Hydrothermally stable mesoporous aluminosilicates as superior FCC catalyst:From laboratory to refinery

Well-ordered aluminosilicates(MAs)were prepared by in-situ assembly of pre-crystallized units of zeolite Y precursors at a commercial scale,and applied in an industrial fluid catalytic cracking unit for the first time.Compared with incumbent equilibrium catalyst,the surface area of trial equilibrium catalysts(30%inventory ratio)increased from 110 m^(2)g^(-1)to 120m^(2)g^(-1).Moreover,a significant increase of the mesoporous surfaceareaof trial equlibrium catalysts(30%inventoryrati)from 33 m g/to 40magi(22%increase).Furthermore,the equilibrium catalyst that contain 80%LPC-65 yields significantly lower heavy oil(0.23%)and higher total liquids(0.53%)compared with LDO-70.The industrial results demonstrated excellent hydrothermal stability and superior catalytic cracking properties,showing the promising futurein the industrial units.

Comparative studies on flotation of aluminosilicate minerals with Gemini cationic surfactants BDDA and EDDA

Gemini quaternary ammonium salt surfactants, butane-a, co-bis（dimethyl dodeculammonium bromide） （BDDA） ethane-a, fl-bis（dimethyl dodeculammonium bromide） （EDDA） were adopted to comparatively study the flotation behaviors of kaolinite, pyrophyllite and illite. It was found that three silicate minerals all exhibited good floatability with Gemini cationic surfactants as collectors over a wide pH range, while BDDA showed a stronger collecting power than EDDA. FTIR spectra and zeta potential analysis indicated that the mechanism of adsorption of Gemini collector molecules on three silicate minerals surfaces was almost identical for the electronic attraction and hydrogen bonds effect. The theoretically obtained results of density functional theory （DFT） at B3LYP/6-31G （d） level demonstrated the stronger collecting power of BDDA presented in the floatation test and zeta potential measurement.

Mechanical properties of gangue-containing aluminosilicate based cementitious materials

High performance aluminosilicate based cementitious materials were produced using calcined gangue as one of the major raw materials. The gangue was calcined at 500℃. The main constituent was calcined gangue, fly ash and slag, while alkali-silicate solutions were used as the diagenetic agent. The structure of gangue-containing aluminosilicate based cementitious materials was studied by the methods of IR, NMR and SEM. The results show that the mechanical properties are affected by the mass ratio between the gangue, slag and fly ash, the kind of activator and additional salt. For 28-day curing time, the compressive strength of the sample with a mass proportion of 2：1：1 （gangue： slag： fly ash） is 58.9 MPa, while the compressive strength of the sample containing 80wt% gangue can still be up to 52.3 MPa. The larger K^＋ favors the formation of large silicate oligomers with which AI（OH）4- prefers to bind. Therefore, in Na-K compounding activator solutions more oligomers exist which result in a stronger compressive strength of aluminosilicate-based cementitious materials than in the case of Na-containing activator. The reasons for this were found through IR and NMR analysis. Glauber＇s salt reduces the 3-day compressive strength of the paste, but increases its 7-day and 28-day compressive strengths.

Occurrence mechanism of silicate and aluminosilicate minerals in Sarcheshmeh copper flotation concentrate

The Sarcheshmeh copper flotation circuit is producing 5× 10^4 t copper concentrate per month with an averaging grade of 28% Cu in rougher, cleaner and recleaner stages. In recent years, with the increase in the open pit depth, the content of aluminosilicate minerals increased in plant feed and subsequently in flotation concentrate. It can motivate some problems, such as unwanted consumption of reagents, decreasing of the copper concentrate grade, increasing of Al2O3 and SiO2 in the copper concentrate, and needing a higher temperature in the smelting process. The evaluation of the composite samples related to the most critical working period of the plant shows that quartz, illite, biotite, chlorite, orthoclase, albeit, muscovite, and kaolinite are the major Al2O3 and SiO2 beating minerals that accompany chalcopyrite, chalcocite, and covellite minerals in the plant feed. The severe alteration to clay minerals was a general rule in all thin sections that were prepared from the plant feed. Sieve analysis of the flotation concentrate shows that Al2O3 and SiO2 bearing minerals in the flotation concentrate can be decreased by promoting the size reduction from 53 to 38 μm. Interlocking of the Al2O3 and SiO2 bearing minerals with chalcopyrite and chalcocite is the occurrence mechanism of silicate and aluminosilicate minerals in the flotation concentrate. The dispersed form of interlocking is predominant.

