CN107973559B - Preparation method and application of porous geopolymer microspheres - Google Patents
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- 229920000876 geopolymer Polymers 0.000 title claims abstract description 46
- 239000004005 microsphere Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000003463 adsorbent Substances 0.000 claims abstract description 8
- 230000002285 radioactive effect Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 33
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 229920002545 silicone oil Polymers 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 17
- 239000011268 mixed slurry Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 239000002893 slag Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 230000005284 excitation Effects 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 claims description 2
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims 2
- 239000003921 oil Substances 0.000 claims 2
- 229940083037 simethicone Drugs 0.000 claims 2
- 230000004913 activation Effects 0.000 claims 1
- 150000004645 aluminates Chemical class 0.000 claims 1
- 229910021487 silica fume Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 238000007711 solidification Methods 0.000 abstract description 8
- 230000008023 solidification Effects 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 238000005469 granulation Methods 0.000 abstract description 2
- 230000003179 granulation Effects 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 9
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- PGZIKUPSQINGKT-UHFFFAOYSA-N dialuminum;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O PGZIKUPSQINGKT-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了一种多孔地质聚合物微球的制备方法，采用分散悬浮固化法制得多孔地质聚合物微球。与现有技术相比，本发明无需高温煅烧固化，也不需要添加其他助剂，而是实现了低温固化、一次成型造粒。同时，本发明还实现了固废的大量使用，并且原料来源广泛，成本低廉，工艺简单，整个过程无毒无污染。此外，本发明制备多孔地质聚合物微球效率高，成球度超过90％；粒径大小可调，孔径分布均匀；孔体积较大，可调控，微球比表面积达到110m2/g，可直接用于柱分离的填充柱。试验表明，本发明的多孔地质聚合物微球对重金属吸附效果良好，可用作重金属吸附剂，在去除水中重金属和放射性元素方面应用前景广泛。The invention discloses a preparation method of porous geopolymer microspheres. The porous geopolymer microspheres are prepared by a dispersion suspension solidification method. Compared with the prior art, the present invention does not require high-temperature calcination and solidification, nor does it need to add other additives, but realizes low-temperature solidification and one-time molding and granulation. At the same time, the invention also realizes a large amount of solid waste, and has a wide range of raw material sources, low cost, simple process, and the whole process is non-toxic and non-polluting. In addition, the invention has high efficiency for preparing porous geopolymer microspheres, and the sphericity exceeds 90%; the particle size is adjustable, the pore size distribution is uniform; the pore volume is large and can be adjusted ; Packed columns for direct column separation. Tests show that the porous geopolymer microspheres of the present invention have good adsorption effect on heavy metals, can be used as heavy metal adsorbents, and have wide application prospects in removing heavy metals and radioactive elements in water.
Description
Technical Field
The invention belongs to the technical field of adsorbent carriers, and particularly relates to a preparation method and application of porous geopolymer microspheres.
Background
The column separation method is an effective method for removing heavy metals and radioactive elements in water, partial adsorbing materials such as zeolite molecular sieves and activated carbon can be directly filled into columns, but organic solvents or inorganic adsorbing materials with small particle sizes can be used only by being carried on spherical particle carriers with proper particle sizes. At present, silica gel, polymer-based composite materials and macroporous silicon-based materials are developed and utilized, and the application range of a column separation method is widened. However, the production process is complex and the cost is high, which limits the industrial application.
The geopolymer is prepared by exciting aluminosilicate-containing raw materials (including natural products, artificially synthesized powder, industrial wastes and the like) at normal temperature or high temperature through acidic or alkaline substances4]And [ SiO ]4]Tetrahedral three-dimensional network inorganic gelling materials. Geopolymer phase comparisonOther inorganic polymers have the advantages of excellent performance, simple preparation process, low energy consumption, environmental friendliness and the like, and can be widely applied to the fields of building materials, nuclear waste treatment, casting, metallurgy, refractory materials, plastics and the like. At present, the porous inorganic microspheres prepared at home and abroad mainly adopt a high-temperature calcination method, and the preparation process is complicated and the cost is high.
