CN105036453A - Organic wastewater treatment and recycling method - Google Patents
Organic wastewater treatment and recycling method Download PDFInfo
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- CN105036453A CN105036453A CN201510270362.7A CN201510270362A CN105036453A CN 105036453 A CN105036453 A CN 105036453A CN 201510270362 A CN201510270362 A CN 201510270362A CN 105036453 A CN105036453 A CN 105036453A
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Abstract
The present invention discloses an organic wastewater treatment and recycling method, wherein organic mineral-based powder material adsorption and microporous membrane filtration simultaneous-performing process is used, the process has characteristics of stability, efficiency, high equipment integration degree and small occupation area, and the treated water achieves the safe discharge and production recycling standard. According to the present invention, the hydrophobically modified organic mineral powder material is adopted as the adsorption media, and the method can be widely used in the fields of deep treatment of organic wastewater and difficultly-biodegraded pollutants, and the like.
Description
Technical field
The present invention relates to a kind for the treatment of and reuse method of organic waste water, belong to environment-protective water process field.
Background technology
Organic waste water wide material sources, can be divided into following 3 classes according to its characteristic: (1) sanitary sewage, husbandry, food-processing are the trade effluent of raw material, and the organism in waste water is easy to biological degradation, and the levels of toxic substances simultaneously in waste water is few.(2) organism in the waste water such as printing and dyeing, ore dressing is easy to biological degradation, but toxic content in waste water is more.(3) contained in the waste water such as papermaking, pharmacy organism is difficult to biological degradation, and waste water toxicity may be more simultaneously.The poisonous substance that every profession and trade produces organic waste water comprises organism and inorganics two class, such as H
2s, phenol, inorganic salt, heavy metal etc., microorganism is only 10 ~ 30% to the processing efficiency containing above-mentioned substance waste water, and therefore biochemical process process organic waste water often exists certain technical limitation.
Membrane bioreactor (MBR) has higher processing efficiency compared with traditional biochemical process, but the physicochemical characteristic of filter membrane material makes it inevitably produce surface contamination, causes permeation flux constantly to decline.On the other hand, as long as there is the material suppressing microorganism growth or Stability Analysis of Structures difficult degradation to exist, the processing efficiency of MBR cannot improve equally.
The sorbent material of process organic waste water has resene and gac, and this type of sorbent material price is high, and reclaim equiment is complicated.On the other hand, China's bentonite resource enriches, and areal distribution is wide, and wilkinite is cheap and easy to get, and Study and Development, towards the bentonite base multifunctional ceiling enclosure material for the treatment of of Organic Wastewater, has important economic worth.
For poisonous used water difficult to degradate, active sludge is replaced with the wilkinite through hydrophobically modified, can effectively solve following problem: the pollutent object of (1) biological method to process has selectivity, be not suitable for the process to toxic substance, hard-degraded substance, the sorbent material prepared with bentonite base modification has indiscriminate associated treatment effect to different pollutents.(2) modified wilkinite has higher loading capacity to organic pollutant, possesses surface hydrophobicity characteristic simultaneously, can be well compatible with filter membrane material, to the pollution delayed film surface in membrane filtration processes, significantly improves treatment capacity and processing efficiency.
Summary of the invention
For the treatment and reuse of organic waste water, content of the present invention is:
1) waste water is imported high-order pretreatment pool, in pretreatment pool, add pretreating agent, stirring reaction for some time.Stirring reaction 0.5 ~ 1.0h, controls original water hardness 50 ~ 500mgL
-1, heavy metal content≤500mgL
-1, pH=5 ~ 11, the stirring reaction time is 30 ~ 60min;
2) after step (1) reaction, hydrorrhea flow to high efficient solid and liquid separation pond, and supernatant liquor is again through cartridge filter pre-filtering.
