CN107376849A - A kind of application of ethylenediamine tetraacetic acid modified diatomite adsorbant and preparation method thereof and processing heavy metal ions in wastewater - Google Patents
A kind of application of ethylenediamine tetraacetic acid modified diatomite adsorbant and preparation method thereof and processing heavy metal ions in wastewater Download PDFInfo
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- CN107376849A CN107376849A CN201710678142.7A CN201710678142A CN107376849A CN 107376849 A CN107376849 A CN 107376849A CN 201710678142 A CN201710678142 A CN 201710678142A CN 107376849 A CN107376849 A CN 107376849A
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- diatomite
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- infusorial earth
- modification infusorial
- adsorbent
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- -1 ethylenediamine tetraacetic acid modified diatomite Chemical class 0.000 title claims abstract description 12
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 11
- 150000002500 ions Chemical class 0.000 title claims abstract description 10
- 239000002351 wastewater Substances 0.000 title claims abstract description 8
- 238000012545 processing Methods 0.000 title description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000003463 adsorbent Substances 0.000 claims abstract description 46
- 238000012986 modification Methods 0.000 claims abstract description 28
- 230000004048 modification Effects 0.000 claims abstract description 28
- 229960001484 edetic acid Drugs 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 230000004044 response Effects 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 18
- 238000001179 sorption measurement Methods 0.000 abstract description 15
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 239000011651 chromium Substances 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000010129 solution processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 244000145845 chattering Species 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 229910052905 tridymite 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The present invention discloses a kind of preparation method of modification infusorial earth adsorbent, including：1) diatomite pre-processes：Diatomite is separately immersed in stir process in alkali lye and acid solution, is then washed with water to neutrality, is dried；2) by urea, ethylenediamine tetra-acetic acid and through step 1) handle diatomite mix in organic solvent, 40~60 DEG C stirring 20~30 minutes after, be placed in 160~200 DEG C of 6~8h of heating response in reactor, washed after being cooled to room temperature, dry.Application the invention also discloses ethylenediamine tetraacetic acid modified diatomite adsorbant and its in absorption heavy metal ions in wastewater.The present invention is used as raw material using the discarded object diatomite of brewery, it is cheap, raw material obtains convenient, material modified no danger, nonstaining property, whole operation process is simple, and obtained adsorbent adsorption capacity is strong, there is higher Adsorption efficiency to the Cr VI in sewage, nickelous, do not have other pollutant to produce during whole Adsorption.
Description
Technical field
The invention belongs to water-treatment technology field, particularly a kind of ethylenediamine tetraacetic acid modified diatomite (EDTA-
Diatomite waste, EDTA-DW) adsorbent and preparation method thereof and processing heavy metal ions in wastewater application.
Background technology
With the fast development of industrial production and human society, problem of environmental pollution increasingly aggravates.Substantial amounts of pollutant quilt
It is discharged into water environment, wherein heavy metal contaminants have hypertoxicity or carcinogenicity, and are difficult to biodegradation.In addition,
Heavy metal contaminants are easily enriched with and and then accumulated by food chain in organism or human body in vivo.
In view of chromium and nickel/harmfulness and its extensive use in various industrial productions, manufacturing process, from industrial wastewater
In effectively remove chromium and nickel has great importance.Removing the common method of Cr VI and nickelous in water body has chemistry (also
It is former) precipitation method, electrochemical process, membrane processing method, ion-exchange, biological treatment and absorption method etc..Compared with numerous methods, inhale
Harmful substance in sewage is generally fixed on sorbing material surface so as to remove waste water by attached method using the porous of sorbing material
In chromium and nickel, while there is Non-energy-consumption, the advantages that non-secondary pollution, thus seek the absorption that cost is cheap and adsorption efficiency is high
Agent is of crucial importance.
The content of the invention
The purpose of the present invention is：The adsorbent that a kind of specific surface area is big, cost is cheap is provided, the adsorbent can be efficient
Handle the heavy metal ion in waste water, such as Cr VI, nickelous.
It is a further object of the present invention to provide a kind of simple, the cheap ethylenediamine tetraacetic acid modified diatomite of method
The preparation method of adsorbent.
