CN102276056B - Process for treating coal chemical wastewater by adding active material into activated sludge pool - Google Patents
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Abstract
The invention discloses a process for treating coal chemical wastewater by adding an active material into an activated sludge pool, wherein the active material and biochemical treatment are combined and coordinated to treat the coal chemical wastewater. In the process, the wastewater is introduced to the activated sludge pool in which active coke or active semicoke is added; and macromolecular organic matters and refractory organic matters are effectively removed when the wastewater flows through the active coke or the active semicoke. According to the invention, the problems of operation instability of the activated sludge pool, adsorptivity reduction of an adsorptive material, or long sewage treatment time, high equipment cost and unavailability in fully utilizing the performance of the adsorptive material in the prior art are solved, and the process for treating the coal chemical wastewater, which has the advantages of operation stability, availability of fully utilizing the adsorptive material, high sewage treatment efficiency and low equipment cost, is provided.
Description
Technical field
The present invention relates to a kind of waste water treatment process, specifically a kind of coal chemical wastewater treating technique.
Background technology
Coal Chemical Industry refers to take coal as raw material, making coal conversion through chemical process is gas, liquid and solid phase prod or work in-process, then further be processed into the industry of chemical industry, energy product, wastewater discharge is very large in this process, and the waste water that herein produces is the organic waste water that a kind of chemical oxygen demand COD is high, ammonia-nitrogen content is high, colourity is high and turbidity is high.If these pollutents are discharged in the environment, can cause very big harm to ecotope and HUMAN HEALTH, so the processing of coal gasification waste water, at home and abroad receive much concern in the coal chemical industrial waste water process field always.
The technique of processing coal chemical industrial waste water in the prior art generally comprises three steps, is respectively pretreatment process, second-stage treatment method and deep treatment method.Wherein, pretreatment process comprises oil removal, air supporting, precipitation, acidication etc.; The second-stage treatment method comprises take active sludge as main biochemical treatment system, Main Function is denitrogenation, remove COD, but contain the toxic pollutants such as high density phenols organic pollutant, prussiate in the coal gasification waste water, to the toxic shock action of Sludge System, biochemical water inlet causes easily the problems such as sludge bulking, so will be carried out the requirement that the dilution of certain multiple could be satisfied biochemical water inlet; Because it is up to standard that general secondary biochemical effluent COD and ammonia nitrogen are difficult to, and need to carry out advanced treatment, comprises electrochemical process, coagulant sedimentation, advanced oxidation processes, membrane separation process and absorption method etc.
In Chinese patent literature CN101560045A, a kind of coal chemical wastewater treating technique is disclosed, comprise coal chemical industrial waste water is carried out pre-treatment by air-floating apparatus, the class reagent that will confusingly pause adds pretreated waste water and carries out secondary treatment, waste water after the secondary treatment is passed into the active sludge aeration tank, and the adding active carbon powder carries out advanced treatment in the pond, waste water after the advanced treatment is separated by ultra-filtration membrane, reuse water after obtaining separating, carry out reverse osmosis by the selectivity semi-permeable membranes again, obtain reuse water after the reverse osmosis and carry out namely finishing behind the evaporative crystallization processing to waste water.In this technical scheme, in the active sludge aeration tank, add activity charcoal powder, utilize organism and dissolved oxygen in the activity charcoal powder absorption waste water, but, because gac is difficult for fluidisation, be difficult to select optimal addn and the optimum activity powdered carbon concentration of activity charcoal powder in the activated sludge tank, the activated sludge tank fluctuation of service; In addition, the mud that produces after biochemical treatment in the aeration tank can stop up the hole of gac, and the adsorptive power of gac obviously descends after repeatedly utilizing.
