CN115404569B - PAN-based ACF continuous production method for preparing protective propane sulfide by using vertical carbon activation furnace - Google Patents
PAN-based ACF continuous production method for preparing protective propane sulfide by using vertical carbon activation furnace Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 230000004913 activation Effects 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 230000001681 protective effect Effects 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000010924 continuous production Methods 0.000 title claims abstract description 14
- 239000001294 propane Substances 0.000 title claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 84
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 83
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000004744 fabric Substances 0.000 claims abstract description 61
- 239000000835 fiber Substances 0.000 claims abstract description 54
- 230000003213 activating effect Effects 0.000 claims abstract description 7
- 239000012190 activator Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 18
- 238000002360 preparation method Methods 0.000 abstract description 15
- 238000001994 activation Methods 0.000 description 56
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 18
- 238000003763 carbonization Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 12
- 230000008901 benefit Effects 0.000 description 8
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- 150000001721 carbon Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/32—Apparatus therefor
- D01F9/328—Apparatus therefor for manufacturing filaments from polyaddition, polycondensation, or polymerisation products
Abstract
The invention discloses a PAN-based ACF continuous production method for preparing protective propane sulfide by using a vertical carbon activation furnace, which comprises the following steps: a pre-oxidized cloth woven by polyacrylonitrile pre-oxidized yarns; a vertical carbon activation furnace is adopted; the top surface of the vertical carbon activation furnace is provided with a feed inlet, and the bottom is provided with a discharge outlet; the furnace is internally provided with a first heat treatment area, a second heat treatment area and a third heat treatment area from top to bottom in sequence; the second heat treatment zone and the third heat treatment zone are respectively provided with an activator input line; an output pair roller is arranged at the discharge hole and is connected with the coiler through an output groove; the pre-oxidized fiber cloth is sent to the inside of the furnace body by a double-roller conveyor at the top of the furnace body, sequentially passes through a first heat treatment area, a second heat treatment area and a third heat treatment area, and is filled with an activating agent to prepare the PAN-based activated carbon fiber cloth. The invention discloses a continuous batch preparation method of PAN-based functional activated carbon fibers for preparing efficient protective propane sulfide by utilizing polyacrylonitrile pre-oxidized fiber and using a vertical carbon activation furnace.
Description
Technical Field
The invention relates to the technical field of active carbon fiber preparation, in particular to a PAN-based ACF continuous production method for preparing protective propane sulfide by using a vertical carbon activation furnace.
Background
Future biochemical protective equipment tends to develop toward multifunction, integration and portability. Breathable protective apparel is used as a key protective material for protecting personnel from poisoning in biochemical protective equipment, and the excellent material performance of the breathable protective apparel is directly related to the further development of the biochemical protective equipment. The Active Carbon Fiber (ACF) is an active adsorption material with higher technical content and higher added value and extracted performance. The activated carbon fiber industrial product is represented by Polyacrylonitrile (PAN) based activated carbon fiber, wherein the PAN based activated carbon fiber is formed by carbonizing and activating a fibrous precursor through a certain program, and the PAN based raw material contains a large amount of nitrogen-containing hetero atoms, so that the PAN based raw material has a relatively developed specific surface area and relatively narrow pore size distribution, and has relatively high adsorption and desorption rate and relatively high adsorption capacity. The PAN-based activated carbon fiber also has good textile characteristics, the PAN-based activated carbon fiber is used as an adsorption layer, cotton cloth, non-woven fabrics or chemical fiber cloth is used as base cloth, and the activated carbon fiber breathable protective garment prepared in a bonding mode has the advantages of comfort, moisture permeability, small physiological load, flame retardance, heat radiation resistance and the like, and meanwhile, the activity time can be further prolonged. For breathable protective clothing application, the PAN-based activated carbon fiber to be prepared needs to be in a cloth form with certain strength, and the protection to toxic agents needs to be considered seriously, and the protection capability of the PAN-based activated carbon fiber is generally evaluated at present by taking the protection of toxic agents mustard gas into account like mechanical propyl sulfide protection.
