CN111253573A - Method for preparing polyphenylene sulfide resin - Google Patents
Method for preparing polyphenylene sulfide resin Download PDFInfo
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- CN111253573A CN111253573A CN201911384936.8A CN201911384936A CN111253573A CN 111253573 A CN111253573 A CN 111253573A CN 201911384936 A CN201911384936 A CN 201911384936A CN 111253573 A CN111253573 A CN 111253573A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0268—Preparatory processes using disulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
- C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0277—Post-polymerisation treatment
- C08G75/0281—Recovery or purification
Abstract
A process for preparing polyphenylthioether resin includes such steps as using sodium sulfide dihydrate and p-dichlorobenzene as raw materials, N-methyl-2-pyrrolidone as solvent, adding alkaline stabilizer and lithium salt as assistant, polycondensation reaction, and recovering polyphenylthioether-containing slurry in segments to obtain polyphenylthioether with melt mass flow rate of 100-1200 g/10 min. Meanwhile, the treatment process that the solvent and the auxiliary agent can be recovered and the salt byproduct can be utilized is realized, so that the production cost is reduced, the waste discharge is reduced, and the resource utilization of the wastewater and the waste is realized.
Description
Technical Field
The application relates to the technical field of polyphenylene sulfide resin manufacturing, in particular to a method for manufacturing polyphenylene sulfide resin with recoverable solvent and auxiliary agent and utilizable salt byproduct.
Background
Polyphenylene Sulfide (hereinafter abbreviated as PPS) is a high-performance thermoplastic resin, has the advantages of high mechanical strength, high temperature resistance, difficult combustion, good thermal stability and the like, and is widely applied to the fields of electronics, automobiles, machinery, chemical engineering and the like. The PPS production method at present mainly adopts alkali metal sulfide or hydrosulfide and polyhalogenated aromatic compound in an aprotic organic solvent and in the presence of a reaction stabilizer and an auxiliary agent through polycondensation reaction.
In order to reduce the production cost, the PPS reaction filtrate and the cleaning solution are usually mixed and subjected to fractional rectification, the organic solvent is recycled, and the water used as the cleaning solution is discharged after being treated as wastewater due to the fact that the water contains a small amount of organic substances such as the solvent and other by-products. Meanwhile, in order to improve the product quality, reaction auxiliary agents such as organic acid sodium salt and lithium salt are added into the reaction system, and compared with the former, the lithium salt serving as a polymerization auxiliary agent has certain advantages in the aspects of PPS synthesis control and product quality, but the price is high and the recycling difficulty is high, so that the reduction of PPS production cost is directly limited. The current PPS production process mainly includes precipitation (US5635587A, CN101205298B, CN102276838B and CN106565956B) and organic solvent extraction (US5262137A, CN102675683B, CN104877167B and CN106565581A) with respect to lithium salt recovery, but these measures not only require the addition of a large amount of precipitant or organic solvent, but also do not consider that the accumulation of a large amount of organic substances due to the closed cycle process may hinder the sustainable operation of the salt solution concentration process in the actual production. CN104877167B is directly used for synthesis reaction after removing solid oligomers and salt byproducts in synthesis filtrate by filtration, but the neglect of organic substances and salts dissolved in a solvent in the method can influence the quality stability of PPS products. On the other hand, after the salt byproduct of the CN 103897187B synthesis reaction is treated by burning, the salt byproduct cannot be reasonably utilized, so that the resource is wasted, and meanwhile, the salt byproduct also has negative effects on the ecological environment.
Disclosure of Invention
The invention aims to provide a novel method for preparing polyphenylene sulfide, aiming at the defects of the existing polyphenylene sulfide resin preparation process.
In order to achieve the above purpose, the following technical scheme is adopted in the application.
