CN106902787A - A kind of preparation method of the compound lithium battery Absorbent of egg shell waste material/activated carbon - Google Patents
A kind of preparation method of the compound lithium battery Absorbent of egg shell waste material/activated carbon Download PDFInfo
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- CN106902787A CN106902787A CN201710185956.7A CN201710185956A CN106902787A CN 106902787 A CN106902787 A CN 106902787A CN 201710185956 A CN201710185956 A CN 201710185956A CN 106902787 A CN106902787 A CN 106902787A
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
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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
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
-
- 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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
A kind of preparation method of the lithium battery Absorbent being combined the invention discloses egg shell waste material/activated carbon, eggshell membrane is peeled away into modified being added in raw material, eggshell membrane has specific surface area higher, surface is rich in hydroxyl, carboxyl, amide groups and sulfydryl isoreactivity functional group, lotus or negative electrical charge so that eggshell membrane can become positively charged under different acidity conditions, are adsorbed so as to produce electrostatic force with different metal ions；By after the egg shell calcification after demoulding and phosphoric acid modified activated carbon, activated carbon surface load calcium and phosphate radical simultaneously, the adsorption capacity of activated carbon is increased by ion exchange and surface complex reaction；Again compatibility modified zeolite molecular sieve etc. through the obtained Absorbent raw material sources of granulation are simple, low cost, egg shell waste utilization rate high and heavy metal ion and Adsorption of Organic effect is good, antibacterial effect is obvious.
Description
Technical field
The present invention relates to water-treatment technology field, and in particular to a kind of compound lithium battery of egg shell waste material/activated carbon gives up
The preparation method of water absorbent.
Background technology
Lithium ion battery is referred to as " green because of environment sensitive elements such as the lead without traditional high pollution, cadmium and mercury
Color " battery, is widely used in mobile phone, notebook computer, digital camera and electric tool, energy-storage battery, electric bicycle, mixed
Close the fields such as electric motor car and electric motor car.Lithium battery contains the materials such as iron, copper, aluminium, cobalt, nickel, manganese, lithium, is typically filled by hundreds of times
(using after 2-3a) after electric discharge, electrode expansion, capacity is greatly reduced so that scrapping, and in battery production, by roll-in, divide
Cut, film-making, leftover pieces and pole piece can be produced to scrap after winding, battery enterprise so wastes often directly when waste product is sold
Resource pollutes environment again, is that this Battery Plant takes most of old and useless battery or leftover pieces centralized recovery using treatment, receives one
Determine effect.But still the waste lithium cell for having fraction is directly arbitrarily abandoned because dealing with improperly, adds a huge sum of money for Battery Plant's generation
Category direct discharging of waste water can cause serious metal ion pollution, contaminated soil and water body, then by food chain in human body
Accumulation, endangers the life security of the mankind.
At present, active carbon adsorption is the effective ways for processing metal ion pollution, and Powdered Activated Carbon has equipment investment
Province, fast, cheap adsorption rate, wide material sources, the features such as easily degrade, the quality that its absorption property depends on activated carbon is joined
Number and surface functional group, therefore, the surface chemical modification of carbon can increase the adsorbance to toxic pollutant.Up to the present, perhaps
Many carbon surface method of modifying are all mostly, with reagent modification activated carbon, to also imply that the volume during heavy metal is processed
Outer expense increases.Therefore waste and industry byproduct have powerful attraction as the activating reagent of low cost.Therefore document《Chicken
Heavy metal in eggshell waste material and phosphoric acid modification Powdered Activated Carbon and removal Drinking Water》Calcium is extracted from egg shell discarded object
Solution, is used as a kind of activator of low cost, to improve the absorption property of activated carbon.Experiment shows modified activity
Powdered carbon adsorptivity is high, is met with the running water after the sorbent treatment《Standards for drinking water quality》.