The currently published patent mostly adopts fiber filaments to prepare PAN-based activated carbon fibers, such as a preparation method of high-performance activated carbon fibers with the patent application number of CN201611121811.2, wherein the patent application uses polyacrylonitrile precursor to prepare preoxidized fiber filaments, and then uses a laboratory small furnace to prepare the activated carbon fibers with certain specific surface area and strength by controlling the proportion of water vapor in a single physical or physicochemical activation process under a certain activation temperature condition. The patent application uses fiber tows which are not woven into cloth to realize the preparation of activated carbon fibers with better strength in a laboratory small furnace; however, when the fiber filaments are woven into fiber cloth and are industrially prepared in batches, the fibers of the collected cloth emit a large amount of heat in a short time, so that the problem of serious pulverization caused by fiber surface etching is extremely easy to cause, and the problem of industrialization is not solved.
The invention relates to a biological activated carbon fiber with a patent number of CN1141423C and a preparation method thereof, wherein the biological activated carbon fiber is prepared by controlling the technological parameters of pre-oxidation and carbon activation of the fiber and using a certain activation accelerator and ultrasonic treatment technology, but the biological activated carbon fiber is prepared by adopting fiber precursors, and the technological method has the industrial problems that the fiber is woven into fiber cloth, a large amount of heat is released in a short time during industrialized batch preparation of the fiber cloth, and serious pulverization is caused by fiber surface etching.
The patent application No. CN201010286160.9, which is a method for preparing carbon fibers by boron modified polyacrylonitrile precursor, is characterized in that the fiber precursor is soaked in boric acid and then subjected to a pre-oxidation and pre-carbonization process to prepare the high-strength activated carbon fiber, and the fiber prepared by the patent application does not have an active specific surface area.
The current carbon activation technology for producing PAN-ACF by using PAN-based fiber cloth is a flat-lying furnace, and only viscose-based activated carbon fiber realizes large-scale commercial production, the technical difficulty of industrial preparation of PAN-based activated carbon fiber is high, continuous preparation of PAN-based activated carbon fiber is realized by using flat-lying furnace in the beginning of Shanghai and Tianxiang textile technology limited company, such as the continuous preparation method of activated carbon fiber cloth with high breaking strength and breaking elongation of patent application No. CN200910195927.4, the patent application uses a flat-lying furnace, a cloth cover support frame is arranged in a furnace body, so that the problems of uneven carbon activation, poor structural strength of activated carbon fiber holes and the like caused by sagging of cloth are avoided, water and carbon dioxide are adopted as activated gas, and four temperature sections in the furnace are adopted, so that the high-strength PAN-based activated carbon fiber is finally prepared. However, the method uses the flat carbon activation furnace to produce PAN-based activated carbon fibers, the occupied area of the furnace body is large, the problem of low production efficiency is easily caused, carbon dioxide activation gas is one of chemical activation methods, the reaction is intense and is not easy to control, and the cloth cover support frame arranged in the furnace body is extremely easy to damage under the high-temperature condition, so that the maintenance cost is high, the time consumption is long, and the batch production application is influenced.
Most of the published patents and documents use fiber filaments to prepare PAN-based activated carbon fiber filaments, and the traditional activated carbon fiber (viscose) is industrially produced by adopting a flat-bed furnace, and PAN-ACF with higher strength is preliminarily prepared continuously by utilizing the flat-bed furnace, but the flat-bed furnace needs to have larger occupied area, a plurality of support plates are needed to be placed in the furnace, an air flow extraction device is needed, and the activated carbon fiber prepared by the flat-bed furnace has unstable performance, is more fragile in consumable, and greatly influences the production efficiency and economic benefit. At present, the published data only carries out carbon activation experimental research on PAN-based fiber yarns, but does not carry out industrialized application research on breathable gas-defense clothing in the field of vertical furnace protection.
