CN105819811A - Method for preparing cement-based grouting material from phosphorus solid wastes through wet grinding technology - Google Patents

Abstract

The invention discloses a method for preparing cement-based grouting materials by using a phosphorus solid waste wet grinding process. 50-150 parts of phosphorus tailings are graded and broken, and sieved to obtain phosphorus tailings powder; 50-90 parts of phosphorus slag are crushed by a crusher Crushed into phosphorus slag powder; phosphorus slag powder is added with 6-12 parts of phosphogypsum, 0.5-0.8 parts of grinding aid, 5-10 parts of alkali activator, 50-65 parts of water and placed in a ball mill for ball milling, aging for 2-5 hours, Obtain slurry: Take 100 parts of cement, 0.8-1.5 parts of water reducing agent, 5-8 parts of expansion agent, 1.0-1.8 parts of defoamer plus phosphorus tailings powder, and stir evenly in a slurry mixer to obtain cement-based grouting material. The invention uses phosphorus solid waste as the main raw material, wet material grinding replaces dry material grinding, uses phosphorus tailings as aggregate, and realizes close accumulation and micro-aggregate effect through particle size control, and fully exerts the potential activity of raw materials and compactness. Good, low energy consumption, low production cost, can be widely used in industry and construction projects.

Description

Method for preparing cement-based grouting material by wet grinding process of phosphorus solid waste

technical field

The invention belongs to the field of building materials, and in particular relates to a method for preparing cement-based grouting materials by using a phosphorus solid waste wet grinding process.

Background technique

At present, the phosphoric acid production in my country mainly adopts the wet process phosphoric acid process, and the solid phosphorus waste is the solid waste generated during the production of phosphate rock, including: phosphorus tailings, phosphorus slag, phosphogypsum, etc.

Phosphorus tailings are solid wastes that cannot be utilized during the flotation of phosphate ore concentrates. Although my country's phosphate rock reserves are relatively large, the main feature is "more low-grade ore and less rich ore". According to the requirements of phosphoric acid production process conditions, most of the phosphate rock needs to be enriched by ore dressing to meet the production of phosphoric acid and high-concentration phosphate fertilizer. While some high-grade phosphate rocks are being utilized, a large amount of phosphate tailings are discarded, causing serious environmental pollution due to massive accumulation, and resource utilization of phosphate tailings has become a difficult problem.

Phosphorus slag is the granular slag discharged during the production of yellow phosphorus from phosphate ore. Usually, about 8 to 10 tons of phosphorus slag are discharged for every 1 ton of yellow phosphorus produced. As a potentially active mineral, phosphorus slag is currently used in calcined cement, cement mixture, concrete admixture, bricks, etc., but the total utilization rate is only 50%. The stacking and disposal of a large amount of phosphorus slag has brought great pressure to society and enterprises.

Phosphogypsum is a solid waste with calcium sulfate as the main component discharged during the wet process of phosphoric acid production. It often exists in the form of calcium sulfate dihydrate. About 4.5-5.5t of phosphogypsum is discharged per 1t of P ₂ O ₅ produced, and its utilization rate Low, resulting in cumulative stacking, cumulative stacking not only takes up a lot of land and wastes resources, but also causes serious pollution to the surrounding environment, soil, vegetation, and water systems, so it is imminent to effectively solve the problem of phosphogypsum.

Grouting materials are mainly divided into chemical grouting materials and cement grouting materials according to the types of materials, among which cement grouting materials refer to a kind of raw materials such as cement, aggregate (or no aggregate), admixtures and mineral admixtures, which are prepared and produced The resulting mixture has a reasonable gradation. Cement-based grouting materials are widely used, and there is a large demand in anchor bolt anchorage, secondary grouting, concrete structure reinforcement and reconstruction, and prestressed tunnel grouting.

