CN104671434B - The method that phosphorus improves suction phosphorus/release phosphorus when biological phosphor-removing effect simultaneously is released based on reducing dephosphorization microbiological anaerobic - Google Patents
The method that phosphorus improves suction phosphorus/release phosphorus when biological phosphor-removing effect simultaneously is released based on reducing dephosphorization microbiological anaerobic Download PDFInfo
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- CN104671434B CN104671434B CN201510066994.1A CN201510066994A CN104671434B CN 104671434 B CN104671434 B CN 104671434B CN 201510066994 A CN201510066994 A CN 201510066994A CN 104671434 B CN104671434 B CN 104671434B
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Abstract
The invention belongs to environmental protection technical field, be specifically related to a kind of based on reduce dephosphorization microbiological anaerobic release phosphorus improve simultaneously dephosphorization process inhale phosphorus/release phosphorus than and the method for phosphor-removing effect. First brown coal humus is carried out sulfonation modifying by the method under sulphuric acid existence condition, then it is added in biological removal of phosphorus in wastewater process system, for reducing the anaerobic phosphorus release amount of biological phosphate-eliminating microorganism, the phosphorus of raising suction simultaneously/release phosphorus ratio, thus reaching significantly improving of biological removal of phosphorus in wastewater effect.
Description
Technical field
The invention belongs to environmental protection technical field, be specifically related to a kind of release the method that phosphorus improves suction phosphorus/release phosphorus when biological phosphor-removing effect simultaneously based on reducing dephosphorization microbiological anaerobic. First brown coal humus was entered sulfonation modifying by the method, was then added in sewage biological treatment system again, was used for improving dephosphorization microbial activity, improved the effect of biological removal of phosphorus in wastewater.
Background technology
In sewage (particularly sanitary sewage), the excessive emissions of P elements is the major reason causing body eutrophication. Eutrophication causes water quality deterioration, adds to the difficulties to drinking water treatment; Cover the water surface while also result in dissolved oxygen concentration in water body with algae and reduce, cause aquatile anoxia asphyxia lethal, time serious, more can cause the destruction of whole ecosystem. For preventing and treating body eutrophication problem, phosphorus content in the earphone sewage disposal plant effluent of city has been done strict regulations by China " urban wastewater treatment firm pollutant emission standard " (GB18918-2002), wherein primary standard A standard TP≤0.5mg/L, B standard TP≤1mg/L. As can be seen here, no matter existing sewage treatment plant or newly-built Sewage Plant all suffer from the severe requirement of deep phosphorous removal.
Biological phosphate-eliminating is mainly through the dephosphorization microorganism movable removal realized phosphorus when anaerobic-aerobic blocked operation. Under anaerobic, dephosphorization microorganism absorbs the easily biodegradable organics in sewage, and is saved as material for thermal energy storage poly (hydroxyalkanoate) (PHA), and the energy in this process is mainly derived from the hydrolysis of poly-phosphorus (Poly-P); Intracellular glycogen is also hydrolyzed simultaneously, it is provided that additionally fraction energy and synthesis PHA required for reducing power NADH2. Therefore, the release of a large amount of phosphorus is occurred in that at anaerobic stages. Under aerobic condition, dephosphorization microorganism is with free oxygen for electron acceptor, and the PHA stored under oxidation anaerobism produces energy, is used for absorbing phosphorus, Growth of Cells and glycogen biosynthesis. Therefore, the absorption of phosphorus occurs at aerobic stage. Visible. Only aerobic phosphorus accumulation amount is more than anaerobic phosphorus release amount, can be only achieved the purpose removing phosphor in sewage; It is higher than more that anaerobic phosphorus release is more less, dephosphorization process inhales phosphorus/release phosphorus, and phosphor-removing effect can be more good. But, up to the present, have no about passing through to reduce anaerobic phosphorus release, improve suction phosphorus/release phosphorus ratio, reach to improve the report of biological phosphor-removing effect.
