CN101804330A - Heavy metal ion adsorbent and preparation and application method thereof - Google Patents
Heavy metal ion adsorbent and preparation and application method thereof Download PDFInfo
- Publication number
- CN101804330A CN101804330A CN 201010182211 CN201010182211A CN101804330A CN 101804330 A CN101804330 A CN 101804330A CN 201010182211 CN201010182211 CN 201010182211 CN 201010182211 A CN201010182211 A CN 201010182211A CN 101804330 A CN101804330 A CN 101804330A
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- metal ion
- adsorbent
- wheat
- poor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a heavy metal ion adsorbent and a preparation and application method thereof. Spent grain is adopted as material, mercaptoacetic acid is chosen as reagent for mercaptolation, NaHSO4.H2O is adopted as catalyst, N,N-dimethylformamide is adopted as reaction medium, mercaptolation is carried out, Na2S.9H2O is then added as reducing agent, aqueous ethanol is adopted as reaction medium, reduction reaction is carried out, and thereby the adsorbent is produced. Compared with the conventional sulfhydryl cotton preparation method, the method has the absolute advantages of high efficiency and quickness. The mercaptolated spend grain is rich in ester functional groups and mercapto functional groups, and can be used for the treatment of heavy metal wastewater. When the mercaptolated spend grain is used for treating mixed heavy metal wastewater containing Cu2 plus, Pb2 plus, Zn2 plus and Cd2 plus ions, effluent can meet National Integrated Wastewater Discharge Standard (GB8978-1996). The mercaptolated spend grain can be reused for at least three times, and therefore has a good application value.
Description
Technical field
The invention belongs to field of environment engineering, be specifically related to a kind of adsorbent and methods for making and using same thereof of heavy metal ion.
Background technology
Along with fast development of modern industry, discharged waste water sharply increases.China Environmental State Bulletin showed in 2008, and national surface water pollution is still serious.In the Changjiang river, the Yellow River, the Zhujiang River, Song Hua River, Huaihe River, 409 sections in Haihe River and seven 200 rivers of big water system, the Liaohe River, the section ratio of I-III class, IV-V class and bad V class water quality is respectively 55.0%, 24.2% and 20.8%.2008, national wastewater emission amount was 571.7 hundred million tons, increases by 2.7% than the last year.Wherein, 241.7 hundred million tons of discharged volume of industrial waste water account for 42.3% of wastewater emission amount.Containing contents of many kinds of heavy metal ion in the industrial wastewater of a large amount of dischargings causes China's heavy metal pollution of water body problem very outstanding.These heavy metal ion are enriched in the biological chain through water body, finally enter human body, and human health is caused great harm.Therefore, how to administer the generally attention that heavy metal wastewater thereby has been subjected to domestic and international all circles.The processing method of heavy metal wastewater thereby mainly comprises chemical precipitation method, ion-exchange, electrolysis, membrane separation process and absorption method etc., wherein absorption method handle that heavy metal wastewater thereby is low because of its cost, removal effect good, simple to operate, do not produce advantage such as secondary pollution and receive much concern.
Wheat is poor to be the main accessory substance of brewing industry, accounts for more than 85% of brewing industry accessory substance, and most of wheat is poor well not to be utilized, and mostly as animal feed, even some brewery is the poor directly stacking of wheat, and this has promptly wasted resource and has polluted environment again.The poor main component of wheat is cellulose, hemicellulose and lignin material, and they all contain abundant hydroxyl, introduces the types of functionality group to prepare adsorbent for heavy metal efficiently thereby esterification can take place.Sulphur atom electronegativity in the sulfydryl is little, and radius is bigger, easily loses electronics and the distortion generation negative electric field that easily polarizes, so can capture cation and tend to into key.Therefore, we select to introduce sulfydryl according to the principle of esterification on the poor surface of wheat, to improve the ability of its Adsorption of Heavy Metal Ions.The method of traditional thiolated modified cellulose substances is the last male method in west, and the not male thiolated modified method in west was originated in 1971, and used till today always, does not significantly improve.Traditional sulfhydrylation method is used for the modification of cellulose substances more, its concrete grammar is: with a certain amount of thioglycolic acid, acetic anhydride, acetate and the mixing of the little amount of catalyst concentrated sulfuric acid are added in the cellulose material for the treatment of modification, place 38 ℃ water-bath to react, and stir once every 24 hours, take out after 100 hours, be washed till neutrality with distilled water, suction filtration, oven dry.But the method length consuming time, and for the poor DeGrain of direct thiolated modified wheat.Therefore, the objective of the invention is to develop a kind of brand-new poor method of thiolated modified wheat, can be applied to fast, prepare simply, efficiently sulfhydrylation lignocellulose material.
The present invention selects for use DMF and niter cake respectively as reaction medium and catalyst, introduces sulfydryl thereby make TGA and the wheat hydroxyl on poor that esterification successfully take place on the poor surface of wheat.But sulfydryl is very unstable, and oxidation by air forms disulphide easily, therefore adopts the method for reacting the step reduction that ends that oxidized sulfydryl is restored.This method has shortened the reaction time greatly, and has solved the easily oxidized difficult problem of sulfydryl.Our " thiolated modified wheat be pickled with grains or in wine adsorption technology " of having proposed that heavy metal wastewater thereby administers simultaneously.This technology is to use the poor heavy metal wastewater thereby of handling of thiolated modified wheat, can be in order to the wider heavy metal ion-containing waste water of purified concentrations scope and the metal ion waste water of mixing, and its advantage has: it is little influenced by the pH value; Do not use chemical reagent; Sludge quantity is few; Non-secondary pollution; But discharge water reuse.
Summary of the invention
The present invention seeks to:
(1) making full use of the discarded wheat of brewing industry poor is raw material, reform the thiolated modified method of traditional cellulose substances, develop a kind of efficiently, the poor method of thiolated modified cellulose substances wheat fast, to prepare a kind of high-efficiency adsorbent, be used to adsorb heavy metal wastewater thereby, real realization " treatment of wastes with processes of wastes against one another ";
(2) realize cleaning, efficient, the cheap heavy metal wastewater thereby of handling, heavy metal ion is stable in the water outlet reaches country's " integrated wastewater discharge standard " (GB8978-1996); The heavy metal of the poor absorption of the thiolated modified wheat of success desorb is realized repeatedly recycling, saves cost.
The objective of the invention is to realize in the following manner:
A kind of preparation method of adsorbent for heavy metal may further comprise the steps:
1) mercaptolation
Poor with the wheat of brewery is raw material, removes silt, foreign material etc. through washing, 60 ℃ of oven dry 12 hours, grinds behind 50 mesh sieves as raw material, selects the reagent of TGA as mercaptolation for use, NaHSO
4H
2O is as catalyst, N, and dinethylformamide is as reaction medium; Described TGA is 5mL: 1g, described NaHSO with the volume mass ratio that wheat is pickled with grains or in wine
4H
2The poor mass ratio of O and wheat is 1: 40; Described N, dinethylformamide is 2.5mL: 1g with the volume mass ratio that wheat is pickled with grains or in wine; The mercaptolation temperature is 110-130 ℃, and the time is 3h;
2) reduction reaction
In above-mentioned reacted system, add Na
2S9H
2O is as reducing agent, and absolute ethyl alcohol is as reaction medium; Described Na
2S9H
2The poor mass ratio of O and wheat is: 5: 1; Described absolute ethyl alcohol with the volume mass ratio that wheat is pickled with grains or in wine is: 25mL: 1g; Filtration under diminished pressure behind the magnetic agitation reaction 1h fully washs filter residue with deionized water, and 60 ℃ of oven dry ground 50 orders in vacuum drying chamber, promptly got described adsorbent.
When a large amount of adsorbents of the present invention---thiolated modified wheat was pickled with grains or in wine preparation, the separable recovery of DMF and catalyst with recycling, was saved cost.Usually DMF adopts the method for decompression distillation to reclaim, and inferior sodium phosphate can adopt the simple process of dissolution-crystallization-filtration to reclaim.By the thiolated modified wheat of above method preparation poor with unmodified wheat poor compare from x-ray photoelectron can spectrogram on (Fig. 1) can obviously find out the characteristic peak (168eV) that has occurred sulfydryl after thiolated modified, this has illustrated that the poor thiolated modified process of wheat is successful.
Select suitable sulfhydrylization reagent, reaction medium, catalyst and reducing agent for use, in certain temperature range, react, improved reaction speed, realized preparing fast and efficiently thiolated modified wheat and be pickled with grains or in wine.
The principle of satirizing property of sulfhydrylation wheat in fact also is the esterification principle, thereby the hydroxyl generation esterification that carboxyl by TGA and wheat are rich in poor is introduced sulfydryl.Meeting etching apparatus such as traditional catalyst for esterification reaction such as the concentrated sulfuric acid, NaOH also causes the poor carbonization of wheat, and in order to overcome above shortcoming, we select inorganic salts niter cake (NaHSO for use
4H
2O) as catalyst.
Best reaction medium should have following feature: it is poor to activate wheat, dissolving citric acid but catalyst-solvent not, and the homogeneous phase of being convenient to react carries out the effective recovery with catalyst.Therefore, we select N for use, and dinethylformamide (DMF) is as reaction medium.
The height of esterification reaction temperature has determined the speed of esterification reaction rate, and the high more esterification of temperature is fast more, can burn so that change its surface nature but wheat is pickled with grains or in wine under higher temperature conditions, and sulfhydryl compound also very easily decomposes under higher temperature conditions simultaneously.Therefore, esterification temperature is defined as 110-120 ℃, and this has guaranteed that promptly esterification can finish fast, has avoided the poor decomposition of burning phenomenon and sulfhydryl compound of wheat again.
The mercaptolation time is successfully the key that thiolated modified wheat is poor, and it is incomplete that the reaction time crosses short reaction.By experiment, we determine that the time of reaction is 3h.
A main difficulty that is faced in the thiolated modified process is that sulfydryl easily is oxidized to disulphide, adopts the method protection sulfydryl of logical nitrogen protection in the course of reaction usually, even but the omnidistance logical nitrogen protection of reaction, it is oxidized still to have the part sulfydryl.Therefore, we select Na for use
2S9H
2O restores oxidized sulfydryl in the reaction end of a period as reducing agent, makes that the whole operation process is simple, has avoided the consumption of nitrogen in the course of reaction again simultaneously, has saved cost.
Using the poor method of handling heavy metal wastewater thereby of the thiolated modified wheat of adsorbent of the present invention is: accurately take by weighing 0.1g adsorbent of the present invention and be added in the solution that 50mL contains heavy metal ion, use 0.1molL
-1HNO
3Or 0.1molL
-1About NaOH adjust pH to 6, at rotating speed 200rmin
-1, adsorb 60-90min in the water bath with thermostatic control magnetic stirring apparatus that temperature is 25 ℃, get supernatant liquid filtering.With reference to " water and effluent monitoring analytical method (the 4th edition) ", filtrate is carried out the check and analysis concentration of heavy metal ion with atomic absorption spectrophotometry, and calculates corresponding clearance and adsorbance.
The concrete computational methods of clearance and adsorbance are as follows:
Clearance R=100 * (C
0-C)/C
0
Adsorbance q=(C
0-C) * v/w
In the formula, C
0Mass concentration (mgL for heavy metal ion in the solution before adsorbing
-1); C is the mass concentration (mgL of heavy metal ion in the solution of absorption back
-1); V is reaction solution volume (L); W is adsorbent dry weight (g).
The method of desorb that thiolated modified wheat is poor and utilization again is: the heavy metal ion (Cu that got enrichment
2+, Pb
2+, Zn
2+, Cd
2+) modified spent grain 0.1g, use 0.1molL
-1HCl (25mL) solution at rotating speed 200rmin
-1, desorb 15min in the water bath with thermostatic control magnetic stirring apparatus that temperature is 25 ℃ behind the suction filtration, is used to adsorb each heavy metal ion once more.Repeat absorption-desorption process 3 times, all get supernatant behind wherein each adsorption-desorption,, calculate desorption efficiency with the atomic absorption spectrophotometer concentration of heavy metal ion wherein.The concrete computational methods of desorption efficiency are as follows:
Desorption efficiency η=100 * C
d* v
d/ (C
0-C) v
In the formula, C
0Mass concentration (mgL for heavy metal in the solution before adsorbing
-1); C is the mass concentration (mgL of heavy metal in the solution of absorption back
-1); C
dConcentration for heavy metal ion in the stripping liquid; V is reaction solution volume (L); v
dBe stripping liquid volume (L).
This method agents useful for same wheat is poor, citric acid, DMF, inferior sodium phosphate are all nontoxic.Modification and wastewater treatment process are simple, and be easy to operate.Can be repeatedly used further reuse of the water after the processing after the poor desorb of sulfhydrylation wheat; Content of beary metal height in the slag that obtains after the processing easily reclaims.
Description of drawings
Fig. 1: the x-ray photoelectron energy spectrogram of the poor thiolated modified front and back of wheat;
Fig. 2: pH value of solution influences heavy metal ion treatment effect figure;
Fig. 3: the poor thiolated modified front and back of wheat are to the adsorption effect comparison diagram of heavy metal ion;
Fig. 4: thiolated modified wheat recycling three the adsorption effect figure that are pickled with grains or in wine to heavy metal ion.
The specific embodiment
Following examples or embodiment are intended to further specify the present invention, rather than limitation of the invention.
The preparation process that thiolated modified wheat is pickled with grains or in wine is as follows: get the poor and 0.125g catalyst (NaHSO of 5g wheat respectively
4H
2O) mix, add 12.5mL DMF successively, the 25mL thioglycolic acid, reaction is 3 hours in about 120 ℃.Reaction is cooled to room temperature after finishing.Add 30g Na
2S9H
2O filtration under diminished pressure behind the magnetic agitation reaction 1h in the 125mL anhydrous ethanol medium fully washs filter residue with deionized water, 60 ℃ of oven dry in vacuum drying chamber, and it is standby to grind 50 orders.
Embodiment 1
Getting the 50mL initial concentration respectively is 0.2mmolL
-1Each heavy metal ion (Cu
2+, Pb
2+, Zn
2+, Cd
2+) solution, each adds the 0.1g adsorbent of above-mentioned preparation, and the pH value of regulator solution is respectively 2,3,4,5,6,7,8,9,10, stirring at room absorption 90min.Investigate the poor thiolated modified front and back of wheat as shown in Figure 2 to the clearance of different heavy metal ion under each pH value.In general, thiolated modified wheat is pickled with grains or in wine all has adsorption effect preferably to heavy metal ion in wider pH range, for Cu
2+, Pb
2+, Zn
2+, Cd
2+, absorption optimal adsorption pH scope is respectively 3-7,3-10,6-9,4-9.Good pH adaptability helps that thiolated modified wheat is poor to be applied to adsorb the actual complex industrial wastewater.
Getting the 50mL initial concentration is 10mmolL
-1Cu
2+, Pb
2+, Zn
2+, Cd
2+Four heavy metal species solions add the unmodified wheat of the 0.1g thiolated modified wheat of 0.1g poor or above-mentioned preparation respectively and are pickled with grains or in wine, and use 0.1molL
-1HNO
3Or 0.1molL
-1About NaOH adjust pH to 6, at rotating speed 200rmin
-1, adsorb 30min and 90min respectively in the water bath with thermostatic control magnetic stirring apparatus that temperature is 25 ℃, get supernatant liquid filtering.Measure the concentration of each residual in filtrate heavy metal ion, and calculate corresponding adsorbance, the result as shown in Figure 3.The result shows: thiolated modified wheat is poor to Cu
2+, Pb
2+, Zn
2+, Cd
2+Adsorbance be respectively 89.53,209.45,227.37,303.25mgg
-1, and the poor adsorption capacity to each heavy metal ion of unmodified wheat only is respectively 71.05,67.46,125.76,207.34mgg
-1As can be seen, the poor thiolated modified back of wheat is to Cu
2+, Pb
2+, Zn
2+, Cd
2+The adsorption capacity of each heavy metal ion all is significantly increased.
Take by weighing accurately that the thiolated modified wheat of 0.1g of above-mentioned preparation is poor to be added to 50mL and to contain heavy metal ion (Cu
2+, Pb
2+, Zn
2+, Cd
2+) each 20mgL
-1Mixed solution in, use 0.1molL
-1HNO
3Or 0.1molL
-1About NaOH adjust pH to 6, at rotating speed 200rmin
-1, adsorb 90min in the water bath with thermostatic control magnetic stirring apparatus that temperature is 25 ℃, get supernatant liquid filtering.With reference to " water and effluent monitoring analytical method (the 4th edition) ", filtrate is carried out the check and analysis concentration of heavy metal ion with atomic absorption spectrophotometry, finds Cu
2+, Pb
2+, Zn
2+, Cd
2+0.22,0.88,1.97,0.07mgL the residual concentration of each heavy metal ion is respectively:
-1, all reach country's " integrated wastewater discharge standard " (GB8978-1996).
Embodiment 4
Getting concentration is 0.2mmolL
-1Cu
2+, Pb
2+, Zn
2+, Cd
2+Solution 100mL adds above-mentioned 0.2g esterification modification wheat then and is pickled with grains or in wine, at rotating speed 200rmin
-1, adsorb 90min in the water bath with thermostatic control magnetic stirring apparatus that temperature is 25 ℃, obtain enrichment the esterification modification wheat of each heavy metal ion poor, be used for desorption experiment after 60 ℃ of oven dry.Heavy metal ion (the Cu that got enrichment
2+, Pb
2+, Zn
2+, Cd
2+) modified spent grain 0.1g, use 0.1molL
-1HCl (25mL) solution at rotating speed 200rmin
-1, desorb 15min in the water bath with thermostatic control magnetic stirring apparatus that temperature is 25 ℃ behind the suction filtration, is used to adsorb each heavy metal ion once more.The experimental technique of Adsorption of Heavy Metal Ions and basically identical noted earlier once more, difference are to add earlier the poor pH that correspondingly regulates again of thiolated modified wheat.Repeat absorption-desorption process 3 times, all get supernatant behind wherein each adsorption-desorption, with the atomic absorption spectroscopy determination concentration of heavy metal ion wherein, calculate adsorption rate and desorption efficiency, the result as shown in Figure 4.By the sharp experiment of absorption-desorption-sorption cycle, find to use 0.1molL
-1Hydrochloric acid can be with Cu
2+, Pb
2+, Zn
2+, Cd
2+The success desorb, after being circulated throughout, adsorption rate slightly descends at every turn, but desorption efficiency all has a little rising.The result shows that it is a kind of cheap effective adsorbent that thiolated modified wheat is pickled with grains or in wine, for Cu
2+, Pb
2+, Zn
2+, Cd
2+Can repeatedly reuse.
Claims (7)
1. the preparation method of an adsorbent for heavy metal, its feature may further comprise the steps:
1) mercaptolation
Poor with the wheat that brewery fetches, through washing, dry, grind the back, select the reagent of TGA for use, NaHSO as mercaptolation as raw material
4H
2O is as catalyst, N, and dinethylformamide is as reaction medium; Described TGA is 5mL: 1g, described NaHSO with the volume mass ratio that wheat is pickled with grains or in wine
4H
2The poor mass ratio of O and wheat is 1: 40; Described N, dinethylformamide is 2.5mL: 1g with the volume mass ratio that wheat is pickled with grains or in wine; The mercaptolation temperature is 110-130 ℃, and the time is 3h;
2) reduction reaction
In above-mentioned reacted system, add Na
2S9H
2O is as reducing agent, and absolute ethyl alcohol is as reaction medium; Described Na
2S9H
2The poor mass ratio of O and wheat is 5: 1; Described absolute ethyl alcohol is 25mL: 1g with the volume mass ratio that wheat is pickled with grains or in wine; Filtration under diminished pressure behind the magnetic agitation reaction 1h, the washing filter residue, vacuum drying ground 50 orders and promptly got described adsorbent.
2. the preparation of adsorbent method of heavy metal ion according to claim 1 is characterized in that step 2) in behind the filtration under diminished pressure, fully wash filter residue with deionized water, 60 ℃ of oven dry ground 50 orders in vacuum drying chamber.
3. the preparation of adsorbent method of heavy metal ion according to claim 1 is characterized in that, N after the reduction reaction, dinethylformamide adopt decompression distillation to reclaim.
4. the preparation of adsorbent method of heavy metal ion according to claim 1 is characterized in that, niter cake adopts the mode of dissolution-crystallization-filtration to reclaim after the reduction reaction.
5. the adsorbent of a heavy metal ion is characterized in that, described adsorbent is prepared by the described method of claim 1.
6. the application process of the adsorbent of the described heavy metal ion of claim 5 is characterized in that, accurately takes by weighing the described adsorbent of 0.1g and is added in the solution that 50mL contains heavy metal ion, uses 0.1molL
-1HNO
3Or 0.1molL
-1About NaOH adjust pH to 6, at rotating speed 200rmin
-1, adsorb 60-90min in the water bath with thermostatic control magnetic stirring apparatus that temperature is 25 ℃, get supernatant liquid filtering and get final product.
7. application process according to claim 6 is characterized in that, the adsorbent 0.1g of heavy metal ion that got enrichment uses 25mL 0.1molL
-1HCl solution at rotating speed 200rmin
-1, desorb 15min in the water bath with thermostatic control magnetic stirring apparatus that temperature is 25 ℃ behind the suction filtration, is used to adsorb each heavy metal ion once more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010182211 CN101804330A (en) | 2010-05-25 | 2010-05-25 | Heavy metal ion adsorbent and preparation and application method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010182211 CN101804330A (en) | 2010-05-25 | 2010-05-25 | Heavy metal ion adsorbent and preparation and application method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101804330A true CN101804330A (en) | 2010-08-18 |
Family
ID=42606384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010182211 Pending CN101804330A (en) | 2010-05-25 | 2010-05-25 | Heavy metal ion adsorbent and preparation and application method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101804330A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905148A (en) * | 2010-08-23 | 2010-12-08 | 成都海旺科技有限责任公司 | Method for preparing heavy metal ion adsorbent |
| CN101973619A (en) * | 2010-09-17 | 2011-02-16 | 昆明理工大学 | Method for treating waste water from copper smelting by using modified ardealite |
| CN104722269A (en) * | 2015-03-20 | 2015-06-24 | 黄显怀 | Composite heavy-metal curing agent with beer lees and preparation method thereof |
| CN105923721A (en) * | 2016-04-23 | 2016-09-07 | 徐月苗 | Decolorizing flocculant of dyeing wastewater |
| CN106390936A (en) * | 2016-12-07 | 2017-02-15 | 郑州源冉生物技术有限公司 | Illite adsorbent as well as preparation method and application thereof |
| CN106423046A (en) * | 2016-12-07 | 2017-02-22 | 郑州源冉生物技术有限公司 | Diatomite adsorbent as well as preparation method and application of diatomite adsorbent |
| CN106669589A (en) * | 2016-12-20 | 2017-05-17 | 常州大学 | Preparation method and application of sulfydryl-based efficient adsorbent |
| CN106824112A (en) * | 2017-03-06 | 2017-06-13 | 济南大学 | A kind of preparation of 2 mercaptopyrimidine modified magnetic cotton stalk skins adsorbent |
| CN107583612A (en) * | 2017-09-28 | 2018-01-16 | 青岛农业大学 | Charcoal preparation method and preparation system and mercury absorbent based on corncob |
| CN108295817A (en) * | 2018-03-16 | 2018-07-20 | 嘉兴学院 | A kind of surface sulfhydrylation carbon fiber and preparation method thereof |
| CN108380183A (en) * | 2018-03-16 | 2018-08-10 | 嘉兴学院 | A kind of surface sulfhydrylation carbon fiber production method being modified based on carboxylated |
| CN108410474A (en) * | 2018-05-10 | 2018-08-17 | 张鑫 | Active soil conditioner of a kind of reduction heavy metal in soil and preparation method thereof |
| CN109158089B (en) * | 2018-11-07 | 2021-05-18 | 福州大学 | Ultrasonic-assisted sulfhydryl modified cellulose aerogel and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428891A (en) * | 2008-12-09 | 2009-05-13 | 中南大学 | Method for treating plumbum-containing wastewater with modified spent grain |
-
2010
- 2010-05-25 CN CN 201010182211 patent/CN101804330A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428891A (en) * | 2008-12-09 | 2009-05-13 | 中南大学 | Method for treating plumbum-containing wastewater with modified spent grain |
Non-Patent Citations (1)
| Title |
|---|
| 《Bioresource Technology》 20100324 Liyuan Chai，et al Synthesis of thiol-functionalized spent grain as a novel adsorbent for divalent metal ions 6269-6272 1-7 第101卷, 2 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905148A (en) * | 2010-08-23 | 2010-12-08 | 成都海旺科技有限责任公司 | Method for preparing heavy metal ion adsorbent |
| CN101973619A (en) * | 2010-09-17 | 2011-02-16 | 昆明理工大学 | Method for treating waste water from copper smelting by using modified ardealite |
| CN104722269A (en) * | 2015-03-20 | 2015-06-24 | 黄显怀 | Composite heavy-metal curing agent with beer lees and preparation method thereof |
| CN105923721A (en) * | 2016-04-23 | 2016-09-07 | 徐月苗 | Decolorizing flocculant of dyeing wastewater |
| CN106390936A (en) * | 2016-12-07 | 2017-02-15 | 郑州源冉生物技术有限公司 | Illite adsorbent as well as preparation method and application thereof |
