CN103212378A - Preparation method and application of citric acid modified palm tree bark adsorbing agent - Google Patents
Preparation method and application of citric acid modified palm tree bark adsorbing agent Download PDFInfo
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- CN103212378A CN103212378A CN2013101477263A CN201310147726A CN103212378A CN 103212378 A CN103212378 A CN 103212378A CN 2013101477263 A CN2013101477263 A CN 2013101477263A CN 201310147726 A CN201310147726 A CN 201310147726A CN 103212378 A CN103212378 A CN 103212378A
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Abstract
The invention discloses a preparation method and an application technology of a citric acid modified palm tree bark adsorbing agent. The preparation method is characterized by comprising the following steps of: washing palm tree bark by water to remove mud and impurities, drying and crushing the washed palm tree bark, mixing the crushed palm tree bark with a 8%-20% citric acid solution according to the proportion of 1g: 5ml-15ml after the palm tree bark is dried by a NaOH aqueous solution, reacting the mixture for 35-60 minutes at room temperature, heating the reacted mixture to 50-60 DEG C, reacting the heated mixture for 24-36 hours, heating the reacted mixture to 120-130 DEG C, reacting the heated mixture for 1-2 hours, cooling the reacted mixture, washing the cooled mixture with distilled water until no citric acid exists in washing liquid, mixing the washing liquid with a 10%-20% magnesium chloride solution according to the proportion of 1g: 5ml-12ml, reacting the mixture at room temperature, performing suction filtration on the reacted mixture, washing the filtered mixture with a 5%-10% magnesium chloride solution, and finally, baking washing liquid to obtain the citric acid modified palm tree bark adsorbing agent. The adsorbing agent has high adsorption capacity to basic dye, good physical and chemical properties, high mechanical stability and strong regeneration capacity, and is recyclable, low in cost and environment-friendly.
Description
Technical field
The present invention relates to a kind of preparation method of biological adsorption agent and the applied technical field that dyestuff in the industrial wastewater is adsorbed, particularly a kind of citric acid modification palm bark adsorbent preparation method and application technology.
Background technology
Along with the fast development of industry, the consumption of dyestuff is also increasing, and synthetic dyestuffs are compared with natural dye, has 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 present most of synthetic dyestuffs has complicated aromatic ring structure, and character is very stable, is difficult to biodegradation.These dyestuffs can threaten to human beings'health, enter food chain, may cause people's allergy, the various injuries such as sudden change of cancer and gene.Dyestuff widely-used causes being discharged in a large number in the natural water of dye wastewater, cause I i of water body right, even if the discharging of a spot of waste water from dyestuff 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 the 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 technology simple for absorption method, the adsorption rate height, and applied widely, characteristics such as stable in properties are used widely in sewage disposal.
Since the 20 actual nineties, 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 the 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)); The fallen leaves that Runping Han etc. has studied the Chinese parasol tree tree adsorb the methylene blue in the 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 modification bamboo bits absorption methylene blue, and its maximum adsorption capacity to methyl blue is: 125mg/g, (Gong Xinhuai etc., the dynamics and the thermodynamic analysis of citric acid modification bamboo bits absorption methylene blue, Yichun College's journal, 2012,34(8), 47 ~ 49); Poplar is superfine, the research that peanut hull meal is removed azo dyes in the aqueous solution as biological adsorption agent, biology magazine, 2005,22(2) 45 ~ 48; Li Ronghua etc., studied of the absorption of citric acid modification orange skin to methyl blue in the water, its maximum adsorption capacity to methyl blue is: 189.92mg/g, (Li Ronghua etc., citric acid modification orange skin is to the absorption of methyl blue in the water, Xibei Univ. of Agricultural ﹠ Forest Science ﹠ Technology's journal (natural science edition), 2009,37(10), 173 ~ 179); Deng Jun is strong etc., has studied the absorption property of bagasse to dimethyl diaminophenazine chloride, and its maximum adsorption capacity to dimethyl diaminophenazine chloride is: 27.10mg/g, (Deng Junqiang etc., bagasse are to the research of the experiment of the absorption property of dimethyl diaminophenazine chloride, hydroscience and engineering, 2012(5), 24 ~ 28); Chinese patent application number is: disclose a kind of citric acid modification rape stalk preparation of adsorbent method and application in 201110208310.9 the patent, it is characterized in that, wash clean and dry rape straw soak 24h with 20% isopropyl alcohol, use the soaking with sodium hydroxide of 0.1mol/L after the separation drying again, 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, the cooling washing; These agriculture and forestry are discarded to be utilized adsorbent as water treatment and to have advantages such as renewable, degradable, environmental protection close friend, cheapness, be important living resources, but part also comes with some shortcomings, as their bad mechanical strength, corrosion easily in water, the reusable number of times of adsorbent is very low, and adsorption capacity is limited.
