CN1689992A - Technique for treating waste water containing natural gas antifreezing agent by ozone and biochemical process - Google Patents
Technique for treating waste water containing natural gas antifreezing agent by ozone and biochemical process Download PDFInfo
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- CN1689992A CN1689992A CN 200410022411 CN200410022411A CN1689992A CN 1689992 A CN1689992 A CN 1689992A CN 200410022411 CN200410022411 CN 200410022411 CN 200410022411 A CN200410022411 A CN 200410022411A CN 1689992 A CN1689992 A CN 1689992A
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Abstract
The present invention is ozone plus biochemical process for treating waste water containing natural gas and antifreezing fluide, and features that the technological process consists of three stages of pre-treatment, ozone oxidation and microbial treatment. The technological process includes the steps of: separating oil from water, flocculating deposition, oxidation with ozone, two stage aerobic oxidation biological treatment with special microbe, deposition in the depositing pond, and draining the supernatant as effluent reaching the standard.
Description
Technical field
The present invention relates to a kind of technology for treating industrial waste water, particularly a kind of ozone+biochemical process is handled and is contained Sweet natural gas frostproofer waster water process.
Background technology
Can make frostproofer because of traffic requirements adds ethylene glycol in the gas production factory production process, the freezing point of deicing fluid is determined by glycol content.Ethylene glycol content is high more, and antifreeze ability is strong more.40% ethylene glycol and the composite deicing fluid of 60% soft water, antifreeze temperature is-25 ℃; When ethylene glycol in the deicing fluid and water respectively accounted for 50%, antifreeze temperature was-35 ℃.General ethylene glycol reasonable content in cooling fluid should be between the 40%-60%.Gas production factory often regulates antifreeze temperature by glycol concentration in the control water.
So, in the process that reclaims deicing fluid,, can produce the organic polluting water that contains frostproofer because frostproofer reclaims not exclusively.The frostproofer that uses mainly is hypotoxicity alcohols (being mainly ethylene glycol an etc.) frostproofer at present, its chemical oxidation weak effect, and biodegradability is not strong etc.Domestic common treatment process is with this type of waste water uncontrollable discharge or enters near urban pipe network (most of factories do not possess this condition).Though to containing frostproofer (mainly being ethylene glycol) waste water more research is arranged at present, not very desirable to the treatment effect of high density ethylene glycol waste water, also be in initial stage at home and abroad at present, still there is not similar comparable technology.
Ethylene glycol, English name: Ethylene glycol; Glycol; Product another name: glycol; 1,2 ethylene glycol; Molecular formula: HOCH
2CH
2OH; The water white transparency thick liquid, it is sweet to distinguish the flavor of, and has water absorbability, inflammable.Relative density 1.1088 (20/4 ℃).198 ℃ of boiling points.Zero pour-11.5 ℃.Density (vacuum, 20 ℃) 1.11336g/ml.Refractive index n D (20 ℃) 1.4318.116 ℃ of flash-points.Viscosity (20 ℃) 21mPas.Specific heat capacity (20 ℃) 2.35J/ (g ℃).Mole generates heat-452.3kJ/mol.Heat of fusion 187.025J/g.Vaporization heat 799.14J/g.Surface tension (20 ℃) 48.4mN/m.Vapour pressure (20 ℃) 7.999Pa, 412.8 ℃ of spontaneous ignition temperatures.Miscible with water, lower aliphatic alcohols, glycerine, acetic acid, acetone and similar ketone, aldehydes, pyridine and similar coal tar bases, be slightly soluble in ether (1: 200), be dissolved in benzene and homologue thereof, hydrochloric ether, sherwood oil and oils hardly.
