CN101660254B - Continuous preparation method of activated carbon fiber cloth with high breaking strength and elongation at break - Google Patents
Continuous preparation method of activated carbon fiber cloth with high breaking strength and elongation at break Download PDFInfo
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Abstract
The invention discloses a continuous preparation method of activated carbon fiber cloth with high breaking strength and elongation at break, which comprises the following steps: (a) providing polyacrylonitrile oxidized fiber cloth; (b) providing a heat treating furnace which comprises at least four reaction regions and is provided with a feeding mechanism and a discharging mechanism; (c) providing activated gas vapor and carbon dioxide; and (d) enabling the polyacrylonitrile oxidized fiber cloth to carry out the carbon activating reaction. The invention is characterized in that the feeding mechanism and the discharging mechanism are used for controlling the meridional overfeeding amount of the polyacrylonitrile oxidized fiber cloth in the carbon activating process to be 15-40%.
Description
Technical field
The present invention relates to the continuous preparation method of improved activated carbon fiber cloth, specifically, the present invention relates to the continuous preparation method of the activated carbon fiber cloth of a kind of high ultimate strength and elongation at break.
Background technology
Activated carbon is a kind of very tiny carbon granules, and very big surface area is arranged, and also has more tiny hole---capillary in the carbon granules.This capillary has very strong adsorption capacity, because the surface area of carbon granules is very big, so can fully contact with gas (impurity).Run into capillary when these gases (impurity) and be adsorbed aseptic.Therefore, activated carbon is widely used in each side such as chemical protection and environmental protection.The form of traditional activated carbon when using, often is subjected to the restriction of its form all based on powder or particle.Therefore, in recent years, arise at the historic moment with the developmental research that fibrous material is made the activated carbon of fibrous or textile-like as precursor, because the activated carbon of this form has the characteristic that is easy to be shaped and keeps different shape, thereby be applicable to various uses, and as: be applied to chemistry, medical treatment or military protection, protective clothing, breathing mask or the like.
Fibrous activated carbon is more crisp, and percentage elongation is lower than 3%, and as if processes such as adopting comb and parallel cotton fibers prior to spinning, spin or weave cotton cloth, therefore fracture easily, is only applicable to modes such as fibre bundle moulding, nonwoven fabric and system paper, and is not suitable for being woven into cloth; Thereby it is that to be treated as the textile-like activated carbon be activated carbon fiber cloth to presoma with fabric directly that the people is arranged.Activated carbon fiber cloth can be divided into Lignins, phenol resin system, pitch system and polyacrylonitrile based etc., yet, Lignins, phenol resin system, pitch is the isoreactivity carbon cloth, because itself fracture strength and elongation at break are not good, cause the activated carbon fiber cloth washability, the tension brute force, DE is very poor, for a long time always can't be near the characteristic of general textiles, as cotton etc., all the time can't satisfy military frog suit, uses of fabric requirements such as civilian clothing clothes class and bedding class, yet, the activated carbon fiber cloth of polyacrylonitrile based is because of having good textiles characteristic, cost is also placed in the middle, therefore the most suitable Application and Development.
Phase late 1990s so far in addition, has anion, the finishing agent of far infrared function, adopt postfinishing process to add on the textiles cloth, on market, used widely, studies confirm that both at home and abroad it has health-care effect, yet, traditional anion, far infrared line style textiles is not generally having anion, or in the common fabric of low far infrared emission function, utilize suitable spinning technique or postfinishing process to add and have anion, the additive of far infrared emission function, as tourmaline, opal, diatomite powder etc., play certain anion, the emission function of far infrared, therefore, traditional anion, the anion of far infrared line style textiles, far infrared effect and content of additive and the additive degree of adhesion in fabric has much relations, if additive is lost in the repeatedly washing of fabric, then function corresponding will descend greatly, as according to the literature, after washing 20 times to 30 times, the conventional negative ion, the performance of far infrared line style textiles has all dropped to below 1/3 of original index, after washing 50 times, then lost original performance substantially, therefore, exploitation has permanent anion, the polyacrylonitrile based activated carbon fiber cloth of far infrared effect can make it use more extensive at piece market.
United States Patent (USP) 6156287 discloses a kind of preparation method of polyacrylonitrile based activated carbon fiber cloth, this method with polyacrylonitrile based oxidized fibre cloth as raw material, in 700-1000 ℃ of temperature range, heated one minute to one hour, and in heating process, import the carbon dioxide that contains moisture, make the activation of polyacrylonitrile based oxidized fibre cloth; When heat-treatment furnace was handled, the warp thread of polyacrylonitrile based oxidized fibre cloth supported with the tension roller group, with can be according to predetermined numerical value, the shrinkage of restriction warp thread, and the weft yarn of polyacrylonitrile based oxidized fibre cloth, support with two weft tension control device, convertible spacing distance is adjusted weft tension, limiting the shrinkage of weft yarn according to predetermined numerical value, be controlled in the scope of desired value, comparative optimization be, PAN series fiber cloth through the weft yarn shrinkage, be in 30% the scope of being controlled in.
