Temperature and pressure effects on zeta potential values of reservoir minerals

An experimental study of the effect of temperature and pressure on zeta potential of typical reservoir minerals, including quartz, kaolinite, and calcite, is presented. Experiments included the design and construction of an electrophoretic cell for zeta potential measurements at variable pressure and temperature. Electrolyte concentration was varied in the range from 0.0001 to 0.1 M in the pH range from 2 to 9. For all the minerals it is found that the zeta potential decreases with temperature at a rate characteristic of each mineral; values are around -2.3 mV/degrees C for quartz, -0.96 mV/degrees C for kaolinite, and -2.1 mV/degrees C for calcite for pressure values less than 45 psi. The effect of pressure is found to depend on the mineral nature and pH of the electrolytic solution. In the case of quartz, a systematic increase in the value of the zeta potential with pressure is observed, whereas a decreasing trend is measured for the kaolinite. In the case of calcite, a decreasing trend is observed for pressures up to 45 psi, whereas the experimental data suggest an increasing trend for higher pressure values.     

高温气化条件下煤直接液化残渣中矿物质演化行为的研究

利用XRD和FT-IR分析了高温(1 100~1 500 ℃)气化条件下液化残渣中矿物质的演变行为,并利用穆斯堡尔谱仪对残渣灰中的含铁相及铁的价态铁进行了定量分析。结果表明,煤直接液化残渣中的主要矿物质为石英、硫酸钙、紫铝铁矾、磁黄铁矿、高岭石和方解石。高温气化条件下残渣灰中主要矿物质为钙长石、钙黄长石、磁赤铁矿和磁铁矿。由于钙长石、钙黄长石等含钙化合物低温共熔作用,使得残渣灰具有较低的熔融温度。残渣灰中的含铁相主要为磁赤铁矿、磁铁矿、铁橄榄石和玻璃体,并且随温度的升高,玻璃体中的铁含量逐渐增加。同时,残渣灰中Fe²⁺/Fe³⁺出现先增加后降低再增加的变化趋势。当温度由1 100 ℃升高至1 200 ℃时,由于磁赤铁矿的还原,Fe²⁺/Fe³⁺由1.08升高至2.39;1 200 ℃以上Fe²⁺/Fe³⁺的变化不明显。另外,玻璃体中铁含量的增加是引起残渣灰液相含量随温度升高而增加的重要原因,铁含量高是导致残渣灰熔融温度低的主要原因。     

A new differential method for determining orders and rates of reactions and its application to solid state reactions. Part I. Some simple decompositions

The thermal dehydroxylation of natural Al-bearing geothite was investigated by IR spectroscopy. Venezuelan lateritic bauxites (which in addition to goethite contain kaolinite, gibbsite, ilmenite and quartz), as well as chemically isolated samples of Al-goethites, were heated to 300, 600 and 1000°C. The spectral features of the iron oxides formed during the thermal treatment depend on the heating temperature, showing that the first dehydroxylation product is Al-bearing protohematite which at temperatures above 600°C is recrystallized to Al-bearing hematite. Part of the aluminum which is occuled in this hematite originates from the gibbsite and to a smaller extent from the kaolinite.     

Solid-state transformation mechanisms of associated minerals to aluminosilicates

Thermochemical and mechanochemical transformation mechanisms of associated minerals in clay (quartz, calcite, Al and Fe oxyhydroxides) are comparatively examined. The phase transformation sequence resulting from heating and, on the other hand from dry grinding of each of the associated minerals, depends on the structure and physicochemical properties of the starting materials.Grinding treatments may cause local heating and local pressure effects in some selective metal oxides and in calcite, respectively, accounting for their structural conversions.Dedicated to Dr. Robert Mackenzie on the occasion of his 75th birthday     

