Anti-corrosion cement grinding aid and preparation method thereof

Abstract

The invention discloses an anti-corrosion cement grinding aid and a preparation method thereof, and belongs to the technical field of cement environment-friendly material processing. The anti-corrosion cement grinding aid comprises water, inorganic components, alcohol amines, alcohols, other organic matters, a cement metal ion catalyst and graphene dispersion liquid. The preparation method comprises the following steps: mixing and dissolving water and inorganic components, sequentially adding alcohol amines, alcohols, the cement metal ion catalyst and other organic matters, fully stirring and uniformly mixing, finally adding graphene dispersion liquid, uniformly stirring to form a uniform system, and detecting to ensure that the system meets the standard. According to the grinding aid, through the synergistic effect of all the components and uniform dispersion of graphene, the grinding efficiency, the early strength of cement and the slump retaining performance are effectively improved, the hydration temperature peak is delayed, and complete hydration is promoted. The cement additive is adjustable in component proportion, adapts to different cement types, does not need equipment transformation, has no pungent smell, and has the characteristics of high efficiency and environmental protection.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of environmental protection materials, and particularly relates to an anti-erosion cement grinding aid and a preparation method thereof. BACKGROUND

[0002] Traditional grinding aids usually only add organic matters such as alcohol amine and alcohol to improve the cement grinding efficiency, however, there are obvious short boards and deficiencies in enhancing the erosion resistance of cement. In the prior art, the ordinary strength-enhancing grinding aid can improve the early strength of cement, but cannot effectively reduce the diffusion coefficient of chloride ions, which greatly limits the durability of concrete. In addition, the formula of the conventional grinding aid is usually fixed and cannot be flexibly adjusted and optimized according to different types of cement, so that the functions thereof cannot be fully played. Meanwhile, the prior art also fails to fully utilize the unique properties of nanomaterials (such as graphene). Graphene can theoretically optimize the hydration process of cement and effectively seal the pores inside the cement due to its high specific surface area and excellent chemical stability. However, the dispersion process and synergistic compounding mechanism of graphene in the grinding aid are not mature at present, which leads to unstable effect or high cost of graphene in practical application, and it is difficult to be widely applied. Therefore, it is urgent to develop a composite grinding aid which can not only efficiently grind, but also significantly enhance the strength and has long-term anti-erosion performance, so as to meet the demand of the building industry for high-quality cement. SUMMARY

[0003] The present application aims at the above-mentioned problems existing in the prior art, and provides an anti-erosion cement grinding aid and a preparation method thereof. It is found that the grinding aid can reduce the chloride ion diffusion coefficient of cement by 30%-40% after the organic-inorganic is compounded and the graphene is ingeniously introduced, which indicates that the grinding aid improves the erosion resistance of cement. In addition, the grinding aid can improve the 3-day compressive strength of cement by 15%-19% and the 28-day strength by 9%-17%, which further indicates the excellent performance of the grinding aid in improving the strength of cement.

[0004] To achieve the above-mentioned purposes, the technical scheme of the present application is as follows:

[0005] An anti-erosion cement grinding aid comprises the following components in mass percentage:

[0006] Water: 20%-60%;

[0007] Inorganic component: 3%-10%;

[0008] Alcohol amine component: 20%-45%;

[0009] Alcohol component: 2%-15%;

[0010] Cement metal ion catalyst; 2-8%

[0011] Other organic matter: 2%-10%;

[0012] Graphene dispersion liquid: 0.03%-0.1% by mass of graphene.

[0013] Further, the inorganic component is sulfate and silicate; the alcohol amine component is triethanolamine and / or diethyl mono isopropanolamine; the alcohol component is ethylene glycol and / or propylene glycol; the other organic matter is lignin sulfonate and / or polycarboxylic acid water reducer; and the cement metal ion catalyst is anhydrous cobalt chloride and / or cobalt residue.

[0014] Further, the preferred addition amount of the graphene dispersion liquid is 0.04%-0.08%.

[0015] Further, the sulfate is anhydrous sodium sulfate or aluminum sulfate, and the silicate is sodium silicate or sodium metasilicate; and the mass ratio of the sulfate and silicate compound is 1:1-1:2.

[0016] The application also provides a preparation method of the corrosion-resistant cement grinding aid, comprising the following steps:

[0017] (1) mixing and stirring water and the inorganic component until completely dissolved;

[0018] (2) sequentially adding the alcohol amine, the alcohol, the cement metal ion catalyst, and the other organic matter, and stirring for 10-15 minutes each time;

[0019] (3) finally adding the graphene dispersion liquid, and stirring for 30-40 minutes to form a uniform system;

[0020] (4) detecting the pH value, the solid content, and the chloride ion content.

[0021] Further, the addition temperature of the graphene dispersion liquid in step (3) is 25-35°C.

[0022] Further, the corrosion-resistant cement grinding aid further comprises 0%-2% of isocyanate.