Technical scheme：The present invention provides a kind of preparation method of modification infusorial earth adsorbent, comprises the following steps：
1) diatomite pre-processes：Diatomite is separately immersed in stir process in alkali lye and acid solution, is then washed with water
To neutrality, drying；
2) by urea, ethylenediamine tetra-acetic acid and through step 1) handle diatomite mix in organic solvent, 40~60 DEG C
After stirring 20~30 minutes, 160~200 DEG C of 6~8h of heating response in reactor are placed in, are washed after being cooled to room temperature, dried.
Diatomite surface attachment after being used due to brewery as filtration adjuvant has microorganism and organic matter, such as yeast and
Protein etc., be advantageous to the absorption of heavy metal ion, therefore, discard diatomite using brewery and adsorbed as modification infusorial earth
The diatomite material of agent.
Contain symbiosis impure mineral because brewery is discarded outside diatomite, clay impurity is contained in inside, and its is intrapore
The pore structure that impurity can block inside diatomite, diatomaceous absorption property is influenceed, therefore, in order to improve its absorption property,
Make in step 1), alkali lye is 2~4mol/L NaOH or KOH solution, and the time that diatomite is handled in alkali lye is 20~30 points
Clock；Acid solution is 2~4mol/L strong acid solution, and the time that diatomite is handled in acid solution is 20~30 minutes, and strong acid is molten
Liquid is hydrochloric acid solution；Drying condition dries 8~14 hours for 120 DEG C~150 DEG C in an oven.
In order to obtain the preferable adsorbent of absorption property, make in step 2), the urea and the matter of ethylenediamine tetra-acetic acid used
Amount is than being 4~6: 1；Urea is 1.5~2.5: 1 with the diatomaceous mass ratio handled through step 1)；Organic solvent is ethylene glycol,
It is deionized water to wash the solvent used；Drying temperature is 60~80 DEG C.
Another aspect of the present invention provides a kind of ethylenediamine tetraacetic acid modified diatomite adsorbant, and the adsorbent is by above-mentioned system
Preparation Method is made.
Another aspect of the invention provides above-mentioned ethylenediamine tetraacetic acid modified diatomite adsorbant huge sum of money in waste water is adsorbed
Belong to the application of ions.
Beneficial effect：The present invention is cheap using the discarded object diatomite of brewery as raw material, and it is convenient that raw material obtains,
The purpose of recovery waste and old resource can be reached using industrial waste synthesis modification adsorbent, and without extra cost of material；Make
For the diatomite of brewery's filtration adjuvant, there is the good characteristics such as high porosity, high osmosis, the silicon after brewery's filtering use
Some organic matters on diatomaceous earth surface, such as yeast and protein, are more beneficial for the absorption of its heavy metal ion；Ethylenediamine tetrem
Sour (EDTA) is a kind of excellent chelating agent, and stable chelate can be formed with most of heavy metal ion；Material modified no danger
Dangerous, nonstaining property, whole operation process is simple.Final adsorbent specific surface area is big, and adsorption capacity is strong, and cost is cheap, right
Cr VI, the adsorption efficiency of nickelous are high, have higher Adsorption efficiency to the Cr VI in sewage, nickelous, entirely
There is no other pollutant to produce during Adsorption, the harmful material of the person is not produced.Meanwhile the present invention makes full use of
Waste material, make the best use of everything, reach to give up and control useless, the purpose of energy-conserving and environment-protective.
Brief description of the drawings
Fig. 1 be before modified after diatomaceous SEM image and EDS spectrogram, wherein Fig. 1 (a) is unmodified diatomite SEM
Figure, Fig. 1 (b) are unmodified diatomaceous energy dispersion X-ray (EDS) spectrogram, and Fig. 1 (c) is modified diatomite SEM figures,
Fig. 1 (d) is modified diatomaceous energy dispersion X-ray (EDS) spectrogram；
Fig. 2 be before modified after diatomaceous infrared (FTIR) spectrogram；
Fig. 3 be before modified after diatomaceous X-ray diffraction (XRD) collection of illustrative plates.
