CN103566909A - Preparation method and application of citric acid cotton stalk skins - Google Patents
Preparation method and application of citric acid cotton stalk skins Download PDFInfo
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Abstract
The invention discloses a preparation method and an application technology of citric acid cotton stalk skins. The preparation method is characterized by comprising the steps of in a reactor, adding the following components in percentage by mass: 40-75% of deionized water, 10-35% of citric acid, 2-10% of sodium hypophosphite and 8-20% of unglued cotton stalk skins; reacting for 2-6 hours at room temperature, heating to 60-70 DEG C to react for 20-30 hours, then heating to 130 DEG C to react for 2-4 hours, cooling, washing with deionized water, performing suction filtration, soaking in a 10-20% magnesium sulfate solution according to a standard that solids are completely soaked into the solution, performing suction filtration, washing with a 2-4% magnesium sulfate solution, and drying to obtain a citric acid cotton stalk skin adsorbent. The adsorbent can be directly used for adsorbing various dyes in a water body, and is high in adsorption efficiency and adsorption rate, strong in regeneration capacity and capable of being used repeatedly, so that wastes of cotton stalks are utilized, the cost is saved and an effect of environmental protection is achieved.
Description
Technical field
The invention belongs to chemosynthesis technical field, relate to preparation method and the application technology of the cotton stalk skin of citric acid, specifically a kind of cotton stalk skin method of citric acid and application technology to organic dyestuff absorption in water body prepared.
Background technology
China is Chan Mian big country in the world, and sown areas of cotton are at more than 50 ten thousand hectares.Cotton stalk is that cotton grower wins the discarded object after cotton, and cotton stalk skin is a kind of good bast that is grown in cotton stalk surface.Cotton stalk is produced in about 4000kg in per hectare cotton field, and cotton stalk skin accounts for 26% left and right, and the cotton stalk annual production of China reaches more than 1,500 ten thousand tons, has the cotton stalk skin resource of cotton stalk skin approximately 400 Duo Wan Dun，Yi Ci China and abundant.Cotton stalk, as agricultural residue, is burnt as fuel mostly in rural area, and all the other cannot utilize and become waste material, very unfortunate.Made full use of these and can create considerable economic benefit, we utilize cotton stalk hide fiber element synthesizing new adsorbent for the absorption of Heavy Metals in Waters ion, make this adsorbent have natural, green, biodegradable feature.
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 I i of water body right, 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. conventionally.Wherein to have technique simple for absorption method, and adsorption rate is high, applied widely, and the features such as stable in properties are used widely in sewage disposal.
Since the nineties in 20th century, people utilize natural fiber cheap and easy to get as adsorbent, in the processing of waste water from dyestuff, to obtain more research.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); Gong Xinhuai etc., have studied citric acid-modified bamboo bits absorption methylene blue, and it to the maximum adsorption capacity of methyl blue is: 125mg/g, (Gong Xinhuai etc., dynamics and the thermodynamic analysis of citric acid-modified bamboo bits absorption methylene blue, Yichun College's journal, 2012,34(8), 47 ~ 49); Poplar is superfine, and peanut hull meal is removed the research of azo dyes in the aqueous solution, biology magazine, 2005,22(2) 45 ~ 48 as biological adsorption agent; Li Ronghua etc., studied the absorption of citric acid-modified orange skin to methyl blue in water, it to the maximum adsorption capacity of methyl blue is: 189.92mg/g, (Li Ronghua etc., the absorption of citric acid-modified orange skin to methyl blue in water, Journal of Northwest Sci Tech University of Agriculture and Forestry (natural science edition), 2009,37(10), 173 ~ 179); Chinese Patent Application No. is: in 201110208310.9 patent, disclose a kind of preparation method and application of citric acid modified rape straw adsorbent, it is characterized in that, wash clean dry rape straw soak 24h with 20% isopropyl alcohol, after separated being dried, use again the soaking with sodium hydroxide of 0.1mol/L, stirring reaction 1 h, be washed to pH=7, dry, react 30min with the citric acid stirring at room of 0.5mol/L again, be warming up to 50 ℃ of forced air drying 24 h, thermalization reaction 90min under the 120 ℃ of air blast conditions that heat up again, cooling washing; These agriculture and forestry are discarded to be utilized adsorbent as water treatment and to have the advantages such as renewable, degradable, environmental protection be friendly, cheap, important living resources, but part also comes with some shortcomings, as their bad mechanical strength, easily corrosion in water, the reusable number of times of adsorbent is very low, and adsorption capacity is limited.