[0023] The application also provides a preparation method of the corrosion-resistant cement grinding aid, comprising the following steps:

[0024] (1) mixing and stirring water and the inorganic component until completely dissolved;

[0025] (2) sequentially adding the alcohol amine, the alcohol, the cement metal ion catalyst, the isocyanate, and the other organic matter, and stirring for 10-15 minutes each time;

[0026] (3) Finally add graphene dispersion liquid, stir for 30-40 minutes to form a uniform system;

[0027] (4) Detect pH value, solid content and chloride content.

[0028] The application further provides application of the grinding aid in ordinary portland cement, and the mixing amount is 0.01%-0.05% of the mass of the cement.

[0029] The application further provides application of the grinding aid in high sulfate-resistant cement, and the mixing amount is 0.02%-0.04% of the mass of the cement.

[0030] Compared with the prior art, the application has the following beneficial effects:

[0031] 1. The scheme of the application adopts a step-by-step adding strategy of ''water + inorganic components -> alcohol amine -> alcohol -> other organic substances -> metal ion catalyst -> isocyanate -> graphene dispersion liquid'', and sufficient stirring is performed after each step. In particular, graphene dispersion liquid is added at last and continuous stirring is performed, which breaks through the problem of easy agglomeration of graphene in a complex system, successfully realizes high uniform dispersion of graphene in the grinding aid, and significantly plays the nano-enhancing effect of graphene. Each batch of product is detected according to the strict GB / T26748-2011 standard (irritating odor, solid content, pH value, chloride content and the like), so that the product performance is stable and reliable and environment-friendly.

[0032] 2. The synergistic effect of early strength and exothermic reaction is due to the unique complexation and exothermic reaction between the alkanolamine component (triethanolamine / diethylisopropanolamine) and cement calcium ions, promoting the formation of amorphous calcium hydroxide, significantly improving the early strength of cement and releasing heat. The designed isocyanate reacts in situ with the alcohol component to form carbamate, releasing a large amount of heat. The -CO- and -NH- structures in the product can effectively embed into the cement lattice, improving cement fluidity. The synergistic effect of sulfate and silicate complexes not only significantly improves grinding efficiency and overall cement performance, but more importantly, it synergistically delays cement hydration and postpones the crystallization of hydration products, thereby significantly improving the slump retention of concrete. The combination of lignin sulfonate and polycarboxylate superplasticizer goes beyond simple physical dispersion; its specific groups adsorb cement minerals and calcium ions and participate in the reaction. In this unique system, it can effectively delay and increase the peak hydration temperature of cement, promoting more complete hydration. The main components of cement metal ion catalysts are metalloporphyrin coordination compounds and their derivatives. The core component is a stable complex formed by metal ions and porphyrins (or porphyrin derivatives) through coordination bonds. These catalysts can alter the surface potential and active sites of cement particles by adsorbing onto the surface or participating in chemical reactions. Using organometallic compounds as precursors, a unique metal dispersion technology in organic alcohol amines achieves a breakthrough in the mild catalysis of cement metal ions. They can be dispersed in diethanolamine monoisopropanolamine to catalyze cement metal ions, improving their complexation effect, especially showing significant strengthening effects in cement with low tricalcium aluminate content. They can also be simultaneously dispersed in multiple alcohol amines for multi-element catalysis of cement metal ions, achieving combined enhancement of cement strength through multiple materials. Furthermore, they can be dispersed in hydroxyl groups to catalyze metal ions in slag, improving the activity of the slag.

[0033] 3. Synergistic stabilization of graphene dispersion by inorganic and organic components. In-depth research has determined that at a critical addition level of 0.03%-0.1%, graphene can simultaneously optimize the surface energy and hydration kinetics of cement particles, significantly improving the overall performance of the grinding aid. This is one of the core innovations of this invention, greatly reducing the increased costs associated with relying on large amounts of graphene. The component ratio of the grinding aid in this invention can be dynamically and flexibly adjusted according to different cement types, achieving precise and differentiated control over grinding aid, strengthening, and corrosion resistance properties. This dynamic formulation design significantly broadens the applicability of the grinding aid, meeting diverse production needs. This grinding aid is fully compatible with existing cement production lines, requiring no equipment modification and can be applied directly. The production process is odorless, meeting environmental protection requirements, and providing enterprises with a convenient, efficient, and green solution. Attached Figure Description

[0034] Figure 1 This is a process flow diagram of the present invention. Detailed Implementation

[0035] In order to make the above objectives, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application are described in detail below. In the following description, a large number of specific details are set forth in order to facilitate a thorough understanding of the present application. However, the present application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the spirit of the present application, so the present application is not limited to the specific implementation disclosed below.

[0036] The sulfate is anhydrous sodium sulfate or aluminum sulfate; the silicate is sodium silicate or sodium metasilicate; the lignin sulfonate is sodium lignin sulfonate or calcium lignin sulfonate, cobalt residue, and graphene dispersion liquid, etc. The raw materials used can be purchased on the market.

[0037] The applicant uniformly uses anhydrous sodium sulfate, sodium silicate, and sodium lignin sulfonate for the following examples.

