CN106000335A - Coated type nanoscale zero-valent iron as well as preparation method and application thereof - Google Patents
Coated type nanoscale zero-valent iron as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN106000335A CN106000335A CN201610325642.8A CN201610325642A CN106000335A CN 106000335 A CN106000335 A CN 106000335A CN 201610325642 A CN201610325642 A CN 201610325642A CN 106000335 A CN106000335 A CN 106000335A
- Authority
- CN
- China
- Prior art keywords
- valent iron
- zero
- cladding nanometer
- iron
- preparation
- 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.)
- Granted
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 256
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 53
- 239000000661 sodium alginate Substances 0.000 claims abstract description 53
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 53
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 53
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 5
- 238000005253 cladding Methods 0.000 claims description 97
- 229910052742 iron Inorganic materials 0.000 claims description 72
- 229910052793 cadmium Inorganic materials 0.000 claims description 52
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000000725 suspension Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000012279 sodium borohydride Substances 0.000 claims description 18
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 15
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 abstract description 6
- 230000008439 repair process Effects 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 230000009931 harmful effect Effects 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 49
- 229910021642 ultra pure water Inorganic materials 0.000 description 16
- 239000012498 ultrapure water Substances 0.000 description 16
- 239000008187 granular material Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 239000006228 supernatant Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000005012 migration Effects 0.000 description 8
- 238000013508 migration Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229960001126 alginic acid Drugs 0.000 description 5
- 235000010443 alginic acid Nutrition 0.000 description 5
- 239000000783 alginic acid Substances 0.000 description 5
- 229920000615 alginic acid Polymers 0.000 description 5
- 150000004781 alginic acids Chemical class 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052603 melanterite Inorganic materials 0.000 description 4
- 238000005374 membrane filtration Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000003749 cleanliness Effects 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 206010053759 Growth retardation Diseases 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 241000082085 Verticillium <Phyllachorales> Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 210000000476 body water Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000001 growth retardation Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000005405 multipole Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010627 oxidative phosphorylation Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002423 protozoacide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses coated type nanoscale zero-valent iron as well as a preparation method and an application thereof. The coated type nanoscale zero-valent iron comprises nanoscale zero-valent iron and sodium alginate, wherein the nanoscale zero-valent iron is coated with sodium alginate, and a mass ratio of sodium alginate to the nanoscale zero-valent iron is (0.1-0.4):1. The preparation method of the coated type nanoscale zero-valent iron comprises the step that the nanoscale zero-valent iron and a sodium alginate solution are mixed and subjected to ultrasonic treatment, and the coated type nanoscale zero-valent iron is obtained. The coated type nanoscale zero-valent iron can be used for treating sediment with heavy metal pollution, is simple and convenient to operate, good in stabilizing effect, good in mobility, low in repair cost, clean and pollution-free, has no toxic and harmful effects on the environment and has broad application prospect in the technical field of treatment of heavy metal pollution of the sediment.
Description
Technical field
The invention belongs to the physical chemistry process field of heavy metal in polluted bed mud, be specifically related to a kind of cladding nanometer zero
Valency ferrum and preparation method thereof and the application in heavy metal cadmium in stable bed mud of this cladding nanometer Zero-valent Iron.
Background technology
In recent years, during Chinese national economy fast development, substantial amounts of heavy metal contaminants enter river, river, lake,
Sea, makes water body and bed mud be contaminated.In bed mud, the heavy metal of excess deposition discharges into water body the most again, affects upper strata water body
Water quality, forms secondary pollution；Also will in aquatic ecosystem such as aquatic macrophyte, algae, zoobenthos, Fish and micro-life
Things etc. cause harm in various degree；It is enriched with even with food chain, human health is constituted a threat to.Heavy Metal Pollution in Sediments is controlled
Manage critically important to ecological environment and health, be problem demanding prompt solution.
Cadmium is the heavy metal element of effect toxic to organism, and the toxicity of compound of cadmium is very big, and belongs to savings,
Cause the incubation period of chronic poisoning up to 10～30 years as long as.Cadmium can reduce the activity of ATP enzyme in plant cell, hinders potassium to root
Conveying, reduce the plant absorption to potassium；Cadmium, as the conjugant DNP of oxidative phosphorylation, can seriously hinder the suction of phosphorus, potassium
Receive；Excess cadmium can make crop produce verticillium wilt, withered, growth retardation, yield decline.People is just eaten for a long time " the cadmium rice " of cadmium pollution
Can suffer from Itai-itai diseases, the lighter also can cause hypertension and enzyme system, fertility rate to be affected.
In bed mud, the minimizing technology of heavy metal cadmium generally comprises Physical, chemical method, bioanalysis.Physical mainly includes covering
Cover is main in-situ immobilization method and the showering method that dredging is master.Shelter can effectively prevent in bed mud heavy metal to enter water body and
Cause secondary pollution, water quality is improved significantly.But quantities is big, need substantial amounts of cleaning silt etc., source difficulty.
Sediment Dredging because of can by permanent for polluted bed mud removal, but dredging work amount is big, puts into big, the bed mud dredged out is not if entered one
Step processes or deals with improperly, then environment can be caused secondary pollution；Method of chemical treatment is typically will with sulphuric acid, nitric acid or hydrochloric acid etc.
The acidity of bed mud reduces, and by dissolution, makes the metallic compound of indissoluble state form soluble metal ion, or uses
The chelating agent such as EDTA, citric acid is by chlorination, acidization, ion exchange, chelating agen and the network of surfactant
Cooperation use, separates heavy metal therein, reaches to reduce the purpose of total metals in bed mud.But chemical method needs to throw
Add substantial amounts of chemical substance, improve the cost of improvement, and the chemical reagent being not efficiently used will cause environment
Secondary pollution.Simultaneous reactions condition is wayward, operation is the most cumbersome, and the side effect to bed mud is relatively big, affect bed mud or
Existence biological in water body；Bioremediation technology is that the vital movement of application organism (microorganism, protozoacide or plant) will
Heavy metal in bed mud is transformed into the relatively low hypotoxicity form of effectiveness or pouring extracts out and reaches to repair.Mainly include microorganism
Reparation, phytoremediation and plant-microorganism combine d bioremediation.Biological restoration low cost, practical, applied widely, to environment
The advantages such as non-secondary pollution.Though but biological restoration is still in laboratory stage at present, and bioremediation technology is general only to list
The adsorption effect of an only heavy metal species is preferable, and the heavy metal amount of reparation is the most less.