Summary of the invention
One of object of the present invention is to provide the cotton stalk peel preparation method of a kind of citric acid, mainly makes the cotton stalk skin of citric acid that obtains larger as the adsorbance of the adsorbent of organic dyestuff in aqueous systems.
Object of the present invention is achieved through the following technical solutions.
A cotton stalk skin absorbent preparation method, is characterised in that the method has following processing step:
(1) the cotton stalk skin of pretreatment: get cotton stalk and soak 24 ~ 36 h in room temperature water, peel off the outer field skin of cotton stalk, washing, impurity elimination, pulverize after dry, by 20-40 object sieve, obtain the cotton stalk skin of pretreatment;
(2) the cotton stalk peel preparation method that comes unstuck: the urea liquid and 1 ~ 2% hydrogen peroxide mixed solution soaking at room temperature 20 ~ 30min that are 1.0 ~ 4.0% by mass percentage concentration by the cotton stalk skin of pretreatment, the solid-to-liquid ratio of the cotton stalk skin of pretreatment and mixed solution is 1g:4.0 ~ 15mL, after soaking, suction filtration, washing, by concentration, be 0.5 ~ 0.8mol/LNaOH solution soaking at room temperature, 5 ~ 10 h, boil again 30 ~ 40 min, cooling rear extremely neutral with deionized water washing, after suction filtration, at 60 ~ 70 ℃, dry, cotton stalk skin obtains coming unstuck;
(3) the cotton stalk skin of citric acid absorbent preparation: in reactor, add deionized water: 40 ~ 75% by following composition mass percent; Citric acid: 10 ~ 35%, inferior sodium phosphate: 2 ~ 10%, cotton stalk skin comes unstuck: 8 ~ 20%, room temperature reaction 2 ~ 6 h, heat up 60 ~ 70 ℃, react 20 ~ 30 h, be warming up to 130 ℃, reaction 2 ~ 4 h, cooling after, by deionized water, wash in washing lotion and exist without citric acid, suction filtration, be immersed in mass percentage concentration and be in 10 ~ 20% Adlerika, with solid, be all dipped in solution and be as the criterion, under room temperature, soaked 6.5 ~ 10 h, suction filtration, Adlerika washing with 2 ~ 4%, 80 ~ 100 ℃ of oven dry, obtains the cotton stalk skin of citric acid adsorbent.
Another object of the present invention be to provide the cotton stalk skin adsorbent of a kind of lemon acid in aqueous systems to the application in basic-dyeable fibre absorption, feature is: deionized water for the cotton stalk skin adsorbent of lemon acid preparing is soaked to 30 ~ 50 min, by static method, adsorb.
The cotton stalk skin adsorbent of lemon acid preparing can also be soaked to 30 ~ 50 min by deionized water, by dynamic method, adsorb.
Advantage of the present invention and effect are:
(1) the cotton stalk skin adsorbent of lemon acid that the present invention obtains has good physical and chemical stability and excellent mechanical strength, the adsorption capacity that compares dyestuff with citric acid-modified tangerine peel, citric acid-modified bamboo bits, citric acid modification broomcorn straw is large, Reusability number of times improves greatly, can improve 30%;
(2) the directly absorption to water body Methylene Blue, crystal violet, the various basic-dyeable fibres of basic fuchsin of the lemon cotton stalk skin adsorbent of acid that the present invention obtains, adsorption efficiency is high, and the speed of absorption is fast, and desorption performance is good, can within the scope of wider soda acid, use;
(3) technique of the present invention is simple, and condition is easy to control, and production cost is low, is easy to suitability for industrialized production, in whole production process, without " three wastes " discharge, belongs to process for cleanly preparing;
(4) the cotton stalk skin that the present invention uses is that natural regeneration macromolecular material is made adsorbent, the more important thing is the waste utilization of cotton stalk skin, has so both saved raw-material cost and can create considerable economic benefit; By citric acid modification, use this adsorbent environmentally safe, the advantage such as production cost is low, and discarded object is biodegradable.
