CN109847718A - A kind of hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl and its preparation method and application - Google Patents
A kind of hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl and its preparation method and application Download PDFInfo
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- CN109847718A CN109847718A CN201811607829.2A CN201811607829A CN109847718A CN 109847718 A CN109847718 A CN 109847718A CN 201811607829 A CN201811607829 A CN 201811607829A CN 109847718 A CN109847718 A CN 109847718A
- Authority
- CN
- China
- Prior art keywords
- hzo
- zirconium oxide
- strontium
- hydrous zirconium
- alginic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 89
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 67
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 235000010443 alginic acid Nutrition 0.000 title claims abstract description 64
- 229920000615 alginic acid Polymers 0.000 title claims abstract description 64
- 229960001126 alginic acid Drugs 0.000 title claims abstract description 62
- 239000000783 alginic acid Substances 0.000 title claims abstract description 62
- 150000004781 alginic acids Chemical class 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000011324 bead Substances 0.000 claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- 159000000008 strontium salts Chemical class 0.000 claims abstract description 21
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000661 sodium alginate Substances 0.000 claims abstract description 16
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 16
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 10
- 125000000129 anionic group Chemical group 0.000 claims abstract description 9
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 9
- 231100000719 pollutant Toxicity 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 12
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 12
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 12
- 230000001112 coagulating effect Effects 0.000 claims description 10
- 238000001246 colloidal dispersion Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000003754 zirconium Chemical class 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 230000002045 lasting effect Effects 0.000 claims description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 3
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 abstract description 9
- 239000010452 phosphate Substances 0.000 abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000012266 salt solution Substances 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract description 4
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 abstract description 3
- 229940000489 arsenate Drugs 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229910001427 strontium ion Inorganic materials 0.000 abstract description 3
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 13
- 239000003463 adsorbent Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- -1 Phosphate anion Chemical class 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- 229940000488 arsenic acid Drugs 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940072056 alginate Drugs 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 229940053652 fluorinse Drugs 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Cosmetics (AREA)
Abstract
The present invention relates to a kind of alginic acid strontium gel beads products and its adsorption applications for wrapping up hydrous zirconium oxide(HZO).It by hydrous zirconium oxide(HZO) dispersion liquid and sodium alginate aqueous solution, mixes, is added dropwise in strontium salt solution according to a certain volume, stirred, form gel beads, washing removes excessive strontium ion, obtains hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl that partial size is 0.1~5mm.The gel beads can be used for the anionic pollutant in Adsorption water.Plural gel pearl is to phosphate, and fluoride, the Langmuir saturated extent of adsorption of arsenate micro-polluted water is respectively up to 53mg/g, 36mg/g, 61mg/g.The present invention can solve the separation problem of hydrous zirconium oxide(HZO) while ensuring hydrous zirconium oxide(HZO) high adsorption activity, have certain potential using value in field of water quality purification.
Description
Technical field
The present invention relates to the adsorbent material fields applied towards purification of water quality, and in particular to a kind of hydrous zirconium oxide(HZO)/seaweed
Sour strontium plural gel pearl and its preparation method and application.
Background technique
With the rapid development of the national economy, environmental pollution is getting worse.Lake, river, underground water etc. by
The different degrees of pollution of large area, seriously threatens population health.Phosphate anion, fluorine ion, arsenic acid radical ion etc. are with generation
A kind of anionic pollutant of table.These anionic pollutant too high levels can cause water eutrophication, fluorosis of bone, in arsenic
The problems such as malicious.Currently, the contaminant water of high concentration generally using means such as chemical precipitation, UF membranes, is effectively removed,
But for micro-polluted water, often cost is excessively high for these methods, inconvenient to use.
