CN1029114C - Technology for treatment of waste liquid pollution in small paper pulp mill - Google Patents

Technology for treatment of waste liquid pollution in small paper pulp mill Download PDF

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CN1029114C
CN1029114C CN91103952A CN91103952A CN1029114C CN 1029114 C CN1029114 C CN 1029114C CN 91103952 A CN91103952 A CN 91103952A CN 91103952 A CN91103952 A CN 91103952A CN 1029114 C CN1029114 C CN 1029114C
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treatment
black liquor
waste liquid
active sludge
waste
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CN1058202A (en
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谷萸英
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YUNNAN POLYTECHNIC COLLEGE
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YUNNAN POLYTECHNIC COLLEGE
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Abstract

The present invention relates to a novel process for treating waste liquid pollution in a small paper pulp mill, which belongs to the technical field of water quality environment protection. A reliable and perfect process flow is formed in the present invention, and the process flow and equipment are simple. When used for treating the waste liquid, the present invention has the advantages of high efficiency and low energy consumption. Besides the use of a small amount of chlorine liquid, the present invention only adopts waste to be treated to replace chemical reagents, so the present invention has the characteristics of comprehensive treatment and waste treatment by using the waste. The waste liquid after the treatment of the present invention reaches national secondary emission standard. The present invention is suitable for waste liquid pollution treatment in the small paper pulp mill.

