CN106268621B - 吸附材料及其制造方法 - Google Patents
吸附材料及其制造方法 Download PDFInfo
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- CN106268621B CN106268621B CN201510807941.0A CN201510807941A CN106268621B CN 106268621 B CN106268621 B CN 106268621B CN 201510807941 A CN201510807941 A CN 201510807941A CN 106268621 B CN106268621 B CN 106268621B
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- adsorbent material
- silicate particles
- porosity
- silicate
- particles
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 122
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 136
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000002245 particle Substances 0.000 claims abstract description 73
- 239000011521 glass Substances 0.000 claims abstract description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 15
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 15
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims description 46
- 239000000843 powder Substances 0.000 claims description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 39
- 239000004615 ingredient Substances 0.000 claims description 17
- 229910000765 intermetallic Inorganic materials 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 4
- 229910003978 SiClx Inorganic materials 0.000 claims 2
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 45
- 238000001179 sorption measurement Methods 0.000 description 37
- 238000012360 testing method Methods 0.000 description 30
- 239000000126 substance Substances 0.000 description 28
- 239000002351 wastewater Substances 0.000 description 24
- 239000010842 industrial wastewater Substances 0.000 description 23
- 150000002500 ions Chemical class 0.000 description 23
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 22
- 238000003795 desorption Methods 0.000 description 21
