CN105214625A - A kind for the treatment of process of coking chemical waste water activating brown coal and apply these activation brown coal - Google Patents
A kind for the treatment of process of coking chemical waste water activating brown coal and apply these activation brown coal Download PDFInfo
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Abstract
The present invention relates to field of Environment Protection, relate to a kind for the treatment of process of coking chemical waste water activating brown coal and apply these activation brown coal, concrete employing activation brown coal carry out pretreatment as sorbing material to coking chemical waste water, afterwards the waste water after process is entered internal circulating anaerobic bioreactor for treatment, and then get final product qualified discharge after carrying out conventional anoxic and Aerobic Process for Treatment and advanced treating; Technical scheme of the present invention compared with prior art, the activation brown coal adopted can reuse and uptake is higher, cost is far below active carbon, adopt internal circulating anaerobic bioreactor for treatment simultaneously, replace conventional anaerobic organism pond, underground, increased substantially the treatment effeciency of anaerobic organism, reduced the load of subsequent treatment engineering, achieve qualified discharge, fill up the blank of Treatment of Coking Effluent in prior art.
Description
Technical field
The present invention relates to environmental technology field, relate to a kind for the treatment of process of coking chemical waste water activating brown coal and apply these activation brown coal.
Background technology
Coke is a kind of important metallurgical industry raw material, utilizes coking coal high-temperature retorting to make.In coking coal destructive distillation, gas purification and tar is done raw material and produce in the process of a series of chemical products and produce a large amount of waste water.These waste water mainly comprise: 1. the residue waste water after dephenolize ammonia still process; 2. crude phenols Separation of Water; 3. water seal for coal gas leads trickle; 4. the maintenance waste water of recycle section; 5. the waste water that produces of accident unrestrained groove; 6. the nitrogenous whole cold water of part reaching the need displacement of 400mg/l; 7. equipment cleaning waste water; 8. part sanitary sewage etc.Coking chemical waste water complicated component, containing multiple phenols, benzene and polycyclic aromatic hydrocarbon and oxygen sulfur-nitrogen compound, belongs to the comparatively large and high-concentration organic industrial waste water of difficult for biological degradation of toxicity.The process of coking chemical waste water is one of difficult problem in domestic and international field of industrial waste water treatment always.
At present, domestic in coking waste water treatment process, mainly comprise pretreatment, biochemical treatment and advanced treating three part.
Mainly comprise at preprocessing part: cooling, adjustment, oil removal, coagulation air-float and these conventional methods of anaerobic organism.Its objective is by reducing water temperature, regulating water quality, every walking surperficial oil slick, coagulation air-float removes suspended oil and a small amount of suspension in waste water and utilize anaerobic organism means etc. to reduce the load of contaminated wastewaters, the biological treatment (anoxic and aerobic) being beneficial to lower step is carried out.Anaerobic organism pond is generally underground structure.
In biological treatment, workshop section mainly comprises: anoxic and Aerobic biological process and second pond.Aerobe pond (aeration and biological pond) water outlet returns anoxic pond, utilizes denitrifying bacterium in anoxic pond to the NO in the water outlet of aeration tank
2 -, NO
3 -carry out denitrification, by NO
2 -, NO
3 -be converted into N
2overflow from water, thus realize denitrogenation.
From the domestic built operation conditions having the engineering of coking chemical waste water, biochemical secondary clarifier effluent great majority exceed coking industry pollution discharge standard COD and are generally greater than 150mg/l, when raw water quality is higher, biochemical secondary clarifier effluent COD is even close to 1000mg/l.Therefore carry out advanced treating to bio-chemical effluent to have become and must establish means in Treatment of Coking Effluent engineering.These advanced treating means mainly contain: 1. catalytic oxidation.As Fenton reagent method, photocatalytic oxidation, catalyst oxidation method; 2. wet oxidation process.Under high temperature, high pressure and catalyst existence condition, utilize air (oxygen) that the organic matter in waste water is finally converted into innocuous substance H
2o, CO
2, NO
3 -, SO
4 2-deng; 3. absorption method.Utilize adsorbent as organic matter residual in the absorption such as active carbon, sulfonated coal, slag, diatomite bio-chemical effluent; 4. chemical oxidation.As NaClO, Ca (ClO)
2deng; 5. electrochemical oxidation; 6. coagulating sedimentation.As added PAC, PAM, PFS etc., by chemical coagulation reaction, the organic matter in bio-chemical effluent is separated from water with flocculate state; 7. Ozonation.
