CN105771876B - The preparation method of modified eggshell magnetic adsorbent and the method for removing heavy metal in water removal - Google Patents
The preparation method of modified eggshell magnetic adsorbent and the method for removing heavy metal in water removal Download PDFInfo
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- CN105771876B CN105771876B CN201610333371.0A CN201610333371A CN105771876B CN 105771876 B CN105771876 B CN 105771876B CN 201610333371 A CN201610333371 A CN 201610333371A CN 105771876 B CN105771876 B CN 105771876B
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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
- B01J20/02—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
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
Abstract
The method that a kind of preparation method of modified eggshell magnetic adsorbent is provided and removes heavy metal in water removal, using domestic refuse eggshell as raw material, heavy metal wastewater thereby absorption magnetic adsorbent that is cheap, excellent, stable, environmentally friendly and being easily recycled is obtained by chemically and physically modified its magnetism that assigns.The present invention solves current heavy metal containing wastewater treatment difficulty, and reagent treatment or material price are high, effect is poor, preparation process is complicated, recycling is difficult, easily causes the technical barrier of secondary pollution, have higher practical value.
Description
Technical field
The invention belongs to changing waste into resources utilization and water-treatment technology fields, and in particular to a kind of modified eggshell magnetic adsorbent
Preparation method and go water removal in heavy metal method.
Background technology
With the improvement of living standards with the development of food service industry, the people need to consume a large amount of fowl in daily life
Egg, eggshell typically use landfill disposal, easily cause serious environmental pollution as a kind of waste, and eggshell it is main at
It is calcium carbonate to divide, and Exploitative potential is very big.And adsorbent is made using eggshell to handle heavy metal wastewater thereby, it is many people's researchs at present
Project, entitled a kind of eggshell heavy metal ion adsorbent and preparation method thereof, the patent of Patent No. 201210119055
In file, the preparation method using eggshell as adsorbent for heavy metal is described, this method soaks eggshell in aqueous slkali
Inner membrance is removed after bubble, then cleans, filter, and is placed in heat-treatment furnace and is calcined after being dried in drying box, then cooling is
At.Using adsorbent made of this method, although there is certain absorption property, adsorption efficiency is low, and adsorbent is difficult to recycle,
It cannot reuse, it is therefore necessary to propose to improve.
Invention content
Present invention solves the technical problem that：A kind of preparation method of modified eggshell magnetic adsorbent and remove heavy metal in water removal
Method, using domestic refuse eggshell as raw material, by chemically and physically it is modified assign its magnetism obtain it is cheap, excellent
Good, stable, environmental protection and the heavy metal wastewater thereby absorption magnetic environment material being easily recycled, have higher practical value.
The technical solution adopted by the present invention：The preparation method of modified eggshell magnetic adsorbent, including following step：
1) chemical modification of eggshell：The eggshell of collection concentration is washed, be then placed in drying box be heated up to 60 DEG C-
80 DEG C of drying, the eggshell after drying crushed 80-120 mesh sieve, and egg-shell meal and water are pressed 1:2 ratios impregnate and egg-shell meal weight are added
The modifying agent of amount 5% obtains modified eggshell solution by the speed concussion 1.5-2h of 150-180 turns/min；
2) preparation of eggshell centre product：Molysite is added in deionized water and fully dissolves to obtain iron salt solutions, it then will be ferrous
Salt, which is added in iron salt solutions, fully dissolves to obtain mixed solution, and mixed solution is heated up to 50 DEG C -60 DEG C and turns/min by 400-800
Speed be stirred to react 30min or so, eggshell solution is added in mixed solution to obtain in modified eggshell solution, will with 5% aqueous slkali
The pH value of eggshell solution is adjusted to 9-10, then heats to 70 DEG C -80 DEG C, and be stirred to react 2h by the speed of 400-800 turns/min
Left and right, directly filters to obtain filter product, and 60 DEG C of -80 DEG C of drying are heated up to after then alternately being washed filter product to neutrality with clear water and alcohol
Product among eggshell are obtained, above-mentioned steps carry out under inert gas protection；
3) physical modification：Product among eggshell are put into Muffle furnace and are filled with inert gas, are heated up to 450 DEG C of -540 DEG C of guarantors
The rear taking-ups of warm 2h or so, at room temperature cooling get product magnetic adsorbent.
Above-mentioned steps 1) in, the modifying agent is the mixture of zinc chloride, magnesium chloride or both, when for the mixing of the two
When object, the mixed proportion of the zinc chloride and magnesium chloride is 1:2.
