CN106277358A - The flocculant of a kind of quasi-east coal chemical industrial waste water process and processing method thereof - Google Patents

The flocculant of a kind of quasi-east coal chemical industrial waste water process and processing method thereof Download PDF

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CN106277358A
CN106277358A CN201610745410.8A CN201610745410A CN106277358A CN 106277358 A CN106277358 A CN 106277358A CN 201610745410 A CN201610745410 A CN 201610745410A CN 106277358 A CN106277358 A CN 106277358A
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waste water
flocculant
quasi
described step
fermentation
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蒋远华
杨晓勤
冯加新
黄万铭
李锐
胡智
黄志亮
杨晓华
李铸磊
程鸿鸣
江传福
张战利
关勇
张书培
王云强
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YIHUA GROUP CO Ltd HUBEI PROV
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YIHUA GROUP CO Ltd HUBEI PROV
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
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    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The present invention relates to quasi-east coal chemical industrial waste water processing technology field, the flocculant processed more particularly to a kind of quasi-east coal chemical industrial waste water and method of wastewater treatment thereof.Described flocculant includes following components: zeolite group mineral 15 20 parts, polyacrylamide 5 10 parts, Kaolin 15 25 parts, aluminium polychlorid 8 15 parts, lime cream 8 15 parts, modified activated carbon 30 ~ 45 parts, 10 ~ 25 parts of grain expansion graphite；Component B: biological flocculant 10 ~ 15 parts, Rhizoma amorphophalli glucosan 5 ~ 15 parts.The present invention is by chemistry, physics and biological flocculant organic assembling, different waste water processing stage, different material in waste water is processed, can efficiently, adsorb rapidly, the impurity such as the Organic substance of removing in waste water and inorganic matter, realize the qualified discharge of waste water, and the method low cost, nontoxic, non-corrosiveness.

Description

The flocculant of a kind of quasi-east coal chemical industrial waste water process and processing method thereof
Technical field
The present invention relates to quasi-east coal chemical industrial waste water processing technology field, process more particularly to a kind of quasi-east coal chemical industrial waste water Flocculating agent composition and method of wastewater treatment.
Background technology
Processing method majority for coal chemical industrial waste water is anaerobic and aerobic Combined Treatment the most both at home and abroad, anaerobic technique Function is to improve wastewater biodegradability and reduce subsequent treatment structures load, and aerobic process is the main process that waste water processes. But some organic substance in the coal waste water of quasi-east cannot function as microbial nutrition substrate, or can be directly with this material as nutrition The microbe species of substrate is limited, not only containing such polluter in the water outlet of anaerobic reactor, and enters aerobic reaction After device, such material still can not thoroughly be degraded, and then causes quasi-east coal biological process of wastewater treatment usefulness relatively low, adds The difficulty of successive depths process and load, therefore, removing the most in process can not be directly as the dirt of microbial nutrition material Dye point or improve the microorganism species quantity of such material of degradable and promote flora function, be economical, effectively process brown coal The key of upgrading waste water.
Summary of the invention
Based on this, the present invention provides a kind of quasi-east flocculating agent composition that coal chemical industrial waste water processes and waste water process side thereof Method, can make that pollutant are degradable, process waste water energy qualified discharge or the waste water treatment process of recovery.
Technical solution of the present invention:
The flocculating agent composition that a kind of quasi-east coal chemical industrial waste water processes, described flocculant includes following components:
Component A: zeolite group mineral 15-20 part, polyacrylamide 5-10 part, Kaolin 15-25 part, aluminium polychlorid 8-15 Part, lime cream 8-15 part, modified activated carbon 30 ~ 45 parts, 10 ~ 25 parts of grain expansion graphite；
Component B: biological flocculant 10 ~ 15 parts, Rhizoma amorphophalli glucosan 5 ~ 15 parts.
Activated carbon, also known as activated carbon black, obtains through carbonization, activation and post processing with raw materials such as coal, timber and shells Black powder or granular amorphous carbon.Activated carbon structurally due to microcrystalline carbon irregular alignment, interconnection it Between have pore, can produce carbon tissue defects during activation, therefore it is a kind of porous carbon, and bulk density is low, and pore structure is flourishing, than Surface area is big (more than 1500m2/g), high adsorption capacity.After soda acid alternately modified processes, acid in removable activated carbon granule Alkali-soluble material, the most modified activated carbon pore size structure keeps constant, and specific surface area is from 720m2/ g improves extremely 1400m2/ g, average pore radius is 60 to 110A, has more preferably adsorption effect than conventional normal activated carbon, obtains identical In the case of adsorption effect, use the usage amount of modified activated carbon can reduce about half, reduce the cost that waste water processes.The present invention Composite adsorption process material and use modified activated carbon and grain expansion graphite and composite flocculation auxiliary agent compound compounding, obtain through experiment Rational quality proportioning, raw materials used can be recycled after Regeneration Treatment, this greatly reduces cost for wastewater treatment, helps In expanding the activated carbon application in waste water treatment industry.
Zeolite group mineral is the aluminum silicate mineral of a kind of aqueous alkali metal or alkaline-earth metal, has by silicon (aluminum) oxygen tetrahedron The three-dimensional framework constituted, has hole of all sizes and passage in skeleton, these holes and passage play filter and divide The effect of son sieve, can optionally adsorb or the Organic substance in filtered wastewater or inorganic matter, therefore be widely used in sewage clean The aspects such as change.
Montmorillonite has another name called montmorillonite, is the layer mineral being made up of the hydrous alumino silicates that granule is superfine, has very Strong absorption affinity and cation exchange property, be widely used in chemical reaction to produce adsorption and purification.When When montmorillonite and zeolite group mineral are used together, are exchanged by micro-porous adsorption and ion and montmorillonite and zeolite group mineral can be made to play mutually Mend collaborative effect.
Polyacrylamide is molecular weight by millions of to several macromolecular water-soluble organic polymers of ten million, has good Flocculability, can reduce the frictional resistance between liquid, forms bigger flco and thus produce huge surface between granule Adsorption.Process for waste water and use polyacrylamide to be generally divided into two processes: one is polyelectrolyte and particle table The charging neutrality in face；Two is that long-chain and the tiny suspended particles of polyelectrolyte are built bridge and formed thicker floc sedimentation, along with The increase of floc sedimentation, sedimentation velocity is gradually increased.Current domestic representational high polymer polyacrylamide has: nonionic polypropylene Amide (writing a Chinese character in simplified form NPAM, molecular weight 800-1500 ten thousand), anion-polyacrylamide (write a Chinese character in simplified form APAM, molecular weight 800-2000 Ten thousand), PAMC (writing a Chinese character in simplified form CPAM, molecular weight 800-1200 ten thousand, ion degree 10%-80%).
Aluminium polychlorid is a kind of high-molecular coagulant adopting water-purifying material.Due to it have adding less, purification efficiency is high, filter Rear water quality is good, low cost.
Calcium hydroxide is commonly called as Calx or slaked lime, for white solid, is slightly soluble in water, and its aqueous solution is frequently referred to lime water, In alkalescence, there is the general character of alkali, but its alkalescence or corrosivity are all weak than sodium hydroxide.Use calcium hydroxide can neutralize coal washing Acid ingredient in waste water, improves the adsorption of above-mentioned each adsorbent.
