CN107321298B - 改性磁石的制备方法及其在重金属污染修复中的应用 - Google Patents
改性磁石的制备方法及其在重金属污染修复中的应用 Download PDFInfo
- Publication number
- CN107321298B CN107321298B CN201710534395.7A CN201710534395A CN107321298B CN 107321298 B CN107321298 B CN 107321298B CN 201710534395 A CN201710534395 A CN 201710534395A CN 107321298 B CN107321298 B CN 107321298B
- Authority
- CN
- China
- Prior art keywords
- magnetite
- modified
- preparation
- soil
- heavy metal
- 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.)
- Active
Links
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229960002163 hydrogen peroxide Drugs 0.000 claims abstract description 20
- 238000012986 modification Methods 0.000 claims abstract description 19
- 230000004048 modification Effects 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002689 soil Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 11
- 239000003643 water by type Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 description 29
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 29
- 229910052785 arsenic Inorganic materials 0.000 description 20
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 14
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000011565 manganese chloride Substances 0.000 description 6
- 229940099607 manganese chloride Drugs 0.000 description 6
- 235000002867 manganese chloride Nutrition 0.000 description 6
- 230000010355 oscillation Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 102100036912 Desmin Human genes 0.000 description 4
- 101000928044 Homo sapiens Desmin Proteins 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 102100038530 Chorionic somatomammotropin hormone 2 Human genes 0.000 description 2
- 101000956228 Homo sapiens Chorionic somatomammotropin hormone 2 Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229940093932 potassium hydroxide Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 101150003532 CSH gene Proteins 0.000 description 1
- 102100021809 Chorionic somatomammotropin hormone 1 Human genes 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000895818 Homo sapiens Chorionic somatomammotropin hormone 1 Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/0262—Compounds of O, S, Se, Te
-
- 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
- B01J20/28—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