Above-mentioned steps 2) in, the additional proportion of the molysite and ferrous salt is 1:2, the ratio of the two and deionized water is 1：
20。
Above-mentioned steps 2) in, in the eggshell solution, the ratio of modified eggshell solution and mixed solution is 2:3.
Above-mentioned steps 2) and step 3) in, the inert gas be nitrogen.
Above-mentioned steps 2) in, the aqueous slkali is sodium hydroxide or ammonium hydroxide.
A kind of method that modified eggshell magnetic adsorbent removes heavy metal in water removal is also provided, including following step：
1) pH value of heavy metal wastewater thereby is made to be maintained at acid state；
2) the finished product magnetic adsorbent of acquisition is pressed 1~2.5:50 ratios are added in heavy metal wastewater thereby, stirring at normal temperature absorption
1h is reacted, makes the impurity absorption in heavy metal wastewater thereby on finished product magnetic adsorbent；
3) supernatant in wastewater disposal basin is banished to sedimentation basin, additional magnet will be adsorbed with the finished product magnetic adsorbent of impurity
It is sucked out, continues to recycle after removing impurity thereon.
The present invention compared with prior art the advantages of：
1, it is difficult to be directed to current heavy metal containing wastewater treatment, reagent treatment or material price height, effect is poor, recycling is difficult, no
It can reuse, easily cause secondary pollution problems, using domestic refuse egg shell as raw material, pass through chemically and physically side
Method is modified and carries magnetic, obtains the magnetic environment material for having good adsorbent performance to heavy metal in waste water, reached change give up into
Precious, the treatment of wastes with processes of wastes against one another the purpose, reduces wastewater treatment expense；
2, the magnetic material that the present invention is obtained overcomes the difficult problem of sorbing material recycling, and recyclable recycling；
3, zinc chloride and the magnesium-modified microstructure that material can be changed through high-temperature calcination of chlorination is added, increases its porosity,
Improve its absorption property；
4, the magnetic material that is obtained of the present invention, in application process non-secondary pollution risk.
Specific implementation mode
The embodiment of the present invention is described below.
Embodiment one：The preparation method of modified eggshell magnetic adsorbent, including following step：
1) chemical modification of eggshell：The eggshell concentration of collection is washed, is then placed in drying box and is heated up to 60 DEG C
Drying, the eggshell after drying crushed 80 mesh sieve, and egg-shell meal and water are pressed 1:2 ratios impregnate and egg-shell meal weight 5% are added
Modifying agent obtains modified eggshell solution by the speed concussion 1.5h of 150 turns/min, and above-mentioned modifying agent is zinc chloride.
2) preparation of eggshell centre product：Molysite is added in deionized water and fully dissolves to obtain iron salt solutions, it then will be ferrous
Salt, which is added in iron salt solutions, fully dissolves to obtain mixed solution, and the additional proportion of above-mentioned molysite and ferrous salt is 1:2, the two and go from
The ratio of sub- water is 1：20；Mixed solution is heated up to 50 DEG C and is stirred to react 30min or so by the speed of 400 turns/min, it will
Modified eggshell solution is added in mixed solution to obtain eggshell solution, in the eggshell solution, modified eggshell solution and mixed solution
Ratio is 2:3；The pH value of eggshell solution is adjusted to 9 with 5% sodium hydroxide solution, then heats to 70 DEG C, and press 400 turns/min
Speed be stirred to react 2h or so, directly filter to obtain filter product, after then alternately filter product are washed to neutrality with clear water and alcohol plus
Temperature to 60 DEG C dry among eggshell product, above-mentioned steps carry out under nitrogen protection；
3) physical modification：Product among eggshell are put into Muffle furnace and are filled with nitrogen, after being heated up to 450 DEG C of heat preservation 2h or so
It takes out, cooling at room temperature gets product magnetic adsorbent.