There are problems in above seven class methods in for Treatment of Coking Effluent.Such as practice shows, in pretreatment workshop section, the clearance of coagulation air-float is very low, generally be not more than 20%, even close to zero, anaerobic organism pond, underground clearance is also close to zero, and thus many enterprises take water-reducible for anaerobic pond way with other waste water (as sludge dewatering machine drainge), diluted and COD concentration is reduced, to guarantee the follow-up more favourable operation of biochemical workshop section.
In anoxic-aerobic biochemical workshop section, the to the effect that clearance existed at present is not high, and energy consumption is large.As in order to make aerobic biochemical workshop section water outlet COD lower, increase reflux ratio and the aeration rate of outputted aerobic water mixed liquor, can guarantee in the case by " anoxic-aeration-bis-heavy " three process make COD clearance close to 70%, but the two water COD that settle out still obviously exceed discharge standard--COD≤150mg/l.
In advanced treating workshop section, from current engineering practice situation, no matter be take any materilization freatment method in above seven class methods, its operating cost is all higher, as the processing cost of one ton of waste water between 12-15 yuan, only expenses for medicine this just account for about 50% of waste water overall running cost greatly.
Therefore, the processing cost how solving the above-mentioned all difficult problems occurred in Coking Waste Water Treatment Process and reduction coking chemical waste water becomes one of problem demanding prompt solution in coked waste water process field.
Summary of the invention
The present invention is directed to the problems that prior art exists, provide a kind of brand-new activation brown coal and apply the treatment process of coking chemical waste water of these activation brown coal, concrete employing activation brown coal process coking chemical waste water as sorbing material, afterwards the waste water after process is carried out internal circulating anaerobic bioreactor for treatment, then after carrying out conventional anoxic and Aerobic Process for Treatment and advanced treating, get final product qualified discharge; Technical scheme of the present invention compared with prior art, the activation brown coal adopted can reuse and uptake is higher, cost is far below active carbon, use internal circulating anaerobic bioreactor for treatment simultaneously, replace anaerobic organism pond, underground and increase substantially anaerobic organism clearance, achieve qualified discharge, fill up the blank of Treatment of Coking Effluent in prior art.
Concrete technical scheme of the present invention is: provide firstly a kind of activation brown coal, described activation brown coal have carried out activation process with alkaline solution to mineral brown coal, and concrete activation treatment step is as follows:
First mineral brown coal are ground into the particle that particle diameter is 5mm ~ 10mm size in advance, after brown coal particle is placed in corrosion-resistant container, the NaOH solution adding 10 ~ 30wt% is again soaked brown coal, and the volume ratio of the two is NaOH solution: brown coal particle=1 ~ 3:1, soak time 24h; By the brown coal after the activation of above-mentioned alkali lye, pull out after rear running water is washed till neutrality from alkali lye, be placed in air dry oven 105 DEG C and dry to weight, namely can be used for the absorption of waste water.
Brown coal of the present invention, be a kind of degree of coalification only higher than the coal of mud coal, be a kind of sepia, lacklustre grizzle between mud coal and pitch coal.Brown coal have following feature: 1. moisture is high, and water content is generally between 32%-42%; 2. volatile matter is high, generally between 40%-50%; 3. caloric value is low, generally lower than 3000 kilocalories; 4. density is low, easy-weathering, meets fiery spontaneous combustion; 4. ash fusion point is low, generally at 1150 DEG C.Analyzed by FTIR spectrum, X-ray diffraction spectrum, electron paramagnetic resonance spectrum (EPR), carbon-13 nmr spectra and gas isothermal adsorption method, find that there are many pores brown coal inside, size is all less than 0.01 μm, and drying process back aperture can increase to 1.0 μm.
