CN103920469A - Preparation method of citric acid silk adsorbent - Google Patents
Preparation method of citric acid silk adsorbent Download PDFInfo
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- CN103920469A CN103920469A CN201410186346.5A CN201410186346A CN103920469A CN 103920469 A CN103920469 A CN 103920469A CN 201410186346 A CN201410186346 A CN 201410186346A CN 103920469 A CN103920469 A CN 103920469A
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Abstract
The invention discloses a preparation method of a citric acid silk adsorbent and an application technology. The preparation method is characterized by comprising the following steps: adding 32 to 48 mass percent of citric acid and 28 to 46 mass percent of de-ionized water into a reactor, stirring the citric acid and the de-ionized water for dissolution, adding 16 to 30 mass percent of amidated silk, performing stirring at constant temperature of 90 to 100 DEG C, performing reflux reaction for 2 to 4 hours, performing washing and suction filtration by de-ionized water until filtrate is neutral, performing washing by a small amount of ethanol, and performing drying in a drying oven at 50 DEG C to obtain the citric acid silk adsorbent, wherein the total amount of the components is 100 percent. The citric acid silk adsorbent has high organic dye adsorption capacity, can be directly used for adsorbing and eluting various organic dyes in water, and is high in adsorption efficiency and adsorption speed, low in cost, environmentally friendly and high in physiochemical and mechanical stability.
Description
Technical field
The invention belongs to chemosynthesis technical field, relate to preparation method and the application technology of citric acid silk, specifically a kind of citric acid silk method and application technology to organic dyestuff absorption in water body prepared.
Background technology
Silk (silk) is matured silkworm concretionary continuous fiber of secreted silk liquid while cocooing, and also claims natural silk, is a kind of natural fiber.One of human use's animal origin the earliest, silk is the lightest the thinnest the most soft natural fiber of occurring in nature, can easily restore to the original state after cancelling external force, evenly soft, ventilative, the water vapour permeability that have, make silk feel more sliding, refreshing not warm, temperature and not dry.Mulberry silk is mainly comprised of animal protein, is rich in 18 kinds of necessary amino acid of human body, can promote Skin Cell vigor, have " human body the second skin ", " fiber queen's " good reputation.The silk fibre of silk cocoon is very thin, only has 20 to 30 microns, is one of most valuable ecological resources, is a kind of renewable resource, is very precious long fibered raw material.This natural macromolecular material application is made absorption and is had 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.Silk is carried out to modification and prepare adsorbent and can overcome above-mentioned shortcoming, less to Natural Silk Chemistry modification and absorption property report both at home and abroad.
Summary of the invention
One of object of the present invention is to provide a kind of preparation method of citric acid silk adsorbent, the absorption of citric acid silk adsorbent to organic dyestuff in aqueous systems.
Object of the present invention is achieved through the following technical solutions.
A preparation method for citric acid silk adsorbent, is characterised in that the method has following processing step:
(1) silk pretreatment: silk cocoon is washed with water and removes impurity and silkworm chrysalis, put into container and be soaked in water 1 ~ 2 day, the be cut into small pieces useless silk of Qing Huoqu silk factory of silk cocoon is washed, after vacuum drying, pulverize, by 20 object sieve, obtain pretreatment silk;
(2) boiled silk preparation: be 1:15 ~ 30mL by pretreatment silk by solid-to-liquid ratio, the aqueous sodium carbonate that is 2 ~ 6% by mass percentage concentration soaks 12 ~ 18h, boils 10 ~ 20min, cooling rear extremely neutral with deionized water washing, after suction filtration, be placed on 50 ℃ of oven dryings, obtain boiled silk;
(3) amidatioon silk preparation: in reactor, add deionized water: 30 ~ 50% by following composition mass percentage concentration, ethylenediamine: 22 ~ 42%, boiled silk: 20 ~ 40%, each component sum is absolutely, constant temperature at 75 ~ 85 ℃, stir, back flow reaction 2 ~ 4 h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after the washing of a small amount of ethanol, be placed in 50 ℃ of baking ovens and be dried, obtain amidatioon silk;
(4) citric acid silk absorbent preparation: in reactor, add citric acid: 32 ~ 48% by following composition mass percentage concentration, deionized water: 28 ~ 46%, after stirring and dissolving, then add amidatioon silk: 16 ~ 30%, each component sum is absolutely, constant temperature at 90 ~ 100 ℃, stirs back flow reaction 2 ~ 4 h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after a small amount of ethanol washing, be placed in 50 ℃ of baking ovens and be dried, obtain citric acid silk adsorbent.