[0038] Example 1

[0039] An erosion-resistant cement grinding aid, comprising the following components by mass percentage:

[0040] Water 20%; cobalt residue 2%; anhydrous sodium sulfate 5%; sodium silicate 6%; diethyl mono isopropanolamine 21%; triethanolamine 21.97%; propylene glycol 15%; polycarboxylic acid water reducer 10%; graphene dispersion liquid: 0.03% by mass of graphene.

[0041] A preparation method of the erosion-resistant cement grinding aid, comprising the following steps:

[0042] (1) Mix and stir water, anhydrous sodium sulfate, and sodium silicate until completely dissolved;

[0043] (2) Add triethanolamine, diethyl mono isopropanolamine, propylene glycol, cobalt residue, and polycarboxylic acid water reducer in sequence, and stir for 10 minutes each time;

[0044] (3) Finally, add graphene dispersion liquid at 25°C, and stir for 30 minutes to form a uniform system;

[0045] (4) Detect pH value, solid content, and chloride ion content.

[0046] Example 2

[0047] An erosion-resistant cement grinding aid, comprising the following components by mass percentage:

[0048] Water 21.9%; anhydrous cobalt chloride 2%; anhydrous sodium sulfate 3%; sodium silicate 3%; diethyl mono isopropanolamine 45%; ethylene glycol 7%; propylene glycol 8%; sodium lignin sulfonate 10%; graphene dispersion liquid: 0.1% by mass of graphene.

[0049] A preparation method of the corrosion-resistant cement grinding aid, comprising the following steps:

[0050] (1) mixing and stirring water, anhydrous sodium sulfate and sodium silicate until completely dissolved;

[0051] (2) sequentially adding diethyl monoisopropanolamine, ethylene glycol, propylene glycol, sodium lignosulfonate, anhydrous cobalt chloride and sodium lignosulfonate, and stirring for 15 minutes each time;

[0052] (3) finally adding a graphene dispersion liquid at 35°C, and stirring for 40 minutes to form a uniform system;

[0053] (4) detecting the pH value, solid content and chloride ion content.

[0054] Example 3

[0055] A corrosion-resistant cement grinding aid, comprising the following components in mass percentage:

[0056] water 50%; anhydrous cobalt chloride 3.96%; anhydrous sodium sulfate 1.5%; sodium silicate 1.5%; diethyl monoisopropanolamine 17%; triethanolamine 18%; ethylene glycol 2%; propylene glycol 4%; sodium lignosulfonate 1%; polycarboxylic acid water reducer 1%; graphene dispersion liquid: 0.04% by mass of graphene.

[0057] A preparation method of the corrosion-resistant cement grinding aid, comprising the following steps:

[0058] (1) mixing and stirring water, anhydrous sodium sulfate and sodium silicate until completely dissolved;

[0059] (2) sequentially adding diethyl monoisopropanolamine, triethanolamine, ethylene glycol, propylene glycol, anhydrous cobalt chloride, polycarboxylic acid water reducer and sodium lignosulfonate, and stirring for 10 minutes each time;

[0060] (3) finally adding a graphene dispersion liquid at 30°C, and stirring for 30 minutes to form a uniform system;

[0061] (4) detecting the pH value, solid content and chloride ion content.

[0062] Example 4

[0063] A corrosion-resistant cement grinding aid, comprising the following components in mass percentage:

[0064] water 48%; cobalt residue 3.45%; anhydrous sodium sulfate 10%; diethyl monoisopropanolamine 22.5%; triethanolamine 10%; ethylene glycol 1%; propylene glycol 1%; sodium lignosulfonate 2%; polycarboxylic acid water reducer 2%; graphene dispersion liquid: 0.05% by mass of graphene.

[0065] A preparation method of the corrosion-resistant cement grinding aid, comprising the following steps:

[0066] (1) mixing and stirring water with anhydrous sodium sulfate until completely dissolved;

[0067] (2) sequentially adding diethyl mono-isopropanolamine, triethanolamine, ethylene glycol, propylene glycol, cobalt residue, sodium lignosulfonate, and polycarboxylic acid water reducing agent, and stirring for 15 minutes each time;

[0068] (3) finally adding graphene dispersion liquid at 35°C, and stirring for 40 minutes to form a uniform system;

[0069] (4) detecting pH value, solid content, and chloride content.

[0070] Example 5

[0071] A corrosion-resistant cement grinding aid, comprising the following components in mass percentage:

[0072] water 60%; cobalt residue 4.94%; anhydrous sodium sulfate 4%; sodium silicate 4%; diethyl mono-isopropanolamine 2%; triethanolamine 1%; ethylene glycol 15%; sodium lignosulfonate 3%; polycarboxylic acid water reducing agent 6%; graphene dispersion liquid: 0.06% by mass of graphene.

[0073] A preparation method of the corrosion-resistant cement grinding aid, comprising the following steps:

[0074] (1) mixing and stirring water with anhydrous sodium sulfate and sodium silicate until completely dissolved;

[0075] (2) sequentially adding diethyl mono-isopropanolamine, triethanolamine, ethylene glycol, cobalt residue, polycarboxylic acid water reducing agent, and sodium lignosulfonate, and stirring for 15 minutes each time;

[0076] (3) finally adding graphene dispersion liquid at 35°C, and stirring for 40 minutes to form a uniform system;

[0077] (4) detecting pH value, solid content, and chloride content.