Disclose a kind of coal chemical wastewater treating technique among the Chinese patent literature CN102001789A, coal chemical industrial waste water has been passed into the adsorption tank that adds sorbing material, Adsorption larger molecular organics and hardly degraded organic substance; Waste water after adsorption tank is processed enters the settling pond precipitation, and sorbing material is discharged at the bottom of the pond, and waste water enters biochemical unit and carries out biochemical treatment; Waste water after the biochemical treatment enters settling tank and carries out precipitation process.In this technical scheme, carry out first carrying out biochemical treatment after the physical adsorption, two steps have separately solved the problem that activated sludge tank fluctuation of service, biochemical treatment among the CN101560045A affect the activity charcoal powder adsorptive power, but also prolonged the time of sewage disposal, increased equipment cost, gac, activated coke isoreactivity material have only played the effect of physical adsorption simultaneously, still do not maximize the use.
Therefore, in the coal chemical wastewater treating technique of prior art, or the absorption property of activated sludge tank fluctuation of service, sorbing material reduces, or the sewage disposal time is long, equipment cost is high, the activity of sorbing material can not take full advantage of.
Summary of the invention
For this reason, technical problem to be solved by this invention is to overcome in the existing coal chemical wastewater treating technique, the absorption property of activated sludge tank fluctuation of service, sorbing material reduces, or the sewage disposal time is long, equipment cost is high, the performance of sorbing material can not take full advantage of, thereby provides that a kind of stable, sorbing material actively takes full advantage of, sewage treating efficiency height and the low coal chemical wastewater treating technique of equipment cost.
For solving the problems of the technologies described above, a kind of coal chemical wastewater treating technique of the present invention, adopt active material and the biochemical treatment associated treatment coal chemical industrial waste water that combines, waste water is passed into activated sludge tank, activated coke or active carbocoal have been added in the described activated sludge tank, when containing the active sludge of activated coke or active carbocoal, the macromole hardly degraded organic substance can and then obtain by active adsorption removing described wastewater streams through described.Active material refers to have the sorbing material of specific surface area prosperity or mesopore prosperity.
Before sewage enters the activated sludge tank processing, also comprise pre-treatment step: waste water is passed into pretreatment unit, described coal chemical industrial waste water is carried out oil removing, oil removal processing.
After sewage enters the activated sludge tank processing, also comprise settling step: described waste water after activated sludge tank is processed is passed into settler precipitate, described activated coke or active carbocoal separate with waste water with mud, and described activated coke or active carbocoal and mud are discharged at the pond bottom sediments and at the bottom of the pond.
After described precipitation process, also comprise filtration step: described waste water after settler separates is passed into filtration unit, and the suspended substance in the waste water obtains removing.
In the described activated coke or active carbocoal and mud through discharging at the bottom of the settling tank, account for the described activated sludge tank that is partly refluxed to of its quality 20% to 100%.
Described pretreatment unit comprises air flotation pool, hydrolysis acidification pool or anaerobic reactor.
Described activated sludge tank comprises ordinary activated sludge aeration tank, list type intermittently activated sludge tank, circulating type active sludge pond or oxidation ditch.
The particle diameter of described activated coke or active carbocoal is 0.047mm to 1.0mm.
The described waste water that enters activated sludge tank is 20000:1 to 10:1 with the quality of described activated coke or active carbocoal than mass ratio.
Described activated coke or the active carbocoal mass concentration in the described waste water that enters activated sludge tank is 0.05g/L to 100g/L.
Technique scheme of the present invention has the following advantages compared to existing technology,
(1) coal chemical wastewater treating technique of the present invention, activated coke or active carbocoal are added activated sludge tank, described activated coke and active carbocoal are a kind of porous carbonaceous materials of similar gac, can be that raw material is prepared from by brown coal, and be cheap with respect to conventional gac.In addition, gac centering small organic molecule adsorption effect is strong, and activated coke or active carbocoal mesopore are flourishing, adsorption effect to the macromole Persistent organic pollutants is stronger, greatly increased the residence time of this type organic in Sludge System, for the high characteristics of macromole hardly degraded organic substance ratio in the coal chemical industrial waste water, add activated coke or active carbocoal and have extraordinary effect:
At first, because the existence of activated coke or active carbocoal, organism is attracted to the activated coke surface, has prolonged the residence time of hardly degraded organic substance in activated sludge tank, makes the microorganism can be abundant to organic substance decomposing; Secondly, because activated coke, active carbocoal porous and mesopore and transitional pore proportion are larger, it is thrown in the activated sludge tank, hole can not stopped up by mud, so adsorptive power, promotion organic substance decomposing isoreactivity are unaffected; Again, activated coke or active carbocoal are thrown in after the active sludge, and activated coke or active carbocoal surface bioactive improve, and have improved the efficient of microorganism decomposing organic matter.Wherein the activated coke activation degree is higher, and wherein the boring ratio example is large, and the active carbocoal activation degree is low or only pass through carbonization Duan Erwu activation section, and wherein boring ratio example specific activity is burnt low, and activated coke is comparatively preferred.
