CN102432100A - Method for efficiently degrading morpholine waste water - Google Patents
Method for efficiently degrading morpholine waste water Download PDFInfo
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- CN102432100A CN102432100A CN2011103314011A CN201110331401A CN102432100A CN 102432100 A CN102432100 A CN 102432100A CN 2011103314011 A CN2011103314011 A CN 2011103314011A CN 201110331401 A CN201110331401 A CN 201110331401A CN 102432100 A CN102432100 A CN 102432100A
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Abstract
The invention relates to a method for efficiently degrading morpholine waste water. The method comprises the following steps of: putting multiple microorganisms and sludge into a reactor, wherein the multiple microorganisms include Delftia tsuruhatensis WXZ-9 CGMCC No.1797 and comamonas WXZ-17 CGMCC No.3048 and keeping the temperature at 20-30 DEG C; adding morpholine waste water, mechanically stirring, and running in the anoxic state at the pH 7.8-8.2 for 6-48 hours; entering an aerobic section from an anoxic section, mechanically stirring while blowing and aerating, and running at the pH 7.8-8.2 for 14-34 hours; entering the anoxic section from the aerobic section and mechanically stirring at the pH 7.8-8.2 for 0-22 hours; and after the anoxic process is completed, standing for two hours and draining. In the method, biochemistry, nitrification and denitrification are performed simultaneously under the same aerobic condition in the same reaction system, so that the investment expense and running cost are reduced greatly.
Description
Technical field
The present invention relates to a kind of method of efficient degradation morpholine waste water; Specifically; Be a kind of carbon in the morpholine waste water, nitrogen heterocyclic to be carried out biochemical reaction through the mikrobe in the active sludge in same reactor drum, the treatment process that makes it to degrade belongs to technical field of sewage.
Background technology
Domestic processing research report to morpholine waste water is less.For the processing of morpholine raffinate, Tian Huaiguang has proposed the method for burning disposal, and the water cut of light constituent is 86.23% in the morpholine raffinate, and the COD value is up to 346000mg/L, and this is favourable to burning disposal.What domestic present research was hot is from morpholine waste water, to reclaim N-methylmorpholine and N-ethylmorpholine, reduces its quantity discharged, and recyclable utilization.But the technical study of handling morpholine waste water with biochemical process does not almost have.
From nineteen eighty-two, people such as Knapp at first isolate two strains from active sludge can utilize the bacterial strain of morpholine as sole carbon source, nitrogenous source and the energy, has carried out the research to the morpholine biochemical degradation.1998, S.Chandrasekaran and D.Lalithakumari concentration and separation from contaminated soil went out the strain Pseudomonas fluorescens CAS102 rapidly that grows, and it can utilize the unique energy of morpholine as it, thus the morpholine of degrading effectively.In the same year, people such as B.COMBOURIEU isolate the strain mycobacterium fast that grows from contaminated active sludge, and it can be morpholine as unique nitrogenous source, carbon source and the energy.They have found the degradation pathway of morpholine, and find that this bacterium contains Cytochrome P450.2000; People such as Thomas Schrader isolate a strain bacterial strain HE5 from forest soil; This bacterial strain is analyzed through 16SrDNA and is accredited as the strain mycobacterium fast that grows, and it can be morpholine as unique nitrogenous source, carbon source and the energy, and find that this bacterial strain contains Cytochrome P450.The optimum growing condition of bacterial strain HE5 is the 30mM morpholine, pH7.2, and 30 ℃, the morpholine of the 10～15mM that can in 10 hours, degrade, this is the fastest bacterial strain of reporting up to now of degraded morpholine.Domestic report about decomposition morpholine bacterial strain is not seen as yet yet.
Summary of the invention
Contain morpholine, N-methylmorpholine and N (2-hydroxyethyl) morpholine etc. in the morpholine waste water, account for 35%～60% of total organic content greatly, biodegradability is poor, is difficult to degraded.Therefore must adopt special, biochemical processing process is handled targetedly.The objective of the invention is to through the superior microorganism colony in the acclimation shaking culture active sludge and add special bacterial strain, utilize in process of growth that relevant pollution substance carries out metabolism in the water, morpholine waste water is degraded significantly.
