SK500382020A3 - Clean cubic form of crystalline analcime and method of preparation thereof - Google Patents
Clean cubic form of crystalline analcime and method of preparation thereof Download PDFInfo
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- metakaolin
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 13
- 229910052908 analcime Inorganic materials 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 32
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract 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 24
- 239000011734 sodium Substances 0.000 claims description 7
- 230000000202 analgesic effect Effects 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 230000036592 analgesia Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 229920000876 geopolymer Polymers 0.000 abstract description 7
- 230000009466 transformation Effects 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 239000007858 starting material Substances 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 239000010457 zeolite Substances 0.000 description 25
- 229910021536 Zeolite Inorganic materials 0.000 description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000012491 analyte Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 229910001684 gmelinite-Na Inorganic materials 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- -1 silicate anion Chemical class 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000010435 syenite Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910052663 cancrinite Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- NZWOPGCLSHLLPA-UHFFFAOYSA-N methacholine Chemical compound C[N+](C)(C)CC(C)OC(C)=O NZWOPGCLSHLLPA-UHFFFAOYSA-N 0.000 description 1
- 229960002329 methacholine Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
Description
Vynález sa týka prípravy analcímu z metakaolínu. Patrí do oblasti prípravy zeolitov hydrotermálnym spôsobom na základe transformácie z geopolymérov.The invention relates to the preparation of metakaolin analgesia. It belongs to the field of preparation of zeolites in a hydrothermal manner based on the transformation from geopolymers.
Doterajší stav technikyPrior art
Analcím NaAKSizOeíríHzO) je mikroporózny zeolit s nepravidelnými kanálmi. Disponuje vysokou tepelnou stabilitou, ktorá je následkom jeho kompaktnej a ohybnej štruktúry, ktorá zabraňuje zmene tvaru atómového usporiadania analcímu počas ohrevu. Aplikácie analcímu zaznamenávajú v súčasnosti prudký rozmach. Používa sa ako absorbent pri čistení vody a v prípade analcímu modifikovaného kovmi ako heterogénny katalyzátor v selektívnych adsorpčných reakciách, napríklad v nanoelektronike.Analyzes of NaAKSizOeírí (O 2) is a microporous zeolite with irregular channels. It has a high thermal stability, which is due to its compact and flexible structure, which prevents the shape of the atomic arrangement from changing during heating. Analytical applications are currently booming. It is used as an absorbent in water purification and, in the case of metal-modified analysis, as a heterogeneous catalyst in selective adsorption reactions, for example in nanoelectronics.
Hoci sa prírodný analcím nachádza v rôznych typoch prostredia (napríklad v dutinách mafických vulkanických hornín, v nízkoteplotných hydrotermálnych ložiskách), jeho ložiská sú sústredené v niektorých oblastiach sveta, čo viedlo k snahám pripraviť ho synteticky. Okrem syntézy z chemických reagentov, kremičitanu a hlinitanu sodného, boli publikované aj prípravy s použitím ekonomických a lokálne dostupných zdrojov hlinitokremičitanových materiálov, ako sú ryžové šupky, kaolín, prírodný slinok, uhoľný popolček, či perlit (Sandoval MV, Henao JA, Rios CS, Williams CD, Apperley DC. Synthesis and characterization of zeotype ANA framework by hydrothermal reaction of natural clinker. Fuel 2009;88: 272-281). Nedávno bola uskutočnená hydrotermálna príprava analcímu z kremenného syenitu a roztoku NaOH (Ma X, Yang J, Ma H, Liu Ch, Zhang P. Synthesis and characterization of analcime using quartz syenite powder by alkalihydrothermal treatment. Microporous and Mesoporous Materials 2015; 201: 134-140).Although natural analgesia is found in various types of environments (for example, in the cavities of mafic volcanic rocks, in low-temperature hydrothermal deposits), its deposits are concentrated in some areas of the world, which has led to efforts to prepare it synthetically. In addition to synthesis from chemical reagents, silicate and sodium aluminate, preparations have been published using economically and locally available sources of aluminosilicate materials such as rice husks, kaolin, natural clinker, coal ash or perlite (Sandoval MV, Henao JA, Rios CS, Williams CD, Apperley DC Synthesis and characterization of zeotype ANA framework by hydrothermal reaction of natural clinker.Fuel 2009; 88: 272-281). Recently, hydrothermal preparation of an analyte from quartz syenite and NaOH solution (Ma X, Yang J, Ma H, Liu Ch, Zhang P. Synthesis and characterization of analcime using quartz syenite powder by alkalihydrothermal treatment. Microporous and Mesoporous Materials 2015; 201: 134) has been performed. -140).