Humus is the larger molecular organics matter being widely present in nature, and it is the stable and complicated Organic substance that plant and animal residues is formed through long term physical, chemistry, biological agent, is widely used in the fields such as Agriculture, forestry And Animal Husbandry, oil, chemical industry, building materials. A lot of researchs at present show, humic acid is possible not only to affect the Transport And Transformation of inorganic metal can also promote complicated organic biodegradation. Brown coal humus is a kind of natural humus class material being present in brown coal. Owing to its toxic and side effects is little, thus the scope of application is very wide, but not yet finds that the brown coal humus after using sulfonation modifying improves biological phosphate-eliminating microbiological anaerobic and becomes reconciled the report of oxygen activity.
The present invention from reduce sewage dephosphorization system anaerobic phosphorus release amount, improve dephosphorization process to inhale the angle of phosphorus/release phosphorus ratio and set out simultaneously, propose by adding sulfonation modifying brown coal humus to biological removal of phosphorus in wastewater system, realize Enhanced Biological Phosphorus Removal stable, reliable, efficient, quick, process to China's phosphorus-containing wastewater, has great importance.
Summary of the invention
The invention belongs to environmental protection technical field, be specifically related to a kind of release phosphorus by using modified brown coal humus to reduce dephosphorization microbiological anaerobic, the method simultaneously improving dephosphorization process suction phosphorus/release phosphorus when biological removal of phosphorus in wastewater effect. First brown coal humus was entered sulfonation modifying by the method, was then added in sewage biological treatment system by this modified brown coal humus, was used for improving dephosphorization microbial activity, improved the effect of biological removal of phosphorus in wastewater.
The technical solution used in the present invention is as follows:
What the present invention proposed releases the method that phosphorus improves suction phosphorus/release phosphorus when biological phosphor-removing effect simultaneously based on reducing dephosphorization microbiological anaerobic, comprises the following steps:
(1) brown coal humus is mixed with certain proportion with concentrated sulphuric acid, and ensure that concentrated sulphuric acid is totally submerged brown coal humus. It is simultaneously introduced bead, reacts the regular hour under the high temperature conditions; Described brown coal humus mixes with the ratio of every gram of brown coal humus 3 ~ 5ml with concentrated sulphuric acid, and reaction temperature controls at 150 ~ 180 ° of C, and the response time controls at 1 ~ 3h;
(2) reactant mixture that step (1) obtains is placed in distilled water cools down, be stirred simultaneously, stand regular hour, abandoning supernatant afterwards, obtain lower floor's mixture;
(3) lower floor's mixture washing step (2) obtained, is placed in bag filter and dialyses in ultra-pure water environment, wherein change ultra-pure water with certain number of times;
(4) the dialysis product that step (3) obtains is carried out lyophilization, both obtain sulfonation modifying brown coal humus;
(5) the sulfonation modifying brown coal humus that step (4) obtains is added in the water inlet of biological removal of phosphorus in wastewater system, the phosphorus in water can be removed.
In the present invention, the time of repose in step (2) is 12 ~ 24h.
In the present invention, wherein the number of times of ultra-pure water is changed in the dialysis in step (3) is 3 ~ 5 times.
In the present invention, wherein the content in water inlet of the sulfonation modifying brown coal humus in step (5) is 100 ~ 400mg/L.
The method have the advantages that
(1) addition of sulfonation modifying brown coal humus, it is possible to significantly reduce the anaerobism burst size of sewage dephosphorization system phosphorus, the dephosphorization process suction phosphorus of raising raising simultaneously/release phosphorus ratio, thus improve the effect of biological removal of phosphorus in wastewater.
(2) this method is under rational operational factor, and the total tp removal rate in municipal sewage can reach more than 99%, and water outlet reaches sewage treatment plant's first discharge standard.
(3) utilize the brown coal humus being widely present to carry out the modified brown coal humus that sulfonating reaction obtains, at the recycling being simultaneously achieved humus improving biological removal of phosphorus in wastewater effect, be a kind of protection environment method for the treatment of of wastes with processes of wastes against one another.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1:
(1). the sulfonation modifying of brown coal humus
Take 5g brown coal humus, mix with 20ml concentrated sulphuric acid, add bead, under 160 ° of C, react 2h. The reactant mixture obtained is placed in distilled water and cools down, be stirred simultaneously, stand 24h, abandoning supernatant afterwards, obtain lower floor's mixture. The lower floor's mixture washing that will obtain, is placed in bag filter and dialyses in ultra-pure water environment, wherein change ultra-pure water 3 times; Afterwards dialysis product is carried out lyophilization, obtain sulfonation modifying brown coal humus.