Disclosure of Invention
The invention aims to provide a simple, cheap and environment-friendly preparation method and application of porous geopolymer microspheres.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the porous geopolymer microspheres adopts a dispersion suspension solidification method and specifically comprises the following operations: and mixing and stirring the powder with alkali-activated activity and an alkali solution uniformly to obtain mixed slurry, slowly adding the uniformly dispersed pore-forming agent aqueous solution into the mixed slurry, continuously stirring, finally dripping the uniformly stirred slurry into the high-speed dispersed hot dimethyl silicone oil, curing in an oven, pouring out the cured synthetic product from the dimethyl silicone oil, filtering and calcining to obtain the composite material.
The powder with alkali excitation activity is slag, steel slag, water granulated slag, fly ash, silicon micropowder, red mud, metakaolin and synthetic powder.
The alkaline solution is a solution of sodium water glass, potassium water glass, sodium hydroxide, potassium hydroxide, lithium hydroxide, strontium hydroxide, cesium hydroxide, carbonate, bicarbonate, sulfate, bisulfate, aluminate, and aluminosilicate.
The pore-forming agent is calcium carbonate, ammonium bicarbonate, sodium bicarbonate, polyethylene glycol, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, sodium alginate and polystyrene.
The preparation method of the porous geopolymer microspheres comprises the following steps:
(1) preparing slurry: mixing and stirring the powder with alkali-activated activity and an alkali solution uniformly to form mixed slurry, then slowly adding the uniformly dispersed pore-forming agent aqueous solution into the mixed slurry, and continuously stirring, wherein the stirring speed is 500-4000 revolutions per minute, and stirring for 1-5 minutes to form a uniform slurry;
(2) balling: dripping the uniform slurry obtained in the step (1) into high-speed dispersed hot dimethyl silicone oil;
(3) and (3) curing: putting the dimethyl silicone oil obtained in the step (2) and the obtained product into an oven for curing and solidification;
(4) and (3) filtering: performing vacuum filtration on the dimethyl silicone oil obtained in the step (3) and the obtained product to obtain geopolymer microspheres;
(5) and (3) calcining: and (4) calcining the geopolymer microspheres obtained in the step (4) in a muffle furnace to obtain the porous geopolymer microspheres.
In the step (1), the powder with alkali-activated activity is calculated by slag, the alkali solution is calculated by sodium silicate, the solvent is calculated by water, and the pore-forming agent is calculated by polymethyl methacrylate, wherein the mass ratio of the slag to the sodium silicate to the water to the polymethyl methacrylate is 1:0.1-0.7: 0-0.005.
The temperature of the hot dimethyl silicone oil in the step (2) is 40-150 ℃, and the stirring speed is 200-2000 r/min;
the temperature of the oven in the step (3) is 50-150 ℃, and the curing time is 5 minutes-48 hours;
the calcining temperature in the step (5) is 200-900 ℃, and the calcining time is 0.5-12 hours.
The porous geopolymer microspheres prepared above are used as adsorbents.
The porous geopolymer microspheres prepared by the method are used as heavy metal or radioactive element adsorbents.
