CN103058465A - Technique for effectively treating trihydroxy methyl propane waste water - Google Patents
Technique for effectively treating trihydroxy methyl propane waste water Download PDFInfo
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Abstract
The invention discloses a technique for effectively treating trihydroxy methyl propane waste water and belongs to the technical field of sewage treatment. The technique orderly adopts an iron carbon micro-electrolytic cell, a Fenton oxidation pond and an MSBR (Modified Sequencing Batch Reactor) reaction tank connected in series for sewage treatment. By creatively combining three mature techniques, the technique is adaptive to the impact of the waste water discharged by a factory, realizes good treatment effect, increases biodegradability of the original waste water, realizes stability in performance, has a wide raw material source (such as waste iron and the like), cause little mud residue, is simple to operate and saves labor and materials.
Description
Technical field
The present invention relates to a kind of processing method of effective processing trihydroxy methyl propane waste water; This technological operation is simple, stable performance, and the continous-stable that can be used for waste water through the system after adjusting is processed, and more particularly contains the waste water than difficult for biological degradation, is a kind of effective processing mode, belongs to technical field of sewage.
Background technology
Trihydroxy methyl propane (Trimethylolpropane, be called for short TMP), chemical name is 2-ethyl-2-methylol-1, ammediol, have another name called trihydroxymethyl propane, 2,2-dihydroxymethyl butanols is a kind of broad-spectrum Organic Chemicals and Chemicals, not only can be used for the manufacturing fields such as Synolac, urethane, unsaturated polyester, vibrin, coating, aircraft oil, printing-ink, also can be used as the thermo-stabilizer of textile auxiliary agent and polyvinyl chloride (PVC) RESINS etc.Because the range of needs of trihydroxy methyl propane is wide, its global annual output is about 120,000 tons, and China is annual 500 tons, and annual production is also increasing year by year.The year by year increase of trihydroxy methyl propane output, the subject matter of thereupon bringing is exactly the increase of unmanageable trihydroxy methyl propane wastewater flow rate, this waste strength is high, biodegradability is poor, smell is large, add and used formaldehyde in the production technique, make in the waste water of generation and carried a large amount of formaldehyde secretly, intractability is increased greatly, can on the far-reaching and expendable impact of water body environment formation, finally affect human Sustainable development and be the mankind's development and stable the hiding some dangers for of ecology in the long-time situation.
In view of, present trihydroxy methyl propane waste water treatment process complicated (catalytic wet oxidation, catalytic ozonation etc.), processing cost is high, treatment effect is undesirable, can not satisfy day by day water emission standard and the enterprise of improving and pursue the maximized requirement of interests, so for the characteristics of this type of waste water, through selection and the design and operation of science, the treatment process of maturation of series connection has been proposed, such as iron-carbon micro-electrolysis, Fenton oxidation, MSBR etc.Down each technique is simply introduced.
Iron-carbon micro-electrolysis technique, principle is: because the difference in Electrode Potential that exists between iron and the carbon, when iron filings and carbon granules are immersed in the acid waste water, just can form numerous small iron carbon galvanic cell in the waste water.And these small galvanic cells are take the low iron of current potential as anode, and the carbon that current potential is high is negative electrode, in being the acid aqueous solution electrochemical reaction occur.The result of this reaction is that iron is corroded the iron ion that becomes divalence and enters solution, simultaneously because iron ion has coagulation, can with pollutent in inhale mutually with the particulate of faint negative charge, and then form more stable throw out (also being iron mud) and be removed.Reaction process is as follows:
Anode (Fe): Fe-2e → Fe
2+
Negative electrode (C): 2H
++ 2e → 2[H] → H
2
In the situation that aeration is arranged, can prevent that not only iron filings from hardening, and can generate the larger Fe of the polymerization degree (OH)
3The colloid flocculation agent has strengthened the decontamination effect improving to waste water.Recent years, the iron-carbon micro-electrolysis technological development is rapid, now has been used for the trade effluent such as printing and dyeing, plating and contains in the middle of the processing engineering of arsenic, fluoride waste, and received good economic benefit and environment protecting.Iron-carbon micro-electrolysis technique is not limited by raw material, can reach the treatment of wastes with processes of wastes against one another, and working cost is low, and coloured waste water is had good decolorizing effect, therefore has a good application prospect in China.
