CN1566513A - Antibacterial active carbon fiber - Google Patents

Antibacterial active carbon fiber Download PDF

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Publication number
CN1566513A
CN1566513A CN 03147863 CN03147863A CN1566513A CN 1566513 A CN1566513 A CN 1566513A CN 03147863 CN03147863 CN 03147863 CN 03147863 A CN03147863 A CN 03147863A CN 1566513 A CN1566513 A CN 1566513A
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ion
silver
activated carbon
carbon fiber
salt
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CN 03147863
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王家君
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Abstract

The invention discloses an antibiotic activated carbon fiber and its preparing method. The preparing method includes: steeping the activated carbon fiber in solution containing at least one of silver ion, copper ion or zinc ion; covering silver ion, copper ion and zinc ion on the activated carbon fiber by adsorption and chemical reactions; and drying. The invention has good adsorption, sterilization and bacteriostasis functions.

Description

A kind of antibacterial fibre of activated carbon
Technical field
Disclosed in this invention is a kind of antibacterial fibre of activated carbon and preparation method thereof, belongs to new function material technology category.
Background technology
The present activated carbon fiber of producing, be mainly used in filter and absorbed air in suspended particulate substance and pernicious gas to purify air, absorbing heavy metal ions in water, bacterium and suspended matter purify water, and are applied in the solution occasion such as noble metal recovery.Activated carbon fiber is owing to have good chemical stability, very high specific area, can connect chelation group by surface modification and give special chemism and selectivity, and be easy to make the Filters of the different shape that is suitable for different occasions uses, as active carbon fiber felt, activated carbon fiber cloth etc., be a kind of desirable absorption, filtering material.
By absorption and filtration, be the main means of removing suspended particulate substance, bacterium in water body, the air at present.According to adsorption mechanism, no matter be physical absorption or chemisorbed, adsorption and desorption is a reversible process.Promptly in adsorption process, there is the phenomenon of desorb to exist; When absorption had just begun, based on adsorption reaction, its inverse process was separated suction phenomenon and can be ignored; But after reaching certain adsorbance, the speed of desorb is just apparent in view; When adsorption and desorption speed equates, reach adsorption equilibrium.From the statistics angle, ion or suspended particulate from be adsorbed the material sorption to coming off fully from sorbing material, have the regular hour yardstick; The length of this time scale, relevant with specific area, temperature and the pressure factor of the concentration of the character of adsorbate (ion that is adsorbed or suspended particulate) and adsorbent (sorbing material), adsorbate, adsorbent.When external environment is constant, for specific adsorbent (sorbing material), higher specific surface area, relatively low adsorption density increases the adsorbent consumption, helps increasing the mean residence time of adsorbate on adsorbent, improves filter effect.
But in actual the use, the use amount that increases adsorbent simply is unpractical.The bacterium of required filtration, virus, the possible survival ability that has is stronger, can survive for a long time under the normal temperature, is far longer than the mean residence time on adsorbent.Therefore, filter bacterium, virus and the suspended particulate substance of high concentration by the sorbing material of high-specific surface area merely, can produce the desorb of bacterium, virus inevitably, reenter air and water body and form pollution along with the increase of adsorbance.
People wish to release the sorbing material of the high-specific surface area with antibacterial action, to address this problem.Patent 02115175 is released antibacterial fibre of activated carbon containing nano silver particles; be to adopt concentrated phosphoric acid to soak matrix fiber and boil solution, high temperature cabonization under the inert gas shielding condition then, the residual acid of the flush away that is soaked in water; with the silver ion solution immersion it being covered again carries, gives sterilization, antibacterial functions.This method in its fiber activation process, can connect a large amount of phosphate radicals with absorption and stable silver ion on fiber base, the fiber after the processing can slowly discharge silver ion in solution, reach the effect of killing and suppressing bacterium, virus.But the antibacterial fibre of activated carbon of this method preparation, the processing technology complexity, its mechanical strength can not guarantee, its cost and practical ranges are restricted.
Patent 00127594 is released the manufacture method of a kind of broad-spectrum antibacterial and anti-mildew air-conditioning filter net and used antibacterial antimildew polyacrylic fibres thereof, by the chemical reaction nano level silver of absorption and silver oxide particle in the surface of silicate clay and micropore, method by spinning is spun into the polyacrylic fibres that has nanometer-level silver on the surface then, forms the air-conditioning filter net with antibacterial and mouldproof effect by weaving again.But can not guarantee that a large amount of Nano Silvers and silver oxide in spinning process, are covered by macromolecule, thereby make greatly discount of antibiotic, fungistatic effect, and its specific area of not activated fiber is less relatively, its filter and adsorption effect not high.And the Ag-carried multifunctional tourmalinite fibre that patent 02111545 is released, tourmaline and viscose glue wet spinning by the absorption silver ion make fiber carry silver, reach antibiotic, antibacterial purpose, also have same defective.
In sum, for the sorbing material of the high-specific surface area of being convenient to produce with antibacterial action is provided, in the sterilization that improves activated carbon fiber, the toxic effect of going out fruit, do not influence its mechanical property, cost is suitable, and technology is simple, and the spy finishes the present invention.
Summary of the invention
The purpose of this invention is to provide that a kind of cost is suitable, production technology simple, have antibacterial action the activated carbon fiber of high-specific surface area.
Design of the present invention is such:
Metal ion Ag +, Cu 2+, Zn 2+Bacterium, virus there are good inhibition and killing effect, especially Ag +, Cu 2+To the inhibition of bacterium, virus with kill and possess broad spectrum activity.The high-ratio surface activated carbon fiber is as sorbing material, in absorption and desorption process, because kinetic factor will make bacterium, virus take place at adsorbent surface there is certain time of staying before the desorb.Contain a metal ion species Ag less if cover to be loaded onto on the activated carbon fiber surface +, Cu 2+, Zn 2+Salt because the hydrone in the environment is also adsorbed in the surface of activated carbon fiber in absorption bacterium, virus, form to be dissolved with and contain a metal ion species Ag at least +, Cu 2+, Zn 2+Liquid film, the metal ion that is dissolved and absorption and the bacterium, the virus that are enriched in identical activated carbon fiber surface interact inhibition and kill bacteria and virus.When promptly guaranteeing the adsorption filtration effect, adsorbed bacterium, virus there is very strong killing effect.
Because Ag +When concentration is several ppb, just possess the ability of inhibition and kill bacteria, consider in the running water Ag +, Cu 2+, Zn 2+Strict restriction arranged, cover on the surface of the activated carbon fiber of high-specific surface area and carry an Ag +The time, can adopt chemical reaction to form the microsolubility salt and be adsorbed on the sorbing material surface, oven dry is made then, is used for filtration, the sterile material of running water system, Ag +Slowly release both can be satisfied long-term result of use, can satisfy tap water confrontation Ag again +The requirement of concentration.The microsolubility salt that can satisfy these requirements has silver orthophosphate, silver oxalate, silver thiocyanate, silver carbonate etc.
Be applied to the adsorption filtration sterile material of air filtration and other water bodys, can adopt Ag +, Cu 2+, Zn 2+Solubility salt solution directly be adsorbed on the activated carbon fiber surface, or the nano particle that adopts the mode of chemical reaction to form microsolubility salt and argent, copper covers and is loaded in the activated carbon fiber surface, oven dry is made then; Among this two class preparation method, containing Ag +Solubility salt solution or go back microsolubility salt system, unsuitable and Cu 2+, Zn 2+Halide combination.
From cost consideration, Ag +The solubility salt is proper with employing silver citrate, silver nitrate, Cu 2+, Zn 2+The solubility salt can adopt nitrate, sulfate, hydrochloride, citrate, oxalates.Cu 2+, Zn 2+The microsolubility salt can adopt carbonate.
In actual the use, the activated carbon fiber of adsorbing metal ions and the activated carbon fiber of adsorbing metal ions not can be used in combination, both guarantee very high adsorption filtration sterilization effect, can reduce the consumption of argent and copper again, reduce cost.Single configuration metal ions Zn 2+Higher to the concentration that the bacterium generation significantly suppresses and killing action is required, cover when carrying on the activated carbon fiber surface, should adopt solubility salt solution directly to adsorb, oven dry is made then.
When covering carrying metal ion by absorption or chemical reaction, the total concentration of corresponding metal ion should not be lower than 1.0mMol/l in the preceding solution of absorption and reaction, otherwise will increase absorption or reaction time, is unfavorable for reducing production cost.
The present invention has following feature:
1. adopt to cover in the absorption of activated carbon fiber surface to be loaded with a kind of of silver ion, copper ion and zinc ion at least, oven dry is made then.
2. when activated carbon fiber covers Ag-bearing ion, copper ion and zinc ion, adopt the soluble-salt solution at the corresponding metal ion directly to adsorb, oven dry is made then.
3. when activated carbon fiber covers carrying silver ion, copper ion, the nano particle that can adopt the mode of chemical reaction to form microsolubility salt and argent, copper covers and is loaded in the sorbing material surface, and oven dry is made then.
4.Ag +The solubility salt can adopt silver citrate, silver nitrate; The microsolubility salt can adopt silver orthophosphate, silver oxalate, silver thiocyanate, silver carbonate.
5.Cu 2+, Zn 2+The solubility salt can adopt nitrate, sulfate, hydrochloride, citrate, oxalates; Cu 2+, Zn 2+The microsolubility salt can adopt carbonate.
6. when activated carbon fiber covered carrying silver ion, copper ion and zinc ion processing, the concentration that GOLD FROM PLATING SOLUTION belongs to ion was not less than 1.0mMol/l.
Description of drawings
Figure (1) covers the field emission electron scanned photograph of carrying metallic copper, silver composite for the activated carbon fiber surface of embodiment 7, and enlargement ratio is 100000.The metallic copper, the silver composite that are reduced have nanoscale.
The specific embodiment
Being described further below in conjunction with embodiment, is not limitation of the invention.
According to the antibacterial fibre of activated carbon of the high-ratio surface that covers carrying metal ion of embodiment preparation, the performance test methods of its kill bacteria, virus is with reference to GB15979, and its test result sees Table (1).
Embodiment 1
With the specific surface of 80mm * 125mm is 1200M 2/ g, thickness are that the active carbon fiber felt of 5~6mm is immersed in 200ml0.02M AgNO 3In the aqueous solution 1 hour, after the taking-up, drain 60~80 ℃ of vacuumizing and drying 2 hours.
Embodiment 2
With the specific surface of 80mm * 125mm is 1200M 2/ g, thickness are that the active carbon fiber felt of 5~6mm is immersed in 200ml0.02M CuSO 4With 0.1M ZnCl 2In the mixed aqueous solution 1.5 hours, after the taking-up, drain 120~150 ℃ of oven dry 2 hours.
Embodiment 3
With the specific surface of 80mm * 125mm is 1000M 2/ g, thickness are that the active carbon fiber felt of 8~10mm is immersed in 200ml0.01M AgNO 3With 0.02M CuSO 4In the mixed aqueous solution 1 hour, after the taking-up, drain 80 ℃ of vacuumizing and drying 2 hours.
Embodiment 4
With the specific surface of 80mm * 125mm is 700M 2/ g, thickness are that the active carbon fiber felt of 5~8mm is immersed in the 200ml0.01M silver citrate aqueous solution 1 hour, after the taking-up, drain 100 ℃ of vacuumizing and drying 2 hours.Wherein there is part citric acid silver to be reduced into nano-Ag particles.
Embodiment 5
With the specific surface of 120mm * 120mm is 1200M 2The activated carbon fiber cloth of/g is immersed in 200ml 0.02M AgNO 3In the aqueous solution, stir and to add 0.05M oxalic acid 20ml down, stirred 20 minutes, form silver oxalate precipitation (slightly soluble), filtration, distilled water wash 3 times, 80 ℃ of vacuumizing and drying 2 hours.
Embodiment 6
With 120mm * 120mm specific surface is 1200M 2The activated carbon fiber cloth of/g is immersed in 200ml 0.1M ZnSO 4In the aqueous solution 1 hour, filter 120~150 ℃ of oven dry 2 hours.
Embodiment 7
With the specific surface of 120mm * 120mm is 1200M 2The activated carbon fiber cloth of/g is immersed in 200ml 0.02M AgNO 3In 0.20M copper nitrate mixed solution, under stirring, 50ml 3.0M hydrazine hydrate is added in the mixed solution, stirred 20 minutes, filter, distilled water wash 3 times, absolute ethanol washing 2 times was dried 2 hours for 100~120 ℃.
Table (1), cover the sterilizing rate (%) of the activated carbon fiber of carrying metal ion
Figure A0314786300071