The application discloses a method for preparing polyphenylene sulfide resin, which comprises adopting sodium sulfide (Na for short) in multiple water2S) and p-dichlorobenzene (hereinafter referred to as p-DCB) are taken as raw materials, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) is taken as a solvent, and an alkaline stabilizer and a lithium salt auxiliary agent are simultaneously added, so that the polyphenylene sulfide with the melt mass flow rate (hereinafter referred to as MFR) of 100-1200 g/10min is synthesized through polycondensation, and the preparation method of the polyphenylene sulfide resin with the recoverable solvent and auxiliary agent and the utilizable salt byproduct is realized. The method comprises the following specific steps:
(1) sequentially adding NMP and Na into a reaction kettle under the protection of nitrogen2S, an alkaline stabilizer and a lithium salt auxiliary agent, then raising the temperature from the normal temperature to 130-160 ℃ at the speed of 1-2 ℃/min, and then raising the temperature to 185-220 ℃/min at the speed of 0.1-0.4 ℃/min until the dehydration rate reaches 60-85%;
(2) after the step (1), adding p-DCB and NMP into a reaction kettle, heating to 220-235 ℃ at the speed of 0.5-1 ℃/min, keeping the temperature for 1-3 h, heating to 255-270 ℃ at the speed of 0.5-1 ℃/min, keeping the temperature for 2-4 h, and cooling to 120-150 ℃ for 1-2 h after finishing, thus obtaining polyphenylene sulfide synthetic slurry;
(3) after the step (2), carrying out centrifugal filtration on the slurry containing polyphenylene sulfide, washing filter cakes with hot water at the temperature of 80-90 ℃ until the conductivity is qualified, then carrying out centrifugal filtration, drying filter cakes to obtain polyphenylene sulfide resin I, further carrying out solid-liquid separation on the slurry filtrate, washing the filter cakes to obtain polyphenylene sulfide resin II, combining all filtrates, further filtering and washing the filter cakes to obtain polyphenylene sulfide resin III;
(4) combining all the filtrates in the step (3), carrying out reduced pressure distillation and rectification to respectively recover NMP and water;
(5) and (4) treating the distillation residues in the step (4) by a process system of self-propagating incineration pyrolysis treatment with an exhaust gas treatment system. The process system comprises a dry salt pretreatment system, a self-propagating pyrolysis system and a flue gas purification system; the dry salt pretreatment system comprises a dry salt cooling device, a pelletizing device and a mixing device which are sequentially arranged; cooling the byproduct dry salt in the dry salt bin by a cooling screw, pelletizing in a pelletizer, and feeding the pelletized pellets and the green additive in the auxiliary bin into a mixing device for fully mixing; the self-propagating pyrolysis system comprises a self-propagating negative pressure heat accumulation pyrolysis device, a secondary combustion chamber, a distributor, a heat exchanger, an induced draft fan, a residue bin and a crusher; the self-propagating negative-pressure heat-accumulation pyrolysis device comprises a chain belt conveyor, wherein the chain belt conveyor consists of a driving mechanism, a chain wheel and a chain belt matched with the chain wheel; a distributing device and an upper shell are sequentially arranged above the head of the chain belt conveyor along the advancing direction of the chain belt; the upper shell is sequentially divided into a preheating section, an ignition section, an incineration section and a cooling section; a plurality of air draft hoods are distributed at positions, corresponding to the upper shell, of a cavity formed by the chain belt, and the air draft hoods, the fans and the air draft pipeline are communicated to form a smoke passage; in the flue gas passage, flue gas of the preheating section and the ignition section enters the incineration section, the flue gas of the incineration section forms one-stage or multi-stage circulation in the incineration section, the flue gas of the last stage of the incineration section enters the preheating section, and the flue gas of the cooling section enters the flue gas purification system; the self-propagating pyrolysis refers to that on the premise that dry salt pellets are not turned over, after a green additive in a mixed material is ignited through an ignition section, heat is generated and self-propagating pyrolysis treatment is carried out on the dry salt pellets or particles, and the dry salt pellets are completely pyrolyzed at the tail end of a chain belt conveyor to obtain finished salt;
the top of the tail end of the chain belt conveyor is provided with a tail seal matched with the upper shell, the top of the tail seal is provided with a cloth bag dust removal device, a finished product bin matched with the chain belt and the tail seal is arranged below the tail end of the chain belt conveyor, pyrolysis salt in the finished product bin is crushed by a single tooth roller to enter a residue buffer bin, then is subjected to deep crushing by a hammer crusher and/or a three-roller crusher and finally is conveyed to the residue bin, one end of the residue bin is matched with the finished product bin, the other end of the residue bin extends to the lower part of a return chain belt, and the return chain is positioned below the chain wheel to return and convey residues. The particle size of the pyrolysis finished salt is 20-50 meshes after the pyrolysis finished salt is crushed. The crushed powder salt is dissolved by deionized water, acidified, filtered and purified, and then sodium chloride which can be directly used in chlor-alkali chemical industry and lithium salt which can be used as a polyphenylene sulfide synthesis aid are recovered by evaporation, concentration and segmentation.