Fenton oxidation is the reaction with chemist Fenton name, namely with ferrous ion (Fe
2+) be catalyzer, with hydrogen peroxide (H
2O
2) carry out a kind of reaction of chemical oxidation, and the system that forms with ferrous ion and hydrogen peroxide is called Fenton reagent.Its principal reaction that relates to is as follows:
Fe
2++H
2O
2→Fe
3++OH
-+gHO
Fe
3++H
2O
2+OH
-→Fe
2++H
2O+gHO
Fe
3++H
2O
2→Fe
2++H
++gHO
2
gHO
2+H
2O
2→H
2O+O
2↑+gHO
By above-mentioned reaction as can be known, generated the hydroxyl radical free radical (OH) that oxidation capacity (2.8V) is only second to fluorine in the reaction process, and hydroxyl radical free radical there are higher electronegativity or Electron Affinities (569.3kJ), can the most organism of oxidation.Therefore, Fenton process is specially adapted in the waste water that contains hardly degraded organic substance or biological treatment is had the trade effluent of side effect, as to the processing of the organic wastewaters such as nitrobenzene-containing, ABS and to the deodorizing of some special water, decolouring etc.
MSBR, i.e. Improvement type order batch reaction device, be the people such as C.Q.Yang on the basis of original sbr reactor device, combine the characteristics of traditional activated sludge process, a kind of more preferably Sewage treatment systems of researching and developing.The characteristics of MSBR are that cutout can move continuously with steady flow in the water-filled situation of reactor, and save preliminary sedimentation tank and second pond, and then save more pipeline, valve etc. between need not.Situation by the Sewage Plant of going into operation as seen, MSBR is a kind of economical and effective, the reliable and sewage treatment process that easily is automated control, and to BOD
5, TSS and phosphorus has preferably treatment effect.
Constantly strengthen and advocate today of environmental protection, Sustainable development in the public's environmental consciousness, reinforcement is constantly put on agenda to the improvement of the waste water of one of three wastes.Sharp increase along with population in the world, water resources has become the important factor of restriction human development, the processing of waste water and recycling are subject to human attention gradually, reinforcement is to the management of waste water, this just has higher requirement to the sewage work of factory, therefore designs cost-effective treatment system, and the negative impact that waste water is brought weakens even disappears, and be related to the interests of enterprise, especially to environment and our are human is responsible for.
Summary of the invention
The purpose of this invention is to provide a kind of technique that is applied to process trihydroxy methyl propane waste water, wherein technological effect characterizes with CODcr and formaldehyde clearance.The characteristics of this technology utilization each processing unit are processed trihydroxy methyl propane waste water and formaldehyde wherein, improve the processing efficiency of waste water.
The treatment process of trihydroxy methyl propane waste water of the present invention is by being realized such as following technical scheme:
(1) used process system comprises successively the following equipment of series connection: equalizing tank A(1) with iron-carbon micro-electrolysis pond (2) equalizing tank B(6), Fenton oxidation pond (8), equalizing tank C(10) and MSBR reaction tank, equipment is all available from the environmental protection equipment factory of specialty, reliable with safeguards system; (10 ~ 20L), ((10 ~ 15L), the treating processes flow rate control is at 3 ~ 6L/h for 10 ~ 20L), MSBR reaction tank volume for the Fenton oxidation pool volume for the iron-carbon micro-electrolysis pool volume.
(2) treatment process: at first former water enters equalizing tank A(1 after reclaiming), make water temperature reduce (generally lowering 3 ~ 8 ℃) at equalizing tank A (1) Central Plains water through open-air the processing, reduce the impact on follow-up each unit; The waste water that flows out from equalizing tank A (1) enters iron-carbon micro-electrolysis pond (2), raw material Controlling System A (3) by the conditioned reaction pond regulates: iron filings consumption 1 ~ 1.5g/L, iron carbon mol ratio are 1.5 ~ 3.0, the pH of reaction tank be 3.5 ~ 4.5 and aeration rate be 0.5 ~ 3L/min etc., flocculation iron mud effluxes part (4) in the treating processes, and iron-carbon micro-electrolysis pond 2 water outlet CODcr and concentration of formaldehyde are reduced; Iron-carbon micro-electrolysis pond (2) water outlet enters equalizing tank B(6), again with the iron mud part reuse (5) of iron-carbon micro-electrolysis pond (2) to equalizing tank B(6) (sludge quantity of preferred reuse be the iron-carbon micro-electrolysis pond total mass that produces iron mud 20% ~ 60%), and adjusting equalizing tank B(6) gets pH=6.0 ~ 9.0, at this equalizing tank B(6) in the part iron ion further form flocculation sediment (7), equalizing tank B(6) water outlet enters in the Fenton oxidation pond (8) after further reducing CODcr and concentration of formaldehyde, the waste water in Fenton oxidation pond (8) is through raw material Controlling System B(9) regulate: hydrogen peroxide dosage (4 ‰ ~ 6 ‰, be that every liter of waste water adds 4 ~ 6mL30% hydrogen peroxide solution), hydrogen peroxide ferrous ion mol ratio is 5:1 ~ 7:1 and pH(3 ~ 4), CODcr and the concentration of formaldehyde of Fenton oxidation pond (8) water outlet are further reduced; Fenton oxidation pond (8) water outlet enters equalizing tank C(10), the iron mud part reuse (5) in iron-carbon micro-electrolysis pond (2) is to equalizing tank C(10) in (sludge quantity of preferred reuse be the iron-carbon micro-electrolysis pond total mass that produces iron mud 20% ~ 60%) and equalizing tank C(10) pH6 ~ 9, at this equalizing tank C(10) further form flocculation sediment (11), reduce simultaneously CODcr and concentration of formaldehyde; Equalizing tank C(10) water outlet enters MSBR reaction tank (12), the active sludge of active sludge for cultivating through long-time domestication in the MSBR reaction tank (12), in MSBR reaction tank (12) take waste water as sole carbon source, the pH that regulates waste water by raw material Controlling System C (13) is 6 ~ 7, hydraulic detention time 6 ~ 8h, make active sludge to the processing of target compound (CODcr, formaldehyde), with this understanding ideal treatment effect and stable.
