CN105731486A - Method for preparing spherical analcite mesoporous material by using low-quality attapulgite clay tailings - Google Patents
Method for preparing spherical analcite mesoporous material by using low-quality attapulgite clay tailings Download PDFInfo
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- CN105731486A CN105731486A CN201610110163.4A CN201610110163A CN105731486A CN 105731486 A CN105731486 A CN 105731486A CN 201610110163 A CN201610110163 A CN 201610110163A CN 105731486 A CN105731486 A CN 105731486A
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- attapulgite clay
- analcime
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- mine tailing
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 82
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 82
- 239000004927 clay Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 229910052908 analcime Inorganic materials 0.000 claims description 56
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 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 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- FANSKVBLGRZAQA-UHFFFAOYSA-M dipotassium;sulfanide Chemical compound [SH-].[K+].[K+] FANSKVBLGRZAQA-UHFFFAOYSA-M 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 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
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 235000015424 sodium Nutrition 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 5
- 239000011707 mineral Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 239000000975 dye Substances 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract 5
- 231100000678 Mycotoxin Toxicity 0.000 abstract 1
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000003242 anti bacterial agent Substances 0.000 abstract 1
- 229940088710 antibiotic agent Drugs 0.000 abstract 1
- 229910052792 caesium Inorganic materials 0.000 abstract 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 abstract 1
- 239000002636 mycotoxin Substances 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 229910052701 rubidium Inorganic materials 0.000 abstract 1
- -1 rubidium and cesium Chemical class 0.000 abstract 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 239000010457 zeolite Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 5
- 230000001143 conditioned effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000004098 Tetracycline Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229960002180 tetracycline Drugs 0.000 description 4
- 235000019364 tetracycline Nutrition 0.000 description 4
- 229930101283 tetracycline Natural products 0.000 description 4
- 150000003522 tetracyclines Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004099 Chlortetracycline Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 description 2
- 229960004475 chlortetracycline Drugs 0.000 description 2
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 description 2
- 235000019365 chlortetracycline Nutrition 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000726103 Atta Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052652 orthoclase Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 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
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for preparing a spherical analcite mesoporous material by using low-quality attapulgite clay tailings, which is characterized in that the attapulgite clay tailings with low grade, complex components and poor adsorption performance are converted into micron-sized spherical mesoporous adsorption materials with uniform and controllable pore size distribution and excellent adsorption performance through one-step hydrothermal reaction. According to the invention, on the premise of not introducing an organic surfactant pore-forming agent, the crystal structure and the aggregation state of attapulgite are converted through one-step hydrothermal reaction, and associated minerals are dissolved, crystallized and recombined to obtain the mesoporous cubic zeolite material with the micron-sized spherical form, the product has narrow pore size distribution, simple process, stable product performance, controllable pore size distribution and excellent adsorption performance, and is widely used as an adsorbent in the fields of efficient adsorption removal of antibiotics, mycotoxins, dyes and heavy metals, enrichment of noble metal ions such as rubidium and cesium, and the like.
Description
Technical field
The present invention relates to a kind of method utilizing low-quality attapulgite clay mine tailing to prepare spherical analcime mesoporous material, belong to nonmetallic ore deep processing and mesoporous nano field of material synthesis technology.
Background technology
China has and accounts for more than half attapulgite clay resource of world's gross reserves, but owing to the attapulgite clay ore deposit of China results from Middle Cenozoic continental basins mostly, main tax is stored in Tertiary Stratigraphy, based on the gyittja origin cause of formation.Attapulgite in forming process due to the change of geological conditions, often symbiosis simultaneously goes out other mineral many, the crystal development degree of attapulgite can be produced impact by the presence of which, and finally affects the chemical composition of attapulgite, rod crystal structure and serviceability.Therefore, in China's attapulgite clay ore deposit, attapulgite content is between 10%～80%, and wherein the content low-grade ore lower than 40% is in the majority, causes that added value of product is relatively low, and resource utilization is not high.
