CN111453908A - Treatment method of phenol-containing wastewater - Google Patents
Treatment method of phenol-containing wastewater Download PDFInfo
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- CN111453908A CN111453908A CN202010292753.XA CN202010292753A CN111453908A CN 111453908 A CN111453908 A CN 111453908A CN 202010292753 A CN202010292753 A CN 202010292753A CN 111453908 A CN111453908 A CN 111453908A
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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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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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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Abstract
The invention discloses a method for treating phenolic wastewater, and belongs to the technical field of wastewater treatment. The invention utilizes the principle that the distribution coefficient of organic phenolic substances in saline water is small, phenolic wastewater is prepared into 10-30% saline water, then the phenolic substances are removed or recovered by extraction, the extraction solvent is recovered by distillation or alkali washing, and the recovered solvent can be used in the extraction process again; and distilling and concentrating the extracted water layer, and recycling the water layer for preparing the phenolic salt-containing water. The invention is not only effective for the waste water containing phenol, cresol and other unit phenol or volatile phenol, but also has good treatment effect for polyhydric phenol or non-volatile phenol, such as hydroquinone, catechol, TBHQ (tert-butyl hydroquinone) and the like. The method is a simple and efficient treatment method of the phenolic wastewater, not only removes phenolic substances in the wastewater, but also realizes the recovery and cyclic utilization of solvents and salts, reduces the wastewater treatment cost, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a treatment method of phenol-containing wastewater.
Background
The phenol-containing wastewater is wastewater containing phenolic organic matters generated in industrial production such as coking, pharmacy, papermaking, pigments, petrochemical industry and the like, and is one of common industrial wastewater, the phenol-containing wastewater not only belongs to toxic and harmful pollutants, but also is extremely difficult to degrade, and can bring huge pollution and harm to the environment once being discharged without treatment, the content of phenol in factory drainage specified in the comprehensive wastewater discharge standard of China is less than 2.0 mg/L, and the national primary discharge standard is that the content of phenol is less than 0.5 mg/L.
At present, the phenol-containing wastewater is researched more at home and abroad, and the treatment method is various and generally divided into a physical method, a chemical method, a biological degradation method and the like. The biodegradation method has the lowest cost, but the phenolic compounds have toxicity, and the degradation of microorganisms can be inhibited by overhigh concentration, so the method is mainly suitable for the low-concentration phenolic wastewater.
The physical extraction method and the adsorption method are industrially applied more, but the extraction method has the problems of complex process, large investment, high treatment cost and the like, for example, phenolic wastewater is generally alkaline, and phenol removal by extraction needs to be carried out under an acidic condition, so a large amount of acid is needed during extraction, the extraction method needs a certain temperature, secondary pollution is easily generated, and high energy consumption is needed for recovering an extracting agent; the activated carbon adsorption method has the defects of easy saturation and difficult analysis, and has high regeneration cost and easy secondary pollution.
The choice of dephenolizing extractant is of the greatest importance using physical extraction methods. As phenolic hydroxyl is partially hydrolyzed into phenolic oxygen anions in water, the phenolic oxygen anions have larger polarity and larger solubility in water. Therefore, the effect of extracting phenolic substances from wastewater by using a conventional solvent is poor, and even if the pH value of wastewater is adjusted to an acidic range to inhibit the hydrolysis of phenolic hydroxyl groups, complete extraction is difficult. In the published literature, most of the extractants or complex extractants with higher cost are used, such as organic amine as an extractant, wherein the organic amine is a weak base, has a greater affinity with a weakly acidic phenolic hydroxyl group, is beneficial to extracting phenolic substances from a water phase to an organic phase, and the organic quaternary ammonium salt also has a similar effect. Patent application CN 108069484a uses organic amines such as triallylamine, trioctylamine and organic solvents (such as toluene, kerosene) as complex extractant. Patent application CN 109384346a uses eucalyptol as extractant. Patent application CN 108558054a discloses a method for treating high-content phenol-containing wastewater, which comprises the steps of (1) pretreatment: extracting the phenol-containing wastewater for multiple times by using an organic solvent, and reducing the phenol content in the wastewater; (2) adding a catalyst filler into the pretreated wastewater, adding hydrogen peroxide under an acidic condition to catalyze the degradation of the oxidized phenol, and repeating the step for multiple times; (3) soaking the catalyst filler in an organic solvent for regeneration; (4) and (4) recovering the organic solvent in the steps (1) and (3). In the method, the step (2) is repeated for 3-5 times, and the concentration of phenol in the wastewater can meet the requirement of standard discharge. Patent application CN 107399779a discloses a method for treating phenol-containing wastewater, which is to add organic quaternary ammonium salt compounds as phenol removing agents (such as trioctylmethylammonium chloride, trioctylmethylammonium carbonate, trioctylmethylammonium sulfate, trinonylmethylammonium chloride or trinonylmethylammonium carbonate) into phenol-containing wastewater, stir and extract, and stand for layering. The regenerant of the remover is a carbonate-containing salt solution, or a sulfate-containing salt solution, or a chloride-containing salt solution. The treated waste water contains about 10ppm of phenol and does not meet the requirement of standard discharge.