The mud that described biological flocculant is obtained with the flocculation of quasi-east coal chemical industrial waste water by the acid hydrolysate of agricultural crop straw, mixed Closing and make through Rhodococcus fascians or bacillus subtilis or penicillium funiculosum fermentation, specific make step is as follows:
1) seed culture of bacterial strain: bacterial strain is inoculated into seed culture medium from storage medium, in 32～35 DEG C, 130～ 6～24h are cultivated, it is thus achieved that seed liquor under conditions of 150rpm；
2) preparation of fermentation medium: agricultural crop straw with the sulphuric acid of weight percent concentration 1.2%～1.8% with solid-to-liquid ratio is 1:7～1:10, soaks 1～2h, precipitates 10～20min under the conditions of 4000～6000rpm, takes clear liquid and gives up with quasi-east Coal Chemical Industry The mud that water flocculation obtains is with volume ratio as 1:5～1:10 mixes, and mixed liquor sterilization treatment obtains fermentation medium；
3) preparation of fermentation liquid: seed liquor step 1) obtained concentration 0.5% by weight percentage～1.0% is seeded to described step Rapid 2) fermentation medium, fermentation culture under conditions of 25～30 DEG C, 150～170rpm, after fermentation culture 8～15h, mend Fill 0.2～0.5g/LK2HPO4With 0.1～0.2g/LKH2PO4, continue fermentation 6～12h, after supplementing 100～200mL/L sterilizings Quasi-east coal chemical industrial waste water flocculate the mud obtained, continue fermentation 18～24h, obtain fermentation liquid；
4) extraction of microbial flocculant: the fermentation liquor sonicator that step 3) obtains crushes, on centrifuge first Secondary centrifugal, take broken centrifugal rear supernatant, in this supernatant, be slowly added to 95% after the pre-cooling of this supernatant two volumes Ethanol, is mixed uniformly and makes flocky precipitate occur in this solution；The solution of existing flocky precipitate is carried out on centrifuge Second time is centrifugal, filters off supernatant, and the precipitate obtained after filtering washs three times with a small amount of ethanol solution；The precipitation obtained Being positioned in vacuum drying oven 40 ~ 60 DEG C to be dried, its dry product is biological flocculant.Centrifugal speed is 4000 ~ 5000r/min, Centrifugation time is 14 ~ 16 min.
Moisture content and the resistivity of the mud that described quasi-east coal chemical industrial waste water flocculation obtains are respectively 95.6%～98.4%, 2.5 ×1013～3.4 × 1013M, in mud supernatant, the content of COD and ammonia nitrogen is respectively 500～700mg/L, 160～220mg/ L。
Flocculant described in employing carries out the method that quasi-east coal chemical industrial waste water processes, and said method comprising the steps of:
1) pretreatment: waste water, after clarification naturally, adds the component A mixing in described flocculant in upper liquid, then enters Entering mud-water separation region, obtain supernatant and mud, mud enters sludge treating system and processes；
2) in the supernatant that described step 1) obtains, add oxidant, carry out oxidation reaction, organic in oxidation Decomposition waste water Thing, obtains the waste water that Organic substance is decomposed；
3) to described step 2) in the waste water that is decomposed of Organic substance adds alkaline solution, be neutralized reaction and regulate waste water PH value is to 7-9, the waste water after being neutralized；
4) in described step 3) and after waste water in add component B in flocculant after carry out solid-liquid separation process again, remove Float in waste water, obtains the waste water through chemical oxidation treatment；
5), by described step 4) through the waste water of chemical oxidation treatment and ozone contact, during ozone adds, protect in reactor Hold certain vacuum, and the waste water of contact is carried out anaerobic treatment and Aerobic biological process, the waste water after being carried out a biological disposal upon；
6) advanced treating: by the waste water after the process of described step 5) biological after coagulation, multi-medium filtering, then through ozone Oxidation carries out disinfection, decolours and remove Recalcitrant chemicals；Described ozone oxidation reaction temperature is 20～50 DEG C, pH be 5～ 8, hydraulic detention time is 10～60min；
7) film desalting processing
Described advanced treating water outlet is entered film processing system desalination；Described film processing system includes ultrafiltration, nanofiltration or reverse osmosis In two or three combination.
Described step 2) oxidant is one or more in sodium peroxydisulfate, potassium peroxydisulfate or Potassium Monopersulfate so that Join the mass concentration of the described oxidant in former water and the COD of former water ratio be 1 ~ 5:1.
Described step 2) described step 2) in also include to surfactant be cetyl trimethylammonium bromide (CTAB), In Dodecyl trimethyl ammonium chloride (DTAB), hexadecyltrimethylammonium chloride (CTAC), DTAB solution Any one；Described oxidant and surfactant mole ratio be 1～5:1.
Surfactant adds stirring in waste water, safe and efficient and energy natural degradation to, and utilizes surfactant to carry The high sedimentation velocity of biological flocculant, effectively controls the water content of filter cake.The surfactant degradable that the present invention uses Property strong, non-secondary pollution.
One or more in sodium hydroxide, sodium carbonate, sodium bicarbonate of alkaline solution described in described step 3).
Described step 4) is additionally added flocculation aid calcium chloride when adding flocculant component B, and its addition is flocculant component B The 1.2% of gross weight.
It is first to add 1.0～2.0g/L in quick agitation phases that described step 4) adds the method for flocculant component B Microbial flocculant in flocculant component B, rotating speed 180～240rpm, quickly after stirring 2～5min, stirs at a slow speed Mix, rotating speed 40～50 rpm, start at low rate mixing respectively, start after 1～2 min, 3～4 min, 5～7 min, 8～ 10 min add the Rhizoma amorphophalli glucosan that 0.5～0.8 g/L coagulates in agent component B, and low rate mixing amounts to 20～30 min, quiet heavy 30～40 min.After this flocculant component B processes, the moisture content of above-mentioned mud and resistivity be respectively 76.4%～83.5%, 1.4×1013～1.5 × 1013 M, in mud supernatant the content of COD and ammonia nitrogen be reduced to respectively 45～52 mg/L, 16 ～22 mg/L.
It is 0.1～1.6g/L that described step 6) advanced treating is additionally included in adding concentration in the photoreaction pipe of printing opacity Fe-Ti active sludge carbon, the H of 0.5～0.9g/L2O2, described photoreaction pipe be material be attached with transition metal ions Color glass, described transition metal is Co, Cr and Cu, and wherein, Co accounts for 0 .1%～2% of the total molar percentage of transition metal, Cr Accounting for 0 .1%～2% of the total molar percentage of transition metal, Cu accounts for the 0.1%～0.3% of the total molar percentage of transition metal, and remaining is Glass.
Ozone oxidation agent injected volume described in described step 5) is 20 ~ 40 mg/L waste water, and ozone can effectively remove COD, Reduce colourity, improve the biodegradability of waste water simultaneously, do preferable pretreatment for follow-up biochemical reaction.
Described step 5) vacuum is 0.03 ~ 0.06MPa, can improve the dissolubility of ozone.
The technology of the present invention effect:
1, the present invention is by chemistry, physics and biological flocculant organic assembling, different waste water processing stage, to not jljl in waste water Matter processes, can efficiently, adsorb rapidly, the impurity such as the Organic substance of removing in waste water and inorganic matter, it is achieved reaching of waste water Mark discharge, and the method low cost, nontoxic, non-corrosiveness.
