CN104030502A - Steel pickling waste water resourcization and zero discharge process - Google Patents
Steel pickling waste water resourcization and zero discharge process Download PDFInfo
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Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a steel pickling waste water resourcization and zero discharge process. The steel pickling waste water resourcization and zero discharge process comprises the following process steps of: (a) introducing steel pickling waste water; (b) carrying out Fenton reaction on the steel pickling waste water to reduce the COD (Chemical Oxygen Demand) of the steel pickling waste water to be less than or equal to 60 mg/L, convert Fe<2+> into Fe<3+> and reduce TDS (Total Dissolved Solids) to be less than or equal to 2000 mg/L; (c) carrying out FeC microelectrolysis reduction reaction on the steel pickling waste water; (d) carrying out neutralization flocculation; (e) desalting a membrane assembly to reduce the TDS of the steel pickling waste water to be less than or equal to 200 mg/L; (f) recycling effluent water. The steel pickling waste water resourcization and zero discharge process disclosed by the invention realizes the cleaning production, realizes the resourcization utilization of waste water, waste acid and iron mud, generates the benefit and realizes the zero discharge.
Description
Technical field
The invention belongs to water-treatment technology field, particularly steel pickling waste liquor resource utilization and technique of zero discharge.
Background technology
Steel pickling waste liquor, comprises spent acid and waste water two parts.Wherein spent acid accounts for total Water 2-3%, and one is as shown in the table for the pollution index of this waste water:
。Deal with improperly and enter water body as steel pickling waste liquor, can cause following pollution: 1, reduce water pH value, cause pasture and water, algae, fish kills.2, Fe
2+in water body, form colloid Fe (OH)
2, Fe (OH)
3, but under river course hydraulics, can not generate flocs unit precipitation, but with river course water in organosulfur, humic acids form yellow-gray, black colloid pollution band, sense organ extreme difference.3, the organic chemistry material of formation COD is tensio-active agent, phosphoric acid salt, lubricating oil, is to reverse to the eutrophication pollution of water body.
The current output of steel of China has exceeded 100,000,000 tons, and wherein half is for the production of steel pipe, rolls plate and shaped steel.Mostly to just can dispatch from the factory through cleanup acid treatment in process of production, after various source mill have been arrived in market, must, again through a pickled surface processing, just can be processed into various finished products of terminal company again.The every cleanup acid treatment of every 10,000 tons of steel 1 time, 20,000 tons of average generation pickling waste waterss, 600 tons, spent acid.Get off like this, the whole nation produces 300,000,000 tons/year of pickling waste waterss, 6,000,000 tons/year, spent acid, ten thousand tons/year of COD20,8,500,000 tons of years of iron mud, 20,000 tons of years of phosphorus.
Steel pickling waste liquor is in the medium and small enterprises and institutions of families up to ten thousand of the whole nation several thousand, and considerable part is untreated direct discharge, and the processing of more regular enterprise is all used in lime, caustic soda and rear discharge mostly, and considerable part is the processing that is mixed of waste water and spent acid.Its primitive reaction is: first H
++ OH
-→ H
2o, making discharge water is that 2 neutralizations are 7 to pH value by pH value; Then Fe
2++ OH
-→ Fe (OH)
2↓, Fe
2+become Fe (OH)
2remove, the technique of this primitive reaction as shown in Figure 1.
This technique, compared with untreated direct discharge, has alleviated environmental pollution pressure, still has following shortcoming but have:
1. cost is very high: in theory, make pH value be 2 waste water to neutralize pH value be 7, scale consumption 1.5kgNaOH per ton, part replaces NaOH with lime, the artificial depreciation of additional power consumption, processing cost is 4.5 yuan/ton of water.
2. discharge water limpid at that time, enter water drain or river with regard to yellowing, blacking up, smelly.This be because, Fe (OH)
2solubleness is larger, is Kp=1.6 × 10
-4, draining at that time limpid pH value is 7, but dissolves Fe
2+all at 5～10ppm.Fe
2+in water, can automatic hydrolysis become Fe (OH)
2, but also must just have Function For Purifying Water by regeneration flocs unit.And to generate Fe (OH)
2flocs unit must have a hydraulics: low rate mixing Re > 10 fully
4, but water drain or river do not possess this hydraulics.So part Fe
2+with in water, dissolve O
2in conjunction with, generate Fe (OH)
3colloid, water body just turns to be yellow; Part Fe
2+generate FeS colloid or humic acids iron with organosulfur in water, water body becomes grey black.These colloids are highly stable, can not change flocs unit into and make water body become clear.
