CN106540666B - Adsorb the preparation method of the modified Carbon Materials of heavy metal ion silk cocoon - Google Patents
Adsorb the preparation method of the modified Carbon Materials of heavy metal ion silk cocoon Download PDFInfo
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- 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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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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Abstract
The invention discloses a kind of preparation methods of modified Carbon Materials of absorption heavy metal ion silk cocoon, belong to functional charing adsorbent material technical field.Adsorb the preparation method of the modified Carbon Materials of heavy metal ion silk cocoon, step are as follows: using silk cocoon as raw material, it is modified to be carbonized in Muffle furnace, shown in charing be that 100 DEG C are warming up to from 20 DEG C of rates with 2 DEG C/min, heat preservation 120min is raised to 200 DEG C from 100 DEG C of rates with 1 DEG C/min again, keeps the temperature after 120min up to the modified Carbon Materials of silk cocoon.The present invention carries out low-temperature carbonization using silk cocoon as raw material, after modified processing and Carbon Materials is made, and yield is high, and pollution is few, and product is good to the absorption property of heavy metal ion.
Description
Technical field
The invention belongs to functionality to carbonize adsorbent material technical field, and in particular to a kind of absorption heavy metal ion silk cocoon changes
The preparation method of property Carbon Materials.
Background technique
Carbon Materials have highly developed pore structure and huge specific surface area, have acid and alkali-resistance, not soluble in water, easy
The features such as regeneration, since it has many advantages, such as degree for the treatment of height and stable effluent quality when handling sewage, and is widely used in
Water-treatment technology field.When being used for water process, Carbon Materials can be used to purify source of sewage, the main color including in removal sewage,
It smells, taste and organic matter etc.；The inorganic matter that can be used in Adsorption water simultaneously, mainly including Cu2+, Pd2+, Cd2+ etc. with much money
Belong to ion；It mainly include BOD, COD and some organic matters difficult to degrade in addition it can the organic matter gone in water removal.
The absorption property for influencing Carbon Materials mainly has two aspect factors: first is that pore structure, such as specific surface area, aperture and hole point
Cloth etc. can adjust control Carbon Materials to a certain extent by reaction conditions such as the selection of raw material, activated media, temperature, times
The pore structure and pore-size distribution of material；Second is that surface chemical structure, such as the type and content of surface functional group, it and adsorptivity
The Relationship Comparison complexity of energy still needs to be understood in depth；In addition, adsorbance is also related with the characteristic of adsorption molecule itself.
Silk is current one of maximum natural fiber of yield in the world, mainly by 2 kinds of protein of fibroin albumen and silk gum
Composition.Fibroin albumen is main component part in silk, accounts for about the 70% of total weight, and has the characteristics that can be easily separated purification,
Fibroin albumen after purification has many unique physicochemical properties and excellent biocompatibility, can be prepared into film, gel,
The variforms such as microcapsules.Therefore, fibroin albumen is especially defeated in tissue engineering bracket material, drug in field of biomedicine
It send, medical dressing etc. has huge application potential.Fibroin albumen is kind of a high molecular weight protein, comprises more than 5000
Amino acid, most of main peptide chain is made of the low glycine of reactivity and alanine, however, still having can largely make
Active group for modified center is present in the main peptide chain of fibroin albumen amino acid and side chain, as accounted for mass percent 12.1%
Serine, the hydroxyl of threonine (0.9%), the phenolic hydroxyl group of tyrosine (5.3%), aspartic acid (0.5%) and glutamic acid (0.6%)
Carboxyl, the guanidine radicals of arginine (0.3%) and amino of lysine (0.2%) etc..
Common chemical modification method has grafting, copolymerization and modification, interpenetrating networks modified and cross-linking modified etc..Under normal circumstances,
Its certain side group can be changed by chemical reaction, or by introducing other function group with reacting for side group, such as sulfonic group, phosphorus
Acidic group, epoxy group etc. carry out chemical modification to fibroin albumen.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of modified Carbon Materials of absorption heavy metal ion silk cocoon.
The present invention is modified through processing silk cocoon with formaldehyde crosslinking and Lauxite respectively using silk cocoon as raw material, nitrogenous to increase
Functional group and it is easily formed pore structure, by the available better performances of low-temperature carbonization, is suitable for absorption heavy metal ion raw material of wood-charcoal
Material.
