CN111282541A - 一种除砷复合材料及其制备方法 - Google Patents
一种除砷复合材料及其制备方法 Download PDFInfo
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- CN111282541A CN111282541A CN202010123855.9A CN202010123855A CN111282541A CN 111282541 A CN111282541 A CN 111282541A CN 202010123855 A CN202010123855 A CN 202010123855A CN 111282541 A CN111282541 A CN 111282541A
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- titanium
- salt
- arsenic
- arsenic removal
- iron
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 57
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- UWIMQBMUGNMYPA-UHFFFAOYSA-N [Ti].[Mn].[Fe] Chemical compound [Ti].[Mn].[Fe] UWIMQBMUGNMYPA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 150000003608 titanium Chemical class 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- -1 salt modified montmorillonite Chemical class 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 239000013618 particulate matter Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- BVNOLBONQDKEPQ-UHFFFAOYSA-N [O-2].[Ti+4].[Fe+2].[Mn+2].[O-2].[O-2].[O-2] Chemical compound [O-2].[Ti+4].[Fe+2].[Mn+2].[O-2].[O-2].[O-2] BVNOLBONQDKEPQ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 5
- 239000000440 bentonite Substances 0.000 description 5
- 229910000278 bentonite Inorganic materials 0.000 description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 4
- 239000003673 groundwater Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052603 melanterite Inorganic materials 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 230000035622 drinking Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910018512 Al—OH Inorganic materials 0.000 description 1
- 208000008316 Arsenic Poisoning Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 208000012641 Pigmentation disease Diseases 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 230000037380 skin damage Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