Chemically analysis of components result is seen, brown coal are mainly containing fragrance point, and pitch divides, Jiao Zhi, carbene, colloid etc.Fragrance mainly contains humic acid in dividing, and humic acid mainly comprises ulmic acid, humic acid and fulvic acid; This three kinds of humic acid water solubles, acetone, ethanol, diluted acid and diluted alkaline equal solvent.Containing aromatic rings and cycloaliphatic ring in humic acid molecule, and ring is connected with the organo-functional groups such as carboxyl, hydroxyl, carbonyl, quinonyl, methoxyl group, thus there is the effects such as ion-exchange, absorption, complexing and chelating.
The present invention structurally has the characteristic of a large amount of pore and organo-functional group just according to above brown coal, adopt NaOH to carry out activation process to brown coal.Run-inflation effect is produced after brown coal contact with NaOH, capillary aperture in brown coal expands further, organo-functional group in humic acid is activated, cation state is changed into after organic high energy group runs into OH-, when it touches electronegative organic compound molecule (when organic compound is in water, by the OH-base function influence that dissociates water molecules goes out, H+ in organic compound leaves and enters the aqueous solution from molecule, make itself with negative electrical charge), organic compound molecule can be adsorbed onto in brown coal molecular structure under physics and chemistry (chemical bond) two kinds effect, make brown coal can be adsorbed onto large weight organic compounds.Owing to having in brown coal in a large number by the pore not of uniform size after swelling increase, and hole inwall is filled with in a large number with the organo-functional group of positive charge, the brown coal after therefore being activated by alkali can binding molecule amount not of uniform size, the organic compound containing various functional group.
When a large amount of pore in brown coal structure and functional group are taken by organic derivative molecular, after the adsorption activity of functional group is depleted, can not adsorb organic compound be continued, namely there will be the saturated accumulation phenomena of absorption.
Now can process the brown coal reaching absorption saturation state with diluted acid, diluted acid can be considered as a kind of solvent, the organic pollutant molecule existed with sodium-salt form can be dissolved out from brown coal pore and carry out desorption reaction, active lignite after pickling is regenerated by the NaOH solution that concentration is 10 ~ 30wt% again, the organo-functional group in brown coal molecule is made again to return to the state of original positive charge, recover its activated adoption ability, and then again can carry out strong absorption to organic contamination compound.Inventors performed test of many times for this situation, wherein representative test is as follows:
The activation brown coal of brand-new are utilized to coordinate technique of the present invention to process coking chemical waste water, after absorption reaches capacity state, the brown coal reaching absorption saturation state are taken out from adsorption column, take out 20g, with the hydrochloric acid solution of 10wt%, regeneration process is carried out to above-mentioned saturated brown coal, time of contact is 24h, then neutrality is washed till, regeneration activating 24h is carried out again by the NaOH solution that concentration is 10wt%, then Static Adsorption is carried out to it, above-mentioned identical mode is adopted to carry out secondary recycling activation after absorption reaches capacity, and then Static Adsorption is carried out to it, final adsorption test result is as follows:
From data in table, though its clearance of the active lignite after repeatedly activating has decline, but still can form effective absorption to the material in coking chemical waste water, and eliminating rate of absorption is higher than active carbon removal efficiency (about 30%-40%) of the prior art, and cost is lower.
Visible, the activation brown coal adopted in the present invention make great progress compared to prior art, and there is obvious specific aim, than adsorbent better effects if such as the active carbons that routine uses, and cost is lower, brown coal wide material sources, in addition the means of diluted acid and alkali liquid regeneration can be adopted its re-activation, greatly reduce the cost of adsorption treatment, and stronger for Adsorption of Organic ability, there is better promotional value.
