CN111003904A - Resourceful treatment method of high-concentration phenol-containing wastewater - Google Patents

Resourceful treatment method of high-concentration phenol-containing wastewater Download PDF

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CN111003904A
CN111003904A CN201911424002.2A CN201911424002A CN111003904A CN 111003904 A CN111003904 A CN 111003904A CN 201911424002 A CN201911424002 A CN 201911424002A CN 111003904 A CN111003904 A CN 111003904A
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resin
phenol
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季民
王帅帅
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F9/00—Multistage treatment of water, waste water or sewage
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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
    • C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
    • C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
    • 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
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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    • C02F2101/34—Organic compounds containing oxygen
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Abstract

The invention discloses a resource treatment method of high-concentration phenol-containing wastewater, which comprises the steps of refining, impurity removal, hydrogenation reduction, resin adsorption, treatment of adsorbed effluent and the like. Wherein, non-ionic polyacrylamide and diatomite powder are adopted to remove impurities, a catalyst in the hydrogenation reduction process is a palladium-carbon catalyst, macroporous adsorption resin is adopted to absorb phenol in the resin adsorption process, the phenol recovery is resin regeneration liquid, and the mother liquid can be recycled. The method recovers the phenol in the sewage through hydrogenation reduction and resin adsorption, and the obtained phenol product has high yield and content of more than 99 percent and can be directly used as a raw material for synthesizing and producing pesticides. Wherein, the methanol water solution is used as the resin regeneration liquid, the recovery rate of the methanol reaches 98 percent, and all eluent can be reused in the regeneration process without generating any waste water and waste residue. The invention realizes the recycling of phenol in sewage, has no secondary pollution, stable effluent index, no inhibition to biochemistry, and carries out harmless and resource treatment on high-concentration phenol-containing wastewater.

Description

Resourceful treatment method of high-concentration phenol-containing wastewater
Technical Field
The invention relates to a sewage treatment method, in particular to a resource treatment method of high-concentration phenol-containing wastewater.
Background
The phenolic compound is used as an important chemical raw material and an intermediate, and is widely applied in the production process of pesticides. The phenolic compounds have stable benzene ring structures, are not easy to degrade and are easy to oxidize to generate red quinone substances, so that the wastewater is difficult to treat. The phenol-containing wastewater generated in the pesticide industry has the characteristics of complex composition, high content of phenolic compounds and poor biodegradability. The phenolic compounds can solidify protein, are toxic to almost all organisms, can cause chronic accumulated poisoning after being exposed to high-concentration steam for a long time or drinking water polluted by phenol, cause canceration, mutation and distortion effects on human bodies, and have great harm, thereby being one of toxic and harmful waste water which is mainly solved in national water pollution control. Phenol chemically reacts by contact with human skin and mucous membranes to form insoluble proteins, which can cause cell viability, and high concentrations of phenol can cause protein coagulation. The phenol substances are discharged into water, and can cause great harm to water bodies and organisms in the water bodies. Therefore, the phenol content in the phenol-containing wastewater must be reduced to an acceptable range, the pollution and damage to the environment are reduced, and the recovery and the reuse of the phenol compounds are important ways for treating the phenol-containing wastewater.
The high-concentration phenol-containing wastewater can be treated by a physical-chemical method, a biological method, a chemical oxidation method and the like. The physical and chemical methods comprise an adsorption method, an extraction method, a liquid membrane separation technology, a gas stripping and distillation gas stripping method and a rectification method, and the biochemical methods comprise an activated sludge method, a biological contact oxidation method, a biofilm method and the like. For example, the chinese patent application publication No. CN108715493A discloses a method for treating phenol-containing wastewater in petrochemical industry, which utilizes resin adsorption to adsorb and recover phenol-containing compounds in wastewater, wherein a resin regeneration solution contains a sodium hydroxide solution and an organic solvent, the regeneration solution needs to be recovered after rectification, the energy consumption is high, secondary pollution is caused by resin desorption, and the resource effect is poor. Therefore, it is necessary to develop a high-efficiency, stable and convenient-to-operate phenolic wastewater recycling treatment process.