Thermal evolution of a slate

The thermal evolution of a slate rock sample (Berja, Almería, Spain) has been studied. The phase minerals identified in this sample were mica (illite), chlorite (clinochlore) and quartz as major components, with minor microcline, iron oxide and a mixed-layer or interstratified phase (montmorillonite-chlorite). This slate is highly silico-aluminous (48.33 mass% silica, 22.04 mass% alumina), and ca. 20 mass% of other elements, mainly Fe₂O₃ (8.35 mass%), alkaline-earths and alkaline oxides. Two main endothermic DTA effects, centered at 640 and 730°C, were observed. The more important contribution of total mass loss (7.15 mass%) was found between 500–900°C, with two DTG peaks detected at 630 and 725°C. All these effects were associated to the dehydroxylation of structural OH groups of 2:1 layered silicates mixed in the slate. The dehydroxylation of the layered silicates evidenced by dilatometry, produced a rapid increase of expansion between 600–800°C. The thermal evolution of the slate upper 800°C indicated the first sintering effects associated to shrinkage, which is also favoured by its low particle size (average 23 μm) and the presence of a liquid or vitreous phase as increasing the heating temperature. The application of thermal diffractometry to the slate sample allowed to study the formation of dehydroxylated crystalline phases from the layered silicates after heating. At 1000°C, β-quartz, dehydroxylated illite, iron oxide, relicts of microcline and the vitreous phase were present in the sample. All these results are interesting to know the thermal behaviour of a complex mineral mixture as identified in the slate.     

Thermal behaviour of some minerals

Thermal behaviour of some minerals (kaolinite, halloysite, two montmorillonites, quartz and calcite) for different sample amounts and heating rates has been investigated using differential thermal analysis. On the basis of the DTA analysis carried out, the PA curves of each mineral have been obtained for different heating rates. These diagrams can be employed in the semiquantitative evaluation of identical substances contained in uncharacterized polymineral samples.     

Spectroscopic study of phase transitions in natural calcite mineral

The process and the formation of new minerals upon heating the carbonate rocks containing clay minerals, together with calcite are determined with thermal analysis, X-ray diffraction, infrared and Raman spectroscopy. The calcite-calcium oxide phase transition sequence was followed up to 947 degrees C in naturally occurring limestone samples. The spectral variations of the internal modes of the carbonate trigonal (nu(1), nu(2), nu(3) and nu(4)) were used to probe the structural phase transitions. The calcium oxide phase (which on reaction with atmospheric water forms portlandite) with an onset temperature of around 950 degrees C was also characterized by the appearance of the infrared mode around 450 cm(-1). The minerals, which were formed upon heating the calcite, were calcium oxide and wollastonite.     

Thermal desorption gas chromatography with mass spectrometry study of outgassing from polymethacrylimide foam (Rohacell®)

Polymethacrylimide foams are used as light structural materials in outer‐space devices; however, the foam closed cells contain volatile compounds that are outgassed even at low temperatures. These compounds ignite as plasmas under outer‐space radiation and the intense radio‐frequency fields used in communications. Since plasmas may cause spacecraft fatal events, the conditions in which they are ignited should be investigated. Therefore, qualitative and quantitative knowledge about polymethacrylimide foam outgassing should be established. Using thermogravimetric analysis, weight losses reached 3% at ca. 200°C. Thermal desorption gas chromatography with mass spectrometry detection was used to study the offgassed compounds. Using successive 4 min heating cycles at 125°C, each one corresponding to an injection, significant amounts of nitrogen (25.3%), water (2.6%), isobutylene (11.3%), tert‐butanol (2.9%), 1‐propanol (11.9%), hexane (25.3%), propyl methacrylate (1.4%), higher hydrocarbons (11.3%), fatty acids (2.2%) and their esters (1.3%), and other compounds were outgassed. Other compounds were observed during the main stage of thermal destruction (220–280°C). A similar study at 175°C revealed the extreme difficulty in fully outgassing polar compounds from polymethacrylimide foams by baking and showed the different compositions of the offgassed atmosphere that can be expected in the long term.     