2, after soda acid alternately modified processes, in removable activated carbon granule, soda acid solable matter, the most modified Activated carbon pore size structure keeps constant, and specific surface area is from 720m2/ g improves to 1400m2/ g, average pore radius be 60 to 110A, has more preferably adsorption effect than conventional normal activated carbon, in the case of obtaining identical adsorption effect, uses modification to live Property charcoal usage amount can reduce about half, reduce waste water process cost.The composite adsorption of the present invention processes material and uses modification Activated carbon is compound with grain expansion graphite and composite flocculation auxiliary agent compounding, obtains rational quality proportioning through experiment, raw materials used Can be recycled after Regeneration Treatment, this greatly reduces cost for wastewater treatment, contributes to expanding activated carbon at waste water treatment row The application of industry.
3, the dirty mud as a raw material that the present invention utilizes agricultural crop straw and the flocculation of quasi-east coal chemical industrial waste water to obtain prepares microorganism Flocculant, organic matter abundant in the product after lignocellulose hydrolysis abundant in agricultural crop straw and residual active sludge, Can be used to cultivating microorganism and prepare microbial flocculant.Thus, while reducing microbial flocculant preparation cost, it is achieved useless The comprehensive utilization of gurry, reduces environmental pollution, and prepared microbial flocculant can substitute conventional use of inorganic and organic Synthetic flocculant, is applied to waste water and processes and in sludge dehydration process.
4, the present invention is in biological flocculant makes sweat, supplements the phosphorus source needed for microorganism in the specifically fermentation time (main regulation medium pH is stable) and other nutrient substance (supplementing in form of a sludge), when can be greatly shortened fermentation Between (30～48h), reduce material utilization, improve microbial flocculant combined coefficient；
5, the present invention make microbial flocculant there is efficient flocculating property, flocculating rate is up to more than 97.5%；Useless Water processes and in the application of sludge dewatering, uses stage to add the mode of flocculating agent B component, it is possible to reduce microbial flocculant Usage amount, and effectively reduce the pollutant load in waste water, the dewatering efficiency of mud be greatly improved；Thus, reduce inorganic The secondary environmental pollution easily caused with organic synthesis high polymer coagulant；
6, the microbial flocculant Applicable temperature that prepared by the present invention is 20～120 DEG C, applicable pH range 3～11, has widely Application potential；
7, the present invention uses Rhizoma amorphophalli glucosan, be that a kind of water solublity is fabulous present in Amorphophallus konjac plant, high molecular non- Ion-type heteropolysaccharide, has the characteristics such as molecular weight is big, hydratability strong, neutral, and these characteristics determine it and have excellent Gelling performance, the present invention uses Rhizoma amorphophalli glucosan to replace the effect of polypropylene segment amide in quasi-east coal waste water processes, should Environment is not polluted by molecule, and flocculation ability is strong；
8, the present invention uses the purpose of ozone oxidation not to be to make mineralization of organic material completely, it is therefore an objective to removing the same of partial contamination thing Time, improve the biodegradability of waste water, therefore oxidization time is short, and consumption is few；And ozone is extremely strong oxidant, and it is different from wadding The reactions such as solidifying, fenton, can decompose voluntarily in the short time, do not have secondary pollution, it is to avoid adds substantial amounts of oxidant in water Cost is high, and secondary pollution and the problem increasing salinity occurs；
9, the group technology flow process of the present invention is used both can effectively to have removed COD, ammonia nitrogen etc. during traditional coal gasification waste water processes Major pollutants, have been greatly reduced salinity in water outlet simultaneously, reach country's standard about coal gasification waste water zero-emission.This The clear water response rate of the waste water after invention process, up to more than 93%, can obtain as the boiler replenishing water in Coal Chemical Industry, recirculated water To recycling；
10, in the coal chemical industrial waste water water outlet that the present invention processes, COD value is low, only 78～83mg/L；NH3-N value is reduced to 8 ～11mg/L, BOD to be reduced to 13mg/L, water outlet pH be 7.0～8.0, the water outlet after process reaches " integrated wastewater discharge mark Accurate " first discharge standard of (GB18466-2005)；
11, the inventive method processes coal chemical industrial waste water secondary biochemical treatment water outlet, initially with chemical oxidation treatment by waste water Phenols, nitrogen-containing heterocycle compound, amine, benzene homologues, polycyclic aromatic hydrocarbon, long chain alkane, halides and esters etc. are difficult to by microorganism The organic pollutant degradation utilized is prone to the Organic substance utilized by microorganism for acetic acid, propanoic acid etc., and recycling microorganism is to these Organic substance carries out biochemical oxidation, finally realizes the degraded of some organic pollutants in waste water, thus reduces waste water COD.
12, in advanced treating, light source uses sunlight, at TiO2Catalytic action under, except some pollutant can directly divide Relieving the exterior syndrome, the hydroxo complex of ferrum has preferable photo absorption performance, and absorbs photodissociation, produces more OH, and response speed is fast；Illumination Fe can also be strengthened3+Reduction, improve Fe2+Concentration, beneficially H2 O2Catalytic decomposition, thus improve the pollutant degree of depth Discomposing effect, colourity there has also been the biggest removal.
13, the inventive method is high to the treatment effeciency of coal chemical industrial waste water, and purification of waste water is effective, and COD removal rate reaches 33%～42%, the efficiency of chemical oxidation treatment is high, can significantly remove part in waste water and be difficult to the Organic substance utilized by microorganism；Raw Thing chemical oxidation treatment operating cost is low, reduces the processing cost of waste water.
14, the coal chemical industry wastewater treating method of the present invention, technological operation is simple, and waste water treatment efficiency is high, consumes energy low, ring Protecting, operating procedure condition is easily controlled, and effluent characteristics controllability is strong.
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment, but the scope of protection of present invention is not limited to implement The scope of example statement.
Embodiment 1
The flocculating agent composition that a kind of quasi-east coal chemical industrial waste water processes, described flocculant includes following components:
Component A: zeolite group mineral 15-20 part, activated carbon 15-30 part, polyacrylamide 5-10 part, Kaolin 15-25 part, poly- Close aluminum chloride 8-15 part, lime cream 8-15 part；
Component B: biological flocculant 10 ~ 15 parts, Rhizoma amorphophalli glucosan 5 ~ 15 parts.
The modification method of described modified activated carbon is as follows:
1) activated carbon, being crushed to granularity is 0.5-5mm
2) alkali leaching processes: be placed in container by step 1) gained activated carbon granule, and adding concentration is the NaOH solution of 8%, solid-to-liquid ratio 2 ~ 6:1, impregnates 3 ~ 6h under room temperature, washes and freeze-day with constant temperature 1 ~ 4h at 120 DEG C after dipping；
3) acidleach processes: be placed in container by the activated carbon granule processed through alkali leaching, and adding concentration is the HCl solution of 10%, solid-liquid Ratio 2 ~ 6:1, impregnates 2 ~ 6h under room temperature, washes and freeze-day with constant temperature 0.5 ~ 2h at 120 DEG C, obtain modified activated carbon after dipping.