Palm is perennial aiphyllium plant, 7 meters of Gao Keda; Do upright, branch not, the palm-bark rain cape that forms by leaf sheath is wrapped; Therefore the fiber of palm bark is very long, intensity is big, as making mattress, is one of most valuable ecological resources usually, is a kind of renewable resource.Palm is extensively planted area on the south the Changjiang river at present, is very precious long fibered raw material.This natural macromolecular material is used to make to adsorb has characteristics such as natural, green, biodegradable, that mechanical strength is big, resistance to corrosion is strong, the palm bark as the renewable repeated use of adsorbent repeatedly, and dyestuff had big adsorption capacity, abroad palm bark chemical modification and absorption property are not appeared in the newspapers.
Summary of the invention
One of purpose of the present invention provides a kind of citric acid modification palm bark adsorbent preparation method, mainly makes the citric acid modification palm bark adsorbent that obtains bigger as the adsorption capacity of the adsorbent of dyestuff in the aqueous systems.
Purpose of the present invention is achieved through the following technical solutions.
A kind of citric acid modification palm bark adsorbent preparation method is characterised in that this method has following processing step:
(1) palm bark preliminary treatment: wash the palm bark with water removal earth and impurity, putting into container was soaked in water 7 ~ 10 days, to remove non-fibrous material, the palm bark clear water that is cut into small pieces is cleaned, pulverize after the vacuum drying, with 20 ~ 40 purpose sieve, obtain preliminary treatment palm bark;
(2) palm bark basification: with preliminary treatment palm bark mass percentage concentration is NaOH aqueous solution soaking 10 ~ 20h of 4 ~ 10%, boils 10 ~ 30nim, spends deionised water after the cooling to neutral, 100 ~ 120 ℃ of oven dry behind the suction filtration, and the palm bark must alkalize;
(3) citric acid palm leather is equipped with: in reactor, to alkalize the palm bark with after the citric acid solution of quality percentage 8 ~ 20% mixes with the ratio of 1g:5 ~ 15mL, room temperature reaction 35 ~ 60nim, heat up 50 ~ 60 ℃, reaction 24 ~ 36 h are being warming up to 120 ~ 130 ℃, reaction 1 ~ 2 h, after the cooling, wash no citric acid existence in the washing lotion, obtain citric acid palm bark with distilled water;
(4) preparation of palm bark adsorbent is modified in lemon acid: with citric acid palm bark with after the magnesium chloride solution of quality percentage 10 ~ 20% mixes with the ratio of 1g:5 ~ 12mL, room temperature reaction 1 ~ 6 h, suction filtration, magnesium chloride solution washing with 5 ~ 10%, 100 ~ 120 ℃ of oven dry, promptly get lemon acid and modify palm bark adsorbent.
Another object of the present invention provide the acid of a kind of lemon modify palm bark adsorbent in aqueous systems to the application in the basic-dyeable fibre absorption, characteristics are: palm bark adsorbent is modified in the lemon acid for preparing soaked 1 ~ 2 h with deionized water, by static method absorption.
The lemon acid for preparing can also be modified palm bark adsorbent and soak 1 ~ 2 h, by dynamic method absorption with deionized water.
