CN109759007A - A kind of sepiolite composite material and preparation method and application loading nanometer carbonate-hydroxylapatite - Google Patents
A kind of sepiolite composite material and preparation method and application loading nanometer carbonate-hydroxylapatite Download PDFInfo
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- CN109759007A CN109759007A CN201910149408.8A CN201910149408A CN109759007A CN 109759007 A CN109759007 A CN 109759007A CN 201910149408 A CN201910149408 A CN 201910149408A CN 109759007 A CN109759007 A CN 109759007A
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- hydroxylapatite
- composite material
- sepiolite
- carbonate
- nanometer carbonate
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- 239000002131 composite material Substances 0.000 title claims abstract description 107
- 239000004113 Sepiolite Substances 0.000 title claims abstract description 104
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 104
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 104
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 78
- 238000011068 loading method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 19
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 17
- 238000010521 absorption reaction Methods 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 15
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 235000021317 phosphate Nutrition 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000012851 eutrophication Methods 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 229910052745 lead Inorganic materials 0.000 description 12
- 238000002161 passivation Methods 0.000 description 11
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 3
- 235000019838 diammonium phosphate Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 210000003608 fece Anatomy 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010871 livestock manure Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- TVBSSDNEJWXWFP-UHFFFAOYSA-N nitric acid perchloric acid Chemical compound O[N+]([O-])=O.OCl(=O)(=O)=O TVBSSDNEJWXWFP-UHFFFAOYSA-N 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- CGMRCMMOCQYHAD-UHFFFAOYSA-J dicalcium hydroxide phosphate Chemical compound [OH-].[Ca++].[Ca++].[O-]P([O-])([O-])=O CGMRCMMOCQYHAD-UHFFFAOYSA-J 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012852 risk material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of sepiolite composite material and preparation methods and application for loading nanometer carbonate-hydroxylapatite.The composite material includes sepiolite and nanometer carbonate-hydroxylapatite, and nanometer carbonate-hydroxylapatite is supported on sepiolite.Preparation method are as follows: sepiolite powder is added in calcium base (phosphorus base) solution and is sufficiently mixed, add phosphorus base (calcium base) solution, it adjusts pH value and precipitation reaction generation nanometer carbonate-hydroxylapatite occurs, and be supported on sepiolite, obtain the sepiolite composite material of load nanometer carbonate-hydroxylapatite.Nanometer carbonate-hydroxylapatite is carried on sepiolite surface by resulting composite material, avoids the reunion of nanometer carbonate-hydroxylapatite, remains it to the superior adsorption capacity of heavy metal；Its stability is enhanced, the loss of phosphorus and the risk of eutrophication are avoided.The absorption that prepared material can be applied in water with heavy metal element lead, cadmium in bed mud is fixed, and has application prospect in water body purification field.
Description
Technical field
Present invention relates particularly to it is a kind of load nanometer carbonate-hydroxylapatite sepiolite composite material and preparation method and
Remove heavy metal contaminants lead in bed mud and water, the application in cadmium.
Background technique
In recent years, heavy metal element such as lead, cadmium etc. is attracted wide attention into the pollution problem of environment bring.Lead, cadmium
Equal heavy metal contaminants have the characteristics that high toxicity, persistence and difficult to degrade, not only influence environmental quality, but also be easy to pass through food
Object chain enters human body, seriously endangers human health.It therefore, is environment remediation neck to the reparation of the heavy metal-polluted waters such as lead, cadmium
The research hotspot in domain.