The water outlet of MSBR reaction tank (12) also can enter sterilization pool (15) disinfection again among the present invention.
In the above-mentioned steps effect of parameters as: the iron filings consumption is seen Fig. 2 to the impact of trihydroxy methyl propane and formaldehyde removal effect in the iron-carbon micro-electrolysis pond, iron carbon mol ratio is seen Fig. 3 to the impact of trihydroxy methyl propane and formaldehyde removal effect in the iron-carbon micro-electrolysis pond, pH sees Fig. 4 to the impact of trihydroxy methyl propane and formaldehyde removal effect in the iron-carbon micro-electrolysis pond, aeration rate is seen Fig. 5 to the impact of trihydroxy methyl propane and formaldehyde removal effect in the iron-carbon micro-electrolysis pond, the hydrogen peroxide dosage is seen Fig. 6 to the impact of trihydroxy methyl propane and formaldehyde removal effect in the Fenton oxidation pond, hydrogen peroxide ferrous ion mol ratio is seen Fig. 7 to the impact of trihydroxy methyl propane and formaldehyde removal effect in the Fenton oxidation pond, pH sees Fig. 8 to the impact of trihydroxy methyl propane and formaldehyde removal effect in the Fenton oxidation pond, pH sees Fig. 9 to the impact of trihydroxy methyl propane and formaldehyde removal effect among the MSBR, hydraulic detention time is seen Figure 10 to the impact of trihydroxy methyl propane and formaldehyde removal effect among the MSBR, and effluent quality is seen Figure 12 after the process stabilizing operation.
The domestication culturing process of used active sludge comprises as follows in the above-mentioned MSBR reaction tank: the domestication of active sludge is cultivated the waste water that contains trihydroxy methyl propane, formaldehyde except use mud is tamed the cultivation, also used the nutritive mediums such as glucose, trace element to replenish C, N, P source, to guarantee the good growth of mud.Because the gained active sludge is to process equalizing tank C(10) water outlet (the two is more or less the same, can be general) in water outlet or Fenton oxidation pond 8, final active sludge must adapt to equalizing tank C(10) water outlet in water outlet or Fenton oxidation pond 8.
Convert according to the water outlet in Fenton oxidation pond 8, draw 8 water outlets of Fenton oxidation pond or equalizing tank C(10) trihydroxy methyl propane concentration M mg/L and concentration of formaldehyde N mg/L in the water outlet.Because 8 water outlets of Fenton oxidation pond or equalizing tank C(10) trihydroxy methyl propane concentration M mg/L scope is 450 ~ 940mg/L in the water outlet, the scope of concentration of formaldehyde N mg/L is 100 ~ 210mg/L.Therefore, in cultivating the domestication process, total CODcr and increases the concentration of the concentration of trihydroxy methyl propane and formaldehyde until consistent with the water outlet in Fenton oxidation pond 8 gradually in the control nutrient solution about 2000mg/L.
The cultivation domestication concrete steps of mud are as follows:
(1) mud of buying is adopted first the mixed solution of waste water, solution A, solution B and solution C modulation cultivate as nutrient solution (1), wherein the trihydroxy methyl propane concentration is 45mg/L, concentration of formaldehyde 10mg/L in the mixed solution, contain the solution A of 19ml, the solution B of 19ml, the solution C of 19ml in every liter of mixed solution, the residence time 6 ~ 8h, precipitation 1h; And then adopt identical nutrient solution (1) to continue to cultivate: the residence time 6 ~ 8h, precipitation 1h change nutrient solution, so adopt nutrient solution (1) time in one week of Cyclic culture.
