CN110511045B - Coagulation-promoting type composite efficient dispersant for refractory castable and preparation method thereof - Google Patents
Coagulation-promoting type composite efficient dispersant for refractory castable and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 49
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 27
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 26
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 26
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 26
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 230000015271 coagulation Effects 0.000 claims abstract description 15
- 238000005345 coagulation Methods 0.000 claims abstract description 15
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 10
- 239000011819 refractory material Substances 0.000 claims abstract description 7
- 230000001737 promoting effect Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 230000000740 bleeding effect Effects 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 24
- 229910021487 silica fume Inorganic materials 0.000 abstract description 14
- 229910052742 iron Inorganic materials 0.000 abstract description 12
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010431 corundum Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 10
- 238000010276 construction Methods 0.000 description 6
- 239000004568 cement Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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Abstract
The invention discloses a coagulation-promoting type composite efficient dispersing agent for a refractory material castable, which is prepared by taking an FDN water reducing agent, sodium hexametaphosphate and sodium aluminate as main raw materials, wherein the mass ratio of the FDN water reducing agent to the sodium hexametaphosphate to the sodium aluminate is 60: 10-30: 30-10. The composite high-efficiency water reducing agent is suitable for the fields of unshaped refractory materials such as iron runner castable, high-silica-fume corundum self-flow material, high-silica-fume aluminum-silicon system castable and the like. Compared with the traditional pure organic dispersing agent, the inorganic salt electrolyte raw materials of sodium hexametaphosphate and sodium aluminate are introduced, so that the water reducing efficiency of the water reducing agent is higher, and the system is more stable; meanwhile, the coagulation promoting effect of the water reducing agent can be flexibly adjusted by adjusting the proportion of the sodium aluminate, so that the composite functions of water reduction and low-temperature coagulation promotion are achieved.
Description
Technical Field
The invention belongs to the field of inorganic chemistry and organic polymer materials, and relates to a coagulation promoting type composite efficient dispersant for a refractory castable and a preparation method thereof.
Background
The dispersing agent is also called as water reducing agent, is an essential additive for refractory castable, and is of great importance to the flow property and the workability of the castable, and the setting property and the high-temperature property of pure calcium aluminate cement.
The high silica fume system castable is a type of castable commonly used in the field of refractory materials, and comprises an iron runner castable, a corundum self-flowing material with high silica fume content, an aluminum-silicon system castable with high silica fume content and the like. Generally, high silica fume castable is difficult to disperse, mainly for the following reasons: the silica fume has very fine granularity, shows very high specific surface energy and is easy to agglomerate; meanwhile, the high silica fume system castable contains a certain amount of alumina micropowder, so that the dispersion difficulty of the castable is further increased.
At present, the high-efficiency water reducing agent used by the high-silica-content system castable is mainly a German Basf (BASF) product, represented by Castent-FS 20. Although the high-efficiency water reducing agent mainly comprising the high polymer shows higher water reducing efficiency, when the castable is constructed on site at low temperature, the setting time of the castable is very long, and in some castable schemes, the setting time exceeds 50 hours, so that the construction period progress of the construction site is seriously influenced.
Sodium tripolyphosphate and sodium hexametaphosphate are also traditional water reducing agents of high silica fume system castable, have certain water reducing efficiency, but require higher water adding amount of the castable, and cause damage to high temperature performance in the later period. In addition, the water reducing agent has the problem of overlong setting time of the castable during on-site low-temperature construction.
Disclosure of Invention
Aiming at the problem that the low-temperature setting time of the high-silica-fume system castable is too long, the invention prepares the high-efficiency dispersant with low-temperature setting accelerating performance by taking sodium hexametaphosphate, an FDN water reducing agent and sodium aluminate as raw materials, and the dispersant has the advantages of wide raw material source, low cost, strong applicability, high water reducing rate and obvious low-temperature setting accelerating effect.
The purpose of the invention is realized by the following technical scheme:
the coagulation-promoting type composite high-efficiency dispersing agent for the refractory material castable is prepared by taking an FDN water reducing agent, sodium hexametaphosphate and sodium aluminate as main raw materials, wherein the mass ratio of the FDN water reducing agent to the sodium hexametaphosphate to the sodium aluminate is 60: 10-30: 30-10.
