CN110092385B - A kind of preparation method of magnesium aluminum silicate hydrogel - Google Patents
A kind of preparation method of magnesium aluminum silicate hydrogel Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 title claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 24
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 11
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 abstract description 37
- 239000013078 crystal Substances 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000012670 alkaline solution Substances 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 238000002288 cocrystallisation Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 229940091250 magnesium supplement Drugs 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- -1 ethyl acetate Diol Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229960002337 magnesium chloride Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0073—Preparation of non-Newtonian sols, e.g. thixotropic solutions
- B01J13/0078—Preparation of non-Newtonian sols, e.g. thixotropic solutions containing inorganic material and water
-
- 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
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
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- Inorganic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
一种镁铝硅酸盐水凝胶的制备方法，所述制备方法为：将碳酸氢钠、氢氧化钠、去离子水和乙二醇混合，配制成碱液，将镁盐、铝盐和去离子水混合，配制成含镁铝的水溶液，在恒温40～60℃、搅拌条件下，先将水玻璃滴加到碱液中，得到含硅液，再将含镁铝的水溶液滴加到含硅液中，得到反应液，将所得反应液在恒温90～140℃下搅拌8～24h，之后冷却至室温，离心，水洗，干燥，破碎、过筛，得到镁铝硅酸盐粉体，将其加到去离子水中，搅拌均匀，静置，即得成品；本发明通过乙二醇水溶液作为共沸体系，强化传热，保护水不被蒸发，避免反应液中的构晶物质出现过饱和状态而析出，可以抑制杂质共晶、共沉淀，减少晶体缺陷，使制备的产物粒径细微均一，有利于形成水凝胶。A preparation method of magnesium-aluminosilicate hydrogel, the preparation method comprises the following steps: mixing sodium bicarbonate, sodium hydroxide, deionized water and ethylene glycol to prepare lye, mixing magnesium salt, aluminum salt and ethylene glycol. Mixed with deionized water to prepare an aqueous solution containing magnesium and aluminum. Under the condition of constant temperature of 40-60 ° C and stirring, water glass was first added dropwise to the alkaline solution to obtain a silicon-containing liquid, and then the aqueous solution containing magnesium and aluminum was added dropwise to the solution. In the silicon-containing liquid, a reaction liquid is obtained, and the obtained reaction liquid is stirred at a constant temperature of 90 to 140 ° C for 8 to 24 hours, then cooled to room temperature, centrifuged, washed with water, dried, crushed and sieved to obtain magnesium aluminosilicate powder, Add it to deionized water, stir evenly, and let stand to obtain the finished product; the present invention uses ethylene glycol aqueous solution as an azeotrope system to strengthen heat transfer, protect water from being evaporated, and avoid the occurrence of crystalline substances in the reaction solution. Precipitation in a saturated state can inhibit co-crystallization and co-precipitation of impurities, reduce crystal defects, and make the prepared product fine and uniform in particle size, which is conducive to the formation of hydrogels.
Description
(一)技术领域(1) Technical field
本发明涉及一种镁铝硅酸盐水凝胶的制备方法。The present invention relates to a preparation method of magnesium aluminum silicate hydrogel.
(二)背景技术(2) Background technology
典型的层状镁铝硅酸盐矿物，如镁皂石，它的每个片层由两层硅氧四面体晶片夹着中间一层镁氧八面体晶片构成，每个片层带负电荷，两个片层之间吸附一些水合金属阳离子，用于平衡片层上的负电荷。层状镁铝硅酸盐矿物具有片层尺寸小，层间阳离子可交换性，层电荷低，在水相容易剥离形成水凝胶，易被改性修饰，可应用于流变助剂、增稠剂、吸附剂、催化剂、阻燃剂等。Typical layered magnesium-aluminosilicate minerals, such as magnesia saponite, each sheet is composed of two silicon-oxygen tetrahedral wafers sandwiched by a magnesium-oxygen octahedral wafer in the middle, each sheet is negatively charged, Some hydrated metal cations are adsorbed between the two sheets to balance the negative charge on the sheets. Layered magnesium-aluminosilicate minerals have small lamellar size, interlayer cation exchangeability, low layer charge, easy to peel off in the aqueous phase to form hydrogels, easy to be modified and modified, and can be used in rheology additives, enhancers, etc. Thickener, adsorbent, catalyst, flame retardant, etc.