The method of efficient degradation morpholine waste water provided by the invention; Be that morpholine waste water is added in the reactor drum; Bubbling air behind the anaerobic treatment certain hour, the nitration denitrification process that also will carry out aerobic denitrogenation after decomposing because of biochemistry, so DO need keep higher level and carries out aerobic treatment.Concrete steps comprise:
A. adopt common SBR (sequence intermittent activated sludge process) reactor drum; Be equipped with composite flora and mud in the reactor drum, composite flora consist of the Ford bacterium WXZ-9 of Dell (Delftia tsuruhatensis), its preserving number is CGMCC No.1797; Preservation day is on September 7th, 2006; Depositary institution is China Committee for Culture Collection of Microorganisms common micro-organisms center and comamonas WXZ-17 (Comamonas sp.), and its preserving number is CGMCC No.3048; Preservation day is on April 30th, 2009; Depositary institution is China Committee for Culture Collection of Microorganisms common micro-organisms center, and composite flora and mud mix, and temperature of reaction remains on 20～30 ℃; The sbr reactor cycle by: anoxic → aerobic-anoxic leaves standstill to be formed.
B. morpholine waste water is added in the reactor drum, and adopt mechanical stirring that muddy water is mixed, the anoxic operation, pH is controlled at 7.8～8.2, and be 6～48h hour working time, and working time is relevant with influent concentration, down together;
C. get into aerobic section by the anoxic section, adopt mechanical stirring to add blast aeration, pH is controlled at 7.8～8.2, and be 14～34 hours working time; Adopt gas blower (or air compressor machine) and efficient microporous diffuser in reactor drum, to carry air, make to keep the high-solubility oxygen state in the reactor drum;
D. get into the anoxic section by aerobic section, adopt mechanical stirring, the anoxic operation, pH is controlled at 7.8～8.2, and be 0～22 hour working time;
E. the anoxic process leaves standstill water outlet in 2 hours after accomplishing.
The COD of pending morpholine waste water (COD) is 1000～3300mg/L among the present invention, and TN (total nitrogen) is 130～570mg/L, and wherein morpholine, N-methylmorpholine and N (2-hydroxyethyl) morpholine accounts for 35%～60 quality % of total organic matter.
In the composite flora, the mass ratio of Ford bacterium WXZ-9 CGMCC No.1797 of Dell and comamonas WXZ-17CGMCC No.3048 is 1: 1; The quality of composite flora is 10～40% of a mud dry substance matter quality.
Described mud is common sludge treatment plant mud.After morpholine waste water added reactor drum, the concentration of mud was 2～6g/L in the reactor drum.
In step b and the steps d anoxic process, DO (dissolved oxygen) is 0～0.5mg/L in the controlling reactor.
In the step c aerobic processes, DO is 4～5mg/L in the controlling reactor.
In the steps d, be 0～9 hour described working time.
The COD of water outlet is 200～1265mg/L among the present invention, and TN is 40～188mg/L, NH
3Be 8～12mg/L, wherein NH
3Reached emission standard.The clearance of COD is 45～90% in the morpholine waste water, and the clearance of TN is 45～80%.
The Ford bacterium WXZ-9 of Dell provided by the invention (Delftia tsuruhatensis) on September 7th, 2006, is preserved in China Committee for Culture Collection of Microorganisms common micro-organisms center in Beijing, its preserving number is CGMCC No.1797.Comamonas WXZ-17 (Comamonas sp.) on April 30th, 2009, is preserved in China Committee for Culture Collection of Microorganisms common micro-organisms center in Beijing, its preserving number is CGMCC No.3048.
The inventive method is handled morpholine waste water, has mainly solved a following difficult problem:
1, morpholine waste water is a kind of high organonitrogen concentration, high COD
CrConcentration and low BOD
5/ COD
CrThe waste water of ratio.Because morpholine, N-methylmorpholine are all as the nitrogen oxygen helerocyclics, the dual factor of its ring texture and itrogenous organic substance has strengthened the biochemical degradation difficulty.The present invention adopts special bacterial strain to combine patented technology, through domestication for a long time, turns out the mud of suitable degraded morpholine, has improved the degradation rate of morpholine greatly.
2, its ammonia-nitrogen content of present technique application morpholine waste water is extremely low; The overwhelming majority is the organonitrogen on the nitrogen oxa-ring; When therefore moving water inlet just, need to replenish carbon source, the nitrogenous source (like glucose, ammonium sulfate) that partly is prone to degraded, progressively improve the morpholine waste water proportioning that adds in the domestication process again.
3, handle in the process of morpholine waste water in present method, biochemical, nitrated, denitrification three-step reaction is compared, and biological process is most important, the difficulty maximum.In case ammonia nitrogen generates, nitrated, denitrification promptly carries out simultaneously, and this is the important feature of present technique.And the carbon source that denitrification needs is directly absorbed from morpholine waste water.
4, simplify pH regulator.Present technique adopts synchronous nitration/denitrification denitrogenation, makes acid of nitrifying process product and denitrification process produce alkali and cancels out each other, and simplifies pH regulator, has reduced the consumption of pharmaceutical chemicals.