[0078] Example 6

[0079] A corrosion-resistant cement grinding aid, comprising the following components in mass percentage:

[0080] water 25%; cobalt residue 2.93%; anhydrous sodium sulfate 4%; sodium silicate 4%; triethanolamine 1%; ethylene glycol 6%; propylene glycol 3%; sodium lignosulfonate 5%; polycarboxylic acid water reducing agent 5%; graphene dispersion liquid: 0.07% by mass of graphene.

[0081] A preparation method of the corrosion-resistant cement grinding aid, comprising the following steps:

[0082] (1) Mix water with anhydrous sodium sulfate and sodium silicate and stir until completely dissolved;

[0083] (2) Add triethanolamine, ethylene glycol, propylene glycol, cobalt residue, cobalt residue, polycarboxylate superplasticizer and sodium lignosulfonate in sequence, and stir for 10 minutes each time;

[0084] (3) Finally add 25℃ graphene dispersion liquid, stir for 30 minutes to form a uniform system;

[0085] (4) Detect pH value, solid content and chloride content.

[0086] Example 7

[0087] An erosion-resistant cement grinding aid, comprising the following components by mass percentage:

[0088] Water 56.92%; anhydrous cobalt chloride 2%; cobalt residue 6%; anhydrous sodium sulfate 2%; sodium silicate 2%; diethyl mono isopropyl alcohol amine 10%; triethanolamine 10%; ethylene glycol 4%; propylene glycol 2%; sodium lignosulfonate 3%; polycarboxylate superplasticizer 2%; graphene dispersion liquid: 0.08% by mass of graphene.

[0089] A preparation method of the erosion-resistant cement grinding aid, comprising the following steps:

[0090] (1) Mix water with anhydrous sodium sulfate and sodium silicate and stir until completely dissolved;

[0091] (2) Add diethyl mono isopropyl alcohol amine, triethanolamine, ethylene glycol, propylene glycol, anhydrous cobalt chloride, cobalt residue, polycarboxylate superplasticizer and sodium lignosulfonate in sequence, and stir for 15 minutes each time;

[0092] (3) Finally add 35℃ graphene dispersion liquid, stir for 40 minutes to form a uniform system;

[0093] (4) Detect pH value, solid content and chloride content.

[0094] Example 8

[0095] An erosion-resistant cement grinding aid, comprising the following components by mass percentage:

[0096] Water 45%; cobalt residue 2.91%; sodium silicate 10%; diethyl mono isopropyl alcohol amine 12.5%; triethanolamine 12.5%; ethylene glycol 5%; propylene glycol 6%; sodium lignosulfonate 5%; polycarboxylate superplasticizer 5%; graphene dispersion liquid: 0.09% by mass of graphene.

[0097] A preparation method of the erosion-resistant cement grinding aid, comprising the following steps:

[0098] (1) Mix water with sodium silicate and stir until completely dissolved;

[0099] (2) Add diethyl mono-isopropyl amine, triethanolamine, ethylene glycol, propylene glycol, cobalt residue, polycarboxylic acid water reducing agent and sodium lignosulfonate in sequence, stirring for 10 minutes each time;

[0100] (3) Finally add graphene dispersion liquid at 30℃, stirring for 35 minutes to form a uniform system;

[0101] (4) Detect pH value, solid content and chloride content.

[0102] Example 9

[0103] An erosion-resistant cement grinding aid, comprising the following components in mass percentage:

[0104] Water 40%; cobalt residue 1.91%; anhydrous sodium sulfate 3%; sodium silicate 6%; diethyl mono-isopropyl amine 20%; triethanolamine 6%; ethylene glycol 8%; propylene glycol 5%; sodium lignosulfonate 4%; polycarboxylic acid water reducing agent 5%; graphene dispersion liquid: 0.09% by mass of graphene; isocyanate 1%.

[0105] A preparation method of the erosion-resistant cement grinding aid, comprising the following steps:

[0106] (1) Mix water with sodium silicate and anhydrous sodium sulfate and stir until completely dissolved;

[0107] (2) Add diethyl mono-isopropyl amine, triethanolamine, ethylene glycol, propylene glycol, cobalt residue, isocyanate, polycarboxylic acid water reducing agent and sodium lignosulfonate in sequence, stirring for 10 minutes each time;

[0108] (3) Finally add graphene dispersion liquid at 25℃, stirring for 30 minutes to form a uniform system;

[0109] (4) Detect pH value, solid content and chloride content.

[0110] Example 10

[0111] An erosion-resistant cement grinding aid, comprising the following components in mass percentage:

[0112] Water 36.1%; anhydrous cobalt chloride 3.5%; cobalt residue 3.5%; anhydrous sodium sulfate 2%; sodium silicate 4%; diethyl mono-isopropyl amine 2%; triethanolamine 25.33%; ethylene glycol 10%; propylene glycol 1.5%; sodium lignosulfonate 2%; polycarboxylic acid water reducing agent 8.5%; graphene dispersion liquid: 0.07% by mass of graphene; isocyanate 1.5%.

