CN103451920A - Preparation method of silver-loaded active wood carbon fiber - Google Patents
Preparation method of silver-loaded active wood carbon fiber Download PDFInfo
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- CN103451920A CN103451920A CN2013103598525A CN201310359852A CN103451920A CN 103451920 A CN103451920 A CN 103451920A CN 2013103598525 A CN2013103598525 A CN 2013103598525A CN 201310359852 A CN201310359852 A CN 201310359852A CN 103451920 A CN103451920 A CN 103451920A
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Abstract
The invention relates to a preparation method of silver-loaded active wood carbon fiber. The preparation method comprises the steps of steeping active wood carbon fiber in a silver nitrate solution at atmospheric pressure, and performing thermal decomposition under an anaerobic condition to obtain the silver-loaded active wood carbon fiber. The silver-loaded active wood carbon fiber obtained by optimizing and regulating the silver nitrate concentration and thermal decomposition temperature through taking the active wood carbon fiber with a larger pore size structure as a raw material is low in silver ion dissolution rate only achieving 0.226% on the premise of keeping the antibacterial ratio at 100%, the safety and durability of the silver-loaded active wood carbon fiber can be increased, and energy consumption in the preparation process can also be decreased, and the process steps can be simplified.
Description
Technical field
The present invention relates to the carbon fiber preparation field, specifically, relate to a kind of method of flooding the silver nitrate preparation year active wooden carbon fiber of silver by normal pressure.
Background technology
Activated carbon fiber has the specific area of abundant micropore and super large, excellent absorption property and high adsorption desorption speed, good resistance to acids and bases and chemical stability, and its product can also change form as required.Therefore, activated carbon fiber is widely used in environmental protection and medical field, for example pernicious gas absorption and purification of waste water.But activated carbon fiber, because of its excellent adsorptivity, also can adsorb a lot of bacteriums, makes it to become the pollution sources of microorganism, affects the effect of its use.Silver, as a kind of efficient inorganic antiseptic, can be adsorbed by activated carbon fiber, thereby give the activated carbon fiber anti-microbial property.
In " active carbon loading silver fiber " (ten thousand happy kitchen ranges etc., University Of Tianjin's journal, the 32nd the 5th phase of volume, P621, in September, 1999), adopt vacuum impregnation and vacuum to decompose preparation and carry silver-colored wooden carbon fiber.Vacuum condition has not only increased the complexity of technique, and the dissolution rate of silver ion is also increased, and affects its security and durability.(remaining water " structure of silver-colored type antibacterial fibre of activated carbon and the researchs of anti-microbial property thereof " such as being held under the arm, Materials Science and Engineering, the 19th the 4th phase of volume, P66, December calendar year 2001) in, mention sisal based activated carbon fiber, viscose base activated carbon fiber through steam activation are dipped in to silver salt solution after low temperature drying obtain the activated carbon fiber containing AgCl or AgI.But the antibacterial effect of the silver compound activated carbon fiber of this year indissoluble is poor lower than the antibacterial effect of the activated carbon fiber, particularly silver iodide that carry argent, and silver chlorate only has and reaches a certain amount of when its mass fraction, and antibiotic rate just can reach 100%.
For above-mentioned weak point, propose a kind of new active wooden carbon fiber of silver that carries and be of great significance.
Summary of the invention
The purpose of this invention is to provide a kind of method of flooding the silver nitrate preparation year active wooden carbon fiber of silver by normal pressure.
In order to realize the object of the invention, the present invention adopts following technical scheme.
The preparation method of a kind of year active wooden carbon fiber of silver, by the thermal decomposition and obtaining under oxygen free condition after liquor argenti nitratis ophthalmicus normal pressure dipping of the wooden carbon fiber of activity.
In above-mentioned preparation method, described nitrate concentration is 0.05-0.4molL
-1, preferred 0.2molL
-1; Dip time is 20-30h, preferably 24h; Described heat decomposition temperature is 150-450 ℃, preferably 350 ℃, and time 30-100min, preferably 90min.
