Additive for improving mechanical strength of high belite sulphoaluminate cement
阅读说明：本技术 一种提高高贝利特硫铝酸盐水泥力学强度的外加剂 (Additive for improving mechanical strength of high belite sulphoaluminate cement ) 是由 王剑锋 王艳 兰明章 常磊 崔素萍 王亚丽 刘辉 于 2021-10-26 设计创作，主要内容包括：一种提高高贝利特硫铝酸盐水泥力学强度的外加剂,属于水泥外加剂技术领域。主要由氨基羧酸盐、多元醇胺酯、二元醇、强电解质和水组成。本发明制备的外加剂掺加量为HBSAC重量的0.1％时,HBSAC1d力学强度最高可提高7.6MPa,7d力学强度最高可提高10.4MPa,28d力学强度最高可提高14.1MPa,表现出了良好的应用效果。(An additive for improving the mechanical strength of high belite sulphoaluminate cement, belonging to the technical field of cement additives. Mainly comprises amino carboxylate, polyol amine ester, dihydric alcohol, strong electrolyte and water. When the addition amount of the admixture prepared by the invention is 0.1 percent of the weight of the HBSAC, the mechanical strength of the HBSAC1d can be improved by 7.6MPa to the maximum, the mechanical strength of 7d can be improved by 10.4MPa to the maximum, the mechanical strength of 28d can be improved by 14.1MPa to the maximum, and good application effect is shown.)
1. An additive for improving the mechanical strength of high belite sulphoaluminate cement is characterized by mainly comprising amino carboxylate, polyol amine ester, dihydric alcohol, strong electrolyte and water; which comprises the following components in percentage by weight:
the aminocarboxylate is one or two of trisodium nitrilotriacetate (NTA-3Na), disodium ethylene diamine tetraacetic acid (EDTA-2Na) and pentasodium diethylenetriamine pentacarboxylate (DTPA-5 Na);
the polyol amine ester is a compound obtained by esterifying hydroxyl in polyol amine and carboxyl in organic acid, and the obtained product contains unesterified hydroxyl;
the strong electrolyte is sodium chloride (NaCl) and sodium thiosulfate (Na)2S2O3) And sodium thiocyanate (NaSCN).
2. The admixture for improving the mechanical strength of high belite sulphoaluminate cement of claim 1 wherein the corresponding polyalcohol amine in the polyalcohol amine ester is selected from one or both of diethanol monoisopropanolamine (DEIPA), monoethanol diisopropanolamine (EDIPA) and Triisopropanolamine (TIPA); the organic acid is selected from acetic acid, succinic acid, and maleic anhydride.
3. The admixture for improving the mechanical strength of high belite sulphoaluminate cement of claim 1 wherein the polyamine ester is selected from one or two of acetic acid and diethanol monoisopropanolamine esterified polyamine ester (HD) with an esterification rate of 50%, acetic acid and monoethanol diisopropoxyamine esterified polyamine ester (HE) with an esterification rate of 50%, maleic acid and diethanol monoisopropanolamine esterified polyamine ester (MD) with an esterification rate of 46.38%, maleic acid and monoethanol diisopropoxyamine esterified polyamine ester (ME) with an esterification rate of 50%.
4. The admixture for improving the mechanical strength of high belite sulphoaluminate cement of claim 1 wherein the glycol is one of Ethylene Glycol (EG), 1,2 butanediol (1,2BD), Diethylene Glycol (DG).
5. The use of the admixture for improving the mechanical strength of the high belite sulphoaluminate cement of claim 1 to improve the mechanical strength of the high belite sulphoaluminate cement for 1 to 28 days.
6. Use according to claim 5, wherein the admixture is added in an amount of 0.1% by weight based on the HBSAC.
Technical Field
The invention relates to an additive for improving mechanical strength of sulphoaluminate cement, in particular to an additive capable of improving mechanical strength of high belite sulphoaluminate cement in a key age, and belongs to the technical field of cement additives.