It is also reported in the literature that the aqueous two-phase principle is used to extract contaminants from wastewater, as in the literature: the chemical research and application, 2009,21(7): 1064-. Although the extraction efficiency of the phenols is better, the organic phase recovery problem generally exists in the double aqueous phase treatment process. That is, during the distillation recovery or regeneration treatment of the organic phase, phenolic substances (especially volatile phenol) can be accumulated in the organic phase, which affects the treatment effect, and finally, the wastewater treatment process cannot be continuously carried out.
In summary, when the extracting agent is used for extracting and dephenolizing volatile phenol in the prior art, the extraction dephenolizing rate is low; when the high-efficiency extracting agent is adopted, the cost of the special solvent is high, the solubility of the solvent in water is high, the energy consumption for recovering the solvent is high, the loss is large, and the process cost is high.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for treating phenolic wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for treating phenolic wastewater comprises the following steps:
(1) preparing phenolic wastewater into a high-salt solution;
(2) extracting the phenol-containing high-salt solution for 1-5 times by using a solvent;
(3) recovering the extraction solvent from the extracted and layered phenol-containing solvent layer in a distillation or alkali washing mode, and continuously extracting the high-salt phenol-containing wastewater;
(4) distilling and concentrating the extracted water layer, discharging the fraction if the fraction meets the discharge requirement, and performing biochemical treatment if the fraction does not meet the discharge requirement; the concentrate was used to prepare a phenol-containing brine.
The mass fraction a of salt in the phenol-containing wastewater in the step (1) is 0-30%, and the method comprises the following steps:
(1) preparing phenolic wastewater into phenolic wastewater with the mass fraction of b, wherein the value range of b is 10-30%, and b is more than or equal to a;
(2) extracting the phenol-containing wastewater prepared in the step (1) by using a solvent for 1-5 times;
(3) recovering the extraction solvent from the organic phase obtained after the layering in the step (2) in a distillation or alkali washing mode, and continuously using the recovered solvent in the step (2);
(4) and (3) continuously using the concentrate obtained after the layering in the step (2) and obtained after the distillation and concentration of the water phase for preparing the phenol-containing wastewater in the step (1).
Furthermore, the phenolic substances in the phenolic wastewater comprise at least one of phenol, cresol, hydroquinone, catechol and tert-butyl hydroquinone.
Further, the salt is a sulfate, a hydrochloride, a carbonate or a mixture thereof.
Further, the salt is sodium sulfate, sodium chloride or a mixture thereof.
Further, the extraction solvent is at least one of ethyl acetate, methyl acetate, chloroform, dichloromethane, tetrachloroethylene, toluene or xylene.
Furthermore, the mass ratio of the solvent to the prepared phenol-containing wastewater during extraction is 0.2: 1-2: 1.
Compared with the prior art, the invention has the following beneficial effects:
the method for treating the phenolic wastewater provided by the invention utilizes the principle that organic phenolic substances have small distribution coefficient in saline water, and uses a conventional solvent to extract the phenolic wastewater with certain salt concentration, so that the phenolic substances can be removed or recovered from the wastewater. The extraction solvent can be recovered by distillation or caustic washing, and the recovered solvent can be reused in the extraction process. The water layer separated after extraction is distilled and concentrated to obtain concentrate (mainly salt) which can be circularly prepared into the phenol-containing brine.