The mud that described biological flocculant is obtained with the flocculation of quasi-east coal chemical industrial waste water by the acid hydrolysate of agricultural crop straw, mixed Closing and make through Rhodococcus fascians or bacillus subtilis or penicillium funiculosum fermentation, specific make step is as follows:
1) seed culture of bacterial strain: bacterial strain is inoculated into seed culture medium from storage medium, in 32～35 DEG C, 130～ 6～24h are cultivated, it is thus achieved that seed liquor under conditions of 150rpm；
2) preparation of fermentation medium: agricultural crop straw with the sulphuric acid of weight percent concentration 1.2%～1.8% with solid-to-liquid ratio is 1:7～1:10, soaks 1～2h, precipitates 10～20min under the conditions of 4000～6000rpm, takes clear liquid and gives up with quasi-east Coal Chemical Industry The mud that water flocculation obtains is with volume ratio as 1:5～1:10 mixes, and mixed liquor sterilization treatment obtains fermentation medium；
3) preparation of fermentation liquid: seed liquor step 1) obtained concentration 0.5% by weight percentage～1.0% is seeded to described step Rapid 2) fermentation medium, fermentation culture under conditions of 25～30 DEG C, 150～170rpm, after fermentation culture 8～15h, mend Fill 0.2～0.5g/LK2HPO4With 0.1～0.2g/LKH2PO4, continue fermentation 6～12h, after supplementing 100～200mL/L sterilizings Quasi-east coal chemical industrial waste water flocculate the mud obtained, continue fermentation 18～24h, obtain fermentation liquid；
4) extraction of microbial flocculant: the fermentation liquor sonicator that step 3) obtains crushes, on centrifuge first Secondary centrifugal, take broken centrifugal rear supernatant, in this supernatant, be slowly added to 95% after the pre-cooling of this supernatant two volumes Ethanol, is mixed uniformly and makes flocky precipitate occur in this solution；The solution of existing flocky precipitate is carried out on centrifuge Second time is centrifugal, filters off supernatant, and the precipitate obtained after filtering washs three times with a small amount of ethanol solution；The precipitation obtained Being positioned in vacuum drying oven 40 ~ 60 DEG C to be dried, its dry product is biological flocculant.Centrifugal speed is 4000 ~ 5000r/min, Centrifugation time is 14 ~ 16 min.
Moisture content and the resistivity of the mud that described quasi-east coal chemical industrial waste water flocculation obtains are respectively 95.6%～98.4%, 2.5 ×1013～3.4 × 1013M, in mud supernatant, the content of COD and ammonia nitrogen is respectively 500～700mg/L, 160～220mg/ L。
Flocculant described in employing carries out the method that quasi-east coal chemical industrial waste water processes, and said method comprising the steps of:
1) pretreatment: waste water, after clarification naturally, adds the component A mixing in described flocculant in upper liquid, then enters Entering mud-water separation region, obtain supernatant and mud, mud enters sludge treating system and processes；
2) in the supernatant that described step 1) obtains, add oxidant, carry out oxidation reaction, organic in oxidation Decomposition waste water Thing, obtains the waste water that Organic substance is decomposed；
3) to described step 2) in the waste water that is decomposed of Organic substance adds alkaline solution, be neutralized reaction and regulate waste water PH value is to 7-9, the waste water after being neutralized；
4) in described step 3) and after waste water in add component B in flocculant after carry out solid-liquid separation process again, remove Float in waste water, obtains the waste water through chemical oxidation treatment；
5), by described step 4) through the waste water of chemical oxidation treatment and ozone contact, during ozone adds, protect in reactor Hold certain vacuum, and the waste water of contact is carried out anaerobic treatment and Aerobic biological process, the waste water after being carried out a biological disposal upon；
6) advanced treating: by the waste water after the process of described step 5) biological after coagulation, multi-medium filtering, then through ozone Oxidation carries out disinfection, decolours and remove Recalcitrant chemicals；Described ozone oxidation reaction temperature is 20～50 DEG C, pH be 5～ 8, hydraulic detention time is 10～60min；
7) film desalting processing
Described advanced treating water outlet is entered film processing system desalination；Described film processing system includes ultrafiltration, nanofiltration or reverse osmosis In two or three combination.
Described step 2) oxidant is one or more in sodium peroxydisulfate, potassium peroxydisulfate or Potassium Monopersulfate so that Join the mass concentration of the described oxidant in former water and the COD of former water ratio be 1 ~ 5:1.
Described step 2) in also include to surfactant be cetyl trimethylammonium bromide (CTAB), dodecyl three Any one in methyl bromide ammonium (DTAB), hexadecyltrimethylammonium chloride (CTAC), DTAB solution；Institute State oxidant and surfactant mole ratio be 1～5:1.
One or more in sodium hydroxide, sodium carbonate, sodium bicarbonate of alkaline solution described in described step 3).
Described step 4) is additionally added flocculation aid calcium chloride when adding flocculant component B, and its addition is flocculant component B The 1.2% of gross weight.
It is first to add 1.0～2.0g/L in quick agitation phases that described step 4) adds the method for flocculant component B Microbial flocculant in flocculant component B, rotating speed 180～240rpm, quickly after stirring 2～5min, stirs at a slow speed Mix, rotating speed 40～50 rpm, start at low rate mixing respectively, start after 1～2 min, 3～4 min, 5～7 min, 8～ 10 min add the Rhizoma amorphophalli glucosan that 0.5～0.8 g/L coagulates in agent component B, and low rate mixing amounts to 20～30 min, quiet heavy 30～40 min.After this flocculant component B processes, the moisture content of above-mentioned mud and resistivity be respectively 76.4%～83.5%, 1.4×1013～1.5 × 1013 M, in mud supernatant the content of COD and ammonia nitrogen be reduced to respectively 45～52 mg/L, 16 ～22 mg/L.
Ozone oxidation agent injected volume described in described step 5) is 20 ~ 40 mg/L waste water, and ozone can effectively remove COD, Reduce colourity, improve the biodegradability of waste water simultaneously, do preferable pretreatment for follow-up biochemical reaction.
It is 0.1～1.6g/L that described step 6) advanced treating is additionally included in adding concentration in the photoreaction pipe of printing opacity Fe-Ti active sludge carbon, the H of 0.5～0.9g/L2O2, described photoreaction pipe be material be attached with transition metal ions Color glass, described transition metal is Co, Cr and Cu, and wherein, Co accounts for 0 .1%～2% of the total molar percentage of transition metal, Cr Accounting for 0 .1%～2% of the total molar percentage of transition metal, Cu accounts for the 0.1%～0.3% of the total molar percentage of transition metal, and remaining is Glass.
Embodiment 2
The flocculating agent composition that a kind of quasi-east coal chemical industrial waste water processes, described flocculant includes following components:
Component A: zeolite group mineral 15 parts, activated carbon 15 parts, polyacrylamide 5 parts, Kaolin 15 parts, aluminium polychlorid 8 parts, stone Ash breast 8 parts；
Component B: biological flocculant 10 parts, Rhizoma amorphophalli glucosan 5 parts.
The modification method of described modified activated carbon is as follows:
1) activated carbon, being crushed to granularity is 0.5mm
2) alkali leaching processes: be placed in container by step 1) gained activated carbon granule, and adding concentration is the NaOH solution of 8%, solid-to-liquid ratio 2:1, impregnates 3h under room temperature, washes and freeze-day with constant temperature 1h at 120 DEG C after dipping；
3) acidleach processes: be placed in container by the activated carbon granule processed through alkali leaching, and adding concentration is the HCl solution of 10%, solid-liquid Ratio 2:1, impregnates 2h under room temperature, washes and freeze-day with constant temperature 0.5h at 120 DEG C, obtain modified activated carbon after dipping.
