CN109679040B - Method for preparing phenolic resin by using wastewater generated in production of polyester polyol - Google Patents
Method for preparing phenolic resin by using wastewater generated in production of polyester polyol Download PDFInfo
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- CN109679040B CN109679040B CN201811456768.4A CN201811456768A CN109679040B CN 109679040 B CN109679040 B CN 109679040B CN 201811456768 A CN201811456768 A CN 201811456768A CN 109679040 B CN109679040 B CN 109679040B
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Water Treatments (AREA)
- Degasification And Air Bubble Elimination (AREA)
Abstract
The invention belongs to the field of industrial wastewater treatment, and particularly relates to a method for preparing phenolic resin by using wastewater generated in polyester polyol production, which comprises the following steps: (1) wastewater treatment: the method comprises the following steps of (1) enabling waste water for producing polyester polyol to pass through a stripping tower, and carrying out stripping action to obtain a steam-water mixture and treated waste water, wherein the total content of harmful substances in the treated waste water is lower than 50 mg/L; (2) preparation of phenolic resin: and (2) mixing the wastewater treated in the step (1) with solid formaldehyde and phenol according to a preset ratio to prepare the phenolic resin. The implementation of the invention can effectively reduce the investment of polyester wastewater treatment equipment, has short treatment flow, low operating cost and no wastewater discharge, is beneficial to environmental protection, and can utilize the polyhydric alcohol and the oligomer thereof in the wastewater in the production process of the polyester polyol, thereby improving the economic benefit.
Description
Technical Field
The invention belongs to the field of industrial wastewater treatment, and particularly relates to a method for preparing phenolic resin by using wastewater generated in polyester polyol production.
Background
The polyurethane elastomer is a variety of polyurethane synthetic materials, can be molecularly designed due to the structure of the polyurethane elastomer with two soft and hard chain segments to endow the materials with high strength, good toughness, wear resistance, oil resistance and other superior performances, has the high elasticity of rubber and the rigidity of plastics, is called as wear-resistant rubber, has good physical and mechanical properties, and is widely applied to the fields of manufacturing industry, petroleum industry, mining industry, electrical appliance and instrument industry, leather and shoe industry, building industry, medical sanitation, sports article manufacturing and the like.
The polyester polyol is produced by esterification polycondensation of dihydric alcohol and dibasic acid to produce polyester, and water is produced in the esterification reaction, so that a large amount of small molecular organic matters such as ethylene glycol, propylene glycol, butanediol, acetaldehyde, tetrahydrofuran, a small amount of oligomers and the like are carried in the process of removing the water produced in the reaction from a reaction kettle, the chemical oxygen demand can reach 10-20 ten thousand, and the acetaldehyde, the tetrahydrofuran and the like have pungent smells and are easy to volatilize. At present, the traditional treatment technology at home and abroad adopts biochemical treatment methods such as anaerobic treatment, aerobic treatment and the like, but acetaldehyde, tetrahydrofuran and other organic matters have high toxicity and are not beneficial to bacterial growth, so that the efficiency of treating wastewater in a biochemical mode is low, the investment cost for treating high-concentration organic wastewater in the biochemical treatment mode is higher, the structure of treatment equipment is more and more complex, and the treatment and maintenance cost is higher.
In conclusion, there is a need to develop a method for preparing phenolic resin by using wastewater from polyester polyol production, which can effectively reduce the investment of polyester wastewater treatment equipment, has short treatment process, low operation cost, no wastewater discharge, is beneficial to environmental protection, and can utilize the polyol and oligomers thereof in the wastewater from polyester polyol production and improve economic benefits.
Disclosure of Invention
The invention aims to provide a method for preparing phenolic resin by using the wastewater from polyester polyol production, which can effectively reduce the investment of polyester wastewater treatment equipment, has short treatment flow, low operating cost and no wastewater discharge, is beneficial to environmental protection, and can utilize the polyol and the oligomer thereof in the wastewater from polyester polyol production and improve the economic benefit.
The above purpose is realized by the following technical scheme: a method for preparing phenolic resin by using wastewater generated in the production of polyester polyol comprises the following steps:
(1) wastewater treatment: the method comprises the following steps of (1) enabling waste water for producing polyester polyol to pass through a stripping tower, and carrying out gas stripping to obtain a steam-water mixture and treated waste water, wherein the total content of tetrahydrofuran, butyraldehyde and acetaldehyde in the treated waste water is lower than 50 mg/L;
(2) preparation of phenolic resin: and (2) mixing the wastewater treated in the step (1) with solid formaldehyde and phenol according to a preset ratio to prepare the phenolic resin.