层状镁铝硅酸盐非金属矿物在自然界中非常稀少，而且纯度低，提纯十分困难。因此，通常采用人工合成的方法制备。人工合成方法一般采用水热合成法，实验室通常在恒温90-450℃、自生水压下，反应液经过几个小时到几天的晶化来制备镁铝硅酸盐矿物。水热合成法装置简单，但能耗大，对反应釜的密封要求高。由于静置的反应釜处于长时间高温，反应釜中反应体系所含的液态水变为水蒸汽，容易泄漏，导致反应液中液态水减少甚至消失；当晶化温度高于374℃，液态水几乎不存在。在水热法合成镁铝硅酸盐矿物过程中，由于反应釜中液态水的损失，出现固液不平衡，使反应液中的构晶物质出现过饱和状态而析出，限制构晶离子进入晶胞结构，导致晶体缺陷，不利于镁铝硅酸盐矿物纯净晶核的形成和长大。乙二醇水溶液作为共沸体系，强化传热，用于制备镁铝硅酸盐矿物的水热反应介质，可保护水不被蒸发，避免局部过饱和，可以抑制杂质共晶、共沉淀，减少晶体缺陷，使制备的产物粒径细微均一，有利于形成水凝胶。Layered magnesium-aluminosilicate non-metallic minerals are very rare in nature, and their purity is low, making it very difficult to purify. Therefore, it is usually prepared by synthetic methods. The artificial synthesis method generally adopts the hydrothermal synthesis method. In the laboratory, the reaction solution is usually crystallized for several hours to several days under the constant temperature of 90-450 ° C and the autogenous water pressure to prepare the magnesium-aluminosilicate minerals. The hydrothermal synthesis method is simple in device, but consumes a lot of energy and requires high sealing of the reactor. Because the standing reaction kettle is at a high temperature for a long time, the liquid water contained in the reaction system in the reaction kettle becomes water vapor, which is easy to leak, resulting in the reduction or even disappearance of the liquid water in the reaction solution; when the crystallization temperature is higher than 374 ℃, the liquid water almost non-existent. In the process of hydrothermal synthesis of magnesium-aluminosilicate minerals, due to the loss of liquid water in the reaction kettle, a solid-liquid imbalance occurs, so that the crystalline substances in the reaction solution are supersaturated and precipitated, limiting the entry of crystalline ions into the crystal. Cell structure, resulting in crystal defects, is not conducive to the formation and growth of pure nuclei of magnesium-aluminosilicate minerals. As an azeotropic system, ethylene glycol aqueous solution enhances heat transfer and is used to prepare a hydrothermal reaction medium for magnesium-aluminosilicate minerals, which can protect water from evaporation, avoid local supersaturation, inhibit eutectic and co-precipitation of impurities, reduce Crystal defects make the particle size of the prepared product fine and uniform, which is conducive to the formation of hydrogel.
(三)发明内容(3) Contents of the invention
本发明目的在于提供一种镁铝硅酸盐水凝胶的制备方法。通过改变水热合成传统工艺，采用乙二醇水溶液作为共沸体系，强化传热，避免反应液中的构晶物质出现过饱和状态而析出，从而抑制杂质共晶、共沉淀，减少晶体缺陷，使制备的产物粒径细微均一，有利于形成水凝胶。The purpose of the present invention is to provide a preparation method of magnesium aluminosilicate hydrogel. By changing the traditional process of hydrothermal synthesis, using ethylene glycol aqueous solution as the azeotrope system to strengthen heat transfer, avoid the precipitation of crystalline substances in the reaction liquid in a supersaturated state, thereby inhibiting the co-crystallization and co-precipitation of impurities, reducing crystal defects, The particle size of the prepared product is fine and uniform, which is beneficial to the formation of hydrogel.
