WO2023045156A1 - Preparation method for intercalation modified c-s-h gel nanodispersion - Google Patents
Preparation method for intercalation modified c-s-h gel nanodispersion Download PDFInfo
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- WO2023045156A1 WO2023045156A1 PCT/CN2021/141648 CN2021141648W WO2023045156A1 WO 2023045156 A1 WO2023045156 A1 WO 2023045156A1 CN 2021141648 W CN2021141648 W CN 2021141648W WO 2023045156 A1 WO2023045156 A1 WO 2023045156A1
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- filter cake
- press filter
- stage press
- quartz sand
- intercalation
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- 230000002687 intercalation Effects 0.000 title claims abstract description 58
- 238000009830 intercalation Methods 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000843 powder Substances 0.000 claims abstract description 49
- 239000006004 Quartz sand Substances 0.000 claims abstract description 48
- 239000006185 dispersion Substances 0.000 claims abstract description 42
- 238000000498 ball milling Methods 0.000 claims abstract description 34
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 31
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 31
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 31
- 150000003384 small molecules Chemical class 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000011085 pressure filtration Methods 0.000 claims abstract description 16
- 239000012065 filter cake Substances 0.000 claims description 90
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 38
- 239000003381 stabilizer Substances 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000003607 modifier Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004364 calculation method Methods 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 125000000185 sucrose group Chemical group 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- JLDKGEDPBONMDR-UHFFFAOYSA-N calcium;dioxido(oxo)silane;hydrate Chemical compound O.[Ca+2].[O-][Si]([O-])=O JLDKGEDPBONMDR-UHFFFAOYSA-N 0.000 abstract description 38
- 238000000034 method Methods 0.000 abstract description 16
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical class [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000002925 chemical effect Effects 0.000 abstract 3
- 235000012241 calcium silicate Nutrition 0.000 description 9
- 229910052918 calcium silicate Inorganic materials 0.000 description 9
- 239000000378 calcium silicate Substances 0.000 description 8
- 239000004568 cement Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000006703 hydration reaction Methods 0.000 description 6
- 230000036571 hydration Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 230000001568 sexual effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/24—Alkaline-earth metal silicates
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
Definitions
- the invention belongs to the technical field of production of inorganic nanocomposite materials, and in particular relates to a preparation method of intercalation modified C-S-H gel nano-dispersion liquid.
- Calcium silicate hydrate (C-S-H) gel is one of the main hydration products of Portland cement and one of the main strength sources of hardened cement-based materials.
- C-S-H Calcium silicate hydrate
- Commonly used raw materials include sodium silicate, potassium silicate, lithium silicate, calcium nitrate, calcium chloride, etc.; hydrothermal synthesis method It is prepared by mixing crystalline or amorphous silicon dioxide micropowder with calcium hydroxide and then chemically reacting under high temperature and pressure in an autoclave; the single mineral hydration method first prepares dicalcium silicate ( C 2 S) or tricalcium silicate (C 3 S) single ore, and then hydrate the single ore with water.
- C 2 S dicalcium silicate
- C 3 S tricalcium silicate
- the present invention aims to provide a low-cost preparation method of intercalation-modified calcium silicate hydrate nano-dispersion.
- a kind of preparation method of intercalation modified C-S-H gel nano-dispersion it is characterized in that the preparation method of described intercalation modification C-S-H gel nano-dispersion comprises the following steps:
- (1) preparing molar concentration is the sodium hydroxide aqueous solution of 0.5 ⁇ 1.0mol
- step 2 (3) adding the mixture in step 2 to a ball mill for ball milling, the ball milling time is 90-240min;
- the primary press filter cake is dispersed in deionized water, after repeated press filter and dispersion treatment, adding a stabilizer, and stirring evenly, to obtain a C-S-H gel nano-dispersion liquid modified by intercalation.
- the secondary press filter cake is dispersed in deionized water, after stirring evenly, the third-stage press filter is carried out to obtain the third-stage press filter cake;
- the preparation method of the present invention may also comprise the following steps:
- the secondary press filter cake is dispersed in the fourth-stage press water described in the above technical solution, after stirring evenly, the third-stage press filter is carried out to obtain the third-stage press filter filter cake;
- the ball mill is a high-energy ball mill such as a vibration ball mill, a planetary ball mill, or a colloid mill;
- the soluble small organic molecule intercalation modifier is sucrose, glucose, EDTA, low molecular weight PEG, low molecular weight PVA.
- the specific surface area of the ultrafine quartz sand powder is more than 500m2/kg
- the specific surface area of the ultrafine quartz sand powder is above 1000m2/kg.
- the molecular weight of the low molecular weight PEG is below 10,000.
- the molecular weight of the low molecular weight PVA is below 20,000.
- the stabilizer is the same as the soluble organic small molecule intercalation modifier used.
- the beneficial effects of the present invention are mainly reflected in the full use of the mechanochemical effect in the ball milling process, using sodium hydroxide as an intermediate component of the chemical reaction of quartz sand powder under mechanochemical action, and promoting low-cost quartz sand powder and hydrogen oxidation.
- the chemical reaction of calcium under the action of mechanochemistry so that cheap and easy-to-obtain quartz sand powder and calcium hydroxide can be used as raw materials to prepare intercalated modified calcium silicate hydrate gel nanodispersion, and the preparation process cost Inexpensive, sodium hydroxide and press filtered water can be recycled.
- Fig. 1 is the XRD spectrum obtained after the intercalation modified C-S-H gel nano-dispersion liquid of Example 1 is dried and subjected to XRD analysis.
- Fig. 2 is the XRD spectrum obtained after the intercalation modified C-S-H gel nano-dispersion liquid of Example 2 is dried and subjected to XRD analysis.
- Fig. 3 is the XRD pattern obtained after the intercalation modified C-S-H gel nano-dispersion liquid of Example 3 is dried and subjected to XRD analysis.
- a preparation method of intercalation modified C-S-H gel nano-dispersion comprises the following steps:
- (1) preparing molar concentration is the sodium hydroxide aqueous solution of 0.5mol
- step 2 Add the mixture in step 2 to a ball mill for ball milling, and the ball milling time is 90min;
- the ball mill is a vibration ball mill
- the soluble small organic molecule intercalation modifier is sucrose.
- the specific surface area of the ultrafine quartz sand powder is 1058m 2 /kg
- Fig. 1 shows the XRD pattern obtained after drying the obtained nano-dispersion liquid. It can be seen from Fig. 1 that the intercalation-modified C-S-H gel nano-dispersion liquid can be obtained by using this preparation method.
- a kind of preparation method of intercalation modified C-S-H gel nano-dispersion it is characterized in that the preparation method of described intercalation modification C-S-H gel nano-dispersion comprises the following steps:
- (1) preparing molar concentration is the sodium hydroxide aqueous solution of 1.0mol
- step 2 The mixture in step 2 is added into a ball mill for ball milling, and the ball milling time is 240min;
- the ball mill is a planetary ball mill
- the soluble small organic molecule intercalation modifier is glucose
- the specific surface area of the ultrafine quartz sand powder is 512m2/kg.
- Fig. 2 shows the XRD pattern obtained after drying the obtained nano-dispersion liquid. It can be seen from Fig. 2 that the intercalation-modified C-S-H gel nano-dispersion liquid can be obtained by using this preparation method.
- a preparation method for intercalation modified C-S-H gel nano-dispersion comprising the following steps:
- Example 1 After mixing the primary aqueous solution of pressure filtration obtained in Example 1 and the secondary aqueous solution of press filtration, it is tested that its concentration of sodium hydroxide is 0.44mol/L, then sodium hydroxide is added in the mixed solution, and the molar concentration is mixed with 0.5mol/L sodium hydroxide solution;
- the secondary press filter cake is dispersed in the fourth-stage press water described in Example 2, after stirring evenly, the third-stage press filter is carried out to obtain the third-stage press filter cake ;
- the ball mill is a colloid mill
- the soluble small organic molecule intercalation modifier is low molecular weight PEG.
