CN108101299A - A kind of high vanadium SCR denitration regenerative wastewater processing method - Google Patents
A kind of high vanadium SCR denitration regenerative wastewater processing method Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 110
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 44
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000001172 regenerating Effects 0.000 title claims abstract description 30
- 238000003672 processing method Methods 0.000 title claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 67
- 230000003647 oxidation Effects 0.000 claims abstract description 41
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000005484 gravity Effects 0.000 claims abstract description 25
- 239000002244 precipitate Substances 0.000 claims abstract description 25
- 238000005273 aeration Methods 0.000 claims abstract description 24
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 20
- 230000020477 pH reduction Effects 0.000 claims abstract description 20
- 238000005189 flocculation Methods 0.000 claims abstract description 18
- 230000016615 flocculation Effects 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000003814 drug Substances 0.000 claims abstract description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L Iron(II) sulfate Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000010802 sludge Substances 0.000 claims description 34
- -1 iron-carbon Chemical compound 0.000 claims description 31
- 239000012528 membrane Substances 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 238000011068 load Methods 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 238000005276 aerator Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 230000033228 biological regulation Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000004907 flux Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 description 20
- 238000004140 cleaning Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000001112 coagulant Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitrogen oxide Substances O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N Sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic Effects 0.000 description 2
- 230000004059 degradation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052813 nitrogen oxide Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 2
- 241000276438 Gadus morhua Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000003078 antioxidant Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000024881 catalytic activity Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000019516 cod Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000460 iron oxide Inorganic materials 0.000 description 1
- 230000002045 lasting Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004069 wastewater sedimentation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
Abstract
The invention discloses a kind of high vanadium SCR denitration regenerative wastewater processing method, including：a：Waste water initially enters preformed precipitate case and is precipitated；b：Circulate pond, to flow cell plus NaOH medicaments, then flows into wastewater disposal basin；c：Iron-carbon micro-electrolysis case is promoted to pump；d：Into three headers, three headers include the reaction chamber arranged in order, neutralize case, flocculation tanks；FeSO4 is added in reaction chamber, case is neutralized and adds alkali, flocculation tanks add flocculation aid；e：Into settling tank, precipitation removes vanadium and other heavy metals in water removal；f：Gravity flow enters hydrolysis acidification pool, contact-oxidation pool and aeration oxidation pool successively；g：Gravity flow enters integrated MBR system；h：Ozone oxidation tower is pumped to by MBR system suction, further removes hardly degraded organic substance and decoloration；i：Gravity flow enters clear water reserviors.The invention has the advantages that the treatment effeciency to high vanadium SCR denitration regenerative wastewater can be improved, processing cost is reduced, reduces the volume of solid-state castoff.
Description
Technical field
The invention belongs to field of Environment Protection, are specifically a kind of high vanadium SCR denitration regenerative wastewater processing method.
Background technology
Thermal power plant burns a large amount of coal next life electricity production power, and the nitrogen oxides containing significant proportion in the flue gas after burning needs
It to be handled using SCR denitration, to reduce amount of nitrogen oxides, qualified discharge.SCR denitration is using one
It is regenerated after the section time, to recover its catalytic activity.SCR commercial catalysts are substantially using TiO2 as base material at present,
Using V2O5 as main active ingredient, using WO3, MoO3 as anti-oxidant, antitoxinization auxiliary ingredients.Chinese patent literature
CN104667997A disclosed " a kind of SCR catalyst regeneration method " on June 3rd, 2015, and that be directed to is exactly the SCR containing vanadium
Denitrating catalyst.SCR catalyst washing regeneration is mainly concerned with four steps, i.e. prerinse, sour cleaning, chemical cleaning, activity
Component load etc., wherein activity load does not generate waste water, the waste water that remaining three process generates can be uniformly processed after collection.Through
Detection, waste water major pollutants are suspended matter, heavy metal, surfactant, ammonia nitrogen etc..Therefore catalyst denitration wastewater shows
The features such as Gao Fan, high organic matter, heavy metal etc., biodegradability is poor, and pollution is big, and intractability is high.The out of stock catalyst regenerations of SCR
Waste water has to pass through suitable processing scheme, reaches discharge standard and is discharged.Since environmental requirement increasingly improves, SCR catalysis
The regeneration frequency of agent also increasingly improves, and the treatment sewage quantity generated in regenerative process also increasingly increases.At present, to high vanadium
The research of SCR denitration regenerative wastewater processing continues to use the biographies such as ion-exchange and chemical precipitation method still in the starting stage
System sewage disposal means not only invest big, operating cost height, and the removal efficiency of vanadium is low, is unfavorable for final harmlessness disposing,
Therefore it is badly in need of a kind of high efficient technology to be effectively treated high vanadium SCR denitration regenerative wastewater.
