CN104529057A - Papermaking waste water treatment method - Google Patents
Papermaking waste water treatment method Download PDFInfo
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- CN104529057A CN104529057A CN201410742665.XA CN201410742665A CN104529057A CN 104529057 A CN104529057 A CN 104529057A CN 201410742665 A CN201410742665 A CN 201410742665A CN 104529057 A CN104529057 A CN 104529057A
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- waste water
- treatment method
- hydrogen peroxide
- papermaking
- wastewater treatment
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Abstract
The invention discloses a papermaking waste water treatment method. The papermaking waste water treatment method comprises the following steps of adjusting a pH value of papermaking waste water subjected to two-stage biochemical treatment to 5-7, discharging the waste water subjected to pH adjustment into an oxidation reaction tank, orderly adding 5-15wt% of ferroxidase and 5-20% of hydrogen peroxide into the waste water, carrying out stirring for a reaction lasting for 15-30min, discharging the reacted waste water into a high-density flocculation clarification tank, adjusting pH of the waste water to 6-9 by alkali, adding 0.1-0.5wt% of polyacrylamide into the waste water, carrying out coagulation deposition for a certain time, and discharging the waste water subjected to coagulation deposition and satisfying discharge standards or filtering and recycling the deposition supernatant according to demands. The papermaking waste water treatment method has the advantages of fast starting rate, mild reaction condition, simple equipment, less energy consumption, low operation cost, high COD and chroma clearance, high oxidizability, stable and reliable stabilization process, simple operation, easy dehydration of sludge, and considerable economic benefits.
Description
Technical field
The invention belongs to field of waste water treatment, specifically a kind of pulping wastewater treatment method.
Background technology
Papermaking is the important industry of national economy, for society provides a large amount of products, tax revenue and job opportunity; But be also pollute one of the most serious industry simultaneously, the waste water that it produces belongs to high chroma, high alkalinity, high organic pollutant, highly difficult trade effluent that bio-degradable is low, containing organism and derivative, polymkeric substance, halides such as multiple alkane, hydrocarbon, phenol, acid, benzene, alcohol, aldehyde, ketone, ether, anthracene, quinone, sugar, amine, Mierocrystalline cellulose, hemicellulose and xylogen in sewage.Papermaking enterprise has generally all carried out secondary biochemical treatment to its waste water, but the COD of its water outlet is generally at more than 150mg/L, and the extension rate of colourity is greater than 64 times, cannot meet new national standard therefore must at the laggard row relax of existing secondary biochemical treatment.
The papermaking sewage treating process occurred for new standard at present generally adopts physico-chemical process, as: materialization flocculation sediment+filtration method, the method technique is simple, one-time investment is less, can remove part pollutent, but the xylogen in biochemical rear wastewater treatment pollutent is water miscible, after clearance acquires a certain degree, be difficult to improve again, along with emission standard improves constantly, be difficult to reach requirement; Flocculation sediment+sand filtration+ozone oxidation+active carbon adsorption, this processing contaminants clearance is high, can qualified discharge, but long flow path, equipment are complicated, one-time investment is large, the saturated rear inefficacy of charcoal absorption, working cost is high, is generally difficult to economically accept; Electrolytic process, the method technique is simple, and processing speed is fast, but energy consumption is too high, and economy is poor; UF+RO embrane method is very good to reduction suspended substance, desalting effect, but one-time investment and working cost are all very high.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of pulping wastewater treatment method applying iron oxygenase high-level oxidation technology is provided, the method have reaction start fast, reaction conditions is gentle, equipment is simple, energy consumption little saving working cost, COD and chroma removal rate is high, oxidisability is strong, operational process is reliable and stable, operation also very easy, mud easily dewater and the advantage such as economic benefits.