Ethylene glycol mainly as producing synthetic resins, tensio-active agent and explosive and making frostproofer, does not have serious toxicity to rudimentary vertebrates, but then different to the mankind, can very big toxic action be arranged to physical environment and human health.Because ethylene glycol boiling point height, steam forces down, and does not generally have the suction intoxicating phenomenon.Infiltration capacity to damaged skin not is little.Can cause stimulation to eye.Can stimulate nervus centralis but drink (one or two people not enough 50g) in a large number, cause vomiting, tired, lethargic sleep, have difficulty in breathing, tremble, kidney is congested and hemorrhage, fat is prevented liver, renal shutdown (uriniferous tubules crystallization obstruction), bronchitis, pneumonia and cause death.Rat, cavy per os LD50 are respectively 8.54,6.61g/kg, and its mouse oral LD50 is 13.79ml/kg.About 1.4ml/kg of human body LD or 100ml.The person of wrongly taking uses potassium permanganate solution gastric lavage in 1: 2000 and catharsis immediately.Severe patient is sent diagnosis and treatment to hospital.Should indicate " poisonous " printed words on the ethylene glycol container, prevent to wrongly take and suck the ethylene glycol steam.Operator should dress safety appliance, regularly check UP, particularly routine urianlysis.Should seal during storage, long storage is wanted nitrogen envelope, protection against the tide, fire prevention, antifreeze.Press the storing of ignition control compound regulation.
Summary of the invention
In view of to containing the low toxicity alcohols, it mainly is the present situation that the Industrial Wastewater Treatment of frostproofer such as ethylene glycol exists, the bright purpose of setting out provides a kind ofly does pre-treatment with ozone oxidation, and be aided with the organic contamination in the high-effective microorganism oxidation style removal trade effluent, make trade effluent reach the waste water treatment process of discharging standards.
The present invention is that ozone+biochemical process processing contains Sweet natural gas frostproofer waster water process, it is characterized in that this technology is made of pre-place ozone oxidation and microorganism three phases, and concrete steps are:
One, the employing water-and-oil separator is removed the oily substance in the waste water;
Two, the coagulation that flocculates is removed the suspended substance in the waste water; Requiring the ph value is 6~9,20~35 ℃ of temperature;
Three, the waste water that will carry out above-mentioned two procedures is introduced oxidizing tower, improves the biodegradability of waste water by ozone oxidation;
Four, through the sampling of wastewater of ozone Oxidation Treatment, monitor the composite water quality situation of water sample, determine the dosage of ozone;
Five, inject obligate microorganism dominant bacteria, carry out the one-level aerobic oxidation and handle, regulate gas-water ratio and oxidation and control the biochemical treatment effect duration of contact.
Six, inject obligate microorganism dominant bacteria, carry out the processing of secondary aerobic oxidation waste water is carried out further biochemical treatment;
Seven, the waste water of handling through the secondary aerobic oxidation enters the settling tank precipitation, and supernatant liquor is discharged, and the mud pump around circuit is to biochemical unit.
Eight, the mud of post precipitation is refluxed respectively carry out one-level aerobic oxidation and secondary aerobic oxidation once more respectively and handle.
In step before the oily water separation and before the one-level aerobic oxidation, all utilize COD on-line monitoring view to carry out online detection, regulate gas-water ratio, ph value and oxidation duration of contact according to the water body situation, guarantee effluent quality.
The organic polymer coargulator chitosan of flocculation agent employing non-toxic degradable and inorganic flocculating agent alkali aluminium are as flocculation agent, and the ratio of the two weight is 1: 6.The dosage of chitosan is 1.67 mg/litre, and alkali aluminium is 10 mg/litre, and ph value scope is 6~7.
Utilizing art breading of the present invention is the trade effluent of frostproofer with ethylene glycol; make the waste water index of discharging reach China GB8978-1996 comprehensive discharge primary standard fully; solved the water pollution problem that brings by frostproofer (mainly being ethylene glycol) preferably, brought into play positive effect preserving the ecological environment, avoid water pollution.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment
After waste water comes out from water-and-oil separator, the coagulation that flocculates is handled, when coagulation that sewage is flocculated is handled, normally single use polymeric flocculant, and based on organic floculant PAM class flocculation agent, the flocculation of PAM class is difficult to degraded, and itself also has unpolymerized strong carinogenicity monomer---third rare acid amides and third rare nitrile; Inorganic flocculating agent alkali aluminium also often is used, but it exists characteristics such as consumption is many, treatment effect is not good.So this technology when the waste water that contains the glycols frostproofer is carried out pre-treatment, utilizes the organic polymer coargulator chitosan of non-toxic degradable and inorganic flocculating agent alkali aluminium (PAC) to be used as built-up flocculant.
