CN104944678A - Process for treating comprehensive high-concentration and high-salt refractory wastewater - Google Patents
Process for treating comprehensive high-concentration and high-salt refractory wastewater Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 35
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- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 238000001704 evaporation Methods 0.000 claims abstract description 22
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- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 238000009833 condensation Methods 0.000 claims description 9
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- 239000003344 environmental pollutant Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
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- 239000012028 Fenton's reagent Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of environment protection and particularly relates to a process for treating comprehensive high-concentration and high-salt refractory wastewater. The process concretely comprises the steps of heating to evaporate water after regulating the pH value of high-salt and high-concentration refractory wastewater, on the one hand, collecting water steam obtained after evaporation to form condensed water, and treating the condensed water in a biochemical system; and on the other hand, directly incinerating the residual concentrated solution obtained after evaporation. The process disclosed by the invention has a relatively good effect on treating COD, NH3-N, TN, TP, salts and the like in a water body and can be used for effectively relieving the inhibiting effect of the salts to microbial growth and ensuring the normal function of the subsequent biological treatment stage.
Description
Technical field
The invention belongs to environmental protection technical field, particularly a kind for the treatment of process method for comprehensive high density height salt used water difficult to degradate.
Background technology
Microorganism treating sewage is utilized to be for taking as the leading factor with photosynthetic bacteria group and yeast flora, other beneficial microorganism actings in conjunction collaborative, produce antioxidant, oxidation of organic compounds is decomposed by approach such as redox fermentations, degraded, transformation are risen to harmful organic compounds in sewage, harmful and noxious substance is converted into nontoxic material, but simple microbiological treatment technology is only applicable to the very low sewage disposal of Pollutant levels.Because the tolerance of microbe is very limited, therefore not only too many effect is not but had for the sewage that concentration is slightly high, and microorganism can be caused to be subject to serious infringement and cannot to regenerate.
A difficult problem for the process of high density high-salt wastewater in prior art always, such high pollution waste water is difficult to purify separately, and often need to introduce low concentration wastewater or even clean water distribution, and turn down the concentration of high pollution Pollutants in Wastewater, could further to purification of water quality process.Such as: first adopt and add polymerize aluminum chloride and the polyacrylamide mode as flocculation agent and coagulating agent, react with SS a large amount of in former water and generate flco, precipitate and separate removal SS; After enter stripping tower, utilize chemical process remove free ammonia; Then waste water is entered anaerobic reactor and (adopt UASB pond type, bottom water inlet, top water outlet, fluidised form in reactor is upwelling), utilize the effect that anaerobion is effectively decomposed organism, in waste water, the COD (BOD) of part is removed, to alleviate the load of follow-up aerobic treatment; Water outlet after anaerobic reaction still has higher COD and ammonia nitrogen, if directly enter follow-up Aerobic biological process, and will be toxic to microorganism, therefore, introduce low concentration wastewater, and part water distribution, ensure the scope that mixed waste water quality reaches aerobe and can tolerate.In Aerobic Pond, adopt plate-type aerator to provide dissolved oxygen for biochemical reaction, utilize the principle of microbial assimilation alienation and nitration denitrification, remaining COD and ammonia nitrogen are removed further.
Above-mentioned purification process needs to introduce the auxiliary processes such as a large amount of water distributions, greatly increases the running cost of system, can produce a large amount of mud simultaneously, increases the expense of specific resistance to filtration.Meanwhile, due to influent COD and ammonia nitrogen isoconcentration higher, microbial biochemical system cloud gray model load is comparatively large, and effluent quality is difficult to effectively be ensured; Simultaneously because water inlet salt concentration is too high, restraining effect is produced to microbial growth in system, further influential system treatment effect.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of can directly for the treatment and purification technique of high-concentration hardly-degradable waste water, without the need to additionally introducing low concentration wastewater or clean water distribution; And do not produce extra secondary settlement pollution.
For solving the problems of the technologies described above, the technical solution used in the present invention is: after regulating the pH value of high salt high-concentration hardly-degradable waste water (calling in the following text " water inlet "), carry out heating evaporation moisture, the water vapor obtained after collecting evaporation on the one hand forms water of condensation, water of condensation is entered biochemical system and processes; On the other hand the concentrated solution of remaining after evaporation is directly burned,
Wherein, described high salt high-concentration hardly-degradable waste water is for containing COD, NH
3the waste water of-N, TN, TP and salinity, the pH value regulating waste water is 6 ~ 8, and in waste water, the content of COD is 62000mg/L to the maximum, NH
3the content of-N is 1500mg/L to the maximum, and the content of TN (total nitrogen) is 2500mg/L to the maximum, and the content of TP (total phosphorus) is 500mg/L to the maximum, and the content of salinity is 60000mg/L to the maximum,
Above-mentioned heating evaporation temperature is set greater than evaporation of water temperature, and is less than COD, NH
3the vaporization temperature of-N, TN, TP and salinity, further: heating evaporation temperature is about 100 DEG C,
To waste water heating evaporation, the temperature of waste water is raised, because the pollution substances such as the salinity in waste water, solvability COD are higher than the boiling point of water a lot, when wastewater temperature raises the boiling point reaching water gradually, moisture in waste water starts evaporation and forms water vapor effusion system, pollution substance is then left in solution, along with the continuous evaporation of water, the concentration of Pollutants in Wastewater also constantly raises, remaining dope then constantly reduces, this completes being separated, due to influent COD and NH in this programme of (part) water and pollution substance
3-N concentration is higher, some volatility COD and NH
3can form water of condensation with water vapor, therefore distilling the water of condensation obtained still needs to enter biochemical system and processes, but the pollution pressure that now Institute of Micro-biology faces in biochemical system is much smaller, completely within its tolerance scope,
As preferably: when carrying out heating evaporation to high salt high-concentration hardly-degradable waste water, adopt the mode of " steam heating ", adopt during which heating and the secondary steam that evaporation produces all can be collected, again as the thermal source of evaporation after improving its pressure and temperature by mechanically compress mode;
And for the concentrated solution of remaining after evaporation, salinity material main in concentrated solution is Na
2sO
4, the COD of concentrated solution is high simultaneously, and can reach 100,000 even hundreds thousand of mg/L, calorific value is very high, directly burns the heat that both can make full use of COD in concentrated solution to it, can not produce the secondary pollution materials such as dioxin again simultaneously.
Beneficial effect of the present invention is: technique of the present invention is for COD, the NH in water body
3-N, TN, TP and salt grade all has the removal effect of good treatment effect, particularly salinity to be far superior to other existing techniques such as advanced oxidation, effectively can alleviate the restraining effect of salinity for microorganism growth, ensures the normal function of subsequent biological treatment workshop section; In technique, stoste is concentrated, effectively can reduce the output of dope, adopt the technique of the concentrated solution that directly burns, make full use of the high calorie in concentrated solution contained by COD, turn waste into wealth.
Embodiment
Embodiment 1
Obtain " water inlet " after regulating the pH value of high salt high-concentration hardly-degradable waste water, " water inlet " is carried out heat (Heating temperature is 100-105 DEG C) transpiring moisture, be evaporated to COD, NH in waste water system
3in-N, TN, TP or salinity, there is any one to pollute solute and reach capacity.On the one hand the concentrated solution of remaining after evaporation is directly burned; The water vapor obtained after collecting evaporation on the other hand forms water of condensation, and water of condensation is entered biochemical system and processes, the water of condensation obtained after process is called " water outlet ", and detect " water inlet " and " water outlet " in the present embodiment, result is as shown in table 1:
Table 1
| Project | Unit | Water inlet | Water outlet | Clearance (%) |
| pH | Zero dimension | 6 | 5.35 | - |
| COD cr | mg/L | 61600 | 8900 | 85.5 |
| NH 3-N | mg/L | 1414 | 52 | 96.3 |
| TN | mg/L | 2500 | 115 | 95.4 |
| TP | mg/L | 486.4 | 32 | 93.4 |
| Salinity | mg/L | 59426 | 180 | 99.7 |
Comparative example 1 (FBR-Fenton technique)
Fenton oxidation method utilizes Fenton reagent (H
2o
2with Fe
2+) strong oxidizing property oxidized waste water in a kind of method of wastewater treatment of hard-degraded substance.
The principle of Fenton's reaction is: Fenton's reaction take ferrous ion as a series of free radical reactions of catalyzer.Principal reaction is roughly as follows:
Fe
2++H
2O
2＝＝Fe
3++OH
-+·HO
Fe
3++H
2O
2+OH
-＝＝Fe
2++H
2O+·HO
Fe
3++H
2O
2＝＝Fe
2++H
++HO
2
HO
2+H
2O
2＝＝H
2O+O
2↑+·HO
Fenton reagent is by above reaction, and (hydroxyl radical free radical, electrode potential 2.80EV, is only second to F constantly to produce HO
2), make whole system have strong oxidizing property, the material that chlorobenzene, Benzyl Chloride, grease etc. are difficult to be oxidized by general oxygenant (chlorine, clorox, dioxide peroxide, ozone) can be oxidized.Usually can by most of organic compound as carboxylic acid, alcohol, ester class be oxidized to inorganic states, oxidation effectiveness is fairly obvious.
Experimental program
(1) analyze former water COD value and determine for removing COD amount, and calculate hydrogen peroxide chemical feeding quantity and ferrous sulfate chemical feeding quantity, conversion is to the revolution of pump;
(2) Jiang Yuanshui inserts former bucket, regulates pH;
(3) H is got out
2o
2and ferrous sulfate, pumping capacity and revolution relation are adjusted to and need revolution;
(4) start H simultaneously
2o
2pump, waste water pump, reflux pump;
(5) stable reaction, collects out flowing water, adjusts pH, adds PAM, coagulating sedimentation, leaves standstill and gets supernatant liquor survey COD.
Experimental data and result
Get secondary clarifier effluent to test, former water COD be diluted to about 300mg/L, FBR-Fenton test chemical feeding quantity and Inlet and outlet water COD value as shown in table 2.
Table 2
| Project | Unit | Numerical value |
| Influent COD cr | mg/L | 299 |
| Flooding velocity | L/h | 13 |
| 27.5％H 2O 2Chemical feeding quantity | L/m 3 | 1.90 |
| 90% purity FeSO 4-7H 2O chemical feeding quantity | kg/m 3 | 4.1 |
| Water outlet COD cr | mg/L | 69 |
| COD clearance | ％ | 76.92 |
Comparative example 2 (advanced oxidation processes)
Pass through medicine sedimentation coagulation to the sewage of homogeneous in this programme, remove a certain proportion of organism, the part inorganics that can produce COD is removed in neutralization simultaneously.Pretreated water directly enters HECAF treater, in treater, according to the kind and the corresponding proprietary material of character filling, catalyzer and other auxiliarys that need the pollutent removed in waste water, composition removes certain or a certain class is inorganic or the best mixed packing material of organic pollutant, and they is placed in the flocculating bed of compact construction.Wastewater streams is when flocculation bed device, under certain operating conditions, just a series of physics chemical action can be there is with the pollutent of waste water in the stopping composition in device, produce the coagulating agent of one or more status nascendis and the oxygenant of status nascendi, by multiple physics chemical action such as coagulation, catalyzed oxidation decomposition, displacements, the pollutent in waste water is removed rapidly.
After above pre-treatment, water outlet enters the advanced oxidation equipment for long-chain and benzene type organic sewage.This technology is Using Electrochemical Reactor with Three-dimensional Electrode technology and being coupled of catalytic oxidation technologies, and from the principle of three-diemsnional electrode, do carrier with specific filler etc., inorganic oxide is initiator, develops the efficient mosaic electrode material of chemical property.Do excitation energy with electric energy, under lower safety voltage (<50V), utilize the O in air
2, the H of status nascendi is generated by a series of chemical reaction mechanism
2o
2, decompose the hydroxyl radical free radical (OH) producing and there is extremely strong oxidisability further thereupon.The organism of major part microorganism difficult degradation is all cloud density many rings pockety or heterocyclic arene class in molecule, there is just because of hydroxyl radical free radical (OH) feature of attacking cloud density eminence in organic molecule, OH free radical can make it to be degraded to easily by the small organic molecule that microorganism is decomposed further by rapid oxidation, or is directly CO by the thorough mineralising of OH free radical
2and H
2o.
Experimental data and result
Use former water to test, it is as shown in table 3 that advanced oxidation tests the every processing rate obtained.
Table 3
| Project | Unit | Water inlet | Water outlet | Clearance (%) |
| pH | Zero dimension | 5.29 | 4.9 | - |
| COD cr | mg/L | 58100 | 423 | 99.3 |
| NH 3-N | mg/L | 610 | 8 | 98.7 |
| TN | mg/L | 650 | 30 | 95.4 |
Technique in embodiment 1, comparative example 1,2 is to the comparison of the clearance of various pollution substance, and result is as shown in table 4:
Table 4
| Technique | COD cr | NH 3-N | TN | TP | Salinity |
| FBR-Fenton | 76.92％ | 7.12％ | 6.34％ | 14.65％ | 2.31％ |
| Advanced oxidation | 99.3％ | 98.7％ | 95.4％ | 16.24％ | 3.15％ |
| MVC | 85.5％ | 96.3％ | 95.4％ | 93.4％ | 99.7％ |
Claims (10)
1. the treatment process of one kind high salt high-concentration hardly-degradable waste water, it is characterized in that: described treatment process is, after regulating the pH value of described high salt high-concentration hardly-degradable waste water, carry out heating evaporation moisture, the water vapor obtained after collecting evaporation on the one hand forms water of condensation, described water of condensation is entered biochemical system and processes; On the other hand the concentrated solution of remaining after evaporation is directly burned.
2. the treatment process of high salt high-concentration hardly-degradable waste water as claimed in claim 1, is characterized in that: described high salt high-concentration hardly-degradable waste water is for containing COD, NH
3the waste water of-N, TN, TP and salinity.
3. the treatment process of high salt high-concentration hardly-degradable waste water as claimed in claim 2, is characterized in that: in described high salt high-concentration hardly-degradable waste water, the content of described COD is 62000mg/L to the maximum.
4. the treatment process of high salt high-concentration hardly-degradable waste water as claimed in claim 2, is characterized in that: in described high salt high-concentration hardly-degradable waste water, described NH
3the content of-N is 1500mg/L to the maximum.
5. the treatment process of high salt high-concentration hardly-degradable waste water as claimed in claim 2, is characterized in that: in described high salt high-concentration hardly-degradable waste water, the content of described TN is 2500mg/L to the maximum.
6. the treatment process of high salt high-concentration hardly-degradable waste water as claimed in claim 2, is characterized in that: in described high salt high-concentration hardly-degradable waste water, the content of described TP is 500mg/L to the maximum.
7. the treatment process of high salt high-concentration hardly-degradable waste water as claimed in claim 2, is characterized in that: in described high salt high-concentration hardly-degradable waste water, the content of described salinity is 60000mg/L to the maximum.
8. the treatment process of high salt high-concentration hardly-degradable waste water as claimed in claim 1, is characterized in that: the pH value of the high salt high-concentration hardly-degradable waste water described in adjustment is 6 ~ 8.
9. the treatment process of high salt high-concentration hardly-degradable waste water as claimed in claim 2, is characterized in that: described heating evaporation temperature is 100 DEG C.
10. the treatment process of high salt high-concentration hardly-degradable waste water as claimed in claim 1, is characterized in that: during described heating evaporation, adopts the mode of " steam heating ".
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| CN106885252A (en) * | 2017-03-24 | 2017-06-23 | 东南大学 | Device and method for treating high-concentration organic wastewater containing salt |
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| CN105174648A (en) * | 2015-10-13 | 2015-12-23 | 广州中环万代环境工程有限公司 | Processing method of high-concentration high-salinity wastewater |
| CN106885252A (en) * | 2017-03-24 | 2017-06-23 | 东南大学 | Device and method for treating high-concentration organic wastewater containing salt |
| CN110066077A (en) * | 2019-06-11 | 2019-07-30 | 泉州南京大学环保产业研究院 | A kind of processing method of cymoxanil agricultural chemicals waste water |
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