CN108328847B - Comprehensive treatment method of functional resin sewage for tires - Google Patents
Comprehensive treatment method of functional resin sewage for tires Download PDFInfo
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- CN108328847B CN108328847B CN201710042064.1A CN201710042064A CN108328847B CN 108328847 B CN108328847 B CN 108328847B CN 201710042064 A CN201710042064 A CN 201710042064A CN 108328847 B CN108328847 B CN 108328847B
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
Abstract
The invention discloses a comprehensive treatment method of functional resin production sewage for tires, which comprises the following steps: adding phenol into the sewage according to the proportion, adjusting the pH, heating and refluxing, and discharging the resin at the lower layer after polycondensation to obtain a water solution; adding alkali into the aqueous solution, heating for disproportionation reaction, rectifying the reaction solution by a rectifying tower, collecting the methanol from the tower top, feeding the solid-containing liquid at the tower bottom into a distillation kettle, distilling to obtain a water phase, drying and incinerating the solid residual phase, cooling the distilled water phase, adsorbing by macroporous adsorption resin, and finally performing aerobic biochemical treatment on the distilled water phase. The method of the invention has the advantages that the removal rate of formaldehyde and free phenol can reach 100 percent, and the removal rate of COD can reach more than 99.5 percent. The method has the advantages of simple equipment, less investment, good treatment effect, capability of further utilizing reaction products and good economic benefit.
Description
Technical Field
The invention relates to a comprehensive treatment method of high-aldehyde low-phenol sewage generated in the production process of functional resin for tires, in particular to a method for carrying out advanced treatment on the sewage and utilizing products in the treatment process.
Background
Phenol and formaldehyde belong to substances which are extremely harmful and difficult to treat, have high biological toxicity, seriously inhibit the growth of microorganisms and are difficult to directly carry out biochemical treatment.
The content of formaldehyde and phenol in the sewage generated by the functional resin for the tire is high, and the treatment difficulty is very high. At present, domestic treatment methods for the sewage comprise the following steps: the method comprises the following steps of extraction, rectification, polycondensation, chemical oxidation, photocatalytic oxidation, wet oxidation and the like, wherein the most used method is a polycondensation method, namely, under an acidic condition, a proper amount of formaldehyde or phenol is added to perform polycondensation with phenol or formaldehyde in sewage to generate liquid resin for removal, but the phenol and formaldehyde in the sewage after treatment are still high, biochemical treatment cannot be performed, and the sewage needs to be further treated by combining other methods.
Disclosure of Invention
The invention overcomes the problems in the prior art, and provides a method for deeply treating high-formaldehyde low-phenol sewage of functional resin for tires by combining a series of methods such as disproportionation, rectification, distillation, adsorption, biochemistry and the like on the basis of polycondensation, wherein the removal rate of formaldehyde and free phenol reaches 100 percent; the removal rate of COD is more than 99.5 percent, and simultaneously, the reaction product can be utilized, thereby having good economic benefit.
The invention provides a method for treating functional resin phenolic aldehyde sewage for tires, which comprises the steps of adding phenol into the sewage according to a ratio, adding an acidic catalyst to adjust the pH value, heating to perform polycondensation reaction, then periodically discharging resin at the lower layer, obtaining a water solution after the reaction is finished, then adding alkali, heating to perform disproportionation reaction, rectifying a reaction liquid by a rectifying tower, collecting methanol at the tower top, feeding a solid-containing liquid at the tower bottom into a distillation kettle, distilling a water phase, performing drying incineration treatment on the solid residual phase, cooling the distilled water phase, adsorbing by an adsorption resin, and further performing aerobic biochemical treatment.