(2) cultivate the mud of taming through step (1), adopt the mixed solution of waste water, solution A, solution B and solution C modulation to cultivate as nutrient solution (2), wherein the trihydroxy methyl propane concentration is 90mg/L, concentration of formaldehyde 20mg/L in the mixed solution, contain the solution A of 18ml, the solution B of 18ml, the solution C of 18ml in every liter of mixed solution, the residence time 6 ~ 8h, precipitation 1h; And then adopt identical nutrient solution (1) to continue to cultivate: the residence time 6 ~ 8h, precipitation 1h change nutrient solution, so adopt nutrient solution (2) time in one week of Cyclic culture.
(3) cultivate the mud of taming through step (2), adopt the mixed solution of waste water, solution A, solution B and solution C modulation to cultivate as nutrient solution (3), wherein the trihydroxy methyl propane concentration is 135mg/L, concentration of formaldehyde 30mg/L in the mixed solution, contain the solution A of 17ml, the solution B of 17ml, the solution C of 17ml in every liter of mixed solution, the residence time 6 ~ 8h, precipitation 1h; And then adopt identical nutrient solution (1) to continue to cultivate: the residence time 6 ~ 8h, precipitation 1h change nutrient solution, so adopt nutrient solution (2) time in one week of Cyclic culture.
(4) be cycled to repeat: the mud of cultivating domestication through previous step, adopt the mixed solution of waste water, solution A, solution B and solution C modulation to proceed to cultivate as nutrient solution (m), wherein the trihydroxy methyl propane concentration increases 45mg/L, concentration of formaldehyde increase 10mg/L with respect to trihydroxy methyl propane concentration in the last nutrient solution in the mixed solution, contain solution A, solution B, solution C in every liter of mixed solution and all lack 1ml with respect to the content of solution A, solution B, solution C in every liter of nutrient solution of last Cyclic culture, the residence time is still 6 ~ 8h, precipitation is still 1h; And then adopt identical nutrient solution (m) to continue to cultivate: the residence time is still 6 ~ 8h, precipitation is still 1h and changes nutrient solution; So adopt the time in nutrient solution (m) one week of Cyclic culture.
By that analogy, until the nutrient solution of last circulation is when proceeding to cultivate, wherein the trihydroxy methyl propane concentration increases 1-45mg/L with respect to trihydroxy methyl propane concentration in the last nutrient solution in the mixed solution, concentration of formaldehyde increases 1-10mg/L, contain solution A in every liter of mixed solution, solution B, solution C is all with respect to solution A in every liter of nutrient solution of last Cyclic culture, solution B, the content of solution C all lacks 1ml or 0.5ml or 0.25ml, and trihydroxy methyl propane concentration and concentration of formaldehyde and equalizing tank C(10 in the mixed solution) water outlet or equalizing tank C(10) trihydroxy methyl propane concentration M is the same with concentration of formaldehyde N in the water outlet, and the residence time is still 6 ~ 8h during cultivation, precipitation is still 1h; The same nutrient solution Cyclic culture that adopts last circulation in this Cyclic culture process, is irregularly monitored the state of active sludge, until mud is in stable condition, namely CODcr clearance, formaldehyde clearance reach stable, obtain active sludge.
(5) will adopt again Fenton oxidation pond 8 or equalizing tank C(10 through the mud that step (4) is cultivated) in water outlet cultivate domestication, when CODcr clearance and formaldehyde clearance maintain respectively between 40% ~ 50%, just can directly use.
Tame cultivation stage, namely progressively increase the input ratio of waste water, reduce the additional proportion of solution A, B, C, until last waste water replaces solution A, B, C, become the unique nutrition source of mud.
Wherein: the consisting of of solution A: glucose 103.18g/L;
Solution B forms: K
2HPO
40.7663g/L, KH
2PO
40.9146g/L, (NH
4)
2SO
47.3684g/L;
Solution C forms: MgSO
415g/L, FeSO
40.5g/L, ZnSO
40.5g/L, CaCl
22g/L, MnSO
40.4g/L.
Waste water is pending waste water.Mud is the aerobic sludge that Sewage Plant is bought.
Contain 10mL A, 10mL B and 10mL C in every liter of solution and be equivalent to 1000mg CODcr/L.
Make configuration proportion and the water outlet average removal rate of cultivating each Stage Nutrition liquid of domestication according to above condition, can see table 1.