Catalytic efficiency of iron(III) oxides in decomposition of hydrogen peroxide: competition between the surface area and crystallinity of nanoparticles

Various iron(III) oxide catalysts were prepared by controlled decomposition of a narrow layer (ca. 1 mm) of iron(II) oxalate dihydrate, FeC(2)O(4).2H(2)O, in air at the minimum conversion temperature of 175 degrees C. This thermally induced solid-state process allows for simple synthesis of amorphous Fe(2)O(3) nanoparticles and their controlled one-step crystallization to hematite (alpha-Fe(2)O(3)). Thus, nanopowders differing in surface area and particle crystallinity can be produced depending on the reaction time. The phase composition of iron(III) oxides was monitored by XRD and (57)Fe M?ssbauer spectroscopy including in-field measurements, providing information on the relative contents of amorphous and crystalline phases. The gradual changes in particle size and surface area accompanying crystallization were evaluated by HRTEM and BET analysis, respectively. The catalytic efficiency of the synthesized nanoparticles was tested by tracking the decomposition of hydrogen peroxide. The obtained kinetic data gave an unconventional nonmonotone dependence of the rate constant on the surface area of the samples. The amorphous nanopowder with the largest surface area of 401 m(2) g(-1) revealed the lowest catalytic efficiency, while the highest efficiency was achieved with the sample having a significantly lower surface area, 337 m(2) g(-1), exhibiting a prevailing content of crystalline alpha-Fe(2)O(3) phase. The obtained rate constant, 26.4 x 10(-3) min(-1) (g/L)(-1), is currently the highest value published. The observed rare catalytic phenomenon, where the particle crystallinity prevails over the surface area effects, is discussed with respect to other processes of heterogeneous catalysis.     

Intercalation of n-alkyltrimethylammonium ions into layered calcium octyl phosphates thermally treated in vacuo

Layered calcium octyl phosphate (CH3(CH2)7OPO3Ca.1.6H2O: CaOP), which is composed of a multilayer alternating bilayer of octyl phosphates and a dicalcium phosphate dihydrate (DCPD)-like phase, was thermally treated in vacuo and the intercalation of n-alkyltrimethylammonium ions into the materials was examined. The octyl groups in the layer were eliminated by outgassing above 250 degrees C to give the amorphous calcium phosphates. Further, the specific surface area was steeply increased and mesopores with a diameter of ca. 2.0 nm were formed. IR results indicated that the surface P-OH groups were generated by outgassing at 250 degrees C. When the CaOP outgassed at 250 degrees C was treated with n-alkyltrimethylammonium ion solutions (carbon number of alkyl group, n=14-18), three XRD peaks reappeared below 2theta=15 degrees and the d-spacing ratio of these peaks was 1:1/2:1/3. These facts indicate that the n-alkyltrimethylammonium ions were intercalated into the amorphous calcium phosphate phases.     

Thermal investigations of direct iron ore reduction with coal

In this paper, fundamental mechanisms for iron ore reduction in coal–ore mixtures have been investigated using several advanced experimental techniques. Firstly, the thermal properties of coal–ore mixtures were studied and apparent specific heat of coal–ore mixtures against temperature was obtained at a heating rate of 10 °C/min. Several exothermic and endothermic peaks were observed which were related to the decomposition reactions and reduction. The flue gases from the mixture were analysed using a mass spectrometer. Secondly, the X-ray diffraction (XRD) and the iron phase analytical techniques were applied to identify the iron phase changes with the temperature. It has been found that coal devolatilisation and iron oxides reduction occur simultaneously during the heating of the mixture. H₂ and CO gases produced from coal devolatilisation and char gasification were responsible for the reduction of iron oxides at these temperatures. Iron oxides undergo step-wise reduction over the whole process. The results in this work provide a fundamental understanding for the direct reduced ironmaking processes.     