Description

Technology for treatment of waste liquid pollution in small paper pulp mill
The present invention relates to a kind of small paper pulp mill waste liquor contamination treatment process, belong to water quality environment protection field.
China has 9000 of enterprises in pulp and paper industry now approximately, and the factory that produces per year more than ten thousand tons only has about 160, and little factory just accounts for more than 95%.The organism amount of pulping and paper-making discharging accounts for 1/4th of national industrial discharge organic substance, and wastewater discharge accounts for 1/10th of national discharged volume of industrial waste water, and the waste liquid of pulp mill is extremely serious to the pollution of water quality.
The waste liquid of pulp mill is mainly formed by the black liquor of cooking section and the middle-stage wastewater of bleachery.The black liquor look black, and the foul smelling flavor belongs to the strong basicity high concentrated organic waste liquid, is one of primary pollution source of at present domestic and international water quality.The black liquor of large-scale pulp mill can be handled by alkali reclaiming method, but for numerous little factories, can't balance because of little, siliceous many, the material heat energy of black liquor amount, and alkali recovery process is too complicated, so little factory can't use alkali reclaiming method processing black liquor.And middle-stage wastewater mainly is made up of chloride higher bleaching waste liquor, and its hazardous material mainly is a chlorine, secondly is its compound etc.The pollution problem of black liquor and middle-stage wastewater can not get solving so far.
With the high concentrated organic wastewater that produces in the Anaerobic Digestion pulping and papermaking processes, caused very big concern at home and abroad, and be considered to the most important treatment process of the nineties.But according to relevant, handle the pulping and paper-making high concentrated organic waste liquid both at home and abroad, have following fatal shortcoming with this method:
1, starting is slow, benefit is low;
2, adopt the medium and high temperature fermentation, energy consumption is big;
3, the reliable perfect technical process of none, Digestive system does not reach emission standard.
The method that the purpose of this invention is to provide the comprehensive treating process small paper pulp mill waste liquor contamination of a kind of normal temperature anaerobic digestion and chemical industry method and usefulness, the pollution problem that solves the small paper pulp mill waste liquid.
The present invention is the method that is used for the useless bleaching liquor of the black liquor of comprehensive treating process small paper pulp mill cooking section and bleachery, is made up of active sludge treatment, batching, normal temperature anaerobic digestion, precipitation and coagulation, six processes of chlorination.Existing division is as follows:
1, active sludge treatment: inoculation of activated-sludge in the alkaline straw-pulp waste liquid pool, mix with active sludge after mechanical separation from the black liquor of cooking section, its volume percent is 70～90: 30～10, under the active sludge effect, polysaccharide, (C such as macromolecule organic matter such as Mierocrystalline cellulose in the black liquor 6H 12O 6) XThe class material is degraded to the low molecular compound of Yi Rong, in a large number as acetate, CH 3COOH etc.Owing in easy the to be molten low molecular compound that degraded generates and the free alkali in the black liquor,, be suitable for carrying out the normal temperature anaerobic digestion process so make pH value drop to neutrality.This method has not only been created the suitable pH value condition of normal temperature anaerobic digestion, but also for methane fermentation provides abundant matrix, the main chemical reactions formula is:
Carbohydrate water acetate hydrogen carbon dioxide packing
2, batching
Organic matter in the pulping back liquor, major ingredient are Mierocrystalline cellulose, hemicellulose and lignin, and they mainly provide abundant carbon source.According to the biological basis theoretical investigation, the nutrition in the anaerobic digestion is compared with C: N: P=100: be advisable at 2.5: 0.5, so anaerobic digestion must increase N, P nutrition in the black liquor.
Present method provides N, P nutrition with leather-making mud, vinasse or rotten slag.Its method is to drop into leather-making mud, vinasse, rotten slag in the black liquor after active sludge treatment to replace chemical reagent, increases required N, the P nutrition of anaerobic reaction.The present invention throws in tannery waste and handles back depleted mud in batching, volume ratio is black liquor: mud=3: 1.Or throw in brewery's waste vinasse, volume ratio is black liquor: vinasse=7: 3.Again or throw in rotten slag, volume ratio is black liquor: rotten slag=50～70: 50～30.Owing to contain amounts of protein and fat etc. in leather-making mud, vinasse and the rotten slag, abundant N, P nutrition are arranged, impel anaerobic digestion to carry out well.
3, normal temperature anaerobic digestion
According to the relevant basic theories of biology, and the prior art of environmental pollution and biopurification, present method adopts mixes the anaerobic digestion of reorganization active sludge realization normal temperature.
Mixing the reorganization active sludge is difference inoculation of activated-sludge from the waste liquid pool of tannery, brewery, alkaline straw-pulp factory, from alkaline straw-pulp factory, get concentrated black liquid, active sludge is mixed rapidly with concentrated black liquid, make pH value=6～9, in anaerobic device, carry out 2 ℃～28 ℃ domestications of normal temperature then, vigorous and can light the time when aerogenesis, mix the reorganization active sludge and just can use.
Anaerobic digestion process is: at normal temperatures, to have through the material input behind the blending process in the anaeroic digestor that mixes the reorganization active sludge, start volume ratio and be material: mix reorganization active sludge=70～50 through preparing: 30～50, under the condition of pH value=6～9, carry out anaerobic digestion.When treating that the vigorous digestion gas of aerogenesis can be lighted, start successfully, begin to enter the normal operation stage.Can go out laggardly when reloading earlier, the input and output material volume ratio is controlled at 10% at every turn.This process main chemical reactions formula is:
Carbohydrate water acetate hydrogen carbon dioxide packing
Protein:
Fat, oils:
Through the digestion gas that the normal temperature anaerobic digestion process produces, promptly biogas can be used as after H2S is removed in washing for the incendiary energy, and the sedimentation mud of generation can be made for farming after dehydration, woods fertilizer uses.
4, precipitation
Precipitation process is for to separate Digestive system with sedimentation mud, Digestive system send coagulation process to handle.
5, coagulation
Coagulation process is: chlorine-contained wastewater and waste iron filing reaction from bleachery generate FeCl 3Coagulating agent, will be through the Digestive system and the coagulating agent thorough mixing of post precipitation, coagulation is finished under the alkaline condition of system when depleted milk of lime exists during bleaching liquor, this moment colloid ironic hydroxide absorption fine suspension and the solvability colloid is organic as xylogen and pigment etc. through post precipitation for building materials usefulness.
6, chlorination
Clear liquid after coagulating treatment, transfer to by chocolate filbert, but in filbert Digestive system also residual some deleterious organism, inorganics, pigment and smell, also have certain distance apart from discharging standards.In this clear liquid, add micro-liquid chlorine, chlorine and the water generation hypochlorous acid that reacts, and be dissociated into H thereupon ++ OCI -Hypochlorous acid is strong oxidizer, OCI -+ H +Immediately with Digestive system in residual deleterious organism, inorganics etc. produce a series of redox reaction, reach the purpose of removing dirt, remove crude removal after, filbert liquid just is the water white transparency shape, reaches the relevant emission standard of national regulation.
This process main chemical reactions formula is:
Hypochlorous acid
The present invention compared with prior art mainly possesses following characteristics:
1, formed reliable perfect technical process, and technical process and equipment is simple, are applicable to the comprehensive regulation of small paper pulp mill waste liquor contamination.(as figure)
2, efficient.Waste liquid can reach the relevant emission standard of national regulation after this technology is administered.
3, realize the normal temperature anaerobic digestion, simplified heating installation, energy efficient.
4, low medicine consumption.The entire treatment process is thrown in a small amount of liquid chlorine during except that chlorination, and other all adopts pending waste to replace chemical reagent, has the characteristics of the treatment of wastes with processes of wastes against one another, the comprehensive regulation.
Embodiment:
Embodiment 1:
Waste liquid: Yun Feng paper mill alkaline straw-pulp black liquid
Yun Feng paper mill alkaline straw-pulp black liquid pollution condition
Country allows emission standard
Project Kunming Yun Feng paper plant black liquor
Long-established enterprise of new enterprise
PH value 7 6-8 13
CODcr 300 450 （6-12）X10 4mg/L
BOD5 60 150 （3-4）X10 4mg/L
Main treating processes: active sludge treatment, batching, normal temperature anaerobic digestion, precipitation, coagulation, chlorination.
Batching: Yun Feng paper mill alkaline straw-pulp black liquid, drop into the leather-making mud of 1/3 volume ratio.Kraft cooking bagasse and Herba Poae Sphondylodis, slag: grass=the gained black liquor was used after Wastewater Treated by Activated Sludge Process in 2: 1.
Equipment: 3L anaerobic digestion device.
Condition: PH=7-9; Normal temperature; 14 days residence times; The semi continuous operation mode.
Effect: COD in the Digestive system CrThe rate of removing can reach 89%; Methane content can reach 78% in the digestion gas; Factor of created gase is 3.3L gas/L black liquor d.See following table for details:
Yun Feng paper mill alkaline straw-pulp black liquid normal temperature anaerobic digestion situation:
COD CrTest-results
Item black liquor COD CrDigestive system COD CrCOD CrClearance residence time
Group mg/L mg/L % d
G mean value maximum mean value maximum mean value maximum mean value maximum
62260????67150????10166????6553????84.30????88.58????14????14
The biogas production situation
Item black liquor COD CrDigestive system COD CrEvery day every liter of waste water methane content
Group mg/L clearance % gas production rate L/L.d %
G mean value maximum mean value maximum mean value maximum mean value maximum
62260????67150????84.30????88.58????3.19????3.26????77.74????77.74
Embodiment 2:
Waste liquid: Yun Feng paper mill alkaline straw-pulp black liquid
Main treating processes: active sludge treatment, batching, normal temperature anaerobic digestion, precipitation, coagulation, chlorination.
Batching: with the vinasse mix, the mixed volume ratio is black liquor: vinasse=7～8: 3～2 after the usefulness black liquor active sludge treatment.
Equipment: use the 10L anaerobic digestion device.
Condition: PH=7-9; Normal temperature; 8 days residence times; The semi continuous operation mode.
Effect: CODcr removes rate 70% in the Digestive system; Methane content is 69% in the digestion gas; Factor of created gase is 3.37(L gas/L black liquor d).See following table for details:
COD CrTest-results
Item black liquor COD CrDigestive system COD CrCOD CrClearance residence time
Order mg/L mg/L % d
Group preface mean value maximum mean value maximum mean value maximum
I8d????66526????67150????20295????19308.8????69.35????70.42????8
I10d????65150????65150????21275????21275????68.30????68.30????10
The biogas production situation
Item black liquor COD CrDigestive system COD CrEvery day every liter of waste water methane content
Order mg/L clearance % gas production rate L/Ld %
Group preface mean value maximum mean value maximum mean value maximum mean value maximum
I8d????66526????67150????69.35????70.42????2.64????3.37????68.65????69.3
I10d????65150????65150????68.30????68.30????2.82????2.82????60.27????60.27
Embodiment 3:
Waste liquid: paper mill, Luliang alkali straw pulp concentrated black liquid and useless bleaching liquor.
Main treating processes: active sludge treatment, batching, normal temperature anaerobic digestion, precipitation, coagulation, chlorination.
Batching: with black liquor after the active sludge treatment and rotten slag mix, the mixed volume ratio is black liquor: rotten slag=5～7: 5～3.
Equipment: use the 30L anaerobic digestion device.
Condition: pH value=6-9; Normal temperature: 2 ℃-30 ℃; 14 days residence times; The semi continuous operation mode.
Effect:
Paper mill, Luliang black liquor pollution situation
Value country allows paper mill, Luliang concentrated black liquid
The project emission standard
COD crmg/L 450 （3-9）×10 4
BOD 5mg/L 150 （1-3）×10 4
PH value 6-8 13
Anaerobic digestion CODcr test result
Concentrated black liquid COD CrMg/L Digestive system COD CrMg/L COD CrClearance %
Mean value maximum mean value optimum value is on average best
63726????86721????24495????24001????62????72
The BOD5 test result
Concentrated black liquid BOD5 mg/L Digestive system BOD5 mg/L BOD5 clearance %
Mean value maximum mean value optimum value is on average best
21242????15480????7265????3285????66????78
Coagulation clear liquid test result
COD CrMg/L BOD 5Mg/L pH value and outward appearance
Mean value 2,162 630 7～8
Optimum value 1,427 150 is filbert
Average removal rate % 96 97 transparent clear
Best clearance % 98 99
Illustrate: concentrated black liquid reaches useless chemicking so far, not heat dissipation and chemical reagent
Embodiment 1～3 treatment effect again is listed as follows:
Handle extracted test again
Item raw black liquid Digestive system coagulation clear liquid chlorination clear liquid
COD CrThe outer COD of PH CrGo COD to remove COD CrBOD 5Outside the PH
Group mg/L sees and removes rate % except that rate % mg/L mg/L sight
1 53,295 11 black opaque 46.66 96.53＜400＜150 7 water white transparencies
2 53,295 11 is the same
3 78,896 12 the same 57.32 99.14＜400＜150 7 is the same
4 53,255 11 the same 64.46 96.30
5 104,005 13 the same 81.19 99.57＜300＜50 7 is the same
6 22,540 11 the same 81.19 99.57
7 104,005 13 the same 81.19 99.65 250＜50 7 is the same
Can make the fertile and building materials usefulness of agricultural after the precipitating sludge dehydration of embodiment 1-3.