Embodiment two：The preparation method of modified eggshell magnetic adsorbent, including following step：
1) chemical modification of eggshell：The eggshell concentration of collection is washed, is then placed in drying box and is heated up to 80 DEG C
Drying, the eggshell after drying crushed 120 mesh sieve, and egg-shell meal and water are pressed 1:2 ratios impregnate and egg-shell meal weight 5% are added
Modifying agent, the modifying agent are magnesium chloride, and modified eggshell solution is obtained by the speed concussion 2h of 180 turns/min；
2) preparation of eggshell centre product：Molysite is added in deionized water and fully dissolves to obtain iron salt solutions, it then will be ferrous
Salt, which is added in iron salt solutions, fully dissolves to obtain mixed solution, and the additional proportion of above-mentioned molysite and ferrous salt is 1:2, the two and go from
The ratio of sub- water is 1：20；Mixed solution is heated up to 60 DEG C and is stirred to react 30min or so by the speed of 800 turns/min, it will
Modified eggshell solution is added in mixed solution to obtain eggshell solution, in the eggshell solution, modified eggshell solution and mixed solution
Ratio is 2:3；The pH value of eggshell solution is adjusted to 10 with 5% ammonium hydroxide, then heats to 80 DEG C, and by the speed of 800 turns/min
It is stirred to react 2h or so, directly filters to obtain filter product, 80 are heated up to after then alternately being washed filter product to neutrality with clear water and alcohol
DEG C dry among eggshell product, above-mentioned steps carry out under protection of argon gas；
3) physical modification：Product among eggshell are put into Muffle furnace and are filled with argon gas, after being heated up to 540 DEG C of heat preservation 2h or so
It takes out, cooling at room temperature gets product magnetic adsorbent.
Embodiment three：The preparation method of modified eggshell magnetic adsorbent, including following step：
1) chemical modification of eggshell：The eggshell concentration of collection is washed, is then placed in drying box and is heated up to 70 DEG C
Drying, the eggshell crushing after drying sieve with 100 mesh sieve, and egg-shell meal and water are pressed 1:2 ratios impregnate and egg-shell meal weight 5% are added
Modifying agent, the modifying agent is the mixture of zinc chloride and magnesium chloride, and the mixed proportion of zinc chloride and magnesium chloride is 1:
2, the speed concussion 1.8h for then pressing 160 turns/min obtains modified eggshell solution；
2) preparation of eggshell centre product：Molysite is added in deionized water and fully dissolves to obtain iron salt solutions, it then will be ferrous
Salt, which is added in iron salt solutions, fully dissolves to obtain mixed solution, and the additional proportion of the molysite and ferrous salt is 1:2, the two and go from
The ratio of sub- water is 1：20；Mixed solution is heated up to 55 DEG C and is stirred to react 30min or so by the speed of 600 turns/min, it will
Modified eggshell solution, which is added in mixed solution, obtains eggshell solution, and the ratio of modified eggshell solution and mixed solution is 2:3, with 5%
Sodium hydroxide the pH value of eggshell solution is adjusted to 8, then heat to 75 DEG C, and 2h is stirred to react by the speed of 600 turns/min
Left and right, directly filters to obtain filter product, and being heated up to 70 DEG C after then alternately being washed filter product to neutrality with clear water and alcohol dries to obtain egg
Product among shell, above-mentioned steps carry out under nitrogen protection；
3) physical modification：Product among eggshell are put into Muffle furnace and are filled with nitrogen, after being heated up to 500 DEG C of heat preservation 2h or so
It takes out, cooling at room temperature gets product magnetic adsorbent.
The method for removing heavy metal in water removal using above-mentioned modified eggshell magnetic adsorbent, including following step：
1) pH of heavy metal wastewater thereby is made to be maintained at 3~6；
2) the finished product magnetic adsorbent of acquisition is pressed 1~2.5:50 ratios are added in heavy metal wastewater thereby, and 30min~1h makes
It is heavy metal ion adsorbed on finished product magnetic adsorbent in waste water；
3) reaction to be adsorbed terminates, and the supernatant in wastewater disposal basin is banished to sedimentation basin, will be adsorbed with by additional magnet
After the finished product magnetic adsorbent of heavy metal pollution ion is adsorbed in sedimentation basin pool wall, clear liquid is discharged, recycling is adsorbed with heavy metal-polluted
The adsorbent for contaminating ion continues to recycle after being used in combination 0.5%~1% acid solution to vibrate desorption after 60 DEG C of -80 DEG C of drying.
Above-described embodiment, only presently preferred embodiments of the present invention, is not used for limiting the scope of the present invention, therefore all with this
The equivalence changes that content is done described in invention claim should all be included within scope of the invention as claimed.