本发明的技术方案如下：The technical scheme of the present invention is as follows:
一种镁铝硅酸盐水凝胶的制备方法，所述制备方法包括如下步骤：A preparation method of magnesium-aluminosilicate hydrogel, the preparation method comprises the steps:
(1)将碳酸氢钠、氢氧化钠、去离子水和乙二醇混合，配制成碱液；(1) mix sodium bicarbonate, sodium hydroxide, deionized water and ethylene glycol to prepare lye;
所述碳酸氢钠、氢氧化钠、去离子水、乙二醇的质量比为1：1～2：8～9：7.5～23；The mass ratio of the sodium bicarbonate, sodium hydroxide, deionized water and ethylene glycol is 1:1-2:8-9:7.5-23;
(2)将镁盐、铝盐和去离子水混合，配制成含镁铝的水溶液；(2) mixing magnesium salt, aluminum salt and deionized water to prepare an aqueous solution containing magnesium and aluminum;
所述镁盐以所含镁计、铝盐以所含铝计、去离子水的质量比为1：0.05～0.075：22～26；The magnesium salt is calculated as the contained magnesium, the aluminum salt is calculated as the contained aluminum, and the mass ratio of the deionized water is 1:0.05-0.075:22-26;
所述镁盐例如为氯化镁或硝酸镁；The magnesium salt is, for example, magnesium chloride or magnesium nitrate;
所述铝盐例如为氯化铝或硝酸铝；The aluminium salt is, for example, aluminium chloride or aluminium nitrate;
(3)在恒温40～60℃、搅拌条件下，先将水玻璃滴加到步骤(1)配制的碱液中，得到含硅液，再将步骤(2)配制的含镁铝的水溶液滴加到含硅液中，得到反应液，将所得反应液在恒温90～140℃下搅拌8～24h，之后冷却至室温(20～30℃)，离心，水洗，干燥(60～90℃，6～24h)，破碎、过筛(100目)，得到镁铝硅酸盐粉体；(3) Under the condition of constant temperature of 40～60°C and stirring, first add water glass dropwise to the alkali solution prepared in step (1) to obtain a silicon-containing solution, and then dropwise add the magnesium-aluminum-containing aqueous solution prepared in step (2). Add it to the silicon-containing solution to obtain a reaction solution, stir the obtained reaction solution at a constant temperature of 90-140 °C for 8-24 hours, then cool to room temperature (20-30 °C), centrifuge, wash with water, and dry (60-90 °C, 6 ~24h), crushed and sieved (100 mesh) to obtain magnesium-aluminosilicate powder;
所述碱液中所含碳酸氢钠、水玻璃中所含二氧化硅的质量比为1：0.32～0.33；The mass ratio of sodium bicarbonate contained in the alkali solution to silicon dioxide contained in the water glass is 1:0.32-0.33;
所述反应液中所含硅与铝的物质的量之比为19～28.5：1；The ratio of the amount of silicon to aluminum contained in the reaction solution is 19-28.5:1;
所述反应液中所含镁的物质的量与铝、硅的物质的量之和的比为1：1.31～1.35，优选1.33；The ratio of the amount of magnesium contained in the reaction solution to the sum of the amounts of aluminum and silicon is 1:1.31-1.35, preferably 1.33;
(4)将步骤(3)所得镁铝硅酸盐粉体加到去离子水中，搅拌均匀，静置，即得所述镁铝硅酸盐水凝胶；(4) adding the magnesium-aluminosilicate powder obtained in step (3) to deionized water, stirring evenly, and standing to obtain the magnesium-aluminosilicate hydrogel;
所述镁铝硅酸盐粉体与去离子水的质量比为2～5：100。The mass ratio of the magnesium-aluminosilicate powder to deionized water is 2-5:100.
本发明的有益效果在于：The beneficial effects of the present invention are:
传统的高温水热合成方法容易出现固液不平衡，限制构晶离子进入晶胞结构，导致晶体缺陷。本发明通过乙二醇水溶液作为共沸体系，强化传热，用于制备镁铝硅酸盐矿物的水热反应介质，保护水不被蒸发，避免反应液中的构晶物质出现过饱和状态而析出，可以抑制杂质共晶、共沉淀，减少晶体缺陷，使制备的产物粒径细微均一，有利于形成水凝胶。Traditional high-temperature hydrothermal synthesis methods are prone to solid-liquid imbalance, restricting the entry of crystalline ions into the unit cell structure, resulting in crystal defects. In the invention, the ethylene glycol aqueous solution is used as an azeotrope system to enhance heat transfer, and is used to prepare a hydrothermal reaction medium for magnesium-aluminosilicate minerals, so as to protect water from being evaporated, and to avoid supersaturation of the crystalline substances in the reaction solution. Precipitation can inhibit co-crystallization and co-precipitation of impurities, reduce crystal defects, and make the particle size of the prepared product fine and uniform, which is conducive to the formation of hydrogel.