At present, the research on the preparation of cement-based grouting materials by adding solid waste has been reported at home and abroad. For example, CN104496354 discloses a cement-based grouting material and its preparation method: cement 350-450, gravel 300-400, medium sand 150-200, fine sand 50-100, filler 20-70, expansion agent 40-50, water reducing Agent 6-10, auxiliary agent 1-3, water 13-20, during preparation, all raw materials are mixed and stirred to obtain dry powder cement-based grouting material; CN103641424 discloses a large-volume steel slag grouting material, which consists of the following parts by weight Raw materials: steel slag 0% to 80%, sulphoaluminate cement 0% to 16%, portland cement 0% to 31%, fly ash 0% to 15%, sand 0% to 50%, activator 0.2% to 2.0%, water reducing agent 0.4% to 1.5%, and expansion agent 0.02% to 0.05%. CN102515651 discloses a cement-based grouting material and its preparation method, which consists of the following three parts, A: thinner: 1-10 parts, defoamer: 0-1 part, coupling agent: 1-5 parts, group B Component C includes water-soluble amine curing agent with emulsifying function. Component C includes 30-50 parts of cement, 2-4 parts of ultra-fine mineral powder, 0-1 part of silicon micropowder, 2-4 parts of expansion agent, and 0 parts of water reducing agent. -1 part, 40-60 parts of river sand, the weight ratio of the three components A, B and C is 60-100:90～150:400～800. The processing of raw materials in the above patents all adopts a dry grinding process, and the energy consumption of dry grinding is higher than that of wet grinding. Because grouting materials have high requirements on structural compactness, the particles in grouting materials need to be designed according to the principle of compound particle grading, such as the large-volume steel slag grouting material of CN103641424, which has poor structural compactness. CN102515651 discloses a cement-based grouting material and a preparation method thereof. Cement is used as the main cementitious material, and the cost is relatively high.

Therefore, it is of great significance and practical demand to invent a grouting material with low energy consumption, good compactness, low cost and high waste rate and its preparation method.

Contents of the invention

The purpose of the present invention is to aim at the above-mentioned status quo, aiming to provide a kind of prepared material with good compactness, low energy consumption, low production cost, high waste rate, and performance that can meet the requirements of relevant standards to prepare cement by using phosphorus solid waste wet grinding process The method of base grouting material.

The way to achieve the object of the present invention is to prepare the method of cement-based grouting material with phosphorus solid waste wet grinding process, and the specific steps are as follows:

1) Weigh 50-150 parts by weight of phosphorus tailings, carry out 4.75mm, 2.36mm, 1.18mm, 600μm, 300μm, 150μm graded crushing, and the cumulative sieve residues of the square sieve holes are: 0%, 0- 25%, 10-50%, 41-70%, 70-92%, 80-100%, get phosphorus tailings powder;

2) taking by weight the phosphorus slag of 50-90 parts, crushing with a crusher to an average particle size of 2-10 mm to obtain phosphorus slag powder;

3) Weigh 6-12 parts by weight of phosphogypsum, 0.5-0.8 parts of grinding aid, and add 5-10 parts of alkali activator into the phosphorous slag powder obtained in step 2) and 50-65 parts by weight of Put the water in a ball mill and mill until the specific surface area is 300-1100m ² /kg, the average particle diameter is 1-50μm, and aged for 2-5h to obtain the slurry;

4) Weigh 100 parts by weight of cement, 0.8-1.5 parts of water reducer, 5-8 parts of expansion agent, 1.0-1.8 parts of defoamer and add the phosphorous tailings powder obtained in step 1) and step 3) The obtained slurry is placed in a mixer and stirred until it is evenly stirred to obtain a cement-based grouting material;

Described cement is ordinary portland cement;

The phosphorus tailings, phosphorus slag, and phosphogypsum are solid wastes discharged from phosphorus chemical production;

The alkali activator is one or more of Glauber's salt, lime, water glass;

The water reducer is one or more of melamine-based water-reducer, polycarboxylate-based water-reducer, and naphthalene-based water-reducer;

The expansion agent is any one or more of HCSA expansion agent, CEA composite expansion agent, and FEA dispersion expansion agent;

The grinding aid is one or more of polymeric polyol-based grinding aids, triethanolamine-based grinding aids, and triisopropanolamine-based grinding aids;

The defoamer is one or both of polyol-based defoamers and polysiloxane-based defoamers.

The invention uses phosphorus solid waste as the main raw material, wet material grinding replaces dry material grinding, uses phosphorus tailings as aggregate, and realizes close accumulation and micro-aggregate effect through particle size control, fully exerting the potential activity of raw materials and low energy consumption , low production cost, high waste rate.