- 239000002253 acid Substances 0.000 description 18
- 239000010949 copper Substances 0.000 description 16
- 239000011701 zinc Substances 0.000 description 16
- 239000011651 chromium Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000011133 lead Substances 0.000 description 13
- 238000011069 regeneration method Methods 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 11
- 230000008929 regeneration Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000003295 industrial effluent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- -1 BaO Chemical class 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 230000009514 concussion Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000002338 electrophoretic light scattering Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000003238 silicate melt Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910006283 Si—O—H Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000013547 langmuir monolayer Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
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Abstract
一种吸附材料,其包含具有玻璃相结构的多个多孔性硅酸盐粒子。该多孔性硅酸盐粒子的成分包含氧化硅、氧化铝、氧化钡、氧化锶以及氧化硼,其中,该多孔性硅酸盐粒子的平均孔径介于3至50纳米,及于pH值介于1至5的环境下,该多孔性硅酸盐粒子的电动电势为负值。此外,还提供一种制造该吸附材料的方法。
Description
技术领域
本发明是关于一种吸附材料,尤其关于以废弃玻璃做为原料的吸附材料及其制造方法。
背景技术
随着消费性电子产品的需求成长,LCD制造厂更不断扩充产能,以满足市场需求。然而,随着使用年限将届,越来越多的废弃LCD产生。目前台湾废弃LCD的数量已达万吨/年,而且预估废弃量将逐年攀升。由于LCD面板玻璃的成分为不含碱金属氧化物的铝硅酸玻璃熔体(RO-Al2O3-SiO2,其中,RO表示碱土金属化合物如:BaO,CaO,MgO,SrO),此种材料具有成分单一、不易发生化学反应、耐高温、高玻璃转化温度、高融点、高硬度等特性,以致废弃LCD面板玻璃无法以一般钠钙玻璃的制造设备予以加工再利用,目前绝大多数的废弃LCD面板玻璃仍以掩埋处理为主,但相关废弃LCD面板玻璃的回收利用已成为环境保护的重要课题。
伴随着产能的扩张,各种工业制程产出大量工业废水,例如半导体制程常用的砷、或是电镀厂废水常见的重金属成分(铅、铜、铬、镉、镍、锌)等。这些工业废水主要以传统化学沉淀法进行处理,此种废水处理方式不仅成本居高不下,化学污泥未妥善处理,还可能造成二次污染。另一种常见的方式是采用沸石进行废水处理,但沸石在强酸中会发生崩解或丧失吸附力,而无法直接应用于强酸性废水处理。
