Phase changes in the syrian phosphorite–ammonium sulphate system

With a complex of physico-chemical methods for analysis it is proved that in the course of mechanochemical treatment of a Syrian phosphorite and ammonium sulphate mixture new phases have been formed. The thermal analysis proves an increase in the reaction properties of the ammonium sulphate and the Syrian phosphorite which is a prerequisite for the increase in the content of P₂O₅^assimilated , in the activated phosphorite mixtures and the possibility to use them in the production of NP complex fertilizers.     

Mechanochemical activation of ordinary phosphorite powder of Central Kyzylkum mixed with urea nitrate and ammobium carbonate salts

Grinding of ordinary phosphorite powder of Central Kyzylkum with urea nitrate and ammonium carbonate salt to the particles size less than 0.16 mm is shown leading to significant increase in content of consumable by plants form of P₂O₅ in the products.     

高镁磷尾矿中钙、镁、磷赋存状态研究

选择了贵州省重要磷矿生产基地—瓮福磷矿浮选尾矿为代表,对其中钙、镁、磷的矿物学重要特征进行了比较系统的研究,获得了一些重要结论,从而为高镁磷尾矿的综合利用、白云石与胶磷矿的分离等提供理论依据,对实现磷尾矿资源的二次利用、指导开发者设计科学合理的矿石选冶工艺流程都有十分重要的意义。按照元素赋存形态分析的方法,选用了化学成分、化学物相、电子能谱、扫描电子显微镜、X射线粉晶衍射分析方法等多种手段系统、全面地测定了磷尾矿结构、形貌的重要特征,获得了钙、镁、磷赋存状态的重要结论,发现了尾矿及其原矿的异同性:磷尾矿中含量最高的组分及其含量分别是:氧化钙34.11%,氧化镁17.65%,五氧化二磷5.30%;镁主要以白云石的形式赋存,并有少量以磷酸盐、硅酸盐形式存在,其在各相占的比例分别为99.80%、0.10%、0.10%;磷主要以磷灰石的形式赋存(占97.08%),并有少量以铁氧化物(1.04%)、独居石(0.19%)、磷钇矿(1.83%)形式存在;钙主要以白云石的形式赋存(占96.95%),并有少量以方解石(1.11%)、磷酸盐(1.94%)形式存在。贵州瓮福地区高镁磷尾矿中的镁、磷、钙主要赋存形式分别为白云石、磷灰石、白云石。     

Nitrogen-phosphoric fertilizers produced by introduction of Central Kyzylkum phosphate raw material into ammonium nitrate melt

Composition of nitrogen-phosphoric fertilizers produced by introduction into ammonium nitrate melt of ordinary phosphorite powder, dust fraction and mineralized mass of Central Kyzylkum phosphorites in the amount necessary for providing final product with 0.5 to 5% of P₂O₅ is described.     

Hardness of the granules of ammonium nitrate doped with the Central Kyzylkum Phosphorite

The results are displayed of measuring hardness of the ammonium nitrate granules when the preceding melt is doped at 180°C either with ordinary powdered phosphorite, or with dust fraction, or with mineralized mass of the Central Kyzylkum Phosphorite in amount from 0.5 to 5.0% of P₂O₅.     

Effect of high-energy milling and thermal treatment on the solid-phase reactions in apatite–ammonium sulphate system

The phosphorous fertilizers are a product of natural sedimentary phosphorite ores. Using this raw material to produce phosphoric acid and classic phosphorous fertilizers has generated well-known ecological problems. A new and perspective way to use the same materials is creating a new type of time-delayed fertilizers applying high-energy milling (HEM) activation method. The impact of the mechanical forces over the solids is mostly revealed through the changes of the quantities being related to the energetic stability and reactivity of the solid phase. The aim of this work is to report the results from the investigation on the chemical and thermal reactions in composites of natural apatite , which are HEM activated for different times and thermally treated, (from Tunisia) and ammonium sulphate. The Tunisian phosphorite belongs to the ‘basic’ apatites having a Ca/P ratio of 1.70–1.77 and is characterized by a complex mineral composition with major component carbonate-fluorapatite. The used ammonium sulphate—(NH₄)₂SO₄ is obtained as a by-product from cleaning industrial waste gases, using e-beam technology. The composites of Tunisian phosphorite ores and ammonium sulphate, mixed in a mass ratio 1:1, were HEM activated during 10 min to 50 h with 20 mm Fe-milling bodies and temperature treated up to 1,100 °C. As a result, the chemical properties of the treated composites changed. Proofs were found for (i) formation of new phases during HEM activation such as NH₄Ca(PO₃)₃ (NH₄)₂CaH₄(P₂O₇)₂, (NH₄)₂Ca₃(P₂O₇)₂.6H₂O, CaH₂P₂O₇ and α-Ca₂P₂O₇; and (ii) decreasing of temperature intervals of phase changes in comparison to untreated composite.     