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Soil Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了一种改性磁石的制备方法,包括以下步骤:1)、将铁含量≥40%的磁石经60~300目过筛后,用水清洗至洗涤液为pH5.5~6.5;2)、将步骤1)所得磁石与过氧化氢溶液按固液比为1g/1~20ml的比例混合后,室温下浸泡;所述过氧化氢溶液的质量浓度为6~30%;3)、将步骤2)所得磁石用水洗涤直至洗涤液pH5.5~6.5,然后干燥至恒重,得到改性磁石。该改性磁石用于重金属污染环境修复。
Description
技术领域
本发明属于环保技术领域。具体地,本发明涉及一种改性磁石的制备方法及其在重金属污染修复中的应用。
背景技术
近年来,随着我国工业化、城市化、农业集约化的快速发展,土壤环境污染日益加剧,已对农业产品安全、人居健康安全以及经济社会可持续发展构成了严重威胁。据2014年全国土壤污染状况调查公报显示,全国土壤环境状况总体不容乐观,部分地区土壤污染较重,耕地土壤环境质量堪忧,工矿业废弃地土壤环境问题突出,全国土壤总的点位超标率为16.1%,其中镉、汞、砷、铜、铅、铬、锌、镍8种无机污染物点位超标率分别为7.0%、1.6%、2.7%、2.1%、1.5%、1.1%、0.9%、4.8%。土壤重金属污染治理已成为我国亟待解决的重大环境问题。
目前针对土壤重金属污染修复常采用添加海泡石、生物炭、石灰、磷矿、改性石墨烯等材料原位钝化重金属的生物有效性,然而这些材料往往只能钝化一种或某几种阳离子型重金属元素,对含阴离子型砷等单一或复合污染土壤钝化效果不佳;而纳米零价铁、磁性石墨烯等材料虽然对重金属镉、砷等复合污染土壤钝化效果好,但材料和土壤反应作用后难于从土壤中分离回收,且成本昂贵难于大规模实际应用。因此,迫切需要寻求一种高效的低廉的可回收的材料去修复受重金属污染的土壤。而磁石是一种容易获取的天然磁性材料,为氧化物类矿物尖晶石族磁铁矿,除了磁性物质可直接吸附部分金属离子以外,有研究报道富铁物质对于环境中重金属的有效态含量也有所影响。原磁石对重金属的吸附效率很低,通过改性手段可以进一步提高磁性材料对于重金属的吸附性能。然而,关于磁石的改性及其在土壤或水体中重金属污染修复中的应用鲜有报道。
发明内容
本发明所要解决的技术问题是提供一种改性磁石的制备方法以及该改性磁石在重金属污染修复中的应用;采用本发明方法制备而得的改性磁石对重金属污染的吸附能力强。
为了解决上述技术问题,本发明提供一种改性磁石的制备方法,以下步骤:
1)、将铁含量≥40%(质量%)的磁石经60~300目过筛后,用水(蒸馏水)清洗至洗涤液为pH5.5~6.5;
2)、将步骤1)所得磁石与过氧化氢溶液按固液比为1g/1~20ml的比例混合后,室温下浸泡(浸泡时间约为1~24小时);所述过氧化氢溶液的质量浓度为6~30%;
3)、将步骤2)所得磁石用水(蒸馏水)洗涤直至洗涤液pH5.5~6.5,然后干燥至恒重,得到改性磁石。
作为本发明的改性磁石的制备方法的改进:所述步骤1)中,磁石200目过筛。
作为本发明的改性磁石的制备方法的进一步改进:所述步骤2)中,固液比为1g/10ml;过氧化氢溶液的质量浓度15~30%。
作为本发明的改性磁石的制备方法的进一步改进:所述步骤2)中,浸泡时间为6~12h。
作为本发明的改性磁石的制备方法的进一步改进:所述步骤3)中的干燥条件为于60±10℃的烘箱内下恒温干燥至恒重(约24h)。
本发明还同时提供了如上述方法制备而得的改性磁石的用途:用于重金属(主要指镉、砷)污染环境修复。
作为本发明的改性磁石的用途的改进:用于对土壤中重金属的修复与去除;或者用于对水体中重金属离子的吸附去除。
在本发明中,当改性磁石用于对土壤中重金属的修复与去除时,按照如下步骤:
(1)、按改性磁石:土体干重=1~10:100(优选5:100)的质量比将其加入待修复的土壤中,且混合均匀;
(2)、将上述步骤(1)所得的混合土体淹水(被水淹没)在室温条件下培养20-60天(优选30天);
(3)、步骤培养结束后采用磁铁或电磁铁吸附分离出富集重金属(包括镉、砷、铅等元素)的改性磁石。
上述使用后的改性磁石经后续的进一步处理,可实现重复利用。
在本发明中,当改性磁石用于对水体中重金属离子的吸附去除,包括如下步骤:
S1、量取100ml一定浓度的重金属如镉、砷等离子水溶液置于塑料容器中;
S2、按改性磁石:含重金属离子溶液=1~10:100(优选5:100)的固液比将其加入上述步骤S1中;
S3、将上述步骤S2中塑料容器置于恒温振荡器中水平振荡6~24h,振荡速率120~250rpm(优选振荡时间为12h,振荡速率为200rpm);
S4、上述步骤S3结束后采用磁铁或电磁铁分离吸附有镉或砷离子的改性磁石。
本发明具有如下技术优势:
1、本发明采用过氧化氢改性磁石,所得的改性磁石在重金属污染土壤和水体环境中具有应用潜力。
2、本发明所得的改性磁石能同时用于镉、砷等重金属污染土壤的修复与去除。
3、本发明所得的改性磁石能同时应用于废水中镉、砷等离子化合物的去除。
本发明利用磁石(天然磁石)进行化学改性,该改性磁石不但可以固定吸附水体或土壤中重金属元素,还能通过磁铁或电磁铁将水体或土壤中富集重金属元素的改性磁石物理分离,并可以对吸附材料进行改性再生。材料成本低廉,操作简单实用;本发明利用改性磁石吸附土壤或水体中镉、砷等重金属元素的方法,显著降低土壤或水体中重金属的含量及有效性,并实现重金属元素的回收。本发明的研究还可以推及应用到受镉、砷等重金属污染的沉积物、淤泥、半固体类垃圾等对象。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此。
