CN105214606B - A kind of method for improving mesopore molecular sieve absorption heavy metal efficiency - Google Patents
A kind of method for improving mesopore molecular sieve absorption heavy metal efficiency Download PDFInfo
- Publication number
- CN105214606B CN105214606B CN201510737346.4A CN201510737346A CN105214606B CN 105214606 B CN105214606 B CN 105214606B CN 201510737346 A CN201510737346 A CN 201510737346A CN 105214606 B CN105214606 B CN 105214606B
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- molecular sieve
- silicon
- based mesoporous
- template
- 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.)
- Expired - Fee Related
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 43
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000000356 contaminant Substances 0.000 claims abstract description 3
- 230000009514 concussion Effects 0.000 claims abstract 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to Heavy Metal Pollution Control technical field, and in particular to a kind of method for improving mesopore molecular sieve absorption heavy metal efficiency.This method comprises the following steps：The silicon-based mesoporous molecular sieve for retaining template is put into the water containing heavy metal, regulation pH is neutrality, normal temperature concussion, molecular sieve is separated from the water and realizes that heavy metal contaminants remove.The present invention solves the problems, such as that silicon-based mesoporous molecular sieve heavy metal adsorption is low, while realizes the Selective Separation of heavy metal.
Description
Technical field
The invention belongs to Heavy Metal Pollution Control technical field, and in particular to one kind improves mesopore molecular sieve absorption heavy metal
The method of efficiency.
Background technology
With the expansion in city and the development of large-scale industry, air, soil, heavy metal pollution day present in water environment
Benefit increase.Heavy metal pollution is one of subject matter of water pollution, mining, metal smelt, chemical production wastewater, using agriculture
The artificial pollution such as medicine chemical fertilizer and house refuse, and the natural factor such as geologic erosion, weathering can cause heavy metal with various shapes
Formula enters water body.Because heavy metal has, toxicity is big, is not easy to be metabolized, be easily bioaccumulation and have biomagnification effect in the environment
The features such as answering so that the existence of the heavy metal pollution serious threat aquatile of water environment and human health.Therefore, in water environment
Heavy metal pollution control has turned into is related to the major issue that environmental protection, sustainable development and Living consumption improve.
Adsorption technology adds the heavy metal removal technology generally acknowledged as researcher because of its simple low consumption, without chemicals, grinds
Study carefully staff development and go out a variety of sorbing materials.Wherein, silicon-based mesoporous molecular sieve is because it has controllable structure and morphology and good
Architecture basics enjoy favor.However, silicon-based mesoporous molecular sieve belongs to inorganic material, heavy metal ionic adsorption efficiency is bad.Cause
This, studies appropriate method and improves the absorption property of silicon-based mesoporous molecular sieve heavy metal to expanding silicon-based mesoporous molecular sieve in weight
The application of metallic pollution control field has stronger realistic meaning.
The content of the invention
To solve the problems, such as that silicon-based mesoporous molecular sieve heavy metal adsorption is low, while realize the selection of heavy metal
Property separation, the invention provides it is a kind of improve silicon-based mesoporous molecular sieve absorption heavy metal efficiency method.
Specifically, this method comprises the following steps：Comprise the following steps：The silicon-based mesoporous molecular sieve for retaining template is thrown
Enter into the water containing heavy metal, input amount is 0.5~1.5g/L, regulation pH for neutrality, normal temperature shake 2~4h, by molecular sieve from
Separation realizes that heavy metal contaminants remove in water.
Wherein, the silicon-based mesoporous molecular sieve of described reservation template is prepared with the following method：Xiang Shuizhong is added
Quaternary surfactant, dosage are 2~8g/L, fully sequentially add ethanol and ammoniacal liquor after dissolving, dosage is respectively 200~
300mL/L and 50~100mL/L, mix, stir lower addition tetraethyl orthosilicate, dosage is 10~30mL/L, carries out dehydrating condensation
Reaction, 12~36h, separation are aged, washing obtains white depositions, dries, grinding.
Wherein, described quaternary surfactant is cetyl trimethylammonium bromide, trimethyl bromination
Ammonium, TTAB or Cetyltrimethylammonium bromide.
Wherein, the described dehydration condensation time is 15~30min.
Wherein, described digestion time is 10~30h.
Wherein, described heavy metal is copper, cadmium, zinc or lead.
The inventive method principle is as follows：By retaining the template quaternary ammonium used in silicon-based mesoporous molecular sieve building-up process
Cationic surfactants, the sun based on the cation end of quaternary cationics is formed in mesopore orbit
Ion interface layer, and then silicon-based mesoporous molecular sieve heavy metal ion is improved by the anion in cation boundary layer combination water
Adsorption.
The present invention is not related to chemicals consumption, energy resource consumption, is a kind of environment friendly material performance regulation and control method, compared with
Had a clear superiority using silicon-based mesoporous molecular sieve heavy metal absorption property is improved the methods of chemical modification.