Treatment technology of the present invention uses the method for biochemical treatment; Processing efficiency is high; Technical process is simple; And mikrobe is reacted in structures, need not on time and space, to divide the different operation unit, having reduced the complicacy of disposable facility investment, working cost and operation widely.
When influent quality is COD=2466mg/L, the waste water of TN=435mg/L can reach water outlet COD through the processing of one-period and be about 200mg/L, and TN is about 100mg/L, NH
3Be about 10mg/L.
The present invention has the following advantages:
1, in the above-mentioned treatment process of present technique; Owing to introduced bacterial strain with special degradability; And the technology that combination is biochemical, nitrated and denitrification carries out in same reactive system simultaneously; Successfully reach biochemical degradation and handle the purpose of morpholine waste water, and the difficulty that effectively simplifies the operation, investment cost and running cost reduced greatly.
2, in the above-mentioned treatment process of present technique; Because nitrification and denitrification carries out simultaneously in same reactor drum and accomplishes; Changed the demand that there are strong opposite potential of hydrogen in traditional aerobic nitrification and anoxic denitrification system, thereby the variation of potential of hydrogen has been had very strong shock absorption.
3, owing to biochemical, the nitrated and denitrification flora of growing simultaneously in the composite flora, reactant directly becomes the substrate of next step reaction, avoids the accumulation of reactant, the process of accelerated reaction.C/N can be adapted to than the influent load that alters a great deal, very high organic influent load and ammonia nitrogen loading can be adapted to simultaneously.
4, save reactor volume and structures floor space, reduce investment.
The present invention contains the aerobic nitrification/denitrification mud of special bacterial strain through domestication; Handle morpholine waste water through anoxic and step in sbr reactor device multistage such as aerobic; PH remains on 7.8～8.2, need not add microcosmic salt, under the situation of adding a small amount of carbon source and nitrogenous source; Through the operation of nearly half a year, morpholine influent waste water COD
CrBe about 2500mg/L and 415mg/L respectively with total average nitrogen concentration, need not other pre-treatment, reactor drum water outlet COD is about 200mg/L, and TN is about 100mg/L, NH
3-N is about 10mg/L.Wherein the COD clearance reaches more than 90%, and the TN clearance reaches more than 75%.
Description of drawings
Fig. 1 is the synoptic diagram of waste water treatment process reactor drum of the present invention.
Embodiment
Below foregoing of the present invention is done further to specify, but should this scope that is interpreted as the above-mentioned theme of the present invention only be confined to following instance through concrete enforcement example.All same quadrat methods that is realized based on the above-mentioned theme of the present invention all should belong to scope of the present invention.
As shown in Figure 1, be the synoptic diagram of equipment therefor of the present invention.Wherein, 1 is SBR (sequence intermittent activated sludge process) reactor drum, and 2 is electric mixer, and 3 is microporous diffuser, and 4 is air compressor machine, and 5 is under meter, and 6 is unit, and 7 is riser, and 8 is water port, and 9 is mud discharging mouth, and 10 is heating rod.
The method of efficient degradation morpholine waste water provided by the invention, for morpholine waste water is introduced in the reactor drum, bubbling air behind the anaerobic treatment certain hour makes DO keep higher level and carries out aerobic treatment.Concrete steps comprise:
A. in sbr reactor device 1, add the composite flora of total sludge quantity (dry substance matter quality) 10～40%.The composite flora source is: Ford bacterium WXZ-9 (Delftia tsuruhatensis) CGMCCNo.1797 of laboratory strains Dell and comamonas WXZ-17 (Comamonas sp.) CGMCC No.3048 are mixing in 1: 1 with mass ratio.Composite flora and mud mix, and temperature of reactor keeps 20～30 ℃, so that bacterial activity is the highest; Mud is common sludge treatment plant mud; Reactor drum effective volume 5L, phase water outlet 2L remains 3L weekly, gets into next cycle and mends into 2L;
Ford bacterium WXZ-9 CGMCC No.1797 of Dell and comamonas WXZ-17 CGMCC No.3048 enlarged culturing condition: 30 ℃, 140r/min cultivated 72 hours;
Enlarged culturing base: LB substratum, KNO
31g, KH
2PO
41g, FeCl
26H
2O 0.05g, CaCl
27H
2O0.02g, MgSO
47H
2O 1g, trisodium citrate 5.1g, zero(ppm) water 1000mL, 121 ℃ of sterilization 20min.
B. the COD (COD) of will intaking is 1000～3300mg/L, and TN (total nitrogen) is that the morpholine waste water of 130～570mg/L adds reactor drum, adopts mechanical stirring to guarantee that muddy water mixes, and sludge concentration is 2～6g/L in the reactor drum, carries out the operation of anoxic section; PH is controlled at 7.8～8.2, and be 6～48 hours working time.In the anoxic process, DO (dissolved oxygen) is 0～0.5mg/L in the may command reactor drum.