| CN106423046A (en) * | 2016-12-07 | 2017-02-22 | 郑州源冉生物技术有限公司 | Diatomite adsorbent as well as preparation method and application of diatomite adsorbent |
| CN106669589A (en) * | 2016-12-20 | 2017-05-17 | 常州大学 | Preparation method and application of sulfydryl-based efficient adsorbent |
| CN106824112A (en) * | 2017-03-06 | 2017-06-13 | 济南大学 | A kind of preparation of 2 mercaptopyrimidine modified magnetic cotton stalk skins adsorbent |
| CN107583612A (en) * | 2017-09-28 | 2018-01-16 | 青岛农业大学 | Charcoal preparation method and preparation system and mercury absorbent based on corncob |
| CN108295817A (en) * | 2018-03-16 | 2018-07-20 | 嘉兴学院 | A kind of surface sulfhydrylation carbon fiber and preparation method thereof |
| CN108380183A (en) * | 2018-03-16 | 2018-08-10 | 嘉兴学院 | A kind of surface sulfhydrylation carbon fiber production method being modified based on carboxylated |
| CN108380183B (en) * | 2018-03-16 | 2021-02-02 | 嘉兴学院 | Preparation method of surface sulfhydrylation carbon fiber based on carboxylation modification |
| CN108410474A (en) * | 2018-05-10 | 2018-08-17 | 张鑫 | Active soil conditioner of a kind of reduction heavy metal in soil and preparation method thereof |
| CN109158089B (en) * | 2018-11-07 | 2021-05-18 | 福州大学 | Ultrasonic-assisted sulfhydryl modified cellulose aerogel and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101804330A (en) | Heavy metal ion adsorbent and preparation and application method thereof | |
| CN103351020B (en) | A kind of production method of basic copper chloride | |
| CN101538652B (en) | Method for separating and recovering vanadium and chrome from vanadium and chrome-containing waste | |
| CN105084591B (en) | One kind fluorination high fluoride wastewater treatment technique of work | |
| CN102107978B (en) | Method for resource utilization and innocent treatment of etching waste liquid containing copper in circuit board industry | |
| CN108483501B (en) | Comprehensive utilization method of electrolytic manganese slag washing liquid | |
| CN102935352B (en) | Method for absorbing and removing heavy metal and hexavalent chromium from waste liquid by using mangosteen slag | |
| CN110935710A (en) | Washing desalination treatment system, method and application of household garbage incineration fly ash | |
| CN101491771A (en) | Fenton and Fenton-like reaction catalyst regeneration and reclamation method | |
| CN104609683B (en) | A kind of renovation process of chrome tanning Heavy Metals in Sludge chromium | |
| CN102671634B (en) | Modified cellulose adsorbent and preparation method as well as application thereof | |
| CN102936070A (en) | Method for treating mercury-containing wastewater during PVC (Polyvinyle Chloride) production through two-step process | |
| CN106435197A (en) | Process and device for alkaline extraction and recovery from waste catalysts in SCR (selective catalytic reduction) denitrification | |
| CN101811029A (en) | Adsorbent for treating heavy metal waste water and preparation method and application method thereof | |
| CN106399715A (en) | Method for producing electrolytic zinc through high-chloride zinc ash material ammonia leaching ion exchange combined process | |
| CN105198030B (en) | A kind of method of chlorion in utilization garlic waste removing water | |
| CN113754162A (en) | Method and system for recovering chloride by crystallizing acidic washing wastewater | |
| CN105944688B (en) | A kind of preparation method and heavy metal in waste water minimizing technology of modified pineapple peel magnetic adsorptive material | |
| CN102910760A (en) | Treatment process of contaminated acid containing heavy metals | |
| CN114421044A (en) | Purification treatment method and system for phosphorus-iron slag mixture containing Al and Cu impurities | |
| CN104193061A (en) | Treatment method for paraquat pesticide wastewater | |
| CN103641262B (en) | Method for recycling heavy metals in electroplating wastewater by using modified titanium nanotube | |
| CN102688677B (en) | Method for enhancing total mercury recovery rate of metallurgical fume by reducing bivalent mercury | |
| CN109368850A (en) | A kind of desulfurization wastewater recycling treatment system and application method | |
| CN101733078A (en) | Method for preparing phosphorous-removing adsorbent by using cane shoots leaves |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100818 |