CN107129019B - Treatment method of phenol-containing wastewater - Google Patents
Treatment method of phenol-containing wastewater Download PDFInfo
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- CN107129019B CN107129019B CN201610112512.6A CN201610112512A CN107129019B CN 107129019 B CN107129019 B CN 107129019B CN 201610112512 A CN201610112512 A CN 201610112512A CN 107129019 B CN107129019 B CN 107129019B
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/005—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up
- C07C37/009—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up from waste water
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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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 relates to a method for treating phenolic wastewater, which comprises the step of oxidizing phenol in the wastewater into organic acid, wherein in the step, a catalyst is a titanium silicalite molecular sieve, the pH value is 1-9, and an oxidant is H2O2. The method has the advantages of high phenol removal rate and low hydrogen peroxide consumption, and can remarkably improve the biodegradability of the phenol-containing wastewater.
Description
Technical Field
The invention relates to a method for treating phenolic wastewater.
Background
In various production processes of oil refining, synthetic resins, synthetic fibers, synthetic chemicals, synthetic dyes, etc., wastewater containing phenolic compounds (phenolic wastewater) can be produced. These phenolic compounds are highly toxic substances, and direct discharge thereof can seriously pollute the environment, and therefore, they must be subjected to harmless treatment.
The method for treating the phenol-containing wastewater mainly comprises a physical method and an oxidation method.
The physical method mainly comprises an extraction method and an adsorption method. The extraction method is suitable for treating high-concentration phenol-containing wastewater, can recover phenols, and realizes resource utilization of waste. The commonly used extractant mainly comprises benzene, heavy solvent naphtha, butyl acetate, isopropyl ether and other solvents or complexing agents such as tributyl phosphate (TBP), n-octanol, methyl tert-butyl ketone and the like are added into the solvents. The above extractant can only extract phenol at a lower pH value, and if the extractant is used for treating alkaline wastewater, the pH value needs to be adjusted first. The alkaline residue wastewater has strong alkalinity (pH is more than or equal to 12), and if the pH value is adjusted by acid, a large amount of acid is consumed.
The oxidation method mainly comprises the following steps: catalysis H2O2Oxidation, photocatalytic oxidation, electrochemical oxidation, ozone oxidation, catalytic wet air oxidation, supercritical water oxidation, and the like. Catalysis H2O2The oxidation process, Fenton, is carried out by reacting H with iron catalyst2O2Generates hydroxyl free radicals with strong oxidizability, and thoroughly oxidizes organic pollutants into harmless carbon dioxide. Iron catalysts can completely convert phenol, but consume large amounts of hydrogen peroxide.
The biological method is a wastewater treatment method with low cost, but phenolic compounds are high toxic substances, so that phenolic wastewater cannot be directly treated by the biological method. Biochemical BOD of wastewater5COD characterisation, generally considered when B/C>When 0.45, the sewage is easily biochemical sewage; when B/C>When 0.3, the sewage is biochemical sewage; when B/C<When 0.3, the sewage is difficult to be biochemically treated; when B/C<When 0.2, the sewage is difficult to be biochemically treated.
Disclosure of Invention
The invention provides a method for treating phenol-containing wastewater, which has the advantages of higher phenol removal rate and lower hydrogen peroxide consumption, and can obviously improve the biodegradability of the phenol-containing wastewater, so that the phenol-containing wastewater is suitable for biochemical treatment.
The present invention is explained in detail below.
A treatment method of phenol-containing wastewater comprises the step of oxidizing phenol in the wastewater into organic acid, wherein in the step, a catalyst is a titanium silicalite molecular sieve, the pH value is 1-9, and an oxidant is H2O2。
According to the invention, the phenol is phenol and/or cresol.
According to the invention, the titanium silicalite molecular sieve is a hollow titanium silicalite molecular sieve. The hollow titanium silicalite molecular sieve can be obtained commercially or prepared by the following method: hydrolyzing silicate ester and titanate with organic amine and organic ammonium in the presence of a surfactant, crystallizing at 150-190 ℃ for 12-72 hours, filtering, washing, drying, roasting at 500-850 ℃ for 1-4 hours, treating with inorganic acid at 30-90 ℃ for 1-5 hours, adding a surfactant, organic amine and other alkaline organic matters, reacting at 150-190 ℃ for 8-24 hours, filtering, washing, drying, and roasting at 500-850 ℃ for 1-4 hours to obtain the hollow titanium-silicon molecular sieve.
According to the invention, the pH value is preferably 1-8.