V prípade hydrotermálnej prípravy z prírodných hlinitokremičitanov patria medzi dôležité faktory, ktoré ovplyvňujú zloženie a vlastnosti pripravených zeolitov, molámy pomer S1O2/AI2O3 (Si/Al) vo východiskovej zmesi, čas a teplota metakaolinizácie (tepelnej aktivácie metakaolínu), podmienky zretia, kryštalizačný čas a teplota.In the case of hydrothermal preparation from natural aluminosilicates, important factors influencing the composition and properties of the prepared zeolites include the molar ratio S1O2 / Al2O3 (Si / Al) in the starting mixture, the time and temperature of metakaolinization (thermal activation of metakaolin), ripening conditions, crystallization time and temperature.
Okrem nich má významný vplyv na proces polymerizácie aj alkalita, ktorá je v Na2O- AI2O3-S1O2-H2O systéme definovaná molámym pomerom H2O/Na2O alebo OH7SiIV+. Čím je alkalita vyššia, tým je vyššia aj rozpustnosť zdrojov Si a Al katiónov, nižší stupeň polymerizácie kremičitanového aniónu a nakoniec aj rýchlejšia polymerizácia poly-kremičitanových a hlinitých aniónov. Indukčná a nukleačná perióda sa skracujú a kryštalizácia zeolitov je lýchlejšia. V systémoch s vyššou alkalitou bola demonštrovaná aj prítomnosť častíc s menšou veľkosťou a užšou distribúciou veľkosti častíc (Jihong Y. Synthesis of zeolites. In: Čejka J, van Bekkum H, Corma A, Schuth F. editors. Introduction to Zeolite Science and Pracúce; Studies in Surface Science and Catalysis. Amsterdam: Elsevier; 2007 pp. 39-103). Zatiaľ čo koncentrácia NaOH vyššia ako 3,5 M vedie k tvorbe hydroxysodalitu, nižšie koncentrácie spôsobujú tvorbu zeolitu Na-Pl (Alkan M., Hopa C., Yilmaz, Z., Gúler, H. The effect of alkali concentration and solid/liquid ratio on the hydrothermal synthesis of zeolite NaA from natural kaolinite. Microporous and Mesoporous Materials 2005; 86: 176-184). Reyes a kol. (Reyes, CAR, Williams, CD, Alarcón, OMC. Synthesis of zeolite LTA from thermally treated kaolinite. Revista Facultad de Ingenieria Antioquia. 2010; 53: 30-41) syntetizovali zeolit LTA hydrotermálnym spracovaním metakaolínu, pričom použili prídavok precipitovaného S1O2, nízku koncentráciu NaOH (1,33 M) aj teplotu (100 °C). Vyššia koncentrácia NaOH (3,99 M) a teplota (200 °C) mali za následok tvorbu viacerých zeolitických fáz (sodalitu, kankrinitu, zeolitzu JBW a analcímu). Čistý LTA zeolit bol pripravený hydrotermálnym spracovaním pri nízkej teplote (60 °C), ktorému predchádzalo alkalické tavenie metakaolinitu (1 h pri 600 °C).In addition, the alkalinity, which is defined in the Na 2 O-Al 2 O 3 -S1O 2 -H 2 O system by the molar ratio H 2 O / Na 2 O or OH 7 Si IV + , also has a significant effect on the polymerization process. The higher the alkalinity, the higher the solubility of the Si and Al cation sources, the lower the degree of polymerization of the silicate anion and, finally, the faster the polymerization of the polysilicate and aluminum anions. The induction and nucleation periods are shortened and the crystallization of zeolites is faster. In higher alkalinity systems, the presence of particles with smaller size and narrower particle size distribution was also demonstrated (Jihong Y. Synthesis of