Yet, this method uses the carbon dioxide that contains moisture as activated gas activation polyacrylonitrile based oxidized fibre cloth, and restriction is through the shrinkage of weft yarn in the activation of the pyrocarbon about the 1000 ℃ reflection environmental process, assemblies such as the mechanical material of its weft tension control device and transmission mechanism are when producing continuously, be difficult to bear for a long time the reaction environment of pyrocarbon activation like this and produce and be out of shape or damage, thereby influence the quality of production, therefore the fracture strength and the elongation at break and unsatisfactory of the polyacrylonitrile based activated carbon fiber cloth that makes of this method, and be difficult to reach continuous production, product quality can't be stablized.
Therefore, need a kind of continuous preparation method of long-time and continuous stable mass production activated carbon fiber cloth, and it is bad to solve the fracture strength and the elongation at break of polyacrylonitrile based activated carbon fiber cloth, thus the problem of influence on textile application.
Summary of the invention
First technical problem that the present invention will solve provides the continuous preparation method of the activated carbon fiber cloth of a kind of high ultimate strength and elongation at break, improve the bad shortcoming of activated carbon fiber cloth ultimate strength and elongation at break, this purpose is achieved through the following technical solutions:
A) provide polyacrylonitrile based oxidized fibre cloth;
B) provide and have the heat-treatment furnace in four reaction areas territory at least, described heat-treatment furnace is provided with feeding mechanism and discharging mechanism;
C) provide activated gas steam and carbon dioxide;
D) make polyacrylonitrile based oxidized fibre cloth carry out the carbon priming reaction;
It is characterized in that using the warp-wise overfeed ratio of feeding mechanism and discharging mechanism control polyacrylonitrile based oxidized fibre cloth in carbon activation process is 15 to 40%.
Described polyacrylonitrile based oxidized fibre cloth, use commercially available mass-produced polyacrylonitrile (Polyacrylonitrile PAN) is oxidized fibre bundle or staple fibre, behind spinning and processing step such as weave cotton cloth, the polyacrylonitrile based oxidized fibre cloth of making.
As a further improvement on the present invention, described polyacrylonitrile based oxidized fibre cloth shrinking naturally through broadwise in carbon activation process reaches tension-free state.
As a further improvement on the present invention, the broadwise of described polyacrylonitrile based oxidized fibre cloth nature shrinkage is controlled at 25 to 50%.
As a further improvement on the present invention, in the carbonisation of living, steam is imported in first to fourth zone of heat-treatment furnace and be evenly distributed, carbon dioxide is imported in the 4th zone of heat-treatment furnace and make correction-compensation.The weight ratio of described steam/carbon dioxide is 5 to 35.The reaction temperature of described carbon priming reaction is 800 to 1100 ℃, is preferably 900 to 1005 ℃; Reaction time is 5 to 50 minutes.
As a further improvement on the present invention, in stove, install several cloth cover bracing frames (can be the metal or the nonmetal exotic material of shelf, net, rod, line, plate or other form) additional and support cloth cover, keep the cloth surface evenness.
As a further improvement on the present invention, described heat-treatment furnace also is provided with charging aperture and discharging opening.
As a further improvement on the present invention, described charging aperture and discharging opening use carbon dioxide as sealing gland gas, and described sealing gland gas flow rate is preferably 0.02 to 0.8m/s.
As a further improvement on the present invention, the charging aperture and the discharging opening of heat-treatment furnace are provided with scrubbing plant, and the flow velocity of bleeding of described scrubbing plant is preferably 1 to 10m/s, and the accessory substance waste gas that carbon priming reaction in the stove is produced detaches.
Second technical problem that the present invention will solve provides the high ultimate strength that the present invention that a kind of as above-mentioned continuous preparation method obtains obtains and the activated carbon fiber cloth of elongation at break, the far infrared transmissivity 85 to 89% of described activated carbon fiber cloth, 4010 to 5700/cm of negative ion concentration
3, even still can keep similar far infrared transmissivity 82 to 86% and 4730 to 6190/cm of negative ion concentration after washing through acid (for example hydrofluoric acid of 10 weight %) for several times
3
The specific area of activated carbon fiber cloth provided by the present invention is 500 to 1500m
2/ g; The warp-wise ultimate strength is 90 to 300N, the warp-wise elongation at break is 20 to 50%; The broadwise ultimate strength is 40 to 150N, the broadwise elongation at break is 30 to 60%.
The carbon content of activated carbon fiber cloth provided by the present invention＞80 weight %, nitrogen content are 4 to 7 weight %, average pore size＜30
Total pore volume＞0.08cm
3/ g.
Above-mentioned feature of the present invention and target are incited somebody to action interior hereinafter complete description, and specifically describe the present invention with embodiment.