(2). add sulfonated lignite humus and improve the phosphorus ligands effect of Enhanced Biological Phosphorus Removal
In pending phosphorus-containing wastewater, COD is 300mg/L, total phosphorus (TP) 17mg/L, and adding sulfonation modifying brown coal humus concentration is 400mg/L. When being 10.2h and 12 days ages of mud mud for 0.785:1, the water conservancy time of staying by water-filling ratio, this sewage is added in anaerobic-aerobic sequencing batch reactor (SBR), under anaerobic stirs 2h, then aerobic aeration 3h. The phosphorus amount of releasing of anaerobic stages is 54.3mg/L, the P uptake by plants of aerobic stage is 66.9mg/L, and clean P uptake by plants is 12.6mg/L, and the suction phosphorus of dephosphorization process/release phosphorus ratio is 1.23, the total phosphorus concentration of water outlet simultaneously is 0.2mg/L, and effluent quality meets sewage treatment plant's first discharge standard.
Embodiment 2:
The composition of pending phosphorus-containing wastewater, with embodiment 1, is added without the sulfonation modifying brown coal humus described in embodiment 1 and is made directly biological phosphate-eliminating, and other operations are with embodiment 1. The phosphorus amount of releasing of anaerobic stages is 98.5mg/L, the P uptake by plants of aerobic stage is 108.9mg/L, and clean P uptake by plants is 10.4mg/L, and the suction phosphorus of dephosphorization process/release phosphorus ratio is 1.10, water outlet total phosphorus concentration is 2.3mg/L, and effluent quality does not meet sewage treatment plant's first discharge standard.
Comparative example 1 and 2 is visible, adds sulfonation modifying brown coal humus, it is possible to reduce anaerobic phosphorus release amount in phosphorus-containing wastewater, improves dephosphorization process simultaneously and inhales phosphorus/release phosphorus ratio, improves the effect of biological phosphate-eliminating.
Embodiment 3:
Modifiying with embodiment 1 of brown coal humus, in pending phosphorus-containing wastewater, COD is 260mg/L, total phosphorus (TP) 20mg/L, and adding sulfonation modifying brown coal humus concentration is 300mg/L. When being 11.2h and 12 days ages of mud mud for 0.714:1, the water conservancy time of staying by water-filling ratio, this sewage is added in sequencing batch reactor (SBR), under anaerobic stirs 1.5h, then aerobic aeration 2.5h. The phosphorus amount of releasing of anaerobic stages is 65.0mg/L, and the P uptake by plants of aerobic stage is 79.1mg/L, and clean P uptake by plants is 14.1mg/L, and the suction phosphorus of dephosphorization process/release phosphorus ratio is 1.21, and water outlet total phosphorus concentration is 0.3mg/L, and effluent quality meets sewage treatment plant's first discharge standard.
Embodiment 4:
The composition of pending phosphorus-containing wastewater, with embodiment 3, is added without the sulfonation modifying brown coal humus described in embodiment 1 and is made directly biological phosphate-eliminating, and other operations are with embodiment 3. The phosphorus amount of releasing of anaerobic stages is 92.8mg/L, the P uptake by plants of aerobic stage is 104.6mg/L, and clean P uptake by plants is 11.80mg/L, and the suction phosphorus of dephosphorization process/release phosphorus ratio is 1.12, water outlet total phosphorus concentration is 2.6mg/L, and effluent quality does not meet sewage treatment plant's first discharge standard.