Currently, adsorbing the huge sum of money in fixed water body, deposit and soil environment using nano-apatite class phosphorated material
Belong to element, it is considered to be a kind of pollution control technology of great application prospect.Compared with conventional repair materials, nano-apatite tool
There is good biocompatibility, it is nontoxic, it is a kind of fixed material of environmentally friendly absorption；Simultaneously because its unique chemistry
Composition and crystal structure have good adsorption capacity to detection device for multi metallic elements, and to the fixed energy of the absorption of lead and cadmium
Power best (Geochemical Journal, 2010,44 (3) 233-239; Arabian Journal of
Chemistry, 2012,5 (4), 439-446).Particularly, the nanometer carbonate-hydroxylapatite containing carbonate, i.e. nano-sized carbon hydroxyl
Apatite, crystallization degree is lower, and specific surface area is bigger, stronger to the absorption crystallized ability of heavy metal.U.S. environment Journal of Management
(Journal of Environmental Management, 2008,86 (1), 319-328.) report heavy using neutralizing
Absorption of the hydroxyapatite containing carbonate of shallow lake method preparation to lead ion in aqueous solution；U.S. environment engineering science magazine
(Environmental Engineering Science, 2008,25,725-736.), which is reported, utilizes Fishbone preparation
Fixation of the nanometer carbonate-hydroxylapatite to lead in soil；U.S.'s risk material magazine (Journal of Hazardous
Materials, 2010,177 (1-3), 126-130.) report using eggshell preparation carbonate-hydroxylapatite to lead in water from
The absorption of son.
But above-mentioned carbonate-hydroxylapatite as adsorbent apply when there are significant defects.On the one hand, as a kind of phosphorous
The carbonate-hydroxylapatite solubility of material, Nano grade is higher, release phosphate radical is easy when water body uses, so in practical application
In easily bring the risk of water eutrophication, therefore be not suitable for directly applying to the reparation of water body or bed mud；On the other hand, nanometer
Carbonate-hydroxylapatite is as a kind of nano material, and large specific surface area, surface-active is high, and very solution is reunited in the solution, is formed
Micron level, larger-size aggregate lose reactivity, to reduce the adsorption efficiency to heavy metal ion.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of sepiolite composite wood for loading nanometer carbonate-hydroxylapatite
Material and its preparation method and application, is carried on sepiolite surface for nanometer carbonate-hydroxylapatite, avoids nanometer carbonate-hydroxylapatite
Reunite, remains it to the superior adsorption capacity of heavy metal；It enhances its stability, avoids the loss and eutrophication of phosphorus
Risk.The absorption that prepared material can be applied in water with heavy metal element lead, cadmium in bed mud is fixed.
In order to achieve the above objectives, technical solution provided by the invention are as follows:
A kind of sepiolite composite material loading nanometer carbonate-hydroxylapatite, the sepiolite composite material include sepiolite and receive
Rice carbonate-hydroxylapatite, the nanometer carbonate-hydroxylapatite are supported on the sepiolite.
Preferably, the nanometer carbonate-hydroxylapatite is attached in the surface and pore structure of sepiolite.
Preferably, the nanometer carbonate-hydroxylapatite granularity in the sepiolite composite material is no more than 100 nm.
The preparation method of the sepiolite composite material of above-mentioned load nanometer carbonate-hydroxylapatite, comprising the following steps:
(1) calcium based solution of 0.167-1.67mol/L is prepared；
(2) the phosphorus based sols of 0.1-1.0mol/L are prepared；
(3) sepiolite powder of 100-300 mesh is added in calcium based solution according to the ratio of solid-to-liquid ratio 1g:(5-10) mL, is being filled
Divide in the case where mixing and being stirred continuously, mix phosphorus based sols with above-mentioned solution according to the ratio of Ca/P molar ratio 5:3, and adds
Entering aqueous slkali maintains pH value to be higher than 10, and reaction is separated by solid-liquid separation after 30-60 minutes, and obtained solid is washed with deionized 3-5 times, cold
The dry rear sepiolite composite material for obtaining load nanometer carbonate-hydroxylapatite is lyophilized；Or by the sepiolite powder of 100-300 mesh according to
Solid-to-liquid ratio 1g:(5-10) ratio of mL is added in phosphorus based sols, in the case where being sufficiently mixed and being stirred continuously, according to Ca/P
The ratio of molar ratio 5:3 mixes calcium based solution with above-mentioned solution, and aqueous slkali is added, pH value is maintained to be higher than 10, reacts 30-60
It is separated by solid-liquid separation after minute, obtained solid is washed with deionized 3-5 times, and load nanometer carbonate-hydroxylapatite is obtained after freeze-drying
Sepiolite composite material.
Preferably, the calcium based solution in step (1) is the true solution or suspended of calcium hydroxide, calcium nitrate or calcium chloride
Liquid.