Process control condition
Contain the pre-treatment explanation of frostproofer waste water (mainly being ethylene glycol)
1. instrument and reagent
Bull magnetic force heated and stirred instrument; The electric heating constant temperature air dry oven; The 721B spectrophotometer; The accurate used chitosan of pH meter (the taking off caproyl 85%) concentration of pHS-3c is 225mg/L, and PAC concentration is 1350mg/L.
2. analysis project and method
The COD value is measured with potassium dichromate process (GB/T11914).
3. experimental technique and content
(1) experimental technique: raw wastewater pH value is 6.7, add flocculation agent after, stir 5min fast, leave standstill, flocculating settling 40min the SVI value of measure sample then, dewatering rate, and the COD value of supernatant liquor, SS value and transmittance.
(2) coagulate the determining of best dosage of agent alkali aluminium: in 3 graduated cylinders that the 500mL water sample is housed, add the flocculation agent alkali aluminium of different amounts respectively, handle water sample by the method for (1), the quality of flocculating effect is relatively determined the best dosage of flocculation agent alkali aluminium.
(3) optimum compound proportion of flocculation agent chitosan and alkali aluminium determines.In 6 graduated cylinders that the 500mL water sample is housed, add the chitosan and the alkali aluminium of different ratios respectively, handle sample by the method for (1), determine the optimum compound proportion of chitosan and alkali aluminium.
Definite experiment of the best dosage of flocculation agent alkali aluminium
Add the alkali aluminium of different amounts, treatment effect sees the following form
The treatment effect of Different Alkali aluminium dosage
Sample number into spectrum | No. 1 | No. 2 | No. 3 | No. 4 |
Alkali aluminium dosage, mg/l | ??5 | ??10 | ??15 | ??25 |
The SVI value, % | ??69.0 | ??78.0 | ??72.3 | ??65.5 |
Transmittance, % | ??75.8 | ??85.0 | ??75.0 | ??71.3 |
This shows that peak value occurs near alkali aluminium dosage is 10mg/l.Be that alkali aluminium dosage exists optimum value near 10mg/l.
Determining of flocculation agent optimum compound proportion
Determine alkali aluminium dosage 10mg/l, change the dosage of chitosan, result is as follows:
Optimum compound proportion is determined experimental result
Sample number into spectrum | No. 1 | No. 2 | No. 3 | No. 4 | No. 5 | No. 6 | No. 7 | No. 8 |
Composite ratio | ??1∶1 | ??1∶2 | ??1∶4 | ??1∶5 | ??1∶6 | ??1∶7 | ??1∶8 | ??1∶10 |
The SVI value, % | ??73.0 | ??73.2 | ??73.9 | ??74.7 | ??77.2 | ??73.5 | ??72.4 | ??71.2 |
Dehydration rate, % | ??72.8 | ??74.1 | ??74.4 | ??74.9 | ??76.2 | ??74.5 | ??73.9 | ??73.2 |
Transmittance, % | ??74.0 | ??83.5 | ??80.8 | ??84.9 | ??92.7 | ??83.0 | ??86.9 | ??89.7 |
Experimental phenomena | Supernatant liquor is more turbid, and the wadding piece is less | Supernatant liquor is more clear, and the wadding piece is bigger | Supernatant liquor is more clear, and the wadding piece is bigger | Supernatant liquor is more clear, and the wadding piece is bigger | Supernatant liquor is limpid, and the wadding piece is big | Supernatant liquor is limpid, and the wadding piece is bigger | Supernatant liquor is limpid, and the wadding piece is medium | Supernatant liquor is more clear, and the wadding piece is medium |
As can be seen from the above table, composite than (chitosan: alkali aluminium) 1: 6 o'clock best results.