Embodiment 5:
Take 5g brown coal humus, mix with 25ml concentrated sulphuric acid, add bead, under 150 ° of C, react 3h. The reactant mixture obtained is placed in distilled water and cools down, be stirred simultaneously, stand 12h, abandoning supernatant afterwards, obtain lower floor's mixture. The lower floor's mixture washing that will obtain, is placed in bag filter and dialyses in ultra-pure water environment, wherein change ultra-pure water 4 times; Afterwards dialysis product is carried out lyophilization, obtain sulfonation modifying brown coal humus;
In pending phosphorus-containing wastewater, COD is 250mg/L, total phosphorus (TP) 15mg/L, and adding sulfonation modifying brown coal humus concentration is 250mg/L. When being 11.2h and 12 days ages of mud mud for 0.735:1, the water conservancy time of staying by water-filling ratio, this sewage is added in sequencing batch reactor (SBR), under anaerobic stirs 3h, then aerobic aeration 4h. The phosphorus amount of releasing of anaerobic stages is 63.0mg/L, the P uptake by plants of aerobic stage is 77.25mg/L, and clean P uptake by plants is 14.3mg/L, and the suction phosphorus of dephosphorization process/release phosphorus ratio is 1.22, water outlet total phosphorus concentration is 0.15mg/L, and effluent quality meets sewage treatment plant's first discharge standard.
Embodiment 6:
The composition of pending phosphorus-containing wastewater, with embodiment 5, is added without the sulfonation modifying brown coal humus described in embodiment 5 and is made directly biological phosphate-eliminating, and other operations are with embodiment 5. The phosphorus amount of releasing of anaerobic stages is 91.4mg/L, the P uptake by plants of aerobic stage is 103.9mg/L, and clean P uptake by plants is 12.5mg/L, and the suction phosphorus of dephosphorization process/release phosphorus ratio is 1.13, water outlet total phosphorus concentration is 1.9mg/L, and effluent quality does not meet sewage treatment plant's first discharge standard.
Embodiment 7:
Take 5g brown coal humus, mix with 15ml concentrated sulphuric acid, add bead, under 180 ° of C, react 1h. The reactant mixture obtained is placed in distilled water and cools down, be stirred simultaneously, stand 18h, abandoning supernatant afterwards, obtain lower floor's mixture. The lower floor's mixture washing that will obtain, is placed in bag filter and dialyses in ultra-pure water environment, wherein change ultra-pure water 5 times; Afterwards dialysis product is carried out lyophilization, obtain sulfonation modifying brown coal humus;
In pending phosphorus-containing wastewater, COD is 200mg/L, total phosphorus (TP) 10mg/L, and adding sulfonation modifying brown coal humus concentration is 100mg/L. When being 11.2h and 12 days ages of mud mud for 0.714:1, the water conservancy time of staying by water-filling ratio, this sewage is added in sequencing batch reactor (SBR), under anaerobic stirs 1.5h, then aerobic aeration 1.5h. The phosphorus amount of releasing of anaerobic stages is 73.2mg/L, and the P uptake by plants of aerobic stage is 87.4mg/L, and clean P uptake by plants is 14.2mg/L, and the suction phosphorus of dephosphorization process/release phosphorus ratio is 1.19, and water outlet total phosphorus concentration is 0.2mg/L, and effluent quality meets sewage treatment plant's first discharge standard.
Embodiment 8:
The composition of pending phosphorus-containing wastewater, with embodiment 7, is added without the sulfonation modifying brown coal humus described in embodiment 7 and is made directly biological phosphate-eliminating, and other operations are with embodiment 7. The phosphorus amount of releasing of anaerobic stages is 85.9mg/L, the P uptake by plants of aerobic stage is 98.8mg/L, and clean P uptake by plants is 12.9mg/L, and the suction phosphorus of dephosphorization process/release phosphorus ratio is 1.14, water outlet total phosphorus concentration is 1.5mg/L, and effluent quality does not meet sewage treatment plant's first discharge standard.