The beneficial effects of the present invention are:

1. Using phosphorus tailings as aggregates, through the classification and crushing process, the gradation of aggregate particles is strictly controlled, combined with ultra-fine mineral admixtures, to achieve dense accumulation and micro-aggregate effects, and achieve a compact structure;

2. Raw material grinding adopts wet grinding process, which produces synergistic effect under the condition of alkali activator, fully stimulates the potential activity of mineral admixture, has good compactness and low energy consumption;

3. Make full use of phosphorus solid waste, low production cost, high waste rate, and realize the resource utilization of solid waste.

The performance of the grouting material provided by the invention meets the standard requirements of the "Technical Specifications for Application of Cement-Based Grouting Materials" (GB/T50448-2015), and can be applied to industrial and construction projects.

detailed description

Grinding is a production method in which materials are ground into slurry by adding water powder. Its products have uniform fineness, low energy consumption per unit weight of products, no dust flying, and low noise. Based on the current situation that "phosphorus solid waste" is difficult to utilize and the demand for grouting materials is large, combined with the characteristics of the synergistic effect of various components in the wet grinding process, the present invention prepares cement-based grouting materials by modifying the mineral admixture through the wet grinding process. Realize the resource utilization of solid waste.

In the present invention, 50-150 parts of phosphorus tailings are graded and broken, and sieved to obtain phosphorus tailings powder; 50-90 parts of phosphorus slag are crushed into phosphorus slag powder by a crusher; phosphorus slag powder is added with 6-12 parts of phosphogypsum, 0.5 - 0.8 parts of grinding aid, 20-40 parts of water placed in a ball mill for wet grinding to obtain slurry; 100 parts of cement, 0.8-1.5 parts of water reducer, 0.15-0.3 parts of expansion agent, 0.8-1.8 parts of defoamer plus phosphorus Mix tailings powder and slurry in a mixer to obtain cement-based grouting materials.

The soluble phosphorus in the phosphogypsum is ≤1%, and the organic matter is ≤0.8%.

The present invention is described in detail below with specific examples.

Example 1:

1) Weigh 100 parts by weight of phosphorous tailings, carry out 4.75mm, 2.36mm, 1.18mm, 600μm, 300μm, 150μm graded crushing, and the cumulative sieve residues of the square sieve holes are: 0%, 0-25% , 10-50%, 41-70%, 70-92%, 80-100%, to get phosphorus tailings powder;

2) taking by weight 70 parts of phosphorus slag, crushing it with a crusher to an average particle size of 2-10 mm to obtain phosphorus slag powder;

3) Weigh 8 parts by weight of phosphogypsum, 0.6 parts of polymerized polyol grinding aid, and add 7 parts of water glass into the obtained phosphorus slag powder in step 2) and place 54 parts by weight of water in a ball mill Ball milling until the specific surface area is 300-1100m ² /kg, the average particle diameter is 1-50μm, and aging for 2-5h to obtain slurry;

4) Weigh 100 parts by weight of cement, 0.8 parts of melamine-based water reducer, 7 parts of HCSA expansion agent, and 1.2 parts of polyol defoamer and add the phosphorous tailings powder obtained in step 1) and step 3) The obtained slurry is placed in a mixer and stirred until it is evenly stirred to obtain a cement-based grouting material.

The performance test was carried out in accordance with the requirements of the "Technical Specifications for the Application of Cement-based Grouting Materials" (GB/T 50448-2015).

The material properties meet the requirements of the "Technical Specifications for the Application of Cement-based Grouting Materials" (GB/T 50448-2015).

Embodiment 2: with embodiment 1, the difference is,

1) taking 125 parts by weight of phosphorous tailings for classification and crushing, and sieving to obtain phosphorous tailings powder;

2) taking by weight is 90 parts of phosphorus slag, and the crusher is crushed to obtain phosphorus slag powder;

3) Weigh 12 parts by weight of phosphogypsum, 0.8 part of triethanolamine grinding aid, add 10 parts of lime into the phosphorous slag powder obtained in step 2), and place 63 parts by weight of water in a ball mill for ball milling, aging 2-5h, get slurry;

4) Weigh 100 parts by weight of cement, 1.2 parts of polycarboxylate water reducer, 5 parts of CEA composite expansion agent, and 1.0 part of polysiloxane defoamer to add the phosphorus tail obtained in step 1). The mineral powder and the slurry obtained in step 3) are placed in a mixer and stirred until they are evenly stirred to obtain a cement-based grouting material.

