CN106925205A - A kind of lime-preserved egg shell adsorbent of uranium and its preparation method and application - Google Patents
A kind of lime-preserved egg shell adsorbent of uranium and its preparation method and application Download PDFInfo
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- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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- 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
- B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
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Abstract
The present invention relates to a kind of lime-preserved egg shell adsorbent of uranium rapidly and efficiently, preparation process is as follows：（1）Cleaning lime-preserved egg shell simultaneously removes egg film；（2）The lime-preserved egg shell that will be handled well is placed on clear water or 20% sodium hydroxide solution soaks 8 12h, is filtered dry；（3）To consider during dry lime-preserved egg shell is put into baking oven and dry；（4）To being crushed or being ground the lime-preserved egg shell of drying, 200 the polished standard screens are crossed；（5）Skin egg-shell meal after sieving is put into drying box and is dried, lime-preserved egg shell adsorbent is obtained.The optimal adsorption condition that the present invention is provided is that uranium-bearing pH value of solution is 3 or so, and dosage is about 0.1g/l or so, and adsorption time is 4h or so.Under optimum condition, lime-preserved egg shell adsorbent can reach 88% or so to the adsorption efficiency of uranium.Obtained adsorbent wide material sources of the invention, cost are extremely low, and using will not pollute to environment, and the adsorption efficiency to uranium is high.
Description
Technical field
The invention belongs to technical field of biological material, it is related to the lime-preserved egg shell adsorbent of uranium.
Background technology
Industrial activity be continuously increased be most of problem of environmental pollutions and ecological disruption arch-criminal, put containing dangerous
The soil of penetrating property chemical substance, underground water, deposit and air bring significant problem to mankind's Health and Living environment.Uranium-bearing gives up
The source of water be it is quite varied, such as nuclear weapon test, some wars relevant with depleted uranium bomb, uranium ore enterprise discharge waste water,
Nuclear power station has the discharge of radiological material, abnormal accident (such as Chernobyl nuclear leakage and uranium raw material processing factory nuclear catastrophe)
Etc. uranium content in the aqueous solution can increased.The risk of uranium-containing waste water mainly has two aspects：One is that the mankind are depended on for existence
Ecological environment damage, two be to mankind itself health produce threat.Uranium-containing waste water can to we survive environment and
Health care belt carrys out very big risk, if not processing and being directly discharged into environment, the pollution for being brought is that we are out of one's imagine.
And uranium has radioactivity and chemical toxicity, the uranium in waste water can be permeated the ground in water, and not only water resource is polluted, and be returned
Local agricultural and fishery bring serious harm, can also transmits by food chain, and it is healthy to eventually enter into harm, induction
A series of diseases, can lead causing death when serious.Therefore, uranium in wide material sources, efficient absorption solution cheap and easy to get is filtered out
Adsorbent have good application prospect.
Eggs have high demand as a big product of food service industry.Eggshell gives up as one kind of food service industry
Gurry, can cause destruction to a certain extent to environment.Patent 20121011905.5, discloses a kind of eggshell heavy metal ion
Adsorbent and preparation method thereof, adsorbent is made by raw material of eggshell, and absorbent powder granularity is 40~100 mesh, it is adaptable to pH
It is worth the treatment of the acidic industrial effluent for 3~6, the addition of adsorbent is 2~2.5g/L；What be can be used in adsorbent solution is all
Such as Cd2+、Pb2+、Cu2+、Ni2+、Cr3+And Cr2+Etc. heavy metal ion.The eggshell heavy metal ion adsorbent has stronger at normal temperatures
Adsorption capacity, preparation method is simple, with low cost, to the acidic industrial effluent high treating effect containing heavy metal ion.For
For the efficient absorption effect of uranium ion in solution, adsorbent also has space and the value of further research.
The content of the invention
The raw material of present invention application are lime-preserved egg shell, due to during lime-preserved egg is made, being wrapped up for a long time outside eggshell
Alkaline matters such as quick lime (or plant ash or sodium carbonate or NaOH), lime-preserved egg shell is when adsorbent is made without use hydrogen again
Sodium hydroxide solution immersion treatment, not only material-saving, save operation, saved the time, improve work material rate, and research table
Adsorption efficiency of the adsorption efficiency of bright lime-preserved egg shell adsorbent adsorption uranium better than chicken and duck eggshell adsorbent.
