtain a compound activator optimized formula which meets the requirements of filling body strength and expansion rate of the filled mine and has the lowest cost of the low-cost filling cementing material.

Determining the strength indexes [ R ] of the cemented filling bodies 7d and 28d produced safely in the mine by means of engineering experience and filling mining design according to the mining technical conditions, mining method and stoping process of the filling mine_7d]、[R_28d]And a permissible value [ V ] of the expansion coefficient of the filler_28d]。

The method comprises the following steps of establishing a low-cost filling cementing material ratio optimization model by taking the cost of the low-cost filling cementing material as an optimization target and the strength and the volume expansion rate of a cemented filling body as constraint conditions:

optimizing the target: MinC_T＝MinF₄(Y) (1)

Constraint conditions are as follows: r_7d＝F₁(Y)≥[R_7d](2)

R_28d＝F₂(Y)≥[R_28d](3)

V_28d＝F₃(Y)≤[V_28d](4)

The filling cementing material proportion optimization model obtains a compound excitant optimization formula with the lowest cost of the filling cementing material, which meets the strength and volume expansion rate of a cemented filling body required by the safety production of filling mines.

Step 104: and preparing the low-cost cementing material according to the obtained compound excitant optimized formula.

According to the cement mortar strength test method B/T17671-1999, the low-cost filling cementing material is subjected to a strength verification test of a cemented filling body, and then the filling cementing material is subjected to economic analysis and evaluation.