Claims (8)

1, a kind of method that adopts Coagulation Method, activated sludge process, anaerobic digestion to handle the small paper pulp mill waste liquid is characterized in that the method for the useless bleaching liquor of the black liquor of comprehensive treating process small paper pulp mill cooking section and bleachery is made up of active sludge treatment, batching, normal temperature anaerobic digestion, precipitation, coagulation, six processes of chlorination.
2, by the said treatment process of claim 1, it is characterized in that above-mentioned Wastewater Treated by Activated Sludge Process process is: inoculation of activated-sludge in the alkaline straw-pulp waste liquid pool, mix with active sludge after mechanical separation from the black liquor of cooking section, its volume percent is 70～90: 30～10, macromolecule organic matter is degraded to low molecular compound in a large number in the black liquor, makes pH value drop to 9-6.
3, by the said treatment process of claim 1, it is characterized in that above-mentioned blending process is in the black liquor after active sludge treatment, to drop into leather-making mud, vinasse, rotten slag, the input ratio is respectively, black liquor: leather-making mud=3: 1; Black liquor: vinasse=7: 3; Black liquor: rotten slag=50～70: 50～30.
4, by the said treatment process of claim 1, it is characterized in that above-mentioned normal temperature anaerobic digestion process is: at normal temperatures, to have through the material input behind the blending process in the anaeroic digestor of the active sludge that mixes reorganization, the startup ratio is, material through preparing: active sludge=70～50 of mixing reorganization: 30～50, the input and output material amount is controlled at 10%, carries out anaerobic digestion under the condition of PH=6～9.
5, by the said treatment process of claim 4, the active sludge that it is characterized in that above-mentioned mixing reorganization is a difference inoculation of activated-sludge from the waste liquid pool of tannery, brewery, alkaline straw-pulp factory, from alkaline straw-pulp factory, get concentrated black liquid, active sludge is mixed rapidly with concentrated black liquid, make pH value=6～9, in anaerobic device, finish obtaining after the normal temperature domestication then.
6, by the said treatment process of claim 1, it is characterized in that above-mentioned precipitation process is: Digestive system is separated with sedimentation mud, and Digestive system send coagulation process to handle.
7, by the said treatment process of claim 1, it is characterized in that above-mentioned coagulation process is: use chlorine-contained wastewater and waste iron filing reaction to generate FeCl from bleachery 3Coagulating agent makes the Digestive system and the FeCl of post precipitation 3The coagulating agent thorough mixing.
8, by the said treatment process of claim 1, it is characterized in that above-mentioned chlorination process is: add micro-liquid chlorine in the clear liquid after coagulating treatment.
CN91103952A 1991-06-07 1991-06-07 Technology for treatment of waste liquid pollution in small paper pulp mill Expired - Fee Related CN1029114C (en)

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Application Number Priority Date Filing Date Title
CN91103952A CN1029114C (en) 1991-06-07 1991-06-07 Technology for treatment of waste liquid pollution in small paper pulp mill

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Application Number Priority Date Filing Date Title
CN91103952A CN1029114C (en) 1991-06-07 1991-06-07 Technology for treatment of waste liquid pollution in small paper pulp mill

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CN1058202A CN1058202A (en) 1992-01-29
CN1029114C true CN1029114C (en) 1995-06-28

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