Specifically, the method comprises the following steps:
(1) adding phenol into the sewage containing the phenol aldehyde, adding an acidic catalyst to adjust the pH value, heating to perform polycondensation reaction, discharging resin at the lower layer, and obtaining an aqueous solution after the reaction is finished;
(2) adding alkali into the aqueous solution obtained in the step (1), and heating for carrying out disproportionation reaction;
(3) introducing the reaction liquid obtained after the disproportionation reaction in the step (2) into a rectifying tower, and respectively collecting methanol and solid-containing liquid;
(4) the solid-containing liquid collected by the rectifying tower in the step (3) is distilled out of a water phase in a distillation kettle, and the residual solid phase is dried and incinerated;
(5) cooling the water phase distilled in the step (4) and adsorbing the water phase by using adsorption resin;
(6) and (5) carrying out aerobic biochemical treatment on the sewage adsorbed in the step (5).
In the step (1), the functional resin phenolic aldehyde sewage for the tire is phenol-aldehyde-containing sewage generated in the production process of phenolic resin for the tire, wherein the aldehyde content is 1000-80000 mg/L, the phenol content is 150-7000 mg/L, and the COD is 1500-120000 mg/L.
In the step (1), the mole ratio of formaldehyde to added phenol in the functional resin phenolic sewage for the tire is 5: 1-15: 1; preferably, it is 5: 1-10: 1.
in step (1), the acidic catalyst is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, hypochlorous acid, p-toluenesulfonic acid and oxalic acid; preferably, hydrochloric acid, p-toluenesulfonic acid, hypochlorous acid, or a mixed acid of oxalic acid and sulfuric acid.
In step (1) of the present invention, the acidic catalyst is adjusted to a pH of 1 to 2.
In the step (1), the temperature of the polycondensation reaction is 80-100 ℃; preferably, the temperature is 90-100 ℃; more preferably, the temperature is 80 ℃, 85 ℃, 90 ℃, 100 ℃.
In the step (1), the polycondensation reaction is carried out for 6-10 hours; preferably 6 hours, 7 hours, 8 hours, 9 hours.
In the step (1), a mode of periodically discharging the resin at the lower layer is required, the periodic time for discharging the resin at the lower layer is 1-2 hours, and the specific method is that a kettle bottom valve is opened every 1-2 hours, and the valve is closed after the white oily resin is completely discharged.
In step (2) of the present invention, the alkali is selected from one or more of solid sodium hydroxide, sodium hydroxide solution, solid potassium hydroxide and potassium hydroxide solution; preferably, the concentration is 30-50% (weight percentage) of sodium hydroxide solution; further preferably, it is a sodium hydroxide solution having a concentration of 30% (by weight), a sodium hydroxide solution having a concentration of 40% (by weight), or a sodium hydroxide solution having a concentration of 50% (by weight).
In the step (2) of the invention, the molar ratio of the alkali to formaldehyde in the functional resin phenolic wastewater for the tire is 1: 2.
in the step (2), the temperature of the disproportionation reaction is 60-100 ℃; preferably, the temperature is 60-65 ℃, 65-85 ℃, 80-100 ℃ and 85-100 ℃; more preferably, the temperature is 60 ℃, 65 ℃, 80 ℃, 85 ℃, 100 ℃.
In the step (2), the disproportionation reaction is carried out for 1-2 hours; preferably 1 hour, 1.5 hours, 2 hours.
In the step (3), the temperature range of methanol collected in the rectifying tower is 64-65 ℃.
In the step (4), the temperature of the water phase collected in the distillation kettle is 100 ℃; the BOD/COD of the aqueous phase obtained by distillation was 0.4.
In the step (5), the adsorption resin is preferably macroporous adsorption resin, and the aperture is 0.3-1.2 mm; the model can be one or more of D113, D201, D101, D900, H103, HPD100 and HPD 400.
In the step (6), aerobic biochemical treatment is carried out by adopting a traditional method.
The invention relates to a method for treating functional resin phenolic aldehyde sewage for tires, which comprises the following steps:
(1) the method comprises the steps of proportioning the sewage and phenol generated in the production process of functional resin for the tire according to the weight ratio of phenolic aldehyde, placing the mixture into a polycondensation reaction kettle, uniformly mixing the mixture by a stirring device in the polycondensation kettle, adding an acid catalyst to adjust the pH value to 1-2, heating to a reflux state, carrying out polycondensation reaction, periodically discharging the resin at the lower layer, and obtaining an aqueous solution after the reaction is finished.