下文中天然磁石的铁含量为48.6%,总镉和总砷的含量分别为0.09mg/kg和15.37mg/kg。
实施例1、一种改性磁石的制备方法,依次进行以下步骤:
1)、将天然磁石经200目过筛后称取10g;之后用蒸馏水清洗以除去其表面浮尘和杂质,多次清洗后直至洗涤液pH为5.88;采用磁铁分离磁石。
2)、对步骤1)所得的磁石加入100ml浓度为15%的过氧化氢溶液,浸泡12h后,再用蒸馏水清洗数次直至洗涤液pH为5.90;采用磁铁分离磁石。
3)、将步骤1)所得的磁石于60℃烘箱内烘干24h,即获得改性磁石。
原磁石(过200目的天然磁石)以及上述实施例1所得的15%过氧化氢改性磁石分别记为CS和CSH。
实验1、
改性磁石对土壤重金属修复与去除的方法:
选择两种重度重金属污染土壤A和土壤B,土壤A性质:pH为8.04,镉、砷的总量和有效性含量分别为17.12mg/kg、118.65mg/kg和3.08mg/kg和37.48mg/kg;土壤B性质:pH为5.13,镉、砷的总量和有效性含量分别为4.72mg/kg、4651.65mg/kg和0.83mg/kg和42.26mg/kg。按土壤干重的5%将CS和CSH以及加入土壤A和土壤B中,室温条件下淹水培养(每个组别,水的用量均保持一致)30天,每种处理6次重复;同时做不添加磁石空白处理3个。培养结束后,其中每个处理3份采用磁铁分离出磁石,用蒸馏水超声清洗干净后于烘箱内60℃下烘干后测定磁石中重金属含量;另3份培养土壤冷冻干燥后测定土壤中重金属的有效性。测定结果表明:
CSH处理显著降低土壤A和土壤B中有效态镉、砷等重金属元素的含量,CSH处理对重金属钝化效果显著优于CS处理。与原磁石相比,土壤A中CSH吸附固持态镉和砷含量分别增加了51倍和9倍;土壤B中CSH吸附固持态镉和砷含量分别增加了11倍和26倍。土壤中重金属的含量的检测结果如表1所述。
表1、磁石及改性磁石吸附后土壤中有效镉和砷的含量。
实施例2、将实施例1步骤2)中过氧化氢溶液由“15%”改成“6%”,其余等同于实施例1。
实施例3、将实施例1步骤2)中过氧化氢溶液由“15%”改成“30%”,其余等同于实施例1。
将上述实施例2和实施例3所得的改性磁石按照实验一所述方法进行检测,所得结果如表1所述。
实验2、改性磁石对水体中重金属离子吸附去除的方法:
采用吸附实验研究改性磁石对水体中镉、砷等金属离子的去除效果,首先采用6%、15%、30%的过氧化氢对磁石(CS)进行改性,即为实施例1~实施例3所得的改性磁石。将得到的改性磁石分别记为CSH1(实施例1,15%的过氧化氢)、CSH2(实施例2,6%的过氧化氢)、CSH2(实施例3,30%的过氧化氢)。按照5g/L的添加量,称取一定量的改性磁石于塑料瓶中,加入100mL含镉或砷离子的水溶液,镉离子初始浓度为20和50mg/L,砷离子初始浓度为2和5g/L;采用0.1mol/L氢氧化钠和0.1mol/L盐酸将原金属离子废水pH调至6.00,然后置于恒温振荡器上,在室温和200rpm条件下遮光振荡12h,每个处理3次重复;振荡结束后取样测定滤液中镉和砷离子的浓度,计算改性磁石对镉和砷离子的去除率,相比原磁石,采用15%浓度的过氧化氢改性磁石,显著提升了磁石对水体中镉和砷离子的去除效率,数据如表2所示。
表2、磁石及改性磁石对水体中镉和砷离子的去除率
对比实验:为了获得对水体中镉、砷等重金属吸附效果好的改性磁石,我们考察了醋酸、氢氧化钾、氯化锰、过氧化氢等化学试剂对磁石吸附性能的影响。
具体改性方法如下:
对比例1、醋酸改性:将10克磁石在650℃置于马弗炉内煅烧1小时后取出立马加入100mL浓度为5%的醋酸,反应冷却后用蒸馏水清洗至pH为6.0左右,于烘箱内干燥,醋酸改性磁石记为CSC。
对比例2-1、氢氧化钾改性:称取10克磁石按固液比1:10加入100ml浓度为0.1M的氢氧化钾溶液,浸泡24小时后,用蒸馏水清洗至清洗液pH为6.0左右,于烘箱内干燥,0.1M氢氧化钾改性的磁记为CSJ1。
对比例2-2、将对比例2-1中氢氧化钾溶液浓度由“0.1M”更改为“1M”,其余等同于对比例2-1,将1.0M氢氧化钾改性的所获得的磁石记为CSJ2。
对比例3-1、氯化锰改性:称取10克磁石按固液比1:10加入100ml浓度为5%的氯化锰溶液,浸泡24小时后,用蒸馏水清洗至清洗液pH恒定,于烘箱内干燥,5%浓度氯化锰改性的磁石记为CSM1。
对比例3-2、将对比例3-1中氯化锰溶液浓度由“5%”更改为“10%”,其余等同于对比例3-1,将10%浓度氯化锰溶液改性的所获得的磁石记为CSM2。
备注说明:上述所有对比例中的磁石均是指如同实施例1步骤1)所得的磁石。
按照5g/L的添加量,称取一定量的改性磁石(CS、CSC、CSJ1、CSJ2、CSJ3、CSM1、CSM2、CSH)于塑料瓶中,加入100mL含镉或砷离子的废水溶液,镉离子初始浓度为20和50mg/L,砷离子初始浓度为2和5g/L;采用0.1mol/L氢氧化钠和0.1mol/L盐酸将原金属离子废水pH调至6.00,然后置于恒温振荡器上,在室温和200rpm条件下遮光振荡12h,每个处理3次重复;振荡结束后取样测定滤液中镉和砷离子的浓度,计算改性磁石对镉和砷离子的去除率。
表3、磁石及改性磁石对水体中镉和砷离子的去除率
