CN217103657U - Device for preparing polyacrylonitrile high-hydrophilicity spinning solution through ammoniation - Google Patents
Device for preparing polyacrylonitrile high-hydrophilicity spinning solution through ammoniation Download PDFInfo
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- CN217103657U CN217103657U CN202123289512.9U CN202123289512U CN217103657U CN 217103657 U CN217103657 U CN 217103657U CN 202123289512 U CN202123289512 U CN 202123289512U CN 217103657 U CN217103657 U CN 217103657U
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Abstract
The utility model relates to a device of high hydrophilicity spinning solution of ammoniation preparation polyacrylonitrile, connect the integrated display instrument one of online PH to be used for monitoring to mix many places PH change in the cauldron including mixing the cauldron, the monitoring is mixed cauldron bottom and is connected turbine flowmeter one, turbine flowmeter is connected with ammoniation reaction cauldron, the integrated display instrument two of online PH of ammoniation reaction cauldron external connection, turbine flowmeter is connected at the ammoniation reaction cauldron top, the storage tank is connected to turbine flowmeter two, ammoniation reaction cauldron and storage tank are connected with polymeric kettle respectively, polymeric kettle passes through the gear pump and takes off single deaeration cauldron and link to each other, be used for getting into through the gear pump with the material in the polymeric kettle and take off single deaeration cauldron.
Description
Technical Field
The utility model belongs to the technical field of the carbon fiber preparation, concretely relates to device of high hydrophilicity spinning solution of ammoniation preparation polyacrylonitrile.
Background
Carbon fibers are fibers composed mainly of carbon elements and contain carbon in an amount of more than 90%. The carbon fiber is highly oriented along the axial direction, the carbon atoms are regularly arranged, the theoretical tensile strength is 180GPa, and the tensile modulus is 1020 GPa. Currently, carbon fibers are commercially available with tensile strengths up to 7.02GPa (T1000) and tensile moduli up to 690GPa (M70J). The quality of the carbon fiber product is improved.
The carbon fiber is formed by carbonizing a precursor fiber protofilament containing carbon at a high temperature to remove other miscellaneous elements. During carbonization, the structural defects of the precursor are difficult to eliminate and are continued to be even amplified into carbon fiber products. High-quality precursor is an important prerequisite for preparing high-performance carbon fiber.
The polyacrylonitrile fiber (PAN) is used as the precursor to prepare the carbon fiber, the comprehensive advantages are the best, and the current yield of the polyacrylonitrile-based carbon fiber (PAN-CF) accounts for more than 90 percent of the total world carbon fiber yield. The PAN protofilament is subjected to high-temperature carbonization and then is subjected to preoxidation reaction to generate a heat-resistant ladder-shaped structure; because the pre-oxidation cyclization reaction of homopolymerization PAN is a free radical reaction, the heat release is concentrated, and the fire is caused by heat storage due to volatile control, the PAN protofilament is generally copolymerized PAN; itaconic acid (IA; itaconic acid) in the comonomer has the highest use frequency and is the first comonomer commonly used at home and abroad. Carboxyl groups in itaconic acid improve the hydrophilicity of copolymerized PAN (IA-PAN) compared with homopolymerized PAN; however, the hydrophilicity of the carboxyl group is not high (the hydrophilic-lipophilic balance HLB is only 2.1), and the hydrophilicity of IA-PAN is still low; in the process of solidification and fiber formation, the phase separation process of the IA-PAN spinning solution with low hydrophilicity is carried out very fast, so that the formed solidified filament is loose, contains a plurality of macropores inside, and is easy to break in the process of drawing. In order to improve the hydrophilicity of PAN dope, ammonium carboxylate is often produced by aminating carboxyl group, considering that the hydrophilicity of carboxylate is high (HLB ≈ 20).
In production, an ammoniation scheme of introducing ammonia gas into a polymerization kettle at the final stage of polymerization reaction is adopted. According to the scheme, the introduced ammonia gas can be used as a chain transfer agent to terminate the polymerization reaction while ammoniation is carried out, so that a material system is more stable in the subsequent process. However, firstly, the viscosity of the polymer solution synthesized at the final stage of the polymerization reaction is high, and uniform ammoniation is difficult; secondly, residual ammonia gas can pollute the polymerization kettle and hinder the polymerization reaction of the next batch; thirdly, the introduced ammonia gas is difficult to fully contact and react with the high-viscosity polymerization liquid, the ammoniation degree is difficult to control, the introduced amount of ammonia gas is too little, the ammoniation effect is not obvious, the introduced amount is too much, and the polymerization liquid is further tackified, so that the subsequent demonomerization and defoaming are difficult.
