CN106242179A - The compositions of a kind of quasi-east coal chemical industrial waste water process and method of wastewater treatment thereof - Google Patents
The compositions of a kind of quasi-east coal chemical industrial waste water process and method of wastewater treatment thereof Download PDFInfo
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Abstract
The present invention relates to quasi-east coal chemical industrial waste water processing technology field, the compositions processed more particularly to a kind of quasi-east coal chemical industrial waste water and method of wastewater treatment thereof.Described compositions includes following components: component A: zeolite group mineral 15 20 parts, activated carbon 15 30 parts, polyacrylamide 5 10 parts, Kaolin 15 25 parts, aluminium polychlorid 8 15 parts, lime cream 8 15 parts;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
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
Compositions 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 compositions that coal chemical industrial waste water processes and method of wastewater treatment thereof, 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 compositions that a kind of quasi-east coal chemical industrial waste water processes, described compositions 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.
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), and high adsorption capacity, the degree of depth being widely used in drinking water, water for industrial use and waste water is clean
In change, industry purification of water quality and Gas Phase Adsorption, such as power plant, petrochemical industry, oil plant, food and drink, sugaring alcoholic, medicine, electronics, support
The purification of water quality of the industry such as fish, sea-freight processes, free chlorine, phenol, sulfur and other organic pollution in energy active adsorption water, especially
It is the precursor of mutagen (THM), reaches purification and impurity removal and go the purpose of abnormal flavour.
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 with Rhodococcus erythropolis Rhodococcus fascians or penicillium funiculosum fermentation through rhodococcus erythropolis, 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。
Compositions 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) after the waste water of chemical oxidation treatment carries out anaerobic biochemical treatment, aerobic treatment is carried out,
In Aerobic, it is passed through ozone, during ozone adds, keeps certain vacuum in reactor, obtain at biology
Waste water after reason;
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 in Xiang Yuanshui add initiator, described initiator is sodium sulfite, potassium sulfite, Asia
One or more in sodium bisulfate, Potassium acid sulfite, ferrous chloride or ferrous sulfate;Described oxidant and initiator 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
Rhizoma amorphophalli glucosan in flocculant component B, rotating speed 180~250rpm, quickly after stirring 2~3min, carry out low rate mixing, turn
Speed 40~60 rpm, respectively after low rate mixing starts 1~3 min, 4~5 min, 5.5~6 min, 7~9 min add
0.5~0.9 g/L coagulates the microbial flocculant 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 are 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.
Described step 5) vacuum is 0.03 ~ 0.06MPa, can improve the dissolubility of ozone, improves treatment effect.
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, 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.
3, 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;
4, 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;
5, 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;
6, 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;
7, 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
Solidifying wait reaction, can decompose voluntarily in the short time, there is no secondary pollution, it is to avoid it is high to add substantial amounts of oxidant cost in water,
And secondary pollution and the problem increasing salinity occur;First carry out anaerobic treatment through ozone processed waste water, then carry out aerobic
Process, alternately, improve the treatment effeciency of waste water, simultaneously in Aerobic Process for Treatment, add ozone, improve the process of aerobic stage
Effect;
8, 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;
9, 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 be reduced to 8~
It is 7.0~8.0 that 11mg/L, BOD are reduced to 13mg/L, water outlet pH, and the water outlet after process reaches " integrated wastewater discharge standard "
(GB18466-2005) first discharge standard;
10, 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.
11, 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%~45%, 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.
12, the long-chain in waste water, larger molecular organics can be decomposed into short chain, small organic molecule by anaerobic biochemical treatment,
Improve the biodegradability of waste water, it is possible to denitrification denitrogenation;Aerobic treatment reduces BOD, COD of waste water, and handle further
Mineralized nitrogen in waste water is absorbable nitrate or nitrite, is back to anaerobism section and carries out denitrification denitrogenation, with
Time eliminate waste water abnormal flavour.
13, 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 compositions that a kind of quasi-east coal chemical industrial waste water processes, described compositions 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 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 with Rhodococcus erythropolis Rhodococcus fascians or penicillium funiculosum fermentation through rhodococcus erythropolis, 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。
Compositions 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) after the waste water of chemical oxidation treatment carries out anaerobic biochemical treatment, aerobic treatment is carried out,
In Aerobic, it is passed through ozone, during ozone adds, keeps certain vacuum in reactor, obtain at biology
Waste water after reason;
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 in Xiang Yuanshui add initiator, described initiator is sodium sulfite, potassium sulfite, Asia
One or more in sodium bisulfate, Potassium acid sulfite, ferrous chloride or ferrous sulfate;Described oxidant and initiator 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
Rhizoma amorphophalli glucosan in flocculant component B, rotating speed 180~250rpm, quickly after stirring 2~3min, carry out low rate mixing,
Rotating speed 40~60 rpm, respectively after low rate mixing starts 1~3 min, 4~5 min, 5.5~6 min, 7~9 min throw
Adding 0.5~0.9 g/L coagulates the microbial flocculant in agent component B, low rate mixing amounts to 20~30 min, and quiet heavy 30~40
min。
After this flocculant component B processes, the moisture content of above-mentioned mud and resistivity are 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.