(2) And (2) introducing the aqueous solution obtained in the step (1) into a disproportionation reaction kettle, adding alkali, uniformly mixing by using a stirring device in the kettle, and heating and refluxing.
(3) Introducing the reaction liquid obtained in the step (2) into a rectifying tower, and respectively collecting methanol and solid-containing liquid;
(4) the solid-containing liquid collected by rectification in the step (3) is passed through a distillation still, a water phase is distilled out, and the solid residual phase is dried and incinerated;
(5) cooling the water phase distilled in the step (4), and adsorbing by macroporous adsorption resin;
(6) and (4) carrying out aerobic biochemical treatment on the sewage adsorbed in the step (5) to meet the discharge requirement.
The invention discloses a comprehensive treatment method of functional resin sewage for tires, which has the following principle: performing polycondensation reaction on phenol and formaldehyde in functional resin sewage for tires under an acidic condition to generate liquid resin, separating the liquid resin, and removing most of the formaldehyde; the remaining aqueous solution contains formaldehyde and alkali which undergo a disproportionation reaction to generate methanol, and further remove the formaldehyde; the reaction liquid enters a rectifying tower and methanol is collected; solid-containing liquid enters a distillation kettle, and after distillation, a water phase (sewage) is cooled and then is absorbed by macroporous resin to remove most phenol; and finally, further degrading COD through an aerobic biochemical tank to meet the discharge requirement.
The treatment method of the invention not only removes high-concentration formaldehyde and phenol, but also improves BOD/COD of the sewage, can conveniently carry out biochemical treatment on the sewage further, realizes standard discharge, and simultaneously, in the process of treating the high-concentration sewage into low-concentration sewage, the obtained reaction product can be further utilized, thereby having good economic benefit.
The method has the beneficial effect that the method can bear the functional resin sewage for the tire with COD of 1500-120000 mg/L, aldehyde (mainly formaldehyde) content of 1000-80000 mg/L and phenol content of 150-7000 mg/L. After formaldehyde and phenol in the sewage are fully treated, BOD/COD of the rectified water is 0.4, and the biodegradability of the sewage is greatly improved. The liquid resin and methanol produced in the treatment process can be recycled. By using the treatment method, the concentration of formaldehyde and free phenol can be reduced to 0mg/L, and the removal rate reaches 100 percent; the removal rate of COD is more than 99.5 percent. The equipment required by the invention is a reaction kettle, a rectifying tower, a distillation kettle, an adsorption column and a biochemical pool, and the equipment is simple, the cost is low and the economic benefit is high.
Drawings
FIG. 1 is a schematic view of the method for treating a phenol-aldehyde-containing wastewater of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Examples 1 to 4
Putting the sewage generated in the production process of the functional resin for the 7t tire into a polycondensation reaction kettle, adding phenol according to the phenolic aldehyde molar ratio for proportioning, uniformly mixing the mixture by a stirring device in the kettle, then adding an acid catalyst to adjust the pH value to 1-2, heating the mixture to a reflux state, periodically discharging resin on the lower layer, reacting for 6-10 hours, obtaining an aqueous solution after the reaction is finished, introducing the aqueous solution into a disproportionation reaction kettle, adding alkali, stirring and mixing uniformly, heating and refluxing for 1-2 hours, introducing the reaction liquid into a rectifying tower, controlling the temperature to rise, collecting methanol at the tower top at 64-65 ℃, introducing solid-containing liquid at the tower bottom into a distillation kettle, distilling out a water phase at 100 ℃, carrying out drying incineration treatment on the solid residual phase, cooling the distilled sewage to room temperature, introducing the sewage into an adsorption column filled with macroporous adsorption resin (the aperture is between 0.3 and 1.2 mm) through a lift pump for adsorption, and directly introducing the adsorbed sewage into aerobic biochemical treatment.
