CN102350311A - Preparation of keratin adsorbent, and method for treating wastewater containing trivalent chromium - Google Patents
Preparation of keratin adsorbent, and method for treating wastewater containing trivalent chromium Download PDFInfo
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- CN102350311A CN102350311A CN2011101980272A CN201110198027A CN102350311A CN 102350311 A CN102350311 A CN 102350311A CN 2011101980272 A CN2011101980272 A CN 2011101980272A CN 201110198027 A CN201110198027 A CN 201110198027A CN 102350311 A CN102350311 A CN 102350311A
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Abstract
The invention discloses a method for preparing a keratin adsorbent. The method comprises the following steps of: 1, cleaning waste cattle hair or wool, and drying for later use; 2, pre-treating the cattle hair or wool ; and 3, grafting and modifying the pre-treated cattle hair or wool, namely putting the pre-treated cattle hair or wool in a maleic anhydride and N,N-dimethyl formyl solution and modifying. The method for treating wastewater containing trivalent chromium by using the keratin adsorbent comprises the following steps of: 1, washing a certain amount of modified cattle hair or wool keratin adsorbent for later use and adjusting pH by using clear water; 2, putting modified cattle hair or wool in the step 1 in an adsorption tower and mixing the modified cattle hair or wool and water containing trivalent chromium; and 3, desorbing, putting the keratin adsorbent after adsorption into a sulfuric acid solution, washing the filtered and desorbed cattle hair or wool by using clear water until pH value is 6 to 8 to obtain a product which can be recycled. The method has the characteristics of energy conversation, environment-friendliness, reasonable design, and simplicity, and is easy and convenient to operate.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to the method that a kind of keratin preparation of adsorbent method and processing thereof contain trivalent chromium waste water.
Background technology
The chromium compound industrial use is very wide, is all using in the industries such as metal processing, plating, timber are deposited, chemical, process hides.Environment chromium mainly?
and
exists in two forms.
toxicity to humans is far greater than
, most studies have focused on containing
wastewater treatment.As in some cases three will change to hexavalent chromium, thus containing
wastewater treatment more and more attention to environmental protection workers.
Currently, treatment with
Waste There are many ways, for example: alkali precipitation method, recycling, extraction, electrolysis, membrane treatment, adsorption method.Alkali precipitation method technology is simple, technology maturation, but this method be prone to clearance can not be up to standard fully, deposition not thoroughly, separate problems such as not thorough.Chrome Tanning Wastewater recycles in the tanning production; Can make full use of the active ingredient in the Chrome Tanning Wastewater; Practice thrift industrial chemicals; But; In the process of active DO-loop method processing Chrome Tanning Wastewater, still will consider the influence to finished leather of accumulation, cycle-index and the material balance problem of impurity, the control of stock trick art is had relatively high expectations.The patent No. be [
200710061383.3], name is called a kind of process patent of handling chroming waste liquor; Providing a kind of handles and the method for utilizing chroming waste liquor again; Chroming waste liquor to leather production is collected; Remove impurity such as skin bit wherein; Add the chromium ion trapping agent and the chromium ion in the chroming waste liquor is captured form solids precipitation, separate obtaining the supernatant that big molecule chromium and suitable pickling are used.Belong to recycling method.The patent No. is the patent of invention that [87106823.0], name are called Chrominum extinctive absorption in hide processing; This patent is at process hides pickling technology utilization chroming waste liquor (only once multiplexing); Adopt crosslinking agent and automatic nertralizer during tanning; Make that chrome tanning agent is utilized in the chrome tanning process; Can save arsenic about 40%; Trivalent chromium concentration can be reduced to below the 3mg/L in the combined sewage, and waste water then can reach discharging standards without any processing; The grain of processing in this way is fine and smooth, smooth, plentiful.Both invention is to reduce the tanning process improvements and lower chrome tanning tannery wastewater containing
volume.Methods such as extraction, electrolysis, film processing are used less in commercial production.Absorption method grew up in recent years, was considered to one of best processing method, but the shortage of function admirable, cheap adsorbent has influenced its promotion and application.