因此,发展更便利且更有效率的水中重金属污染的处理方法已是刻不容缓。如何解决大量废弃LCD面板玻璃的问题以减轻环境负荷,同时提供废弃LCD面板玻璃更有效益的再利用方式以创造材料的永续价值,即为本发明的主要目的。
发明内容
于本发明的构想,依据LCD面板玻璃的物理及化学特性,以改性剂对LCD面板玻璃的成分组成与化学结构进行重置,一方面保留其在酸碱环境下的稳定性,一方面改变其表面性质以增加化学活性和物理吸附性,从而可利用废弃LCD面板玻璃作为原料,制造出具有高吸附能力且可多次循环利用的吸附材料。
根据上述构想,本发明提供一种吸附材料,其包含具有玻璃相结构的多个多孔性硅酸盐粒子。该多孔性硅酸盐粒子的成分包含氧化硅、氧化铝、氧化钡、氧化锶以及氧化硼,其中,该多孔性硅酸盐粒子的平均孔径介于3至50纳米,及于pH值介于1至5的环境下,该多孔性硅酸盐粒子的电动电势为负值。
本发明还提供一种制造吸附材料的方法,其包含准备硅酸盐粉体以及金属化合物,其中,该硅酸盐粉体的成分包含氧化硅、氧化铝、氧化钡、氧化锶以及氧化硼;于800至1500℃的反应温度,使该硅酸盐粉体与该金属化合物反应,形成具有玻璃相结构的多个多孔性硅酸盐粒子,其中,该多孔性硅酸盐粒子的成分包含氧化硅、氧化铝、氧化钡、氧化锶以及氧化硼,其中,该多孔性硅酸盐粒子的平均孔径介于3至50纳米,于pH值介于1至5的环境下,该多孔性硅酸盐粒子的电动电势为负值,及该硅酸盐粉体与该金属化合物的重量比介于1∶1至1∶20。
本发明以金属化合物对废弃LCD面板玻璃的成分组成与分子结构进行重置,从而获得包含具有玻璃相结构的多个多孔性硅酸盐粒子的吸附材料。由于该多孔性硅酸盐粒子的平均孔径介于3至50纳米,纳米级的孔洞可有效吸附重金属离子,此外,于酸性环境下,该多孔性硅酸盐粒子的电动电势仍可为负值,表示其可通过表面负电荷吸附酸性溶液中带正电荷的重金属离子,故本发明的该多孔性硅酸盐粒子做为吸附材料可用于处理强酸性废水中的有害物质(例如重金属),处理后的废水不仅可达到排放标准,且已吸附有害物质的吸附材料亦可经由再生而循环利用。
附图说明
图1A为废弃LCD面板玻璃粉体的扫描电子显微镜(SEM)影像图,图1B为本发明的吸附材料的SEM图;
图2为本发明的吸附材料的透射电子显微镜(TEM)影像图;
图3A为废弃LCD玻璃粉体X射线衍射(XRD)图谱,图3B为本发明的吸附材料的X射线衍射(XRD)图谱;
图4A为多孔性硅酸盐粒子于吸附态的表面结构示意图,图4B为多孔性硅酸盐粒子于脱附态的表面结构示意图,图4C为多孔性硅酸盐粒子于再生态的表面结构示意图;
图5为吸附材料的电动电势对pH的关系图;以及
图6A至6F分别为吸附材料对各浓度的铜(Cu)、镍(Ni)、镉(Cd)、铬(Cr)、锌(Zn)、铅(Pb)的吸收关系图。
具体实施方式
除非文中另有说明,说明书及权利要求书中所使用的单数形式“一”及“该”包括多个个体。
在本发明中,术语“玻璃相”指非结晶性的凝固状态。此外,由于具有玻璃相结构的硅酸盐的结构非常复杂,其组成不以盐的形式而以各金属的氧化物表示。术语“重金属”包含具有生物毒性的过渡金属及类金属元素砷。
本发明以废弃LCD面板玻璃做为原料制造吸附材料。制造吸附材料的方法包含下列步骤。首先,准备由废弃LCD面板玻璃做为主要原料所制成的硅酸盐粉体以及金属化合物,其中,该硅酸盐粉体包含氧化硅、氧化铝、氧化钡、氧化锶以及氧化硼。接着,于800至1500℃的反应温度,使该硅酸盐粉体与该金属化合物反应,以形成具有玻璃相结构的多个多孔性硅酸盐粒子,其中,该多孔性硅酸盐粒子的孔径介于1至100纳米,且以平均值而言,该多孔性硅酸盐粒子的平均孔径介于3至50纳米。
具体而言,可经由粉碎废弃LCD面板玻璃而制备该硅酸盐粉体,该硅酸盐粉体的大小并无特别限制,例如数微米至数毫米。该硅酸盐粉体的成分包含氧化硅、氧化铝、氧化硼、氧化钡以及氧化锶,其中,以该硅酸盐粉体的重量计算,该氧化硼的含量高于5%。
在一些实施例中,可使用废弃LCD面板玻璃以及一般钠钙玻璃,以制备该硅酸盐粉体。因此,该硅酸盐粉体的成分可进一步包含氧化钠、氧化镁及氧化钙。