But the activated carbon powder Base Metal sorbing material being modified in document is only to dirty Organic substance in water and heavy metal particles
There is certain adsorptivity, anti-microbial property is poor, and be only that egg shell is made calcium activator in text, eggshell membrane is not subject to fully
Utilize.Because eggshell membrane has microcosmic network structure, its principal component is protein, with stronger absorption property and antibacterial
Property, the modified eggshell membrane of compatibility improves adsorbent antibiotic property simultaneously to prepare calcium activator modified activated carbon using eggshell in the prior art
Research have not been reported, and existing adsorbent complex process, adsorption effect is general, it is necessary to improve.
The content of the invention
A kind of preparation of the lithium battery Absorbent being combined it is an object of the invention to provide egg shell waste material/activated carbon
Method, to overcome the deficiencies in the prior art.
The object of the present invention is achieved like this：
The preparation method of the compound lithium battery Absorbent of a kind of egg shell waste material/activated carbon, it is characterised in that including following
Step：
（1）Eggshell membrane is separated from egg shell and is cleaned up, at 40 DEG C drying and attrition grinding to 80-100 mesh or so,
By 48h is stirred in the liquor potassic permanganate that solid-to-liquid ratio is 1: 10 addition 5wt.%, clean, the baking at 70 DEG C is washed with deionized water
It is dry, obtain modified eggshell membrane powder；
（2）By step（1）Egg shell after demoulding grinds to form tiny particle, is stirred after being soaked with 25wt.% acetic acid, filtered
Calcium liquid activator；
（3）Activated Carbon Pretreatment：The impurity on surface is first washed away with distilled water, is then placed in 1mol/L hydrochloric acid solutions and is boiled
Boiling, is placed in 1mol/L sodium hydroxide solutions and boils again after rinsing well, rinses drying well and pulverizes；
（4）By step（3）In pretreated activated carbon first processed with phosphoric acid, then use step（2）Extracted from egg shell waste material
Calcium immersion bubble, finally by calcium immersion steep activated carbon be heat-treated to obtain modified active powdered carbon；
（5）Count by weight, by 80-85 parts of modified active powdered carbon, 20-23 parts of modified zeolite molecular sieve, 10-20 parts of modified chicken
Egg membrane powder is stirred and evenly mixed with 12-15 parts of binding agent, granulation discharging.
The step（1）Eggshell membrane separation be by egg shell with 25% acetic acid soak 8-10 hours, you can by egg
Film is separated with eggshell.
The step（2）In add the ratio of 10mL acetic acid (25wt.%) to soak by the demoulding egg shell powder of 0.5 g, with
150r/min stirs 3h.
The step（3）Middle boiling time is 1-2 hours.
The step（4）Phosphoric acid, calcium liquid immersion treatment activated carbon are added the phosphoric acid or calcium liquid of 10mL by the activated carbon of 2g
Ratio, at 30 DEG C, is stirred continuously (150r/min) reaction 2h, and 15h, described heat treatment are dried in 55 DEG C of evaporations and in 100 DEG C
Temperature is 460-480 DEG C.
The step（5）Binding agent be waterglass.
Described modified zeolite molecular sieve is that zeolite molecular sieve is put into mixing in the NaOH solution of 0.4mol/L, is placed in and shakes
Swing and 24h is vibrated on device, with deionized water centrifuge washing is to neutrality and dries.
The present invention has following beneficial effect：The present invention by eggshell membrane peel away it is modified be added in raw material, eggshell membrane
With specific surface area higher, surface is rich in hydroxyl, carboxyl, amide groups and sulfydryl isoreactivity functional group so that eggshell membrane exists
Can become positively charged lotus or negative electrical charge under different acidity conditions, so as to produce electrostatic force and quilt with different metal ions
Absorption；By after the egg shell calcification after demoulding and phosphoric acid simultaneously modified activated carbon, activated carbon surface load calcium and phosphate radical, pass through
Ion exchange and surface complex reaction increase the adsorption capacity of activated carbon；Compatibility modified zeolite molecular sieve etc. is obtained through granulation again
Absorbent raw material sources are simple, low cost, egg shell waste utilization rate high and heavy metal ion and organic pollution are inhaled
Attached effect is good, antibacterial effect is obvious.