The present invention is achieved by the following technical solutions:
A kind of preparation method of the modified Carbon Materials of the silk cocoon adsorbing heavy metal ion:
It is modified to be carbonized in Muffle furnace using silk cocoon as raw material, shown in charing be rate liter from 20 DEG C with 2 DEG C/min
For temperature to 100 DEG C, heat preservation 120min is raised to 200 DEG C from 100 DEG C of rates with 1 DEG C/min again, changes after keeping the temperature 120min up to silk cocoon
Property Carbon Materials.
Further, the modification is that formaldehyde crosslinking is modified, specifically shreds silk cocoon and NaHCO3It is water-soluble with formaldehyde
Liquid mixes in three-necked flask, under the conditions of 95 DEG C after magnetic agitation reaction 5h, removes condenser pipe, and tailing adapter tube reacts 0.5h,
Described in formalin mass concentration be 37%, the silk cocoon: NaHCO3Mass ratio be 3:3.6, the silk cocoon
Mass volume ratio with formalin is 3:7,
The modification is that formaldehyde crosslinking modification is specifically to be hydrolyzed after shredding silk cocoon with NaOH, and NaHCO is then added3With
Formalin mixes in three-necked flask, under the conditions of 95 DEG C after magnetic agitation reaction 5h, removes condenser pipe, tailing adapter tube reaction
0.5h。
The modification is that Lauxite is modified, and after specifically shredding silk cocoon, urea, NaHCO is added3It is water-soluble with formaldehyde
Liquid mixes in three-necked flask, at 95 DEG C, after magnetic agitation reacts 5h, removes condenser pipe, tailing adapter tube reacts 0.5h again.
Further, the invention discloses a kind of preparation methods of the modified Carbon Materials of silk cocoon for adsorbing heavy metal ion:
Silk cocoon is carbonized in Muffle furnace, the charing is that 100 DEG C are warming up to from 20 DEG C of rates with 2 DEG C/min, is protected
Warm 120min is raised to 200 DEG C from 100 DEG C of rates with 1 DEG C/min again, keeps the temperature 120min, NaHCO is then added3And formalin
Solution, in a three-necked flask, temperature is at 95 DEG C, and magnetic agitation reacts 5h for mixing, removes condenser pipe, tailing adapter tube is anti-again
Answer 0.5h to get.
Silk cocoon is carbonized in Muffle furnace, the charing is that 100 DEG C are warming up to from 20 DEG C of rates with 2 DEG C/min, is protected
Warm 120min is raised to 200 DEG C from 100 DEG C of rates with 1 DEG C/min again, keeps the temperature 120min, and urea then is added and formaldehyde is water-soluble
Liquid, in a three-necked flask, temperature is at 95 DEG C, and magnetic agitation reacts 5h for mixing, removes condenser pipe, and tailing adapter tube reacts again
0.5h to get.
The present invention pre-processes silk cocoon using silk cocoon as raw material, with different methods, and raw material of wood-charcoal is made after different temperatures charing
Material, obtained Carbon Materials all remain with nitrogen-containing functional group, and have adsorption function to metal ion, wherein silk cocoon is joined after hydrolysis
With react the obtained Carbon Materials of charing, the Carbon Materials that react with Lauxite than the Carbon Materials reservation that is obtained with formaldehyde crosslinking
More nitrogen-containing functional groups have bigger adsorbance to ion；The Carbon Materials carbonized at 200 DEG C than 300 DEG C at carbonize
Carbon Materials remain more nitrogen-containing functional groups, the Carbon Materials carbonized at 300 DEG C than 200 DEG C at the Carbon Materials that carbonize have it is more
Pore structure.
Compared with prior art, the present invention carries out low-temperature carbonization using silk cocoon as raw material, after modified processing and Carbon Materials is made,
Yield is high, and pollution is few, and product is good to the absorption property of heavy metal ion.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of CJ200-4 and CJ200-4-UF；
Fig. 2 is the infrared spectrogram of CJ300-0-UF and CJ300-4-UF；
Fig. 3 is the infrared spectrogram of CJ200-4-UF and CJ300-4-UF；
Fig. 4 is silk cocoon, 200 DEG C of charing silk cocoons and C200J infrared spectrogram after silk cocoon, hydrolysis.Specific embodiment
The invention will be further described with reference to embodiments.