Table 1 is cultivated configuration proportion and the water outlet average removal rate of each Stage Nutrition liquid of domestication
After trihydroxy methyl propane and concentration of formaldehyde reach respectively 945mg/L, 210mg/L, continue culture sludge until mud reaches stable, namely can replace nutritive medium A, B, C fully by waste water, clearance can maintain respectively between 40% ~ 50% substantially simultaneously, just can directly use.
The CODcr and the method for determining formaldehyde that wherein relate to are as follows:
CODcr adopts little reflux ratio color method, and step is as follows:
A) add the 30mg Mercury bisulfate in the digestion tube;
B) 3mL sulfuric acid-silver sulfate solution (sulfuric acid-silver sulfate solution: the 5g Sulfuric acid disilver salt is dissolved in the 500mL vitriol oil);
C) 1mL potassium bichromate (0.01225g/mL)
D) 2mL water sample, cover lid shakes up, and clears up 2h under 150 ℃;
E) clear up good sample and put to room temperature, under 600nm, survey absorbancy, read the CODcr value according to graticule;
Formaldehyde is removed and is adopted the methyl ethyl diketone spectrophotometry.Comprise the steps:
A) accurately pipette an amount of sample (contain formaldehyde in 80 μ g, volume is no more than 25ml) and in the 25ml color-comparison tube, be diluted with water to scale;
B) in above-mentioned colorimetric cylinder, add respectively 2.50ml methyl ethyl diketone solution, shake up.In (60 ± 2) ℃ water-bath, heat 15min, take out cooling;
C) at wavelength 414nm place, take water as the reference measurement absorbancy, deduct the measured absorbancy of blank test, find formaldehyde amount the sample from standard.
Characteristics of the present invention: elder generation one constant volume (10 ~ 20L) iron-carbon micro-electrolysis pond, a rear constant volume (10 ~ 20L) Fenton oxidation pond, last constant volume (MSBR reaction tank of 10 ~ 15L).The invention provides a kind of technique that can effectively process trihydroxy methyl propane waste water.This process innovation with three the technique of comparative maturity combine, can adapt to the impact that factory discharges waste water, treatment effect is good, improve the biodegradability of raw wastewater, stable performance, raw material wide (such as scrap iron etc.), excess sludge is few, and is simple to operate, uses manpower and material resources sparingly.The more important thing is, unit is can be mutually complementary, (contains Fe such as the water outlet in iron-carbon micro-electrolysis pond
2+) raw material and the treated iron mud waste material that can be used as the Fenton oxidation pond can be back to use equalizing tank 6, equalizing tank 10, and the iron ion of raw material can be used as the nutrition of degradation bacteria in the MSBR reaction tank.In treating processes, except the distinctive principles such as oxidative degradation to organic waste water, also be mingled with organic flocculation sediment removal etc., active sludge in the MSBR reaction tank is through cultivating for a long time simultaneously, can produce stronger Degradation to trihydroxy methyl propane waste water, degradation efficiency is greatly improved, and makes stable water outlet.These characteristics has guaranteed that this technique can be applicable to effective processing of trihydroxy methyl propane waste water, makes water outlet reach three grades or above emission standard, is easy to practical implementation.
Contrast before and after this trihydroxy methyl propane wastewater treatment is such as following table 2.
The variation of waste water quality before and after table 2 is processed
Description of drawings
Fig. 1. the present invention processes the artwork of trihydroxy methyl propane waste water
Reference numeral
1. equalizing tank A 2. iron-carbon micro-electrolysis ponds 3. raw material Controlling System A, 4. iron mud efflux 5. iron mud reuses, 6. equalizing tank B 7. precipitation and efflux 8. Fenton oxidation ponds, 9. raw material Controlling System B, 10. equalizing tank C, 11. precipitations and efflux 12.MSBR reaction tank 13. raw material Controlling System C 14. mud and transport outward 15. sterilization pools
Fig. 2. the iron filings consumption is on the impact of trihydroxy methyl propane and formaldehyde removal effect in the iron-carbon micro-electrolysis pond
Fig. 3. iron carbon mol ratio is on the impact of trihydroxy methyl propane and formaldehyde removal effect in the iron-carbon micro-electrolysis pond
Fig. 4. pH is on the impact of trihydroxy methyl propane and formaldehyde removal effect in the iron-carbon micro-electrolysis pond
Fig. 5. aeration rate is on the impact of trihydroxy methyl propane and formaldehyde removal effect in the iron-carbon micro-electrolysis pond
Fig. 6. the hydrogen peroxide dosage is on the impact of trihydroxy methyl propane and formaldehyde removal effect in the Fenton oxidation pond
Fig. 7. hydrogen peroxide ferrous ion mol ratio is on the impact of trihydroxy methyl propane and formaldehyde removal effect in the Fenton oxidation pond
Fig. 8. pH is on the impact of trihydroxy methyl propane and formaldehyde removal effect in the Fenton oxidation pond
PH is on the impact of trihydroxy methyl propane and formaldehyde removal effect among Fig. 9 .MSBR
Hydraulic detention time is on the impact of trihydroxy methyl propane and formaldehyde removal effect among Figure 10 .MSBR
Figure 11. cultivate the scanning electron microscope (SEM) photograph (a: the first week of domestication different steps microorganism; B: the tenth week; C: the 21 week)
Figure 12. effluent quality after the process stabilizing operation.