zeolites. In: Čejka J, van Bekkum H, Corma A, Schuth F. editors. Introduction to Zeolite Science and Pracúce; Studies in Surface Science and Catalysis, Amsterdam: Elsevier; 2007 pp. 39-103). While NaOH concentrations higher than 3.5 M lead to the formation of hydroxysodality, lower concentrations cause the formation of Na-Pl zeolite (Alkan M., Hopa C., Yilmaz, Z., Güler, H. The effect of alkali concentration and solid / liquid ratio on the hydrothermal synthesis of zeolite NaA from natural kaolinite (Microporous and Mesoporous Materials 2005; 86: 176-184). Reyes et al. (Reyes, CAR, Williams, CD, Alarcón, OMC. Synthesis of zeolite LTA from thermally treated kaolinite. Revista Facultad de Ingenieria Antioquia. 2010; 53: 30-41) synthesized zeolite LTA by hydrothermal treatment of metakaolin, using the addition of precipitated S1O2, low NaOH concentration (1.33 M) and temperature (100 ° C). Higher NaOH concentration (3.99 M) and temperature (200 ° C) resulted in the formation of several zeolitic phases (sodalite, cancrinite, zeolite JBW and analcine). Pure LTA zeolite was prepared by low temperature hydrothermal treatment (60 ° C), which was preceded by alkaline melting of metakaolinite (1 h at 600 ° C).
Azizi a kol. (Azizi SN, Yousefpour M. Synthesis of zeolites NaA and analcime using rice husk ash as silica source without using organic template. Journal of Materials Science 2010; 45: 5692-5697) použili mikrovlny pred hydrotermálnym spracovaním s cieľom urýchliť rozpúšťame, skrátiť čas precipitácie zeolitu a teda skrátiť čas kryštalizácie. Týmto spôsobom bol úspešne pripravený zeolit NaA aj analcím. Maximálna kryštalinita bola dosiahnutá s molámym pomerom Si/Al rovným 18 po 18 h ohreve (2 h mikrovlnné žiarenia, 16 h ohrev za hydrotermálnych podmienok).Azizi et al. (Azizi SN, Yousefpour M. Synthesis of NaA zeolites and analcime using rice husk ash as silica source without using organic template. Journal of Materials Science 2010; 45: 5692-5697) used microwaves before hydrothermal treatment to accelerate dissolution, shorten precipitation time zeolite and thus shorten the crystallization time. In this way, NaA zeolite was successfully prepared by analysis. Maximum crystallinity was achieved with a Si / Al molar ratio of 18 after 18 h of heating (2 h of microwave radiation, 16 h of heating under hydrothermal conditions).
Táto metóda viedla k poklesu veľkosti častíc syntetizovaných zeolitov (3,8 pm) v porovnaní s konvenčným ohrievaním (10 pm).This method resulted in a decrease in the particle size of the synthesized zeolites (3.8 μm) compared to conventional heating (10 μm).
CN104445249A opisuje prípravu analcímu z metakaolínu, kremičitej múčky a NaOH. Pre prípravu blokov analcímu je nutné homogenizovanú východiskovú zmes lisovať pri tlaku 10 MPa až 50 MPa a následne hydrotermálne spracovať pri teplote 80 °C až 220 °C počas 2 - 36 h.CN104445249A describes the preparation of an analyte from metakaolin, silica flour and NaOH. To prepare the analyte blocks, it is necessary to press the homogenized starting mixture at a pressure of 10 MPa to 50 MPa and then hydrothermally process it at a temperature of 80 ° C to 220 ° C for 2 - 36 h.