The specific embodiment
Embodiment 1
(1) the cotton stalk skin of pretreatment: get cotton stalk and soak 36 h in room temperature water, peel off the outer field skin of cotton stalk, washing, impurity elimination, pulverize after dry, by 20-40 object sieve, obtain the cotton stalk skin of pretreatment;
(2) the cotton stalk peel preparation method that comes unstuck: by the cotton stalk skin of 20g pretreatment, being placed in 200 mL is 2% and containing the mixed solution soaking at room temperature 25min of dioxygen 1% containing urea quality percentage concentration, after soaking, suction filtration, washing, by concentration, be 0.6mol/LNaOH solution soaking at room temperature 8h, boil again 30 min, cooling rear extremely neutral with deionized water washing, after suction filtration, at 60 ~ 70 ℃, dry, cotton stalk skin obtains coming unstuck;
(3) the cotton stalk skin of citric acid absorbent preparation: in the triangular flask of tool plug, add 100mL deionized water, 15g citric acid, 4g inferior sodium phosphate, after stirring and dissolving, add the 15g cotton stalk skin that comes unstuck, room temperature reaction 4 h, heat up 60 ℃, react 20 h, be warming up to 130 ℃, reaction 2h, after cooling, by deionized water, wash in washing lotion and exist without citric acid, suction filtration, be immersed in mass percentage concentration and be in 10% Adlerika, with solid, be all dipped in solution and be as the criterion, under room temperature, soak 8 h, suction filtration, Adlerika washing with 3%, 100 ℃ of oven dry, obtain the cotton stalk skin of citric acid adsorbent.
Embodiment 2
(1) the cotton stalk skin of pretreatment: get cotton stalk and soak 30 h in room temperature water, peel off the outer field skin of cotton stalk, washing, impurity elimination, pulverize after dry, by 20-40 object sieve, obtain the cotton stalk skin of pretreatment;
(2) the cotton stalk peel preparation method that comes unstuck: by the cotton stalk skin of 15g pretreatment, being placed in 200 mL is 1% and containing the mixed solution soaking at room temperature 30min of dioxygen 1% containing urea quality percentage concentration, after soaking, suction filtration, washing, by concentration, be 0.8mol/LNaOH solution soaking at room temperature 10h, boil again 35 min, cooling rear extremely neutral with deionized water washing, after suction filtration, at 60 ~ 70 ℃, dry, cotton stalk skin obtains coming unstuck;
(3) the cotton stalk skin of citric acid absorbent preparation: in the triangular flask of tool plug, add 100mL deionized water, 25g citric acid, 6g inferior sodium phosphate, after stirring and dissolving, add the 15g cotton stalk skin that comes unstuck, room temperature reaction 2 h, heat up 70 ℃, react 25 h, be warming up to 130 ℃, reaction 2h, after cooling, by deionized water, wash in washing lotion and exist without citric acid, suction filtration, be immersed in mass percentage concentration and be in 15% Adlerika, with solid, be all dipped in solution and be as the criterion, under room temperature, soak 6.5 h, suction filtration, Adlerika washing with 2%, 90 ℃ of oven dry, obtain the cotton stalk skin of citric acid adsorbent.