Above-mentioned silk used can be to be the silk cocoon of ecosystem or the useless silk of silk factory.
Another object of the present invention is to provide the application to organic dyestuff absorption in aqueous systems as adsorbent of a kind of citric acid silk adsorbent, and feature is: the citric acid silk adsorbent preparing is soaked to 0.5 ~ 1.0 h by deionized water, by static method, adsorb.
The citric acid silk adsorbent preparing can also be soaked to 0.5 ~ 1.0 h by deionized water, by dynamic method, adsorb.
Advantage of the present invention and effect are:
(1) the citric acid silk adsorbent 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 50%;
(2) the citric acid silk adsorbent that the present invention obtains can be directly to the various organic dyestuff absorption such as water body Methylene Blue, crystal violet, basic fuchsin, azo, its adsorption efficiency is high, the adsorption capacity of methylene blue, crystal violet, basic fuchsin, arsenazo Ⅲ can reach respectively 382.2 mg/g, 458.9 mg/g, 392.6 mg/g, 368.26mg/g, the speed of absorption is fast, desorption performance is good, can within the scope of wider soda acid, use, to the clearance of organic dyestuff, can reach 98%;
(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.
(4) advantages such as the silk that the present invention uses is that natural regeneration macromolecular material is made adsorbent, uses this adsorbent environmentally safe, and production cost is low, and discarded object is biodegradable, the useless silk recycling of silk factory.
The specific embodiment
Embodiment 1
(1) silk pretreatment: silk cocoon is washed with water and removes impurity and silkworm chrysalis, put into container and be soaked in water 1 day, the silk cocoon clear water that is cut into small pieces is cleaned, pulverize after vacuum drying, by 20 object sieve, obtain pretreatment silk;
(2) boiled silk preparation: by 10g pretreatment silk, with the aqueous sodium carbonate of 220mL 4%, soak 15h, boil 15min, cooling rear extremely neutral with deionized water washing, after suction filtration, be placed on 50 ℃ of oven dryings, obtain boiled silk;
(3) amidatioon silk preparation: in reactor, add respectively 20mL deionized water, 15mL ethylenediamine, 15g boiled silk, constant temperature at 80 ℃, stir, back flow reaction 3 h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after the washing of a small amount of ethanol, be placed in 50 ℃ of baking ovens and be dried, obtain amidatioon silk;
(4) citric acid silk absorbent preparation: in reactor, add respectively 20g citric acid, 20mL deionized water, after stirring and dissolving, then add 10g amidatioon silk, constant temperature at 95 ℃, stir, back flow reaction 3h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after the washing of a small amount of ethanol, be placed in 50 ℃ of baking ovens and be dried, obtain citric acid silk adsorbent.
Embodiment 2
(1) silk pretreatment: the useless silk of silk factory is washed, pulverize after vacuum drying, by 20 object sieve, obtain pretreatment silk;
(2) boiled silk preparation: by 10g pretreatment silk, with the aqueous sodium carbonate of 150mL 3%, soak 18h, boil 10min, cooling rear extremely neutral with deionized water washing, after suction filtration, be placed on 50 ℃ of oven dryings, obtain boiled silk;
(3) amidatioon silk preparation: in reactor, add respectively 15mL deionized water, 20mL ethylenediamine, 15g boiled silk, constant temperature at 75 ℃, stir, back flow reaction 2h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after the washing of a small amount of ethanol, be placed in 50 ℃ of baking ovens and be dried, obtain amidatioon silk;
(4) citric acid silk absorbent preparation: in reactor, add respectively 16g citric acid, 14mL deionized water, after stirring and dissolving, then add 20g amidatioon silk, constant temperature at 90 ℃, stir, back flow reaction 2h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after the washing of a small amount of ethanol, be placed in 50 ℃ of baking ovens and be dried, obtain citric acid silk adsorbent.
