CN101890337A - Metal ion nanoadsorbent - Google Patents
Metal ion nanoadsorbent Download PDFInfo
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- CN101890337A CN101890337A CN 201010242198 CN201010242198A CN101890337A CN 101890337 A CN101890337 A CN 101890337A CN 201010242198 CN201010242198 CN 201010242198 CN 201010242198 A CN201010242198 A CN 201010242198A CN 101890337 A CN101890337 A CN 101890337A
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- edta
- adsorption
- molecular sieve
- metal ion
- adsorbent
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Abstract
The invention relates to a metal ion nanoadsorbent which can adsorb metal ions in a water body, such as Cr<6+> and Cd<2+>, belonging to the technical field of inorganic functional materials. EDTA is an important chelating agent and can form stable water-soluble complexes with alkali metals, rare earth elements, transition metals and the like through chemical adsorption; however, as the EDTA is often united in the water, the dispersion is poor, and the adsorption effect is not well. The prior art adopts a Zeolite-A zeolite molecular sieve to adsorb the metal ions in the water body through physical adsorption. The adsorbent is characterized in that the chelating agent of the EDTA is distributed in the mesoporous nano-molecular sieve, the adsorbent has multi-adsorption effect including the physical adsorption and the chemical adsorption, and can adsorb 98.0% of Cr<6+> and 99.0% of Cd<2+> in the water body in 30 minutes.
Description
Technical field
The present invention relates to a kind of metal ion nanoadsorbent, the metal ion in can adsorbed water body is as Cr
6+, Cd
2+, belong to the inorganic functional material technical field.
Background technology
In the last few years, along with industrialized development, mankind's activity was more and more serious to the destruction of its living environment.Administering environment has become instant task, also is an obligation one can't decline.The improvement of water body is particularly urgent.Some heavy metal element in the water body as chromium, cadmium, nickel etc., all has bigger harm to human body, so the adsorption treatment of heavy metal element is a emphasis in the current water body treating in the water body.
EDTA (ethylenediamine tetra-acetic acid) is a kind of important chelating agent, can and the stable water soluble complexs of formation such as alkali metal, rare earth element and transition metal, and EDTA molecule can 4 metal ions of complexing, therefore, EDTA can be as a kind of important water treatment agent.Yet because EDTA usually is rendered as holding-like in water, so its dispersiveness is relatively poor, suction-operated is difficult to give full play to; In addition, be the water body treating adsorbent only with EDTA, adsorption capacity is limited.
Published one piece of paper that is entitled as " the Zeolite-A zeolite molecular sieve is removed heavy metal contaminants in the water body " that the firm people of grade writes by Zhan on " physical and chemical inspection-chemical fascicle " 2008 the 44th the 1st phase of volume, the document discloses one with Zeolite-A zeolite molecular sieve absorption Pb
2+, Mn
2+, Cu
2+, Ni
2+Technology Deng metal ion.Its adsorption effect only comes from the physical absorption of molecular sieve itself.
The SBA-15 molecular sieve be a kind of be the mesoporous material that the template agent prepares in acid synthetic system with the triblock copolymer, its aperture size in 4.6～30.0nm scope, its aperture maximum in existing nano molecular sieve material, pore volume can reach 0.85cm
3More than/the g, specific surface is big, heat endurance and good hydrothermal stability, be beneficial to assembly operation, and, have a large amount of silicon hydroxyls on the inside and outside surface of SBA-15 molecular sieve, determined that the SBA-15 molecular sieve has the adsorptivity that is better than the Zeolite-A zeolite molecular sieve, this makes the SBA-15 molecular sieve become a kind of good adsorption material again.
Summary of the invention
The objective of the invention is to obtain a kind of sorbing material, utilize the complexing of chelating agent, the suction-operated of molecular sieve to realize the absorption of metal ion in the water body, and described chelating agent has high dispersion.For this reason, we have invented the present invention's metal ion nanoadsorbent.
The present invention's adsorbent is characterized in that, is distributed with chelating agent EDTA (ethylenediamine tetra-acetic acid) in nano molecular sieve is mesoporous.
The present invention's preparation of adsorbent is such, adopt liquid phase method with EDTA be assembled into nano molecular sieve mesoporous in, main body is a nano molecular sieve, object is EDTA, the two constitutes a kind of compound.
Its technique effect of the present invention is, EDTA be distributed in nano molecular sieve mesoporous in, because mesoporous restriction, one side is eliminated the phenomenon of uniting of EDTA, and makes the EDTA particle be in nanometer scale on the other hand, so, degree of scatter improves, and specific area improves, and the contact rate of metal ion and EDTA improves, EDTA also just improves the complexing rate of metal ion, and suction-operated is strengthened.In addition, because the present invention's adsorbent is a kind of compound, its suction-operated comes from two aspects, and the one, the physical absorption of nano molecular sieve, the 2nd, the chemisorbed of chelating agent EDTA, the suction-operated of adsorbent is further strengthened.And can be by determining suitable mesoporous aperture, the nano-scale of control EDTA particle makes EDTA show quantum size effect, makes it have physisorption again.