To achieve these goals, the present invention is achieved by the following technical solutions:
A kind of pulping wastewater treatment method, comprises the following steps:
(1) by the paper waste after secondary biochemical treatment, with acid for adjusting pH value to 5 ~ 7;
(2) will the waste water of pH value be adjusted to enter oxidizing reaction pond, added concentration expressed in percentage by weight 5 ~ 15% iron oxygenase and 5 ~ 20% hydrogen peroxide successively, stirring reaction 15 ~ 30min;
(3) reacted waste water is entered high-density flocculation clarification tank, with alkali adjust ph to 6 ~ 9, and add the polyacrylamide of concentration expressed in percentage by weight 0.1 ~ 0.5%, coagulating sedimentation for some time;
(4) waste water qualified discharge or supernatant liquid filtering reuse will be precipitated as required after precipitation clarification after coagulation;
The mol ratio of described iron oxygenase, hydrogen peroxide and polyacrylamide add-on is 5 ~ 10: 1: 0.05, and the dosage of described hydrogen peroxide is 1/5 ~ 1/10 of COD removal amount.
The above acid comprises hydrochloric acid and carbonic acid.
The above alkali comprises sodium hydroxide and lime.Wherein lime comprises unslaked lime, milk of lime etc.
Paper waste after the above secondary biochemical treatment, for the papermaking midcourse wastewater after secondary biochemical treatment, the boiling slurry of papermaking midcourse wastewater mainly after black liquid extraction is at pulp washing, screening, bleaching and the waste water discharged in pulling an oar, also comprise the black liquor of small part spill and leakage owing to dealing with improperly, the principal pollutant of papermaking midcourse wastewater are the chlorophenols produced in xylogen and bleaching process, their structure is very stable, there is chromophoric group, be difficult to biochemical degradation, second-stage treatment technology is difficult to remove, its index is influent COD 90 ~ 300mg/L, BOD5 60 ~ 180mg/L, SS 30 ~ 200mg/L.
Process characteristic of the present invention is: application iron oxygenase high-level oxidation technology+flocculation sediment technology, processes paper waste.Iron oxygenase high-level oxidation technology is the chemical reaction utilizing pollutent in the effective degrading waste water of active extremely strong hydroxyl free radical (HO).Iron oxygenase high-level oxidation technology is according to lignin molecule katalysis by native catalase (Extracellular laccase as whiterot fungi secretion) under hydrogen peroxide existent condition, can react with lignin molecule or polysaccharide generation dehydrogenative condensation, thus generate the characteristic of macromole lignin polymers, iron oxygenase is used to replace natural enzyme, control suitable reaction conditions, by difficult degradation remaining in the paper waste of secondary biochemical treatment, the small molecules xylogen condensation of good water solubility generates water-soluble poor macromolecular substance, removed from waste water by solid-liquid separation method again.
The iron oxygenase that the present invention uses is a metalloid ion chelate complex, it can have the function of the native catalase being similar to occurring in nature under hydrogen peroxide existent condition, some the leading role key elements can simulating natural enzyme as active sites, hydrophobic microenvironment, with this interaction of multiple covalent linkage of substrate and synergistic effect etc.
Iron oxygenase of the present invention derive from iron compound produce with particular agent in water react after generate, its kind is as Polyferric Sulfate compound.Described particular agent is a class catalyzer, and iron compound is water-soluble and can not the iron compound of polluted water.
Reaction mechanism of the present invention is:
1. iron oxygenase hydrogen peroxide converting be HO free radical, HO free radical reacts with the lignin derivative existed with ROH (acid of xylogen fragment, lignin, tannin, polyphenol etc.) form and generates RO free radical, by the radical transfer reaction between lignin, condensation forms the polymkeric substance ROR with stable diether linkage structure, make the increase of lignin molecule amount, water-soluble reduction, then by solid-liquid separation process implementation water body purification, the object removing wastewater organic pollutant and reduce colourity is reached.