According to the invention, in the oxidation step, the reaction time is 30 to 180 minutes, preferably 90 to 120 minutes; the reaction temperature is 40-80 ℃, and preferably 60-80 ℃; the molar ratio of the hydrogen peroxide dosage to the phenol is 1-5, preferably 3-5; the dosage of the titanium silicalite molecular sieve is 0.5g/L to 3g/L, preferably 0.5g/L to 2 g/L.
According to the present invention, the concentration of phenol in the phenol-containing wastewater is 0.1 to 5g/L, preferably 0.1 to 3g/L, and more preferably 0.1 to 1.5g/L, in terms of phenol.
According to the invention, the phenol-containing wastewater is the wastewater obtained after phenol is extracted from alkaline residue wastewater.
According to the invention, the concentration of phenol in the alkaline residue wastewater is 5 g/L-40 g/L.
According to the invention, in the process of extracting phenol, the used extracting agent is a solution consisting of a complexing agent and a diluent; wherein the complexing agent contains di- (2-ethylhexyl) phosphate.
The type of diluent according to the invention is well known to the person skilled in the art, for example the diluent may be a hydrocarbon liquid at normal temperature, preferably a hydrocarbon liquid from C6 to C18, such as kerosene and/or gasoline.
According to the invention, the complexing agent is di- (2-ethylhexyl) phosphate; based on the volume of the extracting agent, the content of the complexing agent is 15-50 vol%, and the content of the diluent is 50-85 vol%.
According to the invention, the complexing agent consists of di- (2-ethylhexyl) phosphate and tributyl phosphate; based on the volume of the dephenolizing extractant, the content of di- (2-ethylhexyl) phosphate is 15-30 vol%, the content of tributyl phosphate is 5-20 vol%, and the content of diluent is 50-80 vol%; the volume ratio of the di- (2-ethylhexyl) phosphate to the tributyl phosphate is 1-3: 1.
According to the invention, the process for extracting phenol comprises: and under the extraction condition, uniformly mixing the caustic sludge wastewater with an extracting agent, and then standing for layering, wherein the mixing time is 30-120 minutes, and the standing time is 2-10 minutes.
According to the present invention, the amount of the extractant may be appropriately selected according to the amount of the caustic sludge wastewater to be treated, and generally, the volume ratio of the extractant to the caustic sludge wastewater may be 4:1 to 1:10, and preferably 2:1 to 1: 5. When the complexing agent contains tributyl phosphate besides di- (2-ethylhexyl) phosphate, the dosage of the dephenolizing extractant can be properly reduced, for example, the volume ratio of the dephenolizing extractant to the phenol-containing wastewater can be 2: 1-1: 4, and the method is particularly suitable for phenol-containing wastewater with the pH value being more than or equal to 13.
In addition, the temperature of the extraction may be 20 to 80 ℃, preferably 20 to 60 ℃.
According to the invention, the extraction of phenol can be carried out either batchwise or continuously, for example by bringing the extractant into countercurrent contact with the caustic sludge waste water in an extraction column.
According to the invention, the process for extracting phenol further comprises: and (3) carrying out back extraction on the obtained extract phase rich in phenols by using an inorganic alkaline water solution as a back extraction agent, and recycling the obtained regenerated extraction agent for treating the phenol-containing wastewater.
According to the invention, the volume ratio of the back-extraction agent to the extract phase rich in phenols is 1: 1-1: 5, the back-extraction agent is a sodium hydroxide aqueous solution, the mass concentration of the sodium hydroxide aqueous solution is 4-20 wt%, and the back-extraction temperature is 20-80 ℃.
According to the invention, the caustic sludge wastewater is derived from at least one of phenol-containing alkaline wastewater generated by alkaline washing of catalytic cracking gasoline, diesel oil and liquefied gas in the crude oil refining process, effluent of the wastewater after wet oxidation and mixed wastewater of the wastewater.
According to the invention, the phenol concentration in the alkaline residue wastewater is 5 g/L-40 g/L calculated by phenol.
According to the invention, the oxidation step is carried out in a continuous manner when the phenolic waste water is alkaline (in particular with a pH > 9). At this time, the organic acid generated in the step can neutralize the alkalinity of the phenol-containing wastewater, and partial or all of the pH value regulator is saved.
According to the invention, in the oxidation step, the B/C of the phenolic wastewater is enabled to be more than 0.3.
According to the invention, after said oxidation step, the wastewater is subjected to a biochemical treatment.