- the specific surface area of the ultrafine quartz sand powder is above 800m2/kg.
- the molecular weight of the low molecular weight PEG is about 6000.
- Fig. 3 shows the XRD pattern obtained after drying the obtained nano-dispersion liquid. It can be seen from Fig. 3 that the intercalation-modified C-S-H gel nano-dispersion liquid can be obtained by using this preparation method.
- a preparation method of intercalation modified C-S-H gel nano-dispersion comprises the following steps:
- Example 2 After the primary aqueous solution of pressure filtration obtained in Example 2 is mixed with the secondary aqueous solution of press filtration, it is tested that its concentration of sodium hydroxide is 0.90mol/L, then sodium hydroxide is added in the mixed solution, and the molar concentration is mixed with 1.0mol sodium hydroxide solution;
- Example 2 Disperse the primary press filter cake in the third-stage press water obtained in Example 2 in a weight ratio of 1:3, and after stirring evenly, perform second-stage press filtration to obtain a second-stage press filter cake;
- the secondary press filter cake is dispersed in the fourth-stage press water obtained in Example 2, after stirring evenly, the third-stage press filter is carried out to obtain the third-stage press filter cake ;
- the ball mill is a colloid mill
- the soluble small organic molecule intercalation modifier is low molecular weight PVA.
- the specific surface area of the ultrafine quartz sand powder is 1282m 2 /kg.
- the molecular weight of the low molecular weight PVA is about 12000.
- a preparation method of intercalation modified C-S-H gel nano-dispersion comprises the following steps:
- step 2 The mixture in step 2 is added into a ball mill for ball milling, and the ball milling time is as shown in Table 1;
- a kind of preparation method of intercalation modified C-S-H gel nano-dispersion it is characterized in that the preparation method of described intercalation modification C-S-H gel nano-dispersion comprises the following steps:
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention provides a low-cost preparation method for an intercalation modified calcium silicate hydrate (C-S-H) gel nanodispersion. The preparation method comprises: adding calcium hydroxide, superfine quartz sand powder, and water-soluble small molecules to a certain molar concentration of a sodium hydroxide solution; then adding the mixture to a ball mill for ball milling treatment for 90-240 min; and performing repeated pressure filtration treatment and dispersion treatment on the reaction solution to obtain an intercalation modified C-S-H gel nanodispersion. Beneficial effects of the present invention are mainly that: the mechanical force chemical effect during a ball milling process is fully utilized; sodium hydroxide is used as an intermediate component of the chemical reaction of quartz sand powder under a mechanical force chemical effect, so as to promote the chemical reaction of the low-cost quartz sand powder and calcium hydroxide under the mechanical force chemical effect, so that cheap and easily available quartz sand powder and calcium hydroxide can be used as raw materials to prepare intercalation modified C-S-H gel nanodispersion; the preparation process is low in cost; and the sodium hydroxide and pressure filtration water can be recycled.
Description
本发明属于无机纳米复合材料生产技术领域，具体涉及一种插层改性C-S-H凝胶纳米分散液的制备方法。The invention belongs to the technical field of production of inorganic nanocomposite materials, and in particular relates to a preparation method of intercalation modified C-S-H gel nano-dispersion liquid.
水化硅酸钙(C-S-H)凝胶是硅酸盐水泥的主要水化产物之一，也是硬化水泥基材料主要的强度来源之一。近几十年来的研究发现，在水泥基材料中掺加水化硅酸钙凝胶纳米粒子，掺入的水化硅酸钙凝胶纳米粒子可作为水泥水化过程中水泥水化产物水化硅酸钙凝胶成核生长的晶核，从而可有效促进新拌水泥基材料的水化反应速度，并进一步有效改善硬化水泥基材料性能，尤其是可有效改善硬化水泥基材料耐久性，包括抗氯离子渗透性能、抗渗性等，并已在工程实践中得以一定范围的应用。此外，研究发现，将水化硅酸钙凝胶与有机高分子复合，可制备得到具有一定插层结构的水化硅酸钙凝胶复合物，在水泥基材料中掺加亦对新拌和硬化水泥基材料具有不同程度的影响。Calcium silicate hydrate (C-S-H) gel is one of the main hydration products of Portland cement and one of the main strength sources of hardened cement-based materials. In recent decades, studies have found that adding hydrated calcium silicate gel nanoparticles to cement-based materials can be used as the cement hydration product silicon hydrate in the cement hydration process. Calcium acid gel nucleation and growth crystal nuclei, which can effectively promote the hydration reaction speed of freshly mixed cement-based materials, and further effectively improve the performance of hardened cement-based materials, especially the durability of hardened cement-based materials, including resistance Chloride ion permeability, impermeability, etc., and have been applied in a certain range in engineering practice. In addition, research has found that calcium silicate hydrate gel composites with organic polymers can be prepared to obtain calcium silicate hydrate gel composites with a certain intercalation structure. Cement-based materials have varying degrees of influence.
目前，国内外制备水化硅酸钙凝胶主要有以下几种方法：化学合成法、水热合成法、单矿水化法、纳米二氧化硅与氢氧化钙直接反应法，其中化学合成法是指将碱硅酸盐与钙盐分别配制成溶液后，再进行混合制备而成，常用原材料包括硅酸钠、硅酸钾、硅酸锂和硝酸钙、氯化钙等；水热合成法是指将晶态或非晶态二氧化硅微粉与氢氧化钙混合后，在蒸压釜中的高温高压下发生化学反应制备而成；单矿水化法则首先通过制备出硅酸二钙(C
2S)或硅酸三钙(C
3S)单矿，然后再将单矿与水反应水化而成。
At present, there are mainly the following methods for preparing calcium silicate hydrate gel at home and abroad: chemical synthesis method, hydrothermal synthesis method, single mineral hydration method, direct reaction method of nano-silica and calcium hydroxide, among which chemical synthesis method It refers to the preparation of alkali silicate and calcium salt into solutions and then mixing them. Commonly used raw materials include sodium silicate, potassium silicate, lithium silicate, calcium nitrate, calcium chloride, etc.; hydrothermal synthesis method It is prepared by mixing crystalline or amorphous silicon dioxide micropowder with calcium hydroxide and then chemically reacting under high temperature and pressure in an autoclave; the single mineral hydration method first prepares dicalcium silicate ( C 2 S) or tricalcium silicate (C 3 S) single ore, and then hydrate the single ore with water.
然而这几种水化硅酸钙的制备方法均存在着一定缺点：溶液反应法制备时， 所用钙质原料为可溶性钙盐，如氯化钙、硝酸钙等，其原材料价格较高；水热合成法在高温高压环境下硅质原料和钙质原料反应后大多生成了结晶程度高的托勃莫来石相，并不能制备出半结晶或者无定形的水化硅酸钙凝胶，且该反应需要通过球磨制粉、制备氢氧化钙、两者混合、高温高压养护等步骤，其工艺较为复杂，生产成本较高；单矿法则需要提前制备C
2S、C
3S单矿，其工艺更为复杂，成本更高；采用纳米二氧化硅粉体或硅溶胶与氢氧化钙反应制备时，纳米二氧化硅和硅溶胶本身的成本也很高。除成本因素外，上述四种方法中，除化学合成法之外，其余四种方法均很难制备得到单分散的水化硅酸钙凝胶纳米粒子。
Yet all there is certain shortcoming in these several kinds of preparation methods of calcium silicate hydrate: when solution reaction method is prepared, used calcium raw material is soluble calcium salt, as calcium chloride, calcium nitrate etc., and its raw material price is higher; In the synthesis method, under high temperature and high pressure, the siliceous raw material and the calcareous raw material are reacted to form a tobermullite phase with a high degree of crystallization, and semi-crystalline or amorphous calcium silicate hydrate gel cannot be prepared, and the The reaction requires steps such as ball milling, preparation of calcium hydroxide, mixing of the two, and high temperature and high pressure curing. It is more complicated and the cost is higher; when nano-silica powder or silica sol is prepared by reacting with calcium hydroxide, the cost of nano-silica and silica sol itself is also very high. In addition to the cost factor, among the above four methods, except the chemical synthesis method, it is difficult to prepare monodisperse calcium silicate hydrate gel nanoparticles by the other four methods.