Embodiment
Further describe the present invention below by drawings and Examples, but the present invention is not limited to following embodiment.
Used process system comprises successively the following equipment of series connection: equalizing tank A(1) with iron-carbon micro-electrolysis pond (2) equalizing tank B(6), Fenton oxidation pond (8), equalizing tank C(10) and MSBR reaction tank (see figure 1), equipment is all available from the environmental protection equipment factory of specialty, reliable with safeguards system; (10 ~ 20L), ((10 ~ 15L), the treating processes flow rate control is at 3 ~ 6L/h for 10 ~ 20L), MSBR reaction tank volume for the Fenton oxidation pool volume for the iron-carbon micro-electrolysis pool volume.Used activated sludge culture process is seen activated sludge culture process and the table 1 of summary of the invention.
Embodiment 1:
Adopt the trihydroxy methyl propane waste water that contains formaldehyde of this art breading Ji Hua company.
At first the trihydroxy methyl propane waste water of fetching is carried out the analysis of essential property, pH=4.79, COD
Cr=9182.05mg/L, concentration of formaldehyde are 1281.3mg/L, 34 ℃.Former water enters equalizing tank A1, enter iron-carbon micro-electrolysis pond 2 after reducing water temperature (3 ℃), by Controlling System A3, adding iron filings 1.2g/L(iron carbon mol ratio is 2:1), hydro-oxidation sodium is transferred pH=3.75), aeration rates (2L/min) etc. are surveyed iron-carbon micro-electrolysis pond 2 water outlet CODcr after reaction and the formaldehyde clearance reaches respectively 53.61%, 63.83%; 2 water outlets of iron-carbon micro-electrolysis pond enter equalizing tank 6, by hydro-oxidation sodium (ph=8.2) and iron mud reuse 5(45%), make part iron ion flocculation sediment and efflux 7, make that CODcr and formaldehyde clearance (with respect to former water) reach respectively 60.32%, 66.38% in the equalizing tank B6 water outlet; Equalizing tank B6 water outlet enters Fenton oxidation pond 8, through Controlling System B9, regulating the hydrogen peroxide dosage is 5 ‰ (hydrogen peroxide ferrous ion mol ratio 6:1) and sodium hydroxide (pH=3.9), and Fenton oxidation pond 8 water outlet CODcr and formaldehyde clearance (with respect to former water) are reached respectively; 78.68%, 85.17%; Water outlet enters equalizing tank C10, through iron mud reuse 5(45%) and sodium hydroxide adjusting pH(8.0) reduction CODcr and concentration of formaldehyde; Last waste water enters MSBR reaction tank 12, take waste water as sole carbon source, regulates appropriate pH (6.5) and hydraulic detention time (7.5h) by raw material Controlling System 13, makes COD
Cr, the formaldehyde clearance finally reached 94.27%, 95.43%.
Embodiment 2:
Former water enters equalizing tank A1, enter iron-carbon micro-electrolysis pond 2 after reducing water temperature (5 ℃), by Controlling System A3, adding iron filings 1.4g/L(iron carbon mol ratio is 3:1), hydro-oxidation sodium (pH=4.0), aeration rates (1.5L/min) etc. are surveyed iron-carbon micro-electrolysis pond 2 water outlet CODcr after reaction and the formaldehyde clearance reaches respectively 56.16%, 65.23%; 2 water outlets of iron-carbon micro-electrolysis pond enter equalizing tank B6, by hydro-oxidation sodium (ph=7.9) and iron mud reuse 5(30%), make part iron ion flocculation sediment and efflux 7, make that CODcr and formaldehyde clearance (with respect to former water) reach respectively 64.95%, 68.97% in the equalizing tank B6 water outlet; Equalizing tank B6 water outlet enters Fenton oxidation pond 8, through Controlling System 9, regulating the hydrogen peroxide dosage is 5.5 ‰ (hydrogen peroxide ferrous ion mol ratio 6.5:1) and sodium hydroxide (pH=3.4), and Fenton oxidation pond 8 water outlet CODcr and formaldehyde clearance (with respect to former water) are reached respectively; 80.47%, 85.23%; Water outlet enters equalizing tank C10, through iron mud reuse 5(30%) and sodium hydroxide adjusting pH(8.5) reduction CODcr and concentration of formaldehyde; Last waste water enters MSBR reaction tank 12, take waste water as sole carbon source, regulates appropriate pH (7.0) and hydraulic detention time (6h) by raw material Controlling System 13, makes CODcr, formaldehyde clearance finally reach 94.03%, 95.24%.