In the present invention, the mass concentration of phenol is measured by 4-aminoantipyrine spectrophotometry specified in the HJ 503-2009 standard, and the molar concentration of phenol is calculated from the mass concentration of phenol as phenol only; COD was determined by rapid digestion spectrophotometry as specified in HJ/T399-2007 standard; BOD5Determined according to the dilution and inoculation method specified in the HJ 505-.
Phenol removal rate is 100 × (phenol content in wastewater before treatment-phenol content in wastewater after treatment)/phenol content in wastewater before treatment.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
250mL of 0.1g/L aqueous phenol solution was taken and placed in a flask, and the amount of the titanium silicalite molecular sieve (prepared by the method described above, the same applies below) was 0.5 g/L. Heating in water bath at 60 deg.C, adding H when the temperature is stable2O2(30 m%) of the solution, the molar ratio of hydrogen peroxide to phenol was adjusted to 3, and after 90 minutes of reaction, the phenol concentration, COD and BOD of the wastewater were measured5And a pH value. The test result shows that: the removal rate of phenol is 100%, the B/C value of the solution is increased from 0.2 to 0.7, and the pH value of the solution is reduced from 7 to 5.
Example 2
An aqueous phenol solution was treated in the same manner as in example 1 except that: the concentration of phenol is 0.5g/L, and the addition amount of the titanium silicalite molecular sieve is 1 g/L. The test result shows that: the removal rate of phenol is 100%, the B/C value of the solution is increased from 0.1 to 0.7, and the pH value of the solution is reduced from 6.9 to 4. Taking a small amount of reacted water solution, detecting a reaction product by adopting a high performance liquid chromatography, and finding that the reaction product contains organic acids such as maleic acid, oxalic acid and the like.
Example 3
An aqueous phenol solution was treated in the same manner as in example 1 except that: the concentration of phenol is 3g/L, and the addition amount of the titanium silicalite molecular sieve is 2 g/L. The test result shows that: the removal rate of phenol is 95%, the B/C value of the solution is increased from 0 to 0.32, and the pH value of the solution is reduced from 6.6 to 2.9.
Example 4
250mL of 1g/L aqueous phenol solution is put into a flask, and the addition amount of the titanium silicalite molecular sieve is 1 g/L. Heating in water bath at 60 deg.C, adding H when the temperature is stable2O2(30 m%) of the solution, the molar ratio of hydrogen peroxide to phenol was adjusted to 3, and the reaction was carried out at different pH values for 90 minutes. After the test was completed, the phenol concentration of the wastewater was measured, and the phenol removal rate was calculated, and the results are shown in table 1.
TABLE 1
| pH value of reaction system | 1 | 3 | 5 | 6 | 8 |
| Phenol removal rate (%) | 91.8 | 88.7 | 90.3 | 89.9 | 89.7 |
Example 5
250mL of 1.5g/L aqueous cresol solution is put into a flask, and the addition amount of the titanium silicalite molecular sieve is 1.5 g/L. Heating in water bath at 80 deg.C, adding H when the temperature is stable2O2(30 m%) of the solution, the molar ratio of hydrogen peroxide to cresol was set to 4, and after 90 minutes of reaction, the phenol concentration, COD and BOD of the wastewater were measured5And a pH value. The test result shows that: the removal rate of cresol is 95.6%, the B/C value of the solution is increased from 0 to 0.5, and the pH value of the solution is reduced from 6 to 0.28.
Example 6
This example illustrates the extractive phenol extraction process of the present invention.
The extractant was a gasoline containing 40% HDEHP by volume. Uniformly mixing an extracting agent and phenol-containing wastewater with the pH value of 12.2 according to the volume ratio of 1:1 (the phenol-containing wastewater contains Na with the concentration of 0.1mol/L2SO4) Mixing (stirring, the same below) at 30 deg.C for 30 min, standing for 5 min, and separating phase to obtain extract phase and raffinate water phase. In the treated wastewater, the phenol content in terms of phenol is 245mg/L, and the removal rate of phenols is 95%.
Example 7
This example illustrates the extractive phenol extraction process of the present invention.
The extractant was kerosene containing 40% by volume HDEHP. Uniformly mixing an extracting agent and phenol-containing wastewater with the pH value of 13.5 according to the volume ratio of 1:1 (the phenol-containing wastewater contains Na with the concentration of 0.5mol/L2SO4) Mixing at 30 deg.C for 60 min, standing for 5 min to obtain extract phase and raffinate water phase. The phenol content of the treated wastewater calculated by phenol was 144mg/L, and the phenol removal rate was 97%.