Advantage of the present invention and effect are:
(1) mechanical strength that palm bark adsorbent has good physical and chemical stability and excellence is modified in the lemon acid of the present invention's acquisition, the adsorption capacity that compares dyestuff with citric acid modification tangerine peel, citric acid modification bamboo bits, citric acid modification broomcorn straw is big, access times improve greatly repeatedly, can improve 50%;
(2) the lemon acid that obtains of the present invention is modified palm bark adsorbent and can be reached 367.8mg/g, 447.7mg/g, 378.5mg/g respectively to the adsorption capacity of methylene blue, crystal violet, basic fuchsin, and the clearance of dyestuff in the sewage is reached as high as 99.2%; Can be directly to the absorption and the wash-out of various basic-dyeable fibres in the water body, the adsorption efficiency height, the speed of absorption is fast, desorption performance is good, can use in the soda acid scope of broad;
(3) technology of the present invention is simple, and condition is easy to control, and production cost is low, is easy to suitability for industrialized production;
Advantages such as (4) the palmitic acid bark of the present invention's use is that natural regeneration macromolecular material is made adsorbent, uses citric acid modification, uses this adsorbent environmentally safe, and production cost is low, and discarded object is biodegradable.
The specific embodiment
Embodiment 1
(1) palm bark preliminary treatment: wash the palm bark with water removal earth and impurity, put into container and be soaked in water 7 days, to remove non-fibrous material, the palm bark clear water that is cut into small pieces is cleaned, pulverize after the vacuum drying,, obtain preliminary treatment palm bark with 40 purpose sieve;
(2) palm bark basification: with preliminary treatment palm bark mass percentage concentration is 4% NaOH aqueous solution soaking 20h, boils 30nim, spends deionised water after the cooling to neutral, 110 ℃ of oven dry behind the suction filtration, and the palm bark must alkalize;
(3) citric acid palm leather is equipped with: in reactor, with alkalization palm bark with after the citric acid solution of quality percentage 10% mixes with the ratio of 1g:10mL, room temperature reaction 60nim, heat up 50 ℃, react 30 h, be warming up to 125 ℃, react 1 h, after the cooling, wash no citric acid existence in the washing lotion, obtain citric acid palm bark with distilled water;
(4) preparation of palm bark adsorbent is modified in lemon acid: with citric acid palm bark with after the magnesium chloride solution of quality percentage 15% mixes with the ratio of 1g:5mL, room temperature reaction 6 h, suction filtration, magnesium chloride solution washing with 5%, 110 ℃ of oven dry, promptly get lemon acid and modify palm bark adsorbent.
Embodiment 2
(1) palm bark preliminary treatment: wash the palm bark with water removal earth and impurity, put into container and be soaked in water 10 days, to remove non-fibrous material, the palm bark clear water that is cut into small pieces is cleaned, pulverize after the vacuum drying,, obtain preliminary treatment palm bark with 40 purpose sieve;
(2) palm bark basification: with preliminary treatment palm bark mass percentage concentration is 6% NaOH aqueous solution soaking 15h, boils 20nim, spends deionised water after the cooling to neutral, 100 ℃ of oven dry behind the suction filtration, and the palm bark must alkalize;
(3) citric acid palm leather is equipped with: in reactor, with alkalization palm bark with after the citric acid solution of quality percentage 15% mixes with the ratio of 1g:8mL, room temperature reaction 40nim, heat up 50 ℃, react 24 h, be warming up to 120 ℃, react 1.5 h, after the cooling, wash no citric acid existence in the washing lotion, obtain citric acid palm bark with distilled water;
(4) preparation of palm bark adsorbent is modified in lemon acid: with citric acid palm bark with after the magnesium chloride solution of quality percentage 20% mixes with the ratio of 1g:6mL, room temperature reaction 2 h, suction filtration, magnesium chloride solution washing with 5%, 100 ℃ of oven dry, promptly get lemon acid and modify palm bark adsorbent.