Absorption method is that one kind is easy to operate, compact and flexible, lower-cost to can be used for handling micro- pollution, low concentration pollution water
The effective ways of body.It is the research heat of extensive concern both at home and abroad at present using the absorption method processing micro-polluted water based on nano material
Point.The key of absorption method water process is to find and develop high performance novel absorption material.Hydrous zirconium oxide(HZO) is as a kind of new
Type adsorbent material, absorption property, especially to low phosphorus hydrochlorate, the absorption property of fluoride and arsenate is much higher than it
His traditional calcium, iron, aluminium base adsorbent.A kind of unbodied hydrogen of Yu Su et al. (Water Research, 2013,47,5018)
Phosphorus in zirconium oxide adsorbing seawater and waste water finds that this unbodied zirconium hydroxide is greater than magnalium, magnesium to the absorption property of phosphorus
Iron layered hydroxide.Patent (CN102001722A) discloses a kind of method of mesoporous silicon materials for aoxidizing modified zirconia.Patent
(CN103495390A) a kind of preparation method of zirconium oxide modified activated carbon absorbent is described.Patent (CN102910700A) is public
A kind of method for having opened graphite oxide adsorbent for aoxidizing modified zirconia.The physics shape of the adsorbent product of these patent of invention introductions
State is pulverulence, is settled slowly in sewage, and the hydrous zirconium oxide(HZO) of load is easy to fall off, without fundamentally solving hydration oxygen
It is difficult to settle to change zirconium, the shortcomings that being easy to run off.Paper (Journal of Hazardous Materials, 2015,284,35) uses
Adsorbent HZO-201 is made in hydrous zirconium oxide(HZO) in a kind of polystyrene porous anion exchange resin D-201 load, although can
The separation and recovery problem of very good solution adsorbent, but the price is very expensive for ion exchange resin, and resin is non-degradable
Material, adsorbent are difficult to handle after scrapping, it is possible to produce secondary pollution.Patent (CN106693923A) receives hydrous zirconia gel
Rice material is wrapped in aluminium alginate/polyvinyl alcohol or ferric alginate/polyvinyl alcohol gel, is prepared for can be used in Shui Chu
The gel-type adsorbent of reason.But the gel adsorber can only be disposable, after absorption reaches saturation, cannot regenerate.
Although hydrous zirconium oxide(HZO) has excellent absorption property, the difficult separation of hydrous zirconium oxide(HZO), the problem of being easy to run off
Limit application of the hydrous zirconium oxide(HZO) in micro-polluted water treatment.
Summary of the invention
The primary purpose of the present invention is that separating for existing hydrous zirconium oxide(HZO) difficulty, the problems such as being easy to run off, one kind is provided
Hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl.
Another object of the present invention is to provide above-mentioned hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl preparation method.
Another object of the present invention is to provide the application of above-mentioned hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl.
The biodegradable alginic acid strontium gel of the present invention, wraps hydrous zirconium oxide(HZO), prepares millimetre-sized gel
Pearl adsorbent material.The adsorption activity of hydrous zirconium oxide(HZO) can not only be retained to greatest extent in this way, but also nano material can be overcome difficult
Separation, the shortcomings that being easy to run off.In addition, alginic acid strontium gel salt tolerant more than similar calcium alginate gel, alkaline-resisting, so as to reality
Desorption in present highly basic regenerated liquid with high salt and regenerated.Alginic acid strontium gel is degradable green material, cheap, material
Material itself not will cause environmental pollution.In view of the above advantage, hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl adsorbent is in micro- dirt
Contaminating water treatment field has biggish application prospect.
The invention is realized by the following technical scheme:
A kind of preparation method of hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl, includes the following steps:
(1) water soluble zirconium salt is configured to aqueous solution, aqueous slkali is added into aqueous solution under agitation and adjusts solution
PH is 8~10, and zirconium ion hydrolysis generates hydrous zirconium oxide(HZO) precipitating not soluble in water, the reaction was continued 10min, stops stirring and simultaneously stands
It is complete to white precipitate, supernatant is removed, dilution is added water and stirred and obtains hydrous zirconium oxide(HZO) colloidal dispersion;
(2) before hydrous zirconium oxide(HZO) colloidal dispersion made from step (1) and sodium alginate soln being mixed to get gel beads
Drive object solution;
(3) strontium salt coagulating bath is obtained by strontium salt is soluble in water;
(4) under agitation, gel beads precursor solution described in step (2) is added to described in step (3)
In strontium salt coagulating bath, lasting stirring brings it about cross-linking reaction, after completion of the reaction takes out gel beads, and washing removes excessive strontium
Ion ultimately forms the gel beads of package hydrous zirconium oxide(HZO), the i.e. hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl, coagulates
Glue bead precursor solution and the volume ratio maximum of strontium salt coagulating bath are no more than 30%, otherwise, easily cause gel beads and stick to each other.
Preferably, the concentration of step (1) described water soluble zirconium salt in water is 0.01mol/L~1mol/L.
Preferably, the concentration of step (1) described aqueous slkali is 1~10mol/L.
Preferably, step (1) water soluble zirconium salt be zirconium acetate, zirconium oxychloride, zirconium chloride and zirconium sulfate in extremely
Few one kind.
