CN104961189A - Method for treating chlorophenol-containing wastewater - Google Patents

Abstract

The invention discloses a method for treating chlorophenol-containing wastewater. The method comprises the following steps of (1) preparing a treatment agent which is 1.0CEC-DTAB-Mt and 0.1CEC-CTAB-Mt; (2) adjusting the pH value of the chlorophenol-containing wastewater to be 3-12, and then adding the treatment agent prepared in the step (1) into the wastewater according to the feeding amount of 1.0g/L-8.0g/L; (3) stirring the chlorophenol-containing wastewater at the stirring rate of 100-150r/min for 5 minutes to 6 hours, and then performing centrifugal settlement for 10-15 minutes; (4) discharging the wastewater after the wastewater meets the standard. According to the method, the treatment agent is prepared from Mt rich in ore resource and low in cost and cationic surface active agents DTAB and CTAB, and meanwhile, the required treatment conditions are simple, so that extremely high applicability to different hydraulic conditions is realized; the removal efficiency for treating the chlorophenol-containing wastewater is high, and pollution to the natural water body and underground water is alleviated.

Description

A kind of method processing chlorophenol-containing wastewater

Technical field

The present invention relates to a kind of method for the treatment of chlorophenol-containing wastewater, belong to technical field of sewage.

Background technology

Chlorobenzene phenol organic compound common are organic pollutants in soil and groundwater, is mainly derived from oil refining, coking, papermaking, the industry such as plastics and printing and dyeing.Meanwhile, chlorophenol is also frequent is widely used in wood preservation as organic solvent and produces the fields such as rust-preventive agent, sterilant, Insecticides (tech) & Herbicides (tech), paint and coating.In the production of chlorophenol, storage, transport and application process, some chlorobenzene phenol is inevitably discharged in physical environment, causes serious water pollution, its significant toxicity and be difficult to degradation property and constitute serious threat to human health and ecotope.Chlorophenol type organic has stronger Denaturation to biological tissue, particularly comparatively large to the hydrobiological toxicity such as fish, shellfish, once contact contaminated water body, and meeting intense stimulus skin and mucous membrane, and there is corrodibility.Chlorophenol type organic also may with the cell in blood, and functional protein etc. are had an effect, and cause lung, liver, kidney and nervous system injury.Therefore, chlorobenzene phenols organic pollutant becomes the pollutent of a more concerned class priority acccess control.2-chlorophenol (2-CP) is all included in the pollutent list that in 129 kinds of Environmental protection administration regulation and 68 of Environmental Protection in China portion regulation, Environment Priority controls; 4-chlorophenol (4-CP) and 2; the chlorobenzene aldehydes matters such as 4-chlorophenesic acid (2,4-DCP).Generally speaking, the toxicity of chlorophenol type organic increases along with the increase of chloro degree.Chloro degree is higher, and the lipotropy (lipophilicity) of chlorophenol type organic is larger, and the possibility absorbed by organism is larger, and toxicity is also larger.Due to decompose and biological degradability all very low, chlorophenol type organic residual in environment can existence steady in a long-term, and in the water body of oxygen abundance, the transformation period can reach some months, can reach several years even more than ten years in soil and throw out.Therefore, the trade effluent of chlorinated phenol, before discharge enters municipal sewage plant and reclaims water body, must be removed chlorophenol type organic from water body.4-CP and 2,4-DCP is typical chlorophenol type organic pollutent.

When purifying treatment chlorobenzene phenols organic pollutant, main treatment process has absorption method, chemical oxidization method, Coagulation Method, extraction process, photochemical oxidation method, hydrogenolysis techniques etc.The technical problems such as in these methods, the technology ubiquity removal efficiency of process chlorophenol-containing wastewater is low, and the high and treatment cycle of cost is long.And absorption method is considered to most economical, the most effective, operation is the easiest, the method for the most applicable industrial flow operation.In order to solve problems, people are devoted to develop various efficient, cheap water treatment absorbent always for many years.Meanwhile, the actual process parameter of chlorophenol-containing wastewater seldom has systematic research.Therefore, study a kind of technological method that can be used in chlorophenol-containing wastewater process, processing parameter complete and there is important practical significance.Surfactant-modified polynite to be always used in organic drilling mud and to strengthen crude oil production efficiency, but surfactant-modified polynite always all not by the sorbent material as organic pollutant, is applied to sewage treatment area.