The content of the invention
The technical problem to be solved in the invention is, the high vanadium of existing high vanadium SCR denitration regenerative wastewater, high organic
Object, heavy metal, biodegradability is poor, and pollution is big, and intractability is high, and volume of waste is huge, is taken off so as to provide a kind of high vanadium SCR
Denox catalyst regenerative wastewater processing method can improve treatment effeciency, reduce processing cost, reduce the volume of solid-state castoff.
In order to realize goal of the invention, the present invention adopts the following technical scheme that：A kind of high vanadium SCR denitration regenerative wastewater
Processing method includes the following steps：
a：High vanadium SCR denitration regenerative wastewater initially enters preformed precipitate case and is precipitated, and precipitates bulky grain solid matter
To bottom；
b：It circulates pond by the gravity flow of preformed precipitate treated waste water in step a, to flow cell plus NaOH medicaments, then flows into
Wastewater disposal basin；
c：Waste water pump in wastewater disposal basin in step b is promoted to iron-carbon micro-electrolysis case；
d：Into three headers, three headers include the reaction chamber arranged in order, neutralize case, wadding for processed waste water gravity flow in step c
Solidifying case；FeSO4 is added in reaction chamber, case is neutralized and adds alkali, flocculation tanks add flocculation aid；
e：Into settling tank, precipitation removes vanadium and other heavy metals in water removal for processed waste water gravity flow in step d；
f：Processed waste water is flow automatically successively into hydrolysis acidification pool, contact-oxidation pool and aeration oxidation pool in step e；
g：Processed waste water gravity flow enters integrated MBR system in step f；
h：In step g processed waste water by MBR system suction be pumped to ozone oxidation tower, further remove hardly degraded organic substance and
Decoloration；
i：Processed waste water gravity flow enters clear water reserviors in step h；
j：Step a, by the gravity flow of spoil disposal ditch into sludge-tank, sludge-tank is delivered to the sludge that c, d, e, g are generated by sludge pump
Sludge dewatering equipment is dehydrated, and the sludge after dehydration decrement is periodically cleared；
The equipment that the above method uses includes preformed precipitate case, flow cell, wastewater disposal basin, iron-carbon micro-electrolysis case, three headers, precipitation successively
Case, hydrolysis acidification pool, contact-oxidation pool, aeration oxidation pool, integrated MBR system, ozone oxidation tower and clear water reserviors；Preformed precipitate
Case, iron-carbon micro-electrolysis case, three headers, settling tank and integrated MBR system are connected to sludge-tank by switchable pipeline, dirty
Sludge dewatering equipment is installed by mud sump；The flow cell is equipped with NaOH feeding ports；Iron-carbon micro-electrolysis is equipped in iron-carbon micro-electrolysis case
Filler；Including reaction chamber in three headers successively, neutralize three case, flocculation tanks treatment boxes, reaction chamber is equipped with FeSO4 feeding ports, in
Lye feeding port is equipped with case, flocculation tanks are equipped with flocculation aid feeding port；Contact-oxidation pool and aeration oxidation pool are equipped with aerator.