Description of drawings
Fig. 1 is the little angle XRD curve map of the present invention's adsorbent.Fig. 2 is the SEM figure of the present invention's adsorbent.Fig. 3 is the adsorbent Cr of pH value to the present invention
6+The influence curve figure of adsorption rate.Fig. 4 is the adsorbent Cd of pH value to the present invention
2+The influence curve figure of adsorption rate.Fig. 5 is the adsorbent Cr of temperature to the present invention
6+The influence curve figure of adsorption rate.Fig. 6 is the adsorbent Cd of temperature to the present invention
2+The influence curve figure of adsorption rate.Fig. 7 is the adsorbent Cr of time to the present invention
6+The influence curve figure of adsorption rate, this figure double as is a Figure of abstract.Fig. 8 is the adsorbent Cd of time to the present invention
2+The influence curve figure of adsorption rate.
The specific embodiment
The present invention's adsorbent specifically is achieved in that and is distributed with chelating agent EDTA (ethylenediamine tetra-acetic acid) in nano molecular sieve is mesoporous, and described nano molecular sieve is SBA-15, and described adsorbent is designated as (SBA-15)-EDTA.
The present invention's preparation of adsorbent is such, adopts liquid phase method, and amount is accurately measured the SBA-15 powder on demand, it is joined in the EDTA solution, and magnetic agitation 48h filters, washing, drying obtains the EDTA modified SBA-15, i.e. (SBA-15)-EDTA, wherein, main body is the SBA-15 nano molecular sieve, and object is EDTA, and the two constitutes a kind of compound.
As can be seen from Figure 1, prepared (SBA-15)-EDTA is 0.88 ° at 2 θ a very strong diffraction maximum, corresponding with (100) peak of SBA-15, two more weak diffraction maximums respectively appear at 1.5 °, 1.8 °, corresponding with (110) diffraction maximum, (200) diffraction maximum of SBA-15 respectively, this is typical two-dimentional hexagonal structure characteristic diffraction peak, illustrates that the skeleton structure of (SBA-15)-EDTA keeps order and the same good degree of crystallinity same good with SBA-15.
As shown in Figure 2, the pattern of prepared (SBA-15)-EDTA is for piling up the wheat head shape macrostructure that forms.Calculate (SBA-15)-EDTA crystal grain length and be about 333nm.
Below by the Cr in the adsorbed water body
6+, Cd
2+The suction-operated of checking the present invention's adsorbent.(SBA-15)-EDTA joined respectively contain Cr
6+Perhaps Cd
2+In the water sample, determine water sample pH value, adsorption temp and adsorption time.Filter afterwards, keep filtrate, measure Cr in each water sample filtrate respectively with atomic absorption spectrum
6+, Cd
2+Ion concentration calculates adsorption rate, draws the adsorption rate curve.
That Fig. 3 and Fig. 4 present is respectively water sample pH value and Cr
6+And Cd
2+The adsorption rate relation curve.As can be seen from the figure, increase Cr with the pH value
6+Perhaps Cd
2+Adsorption rate raises gradually.When the pH value reaches 4, reach maximum 98.7%, 98.6% respectively.After this, along with the pH value continues to increase Cr
6+Perhaps Cd
2+Adsorption rate reduces on the contrary.This is that along with hydrogen ion concentration reduces, the probability that metal ion is adsorbed increases because hydrogen ion in the water sample and metal ion competition are adsorbed, and adsorption rate also just raises.And when water sample pH value continues to increase, OH in the water sample
-Concentration increases, a large amount of OH
-Can generate precipitation with metal ion chemical combination, it is mesoporous to block the SBA-15 nano molecular sieve, and therefore adsorption rate reduces.
That Fig. 5 and Fig. 6 present is respectively TWS and Cr
6+And Cd
2+The adsorption rate relation curve.As can be seen from the figure, raise Cr with temperature
6+And Cd
2+Adsorption rate raises gradually, but influence is little.When temperature reaches 35 ℃, reach maximum 98.6%, 98.8% respectively.After this, along with temperature continues to raise, adsorption rate reduces on the contrary.This is that the vibration of metal ion in water sample accelerated because temperature is when raising, and makes its easier diffusion to the SBA-15 nano molecular sieve is mesoporous in, and adsorption rate is just rising also.And when TWS continued to raise, the motion of metal ion was too active, had been diffused out once more by that part of metal ion of physical absorption, and adsorption rate reduces.
That Fig. 7 and Fig. 8 present is respectively adsorption time and Cr
6+, Cd
2+The adsorption rate relation curve.As can be seen from the figure, prolong with adsorption time, adsorption rate raises gradually.When adsorption time reaches 30min, reach maximum 98.0%, 99.0%.After this, along with adsorption time continues to prolong, adsorption rate reduces on the contrary.This is that adsorption rate raises gradually, when reaching maximum, reaches the absorption saturation state because in the absorption incipient stage, the metal ion that is adsorbed is constantly accumulated.And adsorption time continues overtime, in the SBA-15 nano molecular sieve that is in the absorption saturation state is mesoporous, has been begun to occur the desorption phenomenon by that part of metal ion of physical absorption, and therefore adsorption efficiency reduces.