The mud that described biological flocculant is obtained with the flocculation of quasi-east coal chemical industrial waste water by the acid hydrolysate of agricultural crop straw, mixed Closing and make through fermentation of bacillus subtilis, specific make step is as follows:
1) seed culture of bacterial strain: be inoculated into seed culture medium from storage medium by bacterial strain, in 32 DEG C, the condition of 130rpm Lower cultivation 6h, it is thus achieved that seed liquor；
2) preparation of fermentation medium: the sulphuric acid of agricultural crop straw and weight percent concentration 1.2%, with solid-to-liquid ratio as 1:7, soaks Bubble 1h, precipitates 10min under the conditions of 4000rpm, takes clear liquid and flocculates the mud obtained with volume ratio with quasi-east coal chemical industrial waste water Mixing for 1:5, mixed liquor sterilization treatment obtains fermentation medium；
3) preparation of fermentation liquid: seed liquor step 1) obtained concentration by weight percentage 0.5% is seeded to described step 2) Fermentation medium, 25 DEG C, fermentation culture under conditions of 150rpm, after fermentation culture 8h, supplements 0.2g/LK2HPO4With 0.1g/LKH2PO4, continuation fermentation 6h, supplements the mud that the quasi-east coal chemical industrial waste water flocculation after 100mL/L sterilizing obtains, continues Fermentation 18h, obtains fermentation liquid；
4) extraction of microbial flocculant: the fermentation liquor sonicator that step 3) obtains crushes, on centrifuge first Secondary centrifugal, take broken centrifugal rear supernatant, in this supernatant, be slowly added to 95% after the pre-cooling of this supernatant two volumes Ethanol, is mixed uniformly and makes flocky precipitate occur in this solution；The solution of existing flocky precipitate is carried out on centrifuge Second time is centrifugal, filters off supernatant, and the precipitate obtained after filtering washs three times with a small amount of ethanol solution；The precipitation obtained Being positioned in vacuum drying oven 40 DEG C to be dried, its dry product is biological flocculant.Centrifugal speed is 4000r/min, centrifugation time For 14min.
Moisture content and the resistivity of the mud that described quasi-east coal chemical industrial waste water flocculation obtains are respectively 95.6%, 2.5 × 1013M, In mud supernatant, the content of COD and ammonia nitrogen is respectively 500mg/L, 160mg/L.
Flocculant described in employing carries out the method that quasi-east coal chemical industrial waste water processes, and said method comprising the steps of:
1) pretreatment: waste water, after clarification naturally, adds the component A mixing in described flocculant in upper liquid, then enters Entering mud-water separation region, obtain supernatant and mud, mud enters sludge treating system and processes；
2) in the supernatant that described step 1) obtains, add oxidant, carry out oxidation reaction, organic in oxidation Decomposition waste water Thing, obtains the waste water that Organic substance is decomposed；
3) to described step 2) in the waste water that is decomposed of Organic substance adds alkaline solution, be neutralized reaction and regulate waste water The pH value waste water to 7, after being neutralized；
4) in described step 3) and after waste water in add component B in flocculant after carry out solid-liquid separation process again, remove Float in waste water, obtains the waste water through chemical oxidation treatment；
5), by described step 4) through the waste water of chemical oxidation treatment and ozone contact, during ozone adds, protect in reactor Hold certain vacuum, and the waste water of contact is carried out anaerobic treatment and Aerobic biological process, the waste water after being carried out a biological disposal upon；
6) advanced treating: by the waste water after the process of described step 5) biological after coagulation, multi-medium filtering, then through ozone Oxidation carries out disinfection, decolours and remove Recalcitrant chemicals；Described ozone oxidation reaction temperature is 20 DEG C, and pH is 5, and waterpower is stopped Staying the time is 10min；
7) film desalting processing
Described advanced treating water outlet is entered film processing system desalination；Described film processing system includes ultrafiltration, nanofiltration or reverse osmosis In two or three combination.
Described step 2) oxidant is one or more in sodium peroxydisulfate, potassium peroxydisulfate or Potassium Monopersulfate so that Join the mass concentration of the described oxidant in former water and the COD of former water ratio be 1:1.
Described step 2) in also include to surfactant be in cetyl trimethylammonium bromide (CTAB) solution appoint A kind of；Described oxidant and surfactant mole ratio be 1:1.
One or more in sodium hydroxide, sodium carbonate, sodium bicarbonate of alkaline solution described in described step 3).
Described step 4) is additionally added flocculation aid calcium chloride when adding flocculant component B, and its addition is flocculant component B The 1.2% of gross weight.
Described step 4) adds the method for flocculant component B, first adds 1.0g/L flocculation in quick agitation phases Microbial flocculant in agent component B, rotating speed 180rpm, quickly after stirring 2min, carry out low rate mixing, rotating speed 40 Rpm, start at low rate mixing respectively, start after 1min, 3min, 5min, 8 min add 0.5 g/L and coagulate in agent component B Rhizoma amorphophalli glucosan, low rate mixing amounts to 20min, quiet heavy 30min.After this flocculant component B processes, containing of above-mentioned mud Water rate and resistivity are respectively 76.4%, 1.4 × 1013M, in mud supernatant, the content of COD and ammonia nitrogen is reduced to 45 respectively mg/L、16 mg/L。
Described in described step 5), ozone oxidation agent injected volume is 20mg/L waste water, and ozone can effectively remove COD, reduces Colourity, improves the biodegradability of waste water simultaneously, does preferable pretreatment for follow-up biochemical reaction.
It is the Fe-of 0.1g/L that described step 6) advanced treating is additionally included in adding concentration in the photoreaction pipe of printing opacity Ti active sludge carbon, the H of 0.5g/L2O2, described photoreaction pipe be material be to be attached with the coloured glass of transition metal ions, institute The transition metal stated is Co, Cr and Cu, and wherein, Co accounts for 0 .1% of the total molar percentage of transition metal, and Cr accounts for transition metal and always rubs You 0 .1%, Cu of percentage ratio account for the 0.1% of the total molar percentage of transition metal, and remaining is glass.
Embodiment 3
The flocculating agent composition that a kind of quasi-east coal chemical industrial waste water processes, described flocculant includes following components:
Component A: zeolite group mineral 20 parts, activated carbon 30 parts, polyacrylamide 10 parts, Kaolin 25 parts, aluminium polychlorid 15 Part, lime cream 15 parts；
Component B: biological flocculant 15 parts, Rhizoma amorphophalli Dextran 15 part.
The modification method of described modified activated carbon is as follows:
1) activated carbon, being crushed to granularity is 5mm
2) alkali leaching processes: be placed in container by step 1) gained activated carbon granule, and adding concentration is the NaOH solution of 8%, solid-to-liquid ratio 6:1, impregnates 6h under room temperature, washes and freeze-day with constant temperature 4h at 120 DEG C after dipping；
3) acidleach processes: be placed in container by the activated carbon granule processed through alkali leaching, and adding concentration is the HCl solution of 10%, solid-liquid Ratio 6:1, impregnates 6h under room temperature, washes and freeze-day with constant temperature 2h at 120 DEG C, obtain modified activated carbon after dipping.