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- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- 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
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
本发明提供了一种除砷复合材料，包括载体，所述的除砷复合材料还包括附着在所述的载体的表面的铁钛锰复合氧化物，其中，所述的铁钛锰复合氧化物中Fe、Ti、Mn的摩尔比为0.5～5:0.5～4:1。本发明的除砷复合材料的吸附性能好，能够高效稳定去除水体中的砷，并且铁钛锰氧化物可以再生。
Description
技术领域
本发明属于水处理技术领域，具体涉及一种除砷复合材料及其制备方法。
背景技术
砷是一种兼具金属和非金属性质的类金属元素，As(III)主要存在以地下水为代表的还原性环境中，而As(Ⅴ)主要存在以地表水为代表的氧化性环境中，砷主要通过两种途径进入到人体，其一通过饮用含砷地下水，其二食用含砷地下水灌溉过的谷物和蔬菜。地下水砷污染是全球性环境问题。长期饮用高砷水可导致皮肤癌和多种内脏器官癌变，慢性砷中毒患者除有头痛、头晕等症状外，突出表现为皮肤损害，症状为皮肤色素沉着、皮肤角化过度等。因此，对生活中的饮用水的除砷，是一个关系民生的重要课题。
砷污染主要通过物理法、化学法和生物法达到去除的目的，其中，沉淀法、离子交换法、吸附法、膜分离法和生物法等为常见的含砷废水处理方法。吸附法是饮用水除砷的首选方法，该方法除砷效率高，操作简单，成本低廉。粘土矿物常用作吸附剂，主要成分为铝、镁、硅酸盐等，具有粒径小、比表面积大、孔隙率高和较好的离子交换性能，其中伊利石、蒙脱石、高岭土是有效的除砷吸附剂。
CN103084140B公开了一种去除水中砷的复合材料及其制备方法，其通过聚合铁盐、水解钛盐插入膨润土层间，经烘干煅烧，形成铁、钛二元氧化物插层改性复合材料。该发明是通过聚合铁盐、水解钛盐对膨润土进行改性以撑大膨润土的层间孔隙，从而提高除砷效果。但是，该发明的复合材料的除砷效率有待进一步提高，并且除砷时光照条件对除砷效果也有影响，此外，膨润土层间可容纳的改性物的量有限，在吸附容量上没有优势。
发明内容
本发明针对上述问题，提出了一种除砷效率更高的除砷复合材料及其制备方法。
为解决上述技术问题，本发明采用如下技术方案：
本发明一方面提供一种除砷复合材料，包括载体，所述的除砷复合材料还包括附着在所述的载体的表面的铁钛锰复合氧化物，其中，所述的铁钛锰复合氧化物中Fe、Ti、Mn的摩尔比为0.5～5:0.5～4:1。
本发明的除砷复合材料具有较大的比表面积，可提供较多的吸附位点，并且表面带有电荷，在静电作用下可促进砷在水体中的迁移，对水中砷的原位修复具有重要意义。本发明附着在所述的载体的表面的铁钛锰复合氧化物可通过氧化-吸附过程，减少砷的毒性，高效稳定地去除水体砷污染。另外，在除砷复合材料完成砷的吸附后，用强碱溶液使得吸附上的砷脱附下来，从而可以再次用于除砷，或者可以进一步在复合材料表面附着新的铁钛锰氧化物，从而可以进一步提高再生后的复合材料的除砷效率，且再生方法简单，再生周期短，易于推广应用。
优选地，所述的铁钛锰复合氧化物中Fe、Ti、Mn的摩尔比为2～5:1～4:1。
进一步优选地，所述的铁钛锰复合氧化物中Fe、Ti、Mn的摩尔比为3.5～4.5:1.5～2.5:1。
本发明通过优化铁钛锰复合氧化物中Fe、Ti、Mn的摩尔比，可以进一步提高复合材料的性能，减少成本投入。
优选地，所述的铁钛锰复合氧化物通过亚钛盐、高锰酸盐、二价铁盐以及三价铁盐进行氧化还原反应并通过原位沉淀法形成在所述的载体的表面。
进一步优选地，所述的亚钛盐为硫酸亚钛(Ti2(SO4)3)、三氯化钛(TiCl3)中的一种或多种；所述的高锰酸盐为高锰酸钾、高锰酸钠中的一种或多种；所述的二价铁盐为硫酸亚铁(FeSO4)、氯化亚铁(FeCl2)、硝酸亚铁(Fe(NO3)2)中的一种或多种；所述的三价铁盐为硫酸铁(Fe2(SO4)3)、氯化铁(FeCl3)、硝酸铁(Fe(NO3)3)中的一种或多种。