3) step (2) water outlet and organic modified mineral base adsorbent are added in film reaction container, stirring and open under aeration condition the external vacuum primingpump of intake pump, membrane module, realize the synchronous absorption to waste water and ultra-filtration and separation.Film filtration effluent safety dumping or be back to production technique unit.The hydraulic detention time of waste water in adsorptive reactor is 30 ~ 100min, and the particle diameter of sorbent material is 10 ~ 1000 μm, and dosage is 1 ~ 100gL-1, and aeration rate is 100 ~ 2000Lm-2h-1; In absorption with membrane separating process, adopt the operation scheme of " filtration-backwash " cycle alternation, realize PLC and automatically control, it is 15 ~ 300min/ time that frequency is washed in backwash, and the corresponding backwash time is 5 ~ 30min; Described sorbent material is organically-modified mineral original washing powder body sorbing material,
4) upon adsorption dose of exchange capacity reaches capacity, and takes out membrane module, puts into membrane module and recycle after using hydrochloric acid, alkaline reagents to carry out original position desorb, regeneration to sorbent material.
5) when filter membrane permeation flux drops to 60% of initial flux, the hydrochloric acid of 0.1 ~ 5%, sodium hydroxide is used successively to carry out mechanical cleaning to organic membrane surface, control cleaning pH value 1 ~ 13, time 0.5 ~ 10h, drops into membrane module in reaction vessel and continues to use after membrane permeation flux recovery is to 95 ~ 100% of initial flux;
6) chemical cleaning solution of the stripping liquid of sorbent material and filter membrane is imported coagulation oxidation pond, adopt the method for coagulating sedimentation and deep oxidation to process.After process, liquid returns to step (1) front end.
In the preferred embodiment, the COD scope of described organic waste water is 100 ~ 5000mgL
-1.
In the preferred embodiment, step 1) pretreating agent that uses for the treatment of nature water comprises coagulating agent, flocculation agent, tenderizer.
In the preferred embodiment, step 2) hydraulic detention time of solids-liquid separation step is 10 ~ 60min.
In the preferred embodiment, step 3) in mineral based material be flyash, one or more in wilkinite, kaolin, Attapulgite and other clay-type substance mix in any proportion.
In the preferred embodiment, step 3) organically-modified properties-correcting agent is that one or more of Long carbon chain alkyl quaternary ammonium salts mix in any proportion.Described Bentonite Modification Technologies is prior art, is generally mineral based material and makes suspension, then adds a certain amount of Long carbon chain quaternary ammonium alkyl reactant salt.
In the preferred embodiment, step 3) mould material is inorganic ceramic film or resistance to oxidation hollow-fibre membrane, its material is at least one in fluoropolymer, polyolefins, polyethylene kind, polypropylene-base, polysulfones, aromatic polyamide class, and pore size filter is 1 ~ 100nm.
In the preferred embodiment, step 5) use the hydrochloric acid of 1 ~ 10% concentration, alkaline reagents carries out desorb to saturated adsorption agent, control desorption process pH value 1 ~ 13, time 2 ~ 10h, liquid-solid mass ratio is 3 ~ 30 ︰ 1; Alkaline reagents be in sodium hydroxide, potassium hydroxide or sodium carbonate any one or multiplely to mix in any proportion.
In the preferred embodiment, step 5) stripping liquid is mixed by a certain percentage with the chemical cleaning solution of filter membrane, controlling its pH value is 3 ~ 4, then adds ferrous sulfate and hydrogen peroxide in proportion, controls [Fe
2+]/[H
2o
2]=1:1 ~ 10, wherein ferrous sulfate dosage is 500 ~ 10000mgL
-1, the reaction times is 5 ~ 60min.
The invention provides a kind for the treatment of process of organic waste water, the separation of the precision of the adsorption function of modified mineral base adsorbent, filter membrane, material surface characteristic are combined, compared with biochemical method, significantly improve the processing efficiency to organic pollutant all kinds of in waste water.Modified adsorbent is hydrophobic material, and under flow shear effect, absorbent particles cannot be attached to filter membrane surface, and because of for the good biological sludge of wetting ability, speed is blocked up in the dirt that sorbent material of the present invention effectively can slow down filter membrane surface.
Accompanying drawing explanation
Fig. 1 process flow sheet
Fig. 2 membrane reactor figure, in figure, 1-pre-treatment former water 2-intake pump 3-stirring rake 4-membrane module 5-sorbent material 6-boring aeration pipe 7-under meter 8-air pump 9-self-priming go out water pump
Embodiment
The present invention is described further in conjunction with following embodiment, but the present invention is also not only confined to following examples.