Specific embodiment
A kind of preparation method of the compound lithium battery Absorbent of described egg shell waste material/activated carbon, its feature exists
In comprising the following steps：
（1）Eggshell membrane is separated from egg shell and is cleaned up, at 40 DEG C drying and attrition grinding to 80-100 mesh or so,
By 48h is stirred in the liquor potassic permanganate that solid-to-liquid ratio is 1: 10 addition 5wt.%, clean, the baking at 70 DEG C is washed with deionized water
It is dry, obtain modified eggshell membrane powder；
（2）By step（1）Egg shell after demoulding grinds to form tiny particle, is stirred after being soaked with 25wt.% acetic acid, filtered
Calcium liquid activator；
（3）Activated Carbon Pretreatment：The impurity on surface is first washed away with distilled water, is then placed in 1mol/L hydrochloric acid solutions and is boiled
Boiling, is placed in 1mol/L sodium hydroxide solutions and boils again after rinsing well, rinses drying well and pulverizes；
（4）By step（3）In pretreated activated carbon first processed with phosphoric acid, then use step（2）Extracted from egg shell waste material
Calcium immersion bubble, finally by calcium immersion steep activated carbon be heat-treated to obtain modified active powdered carbon；
（5）Count by weight, by 80 parts of modified active powdered carbons, 23 parts of modified zeolite molecular sieves, 20 parts of modified eggshell membrane powder with
12 parts of binding agents are stirred and evenly mixed, granulation discharging.
The step（1）Eggshell membrane separation be by egg shell with 25% acetic acid soak 8-10 hours, you can by egg
Film is separated with eggshell.
The step（2）In add the ratio of 10mL acetic acid (25wt.%) to soak by the demoulding egg shell powder of 0.5 g, with
150r/min stirs 3h.
The step（3）Middle boiling time is 1-2 hours.
The step（4）Phosphoric acid, calcium liquid immersion treatment activated carbon are added the phosphoric acid or calcium liquid of 10mL by the activated carbon of 2g
Ratio, at 30 DEG C, is stirred continuously (150r/min) reaction 2h, and 15h, described heat treatment are dried in 55 DEG C of evaporations and in 100 DEG C
Temperature is 480 DEG C.
The step（5）Binding agent be waterglass.
Described modified zeolite molecular sieve is that zeolite molecular sieve is put into mixing in the NaOH solution of 0.4mol/L, is placed in and shakes
Swing and 24h is vibrated on device, with deionized water centrifuge washing is to neutrality and dries.
Claims (7)
1. the preparation method of the compound lithium battery Absorbent of a kind of egg shell waste material/activated carbon, it is characterised in that including with
Lower step：
（1）Eggshell membrane is separated from egg shell and is cleaned up, at 40 DEG C drying and attrition grinding to 80-100 mesh or so,
By 48h is stirred in the liquor potassic permanganate that solid-to-liquid ratio is 1: 10 addition 5wt.%, clean, the baking at 70 DEG C is washed with deionized water
It is dry, obtain modified eggshell membrane powder；
（2）By step（1）Egg shell after demoulding grinds to form tiny particle, is stirred after being soaked with 25wt.% acetic acid, filtered
Calcium liquid activator；
（3）Activated Carbon Pretreatment：The impurity on surface is first washed away with distilled water, is then placed in 1mol/L hydrochloric acid solutions and is boiled
Boiling, is placed in 1mol/L sodium hydroxide solutions and boils again after rinsing well, rinses drying well and pulverizes；
（4）By step（3）In pretreated activated carbon first processed with phosphoric acid, then use step（2）Extracted from egg shell waste material
Calcium immersion bubble, finally by calcium immersion steep activated carbon be heat-treated to obtain modified active powdered carbon；
（5）Count by weight, by 80-85 parts of modified active powdered carbon, 20-23 parts of modified zeolite molecular sieve, 10-20 parts of modified chicken
Egg membrane powder is stirred and evenly mixed with 12-15 parts of binding agent, granulation discharging.