Separation and determination of uranium and radium-226 in phosphorites and their industrial derivatives by extraction chromatography

An extraction chromatographic method based on microporous polyethylene (Microthene) supporting tri-n-octylphosphine oxide (TOPO) was used to separate uranium and²²⁶Ra from phosphorites and their industrial derivatives. Uranium was then determined by fluorimetry and by alpha-spectrometry after electroplating, and radium by precipitation as Ba(Ra)SO₄ and alpha counting with a ZnS(Ag) alpha detector. The method was checked by using an IAEA phosphorite sample having a certified uranium concentration. Some phosphorite, phosphoric acid and plaster samples supplied by an Italian industrial plant were analyzed; uranium isotopes always resulted in radioactive secular equilibrium.     

贵州瓮福地区磷尾矿中钙、镁、磷的赋存状态测定

应用化学组分分析、X射线衍射分析、扫描电子显微镜及X射线能谱法等多种方法对贵州省瓮福地区磷尾矿中钙、镁及磷的赋存状态作了分析和研究。结果表明:①选自该矿区的磷尾矿为高镁(wMgO17.26%～17.65%),高钙(wCaO34.11%～34.56%),低磷(wP2O55.30%～5.69%)的固体矿物;②尾矿中镁主要以白云石形式存在,并有少量以磷酸盐和硅酸盐形式存在;钙主要也以白云石形式存在,加上少量以方解石和磷酸盐形式存在;磷主要以磷灰石形式存在,有少量存在于铁氧化物及独居石、磷钇矿中。     

Calorimetric study of dissolution kinetics of phosphorite in diluted acetic acid

In this report, we present a thermodynamic and kinetic study of the selective dissolution of calcite from low-grade phosphate ores (Epirus area, Greece) by dilute acetic acid at isothermal conditions. A twin calorimeter with two identical membrane vessels, for the acid dissolution process, and for the reference was used. The curves of rate vs. time of the phosphorite dissolution for various temperatures show that the maximum (.q _max) was increased, whereas the time (t _peak) to achieve the corresponding .q _max values was decreased, as the experimental temperature was increased. The dissolution enthalpy was increased from 13.1 to 16.7 kJ mol⁻¹, as the experimental temperature was increased from 10.0 to 28.0°C. The chemical analysis of the supernatant solutions shows that the main process was the calcite dissolution. The reaction model with general form, ln(1/(1-X))=kt ^m, was found to fitted the experimental data regardless of the experimental temperature. These results were assigned in the presence of two different kinds of particles in the phosphorite. The activation energy of the dissolution process was found 69.7 kJ mol⁻¹. The SEM micrographs of acid dissolution samples showed two different textures after acid dissolution.     

Thermal behavior and phase transformations of nanosized carbonate apatite (Syria)

The phase transformations of Syrian phosphorite upon mechanochemical activation are examined in the present work. The latter is carried out in planetary mill equipped with 20 mm steel milling bodies and duration from 30 to 300 min. The established by means of DTA, DTG, TG analyses transformation of non-activated carbonate fluorine apatite type B into the carbonate hydroxyl fluorine apatite (COHFAp) mixed type A2-B leads to substantial changes in the properties of the activated samples expressed in lowering the degree of crystallinity, strong defectiveness of the structure, and increase of the citric solubility. The thermal analysis gives evidence for the decomposition of the carbonate-containing component within the phosphorite, as from the positions placed in the vicinity of the hexagonal 6₃ axis (type A2), as well as from the positions of the phosphate ion (type B), and from the free carbonates. The data from the thermal analysis, the powder X-ray analysis and the infrared spectroscopy give also evidence for phase transformations of the activated apatite (with admixtures of quartz and calcite) into Ca₁₀FOH(PO₄)₆, β-Ca₃(PO₄)₂, Ca₄P₂O₉, Ca₃(PO₄)₂ · Ca₂SiO₄ and for that one of the quartz—into larnite and wollastonite. The influence of the α-quartz as a concomitant mineral is considered to be positive. The α-quartz forms Si–O–Si–OH bonds retaining humidity in the solid phase thus facilitating the isomorphous substitution OH^? → F^? with the subsequent formation of partially substituted COHFAp. Calcium silicophosphate and Ca₄P₂O₉ are obtained upon its further heating. The presented here results settle a perspective route for processing of low-grade phosphate raw materials by means of tribothermal treatment aiming at preparation of condensed phosphates suitable for application as slowly acting fertilizer components.     