Preferably, the phosphorus based sols in step (2) are phosphoric acid, phosphate solution containing ammonium, solution containing na phosphates or contain potassium
Phosphate solution.
Preferably, aqueous slkali used in step (3) can be ammonium hydroxide, potassium hydroxide or sodium hydroxide.
Heavy metal of the sepiolite composite material of above-mentioned load nanometer carbonate-hydroxylapatite in adsorbed water body or bed mud
Using.
The application side of heavy metal of the sepiolite composite material of above-mentioned load nanometer carbonate-hydroxylapatite in absorption bed mud
Method are as follows: by the sepiolite composite material of the load nanometer carbonate-hydroxylapatite according to mass fraction 0.5-2% ratio be applied to by
In heavy metal lead or/and the bed mud of cadmium pollution, it is uniformly mixed, aging 1 month, the leaching content of lead or/and cadmium can be reduced.
The application side of heavy metal of the sepiolite composite material of above-mentioned load nanometer carbonate-hydroxylapatite in adsorbed water body
Method are as follows: by the sepiolite composite material of the load nanometer carbonate-hydroxylapatite according to the amount of 0.5-5g/L be added to containing lead from
In the water of son or/and cadmium ion, stirring or oscillation can be removed to lead in water or/and cadmium ion.
Compared with prior art, the invention has the following beneficial effects:
(1) nanometer carbonate-hydroxylapatite is supported on sepiolite, composite material is made, can be avoided the group of nanometer carbonate-hydroxylapatite
It is poly-, its dispersibility is improved, nanometer superior adsorption capacity of carbonate-hydroxylapatite counterweight metal is enable to give full play to；
(2) for sepiolite as environmentally friendly inorganic material, itself is nontoxic, and has fabulous stability, utilizes Hai Pao
Masonry is carrier, will not generate secondary pollution；And nanometer carbonate-hydroxylapatite is supported on sepiolite, nano-sized carbon hydroxyl can be enhanced
The stability of apatite prevents its dissolution and phosphorous loss, avoids the risk for bringing water eutrophication；In addition, sepiolite sheet
Body also has stronger ion-exchange capacity to heavy metal ion, the gained composite material in conjunction with nanometer carbonate-hydroxylapatite, can be more
It effectively realizes and the absorption of heavy metal ion is fixed.Show the leaching of the bed mud to lead, cadmium composite pollution through DTPA leaching experiment
Output reduces 77-90% and 69-84% respectively；Water body to lead, cadmium ion composite pollution is, it can be achieved that lead in water, cadmium ion
Removal rate reaches 92-100% and 80-100% respectively.
(3) preparation process of sepiolite supported nano carbonate-hydroxylapatite is simple in the present invention, and reaction condition is content with very little, former
Expect cheap and easy to get, reaction is mild, convenient for operation.
Detailed description of the invention
Fig. 1 is the SEM spectrum of the sepiolite composite material of the sepiolite and load nanometer carbonate-hydroxylapatite in embodiment 2；
Wherein, A is the SEM spectrum of sepiolite, and B is the SEM spectrum for loading the sepiolite composite material of nano-sized carbon hydroxyapatite.
Fig. 2 is the XRD spectrum of the sepiolite composite material of the sepiolite and load nanometer carbonate-hydroxylapatite in embodiment 2.
Fig. 3 is the infrared spectroscopy of the sepiolite composite material of the sepiolite and load nanometer carbonate-hydroxylapatite in embodiment 2
Figure.
Specific embodiment
With reference to the accompanying drawings of the specification and specific embodiment, the present invention is described in detail.
Embodiment 1
100 mesh sepiolite powders are added in the diammonium hydrogen phosphate solution of 0.1mol/L in the ratio of solid-to-liquid ratio 1g:5mL, continuous
Under stirring condition, the calcium hydroxide solution of 0.167mol/L is mixed with above-mentioned solution in the ratio of Ca/P molar ratio 5:3, and
Potassium hydroxide, which is added, maintains pH value to be higher than 10, and reaction is separated by solid-liquid separation after 45 minutes, and obtained solid is washed with deionized 3-5 times,
The sepiolite composite material of load nanometer carbonate-hydroxylapatite is obtained after freeze-drying.