Wherein, the wooden carbon fiber of described activity is prepare by the following method and obtain:
1) wood-curing waste is crushed to the 30-80 order, mixes with phenol under catalyst action, under 150-160 ℃, stir 2-3h, obtain liquefied substance;
2) by after liquefied substance and synthetics mix and blend 0.5-1.5h, be heated to 160-175 ℃ with 10 ℃/h and obtain spinning solution, then insert in weaving loom, when spinning solution is heated to 110-130 ℃, can reels off raw silk from cocoons and obtain synthetic fiber;
3) synthetic fiber are placed in to formaldehyde that volume ratio is 1:1 and the mixed liquor of hydrochloric acid, the heating rate with 10-15 ℃/h, be heated to 85-95 ℃, and insulation 2-4h, be down to room temperature after washing drying, obtains wooden carbon fibre precursor;
4) wooden carbon fibre precursor is heated to 800 ℃, passes into activator, reaction obtains active wooden carbon fiber;
Wherein, in step 1), described phenol and waste material mass ratio are 4-6:1; Catalyst and waste material mass ratio are 0.4-0.6:1.Described catalyst is that phosphoric acid or mass fraction are 36% dilute sulfuric acid; The speed stirred can be adjusted according to the size of inventory and reactor;
Wherein, step 2) in, described synthetics is 0.04-0.06:1 with liquefied substance quality ratio; Described synthetics is hexamethylenetetramine;
Wherein, in step 4), described heating rate is 2-4 ℃ of min
-1, preferred 3 ℃ of min
-1; Described activator is steam, and passing into flow is 1.0-2.5ml/min/g, and the time of passing into is 10-90min, preferably 60min;
The wooden carbon fiber specific area of the activity that said method obtains reaches 740.50-1734.839m
2/ g;
Year active wooden carbon fiber of silver that the present invention also provides above-mentioned preparation method to obtain, its performance indications are as follows:
The antibiotic rate of Escherichia coli and staphylococcus aureus: 100(%)
Silver turnover rate: 0.226-2.213(%)
Specific area: 704.50-1159.434(m
2/ g)
Micropore specific area: 421.153-928.263(m
2/ g)
Total pore volume: 0.376-0.636(cm
3/ g)
Micropore volume: 0.176-0.364(cm
3/ g)
Average pore size: 0.896-1.307(nm)
The present invention be take wood-curing waste as raw material, needn't extract separately the chemical compositions such as cellulose and lignin from living beings, for example, compare with existing biomass carbon fiber (viscose glue base, lignin-base), simplify production technology, reduce production cost, improved the utilization rate of living beings.
The present invention adopts Soaking load silver simple substance, the defect of having avoided vacuum impregnation technology in the prior art etc. to bring.The present invention is by optimizing activation condition, obtain than the wooden carbon fiber of the activity of macroporous structure, as raw material, silver nitrate concentration, dip time, heat decomposition temperature are done further and optimized and revised again, by each factor interaction, obtain carrying silver-colored wooden carbon fiber under the prerequisite that keeps antibiotic rate 100%, the silver ion dissolution rate is low, is only 0.226%, has increased safety and the durability of product, also reduce the energy resource consumption in preparation process, simplify processing step simultaneously.
The specific embodiment
Following examples are used for the present invention is described, but are not used for limiting the scope of the invention.
The preparation of 1 year active wooden carbon fiber of silver of embodiment
After wood machining residues is ground into to 30 orders, put in the middle of liquefying plant.Add the phenol of 4 times of wood powder weight and the phosphoric acid of 0.4 times of wood powder weight, mixture is heated to 160 ℃ again, insulation 2.5h.After timber liquefied matter is down to room temperature, add the hexamethylenetetramine of 4% liquefied substance weight, through 1 hour, be warmed up to 170 ℃, synthetic spinning solution.Subsequently spinning solution is placed in to spinning machine, when spinning solution is heated to 120 ℃, with the speed of receiving 100 rev/mins of roll dies, receives silk.Synthetic fiber is placed in to formaldehyde that volume ratio is 1:1 and the mixed liquor of hydrochloric acid, with the heating rate of 10 ℃/h, is heated to 85 ℃, insulation 2h.Room temperature after washing drying to be down to.The precursor that takes 2.85g is placed in activation furnace; under the protection of nitrogen; after will being warmed up to 800 ℃ with the speed of 3 ℃/min; pass into steam in the time of insulation; flow is 1ml/min/g; and close steam evaporator after 60min, and make activation furnace automatically lower the temperature simultaneously, when reaching 350 ℃, temperature stops passing into nitrogen.To prepare specific area is 1249.511m
2in the silver nitrate concentration that the wooden impregnated carbon fiber of the activity of/g is 0.1mol/L in concentration, after 24h, take out dry.Be about to the wooden carbon fiber of impregnated activity and be placed in nitrogen environment, be heated to 250 ℃, insulation 60min, to be cooledly obtain carrying a silver-colored active wooden carbon fiber to room temperature.