One of technical solution of the present invention is as follows：
A kind of lime-preserved egg shell adsorbent of uranium, its composition is the skin egg-shell meal for filtering 200 mesh standard sieves, its preparation methods steps
It is as follows：
(1) clean lime-preserved egg shell and remove egg film；
(2) the lime-preserved egg shell that will be handled well is placed on clear water or 20% sodium hydroxide solution immersion 8-12h, is filtered dry；
(3) will consider during dry lime-preserved egg shell is put into baking oven and dry；
(4) to being crushed or being ground the lime-preserved egg shell of drying, 200 the polished standard screens are crossed；
(5) the skin egg-shell meal after sieving is put into drying box and is dried, lime-preserved egg shell adsorbent is obtained.
Further, it is preferable to it is as follows to prepare scheme：
(1) lime-preserved egg shell is washed and except egg film；
(2) the lime-preserved egg shell that will be handled well is placed on clear water or 20% sodium hydroxide solution immersion 8-12h, is filtered dry；
(3) dry lime-preserved egg shell will be considered and is put into 60 DEG C --- dried in 120 DEG C of baking ovens；
(4) the lime-preserved egg shell that will be dried with pulverizer crushes broken or grinding, crosses 200 the polished standard screens；
(5) the skin egg-shell meal after sieving is put into 70 DEG C in drying box --- 80 DEG C of dryings, lime-preserved egg shell adsorbent is obtained.
The two of technical solution of the present invention are as follows：
The range of application that is relatively adapted to of the lime-preserved egg shell adsorbent of uranium is that the PH containing uranium solution is 2.8~3.5, the absorption of lime-preserved egg shell
The addition of agent is 0.08~0.12g/l.
The most suitable range of application of the lime-preserved egg shell adsorbent of uranium is that the PH containing uranium solution is 3, and lime-preserved egg shell adsorbent dosage is
0.1g/l, adsorption time is 4-8h.
Beneficial effect of the present invention is obvious：The lime-preserved egg shell adsorbent raw material sources of uranium are extensive, cost is extremely low, from materials, system
It is standby to being polluted all without to environment during applying；During lime-preserved egg shell is made, shell outer wrapping quick lime (or
Plant ash or sodium carbonate or NaOH) etc. alkaline matter, lime-preserved egg shell self structure is loose porous, rich in calcium carbonate, to uranium
Adsorption rate it is high.Same case hypodermis eggshell adsorbent is higher than the adsorption efficiency of egg shell adsorbent and Ovum Anas domestica putamina adsorbent.
Brief description of the drawings
Fig. 1 is 9 μm of scanning electron microscope (SEM) photographs before lime-preserved egg shell adsorbent adsorption uranium；
Fig. 2 is 7 μm of scanning electron microscope (SEM) photographs after lime-preserved egg shell adsorbent adsorption uranium；
Fig. 3 is the X-ray energy spectrogram before lime-preserved egg shell adsorbent adsorption uranium；
Fig. 4 is the X-ray energy spectrogram after lime-preserved egg shell adsorbent adsorption uranium；
Fig. 5 is the infrared spectrogram before and after lime-preserved egg shell adsorbent adsorption uranium.
Specific embodiment
The following examples can make one of ordinary skill in the art that the present invention is appreciated more fully, but not with any side
The formula limitation present invention.
Embodiment 1
It is constant in control other conditions, only in the case of this unitary variant of biomass species, compare not same organism
The absorption property of matter adsorbent.Experiment condition is that under room temperature 298K, in 100ml contains uranium solution, biomass adsorbent is added
It is 0.01g to measure, and initial uranium concentration 5 μ g/ml, pH are 4.5, after absorption 4h, tests adsorption rate of the different biomass adsorbents to uranium.
Test various biomass adsorbents used, the cleaned membrane removal of lime-preserved egg shell adsorbent --- 20% sodium hydroxide solution immersion
--- 105 DEG C of drying --- crushing 200 mesh standard sieves --- 70 DEG C of dried process, remaining biomass absorbent are filtered dry after 12h
Agent is through over cleaning (membrane removal) --- to be filtered dry --- 105 DEG C of drying --- and crushed 200 after 20% sodium hydroxide solution immersion 12h
Mesh standard sieve --- 70 DEG C of dried process.Can be derived that biomass adsorbent not of the same race has difference to the adsorption rate of uranium from table 1
It is different.Wherein, up to more than 80%, the adsorption rate to uranium is highest to the adsorption rate of lime-preserved egg shell adsorbent.