从表3中可以看出,通过醋酸、氢氧化钾、氯化锰和过氧化氢对磁石进行改性,过氧化氢改性磁石对水体中镉和砷离子的去除率都是最高的,而煅烧醋酸改性后对镉和砷吸附效果最差。因此,筛选出过氧化氢改性磁石方法显著提升了磁石的吸附性能。
最后,还需要注意的是,以上列举的仅是本发明的若干个具体实施例。显然,本发明不限于以上实施例,还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形,均应认为是本发明的保护范围。
Claims (8)
1.改性磁石的制备方法,其特征在于包括以下步骤:
1)、将铁含量≥40%的磁石经60~300目过筛后,用水清洗至洗涤液为pH5.5~6.5;所述%为质量%;
2)、将步骤1)所得磁石与过氧化氢溶液按固液比为1g/1~20ml的比例混合后,室温下浸泡;所述过氧化氢溶液的质量浓度为6~30%;
3)、将步骤2)所得磁石用水洗涤直至洗涤液pH5.5~6.5,然后干燥至恒重,得到改性磁石。
2.根据权利要求1所述的改性磁石的制备方法,其特征在于:
所述步骤1)中,磁石200目过筛。
3.根据权利要求1或2所述的改性磁石的制备方法,其特征在于:
所述步骤2)中,固液比为1g/10ml;过氧化氢溶液的质量浓度15~30%。
4.根据权利要求3所述的改性磁石的制备方法,其特征在于:
所述步骤2)中,浸泡时间为6~12h。
5.根据权利要求3所述的改性磁石的制备方法,其特征在于:
所述步骤3)中的干燥为:于60±10℃的烘箱内恒温干燥至恒重。
6.如权利要求1~5任一方法制备而得的改性磁石的用途,其特征在于:
所述改性磁石用于重金属污染环境修复。
7.根据权利要求6所述改性磁石的用途,其特征在于:用于对土壤中重金属的修复与去除。
8.根据权利要求6所述改性磁石的用途,其特征在于对:用于对水体中重金属离子的吸附去除。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710534395.7A CN107321298B (zh) | 2017-07-03 | 2017-07-03 | 改性磁石的制备方法及其在重金属污染修复中的应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710534395.7A CN107321298B (zh) | 2017-07-03 | 2017-07-03 | 改性磁石的制备方法及其在重金属污染修复中的应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107321298A CN107321298A (zh) | 2017-11-07 |
CN107321298B true CN107321298B (zh) | 2019-07-12 |
Family
ID=60198848
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710534395.7A Active CN107321298B (zh) | 2017-07-03 | 2017-07-03 | 改性磁石的制备方法及其在重金属污染修复中的应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107321298B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109837391A (zh) * | 2019-01-22 | 2019-06-04 | 浙江科技学院 | 从铅锌矿尾矿污染土壤中提取铊的方法及所用的吸附剂 |
CN115193901A (zh) * | 2022-08-15 | 2022-10-18 | 青岛冠中环境技术有限公司 | 一种重金属污染盐碱地的治理方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN201517038U (zh) * | 2009-10-13 | 2010-06-30 | 何景泽 | 水质处理器 |
CN102319725A (zh) * | 2011-05-26 | 2012-01-18 | 中国矿业大学(北京) | 去除土壤中重金属的方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7279103B2 (en) * | 2005-09-13 | 2007-10-09 | United States Of America Enviromental Protection Agency | Process for the purification of acidic metal-bearing waste waters to permissible discharge levels with recovery of marketable metal products |
-
2017
- 2017-07-03 CN CN201710534395.7A patent/CN107321298B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN201517038U (zh) * | 2009-10-13 | 2010-06-30 | 何景泽 | 水质处理器 |
CN102319725A (zh) * | 2011-05-26 | 2012-01-18 | 中国矿业大学(北京) | 去除土壤中重金属的方法 |
Non-Patent Citations (2)
Title |
---|