Embodiment 3
(1) the cotton stalk skin of pretreatment: get cotton stalk and soak 24h in room temperature water, peel off the outer field skin of cotton stalk, washing, impurity elimination, pulverize after dry, by 20-40 object sieve, obtain the cotton stalk skin of pretreatment;
(2) the cotton stalk peel preparation method that comes unstuck: by the cotton stalk skin of 20g pretreatment, being placed in 150 mL is 4% and containing the mixed solution soaking at room temperature 20min of dioxygen 2% containing urea quality percentage concentration, after soaking, suction filtration, washing, by concentration, be 0.5mol/LNaOH solution soaking at room temperature 5h, boil again 40 min, cooling rear extremely neutral with deionized water washing, after suction filtration, at 60 ~ 70 ℃, dry, cotton stalk skin obtains coming unstuck;
(3) the cotton stalk skin of citric acid absorbent preparation: in the triangular flask of tool plug, add 80mL deionized water, 15g citric acid, 4g inferior sodium phosphate, after stirring and dissolving, add the 10g cotton stalk skin that comes unstuck, room temperature reaction 3h, heat up 70 ℃, react 30 h, be warming up to 130 ℃, reaction 4h, after cooling, by deionized water, wash in washing lotion and exist without citric acid, suction filtration, be immersed in mass percentage concentration and be in 20% Adlerika, with solid, be all dipped in solution and be as the criterion, under room temperature, soak 7 h, suction filtration, Adlerika washing with 4%, 80 ℃ of oven dry, obtain the cotton stalk skin of citric acid adsorbent.
Embodiment 4
(1) the cotton stalk skin of pretreatment: get cotton stalk and soak 28 h in room temperature water, peel off the outer field skin of cotton stalk, washing, impurity elimination, pulverize after dry, by 20-40 object sieve, obtain the cotton stalk skin of pretreatment;
(2) the cotton stalk peel preparation method that comes unstuck: by the cotton stalk skin of 15g pretreatment, being placed in 100 mL is 3% and containing the mixed solution soaking at room temperature 25min of dioxygen 2% containing urea quality percentage concentration, after soaking, suction filtration, washing, by concentration, be 0.7mol/LNaOH solution soaking at room temperature 8h, boil again 40 min, cooling rear extremely neutral with deionized water washing, after suction filtration, at 60 ~ 70 ℃, dry, cotton stalk skin obtains coming unstuck;
(3) the cotton stalk skin of citric acid absorbent preparation: in the triangular flask of tool plug, add 80mL deionized water, 35g citric acid, 5g inferior sodium phosphate, after stirring and dissolving, add the 20g cotton stalk skin that comes unstuck, room temperature reaction 4 h, heat up 60 ℃, react 20 h, be warming up to 130 ℃, reaction 2h, after cooling, by deionized water, wash in washing lotion and exist without citric acid, suction filtration, be immersed in mass percentage concentration and be in 10% Adlerika, with solid, be all dipped in solution and be as the criterion, under room temperature, soak 8 h, suction filtration, Adlerika washing with 3%, 100 ℃ of oven dry, obtain the cotton stalk skin of citric acid adsorbent.
Embodiment 5
(1) the cotton stalk skin of pretreatment: get cotton stalk and soak 30 h in room temperature water, peel off the outer field skin of cotton stalk, washing, impurity elimination, pulverize after dry, by 20-40 object sieve, obtain the cotton stalk skin of pretreatment;
(2) the cotton stalk peel preparation method that comes unstuck: by the cotton stalk skin of 15g pretreatment, being placed in 200 mL is 1% and containing the mixed solution soaking at room temperature 30min of dioxygen 1% containing urea quality percentage concentration, after soaking, suction filtration, washing, by concentration, be 0.8mol/LNaOH solution soaking at room temperature 10h, boil again 35 min, cooling rear extremely neutral with deionized water washing, after suction filtration, at 60 ~ 70 ℃, dry, cotton stalk skin obtains coming unstuck;
(3) the cotton stalk skin of citric acid absorbent preparation: in the triangular flask of tool plug, add 50mL deionized water, 30g citric acid, 2g inferior sodium phosphate, after stirring and dissolving, add the 18g cotton stalk skin that comes unstuck, room temperature reaction 2 h, heat up 70 ℃, react 25 h, be warming up to 130 ℃, reaction 2h, after cooling, by deionized water, wash in washing lotion and exist without citric acid, suction filtration, be immersed in mass percentage concentration and be in 15% Adlerika, with solid, be all dipped in solution and be as the criterion, under room temperature, soak 6.5 h, suction filtration, Adlerika washing with 2%, 90 ℃ of oven dry, obtain the cotton stalk skin of citric acid adsorbent.