PH is to the influence of flocculating effect
The pH value is to the experimental result that influences of flocculating effect
??PH | ??4 | ??6 | ??7 | ??8 | ??10 |
The SVI value, % | ??76.8 | ??74.5 | ??76.2 | ??75.4 | ??76.1 |
Transmittance, % | ??58.0 | ??88.8 | ??86.8 | ??62.8 | ??60.2 |
Dehydration rate, % | ??77.3 | ??75.7 | ??76.2 | ??75.4 | ??77.2 |
Experimental phenomena | Supernatant liquor is muddy, and the wadding piece is medium | Supernatant liquor is more clear, and the wadding piece is bigger | Supernatant liquor is more clear, and the wadding piece is bigger | Supernatant liquor is muddy, and the wadding piece is bigger | The supernatant liquor muddiness, the wadding piece is bigger |
The treatment effect of composite flocculation agent was better when on the whole, pH was near 6~7 scope
In sum, the optimum compound proportion example of chitosan and alkali aluminium is 1: 6, and promptly the dosage of chitosan is that 1.67mg/L, alkali aluminium dosage are 10mg/L; Best pH scope is 6~7, and the pH scope of waste water is close therewith, therefore need not adjust pH significantly when pre-treatment
Main body biochemical treatment explanation
Ozone oxidation+biochemical process is handled and is contained frostproofer waste water, to chemical oxygen demand COD
CrProcess range between 500~5000mg/L.Studies show that this technology has removal effect preferably to the organic contamination of this scope.In research process, we are at a certain concrete chemical oxygen demand COD of determining
CrValue has been carried out condition experiment research.Main ozone oxidation effect condition test and the microorganism digestion effect condition test of dividing.
At ozone oxidation test, we mainly study ozone amount and organic pollutant ratio, and ozone and organic pollutant duration of contact, pH value three factors are to the work moon of oxidation effectiveness, by studies show that: O
3/ COD
CrValue is 0.5~3.0, HRT=3~15hr, and PH:3~10 all increase to wastewater biochemical; BOD
5/ COD
CrValue can be brought up between 0.2~0.35 from<0.1.
By microorganism digestion Degradation, adopt the obligate aerobic bacteria that organic loading is handled reduction.Successfully isolated obligate SP-II series dominant bacteria in the laboratory, mainly waited and control treatment effect by change sludge loading, hydraulic detention time, PH concentration, studies show that: sludge concentration is at 2000~5000mg/L; HRT:3~15hr; PH:6~9; During T:25~32 ℃, organic contamination index COD
CrClearance from 50% to 98% do not wait.
The optimal pH scope of the obligate bacterium of adopting is 6~9 in this technology, and pH is transferred to 7.6~7.9, and temperature is 27 ℃, under the situation that changes the ozone dosage, and the measured BOD of different hydraulic detention time (HRT)
5/ COD
CrValue as follows:
(1) works as O
3/ COD
Cr=0.5 o'clock,
??HRT(hr) | ??3 | ??6 | ??9 | ??12 | ??15 |
??BOD 5/COD cr | ??0.105 | ??0.150 | ??0.191 | ??0.199 | ??0.223 |
(2) work as O
3/ COD
Cr=0.8 o'clock,
??HRT(hr) | ??3 | ??6 | ??9 | ??12 | ??15 |
??BOD 5/COD cr | ??0.147 | ??0.161 | ??0.198 | ??0.316 | ??0.320 |
(3) work as O
3/ COD
Cr=1 o'clock,
??HRT(hr) | ??3 | ??6 | ??9 | ??12 | ??15 |
??BOD 5/COD cr | ??0.151 | ??0.177 | ??0.223 | ??0.352 | ??0.312 |