The mud that described biological flocculant is obtained with the flocculation of quasi-east coal chemical industrial waste water by the acid hydrolysate of agricultural crop straw, mixed Closing and make through Rhodococcus fascians or bacillus subtilis or penicillium funiculosum fermentation, specific make step is as follows:
1) seed culture of bacterial strain: be inoculated into seed culture medium from storage medium by bacterial strain, in 35 DEG C, the condition of 150rpm Lower cultivation 24h, it is thus achieved that seed liquor；
2) preparation of fermentation medium: the sulphuric acid of agricultural crop straw and weight percent concentration 1.8%, with solid-to-liquid ratio as 1:10, soaks Bubble 2h, precipitates 20min under the conditions of 6000rpm, takes clear liquid and the quasi-east coal chemical industrial waste water mud obtained that flocculates and with volume ratio is 1:10 mixes, and mixed liquor sterilization treatment obtains fermentation medium；
3) preparation of fermentation liquid: seed liquor step 1) obtained concentration by weight percentage 1.0% is seeded to described step 2) Fermentation medium, 30 DEG C, fermentation culture under conditions of 170rpm, after fermentation training 15h, supplements 0.5g/LK2HPO4And 0.2g/ LKH2PO4, continuation fermentation 12h, supplements the mud that the quasi-east coal chemical industrial waste water flocculation after 200mL/L sterilizing obtains, continues fermentation 24h, obtains fermentation liquid；
4) extraction of microbial flocculant: the fermentation liquor sonicator that step 3) obtains crushes, on centrifuge first Secondary centrifugal, take broken centrifugal rear supernatant, in this supernatant, be slowly added to 95% after the pre-cooling of this supernatant two volumes Ethanol, is mixed uniformly and makes flocky precipitate occur in this solution；The solution of existing flocky precipitate is carried out on centrifuge Second time is centrifugal, filters off supernatant, and the precipitate obtained after filtering washs three times with a small amount of ethanol solution；The precipitation obtained Being positioned in vacuum drying oven 60 DEG C to be dried, its dry product is biological flocculant.Centrifugal speed is 5000r/min, centrifugation time It is 16 min.
The moisture content of the mud that described quasi-east coal chemical industrial waste water flocculation obtains and resistivity difference 98.4%, 3.4 × 1013M, dirty In mud supernatant, the content of COD and ammonia nitrogen is respectively 700mg/L, 220mg/L.
Flocculant described in employing carries out the method that quasi-east coal chemical industrial waste water processes, and said method comprising the steps of:
1) pretreatment: waste water, after clarification naturally, adds the component A mixing in described flocculant in upper liquid, then enters Entering mud-water separation region, obtain supernatant and mud, mud enters sludge treating system and processes；
2) in the supernatant that described step 1) obtains, add oxidant, carry out oxidation reaction, organic in oxidation Decomposition waste water Thing, obtains the waste water that Organic substance is decomposed；
3) to described step 2) in the waste water that is decomposed of Organic substance adds alkaline solution, be neutralized reaction and regulate waste water PH value is to 7-9, the waste water after being neutralized；
4) in described step 3) and after waste water in add component B in flocculant after carry out solid-liquid separation process again, remove Float in waste water, obtains the waste water through chemical oxidation treatment；
5), by described step 4) through the waste water of chemical oxidation treatment and ozone contact, during ozone adds, protect in reactor Hold certain vacuum, and the waste water of contact is carried out anaerobic treatment and Aerobic biological process, the waste water after being carried out a biological disposal upon；
6) advanced treating: by the waste water after the process of described step 5) biological after coagulation, multi-medium filtering, then through ozone Oxidation carries out disinfection, decolours and remove Recalcitrant chemicals；Described ozone oxidation reaction temperature is 50 DEG C, and pH is 8, and waterpower is stopped Staying the time is 60min；
7) film desalting processing
Described advanced treating water outlet is entered film processing system desalination；Described film processing system includes ultrafiltration, nanofiltration or reverse osmosis In two or three combination.
Described step 2) oxidant is one or more in sodium peroxydisulfate, potassium peroxydisulfate or Potassium Monopersulfate so that Join the mass concentration of the described oxidant in former water and the COD of former water ratio be 5:1.
Described step 2) in also include to surfactant be cetyl trimethylammonium bromide (CTAB), dodecyl three Any one in methyl bromide ammonium (DTAB), hexadecyltrimethylammonium chloride (CTAC), DTAB solution；Institute State oxidant and surfactant mole ratio be 5:1.
One or more in sodium hydroxide, sodium carbonate, sodium bicarbonate of alkaline solution described in described step 3).
Described step 4) is additionally added flocculation aid calcium chloride when adding flocculant component B, and its addition is flocculant component B The 1.2% of gross weight.
Described step 4) adds the method for flocculant component B, first adds 2.0g/L flocculation in quick agitation phases Microbial flocculant in agent component B, rotating speed 240rpm, quickly after stirring 5min, carry out low rate mixing, rotating speed 50 rpm, Start at low rate mixing respectively, start after 2 min, 4 min, 7 min, 10 min add 0.8 g/L and coagulate in agent component B Rhizoma amorphophalli glucosan, low rate mixing amounts to 30 min, quiet heavy 40 min.After this flocculant component B processes, containing of above-mentioned mud Water rate and resistivity are respectively 83.5%, 1.5 × 1013 M, in mud supernatant, the content of COD and ammonia nitrogen is reduced to respectively 48mg/L、20 mg/L。
Ozone oxidation agent injected volume described in described step 5) is 40 mg/L waste water, and ozone can effectively remove COD, reduces Colourity, improves the biodegradability of waste water simultaneously, does preferable pretreatment for follow-up biochemical reaction.
It is the Fe-of 1.6g/L that described step 6) advanced treating is additionally included in adding concentration in the photoreaction pipe of printing opacity Ti active sludge carbon, the H of 0.9g/L2O2, described photoreaction pipe be material be to be attached with the coloured glass of transition metal ions, institute The transition metal stated is Co, Cr and Cu, and wherein, Co accounts for the 2% of the total molar percentage of transition metal, and Cr accounts for total mole of transition metal The 2% of percentage ratio, Cu accounts for the 0.3% of the total molar percentage of transition metal, and remaining is glass.
Embodiment 4
The flocculating agent composition that a kind of quasi-east coal chemical industrial waste water processes, described flocculant includes following components:
Component A: zeolite group mineral 18 parts, activated carbon 18 parts, polyacrylamide 8 parts, Kaolin 18 parts, aluminium polychlorid 12 parts, Lime cream 13 parts；
Component B: biological flocculant 12 parts, Rhizoma amorphophalli glucosan 13 parts.
The modification method of described modified activated carbon is as follows:
1) activated carbon, being crushed to granularity is 3.5mm
2) alkali leaching processes: be placed in container by step 1) gained activated carbon granule, and adding concentration is the NaOH solution of 8%, solid-to-liquid ratio 4:1, impregnates 5h under room temperature, washes and freeze-day with constant temperature 3h at 120 DEG C after dipping；
3) acidleach processes: be placed in container by the activated carbon granule processed through alkali leaching, and adding concentration is the HCl solution of 10%, solid-liquid Ratio 4:1, impregnates 5h under room temperature, washes and freeze-day with constant temperature 1.5h at 120 DEG C, obtain modified activated carbon after dipping.