Disclosure of Invention
The invention takes PAN-based functional activated carbon fiber as a practical application of an inner layer core adsorption material of the breathable anti-poison suit of biochemical protective equipment as a starting point, and utilizes polyacrylonitrile pre-oxidized cloth to provide a method for continuously and stably preparing PAN-based functional activated carbon fiber with high protective performance in batches by using a vertical carbon activation furnace.
The invention is realized by adopting the following technical scheme:
a PAN-based ACF continuous production method for preparing protective propane sulfide by using a vertical carbon activation furnace comprises the following steps:
a pre-oxidized cloth woven by polyacrylonitrile pre-oxidized yarns; the pre-oxidized fabric can be woven into various kinds of fabrics such as plain weave, herringbone weave and the like. The gram weight of the twill pre-oxidized fabric woven by the polyacrylonitrile pre-oxidized fiber is 120 to 620g/m 2 . Further, the gram weight of the pre-oxidized fiber woven by the polyacrylonitrile pre-oxidized fiber is 230 to 280g/m 2 The continuous burning time of the polyacrylonitrile pre-oxidized fiber cloth is less than or equal to 20 seconds, the smoldering time is less than or equal to 15 seconds, and the oxygen index of the raw material of the polyacrylonitrile pre-oxidized fiber for manufacturing the pre-oxidized fiber cloth is more than or equal to 36 percent.
A vertical carbon activation furnace is adopted; the vertical furnace has small occupied area, can effectively utilize the dead weight of the fiber and the natural chimney effect, does not need to use internal devices such as a supporting frame and the like, effectively improves the productivity and economic benefit, and ensures that the finally prepared active carbon fiber has excellent comprehensive properties such as the protection performance of the propylsulfide and the like. The top surface of the vertical carbon activation furnace is provided with a feed inlet, and the bottom is provided with a discharge outlet; the furnace is internally provided with a first heat treatment area, a second heat treatment area and a third heat treatment area from top to bottom in sequence, wherein the treatment temperature of the first heat treatment area is 200-450 ℃ (more preferably, the treatment temperature of the first heat treatment area is 200-300 ℃), the heat treatment temperature of the second heat treatment area is 400-600 ℃ (more preferably, the heat treatment temperature of the second heat treatment area is 400-500 ℃), and the heat treatment temperature of the third heat treatment area is 850-950 ℃; the second heat treatment zone and the third heat treatment zone are each provided with an activator feed line. The bottom of the furnace body is provided with a discharge hole, an output pair roller is arranged at the discharge hole, and the furnace body is connected with a winding machine through an output groove. Further preferably, the discharge port is provided with a stainless steel nitrogen pressurizing pipe for releasing nitrogen for gas sealing; the air content in the vertical carbon activation furnace is not more than 5%.
The pre-oxygen cloth is sent to the inside of the furnace body by a pair roller conveyor (the rollers of the pair roller conveyor can be elliptic rollers, flattening rollers and other types of rollers) at the top of the furnace body at the speed of 0.01-3 m/min (further preferably, the input speed of the pre-oxygen cloth is 0.2-0.45 m/min, the speed can be adjusted according to the actual vertical furnace height), sequentially passes through a first heat treatment area, a second heat treatment area and a third heat treatment area, and is filled with an activating agent (further preferably, the activating agent is water vapor, carbon dioxide, potassium hydroxide or zinc chloride) in the second heat treatment area and the third heat treatment area, the prepared PAN-based activated carbon fiber cloth is output by the output pair roller of a discharge hole and is wound on a coiler, and the coiler provides traction power.
