scholarly journals Analysis and Prediction of Corrosion of Refractory Materials by Sodium Salts during Waste Liquid Incineration—Thermodynamic Study

Materials ◽  
2020 ◽  
Vol 13 (21) ◽  
pp. 4729
Author(s):  
Guishi Cheng ◽  
Ying Zhao ◽  
Fei Long ◽  
Jiahe Zhang ◽  
Tengfei Zhao ◽  
...  

Incineration of high-content sodium salt organic waste liquid will corrode the refractory material in the incinerator, causing the refractory material to peel off and be damaged. A thermodynamics method was used to study the thermodynamic properties of three common sodium salts (NaCl, Na2CO3 and Na2SO4) on the corrosion of refractory materials (MgO·Cr2O3, MgO·Al2O3, Al2O3, MgO and Cr2O3). The results determined that MgO has the best corrosion resistance and is not corroded by the three sodium salts. On this basis, the thermodynamic corrosion experiments of NaCl corrosion of magnesium oxide at three temperatures of 600, 1000 and 1200 °C were carried out. Analysis of the corrosion product by X-ray diffraction (XRD) showed no corrosion product formation. Studies have shown that thermodynamic calculation can accurately predict the thermodynamic mechanism of alkali metal corrosion to refractory materials, and MgO is a good anti-alkali metal corrosion refractory material.

Materials ◽  
2018 ◽  
Vol 11 (11) ◽  
pp. 2197
Author(s):  
Ying Zhao ◽  
Guishi Cheng ◽  
Yu Xiang ◽  
Fei Long ◽  
Changqing Dong

The corrosion of refractories by sodium salts in waste liquid at high temperature has become a serious problem. This paper focuses on the thermodynamic characterization of sodium carbonate (Na2CO3) corrosion of six refractories by FactSage modelling in combination with X-ray diffraction (XRD). Three of the refractories are oxides (Fe2O3, Al2O3, and Cr2O3), and the other three are synthetics spinels (magnesium chromium, MgO·Cr2O3; magnesioferrite, MgO·Fe2O3; and, magnesium aluminium, MgO·Al2O3). First, thermodynamic simulations were carried out with the FactSage thermodynamics model using the reaction package to predict the direction of the Na2CO3 corrosion reaction in terms of the Gibbs free energy. Then, the reactions between the six refractories and Na2CO3 were conducted through a series of refractories/Na2CO3 reaction tests. The XRD analytical method was used to describe and understand the chemistry and interpret mineral matter transformation. The products of the tests were also determined by X-ray diffraction and the experimental observations were compared with the results of the thermodynamic simulations. Furthermore, the strength of sodium corrosion of the refractory materials was comprehensively discussed. The results show that MgO·Al2O3 has the best thermal stability and it is hard to corrode by Na2CO3, while the chrome-containing refractory reacts easily with Na2CO3 with a considerably high amount of corrosion product at a temperature of 600 °C. These experimental results are in agreement with the thermodynamic calculations.


2020 ◽  
Vol 235 (8-9) ◽  
pp. 275-290
Author(s):  
Michael Schwarz ◽  
Pirmin Stüble ◽  
Katharina Köhler ◽  
Caroline Röhr

AbstractFour new mixed-valent chain alkali metal (A) sulfido ferrates of the general structure family ${A}_{1+x}\left[{\text{Fe}}_{x}^{\text{II}}{\text{Fe}}_{1-x}^{\text{III}}{\text{S}}_{2}\right]$ were synthesized in the form of tiny green-metallic needles from nearly stoichiometric melts reacting elemental potassium with natural pyrite (A = K) or previously prepared Rb2S/Cs2S2 with elemental iron and sulfur (A = Rb/Cs). The crystal structures of the compounds were determined by means of single crystal X-ray diffraction: In the (3+1)D modulated structure of K7.15[FeS2]4 (space group Ccce(00σ3)0s0, a = 1363.87(5), b = 2487.23(13), c = 583.47(3) pm, q = 0,0,0.444, R1 = 0.055/0.148, x = 0.787), a position modulation of the two crystallographically different undulated ${}_{\infty }{}^{1}\left[{\text{FeS}}_{4/2}\right]$ tetrahedra chains and the surrounding K cations is associated with an occupation modulation of one of the three potassium sites. In the case of the new monoclinic rubidium ferrate Rb4[FeS2]3 (x = $\frac{1}{3}$; space group P21/c, a = 1640.49(12), b = 1191.94(9), c = 743.33(6) pm, β = 94.759(4)°, Z = 4, R1 = 0.1184) the undulation of the tetrahedra chain is commensurate, the repetition unit consists of six tetrahedra. In the second new Rb ferrate, Rb7[FeS2]5 (x = 0.4; monoclinic, space group C2/c, K7[FeS2]5-type; a = 2833.9(2), b = 1197.36(9), c = 744.63(6) pm, β = 103.233(4)°, Z = 4, R1 = 0.1474) and its isotypic mixed Rb/Cs-analog Rb3.6Cs3.4[FeS2]5 (a = 2843.57(5), b = 1226.47(2), c = 759.890(10) pm, β = 103.7170(9)°, R1 = 0.0376) the chain buckling leads to a further increased repetition unit of 10 tetrahedra. For all mixed-valent ferrates, the Fe–S bond lengths continuously increase with the amount (x) of Fe(II). The buckling of the chains is controlled through the local coordination of the S atoms by the variable number of A cations of different sizes.