The high vanadium SCR denitration regenerative wastewater processing unit of this programme design, sets successively along the process flow of sewage
Counted preformed precipitate case, flow cell, wastewater disposal basin, iron-carbon micro-electrolysis case, three headers, settling tank, hydrolysis acidification pool, contact-oxidation pool,
Aeration oxidation pool, integrated MBR system, ozone oxidation tower and clear water reserviors.The out of stock waste water of SCR initially enters preformed precipitate case and is sunk
It forms sediment, the bulky grain solid being suspended in waste water is first precipitated as base sludge, enters sludge-tank by the gravity flow of spoil disposal ditch；By preliminary sedimentation
Treated waste water gravity flow of forming sediment circulates pond, and the residence time is not less than 5min, adjusts pH to 3 to flow cell plus NaOH medicaments
Left and right flows to wastewater disposal basin again；Waste water pump in wastewater disposal basin is promoted to iron-carbon micro-electrolysis case, iron-carbon micro-electrolysis case utilizes metal
Corrosion principle method forms primary battery and waste water is handled, to achieve the purpose that a part of COD of removal and vanadium metal；Three headers
That is the combination of reaction chamber, neutralization case, flocculation tanks three since the continuity of processing step in three casees is very strong, can incite somebody to action
Three is combined as three headers, can also be independently arranged, be arranged in order as needed；Wherein, reaction chamber is added in FeSO4 and waste water
Vanadium redox reaction occurs, neutralize case and add pH value that alkali adjusts waste water subsequently to carry out coagulating sedimentation reaction, flocculate
Flocculation aid is added in case to carry out coagulating, by these three steps, the vanadium in waste water and other heavy metals can be generated
Flocculation；Precipitation is precipitated in the flco that settling tank can use gravitational method generate prime coagulating, so as to by the vanadium in waste water and its
He separates heavy metal from water body；The effect of hydrolysis acidification pool is to improve the biodegradability of waste water；Contact-oxidation pool is a kind of life
Based on object biofilm method, the biological treatment device of active mud is had concurrently, by providing oxygen source, the organic matter in sewage is inhaled by Institute of Micro-biology
Attached, degradation, is purified water quality；Filler is set in aeration oxidation pool, as the carrier of biomembrane.Pending is useless
Water flows through filler after oxygenation with certain flow rate, and biofilm contact, biomembrane and the activated sludge collective effect to suspend, can be with
Have the function that purify waste water；Integrated MBR system uses the efficient membrane separation technique of hollow-fibre membrane and traditional activated sludge process
The method being combined, can be with the various organic wastewaters of efficient process, with treatment process is simple, floor space is small, water quality treatment is steady
Calmly, the characteristics of good maintenance management of effluent quality is simple；Ozone oxidation tower can further remove the organic matter of difficult degradation in waste water
And it decolourizes to waste water；Waste water eventually arrives at clear water reserviors, can industrially recycle after completing to handle overall process,
Municipal Storm Sewer Network can also be imported safely carries out subsequent processing.During processing, preformed precipitate case, iron-carbon micro-electrolysis case, three
Header, settling tank and integrated MBR system are there may be sludge, therefore these processing equipments are all designed with and lead to sludge-tank
Spoil disposal ditch.Sludge is sent to sludge-tank, is carried out dehydration decrement by the sludge dewatering equipment of installation by sludge-tank, is periodically transported and do nothing
Evilization processing.By the processing of the present apparatus, the waste water of the heavy metals such as original nitrogen-containing oxide and vanadium is after treatment, it is sufficient to full
The first pollutant of foot《Vanadium industrial discharge standard》（GB26452-2011）, remaining index and《Integrated wastewater discharge standard》（GB
8978-1996）Secondary standard.
Preferably, the surface loading of preformed precipitate case is between 1 ~ 1.5 m3/m2 h in step a.Can so waste water be made to sink
It forms sediment more abundant.