The average particle size of the porous geopolymer microspheres is 5-500 microns, the porosity is 10-60%, and the specific surface area is 20-120m2/g。
Aiming at the problems of the existing porous inorganic microspheres and preparation thereof, the inventor establishes a preparation method of the porous geopolymer microspheres, adopts a dispersion suspension solidification method, and specifically comprises the following steps: mixing and stirring the powder with alkali-activated activity and an alkali solution uniformly to form a mixed slurry, and then slowly adding the uniformly dispersed pore-forming agent aqueous solutionAdding the mixture into the mixed slurry, continuously stirring, finally dripping the uniformly stirred slurry into the high-speed dispersed thermal dimethyl silicone oil, curing the mixture by using an oven, pouring out the cured synthetic product from the dimethyl silicone oil, filtering and calcining the product to obtain the high-performance composite material. Compared with the prior art, the invention realizes low-temperature solidification and one-step molding granulation without high-temperature calcination and solidification and addition of other additives. Meanwhile, the invention also realizes the mass use of the solid wastes, and has the advantages of wide raw material source, low cost, simple process and no toxicity or pollution in the whole process. In addition, the porous geopolymer microspheres prepared by the method have high efficiency, and the balling degree exceeds 90 percent; the particle size is adjustable, and the pore diameter is uniformly distributed; the pore volume is large and controllable, and the specific surface area of the microsphere reaches 110m2And/g, can be directly used for a packed column of column separation. Tests show that the porous geopolymer microsphere has good adsorption effect on heavy metals and radioactive elements, can be used as a heavy metal adsorbent, and has wide application prospect in the aspect of removing the heavy metals and the radioactive elements in water.
Drawings
Figure 1 is an optical microscope micrograph (50 x) of porous geopolymeric microspheres prepared using the preparation method of the present invention.
FIG. 2 is a scanning electron micrograph (1000 times) of porous geopolymer microspheres prepared using the preparation method of the present invention.
FIG. 3 is a scanning electron micrograph (2000 times) of porous geopolymer microspheres prepared using the preparation method of the present invention.
Detailed Description
Example 1
(1) Preparing slurry: mixing 30g of slag and 12g of liquid sodium silicate (modulus 2.5) and stirring uniformly to obtain mixed slurry, then slowly adding the uniformly dispersed pore-forming agent aqueous solution (3g of calcium carbonate and 5g of water) into the mixed slurry and stirring continuously, wherein the stirring speed is 500 revolutions per minute, and the stirring is carried out for 2 minutes, so that the system becomes uniform slurry;
(2) balling: dripping the uniform slurry obtained in the step (1) into high-speed dispersed hot dimethyl silicone oil, wherein the temperature is 50 ℃, and the stirring speed is 200 revolutions per minute;
(3) and (3) curing: putting the dimethyl silicone oil obtained in the step (2) and the obtained product into an oven for curing and solidifying, wherein the temperature is 60 ℃, and the curing and solidifying time is 1 hour;
(4) and (3) filtering: performing vacuum filtration on the dimethyl silicone oil obtained in the step (3) and the obtained product to obtain geopolymer microspheres;
(5) and (3) calcining: and (4) calcining the geopolymer microspheres obtained in the step (4) in a muffle furnace at 700 ℃ for 12 hours to obtain the porous geopolymer.
Through detection, the particle diameter of the microsphere is 5-300 mu m, and the pore volume is 0.1998cm3Per gram, specific surface area 35.36m2/g。
0.06g of the resulting porous geopolymer was weighed out in 100mL of Pb at a concentration of 150ppm2+The adsorbed amount was 268.7mg/g in 24 hours of solution.
Example 2
(1) Preparing slurry: mixing 20g of slag and 8.57g of liquid sodium silicate (modulus 1.5) and stirring uniformly to obtain mixed slurry, then slowly adding the uniformly dispersed pore-forming agent aqueous solution (10g of calcium carbonate +10g of water) into the mixed slurry and stirring continuously, wherein the stirring speed is 1000 revolutions per minute, and the stirring is carried out for 1 minute, so that the system becomes uniform slurry;
(2) balling: dripping the uniform slurry obtained in the step (1) into high-speed dispersed hot dimethyl silicone oil, wherein the temperature is 100 ℃, and the stirring speed is 500 revolutions per minute;
(3) and (3) curing: putting the dimethyl silicone oil obtained in the step (2) and the obtained product into an oven for curing and solidifying, wherein the temperature is 70 ℃, and the curing and solidifying time is 12 hours;
(4) and (3) filtering: performing vacuum filtration on the dimethyl silicone oil obtained in the step (3) and the obtained product to obtain geopolymer microspheres;
(5) and (3) calcining: and (4) calcining the geopolymer microspheres obtained in the step (4) in a muffle furnace at 500 ℃ for 12 hours to obtain the porous geopolymer.
