Scale-Up of Agrochemical Urea-Gypsum Cocrystal Synthesis Using Thermally Controlled Mechanochemistry

Brekalo, Ivana; Martinez, Valentina; Karadeniz, Bahar; Orešković, Patrik; Drapanauskaite, Donata; Vriesema, Hein; Stenekes, Robert; Etter, Martin; Dejanović, Igor; Baltrusaitis, Jonas; Užarević, Krunoslav (2022) Scale-Up of Agrochemical Urea-Gypsum Cocrystal Synthesis Using Thermally Controlled Mechanochemistry. ACS Sustainable Chemistry and Engineering, 10 (20). pp. 6743-6754. ISSN 2168-0485

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Abstract

Atom- and energy-efficient synthesis of a crystalline calcium urea sulfate ([Ca(urea)4]SO4) cocrystal was explored using thermally controlled mechanochemical methods with calcium sulfate compounds containing various amounts of crystalline water (CaSO4·xH2O, x = 0, 0.5, 2). Small-scale (200 mg) experiments in a shaker mill were first performed, and the progress was monitored by in situ Raman spectroscopy and in situ synchrotron powder X-ray diffraction. Time-resolved spectroscopy data revealed that the presence of water in the reagents’ crystalline structure was essential to the reaction and largely determined the observed reactivity of different calcium sulfate forms. Reactions at elevated temperatures were shown to proceed significantly faster on all synthetic scales, while changes in rheology caused by adding external water hindered the reaction progress. The average yield of a 21 mm horizontal twin-screw extruder experiment was ∼5.5 g/min of extrusion (∼330 g/h). Energy consumption during the milling reactions required to achieve complete conversion ranged from 7.6 W h/g at 70 °C for a mixer mill to 3.0 W h/g at a 50 g scale and 4.0 W h/g at a 100 g scale for a planetary mill or 4.0 W h/g at both 70 °C and RT for a twin-screw extruder, showing a significant improvement in energy efficiency at large-scale production. The obtained crystalline cocrystal exhibited a significantly lower solubility in aqueous solutions, nearly 20 times lower per molar basis compared to that of urea. Furthermore, reactive nitrogen emissions in air at 90% relative humidity, measured as NH3, showed slow and nearly linear nitrogen loss for the cocrystal over 90 days, while the same level of emissions was achieved with urea after 1–2 weeks, showing the potential of this cocrystal material as a large-scale nitrogen-efficient fertilizer.

Item Type:	Article
Additional Information:	Izdavač zahtjeva prikaz slijedećeg teksta uz depozitirani rukopis: This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Sustainable Chemistry & Engineering, copyright © 2022 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acssuschemeng.2c00914
Uncontrolled Keywords:	Anions; Calcium; Chemical reactions; Diffraction; Urea; mechanochemistry
Subjects:	NATURAL SCIENCES > Chemistry
Divisions:	Division of Physical Chemistry
Projects:	Project title Project leader Project code Project type Mehanokemijske i bezotopinske strategije za sintezu funkcionalnih poroznih materijala s naprednim fizičko-kemijskim i katalitičkim svojstvima Krunoslav Užarević PZS-2019-02-4129 Znanstveno-istraživački projekti
Depositing User:	dr.sc. Ivana Brekalo
Date Deposited:	30 Nov 2023 14:59
URI:	http://fulir.irb.hr/id/eprint/8205
DOI:	10.1021/acssuschemeng.2c00914

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