In recent years, attapulgite research receives the extensive concern of domestic scholars, the aspects such as resource distribution, physical and chemical performance, surface modification, Organic-inorganic composite and mineral composition have been carried out research by researcher from different angles, but current research focuses mostly in surface modification treatment and function and service etc., just how to change attapulgite rod crystal structure and then prepare the key technology research and development of new and effective function nano material and relate to few.Therefore, prior art still can not utilize low-grade attapulgite clay assorted ore deposit exploitation high-end product, and most low-grade ores are taken as tailings glass, cause the serious waste of resource, seriously constrain the development of industry.
Analcime is a kind of microporous crystalline silico aluminate with three-dimensional screen work, has the heavy metal ion exchange capacity such as bigger specific surface area and higher lead, copper.Therefore, analcime can be used for extracting the field such as repairing and treating and fine chemistry industry of heavy metal ion, sewage disposal, heavy-metal contaminated soil.But the natural reserves of analcime are very low, only originating in the U.S., a few countries such as Japanese and Chinese, therefore most analcimes produce and need synthetic at present.Ghobarkar etc. (MaterialsScienceandEngineering, 1999, B60:163-167) hydro-thermal method prepares the analcime crystal of 50nm～100 μm；Chinese patent CN103572362A discloses with sodium silicate, sodium hydroxide, silica flour, aluminium powder for raw material, adopts a kind of cubic system analcime monocrystal of water heat transfer, and size is about 100μM, but direct synthesis technique is because with chemical reagent for raw material, synthesizing relatively costly.Patent CN103046111A discloses a kind of with flyash for raw material, adopts a kind of nanoscale analcime of water heat transfer, reduces synthesis cost；Atta etc. (AppliedClayScience, 2012,61:8 13), with Kaolin and rice hull ash for raw material, adopt the hydro-thermal one pot process spherical analcime of multiaspect；Ma etc. (MicroporousandMesoporousMaterials, 2015,201:134 140), with quartz-orthoclase for raw material, adopt hydro-thermal alkaline etching method to synthesize analcime equally.Attapulgite ideal structure formula is (Al2Mg2) Si8O20(OH)2(OH2)4·4H2O, can synthesize analcime as natural silicon source and aluminum source.Therefore, utilize natural attapulgite clay mineral resource to be directly synthesized analcime material, be possible not only to obtain the analcime material of high-performance, low cost, and open up new way for low-quality attapulgite clay resource high-value-use.
High-purity attapulgite can change to analcime currently also to have research to confirm.Zhang Pingping etc. (Materials Science and Engineering journal, 28(4): 501-504) with the attapulgite of purification for raw material, are respectively adopted direct alkali solution technique, template agent method and sol-gel self-combustion synthesis and make attapulgite change to analcime.The chemical composition purifying attapulgite adopted is SiO2, 26.37%；Al2O3, 10.32%；Fe2O3, 4.36%；MgO, 17.16%；CaO, 18.14%.Its content of MgO reaches 17.16%, is typical high-grade attapulgite clay.See in raw material, raw materials used for relatively costly high-purity attapulgite (attapulgite content 81%).Seeing at process aspect, preprocessing process is complicated, it is necessary to consuming substantial amounts of acid and water, and need substantial amounts of alkali or template, reaction temperature is higher.See in product structure analysis, direct alkali fusion obtains in product it is observed that analcime characteristic peak, quartz content reduces, but attapulgite peak weakens but does not disappear, even after 200 DEG C of reactions, this peak does not all disappear, illustrating that attapulgite converts not exclusively, the product obtained is analcime, quartz and attapulgite mixture.
(the Chinese Journal of Inorganic Chemistry such as Zhang Pingping, 2009,25(09): 1545-1550) also studied the alkaline etching impact on attapulgite structure, find that attapulgite structure develops, analcime is had to generate in the product, but analcime is only by-product, and attapulgite does not convert completely, what obtain is attapulgite and analcime mixture.Therefore, low-grade attapulgite clay is completely transformed into analcime by simple single step reaction, prepares high-purity analcime, by the high-value-use of low-grade attapulgite clay is significant, but there is no relevant report at present.