C. anoxic connects the operation of oxygen stage after the stage.Aerobic stage adopts mechanical stirring to add the blast aeration mode, and pH is controlled at 7.8～8.2, and be 14～34 hours working time; Aeration employing gas blower (or air compressor machine) and efficient microporous diffuser make and are in the high-solubility oxygen state in the reactor drum.In the aerobic processes, DO is 4～5mg/L in the may command reactor drum.
D. get into the anoxic section after aerobic processes is accomplished, adopt mechanical stirring, pH is controlled at 7.8～8.2, and be 0～22 hour working time; In the anoxic process, DO (dissolved oxygen) is 0～0.5mg/L in the may command reactor drum.
E. the anoxic process leaves standstill water outlet in 2 hours after accomplishing.The COD of water outlet this moment is 200～1265mg/L, and TN is 40～188mg/L, NH
3Be 8～12mg/L, wherein NH
3Reached emission standard.The clearance of COD is 45～90% in the morpholine waste water, and the clearance of TN is 45～80%.
Embodiment 1～8
Water quality treatment is the waste water that certain Group Co.,Ltd's morpholine production process produces; Add an amount of common sludge treatment plant mud or simulation sanitary wastewater (glucose; Ammonium sulfate and the preparation of micronutrient salt), wherein morpholine, N-methylmorpholine and N (2-hydroxyethyl) morpholine accounts for 35%～60 quality % of total organic matter.Dilute according to different requirement of experiment during use.The total useful volume 6L of reactor drum, the bottom is equipped with the micro-pore aeration plate, carries out aeration through air compressor machine, and under meter plays the control flow, sees also Fig. 1.Carry out the degraded of morpholine waste water according to the method described above, DO is at 0～0.5mg/L in the anoxic stage controlling reactor, and reactor drum pH maintains between 7.8～8.2 all the time.Temperature is about 25 ℃, and composite flora concentration is about 2～6g/L.
Biochemical, the nitrated and denitrification of present method carries out in identical aerobic condition and same reactive system simultaneously, reduces investment cost and running cost greatly.
The operation of table 1, embodiment 1-8 and detect parameters
Continuous table
Claims (7)
1. the method for an efficient degradation morpholine waste water comprises the steps:
A. adopt the sbr reactor device; Be equipped with composite flora and mud in the reactor drum; Described composite flora is made up of Ford bacterium WXZ-9 (Delftia tsuruhatensis) CGMCC No.1797 of Dell and comamonas WXZ-17 (Comamonas sp.) CGMCC No.3048; Mix, temperature of reaction remains on 20～30 ℃;
B. morpholine waste water is added in the reactor drum, adopt mechanical stirring, the anoxic operation, pH is controlled at 7.8～8.2, and be 6～48h hour working time;
C. get into aerobic section by the anoxic section, adopt mechanical stirring to add blast aeration, pH is controlled at 7.8～8.2, and be 14～34 hours working time;
D. get into the anoxic section by aerobic section, adopt mechanical stirring, the anoxic operation, pH is controlled at 7.8～8.2, and be 0～22 hour working time;
E. the anoxic process leaves standstill water outlet in 2 hours after accomplishing.
2. the method for efficient degradation morpholine waste water according to claim 1 is characterized in that: the COD of said morpholine waste water is 1000～3300mg/L, and TN is 130～570mg/.
3. the method for efficient degradation morpholine waste water according to claim 1 is characterized in that: in the said composite flora, the mass ratio of Ford bacterium WXZ-9 CGMCC No.1797 of Dell and comamonas WXZ-17 CGMCCNo.3048 is 1: 1; The quality of said composite flora is 10～40% of a said mud dry substance matter quality.
4. the method for efficient degradation morpholine waste water according to claim 3 is characterized in that: after morpholine waste water added reactor drum, the concentration of mud was 2～6g/L in the reactor drum.
5. the method for efficient degradation morpholine waste water according to claim 1 is characterized in that: in step b and the steps d anoxic process, dissolved oxygen is 0～0.5mg/L in the controlling reactor.
6. the method for efficient degradation morpholine waste water according to claim 1 is characterized in that: in the step c aerobic processes, dissolved oxygen is 4～5mg/L in the controlling reactor.
7. the method for efficient degradation morpholine waste water according to claim 1 is characterized in that: the COD of said water outlet is 200～1265mg/L, and TN is 40～188mg/L.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107098513A (en) * | 2017-04-28 | 2017-08-29 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of high concentration morpholine waste water |
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| CN107098513A (en) * | 2017-04-28 | 2017-08-29 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of high concentration morpholine waste water |
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