Embodiment 3
(1) palm bark preliminary treatment: wash the palm bark with water removal earth and impurity, put into container and be soaked in water 7 days, to remove non-fibrous material, the palm bark clear water that is cut into small pieces is cleaned, pulverize after the vacuum drying,, obtain preliminary treatment palm bark with 20 purpose sieve;
(2) palm bark basification: with preliminary treatment palm bark mass percentage concentration is 8% NaOH aqueous solution soaking 12h, boils 15nim, spends deionised water after the cooling to neutral, 120 ℃ of oven dry behind the suction filtration, and the palm bark must alkalize;
(3) citric acid palm leather is equipped with: in reactor, with alkalization palm bark with after the citric acid solution of quality percentage 8% mixes with the ratio of 1g:15mL, room temperature reaction 60nim, heat up 60 ℃, react 36 h, be warming up to 125 ℃, react 1.5 h, after the cooling, wash no citric acid existence in the washing lotion, obtain citric acid palm bark with distilled water;
(4) preparation of palm bark adsorbent is modified in lemon acid: with citric acid palm bark with after the magnesium chloride solution of quality percentage 10% mixes with the ratio of 1g:10mL, room temperature reaction 4 h, suction filtration, magnesium chloride solution washing with 8%, 110 ℃ of oven dry, promptly get lemon acid and modify palm bark adsorbent.
Embodiment 4
(1) palm bark preliminary treatment: wash the palm bark with water removal earth and impurity, put into container and be soaked in water 10 days, to remove non-fibrous material, the palm bark clear water that is cut into small pieces is cleaned, pulverize after the vacuum drying,, obtain preliminary treatment palm bark with 20 purpose sieve;
(2) palm bark basification: with preliminary treatment palm bark mass percentage concentration is 10% NaOH aqueous solution soaking 10h, boils 10nim, spends deionised water after the cooling to neutral, 100 ℃ of oven dry behind the suction filtration, and the palm bark must alkalize;
(3) citric acid palm leather is equipped with: in reactor, with alkalization palm bark with after the citric acid solution of quality percentage 12% mixes with the ratio of 1g:10mL, room temperature reaction 50nim, heat up 55 ℃, react 30 h, be warming up to 130 ℃, react 1 h, after the cooling, wash no citric acid existence in the washing lotion, obtain citric acid palm bark with distilled water;
(4) preparation of palm bark adsorbent is modified in lemon acid: with citric acid palm bark with after the magnesium chloride solution of quality percentage 18% mixes with the ratio of 1g:8mL, room temperature reaction 5 h, suction filtration, magnesium chloride solution washing with 8%, 110 ℃ of oven dry, promptly get lemon acid and modify palm bark adsorbent.
Embodiment 5
(1) palm bark preliminary treatment: wash the palm bark with water removal earth and impurity, put into container and be soaked in water 7 days, to remove non-fibrous material, the palm bark clear water that is cut into small pieces is cleaned, pulverize after the vacuum drying,, obtain preliminary treatment palm bark with 40 purpose sieve;
(2) palm bark basification: with preliminary treatment palm bark mass percentage concentration is 5% NaOH aqueous solution soaking 18h, boils 25nim, spends deionised water after the cooling to neutral, 120 ℃ of oven dry behind the suction filtration, and the palm bark must alkalize;
(3) citric acid palm leather is equipped with: in reactor, with alkalization palm bark with after the citric acid solution of quality percentage 20% mixes with the ratio of 1g:5mL, room temperature reaction 60nim, heat up 55 ℃, react 32 h, be warming up to 125 ℃, react 1 h, after the cooling, wash no citric acid existence in the washing lotion, obtain citric acid palm bark with distilled water;
(4) preparation of palm bark adsorbent is modified in lemon acid: with citric acid palm bark with after the magnesium chloride solution of quality percentage 20% mixes with the ratio of 1g:5mL, room temperature reaction 6 h, suction filtration, magnesium chloride solution washing with 10%, 120 ℃ of oven dry, promptly get lemon acid and modify palm bark adsorbent.
