CN104045195A - Pre-treatment method of semi-coke wastewater - Google Patents
Pre-treatment method of semi-coke wastewater Download PDFInfo
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- CN104045195A CN104045195A CN201410320082.8A CN201410320082A CN104045195A CN 104045195 A CN104045195 A CN 104045195A CN 201410320082 A CN201410320082 A CN 201410320082A CN 104045195 A CN104045195 A CN 104045195A
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Abstract
The invention relates to the field of sewage treatment, and in particular relates to a pre-treatment method of semi-coke wastewater. The method comprises the following steps: 1, adding the semi-coke wastewater into a micro-electrolytic reactor, using Fe scraps and activated carbon particles as filler, and performing micro-electrolysis to obtain wastewater subjected to micro-electrolysis; 2, adding the wastewater subjected to micro-electrolysis into a Fenton reagent reactor, dripping H2O2 into the Fenton reagent reactor, and performing reaction to obtain wastewater subjected to secondary treatment; 3, adding a polyacrylamide coagulant into the wastewater subjected to secondary treatment, regulating the pH value to be 7-9, and performing coagulating sedimentation to obtain pre-treated semi-coke wastewater. The pre-treatment method of the semi-coke wastewater provided by the invention can be used for effectively reducing the concentration of organic pollutants in the wastewater and improving the biodegradability of the wastewater, and can be used for greatly improving the organic matter removal capacity compared with an ordinary pre-treatment method in the prior art; in addition, the pre-treatment method is relatively cheap in required treatment reagent and easily-controllable in reaction conditions.
Description
Technical field
The present invention relates to sewage treatment area, in particular to the pretreatment process of blue charcoal waste water.
Background technology
In blue charcoal (semicoke) production technique, it adopts the production technique of high temperature carbonization (1000 DEG C) different from coke, blue charcoal mainly adopts low-temperature pyrolysis (500 DEG C) method, first by raw coal through seasoning, then rise to furnace roof coal store by chapelet, and adding continuously dry distillation carbonizing furnace, in warp, low-temperature pyrolysis obtains blue charcoal.
Blue charcoal waste water is the waste water producing in the processing and refining process of coal semicoke processed, gas purification and semicoke product, and its water quality changes with raw coal composition and coke making process, is that its complicated component is changeable, toxicity is large containing high density wastewater containing phenol and cyanide.Generally speaking, its contained organism, except phenolic compound, also comprises fats compound, heterogeneous ring compound and the polynuclear compound etc. of difficult for biological degradation; Its contained inorganic components comprises sulfide, prussiate, ammonia nitrogen, is a kind of trade effluent that typically contains biodegradable organic compounds.In the technique that it is processed, such waste water is difficult to directly adopt biochemical treatment, needs first it to be carried out carrying out biochemical treatment after pre-treatment again.
At present, in correlation technique, most domestic Lan Tan enterprise mostly adopts routine " physico-chemical pretreatment+biochemical treatment " method, and wherein conventional physico-chemical pretreatment technique comprises oil removal, extracting and dephenolizing, distillation deamination, ozone oxidation, catalyzed oxidation, coagulating sedimentation, absorption method etc.
But, for the technique of oil removal, extracting and dephenolizing and distillation deamination, its to contaminant removal capacity a little less than, only can effectively remove part pollutent, to many rings, heterocyclic organism be difficult to remove; Therefore, it can not effectively improve the biodegradability of blue charcoal waste water.For ozone oxidation, catalyzed oxidation, coagulating sedimentation and absorption method thereof; It needs a large amount of oxygenant, sorbing material etc., and the price of these materials is all more expensive, and reaction conditions is also harsher, slightly controls improper reduction pretreating effect that can be serious.As can be seen here, in correlation technique, the common pretreatment process to blue charcoal waste water, there is the defect that treatment effect is not good, cost is high in it.Therefore, provide a kind of all kinds of organic and inorganic impurity that can effectively remove in blue charcoal waste water, thereby the pretreatment process that improves its biodegradability is this area technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the present invention is to provide a kind of pretreatment process of blue charcoal waste water, to solve above-mentioned technical problem.