准东煤灰化过程中的矿物演变及矿物添加剂对其灰熔融特性的影响

利用低温灰化、高温灰化和X射线衍射物相分析相结合的方法对准东煤中矿物质在加热过程中的演变规律进行了研究。结果表明,准东煤中原始矿物质以方解石、高岭石为主,随着燃烧温度的升高,煤灰中矿物质最终生成了铁橄榄石、硅酸钙等。此外,向准东煤中掺加不同比例的高岭土和刚玉混合添加剂,发现随着SiO₂/Al₂O₃比值的降低,煤中生成了钙矾石、钙铝榴石等高熔点物质,准东煤的灰熔点逐步升高。     

Thermal behaviour of sericite clays as precursors of mullite materials

Thermal analysis of some sericite clays, from several deposits in Spain, which are not exploited at this time, has been studied. The samples have been previously characterized by mineralogical and chemical analysis. Sericite clays have interesting properties, with implications in ceramics and advanced materials, in particular concerning the formation of mullite by heating. According to this investigation by differential thermal and thermogravimetric analysis (DTA-TG), the sericite clay samples can be classified as: Group (I), sericite–kaolinite clays, with high or medium sericite content, characterized by an endothermic DTA peak of dehydroxylation of kaolinite with mass loss, which overlapped with dehydroxylation of sericite, and Group (II), sericite–kaolinite–pyrophyllite clays, with broader endothermic DTA peaks, in which kaolinite is dehydroxylated first and later sericite and pyrophyllite with the main mass loss, appearing the peaks overlapped. X-ray diffraction analysis of the heated sericite clay samples evidenced the decomposition of dehydroxylated sericite and its disappearance at 1050 °C, with formation of mullite, the progressive disappearance of quartz and the formation of amorphous glassy phase. The vitrification temperature is ~ 1250 °C in all these samples, with slight variations in the temperatures of maximum apparent density (2.41–2.52 g mL^?1) in the range 1200–1300 °C. The fine-grained sericite content and the presence of some mineralogical components contribute to the formation of mullite and the increase in the glassy phase by heating. Mullite is the only crystalline phase detected at 1400 °C with good crystallinity. SEM revealed the dense network of rod-shaped and elongated needle-like mullite crystals in the thermally treated samples. These characteristics are advantageous when sericite clays are applied as ceramic raw materials.     

Influence of morphology and composition of fumed oxides on changes in their structural and adsorptive characteristics on hydrothermal treatment in steam phase at different temperatures

A series of fumed oxides such as silica, titania, alumina, silica/alumina (SA), silica/titania (ST), and alumina/silica/titania (AST), initial and hydrothermally treated (HTT) in the steam phase at T(HTT)=150, 250, and 350 degrees C was studied by adsorption, AFM, XRD, FTIR, and theoretical methods. Diminution of the size of primary particles (corresponding to increasing S(BET)) of initial silica and mixed oxides results in enhancement of their structural changes on HTT with elevating T(HTT) and increasing density of packing of primary particles in the secondary structures. Relative changes in the texture of treated fumed silicas are smaller than those of mesoporous silica gels occurring under similar HTT conditions. On HTT, aggregates of primary particles and their agglomerates become denser but their surface layers become looser because of transfer of silica fragments from one particle to another, and the smaller the initial primary particles, the greater the relative diminution of the specific surface area S(BET) for the same type of primary particle packing in aggregates. Relative changes in the pore volume V(p) (or V(BJHd)) on HTT are more complex than that of S(BET), as for many samples the V(p) value increases especially at T(HTT)=150 degrees C. Alumina and titania partially inhibit structural changes on HTT, which decrease in the series silica > SA > AST approximately ST.     

Surface structure and properties of mixed fumed oxides

A variety of fumed oxides such as silica, alumina, titania, silica/alumina (SA), silica/titania (ST), and alumina/silica/titania (AST) were characterized. These oxides have different specific surface areas and different primary particle composition in the bulk and at the surface. These materials were studied by FTIR, NMR, Auger electron spectroscopy, one-pass temperature-programmed desorption with mass spectrometry control (OP TPDMS), microcalorimetry, and nitrogen adsorption. Nonlinear changes in the surface content of alumina in SA and AST and titania in ST and AST samples with increasing oxide content along with simultaneous changes in their specific surface area cause complex dependencies of the heat of immersion in water and desorption of water on heating on the structural parameters. Simultaneous analysis of changes in the surface phase composition, in the concentration of hydroxyls, and in the structural characteristics reveals that at a low content of the second phase the structural characteristics (e.g., S(BET)) are predominant; however, at a large content of these oxides the phase composition plays a more important role.     