Description of drawings
Fig. 1 is the continuous preparation method's of the activated carbon fiber cloth of high ultimate strength of the present invention and elongation at break process schematic representation.
The specific embodiment
According to Fig. 1, the equipment for preparing polyacrylonitrile based oxidized fibre cloth of the present invention comprises heat-treatment furnace 1, it has at least four heating regions 2 (for dotted portion among Fig. 1 is divided into four zones), and each zone has a plurality of pipelines, and activated gas feeds in the heat-treatment furnace 2 via these pipelines.Heat-treatment furnace 1 is provided with feeding mechanism M1 and discharging mechanism M2.Heat-treatment furnace 1 is provided with charging aperture 3 and discharging opening 4, charging aperture 3 use carbon dioxide are as sealing gland gas and be provided with scrubbing plant, discharging opening 4 use carbon dioxide are as sealing gland gas and be provided with scrubbing plant, and described scrubbing plant can quantitatively be got rid of priming reaction waste gas in the stove.Heat-treatment furnace 1 also is provided with several cloth cover bracing frames 5 (being the metal of bar form or nonmetal exotic material among Fig. 1) and supports cloth cover.
The method that the present invention prepares the activated carbon fiber cloth of high ultimate strength and elongation at break continuously comprises:
A) provide polyacrylonitrile based oxidized fibre cloth;
B) provide and have the heat-treatment furnace in four reaction areas territory at least, described heat-treatment furnace is provided with feeding mechanism and discharging mechanism;
C) provide activated gas steam and carbon dioxide;
D) make polyacrylonitrile based oxidized fibre cloth carry out the carbon priming reaction;
It is characterized in that using the warp-wise overfeed ratio of feeding mechanism and discharging mechanism control polyacrylonitrile based oxidized fibre cloth in carbon activation process is 15 to 40%.
According to the inventive method, can use commercially available mass-produced polyacrylonitrile (Polyacrylonitrile, PAN) be oxidized fibre bundle or staple fibre, for example: the Pyromex series that the Panox series that the Pyron series that U.S. Zoltek company produces, Britain SGL Group company produce, Japanese Toho Tenax company produce, the volume density of these oxidized fibres is at 1.34g/m
3More than, line density is more than 1.6dtex, carbon content is more than 50 weight %, limited oxygen index (Limiting Oxygen Index, LOI) more than 40, again through behind spinning and the processing step such as weave cotton cloth, the polyacrylonitrile based oxidized fibre cloth of making, this cloth oxidized fibre content is 100 weight %, and weight is at 250g/m
2More than, preferred 300 to 400g/m
2
The polyacrylonitrile based oxidized fibre is with polyacrylonitrile (Polyacrylonitrile, PAN) oxidized fibre that processes via a kind of reaction process of pre-oxidation by name of fiber, macromolecular chain intramolecular cyclization and interchain linkage have taken place in the PAN fiber in the pre-oxidation course of reaction, progressively be converted into nonplastic heat-resisting trapezoidal-structure, have characteristics such as TENSILE STRENGTH height, fireproofing and heat resistant, antiacid alkali by thermoplasticity PAN linear molecule chain.
According to the inventive method, polyacrylonitrile based oxidized fibre cloth is again through weaving the cloth that forms behind the oxidized fibre elder generation spun yarn, its via heat-treatment furnace four reaction areas territory temperature under 800 to 1100 ℃, steam is imported in first to fourth zone of heat-treatment furnace, carbon dioxide is imported in the 4th zone of heat-treatment furnace, the weight ratio of steam/carbon dioxide is 5 to 35, carries out about 5 to 50 minutes carbon priming reaction.In carrying out carbon activation tandem reaction sequence, reaction temperature makes oxidized fibre trapezoidal-structure originally to transform to random graphits structure, less trapezoidal-structure unit further carries out crosslinked and polycondensation and follow thermal cracking to discharge many small molecule by-products in this conversion process, therefore cloth will shrink naturally, simultaneously, the non-carbon hydrogen of fiber itself, nitrogen, oxygen is progressively expelled, carbon element content progressively increases and is fixed up, the activated gas reagentia makes the fiber hair pore structure form gradually to increase, this boring effect, cause fiber to produce hole, therefore, along with the increase of carbon priming reaction time and increasing of temperature, and the quantity of hole also obviously promotes, many more its specific areas of fiber hole are also big more, and the intensity of opposite cloth also can reduce, and finally can generate phosphorus content more than 80 weight %, specific area (BET) exists: 500 to 1500m
2/ g, nitrogen content are in 4 to 7 weight %, average pore size＜30
Total pore volume＞0.08cm
3The activated carbon fiber cloth of/g.
