CN115043619B - Preparation method of self-gelling fiber composite material - Google Patents
Preparation method of self-gelling fiber composite material Download PDFInfo
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- CN115043619B CN115043619B CN202210706603.8A CN202210706603A CN115043619B CN 115043619 B CN115043619 B CN 115043619B CN 202210706603 A CN202210706603 A CN 202210706603A CN 115043619 B CN115043619 B CN 115043619B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/38—Fibrous materials; Whiskers
- C04B14/383—Whiskers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a preparation method of a self-gelling fiber composite material, which comprises the following steps of 1) taking phosphogypsum as a raw material, adding the phosphogypsum into an acid solution, stirring and reacting, and filtering a product while the product is hot after the reaction is finished to obtain a filter cake A and a filtrate A; 2) Cooling and crystallizing the filtrate A, and filtering to obtain a filter cake B and a filtrate B; 3) Washing and drying the filter cake A and the filter cake B; 4) And uniformly mixing the dried filter cake A and filter cake B to obtain the self-gelling fiber composite material. Phosphogypsum is used as a raw material to prepare the self-gel fiber composite material, so that the problem of the bonding interface between fibers and a cement matrix in the traditional fiber cement-based composite material is effectively solved, on one hand, the adhesion between the cement and the fibers is enhanced, the toughness and the strength of the cement material are obviously improved, on the other hand, the stacking problem of phosphogypsum can be relieved, and the waste recycling is facilitated.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to a self-gelling fiber composite material, and more particularly relates to a preparation method of the self-gelling fiber composite material.
Background
Cement is the most widely used building material in the world, and the main limitation is its brittleness, which is mainly due to its poor crack resistance and low flexural strength.
A great deal of researches show that the fiber material is added into the cement material, so that the brittleness problem of the cement material is obviously improved by preventing the interaction of the growth and the expansion of microcracks and the fracture, and the cracking resistance and the toughness of the cement material are improved. The nano fiber and the superfine fiber are used as cement matrix composite additives to enhance the strength and toughness of the cement matrix composite additives, and become hot spots for the research of the cement matrix composite materials at present. CaSO (Caso-like conductor) 4 Whisker is an inorganic single crystal with a diameter of 1-4 mu m, an aspect ratio of 40-80, and tensile modulus and tensile strength exceeding 170GPa and 20GPa, respectively, which make it a cement composite materialIdeal microfibers. Li Wenbo and the like, which are named as 'mechanical property and reinforcing mechanism of calcium sulfate whisker cement mortar', show that the calcium sulfate whisker has effective reinforcing and toughening effects on the cement mortar from the research of the adaptability of the calcium sulfate whisker in the cement mortar and from microscopic analysis. Phosphogypsum refers to solid waste residue generated when phosphorite is treated by sulfuric acid in phosphoric acid production, and phosphogypsum is a main byproduct of wet-process phosphoric acid production, and 4.5 tons of phosphogypsum residue is generated per 1 ton of wet-process phosphoric acid. Most phosphogypsum is treated in a stacking mode, so that not only is land occupied and water eutrophication caused, but also resource waste is caused, and therefore, the production of the high-performance and high-added-value gypsum whisker from industrial phosphogypsum is significant. CN103074667B discloses a method for preparing calcium sulfate whisker by recrystallization: the method comprises the steps of adding the raw material with the main component of calcium sulfate into sulfuric acid solution to complete the reaction and aging at the speed of programmed temperature rise and temperature reduction, and has complex production process, low yield and harsh conditions.
The common fiber cement-based composite material has the problems of unsuitable interface bonding strength between fibers and a cement matrix, uneven dispersion and the like. Pan Qing and the like, the article named as "mechanical property and microstructure of calcium sulfate whisker modified cement-based composite material with re-doped silica fume" indicates that the silica fume is used as an excellent gel filling material, can promote the formation of C-S-H gel in cement, and remarkably improves the microstructure and interface bonding strength of whisker-cement. Phosphogypsum is known to contain SiO in addition to a large amount of calcium sulfate dihydrate 2 If SiO therein can be used 2 The phosphogypsum can be more fully utilized by effectively utilizing the phosphogypsum.
Based on the self-gelling fiber composite material and the preparation method thereof, phosphogypsum can be adopted as a raw material to prepare the self-gelling fiber composite material with high length-diameter ratio and strong adhesion, the strength and toughness of the cement material can be increased by the existence of the fiber, the bonding strength of the fiber and the cement-based material can be effectively improved, and phosphogypsum can be fully utilized.
