CN102389778B - Preparation method and use of sulfydryl flax - Google Patents
Preparation method and use of sulfydryl flax Download PDFInfo
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- CN102389778B CN102389778B CN 201110276212 CN201110276212A CN102389778B CN 102389778 B CN102389778 B CN 102389778B CN 201110276212 CN201110276212 CN 201110276212 CN 201110276212 A CN201110276212 A CN 201110276212A CN 102389778 B CN102389778 B CN 102389778B
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- flax
- sulfydryl
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Abstract
The invention discloses a preparation method and use of sulfydryl flax, which is characterized by comprising: adding 45 to 52 mass percent of thioglycolic acid, 35 to 40 mass percent of tetrahydrofuran, 23 to 30 mass percent of degummed flax, 1 to 1.5 mass percent of glacial acetic acid and 0.15 to 0.3 mass percent of concentrated sulfuric acid into a triangular flask with a plug, stirring and refluxing for 4 to 6 hours at 50 to 60 DEG C, washing with deionized water, filtering under vacuum till the filtrate is neutral, washing with a small amount of ethanol, drying in an oven at 35 DEG C, and obtaining the sulfydryl flax. The sulfydryl flax has high metal ion absorbability, has properties of sulfydryl and can be directly use to absorb and elute various metal ions in water, the absorption efficiency and speed are high, the physical, chemical and mechanical properties of the sulfydryl flax are high, the sulfydryl flax can be used in a wide pH value range, the high regenerability of the sulfydryl flax, makes the repeated use number of the sulfydryl flax 30 percent higher than that of sulfydryl cotton, the waste from flax title is utilized, cost is saved, and environment pollution is avoided.
Description
Technical field
The present invention relates to preparation method and the application technology of metal biosorption agent in aqueous systems, particularly a kind of sulfydryl flax preparation method and application technology.
Background technology
Flax is annual herbaceous plant, is one of the most valuable ecological resources, is a kind of renewable resource.The cultivated area of present national flax reaches more than 300 ten thousand mu, long stapled output is generally in 60kg/ mu left and right, flax has a series of premium properties as textile fabric, the characteristics such as good in softness, good luster, well-pressed, nice and cool, moisture pick-up properties and permeability are very precious textile fiber materials.But the short fiber that 2% left and right is arranged in fabrication processes is discarded object, and it is the serious waste of flax resource that these discarded objects can not utilize fully, and the on-site environment of enterprise is polluted.Take full advantage of these short fibers and both can also can create considerable economic benefit by environmental contamination reduction, utilize these short fiber synthesizing new adsorbents to be used for the absorption of Heavy Metals in Waters ion, make this adsorbent have natural, green, biodegradable characteristics.
The male grade received sulfydryl on the macromolecular chain of absorbent cotton first from the end, west of Japan in 1971, since generating a kind of new sulfydryl huge legendary turtle and closing solid absorbent, separation and concentration adsorbent take sulfydryl as functional group is widely used, and this is to use because the active group sulfydryl in the sulfydryl adsorbent and some heavy metal ion have very strong huge legendary turtle cooperation.Have both at home and abroad by chemical reaction sulfydryl is received on natural macromolecular or resin, thereby make sulfhydryl dextran gel, sulphydryl activity charcoal and thiol resin etc., to realize to reach the Absorption quantity of some heavy metal ion the separation of some heavy metal ion.Synthetic and the application of domestic sulfydryl adsorbent, application number is to disclose a kind of method for preparing Sulfhydryl Cotton in 200310115874.3 patent, it is characterized in that using thioglycolic acid, oxolane and the concentrated sulfuric acid are made into reactant liquor, the consumption of each component of reactant liquor by volume calculates, ratio is: thioglycolic acid: oxolane: the concentrated sulfuric acid=1: 1: 0.002, reactant liquor was placed 8～12 minutes in ground wide-mouth bottle reactor; Absorbent cotton is put into reactor, make the complete soak degreasing of reactant liquor cotton, the consumption of reactant liquor and absorbent cotton is that the 100mL reactant liquor adds absorbent cotton 15 grams; At 35～45 ℃ of temperature, place taking-up in 45～50 hours after the ground wide-mouth bottle