于本发明中,利用活性较高的金属化合物,例如是IA族的碱金属化合物或IIA族的碱土金属化合物,与该硅酸盐粉体于800至1500℃的反应温度下混熔而进行反应,活性较高的IA或IIA的金属离子可去除该硅酸盐的化学结构中部份的IIIA族金属离子,例如硼。藉此,一方面改性该硅酸盐的原有硅骨架结构,以创造可吸附具有高反应性的金属离子(例如IA或IIA金属离子)的活性位置(active sites),而高反应性的金属离子可在酸性环境下与重金属离子进行置换反应;另一方面亦可在该硅酸盐的结构中形成大量的纳米级孔洞,纳米级孔洞相较于微米级孔洞更能有效吸附重金属离子。
在一些实施例中,该金属化合物选自碳酸钾、碳酸钠或上述的组合。在其他实施例中,该金属化合物可进一步包含碳酸钙以及碳酸镁的至少之一。该金属化合物以不少于该硅酸盐粉体的重量而与该硅酸盐粉体混熔,具体而言,该硅酸盐粉体与该金属化合物的重量比例如是介于1∶1至1∶20,又例如1∶1至1∶10。
反应该硅酸盐粉体以及该金属化合物的温度例如是介于800至1500℃,又例如900至1300℃。进行反应的时间不超过1小时,例如5至30分钟。于反应完成后,以自然冷却、急速冷却等方式,将反应后的该硅酸盐熔体冷却至常温即可形成具有玻璃相结构的该多个多孔性硅酸盐粒子。
由于可能存在过量的该金属化合物,于冷却反应完成的硅酸盐熔体后,可利用酸性溶液(例如浓度为0.1至1M的硝酸、盐酸及柠檬酸的混合溶液)溶解剩余的该金属化合物以及杂质。接着,经由固液分离而取得固体,之后,以高于110℃的温度烘干固体,而获得具有玻璃相结构的该多孔性硅酸盐粒子。
本发明的吸附材料包含具有玻璃相结构的多个多孔性硅酸盐粒子,该多孔性硅酸盐粒子的成分包含氧化硅、氧化铝、氧化钡、氧化锶以及氧化硼,其中,以该多孔性硅酸盐粒子的重量计算,该氧化硼的含量不大于5%。
具体而言,该多孔性硅酸盐粒子的大小并无特别限制,例如数微米至数毫米。该多孔性硅酸盐粒子的孔径介于1至100纳米。以平均值而言,该多孔性硅酸盐粒子的平均孔径介于3至50纳米,例如8至25纳米。而该多孔性硅酸盐粒子的比表面积介于65至500m2/g。
在一些实施例中,该吸附材料可进一步包含活性金属,该活性金属吸附于该多孔性硅酸盐粒子的表面结构的活性位置。该活性金属包含钠、钾、钙以及镁的至少之一。以该吸附材料的重量(即合计该多孔性硅酸盐粒子与该活性金属的重量)计算,该活性金属的含量介于3至21%。
由于本发明的吸附材料的该多孔性硅酸盐粒子同时具有大量的不对称电荷、离子交换点(即活性位置)及高比表面积的孔洞,故可化学性与物理性吸附废水中的重金属。
本发明的吸附材料可应用于吸附废水中的重金属,因此,该吸附材料具有已吸附重金属的吸附态、去除该重金属的脱附态以及再生高反应性活性金属的再生态。具体而言,于吸附态时,该吸附材料可进一步包含吸附于该多孔性硅酸盐粒子中的重金属,该重金属包含过渡金属以及砷的至少之一。每克该多孔性硅酸盐粒子吸附该重金属的重量可高于10mg。
本发明的废水处理方法包含提供含有重金属离子的废水,其中,该废水的pH值不大于5;以具有玻璃相结构的多个多孔性硅酸盐粒子吸附该废水中的重金属,其中,该多孔性硅酸盐粒子含有氧化硅、氧化铝、氧化钡、氧化锶以及氧化硼,该多孔性硅酸盐粒子的孔径介于1至100纳米,且以平均值而言,该多孔性硅酸盐粒子的平均孔径介于3至50纳米。
于本发明的该吸附材料中,该多孔性硅酸盐粒子可经由脱附及再生而循环使用。藉此,在该多孔性硅酸盐粒子吸附该重金属后,本发明的废水处理方法可进一步包含下列步骤。以酸性溶液脱附该多孔性硅酸盐粒子所吸附的重金属。接着,以碱性溶液再生脱附该重金属的该多孔性硅酸盐粒子。之后,以再生后的该多孔性硅酸盐粒子进行吸附处理,例如再次吸附该废水的重金属。
具体而言,吸附有重金属的该多孔性硅酸盐粒子的脱附,可使用浓度为4至5重量%的硝酸溶液,于常温下反应5至20分钟,使酸性溶液中的H+置换吸附于该多孔性硅酸盐粒子的重金属。脱附后的该多孔性硅酸盐粒子的再生可使用pH 6至10.5的氢氧化钠或氢氧化钾溶液,以溶液中的钠或钾离子置换该多孔性硅酸盐粒子的活性位置的H+,而使该多孔性硅酸盐粒子的活性位置再次形成具有高反应性的活性金属。
以下通过特定的具体实施例说明本发明的实施方式,本领域技术人员可由本说明书所公开的内容了解本发明的其他优点与功效。本发明也可通过其他不同的具体实施例加以施行或应用,本说明书中的各项细节亦可基于不同观点与应用,在不悖离本发明的精神下进行各种修饰与变更。