Embodiment 2
100 mesh sepiolite powders are added in the calcium nitrate solution of 0.835 mol/L in the ratio of solid-to-liquid ratio 1g:10mL, continuous
Under stirring condition, the diammonium hydrogen phosphate solution of 0.5mol/L is mixed with above-mentioned solution in the ratio of Ca/P molar ratio 5:3, and
Ammonia spirit, which is added, maintains pH value to be higher than 10, and reaction is separated by solid-liquid separation after 30 minutes, and obtained solid is washed with deionized 3-5 times,
The sepiolite composite material of load nanometer carbonate-hydroxylapatite is obtained after freeze-drying.
Using scanning electron microscope to the sepiolite composite material of sepiolite powder and obtained load nanometer carbonate-hydroxylapatite
Electron scanning is carried out, SEM spectrum is as shown in Figure 1.Wherein, Figure 1A is the SEM figure of sepiolite, prepared by Figure 1B corresponding embodiment 2
Load nanometer carbonate-hydroxylapatite sepiolite composite material, as can be seen from Figure granularity be less than 100nm nano particle (arrow institute
Show) it is supported on fibrous sepiolite.
Electricity is carried out using sepiolite composite material of the X-ray diffraction to sepiolite powder and obtained load nanometer carbonate-hydroxylapatite
Son scanning, as shown in Fig. 2, as seen from the figure compared with pure sepiolite map, the XRD spectrum of composite material has XRD spectrum simultaneously
The characteristic peak of sepiolite and nanometer carbonate-hydroxylapatite.
It is carried out using sepiolite composite material of the infra-red sepectrometry to sepiolite powder and obtained load nanometer carbonate-hydroxylapatite
Electron scanning, infrared spectrogram have the peak of carbonate as shown in figure 3, can be seen from the chart on sepiolite composite material, and
And have hydroxyl absorption peak at wave number 632, can prove to contain in composite material is carbonate-hydroxylapatite.
Embodiment 3
300 mesh sepiolite powders are added in the calcium chloride solution of 1.67 mol/L in the ratio of solid-to-liquid ratio 1g:10mL, are constantly being stirred
Under the conditions of mixing, the diammonium hydrogen phosphate solution of 1.0mol/L is mixed in the ratio of Ca/P molar ratio 5:3 with above-mentioned solution, and added
Entering sodium hydroxide maintains pH value to be higher than 10, and reaction is separated by solid-liquid separation after 30 minutes, and obtained solid is washed with deionized 3-5 times, cold
The dry rear sepiolite composite material for obtaining load nanometer carbonate-hydroxylapatite is lyophilized.
Embodiment 4
The sepiolite composite material of load nanometer carbonate-hydroxylapatite is made respectively to the bed mud of lead contamination, cadmium pollution in embodiment 2
Bed mud and the bed mud of lead and cadmium composite pollution carry out repairing test.
1, the sepiolite composite material for loading nanometer carbonate-hydroxylapatite is passivated remediating lead-contaminated bed mud
Unpolluted bed mud is taken, by the Pb for adding 500 mg/kg2+, simulation lead contamination bed mud is made, is passivated reparation
Experiment.0.5% and 2% composite material is added, while in bed mud respectively not add the bed mud of composite material as control (CK).
Bed mud and composite material are mixed well, and apply a certain amount of urea and potassium chloride as base manure, is fitted into small basin, every basin dress
Enter the bed mud for being equivalent to 2.0 kg oven-dried weights, each processing is in triplicate.Rape is sowed after aging 1 month.To growth of rape 60
Sampling is harvested after it, is cleared up using nitric acid-perchloric acid method, the Pb content in atomic absorption spectroscopy determination plant sample,
Using available state Pb content in DTPA restricted-access media measurement bed mud.
The sepiolite composite material for loading nanometer carbonate-hydroxylapatite is passivated the influence after repaired to rape overground part Pb content
As shown in table 1.Seen from table 1, with the increase of composite material dosage, rape overground part Pb content is remarkably decreased, when compound use
When amount is 0.5%, rape overground part Pb content reduces 85% than control, and when dosage is 2%, rape overground part Pb content ratio
Control reduces 96%, it is seen then that the sepiolite composite material of load nanometer carbonate-hydroxylapatite of the invention can be effectively reduced plant
Absorption of the object to Pb.