The vertical carbon activation furnace is adopted, and the height of the activation furnace is 15m in practical application, wherein the height of the first heat treatment area is 4.5 meters, the height of the second heat treatment area is 3 meters, and the height of the third heat treatment area is 3 meters, and the spacing is 0.5 meter respectively. The vertical carbon activation furnace has the advantages of small occupied area, resource saving and capability of effectively improving the productivity and economic benefit; meanwhile, the vertical carbon activation furnace can effectively utilize the dead weight of fiber cloth and the natural suction force of a chimney of the vertical furnace, reduce the installation of a cloth support frame and a waste gas pumping device in the furnace, and effectively avoid the problems of easy damage of materials, high maintenance cost and long time consumption in the later-stage high-temperature condition. However, the vertical furnace also causes the problem that oxygen is easy to enter at the bottom discharge port due to the huge chimney effect, so that the activated carbon fiber is easy to be excessively activated or directly burnt, and the high-performance PAN-based functional activated carbon fiber cannot be produced, and the problem can be solved only by using the fully-closed door. The fully-closed door is used to cause that the prepared fiber finished product can only be piled up in the bottom box, and then the furnace door is opened periodically to collect the activated carbon fiber, so that the later-stage workload is greatly increased, and the productivity and economic benefit are reduced. According to the invention, a discharge hole is further formed in the bottom, and a stainless steel nitrogen pressurizing pipe and other modes are adopted for gas sealing, so that the oxygen concentration (2%) can be reduced to the extent that the production of high-performance activated carbon fibers is completely met, and on the basis, the structural change and the graphite crystal layer transformation rule of PAN-based pre-oxidized fibers in the vertical furnace carbon activation process are researched, and finally the PAN-based functional activated carbon fibers with high propyl sulfide protective capability are prepared. In addition, because the gram weight of the polyacrylonitrile-based activated carbon fiber is small, the cloth is easily influenced by air current to contact the furnace wall in the moving process of the furnace, so that burning loss is caused. Therefore, the output counter roller is additionally arranged at the bottom of the furnace, and the finished product of the polyacrylonitrile-based activated carbon fiber cloth is directly pulled and discharged by matching with an opening at the furnace door and a pulling device (a winding machine) arranged outside the furnace. The speed of the traction winding device is adjustable (about 0.1 m/min-3 m/min), and the automatic alignment function is achieved. The rolling machine is provided with a weight column to ensure that the discharging speed of the polyacrylonitrile-based activated carbon fiber cloth is controllable. The whole process is controlled by the power distribution cabinet, and the automatic discharging and winding function is realized.
In the concrete implementation, polyacrylonitrile pre-oxidized fiber is fed from the upper end of a furnace, preferably steam is used as activating gas, the fiber is downwards subjected to carbon activation reaction through 3 thermal reaction areas by self weight by means of gravity, and the fiber is lowered to the bottom of the furnace body; and after the material reaches the discharge port, the material is rolled by a rolling machine, so that the excellent PAN-based functional activated carbon fiber is prepared at high efficiency, continuous preparation of the PAN-based functional activated carbon fiber is realized, and the productivity and economic benefits are improved, and the material has great significance.
The carbon activation is a key step for preparing the activated carbon fiber, and three temperature areas are designed for the whole furnace body in consideration of the influence of the carbon activation technology, the carbon activation temperature and the carbon activation time on the performance of the activated carbon fiber, and the change of the activated carbon fiber in different temperature areas is different.
The first temperature zone is 200-400 ℃, and is mainly carbonization of the activated carbon fiber, wherein the carbonization process is a key step in the preparation process of the activated carbon fiber, and is a solid-phase pyrolysis reaction of the pre-oxidized fiber through a carbonization furnace under the protection of high-purity nitrogen. In this temperature range, non-carbon atoms are continuously removed as the carbonization temperature increases, and the carbon atoms form a trapezoid structure by cyclization polycondensation or the like. The graphitization degree is higher after carbonization, the carbon crystal structure is more perfect, and the orientation degree is higher. The reasonable control of carbonization temperature can lead the plane of the hexagonal carbon net to be rapidly increased, and the stacking density and preferred orientation of the disordered layer graphite structure reach the optimal balance, thereby being beneficial to improving the mechanical property of the activated carbon fiber.
The second temperature zone and the third temperature zone are responsible for the activation of the activated carbon fibers. The activation process is to activate the fiber in oxidizing medium to react the activator with unstable carbon atom and graphite microcrystal structure to result in carbon atom loss, etching fiber to form great amount of pores on the surface of the fiber and to raise specific surface area and form certain active functional group on the surface. The activation temperature is generally controlled between 400 and 950 ℃. In a certain temperature range, the higher the activation reaction temperature is, the better the activation effect is. The activation time can be correspondingly adjusted within 10-120 min basically, and the proper activation time ensures that the fiber has certain strength and excellent adsorption capacity, and is a key for preparing the high-performance PAN-based activated carbon fiber.