Summary of the invention
It is an object of the invention to: a kind of method utilizing low-quality attapulgite clay mine tailing to prepare spherical analcime mesoporous material is provided, only need to introduce a small amount of inorganic salt in hydrothermal reaction process, just can induce the glomerate mesoporous analcime of each component recombination shape in attapulgite clay, in course of reaction, assorted ore deposit and attapulgite are changed into the mesoporous material having good absorption property and higher stability jointly, not only realize the target utilizing attapulgite clay to prepare high-performance adsorbent, and the higher value application for low-grade attapulgite clay opens up new way.
The technical solution of the present invention is: the attapulgite clay mine tailing of low-quality is made powder body, it is distributed in the modifier aqueous solution containing 1 ~ 20% mass fraction by solid-to-liquid ratio 1:60 ~ 1:6, then through ageing 1-12h after supersound process 65min, proceed in the hydro-thermal reaction tank of sealing, at pressure 1.5 ~ 6MPa, 100 ~ 199 ° of C condition hydro-thermal reaction 4 ~ 100h of temperature, product is separated, dry, pulverize, obtain the mesoporous analcime material of the homogeneous microspheroidal of pore-size distribution.
Wherein, described low-quality attapulgite clay mine tailing is low-grade ore and powder body, and its chemical composition range is: Al2O3, 10.5% ~ 26%；MgO, 2.5% ~ 9%；SiO2, 45% ~ 80%.
Wherein, described modifying agent is at least one in sodium thiosulfate, sodium polysulphide, sodium sulfite, sodium sulfite, sodium sulfate, sodium sulfide, sodium carbonate, sodium bicarbonate, Potassium monosulfide., Potassium hyposulfite., potassium sulfite, Potassium acid sulfite, potassium sulfate, potassium carbonate, potassium bicarbonate, sodium metaaluminate, sodium hypochlorite, aluminium hydroxide.
Wherein, it is 1 ~ 20% that described modifying agent accounts for attapulgite clay mine tailing mass percent；The solid-to-liquid ratio of attapulgite clay breeze and reaction solution is 1:60 ~ 1:6.
Wherein, described reaction pressure is 1.5 ~ 6MPa, and reaction temperature is 100 ~ 199 ° of C, and the response time is 4 ~ 100h.
Wherein, described reactant mixture ageing 1-12h after supersound process 65min.
Compared with the conventional method, the invention have the advantages that
1, the raw material adopted is China's rich reserves but is difficult to the low-quality attapulgite clay raw ore of high-value-use, acid treatment program that need not be complicated, the restructuring formation being only achieved that in low-quality attapulgite clay attapulgite and associated minerals crystal structure by a step hydro-thermal reaction has the spherical analcime of meso-hole structure；
2, this preparation method technique is simple, and process is easily controllable, constant product quality, and the nanoporous adsorbent pore-size distribution obtained is homogeneous, stable and aperture is controlled.
3, the present invention utilizes the low-quality attapulgite clay resource of rich reserves to synthesize the mesoporous analcime material that in nature, reserves are rare, and it is applied to the adsorbing separation of the material such as heavy metal, dyestuff, being a kind of novel environment-friendly process meeting sustainable development requirement, the higher value application for attapulgite clay opens up new way simultaneously.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of attapulgite clay and spherical analcime；
Fig. 2 is attapulgite clay and spherical analcime stereoscan photograph；
Fig. 3 is attapulgite clay and spherical analcime pore size distribution curve；
Fig. 4 is attapulgite clay and the spherical analcime absorption property curve to methylene blue；
Fig. 5 is attapulgite clay and the spherical analcime absorption property curve to tetracycline；
Fig. 6 is attapulgite clay and the spherical analcime absorption property curve to chlortetracycline.
Detailed description of the invention
Below in conjunction with embodiment, the technical solution of the present invention being described further, these embodiments are not to be construed as the restriction to technical scheme.
Embodiment 1: by 100g attapulgite clay (Al2O3, 10.5%；MgO, 2.5%；SiO280%) it is scattered in the 600mL aqueous solution containing 1g sodium sulfide, stirring and dissolving, supersound process 65min, ageing 12h, proceed in the 5L hydrothermal reaction kettle sealed, at pressure 6MPa, 199 ° of C conditioned response 100h of temperature, product through centrifugation, dry, pulverize after obtain spherical analcime mesoporous material.