Domestic biomass development and application of adsorbent material has made some achievements, such as: fir sawdust, wood chips and peanut shells, corn cob, husk ash, bagasse and raw sugar cane bagasse, bacterial and fungal strains, chitosan, MTB bacteria, chlorella, Lee Wo (a wet raw chrome Hyperaccumulator), discarded feathers, chaff, starch, cotton, etc. can be modified lignin is
adsorbents, but modified adsorbent obtained after adsorption maximum 20mg / g or so, reach deal with high concentration
wastewater requirements.
Summary of the invention
In order to overcome the deficiency of above-mentioned prior art; The object of the present invention is to provide a kind of keratin preparation of adsorbent method and processing thereof to contain the method for trivalent chromium waste water; Can reduce the waste and the contaminated environment of keratin resource, have energy-saving and environmental protection, reasonable in design, characteristics that technology is simple and easy and simple to handle.
To achieve these goals, the technical scheme of the present invention's employing is:
A kind of keratin preparation of adsorbent method may further comprise the steps:
One, discarded ox hair or wool are cleaned, 50~70 ℃ of oven dry down, subsequent use;
Second, the hairs or wool pretreated specific approach is: ox hair or wool spare parts placed 1-3 mass fraction of 2% hydrogen peroxide 10% in an aqueous solution having a pH of 8.0 to 9.0, the mass volume of liquid ratio of 0.8 to 1.2:45 to 55, at a temperature of 80 ~ 100 ℃, time is 50 ~ 70? min pretreatment conditions, the hairs or wool pretreated to
adsorption capacity reached 12.1 ~ 25.6? mg / g (with chromium oxide meter), obtained was 61% ~ 98.5%;
Three, pretreated ox hair or wool are carried out graft modification; Be specially: getting 1~3 part of preliminary treatment ox or wool, to place mass volume ratio be the maleic anhydride and the N of 10%~14% (w/v); Carry out modification in the N-dimethyl formyl solution; The optimum condition of graft modification is reaction time 6~7h, and the grafting temperature is 70~80 ℃.
A kind of method of utilizing the keratin sorbent treatment to contain trivalent chromium waste water may further comprise the steps:
The first, getting 1~3 part subsequent use modification ox hair or wool keratin adsorbent, to use clear water to be washed till pH be 4.5~7.5;
The second, will go up modification ox hair or wool in the step places adsorption tower and contains chromic waste water and mix; Before adsorption tower is penetrated; Adsorption time 1~3h; Chromic clearance is reached more than 99.2%; The minimum chromic mass concentration of water outlet is below 4mg/L; Adsorption tower is 290~320 min by time of break-through, and adsorption temp is 25~30 ℃;
Three, desorb is handled, and the keratin adsorbent after the absorption is put into 1.0~3.5mol/L sulfuric acid solution, and desorption temperature is 60~80 ℃, and desorption time is 3~5 h, and filtering ox hair or wool after the desorb, to use clear water to be washed till the pH value again be 6~8 promptly reusable.
The present invention is a raw material with discarded ox, wool, and employing preliminary treatment and modification mode make to increase on ox hair or the wool keratin structure has polarity group and ionizable group, can adsorb other organic and inorganic molecule.Adsorption properties of wool keratin adsorbate addition to external factors related to the nature and outside, keratin hair has available the number of adsorption sites is also an important factor, in terms of metal ions, the main adsorption sites point is the free carboxyl group, therefore, is to determine the number of carboxyl groups adsorption hair keratin main factors to solve the waste keratin reducing environmental pollution and wastewater
ion contamination, the waste keratin material modification to the adsorbent to deal with
wastewater, waste is currently recycled keratin-containing
wastewater treatment help, energy saving, environmental protection, rational design process is simple and easy to operate features.
Description of drawings
Fig. 1 is the surface scan Electronic Speculum figure in the wool processing procedure, and wherein, Fig. 1 a is original wool surface scan Electronic Speculum figure; Fig. 1 b is the wool surface scan Electronic Speculum figure that hydrogen peroxide solution was handled; Fig. 1 c is the wool surface scan Electronic Speculum figure after maleic anhydride modified; Fig. 1 d is the preceding wool surface scan Electronic Speculum figure of absorption; Fig. 1 e is the wool surface scan Electronic Speculum figure after adsorbing.
Fig. 2 is that be untreated wool and hydrogen peroxide solution handled the infrared spectrum of wool.
Fig. 3 handles the infrared spectrum of wool and maleic anhydride modified wool for hydrogen peroxide solution.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done further explain.
Embodiment 1
A kind of keratin preparation of adsorbent method may further comprise the steps:
One, discarded ox hair is cleaned, 50 ℃ of oven dry down, subsequent use;
Second, ox hair pretreatment, specific approach is: Take 2 servings placed in standby Niumao mass fraction of 5% hydrogen peroxide aqueous solution having a pH of 8.0, the solid-liquid volume ratio of 0.8:45 mass at a temperature of 80 ℃, time was 50? min pretreatment conditions, pre-treated hairs to
adsorption capacity reached 25.6? mg / g (with chromium oxide meter), obtained 87.5%;
Three, pretreated ox hair is carried out graft modification; Be specially: getting 1 part preliminary treatment ox, to place mass volume ratio be the maleic anhydride and the N of 12% (w/v); Carry out modification in the N-dimethyl formyl solution, the condition of graft modification is reaction time 6h, and the grafting temperature is 70 ℃.
Embodiment 2
A kind of keratin preparation of adsorbent method may further comprise the steps:
One, discarded wool is cleaned, 70 ℃ of oven dry down, subsequent use;
Second, pretreatment of wool, the specific approach is: 1 placed in standby wool mass fraction of 10% hydrogen peroxide in an aqueous solution having a pH of 9.0, solid-liquid ratio of 1.2 mass Volume:? 55, at a temperature of 100 ℃ , the time is 70? min pretreatment conditions, pre-treated wool of
adsorption capacity reached 21.8? mg / g (with chromium oxide meter), the system was 92.5%;
Three, pretreated wool is carried out graft modification; Be specially: get 2 parts to place mass volume ratio through pretreated wool be the maleic anhydride and the N of 10% (w/v); Carry out modification in the N-dimethyl formyl solution, the condition of graft modification is reaction time 7h, and the grafting temperature is 80 ℃.
Embodiment 3
A kind of keratin preparation of adsorbent method may further comprise the steps:
One, discarded ox hair is cleaned, 60 ℃ of oven dry down, subsequent use;
Second, ox hair pretreatment, the specific approach is: 3 parts spare hairs in the mass fraction of 2% hydrogen peroxide aqueous solution having a pH of 8.5, the solid-liquid mass volume ratio of 1.0:? 50, at a temperature of 90 ℃ , the time is 60? min pretreatment conditions, pre-treated hairs to
adsorption capacity reached 25.6? mg / g (with chromium oxide meter), obtained 87.5%;
Three, pretreated ox hair is carried out graft modification; Be specially: getting 3 parts of pretreated ox hairs, to place mass volume ratio be the maleic anhydride and the N of 14% (w/v); Carry out modification in the solution of N-dimethyl formyl, the optimum condition of graft modification is reaction time 6.5h, and the grafting temperature is 75 ℃.
Embodiment 4
A kind of method of utilizing the keratin sorbent treatment to contain trivalent chromium waste water may further comprise the steps:
The first, getting 3 parts of subsequent use modification ox hair keratin adsorbents, to use clear water to be washed till pH be 4.5;
The second, will go up modification ox hair in the step places adsorption tower and contains chromic waste water and mix; Before adsorption tower is penetrated; Adsorption time 1h; Chromic clearance is reached more than 99.2%; The minimum chromic concentration of water outlet is below 4mg/L; Adsorption tower is 290min by time of break-through, and adsorption temp is 25 ℃;
Three, desorb is handled, and the keratin adsorbent after the absorption is put into the 1.0mol/L sulfuric acid solution, and desorption temperature is 60 ℃, and desorption time is 3 h, and filtering ox hair after the desorb, to use clear water to be washed till the pH value again be 6 to get final product.
Embodiment 5
A kind of method of utilizing the keratin sorbent treatment to contain trivalent chromium waste water may further comprise the steps:
The first, getting 1 part of subsequent use modified wool keratin adsorbent, to use clear water to be washed till pH be 7.5;
The second, will go up modified wool in the step places adsorption tower and contains chromic waste water and mix; Before adsorption tower is penetrated; Adsorption time 3h; Chromic clearance is reached more than 99.2%; The minimum chromic concentration of water outlet is below 4mg/L; Adsorption tower is 320 min by time of break-through, and adsorption temp is 28 ℃;
Three, desorb is handled, and the keratin adsorbent after the absorption is put into the 3.0mol/L sulfuric acid solution, and desorption temperature is 80 ℃, and desorption time is 5 h, and filtering wool after the desorb, to use clear water to be washed till the pH value again be 8 to get final product.
Embodiment 6
A kind of method of utilizing the keratin sorbent treatment to contain trivalent chromium waste water may further comprise the steps:
The first, getting 2 parts of subsequent use modification ox hair keratin adsorbents, to use clear water to be washed till pH be 6;
The second, will go up modification ox hair in the step places adsorption tower and contains chromic waste water and mix; Before adsorption tower is penetrated; Adsorption time 2h; Chromic clearance is reached more than 99.2%; The minimum chromic concentration of water outlet is below 4mg/L; Adsorption tower is 300 min by time of break-through, and adsorption temp is 30 ℃;
Three, desorb is handled, and the keratin adsorbent after the absorption is put into the 3.5mol/L sulfuric acid solution, and desorption temperature is 70 ℃, and desorption time is 4h, and filtering ox hair after the desorb, to use clear water to be washed till the pH value again be 7 to get final product.
Referring to Fig. 1,Handling wool with hydrogen peroxide solution and can destroy its surperficial scale layer effectively under alkali condition, and the wool surface texture not have variation basically in maleic anhydride modified and adsorption process.
Referring to Fig. 2,Wool keratin is at 1649 cm
-1, 1531 cm
-1, 1215 cm
-1, 686 cm
-1I acid amides band, II acid amides band, III acid amides band, the IV acid amides band at place all exist, and hydrogen peroxide solution is handled the keratin structure that does not change wool.2924 cm
-1, 2853 cm
-1The place is a methylene peak, and after hydrogen peroxide solution was handled, these two absworption peaks disappeared, and the outer field lipoid layer of this explanation scale layer (main component is 20 acid of ten prestoxs or combines with protein peptide chain with fat key form) is removed.The characteristic peak of carbon-sulfur bond is by 625 cm
-1Move on to 632 cm
-1The place illustrates that the disulfide bond in the keratin is destroyed, at 1176 cm
-1With 1039 cm
-1The two powers peak occurs and be respectively-absworption peak of S=O and S-O, can conclude to be-SO
2-, after visible disulfide bond is interrupted, by hydrogen peroxide oxidation.
Referring to Fig. 3,The I acid amides band of the wool keratin after maleic anhydride modified, II acid amides band, III acid amides band, IV acid amides band all exist, and illustrate that the modification processing does not change the basic structure of wool keratin; At 3319 cm
-1The place-OH and R-NH
2Characteristic peak weakens before comparing modification greatly, and at 1718 cm
-1New peak appears in the position, is-C=C-COOH, illustrates that amidation process has taken place for maleic anhydride and wool in modifying process.
Beneficial effect
Claims (8)
1. a keratin preparation of adsorbent method is characterized in that, may further comprise the steps:
One, discarded ox hair or wool are cleaned, 50~70 ℃ of oven dry down, subsequent use;
Two, to ox hair or wool preliminary treatment; Specific practice is: getting 1~3 part of subsequent use ox hair or wool, to place the hydrogen peroxide solution mass fraction be 2%~10% the aqueous solution; Its pH is 8.0~9.0, the mass volume ratio of solid-liquid is 0.8~1.2:45~55; In temperature is 80~100 ℃, and the time is to carry out preliminary treatment under the condition of 50~70 min;
Three, pretreated ox hair or wool are carried out graft modification; Be specially: getting 1~3 part of preliminary treatment ox or wool, to place mass volume ratio be the maleic anhydride and the N of 10%~14% (w/v); Carry out modification in the N-dimethyl formyl solution; The optimum condition of graft modification is reaction time 6~7h, and the grafting temperature is 70~80 ℃.
2. a kind of keratin preparation of adsorbent method according to claim 1 is characterized in that, may further comprise the steps:
One, discarded ox hair is cleaned, 50 ℃ of oven dry down, subsequent use;
Two, to the ox hair preliminary treatment, specific practice is: getting 2 parts in subsequent use ox hair, to place the hydrogen peroxide solution mass fraction be 5% the aqueous solution, and its pH is 8.0, the mass volume ratio of solid-liquid is 0.8:45, is 80 ℃ in temperature, and the time is to carry out preliminary treatment under the condition of 50 min;
Three, pretreated ox hair is carried out graft modification; Be specially: getting 1 part preliminary treatment ox, to place mass volume ratio be the maleic anhydride and the N of 12% (w/v); Carry out modification in the N-dimethyl formyl solution, the condition of graft modification is reaction time 6h, and the grafting temperature is 70 ℃.
