Background technology
Coking chemical waste water is the waste water that coal is formed in high temperature and medium temperature carbonization, gas purification and chemical productss subtractive process, wherein
Inorganic containing the organic pollutions such as phenols, benzene homologues, polycyclic aromatic hydrocarbon, nitrogen-containing heterocycle compound and ammonia, cyanogen, rhodanides etc.
Pollutant, complicated component, constituent species are various, and organic pollution concentration and Colority of Sewage Water height, toxicity are big, and property is highly stable,
It is a kind of typical difficult degradation complexity toxic industrial organic wastewater.Intractability for meeting qualified discharge is big, relatively costly, such as
Deal with improperly, National Water Environmental will be caused with great harm.
Most domestic enterprise execution steel industry discharge standard GB13456-92 (containing coking industry) at present.In October, 2012
1, country promulgated《Coking chemistry emission of industrial pollutants standard》(GB16171-2012), hereinafter referred to as new standard.Newly
Standard is more strict on Pollutant emission concentration and monitoring range, to float, COD, ammonia nitrogen, petroleum-type and cyanide
Emission request be obviously improved, increased the emission request of BOD5, T-N, benzene and polycyclic aromatic hydrocarbon;Meanwhile, new standard also phase
Ton product water consume should be improved require.For the water process present situation of domestic coking industry, the strict law enforcement of this standard will be to coking
The huge challenge of industry.Substantially domestic all apparatus for treating carbonized waste waters all must carry out upgrading, be only possible to meet discharge and want
Ask;The management level for the treatment of facility also must be lifted further simultaneously.
And Technologies of Coke Plant Wastewater Treatment ripe at present needs to pay the fortune of costliness to stably reach the up-to-date discharge standard of country
Row cost, most domestic coal chemical enterprise cannot bear, and therefore development life cycle cost is lower, the less coking of environmental risk
Waste Water Treatment and the research of specific technique, significant to realize Sustainable Development of Enterprises and raising synthesized competitiveness.
Membrane bioreactor (MBR) is the novel state Waste Water Treatment of membrane separation technique and biologic treating technique combination.
Traditional biological treatment technology end second pond is replaced with membrane module, in bioreactor, keeps high activity sludge concentration, improve life
Thing processes organic loading, thus reducing sewage treatment facility floor space, and reduces surplus sludge volume by keeping low sludge loading,
Thus reducing the investment of waste water disposal facility and the purpose of operation cost.But it is applied to Treatment of Coking Effluent field and still deposits
Water outlet COD higher it is impossible to directly discharge;Membrane module is easily dirty stifled, increases the problem of operation cost.
Enzyme is a kind of protein with catalysiss.It has specificity, efficiency compared with general chemical catalyst
High gentle with reaction condition the advantages of.There is number with the enzyme of hundred million note species in nature, different enzymes can be catalyzed single substrate and occur
Specified chemical is reacted.The water quality characteristic of coking chemical waste water determines the flora species sum that coking chemical waste water biochemical system can be enriched with
Amount, a part of flora therein is had the advantage status, and diazine of can degrading, pyridine, quinoline, indole, naphthalene, uh,
Phenanthrene etc. is multi-ring and microorganism of heteroaromatic organic compound is then in the status of weak tendency relatively.We are by coking chemical waste water
Component and property are analyzed, and search out these multi-ring and heteroaromatic material enzyme of can specifically degrading, are added
To in biochemical treatment system, develop this part weak tendency flora, to improve the activity of this part flora and to be enriched with more quantity, make
It progressively becomes dominant bacteria.The increase of the raising of bacterial activity and quantity means that process load, the raising for the treatment of effeciency,
Originally it was difficult to biodegradable part Organic substance and also obtained different degrees of degraded because of the raising of bacterial activity, made water outlet
COD is greatly reduced.Simultaneously by adding the enzyme of salt resistance, anti-cyaniding species, strengthen biochemical system microorganism
Poison resistance and impact resistance, improve system stability.
Content of the invention
In order to solve the above problems, the invention provides a kind of method of utilization cellulase treatment coking chemical waste water.
