CN112960753B - Method for treating waste liquid containing polyaryl oxadiazole - Google Patents
Method for treating waste liquid containing polyaryl oxadiazole Download PDFInfo
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- CN112960753B CN112960753B CN202110140150.2A CN202110140150A CN112960753B CN 112960753 B CN112960753 B CN 112960753B CN 202110140150 A CN202110140150 A CN 202110140150A CN 112960753 B CN112960753 B CN 112960753B
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- waste liquid
- oxadiazole
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention relates to a method for treating polyaryl oxadiazole-containing waste liquid, which comprises the steps of spreading the waste liquid, carrying out contact degradation with air, adding an alkali solution to react to obtain a suspension, filtering the suspension to obtain filtrate and filter residue, and respectively discharging the filtrate and the filter residue. The treatment method disclosed by the invention well solves the problem that the polyaryl oxadiazole-containing waste liquid cannot be treated, and is simple, low in treatment cost and strong in operability.
Description
Technical Field
The invention relates to a method for treating polymer-containing waste liquid, in particular to a method for treating aromatic oxadiazole-containing waste liquid.
Background
Polyaryl Oxadiazole (POD) is an aromatic heterocyclic polymer material with good heat resistance, oxidation resistance and chemical corrosion resistance, and is insoluble in common solvents such as benzene, n-heptane, carbon tetrachloride and the like.
At present, aromatic dicarboxylic acid, fuming sulfuric acid and hydrazonium salt are used as raw materials to synthesize polyaryl oxadiazole, and the polyaryl oxadiazole can be prepared into fibers by a solution spinning method. The polyaryl oxadiazole fiber and the fabric prepared from the polyaryl oxadiazole fiber have high temperature resistance level and good chemical stability, and are widely applied as high-temperature resistant materials and insulating materials. In the process of synthesizing aromatic polyoxadiazole and preparing fibers, a large amount of aromatic polyoxadiazole-containing waste liquid is generated, the viscosity of the waste liquid is high, the acidity is strong, the waste liquid cannot be directly discharged, and the waste liquid is not received by waste liquid treatment manufacturers. At present, the multi-purpose collecting vessel of enterprise collects the waste liquid, and the waste liquid after the collection does not have relevant processing method, and the waste liquid also can not separate the recovery, can only deposit. In the past, waste liquid is accumulated continuously, and how to treat the waste liquid generated in the synthesis of the aromatic polyoxadiazole and the preparation process of the fiber becomes a problem which needs to be solved by enterprises urgently.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for treating waste liquid containing polyaryl oxadiazole.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a method for treating polyaryl oxadiazole-containing waste liquid, which comprises the steps of spreading the waste liquid, carrying out contact degradation with air, adding an alkali solution for reaction, and filtering.
In some embodiments of the present invention, the waste liquid is mainly concentrated sulfuric acid and polymers such as aromatic polyoxadiazole dissolved in the concentrated sulfuric acid, the waste liquid is spread in a container, the waste liquid contacts with water vapor in the air, the water vapor dilutes sulfuric acid in the stock solution, the polymers in the waste liquid are separated out as the concentration of the sulfuric acid is reduced, the polymers are corroded by the sulfuric acid with the reduced concentration, the polymers are degraded to form white paste, the white paste is transferred into an alkali solution to be stirred and reacted to obtain suspension, and the suspension can be discharged after being filtered. The waste liquid is not contacted with air and is directly added into the alkali solution for reaction, the stock solution and the alkali solution cannot be uniformly mixed due to high viscosity of the stock solution, and a polymer in the stock solution contacted with the alkali solution can be solidified and has certain strength, can wrap a part which is not contacted with the alkali solution and is in a sugar core shape, cannot effectively reach a neutralization state, and further cannot be decomposed into aromatic oxadiazole. If water is directly added into the waste liquid, the water can form a compact film on the surface of the stock solution, so that the residual water is prevented from entering the waste liquid and cannot play a role in degradation. The contact degradation of air and waste liquid does not increase the treatment cost of the waste liquid, and is beneficial to the decomposition of the polyaryl oxadiazole.