2. iron oxygenase reagent is the native catalase that a kind of chelate of metal ion function class is similar to occurring in nature, under mildly acidic conditions, iron oxygenase catalysis H2O2 generates the high hydroxyl free radical of oxidisability, and cause radical chain reaction further, larger molecular organics in water body is degraded to small organic molecule or makes its permineralization be CO2 and H2O, reaction formula is as follows:
Iron oxygenase+H
2o
2→ Fe
3++ OH
-+ HO (1)
RH+HO·→R·+H
2O (2)
R+Fe
3+→ product (chemical reaction product R class)+Fe
2+(3)
Fe
2++HO·→Fe
3++OH
- (4)
Fe
3++H
2O
2→Fe
2++H
++HOO· (5)
Compared with prior art, the invention has the beneficial effects as follows:
1. the iron oxygenase that the present invention adopts is a metalloid ion chelate complex, has the catalysis characteristics of natural enzyme, simultaneously by have Stability Analysis of Structures, reaction conditions loosely, the not advantage that do not possess of easy in inactivation, the natural enzyme such as cheap.
2. speed of response is fast, and reaction conditions is gentle.Reaction conditions of the present invention requires wider than Fenton oxidation technology, only under mild acid conditions, can need react in pH value 5 ~ 7; Most organism oxidation rate constant in the process can reach 106 ~ 109L/ (mol.s).
3. can bring out chain reaction, the electron affinity due to OH is 569.3kJ, the H atom in stable hydrocarbon can be pulled out, forms organic autoxidation, thus organism is degraded, and this is that all kinds of oxygenant can not be accomplished when being used alone.
4.COD and chroma removal rate high, COD clearance is up to more than 65%-85%, and colourity extension rate can be down to less than 30 times.
5. oxidisability is strong, and higher oxidizing potential makes OH almost by all oxidation operations until mineralising, can not produce secondary pollution; And oxygenant participate in reacted residuum can disintegrate, do not stay remnants, be also good flocculation agent simultaneously.
6. equipment is simple, the little saving working cost of energy consumption.
7. operational process is reliable and stable, and does not need special maintenance, operates also very easy, as long as grasp injected volume and treatment cycle.
8. the mud produced after flocculation easily dewaters, waste water after treatment, and every cube of water can produce 0.1 ~ 0.25kg mud, and this mud is easy to dehydration, and the water yield hour can enter original sludge treating system.
9. economic benefits, if Treated sewage reusing can be saved a large amount of clear water resources, brings certain profit simultaneously.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of pulping wastewater treatment method of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to the scope that embodiment represents.
The present invention is produced per year in the process of 9.8 ten thousand tons of bagasse pulp construction waste waters in so-and-so Paper Co., Ltd of Guangxi and uses.
Embodiment 1:
A kind of pulping wastewater treatment method, comprises the following steps:
(1) by the papermaking midcourse wastewater after secondary biochemical treatment, by carbonic acid adjust ph to 6;
(2) will the waste water of pH value be adjusted to enter oxidizing reaction pond, added concentration expressed in percentage by weight 10% iron oxygenase and 20% hydrogen peroxide successively in reaction tank water inlet, stirring reaction 20min;
(3) reacted waste water is entered high-density flocculation clarification tank, with lime adjust ph to 6 ~ 9, and add the polyacrylamide of concentration expressed in percentage by weight 0.5%, coagulating sedimentation for some time;
(4) waste water qualified discharge or supernatant liquid filtering reuse will be precipitated as required after precipitation clarification after coagulation;
The mol ratio of iron oxygenase, hydrogen peroxide and polyacrylamide add-on is 8: 1: 0.05, and the dosage of hydrogen peroxide is 1/8 of COD removal amount.
Papermaking midcourse wastewater after the secondary biochemical treatment of the present embodiment, its index is COD138mg/L, BOD572mg/L, SS120mg/L, after present method process, COD58mg/L, BOD526mg/L, SS15mg/L.