Background
In order to reasonably allocate energy resources, greatly improve the utilization efficiency of the energy resources and reduce the low-carbon environmental protection targets of the total energy consumption of domestic production, carbon dioxide emission and the like, people pay more and more attention to a novel low-calcium cement clinker system, and the high belite sulphoaluminate systemSalt cement (HBSAC) clinker system cements have also evolved. HBSAC in C2S andin a relatively large amount, and C3The S content is very low, compared with Portland cement, the addition amount of calcium raw materials and aluminum raw materials in the raw materials is reduced, so that the energy consumption and CO of the HBSAC clinker are reduced2The emission reduction is more than 20 percent, has the characteristics of low calcium, low emission, low energy consumption and the like, and is compatible with C3S phase ratio, C2The hydration reaction of S requires less water, the hydration heat release is lower, the content of C-S-H gel generated by hydration is increased, and Ca (OH)2Production of C3Half S greatly improves the durability.
The addition of the additive is a common method for improving the hydration activity of the cementing material, and has wide application in the field of cement concrete, such as the addition of a grinding aid in the cement grinding process, the addition of an early strength agent in the concrete production and the like, but no research report is available on the additive specially used for improving the mechanical strength of the HBSAC at present. Research shows that the organic complexing agent can be mixed with Fe3+、Al3 +、Ca2+The metal ions are subjected to a complex reaction in an alkaline environment to promote the dissolution of mineral phase components, so that the solubility of the metal ions is increased, and the hydration process is promoted. The key mineral components for restricting the development of HBSAC mechanical property are calcium silicate and calcium sulphoaluminate, but the complexing agent and Fe used at present3+And Al3+Has strong complexing ability with Ca2+Is relatively weak. Therefore, the research on the admixture capable of improving the mechanical strength of the HBSAC has a positive promoting effect on improving the application level of the HBSAC in building materials and realizing high-quality resource utilization of the HBSAC.
Disclosure of Invention
In order to solve the technical problems, the invention provides an additive compounded by a complexing component and an electrolyte solution, which mainly comprises amino carboxylate, polyol amine ester, dihydric alcohol, strong electrolyte and water. Which comprises the following components in percentage by weight:
aminocarboxylates: 5-30 parts of
Polyol amine ester: 5-20 parts of
Polyol: 0 to 10 portions of
Strong electrolyte: 5-20 parts of
Water: 40-60 parts
Preferably, the aminocarboxylate is one or two of trisodium nitrilotriacetate (NTA-3Na), disodium ethylene diamine tetraacetic acid (EDTA-2Na) and pentasodium diethylenetriamine pentacarboxylate (DTPA-5 Na).
More preferably, the aminocarboxylate is one or two of pentasodium diethylenetriamine pentacarboxylate (DTPA-5Na) and disodium ethylene diamine tetraacetate (EDTA-2 Na).
Further preferably, the aminocarboxylate is pentasodium diethylenetriamine pentacarboxylate (DTPA-5 Na).
Preferably, the polyol amine ester refers to a compound obtained by esterifying hydroxyl groups in a polyol amine with carboxyl groups in an organic acid, and the obtained product contains unesterified hydroxyl groups. Wherein the polyalcohol amine is preferably one or two of diethanol monoisopropanolamine (DEIPA), monoethanol diisopropanolamine (EDIPA) and Triisopropanolamine (TIPA). Still more preferably Diethanolisopropanolamine (DEIPA) or monoethanoldiisopropanolamine (EDIPA); the organic acid is preferably one of acetic acid, succinic acid and maleic anhydride; further preferred is one or two of acetic acid and diethanol monoisopropanolamine esterified polyol amine ester (HD) (esterification rate 50%), acetic acid and monoethanol diisopropoxyamine esterified polyol amine ester (HE) (esterification rate 50%), maleic acid and diethanol monoisopropanolamine esterified polyol amine ester (MD) (esterification rate 46.38%), maleic acid and monoethanol diisopropoxyamine esterified polyol amine ester (ME) (esterification rate 50%).