CN103572362A definuje prípravu monokryštálov analcímu, ktorá pozostáva z viaceíých krokov. Najskôr sa z NaOH, vody a Si prášku pri teplote 90 °C pripraví roztok kremičitanu sodného a z NaOH, vody a Al prášku sa pri laboratórnej teplote pripraví roztok metahlinitanu sodného. V ďalšom kroku sa roztoky filtrujú, miešajú a mikrovlnné ohrievajú. Nasleduje izotermická reakcia pri vysokom tlaku a teplote 200 °C počas 3CN103572362A defines the preparation of analcine single crystals, which consists of several steps. A sodium silicate solution is first prepared from NaOH, water and Si powder at 90 ° C and a sodium metaaluminate solution is prepared from NaOH, water and Al powder at room temperature. In the next step, the solutions are filtered, stirred and heated in the microwave. This is followed by an isothermal reaction at high pressure and 200 ° C for 3
SK 50038-2020 A3 až 6 dní.SK 50038-2020 A3 up to 6 days.
Analcím možno pripraviť aj hydrotermálnym spracovaním zmesi pozostávajúcej z attapulgitového ílu a sulfidu sodného (6 MPa, 199 °C), respektíve uhličitanu sodného a monosulfidu draselného (1,5 MPa, 100 °C), siričitanu sodného a metahlitanu sodného (3 MPa, 180 °C), siričitanu sodného a sulfidu sodného (6 MPa, 160 °C), hydrogénuhličitanu sodného a siričitanu draselného (4 MPa, 180 °C) (CN105731486B). Dĺžka hydrotermálneho spracovania sa v závislosti od východiskových materiálov líši.Analyzes can also be prepared by hydrothermal treatment of a mixture consisting of attapulgite clay and sodium sulphide (6 MPa, 199 ° C) or sodium carbonate and potassium monosulphide (1.5 MPa, 100 ° C), sodium sulphite and sodium metabisulphite (3 MPa, 180 Sodium sulfite and sodium sulfide (6 MPa, 160 ° C), sodium bicarbonate and potassium sulfite (4 MPa, 180 ° C) (CN105731486B). The length of hydrothermal treatment varies depending on the starting materials.
Hoci patrí hydrotermálny spôsob prípravy zeolitov medzi bežné metódy, dokumentované syntézy sú zložitejšie, vyžadujú korekciu zloženia východiskových surovín a mnohokrát nevedú k tvorbe čistej fázy. Tieto nedostatky odstraňuje spôsob prípravy a suroviny špecifikované v tomto vynáleze.Although the hydrothermal process for the preparation of zeolites is a common method, the documented syntheses are more complex, require correction of the composition of the starting materials and often do not lead to the formation of a pure phase. These shortcomings are overcome by the preparation method and raw materials specified in the present invention.
Podstata vynálezuThe essence of the invention
Analcím sa podľa tohto vynálezu pripravuje z metakaolínu a sodného vodného skla. Reaktivitu metakaolínu, ktoiý sa pripravuje tepelným spracovaním kaolínu, zabezpečuje vysoký podiel amorfnej fázy, úzka distribúcia veľkosti častíc a vysoký špecifický povrch. Výhodné je použiť metakaolín s obsahom SiO2 v rozmedzí 44 až 53 hmotn.% a ΑΤΟ? v rozmedzí 38 až 45 hmotn.%, ktorého špecifický povrch je väčší ako 12 m2 kg1, 50. percentil (x5o) sa rovná maximálne 3 pm a X90 sa rovná maximálne 10 pm.According to the invention, the analytes are prepared from metakaolin and sodium water glass. The reactivity of metakaolin, which is prepared by heat treatment of kaolin, is ensured by a high proportion of amorphous phase, a narrow particle size distribution and a high specific surface area. It is preferred to use metakaolin with a SiO 2 content in the range of 44 to 53% by weight and ΑΤΟ? in the range of 38 to 45% by weight, the specific surface area of which is greater than 12 m 2 kg 1 , the 50th percentile (x 50 ° ) is equal to a maximum of 3 μm and X90 is equal to a maximum of 10 μm.