Disclosure of Invention
Aiming at the problems of treatment of the phenol-containing wastewater and the defects of the prior art, the invention provides a resource treatment method of high-concentration phenol-containing wastewater, aiming at solving the problems of high energy consumption, secondary pollution, unstable water outlet effect and the like in the resource treatment process of the phenol-containing wastewater. Realizes the harmlessness and reclamation of the phenol-containing wastewater, has higher environmental protection benefit, low treatment cost and mild adsorption condition, and is suitable for industrial application.
In order to solve the technical problem, the invention provides a resource treatment method of high-concentration phenol-containing wastewater, which comprises the following steps:
step one, refining and impurity removing: regulating the pH value of the wastewater to 1-6 by using recovered hydrochloric acid with the mass concentration of 30%, and separating out a large amount of water-insoluble solids from the system; adding nonionic polyacrylamide accounting for 1% of the mass of the wastewater and diatomite powder with the fineness of 300 meshes accounting for 5 per mill of the mass of the wastewater, wherein the mass concentration of the nonionic polyacrylamide is 2 per mill; filtering after flocculation adsorption for 1-10 hours, and changing the water sample from red black turbidity to deep yellow transparent after filtering;
step two, hydrogenation reduction: adding 5% palladium carbon catalyst according to 0.8 per mill of the mass of the dark yellow transparent solution filtered in the first step, stirring and heating to 70 ℃; introducing hydrogen into the system at the speed of 5-20L/min, and introducing hydrogen for reaction for 2-9 hours at the temperature of 40-120 ℃, so that p-benzoquinone in the wastewater is reduced into phenol, and the system is changed from a dark yellow transparent solution to a light yellow to colorless solution;
step three, resin adsorption, comprising:
step 3-1, macroporous adsorption resin pretreatment: soaking and washing the macroporous adsorption resin for 24 hours by using industrial water according to the volume ratio of 1:1 to fully swell the macroporous adsorption resin, and removing an organic solvent and inorganic salt in the resin;
step 3-2, resin filling: filling the soaked macroporous adsorption resin into an adsorption column, wherein the ratio of the height of the filled resin to the diameter of the adsorption column is 3-20:1, removing bubbles in the resin, and draining industrial water in the adsorption column;
step 3-3, adsorbing phenol: injecting the faint yellow to colorless solution obtained in the step two into an adsorption column at the flow rate which is 1-10 times the volume of the macroporous adsorption resin per hour, collecting the adsorbed colorless transparent liquid, tracking and detecting the phenol content until the phenol content is more than 0.5mg/L, stopping adsorption, and at the moment, the phenol content in the adsorption column is saturated;
step 3-4, phenol recovery: injecting resin regeneration liquid with the volume 3 times that of the macroporous adsorption resin into the adsorption column at the flow rate of 5 times the volume of the macroporous adsorption resin per hour, wherein the resin regeneration liquid is methanol aqueous solution with the volume content of 90% and the water content of 5% -30%, distilling the resin regeneration liquid under negative pressure, evaporating 98% of methanol in the resin regeneration liquid, cooling the residual high-concentration phenol solution to 5 ℃, and filtering and recovering phenol; the mother liquor is recycled to the next batch, and the temperature is continuously reduced to recover the phenol;
step four, adsorbing effluent treatment: and (3) adding 2-5 per mill of sodium hypochlorite solid into the colorless transparent liquid collected and adsorbed in the step (3-3), oxidizing for 2-6 hours, directly discharging into a biochemical system, and discharging after biochemical treatment is qualified.
Furthermore, in the method for recycling high-concentration phenol-containing wastewater of the present invention, in the first step, preferably, the flocculation adsorption time is 2 hours.
In the second step, preferably, the hydrogen introducing temperature is 70 ℃, the hydrogen introducing speed is 10L/min, and the reaction time is 3 hours.
In the step 3-1, the macroporous adsorption resin is one of a styrene-divinylbenzene system nonpolar adsorption resin or a polystyrene type nonpolar adsorption resin.
In step 3-2, preferably, the ratio of the height of the resin to the diameter of the adsorption column after the macroporous adsorption resin is filled is 5: 1.
In step 3-3, preferably, the volume flow rate of the solution when the resin adsorbs phenol is 5 times of the volume flow rate of the macroporous adsorption resin.
In steps 3 to 4, preferably, the aqueous methanol solution of the resin regeneration liquid contains 10% of water.