Claims (2)
1. a metal ion nanoadsorbent is characterized in that, is distributed with chelating agent EDTA (ethylenediamine tetra-acetic acid) in nano molecular sieve is mesoporous.
2. metal ion nanoadsorbent according to claim 1 is characterized in that, described nano molecular sieve is SBA-15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010242198 CN101890337A (en) | 2010-08-02 | 2010-08-02 | Metal ion nanoadsorbent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010242198 CN101890337A (en) | 2010-08-02 | 2010-08-02 | Metal ion nanoadsorbent |
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|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145946A (en) * | 2011-02-21 | 2011-08-10 | 中国科学院生态环境研究中心 | Method for treating trace amount of cadmium in wastewater by chelation, coagulation and ultrafiltration combination |
| CN102485642A (en) * | 2010-12-02 | 2012-06-06 | 上海化学试剂研究所 | Method for producing ultra-pure hydrogen peroxide |
| CN103663663A (en) * | 2013-12-18 | 2014-03-26 | 湘潭大明机电科技有限公司 | Efficient composite heavy metal chelating agent |
| CN108299736A (en) * | 2017-12-25 | 2018-07-20 | 中广核俊尔（上海）新材料有限公司 | A kind of low PP composite material and preparation method thereof distributed of low smell |
| CN110269225A (en) * | 2019-05-23 | 2019-09-24 | 江苏蜂奥生物科技有限公司 | A kind of preparation process of solid removing heavy-metal propolis |
| CN110639226A (en) * | 2019-09-24 | 2020-01-03 | 江苏蜂奥生物科技有限公司 | Method for removing impurities in propolis |
| CN110665470A (en) * | 2019-09-24 | 2020-01-10 | 江苏蜂奥生物科技有限公司 | Adsorbent used in propolis extraction process and preparation method thereof |
| CN115138335A (en) * | 2022-07-28 | 2022-10-04 | 西安热工研究院有限公司 | Modified molecular sieve and preparation method and application thereof |
-
2010
- 2010-08-02 CN CN 201010242198 patent/CN101890337A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 《Microporous and Mesoporous Materials》 20070221 Yijun Jiang et al Intensively competitive adsorption for heavy metal ions by PAMAM-SBA-15 and EDTA-PAMAM-SBA-15 inorganic-organic hybrid materials 316-324 1-2 第103卷, 2 * |
| 《硅酸盐学报》 20061231 于辉等 SBA-15介孔分子筛及其主-客体复合材料研究的某些进展 123-128 1-2 第25卷, 第6期 2 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8715613B2 (en) * | 2010-12-02 | 2014-05-06 | Shanghai Chemical Reagent Research Institute | Method for producing of ultra-clean and high-purity aqueous hydrogen peroxide solution |
| CN102485642A (en) * | 2010-12-02 | 2012-06-06 | 上海化学试剂研究所 | Method for producing ultra-pure hydrogen peroxide |
| US20120141357A1 (en) * | 2010-12-02 | 2012-06-07 | Shanghai Chemical Reagent Research Institute | Method for producing of ultra-clean and high-purity aqueous hydrogen peroxide solution |
| CN102485642B (en) * | 2010-12-02 | 2015-10-07 | 上海化学试剂研究所 | The production method of ultra-pure hydrogen phosphide |
| CN102145946B (en) * | 2011-02-21 | 2013-06-26 | 中国科学院生态环境研究中心 | Method for treating trace amount of cadmium in wastewater by chelation, coagulation and ultrafiltration combination |
| CN102145946A (en) * | 2011-02-21 | 2011-08-10 | 中国科学院生态环境研究中心 | Method for treating trace amount of cadmium in wastewater by chelation, coagulation and ultrafiltration combination |
| CN103663663A (en) * | 2013-12-18 | 2014-03-26 | 湘潭大明机电科技有限公司 | Efficient composite heavy metal chelating agent |
| CN103663663B (en) * | 2013-12-18 | 2016-09-21 | 江俞 | High efficiency composition heavy metal chelant |
| CN108299736A (en) * | 2017-12-25 | 2018-07-20 | 中广核俊尔（上海）新材料有限公司 | A kind of low PP composite material and preparation method thereof distributed of low smell |
| CN110269225A (en) * | 2019-05-23 | 2019-09-24 | 江苏蜂奥生物科技有限公司 | A kind of preparation process of solid removing heavy-metal propolis |
| CN110269225B (en) * | 2019-05-23 | 2022-02-01 | 江苏蜂奥生物科技有限公司 | Preparation process of solid propolis for removing heavy metals |
| CN110639226A (en) * | 2019-09-24 | 2020-01-03 | 江苏蜂奥生物科技有限公司 | Method for removing impurities in propolis |
| CN110665470A (en) * | 2019-09-24 | 2020-01-10 | 江苏蜂奥生物科技有限公司 | Adsorbent used in propolis extraction process and preparation method thereof |
| CN115138335A (en) * | 2022-07-28 | 2022-10-04 | 西安热工研究院有限公司 | Modified molecular sieve and preparation method and application thereof |
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Open date: 20101124 |