The method does not need to adjust the pH value of the phenolic wastewater, and can realize the high-efficiency removal of the phenol in the wastewater only by simple stirring and standing. The invention not only is effective to the waste water containing phenol, cresol and other unit phenols or volatile phenol, but also has good treatment effect to polyhydric phenol or non-volatile phenol, such as hydroquinone, catechol, TBHQ (tert-butyl hydroquinone) and other polyhydric phenols.
The treatment method provided by the invention can effectively treat the high-phenol-content wastewater with the phenol content of 50-10000 mg/L, the phenol removal rate can reach more than 99.9%, and the phenol content in the treated wastewater can be reduced to be less than 2 mg/L, so that the treated wastewater reaches the direct discharge standard.
Drawings
FIG. 1 is a schematic view of the process for treating phenol-containing wastewater according to the present invention.
FIG. 2 is a liquid phase spectrum of phenol-containing wastewater in example 1 of the present invention.
FIG. 3 is a liquid phase spectrum of the wastewater after extraction in example 1 of the present invention.
FIG. 4 is a liquid phase spectrum of a fraction in example 1 of the present invention.
Detailed Description
Comparative example 1
500g of phenol-containing wastewater is taken, and the phenol content is tested (2010ppm, liquid phase external standard method). 670g of chloroform was added each time, and the aqueous layer was separated by 3 times of extraction, and the phenol content in the water was measured to be 261 ppm.
Example 1
500g of phenol wastewater is taken, and the phenol content is tested (2010ppm, liquid phase external standard method). 170g of sodium chloride was added to the wastewater to prepare a 25% sodium chloride solution. 670g of toluene (salt water to toluene mass ratio of 1:1) was added each time during extraction, and the aqueous layer was separated by 3 times extraction, and the phenol content in the aqueous layer was measured to be 0.9 ppm. The separated aqueous layer (about 670g) was distilled under atmospheric pressure and concentrated to about 250g, and the phenol content in the test fraction was 0.4 ppm. The toluene layers were combined and washed once with 150g of 5% sodium hydroxide and the toluene layer was separated for the next extraction. The alkali liquor can be reused for 3 times. FIG. 2 is a liquid phase spectrum of the phenol-containing wastewater of this example. FIG. 3 is a liquid phase spectrum of the wastewater after extraction in this example. FIG. 4 is a liquid phase spectrum of the fraction in this example. In the liquid phase spectra of FIGS. 2-4, the peak time of phenol was about 11.5 minutes.
Comparative example 2
500g of phenol-containing wastewater is taken to test the o-cresol content (2890ppm by a liquid phase external standard method). 143g of ethyl acetate were added to the waste water each time, extraction was carried out 5 times, and the aqueous layer was separated, and the o-cresol content in the aqueous layer was measured to be 125 ppm.
Example 2
500g of phenol-containing wastewater is taken to test the o-cresol content (2890ppm by a liquid phase external standard method). To the wastewater was added 215g of sodium sulfate to prepare a 30% sodium sulfate solution. 143g of ethyl acetate (mass ratio of brine to ethyl acetate 0.2:1) were added each time, extracted 3 times, and the aqueous layer was separated to measure the o-cresol content in the aqueous layer to be 0.5 ppm. The separated aqueous layer (about 715g) was subjected to atmospheric distillation and concentrated to about 290g, and the o-cresol content in the test fraction was 0.8 ppm. The ethyl acetate layer was distilled at normal pressure, and the recovered ethyl acetate was used for the next extraction.
Comparative example 3
500g of phenol-containing wastewater is taken to test the o-cresol content (2890ppm by a liquid phase external standard method). 170g of sodium chloride was added to the wastewater to prepare a 25% sodium chloride solution. The salt-containing waste water is distilled at normal pressure and concentrated to about 250g, and the content of o-cresol in the test fraction is 2647 ppm.