Synthesis of γ-alkoxy-propylamines and their collecting properties on aluminosilicate minerals

alkoxy-propylamines, C12H25O（CH2）3NH2, C14H29O（CH2）3NH2, C16H33O（CH2）3NH2, C18H37O-（CH2）3NH2 were synthesized from aliphatic alcohol and acrylonitrile. The flotation tests of kaolinite, pyrophyllite and illite were conducted. The flotation mechanisms were explained in view of the structures of reagents and aluminium silicate minerals, zeta potential and Fourier transform infrared spectrum measurements. The results show that the synthesized r-alkoxy-propylamines are more effective than dodecyl amine for flotation of kaolinite, pyrophyllite and illite. For flotation kaolinite and illite, the collecting ability is in the order of C18H37O（CH2）3NH2>C16H33O-（CH2）3NH2>C14H29O（CH2）3NH2>C12H25O（CH2）3NH2, but the r-alkoxy-propylamines types of collectors have almost the same collecting ability on pyrophyllite, which demonstrating that γ-alkoxy-propylamines are new selective collectors for reverse floatation to remove aluminium silicate minerals from bauxite.

Effect of quaternary ammonium salts on flotation behavior of aluminosilicate minerals

The electrokinetic properties and flotation of diaspore, kaolinite, pyrophyllite and illite with quaternary ammonium salts collectors were studied. The results of flotation tests show that the collecting ability of quaternary ammonium salts for the four minerals is in the order（from strong to weak） ofoctadecyl dimethyl benzyl ammonium chloride（ODBA）, cetyl trimethyl ammonium bromide（CTAB）, dodecyl trimethyl ammonium chloride（DTAC）. Under the condition of alkalescence, it is possible to separate the diaspore from the silicate minerals such as kaolinite, illite and pyrophyllite using quaternary ammonium salts as collector. Isoelectric points （IEP） of diaspore, kaolinite, pyrophyllite and illite are pH=6.0, 3.4, 2.3 and 3.2, respectively. Quaternary ammonium salts can change ζ-potential of the aluminosilicate minerals obviously. The flotation mechanisms were explained by ζ-potential and Fourier transform infrared spectrum （FT-IR） measurements. The results demonstrate that only electrostatic interaction takes place between aluminosilicate minerals （diaspore, kaolinite, pyrophyllite and illite） and quaternary ammonium salts.

Thermodynamic Stability of Sulfate Ions on Calcium Aluminosilicate Hydrate Microstructure

The thermodynamic stability of sulfate ions on synthesized calcium aluminosilicate hydrate（C-A-S-H） microstructure with different Ca/Si ratios and Al/Si ratios was investigated by XRD, SEM-EDS, 29 Si and 27 Al nuclear magnetic resonance（NMR） and thermodynamic modeling. The results indicate that sulfate attack leads to both decalcification and dealumination for C-A-S-H gels, and the amount of corrosion products（gypsum and ettringite） decreased gradually with decreasing Ca/Si ratios of C-A-S-H. Sulfate ions can also promote the polymerization degree of C-A-S-H gels, improving its resistance to sulfate attack. Moreover, the 4-coordination aluminum（Al[4]） in C-A-S-H, 5-coordination aluminum（Al[5]）, 6-ccordination aluminum（Al[6]） in TAH（third aluminum hydrate） and Al[6] in monosulfate or C-A-H（calcium aluminate hydrate） can be transformed into Al[6] in ettringite by sulfate attack. Furthermore, through thermodynamic calculation, the decrease of Ca/Si ratios and increase of Al/Si ratios can improve the thermodynamic stability of C-A-S-H gels under sulfate attack, which agrees well with the experiment results.