Zdrojom SÍO2 je sodné vodné sklo s molámym pomerom SiOýNaiO v rozmedzí 1,9 až 2,1.The source of SiO2 is sodium water glass with a molar ratio of SiO2NaO in the range of 1.9 to 2.1.
Pri použití surovín s definovanými parametrami nie je potrebné ďalej korigovať zloženie východiskovej zmesi, a to ani prídavkom vody, ani roztokom NaOH. Pre prípravu čistej fázy je teda nutné použiť silikátový modul rovný 1,9 až 2,1, Si/Al molámy pomer rovný 2, ABCh/NaiO molámy pomer je 0,9 až 1,1 a hmotnostný podiel metakolínu a sodného vodného skla v intervale 0,6 až 0,7.When using raw materials with defined parameters, it is not necessary to further correct the composition of the starting mixture, either by the addition of water or NaOH solution. For the preparation of the pure phase it is therefore necessary to use a silicate modulus equal to 1.9 to 2.1, the Si / Al molar ratio equal to 2, the ABCh / Na10 molar ratio is 0.9 to 1.1 and the proportion by weight of methacholine and sodium water glass in the interval 0.6 to 0.7.
V ďalšom kroku sa špecifikované množstvo vodného skla pridáva do metakaolínu za stáleho miešania zmesi. Po dôkladnom zhomogenizovaní sa pripravená zmes vibruje s cieľom odstrániť vzduchové bubliny. Takto upravená zmes sa autoklávuje počas minimálne 18 h pri teplote 150 až 180 °C a tlaku 0,4 až 0,8 MPa v uzavretých formách.In the next step, a specified amount of water glass is added to the metakaolin while stirring the mixture. After thorough homogenization, the prepared mixture is vibrated to remove air bubbles. The mixture thus prepared is autoclaved for at least 18 hours at a temperature of 150 to 180 ° C and a pressure of 0.4 to 0.8 MPa in closed molds.
Príprava čistej analcímovej fázy vyžaduje splnenie ďalších dvoch podmienok. Počas autoklávovania je nutné zamedziť prístupu vodnej pary a potrebné je dodržať definovanú minimálnu dĺžku spracovania pri uvedenom tlaku a teplote.The preparation of the pure analgesic phase requires the fulfillment of two further conditions. During autoclaving, the access of water vapor must be prevented and the defined minimum treatment time at the specified pressure and temperature must be observed.
Za prítomnosti vodnej pary sa táto začleňuje do štruktúry vytvárajúcich sa fáz. Okrem analcímu dochádza aj k tvorbe chabazitu-Na, gmelinitu-Na a zeolitu P2. Za týchto podmienok ani predĺženie dĺžky autoklávovania na 48 h nezabezpečí úplnú transformáciu geopolymérov na zeolity a zloženie materiálu je v priereze nehomogénne. Použitie kratšieho ako definovaného autoklávovania a nižšej ako odporúčanej teploty taktiež vedie k neúplnej transformácii geopolymérov a k tvorbe zmesi zeolitických fáz.In the presence of water vapor, it is incorporated into the structure of the phases formed. In addition to the analysis, chabasite-Na, gmelinite-Na and zeolite P2 are also formed. Under these conditions, even extending the autoclaving length to 48 hours will not ensure the complete transformation of the geopolymers into zeolites and the composition of the material is inhomogeneous in cross section. The use of shorter than defined autoclaving and lower than recommended temperatures also leads to incomplete transformation of geopolymers and to the formation of a mixture of zeolitic phases.