进一步优选地，所述的三价铁盐和所述的二价铁盐的投料摩尔比为2～2.2:1。
优选地，所述的载体为聚合铝盐和/或聚合铁盐改性的蒙脱石，所述的载体为粒径≥200目的颗粒物或粉末。本发明通过采用改性蒙脱石为载体，其层间聚合氯化铝和颗粒边缘的≡Al－OH均能有效与水体中的砷结合，有利于砷的更加高效去除。
本发明中的聚合铝盐和/或聚合铁盐改性的蒙脱石可以直接市购获得，或者按照本领域的常规方法对蒙脱石进行改性即可。
进一步优选地，聚合铝盐可以为聚合氯化铝、聚合硫酸铝中的一种或多种；聚合铁盐可以为聚合氯化铁、聚合硫酸铁中的一种或多种。
本发明的第二方面是提供一种所述的除砷复合材料的制备方法，包括如下步骤：
(1)在厌氧条件下将二价铁盐、三价铁盐、亚钛盐溶解于水中，得到溶液a；
(2)将高锰酸盐、碱性溶液和水混合，得到溶液b；
(3)在所述的溶液a中加入所述的载体，在搅拌的条件下，加入所述的溶液b，继续搅拌30～60min，然后调节pH至6～9；
(4)静置陈化1～4h，然后沉淀物经洗涤、干燥得到所述的除砷复合材料。
本发明采用原位沉淀法一步合成复合材料，制备方法简单，原料成本低廉，可以采用该方面进行铁钛锰氧化物的再生，再生简单，再生周期短。
优选地，步骤(1)中的厌氧条件为充以惰性气体的条件。
优选地，步骤(2)中的碱性溶液，以及步骤(3)中调节pH的试剂为0.2～0.4mol/L的氢氧化钠溶液。
优选地，步骤(4)中，采用乙醇和水进行洗涤。
进一步优选地，采用乙醇和水交替洗涤多次。
由于以上技术方案的实施，本发明与现有技术相比具有如下优点：
本发明的除砷复合材料的吸附性能好，能够高效稳定去除水体中的砷，并且铁钛锰氧化物可以再生。
具体实施方式
下面的实施例为用来说明本发明的几个具体实施方式，但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到，本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。
实施例1
在惰性气体保护气下，将3.8g FeCl3·6H2O、1.8g FeSO4·7H2O和3.84gTi2(SO4)3溶解于500ml去离子水中，得到溶液a。将0.79g KMnO4溶解于50ml去离子水中，与50ml 0.3MNaOH溶液混合，得到溶液b。在溶液a中加入1.0g聚合氯化铝改性蒙脱石，快速搅拌的同时，缓慢滴加溶液b，继续搅拌40min，用0.3M NaOH溶液调节pH至8.0，静置陈化3h，采用乙醇和去离子水充分洗涤过滤陈化后的沉淀物，将过滤后的沉淀物于50-80℃条件下干燥。即获得新型除砷复合材料，其中Fe/Ti/Mn的摩尔比为4:2:1。
实施例2
在惰性气体保护气下，将2.7g FeCl3·6H2O、1.39g FeSO4·7H2O和1.92gTi2(SO4)3溶解于500ml去离子水中，得到溶液a。将0.79g KMnO4溶解于50ml去离子水中，与50ml 0.3MNaOH溶液混合，得到溶液b。在溶液a中加入1.0g聚合氯化铝改性蒙脱石，快速搅拌的同时，缓慢滴加溶液b，继续搅拌40min，用0.3M NaOH溶液调节pH至8.0，静置陈化3h，采用乙醇和去离子水充分洗涤过滤陈化后的沉淀物，将过滤后的沉淀物于50-80℃条件下干燥。即获得新型除砷复合材料，其中Fe/Ti/Mn的摩尔比为3:1:1。
实施例3
在惰性气体保护气下，将0.9g FeCl3·6H2O、0.47g FeSO4·7H2O和1.92gTi2(SO4)3溶解于500ml去离子水中，得到溶液a。将0.79g KMnO4溶解于50ml去离子水中，与50ml 0.3MNaOH溶液混合，得到溶液b。在溶液a中加入1.0g聚合氯化铝改性蒙脱石，快速搅拌的同时，缓慢滴加溶液b，继续搅拌40min，用0.3M NaOH溶液调节pH至8.0，静置陈化3h，采用乙醇和去离子水充分洗涤过滤陈化后的沉淀物，将过滤后的沉淀物于50-80℃条件下干燥。即获得新型除砷复合材料，其中Fe/Ti/Mn的摩尔比为1:1:1。