Nowadays, utilize nano zero valence iron to remove the pollutant in environment and be increasingly becoming a very active research neck
Territory.Nano zero valence iron not only particle diameter is little, specific surface area is big, cheap, and have that reduction potential is high, response speed fast, reaction
The feature that activity is high, can be with reduction adsorption multiple pollutant.But, owing to nano zero valence iron exists the problem being oxidized easily,
Thus reduce its reactivity, simultaneously because its higher surface area, add self polarity, easily cause reunion, thus
Decrease the adsorption site position of nano zero valence iron；In addition the reunion of nano zero valence iron is also unfavorable for its mobility in bed mud.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is provided that one can be stable in the presence of aqueous solution
In, be uniformly dispersed, be difficult to reunite, be difficult to oxidized, without substantially sedimentation, animal migration is good, good penetrability, reactivity high, make
The cladding nanometer Zero-valent Iron of low cost；Additionally provide and a kind of prepare cladded type quick, easy and simple to handle, that cost of manufacture is cheap and receive
The preparation method of rice Zero-valent Iron and the application in stable bed mud heavy metal cadmium of this cladding nanometer Zero-valent Iron, this application process
Have easy and simple to handle, stablizing effect good, animal migration good, rehabilitation cost is low, cleanliness without any pollution, to spies such as environment nonhazardous effects
Point.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
A kind of cladding nanometer Zero-valent Iron, described cladding nanometer Zero-valent Iron includes nano zero valence iron and sodium alginate；Institute
State sodium alginate and be coated on described nano zero-valence iron surface；Described sodium alginate is 0.1 with the mass ratio of described nano zero valence iron
～0.4: 1.
As total technology design, present invention also offers the preparation side of a kind of above-mentioned cladding nanometer Zero-valent Iron
Method, comprises the following steps: is mixed with sodium alginate soln by nano zero valence iron and sonicated obtains cladding nanometer Zero-valent Iron.
In the preparation method of above-mentioned cladding nanometer Zero-valent Iron, it is preferred that the concentration of described sodium alginate soln is
0.05g/L～0.2g/L.
In the preparation method of above-mentioned cladding nanometer Zero-valent Iron, it is preferred that the preparation of described sodium alginate soln includes
Following steps: by sodium alginate stirring and dissolving under 55 DEG C～65 DEG C of water bath condition, be passed through nitrogen carry out deoxidation treatment 10min～
20min, obtains sodium alginate soln.
In the preparation method of above-mentioned cladding nanometer Zero-valent Iron, it is preferred that the preparation of described nano zero valence iron include with
Lower step: by isopyknic NaBH4Solution and FeSO4Solution mix and blend 30min～60min, obtains nano zero valence iron.
In the preparation method of above-mentioned cladding nanometer Zero-valent Iron, it is preferred that described NaBH4BH in solution4 -With described
FeSO4Fe in solution2+Mol ratio be 2: 1.It is further preferred that described NaBH4The concentration of solution is 0.2M～0.4M；Institute
State FeSO4The concentration of solution is 0.1M～0.2M.
In the preparation method of above-mentioned cladding nanometer Zero-valent Iron, it is preferred that the frequency of described supersound process be 30KHZ～
50KHZ；The time of described supersound process is 15min～30min.
As total technology design, present invention also offers a kind of above-mentioned cladding nanometer Zero-valent Iron or above-mentioned
Cladding nanometer Zero-valent Iron application in heavy metal cadmium in stable bed mud that preparation method prepares, comprises the following steps: will contain
The suspension of described cladding nanometer Zero-valent Iron adds to containing carrying out constant temperature standing and reacting in cadmium bed mud, completes a huge sum of money in bed mud
Belong to the stabilizing treatment of cadmium.
In above-mentioned application, it is preferred that the suspension containing described cladding nanometer Zero-valent Iron and the volume matter containing cadmium bed mud
Amount ratio is 5mL～15mL: 1g；In suspension containing described cladding nanometer Zero-valent Iron, the concentration of cladding nanometer Zero-valent Iron is
0.5g/L。
In above-mentioned application, it is preferred that described is 5mg/kg～40mg/ containing the initial concentration of heavy metal cadmium in cadmium bed mud
kg；The described pH value containing cadmium bed mud is 7～8.
In above-mentioned application, it is preferred that the condition of described constant temperature standing and reacting is: the time is 0d～30d, and temperature is 21 DEG C
～24 DEG C.Preferably, the time of described constant temperature standing and reacting is 1d～30d.It is further preferred that described constant temperature standing and reacting
Time is 10d～30d.
The creativeness of the present invention is:
The invention provides a kind of cladding nanometer Zero-valent Iron with sodium alginate (SA) as stabilizer, be coated on nano zero-valence
The surface of ferrum, is possible to prevent nano zero valence iron by Quick Oxidation, improves the reactivity of nano zero valence iron.Further, alginic acid
Sodium surface has electronegative group and produces Electrostatic Absorption with heavy metal cadmium ion, and the hydroxyl on its surface, carboxyl etc. can be with cadmium ions
There is chelation, by being coated on nano zero-valence iron surface, improve the stabilization efficiency of its heavy metal cadmium.
Compared with prior art, it is an advantage of the current invention that:
1, the invention provides a kind of cladding nanometer Zero-valent Iron, sodium alginate is a kind of polyelectrolyte, is multipole
Property, polyhydroxy macromolecular compound, can pass through electrostatic repulsion and space steric effect, make the nano zero valence iron in solution disperse
Uniformly, it is difficult to reunite, can be stable in the presence of in aqueous solution, and be uniformly dispersed, be difficult to reunite, be difficult to oxidized, without substantially sedimentation,
Animal migration is good, and it can penetrate into inside bed mud along with solution, has more preferable permeability and reactivity, and cost of manufacture is low,
Sodium alginate is a kind of natural macromolecule amylose class, has biodegradable, to environment nonhazardous effect, will not produce secondary
Pollute, be suitable for large-scale application.
2, the cladding nanometer Zero-valent Iron of the present invention is compared with uncoated type nano zero valence iron, improves the steady of heavy metal
Determine efficiency, reduce heavy metal animal migration in bed mud and biological effectiveness, decrease the heavy metal harm to organism.
3, in the preparation method of the cladding nanometer Zero-valent Iron that the present invention uses, by isopyknic NaBH4And FeSO4Solution
Prepare nano zero valence iron granule after mixing, nano zero valence iron granule is obtained by ultrasonic disperse in sodium alginate soln
To cladding nanometer Zero-valent Iron, preparation is quick, and easy and simple to handle, cost of manufacture is cheap.
4, the novel cladding nanometer Zero-valent Iron of the present invention can be used for administering heavy metal polluted bed mud, and it is right to make in bed mud
The residual form content of beary metal rising 41.79% that environmental pollution damage is minimum, heavy metal biological availability reduces.The present invention's should
Easy and simple to handle by method, stablizing effect is good, and animal migration is good, and rehabilitation cost is low, and cleanliness without any pollution, to environment nonhazardous effect,
It is with a wide range of applications in Heavy Metal Pollution in Sediments Treatment process field.
Accompanying drawing explanation
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is carried out clear, complete description.
Fig. 1 is the scanning electron microscope (SEM) photograph of uncoated type nano zero valence iron (nZVI) granule.
Fig. 2 is the scanning electron microscope (SEM) photograph of cladding nanometer Zero-valent Iron (SA-nZVI) granule in the embodiment of the present invention 2.