The mud that described biological flocculant is obtained with the flocculation of quasi-east coal chemical industrial waste water by the acid hydrolysate of agricultural crop straw, mixed Closing and make through penicillium funiculosum fermentation, specific make step is as follows:
1) seed culture of bacterial strain: be inoculated into seed culture medium from storage medium by bacterial strain, in 33 DEG C, the condition of 140rpm Lower cultivation 20h, it is thus achieved that seed liquor；
2) preparation of fermentation medium: the sulphuric acid of agricultural crop straw and weight percent concentration 1.6%, with solid-to-liquid ratio as 1:9, soaks Bubble 1.5h, precipitates 15 min under the conditions of 5000rpm, takes clear liquid and flocculates the mud obtained with volume ratio with quasi-east coal chemical industrial waste water Mixing for 1:7, mixed liquor sterilization treatment obtains fermentation medium；
3) preparation of fermentation liquid: seed liquor step 1) obtained concentration by weight percentage 0.59% is seeded to described step 2) Fermentation medium, 29 DEG C, fermentation culture under conditions of 160rpm, after fermentation culture 14h, supplement 0.25g/LK2HPO4With 0.15g/LKH2PO4, continuation fermentation 9h, supplements the mud that the quasi-east coal chemical industrial waste water flocculation after 150mL/L sterilizing obtains, continues Fermentation 19h, obtains fermentation liquid；
4) extraction of microbial flocculant: the fermentation liquor sonicator that step 3) obtains crushes, on centrifuge first Secondary centrifugal, take broken centrifugal rear supernatant, in this supernatant, be slowly added to 95% after the pre-cooling of this supernatant two volumes Ethanol, is mixed uniformly and makes flocky precipitate occur in this solution；The solution of existing flocky precipitate is carried out on centrifuge Second time is centrifugal, filters off supernatant, and the precipitate obtained after filtering washs three times with a small amount of ethanol solution；The precipitation obtained Being positioned in vacuum drying oven 50 DEG C to be dried, its dry product is biological flocculant.Centrifugal speed is 4500r/min, centrifugation time It is 15 min.
Moisture content and the resistivity of the mud that described quasi-east coal chemical industrial waste water flocculation obtains are respectively 97.4%, 2.9 × 1013M, In mud supernatant, the content of COD and ammonia nitrogen is respectively 650mg/L, 210mg/L.
Flocculant described in employing carries out the method that quasi-east coal chemical industrial waste water processes, and said method comprising the steps of:
1) pretreatment: waste water, after clarification naturally, adds the component A mixing in described flocculant in upper liquid, then enters Entering mud-water separation region, obtain supernatant and mud, mud enters sludge treating system and processes；
2) in the supernatant that described step 1) obtains, add oxidant, carry out oxidation reaction, organic in oxidation Decomposition waste water Thing, obtains the waste water that Organic substance is decomposed；
3) to described step 2) in the waste water that is decomposed of Organic substance adds alkaline solution, be neutralized reaction and regulate waste water PH value is to 7-9, the waste water after being neutralized；
4) in described step 3) and after waste water in add component B in flocculant after carry out solid-liquid separation process again, remove Float in waste water, obtains the waste water through chemical oxidation treatment；
5), by described step 4) through the waste water of chemical oxidation treatment and ozone contact, during ozone adds, protect in reactor Hold certain vacuum, and the waste water of contact is carried out anaerobic treatment and Aerobic biological process, the waste water after being carried out a biological disposal upon；
6) advanced treating: by the waste water after the process of described step 5) biological after coagulation, multi-medium filtering, then through ozone Oxidation carries out disinfection, decolours and remove Recalcitrant chemicals；Described ozone oxidation reaction temperature is 40 DEG C, and pH is 7, and waterpower is stopped Staying the time is 50min；
7) film desalting processing
Described advanced treating water outlet is entered film processing system desalination；Described film processing system includes ultrafiltration, nanofiltration or reverse osmosis In two or three combination.
Described step 2) oxidant is one or more in sodium peroxydisulfate, potassium peroxydisulfate or Potassium Monopersulfate so that Join the mass concentration of the described oxidant in former water and the COD of former water ratio be 3:1.
Described step 2) in also include to surfactant be cetyl trimethylammonium bromide (CTAB), dodecyl three Any one in methyl bromide ammonium (DTAB), hexadecyltrimethylammonium chloride (CTAC), DTAB solution；Institute State oxidant and surfactant mole ratio be 3:1.
One or more in sodium hydroxide, sodium carbonate, sodium bicarbonate of alkaline solution described in described step 3).
Described step 4) is additionally added flocculation aid calcium chloride when adding flocculant component B, and its addition is flocculant component B The 1.2% of gross weight.
Described step 4) adds the method for flocculant component B, first adds 1.5g/L flocculation in quick agitation phases Microbial flocculant in agent component B, rotating speed 220rpm, quickly after stirring 3min, carry out low rate mixing, rotating speed 40～50 Rpm, start at low rate mixing respectively, start after 1.5 min, 3.5 min, 5.5 min, 6 min add 0.7g/L and coagulate agent Rhizoma amorphophalli glucosan in component B, low rate mixing amounts to 25 min, quiet heavy 35 min.After this flocculant component B processes, on Moisture content and the resistivity of stating mud are respectively 76.4%, 1.5 × 1013 M, in mud supernatant, the content of COD and ammonia nitrogen is respectively It is reduced to 52 mg/L, 22 mg/L.
Described in described step 5), ozone oxidation agent injected volume is 35mg/L waste water, and ozone can effectively remove COD, reduces Colourity, improves the biodegradability of waste water simultaneously, does preferable pretreatment for follow-up biochemical reaction.
It is 1.4 g/L's that described step 6) advanced treating is additionally included in adding concentration in the photoreaction pipe of printing opacity Fe-Ti active sludge carbon, the H of 0.8g/L2O2, described photoreaction pipe be material be to be attached with the coloured glass of transition metal ions, Described transition metal is Co, Cr and Cu, and wherein, Co accounts for 0 .15% of the total molar percentage of transition metal, and Cr accounts for transition metal 0 .15%, Cu of total molar percentage account for the 0.2% of the total molar percentage of transition metal, and remaining is glass.
The above embodiments are only the preferred technical solution of the present invention, and are not construed as the restriction for the present invention, this Shen Embodiment in please and the feature in embodiment, can mutual combination in any in the case of not conflicting.The protection model of the present invention Enclose the technical scheme should recorded with claim, including the equivalent side of technical characteristic in the technical scheme that claim is recorded Case is protection domain.Equivalent the most in this range is improved, also within protection scope of the present invention.

Claims (10)

1. the flocculant that a quasi-east coal chemical industrial waste water processes, it is characterised in that: described flocculant includes following components:
Component A: zeolite group mineral 15-20 part, polyacrylamide 5-10 part, Kaolin 15-25 part, aluminium polychlorid 8-15 Part, lime cream 8-15 part, modified activated carbon 30 ~ 45 parts, 10 ~ 25 parts of grain expansion graphite；
Component B: biological flocculant 10 ~ 15 parts, Rhizoma amorphophalli glucosan 5 ~ 15 parts.