(四)附图说明(4) Description of drawings
图1：实施例1～4制备的镁铝硅酸盐水凝胶(由左到右)。Figure 1: Magnesium-aluminosilicate hydrogels prepared in Examples 1-4 (from left to right).
(五)具体实施方式(5) Specific implementation methods
下面以具体实施例对本发明的技术方案做进一步说明，但本发明的保护范围不限于此。The technical solutions of the present invention will be further described below with specific examples, but the protection scope of the present invention is not limited thereto.
实施例中用到的水玻璃购自Aldrich，二氧化硅质量分数27％，氢氧化钠质量分数14％。The water glass used in the examples was purchased from Aldrich, the mass fraction of silica was 27%, and the mass fraction of sodium hydroxide was 14%.
实施例1Example 1
本实施例的一种镁铝硅酸盐水凝胶制备方法，包括如下步骤：The preparation method of a magnesium-aluminosilicate hydrogel of the present embodiment comprises the following steps:
(1)按碳酸氢钠∶氢氧化钠∶去离子水∶乙二醇的质量比为1∶1.06∶8.3∶7.9，将碳酸氢钠10.78g、氢氧化钠11.43g、去离子水89g、乙二醇85g混合，配制成碱液。(1) The mass ratio of sodium bicarbonate: sodium hydroxide: deionized water: ethylene glycol is 1: 1.06: 8.3: 7.9, and 10.78g of sodium bicarbonate, 11.43g of sodium hydroxide, 89g of deionized water, ethyl acetate Diol 85g was mixed and prepared into lye.
(2)按镁盐中的镁∶铝盐中的铝∶去离子水的质量比为1∶0.075∶25，将六水氯化镁9.23g、九水硝酸铝1.13g、去离子水27g混合，配制成含镁铝的水溶液。(2) according to the magnesium in the magnesium salt: the mass ratio of the aluminum in the aluminum salt: the deionized water is 1: 0.075: 25, the magnesium chloride hexahydrate 9.23g, the aluminum nitrate nonahydrate 1.13g, the deionized water 27g are mixed to prepare into an aqueous solution containing magnesium and aluminum.
(3)将碱液用油浴加热，配置加热回流冷凝装置，恒温40℃，在搅拌条件下，按碱液含碳酸氢钠∶水玻璃含二氧化硅的质量比为1∶0.320，将12.79g水玻璃滴加到碱液中得到含硅液。按硅与铝的摩尔比为19：1，且镁的摩尔数与铝硅的摩尔数之和的比为1∶1.33，再把含镁铝的水溶液滴加到含硅液中，得到反应液。(3) The lye is heated with an oil bath, a heating reflux condensing device is configured, the constant temperature is 40 ° C, and under stirring conditions, the mass ratio of the lye containing sodium bicarbonate: the water glass containing silica is 1: 0.320, and 12.79 g water glass was added dropwise to the alkaline solution to obtain a silicon-containing solution. According to the molar ratio of silicon and aluminum being 19:1, and the ratio of the number of moles of magnesium to the sum of the number of moles of aluminum and silicon is 1:1.33, the aqueous solution containing magnesium and aluminum is added dropwise to the silicon-containing liquid to obtain a reaction solution. .
(4)反应液继续恒温90℃，搅拌反应8h，之后冷却至室温，离心，水洗，干燥(60℃，24h)，破碎、过筛(100目)，得到镁铝硅酸盐粉体。按镁铝硅酸盐粉体的质量分数5％加入到去离子水，搅拌均匀，静置，得到镁铝硅酸盐水凝胶。(4) The reaction solution was kept at a constant temperature of 90°C, stirred and reacted for 8h, then cooled to room temperature, centrifuged, washed with water, dried (60°C, 24h), crushed and sieved (100 mesh) to obtain magnesium aluminosilicate powder. The magnesium aluminosilicate powder is added to deionized water at a mass fraction of 5%, stirred evenly, and allowed to stand to obtain a magnesium aluminosilicate hydrogel.
图中(a)为实施例1制备的镁铝硅酸盐水凝胶。Figure (a) is the magnesium aluminosilicate hydrogel prepared in Example 1.