Technical scheme is as follows:
A kind of method using cellulase treatment coking chemical waste water is it is characterised in that comprise the steps:
(1) coking chemical waste water entrance anoxia groove carries out anti-nitration reaction, is uniformly mixed merely by stirring water quality and prevents activated sludge from sinking
Long-pending, adjust coking chemical waste water pH 7.5~8.5, add compound common enzyme, described compound ordinary student into described anoxia groove
Thing enzyme includes Digestive Enzyme, cellulase, hemicellulase, amylase and cyanogen hydrase;
(2) described anoxia groove water outlet carries out nitration reaction by overflow entrance aerobic slot, adds compound ordinary student in aerobic slot
Thing enzyme and specific enzymes, adjust nitrification pH 6.5~7.5, and return current ratio of the mixed liquid controls 1:1-5 times of raw water amount, DO controls
In 3~5mg/l, MLSS controls in 4000~6000mg/l, and reaction time is 40~55 hours;Described compound common
Enzyme includes Digestive Enzyme, cellulase, hemicellulase, amylase and cyanogen hydrase, and described specific enzymes are manganese peroxidase
Enzyme;
(3) aerobic slot water outlet divides 2 tunnel conveyings by sludge reflux pump:Anoxia section is returned to remove further to T-N in one tunnel, separately
One tunnel imports membrance separation groove;
(4) wastewater pH in membrance separation groove is maintained at 6.5~7.5, temperature control at 25~35 DEG C, DO (dissolved oxygen)
Control in 3~5mg/l, MLSS (sludge concentration) controls in 6000~10000mg/l, reaction time is 10~25
Hour;
(5) by producing water pump to make mixed liquor solid-liquid separation by way of being filtered by suction, activated sludge is trapped in biochemical system,
After filtration, water outlet subsequently can connect materialization or Advanced Oxidation Technics in Dealing makes water outlet standard discharge or enters depth reclaiming system further deeply
Change is processed.
Method according to utilization cellulase treatment coking chemical waste water of the present invention is it is preferred that be combined in described step (1)
The dosage of the common enzyme of type is 0.1g~0.2g/ ton water.
Method according to utilization cellulase treatment coking chemical waste water of the present invention it is preferred that in described step (1) anoxia
In groove, at 25~35 DEG C, DO controls in below 0.5mg/l temperature control, and reaction time is 16~25 hours.
Method according to utilization cellulase treatment coking chemical waste water of the present invention is it is preferred that answering in described step (2)
The dosage of the common enzyme of mould assembly is 0.2g~0.4g/ ton water, and the dosage of specific enzymes is 0.1g~0.3g/ ton water.
Method according to utilization cellulase treatment coking chemical waste water of the present invention is it is preferred that aerobic in described step (2)
Fluidized bed type floating stuffing is added as carrier to adhere to aerobic enzyme and activated sludge in groove.
It may further be preferable that described fluidized bed type floating stuffing material is polyethylene, specific surface area is 300~1000/m3,
The ratio that adds is for the 10%~20% of aerobic slot volume.
Method according to utilization cellulase treatment coking chemical waste water of the present invention is it is preferred that good in described step (2)
Wastewater temperature in oxygen groove controls at 25~35 DEG C.
According to the method using cellulase treatment coking chemical waste water of the present invention it is preferred that the regulation of described pH is passed through to add
One of NaOH solution, KOH solution or ammonia spirit.
It may further be preferable that the regulation of described pH is by adding NaOH solution.
Method according to utilization cellulase treatment coking chemical waste water of the present invention is it is preferred that film in described step (4)
Separating tank in the form of built-in organic Flat Membrane, PVDF material, membrane aperture be 0.04~0.1 μm,.
Method according to utilization cellulase treatment coking chemical waste water of the present invention is it is preferred that in film in described step (4)
The membranous system of separating tank adopts intermittent filtration drive manner:Produce water pump setting and often take out 1~2min out of service after every suction 8~10min,
Continuously run in this, as a cycle circulation.
Further, produce water pump setting and often take out 1min out of service after every suction 9min, continuously run in this, as a cycle circulation.
Detailed Description Of The Invention:
The present invention is directed to ingredient properties and the difficulty in treatment of coking chemical waste water, creatively by related the answering of difficult for coking chemical waste water component
Close enzyme interpolation membrane separation technique to replace in the AO+MBR system of conventional biochemical sedimentation tank, increased the effect of biochemical reaction
Rate, enhancement microbiological effect and impact resistance are persistently reduced so that reducing water outlet COD with total cyanogen index;When biological enzyme system
After foundation, micelle bacterium takes advantage, and deliquescent oil is effectively degraded, and activated sludge viscosity reduces, and reduces what film dirt was blocked up
Probability, remains that membrane separation technique system sludge output is low, operating cost is low, effluent quality good, that floor space is little is excellent simultaneously
Point, but also reduce the loss of enzyme using the characteristic that film has crown_interception to larger molecular organicses, improve enzyme
Service efficiency, reduce its run use cost.The present invention has farthest played the complementary work of MBR and biological enzyme technology
With being the inexpensive comprehensive treatment technique for Treatment of Coking Effluent exploitation.
The device that the present invention adopts includes anoxia groove, aerobic slot, sludge reflux pump, membrance separation groove, membrane module, produces water pump.Should
Processing system carrying out practically step is as follows:
(1) adjustment tank waste water is pumped into anoxia groove by water delivery and carries out anti-nitration reaction, is played by stirrer paddle in anoxia groove
Uniformly mixing water quality and the effect preventing activated sludge deposition, PH is maintained at 7.5~8.5, temperature control at 25~35 DEG C,
DO controls in below 0.5mg/l, and reaction time is 16~25 hours.