The method comprises the steps of carrying out stripping separation tower treatment on the wastewater generated by a polyester Polyol (PBA) reaction kettle, enabling volatile harmful substances such as tetrahydrofuran, butyraldehyde and acetaldehyde in the wastewater to escape from water under the action of stripping, greatly reducing the content of pungent substances such as tetrahydrofuran, butyraldehyde and acetaldehyde in the stripped wastewater, and enabling the content of the pungent substances to be lower than 50mg/L through detection, wherein the wastewater subjected to stripping treatment is used for preparing a solvent of phenolic resin by taking solid formaldehyde as a raw material, and in the process of the phenolic resin, polyhydric alcohols and oligomers contained in the wastewater can be used as chain extenders in the preparation process of the phenolic resin. The implementation of the invention can effectively reduce the investment of polyester wastewater treatment equipment, has short treatment flow, low operating cost and no wastewater discharge, is beneficial to environmental protection, and can utilize the polyhydric alcohol and the oligomer thereof in the wastewater in the production process of the polyester polyol, thereby improving the economic benefit.
The further technical scheme is that solid formaldehyde and phenol are added into a reaction kettle in proportion in the step (2), and then a predetermined amount of treated wastewater and distilled water are added as solvents for reaction. When the concentration of the treated wastewater is higher, proper distilled water can be added to dissolve the solid formaldehyde.
The further technical scheme is that the mass ratio of the sum of the solid formaldehyde and the phenol to the treated wastewater and the distilled water is 10:1: 0.2.
The further technical scheme is that the stripping tower is a bubbling stripping tower.
The further technical scheme is that the wastewater in the step (1) is heated to 40-50 ℃, and nitrogen and/or air is blown into the tower, wherein the apparent bubbling air speed is 0.06-0.09 m/s, and the bubbling time is 120-180 minutes. Experiments prove that under the process conditions, the wastewater treatment effect is good, the treated wastewater has no pungent smell, and the contents of tetrahydrofuran, butyraldehyde and acetaldehyde are lower than 35mg/L through liquid chromatography analysis.
The further technical proposal is that the wastewater is heated to 45 ℃ in the step (1), the bubbling apparent gas velocity is 0.08m/s, and the bubbling time is 150 minutes.
The further technical scheme is that the steam-water mixture in the step (1) is subjected to gas-liquid separation through a gas-liquid separator, the separated water and the waste water subjected to steam stripping enter a waste water storage tank together for later use, and the waste water participating in the phenolic resin in the step (2) is the waste water in the waste water storage tank. The steam-water mixture containing tetrahydrofuran, butyraldehyde and other substances generated from the bubbling stripping tower passes through a gas-liquid separator to remove most of water carried in the steam-water mixture, the gas-liquid separator is a common gas-liquid separator, and the separated water and the waste water from the stripping tower are mixed together and enter a storage tank to be used for preparing the phenolic resin without waste water discharge.
The further technical proposal is that the space velocity of the gas separated by the gas-liquid separator through the bed layer is 30000h-1Directly discharging after the adsorption device, wherein the adsorbent is molecular sieve or active carbon. The gas with most of water separated by the steam-water separator enters a tail gas absorption device provided with an adsorbent to remove harmful components, the adsorbent is a molecular sieve and activated carbon, and the content of organic matters (non-methane total hydrocarbon concentration) in the adsorbed gas is lower than 100mg/m3Even lower than 75mg/m3And the product reaches the national emission standard and can be directly emitted.
Compared with the prior art, the method has the advantages of reducing the investment of polyester wastewater treatment equipment, having short treatment flow, low operation cost and no wastewater discharge, and simultaneously can utilize the polyhydric alcohol and the oligomer thereof in the wastewater, thereby having better environmental protection benefit and economic benefit.
The specific implementation mode is as follows:
the following are provided as preferred embodiments of the present invention to aid in further understanding of the present invention, but the scope of the present invention is not limited to these examples.