Embodiment 3
(1) silk pretreatment: silk cocoon is washed with water and removes impurity and silkworm chrysalis, put into container and be soaked in water 2 days, the silk cocoon clear water that is cut into small pieces is cleaned, pulverize after vacuum drying, by 20 object sieve, obtain pretreatment silk;
(2) boiled silk preparation: by 100g pretreatment silk, with the aqueous sodium carbonate of 3000mL 2%, soak 12h, boil 20min, cooling rear extremely neutral with deionized water washing, after suction filtration, be placed on 50 ℃ of oven dryings, obtain boiled silk;
(3) amidatioon silk preparation: in reactor, add respectively 50mL deionized water, 25mL ethylenediamine, 25g boiled silk, constant temperature at 85 ℃, stir, back flow reaction 4 h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after the washing of a small amount of ethanol, be placed in 50 ℃ of baking ovens and be dried, obtain amidatioon silk;
(4) citric acid silk absorbent preparation: in reactor, add respectively 32g citric acid, 46mL deionized water, after stirring and dissolving, then add 22g amidatioon silk, constant temperature at 100 ℃, stir, back flow reaction 4h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after the washing of a small amount of ethanol, be placed in 50 ℃ of baking ovens and be dried, obtain citric acid silk adsorbent.
Embodiment 4
(1) silk pretreatment: the useless silk of silk factory is washed, pulverize after vacuum drying, by 20 object sieve, obtain pretreatment silk;
(2) boiled silk preparation: by 50g pretreatment silk, with the aqueous sodium carbonate of 1000mL 6%, soak 12h, boil 10min, cooling rear extremely neutral with deionized water washing, after suction filtration, be placed on 50 ℃ of oven dryings, obtain boiled silk;
(3) amidatioon silk preparation: in reactor, add respectively 45mL deionized water, 35mL ethylenediamine, 20g boiled silk, constant temperature at 80 ℃, stir, back flow reaction 3h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after the washing of a small amount of ethanol, be placed in 50 ℃ of baking ovens and be dried, obtain amidatioon silk;
(4) citric acid silk absorbent preparation: in reactor, add respectively 45g citric acid, 39mL deionized water, after stirring and dissolving, then add 16g amidatioon silk, constant temperature at 95 ℃, stir, back flow reaction 3h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after the washing of a small amount of ethanol, be placed in 50 ℃ of baking ovens and be dried, obtain citric acid silk adsorbent.
Embodiment 5
(1) silk pretreatment: silk cocoon is washed with water and removes impurity and silkworm chrysalis, put into container and be soaked in water 1.5 days, the silk cocoon clear water that is cut into small pieces is cleaned, pulverize after vacuum drying, by 20 object sieve, obtain pretreatment silk;
(2) boiled silk preparation: by 10g pretreatment silk, with the aqueous sodium carbonate of 180mL 6%, soak 12h, boil 10min, cooling rear extremely neutral with deionized water washing, after suction filtration, be placed on 50 ℃ of oven dryings, obtain boiled silk;
(3) amidatioon silk preparation: in reactor, add respectively 35mL deionized water, 30mL ethylenediamine, 35g boiled silk, constant temperature at 80 ℃, stir, back flow reaction 2h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after the washing of a small amount of ethanol, be placed in 50 ℃ of baking ovens and be dried, obtain amidatioon silk;
(4) citric acid silk absorbent preparation: in reactor, add respectively 48g citric acid, 27mL deionized water, after stirring and dissolving, then add 25g amidatioon silk, constant temperature at 90 ℃, stir, back flow reaction 2h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after the washing of a small amount of ethanol, be placed in 50 ℃ of baking ovens and be dried, obtain citric acid silk adsorbent.
Embodiment 6
Take the stubborn lemon acid of 0.10g silk adsorbent 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 lemon acid silk adsorbent, 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, arsenazo Ⅲ can reach respectively 382.2 mg/g, 458.9 mg/g, 392.6 mg/g, 368.26mg/g.
Embodiment 7
Take the stubborn lemon acid of 1.0g silk adsorbent 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 lemon acid silk adsorbent to dyestuff, result shows, this adsorbent pair, methylene blue, crystal violet, basic fuchsin, arsenazo Ⅲ dyestuff going in water processed all more than 95%, reach as high as 98.2%.
Experiment shows, citric acid silk 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 citric acid silk.
During Static Adsorption, citric acid silk 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 citric acid silk 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, citric acid silk adsorption capacity with the pH value of adsorption temp, solution system, the factors such as flow velocity of solution are relevant.