(三)发明内容：(3) Contents of the invention:
基于以上技术背景和存在问题，本发明旨在提供一种插层改性水化硅酸钙纳米分散液的低成本制备方法。Based on the above technical background and existing problems, the present invention aims to provide a low-cost preparation method of intercalation-modified calcium silicate hydrate nano-dispersion.
为达到上述发明目的，本发明采用的技术方案是：In order to achieve the above-mentioned purpose of the invention, the technical scheme adopted in the present invention is:
一种插层改性C-S-H凝胶纳米分散液的制备方法，其特征在于所述的插层改性C-S-H凝胶纳米分散液的制备方法包含以下步骤：A kind of preparation method of intercalation modified C-S-H gel nano-dispersion, it is characterized in that the preparation method of described intercalation modification C-S-H gel nano-dispersion comprises the following steps:
(1)制备摩尔浓度为0.5～1.0mol的氢氧化钠水溶液；(1) preparing molar concentration is the sodium hydroxide aqueous solution of 0.5～1.0mol;
(2)在氢氧化钠水溶液中加入石英砂超细粉、氢氧化钙和水溶性有机小分子插层剂，其中石英砂超细粉和氢氧化钙加入量按Na2O:CaO:SiO2摩尔比为1:1：0.8～1.5进行计算，有机小分子插层剂掺加量按石英砂超细粉加入量的0.5％～2.0％进行计算，充分搅拌均匀，得到石英砂超细粉、氢氧化钙分散在氢氧化钠溶液中的混合物，其中还溶解有有机小分子插层剂；(2) Add quartz sand superfine powder, calcium hydroxide and water-soluble organic small molecule intercalation agent in sodium hydroxide aqueous solution, wherein the addition of quartz sand superfine powder and calcium hydroxide is according to Na2O:CaO:SiO2 molar ratio is 1:1: 0.8~1.5 for calculation, the amount of organic small molecule intercalation agent is calculated according to 0.5%~2.0% of the amount of quartz sand ultrafine powder added, fully stirred evenly, and quartz sand ultrafine powder, calcium hydroxide A mixture dispersed in a sodium hydroxide solution, in which an organic small molecule intercalant is also dissolved;
(3)将步骤2中的混合物加入球磨机进行球磨处理，球磨时间为90～240min；(3) adding the mixture in step 2 to a ball mill for ball milling, the ball milling time is 90-240min;
(4)对球磨处理得到的纳米分散液进行压滤处理，得到经插层改性的纳米C-S-H凝胶初级压滤滤饼；(4) Carry out pressure filtration treatment to the nano-dispersion obtained by ball milling treatment, obtain the primary filter cake of nano C-S-H gel modified by intercalation;
将初级压滤滤饼分散于去离子水中经反复压滤和分散处理后并加入稳定剂，搅拌均匀后，得到经插层改性的C-S-H凝胶纳米分散液。The primary press filter cake is dispersed in deionized water, after repeated press filter and dispersion treatment, adding a stabilizer, and stirring evenly, to obtain a C-S-H gel nano-dispersion liquid modified by intercalation.
作为优选，所述的反复压滤和分散处理步骤如下：As preferably, described repeated pressure filtration and dispersion treatment steps are as follows:
(5)按重量比为1：2～3，将初级滤饼分散于去离子水中，搅拌均匀后，进行第二级压滤，得到二级压滤滤饼；(5) Disperse the primary filter cake in deionized water at a weight ratio of 1:2 to 3, and after stirring evenly, perform a second-stage press filtration to obtain a second-stage press filter cake;
(6)按重量比为1：2～3，将二级压滤滤饼分散于去离子水中，搅拌均匀后，进行第三级压滤，得到三级压滤滤饼；。(6) According to the weight ratio of 1:2-3, the secondary press filter cake is dispersed in deionized water, after stirring evenly, the third-stage press filter is carried out to obtain the third-stage press filter cake;
(7)按重量比为1：2～3，将三级压滤滤饼分散于去离子水中，搅拌均匀后，进行第四级压滤，得到四级压滤滤饼；(7) Disperse the three-stage press filter cake in deionized water in a weight ratio of 1:2 to 3, and after stirring evenly, perform the fourth-stage press filter to obtain a four-stage press filter cake;
(8)按重量比为1：1～2，将四级压滤滤饼分散于去离子水中，并加入稳定剂，稳定剂用量为用水量的0.5～1.0％，搅拌均匀后，得到经插层改性的C-S-H凝胶纳米分散液。(8) According to the weight ratio of 1:1~2, disperse the four-stage press filter cake in deionized water, and add a stabilizer. The amount of stabilizer is 0.5~1.0% of the water consumption. After stirring evenly, the inserted Layer modified C-S-H gel nanodispersion.
作为优选，本发明的制备方法还可以包含以下步骤：As preferably, the preparation method of the present invention may also comprise the following steps:
(1)将初级压滤水溶液加入球磨机，并加入氢氧化钙、石英砂超细粉和有机小分子插层改性剂，其中，按摩尔比计算，在初级压滤水中加入的氢氧化钙与石英砂超细粉掺加量，按CaO：SiO
2摩尔比为1：0.8～1.5进行计算；有机小分子掺加量按石英砂超细粉加入量的0.5～2.0％计算；
(1) Add the primary filter press water solution to the ball mill, and add calcium hydroxide, quartz sand superfine powder and organic small molecule intercalation modifier, wherein, calculated by molar ratio, the calcium hydroxide added in the primary press filter water and The amount of superfine powder of quartz sand is calculated according to the molar ratio of CaO: SiO2 of 1:0.8~1.5; the amount of small organic molecules is calculated according to 0.5~2.0% of the amount of superfine powder of quartz sand;
(3)将球磨机中的混合物进行球磨处理，球磨时间为90～240min；(3) The mixture in the ball mill is subjected to ball milling, and the ball milling time is 90 to 240 minutes;
(4)对球磨处理得到的纳米分散液进行压滤处理，得到经插层改性的纳米C-S-H凝胶初级压滤滤饼；(4) Carry out pressure filtration treatment to the nano-dispersion obtained by ball milling treatment, obtain the primary filter cake of nano C-S-H gel modified by intercalation;
(5)按重量比为1：2～3，将初级压滤滤饼分散于上述技术方案所述的三级 压滤水中，搅拌均匀后，进行第二级压滤，得到二级压滤滤饼；(5) Disperse the primary press filter cake in the three-stage press water described in the above technical solution according to the weight ratio of 1:2 to 3, and after stirring evenly, perform the second-stage press filter to obtain the second-stage press filter cake;
(6)按重量比为1：2～3，将二级压滤滤饼分散于上述技术方案所述的四级压滤水中，搅拌均匀后，进行第三级压滤，得到三级压滤滤饼；(6) According to the weight ratio of 1:2～3, the secondary press filter cake is dispersed in the fourth-stage press water described in the above technical solution, after stirring evenly, the third-stage press filter is carried out to obtain the third-stage press filter filter cake;
(7)按重量比为1：2～3，将三级压滤滤饼分散于去离子水中，搅拌均匀后，进行第四级压滤，得到四级压滤滤饼；(7) Disperse the three-stage press filter cake in deionized water in a weight ratio of 1:2 to 3, and after stirring evenly, perform the fourth-stage press filter to obtain a four-stage press filter cake;
(8)按重量比为1：1～2，将四级压滤滤饼分散于去离子水中，并加入稳定剂，稳定剂用量为用水量的0.5～1.0％，搅拌均匀后，即可得到经插层改性的C-S-H凝胶纳米分散液。(8) According to the weight ratio of 1:1~2, disperse the four-stage press filter cake in deionized water, and add a stabilizer. The amount of the stabilizer is 0.5~1.0% of the water consumption. After stirring evenly, you can get Intercalation-modified C-S-H gel nanodispersion.