In the method, the alkaline stabilizer is sodium hydroxide, and the lithium salt auxiliary agent is lithium chloride.
In the above method, the amount of Na per mole in the step (1) is determined2S, the adding amount of NMP is 5-6.5 mol, the adding amount of sodium hydroxide is 0.04-0.06 mol, and the adding amount of lithium chloride is 0.35-0.65 mol.
In the above method, the amount of Na per mole in the step (2) is determined2S, p-DCB is added in an amount of 0.98 to 1.03mol, and NMP is added to make the total amount of the S, p-DCB in the range of 7 to 10 mol.
In the step (3) of the method, the MFR ranges of the polyphenylene sulfide resins I, II and III are 100-800 g/10min, 150-900 g/10min and 300-1200 g/10min in sequence.
In the step (4) of the method, the conditions of the steam with NMP and water in the reduced pressure distillation are that the temperature of an evaporation tower is 100-130 ℃, the pressure is-50-70 kPa, the steam enters an NMP rectifying tower after being condensed and then is rectified under the conditions of 155-185 ℃ at the bottom and 70-90 ℃ at the top, the steam at the top of the NMP rectifying tower enters a water rectifying tower and then is rectified under the conditions of 80-100 ℃ at the bottom and 90-110 ℃ at the top, and the steam at the top of the water rectifying tower enters a waste gas treatment system.
In the step (5) of the method, granulation treatment is carried out before medium incineration treatment, and the binder for pelletizing is syrup solution with the mass concentration of 8-15%; the compressive strength of the dry salt pellets is more than or equal to 1.5N, the falling frequency is more than or equal to 15, and the particle size of the dry salt pellets is 3-6 mm; the green additive in the auxiliary material bin is biochar or bran shells, and the adding proportion of the biochar or bran shells is 3% and 7% of the mass of the dry salt pellets or particles respectively. And (3) carrying out self-propagating pyrolysis under the negative pressure of 100-6000 Pa, at the temperature of 690 ℃ in the ignition section, at the pyrolysis temperature of 580-700 ℃, and at the incineration time of 45-60min, and dissolving, filtering and removing impurities to obtain refined brine.
The crushed powder salt is dissolved by deionized water, acidified, filtered and purified to obtain refined brine as shown in table 1, and then evaporated and concentrated at 100 ℃ until the content of lithium chloride is lower than 27.05%, NaCl byproduct which can be directly used in chlor-alkali chemical industry is extracted, and is evaporated forcibly and concentrated again until the content of lithium chloride reaches 55.61%, and then the solution is kept warm and settled, and then the clear solution is further concentrated to obtain lithium chloride which is taken as polyphenylene sulfide synthesis auxiliary agent.
TABLE 1
| LiCl,wt.％ | NaCl,wt.％ | H2O,wt.％ | Solid phase |
| 0 | 28.13 | 71.87 | NaCl |
| 27.05 | 4.06 | 68.89 | NaCl |
| 55.44 | 0.64 | 43.92 | LiCl (solid solution containing NaCl) |
| 55.36 | 0.38 | 43.26 | LiCl (solid solution containing NaCl) |
| 55.61 | 0.34 | 44.05 | LiCl |
| 55.86 | 0 | 43.94 | LiCl |
The invention can produce PPS product with MFR of 100-1200 g/10min by controlling the synthesis condition and the cleaning and recycling process, utilizes NMP to generate mixed steam with water at 100-130 ℃ under the decompression condition, and the condensed fluid can recycle NMP for synthesizing polyphenylene sulfide and water for cleaning polyphenylene sulfide by rectifying stage by stage. Since direct incineration of distillation residues leads to melt agglomeration and loss of LiCl through high temperature volatilization, the above effects can be controlled by increasing porosity and controlling incineration temperature through granulation process. The invention can directly recover NaCl and LiCl which meet the national standard without adding any precipitator and organic matters, and the process is simplified.