The FDN water reducer is a commercial FDN water reducer, and the index requirements are shown in Table 1:
TABLE 1 index requirements for FDN Water reducers
| FDN water reducing agent | Index (I) |
| Appearance of the product | In the form of powder or granules |
| Water reduction efficiency (%) | ≥18 |
| Bleeding Rate (%) | ≤90 |
| Gas content (%) | ≤2 |
The index requirements of sodium hexametaphosphate are shown in Table 2:
TABLE 2 index requirements for sodium hexametaphosphate
| Sodium hexametaphosphate | Index (I) |
| Appearance of the product | In the form of powder or granules or flakes |
| Total phosphate (as P)2O5Calculated) content (%) | ≥68 |
| Content of Water-insoluble matter (%) | ≤0.04 |
| pH value Range (10g/L) | 5.5-7.3 |
The index requirements of the sodium aluminate are shown in the following table 3:
TABLE 3 index requirements for sodium aluminate
| Sodium aluminate | Index (I) |
| Appearance of the product | In the form of powder or granules |
| NaAlO2Content (%) | ≥56 |
| Al2O3Content (%) | ≥27 |
| Content of Water-insoluble matter (%) | ≤0.1 |
The invention also aims to provide a preparation method of the accelerating composite high-efficiency dispersing agent for the refractory castable, which comprises the following steps: the sodium hexametaphosphate, the FDN water reducing agent and the sodium aluminate are used as main raw materials, and are mixed uniformly by a mechanical grinding or mixer after being mixed, so that the composite high-efficiency water reducing agent with good dispersibility and good coagulation accelerating performance is prepared.
The method comprises the following specific steps:
step (1), batching: mixing an FDN water reducing agent, sodium hexametaphosphate and sodium aluminate according to the mass ratio of 60: 10-30: 30-10 to obtain a mixture M;
step (2) and mixing: mechanically mixing the mixture M to prepare a composite high-efficiency water reducing agent; wherein, the mechanical mixing is mechanical grinding or mixing by a mixer.
The mechanical grinding adopts a ball mill, the rotating speed of the ball mill is 30-100 r/min, the diameter of grinding balls is 10-40 mm, and the weight ratio of the grinding balls to the mixture M is 2-10: 1.
The rotating speed of the mixer is 20-200 revolutions per minute, and the mixing time is 10-100 minutes.
In the step (2), if the three raw materials are powdery raw materials, mechanically grinding or mixing by a mixer to obtain a uniform composite high-efficiency water reducing agent; if at least one granular or flaky raw material exists, mechanically grinding by using a grinding machine to prepare the uniform composite high-efficiency water reducing agent.
The composite high-efficiency water reducing agent is suitable for the fields of unshaped refractory materials such as iron runner castable, high-silica-fume corundum self-flow material, high-silica-fume aluminum-silicon system castable and the like. The addition amount of the composite high-efficiency water reducing agent in an iron runner castable, a high-silica fume corundum self-flow material and a high-silica fume aluminum-silicon system castable is 0.1-0.5%.
The invention has the beneficial effects that:
sodium hexametaphosphate belongs to electrolyte dispersant, and can form a double-electronic structure after being dissolved in water, and alpha-Al2O3The surface of the micro powder is electrically repelled, so that the micro powder can activate or calcine the alpha-Al2O3The micro powder plays a good role in dispersion; after the FDN water reducing agent is dissolved into water, the potential balance of the solution can be changed, and the FDN water reducing agent can be adsorbed on the surfaces of silicon oxide, aluminum oxide micro powder and cement, so that the FDN water reducing agent has a dispersing effect on the silicon oxide, the aluminum oxide and cement particles; the sodium hexametaphosphate and the FND water reducing agent are used in a combined way, so that the water adding amount of the silica ash containing castable can be obviously reduced. The sodium aluminate in the castable containing pure calcium aluminate cement can promote the reaction of cement minerals to form a large amount of gel, and a certain amount of plate crystal calcium hydroxide and columnar crystal ettringite are distributed in the castable, so that a good coagulation accelerating effect can be achieved even at a very low construction temperature. When the three components are used together, the synergistic effect of potential balance and steric hindrance can be achieved, and higher dispersion and coagulation promotion effects are achieved。
Compared with the traditional pure organic dispersing agent, the inorganic salt electrolyte raw materials of sodium hexametaphosphate and sodium aluminate are introduced, so that the water reducing efficiency of the water reducing agent is higher, and the system is more stable; meanwhile, the coagulation promoting effect of the water reducing agent can be flexibly adjusted by adjusting the proportion of the sodium aluminate, so that the composite functions of water reduction and low-temperature coagulation promotion are achieved.