Production examples of polyester polyols
In this example, the polyester polyol was prepared by a melt method, and the production process thereof was as follows: proportionally adding dihydric alcohol (commonly used alcohol is butanediol) and dibasic acid (commonly used acid is adipic acid) into a reaction kettle, wherein the molar ratio of the alcohol to the acid is n + 1: and n, filling nitrogen into the reaction kettle after the materials are added, heating to raise the temperature, when the temperature in the reaction kettle is raised to 130 ℃, completely melting the materials in the reaction kettle, carrying out an esterification reaction to generate water, condensing the generated water, then feeding the condensed water into a waste liquid tank, slowly raising the temperature to 210-230 ℃, adding a catalyst when no water is present in the condenser, vacuumizing, removing water generated in the esterification reaction, excessive alcohol and an esterification oligomer until the acid value of a product is lower than 1mg KOH/g of the materials, and stopping vacuumizing.
Example 1:
transferring the wastewater of the polyester polyol reaction kettle into a reactor with the volume of 1m3A bubbling stripping tower is heated to 45 ℃, nitrogen is bubbled into the tower, the bubbling apparent gas velocity is 0.08m/s, the bubbling time is 150 minutes, and no pungent smell exists in the wastewater; through liquid chromatography analysis, the contents of tetrahydrofuran, butyraldehyde and acetaldehyde are 35mg/L, and the wastewater enters a storage tank. And the steam-water mixture obtained by steam stripping enters a gas-liquid separator to separate entrained water, and the separated water enters a waste water storage tank. The space velocity of the gas passing through the gas-liquid separator entering the bed layer is 30000h-1The adsorbent of the adsorption device is active carbon, and the content of organic matters (non-methane total hydrocarbon concentration) in the adsorbed gas is 75mg/m3And directly discharging. At 1m3Adding solid formaldehyde, phenol and a catalyst into a reaction kettle in proportion, wherein the total mass is 800 kg, adding 80 kg of treated polyester wastewater and 16 kg of distilled water, and reacting, wherein the reaction process is the same as that of the whole reaction process with the addition of the distilled water.
Example 2:
transferring the wastewater of the polyester polyol reaction kettle into a reactor with the volume of 1m3A bubbling stripping tower is heated to 40 ℃, nitrogen is bubbled into the tower, the bubbling apparent gas velocity is 0.06m/s, the bubbling time is 180 minutes, and no pungent smell exists in the wastewater; through liquid chromatography analysis, the contents of tetrahydrofuran, butyraldehyde and acetaldehyde are 31mg/L, and the wastewater enters a storage tank. And the steam-water mixture obtained by steam stripping enters a gas-liquid separator to separate entrained water, and the separated water enters a waste water storage tank. The space velocity of the gas passing through the gas-liquid separator entering the bed layer is 30000h-1The adsorbent of the adsorption device is active carbon, and the content of organic matters (non-methane total hydrocarbon concentration) in the gas after adsorption is 78mg/m3And directly discharging. At 1m3Solid formaldehyde, phenol and a catalyst are added into a reaction kettle in proportion, the total mass is 800 kg,80 kg of the treated polyester wastewater and 16 kg of distilled water are added for reaction, and the reaction process is the same as that of the whole reaction process with the distilled water.
Example 3:
transferring the wastewater of the polyester polyol reaction kettle into a reactor with the volume of 1m3A bubbling stripping tower is heated to 50 ℃, nitrogen is bubbled into the tower, the bubbling apparent gas velocity is 0.09m/s, the bubbling time is 120 minutes, and no pungent smell exists in the wastewater; through liquid chromatography analysis, the contents of tetrahydrofuran, butyraldehyde and acetaldehyde are 33mg/L, and the wastewater enters a storage tank. And the steam-water mixture obtained by steam stripping enters a gas-liquid separator to separate entrained water, and the separated water enters a waste water storage tank. The space velocity of the gas passing through the gas-liquid separator entering the bed layer is 30000h-1The adsorbent of the adsorption device is active carbon, and the content of organic matters (non-methane total hydrocarbon concentration) in the adsorbed gas is 77mg/m3And directly discharging. At 1m3Adding solid formaldehyde and phenol into a reaction kettle in proportion, wherein the total mass is 800 kg, adding 80 kg of treated polyester wastewater and 16 kg of distilled water, and reacting in the same reaction process as that of adding all distilled water.