Through the process, the solvent, the auxiliary agent and the salt byproduct are recovered while the high-quality polyphenylene sulfide product is synthesized, so that the production cost is reduced, the waste discharge is reduced, and the resource utilization of waste water and waste is realized.
Detailed Description
The present application is described in further detail below by way of specific embodiments, which are provided solely for the understanding and description of the present application and are not to be construed as limiting the present application.
Example 1
In a 100L reaction kettle, 54.52kg (550mol) of N-methyl-2-pyrrolidone (NMP for short) and sodium sulfide monohydrate (Na for short) are added in sequence2S)16.81kg (100mol), 0.18kg (4.5mol) of sodium hydroxide and 1.91kg (45mol) of lithium chloride are heated to 190 ℃ at room temperature at 0.5 ℃/min under the protection of nitrogen until the dehydration rate reaches 70 percent.
And then adding 14.70kg (100mol) of p-dichlorobenzene (hereinafter referred to as p-DCB) and 14.87kg (150mol) of NMP into the reaction solution after the dehydration, heating to 230 ℃ at the speed of 0.5 ℃/min, keeping the temperature for 1h, heating to 270 ℃ at the speed of 0.5 ℃/min, keeping the temperature for 2.5h, and cooling to 140 ℃ through 1h after the completion.
And centrifugally filtering the synthetic slurry, washing a filter cake with hot water at the temperature of 80-90 ℃ until the conductivity is qualified, centrifugally filtering, drying the filter cake to obtain 9.23kg of polyphenylene sulfide resin I, wherein the melt mass flow rate (hereinafter abbreviated as MFR) is 180g/10min, further performing solid-liquid separation on the slurry filtrate and washing the filter cake to obtain 0.41kg of polyphenylene sulfide resin II, the MFR is 200g/10min, combining all the filtrates, and further filtering and washing the filter cake to obtain 0.62kg of polyphenylene sulfide resin III, wherein the MFR is 400g/10 min.
Combining the synthesized and cleaned filtrate, placing the combined filtrate in a distillation device, distilling mixed steam of NMP and water under the conditions of tower kettle temperature of 100 +/-2 ℃ and pressure of-65 kPa, rectifying NMP at 165 +/-2 ℃ at the tower bottom and 85 +/-2 ℃ at the tower top after the mixed steam enters an NMP rectifying tower, rectifying the steam at the tower top of the NMP rectifying tower at 85 +/-2 ℃ at the tower bottom and 90 +/-2 ℃ at the tower top, and feeding the steam at the tower top of the water rectifying tower into a waste gas treatment system.
And drying the distillation residues to obtain a byproduct dry salt with low moisture content, cooling the byproduct dry salt to 80 ℃ by a cooling screw, conveying the byproduct dry salt to a dry material buffer bin by a tubular belt conveyor, conveying the byproduct dry salt to a disc pelletizer by a weighing screw conveyor, and adding 7% of syrup adhesive, wherein the adhesive is 10% of syrup solution by mass concentration. Granulating the mixture to obtain particles with the particle size of 3-10 mm, feeding the prepared small balls and the bran shell additive in the auxiliary bin into a mixing screw machine for fully mixing, and incinerating the mixture by a device with a flue gas treatment system at the highest temperature of 700 ℃ for 50 min. The negative pressure of the self-propagating pyrolysis is 1200 Pa. The particle size after crushing is 20-40 meshes. Dissolving the crushed powder salt with deionized water, acidifying, filtering and removing impurities, evaporating and concentrating the filtrate until the content of lithium chloride is lower than 27.05%, extracting NaCl byproduct which can be directly used in chlor-alkali chemical industry, forcibly evaporating and concentrating until the content of lithium chloride reaches 55.61%, keeping the temperature at 100 ℃ and settling, and further concentrating, separating and drying the clear liquid to obtain the lithium chloride used as the polyphenylene sulfide synthesis aid.