Summary of the invention

The present invention is directed to the shortcoming and defect that existing chlorophenol wastewater treatment exists, provide a kind of method of high-level efficiency, economic process chlorophenol-containing wastewater.

The method of process chlorophenol-containing wastewater of the present invention, comprises the following steps:

(1) preparation for the treatment of agent:

1. according to the ratio of 1g:4mL, polynite (Mt) is dispersed in water with ethanol contend than in the mixing solutions of 1:1, stirs 25-35 minute with the rotating speed of 100-150 rev/min, become polynite dispersion system;

2. according to the ratio of 0.25g:1mL, Trimethyllaurylammonium bromide (DTAB) is dissolved in distilled water; Stir 25-35 minute with the rotating speed of 100-150 rev/min, make the first cationic surfactant solution; Or according to the ratio of 0.31g:1mL, cetyl trimethylammonium bromide (CTAB) is dissolved in distilled water, stirs 25-35 minute with the rotating speed of 100-150 rev/min, make the second cationic surfactant solution;

3. according to 1.0 cation exchange capacities (CEC) step 2. in the first or the second cationic surfactant solution join step 1. in polynite dispersion system in; At the temperature of 50-60 DEG C, with the rotating speed Keep agitation 4-6 hour of 100-150 rev/min, make mixed system;

4. to mixed system repeatedly with distilled water cleaning and centrifugal, unnecessary cats product (DTAB or CTAB) is washed away, until in the supernatant liquid of mixed system without bromide anion existence (pass through AgNO ₃detection method detects), then at 65 DEG C to mixed system dry 12 hours, make treatment agent 1.0CEC-DTAB-Mt or 1.0CEC-CTAB-Mt;

(2) water-quality test is carried out to waste water, test index is pH value, containing 4-CP and 2, the concentration of 4-DCP, if pH value is not between 3-12, be then 3-12 by pH adjusting agent adjust ph, then in waste water, prepared by step (1) treatment agent is added according to the dosage of 1.0g/L-8.0g/L according to containing the concentration of 4-CP and 2,4-DCP;

Adopt Ultraviolet spectrophotometry, measure the concentration of 4-CP and 2,4-DCP at 279nm and 286nm wavelength place respectively; When pH value is greater than 8, measure the concentration of 4-CP and 2,4-DCP at 297nm and 305nm place, because when pH value is greater than 8, the maximum absorption wavelength of 4-CP and 2,4-DCP can slide into 297nm and 305nm.

PH adjusting agent is the one in hydrochloric acid, sodium hydroxide, calcium hydroxide, ammoniacal liquor.

(3) stir chlorophenol-containing wastewater when treatment agent adds, stirring velocity 100-150 rev/min, churning time is 5 minutes-6 hours, then centrifugal settling 10-15 minute;

(4) throw out after collecting by filtration step (3) centrifugal settling; Waste water after process is carried out to the mensuration of remaining 4-CP and 2,4-DCP concentration, rear discharge up to standard, otherwise adjustment treatment agent dosage is until up to standard.

In step (2) in waste water during dosage treatment agent the temperature of waste water be 293K-313K.Reduce the removal that temperature contributes to 4-CP and 2,4-DCP.

For chlorophenol-containing wastewater, stirring is an important influence factor.Select the stirring velocity that suitable, be both conducive to mixing of medicament, the formation of flco, and probability of collision between clay particle and organic pollutant can have been increased again, and be conducive to the absorption for the treatment of agent to pollutent.The length of adsorption time directly affects the pollutant load in water outlet, and shorter deficiency of time is to remove pollutent, but adsorption time is long, and technical process and facility are difficult to accept.Secondly, the pH value of water body, temperature are also one of important factors affecting water pollutant removal.

The present invention adopts Trimethyllaurylammonium bromide (DTAB) and cetyl trimethylammonium bromide (CTAB) as surface-modifying agent, carries out hydrophobically modified to polynite (Mt) particle surface.Through modified, Mt particle surface changes hydrophobicity into by wetting ability, enhance the hydrophobic interaction for the treatment of agent to chlorophenol type organic in water body, and enhance the distributional effects of chlorophenol type organic on the Mt of modification, thus substantially increase the adsorptive power for the treatment of agent to 4-CP and 2,4-DCP.