(2) in the prior art, sewage has the adsorption tank, activated sludge tank, settler of the sorbing materials such as activated coke successively through input after, waste water after obtaining processing, when sorbing material and the sewage mass ratio that enters adsorption tank were 10:1-500:1, the sewage after the processing just can reach discharging standards.And active sludge is two independently technique units after the first activated coke, and coal chemical industrial waste water is through behind the absorbing unit, can Adsorption macromole hardly degraded organic substance, improved the biodegradability of wastewater treatment; Through the burnt mixture of the water after the activated coke absorption, through finishing the separation of Jiao Shui after the precipitation, the good biodegradability of supernatant liquor enters in the activated sludge tank, needs the less residence time just can remove remaining organism, thereby makes waste water reach cleanup standard;
And coal chemical wastewater treating technique of the present invention passes into activated sludge tank with waste water, has added activated coke or active carbocoal in the described activated sludge tank, is a technique unit, and the technique main body is activated sludge tank, i.e. biochemical treatment.Add therein a certain amount of activated coke or active carbocoal, activated coke or active carbocoal carry out physical adsorption to larger molecular organics, hardly degraded organic substance in sludge sump, prolonged the residence time of hardly degraded organic substance in activated sludge tank, make microorganism have time enough that organism is decomposed, activated coke or active carbocoal surface bioactive improve simultaneously, have improved the efficient of microorganism decomposing organic matter.It is simpler that integrated artistic becomes, thereby the adsorptive power of activated coke also greatly improves with burnt amount and greatly reduces, the described waste water that enters activated sludge tank is 20000:1-10:1 with the quality of described activated coke or active carbocoal than scope, when described activated coke or the active carbocoal mass concentration scope in the described waste water that enters activated sludge tank was 0.05g/L-100g/L, the waste water that obtains after precipitation process again can reach country-level A emission standard.Therefore, this technique is not to be the simple superposition of prior art;
And in the application's above-mentioned parameter scope, the stable performances such as the absorption property of activated coke or gac, promotion microorganism decomposing organic matter, so activated sludge tank is stable.
(3) coal chemical wastewater treating technique of the present invention, described activated coke of discharging at the bottom of settling tank or active carbocoal and a mud part are back to described activated sludge tank, and another part is discharged.In the activated coke and mud of discharging, account for the activated coke of its quality 20-100% and sludge reflux to former activated sludge tank; For gac, activated coke, active carbocoal porous and mesopore and transitional pore proportion are larger, therefore it is thrown in the activated sludge tank, and hole can not stopped up by mud, and the part active sludge after precipitation process can again drop into activated sludge tank and recycles.
Description of drawings
For content of the present invention is more likely to be clearly understood, the below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the embodiment schema of coal chemical wastewater treating technique of the present invention;
Fig. 2, Fig. 3, Fig. 4, Fig. 5 be coal chemical wastewater treating technique of the present invention can conversion the schema of concrete embodiment.
Embodiment
Waste water is passed into activated sludge tank, activated coke or active carbocoal have been added in the described activated sludge tank, described wastewater streams larger molecular organics, hardly degraded organic substance when described activated coke or active carbocoal are effectively removed, and the particle diameter of described activated coke or active carbocoal is less than 1.0mm; The mass ratio of the described waste water that enters activated sludge tank and described activated coke or active carbocoal is less than 100:1; Described activated coke or the active carbocoal mass concentration in the described waste water that enters activated sludge tank is less than 100g/L.
