CN103205861A - Electrostatic spun-wool keratin/fibroin composite fiber membrane for absorbing heavy metal ions and preparation method thereof - Google Patents
Electrostatic spun-wool keratin/fibroin composite fiber membrane for absorbing heavy metal ions and preparation method thereof Download PDFInfo
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- CN103205861A CN103205861A CN 201310103966 CN201310103966A CN103205861A CN 103205861 A CN103205861 A CN 103205861A CN 201310103966 CN201310103966 CN 201310103966 CN 201310103966 A CN201310103966 A CN 201310103966A CN 103205861 A CN103205861 A CN 103205861A
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- 102000011782 Keratins Human genes 0.000 title claims abstract description 117
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- 239000012528 membrane Substances 0.000 title claims abstract description 60
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 45
- 150000002500 ions Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000835 fiber Substances 0.000 title abstract description 9
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 21
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Abstract
The invention relates to an electrostatic spun-wool keratin/fibroin composite fiber membrane for absorbing heavy metal ions and a preparation method thereof. The preparation method comprises the steps of: (1) dissolving wool by adopting sodium sulfide/urea/lauryl sodium sulfate; (2) adding a spinning solution formed by mixing wool keratin/fibroin protein into an electrostatic spinning device, and preparing a wool keratin and fibroin composite fiber membrane by using an electrostatic spinning way; and (3) putting the wool keratin/fibroin composite fiber membrane prepared by using the electrostatic spinning way into a methanol solution for 2-4 hours, then washing with de-ionized water, and then airing naturally. The electrostatic spun-wool keratin/fibroin composite fiber membrane prepared by the invention has the characteristics of a great specific surface area, high porosity, many internal holes and the like, can enlarge a contact area with metal ions, increase an absorption amount, shorten the time for achieving absorption balance, absorb heavy metal ions in wastewater efficiently and degrade biologically without causing environment pollution; the wool keratin/fibroin composite fiber membrane after absorbing the heavy metal ions can be degraded, absorbed and recycled under the acid condition; and the degraded and absorbed wool keratin/fibroin composite fiber membrane still can be used repeatedly.
Description
Technical field
The invention belongs to the sorbing material field, particularly a kind of efficiently static of Adsorption of Heavy Metal Ions spins wool keratin/fibroin composite cellulosic membrane.
Background technology
Wool is the important source material of textile industry.It has many good characteristics as natural protein fibre, and, good springiness strong as wettability power, gloss is soft, dyeability is good etc., particularly human body is had the affine and health-care function of physiology.China's wool resource is abundant, is again wool textile industry big producing country, but because the restriction of wool quality, feeding and management and textile technology, annual have a large amount of staple fibres, crude fibre to go out of use.According to statistics, the nearly 2,000,000 tons waste and old wool of the annual generation of China, this has not only caused the waste of keratin resource, and contaminated environment.Thereby discarded keratin regeneration had very important meaning.
Kind of a-amino acid surplus containing 20 in the wool, each seed amino acid (NH
2-CHR-COOH) by peptide bond (CO-NH-) connect into the keratin long-chain, on 2 chains in separately the cysteine-the SH oxidation forms disulfide bond, makes the peptide interchain form the cross-linked network of quite stable.The effect form is different with the difference of R base between keratin molecule, mainly contains hydrogen bond, salt type bond and disulfide bond, is main action mode with disulfide bond wherein.Because the keratin distinctive molecular structure makes it have excellent biological characteristics and good material mechanical performance, obtain using more widely in fields such as material, biology, medical science through artificial keratin of purifying and the product of chemical modification.In addition, the keratin after the purification also can be used as heavy metal chelating agent, cosmetics and food additives, hair nourishing agent, fabric finishing agent etc.
Heavy metal pollution refers to the environmental pollution that caused by heavy metal or its compound.Heavy metal pollution can cause by natural cause (as soil, rock decay and volcano eruption etc.), but mainly is due to mining, industrial manufacturing, sewage irrigation and the human factors such as use heavy metal goods or containing metal pollutant.Heavy metal can not but can be become thousands of times ground enrichment by biodegradation under the biological magnification of food chain, enter human body at last.Although some heavy metal such as manganese, copper, zinc etc. are the essential trace elements of vital movement, most of heavy metal is not that life is necessary.Surpass finite concentration, just will cause damage to health, cause various diseases, as: dehydration, stomachache, nauseating, dizzy, muscle dysfunction, children's nervous system destruction, lung pain, inflammatory eye, fash, vomiting, stomachache, pain, expiratory dyspnea, hepatic injury etc.Along with the fast development of China's economic society, the quickening of population growth, industrialization and urbanization advances, and the industry that relates to heavy metal is just keeping stronger growth, and the heavy metal pollution event takes place frequently, and has brought severe impairment for environment and the people's health.