is jumped a queue, suction filtration adds absolute ethanol washing, in 40 ℃ of dryings; Application number is: the preparation method who discloses hydrosulfide group cellulose modifying material in the patent of 200410084394.X, it is characterized in that, preparation technology is by the preparation of thioglycolic fibre cellulose solution, form the modification of active carbon, washing and the drying process of material with the thioglycolic fibre cellulose solution; Adopted a high proportion of acetic anhydride in the preparation process of described thioglycolic fibre cellulose solution, solution composition percentage is: cotton: 2.0～6.0%; TGA: 25～35%; Acetic anhydride: 52.5～70.9%; Glacial acetic acid: 2.0～6.0%; Sulfuric acid: 0.1～0.5%; Described thioglycolic fibre cellulose solution is that active carbon is soaked in the thioglycolic fibre cellulose solution to the modification of active carbon, at 30～40 ℃ of temperature, places 30 minutes.Above these two patents only have the preparation method of sulfydryl adsorbent, not to the description of adsorption of metal ions.Application number is: disclose the purposes of mercapto-functional silicon dioxide hollow microsphere as mercury ion adsorbent in 200810039202.1 patent, it is to Hg
2+Maximum adsorption capacity be 3477mg/g; Application number is: disclose mercapto-functionalized luffa preparation method and application in 200910019165.2 patent, it is characterized in that: in the triangular flask of tool plug, add by following composition mass percent, TGA: 38～48%, oxolane: 30～40%, alkalization modified luffa: 18～25%, the concentrated sulfuric acid: 0.15～0.3%, jump a queue, place 48h in 40 ℃ of constant temperature, then with deionized water washing, suction filtration, till being neutrality to filtrate, after a small amount of ethanol washing, be placed on drying in 35 ℃ of baking ovens, obtain mercapto-functionalized luffa.It is to Cd
2+Adsorption capacity can be up to 226mg/g, high adsorption rate can reach 99.5%, to Fe
3+Maximal absorptive capacity be 30.12mg/g, to Zn
2+Maximal absorptive capacity be 41.81mg/g, to Cu
2+Maximal absorptive capacity be 29.26mg/g.
Flax chemical modification and absorption property also there is research abroad, M.Cox etc. have studied and have prepared active carbon with flax modification noble metal is adsorbed, its adsorption capacity is 1.708mg/g (M.Cox, Sorption of precious metals onto chemically prepared carbon from flax shive.Hydrometallurgy, 78 (2005), 137-144).Li Xiaomin, HNO
3The research of flax waste material adsorbent of modifying to the zinc ion adsorptivity.Yili Teacher College's journal (natural science edition), 2011 (1), its adsorption capacity of 45-48. is 0.324mmol/g.In the aqueous systems that the modification of employing flax chemical is obtained, the adsorbance of metal biosorption agent is less, and is subjected to the pH of absorption system to affect larger.
Summary of the invention
One of purpose of the present invention is to provide a kind of mercapto-functionalized flax preparation method, mainly makes the sulfydryl flax that obtains larger as the adsorbance of metal biosorption agent in aqueous systems.
A kind of sulfydryl flax preparation method, characteristics are: in the triangular flask of tool plug, add by following composition mass percent, TGA: 45～52%, oxolane: 35～40%, the flax of coming unstuck: 23～30%, glacial acetic acid: 1～1.5%, the concentrated sulfuric acid: 0.15～0.3%, jump a queue, under 50～60 ℃, stir the lower 4～6h of backflow, then with deionized water washing, suction filtration, be neutrality to filtrate till, after washing with a small amount of ethanol, be placed on drying in 35 ℃ of baking ovens, obtain sulfydryl flax.
A kind of sulfydryl flax preparation method, characteristics are: in the triangular flask of tool plug, add by following composition mass percent, TGA: 42～48%, oxolane: 38～42%, the flax of coming unstuck: 23～30%, glacial acetic acid: 1～1.5%, the concentrated sulfuric acid: 0.15～0.3%, jump a queue, place 35-40h in 35 ℃ of constant temperature, then with deionized water washing, suction filtration, be neutrality to filtrate till, after a small amount of ethanol washing, be placed on drying in 35 ℃ of baking ovens, obtain sulfydryl flax.
A kind of flax degumming method, characteristics are: the flax of pulverizing is pressed 30～40% of gross mass, be NaOH solution and 1～2%OP solution mixing azeotropic, the 1～2h of 0.4～0.6mol/L with concentration, constantly add distilled water during azeotropic, keeping liquor capacity constant, cooling rear with deionized water wash to pH be 7, soak 2～4h putting into isopropyl alcohol, after suction filtration, oven dry under 55～60 ℃, obtain the flax of coming unstuck.