The sepiolite composite material passivation that table 1 loads nanometer carbonate-hydroxylapatite, which is repaired, contains rape (dry sample) overground part Pb
The influence of amount
Influence such as 2 institute of table that state Pb is extracted to bed mud DTPA is repaired in the sepiolite composite material passivation for loading nanometer carbonate-hydroxylapatite
Show.As seen from table, with the increase of composite material dosage, bed mud available state Pb content is gradually decreased.When composite material dosage is
When 0.5%, bed mud available state Pb content reduces 78% than control, and when dosage is 2%, bed mud available state Pb content is than control
Reduce 92%.
The shadow that state Pb is extracted to bed mud DTPA is repaired in the sepiolite composite material passivation that table 2 loads nanometer carbonate-hydroxylapatite
It rings
2, the sepiolite composite material for loading nanometer carbonate-hydroxylapatite is passivated restoring cadmium polluted bed mud
Unpolluted bed mud is taken, by the Cd for adding 20 mg/kg2+, simulation lead contamination bed mud is made, it is real to be passivated reparation
It tests.0.5% and 2% composite material is added, while in bed mud respectively not add the bed mud of composite material as control (CK).It will
Bed mud and composite material mix well, and apply a certain amount of urea and potassium chloride as base manure, are fitted into small basin, and every basin is packed into
It is equivalent to the bed mud of 2.0 kg oven-dried weights, each processing is in triplicate.Rape is sowed after aging 1 month.To growth of rape 60 days
Harvest sampling afterwards is cleared up using nitric acid-perchloric acid method, and the Cd content in atomic absorption spectroscopy determination plant sample is adopted
With available state Cd content in DTPA restricted-access media measurement bed mud.
The sepiolite composite material for loading nanometer carbonate-hydroxylapatite is passivated the influence after repaired to rape overground part Cd content
As shown in table 3.Seen from table 3, with the increase of composite material dosage, rape overground part Cd content is remarkably decreased, when compound use
When amount is 0.5%, rape overground part Cd content reduces 73% than control, and when dosage is 2%, rape overground part Cd content ratio
Control reduces 89%, it is seen then that the sepiolite composite material of load nanometer carbonate-hydroxylapatite of the invention can be effectively reduced plant
Absorption of the object to Pb.
The sepiolite composite material passivation that table 3 loads nanometer carbonate-hydroxylapatite, which is repaired, contains rape (dry sample) overground part Cd
The influence of amount
Influence such as 4 institute of table that state Cd is extracted to bed mud DTPA is repaired in the sepiolite composite material passivation for loading nanometer carbonate-hydroxylapatite
Show.As seen from table, with the increase of composite material dosage, bed mud available state Cd content is gradually decreased.When composite material dosage is
When 0.5%, bed mud available state Cd content reduces 70% than control, and when dosage is 2%, bed mud available state Cd content is than control
Reduce 84%.
The shadow that state Pb is extracted to bed mud DTPA is repaired in the sepiolite composite material passivation that table 4 loads nanometer carbonate-hydroxylapatite
It rings
3, the bed mud of lead, cadmium combined pollution is repaired in the sepiolite composite material passivation for loading nanometer carbonate-hydroxylapatite
Somewhere is acquired by lead, the heavily contaminated river bottom mud of cadmium combined pollution, is fitted into plastic barrel after the acquisition of bed mud sample and transports reality back
Room is tested, through the screen to filtrate, after rejecting the foreign matters such as large stone, sawdust, plant and animal residues and house refuse, natural air drying after natural air drying
It is spare.Wherein total lead and total cadmium content are respectively 413 and 14mg/kg.0.5% and 2% composite material is added in bed mud respectively,
Simultaneously not add the bed mud of composite material as control (CK).Bed mud and composite material are mixed well, and applied a certain amount of
Urea and potassium chloride are fitted into small basin as base manure, and every basin is packed into the bed mud for being equivalent to 2.0 kg oven-dried weights, and each processing repeats
Three times.Rape is sowed after aging 1 month.Sampling is harvested after growth of rape 60 days, is cleared up using nitric acid-perchloric acid method, atom
Absorptiometry measure plant sample in Pb, Cd content, using DTPA restricted-access media measurement bed mud in available state Pb,
Cd content.
