CN106007054A - Method for treating aluminum diethyl phosphinate wastewater. - Google Patents
Method for treating aluminum diethyl phosphinate wastewater. Download PDFInfo
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- CN106007054A CN106007054A CN201610356821.8A CN201610356821A CN106007054A CN 106007054 A CN106007054 A CN 106007054A CN 201610356821 A CN201610356821 A CN 201610356821A CN 106007054 A CN106007054 A CN 106007054A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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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
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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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
The invention belongs to the technical field of wastewater treatment, in particular to a method for treating aluminum diethyl phosphinate wastewater. The method provided by the invention comprises the following steps: a) carrying out a heating reaction between the aluminum diethyl phosphinate wastewater and oxidants in the presence of an activated carbon supported metal catalyst to obtain oxidized wastewater, wherein the oxidants comprise hydrogen peroxide and sodium persulfate, and iron element and copper element are supported on the carrier activated carbon of the activated carbon supported metal catalyst; b) mixing the oxidized wastewater with a dephosphorizing precipitant to obtain treated wastewater. The method has the advantages that valence variation of iron and copper supported on the catalyst is fully utilized to catalyze hydrogen peroxide to generate OH<-> and activate sodium persulfate to generate SO<4->., and the two radicals are coupled mutually to oxidize aluminum diethyl phosphinate and degradation products thereof, so that aluminum diethyl phosphinate in the aluminum diethyl phosphinate wastewater is degraded effectively, and phosphorus in the aluminum diethyl phosphinate wastewater is further removed efficiently.
Description
Technical field
The invention belongs to field of waste water treatment, particularly relate to the process side of a kind of aluminum diethylphosphinate waste water
Method.
Background technology
In recent years, alkyl phosphinate fire retardant has become the resistance of phosphorus system as the research of environment-friendly flame retardant agent
One of focus of combustion agent industry development research, aluminum diethylphosphinate [(C2H5C2H5P(O)O)3Al] there is grain
The advantages such as footpath is little, and whiteness is high, Heat stability is good, nontoxic, are widely used in thermoplastic, thermosetting
Fire-retardant, main in the aluminum diethylphosphinate molecular structure chemistry of the products such as plastics, fiber and textile
Key is P-C, P=O, P-O, itself has higher phosphorus content.
During the production and use of aluminum diethylphosphinate, can produce a large amount of containing diethyl phosphinic acid
The waste water of aluminum, owing to the phosphorus in waste water exists with organophosphor form, it is difficult to directly utilized by biology, directly
Biosystem can be caused in bioreactor to collapse, so dephosphorization must be carried out before row outside this waste water
Process.
The dephosphorization treatment of aluminum diethylphosphinate waste water generally includes two steps, first to two in waste water
Ethylphosphinic acid aluminum is degraded, and makes the organophosphor in aluminum diethylphosphinate be converted to Phos；Then
In waste water, add dephosphorization precipitant again, make Phos generate precipitation, thus realize phosphorus taking off from waste water
Remove.But owing to aluminum diethylphosphinate chemical property is highly stable, even if boil at nitric acid and high fluoric acid
Under the conditions of Strong oxdiative, degradation rate is the lowest.The most how to improve the fall of aluminum diethylphosphinate in waste water
Solution rate, thus effectively reduce the phosphorus content in aluminum diethylphosphinate waste water and become current waste water process neck
The important topic in territory.
Summary of the invention
In view of this, it is an object of the invention to provide the processing method of a kind of aluminum diethylphosphinate waste water,
The method that the present invention provides can effectively reduce the phosphorus content in aluminum diethylphosphinate waste water.
The invention provides the processing method of a kind of aluminum diethylphosphinate waste water, comprise the following steps:
A), aluminum diethylphosphinate waste water and oxidant add in the presence of activated carbon supported type metallic catalyst
Thermal response, obtains oxidized waste water；
Described oxidant includes hydrogen peroxide and sodium peroxydisulfate；Described activated carbon supported type metallic catalyst
Ferrum element and copper it is loaded with on carrier active carbon；
B), described oxidized waste water react with dephosphorization precipitant mix, obtain processed waste water.