Comparative example 1
Phenol-containing wastewater was treated in the same manner as in example 7 except that: the extractant was kerosene containing 40% by volume of TBP. The phenol content of the treated wastewater was 4881mg/L in terms of phenol, and the removal rate of phenols was 2%.
Comparative example 2
Phenol-containing waste water was treated in the same manner as in example 7, except that the extractant was gasoline containing 40 vol% of TBP and the phenol-containing waste water had a pH of 10. The phenol content of the treated wastewater calculated by phenol is 2564mg/L, and the removal rate of phenols is 48%.
Comparative example 3
Phenol-containing waste water was treated in the same manner as in example 7, except that the extractant was gasoline containing 40% by volume of t-amyl methyl ether and the pH of the phenol-containing waste water was 9.5. The phenol content of the treated wastewater was 3846mg/L in terms of phenol, and the removal rate of phenols was 23%.
Example 8
This example illustrates the extractive phenol extraction process of the present invention.
Phenol-containing wastewater was treated under the same conditions as in example 2 except that: the extractant was kerosene containing 20 vol% HDEHP and 20 vol% TBP. In the treated wastewater, the phenol content calculated by phenol is 76mg/L, and the removal rate of phenols is 98%.
Example 9
This example illustrates the extractive phenol extraction process of the present invention.
Phenol-containing wastewater was treated in the same manner as in example 8, except that the extracted phenol-rich extract phase was uniformly mixed with a 5% by mass aqueous sodium hydroxide solution at a volume ratio of 1:1, mixed at 30 ℃ for 60 minutes and then allowed to stand for phase separation for 5 minutes. After back extraction, recovery of phenols was 100%.
Example 10
This example illustrates the extractive phenol extraction process of the present invention.
The extractant was a gasoline containing 40% HDEHP by volume. Uniformly mixing an extracting agent and phenol-containing wastewater with the pH value of 10.2 according to the volume ratio of 1:1 (the phenol-containing wastewater contains Na with the concentration of 0.1mol/L2SO4) Mixing at 30 deg.C for 30 min, standing for 5 min to obtain extract phase and raffinate water phase. In the treated wastewater, the phenol content was 285mg/L in terms of phenol, and the phenol removal rate was 94%.
Example 11
This example illustrates the extractive phenol extraction process of the present invention.
The extractant was a gasoline containing 40% HDEHP by volume. Uniformly mixing an extracting agent and phenol-containing wastewater with the pH of 9.1 according to the volume ratio of 1:1 (the phenol-containing wastewater contains Na with the concentration of 0.1mol/L2SO4) Mixing at 30 deg.C for 30 min, standing for 5 min to obtain extract phase and raffinate water phase. The phenol content of the treated wastewater calculated by phenol is 512mg/L, and the removal rate of phenols is 90%.
Example 12
This example illustrates the extractive phenol extraction process of the present invention.
The extractant was a gasoline containing 40% HDEHP by volume. Uniformly mixing an extracting agent and phenol-containing wastewater with the pH value of 4.1 according to the volume ratio of 1:1 (the phenol-containing wastewater contains Na with the concentration of 0.1mol/L2SO4) Mixing at 30 deg.C for 30 min, standing for 5 min to obtain extract phase and raffinate water phase. In the treated wastewater, the phenol content was 903mg/L in terms of phenol, and the phenol removal rate was 82%.
Example 13
This example illustrates the extractive phenol extraction process of the present invention.
The extractant was kerosene containing 15 vol% HDEHP and 10 vol% TBP. Uniformly mixing an extracting agent and phenol-containing wastewater with the pH value of 12.2 according to the volume ratio of 1:6 (the phenol-containing wastewater contains Na with the concentration of 0.1mol/L2SO4) Mixing at 60 deg.C for 120 min, standing for 10 min to obtain extract phase and raffinate water phase. The phenol content of the treated wastewater was 276mg/L in terms of phenol, and the phenol removal rate was 94%.
Example 14
This example illustrates the extractive phenol extraction process of the present invention.
The phenol content in the liquefied gas caustic sludge wastewater of a certain refinery is 35752mg/L, and the pH value is 13.1. The extractant used was a gasoline containing 40% by volume of HDEHP. And uniformly mixing an extracting agent and the alkaline residue wastewater according to the volume ratio of 1:1, mixing for 60 minutes at 30 ℃, standing for phase separation, and standing for 5 minutes. To obtain an extract phase and a raffinate aqueous phase. The phenol content of the treated wastewater was 948mg/L in terms of phenol, and the removal rate of phenols was 97%.
