CN1876227A - Process for preparing cation sorbent and its application - Google Patents
Process for preparing cation sorbent and its application Download PDFInfo
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- CN1876227A CN1876227A CN 200510040485 CN200510040485A CN1876227A CN 1876227 A CN1876227 A CN 1876227A CN 200510040485 CN200510040485 CN 200510040485 CN 200510040485 A CN200510040485 A CN 200510040485A CN 1876227 A CN1876227 A CN 1876227A
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- cation adsorbent
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- adsorbent
- stalk
- waste water
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- 150000001768 cations Chemical class 0.000 title claims abstract description 43
- 239000002594 sorbent Substances 0.000 title description 6
- 238000004519 manufacturing process Methods 0.000 title description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 239000003463 adsorbent Substances 0.000 claims description 53
- 239000002351 wastewater Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 239000003125 aqueous solvent Substances 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 31
- 150000002500 ions Chemical class 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 235000015165 citric acid Nutrition 0.000 description 7
- 241000692870 Inachis io Species 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002154 agricultural waste Substances 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 102100034279 Calcium-binding mitochondrial carrier protein Aralar2 Human genes 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 108010084210 citrin Proteins 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000011017 operating method Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The related preparation method for a cation adsorption agent comprises: adding disintegrated stalk into non-aqueous solvent with citric acid, the weight ratio between acid and stalk not less than 1:1, setting backflow time not less than 12h, filtering, cleaning with distilled water till pH value as neutrality, drying till water content under 5%; at room temperature, stirring and adjusting pH value not less than 3.0, adding prepared cation adsorption agent till not less than 0.8g/L, stirring at least 40min, and separating the agent. Compared to prior art, this invention has obvious economic benefit.
Description
Technical field
The invention belongs to the method and the application that prepare ion adsorbent with the agricultural product castoff deep processing, belong to especially with stalk and prepare the method for cation adsorbent and use this field.
Background technology
China is a country that water resource is very short, water resource of per capita only accounts for 1/4th of world average level, there is insufficient water in the city of China 2/3rds at present, and wherein more serious lack of water city reaches 110, and National urban lack of water total amount is 6,000,000,000 tons.Along with China's industrialization, quickening of urbanization process, water pollutes situation and is on the rise, the rivers and lakes of the whole nation more than 70% suffer to pollute in various degree, Huaihe River, Haihe River, the Liaohe River, Taihu Lake, Dian Chi, Chaohu (Huai, Hai and Liao rivers and Tai, Chao and Dianchi lakes) serious eutrophication, water pollutes the situation of having aggravated fresh water resources shortage in China greatly, and water pollutes a big obstacle that has become restriction and the sustainable development of puzzlement China at present.China's year sewage discharge reaches 60,000,000,000 tons, wherein the unprocessed river,lake and reservior that directly enters more than 80%.In the sewage total release, trade effluent accounts for about 60%, and the control of industrial water pollution has become the top priority of water prevention and cure of pollution.Waste water from dyestuff is a kind of common industrial wastewater, and the concentration of dyestuff is very low in the waste water from dyestuff, is no more than 250mg/l.
China's annual results agricultural crop straw reaches more than 600,000,000 ton, and present utilization rate is less than 20%, accounts for the 65-84% of its total amount as fuel wood or the stalk that directly incinerates, and crop straw burning has polluted atmospheric environment has wasted a large amount of available cheap plant resourceses again.In China, the harm of agricultural wastes more and more draws attention, and the pollution problem of improvement agricultural wastes is extremely urgent, but the agricultural wastes comprehensive treatment technique of suitable China's national situation is few at present.
The foreign agriculture discarded object has been used directly as adsorbent and has carried out wastewater treatment research, but from the practical application angle, the agricultural wastes adsorption capacity a little less than, be difficult to satisfy industrial requirement to adsorbent.
Summary of the invention
It is the method for feedstock production cation adsorbent and the method for handling the waste water that contains the dye of positive ion with prepared cation adsorbent with the stalk that technical problem to be solved by this invention provides a kind of.
The technical scheme of technical solution problem of the present invention is:
1, the preparation method of cation adsorbent.
Stalk adding after pulverizing is dissolved with in the nonaqueous solvents of citric acid, the weight ratio of citric acid and stalk is not less than 1: 1, the volume of used nonaqueous solvents is can dissolve citric acid fully and can reflux and be advisable, the time of refluxing is not less than 12 hours, filter, be washed with distilled water to the pH value again for neutral, dry to water content less than 5%.
Described nonaqueous solvents comprises DMF, methyl alcohol, ethanol, dioxane etc.Preferred nonaqueous solvents is a dioxane.
In order to strengthen the adsorption capacity of cation adsorbent, also need above-mentioned product is added in the strong base solution of 0.01-0.2M, mixing time is not less than 0.5 hour, filters, and is washed with distilled water to pH value again and is neutrality, dry to water content less than 5%.
Described highly basic is NaOH, oxygen potassium oxide, calcium hydroxide etc.Preferred highly basic is NaOH, and preferred concentration is 0.05-0.1M.
2, the method that contains dye of positive ion waste water with prepared sorbent treatment.
Under room temperature, stirring condition, regulate pH value of waste water 〉=3.0 with acid or alkali, add prepared cation adsorbent, make amount 〉=0.8 gram of cation adsorbent in every liter of waste water, continue stirring and be no less than 40 minutes, isolate cation adsorbent, get final product.
Above-mentioned room temperature is 0.5～50 ℃.
Can isolate cation adsorbent with natural subsidence or centrifugal process.
Preferred process conditions are: under room temperature, stirring condition, regulate pH value of waste water 6-8 with acid or alkali, add prepared cation adsorbent, make the amount 0.8-1.5 gram of cation adsorbent in every liter of waste water, continue to stir 40-120 minute, isolate cation adsorbent, get final product.
Citric acid is a multicomponent organic acid, and by esterification, three carboxyls in the citric acid molecule have only the cellulose hydroxyl reaction in a carboxyl and the stalk, and two other carboxyl is used for the dye of positive ion of complexing waste water as active group.
Dissociation yield for two carboxyls improving adsorbent strengthens its cation complexing power, and prepared adsorbent is processed into carboxylic salts with highly basic.
Ion exchange resin is the ion exchange material of using always, but it exists the price height, can not biodegradation etc. shortcoming, the price of the cation adsorbent of the present invention's preparation is less than 1/10th of existing ion exchange resin, effect is lower slightly or be equivalent to ion exchange resin, good biological degradability is also arranged simultaneously, because it is cheap, adsorbent after the absorption can directly burn, do not need to regenerate, required cost is starkly lower than the identical ion exchange resin cost of decolorizing effect, and the present invention compared with prior art, economic benefit is very obvious, and the mankind's environmental protection cause is had significant meaning.
Description of drawings
The IR spectrum of Fig. 1 stalk and esterification stalk (A: stalk B: the esterification stalk)
Fig. 2 pH value is to the influence (dye strength: 250mg/l of Citrin ester stalk cation adsorbent two kinds of dyes of positive ion of absorption (methylenum careuleum and peacock green); Quantity of sorbent: 2g/l; Adsorption time: 10h)
Fig. 3 quantity of sorbent is to the influence (dye strength: 250mg/l of the stalk cation adsorbent absorption dye of positive ion; Adsorption time: 10h; PH:6)
Fig. 4 adsorption time is to the influence (dye strength: 250mg/l of the stalk cation adsorbent absorption dye of positive ion; Quantity of sorbent: 2g/l; PH:6)
The specific embodiment
Below by test obtain optimised process, by embodiment the present invention is made further description, but they are not limitation of the invention.
One, preparation of adsorbent
Technology 1:
Stalk is cut off into fragment about the about 10cm of length, and earth and dust are removed in the running water washing, dry to constant weight, with the stalk fragment crushing screening of oven dry, leave and take the stalk particle of 20-40 order size.At volume is to add 400 milliliters of dioxane and 6.3 gram citric acids in 1 liter the standard ground flask, behind the heating for dissolving citric acid, add 5 gram stalk particles, connect condensation reflux unit, add hot reflux 16～18h after, decompression steams dioxane, residue divides three washings with 400 milliliter of 95% ethanol, repeatedly wash neutrality with distilled water to pH, dry to water content less than 5%, obtain Citrin ester stalk cation adsorbent product.
Technology 2:
Operating procedure is with technology 1, and difference is: add 400 milliliters of absolute ethyl alcohols.
Technology 3:
With the product of technology 1, add the NaOH of 200 milliliter of 0.01 mol, stirred 2 hours, filtration is washed with distilled water to pH neutrality, dry to water content less than 5%, obtain Citrin ester stalk cation adsorbent product.
Technology 4:
Operating procedure is with technology 3, and difference is: add the KOH of 150 milliliter of 0.05 mol, stirred 1.5 hours.
Technology 5:
Operating procedure is with technology 3, and difference is: add the NaOH of 100 milliliter of 0.1 mol, stirred 1.5 hours.
As shown in Figure 1, in technology 1-5,, measured the FFIR of stalk modification front and back, esterification stalk 1732cm for confirming the esterification effect of stalk
-1Tangible carbonylic stretching vibration absworption peak appears in the wave number place, shows in the esterification stalk and has introduced carboxyl.
Two, adsorbent is to the processing of the dye of positive ion
Used adsorbent is the product of technology 5 gained.
Used methylenum careuleum, peacock green meet the reagent standard.
Technology 6:
Under room temperature, stirring condition, contain dye of positive ion pH value of waste water=3.0 with the acid adjusting, add prepared cation adsorbent, the amount that makes cation adsorbent in every liter of waste water is 0.8 gram, continue to stir many 120 minutes, isolate cation adsorbent, get final product.
Technology 7:
Under room temperature, stirring condition, contain dye of positive ion pH value of waste water=7.0 with acid or alkali adjusting, add prepared cation adsorbent, the amount that makes cation adsorbent in every liter of waste water is 1.5 grams, continue to stir 40 minutes, isolate cation adsorbent, get final product.
Technology 8:
Under room temperature, stirring condition, contain dye of positive ion pH value of waste water=8.0 with acid or alkali adjusting, add prepared cation adsorbent, the amount that makes cation adsorbent in every liter of waste water is 2.0 grams, continue to stir 40 minutes, isolate cation adsorbent, get final product.
Detection method:
With 752-W type ultraviolet-visible spectrophotometer (the 752-W type of the supernatant behind the separation cation adsorbent, Shanghai the 3rd analytical instrument factory) under two kinds of dyes of positive ion maximum absorption wavelength separately, measures light absorption value, calculate dye strength in the solution according to calibration curve; Dyestuff adsorption rate (%) q is calculated as follows:
q＝(C
0-C
e)/C
0；
In the formula, C
0(mg/L) be the dye solution initial concentration, C
eDye strength in the solution when (mg/L) being adsorption equilibrium.The experiment triplicate all uses the dye solution of no adsorbent to test in contrast under similarity condition at every turn, thereby gets rid of the error that container may cause dyestuff absorption.
The influence of pH value:
As shown in Figure 2: when pH=2, the adsorption rate of methylenum careuleum and peacock green is minimum, is respectively 95.47 and 33.75%.Along with the pH value rises, the adsorption rate of two kinds of dyestuffs all raises, and methylenum careuleum reaches maximum in pH 〉=3 an o'clock adsorption rate, and peacock green reaches maximum in pH 〉=4 an o'clock adsorption rate, and both maximum adsorption rates are respectively greater than 99% and 98%.Waste water is when hanging down the pH value, and the carboxyl that participates in dyestuff absorption in the adsorbent is in conjunction with H
+Back neutral is unfavorable for the absorption of the dye of positive ion, along with the pH value raises, and the H in the functional group
+Reduce, the ability of removing the dye of positive ion in the waste water strengthens.Consider that the pH value that contains dye of positive ion waste water is neutral substantially, so preferred pH value is 6-8.
The influence of quantity of sorbent:
As shown in Figure 3: the increase of adsorbent consumption increases the adsorption rate of two kinds of dyes of positive ion, when dye strength is 250mg/l, the adsorbent that adds 0.8 gram in every liter of waste water is gone up substantially and can be removed in the waste water 80% the dye of positive ion, reach 1.5g or above adsorbent consumption in every liter of waste water and can remove methylenum careuleum and peacock green in the solution substantially, clearance is respectively greater than 99% and 98%
The influence of adsorption time:
As shown in Figure 4: the absorption of visible incipient stage two kinds of dyestuffs is very fast, it after the quick absorption of dyestuff a diffusion absorption phase that adsorption rate is gradually slow, methylenum careuleum and 40 minutes adsorption rate of peacock green are respectively about 80%, 120 minutes adsorption rate reaches about 90%, and being adsorbed on about 10 hours of last two kinds of dyestuffs reaches adsorption equilibrium.
Claims (6)
1, a kind of preparation method of cation adsorbent, it is characterized in that: the stalk adding after will pulverizing is dissolved with in the nonaqueous solvents of citric acid, the weight ratio of citric acid and stalk is not less than 1: 1, the volume of used nonaqueous solvents is can dissolve citric acid fully and can reflux and be advisable, the time of refluxing is not less than 12 hours, filter, be washed with distilled water to pH value again and be neutrality, dry to water content less than 5%.
2, the preparation method of a kind of cation adsorbent according to claim 1 is characterized in that: nonaqueous solvents is a dioxane.
3, the preparation method of a kind of cation adsorbent according to claim 1, it is characterized in that: the product of claim 1 is added in the strong base solution of 0.01-0.2M, and mixing time is not less than 0.5 hour, filters, be washed with distilled water to the pH value again for neutral, dry to water content less than 5%.
4, the preparation method of a kind of cation adsorbent according to claim 3 is characterized in that: highly basic is NaOH, and concentration is 0.05-0.1M.
5, a kind of application of cation adsorbent, it is characterized in that: under room temperature, stirring condition, regulate pH value of waste water 〉=3.0 with acid or alkali, add prepared cation adsorbent, make amount 〉=0.8 gram of cation adsorbent in every liter of waste water, continue stirring and be no less than 40 minutes, isolate cation adsorbent, get final product.
6, according to the application of the described a kind of cation adsorbent of claim 5, it is characterized in that: regulate pH value of waste water 6-8 with acid or alkali, add the amount 0.8-1.5 gram that makes cation adsorbent in every liter of waste water, mixing time is 40-120 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100404858A CN100345627C (en) | 2005-06-08 | 2005-06-08 | Process for preparing cation sorbent and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100404858A CN100345627C (en) | 2005-06-08 | 2005-06-08 | Process for preparing cation sorbent and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1876227A true CN1876227A (en) | 2006-12-13 |
| CN100345627C CN100345627C (en) | 2007-10-31 |
Family
ID=37508886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100404858A Expired - Fee Related CN100345627C (en) | 2005-06-08 | 2005-06-08 | Process for preparing cation sorbent and its application |
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| Country | Link |
|---|---|
| CN (1) | CN100345627C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101091906B (en) * | 2007-06-13 | 2010-04-07 | 山东大学 | Cationoid adsorbent for quarternary ammonium salt of agricultural waste, and preparation technique |
| CN101342485B (en) * | 2008-07-03 | 2010-06-02 | 山东大学 | Method for preparing quaternary amines salt cationic adsorption agent with plant of high cellulose content |
| CN101733075B (en) * | 2008-11-07 | 2013-07-03 | 中国科学院沈阳应用生态研究所 | Preparation method of modified fungus bran adsorbent for discoloring dye waste water |
| CN103566905A (en) * | 2013-10-29 | 2014-02-12 | 湖南大学 | Modified wood chip adsorbent, and preparation method and application thereof in treating wastewater containing basic dye |
| CN103896358A (en) * | 2014-03-06 | 2014-07-02 | 西安工程大学 | Method of treating printing and dyeing wastewater by adopting cationic protein modified waste straws |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63287593A (en) * | 1987-05-19 | 1988-11-24 | Toray Ind Inc | Straw-type water purifier |
| KR20010087859A (en) * | 2000-03-07 | 2001-09-26 | 류진곤 | Water-purifying device by way of rice straw |
| CN1482106A (en) * | 2002-09-10 | 2004-03-17 | 上海百成生物科技有限公司 | Compound biological bacterium fertilizer |
-
2005
- 2005-06-08 CN CNB2005100404858A patent/CN100345627C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101091906B (en) * | 2007-06-13 | 2010-04-07 | 山东大学 | Cationoid adsorbent for quarternary ammonium salt of agricultural waste, and preparation technique |
| CN101342485B (en) * | 2008-07-03 | 2010-06-02 | 山东大学 | Method for preparing quaternary amines salt cationic adsorption agent with plant of high cellulose content |
| CN101733075B (en) * | 2008-11-07 | 2013-07-03 | 中国科学院沈阳应用生态研究所 | Preparation method of modified fungus bran adsorbent for discoloring dye waste water |
| CN103566905A (en) * | 2013-10-29 | 2014-02-12 | 湖南大学 | Modified wood chip adsorbent, and preparation method and application thereof in treating wastewater containing basic dye |
| CN103566905B (en) * | 2013-10-29 | 2015-08-12 | 湖南大学 | Modified wood chips adsorbent, preparation method and in process containing the application in basic-dyeable fibre waste water |
| CN103896358A (en) * | 2014-03-06 | 2014-07-02 | 西安工程大学 | Method of treating printing and dyeing wastewater by adopting cationic protein modified waste straws |
| CN103896358B (en) * | 2014-03-06 | 2016-08-24 | 西安工程大学 | Use the method that the modified abandoned straw of cationic protein processes dyeing waste water |
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| Publication number | Publication date |
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| CN100345627C (en) | 2007-10-31 |
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