Preferably, in step a), the mode of described heating is microwave exposure.
Preferably, in step a), the temperature of described reacting by heating is 70～90 DEG C；Described reacting by heating
Time is 20～80min.
Preferably, in step a), described aluminum diethylphosphinate waste water, hydrogen peroxide and sodium peroxydisulfate
Mass ratio is: 100:(3～6): (1～5).
Preferably, in step a), the carrier active carbon of described activated carbon supported type metallic catalyst loads
There is Fe2+、Fe3+And Cu2+。
Preferably, described step a) specifically includes:
A1), aluminum diethylphosphinate waste water and hydrogen peroxide exist at activated carbon supported type metallic catalyst
Lower reacting by heating, obtains reactant liquor；
A2), by described reactant liquor and sodium peroxydisulfate reacting by heating, oxidized waste water is obtained.
Preferably, in step b), described dephosphorization precipitant is Cabase compound.
Preferably, in step b), after described oxidized waste water reacts with dephosphorization precipitant mix, then with flocculation
Agent mixes, and obtains processed waste water.
Preferably, in step a), described activated carbon supported type metallic catalyst follows the steps below system
Standby:
After being impregnated in ferrum copper mixed solution by activated carbon, carry out roasting, obtain activated carbon supported type metal
Catalyst；Containing ferrum element and copper in described ferrum copper mixed solution.
Preferably, the total phosphorus content in described aluminum diethylphosphinate waste water is 400～800mg/L.
Compared with prior art, the invention provides the processing method of a kind of aluminum diethylphosphinate waste water.
The method that the present invention provides comprises the following steps: a), aluminum diethylphosphinate waste water and oxidant be in activity
Reacting by heating in the presence of carbon-supported metal catalyst, obtains oxidized waste water；Described oxidant includes peroxide
Change hydrogen and sodium peroxydisulfate；Ferrum unit it is loaded with on the carrier active carbon of described activated carbon supported type metallic catalyst
Element and copper；B), described oxidized waste water react with dephosphorization precipitant mix, obtain processed waste water.
The inventive method makes full use of on catalyst the ferrum of load, copper variation of valence, catalyzing hydrogen peroxide produce OH-,
Activation sodium peroxydisulfate produces SO4 -·, two kinds of free radicals intercouple and aoxidize diethyl hypo-aluminum orthophosphate and degraded thereof
Product, thus the aluminum diethylphosphinate in effective degrading waste water, and then realize aluminum diethylphosphinate
The efficient removing of Phosphorus From Wastewater.Test result indicate that, the method using the present invention to provide processes diethyl
During phosphonic acids aluminum waste water, the organophosphor clearance in waste water is up to 80%.
Detailed description of the invention
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that institute
The embodiment described is only a part of embodiment of the present invention rather than whole embodiments.Based on this
Embodiment in bright, those of ordinary skill in the art are obtained under not making creative work premise
Every other embodiment, broadly falls into the scope of protection of the invention.
The invention provides the processing method of a kind of aluminum diethylphosphinate waste water, comprise the following steps:
A), aluminum diethylphosphinate waste water and oxidant add in the presence of activated carbon supported type metallic catalyst
Thermal response, obtains oxidized waste water；
Described oxidant includes hydrogen peroxide and sodium peroxydisulfate；Described activated carbon supported type metallic catalyst
Ferrum element and copper it is loaded with on carrier active carbon；
B), described oxidized waste water react with dephosphorization precipitant mix, obtain processed waste water.