The method of removing the middle heavy metal ion of anhydrating is a lot, traditional have chemical precipitation method, oxidation-reduction method, ferrite process, electrolysis, evaporation concentration method, ion-exchange-resin process etc., but these methods exist mostly that investment is big, operating cost is high, operational administrative trouble and can produce secondary pollution and can not solve problems such as metal and water resource recycling well.
Using at present more in practice is absorption method, or by electrostatic interaction (interacting between positively charged metal ion and the electronegative matrix), or by chelation (providing lone pair electrons and metal ion to form co-ordinate covalent bond by matrix).Adsorbent commonly used comprises active carbon, bentonite, zeolite and biological adsorption agent, and wherein biological absorption has advantages such as the adsorbent source is abundant, wide in variety, cost is low, adsorption capacity is big, speed is fast, can remedy the defective of conventional process method and has been subjected to extensive concern.The keratin sorbing material is as a kind of very promising biological sorbing material, contain a large amount of amido links, disulfide bond, amino, carboxyl, hydroxyl etc. can with the group of heavy metal ion generation ligand complex effect, heavy metal ion in can adsorbent solution, keratin after the Adsorption of Heavy Metal Ions can reclaim in desorb under the acid condition, and the keratin sorbing material after the desorb is still reusable.
Summary of the invention
The static that the invention provides a kind of Adsorption of Heavy Metal Ions spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, and this composite cellulosic membrane sorbing material is the heavy metal ion in the adsorbent solution efficiently.
The static of a kind of Adsorption of Heavy Metal Ions of the present invention spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that this preparation method comprises following operating procedure:
Discarded wool is cleaned dry for standby under 50-80 ° of C.The wool that 5g is standby is put into and is contained 2g vulcanized sodium, in the 100mL mixed aqueous solution of 1g lauryl sodium sulfate and 42g urea, bath raio 1:20, then at 30-50 ℃ of following dissolving 15-20h, filter solid impurity with the terylene screen cloth after, make wool keratin solution.To 4-5, the wool keratin precipitation is separated out with glacial acetic acid modulation wool keratin pH value of solution value, made the wool keratin powder 40-60 ° of C oven dry.Be dissolved in 98% the formic acid solution ultrasonic processing 1-2h, the wool keratin of configuration quality specific concentration 12-16%/fibroin mixed solution under the fibroin albumen room temperature with the wool keratin of 40-60g and 60-40g.Above-mentioned wool keratin/fibroin mixed solution is joined in the electrospinning device, prepare wool keratin/fibroin composite cellulosic membrane with method of electrostatic spinning, the technology of electrostatic spinning is: voltage 10-15kV, spinning is apart from 8-12cm, spinning solution feed quantity 0.5-2ml/h, environment temperature 20-40 ° of C, ambient humidity 60-70%.After the wool keratin/fibroin composite cellulosic membrane of above-mentioned method of electrostatic spinning preparation placed methanol solution 2-4h, deionized water was cleaned the back natural air drying.
The present invention has following beneficial effect:
Static of the present invention spins wool keratin/fibroin composite cellulosic membrane, have characteristics such as specific area is big, porosity is high, internal void is many, can increase the contact area with metal ion, increase adsorbance, shorten and reach time for adsorption balance, adsorb the heavy metal ion in the waste water effectively, the energy biodegradation, can not cause environmental pollution, wool keratin after the Adsorption of Heavy Metal Ions/fibroin composite cellulosic membrane can reclaim in desorb under the acid condition, and the keratin after the desorb/fibroin composite cellulosic membrane is still reusable.
Description of drawings
The static that Fig. 1 obtains for embodiment 1 step (5) spins wool keratin/fibroin composite cellulosic membrane SEM Electronic Speculum figure, static after methanol solution that Fig. 2 obtains for embodiment 1 step (6) is handled spins wool keratin/fibroin composite cellulosic membrane SEM Electronic Speculum figure, and Fig. 3 spins SEM Electronic Speculum figure behind wool keratin/fibroin composite cellulosic membrane absorbing copper ion for static.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.