Compared with the prior art, the invention has the beneficial effects that:
the method recovers the phenol in the sewage through hydrogenation reduction and resin adsorption, and the obtained phenol product has high yield and content of more than 99 percent and can be directly used as a raw material for synthesizing and producing pesticides. The resin regeneration liquid creatively uses methanol aqueous solution, the recovery rate of methanol reaches 98%, all eluent can be reused in the regeneration process, and no waste water or waste residue is generated. The invention realizes the recycling of phenol in sewage, has no secondary pollution, stable effluent index, no inhibition to biochemistry, and carries out harmless and resource treatment on high-concentration phenol-containing wastewater.
Drawings
FIG. 1 is a schematic process flow diagram of the treatment method of the present invention.
Detailed Description
The invention provides a resource treatment method of high-concentration phenol-containing wastewater, which mainly comprises the steps of refining, impurity removal, hydrogenation reduction, resin adsorption, adsorption effluent treatment and the like. Wherein, non-ionic polyacrylamide and diatomite powder are adopted to remove impurities, a catalyst in the hydrogenation reduction process is a palladium-carbon catalyst, macroporous adsorption resin is adopted to absorb phenol in the resin adsorption process, the phenol recovery is resin regeneration liquid, and the mother liquid can be recycled. The method comprises the following specific steps:
step one, refining and impurity removing: regulating the pH value of the wastewater to 1-6 by using recovered hydrochloric acid with the mass concentration of 30%, and separating out a large amount of water-insoluble solids from the system; adding nonionic polyacrylamide accounting for 1% of the mass of the wastewater and diatomite powder with the fineness of 300 meshes accounting for 5 per mill of the mass of the wastewater, wherein the mass concentration of the nonionic polyacrylamide is 2 per mill; filtering after flocculation adsorption for 1-10 hours, and changing the water sample from red black turbidity to deep yellow transparent after filtering;
step two, hydrogenation reduction: adding 5% palladium carbon catalyst according to 0.8 per mill of the mass of the dark yellow transparent solution filtered in the first step, stirring and heating to 70 ℃; introducing hydrogen into the system at the speed of 5-20L/min, and introducing hydrogen for reaction for 2-9 hours at the temperature of 40-120 ℃, so that p-benzoquinone in the wastewater is reduced into phenol, and the system is changed from a dark yellow transparent solution to a light yellow to colorless solution;
step three, resin adsorption, comprising:
step 3-1, macroporous adsorption resin pretreatment: soaking and washing the macroporous adsorption resin for 24 hours by using industrial water according to the volume ratio of 1:1 to fully swell the macroporous adsorption resin, and removing an organic solvent and inorganic salt in the resin;
step 3-2, resin filling: filling the soaked macroporous adsorption resin into an adsorption column, wherein the ratio of the height of the filled resin to the diameter of the adsorption column is 3-20:1, removing bubbles in the resin, and draining industrial water in the adsorption column;
step 3-3, adsorbing phenol: injecting the faint yellow to colorless solution obtained in the step two into an adsorption column at the flow rate which is 1-10 times the volume of the macroporous adsorption resin per hour, collecting the adsorbed colorless transparent liquid, tracking and detecting the phenol content until the phenol content is more than 0.5mg/L, stopping adsorption, and at the moment, the phenol content in the adsorption column is saturated;
step 3-4, phenol recovery: injecting resin regeneration liquid with the volume 3 times that of the macroporous adsorption resin into the adsorption column at the flow rate of 5 times the volume of the macroporous adsorption resin per hour, wherein the resin regeneration liquid is methanol aqueous solution with the volume content of 90% and the water content of 5% -30%, distilling the resin regeneration liquid under negative pressure, evaporating 98% of methanol in the resin regeneration liquid, cooling the residual high-concentration phenol solution to 5 ℃, and filtering and recovering phenol; the mother liquor is recycled to the next batch, and the temperature is continuously reduced to recover the phenol;
step four, adsorbing effluent treatment: and (3) adding 2-5 per mill of sodium hypochlorite solid into the colorless transparent liquid collected and adsorbed in the step (3-3), oxidizing for 2-6 hours, directly discharging into a biochemical system, and discharging after biochemical treatment is qualified.