1 formaldehyde of embodiment carbonizes after being directly crosslinked
3g silk cocoon is weighed, is shredded, is put into three-necked flask, the NaHCO of 3.6g is added3, 7mL mass concentration be 37%
Formalin, magnetic agitation reacts 5h under the conditions of temperature is 95 DEG C, removes condenser pipe, and tailing adapter tube reacts 0.5h again, will
Above-mentioned cross-linking products are carbonized in Muffle furnace, are warming up to 100 DEG C from 20 DEG C of room temperatures with the rate of 2 DEG C/min, heat preservation 120min is again
200 DEG C are raised to from 100 DEG C of rates with 1 DEG C/min, 120min is kept the temperature at this temperature, obtained Carbon Materials is labeled as
CJ200-0, yield 31%；Change temperature, obtains CJ300-0, yield 18.6%.
It is carbonized after formaldehyde crosslinking after embodiment 2 is degraded
3g silk cocoon is weighed, shreds and polytetrafluoroethyllining lining water heating kettle is added, NaOH solution is added to hydrolyze 3h at 100 DEG C；With
The pH value of silk cocoon after hydrolysis is adjusted to 8-10 by hydrochloric acid, and 3.6g NaHCO is added3, 7mL mass concentration be 37% formaldehyde it is water-soluble
Liquid, in a three-necked flask, magnetic agitation reacts 5h under the conditions of temperature is 95 DEG C for mixing, removes condenser pipe, tailing adapter tube
0.5h is reacted again, and above-mentioned cross-linking products are carbonized in Muffle furnace, are warming up to 100 DEG C from 20 DEG C of room temperatures with the rate of 2 DEG C/min,
Heat preservation 120min is raised to 200 DEG C from 100 DEG C of rates with 1 DEG C/min again, keeps the temperature 120min at this temperature, the charcoal that will be obtained
Material marking is CJ200-4, yield 25.5%；Change temperature, obtains CJ300-4, yield 14.5%.
It is carbonized after 3 ureaformaldehyde forerunner's precursor reactant of embodiment
3g silk cocoon is weighed, is shredded；3g urea, 3.6g NaHCO is added3, 7mL mass concentration be 37% formaldehyde it is water-soluble
Liquid, in a three-necked flask, temperature is after magnetic agitation reacts 5h, to remove condenser pipe, tailing adapter tube is anti-again at 95 DEG C for mixing
Answer 0.5h；Above-mentioned cross-linking products are carbonized in Muffle furnace, heating rate are controlled with temperature controller, from 20 DEG C of room temperatures with 2 DEG C/min
Rate be warming up to 100 DEG C, heat preservation 120min is raised to 200 DEG C from 100 DEG C of rates with 1 DEG C/min again, keeps the temperature at this temperature
Obtained Carbon Materials are labeled as CJ200-0-UF, yield 79.3% by 120min；Change temperature, obtains CJ300-0-UF, yield
68.6%。
It is carbonized after ureaformaldehyde forerunner's precursor reactant after embodiment 4 is degraded
3g silk cocoon is weighed, addition polytetrafluoroethyllining lining water heating kettle is shredded with 1%NaOH concentration and hydrolyzes 3h at 100 DEG C；
The pH value of silk cocoon after hydrolysis is adjusted to 8-10 with hydrochloric acid, 3g urea, 3.6g NaHCO is added3, 7mL mass concentration be 37%
Formalin, in a three-necked flask, temperature is after magnetic agitation reacts 5h, to remove condenser pipe, tailing at 95 DEG C for mixing
Adapter tube reacts 0.5h again；Above-mentioned cross-linking products are carbonized in Muffle furnace, heating rate are controlled with temperature controller, from 20 DEG C of room temperatures with 2
DEG C/rate of min is warming up to 100 DEG C, heat preservation 120min is raised to 200 DEG C from 100 DEG C of rates with 1 DEG C/min again, warm herein
Degree is lower to keep the temperature 120min, and obtained Carbon Materials are labeled as CJ200-4-UF, yield 73.9%；Change temperature, obtains CJ300-4-
UF, yield 65.1%.
5 low-temperature carbonization post-crosslinking of embodiment
About 3g silk cocoon is carbonized in Muffle furnace, heating rate is controlled with temperature controller, from 20 DEG C of room temperatures with the speed of 2 DEG C/min
Rate is warming up to 100 DEG C, and heat preservation 120min is raised to 200 DEG C from 100 DEG C of rates with 1 DEG C/min again, keeps the temperature at this temperature
120min obtains dark brown powder；3.6g NaHCO is added into dark brown powder3, 7mL mass concentration be 37% formaldehyde it is water-soluble
Liquid, in a three-necked flask, temperature is at 95 DEG C, and magnetic agitation reacts 5h for mixing, removes condenser pipe, and tailing adapter tube reacts again
Product Labeling is C200J by 0.5h；
6 low-temperature carbonization post-crosslinking of embodiment
About 3g silk cocoon is carbonized in Muffle furnace, heating rate is controlled with temperature controller, from 20 DEG C of room temperatures with the speed of 2 DEG C/min
Rate is warming up to 100 DEG C, and heat preservation 120min is raised to 200 DEG C from 100 DEG C of rates with 1 DEG C/min again, keeps the temperature at this temperature
120min obtains dark brown powder；3g urea, 3.6g NaHCO into dark brown powder3, 15mL mass concentration be 37% formaldehyde
Aqueous solution, in a three-necked flask, temperature is at 95 DEG C, and magnetic agitation reacts 5h [30] for mixing, removes condenser pipe, tailing connects
Pipe reacts 0.5h again, is C200J-UF by Product Labeling.
7 performance test of embodiment
The various Carbon Materials that embodiment 1-6 is obtained repeatedly are washed to neutrality with distilled water respectively, it is dry, it is ground into powder
End is stored in drier, and structural characterization and adsorption experiment, including infrared, BET experiment are used for.
Adsorption experiment
Absorption of the Carbon Materials to each ion
Weigh CJ200-0, CJ200-4, CJ200-0-UF, CJ200-4-UF, CJ300-0, CJ300- that quality is 0.05g
4, CJ300-0-UF, CJ300-4-UF, C200J and C200J-UF are added separately in the stuffed conical flask of 100mL, to ten
The metal ion stock solution for moving into the 100 μ g/mL of the pH4 of 25mL in conical flask with pipette respectively is 25 DEG C in set temperature
Water-bath constant temperature oscillator in, after oscillation absorption 12h, then stand 12h, take supernatant；Supernatant and original solution dilution is certain
Multiple measures absorbance, absorbance is revert to metal ion standard curve, learns its concentration；
Carbon Materials calculate the adsorbance of metal ion with formula (1):
(1)
Wherein: Qe indicates that the equilibrium adsorption capacity (mg/g) on Carbon Materials, C0 are the initial concentration of metal ion in solution
(mg/L), the concentration (mg/L) of metal ion in solution when Ce is adsorption equilibrium, V are the volume (L) of adsorbent solution, and m is absorption
The dosage (g) of agent.
The NaOH solution for the use of mass fraction being 0-10% hydrolyzes 0-12 hours, and results of hydrolysis shows molten using 1% NaOH
Liquid hydrolyzes 3 hours, and hydrolysis effect is best.
Silk cocoon and formaldehyde and the infrared figure of Lauxite reaction product, wherein the infrared figure of CJ200-4 and CJ200-4-UF is such as
Shown in Fig. 1, it will be seen from figure 1 that the infrared spectroscopy of CJ200-4 and CJ200-4-UF, 1500-1700cm-1Place, CJ200-4 and
CJ200-4-UF has bimodal, belongs to the stretching vibration of amide groups, illustrates all to remain nitrogen-containing functional group；In 3600-
300cm-1There is apparent biabsorption peak at place, belongs to N-H stretching vibration peak, illustrates that CJ200-4 and CJ200-4-UF are remained
More nitrogen-containing functional groups, showing that silk cocoon is added formaldehyde crosslinking and Lauxite presoma is added after hydrolysis can protect well
Nitrogen-containing functional group in silk cocoon, the two comparison is it can be found that silk cocoon directly uses formaldehyde crosslinking after degradation, with addition urea formation urea
Urea formaldehyde degradation silk cocoon cross-linking products prepare Carbon Materials, and functional group is similar.Fig. 2 is the red of CJ300-0-UF and CJ300-4-UF
External spectrum figure, two kinds of Carbon Materials are in 1500-1700cm as can be seen from Figure 2-1Place, CJ300-0-UF and CJ300-4-UF have double
Peak belongs to the stretching vibration of amide groups, illustrates all to remain nitrogen-containing group；In 3600-3300cm-1There is apparent absorption at place
Peak belongs to N-H stretching vibration peak.Fig. 3 is the infrared figure of CJ200-4-UF and CJ300-4-UF, from figure 3, it can be seen that
1500-1700cm-1Place, CJ200-4-UF and CJ300-4-UF have bimodal, belong to the stretching vibration of amide groups, illustrate all to protect
Nitrogen-containing group is stayed；In 3600-300cm-1There is apparent absorption peak at place, belongs to N-H stretching vibration peak, but CJ200-4-UF
It is bimodal to become apparent from, illustrate that CJ200-4-UF and CJ300-4-UF remain more nitrogen-containing functional groups.Fig. 4 is silkworm after silk cocoon, hydrolysis
Cocoon, 200 DEG C of charing silk cocoons and the infrared figure of C200J, from fig. 4, it can be seen that C200J is in 3500-3000cm-1Place and 1500-
1700cm-1Place has apparent bimodal；In 3500-3000cm-1Place, the strong absworption peak of C200J belong to N-H stretching vibration peak；
1500-1700cm-1Place, the bimodal stretching vibration for belonging to amide groups of C200J, show through carbonize and crosslinking Treatment after,
Always nitrogen-containing functional group is remained, the absorption to ion is conducive to.
Carbon Materials absorption property comparing result is as shown in table 1,
The comparison of 1 absorption property of table
As can be seen from Table 1: preparing Carbon Materials using this method has preferable absorption to heavy metal ion, to conventional aluminium, iron
Ionic adsorption is smaller, this is because the Carbon Materials of preparation have abundant nitrogen-containing functional group, has preferable configurational energy with heavy metal ion
Power, but increase with temperature, nitrogen-containing functional group is easy to decompose, while will form abundant pore structure, increases surface area, from 200,300
As can be seen that increasing with temperature, adsorbance generally increases for degree carbonated material absorption.It is prepared with undegraded silk cocoon and degradation silk cocoon
Carbon Materials CJ200-0, CJ300-0, CJ200-4, CJ300-4 absorption as can be seen that easily decomposed in material carbonization process after degradation,
Nitrogen-containing functional group loss is larger, but easily forms hole, increases surface area.Utilize Carbon Materials absorption property prepared by urea-modified material
It significantly improves, this is because forming higher degree of crosslinking product, while increasing nitrogen-containing functional group, degradation silk cocoon is recycled to be easy to point
Solution forms preferable duct, has increased considerably surface area, make the CJ200-4-UF obtained at 200 degree have preferable enriching heavy metal from
Sub- ability does not need the available preferable enriching heavy metal Carbon Materials of very high temperature.
BET characterization
CJ300-0, CJ300-0-UF, CJ200-4-UF, C200J material is selected to carry out BET characterization, as a result such as 2 institute of table
Show,
2 specific surface area of table and hole hold pore-size distribution
| Carbon Materials | Specific surface area (m2/g) | Average pore size (nm) | Micropore total pore volume (cm3/g) | Most probable pore size (nm) |
| CJ300-0 | 10.78 | 8.65 | 0.116 | 1.62 |
| CJ300-0-UF | 106.51 | 6.33 | 1.310 | 2.01 |
| CJ200-4-UF | 196.14 | 2.11 | 2.33 | 1.21 |
| C200J | 2.60 | 9.89 | 0.00095 | 1.06 |
Surface area can be obtained with 200 degree at a lower temperature by formaldehyde crosslinking using silk cocoon, urea as can be seen from Table 2
Larger Carbon Materials, most probable pore size are generally conducive to metal ion sizableness to heavy metal ion in 1-2 ran
Absorption.Silk cocoon post-crosslinking is first carbonized, regardless of whether Carbon Materials adsorption capacity obtained by addition urea is general, this is because silk cocoon charcoal
When change, nitrogen-containing functional group loss in surface is larger, does not form preferable duct, this can also characterize from BET and be verified.
Claims (4)
1. a kind of preparation method of the modified Carbon Materials of the silk cocoon for adsorbing heavy metal ion, which is characterized in that using silk cocoon as raw material,
It is modified after shredding, the modification is by the silk cocoon after shredding and NaHCO3, formalin in three-necked flask mix
It closes, under the conditions of 95 DEG C after magnetic agitation reaction 5h, removes condenser pipe, tailing adapter tube reaction 0.5h, wherein the formaldehyde is water-soluble
The mass concentration of liquid is 37%, the silk cocoon: NaHCO3Mass ratio be 3:3.6, the matter of the silk cocoon and formalin
Amount volume ratio is 3:7；
Modified to carbonize in Muffle furnace, the charing is that 100 DEG C are warming up to from 20 DEG C of rates with 2 DEG C/min, heat preservation
120min is raised to 200 DEG C from 100 DEG C of rates with 1 DEG C/min again, keeps the temperature after 120min up to the modified Carbon Materials of silk cocoon.
2. a kind of preparation method of the modified Carbon Materials of the silk cocoon for adsorbing heavy metal ion, which is characterized in that using silk cocoon as raw material,
It is modified after shredding, the modification is that formaldehyde crosslinking is modified, is hydrolyzed after specifically shredding silk cocoon with NaOH, then
NaHCO is added3It is mixed in three-necked flask with formalin, under the conditions of 95 DEG C after magnetic agitation reaction 5h, removes condenser pipe,
Tailing adapter tube reaction 0.5h；Modified to carbonize in Muffle furnace, the charing is warming up to from 20 DEG C of rates with 2 DEG C/min
100 DEG C, heat preservation 120min is raised to 200 DEG C from 100 DEG C of rates with 1 DEG C/min again, keeps the temperature after 120min up to silk cocoon Modified Activated Carbon
Material.
3. a kind of preparation method of the modified Carbon Materials of the silk cocoon for adsorbing heavy metal ion, which is characterized in that step are as follows: silk cocoon exists
Muffle furnace charing, the charing are that 100 DEG C are warming up to from 20 DEG C of rates with 2 DEG C/min, keep the temperature 120min again from 100 DEG C
200 DEG C are raised to the rate of 1 DEG C/min, 120min is kept the temperature, NaHCO is then added3And formalin, it is blended in one three
In mouthful flask, temperature is at 95 DEG C, and magnetic agitation reacts 5h, removes condenser pipe, tailing adapter tube react again 0.5h to get.
4. a kind of preparation method of the modified Carbon Materials of the silk cocoon for adsorbing heavy metal ion, which is characterized in that step are as follows: silk cocoon exists
Muffle furnace charing, the charing are that 100 DEG C are warming up to from 20 DEG C of rates with 2 DEG C/min, keep the temperature 120min again from 100 DEG C
200 DEG C are raised to the rate of 1 DEG C/min, keeps the temperature 120min, urea and formalin is then added, is blended in one three mouthfuls
In flask, temperature is at 95 DEG C, and magnetic agitation reacts 5h, removes condenser pipe, tailing adapter tube react again 0.5h to get.
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| JPS5332891A (en) * | 1976-09-09 | 1978-03-28 | Agency Of Ind Science & Technol | Production of harmful metal removing agent |
| CN104609391A (en) * | 2015-01-23 | 2015-05-13 | 中北大学 | Preparation method of functional carbon material for removing iron impurities in rare earth |
| CN105502383A (en) * | 2015-11-30 | 2016-04-20 | 北京化工大学 | Silkworm cocoon-based hierarchical porous carbon and preparation method thereof |
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2016
- 2016-11-08 CN CN201610979424.6A patent/CN106540666B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5332891A (en) * | 1976-09-09 | 1978-03-28 | Agency Of Ind Science & Technol | Production of harmful metal removing agent |
| CN104609391A (en) * | 2015-01-23 | 2015-05-13 | 中北大学 | Preparation method of functional carbon material for removing iron impurities in rare earth |
| CN105502383A (en) * | 2015-11-30 | 2016-04-20 | 北京化工大学 | Silkworm cocoon-based hierarchical porous carbon and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| Microporous Carbon Nanoplates from Regenerated Silk Proteins for Supercapacitors;Young Soo Yun;《advanced materials》;20130225;第25卷(第14期);第1993-1998页 |
| 由脲醛树脂制备炭材料及其对金属离子的吸附性能;欧国利;《过程工程学报》;20151031;第15卷(第5期);第876-880页 |
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