Following examples all adopt the equipment of Fig. 1 and Fig. 2 and flow process to carry out
Embodiment 1
Certain beneficiation wastewater, containing poisonous difficult degradation characteristic contamination such as heavy metal, aniline aerofloat, butyl xanthates, water quality situation is as follows: [Pb]=70.35mgL
-1, [Zn
2+]=12.26mgL
-1, COD
cr=400mgL
-1, BOD
5=45mgL
-1, pH=9.66
Implementation step:
1) former water is delivered in pretreatment pool by lift pump, in pretreatment pool, adds Polyferric Sulfate 40mgL
-1, polyacrylamide 5mgL
-1, stirring reaction 30min.
2) step (1) mixed solution overflow is to efficient solid-liquid separation tank.
3) step (2) water outlet overflow is in film reaction container (1 uses for 1), and PVDF hollow-fibre membrane mean pore size is 0.1 μm, opens the continuous process that the external vacuum primingpump of membrane module realizes waste water.Organic bentonite base adsorbent 50gL is added in reactor
-1, sorbent material median size is 500 μm, and react under stirring with aeration condition, hydraulic detention time is 90min.
4) upon adsorption dose of exchange capacity reaches capacity, and sorbent material is imported matting pond, and working concentration is 10% sodium hydroxide desorb, and desorption time is 120min, and solid-to-liquid ratio is 1:10; Use the sulfuric acid of 5% to regenerate sorbent material, the recovery time is 240min, and solid-to-liquid ratio is 1:10.Stripping liquid and regenerated liquid recycle that to import oxidation pond afterwards 5 times pending.
5) under the operating pressure of-0.03Mpa, membrane module initial permeate flux is 50Lm
-2h
-1, when dropping to 30Lm
-2h
-1, take out membrane module, successively use 5% sodium hydroxide, scavenging solution that hydrochloric acid is configured to carries out soaking and washing to filter membrane surface, control cleaning pH=1 ~ 13, alkali cleaning, pickling time are respectively 90min, 90min.Cleaning tail washings imports oxidation pond.
6) chemical cleaning solution of stripping liquid and filter membrane is imported oxidation pond, control pH of mixed=3, in mixed solution, add 3000mgL under agitation
-1ferrous sulfate, 4000mgL
-1hydrogen peroxide, controls hydraulic detention time 20min.Water outlet returns to step (1) front end.
The water quality situation of above-mentioned various processes is as follows:
Step (2) water outlet [Pb]=1.52mgL
-1, [Zn
2+]=0.55mgL
-1, COD
cr=370mgL
-1, pH=7.51;
Step (3) final outflow water [Pb]≤0.01mgL
-1, [Zn
2+]≤0.01mgL
-1, COD
cr=35mgL
-1, pH=7.22; Step (6) water outlet [Pb]=52.05mgL
-1, [Zn
2+]=22.8mgL
-1, COD
cr=12mgL
-1, pH=2.81.
Embodiment 2
Certain beneficiation wastewater, containing characteristic contamination such as diethyldithiocarbamate, butyl xanthate, heavy metals, water quality situation is as follows: [Cu]=0.90mgL
-1, [Zn
2+]=0.32mgL
-1, [Pb
2+]=5.59mgL
-1, CODcr=350mgL
-1, pH=9.25
Implementation step:
1) former water is delivered in pretreatment pool by lift pump, in pretreatment pool, adds Polyferric Sulfate 60mgL
-1, polyacrylamide 5mgL
-1, stirring reaction 20min.
2) step (1) mixed solution overflow is to efficient solid-liquid separation tank, and supernatant liquor is the cartridge filter pre-filtering of 50 μm again through precision.
3) step (2) water outlet overflow is in film reaction container (1 uses for 1), and PVDF hollow-fibre membrane mean pore size is 0.2 μm, opens the continuous process that the external vacuum primingpump of membrane module realizes waste water.Organic attapulgite base adsorbent 100gL is added in reactor
-1, sorbent material median size is 50 μm, and react under stirring with aeration condition, hydraulic detention time is 120min.