1978 ◽  
Vol 56 (24) ◽  
pp. 3078-3083 ◽  
Author(s):  
David Victor Fikis ◽  
Keith Walter Heckley ◽  
William John Murphy ◽  
Robert Anderson Ross

The oxygen exchange reaction between O2/C18O2 and the surfaces of vanadium pentoxide and promoted vanadium pentoxide catalysts has been studied in a circulation system using a quartz differential reactor. Isotopic compositions were analysed with an in-line mass spectrometer. Alkali metal sulphates, Li to Cs, were added to the pentoxide as individual promoters at a concentration level of 9 mol % and the effect of variation of promoter concentration was examined with melts containing potassium sulphate at additional levels of 1, 2, and 5 mol%. The structures of the solids were studied by X-ray diffraction and by ATR and transmission infrared spectroscopy. The latter results have been used to explain the two activity series for the exchange rates: (i)V2O5 < Na < Li < K < Rb < Cs (melts) and (ii) V2O5 < 1 mol% < 2 mol% < 5 mol% < 9 mol% (K), in terms of additive effects on the relative abundance and strength of identified vanadium/oxygen linkages in the surfaces of the catalysts.


Author(s):  
Vaughan H. Stott ◽  
Alfred Hilliard

In the course of an investigation on refractory materials, in which the identification of minerals by their X-ray diffraction patterns had a prominent place, an interesting observation was made on a zircon of gem quality which was lent to us by the courtesy of Mr. B. W. Anderson.It may be recalled that the existence of three allotropes has been postulated in order to explain the considerable variations of physical properties which are found when comparing different specimens of zircon. In particular, densities ranging from 3·95 to 4·86 have been observed, the density of zirconium silicate, calculated from X-ray measurements, being 4·71.


1978 ◽  
Vol 56 (14) ◽  
pp. 1874-1880 ◽  
Author(s):  
Philippe Joubert ◽  
Roland Bougon ◽  
Bernard Gaudreau

The oxypentafluorouranates(VI) MUOF5, where M = NH4, K, Rb, Cs, have been synthetized from reaction of UOF4 with the ammonium or corresponding alkali metal fluoride in liquid SO2. According to X-ray diffraction, Raman and infrared spectroscopy, and from an isomorphism with the corresponding hexafluorouranates(V) MUF6, two different environments around the uranium atom are observed. In CsUOF5 the five fluorine atoms and the oxygen around the uranium result in a pseudo-octahedral surrounding whereas for the other complexes (M = NH4, K, Rb) each uranium is surrounded by eight light atoms forming a dodecahedron. In this structure the dodecahedra are linked together by fluorine atoms to form infinite chains. The UOF5− ion has been characterized by vibrational spectroscopy in the solid state. The proposed assignment, which was made with the assumption of a C4v symmetry of the UOF5− ion, was confirmed by a force constant calculation. From these data and contrary to the values reported for comparable oxypentafluoroanions, the axial fluorine is found to be less ionic than the equatorial ones.


2000 ◽  
Vol 55 (6) ◽  
pp. 495-498 ◽  
Author(s):  
Katerina E. Gubina ◽  
Vladimir A. Ovchynnikov ◽  
Vladimir M. Amirkhanov ◽  
Viktor V. Skopenkoa ◽  
Oleg V. Shishkinb

N,N′-Tetramethyl-N"-benzoylphosphoryltriamide (I) and dimorpholido-N-benzoylphosphorylamide (II), and their sodium salts Nal, Nall were synthesized and characterized by means of IR and 1H, 31P NMR spectroscopy. The structures of I, II were determined by X-ray diffraction: I monoclinic, space group P2i/c with a = 10.162(3), b= 11.469(4), c = 12.286(4) Å , β = 94.04°, V = 1428.4(8) A 3, Z = 4, p(calcd) = 1.187 g/cm3; II monoclinic, space group C2/c with a = 15.503(4), b = 10.991(3), c = 22.000(6) Å, β = 106.39°, V = 3596.3(17) Å3, Z = 8, p(calcd.) = 1.253 g/cm3. The refinement of the structures converged at R = 0.0425 for I, and R = 0.068 for II. In both structures the molecules are connected into centrosymmetric dimers via hydrogen bonds formed by the phosphorylic oxygen atoms and hydrogen atoms of amide groups.


2000 ◽  
Vol 626 ◽  
Author(s):  
Svilen Bobev ◽  
Slavi C. Sevov

ABSTRACTWe have synthesized large single crystals of clathrate-II compounds with frameworks of silicon and germanium by employing mixed alkali metal countercations. The combinations of alkali metals are rationally selected in order to fit the different cages of the clathrate-II structure. This approach leads to the following stoichiometric and fully “stuffed” compounds: Cs8Na16Si136, Cs8Na16Ge136, Rb8Na16Si136 and Rb8Na16Ge136. The structures and the corresponding Si-Si and Ge-Ge distances are elucidated and established with high accuracy from extensive single crystal X-ray diffraction work. The compounds are stoichiometric, metallic, and are very stable at a variety of extreme conditions such as heat, concentrated acids, hydrothermal treatment etc. No evidence was found for vacancies in the silicon and germanium networks or partial occupancies of the alkali metal sites. The stoichiometry of these fully “stuffed” clathrates is consistent with the measured temperature independent Pauli paramagnetism, supported also by the conductivity measurements on single crystals and thermopower measurements on pellets. A new compound with novel clathrate-like structure forms when small and large cations are combined with tin. The new materials, A6Na18Sn46 (A = K, Rb, Cs), are made of clathrate layers and the interlayer space filled with Sn4-tetrahedra and alkali-metal cations. Its formula can be rationalized as A6Na6Sn34 + 3·Na4Sn4 (one clathrate layer and three tin tetrahedra). The compound is stable in air and is being currently tested at other conditions. Detailed measurements of its transport properties are under way.


1990 ◽  
Vol 68 (8) ◽  
pp. 1283-1292 ◽  
Author(s):  
E. Andrukaitis ◽  
P. W. M. Jacobs ◽  
J. W. Lorimer

Coherent deposits of oriented, crystalline MxM′4−xV6O16+δ, with M, M′ = K, Rb, Cs, or NH4, 0.0 ≤ x ≤4.0 and 0.00 ≤ δ ≤ 0.13, have been prepared electrochemically on various conducting substrates from metavanadate solutions containing ammonium or alkali metal cations, singly or in combination. Chemical analysis and X-ray diffraction show that the deposits consist of a continuous series of mixed crystals based on the isomorphic end members M4V6O16 and M′4V6O16.The deposits can be oxidized electrochemically, with removal of M and M′ atoms, and the products can be used as cathodes for insertion of lithium, with the largest capacity achieved about 1.0 mol% of total vanadium. Cycling of the electrodes improves capacity, with insertion of lithium reaching 25 mol% of total vanadium. This gain in capacity results from further removal of alkali metal or ammonium ions from the electrode during the oxidation step of the cycling process.The results extend the range of composition of homogeneous phases in the system (NH4)2O–K2O–V2O4–V2O5. Keywords: alkali metal hexavanadates, electrochemical preparation.On a préparé des dépôts cohérents qui contiennent des cristaux orientés de MxM′4−xV6O16+δ, avec M, M′ = K, Rb, Cs ou NH4, 0,0 ≤ x ≤4,0 et 0,00 ≤ δ ≤ 0,13, par la méthode de voltammétrie cyclique sur des substrats divers et dans des solutions de metavanadates qui contiennent des cations des métaux alcalins ou d'ammonium seuls ou des combinations de tels ions. L'analyse chimique et la diffraction des rayons X ont démontré que les dépôts comprennent une série continue de cristaux mixtes basée sur les membres terminaux M4V6O16 et M′4V6O16.


1989 ◽  
Vol 44 (3) ◽  
pp. 373-374 ◽  
Author(s):  
Horst Sabrowsky ◽  
Karin Hippler ◽  
Petra Vogt

The colourless compound Na4OI2: has been prepared and characterized by X-ray diffraction techniques. Na4OI2: crystallizes in a tetragonal body-centered lattice with a = 467.7(1) pm, c = 1602.0(3) pm (Z = 2) and is isotypic to K2NiF4.


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