Zvýšenie teploty na požadovanú minimálnu hodnotu 150 °C a tlak minimálne 0,4 MPa zabezpečia dehydratáciu primáme vytvorených zeolitických fáz: zeolitu P2, nasledovanú dehydratáciou chabazitu-Na a gmelinitu-Na. Pri dodržaní odporúčaných parametrov prípravy vzniká čistá kubická forma analcímu. Pod pojmom „čistá kubická forma analcímu“ tu rozumieme, že analcím obsahuje také množstvo iných látok, ktoré nie sú zistiteľné RTG, čo znamená, že nami pripravený analcím obsahuje minimálne 97 % hmotn. kubickej formy analcímu. Mikroštruktúra je uniformná a pozostáva z častíc trapezoidného tvare s priemernou veľkosťou 50 až 60 pm.Increasing the temperature to the required minimum value of 150 ° C and a pressure of at least 0.4 MPa will ensure dehydration of the primarily formed zeolitic phases: zeolite P2, followed by dehydration of chabazite-Na and gmelinite-Na. If the recommended preparation parameters are followed, a pure cubic form of analcine is formed. By the term "pure cubic form of the analgesic" we mean here that the analgesic contains an amount of other substances which are not detectable by X-ray, which means that the analgesic prepared by us contains at least 97% by weight. cubic form of analcine. The microstructure is uniform and consists of trapezoidal particles with an average size of 50 to 60 μm.
Metóda adsorpcie dusíka dokázala veľmi jemnú pórovú štruktúru analcímu s obsahom mezopórov (2 až 50 nm) a makropórov (nad 50 nm). Objemové zastúpenie tejto textúry je veľmi malé a reprezentuje iba vonkajší povrch vzoriek. Analcím pripravený definovaným spôsobom neobsahuje mikropóry a disponuje špecifickým povrchom 5bet rovným 0,7 m2 g1. Dlhší čas autoklávovania (48 h) za špecifikovaných podmienok vedie k zvýšeniu Sbet na 0,9 m2 g1, ale veľkosť častíc analcímu sa nezmení.The nitrogen adsorption method proved a very fine pore structure of the analyte containing mesopores (2 to 50 nm) and macropores (above 50 nm). The volume representation of this texture is very small and represents only the outer surface of the samples. Prepared in the defined way, it does not contain micropores and has a specific surface area of 5bet equal to 0.7 m 2 g 1 . A longer autoclaving time (48 h) under the specified conditions leads to an increase in Sbet to 0.9 m 2 g 1 , but the particle size of the analyte does not change.
V porovnaní s predchádzajúcimi spôsobmi prípravy analcímu poskytuje tento vynález nasledovné výhody:The present invention provides the following advantages over previous methods of preparing an analysis:
Východiskové suroviny, metakaolín a sodné vodné sklo, patria medzi bežné a ľahko dostupné priemyselné materiály, ktoré možno ľahko pripraviť s definovanými parametrami.The starting materials, metakaolin and sodium water glass, are common and readily available industrial materials that can be easily prepared with defined parameters.
V porovnaní s NaOH, ktoiý sa používa pri hydrotermálnom spôsobe prípravy analcímu, disponuje sodné vodné sklo špecifikované v tomto vynáleze odolnosťou voči karbonatizácii a nie je hygroskopické.Compared to NaOH, which is used in the hydrothermal process for the preparation of aniline, the sodium water glass specified in the present invention has carbonation resistance and is not hygroscopic.
Spôsob prípravy analcímu podľa tohto vynálezu je rýchlejší, absentuje proces rozpúšťania NaOH a skracuje sa čas homogenizácie.The method of preparation of the analyte according to the invention is faster, the process of dissolving NaOH is absent and the homogenization time is shortened.