采用实施例1至3制得的新型除砷复合材料在吸附剂投加量＝1.0g/L、pH＝7.0±0.1、温度＝25℃的条件下对不同初始As(Ⅲ)浓度的水体进行吸附测试，吸附容量结果见表1。
表1
| 实施例1(mg/g) | 实施例2(mg/g) | 实施例3(mg/g) | |
| 2mg/L | 1.98 | 1.92 | 1.84 |
| 10mg/L | 7.36 | 6.55 | 4.02 |
采用实施例1至3制得的新型除砷复合材料在吸附剂投加量＝1.0g/L、pH＝7.0±0.1、温度＝25℃的条件下对不同初始As(Ⅴ)浓度的水体进行吸附测试，吸附容量结果见表2。
表2
采用实施例1制得的新型除砷复合材料在初始砷浓度＝10mg/L、吸附剂投加量＝1.0g/L、pH＝7.0±0.1、温度＝25℃的条件下对黑暗、自然光、紫外光不同光照进行吸附测试，吸附容量结果见表3。
表3
| As(Ⅲ)吸附量(mg/g) | As(Ⅴ)吸附量(mg/g) | |
| 黑暗 | 6.86 | 5.57 |
| 自然光 | 7.47 | 6.60 |
| 紫外光 | 7.82 | 7.02 |
将实施例1制得的新型除砷复合材料在初始砷浓度＝10mg/L，吸附剂投加量＝1.0g/L、pH＝7.0±0.1、温度＝25℃的条件下吸附饱和后的复合材料进行再生，再生的方法为：将过滤得到的复合材料置于200mL NaOH溶液(0.5M)中，搅拌反应6小时(170rpm，25±1℃)，过滤，洗涤，干燥，得到再生后的复合材料。
采用上述再生后的复合材料在初始砷浓度＝10mg/L、吸附剂投加量＝1.0g/L、pH＝7.0±0.1、温度＝25℃的条件下进行吸附砷测试，连续吸附-脱附3次，吸附容量结果见表4。
表4
| 再生次数 | As(Ⅲ)吸附量(mg/g) | As(Ⅴ)吸附量(mg/g) |
| 0 | 7.36 | 6.47 |
| 1 | 7.02 | 6.13 |
| 2 | 6.60 | 5.65 |
| 3 | 5.89 | 5.03 |
本发明包括但不限于以上实施例，本领域熟练技术人员可在本发明权利要求内变换得到更多实施例。
Claims (10)
1.一种除砷复合材料，包括载体，其特征在于：所述的除砷复合材料还包括附着在所述的载体的表面的铁钛锰复合氧化物，其中，所述的铁钛锰复合氧化物中Fe、Ti、Mn的摩尔比为0.5～5:0.5～4:1。
2.根据权利要求1所述的除砷复合材料，其特征在于：所述的铁钛锰复合氧化物中Fe、Ti、Mn的摩尔比为2～5:1～4:1。
3.根据权利要求2所述的除砷复合材料，其特征在于：所述的铁钛锰复合氧化物中Fe、Ti、Mn的摩尔比为3.5～4.5:1.5～2.5:1。
4.根据权利要求1至3中任一项所述的除砷复合材料，其特征在于：所述的铁钛锰复合氧化物通过亚钛盐、高锰酸盐、二价铁盐以及三价铁盐进行氧化还原反应并通过原位沉淀法形成在所述的载体的表面。
5.根据权利要求4所述的除砷复合材料，其特征在于：所述的亚钛盐为硫酸亚钛、三氯化钛中的一种或多种；所述的高锰酸盐为高锰酸钾、高锰酸钠中的一种或多种；所述的二价铁盐为硫酸亚铁、氯化亚铁、硝酸亚铁中的一种或多种；所述的三价铁盐为硫酸铁、氯化铁、硝酸铁中的一种或多种。
6.根据权利要求1所述的除砷复合材料，其特征在于：所述的载体为聚合铝盐和/或聚合铁盐改性的蒙脱石，所述的载体为粒径≥200目的颗粒物或粉末。
7.一种如权利要求1至6中任一项所述的除砷复合材料的制备方法，其特征在于：包括如下步骤：
(1)在厌氧条件下将二价铁盐、三价铁盐、亚钛盐溶解于水中，得到溶液a；
(2)将高锰酸盐、碱性溶液和水混合，得到溶液b；
(3)在所述的溶液a中加入所述的载体，在搅拌的条件下，加入所述的溶液b，继续搅拌30～60min，然后调节pH至6～9；
(4)静置陈化1～4h，然后沉淀物经洗涤、干燥得到所述的除砷复合材料。
8.根据权利要求7所述的制备方法，其特征在于：步骤(1)中的厌氧条件为充以惰性气体的条件。
9.根据权利要求7所述的制备方法，其特征在于：步骤(2)中的碱性溶液，以及步骤(3)中调节pH的试剂为0.2～0.4mol/L的氢氧化钠溶液。
10.根据权利要求7所述的制备方法，其特征在于：步骤(4)中，采用乙醇和水进行洗涤。
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