The invention will be further described with reference to the following figures and specific examples, which are not intended to limit the invention in any way.
Example 1
The method for recycling the high-concentration phenolic wastewater is used for treating the phenolic wastewater of a certain pesticide factory, and the treatment process is shown in figure 1 and comprises the following steps:
step 1, refining and impurity removal: adjusting the pH value of 8 tons of wastewater to 3 by using 30% by mass of recovered hydrochloric acid, separating out a large amount of water-insoluble solids from the system, adding 80kg of nonionic polyacrylamide (the mass concentration of the nonionic polyacrylamide is 2 per thousand) and 40kg of diatomite powder with the fineness of 300 meshes, flocculating and adsorbing for 1 hour, filtering, and changing the red-black turbid water sample into deep yellow transparent water sample after filtering;
step 2, hydrogenation reduction: adding 6.4kg of 5% palladium carbon catalyst into the filtrate obtained in the step 1, stirring and heating to 40 ℃, introducing hydrogen into the system at the speed of 5L/min, keeping the temperature and introducing the hydrogen for reaction for 2 hours, reducing p-benzoquinone in the wastewater into phenol, and changing the system from a dark yellow transparent solution to a light yellow to colorless solution;
step 3, adsorbing phenol by resin:
(3-1) macroporous adsorption resin pretreatment: soaking and washing 200L of nonpolar adsorption resin of styrene-divinylbenzene system with 200L of industrial water for 24h to fully swell the resin, and removing organic solvent and inorganic salt in the resin;
(3-2) resin packing: filling the soaked and washed resin into an adsorption column, wherein the ratio of the height of the filled resin to the diameter of the adsorption column is 3:1, removing bubbles in the resin, and discharging industrial water in the adsorption column;
(3-3) adsorbing phenol: injecting 7.8 tons of the faint yellow to colorless solution obtained in the step 2 into the adsorption column at a volume flow rate of 2000L/h, collecting 7.7 tons (colorless and transparent) of water after adsorption, tracking and detecting the phenol content until the phenol content is more than 0.5mg/L, stopping adsorption, and at the moment, the phenol content in the adsorption column is saturated;
(3-4) phenol recovery: injecting 600L of 70% methanol aqueous solution (resin regeneration solution) containing 30% water into the saturated adsorption column at a volume flow rate of 2000L/h, distilling the regeneration solution under negative pressure to distill out 411.6L of methanol, cooling the residual high-concentration phenol solution to 0-5 ℃, filtering to recover phenol, recycling the mother solution to the next batch, and continuously cooling to recover phenol.
Step 4, adsorbing effluent treatment: and (4) adding 15.4kg of sodium hypochlorite solid into the water adsorbed in the step (3-3), oxidizing for 2 hours, directly discharging into a biochemical system, and discharging after the biochemical treatment is qualified.
Table 1 shows index values before and after the adsorption treatment of the phenol-making aqueous resin of example 1.
TABLE 1
Figure BDA0002353099200000051
Example 2
The method for recycling the high-concentration phenolic wastewater is used for treating the phenolic wastewater of a certain pesticide factory, and the treatment process is shown in figure 1 and comprises the following steps:
step 1, refining and impurity removal, which is different from the embodiment 1 only in that the flocculation adsorption time is changed from 1 hour to 10 hours, and a water sample is changed from reddish black turbidity to deep yellow transparency after filtration;
step 2, hydrogenation reduction: adding 64kg of 5% palladium carbon catalyst into the filtrate obtained in the step 1, stirring and heating to 120 ℃, introducing hydrogen into the system at the speed of 20L/min, keeping the temperature and introducing the hydrogen for reaction for 9 hours, reducing p-benzoquinone in the wastewater into phenol, and changing the system from a dark yellow transparent solution to a light yellow to colorless solution;
step 3, adsorbing phenol by resin:
(3-1) macroporous adsorption resin pretreatment: soaking and washing 200L of polystyrene nonpolar adsorption resin with 200L of industrial water for 24h to fully swell the resin, and removing organic solvent and inorganic salt in the resin;
(3-2) resin packing: filling the soaked resin into an adsorption column, wherein the ratio of the height of the filled resin to the diameter of the adsorption column is 20:1, removing bubbles in the resin, and discharging industrial water in the adsorption column;
(3-3) adsorbing phenol: injecting 7.8 tons of the faint yellow to colorless solution obtained in the step 2 into the adsorption column at the volume flow rate of 200L/h, collecting 7.7 tons of water (colorless and transparent) after adsorption, tracking and detecting the phenol content until the phenol content is more than 0.5mg/L, stopping adsorption, and at the moment, the phenol content in the adsorption column is saturated;
(3-4) phenol recovery: injecting 600L of methanol aqueous solution (resin regeneration solution) containing 95% of water and 5% of water into the saturated adsorption column at a volume flow rate of 200L/h, distilling the regeneration solution under negative pressure to evaporate 567.7L of methanol, cooling the residual high-concentration phenol solution to 0-5 ℃, filtering and recovering phenol, recycling the mother solution to the next batch, and continuously cooling and recovering phenol.