Physicochemical Properties and Catalytic Performance of a Novel Aluminosilicate Composite Zeolite for Hydrocarbon Cracking Reaction

A novel micro-micro/mesoporous aluminosilicate ZSM-5-Y/MCM-41 composite molecular sieve with a MCM-41 type structure was synthesized through a novel process of the self-assembly of CTAB surfactant micellae with silica-alumina source originated from alkaline treatment of ZSM-5 zeolite. The physical properties of the ZSM-5- Y/MCM-41 composite molecular sieve were characterized by XRD, Py-FTIR and N2 adsorption-desorption techniques. Different kinds of molecular sieves including ZSM-5, Y zeolite, AI-MCM-41, ZSM-5/MCM-41 and ZSM-5-Y/MCM- 41 as cracking catalysts were investigated, using 1,3,5-triisopropylbenzene （1,3,5-TIPB） as the probe molecule. Catalytic tests showed that the ZSM-5-Y/MCM-41 composite molecular sieve exhibited higher catalytic activity compared with the microporous ZSM-5 zeolite, Y zeolite, mesoporous A1-MCM-41 molecular sieve and ZSM-5/MCM-41 composite molecular sieve under the same conditions. The remarkable catalytic activity was mainly attributed to the presence of the hierarchical pore structure and proper acidity in the ZSM-5-Y/MCM-41 composite catalyst. Meanwhile, a carbcnium ion mechanism was put forward for the cracking of 1,3,5-TIPB.

Predication of Component Activities in the Molten Aluminosilicate Slag CaO-Al_2O_3-SiO_2 by Molecular Interaction Volume Model

A novel thermodynamic model-the molecular interaction volume model （MIVM） which can be reduced to the Flory-Huggins equation of polymer solution was employed for the prediction of component activities in the ternary molten aluminosilicate slag CaO-Al2O3-SiO2 at different temperatures. The results show that the predicted values of activity of CaO, Al2O3 and SiO2 are in reasonably agreement with experimental data in some ranges of their concentrations which are about x1 〈0.25 for CaO, x2=0.05-0.55 for Al2O3 and x3=0.03-0.85 for SiO2. This further shows that MIVM requires only two binary parameters for each sub-binary system to predict activities of all components in a multicomponent solution and is the superior alternative in a molten slag.

Effects of Si/Al,Na/Al and H_(2)O/Na_(2)O molar ratios on formaldehyde barrier properties of inorganic aluminosilicate coatings

Wood-based panels containing urea-formaldehyde resin result in the long-term release of formaldehyde and threaten human health.In this study,inorganic aluminosilicate coatings prepared by combining metakaolin,silica fume,NaOH,and H_(2)O were applied to the surfaces of wood-based panels to obstruct formaldehyde release.The Si/Al,Na/Al,and H_(2)O/Na_(2)O molar ratios of the coatings were regulated to investigate their effects on the structure and formaldehyde-resistant barrier properties of coatings.Results showed that the cracks in the coatings gradually disappeared and the formaldehyde resistance rates of the barrier increased as the Si/Al molar ratio was increased from 1.6 to 2.2.This value also increased as the Na/Al molar ratio was increased from 0.9 to 1.2 because of the improvement of the degree of polymerization.As the H_(2)O/Na_(2)O molar ratio was increased from 12 to 15,the thickness of the dry film decreased gradually and led to the reduction in the formaldehyde resistance rate.When the Si/Al,Na/Al,and H_(2)O/Na_(2)O molar ratios were 2.2,1.2,and 12,respectively,the inorganic aluminosilicate coating showed good performance as a formaldehyde-resistant barrier and its formaldehyde resistance rate could reach up to 83.2%.