4) upon adsorption dose of exchange capacity reaches capacity, and sorbent material is imported matting pond, and working concentration is 10% sodium hydroxide desorb, and desorption time is 90min, and solid-to-liquid ratio is 1:10; Use the sulfuric acid of 5% to regenerate sorbent material, the recovery time is 180min, and solid-to-liquid ratio is 1:10.Stripping liquid and regenerated liquid recycle that to import oxidation pond afterwards 5 times pending.
5) under the operating pressure of-0.02Mpa, membrane module initial permeate flux is 60Lm
-2h
-1, when dropping to 30Lm
-2h
-1, take out membrane module, successively use 5% sodium hydroxide, scavenging solution that hydrochloric acid is configured to carries out soaking and washing to filter membrane surface, control cleaning pH=1 ~ 13, alkali cleaning, pickling time are respectively 120min, 120min.Cleaning tail washings imports oxidation pond.
6) chemical cleaning solution of stripping liquid and filter membrane is imported oxidation pond, control pH of mixed=3.2, in mixed solution, add 4000mgL under agitation
-1ferrous sulfate, 6000mgL
-1hydrogen peroxide, controls hydraulic detention time 30min.Water outlet returns to step (1) front end.
The water quality situation of above-mentioned various processes is as follows:
Step (2) water outlet [Cu]=0.26mgL
-1, [Zn
2+]=0.22mgL
-1, [Pb
2+]=1.63mgL
-1, COD
cr=320mgL
-1, pH=7.29
Step (3) final outflow water [Cu]≤0.01mgL
-1, [Zn
2+]≤0.01mgL
-1, [Pb
2+]≤0.01mgL
-1, COD
cr=32mgL
-1, pH=7.12;
Step (6) water outlet [Cu]=11.62mgL
-1, [Zn
2+]=13.96mgL
-1, [Pb
2+]=32.24mgL
-1, COD
cr=15mgL
-1, pH=2.57;
Embodiment 3
Certain dyeing waste water, its characteristic contamination is high salt, bio-refractory azoic dyestuff.Water quality situation is as follows: specific conductivity=15200 μ scm
-1, COD
cr=900mgL
-1, SS is 180mgL
-1, colourity=400, pH=7.52.
Implementation step:
1) former water is delivered in pretreatment pool by lift pump, in pretreatment pool, adds efficient polymeric aluminum chloride (HPAC) 120mgL
-1, polyacrylamide 2mgL
-1, stirring reaction 20min.
2) step (1) mixed solution overflow is to efficient solid-liquid separation tank, and supernatant liquor is the cartridge filter pre-filtering of 30 μm again through precision.
3) step (2) water outlet overflow is in film reaction container (1 uses for 1), and PVDF hollow-fibre membrane mean pore size is 0.5 μm, opens the continuous process that the external vacuum primingpump of membrane module realizes waste water.Organo-clay 70gL is added in reactor
-1, sorbent material median size is 100 μm, and react under stirring with aeration condition, hydraulic detention time is 120min.
4) upon adsorption dose of exchange capacity reaches capacity, and sorbent material is imported matting pond, and working concentration is 10% sodium hydroxide desorb, and control desorption time is 120min, and solid-to-liquid ratio is 1:10; Use the sulfuric acid of 5% to regenerate sorbent material, the control recovery time is 180min, and solid-to-liquid ratio is 1:10.Stripping liquid and regenerated liquid recycle that to import oxidation pond afterwards 5 times pending.
5) under the operating pressure of-0.03Mpa, membrane module initial permeate flux is 45Lm
-2h
-1, when dropping to 27Lm
-2h
-1, take out membrane module, successively use 5% sodium hydroxide, scavenging solution that hydrochloric acid is configured to carries out soaking and washing to filter membrane surface, control cleaning pH=1 ~ 13, alkali cleaning, pickling time are respectively 180min, 180min.It is pending that cleaning tail washings imports oxidation pond.
6) chemical cleaning solution of stripping liquid and filter membrane is imported oxidation pond, control pH of mixed=3.50, in mixed solution, add 3000mgL under agitation
-1ferrous sulfate, 4800mgL
-1hydrogen peroxide, controls hydraulic detention time 25min.Water outlet returns to step (1) front end.
The water quality situation of above-mentioned various processes is as follows:
Step (2) water outlet COD
cr=675mgL
-1, SS is 45mgL
-1, colourity=165, pH=7.46;
Step (3) final outflow water COD
cr=72mgL
-1, SS is 0.01mgL
-1, colourity=20, pH=7.08;
Step (6) water outlet COD
cr=32mgL
-1, colourity=15, pH=2.96.