Claims (3)
1. a preparation method for citric acid silk adsorbent, is characterised in that the method has following processing step:
(1) silk pretreatment: silk cocoon is washed with water and removes impurity and silkworm chrysalis, put into container and be soaked in water 1 ~ 2 day, the be cut into small pieces useless silk of Qing Huoqu silk factory of silk cocoon is washed, after vacuum drying, pulverize, by 20 object sieve, obtain pretreatment silk;
(2) boiled silk preparation: be 1:15 ~ 30mL by pretreatment silk by solid-to-liquid ratio, the aqueous sodium carbonate that is 2 ~ 6% by mass percentage concentration soaks 12 ~ 18h, boils 10 ~ 20min, cooling rear extremely neutral with deionized water washing, after suction filtration, be placed on 50 ℃ of oven dryings, obtain boiled silk;
(3) amidatioon silk preparation: in reactor, add deionized water: 30 ~ 50% by following composition mass percentage concentration, ethylenediamine: 22 ~ 42%, boiled silk: 20 ~ 40%, each component sum is absolutely, constant temperature at 75 ~ 85 ℃, stir, back flow reaction 2 ~ 4 h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after the washing of a small amount of ethanol, be placed in 50 ℃ of baking ovens and be dried, obtain amidatioon silk;
(4) citric acid silk absorbent preparation: in reactor, add citric acid: 32 ~ 48% by following composition mass percentage concentration, deionized water: 28 ~ 46%, after stirring and dissolving, then add amidatioon silk: 16 ~ 30%, each component sum is absolutely, constant temperature at 90 ~ 100 ℃, stirs back flow reaction 2 ~ 4 h, then with deionized water washing, suction filtration, to filtrate, be neutrality till, with after a small amount of ethanol washing, be placed in 50 ℃ of baking ovens and be dried, obtain citric acid silk adsorbent.
2. the preparation method of a kind of citric acid silk adsorbent according to claim 1, is characterized in that described silk is the useless silk of silk cocoon or silk factory.
3. according to the prepared citric acid silk of claim 1 adsorbent, it is characterized in that described citric acid silk adsorbent is to the application in organic dyestuff absorption.
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Cited By (7)
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| CN108404981A (en) * | 2018-03-06 | 2018-08-17 | 济南大学 | Porous magnetic composite silk loads the preparation of praseodymium doped BiOBr photochemical catalysts |
| CN110038520A (en) * | 2019-03-11 | 2019-07-23 | 济南大学 | A kind of preparation method of the aromatic modified soybean fiber adsorbent of cup [8] |
| CN110038521A (en) * | 2019-03-11 | 2019-07-23 | 济南大学 | A kind of preparation method of the porous protein gel adsorbent of calixarenes modified magnetic |
| CN110038526A (en) * | 2019-03-21 | 2019-07-23 | 济南大学 | A kind of preparation method for the magnetic porous wool adsorbent of separating-purifying catechin |
| CN110038527A (en) * | 2019-03-21 | 2019-07-23 | 济南大学 | A kind of preparation method for the chromatography agent of separating-purifying rutin plant fiber |
| CN110064373A (en) * | 2019-03-11 | 2019-07-30 | 济南大学 | A kind of preparation method of the porous wool adsorbent of 2- bipyridyl ketone modified magnetic |
| CN110064374A (en) * | 2019-03-21 | 2019-07-30 | 济南大学 | A kind of preparation method for the magnetic porous biology chromatography agent of separating berberine |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108404981A (en) * | 2018-03-06 | 2018-08-17 | 济南大学 | Porous magnetic composite silk loads the preparation of praseodymium doped BiOBr photochemical catalysts |
| CN110038520A (en) * | 2019-03-11 | 2019-07-23 | 济南大学 | A kind of preparation method of the aromatic modified soybean fiber adsorbent of cup [8] |
| CN110038521A (en) * | 2019-03-11 | 2019-07-23 | 济南大学 | A kind of preparation method of the porous protein gel adsorbent of calixarenes modified magnetic |
| CN110064373A (en) * | 2019-03-11 | 2019-07-30 | 济南大学 | A kind of preparation method of the porous wool adsorbent of 2- bipyridyl ketone modified magnetic |
| CN110038526A (en) * | 2019-03-21 | 2019-07-23 | 济南大学 | A kind of preparation method for the magnetic porous wool adsorbent of separating-purifying catechin |
| CN110038527A (en) * | 2019-03-21 | 2019-07-23 | 济南大学 | A kind of preparation method for the chromatography agent of separating-purifying rutin plant fiber |
| CN110064374A (en) * | 2019-03-21 | 2019-07-30 | 济南大学 | A kind of preparation method for the magnetic porous biology chromatography agent of separating berberine |
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