The phenol formaldehyde resin prepared in the embodiments is subjected to relevant tests, and compared with a phenol formaldehyde resin product prepared by a conventional method, the quality of the phenol formaldehyde resin prepared by the embodiments is not obviously changed, and the obtained phenol formaldehyde resin has good foaming performance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A method for preparing phenolic resin by using wastewater generated in polyester polyol production is characterized by comprising the following steps:
(1) wastewater treatment: the method comprises the following steps of (1) enabling waste water for producing polyester polyol to pass through a stripping tower, heating the waste water to 40-50 ℃, blowing nitrogen and/or air into the tower, wherein the apparent bubbling air speed is 0.06-0.09 m/s, the bubbling time is 120-180 minutes, and carrying out stripping action to obtain a steam-water mixture and the treated waste water, wherein the total content of tetrahydrofuran, butyraldehyde and acetaldehyde in the treated waste water is lower than 50 mg/L;
(2) preparation of phenolic resin: and (2) mixing the wastewater treated in the step (1) with solid formaldehyde and phenol according to a preset ratio to prepare the phenolic resin.
2. The method for preparing phenolic resin using waste water from the production of polyester polyol as claimed in claim 1, wherein in the step (2), solid formaldehyde and phenol are added in proportion to the reaction kettle, and then a predetermined amount of treated waste water and distilled water are added as solvent, and then the reaction is carried out.
3. The method for preparing phenolic resin by using wastewater from the production of polyester polyol as claimed in claim 2, wherein the mass ratio of the sum of solid formaldehyde and phenol to the treated wastewater and distilled water is 10:1: 0.2.
4. The method for preparing phenolic resin by using wastewater from the production of polyester polyol according to claim 3, wherein the stripping tower is a bubble stripping tower.
5. The method for preparing phenolic resin by using wastewater from the production of polyester polyol as claimed in claim 4, wherein the wastewater in the step (1) is heated to 45 ℃, the bubbling apparent gas velocity is 0.08m/s, and the bubbling time is 150 minutes.
6. The method for preparing the phenolic resin by using the wastewater for producing the polyester polyol according to any one of claims 1 to 5, wherein the steam-water mixture in the step (1) is subjected to gas-liquid separation by a gas-liquid separator, the separated water and the wastewater subjected to the stripping action enter a wastewater storage tank for later use, and the wastewater participating in the phenolic resin in the step (2) is the wastewater in the wastewater storage tank.
7. The method for preparing phenolic resin by using wastewater from the production of polyester polyol as claimed in claim 6, wherein the space velocity of the gas separated by the gas-liquid separator through the bed layer is 30000h-1Directly discharging the adsorbent, wherein the adsorbent is activated carbon.
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| CN201811456768.4A CN109679040B (en) | 2018-11-30 | 2018-11-30 | Method for preparing phenolic resin by using wastewater generated in production of polyester polyol |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030429A (en) * | 1988-07-21 | 1989-01-18 | 丹棱县管道工艺材料研究所 | Modified phenolic resins and production method thereof |
| KR19990021572A (en) * | 1997-08-30 | 1999-03-25 | 성재갑 | Method and apparatus for purifying ultra high purity formaldehyde |
| CN101913671A (en) * | 2010-07-12 | 2010-12-15 | 江阴市飞鸿机械有限公司 | Process for decreasing COD (Chemical Oxygen Demand) value in polyester waste water of stripping tower |
| CN107445802A (en) * | 2017-08-21 | 2017-12-08 | 上海聚友化工有限公司 | A kind of method that ethylene glycol and acetaldehyde are reclaimed in polyester waste water |
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2018
- 2018-11-30 CN CN201811456768.4A patent/CN109679040B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030429A (en) * | 1988-07-21 | 1989-01-18 | 丹棱县管道工艺材料研究所 | Modified phenolic resins and production method thereof |
| KR19990021572A (en) * | 1997-08-30 | 1999-03-25 | 성재갑 | Method and apparatus for purifying ultra high purity formaldehyde |
| CN101913671A (en) * | 2010-07-12 | 2010-12-15 | 江阴市飞鸿机械有限公司 | Process for decreasing COD (Chemical Oxygen Demand) value in polyester waste water of stripping tower |
| CN107445802A (en) * | 2017-08-21 | 2017-12-08 | 上海聚友化工有限公司 | A kind of method that ethylene glycol and acetaldehyde are reclaimed in polyester waste water |
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| CN109679040A (en) | 2019-04-26 |
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