The second temperature range is 400-600 deg.c, and the pre-oxidized fiber is converted into trapezoid structure completely. The trapezoid structure is further crosslinked and enlarged into a net structure, so that the content of the carbon-based planar structure is increased, and further dehydrogenation and denitrification are carried out to form a carbon six-element net planar structure. The active carbon fiber has six-membered carbon ring structure containing conjugated II bond and six-membered aromatic structure containing nitrogen to form graphite carbon ring plane structure gradually. And the carbon plane is continuously piled up and grown at the carbonization temperature, so that the carbon microcrystal structure is more perfect.
The third temperature region can smoothly realize the crosslinking and polycondensation reaction between the carbon-based planar structures in the fiber at the temperature of 850-950 ℃. The arrangement of the third temperature zone obviously improves the specific surface area of the polyacrylonitrile active carbon fiber, and simultaneously the breaking strength and the breaking elongation of the polyacrylonitrile active carbon fiber in the longitude and latitude directions are obviously increased.
And water vapor pore pipelines are respectively arranged at the second temperature and the third temperature, and water vapor is introduced as an activating agent. The fiber cloth sample activated by the water vapor has higher mechanical property and can not break when stretched by hands. And the water vapor activation process is an endothermic reaction, so that the reaction temperature is easier to control.
The bottom of the vertical carbon activation furnace is provided with an air seal, so that the air is ensured not to enter the vertical carbon activation furnace while the cloth is smoothly discharged from the vertical carbon activation furnace, and the air content in the vertical carbon activation furnace is not more than 5%.
The PAN-based functional activated carbon fiber prepared by the continuous production device of the vertical carbon activation furnace has excellent comprehensive properties such as breaking strength, pore structure, particularly protection time of the propylsulfide, provides guarantee for efficient and portable use and updating of breathable protective clothing, and is suitable for industrial stable mass production of the PAN-based functional activated carbon fiber with high comprehensive properties.
The PAN-based functional activated carbon fiber continuous batch preparation method for preparing the high-efficiency protective propane sulfide by utilizing the polyacrylonitrile pre-oxidized fiber and using the vertical carbon activation furnace has reasonable design and good practical application value.
Drawings
FIG. 1 shows a schematic diagram of a vertical carbonization furnace.
In the figure: 100-vertical carbonization furnace, 101-feed inlet, 102-discharge outlet, 103-first heat treatment area, 104-second heat treatment area, 105-third heat treatment area, 106-activator input pipeline; 200-output groove, 300-coiler.
Detailed Description
The invention is further described below with reference to examples. The technical means used in the present invention are methods well known to those skilled in the art unless specifically stated.
Example 1
A PAN-based ACF continuous production method for preparing protective propane sulfide by using a vertical carbon activation furnace comprises the following steps:
using twill pre-oxidized cloth with gram weight of 300g/m 2 At the speed of 0.32m/min, the PAN-based activated carbon fiber cloth is fed into the vertical carbonization furnace from a feeding port by using an elliptic roller, the heat treatment temperature in a first heat treatment area in the furnace body is 200 ℃, the heat treatment temperature in a second heat treatment area is 400 ℃, the heat treatment temperature in a third heat treatment area is 890 ℃, water vapor is introduced into the second and third heat treatment areas, the PAN-based activated carbon fiber cloth is prepared, traction is provided by a coiler, and the PAN-based activated carbon fiber cloth is pulled out from an output counter roller of a discharge port and is coiled.