上述技术方案中，所述的球磨机为振动球磨机、行星球磨机、胶体磨等高能球磨机；In the above technical solution, the ball mill is a high-energy ball mill such as a vibration ball mill, a planetary ball mill, or a colloid mill;
上述技术方案中，所述的可溶性有机小分子插层改性剂为蔗糖、葡萄糖、EDTA、低分子量PEG、低分子量PVA。In the above technical solution, the soluble small organic molecule intercalation modifier is sucrose, glucose, EDTA, low molecular weight PEG, low molecular weight PVA.
上述技术方案中，所述的石英砂超细粉的比表面积为500m2/kg以上；In the above technical scheme, the specific surface area of the ultrafine quartz sand powder is more than 500m2/kg;
上述技术方案中，所述的石英砂超细粉的比表面积为1000m2/kg以上。In the above technical solution, the specific surface area of the ultrafine quartz sand powder is above 1000m2/kg.
上述技术方案中，所述低分子量PEG的分子量在10000以下。In the above technical solution, the molecular weight of the low molecular weight PEG is below 10,000.
上述技术方案中，所述低分子量PVA的分子量在20000以下。In the above technical solution, the molecular weight of the low molecular weight PVA is below 20,000.
上述技术方案中，所述稳定剂与所用可溶性有机小分子插层改性剂相同。In the above technical solution, the stabilizer is the same as the soluble organic small molecule intercalation modifier used.
本发明的有益效果主要体现在充分利用球磨过程中的机械力化学效应，采用氢氧化钠作为石英砂粉在机械力化学作用下发生化学反应的中间组分，促进低成本石英砂粉和氢氧化钙在机械力化学作用下的化学反应，从而可利用价廉易得的石英砂粉和氢氧化钙作为原材料，制备插层改性的水化硅酸钙凝胶纳米分散液，其制备过程成本低廉，氢氧化钠和压滤水可循环利用。The beneficial effects of the present invention are mainly reflected in the full use of the mechanochemical effect in the ball milling process, using sodium hydroxide as an intermediate component of the chemical reaction of quartz sand powder under mechanochemical action, and promoting low-cost quartz sand powder and hydrogen oxidation. The chemical reaction of calcium under the action of mechanochemistry, so that cheap and easy-to-obtain quartz sand powder and calcium hydroxide can be used as raw materials to prepare intercalated modified calcium silicate hydrate gel nanodispersion, and the preparation process cost Inexpensive, sodium hydroxide and press filtered water can be recycled.
图1为实施例1的插层改性的C-S-H凝胶纳米分散液经烘干后，进行XRD分析后，得到的XRD图谱。Fig. 1 is the XRD spectrum obtained after the intercalation modified C-S-H gel nano-dispersion liquid of Example 1 is dried and subjected to XRD analysis.
图2为实施例2的插层改性的C-S-H凝胶纳米分散液经烘干后，进行XRD分析后，得到的XRD图谱。Fig. 2 is the XRD spectrum obtained after the intercalation modified C-S-H gel nano-dispersion liquid of Example 2 is dried and subjected to XRD analysis.
图3为实施例3的插层改性的C-S-H凝胶纳米分散液经烘干后，进行XRD分析后，得到的XRD图谱。Fig. 3 is the XRD pattern obtained after the intercalation modified C-S-H gel nano-dispersion liquid of Example 3 is dried and subjected to XRD analysis.
下面结合具体实施例对本发明进行进一步描述，但本发明保护范围不仅限于此：The present invention is further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto:
实施例1Example 1
一种插层改性C-S-H凝胶纳米分散液的制备方法包含以下步骤：A preparation method of intercalation modified C-S-H gel nano-dispersion comprises the following steps:
(1)制备摩尔浓度为0.5mol的氢氧化钠水溶液；(1) preparing molar concentration is the sodium hydroxide aqueous solution of 0.5mol;
(2)在氢氧化钠水溶液中加入石英砂超细粉、氢氧化钙和水溶性有机小分子插层剂，其中石英砂超细粉和氢氧化钙加入量按Na2O:CaO:SiO2摩尔比为1:1：0.8进行计算，有机小分子插层剂掺加量按石英砂超细粉加入量的0.5％进行计算，充分搅拌均匀，得到石英砂超细粉、氢氧化钙分散在氢氧化钠溶液中的混合物，其中还溶解有有机小分子插层剂；(2) Add quartz sand superfine powder, calcium hydroxide and water-soluble organic small molecule intercalation agent in sodium hydroxide aqueous solution, wherein the addition of quartz sand superfine powder and calcium hydroxide is according to Na2O:CaO:SiO2 molar ratio is 1:1:0.8 for calculation, the amount of organic small molecule intercalation agent is calculated according to 0.5% of the amount of quartz sand superfine powder added, fully stirred evenly, to obtain quartz sand superfine powder, calcium hydroxide dispersed in sodium hydroxide A mixture in solution, wherein an organic small molecule intercalant is also dissolved;
(3)将步骤2中的混合物加入球磨机进行球磨处理，球磨时间为90min；(3) Add the mixture in step 2 to a ball mill for ball milling, and the ball milling time is 90min;
(4)对球磨处理得到的纳米分散液进行压滤处理，得到经插层改性的纳米C-S-H凝胶初级压滤滤饼；(4) Carry out pressure filtration treatment to the nano-dispersion obtained by ball milling treatment, obtain the primary filter cake of nano C-S-H gel modified by intercalation;
(5)按重量比为1：3，将滤饼分散于去离子水中，搅拌均匀后，进行第二级压滤，得到二级压滤滤饼；(5) Disperse the filter cake in deionized water at a weight ratio of 1:3, and after stirring evenly, perform a second-stage press filtration to obtain a second-stage press filter cake;
(6)按重量比为1：3，将二级压滤滤饼分散于去离子水中，搅拌均匀后，进行第三级压滤，得到三级压滤滤饼；(6) Disperse the secondary press filter cake in deionized water at a weight ratio of 1:3, and after stirring evenly, perform the third stage press filter to obtain a third stage press filter cake;
(7)按重量比为1：3，将三级压滤滤饼分散于去离子水中，搅拌均匀后，进行第四级压滤，得到四级压滤滤饼；(7) Disperse the three-stage press filter cake in deionized water in a weight ratio of 1:3, and after stirring evenly, perform the fourth-stage press filter to obtain a four-stage press filter cake;
(8)按重量比为1：3，将四级压滤滤饼分散于去离子水中，并加入稳定剂，稳定剂用量为用水量的0.5％，搅拌均匀后，即可得到经插层改性的C-S-H凝胶纳米分散液。(8) According to the weight ratio of 1:3, disperse the four-stage press filter cake in deionized water, and add a stabilizer. The amount of the stabilizer is 0.5% of the water consumption. Sexual C-S-H gel nanodispersion.
上述技术方案中，所述的球磨机为振动球磨机；In the above technical solution, the ball mill is a vibration ball mill;
上述技术方案中，所述的可溶性有机小分子插层改性剂为蔗糖。In the above technical solution, the soluble small organic molecule intercalation modifier is sucrose.
上述技术方案中，所述的石英砂超细粉的比表面积为1058m
2/kg；
In the above technical solution, the specific surface area of the ultrafine quartz sand powder is 1058m 2 /kg;
图1所示为所得纳米分散液经烘干后，得到的XRD图谱，由图1可见，采用该制备方法，可得到插层改性的C-S-H凝胶纳米分散液。Fig. 1 shows the XRD pattern obtained after drying the obtained nano-dispersion liquid. It can be seen from Fig. 1 that the intercalation-modified C-S-H gel nano-dispersion liquid can be obtained by using this preparation method.