[0113] A preparation method of the erosion-resistant cement grinding aid, comprising the following steps:

[0114] (1) Mix water with anhydrous sodium sulfate and sodium silicate and stir until completely dissolved;

[0115] (2) Add diethyl mono-isopropyl amine, triethanolamine, ethylene glycol, propylene glycol, anhydrous cobalt chloride, cobalt residue, isocyanate, polycarboxylic acid water reducer and sodium lignosulfonate in sequence, and stir for 10 minutes each time;

[0116] (3) Finally, add graphene dispersion liquid at 25°C, and stir for 30 minutes to form a uniform system;

[0117] (4) Detect pH value, solid content and chloride ion content.

[0118] Example 11

[0119] An erosion-resistant cement grinding aid, comprising the following components in mass percentage:

[0120] Water 40%; anhydrous cobalt chloride 3.97%; cobalt residue 3%; anhydrous sodium sulfate 4.5%; sodium silicate 4.5%; diethyl mono-isopropyl amine 10%; triethanolamine 12%; ethylene glycol 2%; propylene glycol 10%; sodium lignosulfonate 4%; polycarboxylic acid water reducer 4%; graphene dispersion liquid: 0.03% by mass of graphene; isocyanate 2%.

[0121] A preparation method of the erosion-resistant cement grinding aid, comprising the following steps:

[0122] (1) Mix water with anhydrous sodium sulfate and sodium silicate and stir until completely dissolved;

[0123] (2) Add diethyl mono-isopropyl amine, triethanolamine, ethylene glycol, propylene glycol, anhydrous cobalt chloride, cobalt residue, isocyanate, polycarboxylic acid water reducer and sodium lignosulfonate in sequence, and stir for 10 minutes each time;

[0124] (3) Finally, add graphene dispersion liquid at 25°C, and stir for 30 minutes to form a uniform system;

[0125] (4) Detect pH value, solid content and chloride ion content.

[0126] Example 12

[0127] An erosion-resistant cement grinding aid, comprising the following components in mass percentage:

[0128] Water 38.97%; anhydrous cobalt chloride 3%; cobalt residue 2%; anhydrous sodium sulfate 2%; sodium silicate 2%; diethyl mono-isopropyl amine 12%; triethanolamine 15%; ethylene glycol 10%; propylene glycol 5%; sodium lignosulfonate 5%; polycarboxylic acid water reducer 5%; graphene dispersion liquid: 0.03% by mass of graphene.

[0129] A preparation method of the erosion-resistant cement grinding aid, comprising the following steps:

[0130] (1) Mix water with anhydrous sodium sulfate and sodium silicate and stir until completely dissolved;

[0131] (2) Add diethyl mono-isopropanolamine, triethanolamine, ethylene glycol, propylene glycol, anhydrous cobalt chloride, cobalt residue, polycarboxylic acid water reducer and sodium lignosulfonate in sequence, and stir for 15 minutes each time;

[0132] (3) Finally add graphene dispersion liquid at 35℃, and stir for 40 minutes to form a uniform system;

[0133] (4) Detect pH value, solid content and chloride ion content.

[0134] Example 13

[0135] An erosion-resistant cement grinding aid, comprising the following components in mass percentage:

[0136] Water 45.9%; anhydrous cobalt chloride 6%; cobalt residue 2%; anhydrous sodium sulfate 2%; sodium silicate 4%; diethyl mono-isopropanolamine 10%; triethanolamine 10%; ethylene glycol 7%; propylene glycol 7%; sodium lignosulfonate 3%; polycarboxylic acid water reducer 3%; graphene dispersion liquid: 0.1% by mass of graphene.

[0137] A preparation method of the erosion-resistant cement grinding aid, comprising the following steps:

[0138] (1) Mix water with anhydrous sodium sulfate and sodium silicate and stir until completely dissolved;

[0139] (2) Add diethyl mono-isopropanolamine, triethanolamine, ethylene glycol, propylene glycol, anhydrous cobalt chloride, cobalt residue, polycarboxylic acid water reducer and sodium lignosulfonate in sequence, and stir for 15 minutes each time;

[0140] (3) Finally add graphene dispersion liquid at 35℃, and stir for 40 minutes to form a uniform system;

[0141] (4) Detect pH value, solid content and chloride ion content.

[0142] Example 14

[0143] An erosion-resistant cement grinding aid, comprising the following components in mass percentage:

[0144] Water 36.97%; anhydrous cobalt chloride 1.5%; cobalt residue 1.5%; anhydrous sodium sulfate 3%; sodium silicate 6%; diethyl mono-isopropanolamine 16%; triethanolamine 11%; ethylene glycol 5%; propylene glycol 8%; sodium lignosulfonate 4%; polycarboxylic acid water reducer 6%; graphene dispersion liquid: 0.02% by mass of graphene; isocyanate 1.01%.