The pretreatment process that blue charcoal waste water is provided in an embodiment of the present invention, comprises the following steps:
1), blue charcoal waste water is joined in micro-electrolysis reactor, taking Fe bits and activated carbon granule as filler, carry out micro-electrolysis, obtain waste water after micro-electrolysis;
2), waste water after described micro-electrolysis is joined in Fenton reagent react device, in described Fenton reagent react device, drip H
2o
2, react, obtain secondary treatment waste water;
3), in described secondary treatment waste water, add polyacrylamide coagulating agent, and regulate pH value for 7-9, carry out coagulating sedimentation, obtain blue charcoal waste water after pre-treatment.
The pretreatment process of this blue charcoal waste water provided by the invention, the operation that it has adopted successively micro-electrolysis, Fenton reagent react and added polyacrylamide coagulating agent coagulating sedimentation blue charcoal waste water; In the process of micro-electrolysis, taking Fe bits and activated carbon granule as filler, when filler is immersed in after blue charcoal waste water solution, there is battery effect and form countless small corrosion galvanic cells, metal anode is corroded and consumes, simultaneous electrochemical corrosion has caused again a series of related synergies, comprise the multiple effect combined effects such as flocculation, absorption, bridge formation, volume are swept, coprecipitated, galvanic deposit, electrochemical reduction, the reaction of generation comprises that redox reaction, galvanic cell reaction, electrochemistry enrichment, material resources are adsorbed and the coagulating sedimentation effect of Fe ion; Thereby realize the degradation effect of organic pollutant.
After micro-electrolysis, waste water joins in Fenton reagent react device again, by dripping therein H
2o
2form react, owing to containing Fe in reaction system
2+and H
2o
2, H
2o
2by Fe
2+catalytic decomposition becomes hydroxyl radical free radical (OH), thereby and cause chain reaction and produce more other free radicals, these free radicals have very strong oxidative decomposition capacity, the organic pollutant in the further effective degrading waste water of ability, and then obtain secondary treatment waste water.
Finally, in secondary treatment waste water, owing to containing a large amount of Fe ions, need to be removed, therefore, by add polyacrylamide coagulating agent in secondary treatment waste water, and regulate pH value for 7-9 (meeting reaction requirement), be carried out coagulating sedimentation; In the process of coagulating sedimentation, can preferably remove secondary pollutant Fe ion, also can further remove residual organism simultaneously.After finishing, three steps can obtain blue charcoal waste water after pre-treatment.The blue charcoal waste water obtaining, its biodegradability index improves greatly, can directly carry out follow-up biochemical treatment operation.
This pretreatment process to blue charcoal waste water that the embodiment of the present invention provides, it adopts micro-electrolysis+Fenton reagent+coagulation-settlement process to effectively reduce the organic contamination substrate concentration in blue charcoal waste water, poisonous by high density, the blue charcoal wastewater degradation of harmful difficult degradation is the waste water that lower concentration can directly carry out biochemical treatment, effectively reduce the concentration of Organic Pollutants in Wastewater, and improve the biodegradability of waste water, compared with pretreatment process common in prior art, it is removed organic ability and greatly promotes, in addition, its required reagent treatment is all less expensive, reaction conditions is easy to control.Checking by experiment, blue charcoal waste water after the pre-treatment obtaining, its biodegradability index (BOD
5/ CODcr) can reach more than 0.51, be convenient to very much follow-up biochemical treatment operation.
Optionally, in step 1) in: described Fe bits and described activated carbon granule quality equate, and the particle diameter of described Fe bits is 5-7 millimeter; The particle diameter of described activated carbon granule is 2-3 millimeter; The time of described micro-electrolysis is 80-100 minute.
Optionally, in step 2) in, specifically comprise: waste water after described micro-electrolysis is joined in Fenton reagent react device, in described Fenton reagent react device, drip H
2o
2, and make described H
2o
2volume content reaches 3.5-4ml/L, and reaction 80-100min, obtains secondary treatment waste water.
Optionally, in step 3) in; Described polyacrylamide coagulating agent is that mass percent is 0.1% polyacrylamide solution; And in secondary treatment waste water every liter described, the volume of described 0.1% the polyacrylamide solution adding is 2-3 milliliter.
Optionally, in step 3) in: regulating pH value reagent used is NaOH.