实施例1-11吸附材料的制备
以氢氟酸(HF)溶解废弃LCD面板玻璃粉体后,进行感应耦合等离子-原子发射光谱(ICP/AES)分析其组成及成分比例,分析结果列于表1。
表1
使用废弃LCD面板玻璃制备硅酸盐粉体,并以不同重量比混合该硅酸盐粉体以及金属化合物,再以不同的温度反应硅酸盐粉体以及金属化合物而形成多孔性硅酸盐粒子,从而获得本发明的吸附材料。实施例1至11的原料组成与反应温度列于表2。
表2
以扫描电子显微镜(SEM)、透射电子显微镜(TEM)以及X射线衍射(XRD)分析LCD面板玻璃粉体与实施例的吸附材料。
图1A为废弃LCD面板玻璃粉体的SEM影像图,图1B为本发明的吸附材料的SEM图。图2为本发明的吸附材料的TEM影像图。
图1A显示废弃LCD面板玻璃粉体为无孔洞的平整表面,图1B显示本发明的吸附材料为具有大量孔洞的复杂形貌。由图2的TEM影像可进一步观察本发明的吸附材料的孔洞为纳米级大小。
使用比表面积分析仪以BET法测量吸附材料的比表面积(以相对压力为0.058-0.202的氮氣吸附等温线测量)以及BJH法测量吸附材料的孔径分布(以氮氣脫附分支测量)及各孔径占累积孔洞体积的比例(以氮氣脫附等温线测量),表3列出各吸附材料的比表面积(BET比表面积)、平均孔径(BJH脱附平均孔直径(4V/A))及孔径3至50纳米的孔洞体积比例(BJH脱附孔直径3至50纳米占脱附累积孔洞体积的比例)。
表3
如表3所示,废弃LCD面板玻璃粉体不具有孔洞且比表面积仅0.4m2/g,而本发明的吸附材料具有纳米级孔洞,其中至少60%的孔洞体积为3至50纳米的中孔洞孔径,且吸附材料的比表面积为65.2至163.7m2/g,相较于废弃LCD面板玻璃粉体的比表面积,提升约160至410倍。
以HF溶解实施例3的吸附材料后,进行ICP/AES分析其组成及成分比例,分析结果列于表4。
表4
如表4所示,吸附材料的组成及各成分的含量不同于表1所示的硅酸盐粉体,特别是,多孔性硅酸盐粒子中氧化硼的重量比明显低表1所示的硅酸盐粉体氧化硼中的重量比,此差异表示通过去除LCD面板玻璃粉体中部份的硼成分而产生的孔洞,其孔径为纳米等级。
图3A为废弃LCD玻璃粉体X射线衍射(XRD)图谱,图3B为本发明的吸附材料的X射线衍射(XRD)图谱。
如图3A所示,废弃LCD面板玻璃粉体在25°的2θ位置有非晶(amorphous)玻璃相。对照图3A及3B,本发明的吸附材料在相同的2θ位置(25°)具有相似的图谱形态,表示吸附材料仍保持如改性前废弃LCD玻璃粉体的玻璃相化学结构。由此可知,本发明的吸附材料可具有如同LCD面板玻璃的耐酸性。
图4A至4C为本发明的吸附材料中多孔性硅酸盐粒子的表面结构示意图,其中,图4A为多孔性硅酸盐粒子于吸附态的表面结构示意图;图4B为多孔性硅酸盐粒子于脱附态的表面结构示意图;图4C为多孔性硅酸盐粒子于再生态的表面结构示意图。
图4A至4C中,Si-O-m3+表示多孔性硅酸盐粒子的表面结构,Si-O表示可变电荷位置(Variable-charge sites),Si-O--m3+表示不对称电荷位置,可变电荷位置与不对称电荷位置均属于具有反应性的活性位置。一般硅酸盐吸附材料的成分中氧化硅与氧化铝的重量比(硅铝比)不大于2,而高硅铝比的硅酸盐结构可产生大量的不对称电荷位置,以吸附溶液中的离子。在本发明的多孔性硅酸盐粒子的成分中,硅铝比介于2至5,例如3至4,因此本发明的吸附材料相较于现有硅铝酸盐的吸附材料,具有更高的离子吸附力。
图4A中,M2+表示吸附材料的可变电荷位置所吸附的重金属,例如带2价正电荷的重金属离子,但不以此为限。图4B中,Si-O-H+表示以酸性溶液脱附可变电荷位置的重金属所形成的表面羟基(surface hydroxyl group)。图4C中,M+表示以碱性溶液再生吸附材料而形成于可变电荷位置的活性金属离子,例如碱金属离子,但不以此为限。该活性金属离子可于强酸性溶液中与重金属进行离子交换。如图4A至4C所示,本发明的吸附材料的表面结构具有大量的表面电荷与高效的阳离子交换能力。
以下通过测试例详细说明使用本发明的吸附材料吸附重金属以及处理工业废水的实施方式及效用。
测试例1吸附材料表面电荷与阳离子的交换能力