To the shadow of rape overground part Pb, Cd content after the sepiolite composite material passivation reparation of load nanometer carbonate-hydroxylapatite
It rings as shown in table 5.By table 5 as it can be seen that with composite material dosage increase, rape overground part Pb, Cd content is remarkably decreased, when multiple
When the amount of sharing is 0.5%, rape overground part Pb, Cd content reduces 80% and 71% than control, and when dosage is 2%, Rice-rape fields
Top Pb, Cd content reduces 93% and 86% than control, it is seen then that the sepiolite of load nanometer carbonate-hydroxylapatite of the invention is compound
Material can be effectively reduced absorption of the plant to Pb, Cd.
The sepiolite composite material passivation that table 5 loads nanometer carbonate-hydroxylapatite is repaired to rape (dry sample) overground part Pb, Cd
The influence of content
The influence such as table that state Pb, Cd is extracted to bed mud DTPA is repaired in the sepiolite composite material passivation for loading nanometer carbonate-hydroxylapatite
Shown in 6.As shown in Table 6, with the increase of composite material dosage, bed mud available state Pb, Cd content is gradually decreased.Work as composite material
When dosage is 0.5%, bed mud available state Pb, Cd content reduces 77% and 69% than control respectively, and when dosage is 2%, bed mud
Available state Pb, Cd content reduces 90% and 84% than control respectively.
The sepiolite composite material passivation that table 6 loads nanometer carbonate-hydroxylapatite, which is repaired, extracts state Pb, Cd to bed mud DTPA
It influences
Embodiment 5
Absorption of the sepiolite composite material of nanometer carbonate-hydroxylapatite to Heavy Metals in Waters will be loaded made from embodiment 2.
Sepiolite composite material is added separately in the water containing lead ion, water containing cadmium ion neutralize containing lead from
Son stirs or vibrates 2 hours the removal, it can be achieved that lead, cadmium ion in water with the water of cadmium ion.
1, in the water containing lead ion, sepiolite composite material is to the Pb in water2+Removal effect is as follows:
According to the composite material dosage of 1g/L, in pH5, Pb2+When 600 mg/L of initial concentration, removal rate is up to 95%；
According to the composite material dosage of 5g/L, in pH5, Pb2+When 600 mg/L of initial concentration, removal rate is up to 99%；
According to the composite material dosage of 1g/L, in pH7, Pb2+When 600 mg/L of initial concentration, removal rate is up to 99%；
According to the composite material dosage of 5g/L, in pH7, Pb2+When 600 mg/L of initial concentration, removal rate is up to 100%；
2, in the water containing cadmium ion, sepiolite composite material is to the Cd in water2+Removal effect is as follows:
According to the composite material dosage of 1g/L, in pH5, Cd2+When 20 mg/L of initial concentration, removal rate is up to 85%；
According to the composite material dosage of 5g/L, in pH5, Cd2+When 20 mg/L of initial concentration, removal rate is up to 98%；
According to the composite material dosage of 1g/L, in pH7, Cd2+When 20 mg/L of initial concentration, removal rate is up to 99%；
According to the composite material dosage of 5g/L, in pH7, Cd2+When 20 mg/L of initial concentration, removal rate is up to 100%；
3, in the water containing lead ion and cadmium ion, sepiolite composite material is to the Pb in water2+And Cd2+Removal effect is as follows:
According to the composite material dosage of 1g/L, in pH5, Pb2+When 600 mg/L of initial concentration, Cd2+20 mg/L of initial concentration
When, Pb removal rate up to 92%, Cd removal rate up to 80%；
According to the composite material dosage of 5g/L, in pH5, Pb2+When 600 mg/L of initial concentration, Cd2+20 mg/L of initial concentration
When, Pb removal rate up to 99%, Cd removal rate up to 93%；
According to the composite material dosage of 1g/L, in pH7, Pb2+When 600 mg/L of initial concentration, Cd2+20 mg/L of initial concentration
When, Pb removal rate up to 99%, Cd removal rate up to 98%；
According to the composite material dosage of 5g/L, in pH7, Pb2+When 600 mg/L of initial concentration, Cd2+20 mg/L of initial concentration
When, Pb removal rate up to 100%, Cd removal rate up to 100%.
