CN109336295A - It is a kind of containing organic phosphorus fire retardant producing wastewater treatment - Google Patents
It is a kind of containing organic phosphorus fire retardant producing wastewater treatment Download PDFInfo
- Publication number
- CN109336295A CN109336295A CN201811514612.7A CN201811514612A CN109336295A CN 109336295 A CN109336295 A CN 109336295A CN 201811514612 A CN201811514612 A CN 201811514612A CN 109336295 A CN109336295 A CN 109336295A
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- sludge
- waste water
- organic phosphorus
- containing organic
- fire retardant
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of containing organic phosphorus fire retardant producing wastewater treatment, comprising the following steps: S1, acid for adjusting pH value will be added to be 2~4 containing organic phosphorus waste water, is subsequently added into ferrous sulfate, is stirred to react 1~3h, obtain primary reaction waste water；S2, existing for the catalyst under the conditions of, catalytic ozonation is carried out to the primary reaction waste water that S1 is obtained, 1~2h is reacted, obtains intermediate reaction waste；S3, thickened sludge is mixed with the intermediate reaction waste that S2 is obtained, is stirred to react 20-60min, obtains wastewater sludge mixture；2~8h is concentrated in S4, the wastewater sludge mixture for obtaining S3, obtains the phosphorus containing sludge of lower layer and the waste water on upper layer, then separates phosphorus containing sludge and waste water.The present invention is oxidized to Phos for organic phosphorus, then mixes, reacts, is concentrated with the thickened sludge of Sewage Disposal, and thickened sludge co-precipitation Phos simultaneously adsorbs residual organic phosphorus, reduces total phosphorus content in waste water.
Description
Technical field
The invention belongs to textile waste processing technology fields, and in particular to a kind of to produce at waste water containing organic phosphorus fire retardant
Reason method.
Background technique
In field of textiles, flame-proof treatment is mainly surface-treated fabric during after-finishing of textile products, makes to hinder
Agent fixation is fired on the fabric, to obtain flame retardant effect.Flame-proof treatment is carried out to cotton fabric and dacron, to prevent fire and
Casualties, the property loss reduced in fire is significant.
Traditional Proban method is that fire retardant THPC (tetra methylol sal-ammoniac) pads rear baking, and the method for improvement is
Proban/ ammonia cure technique, for the important method of current durable cotton fabric flame-proof treatment, have good flame retardation effect, fabric drop it is strong it is small,
Feel influences few advantage, and typical process flow is textile pad tetramethylol chloride urea preshrunk body fire retarding treating liquid
(room temperature) → preliminary drying (100~120 DEG C) → ammonia cure → oxidation washing → drying (130~140 DEG C) → preshrunk → finished product.Fire retardant
It is to keep it more stable after ammonia cure solidifies, it is necessary to P3+It is oxidized to P5+, generally use and pad hydrogen peroxide (H2O2) method come
It realizes, neutralizes and wash off again after oxidation, production system is discharged in washing waste water.It is single that flame-proof treatment waste water is mainly derived from oxidation washing
Member, wherein COD, total phosphorus concentration are high, and total phosphorus, mainly based on organic phosphorus, organic phosphorous content is 90% or more, in addition also
Remaining hydrogen peroxide, can cause environment if direct emission seriously to pollute.
Summary of the invention
It is produced at waste water it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of containing organic phosphorus fire retardant
Reason method.
To achieve the above object, the technical solution adopted by the present invention is that:
It is a kind of containing organic phosphorus fire retardant producing wastewater treatment, comprising the following steps:
S1, it will be passed through reaction vessel containing organic phosphorus waste water, adding acid for adjusting pH value is 2~4, it is subsequently added into ferrous sulfate,
It is stirred to react 1~3h, obtains primary reaction waste water；
S2, existing for the catalyst under the conditions of, catalytic ozonation, reaction 1 are carried out to the primary reaction waste water that S1 is obtained
~2h obtains intermediate reaction waste；
S3, thickened sludge is mixed with the intermediate reaction waste that S2 is obtained, is stirred to react 20-60min, obtains wastewater sludge
Mixture；
2~8h is concentrated in S4, the wastewater sludge mixture for obtaining S3, obtains the phosphorus containing sludge of lower layer and the waste water on upper layer,
Then phosphorus containing sludge and waste water are separated, waste water enters subsequent sewage disposal system and is further processed, and phosphorus containing sludge enters sludge
Processing system transports outward disposition after being dehydrated.