选取实施例2及3的吸附材料及改性前废弃LCD面板玻璃粉体,使用电动电势分析仪以电泳光散射法(Electrophoretic Light Scattering,ELS)测量各吸附材料在不同酸碱条件的电动电势(Zeta Potential),以电动电势(毫伏特mV)对酸碱值(pH 0至pH 10)作图求得吸附材料及改性前废弃LCD面板玻璃粉体的等电位点(ZPC)。图5为吸附材料的电动电势对pH的关系图。
如图5所示,改性前废弃LCD面板玻璃粉体的等电位点(即电动电势小于1)出现在pH约8.0,此现象表示在pH值小于8.0的环境下,改性前废弃LCD面板玻璃粉体的正电荷表面对于重金属离子会产生排斥力,从而无法吸附水中的重金属离子。而实施例2及3的吸附材料的等电位点出现在pH约0.8,此现象表示即使在pH值介于1至5的强酸性环境下,具有高硅铝比成分的吸附材料的表面仍为负电荷(negative charge),从而吸附材料可通过表面负电荷吸附酸性溶液中带正电荷的重金属离子。分析测试结果,本发明的吸附材料的阳离子交换能力(cation exchange capacity)可达27meq/100g。
测试例2吸附材料对单一金属离子的最大吸附能力
以实施例3的吸附材料分别对铜、镍、铅、锌、镉、铬等六种重金属离子,进行单一重金属离子的吸附能力测试。以单层吸附模式的朗格缪尔吸附模型(Langmuir model)计算每克吸附材料吸附单一重金属离子的最大能力(mg/g)。每种重金属离子个别配置定量100ml,浓度为5、8、10、15、20、25、40、60、80mg/L的测试溶液,各测试溶液添加0.1g的吸附材料,调整酸度至pH 3以模拟电镀废水及土壤酸洗,进行24小时吸附试验,以滤膜滤取测试溶液直接进行ICP/AES分析吸附后的重金属离子含量。
图6A至6F分别为吸附材料对各浓度的铜(Cu)、镍(Ni)、镉(Cd)、铬(Cr)、锌(Zn)、铅(Pb)的吸收关系图。表5为依据Langmuir model计算的吸附材料吸附单一重金属离子的最大能力。表5列出吸附材料吸附单一重金属离子的最大能力。
表5
如表5所示,本发明的吸附材料在强酸(pH为3)溶液中不仅具有吸附重金属离子的能力,且对各种金属离子的最大吸附能力分别达到:Cu 50.0(mg/g)、Ni 31.9(mg/g)、Cd52.6(mg/g)、Cr 21.7(mg/g)、Zn 22.1(mg/g)、Pb 50.2(mg/g)。
测试例3吸附材料吸附含砷(As)废水
配置初始浓度为110(mg/L)的含As测试溶液,取定量体积200ml分别添加2克的实施例3与6的吸附材料,在室温下以震荡器于180rpm往复式震荡60分钟(mins),利用0.45滤纸滤取测试溶液进行ICP/AES分析吸附后的As含量。表6列出吸附材料吸附含砷(As)废水的测试结果。
表6
如表6所示,通过混熔不同配比的金属化合物所制成的吸附材料,可将As的去除效率由45%提升至84.8%。
测试例4本发明的吸附材料吸附实际废水的最大吸附量
以实施例3、4及5的吸附材料,进行实际取自工厂的电镀废水的多种重金属的吸附实验,用以确认本发明的吸附材料对含有复杂成分的电镀废水的吸附能力。取含有Cr、Cu、Ni与Zn等重金属离子的酸性或碱性电镀废水100ml,分别添加1%重量(1g)的实施例3、4及5的吸附材料以进行吸附测试,测试条件为:震荡强度180rpm,吸附时间60mins,吸附温度为25℃。吸附测试完成后以ICP-AES分析吸附后的电镀废水中的重金属离子浓度。表7列出吸附材料对电镀废水中多种重金属离子的最大吸附量与去除率。
表7
如表7所示,不同组成的吸附材料对酸性或碱性的电镀废水中的多种重金属离子均具有吸附能力,最大吸附量更稳定地达到11mg/g以上。
以下依据欧盟(EPA)放流水的有害物质排放标准,进行本发明的吸附材料处理各种废水的测试例。
测试例5吸附材料处理模拟工业废水
于实验室配制含有As、Pb、Cd、Cr、Ni、Cu、Zn的硝酸盐水溶液以模拟含有多种有害物质的工业废水,并以ICP-AES测得各有害物质的原有浓度。取实施例1、2、9、10的吸附材料各20g分别添加至200g的模拟工业废水(以吸附材料对模拟工业废水的重量百分比计算,添加量为10%w/w)进行震荡吸附,处理条件为:震荡强度180rpm,吸附时间30mins,吸附温度25℃,吸附后模拟工业废水中各有害物质的浓度列示于表8。