Embodiment 2: by 50g attapulgite clay (Al2O3, 16%；MgO, 9%；SiO270%) it is scattered in the 3000mL aqueous solution containing 7.5g sodium carbonate and 2.5g Potassium monosulfide., stirring and dissolving, supersound process 65min, ageing 1h, proceeds in the 5L hydrothermal reaction kettle sealed, at pressure 1.5MPa, 100 ° of C conditioned response 100h of temperature, product through centrifugation, dry, pulverize after, obtain spherical analcime mesoporous material.
Embodiment 3: by 100g attapulgite clay (Al2O3, 26%；MgO, 9%；SiO255%) it is scattered in the 3000mL aqueous solution containing 8g sodium sulfite and 7g sodium metaaluminate, stirring and dissolving, supersound process 65min, ageing 6h, proceeds in the 5L hydrothermal reaction kettle sealed, at pressure 3MPa, 180 ° of C conditioned response 20h of temperature, product through centrifugation, dry, pulverize after, obtain spherical analcime mesoporous material.
Embodiment 4: by 300g attapulgite clay (Al2O3, 14%；MgO, 6.5%；SiO268%) it is scattered in the 3000mL aqueous solution containing 10g sodium sulfite and 5g sodium sulfide, stirring and dissolving, supersound process 65min, ageing 8h, proceeds in the 5L hydrothermal reaction kettle sealed, at pressure 6MPa, 160 ° of C conditioned response 48h of temperature, product through centrifugation, dry, pulverize after, obtain spherical analcime mesoporous material.
Embodiment 5: by 200g attapulgite clay (Al2O3, 14%；MgO, 6.5%；SiO2；75%) it is scattered in the 4000mL aqueous solution containing 10g sodium bicarbonate and 10g potassium sulfite, stirring and dissolving, supersound process 65min, ageing 12h, proceed in the 5L hydrothermal reaction kettle sealed, at pressure 4MPa, 180 ° of C conditioned response 24h of temperature, product through centrifugation, dry, pulverize after, obtain spherical analcime mesoporous material.
Product structure of the present invention characterizes and performance evaluation:
By the X-ray powder diffraction (XRD) shown in accompanying drawing 1 it can be seen that attapulgite clay raw ore is 2θ=8.41 ° of places occur in that (001) crystal face characteristic peak of attapulgite, but after hydro-thermal reaction formation analcime product, the characteristic peak of attapulgite is wholly absent, simultaneously the peak (2 of quartzθ=26.8 °) also it is wholly absent, the XRD curve of product occurs in that (211), (400) and (332) characteristic peak of analcime, illustrates that attapulgite clay and associated minerals are completely transformed into analcime, analcime purity is higher, better crystallinity degree.
By the scanning electron microscope (SEM) shown in accompanying drawing 2 it can be seen that attapulgite clay is Rod-like shape, the brilliant bundle of rod is assembled in bulk, and obtains diameter about 20 after hydro-thermal reactionμThe silicate product that m is spherical.
By the pore size distribution curve shown in accompanying drawing 3 it can be seen that the pore-size distribution of attapulgite clay is divided into two regions: one is the macropore of 10～25nm, and two are distributed across the aperture within the scope of 3.5～4.5nm；Being formed after analcime, pore-size distribution is homogeneous and integrated distribution is in 3.5～4.5nm, illustrates that the product of formation is mesoporous material.
By the absorption property curve of the attapulgite clay shown in accompanying drawing 4 and spherical analcime it can be seen that the attapulgite clay adsorbance only 138mg/g to methylene blue, the analcime that restructuring is formed to the adsorbance of methylene blue up to 198mg/g.
By the absorption property curve of the attapulgite clay shown in accompanying drawing 5 and spherical analcime it can be seen that the attapulgite clay adsorbance only 66.7mg/g to tetracycline, the analcime that restructuring is formed to the adsorbance of tetracycline up to 230.6mg/g.
By the absorption property curve of the attapulgite clay shown in accompanying drawing 6 and spherical analcime it can be seen that the attapulgite clay adsorbance only 75mg/g to chlortetracycline, the analcime that restructuring is formed to the adsorbance of tetracycline up to 295mg/g.