Optionally, in described step 3) in, specifically comprise: set in advance coagulation basin; Waste water after described secondary treatment is passed in described coagulation basin, then adds polyacrylamide coagulating agent, regulate its pH value for 7-9, carry out coagulating sedimentation, obtain blue charcoal waste water after pre-treatment.
Optionally, in the process of described coagulating sedimentation: temperature is controlled at 20-25 DEG C, the time is 140-180 minute.
Brief description of the drawings
In order to be illustrated more clearly in the specific embodiment of the invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
The pretreatment process schema of the blue charcoal waste water that Fig. 1 provides for the embodiment of the present invention one;
In the pretreatment process of the blue charcoal waste water that Fig. 2 provides for the embodiment of the present invention two, the B/C value of waste water at different levels.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer; to technical scheme of the present invention be carried out to clear, complete description below; based on the embodiment in the present invention; all other embodiments that those of ordinary skill in the art obtain under the prerequisite of not making creative work, all belong to the scope that the present invention protects.
Embodiment mono-
The pretreatment process of this blue charcoal waste water that the embodiment of the present invention provides, please refer to Fig. 1, comprises the following steps:
Step 101: blue charcoal waste water is joined in micro-electrolysis reactor, taking Fe bits and activated carbon granule as filler, carry out micro-electrolysis, obtain waste water after micro-electrolysis;
In step 101, in the middle of micro-electrolysis reactor, together with Fe bits are in direct contact with gac, be immersed in conductive blue charcoal waste water solution, battery effect occurs and form countless small corrosion galvanic cells, metal anode is corroded and consumes, and simultaneous electrochemical corrosion has caused again a series of related synergies, comprise the multiple effect combined effects such as flocculation, absorption, bridge formation, volume are swept, coprecipitated, galvanic deposit, electrochemical reduction, thereby realize the degraded of organic pollutant.In addition, the advantages such as this method has that speed of response is fast, applied widely, technical process is simple, treatment effect is stable, investment cost is few, convenient operating maintenance, running cost are low, long service life, and use waste iron filing for raw material, do not need power consumption resource, there is the meaning of " treatment of wastes with processes of wastes against one another ".
Step 102: waste water after described micro-electrolysis is joined in Fenton reagent react device, drip H in described Fenton reagent react device
2o
2, react, obtain secondary treatment waste water;
In step 102, owing to containing ferrous ion in waste water after micro-electrolysis, after being joined in Fenton reagent react device, by dripping H
2o
2after, H
2o
2by Fe
2+catalytic decomposition becomes hydroxyl radical free radical (OH), thereby and cause chain reaction and produce more other free radicals, these free radicals have very strong oxidative decomposition capacity, can be further the effective organic pollutant in degrading waste water.In addition, adding H
2o
2process in, for the sufficient effect of realization response, adopt dropping limit, limit stir mode add H
2o
2.
Step 103: add polyacrylamide coagulating agent in described secondary treatment waste water, and regulate pH value for 7-9, carry out coagulating sedimentation, obtain blue charcoal waste water after pre-treatment.
In secondary treatment waste water, it also contains some residual organism and Fe ion, therefore,, in order further to remove residual organic matter and Fe ion, need to again process, in the present embodiment, employing adds polyacrylamide coagulating agent and makes secondary treatment waste water carry out coagulating sedimentation, in addition, and in the process of coagulation, its pH value is 7-9, to ensure carrying out smoothly of reaction.
For the pretreatment process of the blue charcoal waste water that makes the above embodiment of the present invention is better applied, more effectively be applied in sewage treatment area, the present invention also provides embodiment bis-on the basis of above-described embodiment, embodiment bis-is the further refinement of pretreatment process or increases of the blue charcoal waste water of above-described embodiment, is now described in detail and explains:
Embodiment bis-
In the present embodiment, the preparation method of the pretreatment process of blue charcoal waste water comprises the following steps:
S1: blue charcoal waste water is joined in micro-electrolysis reactor, taking Fe bits and activated carbon granule as filler, carry out micro-electrolysis, obtain waste water after micro-electrolysis;
In this step, described Fe bits and described activated carbon granule quality equate, and the particle diameter of described Fe bits is 5-7 millimeter; The particle diameter of described activated carbon granule is 2-3 millimeter; The time of described micro-electrolysis is 80-100 minute; Have the combination that above-mentioned technique limits, its micro-electrolysis effectiveness is more excellent.
S2: waste water after described micro-electrolysis is joined in Fenton reagent react device, drip H in described Fenton reagent react device
2o
2, react, obtain secondary treatment waste water;
In S2, waste water after described micro-electrolysis is joined in Fenton reagent react device, in described Fenton reagent react device, drip H
2o
2, and make described H
2o
2volume content reaches 3.5-4ml/L, and reaction 80-100min, obtains secondary treatment waste water.
In order to realize H
2o
2abundant decomposition, i.e. H
2o
2by Fe
2+catalytic decomposition becomes hydroxyl radical free radical (OH), and then forms extremely strong oxidative decomposition capacity, preferred, is dripping H
2o
2process in, described H
2o
2volume content reaches 3.5-4ml/L, reaction 80-100min, with 90 minutes for most preferably.
S3: add polyacrylamide coagulating agent in described secondary treatment waste water, and regulate pH value for 7-9, carry out coagulating sedimentation, obtain blue charcoal waste water after pre-treatment;
Preferably, for realizing more excellent treatment effect when, also cost-saving, in the present embodiment, described polyacrylamide coagulating agent is that mass percent is 0.1% polyacrylamide solution; And in secondary treatment waste water every liter described, the volume of described 0.1% the polyacrylamide solution adding is 2-3 milliliter, in addition, regulating in the process of its pH value, reagent used is NaOH.
In addition, above-mentioned steps can specifically complete according to following operation:
1, set in advance coagulation basin;
In the time that wastewater treatment capacity is larger, need to secondary treatment waste water be first focused in the coagulation basin setting in advance and carry out the process of coagulating sedimentation.
2, waste water after described secondary treatment is passed in described coagulation basin, then adds polyacrylamide coagulating agent, regulate its pH value for 7-9, carry out coagulating sedimentation, obtain blue charcoal waste water after pre-treatment;
In addition, in the process of precipitation, preferred, its temperature is controlled between 20-25 DEG C, and the time is 140-180min.
It is to be noted, in embodiments of the present invention, the parallel setting of equipment that whole treating processes is used, blue charcoal waste water is discharged from the bottom of dust-collecting bucket, and enters its inside (dust-collecting bucket setting position is higher than micro-electrolysis reactor) from the bottom of micro-electrolysis reactor.After micro-electrolysis reaction, after micro-electrolysis, waste water is exported from the top of micro-electrolysis reactor, and enters in Fenton reagent react device; And after Fenton reagent react, be directly communicated with formulation coagulating sedimentation in coagulation basin with coagulation basin by water shoot.
In addition, the present embodiment carries out biodegradability Test and Comparison Study to independent iron-carbon micro-electrolysis processed waste water, micro-electrolysis+Fenton reagent method processed waste water and micro-electrolysis+Fenton reagent method+coagulating sedimentation three combination process.Result of study please refer to shown in table 1 and Fig. 2.
Table 1 various combination technological test water outlet result
As shown in Table 1, using Fe-C Micro Electrolysis Method is separately only 38.7% to the CODcr clearance of blue charcoal waste water, adopt micro-electrolysis and Fenton agent combination technique can reach 57.4% to the CODcr clearance of blue charcoal waste water, further adopt the total CODcr clearance of waste water of micro-electrolysis+Fenton reagent+coagulating sedimentation combination process can reach 79.2%, the CODcr treatment effect that visible iron-carbon micro-electrolysis+Fenton reagent+coagulating sedimentation combination process is compared independent micro-electrolysis will be got well.In table 1, former water is without any pretreated blue charcoal waste water.
After adopting pretreatment technology to process blue charcoal waste water, waste water quality can not meet corresponding sewage drainage standard, need further to adopt biochemical process to carry out advanced treatment to pretreated waste water, and the B/C value of waste water is the main standard that judges that can waste water effectively adopt biochemical process to process, specifically in table 2.
Table 2 wastewater treatment biodegradability evaluation reference data
The B/C value of blue charcoal waste water is 0.24, belongs to more difficult biochemical treatment waste water, need to adopt pretreatment technology to process rear its B/C value that improves to it and could meet biochemical treatment requirement.
After microelectrolysis processing, the B/C value of blue charcoal waste water rises to 0.37 by 0.24 of former water, and wastewater biodegradability is significantly improved, and reaching can biochemical treatment requirement.BOD5 concentration by further employing Fenton reagent method and coagulating sedimentation processed waste water is also presenting downtrending, but because the CODcr of water outlet diminishes as more remarkable, after adopting combination process to process, the B/C value of blue charcoal waste water can have original 0.24 to bring up to 0.51, meet easy biochemical treatment requirement, therefore, what adopt that micro-electrolysis+Fenton reagent method+coagulation-settlement process processes water outlet after blue charcoal enterprise wastewater can be biochemical better, and adopting this kind of combination process is effectively desirable to processing this type of waste water.
To sum up, the present embodiment is by adopting micro-electrolysis+Fenton reagent+coagulation-settlement process to effectively reduce the organic contamination substrate concentration in blue charcoal waste water, poisonous by high density, the blue charcoal wastewater degradation of harmful difficult degradation is the waste water that lower concentration can directly carry out biochemical treatment, effectively reduce the concentration of Organic Pollutants in Wastewater, and improve the biodegradability of waste water, and whole processing engineering does not exist the problem of secondary pollution (not form various sensual pleasure groups or auxochrome group material, as 3-methyl isophthalic acid, 3, 6 heptantrienes, 5-norbornylene-2-carboxylic acid, phenol etc.), the ferrous ion producing can be removed by the operation of coagulating sedimentation, for the biochemical treatment of follow-up blue charcoal waste water the discharge index that reaches relevant regulations are laid a good foundation.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (7)
1. the pretreatment process of blue charcoal waste water, is characterized in that, comprises the following steps:
1), blue charcoal waste water is joined in micro-electrolysis reactor, taking Fe bits and activated carbon granule as filler, carry out micro-electrolysis, obtain waste water after micro-electrolysis;
2), waste water after described micro-electrolysis is joined in Fenton reagent react device, in described Fenton reagent react device, drip H
2o
2, react, obtain secondary treatment waste water;
3), in described secondary treatment waste water, add polyacrylamide coagulating agent, and regulate pH value for 7-9, carry out coagulating sedimentation, obtain blue charcoal waste water after pre-treatment.
2. the pretreatment process of blue charcoal waste water according to claim 1, is characterized in that, in step 1) in:
Described Fe bits and described activated carbon granule quality equate, and the particle diameter of described Fe bits is 5-7 millimeter; The particle diameter of described activated carbon granule is 2-3 millimeter; The time of described micro-electrolysis is 80-100 minute.
3. the pretreatment process of blue charcoal waste water according to claim 1, is characterized in that, in step 2) in, specifically comprise:
Waste water after described micro-electrolysis is joined in Fenton reagent react device, in described Fenton reagent react device, drip H
2o
2, and make described H
2o
2volume content reaches 3.5-4ml/L, and reaction 80-100min, obtains secondary treatment waste water.
4. according to the pretreatment process of the blue charcoal waste water described in claim 1-3 any one, it is characterized in that, in step 3) in;
Described polyacrylamide coagulating agent is that mass percent is 0.1% polyacrylamide solution; And in secondary treatment waste water every liter described, the volume of described 0.1% the polyacrylamide solution adding is 2-3 milliliter.
5. the pretreatment process of blue charcoal waste water according to claim 4, is characterized in that, in step 3) in:
Regulating pH value reagent used is NaOH.
6. the pretreatment process of blue charcoal waste water according to claim 5, is characterized in that, in step 3) in, specifically comprise:
Set in advance coagulation basin;
Waste water after described secondary treatment is passed in described coagulation basin, then adds polyacrylamide coagulating agent, regulate its pH value for 7-9, carry out coagulating sedimentation, obtain blue charcoal waste water after pre-treatment.
7. the pretreatment process of blue charcoal waste water according to claim 6, is characterized in that,
In the process of described coagulating sedimentation: temperature is controlled at 20-25 DEG C, the time is 140-180 minute.
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Application publication date: 20140917 |