Preferably, the mass content of the polyaryl oxadiazole in the waste liquid is 5 to 20%, preferably 8 to 15%, and more preferably 10 to 12%.
In some specific and preferred embodiments of the invention, the thickness of the spread waste liquid is 10 to 50mm, preferably 10 to 40mm, more preferably 10 to 30mm, and even more preferably 15 to 25mm.
In some specific and preferred embodiments of the invention, the time for the waste liquid to degrade in contact with air is 24 to 120h, preferably 36 to 120h, more preferably 48 to 100h, and even more preferably 64 to 88h.
Preferably, the mass concentration of the alkali solution is 5 to 30%, preferably 10 to 25%, and more preferably 15 to 20%.
Further preferably, the feeding volume mol ratio of the waste liquid to the alkali is 1L:30 to 50mol, preferably 1L:35 to 45mol, more preferably 1L:40 to 45mol.
Preferably, after the waste liquid is degraded by contacting with air, the reaction time of the waste liquid and the alkaline solution is 0.5 to 5h, preferably 1 to 4h, more preferably 2 to 4h, and even more preferably 2.5 to 3.5h.
Preferably, the base is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate.
Further preferably, the base is sodium hydroxide.
In some specific and preferred embodiments of the present invention, the treatment method further comprises a step of treating the filtrate and the filter residue obtained after the filtration, wherein the filtrate comprises water, sulfate and unreacted alkali, the filtrate is sent to a sewage treatment facility to be treated and discharged after reaching standards, the filter residue comprises oxadiazole, and the filter residue is sent to a solid waste treatment plant to be treated. For example, the white paste is added into a sodium hydroxide solution, a suspension is obtained after stirring and reaction, then filtration is carried out, the main components of the filtrate are water, sodium sulfate and sodium hydroxide which is not completely reacted, the filtrate can be directly introduced into a sewage treatment tank to be treated and discharged after reaching the standard, the main component of the filter residue is an oxadiazole compound with low molecular weight, and for the treatment of oxadiazole, a corresponding treatment manufacturer is available on the market, and the oxadiazole compound is directly collected and sent to the corresponding treatment manufacturer.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the treatment method provided by the invention well solves the problem that the waste liquid containing the polyaryl oxadiazole cannot be treated, and is simple, low in treatment cost and strong in operability.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Unless otherwise specified, the polyaryl oxadiazole of the present invention comprises a repeating unit represented by the following formula (1) and/or formula (2):
（1）
，（2）/>
。
the ordinary temperature in the present invention means 20 to 30 ℃ unless otherwise specified.
Example 1
(1) Taking waste liquid generated in the preparation process of 1L of aromatic oxadiazole fiber, wherein the mass content of aromatic oxadiazole in the waste liquid is 10%, uniformly flattening the waste liquid into a container, the thickness of the flattened waste liquid is 30mm, standing, and contacting with air for 72h to obtain a white paste.
(2) The suspension is transferred into a sodium hydroxide solution with the mass concentration of 30%, the mass of the sodium hydroxide solution is 5.3kg, and the suspension is obtained by stirring and reacting for 3h at normal temperature.
(3) Filtering the suspension to obtain filtrate and filter residue, wherein the main components of the filtrate are water, sodium sulfate and unreacted sodium hydroxide, and the filtrate can be directly led to a sewage tank for treatment and then discharged after reaching the standard; the filter residue mainly contains low molecular weight oxadiazole which can be used as solid waste to be sent to a professional treatment plant for treatment.
Example 2
(1) Taking waste liquid generated in the preparation process of 1L of aromatic oxadiazole fiber, wherein the mass content of aromatic oxadiazole in the waste liquid is 10%, uniformly flattening the waste liquid into a container, the thickness of the flattened waste liquid is 50mm, standing, and contacting with air for 120h to obtain a white paste.
(2) The suspension is transferred into a sodium hydroxide solution with the mass concentration of 30%, the mass of the sodium hydroxide solution is 6.0kg, and the suspension is obtained by stirring and reacting for 5h at normal temperature.