Claims (6)
1. utilize the method that low-quality attapulgite clay mine tailing prepares spherical analcime mesoporous material, it is characterized in that: it is that the attapulgite clay mine tailing of low-quality is made powder body, it is distributed in the modifier aqueous solution containing 1 ~ 20% mass fraction by solid-to-liquid ratio 1:60 ~ 1:6, then through ageing 1-12h after supersound process 65min, proceed in sealing hydro-thermal reaction tank, pressure 1.5 ~ 6MPa, 100 ~ 199 ° of C hydro-thermal reaction 4 ~ 100h of temperature, product is separated, dry, pulverize and obtain the mesoporous analcime material of the homogeneous microspheroidal of pore-size distribution.
2. the method utilizing low-quality attapulgite clay mine tailing to prepare spherical analcime mesoporous material according to claim 1, it is characterised in that: described low-quality attapulgite clay mine tailing is low-grade ore and powder body, and its chemical composition range is: Al2O3, 10.5% ~ 26%；MgO, 2.5% ~ 9%；SiO2, 55% ~ 80%.
3. the method utilizing low-quality attapulgite clay mine tailing to prepare spherical analcime mesoporous material according to claim 1, it is characterised in that: described modifying agent is at least one in sodium thiosulfate, sodium polysulphide, sodium sulfite, sodium sulfite, sodium sulfate, sodium sulfide, sodium carbonate, sodium bicarbonate, Potassium monosulfide., Potassium hyposulfite., potassium sulfite, Potassium acid sulfite, potassium sulfate, potassium carbonate, potassium bicarbonate, sodium metaaluminate, sodium hypochlorite, aluminium hydroxide.
4. the method utilizing low-quality attapulgite clay mine tailing to prepare spherical analcime mesoporous material according to claim 1, it is characterised in that: it is 1 ~ 20% that described modifying agent accounts for attapulgite clay mine tailing mass percent；The solid-to-liquid ratio of attapulgite clay breeze and reaction solution is 1:60 ~ 1:6.
5. the method utilizing low-quality attapulgite clay mine tailing to prepare spherical analcime mesoporous material according to claim 1, it is characterised in that: described reaction pressure is 1.5 ~ 6MPa, and reaction temperature is 100 ~ 199 ° of C, and the response time is 4 ~ 100h.
6. the method utilizing low-quality attapulgite clay mine tailing to prepare spherical analcime mesoporous material according to claim 1, it is characterised in that: described reactant mixture ageing 1-12h after supersound process 65min.
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| CN106809845A (en) * | 2017-04-11 | 2017-06-09 | 明光市安盛非金属材料厂 | A kind of method of modifying of attapulgite |
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| CN108046289A (en) * | 2017-12-08 | 2018-05-18 | 昊青薪材（北京）技术有限公司 | A kind of method that potassium type zeolite is prepared using analcime powder |
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| CN113288820A (en) * | 2021-05-25 | 2021-08-24 | 台州学院 | Organically modified attapulgite-dye hybrid pigment and preparation method and application thereof |
| CN114804134A (en) * | 2022-04-12 | 2022-07-29 | 中国科学院广州地球化学研究所 | Preparation method of clay mineral-based mesoporous material |
| CN114804134B (en) * | 2022-04-12 | 2023-07-25 | 中国科学院广州地球化学研究所 | Mesoporous material preparation method based on clay mineral |
| CN114918238A (en) * | 2022-05-07 | 2022-08-19 | 中国科学院生态环境研究中心 | Resistance heating process for enhancing multiphase extraction and repair effects of DNAPLS (deoxyribonucleic acid/liquid plastics) polluted site |
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Effective date of registration: 20210816 Address after: 730013 No.18 Tianshui Middle Road, Chengguan District, Lanzhou City, Gansu Province Patentee after: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Address before: 211700 No. 3 Dongfang Avenue, Xucheng Town, Xuyi county, Huai'an City, Jiangsu Province Patentee before: XUYI R & D CENTER FOR APPLICATION OF ATTAPULGITE CLAY, LANZHOU INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES |