Kinetic study on selective extraction of HCl and H_3PO_4 in a microfluidic device

In the extraction method for preparing KH2PO4, one of the key processes is the selective extraction of HCI over H3PO4. In our work, extraction kinetic studies have been carried out in a microfluidic device with a coaxial microchannel, using the extractant of 33.3% （by volume） trioctylamine （TOA） dissolved in n-octanol, with differ- ent aqueous phases： the HCI solution, the H3P04 solution, and H3PO4 and KCI solutions of different concentra- tions. The changes of the extraction efficiency of HC1 and H3P04 and the selectivity for HC1 along with the residence time were investigated. We found that fast extraction kinetics could be realized in microfluidic devices, and that HC1 could be extracted faster than H3P04 due to smaller mass transfer resistance and much stronger re- action between HCI and TOA. For the extraction of H3PO4 and KC1 solutions, the selectivity for HC1 first increased and then decreased when TOA was in excess of H3PO4 in the initial feeds, and in contrast, always increased when H3PO4 was in excess of TOA in the initial feeds. The diverse changes of selectivity for HCI along with the residence time indicate that a dynamic control of selectivity in microfluidic devices may be important and accessible for im- proving the KH2P04 conversion efficiency in extraction method.

Effects of temperature and phosphoric acid addition on the solubility of iron phosphate dihydrate in aqueous solutions

As important controlling factors for the synthesis of iron phosphate materials by liquid-phase precipitation, the solubilities of iron phosphate dihydrate were systematically measured at H3PO4 concentrations from 1.13 wt% to 10.7 wt% temperature from 298.15 to 363.15 K, and atmosphere pressure in this work. The solubility was found to increase 5 orders of magnitude or more with increasing the concentration of phosphoric acid, and de- crease 1 to 2 orders of magnitude with increasing the equilibrium temperature. The phosphoric acid addition and temperature were found to affect the solubility of iron phosphate dihydrate by the formation or dissociation of coordination species, which could further accelerate the phase transformation from the amorphous iron phosphate dihydrate to orthorhombic iron phosphate dehydrate by dissolution-recrystallization mechanism. The high dependences of the solubility of iron phosphate materials on HsPO4 concentration and temperature were also well predicted by calibration equations, which are meaningful for quantitatively understanding the precipitation process and sequential crystalline structure transformation and pursuing a rational strategy for syn- thesizing specific iron phosphate materials.

Relationship between breakthrough curve and adsorption isotherm of Ca(Ⅱ)imprinted chitosan microspheres for metal adsorption

In this work, an equilibrium-dispersion model was successfully established to describe the breakthrough performance of Ca（Ⅱ） imprinted chitosan （Ca（Ⅱ）-CS） microspheres packed column for metal adsorption, and the assumptions of Langmuir isotherms and axial dispersion controlled mass transfer process were confirmed. The axial dispersion coefficient in Ca（Ⅱ）-CS microspheres packed column was found to be almost proportional to the linear velocity and fit for prediction through single breakthrough test. Sensitivity analysis for breakthrough curve indicated the axial dispersion coefficient as well as Langmuir coefficient was sensitive variable for deep removal requirement. The retrieval of the adsorption isotherms of Ca（Ⅱ）-CS microspheres from breakthrough curve was fulfilled by modelling calibration. A strategy based on the correlation between adsorption isotherms and breakthrough performance was further proposed to simplify the column adsorption design using absorbents with small/uniform size and fast adsorption kinetics like Ca（Ⅱ）-CS microspheres to cut down the gap between lab and industry.

Synthesis of epichlorohydrin from 1,3-dichloropropanol using solid base

In this work, the synthesis of epichlorohydrin(ECH) from 1,3-dichloropropanol(DCP) by using solid sodium hydroxide(NaOH) is carefully investigated. Inert organic solvent, 1-octanol, is introduced to ensure reaction intensity under control. The reaction performances with respect to apparent kinetics and selectivity are determined to explore optimized reaction conditions and confirm potentials for enhancing productivity in one batch. The dissolution and liquid phase reaction mechanism and instant reaction assumption are proposed and verified through process analysis. A process design towards free additional water is schematically figured out to manipulate solid NaOH, by-product,and unreacted starting materials to realize a nearly closed circuit. This process allows high selectivity over 97% and complete DCP conversion at 323.2 K within a reaction time less than 20 min. Other advantages include near-zero wastewater emission, economically possible NaOH regeneration from NaCl, and robust operating condition window.