2. the preparation side of the compound lithium battery Absorbent of a kind of egg shell waste material/activated carbon according to claim 1
Method, it is characterised in that the step（1）Eggshell membrane separation be by egg shell with 25% acetic acid soak 8-10 hours, you can
Eggshell membrane is separated with eggshell.
3. the preparation side of the compound lithium battery Absorbent of a kind of egg shell waste material/activated carbon according to claim 1
Method, it is characterised in that the step（2）In add the ratio of 10mL acetic acid (25wt.%) to soak by the demoulding egg shell powder of 0.5 g,
3h is stirred with 150r/min.
4. the preparation side of the compound lithium battery Absorbent of a kind of egg shell waste material/activated carbon according to claim 1
Method, it is characterised in that the step（3）Middle boiling time is 1-2 hours.
5. the preparation side of the compound lithium battery Absorbent of a kind of egg shell waste material/activated carbon according to claim 1
Method, it is characterised in that the step（4）Phosphoric acid, calcium liquid immersion treatment activated carbon by the activated carbon of 2g add 10mL phosphoric acid or
The ratio of calcium liquid, at 30 DEG C, is stirred continuously (150r/min) reaction 2h, and 15h is dried in 55 DEG C of evaporations and in 100 DEG C, described
Heat treatment temperature is 460-480 DEG C.
6. the preparation side of the compound lithium battery Absorbent of a kind of egg shell waste material/activated carbon according to claim 1
Method, it is characterised in that the step（5）Binding agent be waterglass.
7. the preparation side of the compound lithium battery Absorbent of a kind of egg shell waste material/activated carbon according to claim 1
Method, it is characterised in that described modified zeolite molecular sieve is that zeolite molecular sieve is put into mixing in the NaOH solution of 0.4mol/L,
It is placed in and 24h is vibrated on oscillator, with deionized water centrifuge washing is to neutrality and dries.
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| CN201710185956.7A CN106902787A (en) | 2017-03-24 | 2017-03-24 | A kind of preparation method of the compound lithium battery Absorbent of egg shell waste material/activated carbon |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190078279A (en) * | 2017-12-26 | 2019-07-04 | 주식회사 포스코 | Method for preparing lithium adsorbent |
| CN111672470A (en) * | 2020-06-22 | 2020-09-18 | 天津科技大学 | Preparation method of biochar for phosphorus removal |
| CN112019091A (en) * | 2019-05-30 | 2020-12-01 | 清华大学 | Device for generating electrical energy |
| CN113764664A (en) * | 2020-07-16 | 2021-12-07 | 住友大阪水泥股份有限公司 | Carbon material carrying metal-adsorbing material, positive electrode for lithium ion secondary battery, positive electrode material, and lithium ion secondary battery |
| CN116618009A (en) * | 2023-04-17 | 2023-08-22 | 哈尔滨工业大学（深圳） | Preparation method of adsorbent for wastewater treatment, product and application of adsorbent |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190078279A (en) * | 2017-12-26 | 2019-07-04 | 주식회사 포스코 | Method for preparing lithium adsorbent |
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| CN112019091B (en) * | 2019-05-30 | 2021-08-31 | 清华大学 | Device for generating electrical energy |
| CN111672470A (en) * | 2020-06-22 | 2020-09-18 | 天津科技大学 | Preparation method of biochar for phosphorus removal |
| CN113764664A (en) * | 2020-07-16 | 2021-12-07 | 住友大阪水泥股份有限公司 | Carbon material carrying metal-adsorbing material, positive electrode for lithium ion secondary battery, positive electrode material, and lithium ion secondary battery |
| CN116618009A (en) * | 2023-04-17 | 2023-08-22 | 哈尔滨工业大学（深圳） | Preparation method of adsorbent for wastewater treatment, product and application of adsorbent |
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Application publication date: 20170630 |