Preferably, the diol is one of Ethylene Glycol (EG), 1,2 butanediol (1,2BD), and Diethylene Glycol (DG).
Preferably, the strong electrolyte is sodium chloride (NaCl), sodium thiosulfate (Na)2S2O3) And sodium thiocyanate (NaSCN).
The additive is used for improving the mechanical strength of the high belite sulphoaluminate cement in 1-28 days.
Due to the adoption of the technical scheme, the invention achieves the following technical effects:
when the addition amount of the admixture prepared by the invention is 0.1 percent of the weight of the HBSAC, the mechanical strength of the HBSAC1d can be improved by 7.6MPa to the maximum, the mechanical strength of 7d can be improved by 10.4MPa to the maximum, the mechanical strength of 28d can be improved by 14.1MPa to the maximum, and good application effect is shown.
The minerals contained in the HBSAC are mainly: dicalcium silicate (C)2S), anhydrous calcium sulphoaluminateGypsum plasterHBSAC hydration can be divided into two processes, one is a dissolution process of cement minerals, and the other is a precipitation process of hydration reaction products. Both processes change the ion concentration in the cement slurry phase, the dissolution of cement minerals increases the ion concentration in the cement slurry phase, and the increase of the ion concentration advances the hydration process, promoting the precipitation of hydration products, mainly calcium silicate hydrate gel (C-S-H), Calcium Hydroxide (CH), calcium sulfoaluminate trisulfide hydrate (AFt) and calcium sulfoaluminate monosulfide (AFm). The precipitation of the hydration products reduces the ion concentration in the liquid phase, thereby promoting the dissolution of the cement minerals. Generally, the mutual promotion and inhibition of the two processes are the key points in the cement hydration process. HBSAC mineral composition C3Content of S is reduced and C2The low hydration activity of S leads to the reduction of the early strength of HBSAC and the insufficient enhancement rate of the later strength, which limits the further development of the high belite sulphoaluminate cement.
The HBSAC system is mixed with water, and then the HBSAC system is mixed with water in the quaternary systemThe chemical reactions that occur are as follows:
C2S+2H→C-S-H+CH(2)
due to C2S begins to hydrate for too long, so the early strength is mainly due toAnd ettringite (AFt) produced by reaction with gypsum. As can be seen from the above reaction, when the gypsum is in a sufficient amount,aluminium gel and C produced by hydration2The hydration products CH of S may react further to form ettringite, but C2S has a weak early hydration activity and its hydration product CH has a very low solubility in solution, and thus (3) the degree of reaction is low. If it can promote C2The ions in S and CH can be dissolved to promote the forward progress of the hydration reactions of (1), (2) and (3), and the improvement of the mechanical property of the cement in the key age period can be greatly facilitated.
The additive prepared by the invention contains a complexing component and a strong electrolyte component, wherein amino carboxylate in the complexing component is organic micromolecule with amines and carboxyl with different charges, and can be complexed with metal ions such as calcium, iron, aluminum and the like, so that the dissolution of iron phase and aluminum phase minerals in cement is accelerated, and the early hydration reaction of the cement is promoted. And aminocarboxylate p-C2The dissolving hydration reaction of S also has obvious promoting effect, and the mechanical property of the cement in the middle and later periods can be obviously improved. Along with the advancing of the hydration process, the aminocarboxylate is continuously consumed, and the polyol amine ester is continuously decomposed into new complex components in the alkaline environment of the hydration solution, so that the hydration speed of the HBSACs of different ages is promoted, which is reflected in that the mechanical strength of the HBSACs of different ages is improved. The polyol in the additive also has stronger complexing ability and has the function of assisting complexing solubilization; the strong electrolyte component can improve the ion diffusion speed in the solution and has positive promotion effect on the dissolution hydration of the early HBSAC.
The specific implementation mode is as follows:
to further illustrate the technical means and effects of the present invention for the predetermined purpose, the following embodiments and application examples are further described in detail, but the present invention is not limited thereto.