Example 15
This example illustrates the extractive phenol extraction process of the present invention.
The phenol content in gasoline alkaline residue wastewater of a certain refinery is 15118mg/L, and the pH value is 13.7. The extractant used was a gasoline containing 30% by volume HDEHP and 20% by volume TBP. Uniformly mixing the extractant and the alkaline residue wastewater according to the volume ratio of 2:1, mixing at 30 ℃ for 120 minutes, standing for phase separation, and standing for 10 minutes. To obtain an extract phase and a raffinate aqueous phase. The phenol content of the treated wastewater was 148mg/L in terms of phenol, and the phenol removal rate was 99%.
Example 16
This example illustrates the extractive phenol extraction process of the present invention.
Phenol-containing wastewater was treated in the same manner as in example 15 except that: the extractant is gasoline containing 50 volume percent of HDEHP, and the extractant and the caustic sludge wastewater are mixed according to the volume ratio of 4: 1. In the treated wastewater, the phenol content calculated by phenol is 152mg/L, and the removal rate of phenols is 99%.
Example 17
This example illustrates the extractive phenol extraction process of the present invention.
The content of phenol in the effluent of the mixed alkaline residue of a certain refinery after mild wet oxidation is 4678mg/L, and the pH value is 12.3. The extractant used was a gasoline containing 40% by volume of HDEHP. Uniformly mixing the extractant and the alkaline residue wastewater according to the volume ratio of 1:1, mixing for 60 minutes at 30 ℃, standing for phase separation, and standing for 2 minutes. To obtain an extract phase and a raffinate aqueous phase. The phenol content of the treated wastewater calculated by phenol is 256mg/L, and the removal rate of phenols is 95%.
Example 18
This example illustrates the extractive phenol extraction process of the present invention.
Phenol-containing wastewater was treated in the same manner as in example 6 except that the content of the inorganic salt dissolved in the phenol-containing wastewater was 0.02 mol/L. In the treated wastewater, the phenol content was 390mg/L in terms of phenol, and the phenol removal rate was 92%. Tests show that after mixing, the time for the extraction system to stand and separate is obviously prolonged compared with the example 1.
From the results of examples 6 to 18, it can be seen that the phenol content in the treated wastewater can be significantly reduced by the process for extracting phenol according to the present invention. As can be seen from the comparison of example 7 with comparative example 1, the treatment of the same wastewater at the pH according to the invention, using TBP as the complexing agent, is far less effective than the treatment of phenol according to the invention. The comparative example 2 and the comparative example 3 are comparative embodiments referring to the prior art, and the actual phenol removal effect can be seen from the actual phenol removal effect, even if the pH value of the phenol-containing wastewater is controlled within the range of 9-10, the actual phenol removal effect of the TBP and the methyl tert-amyl ether which have larger differences with the complexing agent provided by the invention in structure and property is far lower than the phenol removal effect of which the pH value is less than 9. From the results of comparing example 8 with example 7 and comparative example 1, it can be seen that when the mixed extraction system of HDEHP and TBP preferred in the present invention is used, the extraction effect is better and the viscosity of the system can be further reduced due to the synergistic effect between HDEHP and TBP.
Example 19
250mL of the raffinate of example 14 was taken in a flask and H was added2SO4Adjusting the pH value of raffinate phase to 8 by the solution, carrying out chemical demulsification, then standing for layering to recover neutral oil on the upper layer and phenolic wastewater on the lower layer, and adding 1.5g/L titanium silicalite molecular sieve into the wastewater. Heating in water bath at 80 deg.C, adding H when the temperature is stable2O2(30 m%) of the solution, the molar ratio of hydrogen peroxide to phenol was 3 (the number of moles of phenol was determined by converting the wastewater to 948mg/L, which contains only phenol), the reaction time was 90min, and the catalyst was separated by centrifugation. The phenol removal rate is 95%, the biodegradability of the solution is improved from 0 to 0.7, and the difficult-to-biochemically treated sewage is changed into the easy-to-biochemically treated sewage.