Hydrothermal Synthesis and Mechanism for Formation of Novel Micro-Micro-Mesoporous Aluminosilicate Composite Zeolite

A novel micro-micro-mesoporous aluminosilicate LS-BFMZ （low-silica-BEA（beta）-faujasite （Y）-mesoporous） composite zeolite with the MCM-41 type structure was synthesized through a novel process involving the self- assembly of CTAB surfactant micellae with silica-alumina source originated from alkaline treatment of the beta zeolite. The physical properties of the LS-BFMZ composite zeolite were characterized using various techniques, including XRD, IR and SEM techniques. Meanwhile, a possible mechanism regarding the formation of the LS-BFMZ composite zeolite was proposed.

Excellent Cracking Performance of Macroporous Amorphous Aluminosilicate Catalyst

Micrometer-scale macroporous aluminosilicate catalyst was prepared via the sol-gel process. Results of catalytic cracking of 1, 3, 5-triisopropylbenzene showed that the synthesized aluminosilicate catalyst exhibited much higher activity than traditional ZSM-5 zeolite under the same condition. It is worth mentioning that the polymer product selectivity of aluminosilicate was much lower than that of ZSM-5, which might be useful for implementing the catalytic cracking process. The unique structure of macroporous aluminosilicate with interconnected-macropores and continuous skeletons was believed to be responsible for its excellent catalytic activity and low polymer product selectivity. Detailed discussion on the reaction pathway was also conducted.

Coordination properties and structural units distribution of Q_T^i in calcium aluminosilicate melts from MD simulation

The distribution of Al （j） and the structural units distribution of Qi T in calcium aluminosilicate melts were studied by means of molecular dynamics simulation. The results show that provided there exists lower-field strength cation relative to Al3+, such as alkaline and alkaline earth metals, Al will be four-coordinated but not six-coordinated. Meanwhile, if there exist a large number of higher-field strength cations such as Si4+ and little lower-field strength cation, six-coordinated aluminum will be formed. The relation of structural units distribution of Qi T with chemical composition shift was also extracted, showing that as Ca2+ exists, the distributions of Qi Si, Qi Al or Qi T have the similar changing trend with the variation of component. Because of high-temperature effect, the Al-tetrahedral units in melts are greatly active and unstable and there exist dynamic transforming equilibria of Al（3）Al（4） and （Al（5））Al（4）. The three-coordinated oxygen and charge-compensated bridging oxygen are proposed to explain phenomena of the negative charge redundancy of AlO4 and location of network modifier with charge-compensated function in aluminosilicate melts.

Iron Activation of Natural Aluminosilicates to Remove Arsenic from Groundwater

Low-cost adsorbents constituted by Fe-modified-aluminosilicates （laminar and zeolite type minerals） were developed and characterized to be used in the arsenic removal from groundwater. Iron activation was carried out ＂in situ＂ by the synthesis and deposition of mesoporous ferrihydrite. Natural iron-rich aluminosilicate was used as reference. All samples were characterized by X-ray diffraction, Raman spectroscopy, BET N2-adsorption, SEM-EDS microscopy and ICP chemical analysis. Experimental results of arsenic sorption showed that iron-poor raw materials were not active, unlike iron activated samples. The iron loading in all activated samples was below 5% （expressed as Fe203）, whereas the removal capacity of these samples reaches between 200-700 gg of As by g of adsorbent, after reusing between 17 cycles and 70 cycles up to adsorbent saturation. Differences can be associated to mineral structure and to the surface charge modification by iron deposition, affecting the attraction of the As-oxoanion. On the basis of low-cost raw materials, the easy chemical process for activation shows that these materials are potentially attractive for As（V） removal. Likewise, the activation of clay minerals, with natural high content of iron, seems to be a good strategy to enhance the arsenic adsorption ability and consequently the useful life of the adsorbent.