Characterization of dust material emitted during harbour activities by k<Subscript>0</Subscript>-INAA and PIXE

The growing concern about air quality in harbours is a result of the high impact of the operations on human health and environment. Harbour activities such loading, unloading and transport of dusty materials are important emission sources of Atmospheric particulate matter (APM). The assessment of these fugitive emissions is a difficult task because they depend on the materials, the type of operation and the meteorological scenarios. The main objectives of this work were (1) to evaluate if the techniques k₀-based Instrumental neutron activation analysis (k₀-INAA) and Particle induced X-ray emission (PIXE) are suitable techniques to assess fugitive emissions in harbours and (2) to estimate the impact of harbour activities on APM levels and composition. Several experimental campaigns were carried out in a Portuguese harbour, during unloading operations of fertilizer and phosphorite provided from Syria and Morocco. PM_2.5 and PM_2.5–10 were collected, in polycarbonate filters, by Gent samplers. The techniques k₀-INAA and PIXE were applied as sensitive analytical tools to perform a complete chemical characterization of the collected samples. Results showed that manipulation of these materials during harbour operations resulted in high emissions of particles, principally from the coarse fraction. These emissions were very affected by the granulometry and nature of the handled materials. Fertilizer emissions were characterized by high concentration of Ca, P, K, Cr, Br and Zn, whereas phosphorite handling contributed principally for the increase of Ca, P and Cr levels.     

Expedient one-pot organometallics-free synthesis of tris(2-pyridyl)phosphine from 2-bromopyridine and elemental phosphorus

2-Bromopyridine reacts with elemental phosphorus (red or white) in a superbasic KOH/DMSO(H₂O) suspension at 100 °C (for red phosphorus) and 75 °C (for white phosphorus) over 3 h to afford tris(2-pyridyl)phosphine in a 62% yield (from red phosphorus) and a 50% yield (from white phosphorus). Under microwave assistance, the reaction with red phosphorus takes just 20 min to produce tris(2-pyridyl)phosphine in 53% yield. A hitherto unknown complex, [Pd(PPy₃)₂Cl₂]·CH₂Cl₂, synthesized from tris(2-pyridyl)phosphine and PdCl₂, has the cis-configuration; this is unusual for bis(phosphino)palladium dichloride complexes.     

Graphite-furnace atomization of phosphorus

The slopes of the ln (absorbance) vs. T^?1 dependences for platform/graphite furnace atomization of phosphorus in the presence of Ni²⁺ or La³⁺ modifiers are measured, and found to be similar to the theoretical slope calculated for isothermal atomization. It is concluded that in both cases the atomization mechanism is the same and is expressed by P_2(gas) ? 2P_(gas); P_(gas) ? P^*_(gas). The atomic absorption signal for phosphorus appears and reaches its maximum later when the atomization is carried out from the platform in the presence of modifiers. Hence atomization takes place under nearly isothermal conditions and is much more efficient, thus providing the best conditions for the determination of phosphorus. Treatment of a deteriorated graphite surface with ZrOCl₂ solution repairs any defects and improves the sensitivity of phosphorus determination.     

Thermal investigations on phase transformations of Syrian phosphorite: Part I

The phase transformations of Syrian phosphorite upon mechanochemical activation are examined in the present work. The latter is carried out in planetary mill equipped with 20 mm steel milling bodies and duration from 30 to 300 min. The established by means of DTA, DTG, TG analyses transformation of non-activated carbonate fluorine apatite type B into the carbonate hydroxyl fluorine apatite (COHFAp) mixed type A2-B leads to substantial changes in the properties of the activated samples expressed in lowering the degree of crystallinity, strong defectiveness of the structure, and increase of the citric solubility. The thermal analysis gives evidence for the decomposition of the carbonate-containing component within the phosphorite, as from the positions placed in the vicinity of the hexagonal 6₃ axis (type A2), as well as from the positions of the phosphate ion (type B), and from the free carbonates. The data from the thermal analysis, the powder X-ray analysis and the infrared spectroscopy give also evidence for phase transformations of the activated apatite (with admixtures of quartz and calcite) into Ca₁₀FOH(PO₄)₆, β-Ca₃(PO₄)₂, Ca₄P₂O₉, Ca₃(PO₄)₂ · Ca₂SiO₄ and for that one of the quartz—into larnite and wollastonite. The influence of the α-quartz as a concomitant mineral is considered to be positive. The α-quartz forms Si–O–Si–OH bonds retaining humidity in the solid phase thus facilitating the isomorphous substitution OH⁻ → F⁻ with the subsequent formation of partially substituted COHFAp. Calcium silicophosphate and Ca₄P₂O₉ are obtained upon its further heating. The presented here results settle a perspective route for processing of low-grade phosphate raw materials by means of tribothermal treatment aiming at preparation of condensed phosphates suitable for application as slowly acting fertilizer components.     