After obtaining above-mentioned activation brown coal, inventor has been joined in the concrete treatment process of coking chemical waste water, and this technique mainly comprises the steps:
Coking chemical waste water through cooling, regulate, after the pretreatment of oil removal and coagulation air-float, first activation brown coal are utilized to adsorb, reduce organic pollution load in waste water, waste water after overactivation brown coal adsorption treatment enters internal-circulation anaerobic reactor and carries out anaerobic bio-treated, anaerobic effluent is again after the conventional treatment means process in anoxic pond, aeration and biological pond, second pond and advanced treating pond afterwards, gets final product qualified discharge;
Wherein activate brown coal directly to load in packed tower, packed height is 2-4m, first filler loading is carried out again after fully being soaked by activation brown coal water before loading, control coking chemical waste water during absorption and flow through activation brown coal adsorption stuffing tower with the flow velocity of 1BV/h ~ 2BV/h, flow velocity crosses the effect that conference reduces absorption.
Activation brown coal are used in the processing procedure of coking chemical waste water by the present invention's first time, therefore the blank of this area has been filled up, brown coal substantially increase its adsorption capacity after activation process, apparently higher than non-activated original brown coal, also higher than expensive active carbon, therefore processing cost is greatly reduced.Because the brown coal after activation can effectively adsorb organic loading in coking chemical waste water, greatly reduce the COD of coking chemical waste water, thus be conducive to the removal effect improving next anaerobic organism workshop section of workshop section, alleviate its processing load; In addition, the activation brown coal adopted can reach capacity after use after a while, and watery hydrochloric acid and dilute sulfuric acid now can be adopted to be regenerated.And the brown coal after regeneration, its absorption property does not decline substantially, can reuse, and activation total absorptive capacity of brown coal and high-quality activate charcoal and quite even exceed like this, but operating cost is significantly less than active carbon, and can repeatedly use; The step of concrete regeneration is as follows:
Adsorbing the adsorption stuffing tower reached capacity stops water inlet rear emptying, then uses the hydrochloric acid of 10-30wt% or sulfuric acid solution to soak filler 24h, finally discharges acid soak; Use tap water adsorption stuffing tower more afterwards until water outlet is to neutral, finally soak 24h by the NaOH solution that concentration is 10 ~ 30wt%, the regeneration of activation brown coal can be completed;
Wherein adopted acid soak can be reused repeatedly till inefficacy after discharging, and the acid soak of inefficacy is with available NaOH or Ca (OH)
2solution is neutralized to pH=8 ~ 9, then adds PAC or PFS and PAM and carry out coagulating kinetics, and supernatant (COD reduction) can be sent in internal-circulation anaerobic reactor and process further; In addition, in order to save water usage further, the tap water packed tower in regeneration step can be replaced with the qualified discharge water outlet after process of the present invention, realize recycling further of resource, reduce the cost of process simultaneously, and no matter be adopt running water or adopt the water outlet up to standard in the present invention to rinse adsorption stuffing tower, the washing lotion after flushing all needs to enter in anoxic pond and processes, in order to avoid cause secondary pollution;
Activation brown coal are after repeatedly (more than at least 10 times) regeneration uses, after brown coal internal structure repeatedly activated, performance can decline to some extent, at this moment it directly can be discharged by waterpower from absorption tower, load new activation brown coal, and the filtrate of discharging can be mixed into as the use of coking raw material in coking coal after air-dry, also can mix replacement fire coal in steam coal uses, and realizes maximum resource utilization.
In above-mentioned steps, the special purpose reactor that described internal-circulation anaerobic reactor selects inventor to design, specifically can use the SIC internal-circulation anaerobic reactor that Shandong Swan Water Engineering Co., Ltd manufactures and designs, its concrete structure is repeated no more, in addition, the pretreatment of the cooling adopted, adjustment, oil removal and coagulation air-float, the process in anoxic pond, aeration and biological pond, second pond and degree of depth pond is the conventional treatment means of this area, and inventor repeats no longer one by one.