Brief description of the drawings
Fig. 1 is the structural characterization for retaining template silicon-based mesoporous molecular sieve：Figure A and B is respectively without template and contained
The scanning electron microscope (SEM) photograph of the silicon-based mesoporous molecular sieve agent of template；The X-ray diffractogram that C is material is schemed, containing template and without template
The silicon-based mesoporous molecular sieve agent of agent is designated as C respectively16- MCM-41 and MCM-41；Scheme the infrared spectrogram that D is material, contain template
C is designated as respectively with the silicon-based mesoporous molecular sieve agent without template16- MCM-41 and MCM-41.
Fig. 2 retains template silicon-based mesoporous molecular sieve internal structure schematic diagram.
Fig. 3 adsorbs representative heavy metal performance enhancing effects figure using this method to silicon-based mesoporous molecular sieve, i.e., containing template
Silicon-based mesoporous molecular sieve C16- MCM-41 (●) and without template silicon-based mesoporous molecular sieve MCM-41 (zero) heavy metals Cu2+'s
Adsorption contrasts.
Embodiment
The preparation of the molecular sieve of embodiment 1
Template is by taking cetyl trimethylammonium bromide as an example in present embodiment, but template is not only restricted to this example.
6g quaternary surfactant cetyl trimethylammonium bromide is added into 700mL water, is sufficiently stirred dissolving
Afterwards, 250mL ethanol and 80mL ammoniacal liquor are sequentially added, after fully mixing, the tetraethyl orthosilicate added under stirring into 20 is dehydrated
Condensation reaction 20min, the silicon for being made and retaining template is ground to separating, washing gained white deposits, after drying after being aged 24h
Base mesopore molecular sieve, and take sample segment to calcine 6h at 540 DEG C, the silicon-based mesoporous molecular sieve without template is made.Material
Sign is shown in Fig. 1, and material structure schematic diagram is shown in Fig. 2.As shown in Figure 1A and 1B, synthesized material shows the ball of 300nm diameters
Shape particle；As Fig. 1 C show, synthesized material shows four small angle x-ray diffraction (SAXD) peaks, illustrates that material has good Jie
Pore property；As Fig. 1 D show, molecular sieve of the infrared spectrum reality without calcining of synthesized material shows alkyl absworption peak
(2920,2851 and 1474cm-1), pattern of descriptive parts agent is successfully reserved inside molecular sieve.Synthesized molecular sieve internal structure is shown
Intention is shown in Fig. 2, and the silicon substrate skeleton of internal gutter is in hexagon.
The adsorption experiment of embodiment 2
The silicon-based mesoporous fractionated molecule sieve containing template is with using cetyl trimethylammonium bromide preparation in present embodiment
Exemplified by molecular sieve, heavy metal is with Cu2+Exemplified by, but template and heavy metal species are not only restricted to this example.
Verified by adsorption experiment and retain the raising effect that template sieves absorption heavy metal energy to silicon-based mesoporous fractionated molecule.
Above two molecular sieve 0.02g is weighed respectively to be placed in 50mL glass centrifuge tubes, sequentially adds 30mL distilled water and certain volume
Heavy metal ion represent Cu2+, final regulation system volume is 32mL and adjusts after pH is neutrality that normal temperature, which shakes 2 hours, to be reached
Adsorption equilibrium.Cu is measured by sampling2+Residual quantity, the absorption property of material is evaluated, improved so as to verify using reservation template mode
Silicon-based mesoporous molecular sieve adsorbs the effect of heavy metal, and Contrast on effect is shown in accompanying drawing 3.As a result show：With initial Cu2+The increase of concentration,
Equilibrium adsorption capacity Qe is continuously increased, and when initial concentration increases to certain value, equilibrium adsorption capacity is stable in a fixed value, i.e.,
Saturated extent of adsorption.Contrast the molecular sieve for containing template and the silicon-based mesoporous molecular sieve for not containing template, retaining template
There is higher saturated extent of adsorption, illustrate that silicon-based mesoporous molecular sieve heavy metal Cu can be significantly improved by retaining template2+Absorption
Efficiency.
Claims (4)
- A kind of 1. method for improving mesopore molecular sieve absorption heavy metal efficiency, it is characterised in that：Comprise the following steps：Mould will be retained The silicon-based mesoporous molecular sieve of plate agent is put into the water containing heavy metal, and input amount is 0.5~1.5g/L, and regulation pH is neutrality, often Temperature 2~4h of concussion, molecular sieve is separated from the water and realizes that heavy metal contaminants remove, wherein, the silicon of described reservation template Base mesopore molecular sieve is prepared with the following method：Xiang Shuizhong adds quaternary surfactant, and dosage is 2~8g/L, is filled Ethanol and ammoniacal liquor are sequentially added after dividing dissolving, dosage is respectively 200~300mL/L and 50~100mL/L, is mixed, and stirring is lower to be added Enter tetraethyl orthosilicate, dosage is 10~30mL/L, carries out dehydration condensation, is aged 12~36h, separation, and washing obtains white Sediment, drying, grinding.
- 2. the method as described in claim 1, it is characterised in that：Described quaternary surfactant is cetyl trimethyl Ammonium bromide, DTAB, TTAB or Cetyltrimethylammonium bromide.