Example 2
In a 100L reaction kettle, 54.52kg (550mol) of N-methyl-2-pyrrolidone (NMP for short) and sodium sulfide monohydrate (Na for short) are added in sequence2S)16.81kg (100mol), 0.18kg (4.5mol) of sodium hydroxide and 1.91kg (45mol) of lithium chloride are heated to 135 ℃ at room temperature at 2 ℃/min under the protection of nitrogen until the dehydration rate reaches 70 percent.
And then adding 14.70kg (102mol) of p-dichlorobenzene (hereinafter referred to as p-DCB) and 14.87kg (150mol) of NMP into the reaction solution after the dehydration, heating to 230 ℃ at the speed of 0.5 ℃/min, keeping the temperature for 1h, heating to 265 ℃ at the speed of 0.5 ℃/min, keeping the temperature for 3h, and cooling to 120 ℃ through 1h after the completion.
And centrifugally filtering the synthetic slurry, washing a filter cake with hot water at the temperature of 80-90 ℃ until the conductivity is qualified, then centrifugally filtering, drying the filter cake to obtain 9.33kg of polyphenylene sulfide resin I and 410MFRg/10min, further carrying out solid-liquid separation on the slurry filtrate and washing the filter cake to obtain 0.42kg of polyphenylene sulfide resin II and 490MFRg/10min, merging all filtrates, and further filtering and washing the filter cake to obtain 0.62kg of polyphenylene sulfide resin III and 600MFRg/10 min.
Combining the synthesized and cleaned filtrate, placing the combined filtrate in a distillation device, distilling mixed steam of NMP and water under the conditions of tower kettle temperature of 100 +/-2 ℃ and pressure of-65 kPa, rectifying NMP at 165 +/-2 ℃ at the tower bottom and 85 +/-2 ℃ at the tower top after the mixed steam enters an NMP rectifying tower, rectifying the steam at the tower top of the NMP rectifying tower at 85 +/-2 ℃ at the tower bottom and 90 +/-2 ℃ at the tower top, and feeding the steam at the tower top of the water rectifying tower into a waste gas treatment system.
And drying the distillation residues to obtain a byproduct dry salt with low moisture content, cooling the byproduct dry salt to 100 ℃ by a cooling screw, conveying the byproduct dry salt to a dry material buffer bin by a tubular belt conveyor, conveying the byproduct dry salt to a disc pelletizer by a weighing screw conveyor, and adding 8% of syrup adhesive, wherein the adhesive is 12% of syrup solution by mass concentration. Granulating the mixture to prepare particles with the particle size of 5-10 mm, feeding the prepared small balls and a bran shell additive in an auxiliary material bin into a mixing screw machine for fully mixing, distributing the mixed materials, then feeding the mixed materials into a burning main machine, igniting the bran shell and a biochar additive in the mixed materials through an ignition section, generating heat, and performing self-propagating pyrolysis treatment on the generated heat through dry salt small balls or the particles, wherein the dry salt small balls are pyrolyzed completely at the tail end of a chain belt conveyor to obtain finished salt;
the top of the tail end of the chain belt conveyor is provided with a tail seal matched with the upper shell, the top of the tail seal is provided with a cloth bag dust removal device, a finished product bin matched with the chain belt and the tail seal is arranged below the tail end of the chain belt conveyor, pyrolysis salt in the finished product bin is crushed by a single tooth roller to enter a residue buffer bin, then is subjected to deep crushing by a hammer crusher and/or a three-roller crusher and finally is conveyed to the residue bin, one end of the residue bin is matched with the finished product bin, the other end of the residue bin extends to the lower part of a return chain belt, and the return chain is positioned below the chain wheel to return and convey residues. The particle size of the pyrolysis finished salt is 20-50 meshes after the pyrolysis finished salt is crushed. The powdery salt is dissolved by deionized water, acidified, filtered and decontaminated, a NaCl byproduct which can be directly used in chlor-alkali chemical industry is extracted after filtrate is evaporated and concentrated until the content of lithium chloride is lower than 27.05 percent, the NaCl byproduct is forcibly evaporated and concentrated until the content of lithium chloride reaches 55.61 percent, and after heat preservation and sedimentation at 100 ℃, clear liquid is further concentrated, separated and dried to obtain the lithium chloride used as the polyphenylene sulfide synthesis auxiliary agent.