The adsorption rate of the different biomass adsorbents of table 1
Embodiment 2
Constant in control other conditions, in the case of only pH this variable, experiment condition is under room temperature 298K, to compare
The adsorption effect of lime-preserved egg shell adsorbent, egg shell adsorbent and Ovum Anas domestica putamina adsorbent.The cleaned membrane removal of lime-preserved egg shell adsorbent ---
--- 120 DEG C of drying --- crushing 200 mesh standard sieves --- 60 DEG C of dried process, egg shell absorption are filtered dry after clear water immersion 8h
120 DEG C of bakings that agent and Ovum Anas domestica putamina adsorbent are through over cleaning membrane removal --- being filtered dry after 20% sodium hydroxide solution immersion 8h ---
Dry --- crushing 200 mesh standard sieves --- 60 DEG C of dried process.In 100ml contains uranium solution, three kinds of dosages of adsorbent
Respectively 0.01g, the μ g/ml of initial uranium concentration 5, solution ph is adjusted using HCl and NaOH solution, studies three kinds of sorbing materials pair
The adsorption capacity of uranium after absorption 4h, as a result shows three kinds of capacity of eggshell adsorption uranium under PH optimum conditions with the change of pH value
Size is：Lime-preserved egg shell adsorbent ＞ egg shell adsorbent ＞ Ovum Anas domestica putamina adsorbents, lime-preserved egg shell adsorbent absorption property is optimal.
Influences of the PH of table 2 to uranium absorption capacity
Embodiment 3
It is constant in control other conditions, only in the case of this variable of lime-preserved egg shell adsorbent dosage, compare lime-preserved egg shell
The adsorption effect of adsorbent, egg shell adsorbent and Ovum Anas domestica putamina adsorbent.The cleaned membrane removal of lime-preserved egg shell adsorbent --- clear water soaks
--- 60 DEG C of drying --- ground 200 mesh standard sieve --- 80 DEG C of dried process, egg shell adsorbent and ducks are filtered dry after bubble 12h
Eggshell adsorbent is through over cleaning membrane removal --- is filtered dry --- 60 DEG C of drying --- grinding after 20% sodium hydroxide solution immersion 12h
Cross 200 mesh standard sieves --- 80 DEG C of dried process.In 100ml contains uranium solution, three kinds of eggshell adsorbent dosages are in 0.005g
Between~0.05g；Experiment condition is that under room temperature 298K, pH is 4.5, the μ g/ml of initial uranium concentration 5, after absorption 4h, adsorption capacity
As the experimental result for subtracting afterwards occurs first increasing in the increase of dosage, it is in the amount of capacity of the most in good time adsorption uranium of dosage：Lime-preserved egg
Shell adsorbent ＞ egg shell adsorbent ≈ Ovum Anas domestica putamina adsorbents, lime-preserved egg shell adsorbent absorption property is optimal.
Influence of the adsorbent dosage of table 3 to uranium absorption capacity
Embodiment 4
It is constant in control other conditions, only in the case of this variable of uranium initial concentration, compare lime-preserved egg shell adsorbent, chicken
The adsorption effect of eggshell adsorbent and Ovum Anas domestica putamina adsorbent.The cleaned membrane removal of lime-preserved egg shell adsorbent --- filtered after clear water immersion 12h
It is dry that --- 100 DEG C of drying --- crushing 200 mesh standard sieves --- 75 DEG C of dried process, egg shell adsorbent and Ovum Anas domestica putamina are adsorbed
Agent is through over cleaning membrane removal --- to be filtered dry --- 100 DEG C of drying --- and crushed 200 mesh after 20% sodium hydroxide solution immersion 12h
Standard screen --- 75 DEG C of dried process.In 100ml contains uranium solution, uranium initial concentration is in the range of 1~9 μ g/ml；Experiment condition
For under room temperature 298K, pH is 4.5, dosage is 0.01g, after absorption 4h, lime-preserved egg shell adsorbent, egg shell adsorbent and Ovum Anas domestica putamina
Three kinds of capacity of adsorbent adsorption uranium of adsorbent increase and increase with uranium initial concentration, and wherein lime-preserved egg shell adsorbent adsorption capacity is most
Greatly, lime-preserved egg shell adsorbent absorption property is optimal.