Synthesis and Characterization of Mesoporous Aluminosilicates for Copper Removal from Aqueous Medium

In this study the characterization of an aluminosilicate synthesized from commercial Al2(SO4)3 and colloidal SiO2 is presented, as well as its capacity for the removal of copper from aqueous solution. Characterization of the synthesized material was performed using X-ray diffraction, BET nitrogen adsorption-desorption, mass titration and the Boehm method. In order to obtain stable agglomeration and enhance its surface area (165 - 243 m2/g) and solid adsorbing capabilities, the molar ratio SiO2:Al2O3 (1:3, 1:1 and 3:1) was studied, the solubility of the preparation material, synthesis-procedure time and solution pH function were also examined. The maximum capacity to remove copper ions from an aqueous solution by synthesized aluminosilicate was 16 mg/g at pH 4 and 25℃. The Langmuir model fitted better to the copper adsorption experimental data.

Alkaline digestion behavior and alumina extraction from sodium aluminosilicate generated in pyrometallurgical process

In pyrometallurgical process, Al-and Si-bearing minerals in iron and aluminum ores are easily transformed into sodium aluminosilicates in the presence of Na_2O constituents, which alters the leaching behaviors of Al_2O_3 and SiO_2. It was confirmed that sodium aluminosilicates with different phase compositions synthesized at various roasting conditions were effectively digested in the alkaline digestion process. Under the optimum conditions at temperature of 100–120°C, liquid-to-solid ratio(L/S) of 10:2 mL/g, caustic ratio of 4, and Na_2O concentration of 240 g/L, the actual and relative digestion ratio of Al_2O_3 from the synthesized sodium aluminosilicates reached maximums of about 65% and 95%, respectively, while SiO_2 was barely leached out. To validate the superior digestion property of sodium aluminosilicate generated via an actual process, the Bayer digestion of an Al_2O_3-rich material derived from reductive roasting of bauxite and comprising Na_(1.75) Al_(1.75) Si_(0.25)O_4 was conducted; the relative digestion ratio of Al_2O_3 attained 90% at 200°C.

SiO2/Al2O3 RATIO OF HYDRATED SODIUM ALUMINOSILICATE IN ALUMINA PRODUCTION

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Relationship between the microstructure and reaction performance of aluminosilicate

A systematic study was conducted to comprehend the mechanism of thermal activation of silica-alumina materials by using ^29Si and ^27Al magnetic angle spinning nuclear magnetic resonance （MAS NMR） spectroscopy. The reaction performance of silica-alumina-based materials with different molar ratios of Si/Al, which were thermally activated, was also investigated. With the increase in calcining temperature, the coordination of Al in metakaolin becomes four, five, and six firstly, and then transforms completely to four and six. It is indicated by identical coupled plasma optical emission spectroscopy （ICP） and NMR that, the reaction performance of monomeric silicate anions is better than that of polymeric silicate anions which are primarily cross-linked in the alkali solution. Moreover, it also shows that the thermal activation temperature, cooling method, and the molar ratio of Na/Ca have remarkable effects on the reaction performance.

Influence of Associated Cations on the Transport and Adsorption of Chloride Ions in the Nano-channel of Calcium Aluminosilicate Hydrate Gel:A Molecular Dynamics Study

Molecular dynamics simulation was utilized to investigate the transport and adsorption of chloride in the nanopore of calcium aluminosilicate hydrate(C-A-S-H)with associated cation types of Ca,Mg,Na and K.The local ionic structure,atomic dynamics and bond stability were analyzed to elucidate the interaction between cations and chloride ions.The results show that interfacial chloride is absorbed through the ion pairing formation in the vicinity of C-A-S-H substrate.Interfacial cations can simultaneously interact aluminosilicate chains,water molecules and Cl^(-)ions,which restrict the motion of interfacial Cl^(-)ions.Pore solution chloride can be immobilized through the solvation effect of cations.Cations along with their hydration shell can connect to neighboring Cl^(-)ions to decrease their mobility.Owing to the varied ionic chemistry,cations show different interaction strength with neighboring water molecules and anions,which determines the chloride transport behavior in the nanopore of C-A-S-H.The chloride immobilization capacity of C-A-S-H nanopore with different associated cations is listed in following order:Mg^(2+)Ca^(2+)<Na^(+)≈K^(+),which agrees reasonably with previous experiments.

FORMATION AND SOLUBILITY OF POTASSIUM ALUMINOSILICATE

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