Preferably, flow cell should ensure that the residence time not less than 5min in step b, to flow cell plus NaOH medicaments by pH
It adjusts to 3 or so.The acid-base value of waste water so can be fully adjusted, beneficial to the processing of follow-up iron-carbon micro-electrolysis.
Preferably, the iron-carbon micro-electrolysis case residence time is not less than 2 h, gas-water ratio 5 in step c：1, iron carbon filler：Proportion
1.1 tons/m3,1.2 m2/g of specific surface area, 65 % of voidage, 800 kg/cm2 of physical strength, using perforated pipe aerating regulation mode.
Iron-carbon micro-electrolysis technology is used in high sail SCR denitration regenerative wastewater, to initiate in the industry, be this programme innovative point it
One.In tradition, iron-carbon micro-electrolysis case is usually used in degradable organic pollutant, lifting waste water biodegradability.And this programme make use of
The numerous subtle primary battery generated during iron-carbon micro-electrolysis in sewage, in acid condition, Fe2+ can be partly oxidized to
Fe3+, and VO3- can partly be reduced into the VO2+ of tetravalence.Fe3+ can react generation with high price vanadium and form indefinite vanadic acid iron oxide yellow
Color precipitates, and Fe2+ and Fe3+ are as precipitating reagent and vanadic acid reactant salt generation ferric vandate precipitation, and V2O5 is reduced into life after VO2
Into VO2 Xh2O hydrate depositions.Follow-up waste water pH in Step d is adjusted to 9, in alkaline conditions, generation Fe (OH) 2 and Fe
(OH) 3, using the active flocculation of their own, ferric vandate and VO2 Xh2O hydrate co-precipitations enter in sludge.Through
Cross the processing of this step, the removal rate of vanadium is up to more than 80%, the remote super other processing schemes of efficiency.
Preferably, match somebody with somebody mixer in each independent babinet in step d.Set mixer that can enhance to water body
Disturbance, allows the medicament of addition to be sufficiently mixed in water body, and heavy metal and other pollutants is contributed to flocculate.
Preferably, the surface loading of settling tank is between 1 ~ 1.5 m3/m2 h in step e.Wastewater sedimentation can so be made
More fully.
Preferably, hydrolysis acidification pool, contact-oxidation pool filler requirement 99 % of voidage, specific surface area 1246 in step f
M2/m3,4.6 kg/m3 of Unit Weight, film forming weight 60-70 kg/m3；Contact-oxidation pool and aerobic tank need to configure aerating system,
For stomatal frequency not less than 2200/, the m3/ h of throughput 1~3, service area should meet 0.3~0.6 m3/.
Preferably, the film of integrated MBR system is the band hot method PVDF hollow-fibre membranes of liner in step g；Membrane flux is not
Big 15 L/m2 h, membranous system regurgitant volume are not less than 2Q, and the MBR system normal filtration cycle is 8 min of operation, stops 2 min.MBR
In system, using curtain type film assembly, wherein film is the PVDF hollow fiber ultrafiltration membranes produced with thermally induced phase separation, and film section is
Three-dimensional interpenetrating grid, asymmetric pore structure, film outer surface average pore size are 50 nm, and the film is small with film outer surface aperture, outside
Wall edge hole is fine and close, and the features such as gradually increase from outside to inside, film strength is high, and easy cleaning, flow is big, can recover, antipollution energy
Power is strong.Meanwhile PVDF is organic piezoelectric materials, with the tunica fibrosa that PVDF materials make, can be generated when being subject to hydraulic pressure quiet
Electricity, suction-operated is generated to remaining in the heavy metal ion in waste water, has remarkable result for removal vanadium ion.This programme uses
Hot method PVDF hollow-fibre membranes handle high vanadium SCR denitration regenerative wastewater, are pioneering and this programme innovations in the industry
One of point.
Preferably, the aerator of aeration oxidation pool and the aerator of iron-carbon micro-electrolysis case, contact-oxidation pool connect
It is connected to same wind turbine.Wind turbine is devised to share, can energy saving and installation space, investment reduction maximally utilizes and sets
Standby slack resources.
Preferably, being cleaned once about January to the chemical cleaning of MBR films, offline chemical cleaning about half a year, once alkali was safeguarded
Cleaning frequency is 1~3 day, and concentration is used to be cleaned for the NaClO of 500 ppm, and the sour maintainability cleaning frequency is 7~10 days, is used
Concentration is that the citric acid of 0.3 % is cleaned.The lasting treatment effect of MBR films can so be improved.
Preferably, the partial sludge of generation can be also back to by integrated MBR system by sludge reflux pump in step g
Hydrolysis acidification pool, contact-oxidation pool, aeration oxidation pool.So design can ensure the equal of sludge concentration in integrated MBR system
Weighing apparatus is conducive to long-term efficient processing waste water.
Preferably, the ozone oxidation tower residence time is not less than 20~30 mg/ not less than 2 h, ozone concentration in step h
L.It so may insure higher ozone concentration and fully react.
Preferably, the height of the discharge outlet of preformed precipitate case is higher than flow cell liquid level；The height of flow cell discharge outlet is higher than
Wastewater disposal basin liquid level；The height of the discharge outlet of iron-carbon micro-electrolysis case is higher than three header liquid levels；The height of the discharge outlet of three headers is higher than
Settling tank liquid level；The height of the discharge outlet of settling tank is higher than hydrolysis acidification pool liquid level；The height of the discharge outlet of hydrolysis acidification pool is high
In contact-oxidation pool liquid level；The height of the discharge outlet of contact-oxidation pool is higher than aeration oxidation pool liquid level；The draining of aeration oxidation pool
The height of mouth is higher than the liquid level of integrated MBR system；The height of the discharge outlet of ozone oxidation tower is higher than the liquid level of clear water reserviors.At this
In design, waste water is introduced to the iron-carbon micro-electrolysis case of eminence only from wastewater disposal basin to be needed using pump, will from integrated MBR system
The ozone oxidation tower that waste water introduces eminence needs, using pumping, liquid level to be reduced successively according to flow direction between other each processing equipments
Highly, waste water is allow, from upper equipment direct current into next equipment, to reduce the outfit of power-equipment by gravity, saved place
Manage energy consumption.
In conclusion the beneficial effects of the invention are as follows：The processing to high vanadium SCR denitration regenerative wastewater can be improved
Efficiency reduces processing cost, reduces the volume of solid-state castoff.
Description of the drawings
Fig. 1 is the process flow and equipment schematic diagram of the present invention.
Wherein：1 preformed precipitate case, 2 flow cells, 3 wastewater disposal basins, 4 iron-carbon micro-electrolysis casees, 5 three headers, 6 settling tanks, 7 hydrolysis acid
Change pond, 8 contact-oxidation pools, 9 aeration oxidation pools, 10 integrated MBR systems, 11 ozone oxidation towers, 12 clear water reserviors, 13 sludge-tanks,
14 sludge dewatering equipments.
Specific embodiment
Embodiment as shown in Figure 1 is a kind of high vanadium SCR denitration regenerative wastewater processing method, applies in thermoelectricity
In the processing of the regenerative wastewater for the high vanadium SCR denitration that factory uses.
The equipment that this example uses includes preformed precipitate case 1, flow cell 2, wastewater disposal basin 3, iron successively according to the process flow of waste water
Carbon micro-electrolysis case 4, three headers 5, settling tank 6, hydrolysis acidification pool 7, contact-oxidation pool 8, aeration oxidation pool 9, integrated MBR system
10, ozone oxidation tower 11, clear water reserviors 12.Wherein, preformed precipitate case, iron-carbon micro-electrolysis case, three headers, settling tank and integration MBR
System can generate sludge in processing procedure, therefore be connected to sludge-tank 13 by spoil disposal ditch, and dirt is equipped with by sludge-tank
Mud dewaterer 14 can carry out dehydration decrement, in case periodically clearing to collected sludge.
Below according to process flow of the waste water in the present apparatus, to device in itself and process flow is introduced.
a：High vanadium SCR denitration regenerative wastewater initially enters preformed precipitate case and is precipitated, and the surface of preformed precipitate case is born
Lotus is precipitated to bottom between 1 ~ 1.5 m3/m2 h, bulky grain solid matter；
b：It circulates pond by the gravity flow of preformed precipitate treated waste water in step a, flow cell should ensure that the residence time is not less than
PH to flow cell plus NaOH medicaments is adjusted to 3 or so, then flows into wastewater disposal basin by 5min；
c：Waste water pump in wastewater disposal basin in step b is promoted to iron-carbon micro-electrolysis case, the iron-carbon micro-electrolysis case residence time is not less than 2
H, gas-water ratio 5：1, iron carbon filler：1.1 tons/m3 of proportion, 1.2 m2/g of specific surface area, 65 % of voidage, physical strength 800
Kg/cm2, using perforated pipe aerating regulation mode；
d：Into three headers, three headers include the reaction chamber arranged in order, neutralize case, wadding for processed waste water gravity flow in step c
Solidifying case；FeSO4 is added in reaction chamber, redox reaction occurs with the vanadium in waste water, neutralized case and add the pH value that alkali adjusts waste water
Subsequently to carry out coagulating sedimentation reaction, flocculation tanks add such as PAM flocculation aids to carry out coagulating；Each independent babinet
Inside match somebody with somebody mixer；
e：Into settling tank, function is to generate flco by prime coagulating, is sunk for processed waste water gravity flow in step d
Form sediment the vanadium and other heavy metals gone in water removal；The surface loading of settling tank is between 1 ~ 1.5 m3/m2 h；
f：Processed waste water is flow automatically successively into hydrolysis acidification pool, contact-oxidation pool and aeration oxidation pool in step e；Wherein hydrolyze
Acidification pool, contact-oxidation pool filler requirement 99 % of voidage, 1246 m2/m3 of specific surface area, 4.6 kg/m3 of Unit Weight, film forming
Weight 60-70 kg/m3；Contact-oxidation pool and aeration oxidation pool need to configure aerating system, and stomatal frequency is not less than 2200/,
The m3/ h of throughput 1~3, service area should meet 0.3~0.6 m3/；
g：Processed waste water gravity flow enters integrated MBR system in step f；The film of integrated MBR system is the band hot method of liner
PVDF hollow-fibre membranes, the little 15 L/m2 h of membrane flux, membranous system regurgitant volume are not less than 2Q, MBR system normal filtration cycle
8 min are run, stop 2 min, once, once, alkali is safeguarded clear for offline chemical cleaning about half a year cleaning for chemical cleaning about cleaning in January
The cycle is washed as 1~3 day, concentration is used to be cleaned for the NaClO of 500 ppm, the sour maintainability cleaning frequency is 7~10 days, and use is dense
The citric acid spent for 0.3 % is cleaned；Integrated MBR system is additionally provided with sludge reflux to hydrolysis acidification pool, catalytic oxidation
Pond, the sludge reflux pump of aeration oxidation pool, to ensure that sludge concentration is balanced in integrated MBR system, part membrane cisterna sludge passes through
Sludge reflux pump is promoted to hydrolysis acidification pool, contact-oxidation pool, aeration oxidation pool；
h：In step g processed waste water by MBR system suction be pumped to ozone oxidation tower, further remove hardly degraded organic substance and
Decoloration；The ozone oxidation tower residence time is not less than 2 h, and ozone concentration is not less than 20~30 mg/L；
i：Processed waste water gravity flow enters clear water reserviors in step h；Clear water in clear water reserviors can be recycled industrially, also may be used
It is normally recycled with importing municipal Storm Sewer Network safely by recycling sewage treatment plant；
j：Step a, by the gravity flow of spoil disposal ditch into sludge-tank, sludge-tank is delivered to the sludge that c, d, e, g are generated by sludge pump
Sludge dewatering equipment is dehydrated, and the sludge after dehydration decrement is periodically cleared.
In the present apparatus, the aerator of the aerator and iron-carbon micro-electrolysis case, contact-oxidation pool of aeration oxidation pool connects
Be connected to same wind turbine, can energy saving and installation space, investment reduction maximally utilizes the slack resources of equipment.
The height of the discharge outlet of preformed precipitate case is higher than flow cell liquid level；The height of flow cell discharge outlet is higher than wastewater disposal basin liquid
Face；The height of the discharge outlet of iron-carbon micro-electrolysis case is higher than three header liquid levels；The height of the discharge outlet of three headers is higher than settling tank liquid
Face；The height of the discharge outlet of settling tank is higher than hydrolysis acidification pool liquid level；The height of the discharge outlet of hydrolysis acidification pool is higher than contact oxygen
Change pond liquid level；The height of the discharge outlet of contact-oxidation pool is higher than aeration oxidation pool liquid level；The height of the discharge outlet of aeration oxidation pool
Higher than the liquid level of integrated MBR system；The height of the discharge outlet of ozone oxidation tower is higher than the liquid level of clear water reserviors.Only from wastewater disposal basin
Waste water is introduced to the iron-carbon micro-electrolysis case of eminence to be needed using pump, by the ozone of waste water introducing eminence from integrated MBR system
Oxidizing tower needs, using pump, to reduce liquid level successively according to flow direction between other each processing equipments, allow waste water according to
By gravity from upper equipment direct current into next equipment, reduce the outfit of power-equipment, save processing energy consumption.
Claims (10)
1. a kind of high vanadium SCR denitration regenerative wastewater processing method, it is characterized in that, include the following steps：
a：High vanadium SCR denitration regenerative wastewater initially enters preformed precipitate case and is precipitated, and precipitates bulky grain solid matter
To bottom；
b：It circulates pond by the gravity flow of preformed precipitate treated waste water in step a, to flow cell plus NaOH medicaments, then flows into
Wastewater disposal basin；
c：Waste water pump in wastewater disposal basin in step b is promoted to iron-carbon micro-electrolysis case；
d：Into three headers, three headers include the reaction chamber arranged in order, neutralize case, wadding for processed waste water gravity flow in step c
Solidifying case；FeSO4 is added in reaction chamber, case is neutralized and adds alkali, flocculation tanks add flocculation aid；
e：Into settling tank, precipitation removes vanadium and other heavy metals in water removal for processed waste water gravity flow in step d；
f：Processed waste water is flow automatically successively into hydrolysis acidification pool, contact-oxidation pool and aeration oxidation pool in step e；
g：Processed waste water gravity flow enters integrated MBR system in step f；
h：In step g processed waste water by MBR system suction be pumped to ozone oxidation tower, further remove hardly degraded organic substance and
Decoloration；
i：Processed waste water gravity flow enters clear water reserviors in step h；
j：Step a, by the gravity flow of spoil disposal ditch into sludge-tank, sludge-tank is delivered to the sludge that c, d, e, g are generated by sludge pump
Sludge dewatering equipment is dehydrated, and the sludge after dehydration decrement is periodically cleared；
The equipment that the above method uses includes preformed precipitate case successively（1）, flow cell（2）, wastewater disposal basin（3）, iron-carbon micro-electrolysis case
（4）, three headers（5）, settling tank（6）, hydrolysis acidification pool（7）, contact-oxidation pool（8）, aeration oxidation pool（9）, integration MBR systems
System（10）, ozone oxidation tower（11）And clear water reserviors（12）；Preformed precipitate case, iron-carbon micro-electrolysis case, three headers, settling tank and integration
MBR system is connected to sludge-tank by switchable pipeline（13）, sludge dewatering equipment is installed by sludge-tank（14）；The stream
Logical pond is equipped with NaOH feeding ports；Iron-carbon micro-electrolysis filler is equipped in iron-carbon micro-electrolysis case；In three headers successively include reaction chamber, in
With three case, flocculation tanks treatment boxes, reaction chamber is equipped with FeSO4 feeding ports, neutralizes case and is equipped with lye feeding port, flocculation tanks are equipped with and help
Solidifying agent feeding port；Contact-oxidation pool and aeration oxidation pool are equipped with aerator.
2. a kind of high vanadium SCR denitration regenerative wastewater processing method according to claim 1, it is characterized in that, step a
The surface loading of middle preformed precipitate case is between 1 ~ 1.5 m3/m2 h.
3. a kind of high vanadium SCR denitration regenerative wastewater processing method according to claim 1, it is characterized in that, step b
Middle flow cell should ensure that the residence time not less than 5min, is adjusted pH to 3 or so to flow cell plus NaOH medicaments.
4. a kind of high vanadium SCR denitration regenerative wastewater processing method according to claim 1, it is characterized in that, step c
The middle iron-carbon micro-electrolysis case residence time is not less than 2 h, gas-water ratio 5：1, iron carbon filler：1.1 tons/m3 of proportion, specific surface area 1.2
M2/g, 65 % of voidage, 800 kg/cm2 of physical strength, using perforated pipe aerating regulation mode.
5. a kind of high vanadium SCR denitration regenerative wastewater processing method according to claim 1, it is characterized in that, step d
In match somebody with somebody mixer in each independent babinet.
6. a kind of high vanadium SCR denitration regenerative wastewater processing method according to claim 1, it is characterized in that, step e
The surface loading of middle settling tank is between 1 ~ 1.5 m3/m2 h.
7. a kind of high vanadium SCR denitration regenerative wastewater processing method according to claim 1, it is characterized in that, step f
Middle hydrolysis acidification pool, the requirement of contact-oxidation pool filler 99 % of voidage, 1246 m2/m3 of specific surface area, 4.6 kg/ of Unit Weight
M3, film forming weight 60-70 kg/m3；Contact-oxidation pool and aeration oxidation pool need to configure aerating system, and stomatal frequency is not less than
2200/only, the m3/ h of throughput 1~3, service area should meet 0.3~0.6 m3/.
8. a kind of high vanadium SCR denitration regenerative wastewater processing method according to claim 1, it is characterized in that, step g
The film of middle integration MBR system is the band hot method PVDF hollow-fibre membranes of liner；The little 15 L/m2 h of membrane flux, membranous system reflux
Amount is 8 min of operation not less than 2Q, MBR system normal filtration cycle, stops 2 min.
9. a kind of high vanadium SCR denitration regenerative wastewater processing method according to claim 1, it is characterized in that, step g
It is middle integration MBR system can also by sludge reflux pump by the partial sludge of generation be back to hydrolysis acidification pool, contact-oxidation pool,
Aeration oxidation pool.
10. basis is equipped with a kind of high vanadium SCR denitration regenerative wastewater processing method described in claim 1, it is characterized in that,
The ozone oxidation tower residence time is not less than 2 h in step h, and ozone concentration is not less than 20~30 mg/L.
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| WO2020000342A1 (en) * | 2018-06-29 | 2020-01-02 | 江苏海容热能环境工程有限公司 | Method for degrading small molecular organic matter in regenerated wastewater of waste flue gas denitration catalyst |
| CN114315020A (en) * | 2021-12-23 | 2022-04-12 | 张家口卷烟厂有限责任公司 | Be provided with ultrafiltration reverse osmosis system's sewage treatment system |
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| CN206428128U (en) * | 2017-01-18 | 2017-08-22 | 江苏联盟化学有限公司 | Sewage disposal device |
| CN107365021A (en) * | 2017-08-02 | 2017-11-21 | 上海未来企业股份有限公司 | A kind of alum titanium waste water ammonium recovery and zero-discharge technology and system |
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