The performance test was carried out in accordance with the requirements of the "Technical Specifications for the Application of Cement-based Grouting Materials" (GB/T 50448-2015).

The material properties meet the requirements of the "Technical Specifications for the Application of Cement-based Grouting Materials" (GB/T 50448-2015).

Embodiment 3: with embodiment 1, the difference is,

1) taking 150 parts by weight of phosphorous tailings for classification and crushing, and sieving to obtain phosphorous tailings powder;

2) taking by weight is 50 parts of phosphorus slag, and the crusher is crushed to obtain phosphorus slag powder;

3) Weigh 6 parts by weight of phosphogypsum, 0.8 parts of triisopropanolamine grinding aid, add 5 parts of Glauber's salt to the phosphorus slag powder obtained in step 2), and place 50 parts by weight of water in a ball mill for ball milling , aged for 2-5h to obtain slurry;

4) Weigh 100 parts by weight of cement, 1.5 parts of naphthalene-based water reducer, 6 parts of FEA expansion agent, and 1.5 parts of polysiloxane defoamer and add the phosphorous tailings powder obtained in step 1) and the step 3) The obtained slurry is placed in a mixer and stirred until it is evenly stirred to obtain a cement-based grouting material.

The performance test was carried out in accordance with the requirements of the "Technical Specifications for the Application of Cement-based Grouting Materials" (GB/T 50448-2015).

The material properties meet the requirements of the "Technical Specifications for the Application of Cement-based Grouting Materials" (GB/T 50448-2015).

Embodiment 4: with embodiment 1, the difference is,

1) taking 75 parts by weight of phosphorous tailings and grading and crushing, and sieving to obtain phosphorous tailings powder;

2) taking by weight is 90 parts of phosphorus slag, and the crusher is crushed to obtain phosphorus slag powder;

3) Weigh 8 parts by weight of phosphogypsum, 0.2 part of triethanolamine grinding aid + 0.3 part of polymerized polyol grinding aid, 6 parts of lime + 4 parts of Glauber's salt and add the phosphorus slag powder obtained in step 2), in parts by weight 64 parts of water are placed in a ball mill for ball milling, and aged for 2-5 hours to obtain a slurry;

4) Weigh 100 parts by weight of cement, 1.0 part of melamine water reducer + 0.5 part of polycarboxylate water reducer, 5 parts of FEA expansion agent + 3 parts of CEA expansion agent, 1.8 parts of polysiloxanes The defoamer is added to the phosphorous tailings powder obtained in step 1) and the slurry obtained in step 3), and placed in a mixer and stirred until the mixture is evenly stirred to obtain a cement-based grouting material.

The performance test was carried out in accordance with the requirements of the "Technical Specifications for the Application of Cement-based Grouting Materials" (GB/T 50448-2015).

The material properties meet the requirements of the "Technical Specifications for the Application of Cement-based Grouting Materials" (GB/T 50448-2015).

Embodiment 5: with embodiment 1, the difference is,

1) taking 50 parts by weight of phosphorous tailings for classification and crushing, and sieving to obtain phosphorous tailings powder;

2) taking by weight is 60 parts of phosphorus slag, and the crusher is crushed to obtain phosphorus slag powder;

3) Weigh 6 parts of phosphogypsum, 0.1 part of triethanolamine grinding aid + 0.3 part of polymeric polyol grinding aid + 0.2 triisopropanolamine grinding aid, 2 parts of water glass + 4 parts Glauber's salt is added to the phosphorus slag powder obtained in step 2), and 54 parts by weight of water are placed in a ball mill for ball milling, and aged for 2-5 hours to obtain a slurry;

4) Weigh 100 parts by weight of cement, 0.5 part of melamine water reducer + 0.3 part of naphthalene water reducer, 3 parts of FEA expansion agent + 5 parts of HCSA expansion agent, 1.6 parts of polysiloxane type water reducer The foaming agent is added to the phosphorous tailings powder obtained in step 1) and the slurry obtained in step 3), placed in a mixer and stirred until the mixture is evenly stirred to obtain a cement-based grouting material.