Embodiment
Embodiment 1
The preparation method of modification infusorial earth adsorbent is：
(1) brewery discards diatomite pretreatment：
Brewery is discarded into diatomite to be immersed in 3M NaOH solutions, stirring 30 minutes after, centrifuge, obtain through
The discarded diatomite of NaOH solution processing；Then the discarded diatomite handled through NaOH solution is immersed in 3M hydrochloric acid solutions,
After stirring 30 minutes, centrifuge；Then again with water washing is distilled for several times, until cleaning solution reaches neutral.Afterwards in an oven
12h is dried under conditions of 120 DEG C, pretreated brewery is obtained and discards diatomite.
(2) diatomaceous modification：
Take 3.6g urea and 0.7g EDTA to be successively put into the flask for filling 30ml ethylene glycol, and add 1.8g through step
(1) brewery of pretreatment discards diatomite powder, is stirred 30 minutes at 50 DEG C in magnetic stirring apparatus.Then mixture is put
In autoclave, after heating 8h at 200 DEG C, room temperature is cooled to.
(3) post processing of adsorbent：
4 times will be cleaned with ethanol and deionized water, then dry in an oven at 60 DEG C through the modified diatomite of step (2)
It is dry, obtain modification infusorial earth adsorbent, i.e., ethylenediamine tetraacetic acid modified diatomite.
Embodiment 2
The preparation method of modification infusorial earth adsorbent is：
(1) brewery discards diatomite pretreatment：
Brewery is discarded into diatomite to be immersed in 2M NaOH solutions, stirring 20 minutes after, centrifuge, obtain through
The discarded diatomite of NaOH solution processing；Then the discarded diatomite handled through NaOH solution is immersed in 4M hydrochloric acid solutions,
After stirring 20 minutes, centrifuge；Then again with water washing is distilled for several times, until cleaning solution reaches neutral.Afterwards in an oven
12h is dried under conditions of 120 DEG C, pretreated brewery is obtained and discards diatomite.
(2) diatomaceous modification：
Take 2.8g urea and 0.7g EDTA to be successively put into the flask for filling 30ml ethylene glycol, and add 1.9g through step
(1) brewery of pretreatment discards diatomite powder, is stirred 30 minutes at 40 DEG C in magnetic stirring apparatus.Then mixture is put
In autoclave, after heating 8h at 160 DEG C, room temperature is cooled to.
(3) post processing of adsorbent：
4 times will be cleaned with ethanol and deionized water, then dry in an oven at 80 DEG C through the modified diatomite of step (2)
It is dry, obtain modification infusorial earth adsorbent, i.e., ethylenediamine tetraacetic acid modified diatomite.
Embodiment 3
The preparation method of modification infusorial earth adsorbent is：
(1) brewery discards diatomite pretreatment：
Brewery is discarded into diatomite to be immersed in 4M KOH solutions, after stirring 20 minutes, centrifuges, obtains through KOH
The discarded diatomite of solution processing；Then the discarded diatomite handled through KOH solution is immersed in 2M hydrochloric acid solutions, stirring 20
After minute, centrifuge；Then again with water washing is distilled for several times, until cleaning solution reaches neutral.In an oven 120 DEG C afterwards
Under the conditions of dry 12h, obtain pretreated brewery discard diatomite.
(2) diatomaceous modification：
Take 4.2g urea and 0.7g EDTA to be successively put into the flask for filling 30ml ethylene glycol, and add 1.7g through step
(1) brewery of pretreatment discards diatomite powder, is stirred 20 minutes at 60 DEG C in magnetic stirring apparatus.Then mixture is put
In autoclave, after heating 6h at 160 DEG C, room temperature is cooled to.
(3) post processing of adsorbent
4 times will be cleaned with ethanol and deionized water, then dry in an oven at 80 DEG C through the modified diatomite of step (2)
It is dry, obtain modification infusorial earth adsorbent, i.e., ethylenediamine tetraacetic acid modified diatomite.
Comparative example 1
Brewery is discarded into diatomite to be immersed in 3M NaOH solutions, stirring 30 minutes after, centrifuge, obtain through
The discarded diatomite of NaOH solution processing；Then the discarded diatomite handled through NaOH solution is immersed in 3M hydrochloric acid solutions,
After stirring 30 minutes, centrifuge；Then again with water washing is distilled for several times, until cleaning solution reaches neutral.Afterwards in an oven
12h is dried under conditions of 120 DEG C, pretreated brewery is obtained and discards diatomite (diatomite waste, DW).