Preferably, step (1) aqueous slkali is at least one of ammonium hydroxide, sodium hydroxide and potassium hydroxide.
Preferably, adding water and stirring the concentration being diluted to described in step (1) is, in terms of Zr, concentration is 0.01~1.0mol/
L。
Preferably, the time of step (1) described standing is 5min.
Preferably, the volume ratio of step (2) the hydrous zirconium oxide(HZO) colloidal dispersion and sodium alginate soln is 0.5~3:
1。
Preferably, the concentration of step (2) described sodium alginate soln is 0.5~4wt%.
Preferably, the concentration of step (3) the strontium salt coagulating bath is 0.1~2.0mol/L.
Preferably, step (3) strontium salt is at least one of strontium nitrate, strontium chloride and strontium acetate.
Preferably, the time of step (4) described reaction is 10min~10h.
Preferably, step (4) the gel beads precursor solution is added to the strontium with the speed of 0.02~0.05mL/s
In salt coagulating bath.
The hydrous zirconium oxide(HZO) that above-mentioned nano hydrated zirconium oxide/alginic acid strontium plural gel pearl preparation method is prepared/
Alginic acid strontium plural gel pearl.
The hydrous zirconium oxide(HZO)/application of the alginic acid strontium plural gel pearl in Adsorption water in anionic pollutant.
Preferably, the anionic pollutant is at least one of fluorine ion, arsenic acid radical ion and phosphate anion.
Preferably, in the water the middle fluorine ion of anionic pollutant concentration be 1~5mg/L, arsenic acid radical ion it is dense
Degree is 0.01~1mg/L, and the concentration of phosphate anion is 0.5~10mg/L.
Preferably, the hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl is in Adsorption water in anionic pollutant
Application, comprising the following steps: hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl is added in the water containing anionic pollutant
It is adsorbed, hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl additional amount is 20~100g/L, and hydraulic detention time is 6 small
When, fluorinion concentration can be made to be down to 1mg/L hereinafter, arsenic acid ion concentration is down to from 0.1mg/L from 5mg/L in water
0.01mg/L is hereinafter, phosphorus acid ion concentration is reduced to 0.5mg/L or less from 10mg/L.
The hydrous zirconium oxide(HZO)/regeneration of the alginic acid strontium plural gel pearl after adsorbing use, comprising the following steps: will inhale
Hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl after attached use is put into 1~3h of immersion in regenerated liquid, and filtering removes regenerated liquid,
It is cleaned with cleaning solution and removes remaining regenerated liquid and neutralize remaining alkali, final rinse water completes regeneration, and the regenerated liquid is
The saturation aqueous slkali of strontium salt, the cleaning solution are the mixed solution of strontium salt solution and hydrochloric acid solution.
Preferably, the preparation method of the saturation aqueous slkali of the strontium salt, includes the following steps: into 5wt%NaOH solution
Strontium salt solution (strontium salt solution concentration is 0.1~2.0mol/L) is added dropwise to just there is muddy appearance, the content of strontium accounts for the 0.1 of system
~1wt%.
Preferably, strontium salt is at least one of strontium nitrate, strontium chloride and strontium acetate in the cleaning solution.
Preferably, the concentration of strontium salt is 0.01~0.1mol/L in the cleaning solution.
Preferably, the concentration of hydrochloric acid is 0.001~0.01mol/L in the cleaning solution.
The hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl regenerates after adsorbing use, and adsorbance is up to initially after regeneration
95% or more of adsorption capacity.
Compared with prior art, the invention has the following advantages and beneficial effects:
(1) high activity hydrous zirconium oxide(HZO) is fixed in millimetre-sized gel beads, nano material difficulty can be overcome to separate, easily
The shortcomings that loss;
(2) hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl is grade, and gap is big between particle, and filtration resistance is small, easily
Separation, hardly causes the loss of adsorbent;
(3) after hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl adsorption saturation, regeneration can be impregnated by regenerated liquid;
(4) hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl adsorption capacity is strong, to phosphate, fluoride, the micro- dirt of arsenate
The Langmuir saturated extent of adsorption of water is contaminated respectively up to 53mg/g, 36mg/g, 61mg/g.
Detailed description of the invention
Fig. 1 is hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl digital photograph figure made from embodiment 1.
Fig. 2 is hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl digital photograph figure made from embodiment 2.
Fig. 3 is hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl digital photograph figure made from embodiment 3.