Embodiment 1:
The static of a kind of Adsorption of Heavy Metal Ions of the present invention spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that this preparation method comprises following operating procedure:
(1) discarded wool is cleaned dry for standby under 60 ° of C;
(2) wool that 5g is standby is put into and is contained 2g vulcanized sodium, in the 100mL mixed aqueous solution of 1g lauryl sodium sulfate and 42g urea, bath raio 1:20, then at 40 ℃ of dissolving 15h down, filter solid impurity with the terylene screen cloth after, make wool keratin solution;
(3) with glacial acetic acid modulation wool keratin pH value of solution value to 4.5, the wool keratin precipitation is separated out, made the wool keratin powder 50 ℃ of oven dry;
(4) be dissolved in 98% the formic acid solution ultrasonic processing 2h, the wool keratin of configuration quality specific concentration 15%/fibroin mixed solution under the fibroin albumen room temperature with the wool keratin of 50g and 50g;
(5) above-mentioned wool keratin/fibroin mixed solution is joined in the electrospinning device, prepare wool keratin/fibroin composite cellulosic membrane with method of electrostatic spinning, the technology of electrostatic spinning is: voltage 12kV, spinning is apart from 10cm, spinning solution feed quantity 1ml/h, 30 ° of C of environment temperature, ambient humidity 70%.
(6) after wool keratin/fibroin composite cellulosic membrane that above-mentioned method of electrostatic spinning is prepared placed methanol solution 3h, deionized water was cleaned the back natural air drying.
2, the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the molecular weight of the wool keratin that step (3) obtains is between 45,000-55,000.
3, the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the wool keratin that step (5) obtains/fibroin composite cellulosic membrane average diameter 215nm, porosity 73%.
4, the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the wool keratin that step (6) obtains/fibroin composite cellulosic membrane is to Cu
2+Adsorbance be 21mg/g, to Cr
3+Adsorbance be 11mg/g.
Embodiment 2:
The static of a kind of Adsorption of Heavy Metal Ions of the present invention spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that this preparation method comprises following operating procedure:
((1) cleans discarded wool, dry for standby under 60 ° of C;
(2) wool that 5g is standby is put into and is contained 2g vulcanized sodium, in the 100mL mixed aqueous solution of 1g lauryl sodium sulfate and 42g urea, bath raio 1:20, then at 30-50 ℃ of dissolving 15h down, filter solid impurity with the terylene screen cloth after, make wool keratin solution;
(3) with glacial acetic acid modulation wool keratin pH value of solution value to 5, the wool keratin precipitation is separated out, made the wool keratin powder 60 ° of C oven dry;
(4) be dissolved in 98% the formic acid solution ultrasonic processing 1.5h, the wool keratin of configuration quality specific concentration 16%/fibroin mixed solution under the fibroin albumen room temperature with the wool keratin of 60g and 40g;
(5) above-mentioned wool keratin/fibroin mixed solution is joined in the electrospinning device, prepare wool keratin/fibroin composite cellulosic membrane with method of electrostatic spinning, the technology of electrostatic spinning is: voltage 15kV, spinning is apart from 8cm, spinning solution feed quantity 0.5ml/h, 40 ° of C of environment temperature, ambient humidity 70%.
(6) after wool keratin/fibroin composite cellulosic membrane that above-mentioned method of electrostatic spinning is prepared placed methanol solution 2h, deionized water was cleaned the back natural air drying.
2, the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the molecular weight of the wool keratin that step (3) obtains is between 42,000-64,000.
3, the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the wool keratin that step (5) obtains/fibroin composite cellulosic membrane average diameter 350nm, porosity 67%.
4, the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the wool keratin that step (6) obtains/fibroin composite cellulosic membrane is to Cu
2+Adsorbance be 17mg/g, to Cr
3+Adsorbance be 8.5mg/g.
Embodiment 3:
The static of a kind of Adsorption of Heavy Metal Ions of the present invention spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that this preparation method comprises following operating procedure:
(1) discarded wool is cleaned dry for standby under 70 ° of C;
(2) wool that 5g is standby is put into and is contained 2g vulcanized sodium, in the 100mL mixed aqueous solution of 1g lauryl sodium sulfate and 42g urea, bath raio 1:20, then at 50 ℃ of dissolving 20h down, filter solid impurity with the terylene screen cloth after, make wool keratin solution;
(3) with glacial acetic acid modulation wool keratin pH value of solution value to 4, the wool keratin precipitation is separated out, made the wool keratin powder 60 ° of C oven dry;
(4) be dissolved in 98% the formic acid solution ultrasonic processing 2h, the wool keratin of configuration quality specific concentration 12%/fibroin mixed solution under the fibroin albumen room temperature with the wool keratin of 40g and 60g;
(5) above-mentioned wool keratin/fibroin mixed solution is joined in the electrospinning device, prepare wool keratin/fibroin composite cellulosic membrane with method of electrostatic spinning, the technology of electrostatic spinning is: voltage 12kV, spinning is apart from 12cm, spinning solution feed quantity 2ml/h, 40 ° of C of environment temperature, ambient humidity 70%.
(6) after wool keratin/fibroin composite cellulosic membrane that above-mentioned method of electrostatic spinning is prepared placed methanol solution 3h, deionized water was cleaned the back natural air drying.