Claims (8)
1. A process for preparing polyphenylthioether resin features that the polyhydrated sodium sulfide (Na) is used2S) and p-dichlorobenzene (hereinafter referred to as p-DCB) are taken as raw materials, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) is taken as a solvent, and an alkaline stabilizer and a lithium salt auxiliary agent are simultaneously added, so that the polyphenylene sulfide with the melt mass flow rate (hereinafter referred to as MFR) of 100-1200 g/10min is synthesized through polycondensation, and the preparation method of the polyphenylene sulfide resin with the recoverable solvent and auxiliary agent and the utilizable salt byproduct is realized. The method comprises the following specific steps:
(1) sequentially adding NMP and Na into a reaction kettle under the protection of nitrogen2S, alkaline stabilizer and lithium salt assistant, and then 1-2Raising the temperature from normal temperature to 130-160 ℃ at the speed of 0.1-0.4 ℃/min, and then raising the temperature to 185-220 ℃/min at the speed of 0.1-0.4 ℃/min until the dehydration rate reaches 60% -85%;
(2) after the step (1), adding p-DCB and NMP into a reaction kettle, heating to 220-235 ℃ at the speed of 0.5-1 ℃/min, keeping the temperature for 1-3 h, heating to 255-270 ℃ at the speed of 0.5-1 ℃/min, keeping the temperature for 2-4 h, and cooling to 120-150 ℃ for 1-2 h after finishing, thus obtaining polyphenylene sulfide synthetic slurry;
(3) after the step (2), performing centrifugal filtration on the slurry containing polyphenylene sulfide, washing a filter cake with hot water at the temperature of 80-90 ℃ until the conductivity is qualified, then performing centrifugal filtration, drying the filter cake to obtain polyphenylene sulfide resin I, performing solid-liquid separation on the slurry filtrate, washing the filter cake to obtain polyphenylene sulfide resin II, combining all filtrates, and further filtering and washing the filter cake to obtain polyphenylene sulfide resin III;
(4) combining all the filtrates in the step (3), carrying out reduced pressure distillation and rectification to respectively recover NMP and water;
(5) and (4) treating the distillation residues in the step (4) by a process system of self-propagating incineration pyrolysis treatment with a waste gas treatment system. The process system comprises a dry salt pretreatment system, a self-propagating pyrolysis system and a flue gas purification system; the dry salt pretreatment system comprises a dry salt cooling device, a pelletizing device and a mixing device which are sequentially arranged; cooling the byproduct dry salt in the dry salt bin by a cooling screw, pelletizing in a pelletizer, and feeding the pelletized pellets and the green additive in the auxiliary bin into a mixing device for fully mixing; the self-propagating pyrolysis system comprises a self-propagating negative pressure heat accumulation pyrolysis device, a secondary combustion chamber, a distributor, a heat exchanger, an induced draft fan, a residue bin and a crusher; the self-propagating negative-pressure heat-accumulation pyrolysis device comprises a chain belt conveyor, wherein the chain belt conveyor consists of a driving mechanism, a chain wheel and a chain belt matched with the chain wheel; a distributing device and an upper shell are sequentially arranged above the head of the chain belt conveyor along the advancing direction of the chain belt; the upper shell is sequentially divided into a preheating section, an ignition section, an incineration section and a cooling section; a plurality of air draft hoods are distributed at the positions, corresponding to the upper shell, of the cavity formed by the chain belt, and the air draft hoods, the fans and the air draft pipeline are communicated to form a smoke passage; in the flue gas passage, flue gas of the preheating section and the ignition section enters the incineration section, the flue gas of the incineration section forms one-stage or multi-stage circulation in the incineration section, the flue gas of the last stage of the incineration section enters the preheating section, and the flue gas of the cooling section enters the flue gas purification system; the self-propagating pyrolysis refers to that on the premise that dry salt globules are not turned over, after green additives in the mixed material are ignited through an ignition section, heat is generated to carry out self-propagating pyrolysis treatment through the dry salt globules or particles, and the dry salt globules are pyrolyzed at the tail end of the chain belt conveyor completely to obtain finished salt;
the top of the tail end of the chain belt conveyor is provided with a tail seal matched with the upper shell, a cloth bag dust removal device is arranged at the top of the tail seal, a finished product bin matched with the chain belt and the tail seal is arranged below the tail end of the chain belt conveyor, pyrolysis salt in the finished product bin enters a residue buffer bin through single-tooth roller crushing, then is subjected to deep crushing through a hammer crusher and/or a three-roller crusher and finally is conveyed to a residue bin, one end of the residue bin is matched with the finished product bin, the other end of the residue bin extends to the lower part of a return chain belt, and the return chain is located below the chain wheel and returns to convey residues. The particle size of the pyrolysis finished salt is 20-50 meshes after the pyrolysis finished salt is crushed. The crushed powder salt is dissolved by deionized water, acidified, filtered and purified, and then sodium chloride which can be directly used in chlor-alkali chemical industry and lithium salt which can be used as a polyphenylene sulfide synthesis aid are recovered by evaporation, concentration and segmentation.