Synthesis of carbon-coated, porous and water-dispersive Fe3O4 nanocapsules and their excellent performance for heavy metal removal applications;Jinyoung Chun等;《Chemosphere》;20120811;第89卷;全文 |
磁石生、煅品对水煎液中砷溶出量的影响;铁步荣 等;《中国中药杂志》;19951231;第20卷(第5期);全文 |
Also Published As
Publication number | Publication date |
---|---|
CN107321298A (zh) | 2017-11-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Ju et al. | Effective and selective recovery of gold and palladium ions from metal wastewater using a sulfothermophilic red alga, Galdieria sulphuraria | |
Yu et al. | Highly efficient immobilization of environmental uranium contamination with Pseudomonas stutzeri by biosorption, biomineralization, and bioreduction | |
Qu et al. | Bioleaching of rare earth and radioactive elements from red mud using Penicillium tricolor RM-10 | |
Xie et al. | Adsorption of phosphate by sediments in a eutrophic lake: Isotherms, kinetics, thermodynamics and the influence of dissolved organic matter | |
CN107413841A (zh) | 一种重金属污染土壤的微生物修复剂及修复方法 | |
Li et al. | Fe–colloid cotransport through saturated porous media under different hydrochemical and hydrodynamic conditions | |
CN103623782A (zh) | 复合磁性吸附材料的制备和去除废水中重金属离子的方法 | |
CN106623400A (zh) | 一种钝化修复重金属污染土壤的方法 | |
CN113321196B (zh) | 一种从酸性六价铀溶液中直接矿物固铀的方法 | |
CN110899317A (zh) | 一种基于磁性生物炭的镉污染农田土壤修复方法 | |
CN102744041A (zh) | 去除硝酸盐的可渗透反应墙用填充材料及其制备方法 | |
CN107321298B (zh) | 改性磁石的制备方法及其在重金属污染修复中的应用 | |
CN107312933A (zh) | 一种从低浓度重钇稀土废水中回收稀土的生物方法 | |
CN109821878A (zh) | 蛭石负载纳米铁基材料对土壤重金属铅的固定方法 | |
Olufemi et al. | Adsorption of nickel (II) ions from aqueous solution using banana peel and coconut shell | |
CN111570494B (zh) | 一种重金属污染土壤修复方法 | |
CN114377659A (zh) | 一种纳米复合除铊剂的制备方法 | |
Yang et al. | Use of flue gas desulfurization gypsum for leaching Cd and Pb in reclaimed tidal flat soil | |
CN105617980B (zh) | 一种生物表面活性剂改性磁性膨润土的方法及其应用 | |
Grawunder et al. | Rare earth elements in acidic systems–biotic and abiotic impacts | |
CN107051394A (zh) | 一种杯芳烃修饰的磁性纳米吸附剂制备及其吸附低浓度铀的方法 | |
Yang et al. | Enhancing commercially iron powder electron transport by surface biosulfuration to achieve uranium extraction from uranium ore wastewater | |
CN102965312A (zh) | 一种提高细菌重金属吸附能力的修饰方法、吸附剂及其应用 | |
CN109317089B (zh) | 一种磁性吸附材料及其制备和用于处理含铊废水的方法 | |
CN102327893B (zh) | 去除重金属土壤淋洗液中铅的材料及其制备方法与应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |