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Korkmaz, K., Alemrajabi, M., Rasmuson, Å. C. & Forsberg, K. (2020). Separation of Valuable Elements from NiMH Battery Leach Liquor via Antisolvent Precipitation. Separation and Purification Technology, 234, Article ID 115812.
Open this publication in new window or tab >>Separation of Valuable Elements from NiMH Battery Leach Liquor via Antisolvent Precipitation
2020 (English)In: Separation and Purification Technology, ISSN 1383-5866, E-ISSN 1873-3794, Vol. 234, article id 115812Article in journal (Refereed) Published
Abstract [en]

Rare earth elements (REE) have been selectively recovered from NiMH battery leach liquors by antisolvent precipitation. The active anode material was leached using sulfuric acid. The REE were then separated from the other elements by precipitation as sulfates after addition of either ethanol or 2-propanol (antisolvent). In a second step, Ni and Co are separated as sulfates by the same technique. The concentration of elements in different acid alcohol mixtures at 25 degrees C and -10 degrees C respectively are presented as a function of time after addition of the alcohol, and the optimum conditions for separation of the REE in pure form are presented. Under optimum conditions, 5.6 mol/L (Organic/Aqueous (O/A) volumetric ratio = 0.7) of 2-propanol at 25 degrees C, 82% of the REE have precipitated 3 h after addition of the antisolvent and the purity is 99.9%.

Keywords
Hydrometallurgy, Anti-solvent crystallization, NiMH battery recycling, Rare earth recovery
National Category
Chemical Process Engineering
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-256457 (URN)10.1016/j.seppur.2019.115812 (DOI)000491627200002 ()2-s2.0-85072275062 (Scopus ID)
Funder
Swedish Energy Agency
Note

QC 20190902

Available from: 2019-08-23 Created: 2019-08-23 Last updated: 2019-11-08Bibliographically approved
Soto, R. & Rasmuson, Å. C. (2019). Crystal Growth Kinetics of Piracetam Polymorphs in Ethanol and Isopropanol. Crystal Growth & Design, 19(8), 4273-4286
Open this publication in new window or tab >>Crystal Growth Kinetics of Piracetam Polymorphs in Ethanol and Isopropanol
2019 (English)In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 19, no 8, p. 4273-4286Article in journal (Refereed) Published
Abstract [en]

The crystal growth kinetics of two different polymorphs of Piracetam have been investigated in ethanol and isopropanol. Isothermal seeded desupersaturation experiments were carried out at supersaturation ratios below 1.2 within the range of temperature 283-308 K. Liquid concentration was determined by in situ ATR-FTIR spectroscopy by a calibration-free method using principal component analysis. The power law equation and the BCF and B+S models were fitted to the experimental desupersaturation data by nonlinear optimization. The growth rates ranged 10(-7)-10(-8) m/s, the growth rate order is clearly higher than unity, and the activation energies are in the range 39-66 kJ/mol for all the systems studied suggesting surface integration control. The growth of the metastable polymorph is faster than that of the stable form in both solvents. The crystal growth proceeds faster in ethanol than in isopropanol for both polymorphs. The solid-liquid interfacial energy is lower for the metastable form and is for both forms lower in ethanol than in isopropanol. The surface diffusion mass transfer rate is higher for the metastable form compared to the stable form and higher in ethanol than in isopropanol.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-257459 (URN)10.1021/acs.cgd.8b01733 (DOI)000480499600011 ()2-s2.0-85070920349 (Scopus ID)
Note

QC 20190830

Available from: 2019-08-30 Created: 2019-08-30 Last updated: 2019-08-30Bibliographically approved
Lynch, A., Verma, V., Zeglinski, J., Bannigan, P. & Rasmuson, Å. C. (2019). Face indexing and shape analysis of salicylamide crystals grown in different solvents. CrystEngComm, 21(16), 2648-2659
Open this publication in new window or tab >>Face indexing and shape analysis of salicylamide crystals grown in different solvents
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2019 (English)In: CrystEngComm, ISSN 1466-8033, E-ISSN 1466-8033, Vol. 21, no 16, p. 2648-2659Article in journal (Refereed) Published
Abstract [en]

The effect of solvent on salicylamide's crystal habit was investigated. Crystals grown experimentally in acetone, acetonitrile and methanol matched the attachment energy predicted rectangle plate vacuum habit. However, in ethyl acetate irregular hexagonal plate crystals form. This change in habit was found to be caused by the stunted growth of specific crystal faces during the crystallisation process. Single crystal and powder X-ray diffraction was carried out to rule out the possibility of a new polymorph. Given no new polymorphs were discovered, the changing habit makes face indexing of experimentally grown crystals difficult. A combination of experimental and modelling prediction tools was employed for the face indexing process. The interfacial angle between faces combined with preferred orientation P-XRD was found to be the most accurate and reliable method leading to successful identification of each salicylamide crystal face. The surface chemistry of each face was examined on a molecular level with insights into the possible growth attachment sites being made. It is deduced that ethyl acetate is adsorbed more strongly on the faces, the increased size of which, can explain the shape change.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-251835 (URN)10.1039/c9ce00049f (DOI)000465358900004 ()2-s2.0-85064403750 (Scopus ID)
Note

QC 20190529

Available from: 2019-05-29 Created: 2019-05-29 Last updated: 2019-06-11Bibliographically approved
Ahuja, D., Svärd, M. & Rasmuson, Å. C. (2019). Investigation of solid-liquid phase diagrams of the sulfamethazine-salicylic acid co-crystal. CrystEngComm, 21(18), 2863-2874
Open this publication in new window or tab >>Investigation of solid-liquid phase diagrams of the sulfamethazine-salicylic acid co-crystal
2019 (English)In: CrystEngComm, ISSN 1466-8033, E-ISSN 1466-8033, Vol. 21, no 18, p. 2863-2874Article in journal (Refereed) Published
Abstract [en]

The influence of temperature and solvent on the solid-liquid phase diagram of the 1 : 1 sulfamethazinesalicylic acid co-crystal has been investigated. Ternary phase diagrams of this co-crystal system have been constructed in three solvents: methanol, acetonitrile and a 7 : 3 (v/v) dimethylsulfoxide-methanol mixture, at three temperatures. The system exhibits congruent dissolution in acetonitrile and the co-crystal solubility has been determined by a gravimetric technique. The Gibbs energy of co-crystal formation from the respective solid components has been estimated from solubility data, together with the corresponding enthalpic and entropic component terms. The Gibbs energy of formation ranges from -5.7 to -7.7 kJ mol -1, with the stability increasing with temperature. In methanol and the DMSO-methanol mixture, the co-crystal dissolves incongruently. It is shown that the solubility ratio of the pure components cannot be used to predict with confidence whether the co-crystal will dissolve congruently or incongruently. The size of the region where the co-crystal is the only stable solid phase is inversely related to the pure component solubility ratio of salicylic acid and sulfamethazine.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2019
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-252602 (URN)10.1039/c9ce00124g (DOI)000467736200015 ()2-s2.0-85065525446 (Scopus ID)
Note

QC 20190610

Available from: 2019-06-10 Created: 2019-06-10 Last updated: 2019-06-10Bibliographically approved
Zeglinski, J., Kuhs, M., Devi, K. R., Khamar, D., Hegarty, A. C., Thompson, D. & Rasmuson, Å. C. (2019). Probing Crystal Nucleation of Fenoxycarb from Solution through the Effect of Solvent. Crystal Growth & Design, 19(4), 2037-2049
Open this publication in new window or tab >>Probing Crystal Nucleation of Fenoxycarb from Solution through the Effect of Solvent
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2019 (English)In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 19, no 4, p. 2037-2049Article in journal (Refereed) Published
Abstract [en]

Induction time experiments, spectroscopic and calorimetric analysis, and molecular modeling were used to probe the influence of solvent on the crystal nucleation of fenoxycarb (FC), a medium-sized, flexible organic molecule. A total of 800 induction times covering a range of supersaturations and crystallization temperatures in four different solvents were measured to elucidate the relative ease of nucleation. To achieve similar induction times, the required thermodynamic driving force, RT In S, increases in the order: ethyl acetate < toluene < ethanol < isopropanol. This is roughly matched by the order of interfacial energies calculated using the classical nucleation theory. Solvent solute interaction strengths were estimated using three methods: solvent-solute enthalpies derived from calorimetric solution enthalpies, solvent-solute interactions from molecular dynamics simulations, and the FTIR shifts in the carbonyl stretching corresponding to the solvent solute interaction. The three methods gave an overall order of solvent solute interactions increasing in the order toluene < ethyl acetate < alcohols. Thus, with the exception of FC in toluene, it is found that the nucleation difficulty increases with stronger binding of the solvent to the solute.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2019
National Category
Other Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-251212 (URN)10.1021/acs.cgd.8b01387 (DOI)000463843600004 ()2-s2.0-85063372465 (Scopus ID)
Note

QC 20190724

Available from: 2019-07-24 Created: 2019-07-24 Last updated: 2019-07-24Bibliographically approved
Alemrajabi, M., Rasmuson, Å. C., Korkmaz, K. & Forsberg, K. (2019). Processing of a rare earth phosphate concentrate obtained in the nitrophosphate process of fertilizer production. Hydrometallurgy, 189, Article ID 105144.
Open this publication in new window or tab >>Processing of a rare earth phosphate concentrate obtained in the nitrophosphate process of fertilizer production
2019 (English)In: Hydrometallurgy, ISSN 0304-386X, E-ISSN 1879-1158, Vol. 189, article id 105144Article in journal (Refereed) Published
Abstract [en]

In this study, different processes have been developed and applied to treat a rare earth phosphate concentrate obtained within the nitrophosphate process of fertilizer production. Methods to remove impurities such as Fe and Ca have been investigated as well as to separate the phosphorous and thereby facilitate dissolution of the rare earth elements (REE). These methods include thermal treatment with sodium hydroxide and sodium double sulphate precipitation with and without alkaline conversion, followed by selective dissolution in different acids. The proposed processes were compared and analyzed from the perspective of introducing an appropriate intermediate product for further individual REE separation. The results have shown that after thermal treatment with NaOH at 400 °C, the phosphorous can be removed from the rare earth phosphate concentrate by water leaching. Investigation of different REE phosphate concentrates demonstrated that mixed Ca and REE phases, e.g. REEmCan(PO4)3m+2n/3 and CaHPO4 are less likely to dephosphorize than REE(PO4).nH2O and FePO4.H2O under these conditions. The recovery of REE to a mild acidic solution is limited by the presence of remaining phosphate ions and by the formation of REE oxide phases during the thermal treatment. The results also show that a solution containing 40 g/L REE; free of phosphorous, calcium and iron can be obtained after reprecipitation of the rare earth phosphate concentrate as sodium rare earth double sulphates followed by alkaline conversion with sodium hydroxide and dissolution in nitric acid.

Place, publisher, year, edition, pages
Elsevier, 2019
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-257525 (URN)10.1016/j.hydromet.2019.105144 (DOI)2-s2.0-85073007994 (Scopus ID)
Note

QC 20191115

Available from: 2019-09-01 Created: 2019-09-01 Last updated: 2019-11-15Bibliographically approved
Bodnár, K., Hudson, S. P. & Rasmuson, Å. C. (2019). Promotion of Mefenamic Acid Nucleation by a Surfactant Additive, Docusate Sodium. Crystal Growth and Design, 19(2), 591-603
Open this publication in new window or tab >>Promotion of Mefenamic Acid Nucleation by a Surfactant Additive, Docusate Sodium
2019 (English)In: Crystal Growth and Design, Vol. 19, no 2, p. 591-603Article in journal (Refereed) Published
Abstract [en]

The influence of docusate sodium (DOSS) on the nucleation of mefenamic acid (MEF) has been studied in different dimethylacetamide (DMA)-water mixtures. A series of induction time experiments were conducted under moderate supersaturations, varying the solvent composition and the concentration of DOSS. In 40% DMA-60% water, the presence of 0.1 and 0.2 mg/mL DOSS increased the nucleation rate. Evaluating the results by the classical nucleation theory reveals that the pre-exponential factor (A) increases by approximately 50% while the interfacial energy is essentially uninfluenced. It is also found that the crystal growth rate becomes higher in the presence of DOSS. It is thus hypothesized that transport and desolvation of MEF molecules are facilitated in the presence of DOSS. With increasing amount of DMA in the binary solvent mixture, the influence of DOSS appears to decrease. 

National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-260436 (URN)10.1021/acs.cgd.8b00995 (DOI)000458348000013 ()2-s2.0-85060043098 (Scopus ID)
Note

QC 20190930

Available from: 2019-09-30 Created: 2019-09-30 Last updated: 2019-09-30Bibliographically approved
Hjorth, T., Svärd, M. & Rasmuson, Å. C. (2019). Rationalising crystal nucleation of organic molecules in solution using artificial neural networks. CrystEngComm, 21(3), 449-461
Open this publication in new window or tab >>Rationalising crystal nucleation of organic molecules in solution using artificial neural networks
2019 (English)In: CrystEngComm, ISSN 1466-8033, E-ISSN 1466-8033, Vol. 21, no 3, p. 449-461Article in journal (Refereed) Published
Abstract [en]

In this study, the method of artificial neural networks (ANNs) is applied to analyse the effect of various solute, solvent, and solution properties on the difficulty of primary nucleation, without bias towards any particular nucleation theory. Sets of ANN models are developed and fitted to data for 36 binary systems of 9 organic solutes in 11 solvents, using Bayesian regularisation without early stopping and 6-fold cross validation. An initial model set with 21 input parameters is developed and analysed. A refined model set with 10 input parameters is then evaluated, with an overall improvement in accuracy. The results indicate partial qualitative consistency between the ANN models and the classical nucleation theory (CNT), with the nucleation difficulty increasing with an increase in mass transport resistance and a reduction in solubility. Notably, some parameters not included in CNT, including solute molecule bond rotational flexibility, the entropy of melting of the solute, and intermolecular interactions, also exhibit explanatory importance and significant qualitative effect relationships. A high entropy of melting and solute bond rotational flexibility increase the nucleation difficulty. Stronger solute-solute or solvent-solvent interactions are correlated with a facilitated nucleation, which is reasonable in the context of desolvation. A dissimilarity between solute and solvent hydrophobicities is connected with an easier nucleation.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2019
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-244116 (URN)10.1039/c8ce01576g (DOI)000457296300006 ()2-s2.0-85060029104 (Scopus ID)
Funder
Swedish Research Council, 2015-5240
Note

QC 20190219

Available from: 2019-02-19 Created: 2019-02-19 Last updated: 2019-05-02Bibliographically approved
Svärd, M., Zeng, L., Valavi, M., Krishna, G. R. & Rasmuson, Å. C. (2019). Solid and Solution State Thermodynamics of Polymorphs of Butamben (Butyl 4-Aminobenzoate) in Pure Organic Solvents. Journal of Pharmaceutical Sciences, 108(7), 2377-2382
Open this publication in new window or tab >>Solid and Solution State Thermodynamics of Polymorphs of Butamben (Butyl 4-Aminobenzoate) in Pure Organic Solvents
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2019 (English)In: Journal of Pharmaceutical Sciences, ISSN 0022-3549, E-ISSN 1520-6017, Vol. 108, no 7, p. 2377-2382Article in journal (Refereed) Published
Abstract [en]

The solubility of butamben has been measured gravimetrically in pure methanol, 1-propanol, 2-propanol, 1-butanol, and toluene over the temperature range 268-298 K. Polymorph transition and melting temperatures, associated enthalpy changes, and the heat capacity of the solid forms and the supercooled melt have been measured by differential scanning calorimetry. Based on extrapolated calorimetric data, the Gibbs energy, enthalpy and entropy of fusion, and the activity of solid butamben (the ideal solubility) have been calculated from below ambient temperature up to the melting point. Activity coefficients of butamben at equilibrium in the different solvents have been estimated from solubility data and the activity of the solid, revealing that all investigated systems exhibit positive deviation from Raoult's law. Solubility data are well correlated by a semiempirical regression model. On a mass basis, the solubility is clearly higher in methanol than in the other solvents, but mole fraction solubilities are very similar across all 5 solvents. The 2 known polymorphs are enantiotropically related, and the transition point is located at 283 K. Polymorph interconversions occur within 0.3 K of the transition point even in the solid state, and the 2 forms exhibit strong similarities in investigated properties.

Place, publisher, year, edition, pages
Elsevier, 2019
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-260000 (URN)10.1016/j.xphs.2019.02.013 (DOI)000477753400018 ()30807760 (PubMedID)2-s2.0-85063011446 (Scopus ID)
Note

QC 20191004

Available from: 2019-09-30 Created: 2019-09-30 Last updated: 2019-10-29Bibliographically approved
Lynch, A., Jia, L., Svärd, M. & Rasmuson, Å. C. (2018). Crystal Growth of Salicylamide in Organic Solvents. Crystal Growth & Design, 18(12), 7305-7315
Open this publication in new window or tab >>Crystal Growth of Salicylamide in Organic Solvents
2018 (English)In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 18, no 12, p. 7305-7315Article in journal (Refereed) Published
Abstract [en]

Salicylamide was used as a model active pharmaceutical compound to investigate the crystal growth process and its associated kinetics. The impact of organic solvent, supersaturation, and temperature on the crystal growth was studied. The multiparticle crystal growth kinetics were determined using the seeded isothermal desupersaturation method and modeled using several growth rate equations, using different representations of the driving force. The results showed that crystal growth is significantly influenced by experimental conditions. Within the range of experimental conditions, the growth kinetics was affected strongly by the temperature and to a lesser degree by solvent choice. Comparison of the growth order parameter reveals a surface integration controlled growth. Higher than expected activation energies indicate desolvation as a governing process. A comparison of the influence of the solvent on the crystal growth of salicylamide against previously published approximate data at much higher supersaturation shows good agreement, but the influence on the interfacial energy is opposite to that observed for crystal nucleation. In a detailed comparison with crystal growth data of salicylic acid, there is a consistency in the influence of the solvent on the crystal growth of the two compounds. Salicylamide growth kinetics is more strongly affected by increasing temperature than salicylic acid.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-240754 (URN)10.1021/acs.cgd.8b00767 (DOI)000452694000010 ()2-s2.0-85057864398 (Scopus ID)
Note

QC 20190107

Available from: 2019-01-07 Created: 2019-01-07 Last updated: 2019-01-07Bibliographically approved
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ORCID iD: ORCID iD iconorcid.org/0000-0003-1790-2310

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