Through detection, the particle diameter of the microsphere is 50-500 mu m, and the pore volume is 0.2498cm3Specific surface area 65.48 m/g2/g。
0.08g of the resulting porous geopolymer was weighed out in 100mL of Pb at a concentration of 300ppm2+The adsorbed amount was 301.5mg/g after 36 hours in solution.
Example 3
(1) Preparing slurry: mixing and stirring 20g of metakaolin, 10g of slag and 12g of sodium hydroxide solution (the concentration is 10 mol) uniformly to form mixed slurry, then slowly adding the uniformly dispersed pore-forming agent aqueous solution (2g of polymethyl methacrylate and 25g of water) into the mixed slurry, continuously stirring, uniformly mixing, wherein the stirring speed is 300 revolutions per minute, and stirring for 5 minutes to form uniform slurry in a system;
(2) balling: dripping the uniform slurry obtained in the step (1) into high-speed dispersed hot dimethyl silicone oil, wherein the temperature is 90 ℃, and the stirring speed is 700 revolutions per minute;
(3) and (3) curing: putting the dimethyl silicone oil obtained in the step (2) and the obtained product into an oven for curing and solidifying, wherein the temperature is 90 ℃, and the curing and solidifying time is 1 hour;
(4) and (3) filtering: performing vacuum filtration on the dimethyl silicone oil obtained in the step (3) and the obtained product to obtain geopolymer microspheres;
(5) and (3) calcining: and (4) calcining the geopolymer microspheres obtained in the step (4) in a muffle furnace at 800 ℃ for 12 hours to obtain the porous geopolymer.
The detection shows that the particle size of the microsphere is 10-300 mu m, and the pore volume is 0.1836cm3Specific surface area of 28.75 m/g2/g。
0.06g of the resulting porous geopolymer was weighed out in 30mL of Sr at a concentration of 50ppm2+The adsorbed amount was 30.65mg/g in the solution for 1 hour.
Example 4
(1) Preparing slurry: mixing 30g of metakaolin and 20g of sodium hydroxide solution (the concentration is 8 mol) uniformly to form mixed slurry, then slowly adding the uniformly dispersed pore-forming agent aqueous solution (10g of polymethyl methacrylate and 15g of water) into the mixed slurry, continuously stirring, uniformly mixing, wherein the stirring speed is 1200 revolutions per minute, and stirring for 1 minute to enable the system to form uniform slurry;
(2) balling: dripping the uniform slurry obtained in the step (1) into high-speed dispersed hot dimethyl silicone oil, wherein the temperature is 40 ℃, and the stirring speed is 200 revolutions per minute;
(3) and (3) curing: putting the dimethyl silicone oil obtained in the step (2) and the obtained product into an oven for curing and solidifying, wherein the temperature is 60 ℃, and the curing and solidifying time is 2 hours;
(4) and (3) filtering: performing vacuum filtration on the dimethyl silicone oil obtained in the step (3) and the obtained product to obtain geopolymer microspheres;
(5) and (3) calcining: and (4) calcining the geopolymer microspheres obtained in the step (4) in a muffle furnace at the temperature of 400 ℃ for 12 hours to obtain the porous geopolymer.
Through detection, the particle diameter of the microsphere is 20-400 mu m, and the pore volume is 0.2798cm3Specific surface area of 100.56 m/g2/g。
0.06g of the resulting porous geopolymer was weighed out in 30mL of Sr at a concentration of 150ppm2+The adsorbed amount was 50.54mg/g in the solution for 2 hours.
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