Použitie reaktívnych vstupných surovín umožňuje znížiť teplotu a čas autoklávovania, čo znižuje výsledný čas aj cenu prípravy analcímu.The use of reactive feedstocks allows to reduce the temperature and time of autoclaving, which reduces the final time and the cost of preparation of the analyte.
5. Analcím pripravený spôsobom definovaným v tomto vynáleze je homogénny, v závislosti od cieľovej aplikácie je možné pripraviť ho v blokoch želanej veľkosti, prípadne ľahko mlieť.5. The assay prepared by the method defined in the present invention is homogeneous, depending on the target application, it can be prepared in blocks of the desired size, or easily ground.
SK 50038-2020 A3SK 50038-2020 A3
Prehľad obrázkov na výkresochOverview of figures in the drawings
Obrázok 1: Vysokoteplotná RTG analýza zmesi pripravenej podľa tohto vynálezu v príklade 1.Figure 1: High temperature X-ray analysis of the mixture prepared according to the invention in Example 1.
Obrázok 2: RTG záznamy zeolitických vzoriek pripravených podľa tohto vynálezu v príklade 2 a autoklávovaných počas 6, 24 a 48 h pri 165 °C a 0,5 MPa.Figure 2: X-ray record of zeolitic samples prepared according to the invention in Example 2 and autoclaved for 6, 24 and 48 hours at 165 ° C and 0.5 MPa.
Príklady uskutočnenia vynálezuExamples of embodiments of the invention
Príklad 1Example 1
Do mixéra sa navážilo 0,39 hmotnostného dielu metakaolínu Los, ktorého oxidové zloženie je uvedené v tabuľke 1, špecifický povrch stanovený analyzátorom sorpcie plynov je rovný 13,12 m2 kg1 a distribúcia veľkosti častíc určená laserovou granulometrickou analýzou vykazovala hodnoty: 50. percentil (X50) = 2,19 pm, X90 = 7,01 pm a X99 = 11,28 pm. Do metakaolínu sa za stáleho miešania pri rýchlosti 100 ot.min1 postupne a rýchlo pridávalo 0,61 hmotnostného dielu sodného vodného skla. Po pridaní celého množstva sodného vodného skla sa zmes homogenizovala pri 38 000 ot. min1, pokiaľ nie sú v zmesi už viditeľné zvyšky metakaolínového prášku, maximálne však počas ďalších 5 min. Následne sa viskózna zmes preliala do pripravených foriem želaného tvaru a veľkosti, 2 min. sa vibruje a uzavretá sa vloží do autoklávu, kde sa pri teplote 165 °C a tlaku 0,5 MPa ponechala počas 6 h. Po uplynutí definovaného času sa autokláv vypol a pripravený zeolit sa nechal vychladnúť v autokláve.0.39 parts by weight of los metakaolin, the oxide composition of which is given in Table 1, the specific surface area determined by the gas sorption analyzer is 13.12 m 2 kg 1 and the particle size distribution determined by laser particle size analysis showed values of: 50th percentile. (X50) = 2.19 pm, X90 = 7.01 pm and X99 = 11.28 pm. 0.61 part by weight of sodium water glass was gradually and rapidly added to the metakaolin at 100 rpm with constant stirring. After adding all the sodium water glass, the mixture was homogenized at 38,000 rpm. min 1 , if residues of metakaolin powder are no longer visible in the mixture, but for a maximum of another 5 min. Subsequently, the viscous mixture was poured into the prepared molds of the desired shape and size, 2 min. is vibrated and placed in an autoclave, where it is left at a temperature of 165 ° C and a pressure of 0.5 MPa for 6 hours. After a defined time, the autoclave was turned off and the prepared zeolite was allowed to cool in the autoclave.