Claims (16)
1. A treatment method of phenol-containing wastewater comprises the step of oxidizing phenol in the wastewater into organic acid, wherein in the step, a catalyst is a titanium silicalite molecular sieve, the pH value is 1-9, and an oxidant is H2O2(ii) a The reaction time is 90 to 120 minutes; the reaction temperature is 60-80 ℃; the amount of hydrogen peroxide and phenolThe molar ratio of (A) to (B) is 3-5; the dosage of the titanium silicalite molecular sieve is 0.5g/L to 2 g/L; in the phenol-containing wastewater, the concentration of phenol is 0.1 g/L-3 g/L calculated by phenol; the phenolic wastewater is obtained by extracting phenol from alkaline residue wastewater; in the oxidation step, the B/C of the phenolic wastewater is treated>0.3。
2. The process of claim 1, wherein the phenol is phenol and/or cresol.
3. The method of claim 1, wherein the titanium silicalite molecular sieves are hollow titanium silicalite molecular sieves.
4. The method according to claim 1, wherein the concentration of phenol in the phenol-containing wastewater is 0.1g/L to 1.5g/L in terms of phenol.
5. The method of claim 1, wherein the extractant used in the extraction of phenol is a solution of a complexing agent and a diluent; wherein the complexing agent contains di- (2-ethylhexyl) phosphate.
6. The method of claim 5, wherein the diluent is a hydrocarbon that is liquid at ambient temperature.
7. The method of claim 5, wherein the complexing agent is di- (2-ethylhexyl) phosphate; based on the volume of the extracting agent, the content of the complexing agent is 15-50 vol%, and the content of the diluent is 50-85 vol%.
8. The method of claim 5, wherein the complexing agent consists of di- (2-ethylhexyl) phosphate and tributyl phosphate; based on the volume of the extracting agent, the content of the di- (2-ethylhexyl) phosphate is 15-30 vol%, the content of the tributyl phosphate is 5-20 vol%, and the content of the diluting agent is 50-80 vol%; the volume ratio of the di- (2-ethylhexyl) phosphate to the tributyl phosphate is 1-3: 1.
9. The method of claim 5, wherein the extracting phenol comprises: and under the extraction condition, uniformly mixing the caustic sludge wastewater with an extracting agent, and then standing for layering, wherein the mixing time is 30-120 minutes, and the standing time is 2-10 minutes.
10. The method of claim 9, wherein the extraction conditions comprise: the volume ratio of the extracting agent to the alkaline residue wastewater is 4: 1-1: 10; the extraction temperature is 20-80 ℃.
11. The method according to claim 8, wherein the volume ratio of the extracting agent to the caustic sludge wastewater is 2: 1-1: 4; the pH value of the phenolic wastewater is more than or equal to 13.
12. The method of claim 5, wherein the extracting phenol further comprises: and (3) carrying out back extraction on the obtained extract phase rich in phenols by using an inorganic alkaline water solution as a back extraction agent, and recycling the obtained regenerated extraction agent for treating the phenol-containing wastewater.
13. The method according to claim 12, wherein the volume ratio of the stripping agent to the extract phase rich in phenols is 1: 1-1: 5, the stripping agent is an aqueous sodium hydroxide solution, the mass concentration of the aqueous sodium hydroxide solution is 4-20 wt%, and the stripping temperature is 20-80 ℃.
14. The method according to claim 5, wherein the caustic sludge wastewater is derived from at least one of alkaline waste water containing phenol generated by caustic washing catalytic cracked gasoline, diesel oil, liquefied gas in the crude oil refining process, effluent water of the wastewater after wet oxidation and mixed waste water of the wastewater.
15. The method according to claim 14, wherein the phenol concentration of the caustic sludge wastewater is 5 to 40g/L in terms of phenol.
16. The method of claim 5, wherein the oxidizing step is carried out in a continuous manner when the phenolic-containing waste water is alkaline.
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| CN101549294A (en) * | 2008-04-02 | 2009-10-07 | 中国科学院生物物理研究所 | Magnetic nanometer material for processing organic pollutants |
| CN102642887A (en) * | 2012-05-15 | 2012-08-22 | 西安建筑科技大学 | Complexation extraction dephenolization method of semi coke wastewater containing phenol |
| CN104341274A (en) * | 2013-07-31 | 2015-02-11 | 中国石油化工股份有限公司 | Method for simultaneously producing dihydroxybenzene and benzoquinone |
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| CN101549294A (en) * | 2008-04-02 | 2009-10-07 | 中国科学院生物物理研究所 | Magnetic nanometer material for processing organic pollutants |
| CN102642887A (en) * | 2012-05-15 | 2012-08-22 | 西安建筑科技大学 | Complexation extraction dephenolization method of semi coke wastewater containing phenol |
| CN104341274A (en) * | 2013-07-31 | 2015-02-11 | 中国石油化工股份有限公司 | Method for simultaneously producing dihydroxybenzene and benzoquinone |
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