Embodiment 2:
A kind of pulping wastewater treatment method, comprises the following steps:
(1) by the papermaking midcourse wastewater after secondary biochemical treatment, with salt acid for adjusting pH value to 7;
(2) will the waste water of pH value be adjusted to enter oxidizing reaction pond, added concentration expressed in percentage by weight 10% iron oxygenase and 10% hydrogen peroxide successively in reaction tank water inlet, stirring reaction 30min;
(3) reacted waste water is entered high-density flocculation clarification tank, by sodium hydroxide adjust ph to 9, and add the polyacrylamide of concentration expressed in percentage by weight 0.1%, coagulating sedimentation for some time;
(4) waste water qualified discharge or supernatant liquid filtering reuse will be precipitated as required after precipitation clarification after coagulation;
The mol ratio of iron oxygenase, hydrogen peroxide and polyacrylamide add-on is 10: 1: 0.05, and the dosage of hydrogen peroxide is 1/10 of COD removal amount.
Papermaking midcourse wastewater after the secondary biochemical treatment of the present embodiment, its index is COD220mg/L, BOD590mg/L, SS116mg/L, after present method process, COD60mg/L, BOD530mg/L, SS20mg/L.
Prove proof by experiment, the present invention is not only stable, and good treatment effect can be reached, namely COD is down to about 68.3mg/L by about 213.7mg/L of intaking, meet the emission standard that country is new, and operation medicament expense is 0.405 yuan/m3, and required pharmaceutical quantities is only 1/10 of traditional F enton high-level oxidation technology.By added amount of chemical preresearch estimates, its ton of water running cost only needs 0.405 yuan.And all kinds of index of water outlet all can reach the reuse water quality requirement of paper part workshop section, can save great lot of water resources, has huge environmental benefit, economic benefit and social benefit.Simultaneously this technique also have the reaction times compared with short, floor space is little; Required equipment is simple, and one-time investment is less; Less by extraneous factor influence of fluctuations, be convenient to management, be easy to realize the advantages such as control automatically.
The above is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit technology of the present invention, any those skilled in the art are not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be the content not departing from technical solution of the present invention, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (4)
1. a pulping wastewater treatment method, is characterized in that, comprises the following steps: (1) by the paper waste after secondary biochemical treatment, with acid for adjusting pH value to 5 ~ 7; (2) will the waste water of pH value be adjusted to enter oxidizing reaction pond, added concentration expressed in percentage by weight 5 ~ 15% iron oxygenase and 5 ~ 20% hydrogen peroxide successively, stirring reaction 15 ~ 30min; (3) reacted waste water is entered high-density flocculation clarification tank, with alkali adjust ph to 6 ~ 9, and add the polyacrylamide of concentration expressed in percentage by weight 0.1 ~ 0.5%, coagulating sedimentation for some time; (4) waste water qualified discharge or supernatant liquid filtering reuse will be precipitated as required after precipitation clarification after coagulation; The mol ratio of described iron oxygenase, hydrogen peroxide and polyacrylamide add-on is 5 ~ 10: 1: 0.05, and the dosage of described hydrogen peroxide is 1/5 ~ 1/10 of COD removal amount.
2. pulping wastewater treatment method according to claim 1, is characterized in that: described acid comprises hydrochloric acid and carbonic acid.
3. pulping wastewater treatment method according to claim 1, is characterized in that: described alkali comprises sodium hydroxide and lime.
4. the pulping wastewater treatment method according to any one of claims 1 to 3, it is characterized in that: the paper waste after described secondary biochemical treatment, for the papermaking midcourse wastewater after secondary biochemical treatment, its index is influent COD 90 ~ 300mg/L, BOD5 60 ~ 180mg/L, SS 30 ~ 200mg/L.
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| CN201410742665.XA CN104529057A (en) | 2014-12-09 | 2014-12-09 | Papermaking waste water treatment method |
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|---|---|---|---|
| CN201410742665.XA CN104529057A (en) | 2014-12-09 | 2014-12-09 | Papermaking waste water treatment method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362462A (en) * | 2020-03-26 | 2020-07-03 | 四川恒泰环境技术有限责任公司 | Advanced treatment method for papermaking wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362462A (en) * | 2020-03-26 | 2020-07-03 | 四川恒泰环境技术有限责任公司 | Advanced treatment method for papermaking wastewater |
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150422 |
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