The performance test was carried out in accordance with the requirements of the "Technical Specifications for the Application of Cement-based Grouting Materials" (GB/T 50448-2015).

The material properties meet the requirements of the "Technical Specifications for the Application of Cement-based Grouting Materials" (GB/T 50448-2015).

Embodiment 6: with embodiment 1, the difference is,

1) taking 90 parts by weight of phosphorous tailings for classification and crushing, and sieving to obtain phosphorous tailings powder;

2) taking by weight is 90 parts of phosphorus slag, and the crusher is crushed to obtain phosphorus slag powder;

3) Take by weight 12 parts of phosphogypsum, 0.7 part of triisopropanolamine grinding aid, 2 parts of water glass+4 parts of Glauber's salt+4 parts of lime and add the phosphorus slag powder obtained in step 2), the parts by weight are Put 65 parts of water into a ball mill for ball milling, and age for 2-5 hours to obtain a slurry;

4) Weigh 100 parts by weight of cement, 0.6 part of polycarboxylate water reducer+0.8 part of naphthalene water reducer, 3 parts of FEA expansion agent+3 parts of HCSA expansion agent+2 parts of CEA expansion agent, Add 1.0 parts of polyol defoamer + 0.6 part of polysiloxane defoamer to the phosphorous tailings powder obtained in step 1) and the slurry obtained in step 3), and stir in a mixer until the mixture is uniform to obtain cement-based grouting material .

The performance test was carried out in accordance with the requirements of the "Technical Specifications for the Application of Cement-based Grouting Materials" (GB/T 50448-2015).

The material properties meet the requirements of the "Technical Specifications for the Application of Cement-based Grouting Materials" (GB/T 50448-2015).

Each raw material listed in the present invention, as well as the upper and lower limits and interval values of each raw material in the present invention, and the upper and lower limits and interval values of process parameters can all realize the present invention, and the embodiments are not enumerated here one by one.

Claims (2)

1. the method preparing cement-based grouting material with phosphorus solid waste wet-grinding technology and relative device, it is characterised in that: concrete steps are such as Under:

1) weigh the phosphorus mine tailing that parts by weight are 50-150 part, carry out 4.75mm, 2.36mm, 1.18mm, 600 μm, 300 μm, 150 μm graded crushings, rectangular mesh add up screen over-size be respectively as follows: 0%, 0-25%, 10-50%, 41-70%, 70-92%, 80-100%, obtain phosphorus mine tailing；

2) weighing the phosphorus slag that parts by weight are 50-90 part, crusher in crushing, to mean diameter 2-10mm, obtains phosphorus slag Powder；

3) weighing parts by weight is the ardealite of 6-12 part, the grinding aid of 0.5-0.8 part, 5-10 part alkali-activated carbonatite Agent adds step 2) gained phosphorus slag powder and water that parts by weight are 50-65 part is placed in ball milling in ball mill, to than table Area is 300-1100m²/ kg, average diameter of particles is 1-50 μm, is aged 2-5h, obtains slurry；

4) weigh cement that parts by weight are 100 parts, the water reducer of 0.8-1.5 part, the extender of 5-8 part, 1.0-1.8 part defoamer adds step 1) gained phosphorus mine tailing and step 3) gained slurry, it is placed in blender Stirring, to stirring, obtains cement-based grouting material；

Described cement is for being Portland cement；

Described phosphorus mine tailing, phosphorus slag, ardealite are the solid waste of discharge during phosphorous chemical industry produces；

Described alkali-activator is one or more in Natrii Sulfas, Calx, waterglass；

Described water reducer be the one in melamine system water reducer, polycarboxylate based water reducer, naphthalene water reducer or Multiple；

Described extender be HCSA extender, CEA composite expanding agent, FEA dispersion extender in any one or Multiple；

Described grinding aid is polymeric polyols alcohols grinding aid, triethanolamine class grinding aid, triisopropanolamine class grinding aid In one or more；

Described defoamer is one or both in polyalcohols defoamer, polysiloxane-based defoamer.

The method that phosphorus solid waste wet-grinding technology and relative device the most according to claim 1 prepares cement-based grouting material, its It is characterised by: Leaching Properties of Soluble Phosphorus≤1% in ardealite, Organic substance≤0.8%.