Physico-chemical behaviour of hydrated aluminium oxides and associated clay minerals occurring around Pipra,district Sidhi,India

DTA techniques were employed to study the thermal and structural characteristics of hydrated aluminium oxides and aluminous clays of the Pipra pelitic rocks from district Sidhi, India. Detailed microscopic investigations, X-ray and chemical analyses reveal that these clays were derived by the localized weathering of arkosic metasediments. The chemical and normative behaviours have confirmed their formation by the isochemical metamorphism of arkose, aided by a little granitization and followed by minor retrogression. A tentative correlation between the thermal and structural changes of these oxides and clay minerals at various transition temperatures has nicely displayed the presence of kaolinite, diaspore and gibbsite. The exothermic curves of kaolinite confirm the recrystallization. The presence of kaolinite in the clay fractions indicates the detrital origin.     

Mineral reactions and pyrolysis of Israeli oil shale

The mineral reactions of Israeli oil shale fed to the GENESIS ($\text{G}$eneration of $\text{Ene}$rgy from $\text{S}$hale of $\text{Is}$rael) split-stage fluidized-bed reactor have been studied by infrared. X-ray and chemical means. Organically bonded sulphur released during pyrolysis reacts with oxygen from the fluidizing air and with CaO resulting from decomposition of calcite to form CaSO₄, mostly in a surface layer. At pyrolysis and coke-oxidation temperatures near 600°C, kaolinite reacts with calcite to form amorphous modified metakaolinite. At organic gas combustion temperatures near 1000°C, the amorphous phase in overhead fines reacts with additional calcite and quartz to yield gehlenite and larnite.     

Mössbauer Investigation of Characteristic Distribution of Iron Oxides in Sediments from the Antarctica

Sediments from the Admiralty Bay, King George Island, Antarctica, were investigated by ⁵⁷Fe Mössbauer spectroscopy, X-ray diffractometry, and radiometry. Quartz, feldspar, chlorite, calcite, dolomite, mica, kaolinite, hematite and magnetite were identified as constituent minerals in the sediment samples. The phase composition and the iron distribution among the crystallographic sites of iron-bearing minerals (silicates, magnetite and hematite) of samples from different location have been derived from the complex Mössbauer spectra. At different locations sediments had significant characteristic differences in the mineral composition, in the iron distribution among the crystallographic site of silicates, and in the specific radioactivity of Cs radionuclides. These results indicate differences in the rock formation and alteration by the sediments in this maritime part of Antarctica. There is a much higher amount of iron oxides in the sediments from south part of the geological fault across the Admiralty Bay than in the north part. This can be associated with much more alteration in the rocks in the south part compared to the northern one. This finding can contribute to the question of the history of the formation and alteration of volcanic rocks in the border of Antarctica.     

煤中矿物质对灰熔融和燃烧特性的影响

采用化学分步萃取、XRD和SEM-EDS、煤灰灰成分分析等测试方法对五彩湾煤中矿物质的赋存形态进行了研究,并对逐级萃取前后煤样的燃烧特性和灰熔融特性进行了分析和比较.结果表明,五彩湾煤中原始矿物质主要有方解石、硫酸钙、高岭石、石英、黄铁矿等;煤中钠含量很高,主要以水合离子的形态溶于煤的内水中;有机形态的钠、镁和钙提高了煤的燃烧特性;五彩湾煤的煤灰熔融性主要受铁钙物质的量比(F₂O₃/CaO)影响,灰熔融特性温度随铁钙物质的量比(F₂O₃/CaO)的增大而降低.     

Phase Transformations in Mixtures of Calcite and Dolomite with Condensed Phosphates of Calcium during Heating

The thermal interactions of dolomite and calcite with calcium polyphosphates up to 1000°C were studied by thermal (dynamic heating and isobaric conditions) and X-ray diffraction methods. It was found that in mixtures with Ca-polyphosphates less than half of the carbonates reacted before decomposition to oxides with the phosphates. The rates of the reactions of phosphates with MgO were much lower than those with CaO. The scheme of the main crystalline phase transformations was constructed. This revised version was published online in July 2006 with corrections to the Cover Date.