Fig. 4 is hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl electron scanning micrograph made from embodiment 1
Figure, wherein (a) corresponding single gel beads particle surface, (b), (c) and (d) respectively correspond the gel beads under different enlargement ratios
Surface topography map (e) corresponds to the pattern photo figure of gel beads cross section under different enlargement ratios with (f).
Fig. 5 is hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl X ray diffracting spectrum made from embodiment 1.
Fig. 6 is hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl adsorption and dephosphorization curve of adsorption kinetics of embodiment 4.
Fig. 7 is hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl adsorption and dephosphorization adsorption isotherm of embodiment 4.
Fig. 8 is that embodiment 7 regenerates obtained gel beads and repeatedly regenerated the-circulation of adsorption-regeneration, the removal to phosphorus
The relational graph of rate and cycle-index.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of preparation method of hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl, includes the following steps:
(1) ZrCl that configuration 400mL concentration is 0.025mol/L4Aqueous solution instills dropwise while stirring
1mol/L NaOH solution to pH be 9~10.The reaction was continued 10min, it is complete to stop stirring and stand the white precipitates such as 5min,
Fall supernatant, deionized water 300mL washing is added, repeats washing 2 times, all precipitatings are sufficiently transferred to 100ml volumetric flask, it is fixed
Hold the hydrous zirconium oxide(HZO) colloidal dispersion for obtaining that concentration is 0.1mol/L to graduation mark.
(2) 4.0g sodium alginate is weighed, is dissolved in water, 2wt% sodium alginate soln is made.
(3) sodium alginate soln obtained in 8mL step (2), aqua oxidation colloidal zirconia obtained in 12mL step (1) are taken
Dispersion liquid stirs and evenly mixs, and obtains gel beads precursor solution, draws gel beads precursor solution, is added dropwise dropwise by 1mL pipette tips
Entering the strontium chloride solution of the 200mL 0.5mol/L stirred, control rate of addition is 0.05mL/s, it is persistently stirred to react 1h,
So that gel beads are full cross-linked, cross-linking reaction is finished, filtering removal strontium chloride residual solution, into beaker be added 200mL go from
Sub- water impregnates and is slowly stirred 1h, washes repeatedly 3-4 times, sufficiently washes off remaining chlorination strontium ion inside gel micropylar canal, i.e.,
Hydrous zirconium oxide(HZO)/alginic acid strontium plural gel the pearl, partial size 2-4mm is prepared.
The hydrous zirconium oxide(HZO) being prepared/alginic acid strontium plural gel pearl impregnates preservation in deionized water.Fig. 5 is to implement
Hydrous zirconium oxide(HZO) made from example 1/alginic acid strontium plural gel pearl X ray diffracting spectrum, as can be drawn from Figure 5: aqua oxidation
Zirconium is present in plural gel pearl with amorphous form.
Fig. 4 is hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl electron scanning micrograph made from embodiment 1
Figure, wherein (a) corresponding single gel beads particle surface, (b), (c) and (d) respectively correspond the solidifying pearl table under different enlargement ratios
Face shape appearance figure, (c) in the referred to hydrous zirconium oxide(HZO) nano particle of arrow, gel beads (e) and under (f) corresponding different enlargement ratios
The pattern photo figure of cross section.
Embodiment 2
A kind of preparation method of hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl, includes the following steps:
(1) aqueous zirconium acetate solution that configuration 100mL concentration is 0.1mol/L.While stirring, 5mol/ is instilled dropwise
L NaOH solution to pH be 9~10.The reaction was continued 10min, it is complete to stop stirring and stand the white precipitates such as 5min, outwells supernatant
Liquid is added deionized water 100mL washing, repeats washing 2 times, and all precipitatings are sufficiently transferred to 100ml volumetric flask, are settled to quarter
Line is spent, the hydrous zirconium oxide(HZO) colloidal dispersion that concentration is 0.1mol/L is obtained.
(2) 4.0g sodium alginate is weighed, is dissolved in water, 2wt% sodium alginate soln is made.
(3) sodium alginate soln obtained in 8mL step (2), aqua oxidation colloidal zirconia obtained in 12mL step (1) are taken
Dispersion liquid stirs and evenly mixs, and obtains gel beads precursor solution, draws gel beads precursor solution, is dripped dropwise by 200 μ L pipette tips
The strontium nitrate solution of the 200mL 0.25mol/L stirred is added, control rate of addition is 0.02mL/s.Persistently it is stirred to react
1h, so that gel beads are full cross-linked, cross-linking reaction is finished, and filtering removal strontium nitrate residual solution is added 200mL into beaker and goes
Ionized water impregnates and is slowly stirred 1h, washes repeatedly 3-4 times, sufficiently washes off remaining strontium nitrate solution inside gel micropylar canal,
Hydrous zirconium oxide(HZO)/alginic acid strontium plural gel the pearl is prepared.