Embodiment 4
The absorption property test of modification infusorial earth adsorbent：
Configure Cr VI, the bivalent nickel solution of various concentrations；Ethylenediamine tetraacetic acid modified silicon is made with embodiment 1 respectively
It is adsorbent that pretreated brewery made from diatomaceous earth (EDTA-DW), comparative example 1, which discards diatomite (DW), tests adsorbent
To Cr VI, the absorption property of nickelous.Hexavalent chromium solution concentration is 20mg/L, 40mg/L and 60mg/L；Bivalent nickel solution is dense
Spend for 20mg/L, 40mg/L and 60mg/L.Hexavalent chromium solution and bivalent nickel solution volume are 50mL.Adsorbent mass is respectively
0.2g, 0.4g and 0.6g.
In the case where other conditions keep constant, variety classes prepared by embodiment 1 and comparative example 1, different quality
Adsorbent is to the corresponding absorption properties of hexavalent chromium solution, nickelous of various concentrations, respectively as shown in table 1 below, table 2.
It can be seen that initial concentration is higher from the data of table 1, table 2, the adsorbance of corresponding adsorbent is more；Absorption
The increase of agent quality does not cause raising of the unit mass adsorbent to the adsorption capacity of adsorbate.
Simultaneously in table 1, table 2, diatomite is discarded to chromium adsorption number related to nickel by brewery after contrasting before modified
According to, it can be seen that modified brewery its absorption property of discarded diatomite has obtained largely being lifted, adsorption efficiency
Greatly increase.
Table 1
Table 2
Embodiment 5
The absorption property test of modification infusorial earth adsorbent：
Configure Cr VI, the bivalent nickel solution of various concentrations；Respectively with ethylenediamine tetraacetic acid modified made from embodiment 2,3
Diatomite, to discard diatomite (DW) be adsorbent for pretreated brewery made from comparative example 1, test adsorbent to sexavalence
The absorption property of chromium, nickelous.Hexavalent chromium solution concentration is 20mg/L, 40mg/L and 60mg/L；Bivalent nickel solution concentration is
20mg/L, 40mg/L and 60mg/L.Hexavalent chromium solution and bivalent nickel solution volume are 50mL.Adsorbent mass is respectively
0.2g, 0.4g and 0.6g.
In the case where other conditions keep constant, variety classes, the adsorbent pair of different quality of the preparation of embodiment 2,3
The corresponding absorption property of hexavalent chromium solution, nickelous of various concentrations, respectively as shown in table 3 below, table 4.
It can be seen that initial concentration is higher from the data of table 3, table 4, the adsorbance of corresponding adsorbent is more；Absorption
The increase of agent quality does not cause raising of the unit mass adsorbent to the adsorption capacity of adsorbate.
Simultaneously in table 3, table 4, diatomite is discarded to chromium adsorption number related to nickel by brewery after contrasting before modified
According to, it can be seen that modified brewery its absorption property of discarded diatomite has obtained largely being lifted, adsorption efficiency
Greatly increase.
Table 3
Table 4
Embodiment 6
The structural characterization of adsorbent：
Fig. 1 is the sorbent structure phenogram in embodiment 1 and comparative example 1, and wherein Fig. 1 (a) is that comparative example 1 is unmodified
Diatomite SEM schemes, and Fig. 1 (b) is unmodified diatomaceous energy dispersion X-ray (EDS) spectrogram of comparative example 1, and Fig. 1 (c) is real
The SEM figures of the modification infusorial earth of example 1 are applied, Fig. 1 (d) is energy dispersion X-ray (EDS) spectrogram of the modification infusorial earth of embodiment 1.Contrast
Knowable to Fig. 1 (a) and Fig. 1 (c) SEM, unmodified diatomite surface smoother, but some particles in microscopic aperture, point
Analysis is probably impurity, and modified diatomite surface attachment layer of substance, analysis is probably EDTA attachment.Comparison diagram 1 (b) and
Fig. 1 (d) EDS spectrograms are understood, nitrogen are added in modified diatomite, the increase of nitrogen demonstrates diatomaceous change
Property success.