[0145] A preparation method of the corrosion-resistant cement grinding aid, comprising the following steps:

[0146] (1) mixing and stirring water, anhydrous sodium sulfate and sodium silicate until completely dissolved;

[0147] (2) sequentially adding diethyl mono-isopropanolamine, triethanolamine, ethylene glycol, propylene glycol, anhydrous cobalt chloride, cobalt residue, isocyanate, polycarboxylic acid water reducer and sodium lignosulfonate, and stirring for 15 minutes each time;

[0148] (3) finally adding 35℃ graphene dispersion liquid, and stirring for 40 minutes to form a uniform system;

[0149] (4) detecting pH value, solid content and chloride ion content.

[0150] Example 15

[0151] A corrosion-resistant cement grinding aid, comprising the following components in mass percentage:

[0152] water 40%; anhydrous cobalt chloride 3.97%; cobalt residue 3%; anhydrous sodium sulfate 4.5%; sodium silicate 4.5%; diethyl mono-isopropanolamine 10%; triethanolamine 12%; ethylene glycol 2%; propylene glycol 10%; sodium lignosulfonate 4%; polycarboxylic acid water reducer 4%; graphene dispersion liquid: 0.12% by mass of graphene; isocyanate 1.91%.

[0153] A preparation method of the corrosion-resistant cement grinding aid, comprising the following steps:

[0154] (1) mixing and stirring water, anhydrous sodium sulfate and sodium silicate until completely dissolved;

[0155] (2) sequentially adding diethyl mono-isopropanolamine, triethanolamine, ethylene glycol, propylene glycol, anhydrous cobalt chloride, cobalt residue, isocyanate, polycarboxylic acid water reducer and sodium lignosulfonate, and stirring for 15 minutes each time;

[0156] (3) finally adding 35℃ graphene dispersion liquid, and stirring for 40 minutes to form a uniform system;

[0157] (4) detecting pH value, solid content and chloride ion content.

[0158] Example 16

[0159] A corrosion-resistant cement grinding aid, comprising the following components in mass percentage:

[0160] Water 40%; anhydrous cobalt chloride 3.97%; cobalt residue 3%; anhydrous sodium sulfate 4.5%; sodium silicate 4.5%; diethyl mono isopropanol amine 10%; triethanolamine 12%; ethylene glycol 2%; propylene glycol 10%; sodium lignosulfonate 4%; polycarboxylic acid water reducer 4%; graphene dispersion liquid: 0.15% by mass of graphene; isocyanate 1.88%.

[0161] A preparation method of the corrosion-resistant cement grinding aid, comprising the following steps:

[0162] (1) mixing and stirring water, anhydrous sodium sulfate and sodium silicate until completely dissolved;

[0163] (2) sequentially adding diethyl mono isopropanol amine, triethanolamine, ethylene glycol, propylene glycol, anhydrous cobalt chloride, cobalt residue, isocyanate, polycarboxylic acid water reducer and sodium lignosulfonate, and stirring for 15 minutes each time;

[0164] (3) finally adding 35℃ graphene dispersion liquid, and stirring for 40 minutes to form a uniform system;

[0165] (4) detecting pH value, solid content and chloride ion content.

[0166] Example 17

[0167] A corrosion-resistant cement grinding aid, comprising the following components by mass percentage:

[0168] Water 40%; anhydrous cobalt chloride 3.97%; cobalt residue 3%; anhydrous sodium sulfate 4.5%; sodium silicate 4.5%; diethyl mono isopropanol amine 10%; triethanolamine 12%; ethylene glycol 2%; propylene glycol 10%; sodium lignosulfonate 4%; polycarboxylic acid water reducer 4%; graphene dispersion liquid: 0.2% by mass of graphene; isocyanate 1.83%.

[0169] A preparation method of the corrosion-resistant cement grinding aid, comprising the following steps:

[0170] (1) mixing and stirring water, anhydrous sodium sulfate and sodium silicate until completely dissolved;

[0171] (2) sequentially adding diethyl mono isopropanol amine, triethanolamine, ethylene glycol, propylene glycol, anhydrous cobalt chloride, cobalt residue, isocyanate, polycarboxylic acid water reducer and sodium lignosulfonate, and stirring for 15 minutes each time;

[0172] (3) finally adding 35℃ graphene dispersion liquid, and stirring for 40 minutes to form a uniform system;

[0173] (4) detecting pH value, solid content and chloride ion content.

[0174] Example 18

[0175] An anti-erosion type cement grinding aid, comprising the following components by mass percentage:

[0176] Water 45.9%; anhydrous cobalt chloride 6%; cobalt residue 2%; anhydrous sodium sulfate 2%; sodium silicate 6%; diethyl mono-isopropanolamine 10%; triethanolamine 10%; ethylene glycol 6%; propylene glycol 6%; sodium lignosulfonate 3%; polycarboxylic acid water reducer 3%; graphene dispersion liquid: 0.1% by mass of graphene.

[0177] A preparation method of the anti-erosion type cement grinding aid, comprising the following steps:

[0178] (1) mixing and stirring water, anhydrous sodium sulfate and sodium silicate until completely dissolved;

[0179] (2) sequentially adding diethyl mono-isopropanolamine, triethanolamine, ethylene glycol, propylene glycol, anhydrous cobalt chloride, cobalt residue, polycarboxylic acid water reducer and sodium lignosulfonate, and stirring for 15 minutes each time;

[0180] (3) finally adding 35℃ graphene dispersion liquid, and stirring for 40 minutes to form a uniform system;

[0181] (4) detecting pH value, solid content and chloride ion content.