Simulation of the mixing process in a straight tube with sudden changed cross-section

In this work, we revised the expression of mixing intensity to describe the mixing output through a cross section in a flow system by considering heterogeneity of flow field, and carefully investigated the mixing process along a straight tube with expanding/contracting cross section by simulation method. The simulation results show that a sudden expansion of cross section has remarkable mixing intensification effect within a limited period(on the sub-second scale) or tube-length(on the millimeter scale), corresponding to the generation of considerable local vortices determined by both the flow capacity and the ratio of cross section change; a sudden contraction of cross section has instantaneous but weak mixing intensification effect; through introducing a local expansion structure with proper length, as the combination of sudden expansion and sudden contraction, their mixing intensification effects could be superposed. Besides, the rationality and importance are experimentally verified to explore the time profile of mixing intensity and carry out the vortex analysis by simulation for enhancing the selectivity of a complicated reaction system. These progresses may lead to more meaningful quantitative description of mixing process in a flow microreactor for some specific chemical processes.

Highly efficient and flexible preparation of water-dispersed Fe3O4 nanoclusters using a micromixer

Solvent exchange is widely used to synthesize magnetic nanoclusters (MNCs).However,it remains a challenge to increase the production and decrease the addition ofsurfactants,both of which are important for the application and functionalization of MNCs.Herein,we use a rapid and tunable mixing method to control the assembly of Fe3O4 nanoparticles.This method involves shear-mixing in a channel of a Tjunction micromixer.Smaller and more monodisperse MNCs were synthesized with less surfactant,when compared with conventional bulk synthesis.Varying the mixing rate and the formula of the magnetic suspension allowed for the flexible adjustment of the nanocluster size while maintaining a uniformly sized MNCs.The flow synthesis and ease of scale-up make this method potentially suitable for broad industrial application.

Influence of coagulation bath on morphology of cellulose membranes prepared by NMMO method

To control the morphology of cellulose membranes used for separation,they were prepared by the NMMO method using water,methanol,ethanol and their binary solution as coagulation baths.Morphologies of the surface and cross section of dry membranes were observed.The pore structure parameters of wet membranes were determined.By comparison,the process and mechanism of pore formation in dry membranes were suggested,and the relativity of cellulose crystal size to average pore diameter in wet membranes and their influences were discussed.The results show that the morphology of dry membranes is clearly varied with coagulation baths,while the porosity of wet membranes is almost constant.Porous structures can appear in the compact region of dry membranes due to swelling from water.These pores have a virtual effect on the average pore diameter of wet membranes.By changing the composition of coagulation baths,the microstructure of cellulose membranes in a dry or wet environment can be adjusted separately.

Tailoring morphology and bulk density of magnesium ethoxide particles by adding n-hexane and silicone oil

In this work,we used the in ert substances silic one oil a nd n-hexane to modulate the solve nt environ ment,and in so doing tailor the preparation of magnesium ethoxide(Mg(0Et)2)particles.We found the following:(1)non polar n-hexane mainly modulates the polarity of the solvent to control the precipitation rate and size of the Mg(OEt)2 seeds,thereby triggering accelerated nucleation to form small primary particles;and(2)silicone oil(relatively high polarity and viscosity)facilitates the growth and agglomeration stage,to improve inter-particle dispersion and obtain relatively uniform Mg(OEt)2 particles.We summarized these findings in a comm on mechanism for preparing Mg(OEt)2 particles with uniform morphology,small size,and high bulk density as per the synergistic effect of n-hexane and silicone oil.The ratios of silicone oil end n-hexane are flexible,and afford various regular and well-dispersed Mg(OEt)2 particles that are 5-30μm in size and 0.2-0.7 g/cm^3 in bulk density.The nanoparticles thus have the potential to serve in diverse applications such as catalysis.

Preparation and ion exchange properties of egg-shell glass beads with different surface morphologies

A subcritical water treatment method was developed for preparing porous-surfaced glass beads with an egg-shell structure in a batch reactor. Based on the ＂corrosion-ion-migration-recondensation＂ strategy, ordinary soda-lime glass beads with a diameter of about 100 um were made first to react with subcritical water to effect controlled quantity of silicate dissolution of glass by adjusting treatment time and temperature. The dissolved silicate was then made to recondense on the glass core to form different porous shell morphologies： pores, flakes and fibers. Among these, glass beads coated with fibers with surface area of 154.5 m2/g, pore volume of 0.27 cm3/g and pore size of 7.1 nm were obtained at 573 K after 2 h of treatment. The prepared porous-surfaced glass beads were then used as adsorbent for heavy metal ions, showing various ion exchange properties. Glass beads covered with fibers displayed fast kinetics and high sorption capacity because of their egg-shell structure and high surface area. More than 90% of copper ions were adsorbed within 100 min from a solution with an initial concentration of 110 mg/L at 313 K. Ion sorption capacities were 149.33, 81.33 and 42.96 mg/g respectively for Ag＋, Cu2＋ and Ni2＋ at 313 K. A green and low-cost method was thus developed to produce egg-shell-structured porous glass with high sorption capacity.