In the method that the present invention provides, first by aluminum diethylphosphinate waste water and oxidant at activated carbon
Reacting by heating in the presence of load type metal catalyst.Wherein, described aluminum diethylphosphinate waste water refers to two
Producing of ethylphosphinic acid aluminum produces the waste water containing aluminum diethylphosphinate during using.At this
In one embodiment of bright offer, the COD of described aluminum diethylphosphinate waste water is 4000～5000mg/L；
In another embodiment that the present invention provides, the COD of described aluminum diethylphosphinate waste water is
4229～4872mg/L.In the embodiment that the present invention provides, described aluminum diethylphosphinate waste water
TOC is 1000～1500mg/L；In another embodiment that the present invention provides, described diethyl phosphinic acid
The TOC of aluminum waste water is 1013～1315mg/L.In the embodiment that the present invention provides, described diethyl
The organic phosphorous content of phosphinic acid aluminum waste water is 400～800mg/L；In another embodiment that the present invention provides
In, the organophosphor of described aluminum diethylphosphinate waste water is 500～750mg/L；The present invention provide other
In embodiment, the organophosphor of described aluminum diethylphosphinate waste water be 562.5mg/L, 632.42mg/L or
720.83mg/L.In the embodiment that the present invention provides, in described aluminum diethylphosphinate waste water
Organophosphor is all from aluminum diethylphosphinate, say, that in described aluminum diethylphosphinate waste water
The all aluminum diethylphosphinate of organic phosphates pollutant.
In the present invention, described oxidant includes hydrogen peroxide and sodium peroxydisulfate.In the present invention, described
The mass ratio of aluminum diethylphosphinate waste water, hydrogen peroxide and sodium peroxydisulfate is preferably: 100:(3～6):
(1～5), more preferably 100:(3.6～5.4): (2～4).In the embodiment that the present invention provides
In, during aluminum diethylphosphinate waste water and oxidant reacting by heating, the peroxidating in oxidant
Hydrogen adds reaction system, as a example by the hydrogen peroxide of concentration 30wt%, diethyl phosphinic acid with the form of hydrogen peroxide
Aluminum waste water is preferably 100:(10～20 with the volume ratio of hydrogen peroxide), more preferably 100:(12～16).
In the present invention, the carrier active carbon of described activated carbon supported type metallic catalyst is loaded with ferrum unit
Element and copper, be preferably loaded with Fe2+、Fe3+And Cu2+.In the present invention, described diethyl phosphinic acid
The mass ratio of aluminum waste water and activated carbon supported type metallic catalyst is preferably 100mL:(1～5) g, more excellent
Elect 100mL:(2～4 as) g.The source of described activated carbon supported type metallic catalyst is not had by the present invention
It is particularly limited to, commercial goods can be used, it is also possible to prepare according to technique well known to those skilled in the art
Obtain, it is also possible to be prepared in accordance with the following methods:
After being impregnated in ferrum copper mixed solution by activated carbon, carry out roasting, obtain activated carbon supported type metal
Catalyst；Containing ferrum element and copper in described ferrum copper mixed solution.
In the preparation method of the above-mentioned activated carbon supported type metallic catalyst of present invention offer, first will live
Property charcoal is immersed in ferrum copper mixed solution.Wherein, the mesh number of described activated carbon is preferably 20～50 mesh.Described
Containing ferrum element and copper in ferrum copper mixed solution, preferably comprise Fe2+、Fe3+And Cu2+.In the present invention
In the embodiment provided, content F e in described ferrum copper mixed solution2+Preferably 2～4wt%, more excellent
Elect 2.46～3.68wt% as.Most preferably 2.46wt%, 3.07wt% or 3.68wt%.There is provided in the present invention
Content F e in one embodiment, in described ferrum copper mixed solution3+It is preferably 1～4wt%, more preferably
1.73～3.46wt%, most preferably 1.73wt%, 2.3wt% or 3.46wt%.One provided in the present invention
Content Cu in embodiment, in described ferrum copper mixed solution2+It is preferably 0.5～1.5wt%, more preferably
0.67～1.33wt%, most preferably 0.67wt%, 0.8wt%, 1.07wt% or 1.33wt%.In the present invention,
The amount ratio of described activated carbon and ferrum copper mixed solution is preferably 1g:(15～20) mL.In the present invention,
The time that described activated carbon impregnates in ferrum copper mixed solution is preferably 4～8h；The temperature of described dipping is preferred
It it is 80～100 DEG C.In the present invention, activated carbon was preferably first carried out before impregnating；Described clearly
The mode washed is preferably described activated carbon and sequentially passes through pickling and washing；The pickle that described pickling uses is excellent
Elect nitric acid as；The concentration of described nitric acid is preferably 0.1～0.5mol/L；The time of described pickling is preferably
24～48h.In the present invention, after dipping terminates, take out the activated carbon after dipping and carry out roasting.At this
In bright, described roasting is preferably carried out in the presence of protective gas, and described protective gas is preferably nitrogen or dilute
There is rare earth.In the present invention, the temperature of most roastings is preferably 250～400 DEG C；The time of described roasting is excellent
Elect 2～4h as.After roasting terminates, obtain activated carbon supported type metallic catalyst.
In the present invention, described aluminum diethylphosphinate waste water and oxidant are urged at activated carbon supported type metal
In the presence of agent, the temperature of reacting by heating is preferably 70～90 DEG C；The time of described reacting by heating is preferably
20～80min.In the present invention, the mode of described heating is preferably microwave exposure.After reacting by heating terminates,
Obtain oxidized waste water.In the present invention, the phosphorus in described oxidized waste water is many exists with Phos form.
In the embodiment that the present invention provides, described aluminum diethylphosphinate waste water and oxidant heating
Reaction obtains the detailed process of oxidized waste water and includes:
A1), aluminum diethylphosphinate waste water and hydrogen peroxide exist at activated carbon supported type metallic catalyst
Lower reacting by heating, obtains reactant liquor；
A2), by described reactant liquor and sodium peroxydisulfate reacting by heating, oxidized waste water is obtained.
In the embodiment of the above-mentioned acquisition oxidized waste water of present invention offer, first by aluminum diethylphosphinate
Waste water and hydrogen peroxide reacting by heating in the presence of activated carbon supported type metallic catalyst.Wherein, described mistake
Hydrogen oxide preferably adds reaction system with the form of hydrogen peroxide；The temperature of described reacting by heating is preferably
70～90 DEG C；The time of described reacting by heating is preferably 20～40min；The mode of described heating is preferably microwave
Irradiation.After reacting by heating terminates, obtain reactant liquor.Then by anti-with sodium peroxydisulfate heating for described reactant liquor
Should.Wherein, the temperature of described reacting by heating is preferably 70～90 DEG C；The time of described reacting by heating is preferably
10～30min；The mode of described heating is preferably microwave exposure.After reaction terminates, obtain oxidized waste water.
In the present invention, after obtaining oxidized waste water, described oxidized waste water reacts with dephosphorization precipitant mix.
Wherein, described dephosphorization precipitant is preferably Cabase compound, more preferably CaO, CaCl2With Ca (OH)2
In one or more.Described dephosphorization precipitant and the raw material preparing oxidized waste water, i.e. diethyl phosphinic acid
The amount ratio of aluminum waste water is preferably (0.4～1): 100.The temperature of described hybrid reaction is preferably room temperature；Institute
The time stating hybrid reaction is preferably 15～20min.In the present invention, described hybrid reaction is preferably in stirring
Under the conditions of carry out, the speed of described stirring is preferably 300～400rpm, more preferably 320～350rpm.Mixed
Close dephosphorization precipitant in course of reaction and generate precipitation with the Phos in oxidized waste water, after hybrid reaction terminates,
Filter precipitation, obtain processed waste water.In the present invention, for ease of filtering of precipitation, described oxidation is given up
Water mixes with flocculant after reacting with dephosphorization precipitant mix the most again.Wherein, described flocculant is preferably
Polyacrylamide and/or aluminium polychlorid；The time mixed with flocculant is preferably 5～15min.In the present invention
In, mixing with flocculant and carry out the most under agitation, the speed of described stirring is preferably
150～650rpm, more preferably 200～640rpm.The present invention provide an embodiment in, with wadding
During solidifying agent mixing, first stir 2～5min with the speed of 610～640rpm, then with 200～240rpm
Speed stirring 5～10min.With in flocculant mixed process, the flocculate being precipitated, filter flocculate,
Obtain processed waste water.