The antibiotic rate that carries the active wooden carbon fiber of silver of preparation is 100%, and silver-colored turnover rate is 1.394%, specific area 976.433m
2/ g, micropore specific area is 828.115m
2/ g, total pore volume is 0.494cm
3/ g, Micropore volume is 0.327cm
3/ g, average pore size is 1.012nm.
The preparation of 2 years active wooden carbon fibers of silver of embodiment
After wood machining residues is ground into to 60 orders, put in the middle of liquefying plant.Add the phenol of 5 times of wood powder weight and the phosphoric acid of 0.5 times of wood powder weight, mixture is heated to 160 ℃ again, insulation 2.5h.After timber liquefied matter is down to room temperature, add the hexamethylenetetramine of liquefied substance 5% weight, through 1 hour, be warmed up to 170 ℃, synthetic spinning solution.Subsequently spinning solution is placed in to spinning machine, when spinning solution is heated to 120 ℃, with the speed of receiving 100 rev/mins of roll dies, receives silk.Synthetic fiber is placed in to formaldehyde that volume ratio is 1:1 and the mixed liquor of hydrochloric acid, with the heating rate of 10 ℃/h, is heated to 85 ℃, insulation 2h.Room temperature after washing drying to be down to.The precursor that takes 4.49g is placed in activation furnace, under the protection of nitrogen, after will being warmed up to 800 ℃ with the speed of 3 ℃/min; pass into steam in the time of insulation; its flow is 1ml/min/g, and closes steam evaporator after 90min, makes activation furnace automatically lower the temperature simultaneously.When reaching 300 ℃, temperature stops passing into nitrogen.To prepare specific area is 1737.839m
2in the silver nitrate concentration that the wooden impregnated carbon fiber of the activity of/g is 0.1mol/L in concentration, after 24h, take out dry.Be about to the wooden carbon fiber of impregnated activity and be placed in nitrogen environment, be heated to 250 ℃, insulation 90min, to be cooledly obtain carrying a silver-colored active wooden carbon fiber to room temperature.
The antibiotic rate that carries the active wooden carbon fiber of silver of preparation is 100%, and silver-colored turnover rate is 0.348%, specific area 1159.434m
2/ g, micropore specific area is 862.687m
2/ g, total pore volume is 0.636cm
3/ g, Micropore volume is 0.346cm
3/ g, average pore size is 1.097nm.
The preparation of 3 years active wooden carbon fibers of silver of embodiment
After wood machining residues is ground into to 80 orders, put in the middle of liquefying plant.Add the phenol of 5 times of wood powder weight and the sulfuric acid of 0.6 times of wood powder weight, mixture is heated to 160 ℃ again, insulation 2.5h.After timber liquefied matter is down to room temperature, add the hexamethylenetetramine of liquefied substance 6% weight, through 1 hour, be warmed up to 170 ℃, synthetic spinning solution.Subsequently spinning solution is placed in to spinning machine, when spinning solution is heated to 120 ℃, with the speed of receiving 100 rev/mins of roll dies, receives silk.Synthetic fiber is placed in to formaldehyde that volume ratio is 1:1 and the mixed liquor of hydrochloric acid, with the heating rate of 10 ℃/h, is heated to 85 ℃, insulation 2h.Room temperature after washing drying to be down to.The precursor that takes 4.49g is placed in activation furnace, under the protection of nitrogen, after will being warmed up to 800 ℃ with the speed of 2 ℃/min; pass into steam in the time of insulation; its flow is 1.0ml/min/g, and closes steam evaporator after 60min, makes activation furnace automatically lower the temperature simultaneously.When reaching 320 ℃, temperature stops passing into nitrogen.To prepare specific area is 1249.511m
2in the silver nitrate concentration that the wooden impregnated carbon fiber of the activity of/g is 0.2mol/L in concentration, after 24h, take out dry.Be about to the wooden carbon fiber of impregnated activity and be placed in nitrogen environment, be heated to 350 ℃, insulation 90min, to be cooledly obtain carrying a silver-colored active wooden carbon fiber to room temperature.
