CN103464116A - Preparation method and applications of epichlorohydrin-modified vegetable sponge adsorbent - Google Patents
Preparation method and applications of epichlorohydrin-modified vegetable sponge adsorbent Download PDFInfo
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- CN103464116A CN103464116A CN2013104434804A CN201310443480A CN103464116A CN 103464116 A CN103464116 A CN 103464116A CN 2013104434804 A CN2013104434804 A CN 2013104434804A CN 201310443480 A CN201310443480 A CN 201310443480A CN 103464116 A CN103464116 A CN 103464116A
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Abstract
The invention discloses a preparation method and application technology of an epichlorohydrin-modified vegetable sponge adsorbent. The preparation method is characterized by comprising the steps of: removing peels and kernels of matured loofah, washing with water so as to remove mud and impurities, drying, crushing, treating with NaOH and OP water solution to be dried to obtain basified vegetable sponge; in a reactor, adding the following constituents in percentage by mass: 25-40% of epichlorohydrin, 10-25% of basified vegetable sponge, 4-8% of NaOH and 32-55% of water, wherein the sum of all constituents is 100%; stirring and performing reflux reaction at constant temperature of 60-70 DEG C for 1.0-4 hours, cooling and then washing and leaching with deionized water until the filtrate is neutral, washing with less ethanol, drying in a vacuum drying tank with 50-55 DEG C, to obtain the epichlorohydrin-modified vegetable sponge adsorbent. The adsorbent has high adsorption capacity to basic dyestuff, and is excellent in physico-chemical and mechanical properties, strong in regenerative capability, and capable of being repeatedly used, thus being both low-cost and green and environmentally-friendly.
Description
Technical field
The preparation method who the present invention relates to a kind of biological adsorption agent reaches the applied technical field to Dye Adsorption in industrial wastewater, and particularly a kind of epoxychloropropane is modified luffa absorbent preparation method and application technology.
Background technology
Along with industrial fast development, the consumption of dyestuff is also increasing, and synthetic dyestuffs are compared with natural dye, has the advantages such as easy to use, stable in properties, cost be low, wide in variety and is widely used in weaving, papermaking, pharmacy and food industry.Waste water from dyestuff has become one of at present main pollutant effluents of China, and solving problem of environmental pollution is very urgent problem.The structure of most synthetic dyestuffs has complicated aromatic ring structure, and character is very stable, is difficult to biodegradation.These dyestuffs can threaten to the mankind's health, enter food chain, may cause people's allergy, the various injuries such as sudden change of cancer and gene.Being widely used of dyestuff causes being discharged in a large number in natural water of dye wastewater, cause water pollution, even if a small amount of waste water from dyestuff discharge also can cause water body painted, heavy damage the natural, ecological chain of water body, also greatly reduce the economic worth of water body simultaneously.Therefore, the dyestuff of how removing in industrial wastewater is the focus of domestic and international experts and scholars' research.In industrial production, waste water from dyestuff adopts flocculence, oxidizing process, biological treatment, membrane filter method, absorption method etc. usually.Wherein to have technique simple for absorption method, and adsorption rate is high, applied widely, and the characteristics such as stable in properties are used widely in sewage disposal.
Shortage of resources and environmental pollution have become two large subject matters of the world today, therefore, utilize natural reproducible resource, and the friendly type product of development environment and technology will become the inexorable trend of sustainable development.Vascular bundle in the ripening fruits that luffa is Curcurbitaceae annual herb plant sponge gourd is the withered old fruit of sponge gourd in other words.Sponge gourd is China's summer and autumn Common Vegetables, there is product most provinces and regions, the whole nation, for the cultivation product, luffa is the very abundant regenerated resources of the earth, have that light weight is inexpensive, the characteristics such as degradable and environmental friendliness, the net that luffa is formed by the thread fiber interweaving of multilayer, body is light, matter is tough and tensile, can not fracture, simultaneously containing xylan, mannosan, galactan etc., and it has hydrophily, also with abundant dentate, be easy to carry out chemical modification, the application in adsorption of metal ions as adsorbent after domestic luffa modification.
Domestic luffa is the application in adsorption of metal ions as adsorbent, disclose luffa application in adsorption of metal ions as adsorbent to many kinds of metal ions absorption property and luffa in the patent that application number is 200810034734.6, wherein luffa is to Cu
2+and Zn
2+desorption rate all in 40% left and right, luffa is to Cu
2+adsorbance be respectively 0.16mmol/g, to Zn
2+adsorbance be about 0.39mmol/g, in the system that is 1 at pH, desorption rate is respectively 46%, 47%; Disclose alkalization modifying method and the application thereof of luffa in the patent that is 200810034735.0 at application number, its alkali treatment luffa is to Zn
2+adsorbance than Cu
2+height, and the adsorbance gap is larger, and through the Atomic absorption quantitative analysis, luffa is to Cu
2+adsorbance be about 7 ~ 8mg/g, to Zn
2+adsorbance be about 21 ~ 22mg/g; Disclose the preparation method of etherized luffa and the application in adsorption of metal ions thereof in the patent that is 200810034737.X at application number, its etherized luffa is to Fe
3+maximal absorptive capacity be 27.4mg/g.To Zn
2+maximal absorptive capacity be 36.3mg/g; Disclose citric acid loofah sponge preparation method agent application in the patent that application number is 201110276244.9, its citric acid loofah sponge is to Cd
2+adsorption capacity can be up to 189mg/g, high adsorption rate can reach 98.5%, to Pb
2+maximal absorptive capacity be 285mg/g, high adsorption rate can reach 99.2%, to the maximal absorptive capacity of methylene blue, is 316mg/g, high adsorption rate can reach 96.2%, has the carboxylic acid characteristic, can be directly to absorption and the wash-out of each metal ion species, organic dyestuff in water body,
Since the nineties in 20th century, people utilize natural fiber cheap and easy to get to obtain more research as adsorbent in the processing of waste water from dyestuff.Neha Gupta etc. has studied methylene blue and the malachite green in potato stalk adsorbed water, its maximum adsorption capacity is: 52.6mg/g, (Neha Gupta, Application of potato (Solanum tuberosum) plant wastes for the removal of methylene blue and malachite green dye from aqueous solution. Arabian Journal of Chemistry, (2011)); Runping Han etc. has studied the fallen leaves of Chinese parasol tree tree to the methylene blue adsorption number in water, its maximum adsorption capacity is: 89.7mg/g, (Runping Han, Biosorption of methylene blue from aqueous solution by fallen phoenix tree ' s leaves. Journal of Hazardous Materials, 141 (2007) 156 – 162); Li Shan etc., studied methylene blue in epoxychloropropane modified peanut shell adsorbed water, and its maximum adsorption capacity to methyl blue is: 25mg/g, (Li Shan etc., the research of methylene blue in epoxychloropropane modified peanut shell adsorbed water, dyestuff and dyeing, 2008,45(2): 49 ~ 51); Deng Jun is strong etc., has studied the red absorption property of bagasse centering, and the red maximum adsorption capacity of its centering is: 27.10mg/g, (Deng Junqiang etc., the research of the experiment of the absorption property that the bagasse centering is red, water science and engineering technology, 2012(5), 24 ~ 28).Natural macromolecular material is utilized as adsorbent has the advantages such as renewable, degradable, environmental protection be friendly, cheap, is important living resources.
Summary of the invention
One of purpose of the present invention is to provide a kind of epoxychloropropane and modifies luffa absorbent preparation method, and it is larger as the adsorption capacity of the adsorbent of dyestuff in aqueous systems that the epoxychloropropane that mainly makes to obtain is modified the luffa adsorbent.
Purpose of the present invention is achieved through the following technical solutions.
A kind of epoxychloropropane is modified luffa absorbent preparation method, is characterised in that the method has following processing step:
(1) luffa pretreatment: luffa derives from the sponge gourd fruit, by the peeling stoning, obtains, and luffa is cut into small pieces after the clear water cleaning, drying and is pulverized, and by 10 purpose sieve, obtains the pretreatment luffa;
(2) alkalization luffa: the pretreatment luffa is pressed to 100 ~ 200g/L solid-to-liquid ratio, with being 2 ~ 5% and containing the emulsifier op-10 mass percentage concentration solution that is 0.5 ~ 1.5% containing the NaOH mass percentage concentration, soaking at room temperature 24 ~ 36 h, boil again 0.5 ~ 1.0 h, constantly add water during azeotropic, to keep liquor capacity constant, cooling rear extremely neutral with the deionized water washing, put into again isopropyl alcohol and soak 2 ~ 4 h, dry under 75 ℃ after suction filtration, obtain the luffa that alkalizes;
(3) epoxychloropropane is modified the luffa preparation: in reactor, add epoxychloropropane by following composition mass percent: 25 ~ 40%, and alkalization luffa: 10 ~ 25%, NaOH:4 ~ 8%; Water: 32 ~ 55%, each component sum is absolutely, in 60 ~ 70 ℃ of constant temperature, stirring, back flow reaction 1.0 ~ 4 h, after cooling, with deionized water washing, suction filtration, till being neutrality to filtrate, with after a small amount of ethanol washing, be placed on drying in 50 ~ 55 ℃ of vacuum drying chambers, obtain epoxychloropropane and modify luffa.
Another object of the present invention is to provide a kind of epoxychloropropane modification luffa adsorbent adsorbs basic-dyeable fibre in aqueous systems, and characteristics are: the epoxychloropropane prepared is modified to deionized water immersion 4 ~ 6h for the luffa adsorbent, adsorb by static method.
The epoxychloropropane prepared is modified to the luffa adsorbent and by deionized water, soak 4 ~ 6h, by dynamic method absorption.
Advantage of the present invention and effect are:
(1) epoxychloropropane that the present invention obtains is modified the luffa adsorbent and is had good physical and chemical stability and excellent mechanical strength; the adsorption capacity that compares dyestuff with modification tangerine peel, modified bamboo bits, broomcorn straw is large, and the Reusability number of times can reach more than 10 times;
(2) epoxychloropropane that the present invention obtains is modified absorption and the wash-out of luffa adsorbent to various basic-dyeable fibres in water body, and adsorption efficiency is high, and the speed of absorption is fast, and desorption performance is good, can in wider soda acid scope, use;
(3) good stability, be the natural green product, biodegradable;
(4) the synthetic condition of crossing range request is easily controlled, and energy consumption is low, simple to operate, in whole production process, without " three wastes " discharge, belongs to process for cleanly preparing, is easy to suitability for industrialized production.
The specific embodiment
Embodiment 1
(1) luffa pretreatment: luffa derives from the sponge gourd fruit, by the peeling stoning, obtains, and luffa is cut into small pieces after the clear water cleaning, drying and is pulverized, and by 10 purpose sieve, obtains the pretreatment luffa;
(2) alkalization luffa: by pretreatment luffa 10g, with 100mL, containing the NaOH mass percentage concentration, be 2% and containing the emulsifier op-10 mass percentage concentration solution that is 1.0%, soaking at room temperature 24h, boil again 0.5 h, constantly add water during azeotropic, to keep liquor capacity constant, cooling rear extremely neutral with the deionized water washing, put into again isopropyl alcohol and soak 2 h, dry under 75 ℃ after suction filtration, obtain the luffa that alkalizes;
(3) epoxychloropropane is modified the luffa preparation: in reactor, add epoxychloropropane: 15mL, alkalization luffa: 6g, NaOH:4g; Water: 30mL%, in 65 ℃ of constant temperature, stirring, back flow reaction 2 h, cooling after, with deionized water washing, suction filtration, till being neutrality to filtrate, with after a small amount of ethanol washing, be placed in 55 ℃ of vacuum drying chambers dryly, obtain epoxychloropropane modification luffa.
Embodiment 2
(1) luffa pretreatment: luffa derives from the sponge gourd fruit, by the peeling stoning, obtains, and luffa is cut into small pieces after the clear water cleaning, drying and is pulverized, and by 10 purpose sieve, obtains the pretreatment luffa;
(2) alkalization luffa: by pretreatment luffa 20g, with 100mL, containing the NaOH mass percentage concentration, be 3% and containing the emulsifier op-10 mass percentage concentration solution that is 1.0%, soaking at room temperature 24h, boil again 0.5 h, constantly add water during azeotropic, to keep liquor capacity constant, cooling rear extremely neutral with the deionized water washing, put into again isopropyl alcohol and soak 2 h, dry under 75 ℃ after suction filtration, obtain the luffa that alkalizes;
(3) epoxychloropropane is modified the luffa preparation: in reactor, add respectively epoxychloropropane: 25mL, alkalization luffa: 10g, NaOH:5g; Water: 30mL%, in 70 ℃ of constant temperature, stirring, back flow reaction 1 h, cooling after, with deionized water washing, suction filtration, till being neutrality to filtrate, with after a small amount of ethanol washing, be placed in 55 ℃ of vacuum drying chambers dryly, obtain epoxychloropropane modification luffa.
Embodiment 3
(1) luffa pretreatment: luffa derives from the sponge gourd fruit, by the peeling stoning, obtains, and luffa is cut into small pieces after the clear water cleaning, drying and is pulverized, and by 10 purpose sieve, obtains the pretreatment luffa;
(2) alkalization luffa: by pretreatment luffa 15g, with 100mL, containing the NaOH mass percentage concentration, be 4% and containing the emulsifier op-10 mass percentage concentration solution that is 0.5%, soaking at room temperature 30h, boil again 0.8 h, constantly add water during azeotropic, to keep liquor capacity constant, cooling rear extremely neutral with the deionized water washing, put into again isopropyl alcohol and soak 3 h, dry under 75 ℃ after suction filtration, obtain the luffa that alkalizes;
(3) epoxychloropropane is modified the luffa preparation: in reactor, add respectively epoxychloropropane: 27mL, alkalization luffa: 15g, NaOH:3g; Water: 25mL%, in 60 ℃ of constant temperature, stirring, back flow reaction 3 h, cooling after, with deionized water washing, suction filtration, till being neutrality to filtrate, with after a small amount of ethanol washing, be placed in 55 ℃ of vacuum drying chambers dryly, obtain epoxychloropropane modification luffa.
Embodiment 4
(1) luffa pretreatment: luffa derives from the sponge gourd fruit, by the peeling stoning, obtains, and luffa is cut into small pieces after the clear water cleaning, drying and is pulverized, and by 10 purpose sieve, obtains the pretreatment luffa;
(2) alkalization luffa: by pretreatment luffa 30g, with 200mL, containing the NaOH mass percentage concentration, be 5% and containing the emulsifier op-10 mass percentage concentration solution that is 0.5%, soaking at room temperature 36h, boil again 0.5 h, constantly add water during azeotropic, to keep liquor capacity constant, cooling rear extremely neutral with the deionized water washing, put into again isopropyl alcohol and soak 4 h, dry under 75 ℃ after suction filtration, obtain the luffa that alkalizes;
(3) epoxychloropropane is modified the luffa preparation: in reactor, add respectively epoxychloropropane: 20mL, alkalization luffa: 10g, NaOH:2g; Water: 28mL%, in 70 ℃ of constant temperature, stirring, back flow reaction 1 h, cooling after, with deionized water washing, suction filtration, till being neutrality to filtrate, with after a small amount of ethanol washing, be placed in 55 ℃ of vacuum drying chambers dryly, obtain epoxychloropropane modification luffa.
Embodiment 5
(1) luffa pretreatment: luffa derives from the sponge gourd fruit, by the peeling stoning, obtains, and luffa is cut into small pieces after the clear water cleaning, drying and is pulverized, and by 10 purpose sieve, obtains the pretreatment luffa;
(2) alkalization luffa: by pretreatment luffa 30g, with 200mL, containing the NaOH mass percentage concentration, be 2.5% and containing the emulsifier op-10 mass percentage concentration solution that is 1.0%, soaking at room temperature 30h, boil again 0.5 h, constantly add water during azeotropic, to keep liquor capacity constant, cooling rear extremely neutral with the deionized water washing, put into again isopropyl alcohol and soak 3 h, dry under 75 ℃ after suction filtration, obtain the luffa that alkalizes;
(3) epoxychloropropane is modified the luffa preparation: in reactor, add respectively epoxychloropropane: 25mL, alkalization luffa: 25g, NaOH:4g; Water: 46mL%, in 65 ℃ of constant temperature, stirring, back flow reaction 2h, cooling after, with deionized water washing, suction filtration, till being neutrality to filtrate, with after a small amount of ethanol washing, be placed in 55 ℃ of vacuum drying chambers dryly, obtain epoxychloropropane modification luffa.
Embodiment 6
Take 0.50g epoxychloropropane modification luffa adsorbent and be placed in 250mL tool plug conical flask, adding 100mL concentration is in the 550mg/L dye solution, take the pH value of acid or alkali regulation system in 4.5 ~ 8.5 scopes, at room temperature concussion absorption 0.5 ~ 1.5 h, get supernatant, concentration with the spectrophotometric determination dyestuff, concentration difference according to dyestuff in water before and after absorption, calculate epoxychloropropane and modify the adsorption capacity of luffa adsorbent, the prepared epoxychloropropane of embodiment 1 ~ 5 is modified the luffa adsorbent adsorption capacity result of dyestuff is listed in to table 1.
PH value adsorbent not impact of absorption on dyestuff in 4.5 ~ 8.5 scopes as seen from Table 1, more than at room temperature concussion absorption 0.5h, dyestuff adsorbs fully substantially, and the adsorption capacity of methylene blue, crystal violet, basic fuchsin and malachite green can reach 156.5mg/g, 180.5mg/g, 157.1mg/g, 167.2mg/g respectively.
Table 1 epoxychloropropane is modified the adsorption capacity measurement result of luffa adsorbent to dyestuff
| The adsorbent title | pH | Adsorption time (h) | Methylene blue (mg/g) | Crystal violet (mg/g) | Basic fuchsin (mg/g) | Malachite green (mg/g) |
| Embodiment 1 | 4.5 | 0.5 | 155.1 | 178.2 | 156.2 | 165.8 |
| Embodiment 1 | 6.0 | 1.0 | 154.2 | 179.9 | 157.1 | 166.2 |
| Embodiment 2 | 7.0 | 1.5 | 153.2 | 177.5 | 156.5 | 165.6 |
| Embodiment 2 | 8.0 | 1.0 | 153.2 | 178.8 | 156.2 | 166.1 |
| Embodiment 3 | 5.0 | 1.5 | 156.1 | 179.1 | 157.1 | 166.8 |
| Embodiment 3 | 5.5 | 0.5 | 156.5 | 178.2 | 156.2 | 167.2 |
| Embodiment 4 | 6.5 | 1.5 | 155.9 | 180.5 | 154.6 | 164.9 |
| Embodiment 4 | 7.5 | 0.5 | 154.2 | 178.8 | 155.8 | 165.6 |
| Embodiment 5 | 5.5 | 1.2 | 156.5 | 179.5 | 156.2 | 167.1 |
| Embodiment 5 | 8.5 | 1 | 152.5 | 178.7 | 157.4 | 165.2 |
Embodiment 7
Take 1.0g epoxychloropropane modification luffa adsorbent and be placed in 250mL tool plug conical flask, adding 100mL concentration is in the 200mg/L dye solution, take the pH value of acid or alkali regulation system in 5.5 scopes, at room temperature concussion absorption 1 h, get supernatant, concentration with the spectrophotometric determination dyestuff, concentration difference according to dyestuff in water before and after absorption, calculate epoxychloropropane and modify the clearance of luffa adsorbent to dyestuff, the prepared epoxychloropropane of embodiment 1 ~ 5 is modified the luffa adsorbent clearance result of dyestuff is listed in to this adsorbent of table 2. to methylene blue, crystal violet, four kinds of dyestuffs of basic fuchsin and malachite green going in water processed all more than 95%, reach as high as 98.6%%.
Table 2 epoxychloropropane is modified the clearance of luffa adsorbent to dyestuff
| The adsorbent title | Methylene blue (%) | Crystal violet (%) | Basic fuchsin (%) | Malachite green (%) |
| Embodiment 1 | 97.6 | 97.8 | 95.6 | 95.8 |
| Embodiment 2 | 95.5 | 97.2 | 96.6 | 96.2 |
| Embodiment 3 | 98.6 | 97.5 | 98.1 | 96.2 |
| Embodiment 4 | 98.2 | 98.6 | 97.5 | 98.5 |
| Embodiment 5 | 96.5 | 96.5 | 95.6 | 98.2 |
Claims (5)
1. an epoxychloropropane is modified luffa absorbent preparation method, is characterised in that the method has following processing step:
(1) luffa pretreatment: luffa derives from the sponge gourd fruit, by the peeling stoning, obtains, and luffa is cut into small pieces after the clear water cleaning, drying and is pulverized, and by 10 purpose sieve, obtains the pretreatment luffa;
(2) alkalization luffa: the pretreatment luffa is pressed to 100 ~ 200g/L solid-to-liquid ratio, with being 2 ~ 5% and containing the emulsifier op-10 mass percentage concentration solution that is 0.5 ~ 1.5% containing the NaOH mass percentage concentration, soaking at room temperature 24 ~ 36 h, boil again 0.5 ~ 1.0 h, cooling rear extremely neutral with the deionized water washing, put into again isopropyl alcohol and soak 2 ~ 4 h, dry under 75 ℃ after suction filtration, obtain the luffa that alkalizes;
(3) epoxychloropropane is modified the luffa preparation: in reactor, add epoxychloropropane by following composition mass percent: 25 ~ 40%, and alkalization luffa: 10 ~ 25%, NaOH:4 ~ 8%; Water: 32 ~ 55%, each component sum is absolutely, in 60 ~ 70 ℃ of constant temperature, stirring, back flow reaction 1.0 ~ 4 h, after cooling, with deionized water washing, suction filtration, till being neutrality to filtrate, with after a small amount of ethanol washing, be placed on drying in 50 ~ 55 ℃ of vacuum drying chambers, obtain epoxychloropropane and modify luffa.