Claims (2)

1. antibacterial fibre of activated carbon and preparation method thereof, activated carbon fiber is immersed in to contain be in a kind of solution of silver ion, copper ion and zinc ion at least, on activated carbon fiber, cover and be loaded onto a kind of of rare silver ion, copper ion and zinc ion by absorption, chemical reaction, oven dry is made then, it is characterized in that:
(a) when activated carbon fiber covers carrying silver ion, copper ion and zinc ion, adopt soluble-salt solution directly to adsorb at the corresponding metal ion, oven dry is made then;
(b) when activated carbon fiber covers carrying silver ion, copper ion, adopt the mode of chemical reaction to form the microsolubility salt, oven dry is made then;
(c) when activated carbon fiber covers carrying silver ion, copper ion, the nano particle that adopts the mode of chemical reaction to form argent, copper covers and is loaded in the sorbing material surface, and oven dry is made then;
Wherein:
Described soluble silver salt is a kind of of silver citrate, silver nitrate at least;
Described microsolubility silver salt is a kind of of silver orthophosphate, silver oxalate, silver thiocyanate, silver carbonate at least;
Described Cu 2+, Zn 2+The solubility salt be a kind of of nitrate, sulfate, hydrochloride, citrate, oxalates at least;
Described Cu 2+, Zn 2+Slightly soluble salt be carbonate.
2. a kind of antibacterial fibre of activated carbon as claimed in claim 1 and preparation method thereof is characterized in that the concentration of total metal ion is not less than 1.0mMol/l in the solution when activated carbon fiber covers carrying silver ion, copper ion and zinc ion processing.
CN 03147863 2003-06-27 2003-06-27 Antibacterial active carbon fiber Pending CN1566513A (en)