3. a kind of keratin preparation of adsorbent method according to claim 1 is characterized in that, may further comprise the steps:
One, discarded wool is cleaned, 70 ℃ of oven dry down, subsequent use;
Two, to the wool preliminary treatment, specific practice is: getting 1 part of subsequent use wool, to place the hydrogen peroxide solution mass fraction be 10% the aqueous solution, and its pH is 9.0, the mass volume ratio of solid-liquid is 1.2:55, is 100 ℃ in temperature, and the time is to carry out preliminary treatment under the condition of 70 min;
Three, pretreated wool is carried out graft modification; Be specially: getting 2 parts preliminary treatment wool, to place mass volume ratio be the maleic anhydride and the N of 10% (w/v); Carry out modification in the N-dimethyl formyl solution, the condition of graft modification is reaction time 7h, and the grafting temperature is 80 ℃.
4. a kind of keratin preparation of adsorbent method according to claim 1 is characterized in that, may further comprise the steps:
One, discarded ox hair is cleaned, 60 ℃ of oven dry down, subsequent use;
Two, to the ox hair preliminary treatment; Specific practice is: getting 3 parts in subsequent use ox hair, to place the hydrogen peroxide solution mass fraction be 2% the aqueous solution; Its pH is 8.5, the mass volume ratio of solid-liquid is 1.0:50, is 90 ℃ at bath temperature, and the time is to carry out preliminary treatment under the condition of 60 min;
Three, pretreated ox hair is carried out graft modification; Be specially: getting 3 parts of preliminary treatment ox hairs, to place mass volume ratio be the maleic anhydride and the N of 14% (w/v); Carry out modification in the solution of N-dimethyl formyl, the optimum condition of graft modification is reaction time 6.5h, and the grafting temperature is 75 ℃.
5. a method of utilizing the keratin sorbent treatment to contain trivalent chromium waste water is characterized in that, may further comprise the steps:
The first, getting 1~3 part subsequent use modification ox hair or wool keratin adsorbent, to use clear water to be washed till pH be 4.5~7.5;
The second, will go up modification ox hair or wool in the step and place adsorption tower to contain chromic waste water to mix, adsorption time 1~3h, adsorption temp are 25~30 ℃;
Three, desorb is handled, and the keratin adsorbent after the absorption is put into 1.0~3.5mol/L sulfuric acid solution, and desorption temperature is 60~80 ℃, and desorption time is 3~5 h, and filtering ox hair or wool after the desorb, to use clear water to be washed till the pH value again be 6~8 promptly reusable.
6. a kind of method of utilizing the keratin sorbent treatment to contain trivalent chromium waste water according to claim 5 is characterized in that, may further comprise the steps:
The first, getting 3 parts of subsequent use modification ox hair keratin adsorbents, to use clear water to be washed till pH be 4.5;
The second, will go up modification ox hair in the step and place adsorption tower to contain chromic waste water to mix, before adsorption tower was penetrated, adsorption time 1h, adsorption temp were 25 ℃;
Three, desorb is handled, and the keratin adsorbent after the absorption is put into the 1.0mol/L sulfuric acid solution, and desorption temperature is 60 ℃, and desorption time is 3 h, and filtering the ox hair after the desorb and using clear water to be washed till the pH value is 6 to get final product.
7. a kind of method of utilizing the keratin sorbent treatment to contain trivalent chromium waste water according to claim 5 is characterized in that, may further comprise the steps:
The first, getting 1 part of subsequent use modified wool keratin adsorbent, to use clear water to be washed till pH be 7.5;
The second, will go up modified wool in the step and place adsorption tower to contain chromic waste water to mix, adsorption time 3h, adsorption temp are 28 ℃;
Three, desorb is handled, and the keratin adsorbent after the absorption is put into the 3.0mol/L sulfuric acid solution, and desorption temperature is 80 ℃, and desorption time is 5 h, and filtering the wool after the desorb and using clear water to be washed till the pH value is 8 to get final product.
8. a kind of method of utilizing the keratin sorbent treatment to contain chromic waste water according to claim 5 is characterized in that, may further comprise the steps:
The first, getting 2 parts of subsequent use modification ox hair keratin adsorbents, to use clear water to be washed till pH be 6;
The second, will go up modification ox hair in the step and place adsorption tower to contain chromic waste water to mix, adsorption time 2h, adsorption temp are 30 ℃;
Three, desorb is handled, and the keratin adsorbent after the absorption is put into the 3.5mol/L sulfuric acid solution, and desorption temperature is 70 ℃, and desorption time is 4h, and filtering the ox hair after the desorb and using clear water to be washed till the pH value is 7 to get final product.
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Cited By (9)
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CN103496758A (en) * | 2013-09-11 | 2014-01-08 | 昆山市万丰制衣有限责任公司 | Method for treating trivalent chromium in printing and dyeing wastewater by utilizing rabbit hair keratin adsorbent |
CN103721684A (en) * | 2013-12-25 | 2014-04-16 | 中国科学院化学研究所 | Animal hair-grafted polypropylene amine oxime fiber material and preparation method thereof |
CN104353426A (en) * | 2014-10-08 | 2015-02-18 | 苏州汇丰材料科技股份有限公司 | Method for adsorbing chromium ions by virtue of protein fibers |
CN105350319A (en) * | 2015-10-26 | 2016-02-24 | 北京石油化工学院 | Method for grafting and modifying cashmere |
CN105600975A (en) * | 2015-10-30 | 2016-05-25 | 江南大学 | Method for immobilizing cadmium ions in water through using rice proteins |
CN105944690A (en) * | 2016-07-14 | 2016-09-21 | 四川大学 | Biomass adsorbent and preparing method and application thereof |
CN106268687A (en) * | 2016-08-17 | 2017-01-04 | 潘明华 | A kind of composite porous material processing waste water from dyestuff and preparation method thereof |
CN107081134A (en) * | 2016-02-15 | 2017-08-22 | 河海大学 | A kind of modified hair keratin adsorbent and preparation method and application |
CN108554386A (en) * | 2018-03-21 | 2018-09-21 | 中国农业科学院农业资源与农业区划研究所 | Promote the new material and the preparation method and application thereof of efficient passivation Cadmium in Soil |
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CN103496758A (en) * | 2013-09-11 | 2014-01-08 | 昆山市万丰制衣有限责任公司 | Method for treating trivalent chromium in printing and dyeing wastewater by utilizing rabbit hair keratin adsorbent |
CN103721684A (en) * | 2013-12-25 | 2014-04-16 | 中国科学院化学研究所 | Animal hair-grafted polypropylene amine oxime fiber material and preparation method thereof |
CN103721684B (en) * | 2013-12-25 | 2016-08-10 | 中国科学院化学研究所 | A kind of animal hair graft polypropylene base amidoxime fibrous material and preparation method |
CN104353426A (en) * | 2014-10-08 | 2015-02-18 | 苏州汇丰材料科技股份有限公司 | Method for adsorbing chromium ions by virtue of protein fibers |
CN105350319A (en) * | 2015-10-26 | 2016-02-24 | 北京石油化工学院 | Method for grafting and modifying cashmere |
CN105600975A (en) * | 2015-10-30 | 2016-05-25 | 江南大学 | Method for immobilizing cadmium ions in water through using rice proteins |
CN105600975B (en) * | 2015-10-30 | 2017-12-12 | 江南大学 | A kind of method for solidifying cadmium ion in water using rice protein |
CN107081134A (en) * | 2016-02-15 | 2017-08-22 | 河海大学 | A kind of modified hair keratin adsorbent and preparation method and application |
CN105944690A (en) * | 2016-07-14 | 2016-09-21 | 四川大学 | Biomass adsorbent and preparing method and application thereof |
CN106268687A (en) * | 2016-08-17 | 2017-01-04 | 潘明华 | A kind of composite porous material processing waste water from dyestuff and preparation method thereof |
CN108554386A (en) * | 2018-03-21 | 2018-09-21 | 中国农业科学院农业资源与农业区划研究所 | Promote the new material and the preparation method and application thereof of efficient passivation Cadmium in Soil |
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Application publication date: 20120215 |