实施例2Example 2
一种插层改性C-S-H凝胶纳米分散液的制备方法，其特征在于所述的插层改性C-S-H凝胶纳米分散液的制备方法包含以下步骤：A kind of preparation method of intercalation modified C-S-H gel nano-dispersion, it is characterized in that the preparation method of described intercalation modification C-S-H gel nano-dispersion comprises the following steps:
(1)制备摩尔浓度为1.0mol的氢氧化钠水溶液；(1) preparing molar concentration is the sodium hydroxide aqueous solution of 1.0mol;
(2)在氢氧化钠水溶液中加入石英砂超细粉、氢氧化钙和水溶性有机小分子插层剂，其中石英砂超细粉和氢氧化钙加入量按Na
2O:CaO:SiO
2摩尔比为1:1：1.5进行计算，有机小分子插层剂掺加量按石英砂超细粉加入量的2.0％进行计算，充分搅拌均匀，得到石英砂超细粉、氢氧化钙分散在氢氧化钠溶液中的混合物，其中还溶解有有机小分子插层剂；
(2) Add quartz sand superfine powder, calcium hydroxide and water-soluble organic small molecule intercalation agent into sodium hydroxide aqueous solution, wherein the addition amount of quartz sand superfine powder and calcium hydroxide is Na 2 O:CaO:SiO 2 The molar ratio is 1:1:1.5 for calculation, and the amount of organic small molecule intercalation agent is calculated as 2.0% of the added amount of quartz sand ultrafine powder. Stir fully and evenly to obtain quartz sand ultrafine powder and calcium hydroxide dispersed in A mixture in a sodium hydroxide solution, wherein an organic small molecule intercalation agent is also dissolved;
(3)将步骤2中的混合物加入球磨机进行球磨处理，球磨时间为240min；(3) The mixture in step 2 is added into a ball mill for ball milling, and the ball milling time is 240min;
(4)对球磨处理得到的纳米分散液进行压滤处理，得到经插层改性的纳米C-S-H凝胶初级压滤滤饼；(4) Carry out pressure filtration treatment to the nano-dispersion obtained by ball milling treatment, obtain the primary filter cake of nano C-S-H gel modified by intercalation;
(5)按重量比为1：3，将滤饼分散于去离子水中，搅拌均匀后，进行第二级压滤，得到二级压滤滤饼；(5) Disperse the filter cake in deionized water at a weight ratio of 1:3, and after stirring evenly, perform a second-stage press filtration to obtain a second-stage press filter cake;
(6)按重量比为1：3，将二级压滤滤饼分散于去离子水中，搅拌均匀后，进行第三级压滤，得到三级压滤滤饼；(6) Disperse the secondary press filter cake in deionized water at a weight ratio of 1:3, and after stirring evenly, perform the third stage press filter to obtain a third stage press filter cake;
(7)按重量比为1：3，将三级压滤滤饼分散于去离子水中，搅拌均匀后，进行第四级压滤，得到四级压滤滤饼；(7) Disperse the three-stage press filter cake in deionized water in a weight ratio of 1:3, and after stirring evenly, perform the fourth-stage press filter to obtain a four-stage press filter cake;
(8)按重量比为1：2，将四级压滤滤饼分散于去离子水中，并加入稳定剂，稳定剂用量为用水量的1.0％，搅拌均匀后，即可得到经插层改性的C-S-H凝胶纳米分散液。(8) According to the weight ratio of 1:2, disperse the four-stage press filter cake in deionized water, and add a stabilizer. The amount of the stabilizer is 1.0% of the water consumption. Sexual C-S-H gel nanodispersion.
上述技术方案中，所述的球磨机为行星球磨机；In the above technical solution, the ball mill is a planetary ball mill;
上述技术方案中，所述的可溶性有机小分子插层改性剂为葡萄糖。In the above technical solution, the soluble small organic molecule intercalation modifier is glucose.
上述技术方案中，所述的石英砂超细粉的比表面积为512m2/kg。In the above technical solution, the specific surface area of the ultrafine quartz sand powder is 512m2/kg.
图2所示为所得纳米分散液经烘干后，得到的XRD图谱，由图2可见，采用该制备方法，可得到插层改性的C-S-H凝胶纳米分散液。Fig. 2 shows the XRD pattern obtained after drying the obtained nano-dispersion liquid. It can be seen from Fig. 2 that the intercalation-modified C-S-H gel nano-dispersion liquid can be obtained by using this preparation method.
实施例3Example 3
一种插层改性C-S-H凝胶纳米分散液的制备方法，包含以下步骤：A preparation method for intercalation modified C-S-H gel nano-dispersion, comprising the following steps:
(1)将实施例1所得到的初级压滤水溶液和二级压滤水溶液混合后，测试其氢氧化钠浓度为0.44mol/L，然后在混合溶液中加入氢氧化钠，配制成摩尔浓度为0.5mol/L的氢氧化钠溶液；(1) After mixing the primary aqueous solution of pressure filtration obtained in Example 1 and the secondary aqueous solution of press filtration, it is tested that its concentration of sodium hydroxide is 0.44mol/L, then sodium hydroxide is added in the mixed solution, and the molar concentration is mixed with 0.5mol/L sodium hydroxide solution;
(2)在球磨机中加入氢氧化钠溶液，并加入氢氧化钙、石英砂超细粉和有机 小分子插层改性剂，其中，按摩尔比计算，加入的氢氧化钙与石英砂超细粉掺加量，按Na
2O:CaO:SiO
2摩尔比为1:1:1进行计算；有机小分子掺加量按石英砂超细粉加入量的1.0％计算；
(2) Add sodium hydroxide solution to the ball mill, and add calcium hydroxide, quartz sand ultrafine powder and organic small molecule intercalation modifier, wherein, calculated by molar ratio, the added calcium hydroxide and quartz sand ultrafine The dosage of powder is calculated according to the molar ratio of Na 2 O:CaO:SiO 2 is 1:1:1; the dosage of small organic molecules is calculated as 1.0% of the dosage of superfine quartz sand powder;
(3)将球磨机中的混合物进行球磨处理，球磨时间为150min；(3) The mixture in the ball mill is subjected to ball milling, and the ball milling time is 150min;
(4)对球磨处理得到的纳米分散液进行压滤处理，得到经插层改性的纳米C-S-H凝胶初级压滤滤饼；(4) Carry out pressure filtration treatment to the nano-dispersion obtained by ball milling treatment, obtain the primary filter cake of nano C-S-H gel modified by intercalation;
(5)按重量比为1：2.5，将初级压滤滤饼分散于实施例2所述的三级压滤水中，搅拌均匀后，进行第二级压滤，得到二级压滤滤饼；(5) Disperse the primary press filter cake in the three-stage press water described in Example 2 in a weight ratio of 1:2.5, and after stirring evenly, perform a second-stage press filter to obtain a secondary press filter cake;
(6)按重量比为1：2.5，将二级压滤滤饼分散于实施例2所述的四级压滤水中，搅拌均匀后，进行第三级压滤，得到三级压滤滤饼；(6) According to the weight ratio of 1:2.5, the secondary press filter cake is dispersed in the fourth-stage press water described in Example 2, after stirring evenly, the third-stage press filter is carried out to obtain the third-stage press filter cake ;
(7)按重量比为1：2，将三级压滤滤饼分散于去离子水中，搅拌均匀后，进行第四级压滤，得到四级压滤滤饼；(7) Disperse the three-stage press filter cake in deionized water at a weight ratio of 1:2, and after stirring evenly, perform the fourth-stage press filter to obtain a four-stage press filter cake;
(8)按重量比为1：2，将四级压滤滤饼分散于去离子水中，并加入稳定剂，稳定剂用量为用水量的0.8％，搅拌均匀后，即可得到经插层改性的C-S-H凝胶纳米分散液。(8) According to the weight ratio of 1:2, disperse the four-stage filter cake in deionized water, and add a stabilizer. The amount of the stabilizer is 0.8% of the water consumption. Sexual C-S-H gel nanodispersion.