2. the flocculant that a quasi-east coal chemical industrial waste water processes, it is characterised in that: the method for modifying step of described modified activated carbon Rapid as follows:
1) activated carbon, being crushed to granularity is 0.5-5mm；
2) alkali leaching processes: be placed in container by step 1) gained activated carbon granule, and adding concentration is the NaOH solution of 8%, solid-to-liquid ratio 2 ~ 6:1, impregnates 3 ~ 6h under room temperature, washes and freeze-day with constant temperature 1 ~ 4h at 120 DEG C after dipping；
3) acidleach processes: be placed in container by the activated carbon granule processed through alkali leaching, and adding concentration is the HCl solution of 10%, solid-liquid Ratio 2 ~ 6:1, impregnates 2 ~ 6h under room temperature, washes and freeze-day with constant temperature 0.5 ~ 2h at 120 DEG C, obtain modified activated carbon after dipping；
The mud that described biological flocculant is obtained with the flocculation of quasi-east coal chemical industrial waste water by the acid hydrolysate of agricultural crop straw, mixes warp Rhodococcus fascians or bacillus subtilis or silicate bacteria fermentation are made, and specific make step is as follows:
1) seed culture of bacterial strain: bacterial strain is inoculated into seed culture medium from storage medium, in 32～35 DEG C, 130～ 6～24h are cultivated, it is thus achieved that seed liquor under conditions of 150rpm；
2) preparation of fermentation medium: agricultural crop straw with the sulphuric acid of weight percent concentration 1.2%～1.8% with solid-to-liquid ratio is 1:7～1:10, soaks 1～2h, precipitates 10～20min under the conditions of 4000～6000rpm, takes clear liquid and gives up with quasi-east Coal Chemical Industry The mud that water flocculation obtains is with volume ratio as 1:5～1:10 mixes, and mixed liquor sterilization treatment obtains fermentation medium；
3) preparation of fermentation liquid: seed liquor step 1) obtained concentration 0.5% by weight percentage～1.0% is seeded to described step Rapid 2) fermentation medium, fermentation culture under conditions of 25～30 DEG C, 150～170rpm, after fermentation culture 8～15h, mend Fill 0.2～0.5g/LK2HPO4With 0.1～0.2g/LKH2PO4, continue fermentation 6～12h, after supplementing 100～200mL/L sterilizings Quasi-east coal chemical industrial waste water flocculate the mud obtained, continue fermentation 18～24h, obtain fermentation liquid；
4) extraction of microbial flocculant: the fermentation liquor sonicator that step 3) obtains crushes, on centrifuge first Secondary centrifugal, take broken centrifugal rear supernatant, in this supernatant, be slowly added to 95% after the pre-cooling of this supernatant two volumes Ethanol, is mixed uniformly and makes flocky precipitate occur in this solution；The solution of existing flocky precipitate is carried out on centrifuge Second time is centrifugal, filters off supernatant, and the precipitate obtained after filtering washs three times with a small amount of ethanol solution；The precipitation obtained Being positioned in vacuum drying oven 40 ~ 60 DEG C to be dried, its dry product is biological flocculant.
Flocculant the most according to claim 2, it is characterised in that: the mud that described quasi-east coal chemical industrial waste water flocculation obtains Moisture content and resistivity are respectively 95.6%～98.4%, 2.5 × 1013～3.4 × 1013M, COD and ammonia nitrogen in mud supernatant Content is respectively 500～700mg/L, 160～220mg/L.
4. use the flocculant described in claim 1 or 2 or 3 to carry out the method that quasi-east coal chemical industrial waste water processes, it is characterised in that Said method comprising the steps of:
1) pretreatment: waste water, after clarification naturally, adds the component A mixing in described flocculant in upper liquid, then enters Entering mud-water separation region, obtain supernatant and mud, mud enters sludge treating system and processes；
2) in the supernatant that described step 1) obtains, add oxidant, carry out oxidation reaction, organic in oxidation Decomposition waste water Thing, obtains the waste water that Organic substance is decomposed；
3) to described step 2) in the waste water that is decomposed of Organic substance adds alkaline solution, be neutralized reaction and regulate waste water PH value is to 7-9, the waste water after being neutralized；
4) in described step 3) and after waste water in add component B in flocculant after carry out solid-liquid separation process again, remove Float in waste water, obtains the waste water through chemical oxidation treatment；
5), by described step 4) through the waste water of chemical oxidation treatment and ozone contact, during ozone adds, protect in reactor Hold certain vacuum, and the waste water of contact is carried out anaerobic treatment and Aerobic biological process, the waste water after being carried out a biological disposal upon；
6) advanced treating: by the waste water after the process of described step 5) biological after coagulation, multi-medium filtering, then through ozone Oxidation carries out disinfection, decolours and remove Recalcitrant chemicals；Described ozone oxidation reaction temperature is 20～50 DEG C, pH be 5～ 8, hydraulic detention time is 10～60min；
7) film desalting processing
Described advanced treating water outlet is entered film processing system desalination；Described film processing system includes ultrafiltration, nanofiltration or reverse osmosis In two or three combination.
Method the most according to claim 4, it is characterised in that: described step 2) oxidant is sodium peroxydisulfate, potassium peroxydisulfate Or one or more in Potassium Monopersulfate so that join the mass concentration of described oxidant in former water and former water COD ratio be 1-5:1.
Method the most according to claim 5, it is characterised in that: described step 2) in also include to surfactant be 16 Alkyl trimethyl ammonium bromide (CTAB), Dodecyl trimethyl ammonium chloride (DTAB), hexadecyltrimethylammonium chloride (CTAC), Any one in DTAB solution；Described oxidant and surfactant mole ratio be 1～5:1.
Method the most according to claim 4, it is characterised in that: alkaline solution described in described step 3) is selected from hydroxide One or more in sodium, sodium carbonate, sodium bicarbonate.
Method the most according to claim 4, it is characterised in that: described step 4) is additionally added when adding flocculant component B and helps Solidifying agent calcium chloride, its addition is the 1.2% of flocculant component B gross weight.
Method the most according to claim 4, it is characterised in that: described step 4) adds the method for flocculant component B and is, First the microbial flocculant in quick agitation phases adds 1.0～2.0g/L flocculant component B, rotating speed 180～240rpm, Quickly after stirring 2～5min, carry out low rate mixing, rotating speed 40～50 rpm, start at low rate mixing respectively, start after 1～2 Min, 3～4 min, 5～7 min, 8～10 min add the Rhizoma amorphophalli glucosan that 0.5～0.8 g/L coagulates in agent component B, stir at a slow speed Mix 20～30 min altogether, quiet heavy 30～40 min.
Method the most according to claim 4, it is characterised in that: described in described step 5), ozone oxidation agent injected volume is 20 ~ 40 mg/L waste water.
CN201610745410.8A 2016-08-29 2016-08-29 The flocculant of a kind of quasi-east coal chemical industrial waste water process and processing method thereof Pending CN106277358A (en)

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CN107417060A (en) * 2017-08-28 2017-12-01 湖南奇思环保有限公司 A kind of curing agent and its synthetic method and application
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CN108996656A (en) * 2018-08-17 2018-12-14 河北工业大学 A kind of method that thermal activation sodium peroxydisulfate removes coal chemical industrial waste water COD with high salt
CN109293003A (en) * 2018-10-31 2019-02-01 张家界贵友环保材料科技有限公司 A kind of infant industry pollution water purification agent
CN111925060A (en) * 2020-08-12 2020-11-13 陈叶 Sewage treatment agent and preparation method and application thereof
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