Claims (10)
1. a kind of sepiolite composite material for loading nanometer carbonate-hydroxylapatite, it is characterised in that: the sepiolite composite material
Including sepiolite and nanometer carbonate-hydroxylapatite, the nanometer carbonate-hydroxylapatite is supported on the sepiolite.
2. a kind of sepiolite composite material for loading nanometer carbonate-hydroxylapatite according to claim 1, it is characterised in that: institute
The nanometer carbonate-hydroxylapatite stated is attached in the surface and pore structure of sepiolite.
3. a kind of sepiolite composite material for loading nanometer carbonate-hydroxylapatite according to claim 1, it is characterised in that institute
The nanometer carbonate-hydroxylapatite granularity stated in sepiolite composite material is no more than 100 nm.
4. a kind of preparation method of the sepiolite composite material of the load nanometer carbonate-hydroxylapatite as described in claim 1-3,
It is characterized in that, comprising the following steps:
(1) calcium based solution of 0.167-1.67mol/L is prepared；
(2) the phosphorus based sols of 0.1-1.0mol/L are prepared；
(3) sepiolite powder of 100-300 mesh is added in calcium based solution according to the ratio of solid-to-liquid ratio 1g:(5-10) mL, is being filled
Divide in the case where mixing and being stirred continuously, mix phosphorus based sols with above-mentioned solution according to the ratio of Ca/P molar ratio 5:3, and adds
Entering aqueous slkali maintains pH value to be higher than 10, and reaction is separated by solid-liquid separation after 30-60 minutes, and obtained solid is washed with deionized 3-5 times, cold
The dry rear sepiolite composite material for obtaining load nanometer carbonate-hydroxylapatite is lyophilized；Or by the sepiolite powder of 100-300 mesh according to
Solid-to-liquid ratio 1g:(5-10) ratio of mL is added in phosphorus based sols, in the case where being sufficiently mixed and being stirred continuously, according to Ca/P
The ratio of molar ratio 5:3 mixes calcium based solution with above-mentioned solution, and aqueous slkali is added, pH value is maintained to be higher than 10, reacts 30-60
It is separated by solid-liquid separation after minute, obtained solid is washed with deionized 3-5 times, and load nanometer carbonate-hydroxylapatite is obtained after freeze-drying
Sepiolite composite material.
5. the preparation method of the sepiolite composite material of load nanometer carbonate-hydroxylapatite according to claim 4, feature
It is that the calcium based solution in step (1) is the true solution or suspension of calcium hydroxide, calcium nitrate or calcium chloride.
6. the preparation method of the sepiolite composite material of load nanometer carbonate-hydroxylapatite according to claim 4, feature
It is that the phosphorus based sols in step (2) are phosphoric acid, phosphate solution containing ammonium, solution containing na phosphates or phosphate solution containing potassium.
7. the preparation method of the sepiolite composite material of load nanometer carbonate-hydroxylapatite according to claim 4, feature
It is that aqueous slkali used in step (3) can be ammonium hydroxide, potassium hydroxide or sodium hydroxide.
8. the sepiolite composite material of load nanometer carbonate-hydroxylapatite as described in any one of claims 1-3 in adsorbed water body or
The application of heavy metal in bed mud.
9. loading heavy metal of the sepiolite composite material of nanometer carbonate-hydroxylapatite in absorption bed mud according to claim 8
Application, which is characterized in that by the sepiolite composite material of the load nanometer carbonate-hydroxylapatite according to mass fraction 0.5-
2% ratio is applied to by heavy metal lead or/and the bed mud of cadmium pollution, is uniformly mixed, aging 1 month, can reduce lead or/and
The leaching content of cadmium.
10. loading a huge sum of money of the sepiolite composite material of nanometer carbonate-hydroxylapatite in adsorbed water body according to claim 8
The application of category, which is characterized in that by the sepiolite composite material of the load nanometer carbonate-hydroxylapatite according to 0.5-5g/L's
Amount is added in the water containing lead ion or/and cadmium ion, and stirring or oscillation can be removed to lead in water or/and cadmium ion.
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