Fig. 3 is cladding nanometer Zero-valent Iron (SA-nZVI) and uncoated type nano zero valence iron in the embodiment of the present invention 2
(nZVI) x-ray diffraction pattern.
Fig. 4 is uncoated in the cladding nanometer Zero-valent Iron (SA-nZVI) in the embodiment of the present invention 1～4 and comparative example 1
Type nano zero valence iron (nZVI) stablizes the aspect graph of bed mud heavy metal cadmium.
Detailed description of the invention
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but the most therefore and
Limit the scope of the invention.
Raw material and instrument employed in following example are commercially available.
Embodiment 1:
The cladding nanometer Zero-valent Iron of a kind of present invention, this cladding nanometer Zero-valent Iron includes nano zero valence iron and alginic acid
Sodium, sodium alginate is coated on nano zero-valence iron surface, and wherein sodium alginate is 0.1: 1 with the mass ratio of nano zero valence iron.
The preparation method of the cladding nanometer Zero-valent Iron of a kind of above-mentioned the present embodiment, comprises the following steps:
(1)FeSO4The preparation of solution: weigh 2.8000g FeSO4·7H2O puts in beaker, adds the dissolving of appropriate ultra-pure water and turns
Move on to, in 100mL volumetric flask, be settled to graduation mark with ultra-pure water, shake up, obtain the FeSO that concentration is 0.1M4Solution.
(2)NaBH4The preparation of solution: weigh 0.7566g NaBH4Put in beaker, add appropriate ultra-pure water solution transfer and arrive
In 100mL volumetric flask, it is settled to graduation mark with ultra-pure water, shakes up, obtain the NaBH that concentration is 0.2M4Solution.
(3) preparation of sodium alginate soln: the sodium alginate taking 0.005g is dissolved in the water of 100mL, in 60 DEG C of water-bath bars
Stirring and dissolving under part, is passed through nitrogen and carries out deoxidation treatment 15min, obtains the sodium alginate soln that concentration is 0.05g/L.
(4) preparation of nano zero valence iron granule (nZVI): by the FeSO of 100mL, 0.1M4Solution joins the three of 250mL
In mouth flask, it is passed through nitrogen 15min, is to be stirred vigorously under 200r/min, through the meter of stoichiometric proportion in nitrogen protection and rotating speed
Calculate, at BH4 -/Fe2+Mol ratio is under the conditions of mixture ratios of 2.0, by the NaBH of equal-volume 100mL4Solution the most at the uniform velocity instills three mouthfuls
In flask, reaction system blackening, there is bubble (hydrogen) to produce, drip off NaBH4Stir continuously and healthily 30min after solution, obtain black
Color suspension；Then black suspension is transferred in conical flask, is placed on Magnet, remove supernatant, use deoxygenation deionization
Water and the ethanol that volumn concentration is 5% respectively clean three times, obtain nano zero valence iron (nZVI) granule；By nano zero valence iron
(nZVI) being vacuum dried, dried nano zero valence iron (nZVI) is placed in the brown bottle of full nitrogen standby.
(5) preparation of cladding nanometer Zero-valent Iron (SA-nZVI): 0.05g nano zero valence iron (nZVI) is added in 100mL dense
In the degree sodium alginate soln for 0.05g/L, ultrasonic disperse 20min under conditions of 40KHZ, obtain cladding nanometer Zero-valent Iron
(SA-nZVI) suspension, numbered S1, in this suspension, the concentration of cladding nanometer Zero-valent Iron is 0.5g/L.Due to this cladding
Type nano zero valence iron is for the process of bed mud heavy metal, in order to ensure its dispersibility in bed mud, therefore cladding nanometer zeroth order
Tie Tong often preserves with the form of suspension.
In the present embodiment, the time of ultrasonic disperse is 15min～30min；The frequency of ultrasonic disperse is 30KHZ～50KHZ
All can implement.
Embodiment 2:
The cladding nanometer Zero-valent Iron of a kind of present invention, this cladding nanometer Zero-valent Iron includes nano zero valence iron and alginic acid
Sodium, sodium alginate is coated on nano zero-valence iron surface, and wherein sodium alginate is 0.2: 1 with the mass ratio of nano zero valence iron.
The preparation method of the cladding nanometer Zero-valent Iron of a kind of above-mentioned the present embodiment, comprises the following steps:
(1)FeSO4The preparation of solution: weigh 3.3600g FeSO4·7H2O puts in beaker, adds the dissolving of appropriate ultra-pure water and turns
Move on to, in 100mL volumetric flask, be settled to graduation mark with ultra-pure water, shake up, obtain the FeSO that concentration is 0.12M4Solution.
(2)NaBH4The preparation of solution: weigh 0.9079g NaBH4Put in beaker, add appropriate ultra-pure water solution transfer and arrive
In 100mL volumetric flask, it is settled to graduation mark with ultra-pure water, shakes up, i.e. can get the NaBH that concentration is 0.24M4Solution.
(3) preparation of sodium alginate soln: the sodium alginate taking 0.01g is dissolved in the water of 100mL, in 60 DEG C of water bath condition
Lower stirring and dissolving, is passed through nitrogen and carries out deoxidation treatment 15min, obtains the sodium alginate soln that concentration is 0.1g/L.
(4) preparation of nano zero valence iron granule (nZVI): by the FeSO of 100mL, 0.12M4Solution joins the three of 250mL
In mouth flask, it is passed through nitrogen 15min, is to be stirred vigorously under 200r/min, through the meter of stoichiometric proportion in nitrogen protection and rotating speed
Calculate, at BH4 -/Fe2+Mol ratio is under the conditions of mixture ratios of 2.0, by the NaBH of equal-volume 100mL4Solution the most at the uniform velocity instills three mouthfuls
In flask, reaction system blackening, there is bubble (hydrogen) to produce, drip off NaBH4Stir continuously and healthily 30min after solution, obtain black
Color suspension；Then black suspension is transferred in conical flask, is placed on Magnet, remove supernatant, use deoxygenation deionization
Water and the ethanol that volumn concentration is 5% respectively clean three times, obtain nano zero valence iron (nZVI) granule；By nano zero valence iron
(nZVI) being vacuum dried, dried nano zero valence iron (nZVI) is placed in the brown bottle of full nitrogen standby.
(5) preparation of cladding nanometer Zero-valent Iron (SA-nZVI): 0.05g nano zero valence iron (nZVI) is added in 100mL dense
In the degree sodium alginate soln for 0.1g/L, ultrasonic disperse 20min under conditions of 40KHZ, can be prepared by cladding nanometer zero
Valency ferrum (SA-nZVI) suspension, numbered S2, in this suspension, the concentration of cladding nanometer Zero-valent Iron is 0.5g/L.Due to this
Cladding nanometer Zero-valent Iron is for the process of bed mud heavy metal, in order to ensure its dispersibility in bed mud, therefore cladding nanometer
Zero-valent Iron generally preserves with the form of suspension.