The inventive method makes full use of the ferrum of load, copper variation of valence on catalyst, and catalyzing hydrogen peroxide produces
Raw OH-, activation sodium peroxydisulfate produce SO4 -·, two kinds of free radicals intercouple and aoxidize diethyl hypo-aluminum orthophosphate
And catabolite, thus the aluminum diethylphosphinate in effective degrading waste water, and then realize diethyl
The efficient removing of phosphinic acid aluminum Phosphorus From Wastewater.
In the preferred implementation that the present invention provides, in the way of microwave exposure, reaction is heated,
Microwave exposure can make activated carbon surface point position quickly reach high temperature, improves the catalysis activity of catalyst, from
And improve organic matter degradation efficiency further, and then improve the subsequent technique removing efficiency to Phosphorus From Wastewater.
In the preferred implementation that the present invention provides, in waste water, first add hydrogen peroxide, add the most again
Enter sodium peroxydisulfate；Hydrogen peroxide can work in coordination with microwave and sodium peroxydisulfate is played a role by metal ion, promoted
Sodium sulfate activates, thus improves persulfuric acid free radical (SO4 -) generation amount, and then improve oxidant
Utilization ratio.Use the dosing method of this oxidant, oxidant can be improved further to diethyl
Aluminum phosphate and the oxidation of catabolite thereof, improve the subsequent technique removing efficiency to Phosphorus From Wastewater.
Test result indicate that, when the method using the present invention to provide processes aluminum diethylphosphinate waste water, useless
Organophosphor clearance in water is up to 80%.
For the sake of becoming apparent from, it is described in detail below by following example.
In following embodiment, the organophosphor in aluminum diethylphosphinate waste water is all from diethyl time phosphine
Acid aluminum.
Embodiment 1
(1) activated carbon of 40 mesh is put into and 0.3M salpeter solution soaks 24h, then with distilled water repeatedly
Rinse to neutral, dry for standby；
(2) by 20wt% ferrous sulfate aqueous solution, 15wt% ferric chloride aqueous solutions and 5wt% copper sulfate
Aqueous solution is 1:1:1 mix homogeneously in mass ratio, obtain ferrum copper mixed solution (according to raw material dosage convert,
Fe in described ferrum copper mixed solution2+Content 2.46wt%, Fe3+Content 1.73wt% and Cu2+Content
0.67wt%), the activated carbon after step (1) being processed and ferrum copper mixed solution press amount ratio 1g:16mL
In boiled water bathed, place 4h after mixing, after cold filtration, be placed in 300 DEG C of roasting 2h under nitrogen protection,
Obtain activated carbon supported type metallic catalyst；
(3) take 100mL aluminum diethylphosphinate waste water (COD:4229mg/L, TOC:1013mg/L,
Organophosphor: 562.5mg/L), add the activated carbon supported type metallic catalyst 3g that step (2) prepares,
Put into the frequency conversion type microwave reactor with circulation microwave reaction tube, add 30wt% hydrogen peroxide (density
1.11g/mL) 16mL, sets microwave heating temperature as 80 DEG C, heats 32 minutes；
(4) waste water after step (3) processes adds sodium peroxydisulfate 2g, set microwave heating temperature
90 DEG C, heat 10 minutes；
(5) waste water after step (4) processes adds 0.5g calcium oxide solid, stir under 350rpm speed
Mix 20 minutes, add the polyacrylamide solution of 1.5mL 1wt ‰ afterwards, under 620rpm speed, stir 2
Minute, stir 10 minutes under 230rpm speed；
(6) taking the supernatant of step (5) processed waste water, survey organic phosphorus concentration in water, organophosphor is dense
Degree is dropped to 108.33mg/L by 562.5mg/L, and organophosphor clearance is 80.74%.
Embodiment 2
(1) activated carbon of 30 mesh is put into and 0.5M salpeter solution soaks 24h, then with distilled water repeatedly
Rinse to neutral, dry for standby；
(2) by 25wt% ferrous sulfate aqueous solution, 30wt% ferric chloride aqueous solutions and 10wt% copper sulfate
Aqueous solution is 1:1:1 mix homogeneously in mass ratio, obtain ferrum copper mixed solution (according to raw material dosage convert,
Fe in described ferrum copper mixed solution2+Content 3.07wt%, Fe3+Content 3.46wt% and Cu2+Content
1.33wt%), the activated carbon after step (1) being processed and ferrum copper mixed solution press amount ratio 1g: 20mL
In boiled water bathed, place 4h after mixing, after cold filtration, be placed in 250 DEG C of roasting 4h under nitrogen protection,
Obtain activated carbon supported metallic catalyst；
(3) take 100mL aluminum diethylphosphinate waste water (COD:4436mg/L, TOC:1153mg/L,
Organophosphor: 632.42mg/L), add the activated carbon supported type metallic catalyst 2g that step (2) prepares,
Put into the frequency conversion type microwave reactor with circulation microwave reaction tube, add 30wt% hydrogen peroxide (density
1.11g/mL) 14mL, sets microwave heating temperature as 70 DEG C, heats 40 minutes；
(4) waste water after step (3) processes adds sodium peroxydisulfate 4g, set microwave heating temperature
85 DEG C, heat 20 minutes；
(5) waste water after step (4) processes adds 0.8g calcium oxide solid, stir under 320rpm speed
Mix 15 minutes, add the polyacrylamide solution of 3mL 1wt ‰ afterwards, under 610rpm speed, stir 5 points
Clock, stirs 5 minutes under 200rpm speed；
6. take the supernatant of step (5) processed waste water, survey organic phosphorus concentration in water, organic phosphorus concentration by
632.42mg/L drops to 119.08mg/L, and organophosphor clearance is 81.17%.
Embodiment 3
(1) activated carbon of 50 mesh is put into and 0.1M salpeter solution soaks 48h, then with distilled water repeatedly
Rinse to neutral, dry for standby；
(2) by 30wt% ferrous sulfate aqueous solution, 20wt% ferric chloride aqueous solutions and 6wt% copper sulfate
Aqueous solution is 1:1:1 mix homogeneously in mass ratio, obtain ferrum copper mixed solution (according to raw material dosage convert,
Fe in described ferrum copper mixed solution2+Content 3.68wt%, Fe3+Content 2.3wt% and Cu2+Content 0.8wt%),
After activated carbon after step (1) being processed is mixed by amount ratio 1g:18mL with ferrum copper mixed solution
In boiled water is bathed, place 6h, be placed in 400 DEG C of roasting 2h after cold filtration under nitrogen protection, obtain activity
Charcoal metal supported catalyst；
(3) take 100mL aluminum diethylphosphinate waste water (COD:4436mg/L, TOC:1153mg/L,
Organophosphor: 632.42mg/L), add the activated carbon supported type metallic catalyst 4g that step (2) prepares,
Put into the frequency conversion type microwave reactor with circulation microwave reaction tube, add 30wt% hydrogen peroxide (density
1.11g/mL) 12mL, sets microwave heating temperature as 90 DEG C, heats 20 minutes；
(4) waste water after step (3) processes adds sodium peroxydisulfate 2g, set microwave heating temperature
75 DEG C, heat 30 minutes；
(5) waste water after step (4) processes adds 0.6g calcium oxide solid, stir under 340rpm speed
Mix 20 minutes, add the polyacrylamide solution of 1mL 1wt ‰ afterwards, under 640rpm speed, stir 2 points
Clock, stirs 5 minutes under 240rpm speed；
(6) taking the supernatant of step (5) processed waste water, survey organic phosphorus concentration in water, organophosphor is dense
Degree is dropped to 122.50mg/L by 632.42mg/L, and organophosphor clearance is 80.63%.
Embodiment 4
(1) activated carbon of 20 mesh is put into and 0.5M salpeter solution soaks 36h, then with distilled water repeatedly
Rinse to neutral, dry for standby；
(2) by 30wt% ferrous sulfate aqueous solution, 20wt% ferric chloride aqueous solutions and 8wt% copper sulfate
Aqueous solution is 1:1:1 mix homogeneously in mass ratio, obtain ferrum copper mixed solution (according to raw material dosage convert,
Fe in described ferrum copper mixed solution2+Content 3.68wt%, Fe3+Content 2.3wt% and Cu2+Content
1.07wt%), the activated carbon after step (1) being processed and ferrum copper mixed solution press amount ratio 1g: 15mL
In boiled water bathed, place 8h after mixing, after cold filtration, be placed in 350 DEG C of roasting 2h under nitrogen protection,
Obtain activated carbon supported metallic catalyst；
(3) take 100mL aluminum diethylphosphinate waste water (COD:4872mg/L, TOC:1315mg/L,
Organophosphor: 720.83mg/L), add the activated carbon supported type metallic catalyst 4g that step (2) prepares,
Put into the frequency conversion type microwave reactor with circulation microwave reaction tube, add 30wt% hydrogen peroxide (density
1.11g/mL) 16mL, sets microwave heating temperature as 85 DEG C, heats 30 minutes；
(4) waste water after step (3) processes adds sodium peroxydisulfate 3g, set microwave heating temperature
80 DEG C, heat 30 minutes；
(5) waste water after step (4) processes adds 1g calcium oxide solid, stir under 330rpm speed
15 minutes, add the polyacrylamide solution of 2mL 1wt ‰ afterwards, stir 5 minutes under 630rpm speed,
Stir 10 minutes under 220rpm speed；
(6) taking the supernatant of step (5) processed waste water, survey organic phosphorus concentration in water, organophosphor is dense
Degree is dropped to 91.67mg/L by 720.83mg/L, and organophosphor clearance is 87.28%.
The above is only the preferred embodiment of the present invention, it is noted that general for the art
For logical technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvement and profit
Decorations, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a processing method for aluminum diethylphosphinate waste water, comprises the following steps:
A), aluminum diethylphosphinate waste water and oxidant add in the presence of activated carbon supported type metallic catalyst
Thermal response, obtains oxidized waste water；
Described oxidant includes hydrogen peroxide and sodium peroxydisulfate；Described activated carbon supported type metallic catalyst
Ferrum element and copper it is loaded with on carrier active carbon；
B), described oxidized waste water react with dephosphorization precipitant mix, obtain processed waste water.
Processing method the most according to claim 1, it is characterised in that in step a), described in add
The mode of heat is microwave exposure.
Processing method the most according to claim 1, it is characterised in that in step a), described in add
The temperature of thermal response is 70～90 DEG C；The time of described reacting by heating is 20～80min.
Processing method the most according to claim 1, it is characterised in that in step a), described two
The mass ratio of ethylphosphinic acid aluminum waste water, hydrogen peroxide and sodium peroxydisulfate is: 100:(3～6): (1～5).
Processing method the most according to claim 1, it is characterised in that in step a), described work
It is loaded with Fe on the carrier active carbon of property carbon-supported metal catalyst2+、Fe3+And Cu2+。
Processing method the most according to claim 1, it is characterised in that described step a) specifically wraps
Include:
A1), aluminum diethylphosphinate waste water and hydrogen peroxide exist at activated carbon supported type metallic catalyst
Lower reacting by heating, obtains reactant liquor；
A2), by described reactant liquor and sodium peroxydisulfate reacting by heating, oxidized waste water is obtained.
Processing method the most according to claim 1, it is characterised in that in step b), described removes
Phosphorus precipitant is Cabase compound.
Processing method the most according to claim 1, it is characterised in that in step b), described oxygen
After change waste water reacts with dephosphorization precipitant mix, then mix with flocculant, obtain processed waste water.
Processing method the most according to claim 1, it is characterised in that in step a), described work
Property carbon-supported metal catalyst follows the steps below preparation:
After being impregnated in ferrum copper mixed solution by activated carbon, carry out roasting, obtain activated carbon supported type metal
Catalyst；Containing ferrum element and copper in described ferrum copper mixed solution.
10. according to the processing method described in any one of claim 1～9, it is characterised in that described diethyl
Total phosphorus content in base phosphinic acid aluminum waste water is 400～800mg/L.
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| CN110759530A (en) * | 2019-11-04 | 2020-02-07 | 山东泰星新材料股份有限公司 | Recycling method of melamine resin modified flame retardant wastewater |
| CN114471634A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalytic material for catalytic oxidation and preparation method and application thereof |
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