实施例2Example 2
本实施例的一种镁铝硅酸盐水凝胶制备方法，包括如下步骤：The preparation method of a magnesium-aluminosilicate hydrogel of the present embodiment comprises the following steps:
(1)按碳酸氢钠∶氢氧化钠∶去离子水∶乙二醇的质量比为1∶1.20∶8.3∶10.1，将碳酸氢钠10.78g、氢氧化钠12.89g、去离子水89g、乙二醇109g混合，配制成碱液。(1) The mass ratio of sodium bicarbonate: sodium hydroxide: deionized water: ethylene glycol is 1: 1.20: 8.3: 10.1, and 10.78g of sodium bicarbonate, 12.89g of sodium hydroxide, 89g of deionized water, ethyl acetate Diol 109g was mixed to prepare lye.
(2)按镁盐中的镁∶铝盐中的铝∶去离子水的质量比为1∶0.067∶23，将六水硝酸镁11.64g、六水氯化铝0.65g、去离子水25g混合，配制成含镁铝的水溶液。(2) according to the mass ratio of magnesium in the magnesium salt: aluminum in the aluminum salt: deionized water is 1: 0.067: 23, mix 11.64 g of magnesium nitrate hexahydrate, 0.65 g of aluminum chloride hexahydrate, and 25 g of deionized water , formulated into an aqueous solution containing magnesium and aluminum.
(3)将碱液用油浴加热，配置加热回流冷凝装置，恒温45℃，在搅拌条件下，按碱液含碳酸氢钠∶水玻璃含二氧化硅的质量比为1∶0.322，将12.87g水玻璃滴加到碱液中得到含硅液。按硅与铝的摩尔比为21.5：1，且镁的摩尔数与铝硅的摩尔数之和的比为1∶1.33，再把含镁铝的水溶液滴加到含硅液中，得到反应液。(3) The lye is heated with an oil bath, a heating and reflux condensing device is configured, and the constant temperature is 45° C. Under stirring conditions, the mass ratio of the lye containing sodium bicarbonate: the water glass containing silicon dioxide is 1: 0.322, and 12.87 g water glass was added dropwise to the alkaline solution to obtain a silicon-containing solution. According to the molar ratio of silicon and aluminum being 21.5:1, and the ratio of the number of moles of magnesium to the sum of the number of moles of aluminum and silicon is 1:1.33, the aqueous solution containing magnesium and aluminum is added dropwise to the silicon-containing liquid to obtain a reaction solution. .
(4)反应液继续恒温100℃，搅拌反应10h，之后冷却至室温，离心，水洗，干燥(70℃，20h)，破碎、过筛(100目)，得到镁铝硅酸盐粉体。按镁铝硅酸盐粉体的质量分数4％加入到去离子水，搅拌均匀，静置，得到镁铝硅酸盐水凝胶。(4) The reaction solution was kept at a constant temperature of 100°C, stirred and reacted for 10h, then cooled to room temperature, centrifuged, washed with water, dried (70°C, 20h), crushed and sieved (100 mesh) to obtain magnesium-aluminosilicate powder. The magnesium aluminosilicate powder is added to deionized water at a mass fraction of 4%, stirred evenly, and allowed to stand to obtain a magnesium aluminosilicate hydrogel.
图中(b)为实施例2制备的镁铝硅酸盐水凝胶。Figure (b) is the magnesium aluminosilicate hydrogel prepared in Example 2.
实施例3Example 3
本实施例的一种镁铝硅酸盐水凝胶制备方法，包括如下步骤：The preparation method of a magnesium-aluminosilicate hydrogel of the present embodiment comprises the following steps:
(1)按碳酸氢钠∶氢氧化钠∶去离子水∶乙二醇的质量比为1∶1.42∶8.6∶13.7，将碳酸氢钠9.49g、氢氧化钠13.46g、去离子水82g、乙二醇130g混合，配制成碱液。(1) According to the mass ratio of sodium bicarbonate: sodium hydroxide: deionized water: ethylene glycol, it is 1: 1.42: 8.6: 13.7, and sodium bicarbonate 9.49g, sodium hydroxide 13.46g, deionized water 82g, ethyl acetate Diol 130g was mixed and prepared into lye.