In the present embodiment, the time of ultrasonic disperse is 15min～30min；The frequency of ultrasonic disperse is 30KHZ～50KHZ
All can implement.
The cladding nanometer Zero-valent Iron finished product S2 prepared in the present embodiment and uncoated type nano zero valence iron are placed in scanning
Micro-Structure Analysis is carried out under Electronic Speculum.Fig. 1 is the scanning electron microscope (SEM) photograph of uncoated type nano zero valence iron (nZVI) granule, can from Fig. 1
To observe, the nano zero valence iron of uncoated type presents chain structure, disperses uneven, and this is mainly due to its higher surface
Long-pending, add self polarity, easily cause reunion to cause.Fig. 2 is the cladding nanometer Zero-valent Iron (SA-nZVI) of the present embodiment
The scanning electron microscope (SEM) photograph of grain, from Fig. 2 it is observed that granule dispersion is more uniform, presents spherical particle, shows that sodium alginate becomes
Merit is coated on the surface of nano zero valence iron granule.Fig. 3 is cladding nanometer Zero-valent Iron (SA-nZVI) and uncoated in the present embodiment
The x-ray diffraction pattern of type nano zero valence iron (nZVI), Fig. 3 a represents uncoated type nano zero valence iron (nZVI), permissible from Fig. 3 a
Observing, scanning angle of diffraction 2 θ=30 °, 35 °, 57 °, 62.25 ° all there is obvious diffraction maximum, and these angles all represent ferrum
Oxide, 2 θ=44.9 ° represent Fe0；Fig. 3 b represents cladding nanometer Zero-valent Iron (SA-nZVI), can observe from Fig. 3 b
Arriving, only occur in that diffraction maximum at 44.9 °, other diffraction maximum does not all occur, shows that surface cladding type nano zero valence iron is not by oxygen
Change.Can draw, the stability of prepared novel cladding nanometer Zero-valent Iron is preferable, and sodium alginate enhances nano zero-valence
The stability of ferrum, significantly improves the problem that nano zero valence iron is the most oxidized and reunites.
Embodiment 3:
The cladding nanometer Zero-valent Iron of a kind of present invention, this cladding nanometer Zero-valent Iron includes nano zero valence iron and alginic acid
Sodium, sodium alginate is coated on nano zero-valence iron surface, and wherein sodium alginate is 0.3: 1 with the mass ratio of nano zero valence iron.
The preparation method of the cladding nanometer Zero-valent Iron of a kind of above-mentioned the present embodiment, comprises the following steps:
(1)FeSO4The preparation of solution: weigh 5.3200g FeSO4·7H2O puts in beaker, adds the dissolving of appropriate ultra-pure water and turns
Move on to, in 100mL volumetric flask, be settled to graduation mark with ultra-pure water, shake up, obtain the FeSO that concentration is 0.19M4Solution.
(2)NaBH4The preparation of solution: weigh 1.4375g NaBH4Put in beaker, add appropriate ultra-pure water solution transfer and arrive
In 100mL volumetric flask, it is settled to graduation mark with ultra-pure water, shakes up, i.e. can get the NaBH that concentration is 0.38M4Solution.
(3) preparation of sodium alginate soln: the sodium alginate taking 0.015g is dissolved in the water of 100mL, in 60 DEG C of water-bath bars
Stirring and dissolving under part, is passed through nitrogen and carries out deoxidation treatment 15min, obtains the sodium alginate soln that concentration is 0.15g/L.
(4) preparation of nano zero valence iron granule (nZVI): by the FeSO of 100mL, 0.19M4Solution joins the three of 250mL
In mouth flask, it is passed through nitrogen 15min, is to be stirred vigorously under 200r/min, through the meter of stoichiometric proportion in nitrogen protection and rotating speed
Calculate, at BH4 -/Fe2+Mol ratio is under the conditions of mixture ratios of 2.0, by the NaBH of equal-volume 100mL4Solution the most at the uniform velocity instills three mouthfuls
In flask, reaction system blackening, there is bubble (hydrogen) to produce, drip off NaBH4Stir continuously and healthily 30min after solution, obtain black
Color suspension；Then black suspension is transferred in conical flask, is placed on Magnet, remove supernatant, use deoxygenation deionization
Water and the ethanol that volumn concentration is 5% respectively clean three times, obtain nano zero valence iron (nZVI) granule；By nano zero valence iron
(nZVI) being vacuum dried, dried nano zero valence iron (nZVI) is placed in the brown bottle of full nitrogen standby.
(5) preparation of cladding nanometer Zero-valent Iron (SA-nZVI): 0.05g nano zero valence iron (nZVI) is added in 100mL dense
In the degree sodium alginate soln for 0.15g/L, ultrasonic disperse 20min under conditions of 40KHZ, can be prepared by cladding nanometer zero
Valency ferrum (SA-nZVI) suspension, numbered S3, in this suspension, the concentration of cladding nanometer Zero-valent Iron is 0.5g/L.Due to this
Cladding nanometer Zero-valent Iron is for the process of bed mud heavy metal, in order to ensure its dispersibility in bed mud, therefore cladding nanometer
Zero-valent Iron generally preserves with the form of suspension.
In the present embodiment, the time of ultrasonic disperse is 15min～30min；The frequency of ultrasonic disperse is 30KHZ～50KHZ
All can implement.
Embodiment 4:
The cladding nanometer Zero-valent Iron of a kind of present invention, this cladding nanometer Zero-valent Iron includes nano zero valence iron and alginic acid
Sodium, sodium alginate is coated on nano zero-valence iron surface, and wherein sodium alginate is 0.4: 1 with the mass ratio of nano zero valence iron.
The preparation method of the cladding nanometer Zero-valent Iron of a kind of above-mentioned the present embodiment, comprises the following steps:
(1)FeSO4The preparation of solution: weigh 5.6000g FeSO4·7H2O puts in beaker, adds the dissolving of appropriate ultra-pure water and turns
Move on to, in 100mL volumetric flask, be settled to graduation mark with ultra-pure water, shake up, obtain the FeSO that concentration is 0.2M4Solution.
(2)NaBH4The preparation of solution: weigh 1.5132g NaBH4Put in beaker, add appropriate ultra-pure water solution transfer and arrive
In 100mL volumetric flask, it is settled to graduation mark with ultra-pure water, shakes up, obtain the NaBH that concentration is 0.4M4Solution.
(3) preparation of sodium alginate soln: the sodium alginate taking 0.02g is dissolved in the water of 100mL, in 60 DEG C of water bath condition
Lower stirring and dissolving, is passed through nitrogen and carries out deoxidation treatment 15min, obtains the sodium alginate soln that concentration is 0.2g/L.