(4) work as O
3/ COD
Cr=1.3 o'clock,
??HRT(hr) | ??3 | ??6 | ??9 | ??12 | ??15 |
??BOD 5/COD cr | ??0.148 | ??0.156 | ??0.184 | ??0.253 | ??0.241 |
(5) work as O
3/ COD
Cr=1.7 o'clock,
??HRT(hr) | ??3 | ??6 | ??9 | ??12 | ??15 |
??BOD 5/COD cr | ??0.137 | ??0.150 | ??0.164 | ??0.197 | ??0.173 |
(6) work as O
3/ COD
Cr=2.5 o'clock,
??HRT(hr) | ??3 | ??6 | ??9 | ??12 | ??15 |
??BOD 5/COD cr | ??0.128 | ??0.145 | ??0.158 | ??0.182 | ??0.162 |
(7) work as O
3/ COD
Cr=3.0 o'clock,
??HRT(hr) | ??3 | ??6 | ??9 | ??12 | ??15 |
??BOD 5/COD cr | ??0.121 | ??0.137 | ??0.146 | ??0.169 | ??0.151 |
When sludge concentration changes in 2000~5000mg/L scope (the pH scope is 6~9, and pH is transferred to 7.6~7.9, and temperature is 27 ℃, HRT:=12hr), and to BOD
5With COD
CrClearance (%) situation such as following table:
Sludge concentration (mg/L) | ??2000 | ??3000 | ??4000 | ??5000 |
??BOD 5Clearance (%) | ??51.2 | ??68.8 | ??83.2 | ??97.0 |
??COD crClearance (%) | ??53.4 | ??71.2 | ??85.6 | ??98.3 |
This technology biological treatment effect experimental result is as follows:
Time (hr) | Entry glycol concentration mg/L | Water outlet glycol concentration mg/L | Ethylene glycol clearance % |
??3 | ??2747.30±9.31 | ??2214.59±9.85 | ??19.39 |
??6 | ??2747.30±9.31 | ??1193.97±6.58 | ??56.54 |
??9 | ??2747.30±9.31 | ??544.51±6.58 | ??80.18 |
??12 | ??2747.30±9.31 | ??29.95±3.61 | ??98.91 |
In sum, this technology condition that the optimum handling effect that contains ethylene glycol waste water is controlled is:
HRT:12hr; PH:7.6~7.9; T:27 ℃; O
3/ COD
Cr=1; Pressure is normal pressure.
Technical specification
The cultivation of obligate microorganism dominant bacteria:
1, material:
☆ SP-II series dominant bacteria organized enzyme: the biological institute in Chinese Academy of Sciences Chengdu product
☆ helicase: the biochemical institute in Chinese Academy of Sciences Shanghai product
☆ advantage obligate bacterial classification: the bacterial classification of taming, screen, isolate 5 kinds of degraded ethylene glycol in Southwest Oil branch office of the CNPC Chongqing natural gas conditioning head factory Sewage Plant active sludge
Inorganic salt solution: KCl, 0.3g/l; MgSO
47H
2O, 0.5g/l; NaCl, 0.2g/l; MnSO
4H
2O, trace; FeCl
2, 10%, 1; NH
4NO
3, 1.0g/l
☆ enrichment medium: beef extract 5g, peptone 9.5g, sodium-chlor 5.1g, agar 13g, water 1.75L, pH:7.6~7.9
2, required cultivation facility:
SEB-I aseptic technique platform; Opticmicroscope; The DH3600 electro-heating standing-temperature cultivator; The YX-280B steam sterilizer; HZQ-B airbath vibrator (shaking table); 721-A type spectrophotometer; 72HG-2 type constant temperature blender with magnetic force; Self-control super low noise air compressor machine; SJC type ultraviolet germicidal lamp; LGR-10-4.2 type refrigerated centrifuge
3, cultural method:
Carry out the uviolizing breeding with best a kind of of degradation effect in 5 kinds of degraded ethylene glycol bacteriums as starting strain, obtain mutant strain SP-II (1);
With best a kind of as starting strain of degradation effect in 5 kinds of degraded ethylene glycol bacteriums, protoplastis merges to make its and humic spore-A fungi carry out transboundary, the fusant SP-II (2) of the ethylene glycol effect highly significant that obtains to degrade.