The present invention adopts mining deposits to enrich, and cheap Mt and cats product DTAB and CTAB has prepared two kinds for the treatment of agents, and required treatment condition are simple, have good adaptability to different hydraulics.Process removal efficiency for chlorophenol-containing wastewater is high, decreases the pollution to natural water body and underground water.

Accompanying drawing explanation

Fig. 1 is the schematic diagram that in embodiment 1,4-CP and 2,4-DCP clearance change with pH value.

Fig. 2 is the schematic diagram that the Zeta electric potential of two kinds for the treatment of agent 1.0CEC-DTAB-Mt and 1.0CEC-CTAB-Mt in embodiment 1 changes with pH value.

Fig. 3 is the scanning transmission electron microscope photo of the sediment composite that in embodiment 1, two kinds for the treatment of agent 1.0CEC-DTAB-Mt and 1.0CEC-CTAB-Mt are formed after adsorption process with 4-CP and 2,4-DCP respectively.Wherein, (a) is 1.0CEC-DTAB-Mt-4-CP, and (b) is 1.0CEC-DTAB-Mt-2,4-DCP, and (c) is 1.0CEC-CTAB-Mt-4-CP, and (d) is 1.0CEC-CTAB-Mt-2,4-DCP.

Fig. 4 is the schematic diagram that the clearance of 4-CP and 2,4-DCP in embodiment 2 changes with two kinds for the treatment of agent dosages.

Fig. 5 is the schematic diagram that the clearance of 4-CP and 2,4-DCP in embodiment 3 changed with duration of contact.

Fig. 6 is that in embodiment 4,4-CP adsorbs the rear temperature variant schematic diagram of clearance on 1.0CEC-DTAB-Mt and 1.0CEC-CTAB-Mt.

Fig. 7 be in embodiment 42,4-DCP on 1.0CEC-DTAB-Mt and 1.0CEC-CTAB-Mt absorption after the temperature variant schematic diagram of clearance.

Embodiment

First the present invention prepares two kinds for the treatment of agents by following process:

1. according to the ratio of 1g:4mL, polynite (Mt) is dispersed in water with ethanol contend than in the mixing solutions of 1:1, magnetic stirring apparatus stirs 25-35 minute with the rotating speed of 100-150 rev/min, becomes polynite dispersion system;

2. according to the ratio of 0.25g:1mL, Trimethyllaurylammonium bromide (DTAB) is dissolved in distilled water; Magnetic stirring apparatus stirs 25-35 minute with the rotating speed of 100-150 rev/min, makes the first cationic surfactant solution;

3. according to 1.0 cation exchange capacities (CEC) step 2. in cationic surfactant solution join step 1. in polynite dispersion system in; At the temperature of 50-60 DEG C, with the rotating speed Keep agitation 4-6 hour of 100-150 rev/min, make mixed system;

4. to mixed system repeatedly with distilled water cleaning and centrifugal, unnecessary cats product (DTAB) is washed away, until in the supernatant liquid of mixed system without bromide anion existence (AgNO ₃detection method), then at 65 DEG C to mixed system dry 12 hours, make the first treatment agent 1.0CEC-DTAB-Mt;

5. according to the ratio of 0.31g:1mL, cetyl trimethylammonium bromide (CTAB) is dissolved in distilled water, stirs 25-35 minute with the rotating speed of 100-150 rev/min, make the second cationic surfactant solution;

6. according to step, process 3., 4. and 5. prepares the second treatment agent 1.0CEC-CTAB-Mt.

Embodiment 1

Get the waste water two groups containing 4-CP, often organize 10 parts, adopt pH adjusting agent (hydrochloric acid, sodium hydroxide, calcium hydroxide or ammoniacal liquor) that the pH value of 10 parts of waste water in every group is adjusted to 3.0,4.0,5.0,6.0,7.0,8.0,9.0,10.0,11.0 and 12.0 respectively.Get the waste water two groups containing 2,4-DCP, often organize 10 parts, the pH value of 10 parts of waste water in every group is adjusted to 3.0,4.0,5.0,6.0,7.0,8.0,9.0,10.0,11.0 and 12.0 respectively.40 parts of waste water are 1000mL, and the starting point concentration of pollutent 4-CP and 2,4-DCP is 50mg/L, and temperature controls at 293K.All add the first treatment agent of 6.0g 1.0CEC-DTAB-Mt to first group of each part containing in the waste water of 4-CP, all add 6.0g the second treatment agent 1.0CEC-CTAB-Mt to second group of each part containing in the waste water of 4-CP.Add the first treatment agent to first group containing in each part waste water of 2,4-DCP by said process and content, add the second treatment agent to second group containing in each part waste water of 2,4-DCP.