TABLE 1
After the sewage is subjected to polycondensation, disproportionation, rectification, distillation and adsorption treatment, the concentration of formaldehyde and free phenol can be reduced to below 5mg/L, and the BOD/COD of the effluent of the rectification tower is 0.4, so that the method is very favorable for subsequent biochemical treatment, and after comprehensive treatment, the removal rate of formaldehyde and free phenol is up to 100%, and the removal rate of COD is up to more than 99.5%. The total income of liquid resin and methanol generated in the treatment process is 11.66-560 yuan (treating 7t of sewage).
In the present invention, the same technical effects as described above can be achieved by using other acidic catalysts, such as one or more of hydrochloric acid, sulfuric acid, phosphoric acid, hypochlorous acid, p-toluenesulfonic acid, and oxalic acid.
In the present invention, the same technical effects as described above can be achieved by using other alkali, such as one or more of solid sodium hydroxide, solid potassium hydroxide and potassium hydroxide solution.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
Claims (10)
1. The method for treating the sewage containing the phenolic aldehyde is characterized by comprising the following steps of:
(1) adding phenol into the sewage containing the phenol aldehyde, adding an acidic catalyst to adjust the pH value, heating to perform polycondensation reaction, discharging resin at the lower layer, and obtaining an aqueous solution after the reaction is finished;
(2) adding alkali into the aqueous solution obtained in the step (1), and heating for carrying out disproportionation reaction;
(3) introducing the reaction liquid obtained after the disproportionation reaction in the step (2) into a rectifying tower, and respectively collecting methanol and solid-containing liquid;
(4) the solid-containing liquid collected by the rectifying tower in the step (3) is distilled out of a water phase in a distillation kettle, and the residual solid phase is dried and incinerated;
(5) cooling the water phase distilled in the step (4) and adsorbing the water phase by using adsorption resin;
(6) and (5) carrying out aerobic biochemical treatment on the sewage adsorbed in the step (5) to obtain the sewage meeting the discharge requirement.
2. The method according to claim 1, wherein the phenolic aldehyde-containing wastewater has an aldehyde content of 1000 to 80000mg/L, a phenol content of 150 to 7000mg/L, and a COD of 1500 to 120000 mg/L.
3. The method according to claim 1, wherein in the step (1), the molar ratio of the formaldehyde to the added phenol in the phenolic aldehyde-containing wastewater is 5: 1-15: 1.
4. the method according to claim 1, wherein in step (1), the acidic catalyst is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, hypochlorous acid, p-toluenesulfonic acid, and oxalic acid.
5. The method according to claim 1, wherein in step (1), the acidic catalyst is adjusted to a pH of 1 to 2.
6. The method according to claim 1, wherein the temperature of the polycondensation reaction in the step (1) is 80 to 100 ℃.
7. The method according to claim 1, wherein in the step (2), the alkali is selected from one or more of solid sodium hydroxide, sodium hydroxide solution, solid potassium hydroxide and potassium hydroxide solution.
8. The method according to claim 1, wherein in the step (2), the molar ratio of the alkali to the formaldehyde in the phenolic aldehyde-containing sewage is 1: 2.
9. the method according to claim 1, wherein in the step (2), the temperature of the disproportionation reaction is 60-100 ℃.
10. The method according to claim 1, wherein in the step (5), the adsorbent resin is a macroporous adsorbent resin, and the pore diameter is 0.3-1.2 mm.
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| CN201710042064.1A CN108328847B (en) | 2017-01-20 | 2017-01-20 | Comprehensive treatment method of functional resin sewage for tires |
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| IT951611B (en) * | 1971-12-27 | 1973-07-10 | Sir Soc Italiana Resine Spa | PROCEDURE FOR THE RECOVERY OF FORMALDEHYDE AND PHENOL |
| CN100347105C (en) * | 2005-12-05 | 2007-11-07 | 江苏三木集团有限公司 | Process for removing formol and recovering methyl alcohol and butyl alcohol in amino resin waste water |
| CN101037283B (en) * | 2007-02-27 | 2010-12-01 | 海盐华强树脂有限公司 | Treatment method of hydroxybenzene-containing wastewater |
| CN101597117B (en) * | 2009-06-23 | 2011-08-03 | 南京大学 | Industry formaldehyde waste water treatment and recycling recovery process thereof |
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