(2)按镁盐中的镁∶铝盐中的铝∶去离子水的质量比为1∶0.059∶23，将六水氯化镁8.12g、六水氯化铝0.51g、去离子水22g混合，配制成含镁铝的水溶液。(2) the mass ratio of magnesium in the magnesium salt: aluminum in the aluminum salt: deionized water is 1: 0.059: 23, and 8.12 g of magnesium chloride hexahydrate, 0.51 g of aluminum chloride hexahydrate, 22 g of deionized water are mixed, It is formulated into an aqueous solution containing magnesium and aluminum.
(3)将碱液用油浴加热，配置加热回流冷凝装置，恒温50℃，在搅拌条件下，按碱液含碳酸氢钠∶水玻璃含二氧化硅的质量比为1∶0.324，将11.38g水玻璃滴加到碱液中得到含硅液。按硅与铝的摩尔比为24.2：1，且镁的摩尔数与铝硅的摩尔数之和的比为1∶1.33，再把含镁铝的水溶液滴加到含硅液中，得到反应液。(3) The lye is heated with an oil bath, a heating and reflux condensing device is configured, and the constant temperature is 50° C. Under stirring conditions, the mass ratio of the lye containing sodium bicarbonate: the water glass containing silicon dioxide is 1: 0.324, and 11.38 g water glass was added dropwise to the alkaline solution to obtain a silicon-containing solution. According to the molar ratio of silicon and aluminum being 24.2:1, and the ratio of the number of moles of magnesium to the sum of the number of moles of aluminum and silicon is 1:1.33, the aqueous solution containing magnesium and aluminum was added dropwise to the silicon-containing liquid to obtain a reaction solution. .
(4)反应液继续恒温110℃，搅拌反应18h，之后冷却至室温，离心，水洗，干燥(80℃，12h)，破碎、过筛(100目)，得到镁铝硅酸盐粉体。按镁铝硅酸盐粉体的质量分数3％加入到去离子水，搅拌均匀，静置，得到镁铝硅酸盐水凝胶。(4) The reaction solution was kept at a constant temperature of 110°C, stirred and reacted for 18h, then cooled to room temperature, centrifuged, washed with water, dried (80°C, 12h), crushed and sieved (100 mesh) to obtain magnesium aluminosilicate powder. Add 3% of the mass fraction of magnesium aluminosilicate powder to deionized water, stir evenly, and let stand to obtain a magnesium aluminosilicate hydrogel.
图中(c)为实施例3制备的镁铝硅酸盐水凝胶。(c) in the figure is the magnesium-aluminosilicate hydrogel prepared in Example 3.
实施例4Example 4
本实施例的一种镁铝硅酸盐水凝胶制备方法，包括如下步骤：The preparation method of a magnesium-aluminosilicate hydrogel of the present embodiment comprises the following steps:
(1)按碳酸氢钠∶氢氧化钠∶去离子水∶乙二醇的质量比为1∶1.98∶8.7∶23.0，将碳酸氢钠7.91g、氢氧化钠15.66g、去离子水69g、乙二醇182g混合，配制成碱液。(1) The mass ratio of sodium bicarbonate: sodium hydroxide: deionized water: ethylene glycol is 1: 1.98: 8.7: 23.0, and 7.91g of sodium bicarbonate, 15.66g of sodium hydroxide, 69g of deionized water, ethyl acetate Diol 182g was mixed and prepared into lye.
(2)按镁盐中的镁∶铝盐中的铝∶去离子水的质量比为1∶0.051∶24，将六水硝酸镁8.53g、九水硝酸铝0.57g、去离子水19g混合，配制成含镁铝的水溶液。(2) according to the magnesium in the magnesium salt: the aluminum in the aluminum salt: the mass ratio of the deionized water is 1: 0.051: 24, 8.53g of magnesium nitrate hexahydrate, 0.57g of aluminum nitrate nonahydrate, 19g of deionized water are mixed, It is formulated into an aqueous solution containing magnesium and aluminum.