After this step process, activated coke, active carbocoal carry out physical adsorption to larger molecular organics, hardly degraded organic substance in sludge sump, prolonged the residence time of hardly degraded organic substance in activated sludge tank, make microorganism have time enough that organism is decomposed, activated coke or active carbocoal surface bioactive improve simultaneously, have improved the efficient of microorganism decomposing organic matter.Larger molecular organics, hardly degraded organic substance are effectively removed.
Embodiment 1:
Fig. 2 has provided a concrete embodiment of coal chemical wastewater treating technique of the present invention, and described coal chemical industrial waste water is stored in the wastewater equalization pond, and described equalizing tank can make the sewage quality in the pond even, simultaneously can also water yield adjusting.Described activated sludge tank adopts common aeration tank, adopts the combine technique of associated treatment coal chemical industrial waste water of activated coke and biochemical sludge, comprises the steps:
1. the coal chemical industrial waste water in the wastewater equalization pond is passed into pretreatment unit, pretreatment unit is air flotation pool herein, waste water is carried out oil removing, oil removal processing, improve the biodegradability of waste water, the biodegradability when described coal chemical industrial waste water is flowed through described pretreatment unit in the waste water is improved;
2. the waste water after will processing by pretreatment unit passes into the ordinary activated sludge aeration tank, in the pond, added activated coke, realization is to the efficient removal of COD and ammonia nitrogen, and the mass ratio of described coal chemical industrial waste water and activated coke is less than 100:1, at this value 10000:1; In activated sludge tank, the mass concentration of described activated coke and pool inner water is less than 100g/L, at this value 12g/L; The particle diameter of described activated coke is less than 1.0mm, at this value 0.5mm-0.047mm;
3. will pass into settling tank by the waste water after biochemical in the described activated sludge tank and the absorbing synergic processing and precipitate, said active coke powder, mud separate with waste water, and described activated coke and mud are at the pond bottom sediments and give off at the bottom of the pond;
4. will pass into sand filter by the waste water of described settling tank and filter, the flow of suspension in this waste water obtains removing when sand filter.
Coal chemical industrial waste water is through after the above-mentioned art breading, water outlet COD is below 50mg/L, COD refers to chemical oxygen demand (COD), refer under certain conditions, when adopting certain strong oxidizer to process water sample, the oxidant content that consumes, the clearance of ammonia nitrogen are more than 95%, the organic matter removal rate is more than 98%, and the waste water after the processing can reach country-level A emission standard.
Embodiment 2:
As embodiment 2 can conversion embodiment, as shown in Figure 3, pass into activated sludge tank through described by the waste water after the pretreatment unit processing, described activated sludge tank adopts intermittently activated sludge tank (SBR pond) of list type, in the pond, add active carbocoal, realized the efficient removal to COD and ammonia nitrogen.The process of the described coal chemical wastewater treating technique of present embodiment as shown in Figure 3, its concrete steps are as follows:
1. the coal chemical industrial waste water in the wastewater equalization pond is passed into pretreatment unit, pre-treatment unit is hydrolysis acidification pool herein, waste water is carried out oil removing, oil removal processing, improve the biodegradability of waste water, the biodegradability when described coal chemical industrial waste water is flowed through described pretreatment unit in the waste water is improved;
2. the waste water after will processing by pretreatment unit passes into the SBR pond, has added active carbocoal in the pond, realizes the efficient removal to COD and ammonia nitrogen, and the mass ratio of described coal chemical industrial waste water and active carbocoal is less than 100:1, at this value 5000:1; In activated sludge tank, the mass concentration of described active carbocoal and pool inner water is less than 100g/L, at this value 12g/L; The particle diameter of described activated coke is less than 1.0mm, at this value 0.075mm;
3. will pass into mechanical accelerating purifying pool by the waste water after biochemical in the described activated sludge tank and the absorbing synergic processing and precipitate, said active carbocoal powder, mud separate with waste water, and described active carbocoal and mud are at the pond bottom sediments and give off at the bottom of the pond;
4. will pass into sandfiltration pot by the waste water of described settling tank and filter, the flow of suspension in this waste water obtains removing when sand filter.
Coal chemical industrial waste water is through after the above-mentioned art breading, and water outlet COD is below 50mg/L, and the clearance of ammonia nitrogen is more than 95%, and the organic matter removal rate is more than 98%, and the waste water after the processing can reach country-level A emission standard.
Embodiment 3:
As embodiment 1 can conversion embodiment, as shown in Figure 4, pass into activated sludge tank through described by the waste water after the pretreatment unit processing, described activated sludge tank adopts pond, circulating type active sludge pond (CASS), in the pond, add activated coke, realized the efficient removal to COD and ammonia nitrogen.The process of the described coal chemical wastewater treating technique of present embodiment as shown in Figure 4, its concrete steps are as follows:
1. the coal chemical industrial waste water in the wastewater equalization pond is passed into pretreatment unit, pretreatment unit is anaerobic reactor herein, waste water is carried out oil removing, oil removal processing, improve the biodegradability of waste water, the biodegradability when described coal chemical industrial waste water is flowed through described pretreatment unit in the waste water is improved;
2. the waste water after will processing by pretreatment unit passes into the CASS pond, has added activated coke in the pond, realizes the efficient removal to COD and ammonia nitrogen, and the mass ratio of described coal chemical industrial waste water and activated coke is less than 100:1, at this value 20000:1; In activated sludge tank, the mass concentration of described activated coke and pool inner water is less than 100g/L, at this value 10g/L; The particle diameter of described activated coke is less than 1.0mm, at this value 0.05-0.075mm;
3. the waste water after will processing by biochemical in the described activated sludge tank and absorbing synergic passes into concentration basin and precipitates, said active coke powder, mud separate with waste water, described activated coke and mud are at the pond bottom sediments and give off at the bottom of the pond, in the activated coke and mud of discharging, account for the activated coke of its quality 20-100% and sludge reflux to former activated sludge tank, therefore activated coke and mud can reuse, and have reduced the dosage of activated coke;
4. will pass into strainer by the waste water of described settling tank and filter, the flow of suspension in this waste water obtains removing when sand filter.
Coal chemical industrial waste water is through after the above-mentioned art breading, and water outlet COD is below 50mg/L, and the clearance of ammonia nitrogen is more than 95%, and the organic matter removal rate is more than 98%, and the waste water after the processing can reach country-level A emission standard.
Embodiment 4:
As embodiment 1 can conversion embodiment, as shown in Figure 5, pass into activated sludge tank through described by the waste water after the pretreatment unit processing, described activated sludge tank adopts oxidation ditch, in the pond, add active carbocoal, realized the efficient removal to COD and ammonia nitrogen.The process of the described coal chemical wastewater treating technique of present embodiment as shown in Figure 5, its concrete steps are as follows:
Coal chemical industrial waste water is through after the above-mentioned art breading, and water outlet COD is below 50mg/L, and the clearance of ammonia nitrogen is more than 95%, and the organic matter removal rate is more than 98%, and the waste water after the processing can reach country-level A emission standard.
Comparative Examples
Concrete steps are as follows:
Coal chemical industrial waste water is through after the above-mentioned art breading, and water outlet COD is below 50mg/L, and the clearance of ammonia nitrogen is 90%, and the organic matter removal rate is 93%, substantially satisfies one-level B emission standard.
Coal chemical wastewater treating technique of the prior art, coal chemical industrial waste water is carried out pre-treatment by air-floating apparatus, the class reagent that will confusingly pause adds pretreated waste water and carries out secondary treatment, waste water after the secondary treatment is passed into the active sludge aeration tank, and the adding active carbon powder carries out advanced treatment in the pond, waste water after the advanced treatment is separated by ultra-filtration membrane, reuse water after obtaining separating, carry out reverse osmosis by the selectivity semi-permeable membranes again, obtain reuse water after the reverse osmosis and carry out namely finishing behind the evaporative crystallization processing to waste water.The waste water that obtains can reach the requirement of reuse.