(3) Filtering the suspension to obtain filtrate and filter residue, wherein the main components of the filtrate are water, sodium sulfate and unreacted sodium hydroxide, and the filtrate can be directly led to a sewage tank for treatment and then discharged after reaching the standard; the filter residue mainly contains low molecular weight oxadiazole which can be used as solid waste to be sent to a professional treatment plant for treatment.
Example 3
(1) Taking waste liquid generated in the preparation process of 1L of aromatic oxadiazole fiber, wherein the mass content of aromatic oxadiazole in the waste liquid is 10%, uniformly flattening the waste liquid into a container, the thickness of the flattened waste liquid is 30mm, standing, and contacting with air for 72h to obtain a white paste.
(2) The suspension is transferred into a sodium hydroxide solution with the mass concentration of 20%, the mass of the sodium hydroxide solution is 8kg, and the suspension is obtained after stirring reaction for 3h at normal temperature.
(3) Filtering the suspension to obtain filtrate and filter residue, wherein the main components of the filtrate are water, sodium sulfate and unreacted sodium hydroxide, and the filtrate can be directly led to a sewage tank for treatment and then discharged after reaching the standard; the filter residue mainly contains low molecular weight oxadiazole which can be used as solid waste to be sent to a professional treatment plant for treatment.
Comparative example 1
The difference from the example 1 is that the waste stock solution is not contacted with air, and is directly added into the sodium hydroxide solution to be stirred and reacted, and the waste solution cannot be degraded.
The stock solution and the alkali solution cannot be uniformly mixed due to high viscosity of the stock solution, and the polymer in the stock solution contacting the alkali solution can be solidified and has certain strength, can wrap the part which is not contacted with the alkali solution, is in a 'sugar core' shape, and cannot be degraded and neutralized.
Comparative example 2
The difference from example 1 is that the contact time with air in step (1) is 10 hours. After the reaction with the sodium hydroxide solution in the step (2), the solution contains a large amount of yellow adhesive substances (unreacted waste stock solution) in addition to filter residues.
The contact time of the waste liquid and air is too short, so that the stock solution is not completely degraded, and polymers with higher viscosity still remain, when the waste liquid and the air are mixed, the surface of the undegraded polymers is solidified under the action of alkali liquor, the undegraded polymers in the waste liquid are wrapped, and a 'sugar core' phenomenon is formed, so that the degradation and the neutralization cannot be obtained.
Comparative example 3
The difference from example 1 is that the sodium hydroxide solution in step (2) had a mass concentration of 4% and the sodium hydroxide solution had a mass of 40kg. The residue still contained an incompletely reacted white paste.
The concentration of the sodium hydroxide solution is too low, the reaction speed of the white paste and the sodium hydroxide solution is slow, and the white paste and the sodium hydroxide solution cannot completely react within corresponding time.
Comparative example 4
The difference from example 1 is that the sodium hydroxide solution in step (2) had a mass concentration of 15% and the sodium hydroxide solution had a mass of 8kg. The residue still contained an incompletely reacted white paste.
When the amount of sodium hydroxide is insufficient, the white paste cannot completely react with the sodium hydroxide.
Comparative example 5
The difference from example 1 is that, instead of the step (1), the waste liquid was reacted with 3kg of concentrated sulfuric acid having a mass fraction of 70% for 2 hours, and then the steps (2) and (3) were performed. The viscosity of the waste stock solution is lowered, the waste solution cannot be decomposed, and the solution contains a large amount of a low-viscosity binder.
Concentrated sulfuric acid can dissolve and dilute the waste liquid, but cannot react with the waste liquid.
The present invention has been described in detail in order to enable those skilled in the art to understand the invention and to practice it, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the present invention.
Claims (5)
1. A method for treating waste liquid containing polyaryl oxadiazole is characterized by comprising the following steps: the waste liquid is generated in the preparation process of the polyoxadiazole fibers, the waste liquid is concentrated sulfuric acid and a polyoxadiazole polymer dissolved in the concentrated sulfuric acid, the waste liquid is spread in a container, the waste liquid is in contact with water in the air, the sulfuric acid in the waste liquid is diluted by water vapor, the polymer in the waste liquid is precipitated along with the reduction of the concentration of the sulfuric acid, the polymer is corroded by the sulfuric acid with the reduced concentration, the polymer is degraded to form a white paste, the white paste is transferred into an alkaline solution to be stirred and reacted to obtain a suspension, the suspension is filtered and then discharged respectively, the mass content of the polyoxadiazole in the waste liquid is 5-20%, the spreading thickness of the waste liquid is 10-50mm, the degradation time of the waste liquid in contact with the air is 24-120h, the mass concentration of the alkaline solution is 5-30%, and the feeding volume molar ratio of the waste liquid to the alkaline is 1L:30 to 50mol.