(4) preparation of nano zero valence iron granule (nZVI): be the FeSO of 0.2M by 100mL concentration4Solution joins 250mL
There-necked flask in, be passed through nitrogen 15min, nitrogen protection and rotating speed be to be stirred vigorously, through stoichiometric proportion under 200r/min
Calculating, at BH4 -/Fe2+Mol ratio is under the conditions of mixture ratios of 2.0, by the NaBH of equal-volume 100mL4Solution the most at the uniform velocity instills
In there-necked flask, reaction system blackening, there is bubble (hydrogen) to produce, drip off NaBH430min is stirred continuously and healthily after solution,
To black suspension；Then black suspension is transferred in conical flask, is placed on Magnet, remove supernatant, go with deoxygenation
Ionized water and the ethanol that volumn concentration is 5% respectively clean three times, obtain nano zero valence iron (nZVI) granule；By nano zero-valence
Ferrum (nZVI) is vacuum dried, and dried nano zero valence iron (nZVI) is placed in the brown bottle of full nitrogen standby.
(5) preparation of cladding nanometer Zero-valent Iron (SA-nZVI): 0.05g nano zero valence iron (nZVI) is added in 100mL dense
In the degree sodium alginate soln for 0.2g/L, ultrasonic disperse 20min under conditions of 40KHZ, can be prepared by cladding nanometer zero
Valency ferrum (SA-nZVI) suspension, numbered S4, in this suspension, the concentration of cladding nanometer Zero-valent Iron is 0.5g/L.Due to this
Cladding nanometer Zero-valent Iron is for the process of bed mud heavy metal, in order to ensure its dispersibility in bed mud, therefore cladding nanometer
Zero-valent Iron generally preserves with the form of suspension.
In the present embodiment, the time of ultrasonic disperse is 15min～30min, and the frequency of ultrasonic disperse is 30KHZ～50KHZ
All can implement.
Comparative example 1:
The nano zero valence iron (nZVI) of uncoated type, its preparation method is according to the preparation side of nano zero valence iron in embodiment 1
Method is carried out, but without stabilizer sodium alginate (SA).
Embodiment 5:
The application in heavy metal cadmium in stable bed mud of the cladding nanometer Zero-valent Iron of a kind of present invention, including following step
Rapid:
(1) carry out pretreatment containing cadmium bed mud: cadmium bed mud will be contained and air-dry under field conditions (factors), grind, sieve, obtain particle diameter≤
75 μm containing cadmium bed mud.PH, organic matter, organic carbon, cation exchange capacity, moisture content, total nitrogen, total phosphorus in detection bed mud respectively
Etc. index result, measurement result is shown in Table 1.
Table 1: the quality measurements table containing cadmium bed mud
| pH | 7.79 |
| Organic (g/kg) | 13.57 |
| Organic carbon (g/kg) | 7.88 |
| Cation exchange capacity (cmol/kg) | 13.62 |
| Moisture content | 58.72% |
| Total nitrogen (g/kg) | 2.16 |
| Total phosphorus (g/kg) | 0.169 |
As it can be seen from table 1 bed mud moisture content is higher, belong to solid-liquid mixed phase, therefore during pollution administration, hold
Easily there is complicated reaction in solid liquid interface.
(2) in cladding nanometer Zero-valent Iron sample S1, S2, S3, S4 of being utilized respectively in embodiment 1～4 and comparative example 1 not
Cladding nanometer Zero-valent Iron process step (1) obtain containing cadmium bed mud, method particularly includes:
Weighing 0.5g, after pretreatment containing cadmium bed mud, (content of heavy metal cadmium is 20.9mg/kg, the content of residual form cadmium
For 3.24mg/kg), be placed in 50mL centrifuge tube, then by cladding nanometer Zero-valent Iron suspension by with containing cadmium bed mud volume mass
Add in above-mentioned centrifuge tube than the ratio of 10mL: 1g (cladding nanometer Zero-valent Iron suspension vol/bed mud absolute dry mass), in
Constant temperature standing and reacting 30 days at 24 DEG C, use BCR continuous extraction to measure the content of heavy metal cadmium residual form in bed mud.
The concrete extraction step of BCR continuous extraction is:
Weak acid extractable: above-mentioned constant temperature standing is processed the centrifugal 5min under the conditions of 3000r/min of the sample after 30d, uses
The membrane filtration of 0.45 μm, obtains supernatant A and remaining bed mud A.Adding 20mL concentration in remaining bed mud A is 0.11mol/L
CH3COOH solution, in temperature be 25 DEG C, rotating speed be on the shaking table of 250rpm after continuous oscillation 16h, in 4000r/min from
Scheming is centrifuged 20min, with the membrane filtration of 0.45 μm, obtains supernatant B and remaining bed mud B, uses atomic absorption spectrophotometer
Measure the concentration of the heavy metal being extracted in supernatant A and B.
Reducible state: add 20mL distilled water vibration 15min, 4000r/min in remaining bed mud B and be centrifuged 20min, wash
Wash；Remaining bed mud B after washing adds 20mL oxammonium hydrochloride. and HNO3Mixed liquor, wherein oxammonium hydrochloride. in mixed liquor
Concentration is 0.5mol/L, HNO3Concentration be 0.05mol/L (HNO3Effect be regulation pH=1.5), in 250rpm continuous oscillation
16h, 4000r/min are centrifuged 20min, with the membrane filtration of 0.45 μm, obtain supernatant C and remaining bed mud C, divide by Atomic Absorption
The concentration of the heavy metal being extracted in light photometric determination supernatant C.
Oxidable state: add 5mL H in remaining bed mud C2O2, use dense HNO3Regulation pH value is to 2, and lid pine lid, in room temperature
After lower placement 1h (glass rod stirs), in 85 DEG C of waters bath with thermostatic control, keep 1h, open centrifuge tube lid and continue to be heated to volume
It is not more than 3mL, continues to add 5mL H2O2, keep 1h in 85 DEG C of waters bath with thermostatic control, open lid and be heated to volume 1mL, add after cooling
Enter 25mL concentration be 1.0mol/L, pH value be 2.0 (to use dense HNO3Regulation) NH4OAc solution, after continuous oscillation 16h, 4000r/
Min is centrifuged 20min, with the membrane filtration of 0.45 μm, obtains supernatant D and remaining bed mud D, surveys with atomic absorption spectrophotometer
Determine the concentration of the heavy metal being extracted in supernatant D.
Residual form: add 5mL HNO in remaining bed mud D3、5mL HF、3mL HClO4, gained mixed liquor is placed in electric hot plate
Upper heat resolve, divides three phases heat time heating time: heat 40min at 70 DEG C～90 DEG C, heats 60min at 130 DEG C～160 DEG C,
150 DEG C～170 DEG C heating 40min, now have a large amount of white cigarette to emerge, shake scattered white cigarette and observe mixed liquor form, if liquid cannot
Cover whole beaker bottom, then need to observe at any time, be slowly heated to rocking beaker at any time when solution becomes a solution, if liquid
Body maintains static, then clear up successfully, if heat time heating time is long, drop splits, then clear up failure, takes off the sample after clearing up and adds
Enter 5%HNO3Dissolving, last constant volume is to be measured.Measurement result is shown in Table 2.