Tab. 1 Oxidové zloženie metakaolínu LosTab. 1 Oxide composition of metakaolin Los
Vysokoteplotná RTG analýza zmesi (obr. 1) autoklávovanej počas 6 h pri 165 °C a 0,5 MPa. Použité skratky: A - analcím, C - chabazit-Na, G - gmelinit-Na, P - zeolit P2, Q - kremeň, T - anatas, Z - ZK-14.High temperature X-ray analysis of the mixture (Fig. 1) autoclaved for 6 h at 165 ° C and 0.5 MPa. Abbreviations used: A - analgesics, C - chabazite-Na, G - gmelinite-Na, P - zeolite P2, Q - quartz, T - anatase, Z - ZK-14.
Analýza sa realizovala pri rýchlosti ohrevu 10 °C min1 a s použitím Cu(Ka) radiácie.The analysis was performed at a heating rate of 10 ° C min 1 and using Cu (Ka) radiation.
Prezentované RTG záznamy demonštrujú zvyšujúcou sa teplotou indukované zmeny vo fázovom zložení vzoriek a tepelnú stabilitu jednotlivých zeolitov. Od teploty 50 °C prebieha dehydratácia zeolitu P2, po ktorej nasleduje od teploty 200 °C dehydratácia chabazitu-Na a gmelinitu-Na. V teplotnom intervale 300 °C až 400 °C dochádza k transformácii pôvodne kubickej formy analcímu na tetragonálnu formu.The presented X-ray records demonstrate increasing temperature-induced changes in the phase composition of the samples and the thermal stability of individual zeolites. Dehydration of zeolite P2 takes place from 50 DEG C., followed by dehydration of chabazite-Na and gmelinite-Na from 200 DEG C. In the temperature range 300 ° C to 400 ° C, the originally cubic form of the analyte is transformed into the tetragonal form.
Príklad 2Example 2
Použila sa rovnaká vzorka ako v príklade 1, ale spôsob spracovania bol rozdielny. Čas autoklávovania bol 6, 24 a 48 h pri 165 °C a 0,5 MPa.The same sample as in Example 1 was used, but the treatment method was different. The autoclaving times were 6, 24 and 48 hours at 165 ° C and 0.5 MPa.
Analýza sa realizovala s použitím Co(Ka) radiácie.The analysis was performed using Co (Ka) radiation.
Prezentované RTG záznamy (obr. 2) demonštrujú vplyv dĺžky autoklávovania na fázové zloženie vzoriek. V prípade kratšieho ako odporúčaného času autoklávovania pozostáva vzorka zo zmesi rôznych zeolitických fáz. Značne amorfný charakter vzorky potvrdzuje prítomnosť geopolymérov. Pri dodržaní odporúčaných parametrov prípravy vzniká kubická forma analcímu, pričom RTG analýza prítomnosť iných kryštalických fáz nepreukázala. Predĺženie času autoklávovania na 48 h nevedie k ďalšej zmene fázového zloženia pripraveného zeolitu.The presented X-ray records (Fig. 2) demonstrate the effect of autoclaving length on the phase composition of the samples. In the case of a shorter than recommended autoclaving time, the sample consists of a mixture of different zeolitic phases. The highly amorphous character of the sample confirms the presence of geopolymers. If the recommended preparation parameters are observed, a cubic form of analcine is formed, while X-ray analysis did not show the presence of other crystalline phases. Extending the autoclaving time to 48 hours does not lead to a further change in the phase composition of the prepared zeolite.
Priemyselná využiteľnosťIndustrial applicability
Predmetný vynález sa môže využiť na jednoduchú a ekonomicky výhodnú prípravu čistého analcímu požadovaného tvaru a veľkosti, ktoiý bude použitý ako absorbent v procese čistenia vody, alebo ako heterogénny katalyzátor v selektívnych adsorpčných reakciách.The present invention can be used for the simple and economically advantageous preparation of pure analysis of the desired shape and size, which will be used as an absorbent in the water purification process, or as a heterogeneous catalyst in selective adsorption reactions.
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