The antibiotic rate that carries the active wooden carbon fiber of silver of preparation is 100%, and silver-colored turnover rate is 0.226%, specific area 800.083m
2/ g, micropore specific area is 697.741m
2/ g, total pore volume is 0.376cm
3/ g, Micropore volume is 0.275cm
3/ g, average pore size is 0.941nm.
The preparation of 4 years active wooden carbon fibers of silver of embodiment
After wood machining residues is ground into to 60 orders, put in the middle of liquefying plant.Add the phenol of 5 times of wood powder weight and the phosphoric acid of 0.5 times of wood powder weight, mixture is heated to 150 ℃ again, insulation 2.5h.After timber liquefied matter is down to room temperature, add the hexamethylenetetramine of liquefied substance 6% weight, through 1 hour, be warmed up to 175 ℃, synthetic spinning solution.Subsequently spinning solution is placed in to spinning machine, when spinning solution is heated to 120 ℃, with the speed of receiving 100 rev/mins of roll dies, receives silk.Synthetic fiber is placed in to formaldehyde that volume ratio is 1:1 and the mixed liquor of hydrochloric acid, with the heating rate of 10 ℃/h, is heated to 85 ℃, insulation 2h.Room temperature after washing drying to be down to.The precursor that takes 4.31g is placed in activation furnace, under the protection of nitrogen, after will being warmed up to 800 ℃ with the speed of 3 ℃/min; pass into steam in the time of insulation; its flow is 1.0ml/min/g, and closes steam evaporator after 60min, makes activation furnace automatically lower the temperature simultaneously.When reaching 350 ℃, temperature stops passing into nitrogen.To prepare specific area is 1249.511m
2in the silver nitrate concentration that the wooden impregnated carbon fiber of the activity of/g is 0.1mol/L in concentration, after 24h, take out dry.Be about to the wooden carbon fiber of impregnated activity and be placed in nitrogen environment, be heated to 350 ℃, insulation 60min, to be cooledly obtain carrying a silver-colored active wooden carbon fiber to room temperature.
The antibiotic rate that carries the active wooden carbon fiber of silver of preparation is 100%, and silver-colored turnover rate is 1.047%, specific area 1050.483m
2/ g, micropore specific area is 770.711m
2/ g, total pore volume is 0.594cm
3/ g, Micropore volume is 0.208cm
3/ g, average pore size is 1.131nm.
The preparation of 5 years active wooden carbon fibers of silver of embodiment
After wood machining residues is ground into to 80 orders, put in the middle of liquefying plant.Add the phenol of 5 times of wood powder weight and the phosphoric acid of 0.6 times of wood powder weight, mixture is heated to 160 ℃ again, insulation 2.5h.After timber liquefied matter is down to room temperature, add the hexamethylenetetramine of liquefied substance 6% weight, through 1 hour, be warmed up to 170 ℃, synthetic spinning solution.Subsequently spinning solution is placed in to spinning machine, when spinning solution is heated to 120 ℃, with the speed of receiving 100 rev/mins of roll dies, receives silk.Synthetic fiber is placed in to formaldehyde that volume ratio is 1:1 and the mixed liquor of hydrochloric acid, with the heating rate of 10 ℃/h, is heated to 85 ℃, insulation 2h.Room temperature after washing drying to be down to.The precursor that takes 3.0g is placed in activation furnace, under the protection of nitrogen, after will being warmed up to 700 ℃ with the speed of 2 ℃/min; pass into steam in the time of insulation; its flow is 1.0ml/min/g, and closes steam evaporator after 60min, makes activation furnace automatically lower the temperature simultaneously.When reaching 350 ℃, temperature stops passing into nitrogen.To prepare specific area is 1249.511m
2in the silver nitrate concentration that the wooden impregnated carbon fiber of the activity of/g is 0.1mol/L in concentration, after 24h, take out dry.Be about to the wooden carbon fiber of impregnated activity and be placed in nitrogen environment, be heated to 350 ℃, insulation 60min, to be cooledly obtain carrying a silver-colored active wooden carbon fiber to room temperature.