Preferably, in step sl, described organic phosphorus for tetramethylol chloride, tetrakis hydroxymetyl phosphonium sulfuric, normal-butyl pair
At least one of (hydroxypropyl) phosphine oxide, three hydroxypropyl phosphine oxides, cyclooctyl hydroxypropyl phosphine oxide.
Preferably, in step sl, the acid is sulfuric acid or hydrochloric acid.
Preferably, in step s 2, the catalyst is alumina load manganese oxide, alumina load copper oxide, oxidation
At least one of aluminium loading titanium oxide.
Preferably, in step sl, in terms of the volume containing organism P wastewater: in step sl, the ferrous sulfate adds
Entering amount is 8~15g/L, and in step s 2, the additional amount of the ozone is 0.1~0.4g/L.
Preferably, in step s 2, loaded catalyst is the 1/20-1/5 of reaction vessel volume in S1.
Preferably, in step s3, the volume ratio for the intermediate reaction waste that thickened sludge and S2 are obtained is 1~2:1.
Preferably, in step s3, the thickened sludge is textile printing and dyeing enterprises composite wastewater treating stations or sewage treatment
Factory is with the excess sludge of biochemical treatment system thickened sludge as main component.
Compared with prior art, the present invention the beneficial effect is that:
(1) present invention by organic phosphorus is oxidized to Phos using oxidation technology, then with the thickened sludge of Sewage Disposal
Mixing, reaction, concentration, thickened sludge co-precipitation Phos simultaneously adsorb residual organic phosphorus, reduce the total phosphorus content in waste water, total phosphorus
Removal rate is up to 99%.
(2) ferrous sulfate being added in the present invention generates trivalent iron salt after reaction, can after mixing with thickened sludge
Play the role of improving thickened sludge, thus thickened sludge used in the present invention is without additional addition sludge conditioner, reaction
Thickened sludge afterwards can be directly entered the sludge dewatering systems such as plate compression or belt filter press and carry out sludge dewatering, simplify dirt
Mud process flow has saved Treatment of Sludge expense.
(3) it is provided by the invention containing organic phosphorus fire retardant producing wastewater treatment have small investment, processing cost it is low,
The features such as total phosphorus removal effect is good, easy to operate.
(4) present invention solve fire retardant production waste water in it is organic phosphorus be difficult to completely remove, the problem that total phosphorus can not be up to standard,
It can be widely used for the organic phosphorus removal of textile printing and dyeing industry waste water.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.The test method of actual conditions is not specified in the following example, usually according to normal condition, or according to each system
Make condition proposed by quotient.
The thickened sludge used in following embodiment is for textile printing and dyeing enterprises composite wastewater treating stations or sewage treatment plant
With the excess sludge of biochemical treatment system thickened sludge as main component, and in following embodiment ferrous sulfate and ozone plus
Enter amount in terms of the volume containing organism P wastewater.
Embodiment 1
It is a kind of containing organic phosphorus fire retardant producing wastewater treatment, specifically includes the following steps:
S1, the fire retardant containing tetramethylol chloride for being 350mg/L by total phosphorus content produce waste water and are passed through in reaction tank,
Adding salt acid for adjusting pH value is 3, is subsequently added into the ferrous sulfate of 8g/L, is stirred to react 1.5h, obtains primary reaction waste water；
S2, using alumina plate area load copper oxide as catalyst, the primary reaction waste water obtained to S1 carries out ozone and urges
Change oxidation, reacts 1h, obtain intermediate reaction waste；
Wherein: the loadings of catalyst are the 1/20 of reaction tank volume；Ozone dosage is 100mg/L；
S3,1:1 is mixed the intermediate reaction waste for obtaining thickened sludge and S2 by volume, is stirred to react 20min, is obtained
Wastewater sludge mixture；
8h is concentrated in S4, the wastewater sludge mixture for obtaining S3, obtains the phosphorus containing sludge of lower layer and the waste water on upper layer, then
Phosphorus containing sludge and waste water are separated, waste water enters subsequent sewage disposal system and is further processed, and phosphorus containing sludge enters Treatment of Sludge
System transports outward disposition after being dehydrated.
After reaction, through detecting, the total phosphorus content of waste water after treatment is 3.5mg/L, containing organism P wastewater
Total tp removal rate is 99%.
Embodiment 2
It is a kind of containing organic phosphorus fire retardant producing wastewater treatment, specifically includes the following steps:
S1, the fire retardant containing tetrakis hydroxymetyl phosphonium sulfuric for being 600mg/L by total phosphorus content produce waste water and are passed through in reaction tank,
Adding salt acid for adjusting pH value is 2, is subsequently added into the ferrous sulfate of 15g/L, is stirred to react 3h, obtains primary reaction waste water；
S2, manganese oxide is loaded using alumina plate as catalyst, ozone catalytic oxygen is carried out to the primary reaction waste water that S1 is obtained
Change, reacts 2h, obtain intermediate reaction waste；
Wherein: the loadings of catalyst are the 1/5 of reaction tank volume；Ozone dosage is 400mg/L.
S3,1.5:1 is mixed the intermediate reaction waste for obtaining thickened sludge and S2 by volume, is stirred to react 60min, is obtained
To wastewater sludge mixture；
8h is concentrated in S4, the wastewater sludge mixture for obtaining S3, obtains the phosphorus containing sludge of lower layer and the waste water on upper layer, then
Phosphorus containing sludge and waste water are separated, waste water enters subsequent sewage disposal system and is further processed, and phosphorus containing sludge enters Treatment of Sludge
System transports outward disposition after being dehydrated.
After reaction, the total phosphorus content for being detected waste water after treatment is 4mg/L, the total phosphorus containing organism P wastewater
Removal rate is 99.3%.
Embodiment 3
It is a kind of containing organic phosphorus fire retardant producing wastewater treatment, specifically includes the following steps:
S1, the fire retardant containing three hydroxypropyl phosphine oxides for being 400mg/L by total phosphorus content produce waste water and are passed through in reaction tank,
Adding sulphur acid for adjusting pH value is 4, is subsequently added into the ferrous sulfate of 10g/L, is stirred to react 2h, obtains primary reaction waste water；
S2, using alumina plate loading titanium oxide as catalyst, the primary reaction waste water obtained to S1 carries out ozone catalytic oxygen
Change, reacts 1h, obtain intermediate reaction waste；
Wherein: the loadings of catalyst are the 1/10 of reaction tank volume；Ozone dosage is 200mg/L.
S3, thickened sludge is mixed with the intermediate reaction waste that S2 is obtained with 2:1 by volume, is stirred to react 30min, obtains
To wastewater sludge mixture；
4h is concentrated in S4, the wastewater sludge mixture for obtaining S3, obtains the phosphorus containing sludge of lower layer and the waste water on upper layer, then
Phosphorus containing sludge and waste water are separated, waste water enters subsequent sewage disposal system and is further processed, and phosphorus containing sludge enters Treatment of Sludge
System transports outward disposition after being dehydrated.
After reaction, the total phosphorus content for being detected waste water after treatment is 2.7mg/L, containing the total of organism P wastewater
Tp removal rate is 99.3%.
Waste water is produced containing organic phosphorus fire retardant as can be seen that handling by means of the present invention by Examples 1 to 3,
Organic tp removal rate is high, can reach the index request into comprehensive sewage treatment system, it is ensured that efflux wastewater reaches discharge mark
Alignment request.
In conclusion the embodiment of the present invention by being firstly added ferrous sulfate, makes full use of hydrogen peroxide remaining in waste water,
Formation Fenton system catalysis oxidation is organic phosphorus, the pH value or 2~4 of waste water after this elementary reaction is complete, directly carries out ozone and urges
Change oxidation, under acid condition and iron ion and catalyst existence condition, further catalytic ozonation is organic phosphorus, will be in waste water
It is most it is organic phosphorus be converted into Phos, then mix, react, be concentrated with the thickened sludge of Sewage Disposal, sludge is coprecipitated
Shallow lake Phos simultaneously adsorbs residual organic phosphorus, then mud-water separation, achievees the purpose that remove total phosphorus.
It should be noted that involved in claims of the present invention when numberical range, it is thus understood that each numberical range
Any one numerical value can be selected between two endpoints and two endpoints, since the step method of use is identical as embodiment,
It repeats in order to prevent, the present invention describes preferred embodiment and its effect, and once a person skilled in the art knows bases
This creative concept, then additional changes and modifications may be made to these embodiments.So the following claims are intended to be interpreted as
Including preferred embodiment and fall into all change and modification of the scope of the invention.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (8)
1. a kind of containing organic phosphorus fire retardant producing wastewater treatment, which comprises the following steps:
S1, it will be passed through reaction vessel containing organic phosphorus waste water, adding acid for adjusting pH value is 2~4, is subsequently added into ferrous sulfate, is stirred
1~3h is reacted, primary reaction waste water is obtained；
S2, existing for the catalyst under the conditions of, catalytic ozonation is carried out to the primary reaction waste water that S1 is obtained, reacts 1~2h,
Obtain intermediate reaction waste；
S3, thickened sludge is mixed with the intermediate reaction waste that S2 is obtained, is stirred to react 20~60min, it is mixed to obtain wastewater sludge
Close object；
2~8h is concentrated in S4, the wastewater sludge mixture for obtaining S3, obtains the phosphorus containing sludge of lower layer and the waste water on upper layer, then
Phosphorus containing sludge and waste water are separated, waste water enters subsequent sewage disposal system and is further processed, and phosphorus containing sludge enters Treatment of Sludge
System transports outward disposition after being dehydrated.
2. as described in claim 1 containing organic phosphorus fire retardant producing wastewater treatment, which is characterized in that in step S1
In, it is described organic phosphorus for tetramethylol chloride, tetrakis hydroxymetyl phosphonium sulfuric, double (hydroxypropyl) phosphine oxide of normal-butyl, three hydroxypropyls
At least one of phosphine oxide, cyclooctyl hydroxypropyl phosphine oxide.
3. as described in claim 1 containing organic phosphorus fire retardant producing wastewater treatment, which is characterized in that in step S1
In, the acid is sulfuric acid or hydrochloric acid.
4. as described in claim 1 containing organic phosphorus fire retardant producing wastewater treatment, which is characterized in that in step S2
In, the catalyst is alumina load manganese oxide, alumina load copper oxide, at least one in alumina load titanium oxide
Kind.
5. as described in claim 1 containing organic phosphorus fire retardant producing wastewater treatment, which is characterized in that containing organic phosphorus
The stereometer of waste water: in step sl, the additional amount of the ferrous sulfate is 8~15g/L, in step s 2, the ozone
Additional amount is 0.1~0.4g/L.
6. as described in claim 1 containing organic phosphorus fire retardant producing wastewater treatment, which is characterized in that in step S2
In, the loaded catalyst is the 1/20-1/5 of reaction vessel volume in S1.
7. as described in claim 1 containing organic phosphorus fire retardant producing wastewater treatment, which is characterized in that in step S3
In, the volume ratio for the intermediate reaction waste that the thickened sludge and S2 are obtained is 1~2:1.
8. as described in claim 1 containing organic phosphorus fire retardant producing wastewater treatment, which is characterized in that in step S3
In, the thickened sludge is that textile printing and dyeing enterprises composite wastewater treating stations or sewage treatment plant are dirty with the residue of biochemical treatment system
Mud thickened sludge as main component.
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| CN201811514612.7A CN109336295B (en) | 2018-12-12 | 2018-12-12 | Method for treating organophosphorus-containing flame-retardant cloth production wastewater |
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| CN201811514612.7A CN109336295B (en) | 2018-12-12 | 2018-12-12 | Method for treating organophosphorus-containing flame-retardant cloth production wastewater |
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| CN109336295B CN109336295B (en) | 2021-07-27 |
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Cited By (2)
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| CN110937727A (en) * | 2019-12-26 | 2020-03-31 | 河南省科学院化学研究所有限公司 | PROBAN flame-retardant wastewater treatment method |
| CN113045041A (en) * | 2021-03-19 | 2021-06-29 | 常熟理工学院 | Treatment method of high-concentration organic phosphorus wastewater |
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| Publication number | Publication date |
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| CN109336295B (en) | 2021-07-27 |
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