2, the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the molecular weight of the wool keratin that step (3) obtains is between 56,000-68,000.
3, the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the wool keratin that step (5) obtains/fibroin composite cellulosic membrane average diameter 520nm, porosity 54%.
4, the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the wool keratin that step (6) obtains/fibroin composite cellulosic membrane is to Cu
2+Adsorbance be 13mg/g, to Cr
3+Adsorbance be 7mg/g.
Embodiment 4:
The static of a kind of Adsorption of Heavy Metal Ions of the present invention spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that this preparation method comprises following operating procedure:
(1) discarded wool is cleaned dry for standby under 80 ° of C;
(2) wool that 5g is standby is put into and is contained 2g vulcanized sodium, in the 100mL mixed aqueous solution of 1g lauryl sodium sulfate and 42g urea, bath raio 1:20, then at 50 ℃ of dissolving 20h down, filter solid impurity with the terylene screen cloth after, make wool keratin solution;
(3) with glacial acetic acid modulation wool keratin pH value of solution value to 4.5, the wool keratin precipitation is separated out, made the wool keratin powder 60 ° of C oven dry;
(4) be dissolved in 98% the formic acid solution ultrasonic processing 2h, the wool keratin of configuration quality specific concentration 14%/fibroin mixed solution under the fibroin albumen room temperature with the wool keratin of 55g and 45g;
(5) above-mentioned wool keratin/fibroin mixed solution is joined in the electrospinning device, prepare wool keratin/fibroin composite cellulosic membrane with method of electrostatic spinning, the technology of electrostatic spinning is: voltage 12kV, spinning is apart from 10cm, spinning solution feed quantity 1.5ml/h, 40 ° of C of environment temperature, ambient humidity 65%.
(6) after wool keratin/fibroin composite cellulosic membrane that above-mentioned method of electrostatic spinning is prepared placed methanol solution 4h, deionized water was cleaned the back natural air drying.
2, the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the molecular weight of the wool keratin that step (3) obtains is between 46,000-62,000.
3, the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the wool keratin that step (5) obtains/fibroin composite cellulosic membrane average diameter 420nm, porosity 61%.
4, the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the wool keratin that step (6) obtains/fibroin composite cellulosic membrane is to Cu
2+Adsorbance be 15mg/g, to Cr
3+Adsorbance be 10.5mg/g.
Obviously, the above embodiment of the present invention only is for example of the present invention clearly is described, and is not to be restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here can't give exhaustive to all embodiments.Everyly belong to the row that apparent variation that technical scheme of the present invention amplifies out or change still are in protection scope of the present invention.
Claims (4)
1. the static of an Adsorption of Heavy Metal Ions spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that this preparation method comprises following operating procedure:
(1) discarded wool is cleaned dry for standby under 50-80 ° of C;
(2) wool that 5g is standby is put into and is contained 2g vulcanized sodium, in the 100mL mixed aqueous solution of 1g lauryl sodium sulfate and 42g urea, bath raio 1:20 dissolves 15-20h down at 30-50 ℃ then, after filtering solid impurity with the terylene screen cloth, make wool keratin solution;
(3) modulate wool keratin pH value of solution value to 4-5 with glacial acetic acid, the wool keratin precipitation is separated out, make the wool keratin powder 40-60 ° of C oven dry;
(4) be dissolved in 98% the formic acid solution ultrasonic processing 1-2h, the wool keratin of configuration quality specific concentration 12-16%/fibroin mixed solution under the fibroin albumen room temperature with the wool keratin of 40-60g and 60-40g;
(5) above-mentioned wool keratin/fibroin mixed solution is joined in the electrospinning device, prepare wool keratin/fibroin composite cellulosic membrane with method of electrostatic spinning, the technology of electrostatic spinning is: voltage 10-15kV, spinning is apart from 8-12cm, spinning solution feed quantity 0.5-2ml/h, environment temperature 20-40 ° of C, ambient humidity 60-70%;
(6) after wool keratin/fibroin composite cellulosic membrane that above-mentioned method of electrostatic spinning is prepared placed methanol solution 2-4h, deionized water was cleaned the back natural air drying.
2. the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the molecular weight of the wool keratin that step (3) obtains is between 40,000-80,000.
3. the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the wool keratin that step (5) obtains/fibroin composite cellulosic membrane average diameter 120-700nm, porosity 50-80%.
4. the static of a kind of Adsorption of Heavy Metal Ions according to claim 1 spins wool keratin/fibroin composite cellulosic membrane and preparation method thereof, it is characterized in that, the wool keratin that step (6) obtains/fibroin composite cellulosic membrane is to Cu
2+Adsorbance be 3-25mg/g, to Cr
3+Adsorbance be 2-13mg/g.
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