[0182] In order to facilitate comparison of the production effect of the anti-erosion type cement grinding aid of the present application, the cement grinding aids prepared in Examples 1-18 are added to P.O42.5 cement at a dosage of 0.02%: clinker 76%, fly ash 6, metallurgical slag 8%, limestone 5%, gypsum dosage 5%, and the present application grinding aid dosage 0.02%, and are numbered 1-18, respectively. A sample without adding the grinding aid of the present application is prepared as a blank control (0). Production is controlled according to the normal P.O42.5 cement index, and each stage is produced for more than 8 hours, and representative samples are taken. Performance tests are carried out respectively, and the test results are shown in Table 1.

[0183] Table 1: P.O42.5 cement grinding test results

[0184]

[0185] As can be seen from the above table, the 3-day compressive strength of the blank sample of P.O42.5 cement (i.e. the sample without adding the cement grinding aid) is 23.5Mpa, and the 28-day compressive strength is 47.5Mpa.

[0186] As seen from Nos. 9, 10, 11, 14-17, when the addition amount of the graphene dispersion solution exceeds 0.1% or is lower than 0.03%, the strength growth rate will decrease, and even the synergistic effect of the isocyanate and the cement metal ion catalyst cannot compensate for the trend of the grinding aid to reduce the compressive strength of the cement; and from the chloride ion diffusion coefficient, the cement chloride ion diffusion resistance performance is obviously decreased.

[0187] As seen from Nos. 1-8, the chloride ion diffusion coefficient is relatively stable, the compressive strength increases by about 23 Mpa from 3 days to 28 days, and the performance is good, which shows excellent compressive strength compared with the blank control. As seen from Nos. 9-11, the addition of isocyanate can effectively coordinate the compressive strength and chloride ion diffusion resistance performance of the alcohol-based cement grinding aid.

[0188] As seen from Nos. 1-18, the compounded grinding aid with the ratio of anhydrous sodium sulfate and sodium silicate between 1:1-1:2 can improve the performance of the cement. Compared with Nos. 13 and 18, when the ratio of anhydrous sodium sulfate and sodium silicate is 1:3, the chloride ion diffusion coefficient of No. 18 is obviously weaker than that of No. 13, and the compressive strength at 3 days and 28 days is lower than that of No. 13. With the extension of time, the increase is lower and lower. It is found that the ratio of inorganic components can directly affect the performance of the cement, which may be related to the synergy between the components of the compounded grinding aid, and further research is needed to find out the mechanism. It can also be seen that with the increase of the addition amount of the graphene dispersion solution, the compressive strength change is not large, and the best addition amount is 0.03%. This result is a major discovery. In this entire grinding aid, the amount of graphene dispersion solution used is very small, which can break the common understanding that the addition amount of graphene is above 0.2%. This discovery can provide a new direction for reducing the cost of cement material preparation.

[0189] As seen from the data, No. 11 has the best effect on the chloride ion diffusion resistance performance and the compressive strength.

[0190] The following verification test is to investigate the influence of the addition amount of the cement grinding aid in P.O42.5 cement.

[0191] The cement grinding aid prepared in Example 11 of No. 11 is added according to Table 2. The production of P.O42.5 cement is controlled according to the normal P.O42.5 cement index, and under the premise of ensuring normal production, the addition amount of the cement grinding aid is 0, 0.01%, 0.02%, 0.03%, 0.04% and 0.05% respectively, and each stage is produced for more than 8 hours, and representative samples are taken.

[0192] Table 2 Addition amount of grinding aid in P.O42.5 cement large mill test scheme

[0193]

[0194]

[0195] The results are shown in Table 3.

[0196] Table 3 Test results of grinding aids in P.O 42.5 cement

[0197]

[0198] From the above table, the cement grinding aid of Example 6 or Example 10 has an increase in 3-day and 28-day strength of P.O 42.5 cement, and the maximum increase is the sample with a cement grinding aid content of 0.04%. The 3-day strength of the grinding aid of Example 11 increases by 4.39 MPa, and the growth rate is 18.66%. The 28-day strength of the sample with a grinding aid content of 0.04% still has the largest increase, and the grinding aid of Example 11 increases by 7.92 MPa, and the growth rate is 16.67%. From the chloride ion diffusion coefficient, after adding the grinding aid, the chloride ion diffusion coefficient of Example 11 decreases from 1.98*10 -12 m 2 / s to about 1.59*10 -12 m 2 / s, indicating that the chloride ion diffusion resistance of the cement is significantly increased. From the data, with the increase of the addition amount, there is an increase, but when the addition amount is 0.05%, the increase is significantly reduced.

[0199] In order to verify the influence of the cement grinding aid of the present application on the performance of cement again, the project team selects the application of the cement grinding aid in the production of special cement, tests the influence of the cement grinding aid on the high corrosion-resistant cement, especially the influence on the chloride ion diffusion resistance.