Reduced inorganic phosphorus in the natural environment: significance, speciation and determination

It is commonly assumed that phosphorus occurs almost exclusively in the environment as fully oxidized phosphate (primarily H₂PO₄⁻ and HPO₄²⁻, where the oxidation state of phosphorus is +V). Recent developments in the field of microbiology and research on the origin of life have suggested a possibly significant role for reduced, inorganic forms of phosphorus in bacterial metabolism and as evolutionary precursors of biological phosphate compounds. Reduced inorganic forms of phosphorus include phosphorus acid (H₃PO₃, P(+III)), hypophosphorus acid (H₃PO₂, P(+I)) and various forms of phosphides (P(−III)). Reduced phosphorus has been detected in anaerobic sediments, sewage treatment facilities and in industrial and agricultural processes.Microbiological evidence suggests a significant role for reduced phosphorus species in metabolic processes and raises interesting questions regarding the biogeochemistry of this nutrient in the environment. However, the paucity of data on the presence and cycling of reduced phosphorus compounds in the environment requires attention in order to elucidate the role of these compounds in natural systems. This paper discusses the significance of reduced phosphorus in the natural environment, its speciation and methods of detection.     

Zum oxydativen Abbau von elementarem Phosphor,P4, mit CCl4 und 1,2-Dinucleophilen

On the Oxidative Degradation of Elemental Phosphorus, P₄, with CCl₄ and 1.2-Dinucleophiles In the presence of tertiary amins the interaction of elemental phosphorus with CCl₄ and bifunctionally protic nucleophiles such as 1.2-dioles, pyrocatechol, and 2-aminoalcohols leads to an oxidative degradation of P₄. Depending on the reaction conditions acyclic as well as cyclic and even spirocyclic phosphorus(III) and phosphorus(V) compounds are obtained in variable proportions. The formation of the phosphorus(V) spiro compounds exclusively occurs by oxidizing spirocyclic phosphorus(III) compounds in the way of the Atherton-Todd reaction. A procedure for preparing triethylammonium tris(o-phenylenedioxo)phosphate, 8 , directly from P₄, CCl₄, and pyrocatechol is given.     

Organophosphorus Synthesis Without Phosphorus Trichloride: The Case for the Hypophosphorous Pathway

Abstract

The vast majority of organophosphorus compounds is currently synthesized from phosphorus trichloride (PCl₃), even though the final consumer products do not contain reactive phosphorus–chlorine bonds. In order to bypass phosphorus trichloride, significant interest has been devoted to functionalizing elemental phosphorus (P₄, the precursor to PCl₃), red phosphorus (P_red), or phosphine (PH₃). Yet, other industrial-scale precursors are hypophosphorous derivatives (H₃PO₂ and its alkali salts), but their use as phosphorus trichloride replacements has been completely overlooked. Here, the case is made for an alternative approach to the industrial synthesis of organophosphorus compounds based on hypophosphites.     

Struktur und Bindungscharakter von Ba3P2

The structure of the compound Ba₃P₂ was elucidated. It cristallizes with the inverse Th₃P₄ structure, or strictly, with the inverse Ce₂S₃ structure with randomly distributed phosphorus vacancies. The lattice parameter a₀ is 9.775 Å, the x-ray density dx is 4.52 g/cm³. The coordinate parameter x of the barium sites is 0.0665. Barium is surrounded by 6 phosphorus and 5 barium atoms; the distance of 3,81 Å between 3 of the barium atoms is extremely short. Phosphorus is surrounded by 8 barium atoms. The phosphorus atoms are isolated from one another. The structure is best described as a filling of the octahedral spaces in the bee lattice of the barium metal by phosphorus atoms. The partially negative charge of the phosphorus atoms (P^? + 2e ? P^?? + e) causes a strong distortion of the interstitial lattice. The bonding character of Ba₃P₂ has to be interpreted as mixed metallic-ionic.     

Halogen exchange reactions of silicon tetrafluoride with phosphorus trichloride and phosphoryl chloride

Silicon tetrafluoride undergoes halogen exchange reactions with both phosphorus trichloride and phosphoryl chloride at temperatures of 500–600°C yielding mixed chlorofluorides of silicon and phosphorus. It is interesting to note that, at these high temperatures, PCl₃ undergoes complete exchange to form PF₃ while POCl₃ reacts only with partial substitution, the major products being phosphorus chloride difluoride and silicon trichloride fluoride.     

Produkte von Simultanumsetzungen. Amidoderivate des tetrakoordinierten Phosphors mit P?P-Gerüst

Products of Simultaneous Reactions. Amido Derivatives of Tetracoordinated Phosphorus with P? P Structure P? P compounds, in which phosphorus is present in coordination number four, and contain the amido group bonded to phosphorus, are produced in addition to other oxidation products by reaction of red phosphorus with hydrogen peroxide in aqueous ammonia. Isolation and properties of the compounds [(NH₄)₂(P₂O₄(NH₂)₂] and (NH₄)₃[P₂O₅(NH₂)] are reported.