Introduce a fine variety above gained SP-II series bacterium respectively with enrichment medium, mutant strain and fusant are cultivated behind the 24h stand-by in shaking table.
In the inorganic salt nutrient solution, add sodium alginate and be made into 500 milliliters of 0.5% solution, after high pressure (1.5MPa) sterilization, it is 0.5g/ml (the 0.5g wet thallus is suspended from the 1ml aseptic deionized water) bacteria suspension 500ml and a little gelatin that adding becomes concentration through the 36h enrichment culture, dropwise splashes into the CaCl that concentration is 0.05mol/L
2In the sterile solution, leave standstill 10h, gained white micelle promptly forms the calcium alginate gel of SP-II series, median size 2~2.5mm, density 3.19g/cm
3
The mensuration of ☆ chemical oxygen demand (COD): potassium dichromate process (GB/T11914)
The mensuration of ☆ five-day BOD: dilution and inoculation method (GB/T7488)
Nine, the final treatment effect that contains frostproofer waste water
By research to control condition, can find the suitableeest controlling factor, make the treat effluent index reach GB8978-1996 fully and combine row's primary standard, thoroughly solve the water pollution problem that brings by frostproofer (being mainly ethylene glycol), the following index of major control of specifically originating:
Water-quality guideline | Controlled variable |
??COD cr | ??≤100mg/L |
??BOD 5 | ??≤20mg/L |
??SS | ??≤50mg/L |
??pH | ??6~9 |
Petroleum-type | ??≤10mg/L |
Claims (2)
1, ozone+biochemical process is handled and is contained Sweet natural gas frostproofer waster water process, it is characterized in that this technology is made of pre-treatment, ozone oxidation and microorganism three phases, and concrete steps are:
One, water-and-oil separator is removed the oily substance in the waste water;
Two, the coagulation that flocculates is removed the suspended substance in the waste water; Requiring the ph value is 6~9,20~35 ℃ of temperature;
Three, the waste water that will carry out above-mentioned two procedures is introduced oxidizing tower, improves the biodegradability of waste water by ozone oxidation;
Four, through the sampling of wastewater of ozone Oxidation Treatment, monitor the composite water quality situation of water sample, determine the dosage of ozone;
Five, inject obligate microorganism dominant bacteria, carry out the one-level aerobic oxidation and handle, regulate gas-water ratio and oxidation and control the biochemical treatment effect duration of contact.
Six, inject obligate microorganism dominant bacteria, carry out the processing of secondary aerobic oxidation waste water is carried out further biochemical treatment;
Seven, the waste water of handling through the secondary aerobic oxidation enters the settling tank precipitation, and supernatant liquor is discharged, and the mud pump around circuit is to biochemical unit.
Eight, the mud of post precipitation is refluxed respectively carry out one-level aerobic oxidation and secondary aerobic oxidation once more respectively and handle.
Before the oily water separation and before the one-level aerobic oxidation, all utilize COD on-line monitoring view to carry out online detection, regulate gas-water ratio, ph value and oxidation duration of contact according to the water body situation, guarantee effluent quality;
2, ozone according to claim 1+biochemical process is handled and is contained Sweet natural gas frostproofer waster water process, it is characterized in that flocculation agent adopts the organic polymer coargulator chitosan of non-toxic degradable and inorganic flocculating agent alkali aluminium as flocculation agent, the ratio of the two weight is 1: 6.The dosage of chitosan is 1.67 mg/litre, and alkali aluminium is 10 mg/litre, and ph value scope is 6~7.
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Cited By (1)
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CN101357811B (en) * | 2007-08-03 | 2011-06-15 | 中芯国际集成电路制造(上海)有限公司 | Organic waste water recovery and utilization apparatus |
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2004
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101357811B (en) * | 2007-08-03 | 2011-06-15 | 中芯国际集成电路制造(上海)有限公司 | Organic waste water recovery and utilization apparatus |
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