Above-mentioned SIC internal-circulation anaerobic reactor belongs to tower pot type anaerobic biological reactor on the ground.Its operation principle: waste water is by after entering reactor at the bottom of tower, through specially designed water-locator, waste water is from bottom to top flowed with high speed (10m/h-30m/h), and contact with the anaerobic grain sludge in the first reative cell, the organic pollution in water is processed largely and produces a large amount of biogas.Reacted waste water can be brought into rapidly in the gas-liquid separator of reaction cone top part by tedge by these biogas.In this separator the separated rear discharge tank body of biogas laggard enter marsh gas purifying piece-rate system.And waste water is got back to bottom retort by the down-comer of separator lower end in Action of Gravity Field, formed so-called " Inner eycle ", risen to the waste water in second reative cell on top by the first reative cell simultaneously, continue to react with the anaerobe in reative cell again, reduce further from the organic pollution in the water of the first reative cell.Waste water is carried secretly in the gas-liquid separation of cone top part again by the biogas produced in this room, and biogas is separated, and waste water is got back to bottom the first reative cell through down-comer, achieves equally " Inner eycle ".
This internal circulating anaerobic bioreactor is state-of-the-art upflow type anaerobic reactor in technique in current anaerobic waste water biological respinse.IC reactor had very significant advantage compared with current underground type anaerobic reation pool conventional in Treatment of Coking Effluent engineering: in a.IC reactor, the upflow velocity of waste water is " underground type pond " 10-60 times; B. the time of staying only have " underground type pond " 1/6th; C. to COD, BOD
3clearance can up to 70%--80%, and " underground type pond " due to its time of staying long, the waste water rate of climb is low, and under mud and waste water are in (water) substantially, (mud) is two-layer is difficult to abundant contact condition, essentially no effective clearance; D. floor space is large, and underground type pond is " several times of IC reactor "; E.IC reactor reaction speed is fast, and biogas generation can obtain effective Collection and utilization greatly, and " underground type pond " does not produce biogas substantially; F. the intractability of " anoxic+aerobic+second pond " in biochemical workshop section and " advanced treating " workshop section and operating cost are significantly declined and qualified discharge because " IC reactor " water outlet organic pollution load reduces greatly.
In addition, owing to adopting activation brown coal first to carry out adsorption treatment to coking chemical waste water in the present invention, by the multiple harmful substances of carrying in waste water as phenols, benzene and polycyclic aromatic hydrocarbon and oxygen sulfur-nitrogen compound major part are adsorbed, thus reduce the process intensity of follow-up internal circulating anaerobic bioreactor, extend the service life of its anaerobic grain sludge, reduce further the processing cost of coking chemical waste water.
In sum, technical scheme provided by the present invention compared with prior art, the activation brown coal adopted can reuse and uptake is higher, cost is far below active carbon, adopt internal circulating anaerobic bioreactor for treatment to replace the underground type anaerobic organism pond of current domestic extensive employing simultaneously, greatly reduce the pollutional load of subsequent biochemical process and advanced treating workshop section, ensure that the discharge of final process standard water discharge, filled up the blank of Treatment of Coking Effluent in prior art.
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment, those skilled in the art can be made more fully to understand the present invention, but do not limit the present invention in any way.
Embodiment 1
Activate brown coal and apply the treatment process of coking chemical waste water of this activation brown coal, wherein said activation brown coal have carried out activation process with alkaline solution to mineral brown coal, and concrete activation treatment step is as follows:
First mineral brown coal are ground into the particle that particle diameter is 5mm ~ 8mm size in advance, after brown coal particle is placed in corrosion-resistant container, the NaOH solution adding 10wt% is again soaked brown coal, and the volume ratio of the two is NaOH solution: brown coal particle=3:1, soak time 24h; By the brown coal after the activation of above-mentioned alkali lye, pull out after rear running water is washed till neutrality from alkali lye, be placed in air dry oven 105 DEG C and dry to weight;
Apply the treatment process of the coking chemical waste water of above-mentioned activation brown coal, concrete steps are as follows: coking chemical waste water through cooling, regulate, after the pretreatment of oil removal and coagulation air-float, first activation brown coal are utilized to adsorb, after overactivation brown coal adsorption treatment, waste water enters internal-circulation anaerobic reactor and carries out anaerobic bio-treated; Water outlet afterwards, again after the conventional treatment means process in anoxic pond, aeration and biological pond, second pond and advanced treating pond, gets final product qualified discharge;
Wherein activate brown coal directly to load in packed tower, its packed height is 2-4m, first carry out filler hydraulic loading again after fully being soaked by activation brown coal water before loading, control coking chemical waste water during absorption and flow through activation brown coal adsorption stuffing tower with the flow velocity of 1BV/h ~ 2BV/h adsorption treatment is carried out to waste water;
Described internal-circulation anaerobic reactor selects the SIC internal-circulation anaerobic reactor of Shandong Swan Water Engineering Co., Ltd.