Influence of the uranium initial concentration of table 4 to uranium absorption capacity
Embodiment 5
It is constant in control other conditions, only in the case of this variable of adsorption time, compare lime-preserved egg shell adsorbent, egg
The adsorption effect of shell adsorbent and Ovum Anas domestica putamina adsorbent.The cleaned membrane removal of lime-preserved egg shell adsorbent --- 20% sodium hydroxide solution
--- 105 DEG C of drying --- crushing 200 mesh standard sieves --- 70 DEG C of dried process, egg shell adsorbent are filtered dry after immersion 12h
105 DEG C of bakings --- are filtered dry --- after 20% sodium hydroxide solution immersion 12h with Ovum Anas domestica putamina adsorbent through over cleaning membrane removal
Dry --- crushing 200 mesh standard sieves --- 70 DEG C of dried process.In 100ml contains uranium solution, experiment condition is in room temperature
Under 298K, pH is 4.5, and dosage is 0.01g, the μ g/ml of initial uranium concentration 5, and three kinds of capacity of eggshell adsorbent adsorption uranium are with suction
The growth of attached time and increase, tended towards stability in 4h or so, wherein lime-preserved egg shell adsorbent adsorption capacity is maximum,
Lime-preserved egg shell adsorbent absorption property is optimal.
Influence of the adsorption time of table 5 to uranium absorption capacity
Embodiment 6
Taking the discarded lime-preserved egg shell in food production and life carries out cleaning membrane removal, and clear water immersion 12h is filtered dry after at 60 DEG C
12h is dried, then is crushed, crossed 200 the polished standard screens and lime-preserved egg shell adsorbent is obtained.At a temperature of 298K, uranium solution is contained in 100ml
In, during uranium initial concentration is the acidic industrial effluent (pH=3) of 8 μ g/ml, add 0.01g lime-preserved eggs shell manufactured in the present embodiment to inhale
Attached dose, after absorption 4h, the adsorption capacity to U reaches 60mg/g.
Embodiment 7
Taking the discarded lime-preserved egg shell in food production and life carries out cleaning membrane removal, and clear water immersion 10h is filtered dry after at 70 DEG C
12h is dried, then is crushed, crossed 200 the polished standard screens and lime-preserved egg shell adsorbent is obtained.
At a temperature of 298K, in 100ml contains uranium solution, uranium initial concentration is the acidic industrial effluent (pH=of 5 μ g/ml
3) in, 0.01g lime-preserved eggs shell adsorbent manufactured in the present embodiment is added, after absorption 4h, to UO2 2+Adsorption rate reach 80%.
Embodiment 8
To carrying out physical map analysis before and after lime-preserved egg shell adsorbent adsorption uranium.
1. scanning electron microscope analysis (SEM)
Fig. 1 and Fig. 2 are respectively the scanning electron microscope (SEM) photograph before and after lime-preserved egg shell adsorbent adsorption uranium.Fig. 1 inhales for lime-preserved egg shell adsorbent
9 μm of scanning electron microscope (SEM) photographs before attached uranium, Fig. 2 is 7 μm of scanning electron microscope (SEM) photographs after lime-preserved egg shell adsorbent adsorption uranium.It is seen that
There are many micropores in lime-preserved egg shell adsorbent surface before adsorption uranium, lime-preserved egg shell adsorbent surface aperture reduces after adsorption uranium, produce
, there is material transfer after showing the absorption of lime-preserved egg shell adsorbent in changing.
2.X Ray Energy Spectrum Analysis (EDS)
Fig. 3 and Fig. 4 are respectively the X-ray energy spectrograms before and after lime-preserved egg shell adsorbent adsorption uranium, and table 6 and table 7 are respectively corresponding
X-ray energy spectrum tables of data.
X-ray energy spectrum data before the lime-preserved egg shell adsorbent adsorption uranium of table 6
X-ray energy spectrum data after the lime-preserved egg shell adsorbent adsorption uranium of table 7
Be can be seen that from Fig. 3 and Biao 6, the element before lime-preserved egg shell adsorbent absorption thorium includes Ca, C and O；Can from Fig. 4 and Biao 7
Go out, the element after lime-preserved egg shell adsorbent absorption thorium includes Ca, C, O and uranium, it was demonstrated that lime-preserved egg shell adsorbent has adsorbed uranium.
3. infrared spectrum analysis
Fig. 5 is the infrared spectrogram before and after lime-preserved egg shell adsorbent adsorption uranium, and table 8 is C- before and after lime-preserved egg shell adsorbent adsorption uranium
The absorption peak data table of comparisons that O vibrations are produced.