Embodiment 4
Certain pharmacy waste water, is characterized by high salt, nitrobenzene-containing, phenol etc. to biological toxic substance.Water quality situation is as follows: specific conductivity=23600 μ scm
-1, COD
cr=1650mgL
-1, SS is 1200mgL
-1, colourity=420, pH=3.64.
Implementation step:
1) former water is delivered in pretreatment pool by lift pump, in pretreatment pool, adds efficient polymeric aluminum chloride (HPAC) 300mgL
-1, polyacrylamide 5mgL
-1, stirring reaction 30min.Add sodium hydroxide and regulate pH=6.50
2) step (1) mixed solution overflow is to efficient solid-liquid separation tank, and supernatant liquor is the cartridge filter pre-filtering of 30 μm again through precision.
3) step (2) water outlet overflow is in film reaction container (1 uses for 1), and PVDF hollow-fibre membrane mean pore size is 0.1 μm, opens the continuous process that the external vacuum primingpump of membrane module realizes waste water.Palmityl trimethyl ammonium chloride (CTAC) modified alta-mud base adsorbent 90gL is added in reactor
-1, sorbent material median size is 30 μm, and react under stirring with aeration condition, hydraulic detention time is 120min.
4) upon adsorption dose of exchange capacity reaches capacity, and sorbent material is imported matting pond, and working concentration is 10% sodium hydroxide desorb, and control desorption time is 180min, and solid-to-liquid ratio is 1:10; Use the sulfuric acid of 5% to regenerate sorbent material, the control recovery time is 240min, and solid-to-liquid ratio is 1:10.Stripping liquid and regenerated liquid recycle that to import oxidation pond afterwards 3 times pending.
5) under the operating pressure of-0.03Mpa, membrane module initial permeate flux is 40Lm
-2h
-1, when dropping to 24Lm
-2h
-1, take out membrane module, successively use 5% sodium hydroxide, scavenging solution that hydrochloric acid is configured to carries out soaking and washing to filter membrane surface, control cleaning pH=1 ~ 13, alkali cleaning, pickling time are respectively 180min, 180min.It is pending that cleaning tail washings imports oxidation pond.
6) chemical cleaning solution of stripping liquid and filter membrane is imported oxidation pond, control pH of mixed=3.20, in mixed solution, add 6000mgL under agitation
-1ferrous sulfate, 8000mgL
-1hydrogen peroxide, controls reaction hydraulic detention time 25min.Water outlet returns to step (1) front end.
The water quality situation of above-mentioned various processes is as follows:
Step (2) water outlet COD
cr=595mgL
-1, SS is 90mgL
-1, colourity=120, pH=6.50;
Step (3) final outflow water COD
cr=126mgL
-1, SS is 0.01mgL
-1, colourity=10, pH=6.45;
Step (6) water outlet COD
cr=210mgL
-1, colourity=15, pH=2.78.
In above-mentioned case, the filter membrane online anti-cleaning interval is 80min, and the matting cycle is 40d, and the anti-cleaning interval of relatively conventional membrane bioreactor and the time in matting cycle extend more than 200% and 100% respectively; Sorbent material is 100 ~ 500mgg to the organic saturated exchange capacity of difference
-1in shorter hydraulic detention time, more than 90% is reached to the processing efficiency of COD, therefore above-mentioned case study on implementation demonstrates beneficial effect of the present invention and is: (1) adopts hydrophobic adsorbent to replace traditional active sludge, filter membrane flux rate of decay obviously declines, and extends the operational use time of filter membrane; (2) treatment effect of indifference absorption to difficult degradation and toxic substance of modified mineral base is obvious, is better than traditional active sludge membrane bioreactor in clearance and stability.(3) the advanced treatment field for the treatment of of Organic Wastewater and used water difficult to degradate can be widely used in.