Step 4, adsorbing effluent treatment: and (4) adding 15.4kg of sodium hypochlorite solid into the water adsorbed in the step (3-3), oxidizing for 2 hours, directly discharging into a biochemical system, and discharging after the biochemical treatment is qualified.
Table 2 shows index values before and after the adsorption treatment of the phenol-making aqueous resin of example 2.
TABLE 2
Figure BDA0002353099200000061
Example 3
The method for recycling the high-concentration phenolic wastewater is used for treating the phenolic wastewater of a certain pesticide factory, and the treatment process is shown in figure 1 and comprises the following steps:
step 1, refining and impurity removal: adjusting the pH value of 8 tons of wastewater to 3 by using 30% mass concentration recovered hydrochloric acid, separating out a large amount of water-insoluble solids from the system, adding 80kg of nonionic polyacrylamide (the mass concentration of the nonionic polyacrylamide is 2 per thousand) based on the mass of the wastewater, 40kg of diatomite powder with the fineness of 300 meshes based on the mass of the wastewater, flocculating and adsorbing for 4 hours, filtering, and changing the red-black turbid water sample into deep yellow transparent water sample after filtering;
step 2, hydrogenation reduction: adding 64kg of 5% palladium carbon catalyst into the filtrate obtained in the step 1, stirring and heating to 70 ℃, introducing hydrogen into the system at the speed of 9L/min, keeping the temperature and introducing the hydrogen for reaction for 4 hours, reducing p-benzoquinone in the wastewater into phenol, and changing the system from a dark yellow transparent solution to a light yellow to colorless solution;
step 3, adsorbing phenol by resin:
(3-1) macroporous adsorption resin pretreatment: soaking and washing 200L of nonpolar adsorption resin of styrene-divinylbenzene system with 200L of industrial water for 24h to fully swell the resin, and removing organic solvent and inorganic salt in the resin;
(3-2) resin packing: filling the resin after being soaked into an adsorption column, wherein the ratio of the height of the filled resin to the diameter of the adsorption column is 6:1, removing air bubbles in the resin, and discharging industrial water in the adsorption column;
(3-3) adsorbing phenol: injecting 7.8 tons of the faint yellow to colorless solution obtained in the step 2 into the adsorption column at the volume flow rate of 1800L/h, collecting 7.7 tons (colorless and transparent) of water after adsorption, tracking and detecting the phenol content until the phenol content is more than 0.5mg/L, stopping adsorption, and at the moment, the phenol content in the adsorption column is saturated;
(3-4) phenol recovery: injecting 600L of 75% methanol aqueous solution (resin regeneration solution) containing 25% water into the saturated adsorption column at a volume flow rate of 1800L/h, distilling the regeneration solution under negative pressure to distill out 443.3L of methanol, cooling the residual high-concentration phenol solution to 0-5 ℃, filtering to recover phenol, recycling the mother solution to the next batch, and continuously cooling to recover phenol.
Step 4, adsorbing effluent treatment: and (4) adding 15.4kg of sodium hypochlorite solid into the water adsorbed in the step (3-3), oxidizing for 2 hours, directly discharging into a biochemical system, and discharging after the biochemical treatment is qualified.
Table 3 shows the index values before and after the adsorption treatment of the phenol-making aqueous resin of example 3.