Disclosure of Invention
The invention aims to provide a self-gelling fiber composite material which is added into a cement material to obviously improve the strength and toughness of the cement material on one hand and fully utilize phosphogypsum on the other hand so as to meet the green development requirement of enterprises.
To achieve the above object, the present invention is mainly implemented by the following schemes:
the preparation method of the self-gelling fiber composite material is characterized by comprising the following steps of:
(1) Phosphogypsum is taken as a raw material, added with a crystallization aid, added into an acid solution, stirred and reacted at a certain temperature, wherein the reaction temperature is 80-90 ℃, the reaction time is 3-4 hours, and the product is filtered while the product is hot after the reaction is finished to obtain a filter cake A and a filtrate A;
the crystallization aid is citric acid or polyacrylic acid, and the mass ratio of phosphogypsum to the crystallization aid is 1:50-200.
The acid solution is hydrochloric acid solution or nitric acid solution, wherein the solid-to-liquid ratio of phosphogypsum to the acid solution is 0.03-0.1, and the concentration of the acid solution is controlled to be 6% -8%.
And (3) adding a tackifier in the step (1), wherein the tackifier is preferably waterborne polyurethane. The concentration of the tackifier is 50-500g/L, preferably 100-150g/L.
(2) Filtering the filtrate A after cooling crystallization to obtain a filter cake B and a filtrate B;
(3) Washing and drying the filter cake A and the filter cake B;
(4) And uniformly mixing the dried filter cake A and the filter cake B to obtain the self-gelling fiber composite material.
In the technical scheme, phosphogypsum is taken as a raw material in the step (1), after a crystallization promoter is added, the phosphogypsum is added into an acid solution, and stirred for reaction at a certain temperature, wherein the reaction temperature is 80-90 ℃, the reaction time is 3-4h, and the product is filtered while the product is hot after the reaction is finished to obtain a filter cake A and a filtrate A, and the related reaction mainly comprises
CaSO 4 ·2H 2 O (particles) +hcl= Ca 2+ +Cl - +SO 4 2- +2H 2 O (1)
2) The filtrate A is cooled and crystallized, and then is filtered to obtain a filter cake B and a filtrate B, and the main reactions involved are that
Ca 2+ +SO 4 2- +2H 2 O＝＝CaSO 4 ·2H 2 O (fiber) (2)
3) Washing and drying the filter cake A and the filter cake B; the drying temperature is 45 ℃.
4) And uniformly mixing the dried filter cake A and the filter cake B to obtain the self-gelling fiber cement-based composite material, wherein the filter cake B is the microfiber calcium sulfate dihydrate whisker, and the filter cake A is the siliceous ash.
Filtering the obtained filtrate B, and returning to the step 1) to circularly dissolve phosphogypsum.
The self-gelling calcium sulfate fiber composite material can achieve the reinforcing and toughening effects on cement through the existence of calcium sulfate fibers.
The self-gelling fiber composite material contains silica fume which can spontaneously consume a hydration product Ca (OH) when meeting water 2 Gel reaction is generated, the adhesion is strong, the pore size distribution is uniform, the adhesion between the microfiber calcium sulfate whisker and the cement matrix is obviously improved, and the interface bonding strength of the microfiber calcium sulfate whisker and the cement matrix is enhanced, so that the number of pores existing in the cement material is reduced, and the toughness and the strength of the cement material are further improved.
According to the technical scheme, phosphogypsum is used as a raw material, an acid solution dissolution and recrystallization method is used, organic acid is used as a crystallization aid, the calcium sulfate whisker containing silicon ash with the length-diameter ratio is prepared, and is mixed and added into a cement material, so that the strength and toughness of cement are improved by the microfiber calcium sulfate whisker.
The existence of the water-based polyurethane and the whole preparation process ensure that the obtained silica fume has strong adhesiveness, the silica fume slag optimizes the dispersibility of calcium sulfate whisker in a cement matrix, and the Ca (OH) generated by cement hydration is consumed 2 The self-gelation is generated, so that cracks existing between the fibers and the cement are effectively reduced, and the strength and toughness of the cement are further improved.
Realizing the reutilization of wastes and effectively relieving the phosphogypsum piling problem.
The chemical reagent is recycled, so that the production cost of the process is saved.
The whole production process is simple to operate.
Detailed Description
According to the self-gelling fiber composite material and the preparation method thereof, phosphogypsum is treated by adopting a chemical reagent recycling process, calcium sulfate whisker and silica fume-containing filter residues are prepared, and the calcium sulfate whisker and the silica fume-containing filter residues are mixed and added into a cement material, so that on one hand, the strength and toughness of cement are obviously improved, and on the other hand, the stacking problem of phosphogypsum is relieved.