(2) water outlet of anoxia groove carries out nitration reaction by overflow entrance aerobic slot, adjusts nitrification PH to 6.5~7.5, temperature
Degree controls at 25~35 DEG C, and return current ratio of the mixed liquid controls 1:1~5 times of raw water amount, DO controls in 3~5mg/l, MLSS
Control in 4000~6000mg/l, reaction time is 40~55 hours.
(3) aerobic slot water outlet divides 2 tunnel conveyings by sludge reflux pump:Anoxia section is returned to remove further to T-N in one tunnel, separately
One tunnel imports membrance separation groove.
(4) membrance separation groove PH is maintained at 6.5~7.5, and at 25~35 DEG C, DO controls in 3~5mg/l temperature control, MLSS
Control in 6000~10000mg/l, reaction time is 10~25 hours.
(5) by producing water pump to make mixed liquor solid-liquid separation by way of being filtered by suction, activated sludge is trapped in biochemical system,
After filtration, water outlet subsequently can connect materialization or Advanced Oxidation Technics in Dealing makes water outlet standard discharge or enters depth reclaiming system further deeply
Change is processed.
Compound common enzyme is added (including Digestive Enzyme, cellulase, half fibre in anoxia groove in described step (1)
The plain enzyme of dimension, amylase, cyanogen hydrase), wherein dosage is 0.1g~0.2g/ ton water.
Compound common enzyme is added (including Digestive Enzyme, cellulase, half fibre in aerobic slot in described step (2)
The plain enzyme of dimension, amylase, cyanogen hydrase) with specific enzymes-manganese peroxidase, wherein compound common enzyme dosage be 0.2g~
0.4g/ ton water, specific enzymes dosage is 0.1g~0.3g/ ton water.
Fluidized bed type floating stuffing is added dirty to adhere to aerobic enzyme and activity as carrier in described step (2) aerobic slot
Mud, material is polyethylene, and specific surface area is 300~1000/m3, the ratio that adds is for the 10%~20% of aerobic slot volume.
Described step (4) membrance separation groove in the form of built-in organic Flat Membrane, PVDF material, membrane aperture be 0.04~
0.1 μm,.Membranous system adopts intermittent filtration drive manner:Produce water pump setting and often take out 1min out of service after every suction 9min, with this
Continuously run as a cycle circulation.Aeration when not aspirating can realize effective face cleaning effect.
The diaphragm of described Flat Membrane is attached to the both sides of ABS gripper shoe, and diaphragm is filter layer and the PET having polrvinyl chloride material
The composite construction that the supporting layer of non-woven fabrics material is formed.Diaphragm has (0.8 μm) of the small-bore distribution of concentration.Monolithic membrane element
The area of part is 1.4, membrane component quantity totally 50, and total filter area is 70.(structural representation Fig. 2) flat membrane component
Structure includes film, gripper shoe, water producing pipe ozzle etc..
Described biochemical system refers to the waste water treatment process being formed by anoxia+aerobic combination, and in anoxia groove, heterotrophic bacteria is by waste water
In suspended contaminant and dissolved organic matter be hydrolyzed to organic acid, make larger molecular organicses be decomposed into small organic molecule, insoluble
Property Organic substance change into dissolved organic matter, when these through anaerobic hydrolysis products enter aerobic slots carry out Aerobic Process for Treatment when, can
Improve the biodegradability of sewage and the efficiency of oxygen;In anoxia section, the pollutant such as protein, fat are carried out ammonification by heterotrophic bacteria (to be had
N on chain or the amino in aminoacid) ammonia that dissociates (NH3, NH4+), under sufficient oxygen supply condition, autotrophic bacteria
NH3-N (NH4+) is oxidized to NO3- by Nitrification, and the control by flowing back is back to anoxic pond, under anoxic conditions,
NO3- is reduced to molecular nitrogen (N2) and completes C, N, O circulation in ecology by the Denitrification of heterotrophic bacteria, realizes
Sewage harmless treatment.
The Advantageous Effects of a kind of method of utilization cellulase treatment coking chemical waste water that the present invention provides:
(1) original biochemical system floor space is big, biochemical treatment needed for structures can be greatly decreased with treatment technology of the present invention
Use floor space and cost of investment to reduce.
(2) original AO PROCESS FOR TREATMENT water outlet COD is in 250~350mg/l, T-CN in 4~5mg/l, this
Bright technology can be by water outlet COD degradation to below 70mg/l, and T-CN is degraded to below 0.5mg/l, turbidity drop to 1NTU with
Under, subsequently simple materialization just can reach《Coking chemistry emission of industrial pollutants standard》(GB16171-2012) direct discharge standard.
(3) present invention membrane module is greatly reduced simultaneously, enzyme add and follow-up materializing strategy operating cost, technical office
Managing operating cost is<7 yuan/ton of water, more original AO technique has higher economic benefit.