表8
如表8所示,吸附材料可吸附模拟工业废水中各种有害物质,但亦可观察到竞争吸附的现象,吸附材料对各种有害物质的竞争吸附顺序为As>Pb>Cr>Ni>Cu>Zn>Cd。
测试例6吸附材料多次处理取自实际工厂的氰系工业废水
氰系工业废水的原pH值为2.37,在不调整其pH值的条件下,添加10g的实施例3的吸附材料至200g的氰系工业废水(以吸附材料对氰系工业废水的重量百分比计算,添加量为5%w/w),进行多次震荡吸附,处理条件为:震荡强度180rpm,吸附时间为30mins,吸附温度25℃。处理完成后以ICP-AES分析处理后的氰系工业废水的有害物质浓度(离子浓度),测得的有害物质浓度列示于表9。
表9
如表9所示,在第1次吸附前,Cr的原有浓度已低于排放标准。在第1次吸附后,Cr的浓度降低至仪器可侦测浓度以下,Cu的浓度由434ppm降至61.7ppm,Pb的浓度由22.7ppm降至0.20ppm(符合法定排放标准<1ppm),Zn的浓度由111ppm降至103ppm。
在第2次吸附后,Cr的浓度保持在排放标准以下,吸附材料的导入未造成有害物质的脱附,Cu的浓度由61.7ppm降至15.4ppm,Pb的浓度由0.20ppm进一步降至小于0.1ppm,Zn的浓度由103ppm降至39.2ppm。
在第3次吸附后,吸附材料的导入未造成有害物质的脱附,Cu的浓度由15.4ppm降至小于0.1ppm,Zn的浓度由39.2ppm降至0.11ppm,两者均已达到法定排放标准。
由表9所示的数据可以观察到竞争吸附的现象,含有此种组成的工业废水的竞争吸附顺序为Pb>Cr>Cu>Zn。在第1次吸附中,吸附材料对Cu的吸附性优于对Zn的吸附性,因此,在第1次吸附中Zn的浓度变化不大。在第2次吸附中,吸附材料对Zn的吸附性大幅增加。而在第3次吸附中,吸附材料主要吸附Zn,并且第3次吸附后的Zn浓度可达到法定排放标准。
此外,测量第1次吸附后的氰系工业废水的pH值为9.3,测量第2次吸附后的氰系工业废水的pH值为9.2,测量第3次吸附后的氰系工业废水的pH值为9.1。在本测试例中,于吸附处理前并未额外进行氰系工业废水的pH值(原pH值约为3)调整,而处理后的氰系工业废水中的有害物质浓度不仅可达到放流水的排放标准,且处理后的氰系工业废水的pH值亦趨近中性水标准(pH6至9)。
测试例7吸附材料多次处理取自实际工厂的酸性工业废水
酸性工业废水的原pH值为3.54,在不调整其pH值的条件下,添加10g的实施例11的吸附材料至200g的酸性工业废水(以吸附材料对工业废水的重量百分比计算,添加量为5%w/w),进行多批次震荡吸附,处理条件为:震荡强度180rpm,吸附时间为30mins,吸附温度25℃。处理完成后以ICP-AES分析处理后的酸性工业废水的有害物质浓度(离子浓度),测得的有害物质浓度列示于表10。
表10
如表10所示,在第1次吸附前,Pb的原有浓度已低于排放标准,在第1次吸附过程中,吸附材料的导入未造成有害物质的脱附。第1次吸附后,有害物质Cr的浓度由39.4ppm降至小于0.1ppm(已符合排放标准),Cu的浓度由35.5ppm降至1.90ppm(已符合排放标准),Zn的浓度由30.0ppm降至小于0.1ppm(符合法定排放标准)。由表10所示各种有害物质的去除率,可以观察到此种组成的酸性工业废水在第1次吸附后大部分的有害物质已被去除,并且第1次吸附后的酸性工业废水已达到放流水标准。再者,测量第1次吸附后的工业废水的pH值为6.1,测量第2次吸附后的工业废水的pH值为6.7,处理后的酸性工业废水的pH值亦符合放流水的中性水标准(pH6至9)。
测试例8吸附材料的可靠度测试
各取3g的已饱和吸附酸性工业废水中重金属的吸附材料进行五次脱附-再生-吸附的测试,测量每一次吸附量与脱附量,并以第一次吸附量为基准,计算吸附材料的吸附能力维持率,以获得吸附材料的可靠度。
于酸性条件下进行吸附材料的脱附,可选择柠檬酸、硫酸、硝酸、盐酸等无机酸作为脱附剂。在本测试例中,以硝酸配制脱附剂,并以被脱附的重金属的重量对每克吸附材料计算,测量吸附材料的脱附量。脱附条件R1、R2、R3如表11所示。