In the following examples, all parts are parts by weight.
Example 1:
taking 15 parts of NTA-3Na, 10 parts of EDTA-2Na, 20 parts of HD, 10 parts of EG, 5 parts of NaCl and 40 parts of water.
Example 2:
taking 25 parts of NTA-3Na, 5 parts of HD, 15 parts of ME, 10 parts of 1,2BD and Na2S2O35 parts of water and 40 parts of water.
Example 3:
taking 20 parts of NTA-3Na, 10 parts of EDTA-2Na, 5 parts of HE, 15 parts of MD, 10 parts of NaSCN and 40 parts of water.
Example 4:
taking 15 parts of NTA-3Na, 15 parts of MD, 5 parts of BD and Na2S2O35 parts of water and 60 parts of water.
Example 5:
15 parts of EDTA-2Na, 15 parts of DTPA-5Na, 10 parts of ME, 5 parts of EG, 5 parts of NaCl and 50 parts of water.
Example 6:
25 parts of EDTA-2Na, 10 parts of HD, 10 parts of ME, 10 parts of 1,2BD and Na2S2O35 parts of water and 40 parts of water.
Example 7:
15 parts of EDTA-2Na, 15 parts of DTPA-5Na, 10 parts of HE, 5 parts of EG, 5 parts of NaSCN and 50 parts of water.
Example 8:
taking 20 parts of DTPA-5Na, 15 parts of HE, 5 parts of MD, 5 parts of EG, 5 parts of NaCl and 50 parts of water.
Example 9:
20 parts of EDTA-2Na, 15 parts of DTPA-5Na, 15 parts of HE, 5 parts of MD, 5 parts of EG, 5 parts of NaCl and 50 parts of water.
Example 10:
taking 30 parts of DTPA-5Na, 15 parts of HD, 5 parts of ME, 10 parts of NaSCN and 40 parts of water.
Example 11:
the chemical composition of the selected HBSAC is shown in Table 1. In the hydration process of HBSAC, the admixtures of examples 1,2, 3, 4, 5, 6, 7, 8, 9 and 10 were added, and the mechanical strength of HBSAC was measured according to GB20472-2006 and GB/T17671-1999, and the results are shown in Table 2:
TABLE 1 HBSAC chemical composition (%)
CaO
SiO2
Al2O3
MgO
SO3
Fe2O3
K2O
SrO
P2O5
42.19
21.53
17.95
5.46
9.44
0.933
0.528
0.0952
0.111
TABLE 2 results (MPa) of the effect of the admixture of the present invention on the mechanical strength of HBSAC
Additive agent
Mixing amount
1d
1d amplification
7d
7d amplification
28d
28d amplification
Is free of
-
20.0
-
32.3
-
50.4
-
Example 1
0.1
23.1
3.1
36.1
3.8
55.1
4.7
Example 2
0.1
22.7
2.7
34.3
2
56.8
6.2
Example 3
0.1
22.6
2.6
34.4
2.1
58.2
7.8
Example 4
0.1
22.9
2.9
35.8
3.5
57.4
7
Example 5
0.1
23.4
3.4
35.9
3.6
58.5
8.1
Example 6
0.1
24.3
4.3
35.2
2.9
59.7
9.3
Example 7
0.1
24.5
4.5
36.8
4.5
61.6
11.2
Example 8
0.1
27.6
7.6
42.7
10.4
64.5
14.1
Example 9
0.1
25.2
5.2
39.1
6.8
62.8
12.4
Example 10
0.1
25.5
5.5
38.3
6
61.9
11.5
As can be seen from Table 2, when the admixture prepared by the invention is added in an amount of 0.1% of the weight of HBSAC, the highest mechanical strength of HBSAC1d can be improved by 7.6MPa, the highest mechanical strength of 7d can be improved by 10.4MPa, the highest mechanical strength of 28d can be improved by 14.1MPa, and good application effects are shown.
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