Another object of the present invention is to provide a kind of sulfydryl flax as adsorbent application in adsorption of metal ions in aqueous systems, and characteristics are: the sulfydryl flax for preparing is soaked 2～4h with deionized water, by static method absorption.
The sulfydryl flax for preparing can also be soaked 2～4h with deionized water, by dynamic method absorption.
The invention has the beneficial effects as follows: sulfydryl flax of acquisition is to Cd
2+Adsorption capacity can be up to 282mg/g, high adsorption rate can reach 99.6%, to Pb
2+Maximal absorptive capacity be 519mg/g, to Cu
2+Maximal absorptive capacity be 160mg/g; Have the sulfydryl characteristic, can be directly to various metal biosorptions and wash-out in water body, adsorption efficiency is high, the speed of absorption is fast, and selective strong, desorption performance is good, good physical and chemical stability and excellent mechanical stability are arranged, can use in wider soda acid scope; Have larger adsorption capacity with Sulfhydryl Cotton comparison sulfydryl flax, water penetration is better, the number of times of the stronger Reusability of power of regeneration is higher by 30% than Sulfhydryl Cotton; The more important thing is the waste utilization of linen textile, so not only saved raw-material cost but also realized twice laid.
The specific embodiment
Embodiment 1
(1) flax pretreatment: get the discarded short fiber of linen textile, by washing, impurity elimination, pulverize after drying, with 60 purpose sieve;
(2) flax of pulverizing is pressed 32% of gross mass, be NaOH solution and the 1%OP solution mixing azeotropic 1.5h of 0.4mol/L with concentration, constantly add distilled water during azeotropic, to keep liquor capacity constant, cooling rear with deionized water wash to pH be 7, soak 4h putting into isopropyl alcohol, after suction filtration, oven dry under 60 ℃, obtain the flax of coming unstuck.
(3) in the triangular flask of tool plug, add 20mL TGA (filtering precipitation) and 15mL oxolane, add the 0.5mL glacial acetic acid, add two concentrated sulfuric acids, mixing, the flax that adds 9g to come unstuck, jump a queue, under 55 ℃, stir lower backflow 4h, then with deionized water washing, suction filtration, till being neutrality to filtrate, after a small amount of ethanol washing, be placed in 35 ℃ of baking ovens dry, preserve in the drier of lucifuge, obtain sulfydryl flax.
Embodiment 2
(1) flax pretreatment: get the discarded short fiber of linen textile, by washing, impurity elimination, pulverize after drying, with 60 purpose sieve;
(2) flax of pulverizing is pressed 40% of gross mass, be NaOH solution and the 2%OP solution mixing azeotropic 1h of 0.6mol/L with concentration, constantly add distilled water during azeotropic, to keep liquor capacity constant, cooling rear with deionized water wash to pH be 7, soak 3h putting into isopropyl alcohol, after suction filtration, oven dry under 55 ℃, obtain the flax of coming unstuck.
(3) in the triangular flask of tool plug, add 30mL TGA (filtering precipitation) and 20mL oxolane, add the 0.5mL glacial acetic acid, add two concentrated sulfuric acids, mixing, the flax that adds 12g to come unstuck, jump a queue, under 50 ℃, stir lower backflow 6h, then with deionized water washing, suction filtration, till being neutrality to filtrate, after a small amount of ethanol washing, be placed in 35 ℃ of baking ovens dry, preserve in the drier of lucifuge, obtain sulfydryl flax.
Embodiment 3
(1) flax pretreatment: get the discarded short fiber of linen textile, by washing, impurity elimination, pulverize after drying, with 60 purpose sieve;
(2) flax of pulverizing is pressed 35% of gross mass, be NaOH solution and the 1.5%OP solution mixing azeotropic 1h of 0.5mol/L with concentration, constantly add distilled water during azeotropic, to keep liquor capacity constant, cooling rear with deionized water wash to pH be 7, soak 2h putting into isopropyl alcohol, after suction filtration, oven dry under 60 ℃, obtain the flax of coming unstuck.
(3) in the triangular flask of tool plug, add 25mL TGA (filtering precipitation) and 25mL oxolane, add the 0.5mL glacial acetic acid, add two concentrated sulfuric acids, mixing, the flax that adds 12g to come unstuck, jump a queue, under 60 ℃, stir lower backflow 4h, then with deionized water washing, suction filtration, till being neutrality to filtrate, after a small amount of ethanol washing, be placed in 35 ℃ of baking ovens dry, preserve in the drier of lucifuge, obtain sulfydryl flax.