将脱附后吸附材料加入装有水的再生槽(脱附后吸附材料与水的重量比为1∶1),以1M浓度氢氧化钠溶液加入再生槽,直至槽内溶液为碱性(pH为9)时即完成吸附材料的再生。
将再生后的吸附材料再次进行吸附-脱附,测量每一次再生后的吸附材料的吸附量与脱附量,并以该吸附材料在第一次吸附时的吸附量为基准,计算每一次脱附与再生后的吸附材料对重金属吸附能力维持率,以了解循环使用吸附材料的可靠度。可靠度测试结果列示于表12。
表11
表12
如表12所示,本发明的吸附材料经多次吸附-脱附-再生后仍可维持80%以上的吸附效能,故本发明的吸附材料确实具有多次再生使用的能力。
综合上述测试例,由图1B及图2可观察到LCD面板玻璃因成分重置以及结构重排而产生的孔洞形貌,由测试例2可知吸附材料为Langmuir单层吸附模式,由图3B可证明吸附材料具有耐强酸性,由测试例3可证明吸附材料具有吸附As的能力,由测试例4可得出吸附材料对多种有害物质的总吸附量可高于11.66mg/g,由测试例5、6、7确认以吸附材料处理各种工厂废水均可达到法定排放标准,由测试例8的可靠度测试确认吸附材料可经由脱附及再生而多次循环使用。
综上所述,本发明以金属化合物对废弃LCD面板玻璃的成分组成与化学结构进行重置,从而获得包含具有玻璃相结构的多孔性硅酸盐粒子的吸附材料。使用本发明的该多孔性硅酸盐粒子做为吸附材料可处理强酸性废水中的有害物质,处理后的强酸性废水不仅可达到排放标准,且已吸附有害物质的吸附材料亦可经由脱附及再生而循环使用。
上述实施例仅例示性说明,而非用于限制本发明。任何该领域技术人员均可在不违背本发明的精神及范畴下,对上述实施例进行修饰与改变。因此,本发明的权利保护范围,应如权利要求书所载。
Claims (12)
1.一种吸附材料,包含:
具有玻璃相结构的多个多孔性硅酸盐粒子,及吸附于该多孔性硅酸盐粒子的玻璃相结构中的活性金属,该多孔性硅酸盐粒子的成分包含氧化硅、氧化铝、氧化钡、氧化锶以及氧化硼,其特征在于,该多孔性硅酸盐粒子的平均孔径介于3至50纳米,于pH值介于1至5的环境下,该多孔性硅酸盐粒子的电动电势为负值;以该吸附材料的重量计算,该活性金属的含量介于3至21%;及该活性金属为IA族或IIA族的金属离子。
2.如权利要求1所述的吸附材料,其特征在于,该多孔性硅酸盐粒子的比表面积介于65至500m2/g。
3.如权利要求1所述的吸附材料,其特征在于,该多孔性硅酸盐粒子的至少60%的孔洞体积的孔径介于3至50纳米。
4.如权利要求1所述的吸附材料,其特征在于,于该多孔性硅酸盐粒子的成分中,该氧化硅与该氧化铝的重量比介于2至5。
5.如权利要求1所述的吸附材料,其特征在于,该活性金属包含钠、钾、钙以及镁的至少之一。
6.如权利要求1所述的吸附材料,其特征在于,每克该多孔性硅酸盐粒子对重金属的吸附能力高于10mg/g。
7.如权利要求6所述的吸附材料,其特征在于,该重金属包含过渡金属以及砷的至少之一。
8.一种制造吸附材料的方法,其特征在于:
准备硅酸盐粉体以及金属化合物,其中,该硅酸盐粉体的成分包含氧化硅、氧化铝、氧化钡、氧化锶以及氧化硼;及该金属化合物为选自碳酸钾、碳酸钠、碳酸钙以及碳酸镁的至少之一;以及
于800至1500℃的反应温度,使该硅酸盐粉体与该金属化合物反应,形成具有玻璃相结构的多个多孔性硅酸盐粒子,其中,该多孔性硅酸盐粒子的平均孔径介于3至50纳米,于pH值介于1至5的环境下,该多孔性硅酸盐粒子的电动电势为负值,及该硅酸盐粉体与该金属化合物的重量比介于1:1至1:20。
9.如权利要求8所述的制造方法,其特征在于,该硅酸盐粉体以LCD面板玻璃做为原料所制得。
10.如权利要求8所述的制造方法,其特征在于,以该硅酸盐粉体的重量计算,该氧化硼的含量高于5%,以该多孔性硅酸盐粒子的重量计算,该氧化硼的含量不大于5%。
11.如权利要求8所述的制造方法,其特征在于,于该多孔性硅酸盐粒子的成分中,该氧化硅对该氧化铝的重量比介于2至5。
12.如权利要求8所述的制造方法,其特征在于,该多孔性硅酸盐粒子的比表面积介于65至500m2/g。
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