Polyacrylonitrile based oxidized fibre cloth is in the pyrocarbon priming reaction as shown in the above description, can produce the nature shrinkage phenomenon, the high more then shrinkage of carbon activation surpassed distance degree is big more, therefore, the inventive step of the inventive method is, can be via the receipts cloth speed of feeding cloth speed and discharging mechanism of regulation and control feeding mechanism, and reach control polyacrylonitrile based oxidized fibre cloth through the broadwise degree of shrinkage, specifically, be exactly to feed cloth speed when receiving the overfeeding cloth amount of cloth speed about 15 to 40% when the cloth warp-wise, can satisfy the cloth warp-wise nature shrinkage phenomenon in the carbon priming reaction, and make cloth be under the power that parts a little or tension-free state that cloth own heavily produces, allow the cloth broadwise shrink naturally, shrinkage is about 25 to 50%, so can reduce interfibrous space, increase the adsorption filtration effect, this can provide the activated carbon fiber cloth with high ultimate strength and elongation at break, and the warp-wise ultimate strength is 90 to 300N, the warp-wise elongation at break is 20 to 50%, the broadwise ultimate strength is 40 to 150N, the broadwise elongation at break is 30 to 60%.
According to the invention described above method, the polyacrylonitrile based oxidized fibre is distributed in and carries out carbon activation production under the tension-free state, cloth can cause quality problems because of weight generation own hangs down to furnace bottom, therefore, be head it off, be provided with several cloth cover bracing frames (can be the metal or the nonmetal exotic material of shelf, net, rod, line, plate or other form) and support cloth cover in stove, it is smooth so can to keep the cloth cover output.
In addition, in pyrocarbon activation processing procedure, polyacrylonitrile (PAN) is that oxidized fibre cloth can be selected a large amount of micromolecule because of heat scission reaction and produces dieseling, and the air that oxidized fibre cloth itself exists can enter in the stove with the cloth operation, moreover factor such as also may penetrate in the stove because of stove outer air under the concentration difference effect, thereby influence the carbon activation phenomenon for fear of it and influence product quality, the capital adopts inert gas to be used as sealing gland gas, and the general practice that discloses all is to adopt inert gases such as nitrogen, helium, argon gas or its combination to be used as sealing gland gas.According to the inventive method, described heat-treatment furnace is provided with charging aperture and discharging opening, and adopt carbon dioxide as sealing gland gas, the sealing gland gas flow rate is regulated between 0.02 to 0.8m/s, because carbon dioxide is an inert gas also is employed activated gas in the carbon activation processing procedure, therefore, except solving the above-mentioned effect, the steady production quality is arranged also, other inert gas supply equipment is not provided additionally to provide, cost is cheap than other inert gas, obtain easily, advantages such as abundance are stablized in supply.
According to the foregoing invention further improvements in methods, charging aperture and discharging opening in the heat-treatment furnace setting have increased scrubbing plant, the flow velocity of regulating and control to bleed is regulated between 1 to 10m/s, instantaneous the detaching of accessory substance waste gas that carbon priming reaction in the stove is produced, send into the scrubbing filter and reach the environmental protection effect, therefore, carbon priming reaction waste gas in the quantitative instantaneous eliminating stove, do not allow waste gas assemble condensation and form tar, the interior activated gas of stove being formed continue and stable priming reaction environment, is one of key factor of stabilised quality, steady production.
Second purpose of the present invention is the activated carbon fiber cloth with high ultimate strength and elongation at break that is obtained by method for preparing.
According to the inventive method, can obtain having the activated carbon fiber cloth of advantageous property, have following specification: specific area (BET) is 500 to 1500m
2/ g, warp-wise ultimate strength are 90 to 300N, the warp-wise elongation at break is 20 to 50%, the broadwise ultimate strength is 40 to 150N, the broadwise elongation at break is 30 to 60%, carbon content＞80 weight %, nitrogen content are 4 to 7 weight %, average pore size＜30
Total pore volume is＞0.08cm
3/ g.This shows that the activated carbon fiber cloth that is obtained by the improved method of the present invention has high fracture strength and elongation at break especially, can be used for actual volume production, reaches the market demands quality.
Simultaneously, the far infrared transmissivity 85 to 89% of the activated carbon fiber cloth that the present invention obtains, 4010 to 5700/cm of negative ion concentration
3, even after pickling processes is removed inorganic substances, still can keep similar far infrared transmissivity 82 to 86% and 4730 to 6190/cm of negative ion concentration
3, confirm that its function is permanent the existence.
Hereinafter, be that the present invention is more specifically described on the basis with embodiment and Comparative Examples, wherein measuring instrument that is adopted and method are as follows respectively:
(A) assay method of ultimate strength and elongation at break
1. testing standard: measure according to standard GB/T 3923.1-1997 " mensuration of woven fabric ultimate strength and extension at break (galley proof method) ".
2. definition:
A. pulling force: in the tension test process of carrying out under defined terms, sample is broken the maximum, force of record
B. elongation at break: corresponding to the percentage elongation of pulling force.
3. determining instrument: high ferro scientific ﹠ technical corporation, SERVO CONTROL pulling force Try tests machine, model: AI-7000S.