Embodiment 9:
Take 5g brown coal humus, mix with 20ml concentrated sulphuric acid, add bead, under 180 ° of C, react 1.5h.The reactant mixture obtained is placed in distilled water and cools down, be stirred simultaneously, stand 24h, abandoning supernatant afterwards, obtain lower floor's mixture. The lower floor's mixture washing that will obtain, is placed in bag filter and dialyses in ultra-pure water environment, wherein change ultra-pure water 5 times; Afterwards dialysis product is carried out lyophilization, obtain sulfonation modifying brown coal humus;
In pending phosphorus-containing wastewater, COD is 260mg/L, total phosphorus (TP) 15mg/L, and adding sulfonation modifying brown coal humus concentration is 300mg/L. When being 11.2h and 12 days ages of mud mud for 0.714:1, the water conservancy time of staying by water-filling ratio, this sewage is added in sequencing batch reactor (SBR), under anaerobic stirs 2h, then aerobic aeration 3.5h. The phosphorus amount of releasing of anaerobic stages is 71.1mg/L, the P uptake by plants of aerobic stage is 83.7mg/L, and clean P uptake by plants is 12.6mg/L, and the suction phosphorus of dephosphorization process/release phosphorus ratio is 1.18, water outlet total phosphorus concentration is 0.10mg/L, and effluent quality meets sewage treatment plant's first discharge standard.
Embodiment 10:
The composition of pending phosphorus-containing wastewater, with embodiment 9, is added without the sulfonation modifying brown coal humus described in embodiment 9 and is made directly biological phosphate-eliminating, and other operations are with embodiment 9. The phosphorus amount of releasing of anaerobic stages is 98.0mg/L, the P uptake by plants of aerobic stage is 106.9mg/L, and clean P uptake by plants is 8.9mg/L, and the suction phosphorus of dephosphorization process/release phosphorus ratio is 1.09, water outlet total phosphorus concentration is 2.30mg/L, and effluent quality does not meet sewage treatment plant's first discharge standard.
The above-mentioned description to embodiment is to be understood that for the ease of those skilled in the art and apply the present invention. These embodiments obviously easily can be made various amendment by person skilled in the art, and General Principle described herein is applied in other embodiments without through performing creative labour. Therefore, the invention is not restricted to embodiment here, those skilled in the art's announcement according to the present invention, the improvement made for the present invention and amendment all should within protection scope of the present invention.
Claims (4)
1. release phosphorus and improve the method that dephosphorization process inhales phosphorus/release phosphorus when biological phosphor-removing effect simultaneously based on reducing dephosphorization microbiological anaerobic for one kind, it is characterised in that specifically comprise the following steps that
(1) brown coal humus is mixed with the ratio of every gram of brown coal humus 3 ~ 5ml with concentrated sulphuric acid, be simultaneously introduced bead, react 1 ~ 3h when 150 ~ 180 ° of C;
(2) reactant mixture that step (1) obtains is placed in distilled water cools down, be stirred simultaneously, stand 12 ~ 24h, abandoning supernatant, obtain lower floor's mixture;
(3) lower floor's mixture washing step (2) obtained, is placed in bag filter and dialyses in ultra-pure water environment;
(4) the dialysis product that step (3) obtains is dried, namely obtains sulfonation modifying brown coal humus;
(5) the sulfonation modifying brown coal humus that step (4) obtains is added in the water inlet of sewage biological treatment system, the phosphorus in water can be removed.
2. method according to claim 1, it is characterised in that: step (3) changes ultra-pure water 3 ~ 5 times during dialysis.
3. method according to claim 1, it is characterised in that: step (4) adopts lyophilization.
4. method according to claim 1, it is characterised in that: the sulfonation modifying brown coal humus added in step (5) concentration in water inlet is 50 ~ 400mg/L.
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| CN1686864A (en) * | 2005-05-20 | 2005-10-26 | 班宏伟 | Treatment method for home wastewater |
| CN101234839A (en) * | 2008-02-25 | 2008-08-06 | 尹军 | Method for forcedly removing phosphorus in anaerobic digestion sludge liquid phase |
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| JP2696315B2 (en) * | 1996-01-16 | 1998-01-14 | エンザイム株式会社 | Preparation of organic sludge deodorant and alteration inhibitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1686864A (en) * | 2005-05-20 | 2005-10-26 | 班宏伟 | Treatment method for home wastewater |
| CN101234839A (en) * | 2008-02-25 | 2008-08-06 | 尹军 | Method for forcedly removing phosphorus in anaerobic digestion sludge liquid phase |
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