CN108017211A - A kind of recycling treatment process of pyrazolone mother liquor waste water - Google Patents
A kind of recycling treatment process of pyrazolone mother liquor waste water Download PDFInfo
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- CN108017211A CN108017211A CN201711160082.6A CN201711160082A CN108017211A CN 108017211 A CN108017211 A CN 108017211A CN 201711160082 A CN201711160082 A CN 201711160082A CN 108017211 A CN108017211 A CN 108017211A
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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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- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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- 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
- C02F1/66—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
- C02F1/722—Oxidation by peroxides
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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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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 present invention relates to a kind of recycling treatment process of pyrazolone mother liquor waste water.Including：1) pyrazolone mother liquor waste water is subjected to level-one Fenton's reaction, is settled after reaction, press filtration, obtain iron cement and clear liquid；2) clear liquid obtained by step 1) is subjected to two level Fenton's reaction, is flocculated, settled after reaction, press filtration, obtaining iron cement and clear liquid；3) clear liquid obtained by step 2) is subjected to multiple-effect evaporation, then centrifuged, obtain solid ammonium sulfate and centrifuge mother liquor, the recycling condensing water in Multi-effect Evaporation Processes；4) the part centrifugal mother liquor reflux obtained by step 3) is mixed with the mother liquor waste water of step 1), circulation carries out operation of the step 1) to step 3)；Remaining centrifuge mother liquor is mixed with the clear liquid obtained by step 2) carries out multiple-effect evaporation, and circulation carries out the operation of step 3).The present invention finally goes out salt ammonium sulfate and reaches industrial sulphuric acid ammonium quality requirements, condensed water reaches workshop reuse or emission request by continuous Fenton and the mother liquor reflux of evaporation process.
Description
Technical field
The invention belongs to pyrazolone technical field, specifically, is related to a kind of recycling treatment of pyrazolone mother liquor waste water
Technique.
Background technology
Contain pyrazolone structure in the molecule of pyrazolone, and contain azo group.Pyrazolone can be used for preparing azo dye
Material, such as producing acid bordeaux dyestuff, acid red dye, orange, tracid light yellow dyestuff；Pyrazolone can also be used for
Pharmaceutical synthesis, such as producing antipyrine, aminopyrine and analgin；Pyrazolone can be additionally used in organic synthesis, for example use
In preparing 1-phenyl-3-methyl-5-pyrazolones ketone and 1- p-sulfonic acid phenyl -3- methyl -5- pyrazolones.In addition, pyrazolone can
As detection CO, vitamin B12, Fe, Cu and Ni chemical reagent.
The production process of pyrazolone is that water, hydrochloric acid, aniline and sodium nitrite are carried out diazo-reaction, to obtained reaction
Sulfuric acid is added in product to be hydrolyzed, and ammonium hydroxide is passed through in the product obtained to hydrolysis and carries out neutralization reaction, obtained neutralization is anti-
Answer product and butyryl ketoamine to carry out condensation reaction, obtain pyrazolone product.Need to add in pyrazolone production process substantial amounts of
Ammonium hydroxide carries out neutralization reaction, but the ammonium hydroxide added is not introduced in the product of pyrazolone finally, but all dissolvings
In the production waste water of pyrazolone, make to produce in waste water containing substantial amounts of ammonia, nitrogen, pyrazolone in the production waste water of pyrazolone
Ammonia, nitrogen can not efficiently use the waste for causing resource；And the pH value of pyrazolone production waste water relatively low is difficult to handle；In addition,
Pyrazolone mother liquor waste water is mainly characterized by high salt, high COD, high ammonia nitrogen, and color is yellow or yellowish-brown, will if directly discharging
Neighbouring water quality and fish production are impacted, and serious pollution is caused to environment, if straight with other low concentration wastewaters
Mixing is connect, then can increase project cost and operating cost.Therefore, how recycling is carried out to pyrazolone production waste water and receives people
Extensive concern.
Current treatment process is that mother liquor is carried out ammonia still process again with excessive alkali neutralization, recycles certain density ammonium hydroxide and supplies workshop
It is continuing with.The economic value of this method is not high, mainly solves the problems, such as high ammonia nitrogen, and the tower bottom liquid after ammonia still process is still high salt, height
COD, ammonia nitrogen is in 500mg/l or so.Consume a large amount of liquid caustic soda and steam and subsequent treatment difficulty is still larger.
CN105084605A discloses a kind of pretreating process of pyrazolone production waste water, and the technique to pyrazolone by giving birth to
MgSO is added in production waste water4And NaHPO4, ammonia nitrogen in high density is recycled, guanite of the generation with compared with high added value, is tried with Fonton
Agent catalysis oxidation reduces waste water COD, and pH value generation precipitation is adjusted through NaOH.The recyclable ammonia nitrogen in high density of this technique, pyrazolone life
Production waste water COD can be down to below 700mg/L, and ammonia nitrogen concentration can be down to below 80mg/L, and colourity is down to less than 16, after 2 times of dilution
Urban pipe network can be directly discharged into.
Such scheme the applicant also did experiment, it is necessary to first add alkali (sodium hydroxide) to be tuned into alkalescence in pyrazolone mother liquor,
A large amount of alkali are consumed, carry out ammonia still process, recycle ammonium hydroxide.The water after ammonia still process adds magnesium sulfate and dibastic sodium phosphate, general ammonia still process base angle again
Ammonia nitrogen can reach 500mg/l (molecular weight of ammonium root is small, magnesium sulfate and phosphorus, it is necessary to consume substantial amounts of magnesium sulfate and dibastic sodium phosphate
The molecular weight of sour hydrogen sodium is big), the amount of generation ammonium magnesium phosphate (guanite) is very big.If the water ammonia nitrogen after ammonia still process is high again, consumption
Bigger.
" research of pyrazolone mother liquor waste water pretreating process "【Cheng Gaofeng, Jiang Cheng, the vertical ability pyrazolone mother liquor waste waters in side are located in advance
Manage technical study [J], Chemical Industry in Guangzhou, 2012,40 (15)：179-181】Disclose one kind and use Fe-C micro electrolysis+Fenton oxygen
The group technology of change+coagulating sedimentation carries out experimental pretreatment to pyrazolone mother liquor waste water, has inquired into each reaction condition and technique ginseng
Several influences to COD removal effects.The result shows that：Group technology is 48.70% to the total removal rate of COD.After can significantly mitigating
Continuous biochemical treatment load, condition is created for the stable operation of system.But the complex process, it is related to kinds of processes and carries out group
Close, and the removal rate of COD is not high.The method is removed for COD, and actual since waste water salt content is high and ammonia nitrogen is high, biochemistry is
It is not treatable.
But above-mentioned technique is mostly concentrated in terms of reducing COD value, ammonia nitrogen concentration and colourity.However, final pyrrole after testing
Oxazolone mother liquor waste water is low (pH1-3 or so) except COD value high (COD15000mg/l or so), colourity high (256-512 times) and pH value
In addition, also containing a large amount of ammonium roots, sulfate radical, a small amount of sodium ion and chlorion, salt content generally pass through in 15%-20% at present
Directly distillation is carried out to pyrazolone production waste water to recycle the ammonium sulfate in pyrazolone production waste water.But this recovery method obtains
The ammonium sulfate purity arrived is relatively low, it is difficult to utilizes；And the price of ammonium sulfate is cheap, compared to high cost recovery, this time
Receiving method causes very big financial burden to enterprise.The recovery method economy for the pyrazolone production waste water that the prior art provides
It is poor.
In conclusion current method can not effectively recycle ammonium sulfate.
In view of this it is special to propose the present invention.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies of the prior art and provide a kind of pyrazolone mother liquor waste water
Recycling treatment process, which can effectively recycle ammonium sulfate, and the ammonium sulfate recycled can reach the product of industrial sulphuric acid ammonium
Matter requirement.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of recycling treatment process of pyrazolone mother liquor waste water, wherein：The recycling treatment process includes as follows
Step：
1) collect pyrazolone mother liquor waste water, carry out level-one Fenton's reaction, settled after reaction, press filtration, obtain iron cement and
Clear liquid；
2) clear liquid obtained by step 1) is subjected to two level Fenton's reaction, is flocculated, settled after reaction, press filtration, obtaining iron
Mud and clear liquid；
3) clear liquid obtained by step 2) is subjected to multiple-effect evaporation, then centrifuged, obtain solid ammonium sulfate and centrifuge mother liquor,
Recycling condensing water in Multi-effect Evaporation Processes；
4) the part centrifugal mother liquor reflux obtained by step 3) is mixed with the pyrazolone mother liquor waste water of step 1), circulation carries out
Step 1) to step 3) operation；Remaining centrifuge mother liquor mixed with the clear liquid obtained by step 2) carry out multiple-effect evaporation, circulate into
The operation of row step 3).
Further, the reflux described in step 4) controls reflux ratio in the range of 5~8%, and preferably 10%.
Further, the multiple-effect evaporation described in step 3) is triple effect evaporation.
It is preferred that the triple effect evaporation is：
One effect evaporation control pressure 0.2-0.3MPa, 125-135 DEG C of temperature, feed velocity 10-15t/h；
Two effect evaporation control pressure 120-130kPa, 100-110 DEG C of temperature, feed velocity 6-8t/h；
Triple effect evaporation control pressure 45-55kPa, 70-90 DEG C of temperature, feed velocity 7-9t/h.
Further, in step 2), PAM and PAC is added when being flocculated；
Wherein, the addition of the PAM is the 0.5-1.5wt%, preferably 1wt% of pyrazolone mother liquor waste water；
The addition of the PAC is the 1-2wt%, preferably 1.5wt% of pyrazolone mother liquor waste water；
The flocculated condition is：pH8-9.5；
It is preferred that being additionally added pH adjusting agent when being flocculated, the pH adjusting agent is ammonium hydroxide.
Further, in step 1), when carrying out level-one Fenton's reaction, the addition of hydrogen peroxide is pyrazolone mother liquor waste water
0.5-1.5wt%, preferably 1wt%；FeSO4·7H2The addition of O be pyrazolone mother liquor waste water 1-3wt%, preferably 2%；
The condition of the level-one Fenton's reaction is：45~55 DEG C of temperature, pH value 4~6.
Further, pH adjusting agent and/or defoamer are additionally added when carrying out level-one Fenton's reaction；
It is preferred that the pH adjusting agent is ammonium hydroxide.
Further, in step 2), when carrying out two level Fenton's reaction, the addition of hydrogen peroxide is pyrazolone mother liquor waste water
3-5wt%, preferably 4wt%；FeSO4·7H2The addition of O be pyrazolone mother liquor waste water 1-3wt%, preferably 2%；
The condition of the two level Fenton's reaction is：45~55 DEG C of temperature, pH value 4~6.
Further, pH adjusting agent and/or defoamer are additionally added when carrying out two level Fenton's reaction；
It is preferred that the pH adjusting agent is ammonium hydroxide and/or sulfuric acid.
Further, when carrying out level-one Fenton's reaction and two level Fenton's reaction, flow of inlet water is 25-26m3/ h, it is double
Oxygen water flow is 0.25-0.3m3/h。
Further, during level-one Fenton's reaction, the 1-3% that flow is flow of inlet water is controlled when adding catalyst；Two level is fragrant
Reaction when, add catalyst when control flow for flow of inlet water 3-5%.
The present invention is described in detail below：
Final pyrazolone mother liquor waste water contains a large amount of ammonium roots, sulfate radical, a small amount of sodium ion and chlorion, salt content after testing
In 15%-20%, COD value is 15000mg/l or so, and colourity is 256-512 times, pH value 1-3 or so.Current pyrazolone mother liquor
The processing method of waste water can not recycle ammonium sulfate while COD value, ammonia nitrogen concentration and colourity is effectively reduced.
The present invention provides a kind of recycling treatment process of pyrazolone mother liquor waste water, which can not only effectively reduce
COD value, ammonia nitrogen concentration and the colourity of pyrazolone mother liquor waste water, additionally it is possible to effectively recycle ammonium sulfate, and the ammonium sulfate energy recycled
Reach the quality requirements of industrial sulphuric acid ammonium.
Specifically, the recycling treatment process of pyrazolone mother liquor waste water provided by the present invention includes the following steps：
1) collect pyrazolone mother liquor waste water, carry out level-one Fenton's reaction, settled after reaction, press filtration, obtain iron cement and
Clear liquid；
2) clear liquid obtained by step 1) is subjected to two level Fenton's reaction, is flocculated, settled after reaction, press filtration, obtaining iron
Mud and clear liquid；
3) clear liquid obtained by step 2) is subjected to multiple-effect evaporation, then centrifuged, obtain solid ammonium sulfate and centrifuge mother liquor,
Recycling condensing water in Multi-effect Evaporation Processes；
4) the part centrifugal mother liquor reflux obtained by step 3) is mixed with the pyrazolone mother liquor waste water of step 1), circulation carries out
Step 1) to step 3) operation；Remaining centrifuge mother liquor mixed with the clear liquid obtained by step 2) carry out multiple-effect evaporation, circulate into
The operation of row step 3).
Pyrazolone mother liquor waste water is carried out Fenton's reaction, wherein first time Fenton's reaction (i.e. level-one twice by the present invention first
Fenton's reaction) it is mainly used for removing COD, second of Fenton's reaction (i.e. two level Fenton's reaction) is mainly used for reducing colourity.By
Twice after Fenton's reaction, the COD value of pyrazolone mother liquor waste water is 3500mg/l, and colourity is 64-128 times, so as to be follow-up more
Effect evaporation provides good evaporation conditions.
The original pyrazolone waster water process of the applicant is analogous to a kind of pyrazolone production disclosed in CN105084605A
The pretreating process of waste water, the technique add MgSO by being produced to pyrazolone in waste water4And NaHPO4, ammonia nitrogen in high density is recycled,
Guanite of the generation with compared with high added value.
Technique, which mainly first passes through, adds lime adjusting alkalescence, then adds steam by ammonia still, and recycling is highly concentrated at tower top
Ammonium hydroxide is spent, bottom passes through the isolated calcium sulfate of centrifuge (gypsum), the still higher about 200-500mg/l of centrifugal water ammonia nitrogen.
This protocol procedures is shorter.Obtained gypsum can not achieve recycling since the problem of organic matter actually belongs to dangerous waste.It is actually passed through
Pretreatment (level-one, two level Fenton) can also obtain the measured calcium sulfate of matter (gypsum), but the market of gypsum is bad, added value
Less.
The treatment process of the present invention is pyrazolone mother liquor through two-stage Fenton's reaction and triple effect evaporation, be greatly saved steam into
This).Meanwhile two-stage Fenton of the invention mainly further reduces waste water COD and colourity, by the thorough oxygen of organic matter in waste water
Change, obtain the snow-white ammonium sulfate of appearance, improve the added value of salt.
Fenton's reaction has a cost, but if without Fenton's reaction, the ammonium sulfate after evaporative crystallization will have organic matter
Residual, color is bronzing or yellow, may be accredited as hazardous waste, then the intractability brought to enterprise is difficulter
It is huge, it is per ton to the enviromental protection enterprise's processing for having processing qualification, about 5000 yuan of processing cost.The city of the invention for finally going out salt ammonium sulfate
Field price is per ton at 400 yuan, can offset most of processing cost.
Then, then by the pyrazolone mother liquor waste water after Fenton's reaction twice multiple-effect evaporation is carried out so that finally go out salt sulfuric acid
Ammonium quality reaches the quality requirements of industrial sulphuric acid ammonium, while condensed water reaches the requirement of workshop recycle-water requirement or discharge.
Meanwhile mix obtained part centrifugal mother liquor reflux with the pyrazolone mother liquor waste water of step 1), circulation is walked
It is rapid 1) to the operation of step 3)；Remaining centrifuge mother liquor is mixed with the clear liquid obtained by step 2) carries out multiple-effect evaporation, and circulation carries out
The operation of step 3).
The centrifuge mother liquor that the present invention obtains does not flow back all, but has certain reflux ratio, reflux control reflux
Than in the range of 5~8%, preferably 10%, normal control is 10% or so, since centrifuge mother liquor is the water after concentration, COD compared with
Height, the quality of evaporation effect and ammonium sulfate (not white color) can be influenced by not flowing back.
The present invention is by by the mother liquor reflux (process control) of the continuous Fenton of raw water (pretreatment) and evaporation process, finally going out
Salt ammonium sulfate quality reaches the quality requirements of industrial sulphuric acid ammonium, and condensed water reaches the requirement of workshop recycle-water requirement or discharge.
Further, the multiple-effect evaporation described in step 3) is triple effect evaporation.
Specifically, the triple effect evaporation is：One effect evaporation control pressure 0.2-0.3MPa, 125-135 DEG C of temperature, material
Flow velocity 10-15t/h；Two effect evaporation control pressure 120-130KPa, 100-110 DEG C of temperature, feed velocity 6-8t/h；Triple effect steams
Send out control pressure 45-55KPa, 70-90 DEG C of temperature, feed velocity 7-9t/h.
In the present invention, an effect evaporation consumption is live steam, and the heat source of two effect evaporations is the indirect steam of effect evaporation,
The heat source of triple effect evaporation is the indirect steam of two effects evaporation.So save steam consumption.
In the present invention, the condition of level-one Fenton's reaction and two level Fenton's reaction is：45~55 DEG C of temperature, pH value 4~6.
Carry out adding hydrogen peroxide and FeSO when level-one Fenton's reaction and two level Fenton's reaction4·7H2O, wherein FeSO4·
7H2Additions of the O in Fenton's reaction twice is identical, is the 1-3wt% of pyrazolone mother liquor waste water, preferably 2%；And hydrogen peroxide
Different additions is then used, in level-one Fenton's reaction, the addition of hydrogen peroxide is the 0.5- of pyrazolone mother liquor waste water
1.5wt%, preferably 1wt%；In two level Fenton's reaction, the addition of hydrogen peroxide is the 3-5wt% of pyrazolone mother liquor waste water, excellent
Select 4wt%.
For the present invention in two-stage Fenton's reaction, the amount of the hydrogen peroxide of addition is different, and is added in two level Fenton's reaction
The amount of hydrogen peroxide be more than the amount of hydrogen peroxide added in level-one Fenton's reaction, on the one hand since stair oxidation will largely be easy to
The oxidation operation of reaction falls, and remaining material is more difficult to aoxidize some and carries out re-oxidation, it is necessary to increase hydrogen peroxide ratio again, because
This, the amount of the hydrogen peroxide added in two level Fenton's reaction is more than the amount of the hydrogen peroxide added in level-one Fenton's reaction；The opposing party
Face, if the excessive reaction of level-one dosage is too violent, produces a large amount of foams, loses control of；Furthermore present invention selection two-stage Fenton is anti-
Should, hydrogen peroxide twice is added, such treatment effect is better than once adding.
Further, the present invention is by controlling waste water and Fenton reagent in level-one Fenton's reaction and two level Fenton's reaction to add
When flow, to ensure waste water, hydrogen peroxide and FeSO4·7H2O is added with stable flow, so easy to industrial
Stablize；At the same time it may also be ensured that waste water and medicament have enough residence times in system, so that reaction is more abundant；Separately
Outside, Fenton's reaction is for exothermic reaction and with foam, if flow is excessive, it will has a large amount of foam overflow reaction kettles, the present invention
In the generation of this phenomenon is avoided by flow.
Further, in order to which balanced reaction effect and cost, the present invention are anti-in progress level-one Fenton's reaction and two level Fenton
At once, flow of inlet water is 25-26m3/ h, dioxygen water flow are 0.25-0.3m3/ h, controls the flow to be when adding catalyst
The 1-3% of flow of inlet water.
Further, in level-one Fenton's reaction and two level Fenton's reaction, also pH adjusting agent can be added according to actual conditions
And/or defoamer, pH adjusting agent is to control pH4~6, and defoamer is to the foam produced during elimination reaction, its dosage
Those skilled in the art can determine according to actual conditions.
Wherein in level-one Fenton's reaction, the pH adjusting agent is ammonium hydroxide；In two level Fenton's reaction, the pH adjusting agent
For ammonium hydroxide and/or sulfuric acid.
The pH value of pyrazolone mother liquor is 2 or so, and control condition 4-6 of level-one Fenton or so, so to add alkali (ammonium hydroxide)
It is adjusted, therefore, in level-one Fenton's reaction, the pH adjusting agent is ammonium hydroxide；And the pH controls of level-one sedimentation are alkaline, mistake
The clear liquid of filter press is also alkalescence, and the control condition of second order reaction is pH4-6, so want acid adding to adjust, it is therefore, fragrant in two level
Pause in reaction, the pH adjusting agent is ammonium hydroxide and/or sulfuric acid.
The acid-base value controlled is according to actual verification, in order to balance cost and effect for 4-6.
Further, the present invention is flocculated after two level Fenton's reaction is carried out.
Only flocculate in the present invention after two level Fenton's reaction is carried out, because if wadding a quilt with cotton again through two level after level-one flocculation
It is solidifying, then the flco component after two level flocculation is more single, mud cake of the single iron cement flco Jing Guo the densification of press filtration Opportunity formation,
Substantially reduced so as to cause water speed to be passed.Therefore, the present invention is only flocculated after two level Fenton's reaction is carried out.
Specifically, PAM and PAC is added to flocculate；Wherein, the addition of the PAM is pyrazolone mother liquor waste water
0.5-1.5wt%, preferably 1wt%；The addition of the PAC is the 1-2wt% of pyrazolone mother liquor waste water, preferably
1.5wt%；
Flocculated condition is：pH8-9.5；
Also suitable pH adjusting agent can be added according to being actually needed in flocculation process, be 8-9.5 to control pH, it is described
PH adjusting agent is ammonium hydroxide.
After adopting the above technical scheme, the present invention has the advantages that compared with prior art：
The present invention is by by the mother liquor reflux (process control) of the continuous Fenton of raw water (pretreatment) and evaporation process, finally going out
Salt ammonium sulfate quality reaches the quality requirements of industrial sulphuric acid ammonium, and condensed water reaches the requirement of workshop recycle-water requirement or discharge.
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Brief description of the drawings
Fig. 1 is the process flow diagram of the present invention.
It should be noted that these attached drawings and word description are not intended as the design model limiting the invention in any way
Enclose, but idea of the invention is illustrated for those skilled in the art by reference to specific embodiment.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical solution in embodiment is clearly and completely described, following embodiments be used for illustrate the present invention, but
It is not limited to the scope of the present invention.
Embodiment 1
1) pyrazolone mother liquor waste water 660t is collected, which is 15000mg/L, ammonia nitrogen concentration 40000mg/l, color
Spend for 512 or so.The waste water is entered into stair oxidation kettle, hydrogen peroxide and FeSO are added into stair oxidation kettle4·7H2O (dioxygens
The addition of water is the 0.5wt% of pyrazolone mother liquor waste water；FeSO4·7H2The addition of O is pyrazolone mother liquor waste water
1wt%), it is 4 to add pH adjusting agent ammonium hydroxide and control pH, carries out level-one Fenton's reaction in temperature 45 C, reaction time 2h, reacted
Cheng Zhongke adds suitable defoamer according to actual conditions；Reaction solution enters level-one sedimentation kettle and is settled after reaction, controls
PH8-9 processed, sedimentation time 10min；Enter level-one filter press after sedimentation and carry out press filtration, obtain iron cement and clear liquid；
The COD of gained clear liquid is down to 6000mg/L or so.
2) clear liquid obtained by step 1) is entered into secondary oxidation kettle, hydrogen peroxide and FeSO is added into secondary oxidation kettle4·
7H2(addition of hydrogen peroxide is the 3wt% of pyrazolone mother liquor waste water to O；The addition of the catalyst is given up for pyrazolone mother liquor
The 1wt% of water), it is 4 to add pH adjusting agent ammonium hydroxide and adjust pH, the progress two level Fenton's reaction under temperature 45 C, reaction time 2h,
Suitable defoamer can be added in reaction process according to actual conditions；Reaction solution enters flocculation kettle after reaction, to flocculation kettle
Middle addition PAM and PAC flocculates, and the addition of PAM is the 0.5wt% of pyrazolone mother liquor waste water；The addition of PAC is pyrazoles
The 1wt% of ketone mother liquor waste water, it is 8 to add ammonium hydroxide and adjust pH；Enter two level sedimentation kettle after flocculation to be settled, the sedimentation time
20min；Enter two level filter press after sedimentation and carry out press filtration, obtain iron cement and clear liquid；
The COD of gained clear liquid is down to 3500mg/L or so, and colourity is down to 64.
3) clear liquid obtained by step 2) is subjected to multiple-effect evaporation, then centrifuged, obtain solid ammonium sulfate and centrifuge mother liquor,
Recycling condensing water in Multi-effect Evaporation Processes；
4) it is 10% to control reflux ratio, by the part centrifugal mother liquor reflux obtained by step 3) and the pyrazolone mother liquor of step 1)
Waste water mixes, and circulation carries out operation of the step 1) to step 3)；Remaining centrifuge mother liquor is mixed into the clear liquid obtained by step 2)
Row multiple-effect evaporation, circulation carry out the operation of step 3).
Obtained solid ammonium sulfate reaches the quality requirements of industrial sulphuric acid ammonium.
Embodiment 2
1) pyrazolone mother liquor waste water 660t is collected, which is 15000mg/L, ammonia nitrogen concentration 40000mg/l, color
Spend for 512 or so.The waste water is pressed into flow 25m3/ h enters stair oxidation kettle, into stair oxidation kettle add hydrogen peroxide and
FeSO4·7H2(addition of hydrogen peroxide is the 0.5wt% of pyrazolone mother liquor waste water to O；FeSO4·7H2The addition of O is pyrazoles
The 1wt% of ketone mother liquor waste water；The flow for adding time control producing hydrogen peroxide is 0.25m3/ h, FeSO4·7H2The flow of O is flow of inlet water
1%), add pH adjusting agent ammonium hydroxide control pH be 4, temperature 45 C progress level-one Fenton's reaction, reaction time 2h, reacted
Cheng Zhongke adds suitable defoamer according to actual conditions；Reaction solution is with ＞ 25m after reaction3The flow of/h sinks into level-one
Drop kettle is settled, and controls pH8-9, sedimentation time 10min；After sedimentation enter level-one filter press carry out press filtration, obtain iron cement and
Clear liquid；
The COD of gained clear liquid is down to 6000mg/L or so.
2) clear liquid obtained by step 1) is pressed into flow 25m3/ h enters secondary oxidation kettle, and dioxygen is added into secondary oxidation kettle
Water and FeSO4·7H2(addition of hydrogen peroxide is the 3wt% of pyrazolone mother liquor waste water to O；The addition of the catalyst is pyrrole
The 1wt% of oxazolone mother liquor waste water；The flow for adding time control producing hydrogen peroxide is 0.25m3/ h, add catalyst when control flow for into
Water flow 3%), it is 4 to add pH adjusting agent ammonium hydroxide and adjust pH, and two level Fenton's reaction, reaction time are carried out under temperature 45 C
2h, can add suitable defoamer in reaction process according to actual conditions；Reaction solution is with ＞ 25m after reaction3The flow of/h
Into flocculation kettle, into flocculation kettle, addition PAM and PAC flocculates, and the addition of PAM is pyrazolone mother liquor waste water
0.5wt%；The addition of PAC is the 1wt% of pyrazolone mother liquor waste water, and it is 8 to add ammonium hydroxide and adjust pH；Sink after flocculation into two level
Drop kettle is settled, sedimentation time 20min；Enter two level filter press after sedimentation and carry out press filtration, obtain iron cement and clear liquid；
The COD of gained clear liquid is down to 3500mg/L or so, and colourity is down to 64.
3) clear liquid obtained by step 2) is subjected to multiple-effect evaporation, then centrifuged, obtain solid ammonium sulfate and centrifuge mother liquor,
Recycling condensing water in Multi-effect Evaporation Processes；Wherein triple effect evaporation is：
One effect evaporation control pressure 0.2MPa, 125 DEG C of temperature, feed velocity 10t/h；
Two effect evaporation control pressure 120KPa, 100 DEG C of temperature, feed velocity 6t/h；
Triple effect evaporation control pressure 45KPa, temperature 70 C, feed velocity 7t/h.
4) it is 10% to control reflux ratio, by the part centrifugal mother liquor reflux obtained by step 3) and the pyrazolone mother liquor of step 1)
Waste water mixes, and circulation carries out operation of the step 1) to step 3)；Remaining centrifuge mother liquor is mixed into the clear liquid obtained by step 2)
Row multiple-effect evaporation, circulation carry out the operation of step 3).
Obtained solid ammonium sulfate reaches the quality requirements of industrial sulphuric acid ammonium.
Embodiment 3
1) pyrazolone mother liquor waste water 660t is collected, which is 15000mg/L, ammonia nitrogen concentration 40000mg/l, color
Spend for 510 or so.The waste water is pressed into flow 26m3/ h enters stair oxidation kettle, into stair oxidation kettle add hydrogen peroxide and
FeSO4·7H2(addition of hydrogen peroxide is the 1.5wt% of pyrazolone mother liquor waste water to O；FeSO4·7H2The addition of O is pyrazoles
The 3wt% of ketone mother liquor waste water；The flow for adding time control producing hydrogen peroxide is 0.3m3/ h, FeSO4·7H2The flow of O is flow of inlet water
3%), it is 6 to add pH adjusting agent ammonium hydroxide and control pH, carries out level-one Fenton's reactions in 55 DEG C of temperature, reaction time 2h, reacted
Cheng Zhongke adds suitable defoamer according to actual conditions；Reaction solution is with ＞ 25m after reaction3The flow of/h sinks into level-one
Drop kettle is settled, and controls pH8-9, sedimentation time 10min；After sedimentation enter level-one filter press carry out press filtration, obtain iron cement and
Clear liquid；
The COD of gained clear liquid is down to 6000mg/L or so.
2) clear liquid obtained by step 1) is pressed into flow 26m3/ h enters secondary oxidation kettle, and dioxygen is added into secondary oxidation kettle
Water and FeSO4·7H2(addition of hydrogen peroxide is the 5wt% of pyrazolone mother liquor waste water to O；The addition of the catalyst is pyrrole
The 3wt% of oxazolone mother liquor waste water；The flow for adding time control producing hydrogen peroxide is 0.3m3/ h, add catalyst when control flow for into
Water flow 3%), it is 6 to add pH adjusting agent ammonium hydroxide and adjust pH, and two level Fenton's reaction, reaction time are carried out at 55 DEG C of temperature
2h, can add suitable defoamer in reaction process according to actual conditions；Reaction solution is with ＞ 25m after reaction3The flow of/h
Into flocculation kettle, into flocculation kettle, addition PAM and PAC flocculates, and the addition of PAM is pyrazolone mother liquor waste water
1.5wt%；The addition of PAC is the 2wt% of pyrazolone mother liquor waste water；It is 9.5 to add ammonium hydroxide and adjust pH；Enter two level after flocculation
Sedimentation kettle is settled, sedimentation time 20min；Enter two level filter press after sedimentation and carry out press filtration, obtain iron cement and clear liquid；
The COD of gained clear liquid is down to 3500mg/L or so, and colourity is down to 128.
3) clear liquid obtained by step 2) is subjected to multiple-effect evaporation, then centrifuged, obtain solid ammonium sulfate and centrifuge mother liquor,
Recycling condensing water in Multi-effect Evaporation Processes；Wherein triple effect evaporation is：
One effect evaporation control pressure 0.2MPa, 135 DEG C of temperature, feed velocity 15t/h；
Two effect evaporation control pressure 130KPa, 110 DEG C of temperature, feed velocity 8t/h；
Triple effect evaporation control pressure 55KPa, 90 DEG C of temperature, feed velocity 9t/h.
4) it is 10% to control reflux ratio, by the part centrifugal mother liquor reflux obtained by step 3) and the pyrazolone mother liquor of step 1)
Waste water mixes, and circulation carries out operation of the step 1) to step 3)；Remaining centrifuge mother liquor is mixed into the clear liquid obtained by step 2)
Row multiple-effect evaporation, circulation carry out the operation of step 3).
Obtained solid ammonium sulfate reaches the quality requirements of industrial sulphuric acid ammonium.
Embodiment 4
1) pyrazolone mother liquor waste water 660t is collected, which is 15000mg/L, ammonia nitrogen concentration 40000mg/l, color
Spend for 490 or so.The waste water is pressed into flow 25.5m3/ h enters stair oxidation kettle, into stair oxidation kettle add hydrogen peroxide and
FeSO4·7H2(addition of hydrogen peroxide is the 1wt% of pyrazolone mother liquor waste water to O；FeSO4·7H2The addition of O is pyrazolone
The 2% of mother liquor waste water；The flow for adding time control producing hydrogen peroxide is 0.28m3/ h, FeSO4·7H2The flow of O is flow of inlet water
2%) it is 5, to add pH adjusting agent ammonium hydroxide and control pH, and level-one Fenton's reaction, reaction time 2h, reaction process are carried out in temperature 50 C
In can add suitable defoamer according to actual conditions；Reaction solution is with ＞ 25m after reaction3The flow of/h is settled into level-one
Kettle is settled, and controls pH8.5, sedimentation time 10min；Enter level-one filter press after sedimentation and carry out press filtration, obtain iron cement and clear
Liquid；
The COD of gained clear liquid is down to 6000mg/L or so.
2) clear liquid obtained by step 1) is pressed into flow 25.5m3/ h enters secondary oxidation kettle, is added into secondary oxidation kettle double
Oxygen water and FeSO4·7H2(addition of hydrogen peroxide is the 4wt% of pyrazolone mother liquor waste water to O；The FeSO4·7H2O's adds
Enter 2% that amount is pyrazolone mother liquor waste water；The flow for adding time control producing hydrogen peroxide is 0.28m3/ h, adds FeSO4·7H2O time controls
Flow processed for flow of inlet water 2%), it is 5 to add pH adjusting agent ammonium hydroxide and adjust pH, and it is anti-that two level Fenton is carried out under temperature 50 C
Answer, reaction time 2h, suitable defoamer can be added according to actual conditions in reaction process；Reaction solution is with ＞ after reaction
25m3The flow of/h enters flocculation kettle, and PAM and PAC is added into flocculation kettle and is flocculated, the addition of PAM is pyrazolone mother liquor
The 1wt% of waste water；The addition of PAC is the 1.5wt% of pyrazolone mother liquor waste water；It is 9.0 to add ammonium hydroxide and adjust pH；Flocculate laggard
Enter two level sedimentation kettle to be settled, sedimentation time 20min；Enter two level filter press after sedimentation and carry out press filtration, obtain iron cement and clear
Liquid；
The COD of gained clear liquid is down to 3500mg/L or so, and colourity is down to 80.
3) clear liquid obtained by step 2) is subjected to multiple-effect evaporation, then centrifuged, obtain solid ammonium sulfate and centrifuge mother liquor,
Recycling condensing water in Multi-effect Evaporation Processes；Wherein triple effect evaporation is：
One effect evaporation control pressure 0.3MPa, 130 DEG C of temperature, feed velocity 12t/h；
Two effect evaporation control pressure 125KPa, 105 DEG C of temperature, feed velocity 7t/h；
Triple effect evaporation control pressure 50KPa, 80 DEG C of temperature, feed velocity 8t/h.
4) it is 10% to control reflux ratio, by the part centrifugal mother liquor reflux obtained by step 3) and the pyrazolone mother liquor of step 1)
Waste water mixes, and circulation carries out operation of the step 1) to step 3)；Remaining centrifuge mother liquor is mixed into the clear liquid obtained by step 2)
Row multiple-effect evaporation, circulation carry out the operation of step 3).
Obtained solid ammonium sulfate reaches the quality requirements of industrial sulphuric acid ammonium.
Embodiment 5
1) pyrazolone mother liquor waste water 660t is collected, which is 15000mg/L, ammonia nitrogen concentration 40000mg/l, color
Spend for 482 or so.The waste water is pressed into flow 25.2m3/ h enters stair oxidation kettle, into stair oxidation kettle add hydrogen peroxide and
FeSO4·7H2(addition of hydrogen peroxide is the 1.2wt% of pyrazolone mother liquor waste water to O；FeSO4·7H2The addition of O is pyrazoles
The 1.2% of ketone mother liquor waste water；The flow for adding time control producing hydrogen peroxide is 0.26m3/ h, FeSO4·7H2The flow of O is flow of inlet water
1.5%), it is 4 to add pH adjusting agent ammonium hydroxide and control pH, and in 52 DEG C of temperature progress level-one Fenton's reactions, reaction time 2h, reacts
During can add suitable defoamer according to actual conditions；Reaction solution is with ＞ 25m after reaction3The flow of/h enters level-one
Sedimentation kettle is settled, and controls pH8.8, sedimentation time 10min；Enter level-one filter press after sedimentation and carry out press filtration, obtain iron cement
And clear liquid；
The COD of gained clear liquid is down to 6000mg/L or so.
2) clear liquid obtained by step 1) is pressed into flow 25.2m3/ h enters secondary oxidation kettle, is added into secondary oxidation kettle double
Oxygen water and FeSO4·7H2(addition of hydrogen peroxide is the 3.6wt% of pyrazolone mother liquor waste water to O；The FeSO4·7H2O's
Addition is the 1.8% of pyrazolone mother liquor waste water；The flow for adding time control producing hydrogen peroxide is 0.27m3/ h, adds FeSO4·7H2O
When control flow for flow of inlet water 1.5%), it is 6 to add pH adjusting agent ammonium hydroxide and adjust pH, and it is fragrant to carry out two level at 48 DEG C of temperature
Reaction, reaction time 2h, can add suitable defoamer in reaction process according to actual conditions；After reaction reaction solution with
＞ 25m3The flow of/h enters flocculation kettle, and PAM and PAC is added into flocculation kettle and is flocculated, and the addition of PAM is female for pyrazolone
The 0.8wt% of liquid waste water；The addition of PAC is the 1.8wt% of pyrazolone mother liquor waste water；It is 8.8 to add ammonium hydroxide and adjust pH；Flocculation
Enter two level sedimentation kettle afterwards to be settled, sedimentation time 20min；Enter two level filter press after sedimentation and carry out press filtration, obtain iron cement
And clear liquid；
The COD of gained clear liquid is down to 3500mg/L or so, and colourity is down to 90.
3) clear liquid obtained by step 2) is subjected to multiple-effect evaporation, then centrifuged, obtain solid ammonium sulfate and centrifuge mother liquor,
Recycling condensing water in Multi-effect Evaporation Processes；Wherein triple effect evaporation is：
One effect evaporation control pressure 0.3MPa, 126 DEG C of temperature, feed velocity 13t/h；
Two effect evaporation control pressure 128KPa, 102 DEG C of temperature, feed velocity 6.2t/h；
Triple effect evaporation control pressure 48KPa, 72 DEG C of temperature, feed velocity 7.2t/h.
4) it is 10% to control reflux ratio, by the part centrifugal mother liquor reflux obtained by step 3) and the pyrazolone mother liquor of step 1)
Waste water mixes, and circulation carries out operation of the step 1) to step 3)；Remaining centrifuge mother liquor is mixed into the clear liquid obtained by step 2)
Row multiple-effect evaporation, circulation carry out the operation of step 3).
Obtained solid ammonium sulfate reaches the quality requirements of industrial sulphuric acid ammonium.
Embodiment 6
1) pyrazolone mother liquor waste water 660t is collected, which is 15000mg/L, ammonia nitrogen concentration 40000mg/l, color
Spend for 492 or so.The waste water is pressed into flow 25.7m3/ h enters stair oxidation kettle, into stair oxidation kettle add hydrogen peroxide and
FeSO4·7H2(addition of hydrogen peroxide is the 1.3wt% of pyrazolone mother liquor waste water to O；FeSO4·7H2The addition of O is pyrazoles
The 2.7% of ketone mother liquor waste water；The flow for adding time control producing hydrogen peroxide is 0.27m3/ h, FeSO4·7H2The flow of O is flow of inlet water
1.7%), it is 5.6 to add pH adjusting agent ammonium hydroxide and control pH, and level-one Fenton's reactions are carried out in 51 DEG C of temperature, reaction time 2h, instead
Suitable defoamer can be added during answering according to actual conditions；Reaction solution is with ＞ 25m after reaction3The flow of/h enters one
Level sedimentation kettle is settled, and controls pH8.6, sedimentation time 10min；Enter level-one filter press after sedimentation and carry out press filtration, obtain iron
Mud and clear liquid；
The COD of gained clear liquid is down to 6000mg/L or so.
2) clear liquid obtained by step 1) is pressed into flow 25.7m3/ h enters secondary oxidation kettle, is added into secondary oxidation kettle double
Oxygen water and FeSO4·7H2(addition of hydrogen peroxide is the 4.6wt% of pyrazolone mother liquor waste water to O；The FeSO4·7H2O's
Addition is the 2.6% of pyrazolone mother liquor waste water；The flow for adding time control producing hydrogen peroxide is 0.27m3/ h, adds FeSO4·7H2O
When control flow for flow of inlet water 2.7%), it is 4.5 to add pH adjusting agent ammonium hydroxide and adjust pH, and two level is carried out at 51 DEG C of temperature
Fenton's reaction, reaction time 2h, can add suitable defoamer in reaction process according to actual conditions；Reaction solution after reaction
With ＞ 25m3The flow of/h enters flocculation kettle, and PAM and PAC is added into flocculation kettle and is flocculated, the addition of PAM is pyrazolone
The 0.9wt% of mother liquor waste water；The addition of PAC is the 1.3wt% of pyrazolone mother liquor waste water；It is 8.4 to add ammonium hydroxide and adjust pH；Wadding
Enter two level sedimentation kettle after solidifying to be settled, sedimentation time 20min；Enter two level filter press after sedimentation and carry out press filtration, obtain iron
Mud and clear liquid；
The COD of gained clear liquid is down to 3500mg/L or so, and colourity is down to 88.
3) clear liquid obtained by step 2) is subjected to multiple-effect evaporation, then centrifuged, obtain solid ammonium sulfate and centrifuge mother liquor,
Recycling condensing water in Multi-effect Evaporation Processes；Wherein triple effect evaporation is：
One effect evaporation control pressure 0.2MPa, 132 DEG C of temperature, feed velocity 13t/h；
Two effect evaporation control pressure 127KPa, 106 DEG C of temperature, feed velocity 6.5t/h；
Triple effect evaporation control pressure 52KPa, 77 DEG C of temperature, feed velocity 8.8t/h.
4) it is 10% to control reflux ratio, by the part centrifugal mother liquor reflux obtained by step 3) and the pyrazolone mother liquor of step 1)
Waste water mixes, and circulation carries out operation of the step 1) to step 3)；Remaining centrifuge mother liquor is mixed into the clear liquid obtained by step 2)
Row multiple-effect evaporation, circulation carry out the operation of step 3).
Obtained solid ammonium sulfate reaches the quality requirements of industrial sulphuric acid ammonium.
The above is only presently preferred embodiments of the present invention, not makees limitation in any form to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any familiar technology people of the invention
Member without departing from the scope of the present invention, when the technology contents using above-mentioned prompting make it is a little variation or be modified to
The equivalent embodiment of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technical spirit pair according to the present invention
Any simple modification, equivalent change and modification that above example is made, in the range of still falling within the present invention program.
Claims (10)
- A kind of 1. recycling treatment process of pyrazolone mother liquor waste water, it is characterised in that：The recycling treatment process includes Following steps：1) pyrazolone mother liquor waste water is subjected to level-one Fenton's reaction, is settled after reaction, press filtration, obtain iron cement and clear liquid；2) by obtained by step 1) clear liquid carry out two level Fenton's reaction, flocculated, settled after reaction, press filtration, obtain iron cement and Clear liquid；3) clear liquid obtained by step 2) is subjected to multiple-effect evaporation, then centrifuged, obtain solid ammonium sulfate and centrifuge mother liquor, multiple-effect Recycling condensing water in evaporation process；4) the part centrifugal mother liquor reflux obtained by step 3) is mixed with the pyrazolone mother liquor waste water of step 1), circulation carries out step 1) to the operation of step 3)；Remaining centrifuge mother liquor is mixed with the clear liquid obtained by step 2) carries out multiple-effect evaporation, and circulation is walked Rapid operation 3).
- 2. recycling treatment process according to claim 1, it is characterised in that：Reflux control reflux described in step 4) Than in the range of 5~8%, preferably 10%.
- 3. recycling treatment process according to claim 1 or 2, it is characterised in that：Multiple-effect evaporation described in step 3) For triple effect evaporation；It is preferred that the triple effect evaporation is：One effect evaporation control pressure 0.2-0.3MPa, 125-135 DEG C of temperature, feed velocity 10-15t/h；Two effect evaporation control pressure 120-130KPa, 100-110 DEG C of temperature, feed velocity 6-8t/h；Triple effect evaporation control pressure 45-55KPa, 70-90 DEG C of temperature, feed velocity 7-9t/h.
- 4. according to the recycling treatment process described in claim 1-3 any one, it is characterised in that：In step 2), carrying out PAM and PAC is added during flocculation；The addition of the PAM is the 0.5-1.5wt%, preferably 1wt% of pyrazolone mother liquor waste water；The addition of the PAC is the 1-2wt%, preferably 1.5wt% of pyrazolone mother liquor waste water；The flocculated condition is：pH8-9.5；It is preferred that being additionally added pH adjusting agent when being flocculated, the pH adjusting agent is ammonium hydroxide.
- 5. according to the recycling treatment process described in claim 1-4 any one, it is characterised in that：In step 1), one is carried out During level Fenton's reaction, the addition of hydrogen peroxide is the 0.5-1.5wt%, preferably 1wt% of pyrazolone mother liquor waste water；FeSO4·7H2O Addition be pyrazolone mother liquor waste water 1-3wt%, preferably 2%；The condition of the level-one Fenton's reaction is：45~55 DEG C of temperature, pH value 4~6.
- 6. recycling treatment process according to claim 5, it is characterised in that：It is additionally added when carrying out level-one Fenton's reaction PH adjusting agent and/or defoamer；It is preferred that the pH adjusting agent is ammonium hydroxide.
- 7. according to the recycling treatment process described in claim 1-6 any one, it is characterised in that：In step 2), two are carried out During level Fenton's reaction, the addition of hydrogen peroxide is the 3-5wt%, preferably 4wt% of pyrazolone mother liquor waste water；FeSO4·7H2O's adds Enter amount be pyrazolone mother liquor waste water 1-3wt%, preferably 2%；The condition of the two level Fenton's reaction is：45~55 DEG C of temperature, pH value 4~6.
- 8. recycling treatment process according to claim 7, it is characterised in that：It is additionally added when carrying out two level Fenton's reaction PH adjusting agent and/or defoamer；It is preferred that the pH adjusting agent is ammonium hydroxide and/or sulfuric acid.
- 9. according to the recycling treatment process described in claim 1-8 any one, it is characterised in that：Carrying out, level-one Fenton is anti- When should be with two level Fenton's reaction, flow of inlet water be 25-26m3/ h, dioxygen water flow are 0.25-0.3m3/h。
- 10. recycling treatment process according to claim 9, it is characterised in that：During level-one Fenton's reaction, catalyst is added When control flow be flow of inlet water 1-3%；During two level Fenton's reaction, the 1- that flow is flow of inlet water is controlled when adding catalyst 3%.
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| CN110127830A (en) * | 2019-05-27 | 2019-08-16 | 湖北省宏源药业科技股份有限公司 | A kind of explosion-proof processing method of -5 nitroimidazole of 2- methyl production waste water |
| CN110723869A (en) * | 2019-10-09 | 2020-01-24 | 合肥停弦渡生物科技有限公司 | Improved Fenton sewage treatment method based on pre-oxidant |
| CN115367903A (en) * | 2021-05-18 | 2022-11-22 | 丰田自动车株式会社 | Waste liquid treatment method and waste liquid treatment apparatus |
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| US4758347A (en) * | 1986-02-07 | 1988-07-19 | Ciba-Geigy Corporation | Process for purifying dyeing wastewaters |
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