4. sample: apart from selvedge two groups of samples of 15cm place clip at least, one group is warp-wise or longitudinal test piece, and another group is broadwise or horizontal sample.Every group of style be five of clips at least, and the effective width of every sample is 50mm (not comprising burr), and effective length is 250mm.
5. the length of spacing: set 200mm
6. draw speed: set 100mm/min
7. clamping sample: at clamp center clamping sample, to guarantee the mid point of center of drag line by clamp.Sample adopts loose formula clamping.6) measure: open test instrument, tensile sample takes off to disconnected.Record ultimate strength (unit: N) and elongation at break (unit: %).
(B) assay method of specific area BET
1. testing standard: measure according to standard GB/T 5816-1995 " catalyst and adsorbent surface amass determination method ".
2. specific area instrument: U.S. Micromeritics Instrument company makes the Tristar3000 type.
3. according to the BET method of using nitrogen absorption, working sample is at relative pressure P/P
oSpecific area value under=0.20.
(C) assay method of far infrared emissivity
1. testing standard: measure according to national standard FZ/T 64010-2000 " far infrared textiles ".
2. test apparatus:
A. infrared spectrometer: spectral region 4600cm-1 to 400cm-1, wave number precision 0.01cm-1, resolution ratio 4cm-1.
B. blackbody furnace: effective emissivity＞0.998, the Guang Lan aperture is not less than 10mm.
3. sample: from the far infrared sample, apart from selvedge at least 10cm place clip be of a size of 2cm * 2cm.Clip 2cm * 2cm sample, sample as a comparison from the corresponding non-far infrared sample.Respectively sample and contrast sample are bonded on the copper sheet.
4. method of testing: sample and contrast sample are put into baking oven, and 100 ℃ of temperature were dried by the fire 2 hours.Sample is put into blackbody furnace be warming up to 100 ℃, measure SAMPLE METHOD to launching curve.To contrast sample and put into blackbody furnace, be warming up to 100 ℃, measure the normal direction launching curve of contrast sample.
Result of calculation: calculate the normal emittance of sample and contrast sample 8 to 15 mu m wavebands, deduct the improvement value of the difference of contrast sample normal emittance as normal emittance with the sample normal emittance.
(D) assay method of negative ion concentration
1. testing standard:, formulate industry standard SFJJ-QWX25-2006 " negative ion concentration detection detailed rules and regulations " according to it and measure by Shanghai Textile Industry Technology Supervision Institute.
(E) assay method of nitrogen, carbon element content
1. elementary analysis instrument: Italian Carlo Erba company (the Thermo Electron of power ﹠ light company that belongs to the U.S. now) makes, model: EA1110, and organic element analyzer is measured.
(F) assay method of bore dia
1. determining instrument: U.S. Micromeritics Instrument company makes Tristar 3000 types.
2. according to BHJ nitrogen absorption aperture distribution, working sample is at relative pressure P/P
oFor between 0.04-0.99, the bore dia scope is 17
To 3000
Bore dia mean value.
(G) assay method of total pore volume
1. determining instrument: U.S. Micromeritics Instrument company makes Tristar 3000 types.
2. according to BHJ nitrogen adsorption hole volumetric method, working sample is at relative pressure P/P
oFor between 0.04-0.99, the bore dia scope is 17
To 3000
The total pore volume value.
(H) assay method of inorganic element content
1. testing standard: measure according to JY/T 015-1996 " inductively coupled plasma atomic emission spectrum general rule ".
2. inductive coupling plasma emission spectrograph device: HIT makes the P-4010 type.
3. the sample treatment operating procedure is as follows:
A. sample dry about 2h of 105 degree in baking oven.
B. in quartz beaker, weigh the about 0.6g of sample (being accurate to 0.0001g), do blank simultaneously.
C. in sample and blank, all add the nitric acid about 6ml, and on electric hot plate, heat.
D. treat to move into the about 1h of 700 degree heating in the Muffle furnace behind sample and the blank evaporate to dryness fully.
E. treat after the complete ashing of sample, sample and blank the taking-up are cooled off, and dissolve with diluted acid.
F. with constant volume in the sample of dissolving and the blank volumetric flask that moves into 25ml, to be measured.
Embodiment 1
Employing is carried out 1/1 plain weave Cheng Buzhuan fabric by the Pyron series polyacrylonitrile based oxidized fibre that U.S. Zoltek company produces behind spun yarn, its oxidized fibre content is 100 weight %, and weight is 340 to 360g/m
2
With above-mentioned polyacrylonitrile based oxidized fibre cloth; advance cloth from the feeding mechanism overfeeding; it is 15% that cloth overfeed ratio (promptly go into cloth speed＞go out cloth speed) is gone in control; enter heat-treatment furnace via charging aperture; the heat-treatment furnace temperature is 900 ℃; steam is imported in first to fourth zone of heat-treatment furnace; carbon dioxide is imported in the 4th zone of heat-treatment furnace; the weight ratio of steam/carbon dioxide is 10; go out cloth by discharging opening through the carbon priming reaction after 15 minutes; heat-treatment furnace charging aperture and discharging opening use carbon dioxide sealing gland gas shield and scrubbing plant quantitatively to detach carbon activation exhaust gas products, obtain activated carbon fiber cloth by the discharging mechanism rewinding at last.