Described step 5) vacuum is 0.03 ~ 0.06MPa, can improve the dissolubility of ozone, improves treatment effect.
Embodiment 2
The compositions that a kind of quasi-east coal chemical industrial waste water processes, described compositions 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 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 erythropolis 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 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
It is 14 min.
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.
Compositions 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) after the waste water of chemical oxidation treatment carries out anaerobic biochemical treatment, aerobic treatment is carried out,
In Aerobic, it is passed through ozone, during ozone adds, keeps certain vacuum in reactor, obtain at biology
Waste water after reason;
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 in Xiang Yuanshui add initiator, described initiator is sodium sulfite, potassium sulfite, Asia
One or more in sodium bisulfate, Potassium acid sulfite, ferrous chloride or ferrous sulfate;Described oxidant and initiator 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
Rhizoma amorphophalli glucosan in agent component B, rotating speed 180rpm, quickly after stirring 2min, carry out low rate mixing, rotating speed 40 rpm,
After low rate mixing starts, 1 min, 4min, 5.5 min, 7 min add micro-life that 0.5 g/L coagulates in agent component B respectively
Thing flocculant, low rate mixing amounts to 20min, quiet heavy 30 min.
After this flocculant component B processes, the moisture content of above-mentioned mud and resistivity are respectively 76.4%, 1.4 × 1013
M, in mud supernatant, the content of COD and ammonia nitrogen is reduced to 45mg/L, 16 mg/L respectively.
Ozone oxidation agent injected volume described in described step 5) is 20 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.
Described step 5) vacuum is 0.03MPa, can improve the dissolubility of ozone, improves treatment effect.
Embodiment 3
The compositions that a kind of quasi-east coal chemical industrial waste water processes, described compositions includes following components:
Component A: zeolite group mineral 20 parts, activated carbon 30 parts, polyacrylamide 10 parts, Kaolin 25 parts, aluminium polychlorid 15 parts,
Lime cream 15 parts;
Component B: biological flocculant 15 parts, Rhizoma amorphophalli Dextran 15 part.
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 the fermentation of Rhodococcus erythropolis Rhodococcus fascians, 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 4h, 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 culture 15h, supplements 0.5g/LK2HPO4With
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.
Moisture content and the resistivity of the mud that described quasi-east coal chemical industrial waste water flocculation obtains are respectively 98.4%, 3.4 × 1013M,
In mud supernatant, the content of COD and ammonia nitrogen is respectively 700mg/L, 220mg/L.
Compositions 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) after the waste water of chemical oxidation treatment carries out anaerobic biochemical treatment, aerobic treatment is carried out,
In Aerobic, it is passed through ozone, during ozone adds, keeps certain vacuum in reactor, obtain at biology
Waste water after reason;
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 in Xiang Yuanshui add initiator, described initiator is sodium sulfite, potassium sulfite, Asia
One or more in sodium bisulfate, Potassium acid sulfite, ferrous chloride or ferrous sulfate;Described oxidant and initiator 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
Rhizoma amorphophalli glucosan in agent component B, rotating speed 250rpm, quickly after stirring 3min, carry out low rate mixing, rotating speed 60 rpm, divide
After low rate mixing starts, 3 min, 5 min, 6 min, 9 min do not add 0.9 g/L and coagulate the microbial flocculation in agent component B
Agent, low rate mixing amounts to 30 min, quiet heavy 40 min.
After this flocculant component B processes, the moisture content of above-mentioned mud and resistivity are respectively 83.5%, 1.5 × 1013 M,
In mud supernatant, the content of COD and ammonia nitrogen is reduced to 52 mg/L, 22 mg/L respectively.
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.
Described step 5) vacuum is 0.06MPa, can improve the dissolubility of ozone, improves treatment effect.