The absorption peak data control that C-O vibrations are produced before and after the lime-preserved egg shell adsorbent adsorption uranium of table 3
By detecting the structure of lime-preserved egg shell adsorbent with infrared spectrometer, as a result show that C-O participates in the adsorption process of uranium, uranium
The presence of the stretching vibration peak of acyl ion more can be shown that eggshell has adsorbed uranium really.
Claims (6)
1. a kind of lime-preserved egg shell adsorbent of uranium, its composition is the skin egg-shell meal for filtering 200 mesh standard sieves.
2. the preparation method of the lime-preserved egg shell adsorbent of a kind of uranium, it is characterised in that step is as follows：
（1）Cleaning lime-preserved egg shell simultaneously removes egg film；
（2）The lime-preserved egg shell that will be handled well is placed on clear water or 20% sodium hydroxide solution immersion 8-12h, is filtered dry；
（3）To consider during dry lime-preserved egg shell is put into baking oven and dry；
（4）To being crushed or being ground the lime-preserved egg shell of drying, 200 the polished standard screens are crossed；
（5）Skin egg-shell meal after sieving is put into drying box and is dried, lime-preserved egg shell adsorbent is obtained.
3. the preparation method of the lime-preserved egg shell adsorbent of a kind of uranium according to claim 2, it is characterised in that step is as follows：
（1）Wash lime-preserved egg shell and except egg film；
（2）The lime-preserved egg shell that will be handled well is placed on clear water or 20% sodium hydroxide solution immersion 8-12h, is filtered dry；
（3）The lime-preserved egg shell for considering dry is put into 60 DEG C --- dried in 120 DEG C of baking ovens；
（4）The lime-preserved egg shell that will be dried with pulverizer crushes broken or grinding, crosses 200 the polished standard screens；
（5）Skin egg-shell meal after sieving is put into 70 DEG C in drying box --- 80 DEG C of dryings, lime-preserved egg shell adsorbent is obtained.
4. the application of the lime-preserved egg shell adsorbent of a kind of uranium, it is characterised in that the PH containing uranium solution is 2.8~3.5, the absorption of lime-preserved egg shell
The addition of agent is 0.08~0.12g/l.
5. the application of the lime-preserved egg shell adsorbent of a kind of uranium according to claim 4, it is characterised in that lime-preserved egg shell adsorbent is used
In PH be 3 containing uranium solution.
6. the application of the lime-preserved egg shell adsorbent of a kind of uranium according to claim 4 or 5, it is characterised in that lime-preserved egg shell is adsorbed
Agent dosage is 0.1g/l, and adsorption time is 4-8h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252844A (en) * | 2020-02-18 | 2020-06-09 | 四川大学 | Application of eggshell particles in bismuth-containing sewage treatment and use method thereof |
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| JPH0724207A (en) * | 1993-07-15 | 1995-01-27 | Res Dev Corp Of Japan | Method for occluding metal |
| CN102658090A (en) * | 2012-04-20 | 2012-09-12 | 大连交通大学 | Eggshell heavy metal ion adsorbent and preparation method thereof |
| CN105161155A (en) * | 2015-08-10 | 2015-12-16 | 南华大学 | Method absorbing and processing uranium-bearing waste water via sodium hydroxide modified rice straw absorbent |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0724207A (en) * | 1993-07-15 | 1995-01-27 | Res Dev Corp Of Japan | Method for occluding metal |
| CN102658090A (en) * | 2012-04-20 | 2012-09-12 | 大连交通大学 | Eggshell heavy metal ion adsorbent and preparation method thereof |
| CN105161155A (en) * | 2015-08-10 | 2015-12-16 | 南华大学 | Method absorbing and processing uranium-bearing waste water via sodium hydroxide modified rice straw absorbent |
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| Title |
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| HONGSEN ZHANG等: "Synthesis of a hydrotalcite-like compound from oil shale ash and its application inuranium removal", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND APPLICATION IN URANIUM REMOVAL》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111252844A (en) * | 2020-02-18 | 2020-06-09 | 四川大学 | Application of eggshell particles in bismuth-containing sewage treatment and use method thereof |
| CN111252844B (en) * | 2020-02-18 | 2022-01-04 | 四川大学 | Application of eggshell particles in bismuth-containing sewage treatment and use method thereof |
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Application publication date: 20170707 |
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