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Membranes 2020, 10, 371 9 of 14 Membranes 2020, 10, x FOR PEER REVIEW 9 of 14 precipitation, there is already CaSO4·H2O precipitation on the surface of the nanofiltration membrane. there is already CaSO ·H O precipitation on the surface of the nanofiltration membrane. That is 42 2+ −1 That is the reason the concentration of Ca in the bulk collected retentate is only 0.02 g·L , as the feed the reason the concentration of Ca2+ in the bulk collected retentate is only 0.02 g·L−1, as the feed solution has concentrated 10 times. Further, because the total amount of Ca2+ is much lower than that solution has concentrated 10 times. Further, because the total amount of Ca2+ is much lower than of SO42−, this results in the lower concentrated times of Ca2+ than SO42−. In order to reduce the that of SO42−, this results in the lower concentrated times of Ca2+ than SO42−. In order to reduce the membrane scaling caused by calcium sulfate precipitation, it is better to wash the membranes after membrane scaling caused by calcium sulfate precipitation, it is better to wash the membranes after the NF operation. By contrast, Mg2+ can only be continuously accumulated in the collected retentate the NF operation. By contrast, Mg2+ can only be continuously accumulated in the collected retentate without precipitation, resulting in a higher concentration of Mg2+ in the permeate flow. In other without precipitation, resulting in a higher concentration of Mg2+ in the permeate flow. In other words, words, the more Mg2+ that enters the permeate flow, the lower the retention rate of Mg2+. the more Mg2+ that enters the permeate flow, the lower the retention rate of Mg2+. The separation factor of lithium and magnesium (SFLi-Mg) and lithium recovery are shown in The separation factor of lithium and magnesium (SFLi-Mg) and lithium recovery are shown in Figure 3d. It can be seen that the SFLi-Mg rose from 15.4 to 30.1 in the first 30 min, and then gradually Figure 3d. It can be seen that the SF rose from 15.4 to 30.1 in the first 30 min, and then gradually Li-Mg 2+ decrease from 30.1 to 22.8 in the next 75 min. The increasing concentration of Mg2+ in the collected decrease from 30.1 to 22.8 in the next 75 min. The increasing concentration of Mg in the collected retentate is unhelpful for the separation of lithium and magnesium. In addition, the lithium recovery retentate is unhelpful for the separation of lithium and magnesium. In addition, the lithium recovery increased almost linearly, and reached 91.6% at the end of the NF process. Noteworthily, the total increased almost linearly, and reached 91.6% at the end of the NF process. Noteworthily, the total salinity in the retentate liquid is too high, and the residual lithium cannot be directly recycled by NF, salinity in the retentate liquid is too high, and the residual lithium cannot be directly recycled by but this retentate liquid can be returned to the EID system to separate lithium and magnesium, which NF, but this retentate liquid can be returned to the EID system to separate lithium and magnesium, can reduce the waste of lithium. which can reduce the waste of lithium. The final compositions of the permeate flow produced by NF are shown in Table 5. From Table The final compositions of the permeate flow produced by NF are shown in Table 5. From Table 5, 5, it can be seen that the major cationic ions in the permeate flow are Li+, Na+, and Mg2+, and the main it can be seen that the major cationic ions in the permeate flow are Li+, Na+, and Mg2+, and the main anionic ion is Cl−. The concentration of K+ is only 0.03 g·L−1, and other impurities such as Ca2+ and anionic ion is Cl−. The concentration of K+ is only 0.03 g·L−1, and other impurities such as Ca2+ and SO42− can almost be ignored. SO42− can almost be ignored. Table 5. The compositions of the permeate flow produced by NF (g·L-1). Table 5. The compositions of the permeate flow produced by NF (g·L−1). Elements Li+ Na+ K+ Mg2+ Elements Li+ Na+ K+ Mg2+ Concentration 2.2 1.7 0.03 0.21 −2 −1 irneistuiallts3aMrePashtow5.n5 MinPFaigdurein4g. tFhiegRuOrep4raohceasss,hwohwilne theaftltuhxeoofptheerawtiaotnerpdrescsreuarseeidncfroemase4d9 Lfr·omm·the −2 −1 + + 2+ +−2 −1 tioni2ti1a.l83LM·mPa·hto5..F5igMuPraed4ubrisnhgotwhsetRhOatptrhoececsosn,cwenhitlreatihoenfloufxionftshseuwchataesrLdiec,rNease,dMfgrom,a4n9dLK·min·the −2−1 + + + 2+−1 + −1 ctol2le1c.8teLd·mrete·nhtat.eFinigcurereas4ebdshalomwossthlaint tehaerlcyo.nCcoentcraetieolny,oLf ionhsasuinchcraesasLeid,fNroam, 2M.2gg·L, antdoK5.4ign·Lthe 2+ −1−1+ −1+−+1 acnodlleMctgedrinetcernetaastedinfrcoremas0e.d21aglm·Losttolin0e.5a2r5ly.g·CLon.cFriegtuelrye,4Lcishoawsisntchreaatstehdefcronmce2n.2trgat·Lionotof5L.i4,gN·La, 2+ −1−1 ++ and Mg incrtehaesepdefrrmomeat0e.21flogw·L intcore0a.5s2e5dgs·Ligni.fiFciagnutrley4wc sithowthsethcaotntchenctorantcieontrpartiocnesosf,Lbiu,tNthae, 2+ −1 manadxiMmgumincothnecepnetrrmateiaotnefloofwlitihnicuremaseisdstigilnlilfiocwanetrlythwainth0t.h0e4cogn·Lcen,tarnatdionthperolictehsisu,mbutlothssemisaaxlimousmt nceognlciegnibtrlea.tion of lithium is still lower than 0.04 g·L−1, and the lithium loss is almost negligible. Figure 4. Cont. Ca2+ Cl− SO42− Lithium Recovery % Lithium Recovery % Concentration 2.2 1.7 0.03 0.21 91.6 Ca2+ Cl− SO 2− -4 4 3.1×10 14.39 0.0013 91.6 3.1 × 10−4 14.39 0.0013 The permeate flow produced by the NF process was treated by the RO process, and the main 3.2.2. RO Process 3.2.2. RO Process resultTshaerepesrhmoweanteinfloFwiguprreod4.uFciegdubrey4tahehNasFshporowcnestshwatatshtereoaptedrabtiyonthpereRsOsupreroicnecsrse,aasned ftrhoemmtahienPDF Image | Membrane Process for Preparing Lithium Carbonate
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