Embodiment 4
(1) flax pretreatment: get the discarded short fiber of linen textile, by washing, impurity elimination, pulverize after drying, with 60 purpose sieve;
(2) flax of pulverizing is pressed 30% of gross mass, be NaOH solution and the 1.5%OP solution mixing azeotropic 2h of 0.5mol/L with concentration, constantly add distilled water during azeotropic, to keep liquor capacity constant, cooling rear with deionized water wash to pH be 7, soak 3h putting into isopropyl alcohol, after suction filtration, oven dry under 55 ℃, obtain the flax of coming unstuck.
(3) in the triangular flask of tool plug, add 22mL TGA (filtering precipitation) and 28mL oxolane, add the 0.5mL glacial acetic acid, add two concentrated sulfuric acids, mixing, the flax that adds 12g to come unstuck, jump a queue, place 40h in 35 ℃ of constant temperature, then with deionized water washing, suction filtration, till being neutrality to filtrate, after a small amount of ethanol washing, be placed on drying in 35 ℃ of baking ovens, preserve in the drier of lucifuge, obtain sulfydryl flax.
Sulfydryl flax of above embodiment preparation, its sulfhydryl content is identical.
Sulfydryl flax application process: the sulfydryl flax for preparing is soaked 4h with deionized water, by a kind of be static adsorptive method, another kind is dynamic adsorption method, and adsorption of metal ions is used.
Measure absorption property with static adsorptive method, get the metal ion solution 20mL of variable concentrations, the sulfydryl flax that adds under the same conditions equivalent, concussion absorption 2h gets clear liquid, with the concentration of metal ion in the atomic absorption detecting clear liquid, calculate adsorption rate according to metal ion solution change in concentration before and after absorption.
Measure absorption property with dynamic method, a certain amount of sulfydryl flax with the wet method adsorption column of packing into, is got the metal ion solution of variable concentrations, regulate the pH value with diluted acid and diluted alkaline, flow velocity with 6mL/min passes through adsorption column, measures the amount of metal ion of adsorbing on filtered fluid and post, calculates thus adsorption rate.
Prepare as stated above the application of sulfydryl flax in adsorption of metal ions.Sulfydryl flax of the present invention the adsorption of metal ions field be applied as directly to water body in various metal biosorptions and wash-out.Its method is:
(1) for containing K
+, Na
+, Ca
2+, Mg
2+, Ba
2+, Al
3+, Cu
2+, Zn
2+, Cd
2+, Fe
3+, Ag
+, Co
2+, Ni
2+, Pb
2+, Se
4+, Pt
4+, Pd
2+, Au
3+In one or more staying water system, adopt sulfydryl flax to carry out water treatment with the method for Static Adsorption, namely get sulfydryl flax and be immersed in staying water system, 2h is adsorbed in concussion, its Adsorption law is as follows:
A. for alkali and alkaline earth metal ions if any K
+, Na
+, Ca
2+, Mg
2+, Ba
2+, Al
3+Deng not adsorbing, do not affect the absorption property of sulfydryl flax when having alkali and alkaline earth metal ions in sample thus.
B. for precious metal ion, stronger absorption property is arranged, the strong and weak order of absorption is: Pt
4+＞Au
3+＞Pd
2+＞Ag
+
C. heavy metal ion is also had stronger absorption property, the strong and weak order of absorption is: Se
4+, Ag
+＞Cu
2+＞Fe
3+, Pb
2+＞Zn
2+＞Cd
2+＞Co
2+, Ni
2+
In adsorption capacity and sulfydryl flax, the factors such as pH value of sulfhydryl content consumption, adsorption temp, solution system are relevant.
(2) for containing K
+, Na
+, Ca
2+, Mg
2+, Ba
2+, Al
3+, Cu
2+, Zn
2+, Cd
2+, Fe
3+, Ag
+, Co
2+, Ni
2+, Pb
2+, Se
4+, Pt
4+, Pd
2+, Au
3+In one or more staying water system, adopt sulfydryl flax to carry out water treatment with the method for Dynamic Adsorption, the rule of its absorption is the same, and in adsorption capacity and sulfydryl flax, the factors such as flow velocity of the pH value of sulfhydryl content consumption, adsorption temp, solution system, solution are relevant.
The sulfydryl flax that obtains is to Cd
2+Adsorption capacity can be up to 282mg/g, high adsorption rate can reach 99.6%, to Pb
2+Maximal absorptive capacity be 519mg/g, to Cu
2+Maximal absorptive capacity be 160mg/g.