Comparative Examples is compared with embodiments of the invention, and the addition of gac can only reach country-level B emission standard greater than the addition of activated coke or active carbocoal; Comparative Examples compared with prior art, but the treatment step that has all added the gac Comparative Examples is more simple, the sewage after processing in the Comparative Examples has reached national discharging primary standard, also can recycle; Therefore the simple and good sewage processing effect of coal chemical wastewater treating technique step of adding active material in the activated sludge tank among the present invention utilizes activated coke or active carbocoal to combine with biochemical treatment in this technique, has reached beyond thought technique effect.
Obviously, above-described embodiment only is for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive.And the apparent variation of being extended out thus or change still are among the protection domain of the invention.
Claims (8)
1. the coal chemical wastewater treating technique of an adding active material in the activated sludge tank adopts active material and the biochemical treatment associated treatment coal chemical industrial waste water that combines, and it is characterized in that:
Waste water is passed into activated sludge tank, added activated coke or active carbocoal in the described activated sludge tank, when containing the active sludge of activated coke or active carbocoal, the macromole hardly degraded organic substance can and then obtain by active adsorption removing described wastewater streams through described;
Before sewage enters the activated sludge tank processing, also comprise pre-treatment step: waste water is passed into pretreatment unit, described coal chemical industrial waste water is carried out oil removing, oil removal processing;
After sewage enters the activated sludge tank processing, also comprise settling step: described waste water after activated sludge tank is processed is passed into settler precipitate, described activated coke or active carbocoal separate with waste water with active sludge, and described activated coke or active carbocoal and mud are discharged at the pond bottom sediments and at the bottom of the pond.
2. coal chemical wastewater treating technique according to claim 1 is characterized in that: after described precipitation process, also comprise filtration step:
Described waste water after settler separates is passed into filtration unit, and the suspended substance in the waste water obtains removing.
3. coal chemical wastewater treating technique according to claim 1 and 2 is characterized in that:
In the described activated coke or active carbocoal and mud through discharging at the bottom of the settling tank, account for the described activated sludge tank that is partly refluxed to of its quality 20% to 100%.
4. coal chemical wastewater treating technique according to claim 1, it is characterized in that: described pretreatment unit is air flotation pool, hydrolysis acidification pool or anaerobic reactor.
5. coal chemical wastewater treating technique according to claim 1 is characterized in that: described activated sludge tank is ordinary activated sludge aeration tank, list type intermittently activated sludge tank, circulating type active sludge pond or oxidation ditch.
6. the described coal chemical wastewater treating technique of any one according to claim 1 and 2 or in 4 or 5, it is characterized in that: the particle diameter of described activated coke or active carbocoal is 0.047mm to 1.0mm.
7. coal chemical wastewater treating technique according to claim 6 is characterized in that: describedly enter the waste water of activated sludge tank and the mass ratio of described activated coke or active carbocoal is 20000:1 to 10:1.
8. coal chemical wastewater treating technique according to claim 6 is characterized in that: described activated coke or the active carbocoal mass concentration in the described waste water that enters activated sludge tank is 0.05g/L to 100g/L.
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| CN103058455B (en) * | 2012-12-25 | 2014-12-17 | 北京国电富通科技发展有限责任公司 | System for treating printing and dyeing wastewater with activated coke adopted and process thereof |
| CN104229985A (en) * | 2014-10-17 | 2014-12-24 | 苏州新协力环保科技有限公司 | Activated sludge purifying and processing method for wastewater |
| CN106746158B (en) * | 2015-11-19 | 2020-09-11 | 中国石油化工股份有限公司 | Advanced denitrification treatment method for wastewater generated in coal water slurry gasification process |
| CN107226580A (en) * | 2016-08-31 | 2017-10-03 | 无锡市新都环保科技有限公司 | A kind of system and processing method of efficient process oily waste water |
| CN109956553A (en) * | 2017-12-22 | 2019-07-02 | 株式会社久保田 | A kind of wastewater treatment method and device that selective absorption is combined with biological treatment |
| CN109179648A (en) * | 2018-09-18 | 2019-01-11 | 上海晶宇环境工程股份有限公司 | A kind of coal chemical industry oil product synthetic wastewater oil removing process and its special equipment |
| CN109626728A (en) * | 2018-12-26 | 2019-04-16 | 东华大学 | A kind of industrial wastewater organic carbon and interior utilization process |
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