Patent CN 205024370U discloses an ammoniation scheme in which the material of a polymerization kettle is introduced into a spinning solution storage tank, and ammonia gas is introduced into a pipeline of the spinning solution storage tank to a defoaming kettle. The scheme avoids ammonia gas from polluting the polymerization kettle. However, firstly, the viscosity of the polymerization solution is higher after the polymerization solution is cooled in the spinning solution storage tank, and uniform ammoniation is more difficult; secondly, ammonia gas is continuously introduced, and the flow rate is difficult to be continuously and stably measured and controlled.
Patent CN 104611779 a discloses an ammoniation scheme in which a certain amount of ammonia water is mixed with a solvent to prepare an ammonia solution with a known concentration, and the ammonia solution is mixed with a spinning solution obtained after polymer solution is demonomerized and defoamed. The scheme avoids the difficulty that the ammonia gas is difficult to accurately meter. However, when the aqueous ammonia solution is mixed with the spinning dope, the double diffusion phase separation occurs, and the precipitated and solidified polyacrylonitrile is difficult to react with ammonia gas, and the ammoniation is difficult to be performed sufficiently and uniformly.
Patents CN 102336865 a and 202152326U disclose ammoniation schemes in which ammonia gas is mixed with a solvent to prepare an ammonia solution, and the ammonia solution is mixed with a polymerization solution. This arrangement avoids phase separation of the aqueous ammonia solution as it mixes with the polymerization solution. However, dilute ammonia solution (0.1-2.0 wt%) ammoniates the polymerization solution, which reduces the solid content of the spinning solution more, which is not favorable for the subsequent drawing process and the improvement of production efficiency.
SUMMERY OF THE UTILITY MODEL
The technical purpose of the utility model is to polymerization liquid ammoniation preparation high hydrophilicity spinning liquid in-process ammoniation degree is difficult to stable control or even ammoniation is difficult to go on not enough, provides a device of ammoniation preparation polyacrylonitrile high hydrophilicity spinning liquid, establishes the basis for the preparation of high quality polyacrylonitrile precursor and high performance carbon fiber.
The utility model discloses a following technical scheme realizes:
a device for preparing polyacrylonitrile high-hydrophilicity spinning solution through ammoniation comprises a mixing kettle, a first online PH integrated display instrument, a first turbine flow meter, an ammoniation reaction kettle, a storage tank, a second turbine flow meter, a second online PH integrated display instrument, a polymerization kettle, a gear pump and a demonomerization and deaeration kettle; the mixing kettle is connected with an online PH integrated display instrument I and used for monitoring the PH changes at multiple positions in the mixing kettle, the bottom of the monitoring mixing kettle is connected with a turbine flowmeter I, the turbine flowmeter is connected with the ammonification reaction kettle, the outside of the ammonification reaction kettle is connected with an online PH integrated display instrument II, the top of the ammonification reaction kettle is connected with a turbine flowmeter II, the turbine flowmeter II is connected with a storage tank, and the ammonification reaction kettle and the storage tank are respectively connected with the polymerization kettle; the polymerization kettle is connected with the demonomerization and deaeration kettle through a gear pump and is used for feeding materials in the polymerization kettle into the demonomerization and deaeration kettle through the gear pump.
Further, gas is introduced into the mixing kettle by a bubbling method, specifically, a gas cylinder, a pressure reducing valve and a mass flowmeter are utilized, a vent pipe is inserted into a position 10-30cm away from the kettle bottom, and the gas introduction rate of the mixing kettle is 7-16 g/min.
Furthermore, the mixing kettle is provided with a stirring device, and the stirring speed is 30-80 rpm.
Further, an online PH integrated display instrument I is used for determining full mixing; specifically, the judgment is as follows: when the change rate of the online PH integrated display instrument is less than 0.2 percent within 30min and the difference between a plurality of measured values is less than 0.2 percent, the mixing is judged to be sufficient.