Embodiment 4
The compositions that a kind of quasi-east coal chemical industrial waste water processes, described compositions includes following components:
Component A: zeolite group mineral 18 parts, activated carbon 19 parts, polyacrylamide 9 parts, Kaolin 18 parts, aluminium polychlorid 12 parts,
Lime cream 12 parts;
Component B: biological flocculant 13 parts, Rhizoma amorphophalli glucosan 13 parts.
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 6~24h, it is thus achieved that seed liquor;
2) preparation of fermentation medium: the sulphuric acid of agricultural crop straw and weight percent concentration 1.5%, with solid-to-liquid ratio as 1:8, soaks
Bubble 1.5h, precipitates 15min 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 1:8, mixed liquor sterilization treatment obtains fermentation medium;
3) preparation of fermentation liquid: seed liquor step 1) obtained concentration by weight percentage 0.8% is seeded to described step 2)
Fermentation medium, 28 DEG C, fermentation culture under conditions of 160rpm, after fermentation culture 9h, supplements 0.4g/LK2HPO4With
0.15g/LKH2PO4, continuation fermentation 8h, supplements the mud that the quasi-east coal chemical industrial waste water flocculation after 150mL/L sterilizing obtains, continues
Supervention ferment 22h, 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.
Compositions 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) after the waste water of chemical oxidation treatment carries out anaerobic biochemical treatment, aerobic treatment is carried out,
In Aerobic, it is passed through ozone, during ozone adds, keeps certain vacuum in reactor, obtain at biology
Waste water after reason;
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 4:1.
Described step 2) in also include in Xiang Yuanshui add initiator, described initiator is sodium sulfite, potassium sulfite, Asia
One or more in sodium bisulfate, Potassium acid sulfite, ferrous chloride or ferrous sulfate;Described oxidant and initiator mole
Ratio be 4:1.
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
Rhizoma amorphophalli glucosan in agent component B, rotating speed 190rpm, quickly after stirring 2.5min, carry out low rate mixing, rotating speed 50
Rpm, after low rate mixing starts, 1.8 min, 4.5 min, 5.8 min, 8 min add 0.7g/L and coagulate agent component B respectively
In microbial flocculant, low rate mixing amounts to 35 min, quiet heavy 38 min.
After this flocculant component B processes, the moisture content of above-mentioned mud and resistivity are respectively 82.4%, 1.47 × 1013
M, in mud supernatant, the content of COD and ammonia nitrogen is reduced to 48 mg/L, 18 mg/L respectively.
Ozone oxidation agent injected volume described in described step 5) is 25 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.
Described step 5) vacuum is 0.04MPa, can improve the dissolubility of ozone, improves treatment effect.
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 compositions that a quasi-east coal chemical industrial waste water processes, it is characterised in that: described compositions 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.
Compositions the most according to claim 1, it is characterised in that: described biological flocculant is produced by the acidolysis of agricultural crop straw
The mud that thing obtains with the flocculation of quasi-east coal chemical industrial waste water, mixes through rhodococcus erythropolis and Rhodococcus erythropolis Rhodococcus fascians or penicillium funiculosum
Fermentation is 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.
Compositions 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 compositions 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) after the waste water of chemical oxidation treatment carries out anaerobic biochemical treatment, aerobic treatment is carried out,
In Aerobic, it is passed through ozone, during ozone adds, keeps certain vacuum in reactor, obtain at biology
Waste water after reason;
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 in Xiang Yuanshui add cause
Agent, described initiator is in sodium sulfite, potassium sulfite, sodium sulfite, Potassium acid sulfite, ferrous chloride or ferrous sulfate
One or more;Described oxidant and initiator 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 Rhizoma amorphophalli glucosan in quick agitation phases adds 1.0~2.0g/L flocculant component B, rotating speed 180~250rpm,
Quickly after stirring 2~3min, carry out low rate mixing, rotating speed 40~60 rpm, respectively after low rate mixing starts 1~3 min, 4
~5 min, 5.5~6 min, 7~9 min add 0.5~0.9 g/L and coagulate the microbial flocculant 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.
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CN111909750A (en) * | 2019-05-08 | 2020-11-10 | 国家能源投资集团有限责任公司 | Utilization method of waste liquid generated by coal chemical ash removal and coal ash removal method |
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CN111995015A (en) * | 2020-07-07 | 2020-11-27 | 广西夏阳环保科技有限公司 | Composite heavy metal wastewater treatment agent and preparation method thereof |
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CN114804566A (en) * | 2022-05-25 | 2022-07-29 | 威海智洁环保技术有限公司 | High-value resource utilization method for enhancing enzymatic degradation of activated sludge based on advanced oxidation technology |
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