The plural gel pearl product cut size obtained using this method can reduce to 1-2mm, as shown in the picture.
Embodiment 3
A kind of preparation method of hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl, includes the following steps:
(1) zirconium oxychloride aqueous solution that configuration 100mL concentration is 0.1mol/L.While stirring, it instills dropwise
The concentrated ammonia solution of 28wt% to pH be 9~10.The reaction was continued 10min, it is complete to stop stirring and stand the white precipitates such as 5min,
Supernatant is outwelled, deionized water 100mL washing is added, repeats washing 2 times, all precipitatings are sufficiently transferred to 100ml volumetric flask,
It is settled to graduation mark, obtains the hydrous zirconium oxide(HZO) colloidal dispersion that concentration is 0.1mol/L.
(2) 2.0g sodium alginate is weighed, is dissolved in water, 1wt% sodium alginate soln is made.
(3) sodium alginate soln obtained in 10mL step (2), hydrous zirconium oxide(HZO) glue obtained in 10mL step (1) are taken
Dispersion liquid stirs and evenly mixs, and obtains gel beads precursor solution, draws gel beads precursor solution, dropwise by 200 μ L pipette tips
It is added dropwise to the strontium chloride solution of the 200mL 0.25mol/L stirred, control rate of addition is 0.02mL/s.Lasting stirring is anti-
1h is answered, so that gel beads are full cross-linked, cross-linking reaction is finished, and 200mL is added into beaker for filtering removal strontium chloride residual solution
1h is impregnated and be slowly stirred to deionized water, washes repeatedly 3-4 times, and it is molten sufficiently to wash off remaining strontium chloride inside gel micropylar canal
Liquid, that is, be prepared the hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl, and partial size 2-3mm is shown in attached drawing 3.
Embodiment 4
A kind of application of hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl in removing water in P elements
Micro-polluted water is simulated, the sodium dihydrogen phosphate of 10mg/L (in terms of P) is used, is added described in 25ml into conical flask
Sodium dihydrogen phosphate, hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl made from 1.0g embodiment 1, in constant temperature oscillator
It is adsorbed, adsorption time 6h, adsorption temp is 30 DEG C.Phosphate in the water of front and back is adsorbed with Ammonium Molybdate Spectrophotometric Method for Determination
Concentration, the removal rate that phosphorus in solution is calculated is 97.8%, phosphate content better than town sewage discharge 1 grade of A standard (<
0.5mg/L), Langmuir saturated extent of adsorption is 53mg/g.
Embodiment 5
A kind of application of hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl in removing water in fluorine element
Micro-polluted water is simulated, the Fluorinse of 5mg/L (in terms of F) is used, is added described in 25ml and is fluorinated into conical flask
Sodium solution, hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl made from 2.0g embodiment 1, is adsorbed in constant temperature oscillator,
Adsorption time is 6h, and adsorption temp is 30 DEG C.The concentration that fluorine ion in the water of absorption front and back is measured with fluoride ion electrode method, calculates
Into solution, the removal rate of fluorine is 91.8%, and fluorine content is better than national fluorine content of drinking water standard (< 1.0mg/L), Langmuir
Saturated extent of adsorption is 36mg/g.
Embodiment 6
A kind of application of hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl in removing water in arsenic element
Micro-polluted water is simulated, the liquor sodii arsenatis of 0.1mg/L (in terms of As) is used, arsenic described in 25ml is added into conical flask
Acid sodium solution, hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl made from 1.0g embodiment 1, is inhaled in constant temperature oscillator
Attached, adsorption time 6h, adsorption temp is 30 DEG C.The concentration that arsenic ion in the water of absorption front and back is measured with ICP-MS method, calculates
Into solution, the removal rate of arsenic is 93.4%, and content is drunk Water jet cleaning standard (< 0.01mg/L) better than country, and Langmuir is full
It is 61mg/g with adsorbance.