Claims (6)
1. processing method of effectively processing trihydroxy methyl propane waste water, it is characterized in that, used process system comprises successively the following equipment of series connection: equalizing tank A(1) with iron-carbon micro-electrolysis pond (2) equalizing tank B(6), Fenton oxidation pond (8), equalizing tank C(10) and MSBR reaction tank, iron-carbon micro-electrolysis pool volume 10 ~ 20L, Fenton oxidation pool volume 10 ~ 20L, MSBR reaction tank volume 10 ~ 15L, the treating processes flow rate control is at 3 ~ 6L/h;
Treatment process comprises: at first former water enters equalizing tank A(1 after reclaiming), through open-air the processing water temperature is reduced at equalizing tank A (1) Central Plains water, reduce the impact on follow-up each unit; The waste water that flows out from equalizing tank A (1) enters iron-carbon micro-electrolysis pond (2), raw material Controlling System A (3) by the conditioned reaction pond regulates: iron filings consumption 1 ~ 1.5g/L, iron carbon mol ratio are 1.5 ~ 3.0, the pH of reaction tank be 3.5 ~ 4.5 and aeration rate be 0.5 ~ 3L/min, flocculation iron mud effluxes part (4) in the treating processes, and iron-carbon micro-electrolysis pond 2 water outlet CODcr and concentration of formaldehyde are reduced; Iron-carbon micro-electrolysis pond (2) water outlet enters equalizing tank B(6), again equalizing tank B(6 is arrived in the iron mud part reuse (5) of iron-carbon micro-electrolysis pond (2)), and adjusting equalizing tank B(6) gets pH=6.0 ~ 9.0, at this equalizing tank B(6) in the part iron ion further form flocculation sediment (7), equalizing tank B(6) water outlet enters in the Fenton oxidation pond (8) after further reducing CODcr and concentration of formaldehyde, the waste water in Fenton oxidation pond (8) is through raw material Controlling System B(9) regulate: hydrogen peroxide dosage 4 ‰ ~ 6 ‰ (being that every liter of waste water adds 4 ~ 6mL30% hydrogen peroxide solution), hydrogen peroxide ferrous ion mol ratio is that 5:1 ~ 7:1 and adjusting pH are 3 ~ 4, and CODcr and the concentration of formaldehyde of Fenton oxidation pond (8) water outlet are further reduced; Fenton oxidation pond (8) water outlet enters equalizing tank C(10), the iron mud part reuse (5) in iron-carbon micro-electrolysis pond (2) is to equalizing tank C(10) in and equalizing tank C(10) pH6 ~ 9, at this equalizing tank C(10) further form flocculation sediment (11), reduce simultaneously CODcr and concentration of formaldehyde; Equalizing tank C(10) water outlet enters MSBR reaction tank (12), the active sludge of active sludge for cultivating through long-time domestication in the MSBR reaction tank (12), in MSBR reaction tank (12) take waste water as sole carbon source, the pH that regulates waste water by raw material Controlling System C (13) is 6 ~ 7, hydraulic detention time 6 ~ 8h, makes active sludge to the processing of target compound;
The cultivation domestication of mud comprises that step is as follows:
(1) aerobic sludge is adopted first the mixed solution of waste water, solution A, solution B and solution C modulation cultivate as nutrient solution (1), wherein the trihydroxy methyl propane concentration is 45mg/L, concentration of formaldehyde 10mg/L in the mixed solution, contain the solution A of 19ml, the solution B of 19ml, the solution C of 19ml in every liter of mixed solution, the residence time 6 ~ 8h, precipitation 1h; And then adopt identical nutrient solution (1) to continue to cultivate: the residence time 6 ~ 8h, precipitation 1h change nutrient solution, so adopt nutrient solution (1) time in one week of Cyclic culture;
(2) cultivate the mud of taming through step (1), adopt the mixed solution of waste water, solution A, solution B and solution C modulation to cultivate as nutrient solution (2), wherein the trihydroxy methyl propane concentration is 90mg/L, concentration of formaldehyde 20mg/L in the mixed solution, contain the solution A of 18ml, the solution B of 18ml, the solution C of 18ml in every liter of mixed solution, the residence time 6 ~ 8h, precipitation 1h; And then adopt identical nutrient solution (1) to continue to cultivate: the residence time 6 ~ 8h, precipitation 1h change nutrient solution, so adopt nutrient solution (2) time in one week of Cyclic culture;