Embodiment 6
Take by weighing 0.10g lemon acid modification palm bark adsorbent and place 250mL tool plug conical flask, adding 100mL concentration is in the 550mg/L dye solution, pH value with acid or alkali regulation system is in 4.5 ~ 9.0 scopes, 1 ~ 6 h of concussion absorption at room temperature, get supernatant, concentration with the spectrophotometric determination dyestuff, concentration difference according to dyestuff in the water before and after the absorption, calculate the adsorption capacity that palm bark adsorbent is modified in lemon acid, embodiment 1 ~ 5 prepared lemon acid modification palm bark adsorbent is listed table 1. in to the adsorption capacity result of dyestuff
The adsorption capacity measurement result of palm bark adsorbent to dyestuff modified in the acid of table 1 lemon
| The adsorbent title | pH | Adsorption time (h) | Methylene blue (mg/g) | Crystal violet (mg/g) | Basic fuchsin (mg/g) |
| Embodiment 1 | 5.5 | 2 | 365.6 | 446.5 | 375.2 |
| Embodiment 1 | 7.0 | 3 | 366.9 | 445.3 | 376.9 |
| Embodiment 2 | 6.0 | 4 | 367.8 | 447.2 | 377.2 |
| Embodiment 2 | 8.5 | 5 | 367.5 | 447.7 | 378.5 |
| Embodiment 3 | 5.0 | 6 | 366.2 | 446.9 | 378.4 |
| Embodiment 3 | 8.2 | 3.5 | 365.8 | 445.6 | 376.8 |
| Embodiment 4 | 4.5 | 2.5 | 364.8 | 444.2 | 375.1 |
| Embodiment 4 | 7.5 | 4.5 | 365.9 | 445.6 | 376.2 |
| Embodiment 5 | 7.2 | 5.5 | 367.2 | 447.5 | 377.9 |
| Embodiment 5 | 8.8 | 1 | 364.2 | 443.2 | 376.1 |
From table 1 visible pH value 4.5 ~ 9.0 scopes in adsorbent to the absorption of dyestuff less than influencing, more than 1 h of concussion absorption at room temperature, dyestuff adsorbs fully substantially, and the adsorption capacity of methylene blue, crystal violet, basic fuchsin can reach 367.8 mg/g, 447.7 mg/g, 378.5 mg/g respectively.
Embodiment 7
Take by weighing 1.0g lemon acid modification palm bark adsorbent and place 250mL tool plug conical flask, adding 100mL concentration is in the 200mg/L dye solution, pH value with acid or alkali regulation system is in 6.5 scopes, 2 h of concussion absorption at room temperature, get supernatant, concentration with the spectrophotometric determination dyestuff, concentration difference according to dyestuff in the water before and after the absorption, calculate lemon acid and modify the clearance of palm bark adsorbent dyestuff, palm bark adsorbent is modified in the prepared lemon acid of embodiment 1 ~ 5, and that the clearance result of dyestuff is listed in this adsorbent of table 2. is right, methylene blue, crystal violet, three kinds of dyestuffs of basic fuchsin going in water handled all more than 95%, reaches as high as 99.2%.