Utilize the said determination method that the gained activated carbon fiber cloth is carried out every test, gained test result such as table 1 are listed.
Embodiment 2
Employing is carried out 1/1 plain weave Cheng Buzhuan fabric by the Panox series polyacrylonitrile based oxidized fibre that Britain SGL Group company produces behind spun yarn, its oxidized fibre content is 100 weight %, and weight is 340 to 360g/m
2
With above-mentioned polyacrylonitrile based oxidized fibre cloth; advance cloth from the feeding mechanism overfeeding; it is 20% that cloth overfeed ratio (promptly go into cloth speed＞go out cloth speed) is gone in control; enter heat-treatment furnace via charging aperture; the heat-treatment furnace temperature is 965 ℃; steam is imported in first to fourth zone of heat-treatment furnace; carbon dioxide is imported in the 4th zone of heat-treatment furnace; the weight ratio of steam/carbon dioxide is 10; go out cloth by discharging opening through the carbon priming reaction after 15 minutes; heat-treatment furnace charging aperture and discharging opening use carbon dioxide sealing gland gas shield and scrubbing plant quantitatively to detach carbon activation exhaust gas products, obtain activated carbon fiber cloth by the discharging mechanism rewinding at last.
Utilize the said determination method that the gained activated carbon fiber cloth is carried out every test, gained test result such as table 1 are listed.
Embodiment 3
Employing is carried out 1/1 plain weave Cheng Buzhuan fabric by the Panox series polyacrylonitrile based oxidized fibre that Britain SGL Group company produces behind spun yarn, its oxidized fibre content is 100 weight %, and weight is 340 to 360g/m
2
With above-mentioned polyacrylonitrile based oxidized fibre cloth; advance cloth from the feeding mechanism overfeeding; it is 30% that cloth overfeed ratio (promptly go into cloth speed＞go out cloth speed) is gone in control; enter heat-treatment furnace via charging aperture; the heat-treatment furnace temperature is 985 ℃; steam is imported in first to fourth zone of heat-treatment furnace; carbon dioxide is imported in the 4th zone of heat-treatment furnace; the weight ratio of steam/carbon dioxide is 20; go out cloth by discharging opening through the carbon priming reaction after 15 minutes; heat-treatment furnace charging aperture and discharging opening use carbon dioxide sealing gland gas shield and scrubbing plant quantitatively to detach carbon activation exhaust gas products, obtain activated carbon fiber cloth by the discharging mechanism rewinding at last.
Utilize the said determination method that the gained activated carbon fiber cloth is carried out every test, gained test result such as table 1 are listed.
Embodiment 4
Employing is carried out 1/1 plain weave Cheng Buzhuan fabric by the Panox series polyacrylonitrile based oxidized fibre that Britain SGL Group company produces behind spun yarn, its oxidized fibre content is 100 weight %, and weight is 340 to 360g/m
2
With above-mentioned polyacrylonitrile based oxidized fibre cloth; advance cloth from the feeding mechanism overfeeding; it is 30% that cloth overfeed ratio (promptly go into cloth speed＞go out cloth speed) is gone in control; enter heat-treatment furnace via charging aperture; the heat-treatment furnace temperature is 1005 ℃; steam is imported in first to fourth zone of heat-treatment furnace; carbon dioxide is imported in the 4th zone of heat-treatment furnace; the weight ratio of steam/carbon dioxide is 20; go out cloth by discharging opening through the carbon priming reaction after 20 minutes; heat-treatment furnace charging aperture and discharging opening use carbon dioxide sealing gland gas shield and scrubbing plant quantitatively to detach carbon activation exhaust gas products, obtain activated carbon fiber cloth by the discharging mechanism rewinding at last.
Utilize the said determination method that the gained activated carbon fiber cloth is carried out every test, gained test result such as table 1 are listed.
Embodiment 5
Employing is carried out 1/1 plain weave Cheng Buzhuan fabric by the Pyron series polyacrylonitrile based oxidized fibre that U.S. Zoltek company produces behind spun yarn, its oxidized fibre content is 100 weight %, and weight is 340 to 360g/m
2
With above-mentioned polyacrylonitrile based oxidized fibre cloth; advance cloth from the feeding mechanism overfeeding; it is 40% that cloth overfeed ratio (promptly go into cloth speed＞go out cloth speed) is gone in control; enter heat-treatment furnace via charging aperture; the heat-treatment furnace temperature is 1005 ℃; steam is imported in first to fourth zone of heat-treatment furnace; carbon dioxide is imported in the 4th zone of heat-treatment furnace; the weight ratio of steam/carbon dioxide is 30; go out cloth by discharging opening through the carbon priming reaction after 25 minutes; heat-treatment furnace charging aperture and discharging opening use carbon dioxide sealing gland gas shield and scrubbing plant quantitatively to detach carbon activation exhaust gas products, obtain activated carbon fiber cloth by the discharging mechanism rewinding at last.