Embodiment 6
(1) the cotton stalk skin of pretreatment: get cotton stalk and soak 24h in room temperature water, peel off the outer field skin of cotton stalk, washing, impurity elimination, pulverize after dry, by 20-40 object sieve, obtain the cotton stalk skin of pretreatment;
(2) the cotton stalk peel preparation method that comes unstuck: by the cotton stalk skin of 20g pretreatment, being placed in 150 mL is 4% and containing the mixed solution soaking at room temperature 20min of dioxygen 2% containing urea quality percentage concentration, after soaking, suction filtration, washing, by concentration, be 0.5mol/LNaOH solution soaking at room temperature 5h, boil again 40 min, cooling rear extremely neutral with deionized water washing, after suction filtration, at 60 ~ 70 ℃, dry, cotton stalk skin obtains coming unstuck;
(3) the cotton stalk skin of citric acid absorbent preparation: in the triangular flask of tool plug, add 55mL deionized water, 20g citric acid, 5g inferior sodium phosphate, after stirring and dissolving, add the 20g cotton stalk skin that comes unstuck, room temperature reaction 3h, heat up 70 ℃, react 30 h, be warming up to 130 ℃, reaction 4h, after cooling, by deionized water, wash in washing lotion and exist without citric acid, suction filtration, be immersed in mass percentage concentration and be in 20% Adlerika, with solid, be all dipped in solution and be as the criterion, under room temperature, soak 7 h, suction filtration, Adlerika washing with 4%, 80 ℃ of oven dry, obtain the cotton stalk skin of citric acid adsorbent.
Embodiment 7
Take the cotton stalk skin adsorbent of the stubborn lemon acid of 0.10g and be placed in 250mL tool plug conical flask, adding 100mL concentration is in 600mg/L dye solution, take the pH value of acid or alkali regulation system in 3.0 ~ 100 scopes, at room temperature concussion absorption 1h, get supernatant, concentration with spectrophotometric determination dyestuff, according to the concentration difference of dyestuff in water before and after absorption, calculate the adsorption capacity of twisting the cotton stalk skin adsorbent of lemon acid, result shows, pH value adsorbent in 5.0 ~ 8.5 scopes is maximum and stable to the adsorbance of the absorption of dyestuff, so pH value is controlled in 5.0 ~ 8.5 scopes while using this adsorbent absorbing dye, at room temperature concussion absorption 1 ~ 4 h has been in the experiment of adsorption time, more than result shows at room temperature to shake absorption 1 h, dyestuff adsorbs completely substantially, and the adsorption capacity of methylene blue, crystal violet, basic fuchsin can reach respectively 372.8 mg/g, 456.7 mg/g, 382.6 mg/g.
Embodiment 8
Take the cotton stalk skin adsorbent of the stubborn lemon acid of 1.0g and be placed in 250mL tool plug conical flask, adding 100mL concentration is in 200mg/L dye solution, take the pH value of acid or alkali regulation system in 5.0 ~ 8.5 scopes, at room temperature concussion absorption 2 h, get supernatant, concentration with spectrophotometric determination dyestuff, according to the concentration difference of dyestuff in water before and after absorption, calculate and twist the clearance of the cotton stalk skin adsorbent of lemon acid to dyestuff, result shows, this adsorbent pair, methylene blue, crystal violet, three kinds of dyestuffs of basic fuchsin going in water processed all more than 95%, reaches as high as 99.2%.
Experiment shows, the cotton stalk skin of citric acid of the present invention for alkali and alkaline earth metal ions if any K
+, Na
+, Ca
2+, Mg
2+deng not adsorbing, while there is alkali and alkaline earth metal ions in sample thus, do not affect the absorption property of the cotton stalk skin of citric acid.
During Static Adsorption, the cotton stalk skin of citric acid adsorption capacity is relevant with the factors such as pH value of adsorption temp, adsorption time, solution system.
Dynamic Adsorption is to adopt wet method to pack adsorption column in the cotton stalk skin of citric acid adsorbent, and after pretreatment, the pH value of the solution system being adsorbed is that in 5.0 ~ 8.5 scopes, the flow velocity with 5.0mL/min passes through adsorption column, by the concentration of spectrophotometric determination efflux dyestuff.
During Dynamic Adsorption, the cotton stalk skin of citric acid adsorption capacity with the pH value of adsorption temp, solution system, the factors such as flow velocity of solution are relevant.