The clearance of palm bark adsorbent to dyestuff modified in the acid of table 2 lemon
| The adsorbent title | Methylene blue (%) | Crystal violet (%) | Basic fuchsin (%) |
| Embodiment 1 | 96.6 | 98.2 | 97.6 |
| Embodiment 2 | 97.9 | 97.8 | 95.6 |
| Embodiment 3 | 99.2 | 96.9 | 99.2 |
| Embodiment 4 | 99 | 99.1 | 96.7 |
| Embodiment 5 | 98.5 | 98.2 | 97.6 |
Claims (5)
1. citric acid modification palm bark adsorbent preparation method is characterized in that: be that this method has following processing step:
(1) palm bark preliminary treatment: wash the palm bark with water removal earth and impurity, putting into container was soaked in water 7 ~ 10 days, to remove non-fibrous material, the palm bark clear water that is cut into small pieces is cleaned, pulverize after the vacuum drying, with 20 ~ 40 purpose sieve, obtain preliminary treatment palm bark;
(2) palm bark basification: with preliminary treatment palm bark mass percentage concentration is NaOH aqueous solution soaking 10 ~ 20h of 4 ~ 10%, boils 10 ~ 30nim, spends deionised water after the cooling to neutral, 100 ~ 120 ℃ of oven dry behind the suction filtration, and the palm bark must alkalize;
(3) citric acid palm leather is equipped with: in reactor, to alkalize the palm bark with after the citric acid solution of quality percentage 8 ~ 20% mixes with the ratio of 1g:5 ~ 15mL, room temperature reaction 35 ~ 60nim, heat up 50 ~ 60 ℃, reaction 24 ~ 36 h are being warming up to 120 ~ 130 ℃, reaction 1 ~ 2 h, after the cooling, wash no citric acid existence in the washing lotion, obtain citric acid palm bark with distilled water;
(4) preparation of palm bark adsorbent is modified in lemon acid: with citric acid palm bark with after the magnesium chloride solution of quality percentage 10 ~ 20% mixes with the ratio of 1g:5 ~ 12mL, room temperature reaction 1 ~ 6 h, suction filtration, magnesium chloride solution washing with 5 ~ 10%, 100 ~ 120 ℃ of oven dry, promptly get lemon acid and modify palm bark adsorbent.
2. according to the palm bark basification described in claim 1 step (3), it is characterized in that described alkalization palm bark mixes with the ratio of 1g:5 ~ 15mL with the citric acid solution of quality percentage 8 ~ 20%.
3. the preparation of palm bark adsorbent is modified in acid according to the lemon described in claim 1 step (4), it is characterized in that described magnesium chloride is pure for analyzing.
4. according to the preparation of the citric acid modification palm bark adsorbent described in the claim 1, it is characterized in that the application in the basic-dyeable fibre industrial wastewater.
5. be methylene blue, crystal violet, basic fuchsin etc. according to the basic-dyeable fibre described in the claim 4.
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| CN103464118A (en) * | 2013-09-26 | 2013-12-25 | 济南大学 | Preparation method and applications of epichlorohydrin-modified palm tree bark adsorbent |
| CN103464119A (en) * | 2013-09-28 | 2013-12-25 | 济南大学 | Preparation method and application of modified cysteine palm bark adsorbent |
| CN103566909A (en) * | 2013-11-13 | 2014-02-12 | 济南大学 | Preparation method and application of citric acid cotton stalk skins |
| 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 |
| CN103920469A (en) * | 2014-05-06 | 2014-07-16 | 济南大学 | Preparation method of citric acid silk adsorbent |
| CN105668666A (en) * | 2016-04-19 | 2016-06-15 | 魏倩 | Sewage treating agent and preparation method and application thereof |
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| CN109289791A (en) * | 2018-11-29 | 2019-02-01 | 运城学院 | A method of dephosphorization adsorbent is prepared using citric acid-modified |
| CN109482156A (en) * | 2018-12-13 | 2019-03-19 | 重庆工商大学 | Preparation method of modified corn core biological adsorption agent and products thereof and application |
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| CN103464118A (en) * | 2013-09-26 | 2013-12-25 | 济南大学 | Preparation method and applications of epichlorohydrin-modified palm tree bark adsorbent |
| CN103464119A (en) * | 2013-09-28 | 2013-12-25 | 济南大学 | Preparation method and application of modified cysteine palm bark adsorbent |
| 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 |
| 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 |
| CN103566909B (en) * | 2013-11-13 | 2015-08-19 | 济南大学 | A kind of preparation method of citric acid cotton stalk skin and application |
| CN103566909A (en) * | 2013-11-13 | 2014-02-12 | 济南大学 | Preparation method and application of citric acid cotton stalk skins |
| CN103920469A (en) * | 2014-05-06 | 2014-07-16 | 济南大学 | Preparation method of citric acid silk adsorbent |
| CN105664869A (en) * | 2016-02-17 | 2016-06-15 | 济南大学 | Preparation of lauramidopropyl betaine modified palm tree bark adsorbent |
| CN105668666A (en) * | 2016-04-19 | 2016-06-15 | 魏倩 | Sewage treating agent and preparation method and application thereof |
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