The antibiotic rate that carries the active wooden carbon fiber of silver of preparation is 100%, and silver-colored turnover rate is 1.082%, specific area 1050.002m
2/ g, micropore specific area is 732.498m
2/ g, total pore volume is 0.613cm
3/ g, Micropore volume is 0.294cm
3/ g, average pore size is 1.167nm.The preparation of 6 years active wooden carbon fibers of silver of embodiment
After wood machining residues is ground into to 80 orders, put in the middle of liquefying plant.Add the phenol of 5 times of wood powder weight and the phosphoric acid of 0.6 times of wood powder weight, mixture is heated to 160 ℃ again, insulation 2.5h.After timber liquefied matter is down to room temperature, add the hexamethylenetetramine of liquefied substance 5% weight, through 1 hour, be warmed up to 165 ℃, synthetic spinning solution.Subsequently spinning solution is placed in to spinning machine, when spinning solution is heated to 120 ℃, with the speed of receiving 100 rev/mins of roll dies, receives silk.Synthetic fiber is placed in to formaldehyde that volume ratio is 1:1 and the mixed liquor of hydrochloric acid, with the heating rate of 10 ℃/h, is heated to 90 ℃, insulation 2h.Room temperature after washing drying to be down to.The precursor that takes 4.49g is placed in activation furnace, under the protection of nitrogen, after will being warmed up to 800 ℃ with the speed of 4 ℃/min; pass into steam in the time of insulation; its flow is 1.0ml/min/g, and closes steam evaporator after 60min, makes activation furnace automatically lower the temperature simultaneously.When reaching 350 ℃, temperature stops passing into nitrogen.To prepare specific area is 1262.962m
2in the silver nitrate concentration that the wooden impregnated carbon fiber of the activity of/g is 0.4mol/L in concentration, after 24h, take out dry.Be about to the wooden carbon fiber of impregnated activity and be placed in nitrogen environment, be heated to 300 ℃, insulation 70min, to be cooledly obtain carrying a silver-colored active wooden carbon fiber to room temperature.
The antibiotic rate that carries the active wooden carbon fiber of silver of preparation is 100%, and silver-colored turnover rate is 1.352%, specific area 927.038m
2/ g, micropore specific area is 837.267m
2/ g, total pore volume is 0.416cm
3/ g, Micropore volume is 0.328cm
3/ g, average pore size is 0.896nm.
Comparative Examples 1
Silver-colored activated carbon fiber is carried in method preparation according to record " active carbon loading silver fiber " (ten thousand happy kitchen ranges etc., University Of Tianjin's journal, the 32nd the 5th phase of volume, P621, in September, 1999).
After testing, the scope of antibacterial ring width and specimen finish ratio is 15 * 10
-2, dynamically washing away silver-colored turnover rate after 5h is more than 50%, specific area is 523.274m
2/ g.
Comparative Examples 2
According to " structure of silver-colored type antibacterial fibre of activated carbon and the research of anti-microbial property thereof " (remaining water is held under the arm etc., Materials Science and Engineering, the 19th the 4th phase of volume, P66, December calendar year 2001) the method preparation of record carries silver chlorate and a silver iodide activated carbon fiber.
After testing, for staphylococcus aureus, the antibiotic property of silver iodide is poor, and the content of silver chlorate must reach 11wt% when above just the antibiotic rate to Staphylococcus aureus be 100%, and specific area is only 670m
2/ g.
From embodiment 1-6, Comparative Examples 1-2, can find out, what adopt preparation method of the present invention to obtain carries the active wooden carbon fiber of silver under the prerequisite that keeps antibiotic rate 100%, the silver ion dissolution rate is low, minimum is only 0.226%, increased safety and the durability of product, and specific area is large, absorption affinity is strong, also reduce the energy resource consumption in preparation process, simplify processing step, reduce production costs simultaneously.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements, all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a preparation method of carrying the active wooden carbon fiber of silver, is characterized in that, by the wooden carbon fiber of activity after liquor argenti nitratis ophthalmicus normal pressure dipping under oxygen free condition thermal decomposition obtain.
2. preparation method according to claim 1, is characterized in that, described nitrate concentration is 0.05-0.4molL
-1; Dip time is 20-30 hour.