- 3. method as claimed in claim 1 or 2, it is characterised in that：The described dehydration condensation time is 15~30min.
- 4. method as claimed in claim 1 or 2, it is characterised in that：Described heavy metal is copper, cadmium, zinc or lead.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510737346.4A CN105214606B (en) | 2015-11-03 | 2015-11-03 | A kind of method for improving mesopore molecular sieve absorption heavy metal efficiency |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510737346.4A CN105214606B (en) | 2015-11-03 | 2015-11-03 | A kind of method for improving mesopore molecular sieve absorption heavy metal efficiency |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105214606A CN105214606A (en) | 2016-01-06 |
| CN105214606B true CN105214606B (en) | 2017-12-01 |
Family
ID=54984076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510737346.4A Expired - Fee Related CN105214606B (en) | 2015-11-03 | 2015-11-03 | A kind of method for improving mesopore molecular sieve absorption heavy metal efficiency |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105214606B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678278A (en) * | 2019-01-21 | 2019-04-26 | 河南城建学院 | A kind of Groundwater Treatment Methodss of contaminated site |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6369511A (en) * | 1986-09-10 | 1988-03-29 | Idemitsu Kosan Co Ltd | Method for adsorbing and separating oxides |
| CN1262475C (en) * | 2003-12-28 | 2006-07-05 | 王燕春 | Method for producing mesoporous silicon gel |
| CN102241406A (en) * | 2010-05-11 | 2011-11-16 | 哈尔滨工业大学 | Carboxylated MCM-41 mesoporous molecular sieve for adsorbing heavy metal ions, and preparation method thereof |
| CN102908982A (en) * | 2012-10-24 | 2013-02-06 | 陕西省石油化工研究设计院 | Preparation method of novel mesoporous material for absorbing heavy metal ions in wastewater |
-
2015
- 2015-11-03 CN CN201510737346.4A patent/CN105214606B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105214606A (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jung et al. | Fabrication of porosity-enhanced MgO/biochar for removal of phosphate from aqueous solution: application of a novel combined electrochemical modification method | |
| Jung et al. | A novel approach for preparation of modified-biochar derived from marine macroalgae: dual purpose electro-modification for improvement of surface area and metal impregnation | |
| Lee et al. | Enhanced adsorptive removal of fluoride using mesoporous alumina | |
| Liu et al. | Biosorption studies of uranium (VI) on cross-linked chitosan: isotherm, kinetic and thermodynamic aspects | |
| CN102580694A (en) | Method for preparing modified loess with high adsorption performance | |
| CN104353424A (en) | Amine-containing functional mesoporous material and application thereof to separation of rhenium and molybdenum | |
| CN107282021A (en) | A kind of organo-mineral complexing bentonite clay material and its preparation method and application | |
| CN104001471B (en) | Preparation method of silicon dioxide immobilized hydroxyapatite material | |
| CN103977773B (en) | Preparation method and application of eichhornia crassipes cellulose xanthate calcium salt | |
| CN102698711B (en) | Pillared modified kieselguhr for adsorbing Pb<2+> and/or Cd<2+> and preparation method and application of pillared modified kieselguhr | |
| CN109289772A (en) | A kind of carbon nanotube/hydrotalcite material and preparation method removing nitrate nitrogen in water removal | |
| Gao et al. | Preparation of short channels SBA-15-PVC membrane and its adsorption properties for removal of uranium (VI) | |
| CN105214606B (en) | A kind of method for improving mesopore molecular sieve absorption heavy metal efficiency | |
| CN110026161A (en) | A kind of polymer-based nano hydrous zirconia gel material, crystal form and crystallinity regulation method, application and regeneration method | |
| Piñón-Villarreal et al. | Retention and transport of nitrate and ammonium in loamy sand amended with clinoptilolite zeolite | |
| Zhao et al. | Artificial humic acid mediated migration of phosphorus in soil: Experiment and modelling | |
| CN103626939B (en) | The preparation method of a kind of selectivity dynamic Solid-Phase Extraction cerium ion imprinted polymer and application | |
| CN107934972A (en) | It is a kind of using gangue as block aerosil of silicon source and its preparation method and application | |
| Gabor et al. | Magnesium silicate doped with environmentally friendly extractants used for rare earth elements adsorption. | |
| CN105043839A (en) | Method for separating and enriching fulvic acid in soil through activated carbon | |
| CN102993229B (en) | Amphoteric electrolyte-modified hybrid silica gel material and solid-phase extraction method thereof | |
| CN104445499A (en) | Method for adsorbing and recycling heavy metal cadmium by using metal adsorbent employing persimmon leaves as raw material | |
| CN105688828A (en) | Method for preparing plant-inorganic composite adsorbents from phosphoric-acid-modified folium cycas for extracting uranium from seawater | |
| CN109847716B (en) | Natural mineral-based uranium extraction adsorbent from seawater and preparation method thereof | |
| CN106238003A (en) | A kind of Kaolin/Chitosan Composites and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171201 |