Further, the ammonification reaction kettle is provided with a stirring device, and the stirring speed is 30-80 rpm.
Further, the online PH integrated display is used for determining full mixing; specifically, the judgment is as follows: and when the change rate of the second reading of the online PH integrated display instrument is less than 0.2 percent within 30min and the difference between a plurality of measured values is less than 0.2 percent, the mixing is judged to be sufficient.
Furthermore, the monitoring positions of the first online PH integrated display instrument and the second online PH integrated display instrument are 1-5cm below the inner liquid level of the mixing kettle and the polymerization kettle, 1/2 liquid level in the kettle and 1-5cm above the kettle bottom.
Compared with the prior art, the utility model, have and show the advantage:
1. the device provided by the utility model can be applied to NH 3 The solution reacts with itaconic acid solution to generate itaconic acid ammonium solution, and the online PH integrated display determines NH 3 The solution is uniformly mixed and fully subjected to ammoniation reaction, and the mixture is used as an ammoniation reagent to synthesize ammoniated polymer solution; 2. the utility model can conveniently control the ammoniation degree of the spinning solution by controlling the feeding proportion of the solution; 3. the utility model discloses avoided the ammonia flow to be difficult to the reaction of lasting stable control, ammonia and the relatively higher polymerization liquid of viscosity, can realize going on of ammoniation degree stable control, even ammoniation, this has established the basis for the stable preparation of high performance precursor and carbon fiber.
Drawings
Fig. 1 is a schematic structural diagram of the present invention.
In the figure 1, 1-mixing kettle, 2-online PH integrated display instrument I, 3-turbine flowmeter I, 4-ammonification reaction kettle, 5-storage tank, 6-turbine flowmeter II, 7-online PH integrated display instrument II, 8-polymerization kettle, 9-gear pump and 10-demonomerization and debubbling kettle.
Detailed Description
The present invention will be further explained with reference to the accompanying drawings
The device for preparing the polyacrylonitrile high-hydrophilicity spinning solution through ammoniation is characterized by comprising a mixing kettle 1, an online PH integration display instrument I2, a turbine flowmeter I3, an ammoniation reaction kettle 4, a storage tank 5, a turbine flowmeter II 6, an online PH integration display instrument II 7, a polymerization kettle 8, a gear pump 9 and a demonomerization and deaeration kettle 10; the device comprises a mixing kettle 1, an online PH integrated display instrument I2, a turbine flowmeter I3, an ammonification reaction kettle 4, an online PH integrated display instrument II 7, a turbine flowmeter II 6, a storage tank 5, a polymerization kettle 8, a turbine flowmeter II 6, a storage tank 5, a pH sensor I, a pH sensor II and a pH sensor II, wherein the mixing kettle 1 is connected with the online PH integrated display instrument I2 and is used for monitoring the pH change at multiple positions in the mixing kettle 1; the polymerization kettle 8 is connected with a demonomerization and deaeration kettle 10 through a gear pump 9 and is used for feeding materials in the polymerization kettle 8 into the demonomerization and deaeration kettle 10 through the gear pump 9
As shown in fig. 1, a solvent is contained in a mixing kettle 1, and the solvent is the same as the solvent for polymerizing the acrylonitrile solution; using gas cylinder liquid ammonia and adopting pressure reducing valve and mass flowmeter, inserting vent pipe into the position 10-30cm (preferably 10-15cm) away from bottom of kettle, controlling NH 3 The NH is metered in at a rate of 7 to 16g/min (preferably 8 to 10g/min) 3 Introducing into a solvent; NH (NH) 3 Continuously stirring in the whole process, wherein the stirring speed is 30-80rpm (preferably 50-60 rpm); NH (NH) 3 While dissolving, using an on-line PH integrated display instrument 2 to monitor the PH value changes at the position of 3 parts, namely 1-5cm below the liquid level in the mixing kettle 1, 1/2 liquid level in the kettle and 1-5cm above the kettle bottom, until the change rate is less than 0.2 percent and the difference between the measured values at the 3 parts is less than 0.2 percent within 30min of the first 2-index of the on-line PH integrated display instrument to prepare NH with the concentration consistent with that