Embodiment 7
The hydrous zirconium oxide(HZO)/regeneration of the alginic acid strontium plural gel pearl after adsorbing use, comprising the following steps:
(1) by the hydrous zirconium oxide(HZO) after Phosphate Sorption in embodiment 4/alginic acid strontium plural gel pearl 10mL regenerated liquid
In, 1.5h, the phosphate concn after measurement desorption are impregnated, the regenerated liquid is made from following steps: to 5wt%NaOH solution
For middle dropwise addition strontium chloride solution (concentration of strontium chloride solution is 0.2mol/L) to just there is muddy appearance, the content of strontium chloride accounts for body
The 0.8wt% of system;
(2) desorption finishes, and after rinsing gel beads with 40mL water, the mixed solution of 5ml strontium chloride and hydrochloric acid, chlorination is added
Concentration of the strontium in mixed solution is 0.05mol/L, and concentration of the hydrochloric acid in mixed solution is 0.001mol/L, and washing is further
Remaining alkali is neutralized, then is rinsed with 40ml deionized water, regeneration can be completed in gel beads.
Embodiment 7 is regenerated to obtained gel beads to carry out repeating to adsorb using by the step of embodiment 4, regenerated absorption is held
Amount reaches the 94% of initial adsorption capacity.Repeatedly regenerate the-circulation of adsorption-regeneration, removal rate to phosphorus and follows bad number
Relational graph it is as shown in Figure 8.
After the hydrous zirconium oxide(HZO) after absorption use/alginic acid strontium plural gel pearl recycling in embodiment 5 and 6, with implementation
The identical processing of example 7 is regenerated, and regenerative adsorption efficiency can be restored to the 97% and 95% of initial adsorption efficiency respectively.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl preparation method, which comprises the steps of:
(1) water soluble zirconium salt is configured to aqueous solution, it is 8 that aqueous slkali is added into aqueous solution under agitation and adjusts pH value of solution
~10, stop stirring after reacting 10min and stand complete to white precipitate, removes supernatant, add water and stir dilution and be hydrated
Zirconium oxide colloid dispersion liquid;
(2) hydrous zirconium oxide(HZO) colloidal dispersion made from step (1) and sodium alginate soln are mixed to get gel beads predecessor
Solution;
(3) strontium salt coagulating bath is obtained by strontium salt is soluble in water;
(4) under agitation, gel beads precursor solution described in step (2) is added to strontium salt described in step (3)
In coagulating bath, lasting stirring brings it about cross-linking reaction, after completion of the reaction takes out gel beads, washing remove excessive strontium from
Son ultimately forms the gel beads of package hydrous zirconium oxide(HZO), the i.e. hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl, described
Gel beads precursor solution and the volume ratio maximum of strontium salt coagulating bath are no more than 30%.
2. hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl preparation method according to claim 1, which is characterized in that step
Suddenly the concentration of (1) described water soluble zirconium salt in water is 0.01mol/L~1mol/L;The concentration of step (1) described aqueous slkali is 1
~10mol/L.
3. hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl preparation method according to claim 2, which is characterized in that step
Suddenly adding water and stirring the concentration being diluted to described in (1) is, in terms of Zr, concentration is 0.01~1.0mol/L.
4. hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl preparation method according to claim 3, which is characterized in that step
Suddenly the volume ratio of (2) described hydrous zirconium oxide(HZO) colloidal dispersion and sodium alginate soln is 0.5~3:1.
5. the preparation method of any one hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl according to claim 1~4, special
Sign is that the concentration of step (2) described sodium alginate soln is 0.5~4wt%.
6. the preparation method of any one hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl according to claim 1~4, special
Sign is that the concentration of step (3) the strontium salt coagulating bath is 0.1~2.0mol/L.
7. the preparation method of any one hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl according to claim 1~4, special
Sign is that step (4) the gel beads precursor solution is added to the strontium salt coagulating bath with the speed of 0.02~0.05mL/s
In, the time of step (4) described reaction is 10min~10h.
8. the preparation method of any one hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl according to claim 1~4, special
Sign is that step (1) water soluble zirconium salt is at least one of zirconium acetate, zirconium oxychloride, zirconium chloride and zirconium sulfate;Step
Suddenly (1) described aqueous slkali is at least one of ammonium hydroxide, sodium hydroxide and potassium hydroxide;Step (3) strontium salt be strontium nitrate,
At least one of strontium chloride and strontium acetate.
What 9. the preparation method of any one of the claim 1~8 hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl was prepared
Hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl.
10. hydrous zirconium oxide(HZO) described in claim 9/alginic acid strontium plural gel pearl is in Adsorption water in anionic pollutant
Application.
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