Example 3
500g of phenol-containing wastewater is taken, and the TBHQ content is tested to be (3533ppm, liquid phase external standard method). 55.5g of sodium chloride was added to the wastewater to prepare a 10% sodium chloride solution. 1111g of dichloromethane (mass ratio of brine to dichloromethane of 1:2) were added each time, the extraction was performed 1 time, the aqueous layer was separated, and the TBHQ content in the aqueous layer was measured to be 5 ppm. The separated aqueous layer (about 555.5g) was subjected to atmospheric distillation and concentrated to about 139g, and the TBHQ content in the test fraction was 1.8 ppm. The dichloromethane is recovered by atmospheric distillation and used for the next extraction.
Example 4
500g of phenol-containing wastewater is taken to test the content of hydroquinone (0.99 percent by a liquid phase external standard method). 170g of sodium chloride was added to the wastewater to prepare a 25.3% potassium chloride solution. 670g of methyl acetate (1: 1 mass ratio of brine to methyl acetate) was added each time, and the aqueous layer was separated by 2 extractions, and the hydroquinone content in the aqueous phase was measured to be 1.2 ppm. The separated aqueous layer (about 670g) was subjected to atmospheric distillation and concentrated to about 250g, and the hydroquinone content in the test fraction was 0.8 ppm. The methyl acetate layers are combined and then distilled under normal pressure, and the recovered methyl acetate is used for the next extraction.
Example 5
500g of phenol-containing wastewater is taken, and the content of catechol and the content of sodium chloride are tested to be 0.82 percent and 10 percent respectively (a chloride ion titration method). 56g of sodium chloride was added to the wastewater to prepare a 20.1% sodium chloride solution. 556g of chloroform (salt water to chloroform mass ratio 1:1) was added each time, extraction was performed 5 times, an aqueous layer was separated, and the catechol content in the aqueous layer was measured to be 8.9 ppm. The separated aqueous layer (about 556g) was subjected to atmospheric distillation and concentrated to about 220g, and the catechol content in the test fraction was 1.4 ppm. The chloroform layers were combined, washed once with 350g of 5% sodium hydroxide, and the chloroform layer was separated for the next extraction. The alkali liquor can be reused for 3 times.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (7)
1. A method for treating phenolic wastewater, which is characterized in that,
the mass fraction a of salt in the phenol-containing wastewater is 0-30%, and the method comprises the following steps:
(1) preparing phenolic wastewater into phenolic wastewater with a salt mass fraction b, wherein the value range of b is 10-30%, and b is more than or equal to a;
(2) extracting the phenol-containing wastewater prepared in the step (1) by using a solvent for 1-5 times;
(3) recovering the extraction solvent from the organic phase obtained after the layering in the step (2) in a distillation or alkali washing mode, and continuously using the recovered solvent in the step (2);
(4) and (3) continuously using the concentrate obtained after the layering in the step (2) and obtained after the distillation and concentration of the water phase for preparing the phenol-containing wastewater in the step (1).
2. The method according to claim 1, wherein the phenolic substances in the phenolic wastewater comprise at least one of phenol, cresol, hydroquinone, catechol, and tert-butyl hydroquinone.
3. The method according to claim 1, wherein the salt is a sulfate, a hydrochloride, a carbonate, or a mixture thereof.
4. The method according to claim 3, wherein the salt is sodium sulfate, sodium chloride or a mixture thereof.
5. The method for treating phenol-containing wastewater according to claim 1, wherein the solvent is at least one of ethyl acetate, methyl acetate, chloroform, methylene chloride, tetrachloroethylene, toluene, and xylene.
6. The method for treating phenol-containing wastewater according to claim 1, wherein the mass ratio of the solvent to the phenol-containing wastewater during extraction is 0.2:1 to 2: 1.
7. The method for treating phenol-containing wastewater according to claim 1, wherein after the aqueous phase is concentrated by distillation in the step (4), the fraction is discharged if the discharge requirement is met, and is subjected to biochemical treatment if the discharge requirement is not met.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114106220A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Method for reducing phenolic substance odor in molybdenum series 1, 2-polybutadiene production |
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| CN114106220A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Method for reducing phenolic substance odor in molybdenum series 1, 2-polybutadiene production |
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