Table 2: the Cd content of various forms in bed mud before and after reparation
As can be known from the results of Table 2: cladding nanometer Zero-valent Iron S1 for preparing in embodiment 1～4, S2, S3, S4 be to containing at the bottom of cadmium
In mud, the stabilization efficiency of residual form is above the prepared uncoated type nano zero valence iron of comparative example 1 to the stable effect containing cadmium bed mud
Rate, and cladding nanometer Zero-valent Iron S2 is 57.28% to the bed mud residual form heavy metal cadmium stabilization efficiency containing cadmium, before repairing
, make the content of the residual form that environmental pollution harm is minimum in bed mud rise 41.79%, prepare under the conditions of being above other
Cladding nanometer Zero-valent Iron, illustrate that cladding nanometer Zero-valent Iron S2 is most preferred embodiment.
Fig. 4 is uncoated type in the cladding nanometer Zero-valent Iron (SA-nZVI) in the embodiment of the present invention 1～4 and comparative example 1
Nano zero valence iron (nZVI) stablizes the aspect graph of bed mud heavy metal cadmium, and wherein vertical coordinate is heavy metal cadmium each form percentage rate, horizontal
Coordinate is the different stabilizing treatment times.In the abscissa of Fig. 4, what c represented is repair before initial value in bed mud, 0,1,3,5,
7,10,15,30 represent respectively in stabilizing treatment 0 day (referring to same day cladding nanometer Zero-valent Iron being added in bed mud for 0 day), 1
My god, 3 days, 5 days, 7 days, 10 days, 15 days, 30 days time sampling, each time interval has 5 pillars, is from left to right corresponding in turn to
Stabilized treatment for the uncoated type nano zero valence iron (nZVI) in comparative example 1, S1, S2, S3, the S4 in embodiment 1～4 is imitated
Really.As shown in Figure 4, along with the passage of stabilization time, the residual form percentage rate of heavy metal cadmium presents the trend of rising, is above repairing
The residual form percentage rate of cadmium in bed mud before multiple, when treated between be 10 days after, residual form percentage rate reaches higher level, and 10
It～tend towards stability in 30 days；The most a certain degree of bioavailability reducing heavy metal cadmium is described, decreases heavy metal cadmium
Hazardness to organism.It addition, within each sample time, it can be seen that the residual form percentage rate of the cadmium of embodiment S2 is
Height, this most also illustrates that cladding nanometer Zero-valent Iron S2 is best to the stablizing effect of heavy metal cadmium in bed mud.
The present invention utilizes cladding nanometer Zero-valent Iron to stablize heavy metal cadmium in bed mud first, by research cladding nanometer zero
With this, the impact on four kinds of different shapes of cadmium of the valency ferrum, differentiates that heavy metal, to the hazardness of organism in bed mud, solves existing
There is in technology the problem only studying total concentration of heavy metal and the murder by poisoning size of heavy metal can not be reflected.By the present invention's
Cladding nanometer Zero-valent Iron is used for administering heavy metal polluted bed mud, can make the residual form that in bed mud, environmental pollution harm is minimum
Content of beary metal rises 41.79%, and heavy metal biological availability reduces.Add with the form of cladding nanometer Zero-valent Iron suspension
To containing in cadmium bed mud, can preferably penetrate in bed mud under the drive of water, animal migration be high, solves nanometer in prior art
The problem that Zero-valent Iron animal migration is bad.The application process of the present invention is easy and simple to handle, and stablizing effect is good, and animal migration is good, rehabilitation cost
Low, and cleanliness without any pollution, to environment nonhazardous effect, before Heavy Metal Pollution in Sediments Treatment process field has a wide range of applications
Scape.
The above, be only presently preferred embodiments of the present invention, and the present invention not does any pro forma restriction.Though
So the present invention explains as above with preferred embodiment, but is not limited to the present invention.Any it is familiar with those skilled in the art
Member, in the case of without departing from the spirit of the present invention and technical scheme, may utilize in method and the technology of the disclosure above
Hold and the technology of the present invention is made many possible variations and modification, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every
Without departing from the content of technical solution of the present invention, any simply repair made for any of the above embodiments according to the technical spirit of the present invention
Change, equivalent, equivalence change and modify, all still fall within technical solution of the present invention protection in the range of.
Claims (10)
1. a cladding nanometer Zero-valent Iron, it is characterised in that described cladding nanometer Zero-valent Iron includes nano zero valence iron and sea
Sodium alginate；Described sodium alginate is coated on described nano zero-valence iron surface；Described sodium alginate and the matter of described nano zero valence iron
Amount ratio is 0.1～0.4: 1.
2. the preparation method of a cladding nanometer Zero-valent Iron as claimed in claim 1, it is characterised in that include following step
Rapid: nano zero valence iron to be mixed with sodium alginate soln and sonicated obtains cladding nanometer Zero-valent Iron.
The preparation method of cladding nanometer Zero-valent Iron the most according to claim 2, it is characterised in that described sodium alginate is molten
The concentration of liquid is 0.05g/L～0.2g/L.
The preparation method of cladding nanometer Zero-valent Iron the most according to claim 3, it is characterised in that described sodium alginate is molten
The preparation of liquid comprises the following steps: by sodium alginate stirring and dissolving under 55 DEG C～65 DEG C of water bath condition, is passed through nitrogen and takes off
Oxygen processes 10min～20min, obtains sodium alginate soln.
5. according to the preparation method of the cladding nanometer Zero-valent Iron according to any one of claim 2～4, it is characterised in that institute
The preparation stating nano zero valence iron comprises the following steps: by isopyknic NaBH4Solution and FeSO4Solution mix and blend 30min～
60min, obtains nano zero valence iron；Described NaBH4BH in solution4 -With described FeSO4Fe in solution2+Mol ratio be 2: 1.
6. according to the preparation method of the cladding nanometer Zero-valent Iron according to any one of claim 2～4, it is characterised in that institute
The frequency stating supersound process is 30KHZ～50KHZ；The time of described supersound process is 15min～30min.
7. a cladding nanometer Zero-valent Iron as claimed in claim 1 or the preparation side according to any one of claim 2～6
Cladding nanometer Zero-valent Iron application in heavy metal cadmium in stable bed mud that method prepares, it is characterised in that comprise the following steps:
Suspension containing described cladding nanometer Zero-valent Iron is added to containing carrying out constant temperature standing and reacting in cadmium bed mud, completes in bed mud
The stabilizing treatment of heavy metal cadmium.
Application the most according to claim 7, it is characterised in that the suspension containing described cladding nanometer Zero-valent Iron with containing cadmium
The volume mass of bed mud is than for 5mL～15mL: 1g；Cladding nanometer zeroth order in suspension containing described cladding nanometer Zero-valent Iron
The concentration of ferrum is 0.5g/L.
9. according to the application described in claim 7 or 8, it is characterised in that described containing the initial concentration of heavy metal cadmium in cadmium bed mud
For 5mg/kg～40mg/kg；The described pH value containing cadmium bed mud is 7～8.