In the aqueous systems that contains organic dyestuff, adopt the cotton stalk skin of citric acid to carry out water treatment by the method for static state or Dynamic Adsorption, it is very strong to the adsorption capacity of dyestuff.
Claims (4)
1. the cotton stalk skin of a citric acid absorbent preparation method, is characterized in that: be that the method has following processing step:
(1) the cotton stalk skin of pretreatment: get cotton stalk and soak 24 ~ 36 h in room temperature water, peel off the outer field skin of cotton stalk, washing, impurity elimination, pulverize after dry, by 20-40 object sieve, obtain the cotton stalk skin of pretreatment;
(2) the cotton stalk peel preparation method that comes unstuck: the urea liquid and 1 ~ 2% hydrogen peroxide mixed solution soaking at room temperature 20 ~ 30min that are 1.0 ~ 4.0% by mass percentage concentration by the cotton stalk skin of pretreatment, the solid-to-liquid ratio of the cotton stalk skin of pretreatment and mixed solution is 1g:4.0 ~ 15mL, after soaking, suction filtration, washing, by concentration, be 0.5 ~ 0.8mol/LNaOH solution soaking at room temperature, 5 ~ 10 h, boil again 30 ~ 40 min, cooling rear extremely neutral with deionized water washing, after suction filtration, at 60 ~ 70 ℃, dry, cotton stalk skin obtains coming unstuck;
(3) the cotton stalk skin of citric acid absorbent preparation: in reactor, add deionized water: 40 ~ 75% by following composition mass percent; Citric acid: 10 ~ 35%, inferior sodium phosphate: 2 ~ 10%, cotton stalk skin comes unstuck: 8 ~ 20%, and room temperature reaction 2 ~ 6 h, heat up 60 ~ 70 ℃, reaction 20 ~ 30 h, be warming up to 130 ℃, reacting 2 ~ 4 h, cooling after, by deionized water, wash in washing lotion and exist without citric acid, suction filtration, is immersed in mass percentage concentration and is in 10 ~ 20% Adlerika, with solid, is all dipped in solution and is as the criterion, under room temperature, soak 6.5 ~ 10 h, suction filtration,, the Adlerika washing with 2 ~ 4%, 80 ~ 100 ℃ of oven dry, obtain the cotton stalk skin of citric acid adsorbent.
2. according to the cotton stalk skin of a kind of citric acid absorbent preparation method described in claim 1, it is characterized in that the described inferior sodium phosphate date of manufacture of step (3) will be in 6 months.
3. according to the cotton stalk skin of a kind of citric acid absorbent preparation method described in claim 1, it is characterized in that the described magnesium sulfate of step (3) is pure for analyzing.
4. according to the cotton stalk skin of a kind of citric acid absorbent preparation method described in claim 1, it is characterized in that the application in basic-dyeable fibre industrial wastewater.
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| CN103933943A (en) * | 2014-03-13 | 2014-07-23 | 济南大学 | Preparation and application of 2-mercaptobenzothiazole modified cotton stalk cortex adsorbent |
| CN105561941A (en) * | 2016-02-17 | 2016-05-11 | 济南大学 | Preparation of cotton bast adsorbent modified with cocamidopropyl betaine |
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| CN103191702A (en) * | 2013-04-26 | 2013-07-10 | 济南大学 | Preparation method and application of sulfydryl palm bark adsorbent |
| CN103212378A (en) * | 2013-04-26 | 2013-07-24 | 济南大学 | Preparation method and application of citric acid modified palm tree bark adsorbing agent |
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| JP2009039601A (en) * | 2007-08-06 | 2009-02-26 | Katsuyoshi Kondo | Method for removing heavy metal element in biomass and method for decontaminating heavy metal-contaminated soil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103933943A (en) * | 2014-03-13 | 2014-07-23 | 济南大学 | Preparation and application of 2-mercaptobenzothiazole modified cotton stalk cortex adsorbent |
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| CN105561941B (en) * | 2016-02-17 | 2017-09-22 | 济南大学 | A kind of Cocoamidopropyl betaine is modified the preparation of cotton stalk skins adsorbent |
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