Embodiment 2
Activate brown coal and apply the treatment process of coking chemical waste water of this activation brown coal, wherein said activation brown coal have carried out activation process with alkaline solution to mineral brown coal, and concrete activation treatment step is as follows:
First mineral brown coal are ground into the particle that particle diameter is 8mm ~ 10mm size in advance, after brown coal particle is placed in corrosion-resistant container, the NaOH solution adding 20wt% is again soaked brown coal, and the volume ratio of the two is NaOH solution: brown coal particle=2:1, soak time 24h; By the brown coal after the activation of above-mentioned alkali lye, pull out after rear running water is washed till neutrality from alkali lye, be placed in air dry oven 105 DEG C and dry to weight;
Apply the treatment process of the coking chemical waste water of above-mentioned activation brown coal, concrete steps are as follows: coking chemical waste water through cooling, regulate, after the pretreatment of oil removal and coagulation air-float, first activation brown coal are utilized to adsorb, after overactivation brown coal adsorption treatment, waste water enters internal-circulation anaerobic reactor and carries out anaerobic bio-treated; Water outlet afterwards, again after the conventional treatment means process in anoxic pond, aeration and biological pond, second pond and advanced treating pond, gets final product qualified discharge;
Wherein activate brown coal directly to load in packed tower, its packed height is 2-4m, first carry out filler hydraulic loading again after fully being soaked by activation brown coal water before loading, control coking chemical waste water during absorption and flow through activation brown coal adsorption stuffing tower with the flow velocity of 1BV/h ~ 2BV/h adsorption treatment is carried out to waste water;
Described internal-circulation anaerobic reactor selects the SIC internal-circulation anaerobic reactor of Shandong Swan Water Engineering Co., Ltd;
Adsorbing the adsorption stuffing tower reached capacity stops water inlet rear emptying, then uses the hydrochloric acid of 10-30wt% or sulfuric acid solution to soak filler 24h, discharges acid soak afterwards; And then rinse the filler in packed tower with the qualified discharge water outlet after process of the present invention, until rinse water outlet to neutral, finally soak 24h by the NaOH solution that concentration is 10 ~ 30wt% again, the regeneration of activation brown coal can be completed.
The acid reclaim liquid of discharging in filler regenerative process can repeatedly lose efficacy by Reusability afterwards, acid soak NaOH or Ca (OH) of inefficacy
2solution is neutralized to pH=8-9, then adds PAC or PFS and PAM and carry out coagulating sedimentation, and supernatant C OD is lower, can send in internal-circulation anaerobic reactor and process further.
Embodiment 3
Activate brown coal and apply the treatment process of coking chemical waste water of this activation brown coal, wherein said activation brown coal have carried out activation process with alkaline solution to mineral brown coal, and concrete activation process step is as follows:
First mineral brown coal are ground into the particle that particle diameter is 9mm ~ 10mm size in advance, after brown coal particle is placed in corrosion-resistant container, the NaOH solution adding 30wt% is again soaked brown coal, and the volume ratio of the two is NaOH solution: brown coal particle=1:1, soak time 24h; By the brown coal after the activation of above-mentioned alkali lye, pull out after rear running water is washed till neutrality from alkali lye, be placed in air dry oven 105 DEG C and dry to weight.