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Application Number Priority Date Filing Date Title
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101078179B (en) * 2006-05-25 2010-05-12 陈凡 Bactericidal property treatment technique for fibre or fibre products
CN1883897B (en) * 2006-06-13 2010-09-15 上海大不同木业科技有限公司 Wood protective agent
WO2012155344A1 (en) * 2011-05-18 2012-11-22 河南天源环保高科股份有限公司 Fiber capable of absorbing iodine and preparation method and use thereof
CN103316044A (en) * 2013-06-07 2013-09-25 逢甲大学 Composition structure used for inhibiting gastrointestinal bacterial infections
CN106758173A (en) * 2016-11-25 2017-05-31 深圳大学 A kind of carbon fiber of metal-modified and preparation method thereof
CN107789659A (en) * 2017-11-16 2018-03-13 安徽斯麦特医学技术开发有限公司 A kind of medical protection pad
CN108854966A (en) * 2018-07-20 2018-11-23 张家港市东威新材料技术开发有限公司 A kind of preparation method of silica gel supported composite adsorbing material
CN108866807A (en) * 2018-07-13 2018-11-23 合肥洁诺医疗用品有限公司 A kind of antibacterial nonwoven cloth
CN109267023A (en) * 2018-08-29 2019-01-25 江苏理工学院 A kind of antibacterial active carbon fiber material and preparation method thereof
CN109569136A (en) * 2019-01-03 2019-04-05 广州澳企实验室技术股份有限公司 A kind of laboratory hood straight-line chemical exhaust processing unit
CN112226847A (en) * 2020-11-09 2021-01-15 紫灿科技(上海)股份有限公司 Durable antibacterial mildew-proof fiber and application thereof
CN114395912A (en) * 2021-06-29 2022-04-26 台湾塑胶工业股份有限公司 Method for producing antibacterial fiber

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101078179B (en) * 2006-05-25 2010-05-12 陈凡 Bactericidal property treatment technique for fibre or fibre products
CN1883897B (en) * 2006-06-13 2010-09-15 上海大不同木业科技有限公司 Wood protective agent
WO2012155344A1 (en) * 2011-05-18 2012-11-22 河南天源环保高科股份有限公司 Fiber capable of absorbing iodine and preparation method and use thereof
CN103316044A (en) * 2013-06-07 2013-09-25 逢甲大学 Composition structure used for inhibiting gastrointestinal bacterial infections
CN103316044B (en) * 2013-06-07 2015-11-04 逢甲大学 For suppressing the compositions structure of intestines and stomach bacteriological infection
CN106758173A (en) * 2016-11-25 2017-05-31 深圳大学 A kind of carbon fiber of metal-modified and preparation method thereof
CN106758173B (en) * 2016-11-25 2019-03-12 深圳大学 A kind of carbon fiber of metal-modified and preparation method thereof
CN107789659A (en) * 2017-11-16 2018-03-13 安徽斯麦特医学技术开发有限公司 A kind of medical protection pad
CN108866807A (en) * 2018-07-13 2018-11-23 合肥洁诺医疗用品有限公司 A kind of antibacterial nonwoven cloth
CN108854966A (en) * 2018-07-20 2018-11-23 张家港市东威新材料技术开发有限公司 A kind of preparation method of silica gel supported composite adsorbing material
CN109267023A (en) * 2018-08-29 2019-01-25 江苏理工学院 A kind of antibacterial active carbon fiber material and preparation method thereof
CN109569136A (en) * 2019-01-03 2019-04-05 广州澳企实验室技术股份有限公司 A kind of laboratory hood straight-line chemical exhaust processing unit
CN109569136B (en) * 2019-01-03 2024-06-18 广州澳企实验室技术股份有限公司 Laboratory fume chamber direct vent formula chemistry exhaust treatment device
CN112226847A (en) * 2020-11-09 2021-01-15 紫灿科技(上海)股份有限公司 Durable antibacterial mildew-proof fiber and application thereof
CN114395912A (en) * 2021-06-29 2022-04-26 台湾塑胶工业股份有限公司 Method for producing antibacterial fiber
CN114395912B (en) * 2021-06-29 2024-04-16 台湾塑胶工业股份有限公司 Method for manufacturing antibacterial fiber
US12104316B2 (en) 2021-06-29 2024-10-01 Formosa Plastics Corporation Manufacturing method for antibacterial fiber

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