TABLE 3
Figure BDA0002353099200000071
Example 4
The method for recycling the high-concentration phenolic wastewater is used for treating the phenolic wastewater of a certain pesticide factory, and the treatment process is shown in figure 1 and comprises the following steps:
step 1, refining and impurity removal: adjusting the pH value of 8 tons of wastewater to 3 by using 30% by mass of recovered hydrochloric acid, separating out a large amount of water-insoluble solids from the system, adding 80kg of nonionic polyacrylamide (the mass concentration of the nonionic polyacrylamide is 2 per thousand) and 40kg of diatomite powder with the fineness of 300 meshes into the wastewater, flocculating and adsorbing for 5 hours, filtering, and changing the red-black turbid water sample into deep yellow transparent water sample after filtering;
step 2, hydrogenation reduction: adding 64kg of 5% palladium carbon catalyst into the filtrate obtained in the step 1, stirring and heating to 90 ℃, introducing hydrogen into the system at the speed of 13L/min, keeping the temperature and introducing the hydrogen for reaction for 5 hours, reducing p-benzoquinone in the wastewater into phenol, and changing the system from a dark yellow transparent solution to a light yellow to colorless solution;
step 3, adsorbing phenol by resin:
(3-1) macroporous adsorption resin pretreatment: soaking and washing 200L of nonpolar adsorption resin of styrene-divinylbenzene system with 200L of industrial water for 24h to fully swell the resin, and removing organic solvent and inorganic salt in the resin;
(3-2) resin packing: filling the soaked resin into an adsorption column, wherein the ratio of the height of the filled resin to the diameter of the adsorption column is 10:1, removing bubbles in the resin, and discharging industrial water in the adsorption column;
(3-3) adsorbing phenol: injecting the faint yellow to colorless solution obtained in the step 2 into an adsorption column at the volume flow rate of 1000L/h, collecting 7.8 tons (colorless and transparent) of water after adsorption, tracking and detecting the phenol content until the phenol content is more than 0.5mg/L, stopping adsorption, and at the moment, the phenol content in the adsorption column is saturated;
(3-4) phenol recovery: injecting 600L of 80% aqueous methanol solution (resin regeneration solution) containing 20% water into the saturated adsorption column at a volume flow rate of 1000L/h, distilling the regeneration solution under negative pressure to evaporate 473.8kg of methanol, cooling the residual high-concentration phenol solution to 0-5 ℃, filtering and recovering phenol, mechanically applying mother liquor to the next batch, and continuously cooling and recovering phenol.
Step 4, adsorbing effluent treatment: and (4) adding 15.4kg of sodium hypochlorite solid into the water adsorbed in the step (3-3), oxidizing for 2 hours, directly discharging into a biochemical system, and discharging after the biochemical treatment is qualified.
Table 4 shows the index values before and after the adsorption treatment of the phenol-making aqueous resin of example 4.
TABLE 4
Figure BDA0002353099200000081
Example 5
The method for recycling the high-concentration phenolic wastewater is used for treating the phenolic wastewater of a certain pesticide factory, and the treatment process is shown in figure 1 and comprises the following steps:
step 1, refining and impurity removal: adjusting the pH value of 8 tons of wastewater to 3 by using 30% mass concentration recovered hydrochloric acid, separating out a large amount of water-insoluble solids from the system, adding 80kg of nonionic polyacrylamide (the mass concentration of the nonionic polyacrylamide is 2 per thousand) based on the mass of the wastewater, 40kg of diatomite powder with the fineness of 300 meshes based on the mass of the wastewater, flocculating and adsorbing for 9 hours, filtering, and changing the red-black turbid water sample into deep yellow transparent water sample after filtering;
step 2, hydrogenation reduction: adding 64kg of 5% palladium carbon catalyst into the filtrate obtained in the step 1, stirring and heating to 110 ℃, introducing hydrogen into the system at the speed of 18L/min, keeping the temperature and introducing the hydrogen for reaction for 8 hours, reducing p-benzoquinone in the wastewater into phenol, and changing the system from a dark yellow transparent solution to a light yellow to colorless solution;
step 3, adsorbing phenol by resin:
(3-1) macroporous adsorption resin pretreatment: soaking and washing 200L of nonpolar adsorption resin of styrene-divinylbenzene system with 200L of industrial water for 24h to fully swell the resin, and removing organic solvent and inorganic salt in the resin;
(3-2) resin packing: filling the soaked and washed resin into an adsorption column, wherein the ratio of the height of the filled resin to the diameter of the adsorption column is 14:1, removing bubbles in the resin, and discharging industrial water in the adsorption column;
(3-3) adsorbing phenol: injecting the faint yellow to colorless solution obtained in the step 2 into an adsorption column at the volume flow rate of 800L/h, collecting 7.8 tons (colorless and transparent) of water after adsorption, tracking and detecting the phenol content until the phenol content is more than 0.5mg/L, stopping adsorption, and at the moment, the phenol content in the adsorption column is saturated;
(3-4) phenol recovery: injecting 300L of 85% methanol aqueous solution (resin regeneration solution) containing 15% water into the saturated adsorption column at a volume flow rate of 800L/h, distilling the regeneration solution under negative pressure to distill out 504.9kg of methanol, cooling the residual high-concentration phenol solution to 0-5 ℃, filtering to recover phenol, recycling the mother solution to the next batch, and continuously cooling to recover phenol.