2. The method of claim 1, wherein the alkaline stabilizing agent is sodium hydroxide or lithium hydroxide and the lithium salt adjuvant is lithium chloride.
3. The method according to claim 1, wherein in the step (1), the amount of Na is controlled per mole of Na2S, the adding amount of NMP is 5-6.5 mol, the adding amount of alkaline stabilizer is 0.04-0.06 mol, and the total amount of lithium is 0.35-0.65 mol.
4. The method according to claim 1, wherein in the step (2), the amount of Na is controlled per mole of Na2S, p-DCB is added in an amount of 0.98 to 1.03mol, and NMP is added to make the total amount of the S, p-DCB in the range of 7 to 10 mol.
5. The method according to claim 1, wherein in step (3), the polyphenylene sulfide resins I, II, III have MFR in the range of 100 to 800g/10min, 150 to 900g/10min, 300 to 1200g/10min, in that order.
6. The method according to claim 1, wherein the steam with NMP and water is distilled under reduced pressure in step (4) under conditions of an evaporation tower temperature of 100-130 ℃ and a pressure of-50-70 kPa, the steam enters an NMP rectifying tower after being condensed and then is rectified under conditions of a tower bottom of 155-185 ℃ and a tower top of 70-90 ℃, the steam at the top of the NMP rectifying tower enters a water rectifying tower and then is rectified under conditions of a tower bottom of 80-100 ℃ and a tower top of 90-110 ℃, and the steam at the top of the water rectifying tower enters a waste gas treatment system.
7. The method according to claim 1, wherein the step (5) is carried out granulation treatment before incineration treatment, and the binder for pelletizing is a syrup solution with a mass concentration of 8% -15%; the compressive strength of the dry salt pellets is more than or equal to 1.5N, the falling frequency is more than or equal to 15, and the particle size of the dry salt pellets is 3-6 mm; the green additive in the auxiliary material bin is biochar or bran shells, and the adding proportion of the biochar or bran shells is 3% and 7% of the mass of the dry salt pellets or particles respectively. The negative pressure of self-propagating pyrolysis is 100-6000 Pa, the temperature of an ignition section is 690 ℃, the pyrolysis temperature is 580-700 ℃, the burning time is 45-60min, the brine after impurity removal by dissolution and filtration is extracted, evaporation and concentration are carried out at 100 ℃ until the content of lithium chloride is lower than 27.05%, a NaCl byproduct which can be directly used in chlor-alkali chemical industry is extracted, evaporation is forced and concentration is carried out again until the content of lithium chloride reaches 55.61%, heat preservation and sedimentation are carried out, and then the clear liquid is further concentrated to obtain the lithium chloride used as the polyphenylene sulfide synthesis auxiliary agent.
8. The flue gas purification system of claim 1, wherein: after unnecessary flue gas got into flue gas purification system among the pyrolysis system among the flue gas secondary combustion device, flue gas purification system included quench tower, sack cleaner, active carbon adsorption, oxidation denitration, desulfurizing tower, chimney, and the flue gas passes through quench tower, sack cleaner, active carbon adsorption, oxidation denitration and desulfurizing tower in proper order, and all waste gas factors discharge through the chimney after handling up to standard in the flue gas.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114106328A (en) * | 2021-12-15 | 2022-03-01 | 四川轻化工大学 | Method for continuously dehydrating sodium sulfide polyhydrate in polyphenylene sulfide production |
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