of the itaconic acid solution for polymerizing the acrylonitrile solution in the storage tank 5 3 A solution; NH (NH) 3 The solution is firstly metered and introduced into an ammoniation reaction kettle 4 through a turbine flowmeter 3, and then the itaconic acid solution in a storage tank 5 is controlled to be dripped into the ammoniation reaction kettle through a turbine flowmeter 6, so that NH is finally caused 3 The feeding mass ratio of the solution to the itaconic acid solution is 1:8 (the molar ratio is approximately equal to 1: 1); stirring in the ammonification reaction kettle 4 at the rotating speed of 30-80rpm, and dripping itaconic acid solution into the ammonification reaction kettle for continuous stirring in the whole process; while ammoniation reaction, the pH value of 3 positions, namely 1-5cm below the liquid level in the ammoniation reaction kettle 4, 1/2 liquid level in the kettle and 1-5cm above the kettle bottom, of the monitoring position of an online pH integrated display instrument II 7 is changed until the online pH is integratedWhen the change rate of the second indicator 7 within 30min is less than 0.2% and the difference between the measured values at 3 positions is less than 0.2%, preparing an ammonium itaconate solution; replacing itaconic acid in the storage tank 5 with ammonium itaconate of the ammonification reaction kettle 4 to be used as a comonomer to participate in polymerization reaction (preferably replacing 20-30 wt%), and synthesizing a polymerization solution in a polymerization kettle 8; the polymerization solution in the polymerization kettle 8 enters a demonomerization and deaeration kettle 10 through a gear pump 9 to be demonomerized and deaerated to obtain the high-hydrophilicity spinning solution which enters a spinning line.
Claims (4)
1. A device for preparing polyacrylonitrile high-hydrophilicity spinning solution through ammoniation is characterized by comprising a mixing kettle (1), an online PH integration display instrument I (2), a turbine flow meter I (3), an ammoniation reaction kettle (4), a storage tank (5), a turbine flow meter II (6), an online PH integration display instrument II (7), a polymerization kettle (8), a gear pump (9) and a demonomerization and debubbling kettle (10); the device comprises a mixing kettle (1), an online PH integrated display instrument (2), a turbine flowmeter (3), an ammonification reaction kettle (4), an online PH integrated display instrument (7), a turbine flowmeter (6), a storage tank (5), a polymerization kettle (8), a turbine flowmeter (6), a storage tank (5), a turbine flowmeter (6), a turbine flowmeter (3), a turbine flowmeter (4), a turbine flowmeter (7), a turbine flowmeter (6), a storage tank (5), a polymerization kettle (8), a pH sensor, a temperature sensor and the like, wherein the mixing kettle (1) is connected with the online PH integrated display instrument (2) for monitoring the change at multiple places in the mixing kettle (1); the polymerization kettle (8) is connected with the demonomerization and defoamation kettle (10) through a gear pump (9) and is used for feeding materials in the polymerization kettle (8) into the demonomerization and defoamation kettle (10) through the gear pump (9).
2. The device for ammoniation preparation of polyacrylonitrile high hydrophilic spinning solution according to claim 1, wherein the mixing kettle (1) is provided with a stirring device, and the stirring speed is 30-80 rpm.
3. The device for preparing the polyacrylonitrile high hydrophilic spinning solution through ammoniation as claimed in claim 1, wherein the ammoniation reaction kettle (4) is provided with a stirring device, and the stirring speed is 30-80 rpm.
4. The device for ammoniation preparation of polyacrylonitrile high hydrophilic spinning solution according to claim 1, wherein the monitoring positions of the on-line PH integration indicator (2) and the on-line PH integration indicator (7) are located at 1-5cm below the inner liquid level of the mixing kettle (1) and the polymerization kettle (8), 1/2 liquid level in the kettle and 1-5cm above the kettle bottom.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202123289512.9U CN217103657U (en) | 2021-12-24 | 2021-12-24 | Device for preparing polyacrylonitrile high-hydrophilicity spinning solution through ammoniation |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202123289512.9U CN217103657U (en) | 2021-12-24 | 2021-12-24 | Device for preparing polyacrylonitrile high-hydrophilicity spinning solution through ammoniation |
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