Step 4, adsorbing effluent treatment: and (4) adding 15.4kg of sodium hypochlorite solid into the water adsorbed in the step (3-3), oxidizing for 2 hours, directly discharging into a biochemical system, and discharging after the biochemical treatment is qualified. Table 5 shows the index values before and after the adsorption treatment of the phenol-making aqueous resin of example 5.
TABLE 5
Figure BDA0002353099200000091
In the treatment method, the adsorption time influences the removal efficiency of other impurities except phenolic substances in the phenolic wastewater; the reduction efficiency of the quinone substances is influenced by the hydrogen introduction temperature, the hydrogen introduction rate and the heat preservation time; the ratio of height to diameter of the macroporous adsorption resin and the volume flow rate of adsorption and desorption of the resin influence the recovery efficiency of the phenolic substances; the water content of methanol in the regenerated liquid influences the desorption efficiency of resin and the cooling crystallization efficiency of phenol, and the recovery rate of phenol and the biodegradability of the water after adsorption are comprehensively influenced by the factors. The invention reasonably controls the indexes of the above influencing factors within a reasonable range based on the cost and the treatment period of the wastewater; in addition, the high-diameter ratio of the macroporous adsorption resin directly influences the content of organic matters in the adsorbed effluent, and on the premise of controlling reasonable cost, the high-diameter ratio of resin filling is recommended to be improved as much as possible so as to ensure that the index of the adsorbed effluent is qualified and have better biodegradability.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not restrictive, and various modifications which do not depart from the spirit of the present invention and which are intended to be covered by the claims of the present invention may be made by those skilled in the art.

Claims (9)

1. A resource treatment method of high-concentration phenol-containing wastewater is characterized by comprising the following steps:
step one, refining and impurity removing: regulating the pH value of the wastewater to 1-6 by using recovered hydrochloric acid with the mass concentration of 30%, and separating out a large amount of water-insoluble solids from the system; adding nonionic polyacrylamide accounting for 1% of the mass of the wastewater and diatomite powder with the fineness of 300 meshes accounting for 5 per mill of the mass of the wastewater, wherein the mass concentration of the nonionic polyacrylamide is 2 per mill; filtering after flocculation adsorption for 1-10 hours, and changing the water sample from red black turbidity to deep yellow transparent after filtering;
step two, hydrogenation reduction: adding 5% palladium carbon catalyst according to 0.8 per mill of the mass of the dark yellow transparent solution filtered in the first step, stirring and heating to 70 ℃; introducing hydrogen into the system at the speed of 5-20L/min, and introducing hydrogen for reaction for 2-9 hours at the temperature of 40-120 ℃, so that p-benzoquinone in the wastewater is reduced into phenol, and the system is changed from a dark yellow transparent solution to a light yellow to colorless solution;
step three, resin adsorption, comprising:
step 3-1, macroporous adsorption resin pretreatment: soaking and washing the macroporous adsorption resin for 24 hours by using industrial water according to the volume ratio of 1:1 to fully swell the macroporous adsorption resin, and removing an organic solvent and inorganic salt in the resin;
step 3-2, resin filling: filling the soaked macroporous adsorption resin into an adsorption column, wherein the ratio of the height of the filled resin to the diameter of the adsorption column is 3-20:1, removing bubbles in the resin, and draining industrial water in the adsorption column;
step 3-3, adsorbing phenol: injecting the faint yellow to colorless solution obtained in the step two into an adsorption column at the flow rate which is 1-10 times the volume of the macroporous adsorption resin per hour, collecting the adsorbed colorless transparent liquid, tracking and detecting the phenol content until the phenol content is more than 0.5mg/L, stopping adsorption, and at the moment, the phenol content in the adsorption column is saturated;
step 3-4, phenol recovery: injecting resin regeneration liquid with the volume 3 times that of the macroporous adsorption resin into the adsorption column at the flow rate of 5 times the volume of the macroporous adsorption resin per hour, wherein the resin regeneration liquid is methanol aqueous solution with the volume content of 90% and the water content of 5% -30%, distilling the resin regeneration liquid under negative pressure, evaporating 98% of methanol in the resin regeneration liquid, cooling the residual high-concentration phenol solution to 5 ℃, and filtering and recovering phenol; the mother liquor is recycled to the next batch, and the temperature is continuously reduced to recover the phenol;
step four, adsorbing effluent treatment: and (3) adding 2-5 per mill of sodium hypochlorite solid into the colorless transparent liquid collected and adsorbed in the step (3-3), oxidizing for 2-6 hours, directly discharging into a biochemical system, and discharging after biochemical treatment is qualified.
2. The method for recycling high-concentration phenol-containing wastewater according to claim 1, wherein in the first step, the flocculation adsorption time is 2 hours.
3. The method for recycling high-concentration phenol-containing wastewater according to claim 1, wherein in the second step, the hydrogen introduction temperature is 70 ℃.
4. The method for recycling high-concentration phenol-containing wastewater according to claim 1, wherein in the second step, the hydrogen introduction rate is 10L/min.
5. The method for recycling high-concentration phenol-containing wastewater according to claim 1, wherein in the second step, the reaction time is 3 hours after heat preservation and hydrogen introduction.
6. The resource treatment method of the high-concentration phenol-containing wastewater according to claim 1, characterized in that in step 3-1, the macroporous adsorption resin is one of a styrene-divinylbenzene system nonpolar adsorption resin or a polystyrene type nonpolar adsorption resin.
7. The resource treatment method of the high-concentration phenolic wastewater according to claim 1, characterized in that in step 3-2, the ratio of the height of the resin to the diameter of the adsorption column after the macroporous adsorption resin is filled is 5: 1.
8. The method for recycling high-concentration phenol-containing wastewater according to claim 1, wherein in step 3-3, the volume flow rate of the solution when the resin adsorbs phenol is 5 times the volume of the macroporous adsorption resin per hour.
9. The method for recycling high-concentration phenol-containing wastewater according to claim 1, wherein in step 3 to 4, the aqueous methanol solution of the resin regeneration liquid contains 10% water.
CN201911424002.2A 2019-12-31 2019-12-31 Resourceful treatment method of high-concentration phenol-containing wastewater Pending CN111003904A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1669940A (en) * 2005-02-25 2005-09-21 江苏工业学院 Phenolic waste water treatment method by nitrated macroporous absorption resin
CN102718633A (en) * 2012-02-21 2012-10-10 湖北开元化工科技股份有限公司 Hydroquinone preparation method
CN105417774A (en) * 2015-11-24 2016-03-23 湖北鸿鑫化工有限公司 Recycling method of 2-(4-methyl phenyl)-benzoxazole synthetic process wastewater
CN108793493A (en) * 2018-06-22 2018-11-13 西安蓝深环保科技有限公司 O-aminophenol recovery and treatment method in a kind of strong brine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1669940A (en) * 2005-02-25 2005-09-21 江苏工业学院 Phenolic waste water treatment method by nitrated macroporous absorption resin
CN102718633A (en) * 2012-02-21 2012-10-10 湖北开元化工科技股份有限公司 Hydroquinone preparation method
CN105417774A (en) * 2015-11-24 2016-03-23 湖北鸿鑫化工有限公司 Recycling method of 2-(4-methyl phenyl)-benzoxazole synthetic process wastewater
CN108793493A (en) * 2018-06-22 2018-11-13 西安蓝深环保科技有限公司 O-aminophenol recovery and treatment method in a kind of strong brine

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