The each part waste water adding treatment agent is maintained stirring velocity 100-150 rev/min, stirs 6 hours, then centrifugal settling 10-15 minute, collect supernatant liquid, carry out water quality analysis.Under each pH value, the removal efficiency of pollutent 4-CP and 2,4-DCP as shown in Figure 1.

Result of implementation shows, pH=6 is Optimal pH condition.For 4-CP and 2,4-DCP, when pH value is greater than 7 and 10 respectively, their removal efficiency can obviously decline.In addition, the removal efficiency of 2,4-DCP is always apparently higher than the removal efficiency of 4-CP.Determine when pH=6,1.0CEC-CTAB-Mt can reach 91.4% and 96.6% respectively to the removal efficiency of 4-CP and 2,4-DCP; The clearance of 1.0CEC-DTAB-Mt to 4-CP and 2,4-DCP is respectively 55.9% and 94.1%.For treatment agent under different pH value, clay particle surface presents different electric density, therefore, within the scope of pH=3.0-12.0, is studied the Zeta electric potential of 1.0CEC-DTAB-Mt and 1.0CEC-CTAB-Mt.Result of implementation as shown in Figure 2, under pH=6.0 condition, 1.0CEC-DTAB-Mt and 1.0CEC-CTAB-Mt is with positive charge, and particularly 1.0CEC-CTAB-Mt particle surface is with very high positive charge density, and the pollutent for negative charge has very strong electrostatic attraction effect.After adsorption treatment, treatment agent and pollutent define sediment composite as shown in Figure 3, and from pattern and structure, the reactive force between 1.0CEC-DTAB-Mt and 1.0CEC-CTAB-Mt and pollutent is very strong.

Embodiment 2

Get the waste water two groups containing 4-CP, often organize some parts (at least 8 parts).Get the waste water two groups containing 2,4-DCP, often organize some parts (at least 8 parts).Every part of waste water is 1000mL, and pH value is all adjusted to 6.0, and the starting point concentration of pollutent 4-CP and 2,4-DCP is 50mg/L, and temperature controls at 293K.Drop into the first treatment agent 1.0CEC-DTAB-Mt to first group of each part containing in the waste water of 4-CP, the dosage in every part increases progressively within the scope of 1.0g-8.0g; Add the second treatment agent 1.0CEC-CTAB-Mt to second group of each part containing in the waste water of 4-CP, the dosage in every part increases progressively within the scope of 1.0g-8.0g.Add the first treatment agent to first group containing in each part waste water of 2,4-DCP by said process and content, add the second treatment agent to second group containing in each part waste water of 2,4-DCP.

The each part waste water adding treatment agent is maintained mixing speed 100-150 rev/min, churning time 6 hours, then centrifugal settling 10-15 minute, collects supernatant liquid, carry out water quality analysis.Reach 8.0g/L place at the dosage of 1.0CEC-DTAB-Mt and 1.0CEC-CTAB-Mt, the clearance of 2,4-DCP can reach 93.5% and 96.6% respectively; And the clearance of 4-CP can reach 55.9% and 92.3% respectively, as shown in Figure 4.

Embodiment 3

Get the waste water two groups containing 4-CP, often organize some parts (at least 7 parts).Get the waste water two groups containing 2,4-DCP, often organize some parts (at least 7 parts).Every part of waste water is 1000mL, and pH value is all adjusted to 6.0, and the starting point concentration of pollutent 4-CP and 2,4-DCP is 50mg/L, and temperature controls at 293K.Drop into the first treatment agent 1.0CEC-DTAB-Mt to first group of each part containing in the waste water of 4-CP, the dosage in every part is 6.0g; Add the second treatment agent 1.0CEC-CTAB-Mt to second group of each part containing in the waste water of 4-CP, the dosage in every part is 6.0g.Add the first treatment agent to first group containing in each part waste water of 2,4-DCP by said process and content, add the second treatment agent to second group containing in each part waste water of 2,4-DCP.

By when adding each part waste water maintenance stirring velocity 100-150 rev/min after treatment agent, duration of contact was selected in-6 hours window at 5 minutes respectively, then centrifugal settling 10-15 minute, collect supernatant liquid, carry out water quality analysis, when determining to reach 180 minutes duration of contact, absorption reaches equilibrium state substantially, and the result of the present embodiment as shown in Figure 5.

Embodiment 4

Get the waste water two groups containing 4-CP, often organize 3 parts, often in group, the temperature of 3 parts of waste water is respectively 293K, 303K and 313K.Get the waste water two groups containing 2,4-DCP, often organize 3 parts, often in group, the temperature of 3 parts of waste water is respectively 293K, 303K and 313K.Every part of waste water is 1000mL, and pH value is all adjusted to 6.0, and the starting point concentration of pollutent 4-CP and 2,4-DCP is 50mg/L.Drop into the first treatment agent 1.0CEC-DTAB-Mt to first group 3 parts containing in the waste water of 4-CP, the dosage in every part is 6.0g; Add the second treatment agent 1.0CEC-CTAB-Mt to second group of each part containing in the waste water of 4-CP, the dosage in every part is 6.0g.Add the first treatment agent to first group containing in each part waste water of 2,4-DCP by said process and content, add the second treatment agent to second group containing in each part waste water of 2,4-DCP.

Stirring velocity 100-150 rev/min is maintained by adding each part waste water after treatment agent, churning time 6 hours, then centrifugal settling 10-15 minute, collect supernatant liquid, carry out water quality analysis, determine that the process of adsorbing 4-CP and 2,4-DCP from water body is thermopositive reaction, reduce the removal that temperature contributes to 4-CP and 2,4-DCP.The result of the present embodiment as shown in Figure 6 and Figure 7.

Claims (2)

1. process a method for chlorophenol-containing wastewater, it is characterized in that, comprise the following steps:

(1) preparation for the treatment of agent:

1. according to the ratio of 1g:4mL, polynite is dispersed in water with ethanol contend than in the mixing solutions of 1:1, stirs 25-35 minute with the rotating speed of 100-150 rev/min, become polynite dispersion system;

2. according to the ratio of 0.25g:1mL, Trimethyllaurylammonium bromide is dissolved in distilled water; Stir 25-35 minute with the rotating speed of 100-150 rev/min, make the first cationic surfactant solution; Or according to the ratio of 0.31g:1mL, cetyl trimethylammonium bromide is dissolved in distilled water, stirs 25-35 minute with the rotating speed of 100-150 rev/min, make the second cationic surfactant solution;

3. according to 1.0 cation exchange capacities (CEC) step 2. in the first or the second cationic surfactant solution join step 1. in polynite dispersion system in; At the temperature of 50-60 DEG C, with the rotating speed Keep agitation 4-6 hour of 100-150 rev/min, make mixed system;

4. to mixed system repeatedly with distilled water cleaning and centrifugal, unnecessary cats product (DTAB or CTAB) is washed away, until exist without bromide anion in the supernatant liquid of mixed system, then at 65 DEG C to mixed system dry 12 hours, treatment agent 1.0CEC-DTAB-Mt or 1.0CEC-CTAB-Mt is made;

(2) water-quality test is carried out to waste water, test index is pH value, containing 4-CP and 2, the concentration of 4-DCP, if pH value is not between 3-12, then adjust ph is 3-12, then in waste water, prepared by step (1) treatment agent is added according to the dosage of 1.0g/L-8.0g/L according to containing the concentration of 4-CP and 2,4-DCP;

(3) stir chlorophenol-containing wastewater when treatment agent adds, stirring velocity 100-150 rev/min, churning time is 5 minutes-6 hours, then centrifugal settling 10-15 minute;

(4) throw out after collecting by filtration step (3) centrifugal settling; Waste water after process is carried out to the mensuration of remaining 4-CP and 2,4-DCP concentration, rear discharge up to standard, otherwise adjustment treatment agent dosage is until up to standard.

2. the method for process chlorophenol-containing wastewater according to claim 1, is characterized in that, in described step (2) in waste water during dosage treatment agent the temperature of waste water be 293K-313K.