2. modify the luffa absorbent preparation according to the epoxychloropropane described in claim 1, it is characterized in that: pluck when luffa is sponge gourd fruit maturation, pericarp flavescence, inner drying up, remove crust and pulp.
3. modify the luffa absorbent preparation according to the epoxychloropropane described in claim 1, it is characterized in that: in step (2), emulsifier op-10 is the condensation product of alkyl phenol and oxirane, belongs to nonionic surface active agent.
4. modify the luffa absorbent preparation according to the epoxychloropropane described in claim 1, it is characterized in that the application to water neutral and alkali Dye Adsorption.
5. according to the basic-dyeable fibre described in claim 4, be methylene blue, crystal violet, basic fuchsin, malachite green etc.
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| CN103933944A (en) * | 2014-03-13 | 2014-07-23 | 济南大学 | Preparation and application of gamma-(aminopropyl)triethoxysilane modified loofah sponge adsorbent |
| CN105214631A (en) * | 2015-11-16 | 2016-01-06 | 鄢祺丹 | A kind of flexible PCB waste water treating agent based on modification biological sponge iron and preparation method |
| CN105618001A (en) * | 2016-02-17 | 2016-06-01 | 济南大学 | Preparation method of cocamidopropyl betaine modified loofah sponge adsorbent |
| CN107233863A (en) * | 2017-06-23 | 2017-10-10 | 河北省廊坊水文水资源勘测局 | Iron, cadmium, arsenic ion adsorbent and preparation method thereof in a kind of water |
| CN115228444A (en) * | 2022-06-08 | 2022-10-25 | 湖北科技学院 | Radiation preparation method of loofah sponge-based adsorbent capable of efficiently adsorbing cationic dye |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103933944A (en) * | 2014-03-13 | 2014-07-23 | 济南大学 | Preparation and application of gamma-(aminopropyl)triethoxysilane modified loofah sponge adsorbent |
| CN103933944B (en) * | 2014-03-13 | 2015-10-21 | 济南大学 | Gamma-aminopropyl-triethoxy-silane modifies the preparations and applicatio of loofah adsorbent |
| CN105214631A (en) * | 2015-11-16 | 2016-01-06 | 鄢祺丹 | A kind of flexible PCB waste water treating agent based on modification biological sponge iron and preparation method |
| CN105618001A (en) * | 2016-02-17 | 2016-06-01 | 济南大学 | Preparation method of cocamidopropyl betaine modified loofah sponge adsorbent |
| CN105618001B (en) * | 2016-02-17 | 2017-09-22 | 济南大学 | A kind of preparation of Cocoamidopropyl betaine modified loofah sponge adsorbent |
| CN107233863A (en) * | 2017-06-23 | 2017-10-10 | 河北省廊坊水文水资源勘测局 | Iron, cadmium, arsenic ion adsorbent and preparation method thereof in a kind of water |
| CN107233863B (en) * | 2017-06-23 | 2019-08-09 | 河北省廊坊水文水资源勘测局 | Iron, cadmium, arsenic ion adsorbent and preparation method thereof in a kind of water |
| CN115228444A (en) * | 2022-06-08 | 2022-10-25 | 湖北科技学院 | Radiation preparation method of loofah sponge-based adsorbent capable of efficiently adsorbing cationic dye |
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Application publication date: 20131225 |