Utilize the said determination method that the gained activated carbon fiber cloth is carried out every test, gained test result such as table 1 are listed.
Comparative Examples 1
Use raw material and the step identical with embodiment 1, go into the cloth overfeed ratio and change 10% into, the gained activated carbon fiber cloth carries out every test, and gained test result such as table 1 are listed.
Comparative Examples 2
Use raw material and the step identical with embodiment 2, go into the cloth overfeed ratio and change 10% into, the gained activated carbon fiber cloth carries out every test, and gained test result such as table 1 are listed.
Comparative Examples 3
Use raw material and the step identical with embodiment 3, go into the cloth overfeed ratio and change 10% into, the gained activated carbon fiber cloth carries out every test, and gained test result such as table 1 are listed.
Comparative Examples 4
Use raw material and the step identical with embodiment 4, go into the cloth overfeed ratio and change 50% into, the gained activated carbon fiber cloth carries out every test, and gained test result such as table 1 are listed.
Comparative Examples 5
Use raw material and the step identical with embodiment 5, go into the cloth overfeed ratio and change 50% into, the gained activated carbon fiber cloth carries out every test, and gained test result such as table 1 are listed.
As shown in Table 1, compared to the result of Comparative Examples, the resulting activated carbon fiber cloth of the embodiment of the invention also has best elongation at break except that having high fracture strength, therefore, can reach the market demands quality.
Embodiment 6
With embodiment 1 activated carbon fiber cloth that obtains, test inorganic element content, far infrared emissivity and negative ion concentration, gained test result such as table 2 are listed.
Embodiment 7
With embodiment 2 activated carbon fiber cloth that obtains, test inorganic element content, far infrared emissivity and negative ion concentration, gained test result such as table 2 are listed.
Embodiment 8
With embodiment 3 activated carbon fiber cloth that obtains, test inorganic element content, far infrared emissivity and negative ion concentration, gained test result such as table 2 are listed.
Embodiment 9
With embodiment 4 activated carbon fiber cloth that obtains, test inorganic element content, far infrared emissivity and negative ion concentration, gained test result such as table 2 are listed.
Embodiment 10
With embodiment 5 activated carbon fiber cloth that obtains, test inorganic element content, far infrared emissivity and negative ion concentration, gained test result such as table 2 are listed.
Comparative Examples 6
With embodiment 6 activated carbon fiber cloth that obtains, putting into the container bottle that contains 10 weight % hydrofluoric acid aqueous solutions soaked after 72 hours, take out and dry after cloth washs 5 times with pure water, remove fiber surface trace inorganic elements material through this step, and then test inorganic element content, far infrared emissivity and negative ion concentration, gained test result such as table 2 are listed.
Comparative Examples 7
With embodiment 7 activated carbon fiber cloth that obtains, use and Comparative Examples 6 same steps as, gained test result such as table 2 are listed.
Comparative Examples 8
With embodiment 8 activated carbon fiber cloth that obtains, use and Comparative Examples 6 same steps as, gained test result such as table 2 are listed.
Comparative Examples 9
With embodiment 9 activated carbon fiber cloth that obtains, use and Comparative Examples 6 same steps as, gained test result such as table 2 are listed.
Comparative Examples 10
With embodiment 10 activated carbon fiber cloth that obtains, use and Comparative Examples 6 same steps as, gained test result such as table 2 are listed.
Table 2
As shown in Table 2, activated carbon fiber cloth still can keep similar anion, far infrared transmissivity after 10 weight % hydrofluoric acid aqueous solution pickling, confirms that its function is permanent the existence.
The above embodiments only are used for for example embodiments of the present invention, and explain technical characterictic of the present invention, are not to be used for limiting protection category of the present invention.Any be familiar with this operator can unlabored change or the arrangement of the isotropism scope that all belongs to the present invention and advocated, the scope of the present invention should be as the criterion with claim.
Claims (17)
1. the continuous preparation method of the activated carbon fiber cloth of high fracture strength and elongation at break, the warp-wise ultimate strength of wherein said activated carbon fiber cloth is 90 to 300N, the warp-wise elongation at break is 20 to 50%, the broadwise ultimate strength is 40 to 150N, the broadwise elongation at break is 30 to 60%, and described method comprises the steps:
A) provide polyacrylonitrile based oxidized fibre cloth;
B) provide and have the heat-treatment furnace in four reaction areas territory at least, described heat-treatment furnace is provided with feeding mechanism and discharging mechanism;
C) provide activated gas steam and carbon dioxide;
D) make polyacrylonitrile based oxidized fibre cloth carry out the carbon priming reaction;
It is characterized in that using the warp-wise overfeed ratio of feeding mechanism and discharging mechanism control polyacrylonitrile based oxidized fibre cloth in carbon activation process is 15 to 40%, is tension-free state through broadwise, broadwise nature shrinkage is 25 to 50%.
2. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 1 and elongation at break is characterized in that, steam is imported in first to fourth zone of heat-treatment furnace, carbon dioxide is imported in the 4th zone of heat-treatment furnace.
3. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 1 and elongation at break is characterized in that, the weight ratio of described steam and carbon dioxide is 5: 1 to 35: 1.
4. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 1 and elongation at break is characterized in that, the reaction temperature of described carbon priming reaction is 800 to 1100 ℃.
5. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 4 and elongation at break is characterized in that, the reaction temperature of described carbon priming reaction is 900 to 1005 ℃.
6. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 1 and elongation at break is characterized in that, the reaction time of described carbon priming reaction is 5 to 50 minutes.
7. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 1 and elongation at break is characterized in that described heat-treatment furnace is provided with charging aperture and discharging opening.
8. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 7 and elongation at break is characterized in that, described charging aperture and discharging opening use carbon dioxide as sealing gland gas.
9. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 8 and elongation at break is characterized in that, described sealing gland gas flow rate is 0.02 to 0.8m/s.
10. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 7 and elongation at break is characterized in that described charging aperture and discharging opening are provided with scrubbing plant.
11. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 10 and elongation at break is characterized in that, the flow velocity of bleeding of described scrubbing plant is 1 to 10m/s.
12. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 1 and elongation at break is characterized in that, described heat-treatment furnace is provided with several cloth cover bracing frames and supports cloth cover.
13. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 12 and elongation at break is characterized in that, described cloth cover bracing frame is shelf, net, rod, line or the plate that metal or nonmetal exotic material are made.
14. the continuous preparation method of the activated carbon fiber cloth of high ultimate strength according to claim 1 and elongation at break, it is characterized in that, the oxidized fibre content of described polyacrylonitrile based oxidized fibre cloth is 100 weight %, and the weight of described polyacrylonitrile based oxidized fibre cloth is 250g/m
2More than.
15. the activated carbon fiber cloth for preparing according to the arbitrary described method of claim 1 to 14.
16. activated carbon fiber cloth according to claim 15 is characterized in that, the specific area of described activated carbon fiber cloth is 500 to 1500m
2/ g.
17., it is characterized in that the carbon content of described activated carbon fiber cloth＞80 weight %, nitrogen content are 4 to 7 weight %, average pore size＜30 according to claim 15 or 16 described activated carbon fiber cloths
Total pore volume＞0.08cm
3/ g.
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| CN101812782B (en) * | 2010-04-09 | 2013-03-27 | 大连圣海纺织有限公司 | Process for carbonization production of pre-oxidized fiber fabrics |
| EP2738292B1 (en) * | 2011-07-28 | 2019-10-09 | Mitsubishi Chemical Corporation | Flame-retardant heat treatment furnace |
| CN102560889B (en) * | 2012-01-05 | 2014-04-02 | 黑龙江大学 | Method for producing bead-stringed PAN (polyacrylonitrile)-based carbon fiber electrode materials by electrostatic spinning |
| CN102704227A (en) * | 2012-06-12 | 2012-10-03 | 吉林市双鹏碳材料科技开发有限公司 | Preparation method for polyacrylonitrile-based carbon cloth |
| CN103014916B (en) * | 2012-11-19 | 2016-08-17 | 郑经堂 | A kind of device and method of continuous preparation wide cut functional activity Carbon fibe |
| TWI594737B (en) * | 2013-05-23 | 2017-08-11 | Wound covering | |
| CN103251482A (en) * | 2013-06-07 | 2013-08-21 | 科云生医科技股份有限公司 | Wound covering |
| TWI594742B (en) * | 2013-07-05 | 2017-08-11 | Wound covering and method of making the same | |
| CN103356333B (en) * | 2013-07-22 | 2015-04-29 | 科云生医科技股份有限公司 | Wound dressing and preparation method thereof |
| CN105780364B (en) * | 2016-02-26 | 2018-03-16 | 浙江大学 | A kind of method for preparing ultramicropore flexibility carbon cloth and products thereof and application |
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| US11351751B2 (en) * | 2016-10-21 | 2022-06-07 | Board Of Regents, The University Of Texas System | Noise-absorbent and odor-adsorbent fabric cover systems for vehicle interiors |
| US10874547B2 (en) * | 2017-07-10 | 2020-12-29 | David L. Burge | Therapeutic textile articles and methods of use |
| CN114318736A (en) * | 2021-12-30 | 2022-04-12 | 湖南东映特碳沥青材料有限公司 | Device for efficient catalytic dehydration and carbonization of viscose-based fibrofelt and method for realizing catalytic dehydration and carbonization by using device |
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