上述技术方案中，所述的球磨机为胶体磨；In the above technical solution, the ball mill is a colloid mill;
上述技术方案中，所述的可溶性有机小分子插层改性剂为低分子量PEG。In the above technical solution, the soluble small organic molecule intercalation modifier is low molecular weight PEG.
上述技术方案中，所述的石英砂超细粉的比表面积为800m2/kg以上。In the above technical solution, the specific surface area of the ultrafine quartz sand powder is above 800m2/kg.
上述技术方案中，所述低分子量PEG的分子量在6000左右。In the above technical solution, the molecular weight of the low molecular weight PEG is about 6000.
图3所示为所得纳米分散液经烘干后，得到的XRD图谱，由图3可见，采用该制备方法，可得到插层改性的C-S-H凝胶纳米分散液。Fig. 3 shows the XRD pattern obtained after drying the obtained nano-dispersion liquid. It can be seen from Fig. 3 that the intercalation-modified C-S-H gel nano-dispersion liquid can be obtained by using this preparation method.
实施例4Example 4
一种插层改性C-S-H凝胶纳米分散液的制备方法包含以下步骤：A preparation method of intercalation modified C-S-H gel nano-dispersion comprises the following steps:
(1)将实施例2所得到的初级压滤水溶液和二级压滤水溶液混合后，测试其氢氧化钠浓度为0.90mol/L，然后在混合溶液中加入氢氧化钠，配制成摩尔浓度为1.0mol的氢氧化钠溶液；(1) After the primary aqueous solution of pressure filtration obtained in Example 2 is mixed with the secondary aqueous solution of press filtration, it is tested that its concentration of sodium hydroxide is 0.90mol/L, then sodium hydroxide is added in the mixed solution, and the molar concentration is mixed with 1.0mol sodium hydroxide solution;
(2)在球磨机中加入氢氧化钠溶液，并加入氢氧化钙、石英砂超细粉和有机小分子插层改性剂，其中，按摩尔比计算，加入的氢氧化钙与石英砂超细粉掺加量，按Na
2O:CaO:SiO
2摩尔比为1:1:1.2进行计算；有机小分子掺加量按石英砂超细粉加入量的0.8％计算；
(2) Add sodium hydroxide solution to the ball mill, and add calcium hydroxide, quartz sand ultrafine powder and organic small molecule intercalation modifier, wherein, calculated by molar ratio, the added calcium hydroxide and quartz sand ultrafine The dosage of powder is calculated according to the molar ratio of Na 2 O:CaO:SiO 2 is 1:1:1.2; the dosage of small organic molecules is calculated as 0.8% of the dosage of superfine quartz sand powder;
(3)将球磨机中的混合物进行球磨处理，球磨时间为200min；(3) The mixture in the ball mill is subjected to ball milling, and the ball milling time is 200min;
(4)对球磨处理得到的纳米分散液进行压滤处理，得到经插层改性的纳米C-S-H凝胶初级压滤滤饼；(4) Carry out pressure filtration treatment to the nano-dispersion obtained by ball milling treatment, obtain the primary filter cake of nano C-S-H gel modified by intercalation;
(5)按重量比为1：3，将初级压滤滤饼分散于实施例2所得到的三级压滤水中，搅拌均匀后，进行第二级压滤，得到二级压滤滤饼；(5) Disperse the primary press filter cake in the third-stage press water obtained in Example 2 in a weight ratio of 1:3, and after stirring evenly, perform second-stage press filtration to obtain a second-stage press filter cake;
(6)按重量比为1:3，将二级压滤滤饼分散于实施例2所得到的四级压滤水中，搅拌均匀后，进行第三级压滤，得到三级压滤滤饼；(6) According to the weight ratio of 1:3, the secondary press filter cake is dispersed in the fourth-stage press water obtained in Example 2, after stirring evenly, the third-stage press filter is carried out to obtain the third-stage press filter cake ;
(7)按重量比为1:3，将三级压滤滤饼分散于去离子水中，搅拌均匀后，进行第四级压滤，得到四级压滤滤饼；(7) Be 1:3 by weight, disperse the three-stage press filter cake in deionized water, after stirring evenly, carry out the fourth-stage press filter, obtain the four-stage press filter cake;
(8)按重量比为1：2，将四级压滤滤饼分散于去离子水中，并加入稳定剂，稳定剂用量为用水量的0.75％，搅拌均匀后，即可得到经插层改性的C-S-H凝胶纳米分散液。(8) According to the weight ratio of 1:2, disperse the four-stage press filter cake in deionized water, and add a stabilizer. The amount of the stabilizer is 0.75% of the water consumption. Sexual C-S-H gel nanodispersion.
上述技术方案中，所述的球磨机为胶体磨；In the above technical solution, the ball mill is a colloid mill;
上述技术方案中，所述的可溶性有机小分子插层改性剂为低分子量PVA。In the above technical solution, the soluble small organic molecule intercalation modifier is low molecular weight PVA.
上述技术方案中，所述的石英砂超细粉的比表面积为1282m
2/kg。
In the above technical solution, the specific surface area of the ultrafine quartz sand powder is 1282m 2 /kg.
上述技术方案中，所述低分子量PVA的分子量为12000左右。In the above technical solution, the molecular weight of the low molecular weight PVA is about 12000.
实施例5～8Embodiment 5-8
一种插层改性C-S-H凝胶纳米分散液的制备方法包含以下步骤：A preparation method of intercalation modified C-S-H gel nano-dispersion comprises the following steps:
(1)按表1制备一定摩尔浓度的氢氧化钠水溶液；(1) prepare the sodium hydroxide aqueous solution of certain molar concentration by table 1;
(2)在氢氧化钠水溶液中加入石英砂超细粉、氢氧化钙和水溶性有机小分子插层剂，充分搅拌均匀，得到石英砂超细粉、氢氧化钙分散在氢氧化钠溶液中的混合物，其中还溶解有有机小分子插层剂；各组分加入量如表1所示；(2) Add quartz sand superfine powder, calcium hydroxide and water-soluble small organic molecule intercalation agent into the sodium hydroxide aqueous solution, and stir well to obtain quartz sand superfine powder and calcium hydroxide dispersed in the sodium hydroxide solution The mixture of which is also dissolved with organic small molecule intercalant; the addition of each component is as shown in Table 1;
(3)将步骤2中的混合物加入球磨机进行球磨处理，球磨时间如表1所示；(3) The mixture in step 2 is added into a ball mill for ball milling, and the ball milling time is as shown in Table 1;
(4)对球磨处理得到的纳米分散液进行压滤处理，得到经插层改性的纳米C-S-H凝胶初级压滤滤饼；(4) performing pressure filtration on the nano-dispersion obtained by the ball milling treatment to obtain a primary filter cake of nano C-S-H gel modified by intercalation;
(5)将滤饼分散于去离子水中，搅拌均匀后，进行第二级压滤，得到二级压滤滤饼，其中滤饼与去离子水的重量比分别见表1。(5) Disperse the filter cake in deionized water, stir evenly, and perform a second-stage press filtration to obtain a second-stage press filter cake, wherein the weight ratios of the filter cake and deionized water are shown in Table 1, respectively.
(6)将二级压滤滤饼分散于去离子水中，搅拌均匀后，进行第三级压滤，得到三级压滤滤饼，其中滤饼与去离子水的重量比分别见表1。(6) Disperse the secondary press filter cake in deionized water, stir evenly, and perform the third stage press filtration to obtain the third stage press filter cake, wherein the weight ratios of filter cake and deionized water are shown in Table 1 respectively.