Claims (4)
1. being modified the preparation method of eggshell magnetic adsorbent, it is characterised in that include following step：
1) chemical modification of eggshell：The eggshell concentration of collection is washed, is then placed in drying box and is heated up to 60 DEG C -80 DEG C
Drying, the eggshell after drying crushed 80-120 mesh sieve, and egg-shell meal and water are pressed 1:2 ratios impregnate and egg-shell meal weight are added
5% modifying agent obtains modified eggshell solution by the speed concussion 1.5-2h of 150-180 turns/min；
2) preparation of eggshell centre product：Molysite is added in deionized water and fully dissolves to obtain iron salt solutions, then adds ferrous salt
Enter and fully dissolve to obtain mixed solution in iron salt solutions, mixed solution is heated up to 50 DEG C -60 DEG C and by the speed of 400-800 turns/min
Degree is stirred to react 30min, and eggshell solution is added in mixed solution to obtain in modified eggshell solution, with 5% aqueous slkali by eggshell solution
PH value be adjusted to 9-10, then heat to 70 DEG C -80 DEG C, and turn by 400-800/speed of min is stirred to react 2h, directly filtering
Filter product, after filter product are alternately then washed till neutrality with clear water and alcohol, product among eggshell are dried to obtain at 60 DEG C -80 DEG C, on
Step is stated to carry out under inert gas protection；
3) physical modification：Product among eggshell are put into Muffle furnace and are filled with inert gas, are heated up to 450 DEG C of -540 DEG C of heat preservation 2h
After take out, at room temperature cooling get product magnetic adsorbent；
Above-mentioned steps 1) in, the modifying agent is the mixture of zinc chloride, magnesium chloride or both, when for the mixture of the two
When, the mixed proportion of the zinc chloride and magnesium chloride is 1:2；
The additional proportion of the molysite and ferrous salt is 1:2, the ratio of the two and deionized water is 1：20；
Above-mentioned steps 2) in, in the eggshell solution, the ratio of modified eggshell solution and mixed solution is 2:3.
2. the preparation method of modified eggshell magnetic adsorbent according to claim 1, it is characterised in that：Above-mentioned steps 2) and
In step 3), the inert gas is nitrogen or argon gas.
3. the preparation method of modified eggshell magnetic adsorbent according to claim 1, it is characterised in that：Above-mentioned steps 2)
In, the aqueous slkali is sodium hydroxide or ammonium hydroxide.
4. the modification eggshell being prepared using the preparation method of any modification eggshell magnetic adsorbents of claim 1-3
The method that magnetic adsorbent removes heavy metal in water removal, it is characterised in that include following step：
1) pH of heavy metal wastewater thereby is made to be maintained at 3~6；
2) the finished product magnetic adsorbent of acquisition is pressed 1~2.5：50 ratios are added in heavy metal wastewater thereby, stirring at normal temperature adsorption reaction
30min~1h makes heavy metal ion adsorbed on finished product magnetic adsorbent in waste water；
3) reaction to be adsorbed terminates, and the supernatant in wastewater disposal basin is banished to sedimentation basin, and a huge sum of money will be adsorbed with by additional magnet
Belong to contaminated ion finished product magnetic adsorbent be adsorbed in sedimentation basin pool wall after, discharge clear liquid, recycling be adsorbed with heavy metal pollution from
The adsorbent of son continues to recycle after being used in combination 0.5%~1% acid solution to vibrate desorption after 60 DEG C of -80 DEG C of drying.
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| CN106362654B (en) * | 2016-10-08 | 2019-04-02 | 江苏大学 | A kind of method that the Pickering emulsion polymerization technology that magnetism egg-shell meal is stable prepares trace microballoon |
| CN106925233A (en) * | 2017-05-16 | 2017-07-07 | 宝鸡文理学院 | The preparation of the useless modified dephosphorization magnetic adsorptive material of eggshell and the minimizing technology of phosphorus in water |
| CN107686146A (en) * | 2017-09-12 | 2018-02-13 | 南京国龙生物科技有限公司 | A kind of handling process of aquaculture heavy metal in waste water copper |
| CN109926024B (en) * | 2019-03-27 | 2022-03-01 | 湖南工学院 | Preparation method and application of magnetic organic modified nano adsorption material |
| CN110404500A (en) * | 2019-06-18 | 2019-11-05 | 江门市泰汇环保科技有限公司 | A kind of multiple-effect compound type sewage-treating agent and preparation method thereof |
| CN110877921A (en) * | 2019-08-28 | 2020-03-13 | 齐鲁理工学院 | Method for removing total nitrogen in water by using modified eggshells |
| CN111644159B (en) * | 2020-05-25 | 2022-11-22 | 哈尔滨工业大学 | Magnetic adsorbent based on modified eggshell and preparation method and application thereof |
| CN116440866B (en) * | 2023-03-13 | 2023-09-22 | 武汉工程大学 | Preparation method and application of three-dimensional spongy porous heavy metal ion adsorbent based on activated eggshells |
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| CN101713676A (en) * | 2008-09-30 | 2010-05-26 | 日立汽车系统株式会社 | Air flow meter |
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