Example 2
A PAN-based ACF continuous production method for preparing protective propane sulfide by using a vertical carbon activation furnace comprises the following steps:
using plain pre-oxidized cloth with a gram weight of 230g/m 2 At the speed of 0.45m/min, the PAN-based activated carbon fiber cloth is fed into the vertical carbonization furnace from a feeding port by using an elliptic roller, the heat treatment temperature in a first heat treatment area in the furnace body is 200 ℃, the heat treatment temperature in a second heat treatment area is 450 ℃, the heat treatment temperature in a third heat treatment area is 870 ℃, water vapor is introduced into the second and third heat treatment areas, the PAN-based activated carbon fiber cloth is prepared, traction is provided by a coiler, and the PAN-based activated carbon fiber cloth is pulled out from an output counter roller of a discharge port and coiled.
Example 3
A PAN-based ACF continuous production method for preparing protective propane sulfide by using a vertical carbon activation furnace comprises the following steps:
the artificial pre-oxygen cloth is used, and the gram weight of the artificial pre-oxygen cloth is 380g/m 2 At the speed of 0.2m/min, the PAN-based activated carbon fiber cloth is fed into the vertical carbonization furnace from a feeding port by using an elliptic roller, the heat treatment temperature in a first heat treatment area in the furnace body is 300 ℃, the heat treatment temperature in a second heat treatment area is 500 ℃, the heat treatment temperature in a third heat treatment area is 900 ℃, water vapor is introduced into the second and third heat treatment areas, the PAN-based activated carbon fiber cloth is prepared, traction is provided by a coiler, and the PAN-based activated carbon fiber cloth is pulled out from an output counter roller of a discharge port and coiled.
Example 4
A PAN-based ACF continuous production method for preparing protective propane sulfide by using a vertical carbon activation furnace comprises the following steps:
using twill pre-oxidized cloth with gram weight of 280g/m 2 At a rate of 0.4m/min, feeding the material into a vertical carbonization furnace from a feeding port by using an elliptic roller, wherein the heat treatment temperature in a first heat treatment area in the furnace body is 300 ℃, the heat treatment temperature in a second heat treatment area is 500 ℃, the heat treatment temperature in a third heat treatment area is 920 ℃, introducing water vapor into the second and third heat treatment areas to prepare PAN-based activated carbon fiber cloth, providing traction force by a furling machine, and feeding the PAN-based activated carbon fiber cloth from a discharge portIs drawn out and wound up by the pair of output rollers.
Example 5
A PAN-based ACF continuous production method for preparing protective propane sulfide by using a vertical carbon activation furnace comprises the following steps:
using twill pre-oxidized cloth with gram weight of 260g/m 2 At the speed of 0.3m/min, the PAN-based activated carbon fiber cloth is fed into the vertical carbonization furnace from a feeding port by using an elliptic roller, the heat treatment temperature in a first heat treatment area in the furnace body is 300 ℃, the heat treatment temperature in a second heat treatment area is 500 ℃, the heat treatment temperature in a third heat treatment area is 920 ℃, water vapor is introduced into the second and third heat treatment areas, the PAN-based activated carbon fiber cloth is prepared, traction is provided by a coiler, and the PAN-based activated carbon fiber cloth is pulled out from an output counter roller of a discharge port and coiled.
The materials prepared in examples 1 to 5 were tested to evaluate the protection time, specific surface area and breaking strength of propylsulfide.
Propionsulfide protection time tested according to GJB3253-1998 appendix A
Table 1 table of results of characterization property test of PAN-based activated carbon fiber
From table 1, it can be seen that in examples 1 to 5, polyacrylonitrile activated carbon fibers having different specific surface areas, breaking strengths and protection times against propylsulfide were prepared by controlling different carbon activation process conditions. By regulating and controlling the temperatures of different heat treatment areas and the corresponding fiber carbon activation time, the high-performance PAN-based functional activated carbon fiber with the protection time of the propylsulfide far exceeding the index requirement of 80min can be prepared, and the breaking strength of the PAN-based functional activated carbon fiber is far higher than the index requirement of 40N. And the higher the activation temperature, the longer the activation time (example 3, example 5) and the higher the corresponding protection time and specific surface area of the propylsulfide compared with other examples.