Claims (3)
1. sulfydryl flax preparation method is characterized in that: be that the method has following processing step:
(1) flax pretreatment: get the discarded short fiber of linen textile, by washing, impurity elimination, pulverize after drying, with 60 purpose sieve;
(2) flax of pulverizing is pressed 32% of gross mass, be NaOH solution and the 1%OP solution mixing azeotropic 1.5h of 0.4mol/L with concentration, constantly add distilled water during azeotropic, to keep liquor capacity constant, cooling rear with deionized water wash to pH be 7, put into isopropyl alcohol again and soak 4h, after suction filtration, oven dry under 60 ℃, obtain the flax of coming unstuck;
(3) in the triangular flask of tool plug, add 20mL TGA and 15mL oxolane, add the 0.5mL glacial acetic acid, add two concentrated sulfuric acids, mixing adds the 9g flax of coming unstuck, jump a queue, under 55 ℃, stir lower backflow 4h, then with deionized water washing, suction filtration, till being neutrality to filtrate, after a small amount of ethanol washing, be placed in 35 ℃ of baking ovens dry, preserve in the drier of lucifuge, obtain sulfydryl flax.
2. sulfydryl flax preparation method is characterized in that: be that the method has following processing step:
(1) flax pretreatment: get the discarded short fiber of linen textile, by washing, impurity elimination, pulverize after drying, with 60 purpose sieve;
(2) flax of pulverizing is pressed 30% of gross mass, be NaOH solution and the 1.5%OP solution mixing azeotropic 2h of 0.5mol/L with concentration, constantly add distilled water during azeotropic, to keep liquor capacity constant, cooling rear with deionized water wash to pH be 7, put into isopropyl alcohol again and soak 3h, after suction filtration, oven dry under 55 ℃, obtain the flax of coming unstuck;
(3) in the triangular flask of tool plug, add 22mL TGA and 28mL oxolane, add the 0.5mL glacial acetic acid, add two concentrated sulfuric acids, mixing adds the 12g flax of coming unstuck, jump a queue, place 40h in 35 ℃ of constant temperature, then with deionized water washing, suction filtration, till being neutrality to filtrate, after a small amount of ethanol washing, be placed on drying in 35 ℃ of baking ovens, preserve in the drier of lucifuge, obtain sulfydryl flax.
3. according to claim 1～2 described TGA dates of manufacture will in 3 months, will filter before using.
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| CN102389778B true CN102389778B (en) | 2013-05-15 |
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| CN103212376A (en) * | 2013-04-18 | 2013-07-24 | 辽宁科技大学 | Preparation method of nanometer CuS grafting modified bamboo powder capable of adsorbing heavy metal ions |
| CN103191703A (en) * | 2013-04-26 | 2013-07-10 | 济南大学 | Preparation method and application of bagasse mercapto-biosorbent |
| CN103191702A (en) * | 2013-04-26 | 2013-07-10 | 济南大学 | Preparation method and application of sulfydryl palm bark adsorbent |
| CN103464115B (en) * | 2013-09-26 | 2015-10-21 | 济南大学 | One preparations and applicatio growing flax adsorbent |
| CN103933942B (en) * | 2014-03-13 | 2015-10-21 | 济南大学 | A kind of preparations and applicatio of mercaptopropyl trimethoxysilane modification flax adsorbent |
| CN104028302B (en) * | 2014-05-06 | 2016-04-20 | 济南大学 | One grows flax the preparation method of loaded with nano Pd-Ni catalyst and application |
| CN103920467B (en) * | 2014-05-06 | 2016-03-02 | 济南大学 | A kind of preparation method of sulfydryl silk adsorbent and application |
| CN111545178A (en) * | 2020-04-15 | 2020-08-18 | 济南大学 | Preparation method of biological adsorbent for separating sodium cyclamate |
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| WO2008129551A1 (en) * | 2007-04-18 | 2008-10-30 | H2Q Water Industries Ltd. | Filter medium |
| CN101239303A (en) * | 2008-03-18 | 2008-08-13 | 上海大学 | Alkalization modifying method of luffa and use thereof |
| CN101745367A (en) * | 2008-03-18 | 2010-06-23 | 上海大学 | Application of etherized luffa in metallic ion adsorption as adsorbent |
| CN101239306A (en) * | 2008-03-18 | 2008-08-13 | 上海大学 | Method for preparing etherification luffa and application of it in metallic ion adsorption |
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