Apply the treatment process of the coking chemical waste water of above-mentioned activation brown coal, concrete steps are as follows: coking chemical waste water through cooling, regulate, after the pretreatment of oil removal and coagulation air-float, first activation brown coal are utilized to adsorb, after overactivation brown coal adsorption treatment, waste water enters internal-circulation anaerobic reactor and carries out anaerobic bio-treated; Water outlet afterwards, again after the conventional treatment means process in anoxic pond, aeration and biological pond, second pond and advanced treating pond, gets final product qualified discharge;
Wherein activate brown coal directly to load in packed tower, its packed height is 2-4m, first carry out filler hydraulic loading again after fully being soaked by activation brown coal water before loading, control coking chemical waste water during absorption and flow through activation brown coal adsorption stuffing tower with the flow velocity of 1BV/h ~ 2BV/h adsorption treatment is carried out to waste water;
Described internal-circulation anaerobic reactor selects the SIC internal-circulation anaerobic reactor of Shandong Swan Water Engineering Co., Ltd;
Adsorbing the adsorption stuffing tower reached capacity stops water inlet rear emptying, then uses the hydrochloric acid of 10-30wt% or sulfuric acid solution to soak filler 24h, discharges acid soak afterwards; Finally use tap water adsorption stuffing tower again, until water outlet is to neutral, finally soaks 24h by the NaOH solution that concentration is 10 ~ 30wt% again, the regeneration of activation brown coal can be completed;
The acid reclaim liquid of discharging in filler regenerative process can repeatedly lose efficacy by Reusability afterwards, acid soak NaOH or Ca (OH) of inefficacy
2solution is neutralized to pH=8-9, then adds PAC or PFS and PAM and carry out coagulating sedimentation, and supernatant C OD value is lower, can send in internal-circulation anaerobic reactor and process further.
Test example 1
Inventor utilizes the technique in embodiment 1 to process Shandong Qihe group coke-oven waste water, former regimen condition is: CODcr is 2726mg/L, adopt the mode of two same size packed tower series connection, packed tower height is 2.4 meters, and in packed tower, brown coal bulk density is 0.786g/cm
3, result is as follows:
Wherein according to the method in embodiment 1, activating and regenerating is carried out to the brown coal in two packed towers after 34 hours, more former water is adsorbed afterwards, and cumulative calculation adsorption time, result is as following table
The fresh activation brown coal Adsorption efficiency that visible the present invention obtains is higher, and carry out the activation brown coal after activating and regenerating and still can form effective absorption to the material in coking chemical waste water, and eliminating rate of absorption remains unchanged substantially, inventor finally calculates known according to charging ratio and removal effect, activating brown coal adsorption capacity in this test example is 70mg/g, and through repeatedly activation experiments, find when activation brown coal are after regenerating 10 times, eliminating rate of absorption has obvious decline, inventor is gone out to filter, filtrate can be mixed in coking coal and use as coking raw material after air-dry, achieve the recycling of resource.
Test example 2
Inventor utilizes the technique in embodiment 2 to process Shandong Qihe group coke-oven waste water, former regimen condition is: CODcr is 4750mg/L, adopt the mode of two same size packed tower series connection, packed tower height is 2.4 meters, and in packed tower, brown coal bulk density is 0.775g/cm
3, result is as follows:
CODcr wherein due to former water is higher, and namely this test carries out activating and regenerating according to the method in embodiment 2 to the brown coal in two packed towers after 24 hours, adsorbs afterwards to former water again, and cumulative calculation adsorption time, result is as following table:
The fresh activation brown coal Adsorption efficiency that visible the present invention obtains is higher, and carry out the activation brown coal after activating and regenerating and still can form effective absorption to the material in coking chemical waste water, and eliminating rate of absorption remains unchanged even higher substantially, inventor thiss is presumably because that former water CODcr is higher and comes that water unstable causes, do not affect the authenticity of whole test, inventor finally calculates known according to charging ratio and removal effect, activating brown coal adsorption capacity in this test example is 76mg/g, and through repeatedly activation experiments, find that this test example is when activation brown coal are after regenerating 7 times, eliminating rate of absorption has obvious decline, equally also be because reason that former water CODcr is higher causes the minimizing of regeneration times, inventor is gone out to filter, filtrate can mix in steam coal and replace coal-fired use after air-dry, achieve the recycling of resource.