(7)将三级压滤滤饼分散于去离子水中，搅拌均匀后，进行第四级压滤，得到四级压滤滤饼，其中滤饼与去离子水的重量比分别见表1；(7) Disperse the three-stage press filter cake in deionized water, after stirring evenly, carry out the fourth stage press filter, obtain the four-stage press filter cake, wherein the weight ratio of filter cake and deionized water is shown in Table 1 respectively;
(8)将四级压滤滤饼分散于去离子水中，并加入稳定剂，搅拌均匀后，即可得到经插层改性的C-S-H凝胶纳米分散液，其中滤饼与去离子水的重量比和稳定剂用量分别见表1。(8) Disperse the four-stage press filter cake in deionized water, add a stabilizer, and stir evenly to obtain the intercalated modified C-S-H gel nano-dispersion, wherein the weight of the filter cake and deionized water The ratio and dosage of stabilizer are shown in Table 1, respectively.
各实施例所述的球磨机分别见表1；The ball mill described in each embodiment is shown in Table 1 respectively;
各实施例所述的可溶性有机小分子插层改性剂见表1。See Table 1 for the soluble small organic molecule intercalation modifiers described in each example.
各实施例所述的石英砂超细粉的比表面积见表1；The specific surface area of the quartz sand superfine powder described in each embodiment is shown in Table 1;
各实施例所述的小分子插层剂分子量见表1。The molecular weights of the small molecule intercalants described in each example are shown in Table 1.
表1Table 1
实施例9～12Examples 9-12
一种插层改性C-S-H凝胶纳米分散液的制备方法，其特征在于所述的插层改性C-S-H凝胶纳米分散液的制备方法包含以下步骤：A kind of preparation method of intercalation modified C-S-H gel nano-dispersion, it is characterized in that the preparation method of described intercalation modification C-S-H gel nano-dispersion comprises the following steps:
(1)将表1实施例5～实施例8所得到的初级压滤水溶液和二级压滤水溶液混合后，测试得到的氢氧化钠浓度如表2所示，然后在混合溶液中加入氢氧化钠，配制成一定摩尔浓度的氢氧化钠溶液，其摩尔浓度分别见表2；(1) After mixing the primary press filtration aqueous solution and the secondary press filtration aqueous solution obtained in Examples 5 to 8 of Table 1, the concentration of sodium hydroxide obtained by testing is as shown in Table 2, and then hydrogen hydroxide is added to the mixed solution. Sodium, be mixed with the sodium hydroxide solution of certain molar concentration, its molar concentration is shown in Table 2 respectively;
(2)在球磨机中加入氢氧化钠溶液，并加入氢氧化钙、石英砂超细粉和有机小分子插层改性剂，各组分加入量如表2所示；(2) Add sodium hydroxide solution in the ball mill, and add calcium hydroxide, quartz sand superfine powder and organic small molecule intercalation modifier, the addition of each component is as shown in Table 2;
(3)将步骤2中的混合物加入球磨机进行球磨处理，球磨时间如表2所示；(3) Add the mixture in step 2 to a ball mill for ball milling, and the ball milling time is as shown in Table 2;
(4)对球磨处理得到的纳米分散液进行压滤处理，得到经插层改性的纳米C-S-H凝胶初级压滤滤饼；(4) Carry out pressure filtration treatment to the nano-dispersion obtained by ball milling treatment, obtain the primary filter cake of nano C-S-H gel modified by intercalation;
(5)将滤饼分散于去离子水中，搅拌均匀后，进行第二级压滤，得到二级压滤滤饼，其中滤饼与去离子水的重量比分别见表2。(5) Disperse the filter cake in deionized water, stir evenly, and perform a second-stage press filtration to obtain a second-stage press filter cake, wherein the weight ratios of the filter cake and deionized water are shown in Table 2.
(6)将二级压滤滤饼分散于去离子水中，搅拌均匀后，进行第三级压滤，得到三级压滤滤饼，其中滤饼与去离子水的重量比分别见表2。(6) Disperse the secondary press filter cake in deionized water, stir evenly, and then perform the third stage press filtration to obtain the third stage press filter cake, wherein the weight ratios of filter cake and deionized water are shown in Table 2 respectively.
(7)将三级压滤滤饼分散于去离子水中，搅拌均匀后，进行第四级压滤，得到四级压滤滤饼，其中滤饼与去离子水的重量比分别见表2；(7) Disperse the three-stage press filter cake in deionized water, after stirring evenly, carry out the fourth-stage press filter, obtain the four-stage press filter cake, wherein the weight ratio of filter cake and deionized water is shown in Table 2 respectively;
(8)将四级压滤滤饼分散于去离子水中，并加入稳定剂，搅拌均匀后，即可得到经插层改性的C-S-H凝胶纳米分散液，其中滤饼与去离子水的重量比和稳定剂用量分别见表2。(8) Disperse the four-stage press filter cake in deionized water, add a stabilizer, and stir evenly to obtain the intercalated modified C-S-H gel nano-dispersion, wherein the weight of the filter cake and deionized water The ratio and dosage of stabilizer are shown in Table 2, respectively.
各实施例所述的球磨机分别见表2；The ball mill described in each embodiment is shown in Table 2 respectively;
各实施例所述的可溶性有机小分子插层改性剂见表2。See Table 2 for the soluble small organic molecule intercalation modifiers described in each example.
各实施例所述的石英砂超细粉的比表面积见表2；The specific surface area of the quartz sand superfine powder described in each embodiment is shown in Table 2;
各实施例所述的小分子插层剂分子量见表2。The molecular weights of the small molecule intercalants described in each example are shown in Table 2.
表2Table 2
需要说明的是，上述对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其它实施例中而不必经过创造性地劳动。因此，本发明不仅仅限于这里的实施例，本领域技术人员根据本发明的揭示，对于本发明作出的改进和修改都应该在本发明的保护范围之内。It should be noted that the above descriptions of the embodiments are for the convenience of those of ordinary skill in the technical field to understand and apply the present invention. Those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described here to other embodiments without creative effort. Therefore, the present invention is not limited to the embodiments here, and improvements and modifications made by those skilled in the art according to the disclosure of the present invention should fall within the protection scope of the present invention.
Claims (10)
- 一种插层改性C-S-H凝胶纳米分散液的制备方法，其特征在于包含以下步骤：A kind of preparation method of intercalation modified C-S-H gel nano-dispersion liquid, it is characterized in that comprising the following steps:(1)制备摩尔浓度为0.5～1.0mol/L的氢氧化钠水溶液；(1) preparing molar concentration is the sodium hydroxide aqueous solution of 0.5～1.0mol/L;(2)在氢氧化钠水溶液中加入石英砂超细粉、氢氧化钙和水溶性有机小分子插层剂，其中石英砂超细粉和氢氧化钙加入量按Na2O:CaO:SiO2摩尔比为1:1：0.8～1.5进行计算，有机小分子插层剂掺加量按石英砂超细粉加入量的0.5％～2.0％进行计算，充分搅拌均匀，得到石英砂超细粉、氢氧化钙分散在氢氧化钠溶液中的混合物，其中还溶解有有机小分子插层剂；(2) Add quartz sand superfine powder, calcium hydroxide and water-soluble organic small molecule intercalation agent in sodium hydroxide aqueous solution, wherein the addition of quartz sand superfine powder and calcium hydroxide is according to Na2O:CaO:SiO2 molar ratio is 1:1: 0.8~1.5 for calculation, the amount of organic small molecule intercalation agent is calculated according to 0.5%~2.0% of the amount of quartz sand ultrafine powder added, fully stirred evenly, and quartz sand ultrafine powder, calcium hydroxide A mixture dispersed in a sodium hydroxide solution, in which an organic small molecule intercalant is also dissolved;(3)将步骤2中的混合物加入球磨机进行球磨处理，球磨时间为90～240min；(3) adding the mixture in step 2 to a ball mill for ball milling, the ball milling time is 90-240min;(4)对球磨处理得到的纳米分散液进行压滤处理，得到经插层改性的纳米C-S-H凝胶初级压滤滤饼；(4) Carry out pressure filtration treatment to the nano-dispersion obtained by ball milling treatment, obtain the primary filter cake of nano C-S-H gel modified by intercalation;将初级压滤滤饼分散于去离子水中经反复压滤和分散处理后并加入稳定剂，搅拌均匀后，得到经插层改性的C-S-H凝胶纳米分散液。The primary press filter cake is dispersed in deionized water, after repeated press filter and dispersion treatment, adding a stabilizer, and stirring evenly, to obtain a C-S-H gel nano-dispersion liquid modified by intercalation.