Drawings
FIG. 1 is a flow chart of preparation of a coagulation accelerating type composite high-efficiency dispersing agent for refractory castable.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific embodiments.
Example 1:
as shown in FIG. 1, powdered FDN water reducing agent (Guizhou stone doctor science and technology Co., Ltd., brand: DS-2, water reducing efficiency of 20%, gas content of 1.1%, bleeding rate of 62%), sodium hexametaphosphate (total phosphate content of 70.1%, water-insoluble content of 0.03%, pH of 7.0, Weifang City scientific and Industrial chemical Co., Ltd.), and sodium aluminate (NaAlO)2＝60％，Al2O328 percent and 0.03 percent of water-insoluble substances) according to the mass ratio of 60:20:20 to obtain a mixture M1; the mixture M1 is placed in a high-performance mixer (Aili brand, RV24 type), the rotating speed of the mixer is set to be 150 r/min, the mixing time is 30 min, and the composite high-efficiency dispersing agent which is uniformly mixed is prepared.
The composite high-efficiency dispersant of the embodiment 1 is added into an iron runner castable (shown in table 4), and the low-temperature casting performance of the castable is tested at the temperature of 3 ℃, wherein the test scheme of the iron runner castable is shown in table 5.
TABLE 4 iron runner castable formula
Note: metal Al powder and organic fiber are added; the raw materials except the metal Al powder and the organic fiber are added to be 100 percent.
TABLE 5 Water reducing agent investigation protocol and results
Note: the water reducing agent and the water are added, and the added amount is the mass percentage of the iron runner castable except the metal Al powder and the organic fiber.
As can be seen from Table 5, when a single FDN water reducing agent (control 1) or sodium hexametaphosphate (control 2) was used, the amount of water added was high and the setting time was very long; when the FDN water reducing agent and the sodium aluminate are compounded (a control group 3), the solidification time is improved, but the defect of low water reducing efficiency is still shown; the high-efficiency composite dispersant of the embodiment has high water reducing efficiency (the water reducing efficiency is 23%)/low water addition amount and good flow property, the construction time of the iron runner castable can be obviously shortened to 9.2 hours under the conditions of low-temperature construction and maintenance at 3 ℃, a very good use effect is achieved, and even if the high-efficiency composite dispersant of the embodiment is reduced to 0.25%, the good use effect can still be achieved, and the use effect is obviously better than that of a high-addition FDN water reducing agent and/or sodium hexametaphosphate.
Example 2:
powdered FDN water reducing agent (Guizhou stone doctor science and technology Co., Ltd., brand: DS-2, water reducing efficiency of 20%, gas content of 1.1%, bleeding rate of 62%), granular sodium hexametaphosphate (total phosphate content of 70.1%, water insoluble content of 0.03%, pH value of 7.0, Weifang scientific and chemical Co., Ltd.), and granular sodium aluminate (NaAlO)2＝60％，Al2O328 percent and 0.03 percent of water-insoluble substances) according to the mass ratio of 60:25:15 to obtain a mixture M2; placing the mixture M2 in a ball mill, wherein the rotating speed of the ball mill is 50 r/min, the diameter of a grinding ball is 20mm, the weight ratio of the grinding ball to the mixture M2 is 5:1, and the grinding time is 35 minutes.
The low-temperature pouring performance of the castable containing the composite high-efficiency dispersant of the embodiment is examined by referring to the treatment group 2 of the embodiment 1, the water reducing efficiency of the composite dispersant of the embodiment in an iron runner castable system is 23%, and the setting time of the castable is 15.3 hours at 3 ℃, so that a very good using effect is achieved.
Example 3:
powdered FDN water reducing agent (Guizhou stone doctor science and technology Co., Ltd., brand: DS-2, water reducing efficiency 20%, gas content 1.1%, bleeding rate 62%), granular sodium hexametaphosphate (total phosphate content 70.1%, water-insoluble content 0.03%, pH 7.0, Weifang City scientific and chemical Co., Ltd.), and powdered sodium aluminate (NaAlO)2＝60％，Al2O328 percent and 0.03 percent of water-insoluble substances) according to the mass ratio of 60:10:30 to obtain a mixture M3; placing the mixture M3 in a ball mill, wherein the rotating speed of the ball mill is 50 r/min, the diameter of a grinding ball is 20mm, the weight ratio of the grinding ball to the mixture M2 is 5:1, and the grinding time is 35 minutes.