(3) cultivate the mud of taming through step (2), adopt the mixed solution of waste water, solution A, solution B and solution C modulation to cultivate as nutrient solution (3), wherein the trihydroxy methyl propane concentration is 135mg/L, concentration of formaldehyde 30mg/L in the mixed solution, contain the solution A of 17ml, the solution B of 17ml, the solution C of 17ml in every liter of mixed solution, the residence time 6 ~ 8h, precipitation 1h; And then adopt identical nutrient solution (1) to continue to cultivate: the residence time 6 ~ 8h, precipitation 1h change nutrient solution, so adopt nutrient solution (2) time in one week of Cyclic culture;
(4) be cycled to repeat: the mud of cultivating domestication through previous step, adopt the mixed solution of waste water, solution A, solution B and solution C modulation to proceed to cultivate as nutrient solution (m), wherein the trihydroxy methyl propane concentration increases 45mg/L, concentration of formaldehyde increase 10mg/L with respect to trihydroxy methyl propane concentration in the last nutrient solution in the mixed solution, contain solution A, solution B, solution C in every liter of mixed solution and all lack 1ml with respect to the content of solution A, solution B, solution C in every liter of nutrient solution of last Cyclic culture, the residence time is still 6 ~ 8h, precipitation is still 1h; And then adopt identical nutrient solution (m) to continue to cultivate: the residence time is still 6 ~ 8h, precipitation is still 1h and changes nutrient solution; So adopt the time in nutrient solution (m) one week of Cyclic culture;
By that analogy, until the nutrient solution of last circulation is when proceeding to cultivate, wherein the trihydroxy methyl propane concentration increases 1-45mg/L with respect to trihydroxy methyl propane concentration in the last nutrient solution in the mixed solution, concentration of formaldehyde increases 1-10mg/L, contain solution A in every liter of mixed solution, solution B, solution C is all with respect to solution A in every liter of nutrient solution of last Cyclic culture, solution B, the content of solution C all lacks 1ml or 0.5ml or 0.25ml, and trihydroxy methyl propane concentration and concentration of formaldehyde and equalizing tank C(10 in the mixed solution) water outlet or equalizing tank C(10) trihydroxy methyl propane concentration M is the same with concentration of formaldehyde N in the water outlet, and the residence time is still 6 ~ 8h during cultivation, precipitation is still 1h; The same nutrient solution Cyclic culture that adopts last circulation in this Cyclic culture process, is irregularly monitored the state of active sludge, until mud is in stable condition, namely CODcr clearance, formaldehyde clearance reach stable;
(5) will advance the mud that step (4) cultivates and adopt Fenton oxidation pond (8) or equalizing tank C(10) in water outlet cultivate domestication, when CODcr clearance and formaldehyde clearance maintain respectively between 40% ~ 50%, just can directly use;
Wherein: the consisting of of solution A: glucose 103.18g/L;
Solution B forms: K
2HPO
40.7663g/L, KH
2PO
40.9146g/L, (NH
4)
2SO
47.3684g/L;
Solution C forms: MgSO
415g/L, FeSO
40.5g/L, ZnSO
40.5g/L, CaCl
22g/L, MnSO
40.4g/L.
2. according to the method for claim 1, it is characterized in that, the waste water that adopts during the culturing sludge domestication is pending waste water.
3. according to the method for claim 1, it is characterized in that, make water temperature reduce by 3 ~ 8 ℃ at equalizing tank A (1) Central Plains water through open-air the processing.
4. according to the method for claim 1, it is characterized in that, the iron mud part reuse (5) of iron-carbon micro-electrolysis pond (2) is to equalizing tank B(6) amount be 20% ~ 60% of the iron-carbon micro-electrolysis pond total mass that produces iron mud.
5. according to the method for claim 1, it is characterized in that, the iron mud part reuse (5) of iron-carbon micro-electrolysis pond (2) is to equalizing tank C(10) in amount be 20% ~ 60% of the iron-carbon micro-electrolysis pond total mass that produces mud.
6. according to the method for claim 1, it is characterized in that, further comprising the steps of: the water outlet of MSBR reaction tank (12) enters sterilization pool (15) disinfection again.
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