2. The method for treating polyaryl oxadiazole-containing waste liquid according to claim 1, wherein the method comprises the following steps: after the waste liquid is degraded by contacting with air, the reaction time of the waste liquid and the alkaline solution is 0.5 to 5h.
3. The method for treating waste liquid containing polyaryl oxadiazole according to claim 1, wherein the method comprises the following steps: the alkali is one or more of sodium hydroxide, sodium bicarbonate and sodium carbonate.
4. The method for treating a polyaryl oxadiazole-containing waste liquid according to claim 3, comprising the steps of: the alkali is sodium hydroxide.
5. The method for treating waste liquid containing polyaryl oxadiazole according to claim 1, wherein the method comprises the following steps: the treatment method further comprises the step of treating the filtrate and the filter residue obtained after filtration, wherein the filtrate comprises water, sulfate and unreacted alkali, the filtrate is sent to a sewage treatment facility to be treated and discharged after reaching the standard, the filter residue comprises oxadiazole, and the filter residue is sent to a solid waste treatment plant to be treated.
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| CN112960753B true CN112960753B (en) | 2023-03-28 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3655684A (en) * | 1968-09-19 | 1972-04-11 | Hoffmann La Roche | Novel substituted-oxadiazoles and a process for the manufacture thereof |
| EP0041134A2 (en) * | 1980-05-30 | 1981-12-09 | BASF Aktiengesellschaft | Process for the separation of water-soluble salts of aromatic sulphonic acids from sulphonated mixtures |
| JPH11322343A (en) * | 1998-05-21 | 1999-11-24 | Toshin Kagaku Kogyo Kk | Conversion of iron chloride into iron sulfate salt and production of basic ferric sulfate |
| CA2654118A1 (en) * | 2008-02-13 | 2009-08-13 | Gkss-Forschungszentrum Geesthacht Gmbh | Method for the synthesis of a polyoxadiazole polymer |
| CN106045988A (en) * | 2016-08-13 | 2016-10-26 | 广州白云山汉方现代药业有限公司 | Preparation method for atropine sulfate |
| CN106674147A (en) * | 2016-12-28 | 2017-05-17 | 贵州大学 | Styryl-containing 1,3,4-oxadiazole thioether compound, as well as preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB189704048A (en) * | 1897-02-15 | 1897-03-27 | Winfield Scott Robinson | Improvements in Cement and Concrete. |
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2021
- 2021-02-02 CN CN202110140150.2A patent/CN112960753B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3655684A (en) * | 1968-09-19 | 1972-04-11 | Hoffmann La Roche | Novel substituted-oxadiazoles and a process for the manufacture thereof |
| EP0041134A2 (en) * | 1980-05-30 | 1981-12-09 | BASF Aktiengesellschaft | Process for the separation of water-soluble salts of aromatic sulphonic acids from sulphonated mixtures |
| JPH11322343A (en) * | 1998-05-21 | 1999-11-24 | Toshin Kagaku Kogyo Kk | Conversion of iron chloride into iron sulfate salt and production of basic ferric sulfate |
| CA2654118A1 (en) * | 2008-02-13 | 2009-08-13 | Gkss-Forschungszentrum Geesthacht Gmbh | Method for the synthesis of a polyoxadiazole polymer |
| CN106045988A (en) * | 2016-08-13 | 2016-10-26 | 广州白云山汉方现代药业有限公司 | Preparation method for atropine sulfate |
| CN106674147A (en) * | 2016-12-28 | 2017-05-17 | 贵州大学 | Styryl-containing 1,3,4-oxadiazole thioether compound, as well as preparation method and application thereof |
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