The low-temperature pouring performance of the castable containing the composite high-efficiency dispersant of the embodiment is examined by referring to the treatment group 2 of the embodiment 1, the water reducing efficiency of the composite dispersant of the embodiment in an iron runner castable system is 22%, and the setting time of the castable is 7.5 hours at 3 ℃, so that a very good using effect is achieved.
Example 4:
powdered FDN water reducing agent (Guizhou stone doctor science and technology Co., Ltd., brand: DS-2, water reducing efficiency 20%, gas content 1.1%, bleeding rate 62%), sodium hexametaphosphate (total phosphate content 70.1%, water-insoluble content 0.03%, pH 7.0, Weifang City science and chemical industry Co., Ltd.), and sodium aluminate (NaAlO)2＝60％，Al2O328 percent and 0.03 percent of water-insoluble substances) according to the mass ratio of 60:30:10 to obtain a mixture M4; the mixture M4 is placed in a high-performance mixer (Aili brand, model RV 24), the rotating speed of the mixer is set to be 150 r/min, and the mixture is mixed to prepare the uniformly mixed composite high-efficiency dispersing agent.
The low-temperature pouring performance of the castable containing the composite high-efficiency dispersant of the embodiment is examined by referring to the treatment group 2 of the embodiment 1, the water reducing efficiency of the composite dispersant of the embodiment in an iron runner castable system is 23%, and the setting time of the castable is 18 hours at 3 ℃, so that a very good using effect is achieved.
Claims (6)
1. The low-temperature coagulation promoting type composite efficient dispersing agent for the refractory material castable is characterized by being prepared from an FDN water reducing agent, sodium hexametaphosphate and sodium aluminate which serve as raw materials, wherein the mass ratio of the FDN water reducing agent to the sodium hexametaphosphate to the sodium aluminate is 60: 10-30: 30-10;
the index requirements of the FDN water reducing agent are as follows: the appearance is powdery or granular, the water reducing efficiency is more than or equal to 18 percent, the bleeding rate is less than or equal to 90 percent, and the gas content is less than or equal to 2 percent;
the index requirements of the sodium hexametaphosphate are as follows: the appearance is powder or granular or flake, and the total phosphate content is P2O5More than or equal to 68 percent, the content of water insoluble substances is less than or equal to 0.04 percent, and the pH value of 10g/L is 5.5-7.3;
the index requirements of the sodium aluminate are as follows: the appearance is powder or granular, NaAlO2Greater than or equal to 56 percent of Al2O3The content is more than or equal to 27 percent, and the content of water insoluble substances is less than or equal to 0.1 percent.
2. The low-temperature coagulation accelerating type composite high-efficiency dispersing agent for the refractory castable according to claim 1, which is characterized by being prepared by the following method: the method comprises the steps of taking sodium hexametaphosphate, an FDN water reducing agent and sodium aluminate as raw materials, and mixing the raw materials uniformly through mechanical grinding or a mixer to obtain the composite high-efficiency water reducing agent.
3. The preparation method of the low-temperature coagulation accelerating type composite high-efficiency dispersing agent for the refractory castable of claim 1 is characterized by comprising the following steps:
step (1), batching: mixing an FDN water reducing agent, sodium hexametaphosphate and sodium aluminate according to the mass ratio of 60: 10-30: 30-10 to obtain a mixture M;
step (2) and mixing: mechanically mixing the mixture M to prepare a composite high-efficiency water reducing agent; wherein, the mechanical mixing is mechanical grinding or mixing by a mixer.
4. The preparation method of the low-temperature coagulation promoting type composite high efficiency dispersing agent for the refractory castable according to claim 3, wherein in the step (2), if the three raw materials are powdery raw materials, the uniform composite high efficiency water reducing agent is obtained by mechanical grinding or mixing in a mixer; if at least one granular or flaky raw material exists, mechanically grinding by using a grinding machine to prepare the uniform composite high-efficiency water reducing agent.
5. The preparation method of the low-temperature coagulation promoting type composite efficient dispersant for the refractory material castable according to claim 3, characterized in that a ball mill is adopted for mechanical grinding, the rotating speed of the ball mill is 30-100 r/min, the diameter of grinding balls is 10-40 mm, and the weight ratio of the grinding balls to the mixture M is 2-10: 1.
6. The preparation method of the low-temperature coagulation accelerating type composite high-efficiency dispersing agent for the refractory castable according to claim 3, wherein the rotating speed of the mixer is 20-200 rpm, and the mixing time is 10-100 minutes.
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