To better illustrate the above embodiments, the following examples are presented, and the scope of the invention is not limited to the examples presented, but the phosphogypsum used in the examples is produced by Yiduxing chemical Co., ltd, and the ingredients are shown below:
table 1: phosphogypsum components:
example 1
1) 350g phosphogypsum and 7g citric acid are weighed, evenly mixed and added into a reaction kettle, 8750ml of solution is poured into the reaction kettle according to the solid-to-liquid ratio of 0.04, the concentration of hydrochloric acid in the solution is 6.0%, water-based polyurethane is added, the concentration of the water-based polyurethane in the mixed solution is 100g/L, the mixed solution reacts for 3 hours at 80 ℃, and the filtrate A and the filter cake A are obtained after filtering while the mixed solution is hot.
2) And cooling and crystallizing the filtrate A for 12 hours at room temperature, filtering to obtain filtrate B, and returning the filtrate B to the previous step for recycling.
3) And respectively washing and filtering a filter cake A and a filter cake B, drying at 45 ℃, wherein the filter cake A is siliceous ash slag, and the filter cake B is microfiber calcium sulfate dihydrate whisker.
4) The self-gel fiber composite material-1 is prepared by mixing silicon-containing ash and micro-fiber calcium sulfate dihydrate whisker, wherein the length-diameter ratio of the micro-fiber calcium sulfate dihydrate whisker in the self-gel fiber composite material-1 is 68.7, and the viscosity of the silicon ash is 43.1mpa.s.
Example 2
1) 350g phosphogypsum and 70000g citric acid are weighed, evenly mixed and added into a reaction kettle, 7000ml solution is poured into the reaction kettle according to the solid-to-liquid ratio of 0.05, the concentration of hydrochloric acid in the solution is 7.0%, aqueous polyurethane is added, the concentration of the aqueous polyurethane in the mixed solution is 150g/L, the mixed solution reacts for 3 hours at 80 ℃, and the filtrate A and the filter cake A are obtained after filtering while the mixed solution is hot.
2) And cooling and crystallizing the filtrate A for 12 hours at room temperature, filtering to obtain filtrate B, and returning the filtrate B to the previous step for recycling.
3) And washing and filtering a filter cake A and a filter cake B, and drying at 45 ℃, wherein the filter cake A is siliceous ash slag, and the filter cake B is microfiber calcium sulfate dihydrate whisker.
4) The self-gel fiber composite material-2 is prepared by mixing the silicon-containing ash and the microfiber calcium sulfate dihydrate whisker, wherein the length-diameter ratio of the microfiber calcium sulfate dihydrate whisker in the self-gel fiber composite material-2 is 68.1, and the viscosity of the silicon ash is 45.5mpa.s.
Example 3
1) 350g phosphogypsum and 3.5g citric acid are weighed, evenly mixed and added into a reaction kettle, 5000ml of solution is poured into the reaction kettle according to the solid-to-liquid ratio of 0.07, the solution contains 7.3 percent of hydrochloric acid, water-based polyurethane is added, the concentration of the water-based polyurethane in the mixed solution is 200g/L, the mixed solution reacts for 4 hours at 90 ℃, and the filtrate A and the filter cake A are obtained after filtering while the mixed solution is hot.
2) And cooling and crystallizing the filtrate A for 24 hours at room temperature, filtering to obtain filtrate B, and returning the filtrate B to the previous step for recycling.
3) And washing and filtering a filter cake A and a filter cake B, and drying at 45 ℃, wherein the filter cake A is siliceous ash slag, and the filter cake B is microfiber calcium sulfate dihydrate whisker.
4) The silica fume containing slag and the micro fiber calcium sulfate dihydrate whisker are mixed to prepare the self-gelling fiber composite material-3, wherein the length-diameter ratio of the micro fiber calcium sulfate dihydrate whisker in the self-gelling fiber composite material-3 is 73.4, and the viscosity of the silica fume slag is 46.6mpa.s.
Example 4
1) 350g phosphogypsum and 3.5g polyacrylic acid are weighed, evenly mixed, added into a reaction kettle, poured into 3500ml of solution with a solid-to-liquid ratio of 0.1, the solution contains 8.0 percent of hydrochloric acid, added with water-based polyurethane, and reacted for 4 hours at 90 ℃ after the concentration of the water-based polyurethane in the mixed solution is 300g/L, and filtered while the mixed solution is hot, thus obtaining filtrate A and filter cake A.