10. according to the application described in claim 7 or 8, it is characterised in that the condition of described constant temperature standing and reacting is: the time is
0d～30d, temperature is 21 DEG C～24 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610325642.8A CN106000335B (en) | 2016-05-17 | 2016-05-17 | Cladding nanometer Zero-valent Iron and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610325642.8A CN106000335B (en) | 2016-05-17 | 2016-05-17 | Cladding nanometer Zero-valent Iron and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106000335A true CN106000335A (en) | 2016-10-12 |
| CN106000335B CN106000335B (en) | 2018-10-19 |
Family
ID=57098427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610325642.8A Active CN106000335B (en) | 2016-05-17 | 2016-05-17 | Cladding nanometer Zero-valent Iron and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106000335B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106825013A (en) * | 2017-02-27 | 2017-06-13 | 环境保护部南京环境科学研究所 | Using the method for modified Nano Zero-valent Iron heavy metal contaminated soil stabilization processes |
| CN106891017A (en) * | 2017-01-20 | 2017-06-27 | 湖南大学 | Modified Nano Zero-valent Iron and its preparation method and application |
| CN106944630A (en) * | 2017-04-21 | 2017-07-14 | 山东大学 | Stable nano zero valence iron of a kind of marine alga slag and preparation method and application |
| CN106984640A (en) * | 2017-05-08 | 2017-07-28 | 湖南大学 | The method of nano zero valence iron restoration of soil polluted by heavy metal |
| CN107010708A (en) * | 2017-04-21 | 2017-08-04 | 山东大学 | A kind of algal polysaccharides sulfuric ester cladding nano zero valence iron and preparation method and application |
| CN107350469A (en) * | 2017-06-27 | 2017-11-17 | 东南大学 | A kind of process for dispersing of Zero-valent Iron |
| CN107377001A (en) * | 2017-09-04 | 2017-11-24 | 天津工业大学 | A kind of preparation of calcium alginate cladded type Zero-valent Iron and its method for degradation of dye |
| CN108373296A (en) * | 2018-01-30 | 2018-08-07 | 广州市环境保护工程设计院有限公司 | A method of preparing novel water permeable brick using creek bed mud |
| CN108905984A (en) * | 2018-07-23 | 2018-11-30 | 山东建筑大学 | A kind of magnetic microsphere restorative procedure of copper cadmium pollution river water body and bed mud |
| CN109202096A (en) * | 2018-09-27 | 2019-01-15 | 安徽建筑大学 | A kind of Zero-valent Iron haydite and preparation method thereof |
| CN109261133A (en) * | 2018-10-26 | 2019-01-25 | 中国海洋大学 | A kind of ferromagnetism composite balls and its application being easily recycled |
| CN110000371A (en) * | 2018-01-04 | 2019-07-12 | 清华大学 | A kind of nano zero valence iron of cladding and its preparation method and application |
| CN110760309A (en) * | 2019-11-29 | 2020-02-07 | 广西大学 | Reducing agent for treating hexavalent chromium in soil and using method thereof |
| CN111534307A (en) * | 2020-05-25 | 2020-08-14 | 成都新柯力化工科技有限公司 | Double-layer covering soil remediation agent for heavy metal contaminated soil and preparation method |
| CN114029039A (en) * | 2021-11-29 | 2022-02-11 | 陕西省中勘环境地质研究中心有限公司 | Nano zero-valent iron gel ball, preparation method thereof and application of nano zero-valent iron gel ball in removing heavy metal ions |
| CN115403124A (en) * | 2022-09-09 | 2022-11-29 | 浙江工业大学绍兴研究院 | Method for efficiently removing heavy metal pollutants by ball milling of sargassum acidized zero-valent iron composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769033A (en) * | 2014-01-27 | 2014-05-07 | 北京工业大学 | Preparation method and application of modified zeolite permeable reactive wall filling carrying zero-valent iron powder |
| CN104226987A (en) * | 2014-09-30 | 2014-12-24 | 湖南大学 | Modified nanoscale zero-valent iron and preparing method thereof |
| CN104310726A (en) * | 2014-09-30 | 2015-01-28 | 湖南大学 | Method for removing heavy metal chromium in bottom mud by using modified nano zero-valent iron |
-
2016
- 2016-05-17 CN CN201610325642.8A patent/CN106000335B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769033A (en) * | 2014-01-27 | 2014-05-07 | 北京工业大学 | Preparation method and application of modified zeolite permeable reactive wall filling carrying zero-valent iron powder |
| CN104226987A (en) * | 2014-09-30 | 2014-12-24 | 湖南大学 | Modified nanoscale zero-valent iron and preparing method thereof |
| CN104310726A (en) * | 2014-09-30 | 2015-01-28 | 湖南大学 | Method for removing heavy metal chromium in bottom mud by using modified nano zero-valent iron |
Non-Patent Citations (2)
| Title |
|---|
| 朱文会等: ""海藻酸钠固定化Fe-Cu双金属去除Cr(VI)的作用机制"", 《中国环境科学》 * |
| 李梓涵: ""分散性纳米零价铁的制备及其去除地下水中Cr(VI)的研究"", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106891017A (en) * | 2017-01-20 | 2017-06-27 | 湖南大学 | Modified Nano Zero-valent Iron and its preparation method and application |
| CN106891017B (en) * | 2017-01-20 | 2019-05-14 | 湖南大学 | Modified Nano Zero-valent Iron and its preparation method and application |
| CN106825013A (en) * | 2017-02-27 | 2017-06-13 | 环境保护部南京环境科学研究所 | Using the method for modified Nano Zero-valent Iron heavy metal contaminated soil stabilization processes |
| CN106944630A (en) * | 2017-04-21 | 2017-07-14 | 山东大学 | Stable nano zero valence iron of a kind of marine alga slag and preparation method and application |
| CN107010708A (en) * | 2017-04-21 | 2017-08-04 | 山东大学 | A kind of algal polysaccharides sulfuric ester cladding nano zero valence iron and preparation method and application |
| CN107010708B (en) * | 2017-04-21 | 2021-02-19 | 山东大学 | Algal polysaccharide sulfate coated nano zero-valent iron and preparation method and application thereof |
| CN106984640A (en) * | 2017-05-08 | 2017-07-28 | 湖南大学 | The method of nano zero valence iron restoration of soil polluted by heavy metal |
| CN107350469B (en) * | 2017-06-27 | 2019-06-18 | 东南大学 | A kind of dispersing method of Zero-valent Iron |
| CN107350469A (en) * | 2017-06-27 | 2017-11-17 | 东南大学 | A kind of process for dispersing of Zero-valent Iron |
| CN107377001A (en) * | 2017-09-04 | 2017-11-24 | 天津工业大学 | A kind of preparation of calcium alginate cladded type Zero-valent Iron and its method for degradation of dye |
| CN110000371A (en) * | 2018-01-04 | 2019-07-12 | 清华大学 | A kind of nano zero valence iron of cladding and its preparation method and application |
| CN110000371B (en) * | 2018-01-04 | 2022-12-30 | 清华大学 | Coated nano zero-valent iron and preparation method and application thereof |
| CN108373296A (en) * | 2018-01-30 | 2018-08-07 | 广州市环境保护工程设计院有限公司 | A method of preparing novel water permeable brick using creek bed mud |
| CN108373296B (en) * | 2018-01-30 | 2021-04-16 | 广州市环境保护工程设计院有限公司 | Method for preparing novel water permeable brick by using river bottom mud |