[0200] The cement grinding aid of Example 11 numbered 11 is added according to Table 4. The production of high sulfate-resistant cement is controlled according to the normal production index, and under the premise of ensuring normal production, the cement grinding aid contents are 0, 0.01%, 0.02%, 0.03%, 0.04% and 0.05%, respectively, and each stage is produced for more than 8 hours, and representative samples are taken.

[0201] Table 4 Grinding aid content in high sulfate-resistant cement test scheme

[0202]

[0203]

[0204] The results are shown in Table 5.

[0205] Table 5 Test results of grinding aids in P.SHR 42.5 cement

[0206]

[0207] From the above table of special cement grinding test results: high sulfate-resistant cement blank sample 3-day compressive strength 19.8Mpa, 28-day compressive strength 47.2Mpa. Using the cement grinding aid of Example 11 in P.SHR42.5 cement has increased strength at 3 days and 28 days, and the maximum increase is the sample with 0.04% cement grinding aid. The grinding aid of Example 11 has an increase of 4.2Mpa (3-day strength increases to 24.0Mpa, with a growth rate of 21.2%). The 28-day strength of the sample with 0.04% grinding aid has the largest increase, and the grinding aid of Example 11 has an increase of 7.6Mpa (28-day strength reaches 54.8Mpa, with a growth rate of 16.1%). From the chloride ion diffusion coefficient, after adding the grinding aid, the chloride ion diffusion coefficient of Example 11 decreases from 1.68*10 -12 m 2 / s to 1.1*10 -12 m 2 / s, but the best can be reduced to 1.08*10 -12 m 2 / s, and it does not continue to decrease after that. The data from this project shows that the cement chloride ion diffusion resistance performance has increased significantly.

[0208] In summary, the cement grinding aid with the raw material composition and weight ratio of the present application can pass the industrial production test of P.O42.5 cement and high sulfate-resistant cement. The grinding aid designed by the present inventor has a significant cement strength improvement effect, can replace the existing ordinary strength-improving grinding aid, and can be used in ordinary cement production. The cement grinding aid can greatly improve the cement chloride ion diffusion resistance performance, especially in the production of high corrosion-resistant cement, which will greatly improve the cement corrosion resistance and increase the durability of concrete.

[0209] The above description is a detailed description of the preferred embodiments of the present application, but the embodiments are not intended to limit the scope of the patent application.

Claims

1. A corrosion-resistant cement grinding aid, characterized by, Comprise the following components by mass percentage: Water: 20%-60%; Inorganic component: 3%-10%; Alcohol amine component: 20%-45%; Alcohol component: 2%-15%; Cement metal ion catalyst; 2-8％ Other organic matter: 2%-10%; Graphene dispersion liquid: 0.03%-0.1% by mass of graphene.

2. The erosion resistant cement grinding aid of claim 1, wherein: The inorganic component is sulfate and silicate; the alcohol amine component is triethanolamine and / or diethyl mono isopropyl alcohol amine; the alcohol component is ethylene glycol and / or propylene glycol; the other organic matter is lignin sulfonate and / or polycarboxylic acid water reducer; and the cement metal ion catalyst is anhydrous cobalt chloride and / or cobalt residue.

3. The erosion resistant cement grinding aid of claim 1, wherein: The preferred addition amount of the graphene dispersion liquid is 0.04%-0.08%.

4. The erosion resistant cement grinding aid of claim 1, wherein: The sulfate is anhydrous sodium sulfate or aluminum sulfate, and the silicate is sodium silicate or sodium metasilicate; the mass ratio of the sulfate and silicate complex is 1:1-1:

2.

5. The method for preparing the corrosion-resistant cement grinding aid according to any one of claims 1-4, characterized in that, Comprise the following steps: (1) Mix and stir water and inorganic component until completely dissolved; (2) Add alcohol amine, alcohol, cement metal ion catalyst and other organic matter in sequence, stirring for 10-15 minutes each time; (3) Finally add graphene dispersion liquid, stirring for 30-40 minutes to form a uniform system; (4) Detect pH value, solid content and chloride content.

6. The method of claim 5, wherein, The addition temperature of the graphene dispersion liquid in step (3) is 25-35℃.

7. The erosion resistant cement grinding aid of claim 1, wherein: Also include 0%-2% isocyanate.

8. The method for preparing the corrosion-resistant cement grinding aid as described in claim 7, characterized in that, Comprise the following steps: (1) Mix and stir water and inorganic component until completely dissolved; (2) Add alcohol amine, alcohol, cement metal ion catalyst, isocyanate and other organic matter in sequence, stirring for 10-15 minutes each time; (3) Finally add graphene dispersion liquid, stirring for 30-40 minutes to form a uniform system; (4) Detect pH value, solid content and chloride content.

9. Use of the grinding aid of claim 1 in ordinary Portland cement, the dosage being 0.01%-0.05% by mass of cement.

10. Use of the grinding aid of claim 1 in high sulfate-resistant cement, the dosage being 0.02%-0.04% by mass of cement.

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