(3)将碱液用油浴加热，配置加热回流冷凝装置，恒温60℃，在搅拌条件下，按碱液含碳酸氢钠∶水玻璃含二氧化硅的质量比为1∶0.326，将9.54g水玻璃滴加到碱液中得到含硅液。按硅与铝的摩尔比为28：1，且镁的摩尔数与铝硅的摩尔数之和的比为1∶1.33，再把含镁铝的水溶液滴加到含硅液中，得到反应液。(3) The lye is heated with an oil bath, a heating reflux condensing device is configured, and the constant temperature is 60 ° C. Under stirring conditions, the mass ratio of the lye containing sodium bicarbonate: the water glass containing silica is 1: 0.326, and 9.54 g water glass was added dropwise to the alkali solution to obtain a silicon-containing solution. According to the molar ratio of silicon and aluminum being 28:1, and the ratio of the number of moles of magnesium to the sum of the number of moles of aluminum and silicon is 1:1.33, the aqueous solution containing magnesium and aluminum is added dropwise to the silicon-containing liquid to obtain a reaction solution. .
(4)反应液继续恒温120℃，搅拌反应24h，之后冷却至室温，离心，水洗，干燥(90℃，8h)，破碎、过筛(100目)，得到镁铝硅酸盐粉体。按镁铝硅酸盐粉体的质量分数2％加入到去离子水，搅拌均匀，静置，得到镁铝硅酸盐水凝胶。(4) The reaction solution was kept at a constant temperature of 120°C, stirred and reacted for 24h, then cooled to room temperature, centrifuged, washed with water, dried (90°C, 8h), crushed and sieved (100 mesh) to obtain magnesium aluminosilicate powder. The magnesium aluminosilicate powder is added to deionized water at a mass fraction of 2%, stirred evenly, and allowed to stand to obtain a magnesium aluminosilicate hydrogel.
图中(d)为实施例4制备的镁铝硅酸盐水凝胶。(d) in the figure is the magnesium-aluminosilicate hydrogel prepared in Example 4.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1608997A (en) * | 2004-10-27 | 2005-04-27 | 上海大学 | Preparation method of nanometer aluminum hydroxide |
| CN105754140A (en) * | 2016-04-05 | 2016-07-13 | 浙江工业大学之江学院 | Method for preparing magnesium-based layered nano material from alum slurry |
| CN106315604A (en) * | 2016-08-22 | 2017-01-11 | 浙江工业大学之江学院 | Preparation method of silicate powder material containing magnesium, aluminum and phosphorous |
| CN106542533A (en) * | 2016-10-25 | 2017-03-29 | 成都新柯力化工科技有限公司 | A kind of preparation method of inexpensive aqueouss aerosil |
| CN108439421A (en) * | 2018-06-20 | 2018-08-24 | 江苏海明斯新材料科技有限公司 | A kind of low-temperature hydro-thermal synthesis of high viscosity high transparency aluminium-magnesium silicate |
| CN109467371A (en) * | 2019-01-18 | 2019-03-15 | 广州华隆建筑材料有限公司 | A kind of construction wall insulating brick and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10414894B2 (en) * | 2014-07-31 | 2019-09-17 | Virginia Commonwealth University | Method for one-step synthesis, cross-linking and drying of aerogels |
-
2019
- 2019-04-01 CN CN201910256715.6A patent/CN110092385B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1608997A (en) * | 2004-10-27 | 2005-04-27 | 上海大学 | Preparation method of nanometer aluminum hydroxide |
| CN105754140A (en) * | 2016-04-05 | 2016-07-13 | 浙江工业大学之江学院 | Method for preparing magnesium-based layered nano material from alum slurry |
| CN106315604A (en) * | 2016-08-22 | 2017-01-11 | 浙江工业大学之江学院 | Preparation method of silicate powder material containing magnesium, aluminum and phosphorous |
| CN106542533A (en) * | 2016-10-25 | 2017-03-29 | 成都新柯力化工科技有限公司 | A kind of preparation method of inexpensive aqueouss aerosil |
| CN108439421A (en) * | 2018-06-20 | 2018-08-24 | 江苏海明斯新材料科技有限公司 | A kind of low-temperature hydro-thermal synthesis of high viscosity high transparency aluminium-magnesium silicate |
| CN109467371A (en) * | 2019-01-18 | 2019-03-15 | 广州华隆建筑材料有限公司 | A kind of construction wall insulating brick and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Synthesis and structural analysis of a regular Cu-Mg-Al hydrotalcite-like compound";Jian-Song WU et al.;《TURKISH JOURNAL OF CHEMISTRY》;20110222;第35卷(第6期);第881-891页 * |
| "蒙脱石对保水剂效率提升实验研究";彭丽萍等;《中国农村水利水电》;20181115;第11卷;第15-20页 * |
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