2) And cooling and crystallizing the filtrate A for 24 hours at room temperature, filtering to obtain filtrate B, and returning the filtrate B to the previous step for recycling.
3) And washing and filtering a filter cake A and a filter cake B, and drying at 45 ℃, wherein the filter cake A is siliceous ash slag, and the filter cake B is microfiber calcium sulfate dihydrate whisker. The property of the microfibrous calcium sulfate dihydrate whisker is 64.3.
4) The self-gel fiber composite material-4 is prepared by mixing the silicon-containing ash and the microfiber calcium sulfate dihydrate whisker, wherein the length-diameter ratio of the microfiber calcium sulfate dihydrate whisker in the self-gel fiber composite material-4 is named as A-4, and the viscosity of the silicon ash is 47.6mpa.s.
Example 5
The method and the steps are the same as in example 1, only sulfuric acid is used as an acid solution, anhydrous polyurethane is added, the property of the microfiber calcium sulfate dihydrate whisker is 7.2, and the silica fume viscosity is 3.3mpa.s.
Example 6
The method and the steps are the same as in example 1, only polyurethane is added to the concentration of 20g/L, the property of the microfiber calcium sulfate dihydrate whisker is 61.1, and the viscosity of silica fume slag is 38.2mpa.s.
Example 7
The method and the steps are the same as in example 1, only polyurethane is added to the concentration of 50g/L, the property of the microfiber calcium sulfate dihydrate whisker is 63.3, and the viscosity of silica fume slag is 41.4mpa.s.
Example 8
The method and the steps are the same as in example 1, only polyurethane is added to the concentration of 400g/L, the property of the microfiber calcium sulfate dihydrate whisker is 64.7, and the viscosity of silica fume slag is 55.8mpa.s.
Example 9
The procedure and procedure were as in example 1, except that polyurethane was added only to a concentration of 500g/L, the property of the microfibrous calcium sulfate dihydrate whisker was 63.1, and the viscosity of the silica fume was 58.1mpa.s.
Example 10
The method and the steps are the same as in example 1, only polyurethane is added to the concentration of 600g/L, the property of the microfiber calcium sulfate dihydrate whisker is 64.2, and the viscosity of silica fume slag is 59.9mpa.s.
The self-gelling fiber composite material 1-10 prepared by the scheme is mixed and added into cement P.O42.5 respectively according to the mass proportion of 10%, a gel sand test block is molded according to the specified proportion by referring to the national standard of the cement mortar strength test method (ISO method) and maintained for 28 days, the porosity, the compressive strength and the bending strength are tested, and the performance test results are shown in Table 2:
table 2: results of Performance test
| Examples | Compression resistance (MPa) | Bending resistance (MPa) | Porosity (%) |
| Example 1 | 68.7 | 11.8 | 16.5 |
| Example 2 | 69.5 | 11.9 | 15.2 |
| Example 3 | 65.7 | 12.1 | 14.1 |
| Example 4 | 61.8 | 12.4 | 13.7 |
| Example 5 | 51.4 | 8.4 | 36.6 |
| Example 6 | 65.3 | 10.9 | 27.1 |
| Example 7 | 66.7 | 11.3 | 24.0 |
| Example 8 | 53.4 | 11.6 | 12.8 |
| Example 9 | 50.9 | 10.8 | 10.4 |
| Example 10 | 49.7 | 10.5 | 6.2 |
Claims (3)
1. The preparation method of the self-gelling fiber composite material is characterized by comprising the following steps of:
(1) Adding phosphogypsum as a raw material, adding a crystallization aid which is citric acid or polyacrylic acid into an acid solution, controlling the concentration of the acid solution to be 6% -8%, adding tackifier aqueous polyurethane, stirring at 80-90 ℃ for reaction for 3-4 hours, and filtering a product while the product is hot after the reaction is finished to obtain a filter cake A and a filtrate A;
the concentration of the tackifier aqueous polyurethane is 100-150g/L;
(2) Filtering the filtrate A after cooling crystallization to obtain a filter cake B and a filtrate B;
(3) Washing and drying the filter cake A and the filter cake B;
(4) And uniformly mixing the dried filter cake A and the filter cake B to obtain the self-gelling fiber composite material.
2. The method for preparing a self-gelling fiber composite material according to claim 1, wherein the mass ratio of phosphogypsum to the crystallization promoter in the step (1) is (50-100): 1.
3. the method of producing a self-gelling fiber composite according to claim 1, wherein the acid solution in step (1) is a hydrochloric acid solution or a nitric acid solution, and wherein the solid-to-liquid ratio of phosphogypsum to the acid solution is 0.03 to 0.1.
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