- 如权利要求1所述的制备方法，其特征在于所述的反复压滤和分散处理步骤如下：The preparation method according to claim 1, characterized in that the repeated pressure filtration and dispersion treatment steps are as follows:(5)按重量比为1：2～3，将初级滤饼分散于去离子水中，搅拌均匀后，进行第二级压滤，得到二级压滤滤饼；(5) Disperse the primary filter cake in deionized water at a weight ratio of 1:2 to 3, and after stirring evenly, perform a second-stage press filtration to obtain a second-stage press filter cake;(6)按重量比为1：2～3，将二级压滤滤饼分散于去离子水中，搅拌均匀后，进行第三级压滤，得到三级压滤滤饼；(6) Disperse the secondary press filter cake in deionized water according to the weight ratio of 1:2 to 3, and after stirring evenly, perform the third stage press filtration to obtain the third stage press filter cake;(7)按重量比为1：2～3，将三级压滤滤饼分散于去离子水中，搅 拌均匀后，进行第四级压滤，得到四级压滤滤饼；(7) Disperse the three-stage press filter cake in deionized water in a weight ratio of 1:2 to 3, and after stirring evenly, perform the fourth-stage press filter to obtain a four-stage press filter cake;(8)按重量比为1：1～2，将四级压滤滤饼分散于去离子水中，并加入稳定剂，稳定剂用量为用水量的0.5～1.0％，搅拌均匀后，得到经插层改性的C-S-H凝胶纳米分散液。(8) According to the weight ratio of 1:1~2, disperse the four-stage press filter cake in deionized water, and add a stabilizer. The amount of stabilizer is 0.5~1.0% of the water consumption. After stirring evenly, the inserted Layer modified C-S-H gel nanodispersion.
- 如权利要求2所述的制备方法，其特征在于：preparation method as claimed in claim 2, is characterized in that:(1)将初级压滤水溶液和二级压滤水溶液混合后，测试其氢氧化钠浓度，然后在混合溶液中加入氢氧化钠，配制成摩尔浓度为0.5～1.0mol/L的氢氧化钠溶液；(1) After mixing the primary filter press aqueous solution and the secondary press filter aqueous solution, test the concentration of sodium hydroxide, then add sodium hydroxide to the mixed solution to prepare a sodium hydroxide solution with a molar concentration of 0.5 to 1.0 mol/L ;(2)在球磨机中加入配制好的氢氧化钠溶液，并加入氢氧化钙、石英砂超细粉和有机小分子插层改性剂，其中，按摩尔比计算，在初级压滤水中加入的氢氧化钙与石英砂超细粉掺加量，按Na 2O:CaO:SiO 2摩尔比为1:1：0.8～1.5进行计算；有机小分子掺加量按石英砂超细粉加入量的0.5～2.0％计算； (2) Add the prepared sodium hydroxide solution in the ball mill, and add calcium hydroxide, quartz sand superfine powder and organic small molecule intercalation modifier, wherein, calculated by molar ratio, the Calcium hydroxide and ultrafine quartz sand powder are calculated according to the molar ratio of Na2O :CaO: SiO2 being 1:1:0.8~1.5; organic small molecules are added according to the amount of quartz sand ultrafine powder 0.5～2.0% calculation;(3)将球磨机中的混合物进行球磨处理，球磨时间为90～240min；(3) The mixture in the ball mill is subjected to ball milling, and the ball milling time is 90 to 240 minutes;(4)对球磨处理得到的纳米分散液进行压滤处理，得到经插层改性的纳米C-S-H凝胶初级压滤滤饼；(4) Carry out pressure filtration treatment to the nano-dispersion obtained by ball milling treatment, obtain the primary filter cake of nano C-S-H gel modified by intercalation;(5)按重量比为1：2～3，将初级压滤滤饼分散于权利要求2的三级压滤水中，搅拌均匀后，进行第二级压滤，得到二级压滤滤饼；(5) Disperse the primary press filter cake in the three-stage press water according to claim 2 in a weight ratio of 1:2 to 3, and after stirring evenly, perform the second-stage press filter to obtain the second-stage press filter cake;(6)按重量比为1：2～3，将二级压滤滤饼分散于如权利要求2所述的四级压滤水中，搅拌均匀后，进行第三级压滤，得到三级压滤滤饼；(6) According to the weight ratio of 1:2～3, the secondary press filter cake is dispersed in the fourth-stage press water as claimed in claim 2, after stirring evenly, the third-stage press filter is carried out to obtain the three-stage press filter. filter cake;(7)按重量比为1：2～3，将三级压滤滤饼分散于去离子水中，搅 拌均匀后，进行第四级压滤，得到四级压滤滤饼；(7) Disperse the three-stage press filter cake in deionized water in a weight ratio of 1:2 to 3, and after stirring evenly, perform the fourth-stage press filter to obtain a four-stage press filter cake;(8)按重量比为1：1～2，将四级压滤滤饼分散于去离子水中，并加入稳定剂，稳定剂用量为用水量的0.5～1.0％，搅拌均匀后，即得到经插层改性的C-S-H凝胶纳米分散液。(8) Disperse the four-stage press filter cake in deionized water with a weight ratio of 1:1 to 2, and add a stabilizer. The amount of the stabilizer is 0.5 to 1.0% of the water consumption. After stirring evenly, the obtained Intercalation-modified C-S-H gel nanodispersion.
- 如权利要求1或2或3所述的制备方法，其特征在于所述的球磨机为振动球磨机、行星球磨机、胶体磨等高能磨机。The preparation method according to claim 1, 2 or 3, characterized in that the ball mill is a high-energy mill such as a vibration ball mill, a planetary ball mill, or a colloid mill.
- 如权利要求1或2或3所述的制备方法，其特征在于所述的可溶性有机小分子插层改性剂为蔗糖、葡萄糖、EDTA、低分子量PEG、低分子量PVA。The preparation method according to claim 1, 2 or 3, characterized in that the soluble small organic molecule intercalation modifier is sucrose, glucose, EDTA, low molecular weight PEG, low molecular weight PVA.
- 如权利要求1或2或3所述的制备方法，其特征在于所述的石英砂超细粉的比表面积为500m2/kg以上。The preparation method according to claim 1, 2 or 3, characterized in that the specific surface area of the ultrafine quartz sand powder is above 500m2/kg.
- 如权利要求1或2或3所述的制备方法，其特征在于所述的石英砂超细粉的比表面积为1000m2/kg以上。The preparation method according to claim 1, 2 or 3, characterized in that the specific surface area of the ultrafine quartz sand powder is above 1000m2/kg.
- 如权利要求1或2或3所述的制备方法，其特征在于所述低分子量PEG的分子量在10000以下。The preparation method according to claim 1, 2 or 3, characterized in that the molecular weight of the low molecular weight PEG is below 10,000.
- 如权利要求1或2或3所述的制备方法，其特征在于所述低分子量PVA的分子量在20000以下。The preparation method according to claim 1, 2 or 3, characterized in that the molecular weight of the low molecular weight PVA is below 20,000.
- 如权利要求1或3所述的一种插层改性C-S-H凝胶纳米分散液的制备方法，其特征在于所述的稳定剂与所用可溶性有机小分子插层改性剂相同。The preparation method of a kind of intercalation modified C-S-H gel nano-dispersion as claimed in claim 1 or 3, characterized in that the stabilizer is the same as the soluble organic small molecule intercalation modifier used.
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