Claims (8)
1. activate brown coal, it is characterized in that: described activation brown coal have carried out activation process with alkaline solution to mineral brown coal, and concrete activation treatment step is as follows:
First mineral brown coal are ground into the particle that particle diameter is 5mm ~ 10mm size in advance, after brown coal particle is placed in corrosion-resistant container, the NaOH solution adding 10 ~ 30wt% is again soaked brown coal, and the volume ratio of the two is NaOH solution: brown coal particle=1 ~ 3:1, soak time 24h; By the brown coal after the activation of above-mentioned alkali lye, pull out after rear running water is washed till neutrality from alkali lye, be placed in air dry oven 105 DEG C and dry to weight.
2. an application rights requires the treatment process activating the coking chemical waste water of brown coal described in 1, concrete steps are as follows: coking chemical waste water through cooling, regulate, after the pretreatment of oil removal and coagulation air-float, first activation brown coal are utilized to adsorb, after overactivation brown coal adsorption treatment, waste water enters internal-circulation anaerobic reactor and carries out anaerobic bio-treated; Water outlet afterwards, again after the process in anoxic pond, aeration and biological pond, second pond and advanced treating pond, gets final product qualified discharge; It is characterized in that:
Wherein activating brown coal directly loads in glass column or packed tower, its packed height is 2-4m, first carry out filler loading again after fully being soaked by activation brown coal water before loading, control coking chemical waste water during absorption and flow through activation brown coal adsorption stuffing tower with the flow velocity of 1BV/h ~ 2BV/h adsorption treatment is carried out to waste water.
3. treatment process according to claim 2, is characterized in that: adsorb the adsorption stuffing tower reached capacity and stop water inlet rear emptying, use the hydrochloric acid of 10-30wt% or sulfuric acid solution to soak filler 24h afterwards, discharge acid soak afterwards; Use tap water adsorption stuffing tower more afterwards until water outlet is to neutral, finally soak by the NaOH solution of 10 ~ 30wt% the regeneration that 24h can complete activation brown coal again.
4. treatment process according to claim 2, is characterized in that: described internal-circulation anaerobic reactor selects the SIC internal-circulation anaerobic reactor of Shandong Swan Water Engineering Co., Ltd.
5. treatment process according to claim 3, it is characterized in that: activation brown coal reusable edible 10 times after regeneration, gone out filter by waterpower afterwards, filtrate can be mixed in coking coal and use as coking raw material after air-dry, also can mix in steam coal and replace coal-fired use.
6. treatment process according to claim 3, is characterized in that: the acid soak of discharge can Reusability repeatedly, until can abandon when its pH value reaches 6.
7. treatment process according to claim 3, is characterized in that: acid soak NaOH or Ca (OH) abandoned
2solution is neutralized to pH8-9, then adds PAC or PFS and PAM and carry out coagulating sedimentation, and supernatant can be sent in internal-circulation anaerobic reactor and process further.
8. treatment process according to claim 3, it is characterized in that: activation brown coal reusable edible 10 times after regeneration, filter is entered through recycling after it goes out by the activation brown coal water after 10 times from adsorption tanks, filtrate can be mixed in coking coal and use as coking raw material after air-dry, or mixes the coal-fired use of replacement in steam coal; Filter liquor enters anoxic biological tank and processes.
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| CN109485121A (en) * | 2018-12-07 | 2019-03-19 | 铜陵泰富特种材料有限公司 | The method of distilled ammonia wastewater oil removing |
| CN110252244A (en) * | 2019-06-21 | 2019-09-20 | 中南大学 | A coking wastewater treatment method using lignite and semi-coke as new adsorbents |
| CN111271044A (en) * | 2020-02-24 | 2020-06-12 | 成都理工大学 | Method for removing carbonate reservoir carbonaceous asphalt by using sodium hypochlorite solution |
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