3. preparation method according to claim 1, is characterized in that, described heat decomposition temperature is 150-450 ℃, time 30-100min.
4. according to the arbitrary described preparation method of claim 1-3, it is characterized in that, the wooden carbon fiber of described activity is prepare by the following method and obtain:
1) wood-curing waste is broken to the 30-80 order, mixes with phenol under catalyst action, under 150-160 ℃, stir 2-3h, obtain liquefied substance;
2) by after liquefied substance and synthetics mix and blend 0.5-1.5h, be heated to 160-175 ℃ with 10 ℃/h and obtain spinning solution, then insert in weaving loom, when spinning solution is heated to 110-130 ℃, can reels off raw silk from cocoons and obtain synthetic fiber;
3) synthetic fiber are placed in to formaldehyde that volume ratio is 1:1 and the mixed liquor of hydrochloric acid, the heating rate with 10-15 ℃/h, be heated to 85-95 ℃, and insulation 2-4h, be down to room temperature after washing drying, obtains wooden carbon fibre precursor;
4) wooden carbon fibre precursor is heated to 800 ℃, passes into activator, reaction obtains active wooden carbon fiber.
5. preparation method according to claim 4, is characterized in that, in described step 1), phenol and waste material mass ratio are 4-6:1; Catalyst and waste material mass ratio are 0.4-0.6:1.
6. preparation method according to claim 4, is characterized in that, in described step 1), catalyst is phosphoric acid or dilute sulfuric acid.
7. preparation method according to claim 4, is characterized in that, described step 2) in, synthetics is 0.04-0.06:1 with liquefied substance quality ratio.
8. preparation method according to claim 4, is characterized in that, in described step 4), heating rate is 2-4 ℃ of min
-1.
9. preparation method according to claim 4, is characterized in that, in described step 4), activator is steam, and passing into flow is 1.0-2.5ml/min/g, and the time of passing into is 10-90min.
10. year active wooden carbon fiber of silver that the arbitrary described preparation method of claim 1-9 obtains.
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| CN105926277A (en) * | 2016-05-31 | 2016-09-07 | 深圳市微纳集成电路与系统应用研究院 | Conductive fiber and preparation method thereof, and capacitive pressure sensor and preparation method thereof |
| CN106003340A (en) * | 2016-05-25 | 2016-10-12 | 华国平 | Manufacturing method of energy-saving environment-friendly fiber cement board for constructional engineering |
| CN106007625A (en) * | 2016-05-25 | 2016-10-12 | 华国平 | Method for manufacturing environment-friendly fiber cement board for constructional engineering |
| CN106758178A (en) * | 2016-12-18 | 2017-05-31 | 中南大学 | A kind of method that carbonohydrazides complexing silver nitrate prepares antibiotic fabric product |
| CN109385889A (en) * | 2018-11-08 | 2019-02-26 | 珠海鑫康源新材料科技有限公司 | A kind of Anti-bacterial radiation-proof fabric |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106003340A (en) * | 2016-05-25 | 2016-10-12 | 华国平 | Manufacturing method of energy-saving environment-friendly fiber cement board for constructional engineering |
| CN106007625A (en) * | 2016-05-25 | 2016-10-12 | 华国平 | Method for manufacturing environment-friendly fiber cement board for constructional engineering |
| CN105926277A (en) * | 2016-05-31 | 2016-09-07 | 深圳市微纳集成电路与系统应用研究院 | Conductive fiber and preparation method thereof, and capacitive pressure sensor and preparation method thereof |
| CN106758178A (en) * | 2016-12-18 | 2017-05-31 | 中南大学 | A kind of method that carbonohydrazides complexing silver nitrate prepares antibiotic fabric product |
| CN106758178B (en) * | 2016-12-18 | 2018-10-26 | 中南大学 | A kind of method that carbonohydrazides complexing silver nitrate prepares antibiotic fabric product |
| CN109385889A (en) * | 2018-11-08 | 2019-02-26 | 珠海鑫康源新材料科技有限公司 | A kind of Anti-bacterial radiation-proof fabric |
| CN109385889B (en) * | 2018-11-08 | 2021-05-07 | 银维康新材料科技(珠海)有限公司 | Antibacterial and anti-radiation fabric |
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