The PAN-based functional activated carbon fiber is continuously prepared by taking the actual application of the PAN-based functional activated carbon fiber as a core adsorption material of the inner layer of the breathable gas suit of the biochemical protective equipment as a starting point and utilizing the polyacrylonitrile pre-oxidized fiber, and the modified vertical carbon activation furnace is utilized for the first time, so that the purposes of fiber flattening and exhaust gas extraction are achieved through the self weight of the fiber and the suction force of a chimney, and the PAN-based functional activated carbon fiber with excellent comprehensive properties such as excellent toxin agent protection capability and strength is prepared by the carbon activation technology of the vertical carbon activation furnace by using proper carbonization temperature and carbonization rate in combination with the activation temperature and time of an activator. Meanwhile, by researching the structural change and the graphite crystal layer transformation rule of PAN-based pre-oxidized fibers in the carbon activation process in the vertical carbon activation furnace, the PAN-based functional activated carbon fibers with excellent protection capability and excellent strength and pore structure on the propylsulfide are obtained, and meanwhile, the industrialized batch stable preparation of the fiber cloth is realized. The preparation method provided by the invention has great economic benefit for the later industrialized batch preparation of the PAN-based functional activated carbon fiber with high performance.
Finally, it should be noted that the above is to be understood as illustrative and not limiting the scope of the invention, which is defined solely by the claims. Various changes or modifications to the materials ingredients and amounts used in these embodiments will be apparent to those skilled in the art without departing from the spirit and scope of the invention.
Claims (2)
1. A PAN-based ACF continuous production method for preparing protective propane sulfide by using a vertical carbon activation furnace is characterized by comprising the following steps of: a pre-oxidized cloth woven by polyacrylonitrile pre-oxidized yarns;
a vertical carbon activation furnace is adopted; the top surface of the vertical carbon activation furnace is provided with a feed inlet, and the bottom is provided with a discharge outlet; the furnace is internally provided with a first heat treatment area, a second heat treatment area and a third heat treatment area from top to bottom in sequence, wherein the treatment temperature of the first heat treatment area is 200-300 ℃, the heat treatment temperature of the second heat treatment area is 400-500 ℃, and the heat treatment temperature of the third heat treatment area is 850-950 ℃; the second heat treatment zone and the third heat treatment zone are respectively provided with an activator input line; an output pair roller is arranged at the discharge hole and is connected with the coiler through an output groove; the first heat treatment area is 4.5 meters high, the second heat treatment area is 3 meters high, and the third heat treatment area is 3 meters high, with a spacing of 0.5 meter respectively;
the pre-oxidized fiber cloth is sent to the inside of the furnace body by a double-roller conveyor at the top of the furnace body at the speed of 0.2-0.45 m/min, sequentially passes through a first heat treatment area, a second heat treatment area and a third heat treatment area, and is filled with an activating agent, the prepared PAN-based activated carbon fiber cloth is output by a double-roller output port of a discharge port and is wound on a winding machine, and the winding machine provides traction power;
the activator is water vapor, carbon dioxide, potassium hydroxide or zinc chloride;
the gram weight of the twill pre-oxidized fabric woven by the polyacrylonitrile pre-oxidized fiber is 230-280 g/m 2 The continuous burning time of the polyacrylonitrile pre-oxidized fiber cloth is less than or equal to 20 seconds, the smoldering time is less than or equal to 15 seconds, and the oxygen index of the raw material of the polyacrylonitrile pre-oxidized fiber for manufacturing the pre-oxidized fiber cloth is more than or equal to 36 percent;
the air content in the vertical carbon activation furnace is not more than 5%.
2. The continuous production method of PAN-based ACF for preparing protective propane sulfide by using a vertical carbon activation furnace according to claim 1, wherein the continuous production method comprises the following steps: and a stainless steel nitrogen pressurizing pipe is arranged at the discharge port to release nitrogen for gas sealing.
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| DE202016100320U1 (en) * | 2015-12-10 | 2016-12-28 | BLüCHER GMBH | Activated carbon, in particular particulate activated carbon, in particular with defined porosity properties |
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