Utilize the change of diatomite surface organo-functional group after FTIR spectrum research before modified.As shown in Fig. 2 Fig. 2 is real
The adsorbent FTIR spectrum figure in example 1 and comparative example 1 is applied, analysis is understood, 470 and 790cm-1Frequency range by diatomite (DW)
Si-O key chatterings cause, 620 and 1082cm-1Peak value caused due to the stretching and flexural vibrations of N-H groups.And broadband
3458cm-1H in DW may be then attributed to2The O-H of O molecules stretching vibration.It is modified, diatomite (EDTA- after modification
DW 1873 and 1633cm) can be observed in response curve-1Peak value, its correspond to carboxyl functional group in the flexible of C=O keys shake
It is dynamic；In addition, also observed in diatomite (EDTA-DW) response curve after modification in 2362cm-1Locate C=N vibration.Thus
It can be seen that FTIR spectrum shows EDTA successful implantations to diatomite surface, and available adsorption site is provided, accelerate and adsorbed
Journey, indicate the successful synthesis of modified adsorbent.
Fig. 3 is the XRD spectrum of diatomite (DW) and the modified diatomite (EDTA-DW) of embodiment 1 before modified of comparative example 1.
As shown in figure 3, DW XRD spectrum shows some SiO2Characteristic peak, about in 2 θ=21.98,31.21, and 35.91 °, point
Not Dui Yingyu (101), (102) and (200) crystal face.In the corresponding XRD picture of modified diatomite, at 25.86 and 27.19 °
New diffraction maximum is shown, corresponds respectively to (- 113) and (- 213) crystal face, this crystal face is analyzed and belongs to EDTA-DW.Therefore, can be with
Prove that EDTA is successfully attached to diatomite surface, modification infusorial earth successfully synthesizes.
Claims (9)
1. a kind of preparation method of modification infusorial earth adsorbent, it is characterised in that this method comprises the following steps：
1) diatomite is separately immersed in stir process in alkali lye and acid solution, is then washed with water to neutrality, dried；
2) by urea, ethylenediamine tetra-acetic acid and through step 1) handle diatomite mix in organic solvent, 40~60 DEG C stirring
After 20~30 minutes, 160~200 DEG C of 6~8h of heating response in reactor are placed in, are washed after being cooled to room temperature, dried, produce institute
State modification infusorial earth adsorbent.
A kind of 2. preparation method of modification infusorial earth adsorbent according to claim 1, it is characterised in that the diatomite
Diatomite is discarded for brewery.
A kind of 3. preparation method of modification infusorial earth adsorbent according to claim 1, it is characterised in that in step 1),
The alkali lye is 2~4mol/L NaOH or KOH solution, and the time that the diatomite is handled in the alkali lye is 20~30 points
Clock；The acid solution is 2~4mol/L strong acid solution, and the time that the diatomite is handled in the acid solution is 20~30
Minute.
4. the preparation method of a kind of modification infusorial earth adsorbent according to claim 3, it is characterised in that the strong acid is molten
Liquid is hydrochloric acid solution.
A kind of 5. preparation method of modification infusorial earth adsorbent according to claim 1, it is characterised in that in step 2),
The mass ratio of the urea and the ethylenediamine tetra-acetic acid is 4~6: 1；The urea and the diatomite handled through step 1)
Mass ratio be 1.5~2.5: 1.
A kind of 6. preparation method of modification infusorial earth adsorbent according to claim 1, it is characterised in that in step 2),
The organic solvent is ethylene glycol, and the solvent used that washs is deionized water.
A kind of 7. preparation method of modification infusorial earth adsorbent according to claim 1, it is characterised in that in step 2),
The drying temperature is 60~80 DEG C.
8. a kind of ethylenediamine tetraacetic acid modified diatomite adsorbant, it is characterised in that the adsorbent is by claim 1~7
Preparation method described in any one is made.
9. the ethylenediamine tetraacetic acid modified diatomite adsorbant described in claim 8 is in heavy metal ions in wastewater is adsorbed
Using.
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