3. COD is not up to standard.Steel pickling waste liquor COD is not high, one 300～400mg/L, but our test proves, is 10 to reach Fe even if neutralize pH value with alkali
2+deposition condition completely, COD clearance is also no more than 5%.This illustrates that in such waste water, COD is solubility, can not be neutralized precipitate and separate and remove; Fe (OH) is also described
2colloid flco, to this class COD material (tensio-active agent, organophosphate, lubricant etc.) absorption extreme difference.
4. level of residue is very big, extremely difficult.In lime and occasion, stable residual layer can account for 10% volume of water; In caustic soda and occasion, stable residual layer also accounts for 5% volume of water.Residue is commonly called as iron mud, and plate-and-frame filter press press dry water ratio and also reaches 85%, and volume is very big.Fe (OH)
2residue is highly stable, stacks also not solid one-tenth piece half a year, and on landfill yard buries, several years digs out to be still mud shape, can not solidify.
5. draining can not direct reuse.Draining saliferous is very high, TDS >=4500mg/L, and COD >=300mg/L, then the drip washing steel that go back, salinity and COD will be attached on surface of steel workpiece, and steel just get rusty very soon.Rush road surface, floor if be used for, less than 3 months, ground meeting yellowing, browning look.If be used for carwash, vehicle body very soon can be by corrosion.If this high salinity, high COD water quality retrieval system, will infinite loop accumulation in system.Even reuse 50% water yield, in several days systems, TDS just can reach 10000mg/L, and COD reaches 1000mg/L, and intermediate water reuse system just cannot normally carry out.
Summary of the invention
The object of the invention is to provide a kind of for the deficiencies in the prior art and reduce costs, realize steel pickling waste liquor resource utilization and the technique of zero discharge of waste water, spent acid resource utilization.
The object of the present invention is achieved like this.
Steel pickling waste liquor resource utilization and technique of zero discharge, it comprises following processing step:
(a) steel pickling waste liquor water inlet;
(b) steel pickling waste liquor carries out Fenton reaction, the COD of steel pickling waste liquor is dropped to≤60mg/L, Fe
2+change Fe into
3+, drop to≤2000mg/L of TDS;
(c) steel pickling waste liquor carries out the micro-electrolytic reduction reaction of FeC;
(d) neutralization flocculation;
(e) membrane module desalination, drops to the TDS of steel pickling waste liquor≤200mg/L;
(f) effluent reuse.
Wherein, described step (b) steel pickling waste liquor carries out Fenton reaction and is specially: by H
2o
2or O
3add and in Fenton reactor, carry out Fenton reaction.
Wherein, described step (b) steel pickling waste liquor carries out Fenton reaction and is specially, and adopts titanium ruthenium electrode Ti-RuO
2carry out Fenton reaction.
As the water yield≤400T/ days, select to produce UV+O with microwave-excitation
3or H
2o
2or electrooxidation system is as oxygenant; The water yield>=1000T/ days, selects H
2o
2as oxygenant.
Wherein, the membrane module of described step (e) is MF-NF-RO Integrated Films assembly, and after the desalination of MF-NF-RO Integrated Films assembly, water outlet more than 90% is fresh water.
Wherein, after described step (c) steel pickling waste liquor carries out the micro-electrolytic reduction reaction of FeC, the pH of steel pickling waste liquor is more than 3.5; After described step (d) neutralization flocculation, the pH of steel pickling waste liquor is more than 7.
Further, after described step (d) neutralization flocculation, before the desalination of step (e) membrane module, also comprise the circulation of step (d1) underflow; The water outlet of step (d) neutralization flocculation enters the circulation of step (d1) underflow, the water outlet of step (d1) underflow circulation enters the desalination of step (e) membrane module, and the underflow after the desalination of step (e) membrane module is got back in the circulation of step (d1) underflow.
Further, the Fe (OH) that the circulation of described step (d1) underflow produces
3by pressure filter press filtration, making beating dissolving, oxidizing reaction, be prepared into waste water water purification agent.
Wherein, in the process that described making beating is dissolved, add steel pickling waste liquor; Then carry out oxidizing reaction, generate FeCl
3or Fe
2(SO
4).
Wherein, the Fe (OH) that the circulation of described step (d1) underflow produces
3return in step (d) neutralization flocculation by the filtrate of pressure filter press filtration.
Wherein, in described step (d) neutralization flocculation, add NaOH and PAM.
Beneficial effect of the present invention: technique of the present invention is first carried out Fenton reaction to steel pickling waste liquor, COD drops to below 60mg/L from 300～400mg/L, Fe
2+change Fe into
3+, TDS decline at least 50%, drop to below 2000mg/L.Use membrane module advanced desalination, make waste water TDS drop to 200mg/L by 2000mg/L, return to production system; Underflow TDS≤20000mg/L, COD≤600mg/L after membrane module advanced desalination, be dissolved in salt, allocates in spent acid.Waste residue Fe (OH)
3slurry is dissolved in spent acid, improves spent acid Fe content, reduces free acid.Spent acid is reoxidised into FeCl
3or Fe
2(SO
4)
3, adjust iron, aluminium, calcium, phosphorus ratio simultaneously, and the suitable polymerization degree, produce compound prescription water purification agent, sell outward as wastewater purificant; Or directly with FeCl
2or Fe (SO)
2liquid is sold, and is Cr
6+in wastewater reduction agent or dyeing waste-water and discoloring agent.
Steel pickling waste liquor resource utilization of the present invention and technique of zero discharge are realized cleaner production, realize the recycling of waste water, spent acid and iron mud, bring benefits, and realize zero release.
1, the utilization of residue iron mud and spent acid.The main atomic composition of residue iron mud is exactly Fe, is a kind of environment amenable flocculation water purification agent material, has improved on the contrary, and after pickling iron and steel, has produced the spent acid containing HCl3～3.5%, containing FeCl in its reactive behavior after microwave UV radiation
2250～300g/L, if sell outward as water purification agent product, it is excessive containing acid, low again containing Fe, but active iron mud is dissolved in spent acid, reduce, improved containing Fe containing acid, regulated suitable Fe, Al, Ca, P ratio and polymerization degree factory effluent scavenging agent simultaneously, made full use of again component in the dense water of RO, it is a kind of good discoloring agent of dyeing waste-water, or Cr in heavy metal wastewater thereby
6+reductive agent, realizes the treatment of wastes with processes of wastes against one another.2, water resources utilization.The MF-NF-RO combined films technology of technique of the present invention, fresh water productive rate can reach 90%, can complete-reclaiming in producing any workshop section.3, the utilization of microfiltration membrane, saves settling pond.Conventional Waste Water Treatment is all furnished with bulky settling pond, realizes solid-liquid separation.Finally also to join sandfiltration pot, reduce clear water ss suspended solid value, also must configure sheet frame press drier lignin-sludge simultaneously.The three-major-items of routine that Here it is.But due to process microwave treatment, precipitation threshold, the dehydration property of iron mud are fairly good, in this occasion, use microfiltration membrane technology, just can greatly save space, for narrow space, the area that land price is high, benefit is considerable.
Brief description of the drawings
Fig. 1 is the steel pickling waste liquor resource utilization of embodiments of the invention 1 and the schematic diagram of technique of zero discharge.
Fig. 2 is the steel pickling waste liquor resource utilization of embodiments of the invention 2 and the schematic diagram of technique of zero discharge.
Embodiment
With concrete drawings and Examples, the present invention is further illustrated below, but the present invention is not subject to the restriction of following embodiment.
Embodiment 1.
As shown in Figure 1, steel pickling waste liquor resource utilization and technique of zero discharge, it comprises following processing step:
(a) steel pickling waste liquor water inlet;
(b) steel pickling waste liquor carries out Fenton reaction, the COD of steel pickling waste liquor is dropped to≤60mg/L, Fe
2+change Fe into
3+, drop to≤2000mg/L of TDS (total dissolved solidss); By H
2o
2or O
3add and in Fenton reactor, carry out Fenton reaction, or adopt titanium ruthenium electrode Ti-RuO
2carry out Fenton reaction;
(c) steel pickling waste liquor carries out the micro-electrolytic reduction reaction of FeC; After the micro-electrolytic reduction reaction of FeC, the pH of steel pickling waste liquor is more than 3.5;
(d) neutralization flocculation: add NaOH and PAM carry out in and flocculation reaction; After neutralization flocculation, the pH of steel pickling waste liquor is more than 7, and being preferably pH is 7.5; The dosage of NaOH and PAM, according to process requirements, adds according to prior art; [0031] (e) membrane module desalination, drops to the TDS of steel pickling waste liquor≤200mg/L; Membrane module is MF-NF-RO Integrated Films assembly, and after the desalination of MF-NF-RO Integrated Films assembly, water outlet more than 90% is fresh water.MF-NF-RO Integrated Films assembly comprises microfiltration membrane (MF), nanofiltration membrane (NF) and reverse osmosis membrane (RO), microfiltration membrane (MF) microfiltration membrane can be held back the particle between 0.1-1 micron, nanofiltration membrane (NF) can be held back the material of nano level (0.001 micron), reverse osmosis membrane can be held back the material that is greater than 0.0001 micron, the organism that its energy all dissolving salts of effectively catching and molecular weight are greater than 100 allows water molecules to pass through simultaneously.
(f) effluent reuse.
Steel pickling waste liquor resource utilization of the present invention and technique of zero discharge, core technology is Fenton-micro-electrolysis reaction, its principle is as follows.
1, the feature of steel pickling waste liquor is: pH < 2, Fe
2+> 500mg/l, COD < 300～400mg/l, as long as add oxygenant, it just forms a Fenton reaction system, and this individual system can produce [OH] hydroxyl radical free radical in a large number, by all kinds of organic C OD mass degradations, until mineralising is CO
2+ H
2o.
2, the selection of oxygenant.
1. H
2o
2: this is the most classical Fenton condition, only needs 1 cover medicine system, buys H
2o
2available, and system cost is low.By the three-dimensional relationship of system redox potential ORP, reaction times T and COD, control H
2o
2dosage and wastewater flow, can realize the COD value after wastewater oxidation is controlled at below 60mg/L.
2. O
3: in pH≤2, Fe
2+in≤500mg/L system, add O
3, also can form Fenton reaction system.There is ORP-T-COD three-dimensional relationship in it, too can be with ORP value feedback control O equally
3dosage and wastewater flow, can stablize and control processed waste water COD≤60mg/L.O
3there are two approach sources, the one, outsourcing O
3unit; The 2nd, produce UV+O with microwave-excitation
3, the O of this approach
3amount can regulate and control.
3. electrooxidation: make pH≤2, Fe
2+the acidity of≤500mg/L is containing Fe
2+waste water, by titanium ruthenium electrode Ti-RuO
2, same [OH] hydroxyl radical free radical and the nascent state [O] of producing, forms a Fenton reaction system, and this individual system controllability is very high.Ti-RuO
2the current density of electrode can be from 300A/m
2change to 1000A/m
2, voltage across poles can change to 15V from 1.5V, and power input is got over the activity (O) and (O that on large electrode, produce
3) more.This individual system can, by ORP value feedback control wastewater flow, voltage, electric current, make to produce water COD and be stabilized in COD≤60mg/L.
The advantage of electrooxidation system is: (1) compares O
3unit is reliable, simple, and cost compares O
3unit is also low; (2) save and add H
2o
2step; (3) operation is controlled and is stablized, and safeguards simple.
As the water yield≤400T/ days, select to produce UV+O with microwave-excitation
3or H
2o
2or electrooxidation system is as oxygenant; The water yield>=1000T/ days, selects H
2o
2as oxygenant.
3, acceleration---the microwave UV catalysis of Fenton reaction.
The feature of Fenton reaction is to have inductive phase, acceleration period, mild phase, and to different quality system total reaction time from several minutes by several hours not etc., in water, the degraded of Organic Pollutants molecule often will be passed through open loop → straight chain fracture → small molecules → CO
2+ H
2o process, so the rule of Fenton reaction is awave often, there will be 2～3 cycles, and this just produces a how accelerated reaction problem.
The approach that we studied has:
1. heat temperature raising: can accelerated reaction, according to Wu Lun Nice law, 10 DEG C every liter of temperature of reaction, speed of response can be accelerated one times, and effect is very remarkable, just can realize with calrod or steam coil.As the utilization that has surplus heat in factory, be best bet, can also accelerate follow-up membrane filtration.
, just there is transient pressure release once break in 2. Catalyzed by Ultrasonic Wave: ultrasonic wave makes water body produce numerous cavity, and interior pressure can reach dozens of normal atmosphere, produces a large amount of [OH] hydroxyl radical free radicals, the application of empty quick-fried theory that Here it is.
3. microwave catalysis: to inputting 950 or 2450Hz frequency electromagnetic waves in water body, will make organic pollutants molecular chain, produce 95,000,000,000 times or 2,450 hundred million high-frequency vibrations per second and make it fracture, also 5～10 DEG C of left and right of corresponding rising of water temperature simultaneously.Microwave catalysis has individual precondition, be exactly in water, to have the dielectric material that absorbs microwave, these dielectric materials, absorbing after microwave, will produce on surface numerous high temperature hotspot, temperature can reach 800～1450 DEG C, and larger molecular organics is just cleaved on this focus.Activated carbon and Fe class material, be exactly best microwave absorbing medium, and just in steel pickling waste liquor, just have a large amount of Fe
2+the Fe (OH) generating
3, it by microwave calcination after, just having there is variation in self lattice, becomes chain by netted system, is even dehydrated into individually Fe
2o
3.Produce so a very good additional effect: residue precipitation is very fast, solid, water ratio is very low.
4. UV catalysis: select small microwave to excite generation UV-light, produce O simultaneously
3way, effect is quite remarkable.Reaction times was reduced to 30-40 minute from several hours.
Comprehensively above-mentioned, after countless experiments, select microwave UV catalysis Fenton oxidation technology system more excellent.
Embodiment 2.
As shown in Figure 2, the difference of the present embodiment and embodiment 1 is: steel pickling waste liquor resource utilization and the technique of zero discharge of the present embodiment, after described step (d) neutralization flocculation, before the desalination of step (e) membrane module, also comprise the circulation of step (d1) underflow; The water outlet of step (d) neutralization flocculation enters the circulation of step (d1) underflow, the water outlet of step (d1) underflow circulation enters the desalination of step (e) membrane module, and the underflow after the desalination of step (e) membrane module is got back in the circulation of step (d1) underflow.
The Fe (OH) that the circulation of step (d1) underflow produces
3by pressure filter press filtration, making beating dissolving, oxidizing reaction, be prepared into waste water water purification agent.In the process that making beating is dissolved, add steel pickling waste liquor; Then add additive (as the additive containing rare earth element) and air to carry out oxidizing reaction, generate FeCl
3or Fe
2(SO
4).The Fe (OH) that the circulation of step (d1) underflow produces
3return in step (d) neutralization flocculation by the filtrate of pressure filter press filtration.
The steel pickling waste liquor resource utilization of the present embodiment and technique of zero discharge are realized three large systems.
1, microwave UV catalysis Fenton oxidation system: its effect is to reduce waste water COD, improves and loops back water water quality; It has comprised: microwave UV reactor, oxidizing tower, the micro-electrolysis three-phase fluidized bed of Fe/C, neutralization tank, flocculation tank, and can make waste water be dropped to below 60mg/L by 300～400mg/L by COD, TDS is dropped to and is less than 2000mg/L by 4500mg/L.
2, membrane module system: its effect is to realize waste water circulation reuse again.It has comprised MF-NF-RO three-major-items, its the water rate of recovery can reach 90-95%, fresh water TDS≤200mg/L, COD≤20mg/L, pH6～7 meet conventional industrial water quality requirement completely, and dense aquatic products rate only has 5%～10%, can be used on a small quantity preparing diluted acid, all the other produce low water purification agent for dissolved aluminum salt and additive, and one can realize systematic water balance.
3, water purification agent commodity production system: its effect is to produce water purification agent, realizes the commercialization of iron component.Iron mud reoxidizes after being dissolved in spent acid, can produce compound iron-aluminium water purification agent, containing FeCl
310%～15%, Al
2o
33%～5%, free acid≤0.5%, is a kind of low commodity Indian red solution, sells to its other producer's waste water station outward and uses.
The contrast of steel pickling waste liquor resource utilization of the present invention and technique of zero discharge and existing technique is as follows:
Steel pickling waste liquor resource utilization of the present invention and technique of zero discharge obtain desired result in steel pickling waste liquor purification system in the time of 10T/, move and within 3 years, do not need to change film.
Returns of investment are as follows according to pilot project budgetary estimate:
1, treatment capacity: waste water 200T/d, Fe
2+< 500mg/L, COD300～400mg/L, TDS > 4500mg/L; Spent acid 6-8T/d, containing FeCl
210%-15%, HCl2%-3%, pH < 1, COD > 10000mg/L.
2, quantum of output: reuse water 180T/d-190T/d, water-quality COD < 20mg/L, TDS < 200mg/L, pH6-7; Water purification agent 20T/d, containing FeCl
310%～15%, Al
2o
33%～5%, the polymerization degree 30%, pH < 1, reddish brown clear liquid.
3,3,000,000 yuan of gross investments.
4, project operation cost and profit: 1. ton water cost 7 yuan/T, years 300 days × 180T/d × 7 yuan/T water=380,000 first year; 2. ton water purification agent process cost 50 yuan/T, ten thousand first year of years 300 days × 20T/d × 50 yuan/T=30; 3. tap water is saved 300 days × 180T/ days × 2 yuan/T=10.8 ten thousand; 4. year water purification agent sales revenue: 250 yuan/T of product, ten thousand yuan/year of years 300 days × 20T/d × 250 yuan/T=150; 5. annual return=1,500,000+10.8 ten thousand-380,000-300,000=930,000 first year; 6. payback period=3,000,000 yuan ÷ 930,000 yuan/year=3 years.
The present invention, except energy steady running, can also realize profit, has good investment and reclaims, and is with a wide range of applications.
The above is only preferred embodiment of the present invention, and the equivalence of doing according to structure, feature and principle described in patent claim of the present invention therefore all changes or modifies, and is included in patent claim of the present invention.
Claims (10)
1. steel pickling waste liquor resource utilization and technique of zero discharge, is characterized in that: it comprises following processing step:
(a) steel pickling waste liquor water inlet;
(b) steel pickling waste liquor carries out Fenton reaction, the COD of steel pickling waste liquor is dropped to≤60mg/L, Fe
2+change Fe into
3+, drop to≤2000mg/L of TDS;
(c) steel pickling waste liquor carries out the micro-electrolytic reduction reaction of FeC;
(d) neutralization flocculation;
(e) membrane module desalination, drops to the TDS of steel pickling waste liquor≤200mg/L;
(f) effluent reuse.
2. steel pickling waste liquor resource utilization according to claim 1 and technique of zero discharge, is characterized in that: described step (b) steel pickling waste liquor carries out Fenton reaction and is specially: by H
2o
2or O
3add and in Fenton reactor, carry out Fenton reaction.
3. steel pickling waste liquor resource utilization according to claim 1 and technique of zero discharge, is characterized in that: described step (b) steel pickling waste liquor carries out Fenton reaction and is specially, and adopts titanium ruthenium electrode Ti-RuO
2carry out Fenton reaction.
4. steel pickling waste liquor resource utilization according to claim 1 and technique of zero discharge, is characterized in that: the membrane module of described step (e) is MF-NF-RO Integrated Films assembly, and after the desalination of MF-NF-RO Integrated Films assembly, water outlet more than 90% is fresh water.
5. steel pickling waste liquor resource utilization according to claim 1 and technique of zero discharge, is characterized in that: after described step (c) steel pickling waste liquor carries out the micro-electrolytic reduction reaction of FeC, the pH of steel pickling waste liquor is more than 3.5; After described step (d) neutralization flocculation, the pH of steel pickling waste liquor is more than 7.
6. steel pickling waste liquor resource utilization according to claim 1 and technique of zero discharge, is characterized in that: after described step (d) neutralization flocculation, before the desalination of step (e) membrane module, also comprise the circulation of step (d1) underflow; The water outlet of step (d) neutralization flocculation enters the circulation of step (d1) underflow, and the water outlet of step (d1) underflow circulation enters the desalination of step (e) membrane module, and the underflow after the desalination of step (e) membrane module is got back in the circulation of step (d1) underflow.
7. steel pickling waste liquor resource utilization according to claim 6 and technique of zero discharge, is characterized in that: the Fe (OH) that the circulation of described step (d1) underflow produces
3by pressure filter press filtration, making beating dissolving, oxidizing reaction, be prepared into waste water water purification agent.
8. steel pickling waste liquor resource utilization according to claim 7 and technique of zero discharge, is characterized in that: in the process that described making beating is dissolved, add steel pickling waste liquor; Then carry out oxidizing reaction, generate FeCl
3or Fe
2(SO
4)
3.
9. steel pickling waste liquor resource utilization according to claim 8 and technique of zero discharge, is characterized in that: the Fe (OH) that the circulation of described step (d1) underflow produces
3return in step (d) neutralization flocculation by the filtrate of pressure filter press filtration.
10. according to steel pickling waste liquor resource utilization and technique of zero discharge described in claim 1 ~ 9 any one, it is characterized in that: in described step (d) neutralization flocculation, add NaOH and PAM.
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| CN105366899A (en) * | 2015-12-10 | 2016-03-02 | 东华大学 | Ozone-anaerobic iron reduction combined Fenton oxidation technology for sludge reduction |
| CN106995249A (en) * | 2017-05-31 | 2017-08-01 | 浙江冶金环境保护设计研究有限公司 | A kind of segmentation combination treatment method of acid, the useless tank liquor of alkali cleaning |
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