Claims (9)
1. a treatment and reuse method for organic waste water, comprises the steps:
1) pending waste water is imported high-order pretreatment pool, in pretreatment pool, add pretreating agent, stirring reaction 0.5 ~ 1.0h, control original water hardness 50 ~ 500mgL
-1, heavy metal content≤500mgL
-1, pH=5 ~ 11, the stirring reaction time is 30 ~ 60min;
2) after step (1) reaction, hydrorrhea flow to solid-liquid separation tank,
3) supernatant liquor of solid-liquid separation tank pumps in the reaction tank containing organic modified mineral base adsorbent and membrane separation plant, stirring and opening under aeration condition the external vacuum primingpump of intake pump, membrane module, realize to the synchronous absorption of waste water be separated, standard water discharge discharge or be back to production technique unit; The hydraulic detention time of waste water in adsorptive reactor is 30 ~ 100min, and the particle diameter of sorbent material is 10 ~ 1000 μm, and dosage is 1 ~ 100gL-1, and aeration rate is 100 ~ 2000Lm-2h-1; In absorption with membrane separating process, adopt the operation scheme of " filtration-backwash " cycle alternation, it is 15 ~ 300min/ time that frequency is washed in backwash, and the corresponding backwash time is 5 ~ 30min; Described sorbent material is organically-modified mineral original washing powder body sorbing material,
4) upon adsorption dose of exchange capacity reaches capacity, and takes out membrane module, uses alkaline reagents to carry out original position desorb, the use of regeneration Posterior circle to modified mineral base adsorbent;
5) when filter membrane permeation flux drops to 60% of initial flux, the hydrochloric acid of 0.1 ~ 5%, sodium hydroxide is used successively to carry out mechanical cleaning to organic membrane surface, control cleaning pH value 1 ~ 13, time 0.5 ~ 10h, drops into membrane module in reaction vessel and continues to use after membrane permeation flux recovery is to 95 ~ 100% of initial flux;
6) chemical cleaning solution of the stripping liquid of sorbent material and filter membrane is imported coagulation oxidation pond, adopt the method for coagulating sedimentation and deep oxidation to process, after process, liquid returns step (1).
2. the treatment and reuse method of a kind of organic waste water according to claim 1, is characterized in that: the COD scope of described organic waste water is 100 ~ 5000mgL
-1.
3. the treatment and reuse method of a kind of organic waste water according to claim 1, is characterized in that: step 1) pretreating agent that uses for the treatment of nature water comprises coagulating agent, flocculation agent, tenderizer.
4. the treatment and reuse method of a kind of organic waste water according to claim 1, is characterized in that: step 2) hydraulic detention time of solids-liquid separation step is 10 ~ 60min.
5., according to the treatment and reuse method of claim 1 organic waste water, it is characterized in that: step 3) in mineral based material be flyash, one or more in wilkinite, kaolin, Attapulgite and other clay-type substance mix in any proportion.
6. the treatment and reuse method of a kind of organic waste water according to claim 1, is characterized in that: step 3) organically-modified properties-correcting agent is that one or more of Long carbon chain alkyl quaternary ammonium salts mix in any proportion.
7. the treatment and reuse method of a kind of organic waste water according to claim 1, it is characterized in that: step 3) mould material is inorganic ceramic film or resistance to oxidation hollow-fibre membrane, its material is at least one in fluoropolymer, polyolefins, polyethylene kind, polypropylene-base, polysulfones, aromatic polyamide class, and pore size filter is 1 ~ 100nm.
8. according to the treatment and reuse method of claim 1 organic waste water, it is characterized in that: step 5) use the hydrochloric acid of 1 ~ 10% concentration, alkaline reagents carries out desorb to saturated adsorption agent, control desorption process pH value 1 ~ 13, time 2 ~ 10h, liquid-solid mass ratio is 3 ~ 30 ︰ 1; Alkaline reagents be in sodium hydroxide, potassium hydroxide or sodium carbonate any one or multiplely to mix in any proportion.
9. according to the treatment and reuse method of claim 1 organic waste water, it is characterized in that: step 5) stripping liquid is mixed by a certain percentage with the chemical cleaning solution of filter membrane, controlling its pH value is 3 ~ 4, then adds ferrous sulfate and hydrogen peroxide in proportion, controls [Fe
2+]/[H
2o
2]=1:1 ~ 10, wherein ferrous sulfate dosage is 500 ~ 10000mgL
-1, the reaction times is 5 ~ 60min.
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