| CN108905984A (en) * | 2018-07-23 | 2018-11-30 | 山东建筑大学 | A kind of magnetic microsphere restorative procedure of copper cadmium pollution river water body and bed mud |
| CN108905984B (en) * | 2018-07-23 | 2021-04-27 | 山东建筑大学 | Magnetic microsphere repairing method for copper-cadmium polluted river water body and bottom mud |
| CN109202096A (en) * | 2018-09-27 | 2019-01-15 | 安徽建筑大学 | A kind of Zero-valent Iron haydite and preparation method thereof |
| CN109261133A (en) * | 2018-10-26 | 2019-01-25 | 中国海洋大学 | A kind of ferromagnetism composite balls and its application being easily recycled |
| CN110760309A (en) * | 2019-11-29 | 2020-02-07 | 广西大学 | Reducing agent for treating hexavalent chromium in soil and using method thereof |
| CN111534307A (en) * | 2020-05-25 | 2020-08-14 | 成都新柯力化工科技有限公司 | Double-layer covering soil remediation agent for heavy metal contaminated soil and preparation method |
| CN114029039A (en) * | 2021-11-29 | 2022-02-11 | 陕西省中勘环境地质研究中心有限公司 | Nano zero-valent iron gel ball, preparation method thereof and application of nano zero-valent iron gel ball in removing heavy metal ions |
| CN115403124A (en) * | 2022-09-09 | 2022-11-29 | 浙江工业大学绍兴研究院 | Method for efficiently removing heavy metal pollutants by ball milling of sargassum acidized zero-valent iron composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106000335B (en) | 2018-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106000335A (en) | Coated type nanoscale zero-valent iron as well as preparation method and application thereof | |
| Zouboulis et al. | Removal of humic acids by flotation | |
| Kim et al. | Microplastics disrupt accurate soil organic carbon measurement based on chemical oxidation method | |
| US10493425B2 (en) | Hollow iron-manganese composite material prepared by etching template process and application thereof | |
| CN104263837B (en) | The trimerical surface enhanced Raman scattering effect of golden nanometer particle modified based on triple beacon detects Hg in the aqueous solution 2+and/or Ag +method | |
| Igwegbe et al. | Coagulation-flocculation of aquaculture wastewater using green coagulant from garcinia kola seeds: parametric studies, kinetic modelling and cost analysis | |
| Zhang et al. | Adsorption of sediment phosphorus by porous ceramic filter media coated with nano-titanium dioxide film | |
| Kitamura et al. | Effect of ultrasound intensity on the size and morphology of synthesized scorodite particles | |
| CN102718295B (en) | Compound medicament for treating coking wastewater and preparation method thereof | |
| CN104310726A (en) | Method for removing heavy metal chromium in bottom mud by using modified nano zero-valent iron | |
| CN104787994B (en) | Modified Nano chlorapatite is utilized to stablize the method for heavy metal lead in bed mud | |
| Nam et al. | Effect by alkaline flocculation of algae and phosphorous from water using a calcined waste oyster shell | |
| Torres-Quiroz et al. | Oyster shell powder, zeolite and red mud as binders for immobilising toxic metals in fine granular contaminated soils (from Industrial Zones in South Korea) | |
| CN105921763B (en) | The preparation method of sodium alginate/inorganic mineral combined loading type nano zero valence iron | |
| Chen et al. | Transport of polymeric nanoparticulate drug delivery systems in the proximity of silica and sand | |
| Li et al. | Nanoplastic adsorption characteristics of bisphenol A: The roles of pH, metal ions, and suspended sediments | |
| Pasciucco et al. | Recovery strategies of contaminated marine sediments: a life cycle assessment | |
| Maeng et al. | Enhanced flotation technology using low-density microhollow beads to remove algae from a drinking water source | |
| CN105460979B (en) | A kind of preparation of FeS particulates for repairing hexavalent chromium polluted soil and application method | |
| CN105731584A (en) | Method for removing micropollutant ibuprofen in water | |
| CN109879353A (en) | A kind of aquiculture waste water treatment process | |
| CN106944630A (en) | Stable nano zero valence iron of a kind of marine alga slag and preparation method and application | |
| Wang et al. | Adsorption characteristics of modified bamboo charcoal on Cu (II) and Cd (II) in water | |
| CN106865924A (en) | A kind of method for innocent treatment of Sediments | |
| Chen et al. | The impact of recycling sludge on water quality in coagulation for treating low-turbidity source water |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190522 Address after: 410205 22nd and 23rd Floors, F1 Building, Yuyuan, Lugu, 27 Wenxuan Road, Changsha High-tech Development Zone, Changsha City, Hunan Province Patentee after: HUNAN SANYOU EP TECHNOLOGY CO.,LTD. Address before: 410082 College of environmental science and engineering, Hunan University, Hexi Mount Yuelu, Changsha, Hunan Patentee before: Hunan University |
|
| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 410205 22nd and 23rd Floors, F1 Building, Yuyuan, Lugu, 27 Wenxuan Road, Changsha High-tech Development Zone, Changsha City, Hunan Province Patentee after: Hunan Sanyou Environmental Protection Technology Co.,Ltd. Address before: 410205 22nd and 23rd Floors, F1 Building, Yuyuan, Lugu, 27 Wenxuan Road, Changsha High-tech Development Zone, Changsha City, Hunan Province Patentee before: HUNAN SANYOU EP TECHNOLOGY CO.,LTD. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Coated nano zero valent iron and its preparation and Application Effective date of registration: 20200821 Granted publication date: 20181019 Pledgee: Bank of Changsha Limited by Share Ltd. science and Technology Branch Pledgor: Hunan Sanyou Environmental Protection Technology Co.,Ltd. Registration number: Y2020980005234 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220121 Granted publication date: 20181019 Pledgee: Bank of Changsha Limited by Share Ltd. science and Technology Branch Pledgor: Hunan Sanyou Environmental Protection Technology Co.,Ltd. Registration number: Y2020980005234 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation and application of nano iron coating Effective date of registration: 20220324 Granted publication date: 20181019 Pledgee: Changsha Yuelu sub branch of China Everbright Bank Co.,Ltd. Pledgor: Hunan Sanyou Environmental Protection Technology Co.,Ltd. Registration number: Y2022430000020 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20181019 Pledgee: Changsha Yuelu sub branch of China Everbright Bank Co.,Ltd. Pledgor: Hunan Sanyou Environmental Protection Technology Co.,Ltd. Registration number: Y2022430000020 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |