CN101698547B - Composite electrolytic reactor and method for treating pulping waste liquid of chemi-mechanical pulp - Google Patents
Composite electrolytic reactor and method for treating pulping waste liquid of chemi-mechanical pulp Download PDFInfo
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Abstract
The invention discloses a composite electrolytic reactor and a method for treating pulping waste liquid of chemi-mechanical pulp. In the composite electrolytic reactor, conductive particles are prepared by mixing, bonding, extruding and granulating, cutting and drying the following components in percentage by mass: 50 to 55 percent of ferrous powder, 30 to 35 percent of active carbon, 5 to 8 percent of lignosulphonates, 3 to 5 percent of clay, 1 to 2 percent of copper oxide, 1 to 2 percent of zinc oxide and 0.5 to 1 percent of nickel oxide. The method for treating the pulping waste liquid of the chemi-mechanical pulp comprises the following processing steps orderly: lignin acidizing separation, fibre recovery, suspended substance treatment, composite electrolysis, catalytic oxidation treatment, and precipitate treatment. The method for treating the pulping waste liquid of the chemi-mechanical pulp has good treatment effect, low operation cost, and convenient operation and maintenance,saves investment, has a suspended substance removing rate over 95 percent, a CO removing rate over 65 percent, and a chroma removal rate over 95 percent.
Description
Technical field
The present invention relates to the pulping and paper-making field, the treatment unit and the treatment process that belong to the chemical machinery pulp-making effluent are specifically related to the combined electrolysis treatment unit and the treatment process of the chemical machinery pulp-making effluent such as Eucalyptus, pine of a kind of high organic concentration, high chroma.
Background technology
Pulp and paper industry is the basic raw material industry of national economy, and its development degree and level have significant effects to national economy.In recent decades, along with developing rapidly of world economy, the demand of paper is constantly increased, the pulp and paper industry development is very fast.But pulp and paper industry is faced with serious problems such as shortage of raw materials, environmental pollution is serious, energy consumption is big.The chemimechanical pulp investment cost is low, and starting material are extensive, and yield exceeds about one times than chemical pulp, and the multiple paper kind that can be used for manufacturing paper with pulp, have the characteristic of chemical pulp and the advantage of high yield pulp concurrently, have great application potential, become one of important development trend of pulp and paper industry.Therefore, for how handling the waste liquid that contains toxicant that produces in the chemimechanical pulp pulping process, received the very big concern of paper industry.
Chemical machinery pulp waste organic concentration height, colourity are dark, and intractability is very big.In the waste liquid except containing remaining alkali electroless medicine, the organism such as resinous acid, lipid acid, phenols, Polyphenols and degraded product thereof that contain low relative molecular mass volatile acid, dissolved lignin degradation product, high molecular weight, and inorganics such as sulphite, existing organic substance pollutes, and toxic again material pollutes.
Mainly adopt technology such as flocculence, oxidation style, biological process, membrane processing method for the processing of paper-making effluent both at home and abroad.High and the very dark chemical machinery pulp-making effluent of colourity for organic concentration, these technology exist running cost height and/or the inapparent problem of decolorizing effect, and processed waste water is difficult to reach emission standard.Therefore, seek a kind of technology, economically viable chemical machinery pulp-making effluent pretreatment process, significantly reduce waste liquid COD and colourity, and then adopt biological treatment to make waste liquid reach the approach of emission standard, be the important trend of chemimechanical pulp liquid waste disposal, significant to the development of pulp and paper industry.
The method of combined electrolysis groove that patent of invention (patent No. ZL 200710026285.6) provides and the decolouring of change machine pulp-making effluent combined electrolysis thereof, making machine pulp waste decolouring effectively, and reduce the waste liquid COD load, obtained good effect.Problems such as but it is big that this method exists the conducting particles electrode density, is difficult to realize fluidization in the liquid waste disposal process, and running cost and granule electrode cost of manufacture are higher.
Summary of the invention
The objective of the invention is to provides a kind of composite electrolytic reactor that is used for the electrochemical treatment of chemical machinery pulp-making effluent at the deficiencies in the prior art.
Another object of the present invention is to provide a kind of treatment process of chemical machinery pulp-making effluent, specifically be a kind of lignin acidizing separation, combined electrolysis, catalyzed oxidation combination process of utilizing, can handle the treatment process of the chemical machinery pulp waste such as Eucalyptus, pine of high organic concentration, high chroma.
Purpose of the present invention is achieved through the following technical solutions:
A kind of composite electrolytic reactor is separated into a plurality of grooves unit by dividing plate, is provided with the mixture of conducting particles and inert particle in each groove unit, and the volume ratio of conducting particles and inert particle is (1～2): 1; The unitary both sides of each groove are provided with positive plate and negative plate respectively, positive plate and negative plate opposing parallel, and each groove unit bottom is provided with back up pad, aeration tube, recoil water pipe and blow-off pipe;
It is characterized in that: described conducting particles is diameter 2～4mm, the columnar-shaped particle of height 1～3mm, by percentage to the quality, conducting particles by the nickel oxide of 50～55% iron powder, 30～35% activated carbon, 5～8% Sulfite lignin, 3～5% clay, 1～2% cupric oxide, 1～2% zinc oxide and 0.5～1% by mix, cohere, extruder grain, cutting, air-dry forming;
Described inert particle is diameter 2～4mm, the columnar-shaped particle of height 1～3mm, by percentage to the quality, inert particle by the nickel oxide of 20～25% iron powder, 15～20% activated carbon, 45～50% clay, 5～8% Sulfite lignin, 1～2% cupric oxide, 1～2% zinc oxide and 0.5～1% by mix, cohere, extruder grain, cutting, air-dry forming;
The material of described positive plate is a graphite, and the material of negative plate is a stainless steel.
A kind of method for treating pulping waste liquid of chemi-mechanical pulp may further comprise the steps and processing condition:
(1) lignin acidizing separation: regulate pH value to 2～2.5 of chemical machinery pulp-making effluent, the lignin acidizing separation phenomenon takes place, the acid insoluble lignin in the waste liquid is separated out, and becomes solid precipitation or suspended substance; Acid out and sedimentary time are 1～1.5 hour;
(2) fiber recovery and suspended substance are handled: the supernatant liquor of step 1 post precipitation is filtered, to reclaim the fiber fines in the waste liquid, the while filter and remove suspended substances by 50～80 eye mesh screens;
(3) combined electrolysis is handled: the water outlet after step 2 is handled is carried out combined electrolysis and is handled, the extra electric field of combined electrolysis is the 15～25V voltage stabilized source after the rectification, the combined electrolysis reaction times is 40～80min, water outlet pH value is controlled to be 4～5, by the aeration tube air feed, gas-water ratio is 3: 1 by air compressor machine;
(4) catalytic oxidation treatment: the water outlet after step 3 processing is added hydrogen peroxide, mix rapidly, carry out catalytic oxidation treatment;
(5) precipitation: the water outlet that step 4 is obtained adds alkali adjusting pH value to 8～8.5, enters settling tank, precipitation 20～40min, and supernatant liquor is discharged, and mud enters sludge sump.
It is to utilize the joint synergy of little electrolysis, three-diemsnional electrode, electro-catalytic oxidation technology to dispose waste liquid that combined electrolysis of the present invention is handled.
Little electrolysis is to utilize Zero-valent Iron and cathode material in the waste water of slant acidity electrochemical reaction to take place, and forms countless small galvanic cells, by electrode reaction and reaction product Fe
2+Effects such as [H] and pollutants in waste water generation redox reaction and absorption, flocculation remove the organism and the colourity of waste water.Have advantages such as little, the treatment of wastes with processes of wastes against one another of investment, working cost be low, the subject matter of existence is the hardening of bed of packings, back flushing and regeneration difficulty.Electrolysis is under the effect of electric current, and anodic corrosion produces Fe
2+, pass through Fe
2+Oxygenizement and oxidation after form Fe (OH)
3Throwing out, remove COD and colourity in the waste water, exist the problem that power consumption is big, running cost is high.
The present invention is directed to the deficiency that micro-electrolysis method and electrolytic process exist, propose to adopt the method for combined electrolysis to handle the chemical machinery pulp-making effluent.Particle in the composite electrolytic reactor contains Zero-valent Iron, forms galvanic cell with the cathode material gac, plays little electrolytic effect, by electrode reaction and reaction product Fe thereof
2+[H], with pollutants in waste water generation redox reaction, and effect such as absorption, flocculation removes the organism and the chromonic material of waste water.On the other hand, under the effect of extra electric field, particle static induction in the combined electrolysis groove is charged, each particle becomes an independently electrode (the 3rd utmost point), produced numerous miniature electrolyzer in the electrolyzer, the catalytic oxidation reduction reaction is carried out simultaneously at each particle surface, and pollutent is oxidized at anode surface, be reduced at negative electrode, be degraded to small molecules or innoxious substance.Simultaneously, in catalytic oxidation reduction reaction process, electrode surface has generated the active substance H of strong oxidizing property
2O
2And OH, effectively degradable organic pollutant.The generation of countless miniature electrolyzers has greatly improved current efficiency and speed of response, has increased electrode area, makes that the three-diemsnional electrode method has efficiently, the characteristics of low consumption, has improved the removal effect of COD and colourity.
Catalytic oxidation treatment of the present invention is the Fe that utilizes the combined electrolysis process to produce
2+, with the hydrogen peroxide that adds, form the Fenton reagent of strong oxidation capacity, reach the purpose of removing waste liquid COD and colourity.Fenton reagent has very strong oxidation capacity by forming hydroxyl free radical OH, still can there be the higher shortcoming of processing cost in organism in the waste water even refractory organic oxidative degradation.The Fe that the present invention utilizes combined electrolysis to produce
2+, only need to add a spot of hydrogen peroxide, effectively reduce processing cost.
The present invention has strengthened the processing to the chemical machinery pulp waste of high density, high chroma by the joint synergy and the chemical catalytic oxidation effect of little electrolysis, three-diemsnional electrode, electro-catalytic oxidation technology.
Compare with the combined electrolysis groove among the Chinese invention patent ZL200710026285.6, composite electrolytic reactor of the present invention has the following advantages:
1, the present invention has set up the recoil water pipe, its effect is to feed wash-down water at reactor after operation for some time, reactor and particle are carried out back flushing, thereby remove suspended substance and other pollutents that accumulate in the reactor, reactor can long-time continuous be moved; The material of positive plate of the present invention adopts graphite, compares with original positive plate, can obtain same treatment effect, and cost reduces.
2, the granule electrode in the combined electrolysis groove among the patent of invention ZL200710026285.6 is a sinter molding, the cost of manufacture height, among the present invention conducting particles and inert particle by mix, cohere, extruder grain, cutting, air-dry forming, cost of manufacture is low.
3, the conducting particles electrode density in the combined electrolysis groove among the patent of invention ZL200710026285.6 is big, in the liquid waste disposal process, be difficult to realize fluidization, among the present invention, conducting particles density is lower, when aeration, be in fluidized state, improve the contact condition of pollutent and granule electrode in the waste liquid greatly, quicken the mass transfer process of combined electrolysis, thus the enhancement process effect.Simultaneously, the fluidization of particle can effectively prevent hardening and blockage problem between the particle.
Treatment process of the present invention has the following advantages compared with the prior art:
1, acid out under lower pH value (2～2.5) is fully separated out the acid insoluble lignin in the waste liquid, effectively reduces the pollution load of waste liquid, reduces the load of subsequent disposal;
2, filter behind the acid out, reclaim the fiber fines of waste liquid, remove suspended substance, effectively prevent the blockage problem that follow-up combined electrolysis treating processes may occur because concentration of suspension is high simultaneously;
3, use the joint synergy of little electrolysis, three-diemsnional electrode, catalytic oxidation and chemical catalytic oxidation technology, by the redox reaction of anodizing reduction reaction, reaction product, the active group (Fe that reaction process produces
2+, [H], OH) effect and the high current efficiency of three-diemsnional electrode, strengthened processing to the chemical machinery pulp-making effluent of high density, high chroma.
4, because conducting particles and inert particle density are all lower, when aeration, be in fluidized state, improve the contact condition of pollutent and granule electrode in the waste liquid greatly, the mass transfer process of acceleration combined electrolysis, thereby enhancement process effect.Simultaneously, the fluidization of particle can effectively prevent hardening and blockage problem between the particle;
5, the combined electrolysis treatment time shorter, extra electric field voltage is lower, has reduced the processing cost of waste liquid.
6, treatment effect of the present invention is good, working cost is low, convenient operating maintenance, reduced investment, and the suspended substance removal rate is more than 95%, and the COD clearance is more than 65%, and chroma removal rate is more than 95%.
Description of drawings
Fig. 1 is the composite electrolytic reactor synoptic diagram.
Fig. 2 is that synoptic diagram is looked on the left side of composite electrolytic reactor shown in Figure 1.
Among the figure, 1: the waste liquid input tube; 2: composite electrolytic reactor; 3: conducting particles; 4: inert particle; 5: back up pad; 6: positive plate; 7: dividing plate; 8: the recoil water pipe; 9: aeration tube; 10: blow-off pipe; 11: negative plate.
Embodiment
The present invention is described further below in conjunction with drawings and Examples, but the scope of protection of present invention is not limited to the content of embodiment statement.
As shown in Figure 1 and Figure 2, composite electrolytic reactor of the present invention is separated into a plurality of grooves unit by dividing plate 7, the conducting particles 3 of certain particle size and the mixture of inert particle 4 are set in each groove unit, the unitary both sides of each groove are provided with positive plate 6 and negative plate 11 respectively, positive plate 6 is placed with negative plate 11 opposing parallel, and each groove unit bottom is provided with back up pad 5, aeration tube 9, recoil water pipe 8 and blow-off pipe 10.
Adopt method of the present invention to handle Eucalyptus chemimechanical pulp defibrination waste liquid, the waste liquid characteristic is CODcr:18600mg/L, colourity: 14700C.U., SS:2015mg/L.
(1) regulate chemimechanical pulp waste liquor PH value to 2.5, the lignin acidizing separation phenomenon takes place, the acid insoluble lignin in the waste liquid is separated out, and becomes solid precipitation or suspended substance.Acid out and sedimentary time are 1 hour;
(2) supernatant liquor of step (1) post precipitation is filtered by 50 eye mesh screens, to reclaim the fiber fines in the waste liquid, the while filter and remove suspended substances;
(3) combined electrolysis is carried out in the water outlet after step (2) processing and handle, the extra electric field of combined electrolysis is the 15V voltage stabilized source after the rectification, and the combined electrolysis reaction times is 40min, and water outlet pH value is controlled to be 4, and by the aeration tube air feed, gas-water ratio is 3: 1 by air compressor machine.
Conducting particles is diameter 4mm, the columnar-shaped particle of height 3mm, columnar-shaped particle comprises the iron powder of 50% (mass percent, together following), 35% activated carbon, 6% Sulfite lignin, 5% clay, 2% cupric oxide, 1% zinc oxide, 1% nickel oxide, by mentioned component by mix, cohere, extruder grain, cutting, air-dry forming.
Inert particle is diameter 4mm, and the columnar-shaped particle of height 3mm, columnar-shaped particle comprise the iron powder of 20% (mass percent, together following), 20% activated carbon, 50% clay, 6.5% Sulfite lignin; 2% cupric oxide, 1% zinc oxide, 0.5% nickel oxide, by mentioned component by mix, cohere, extruder grain, cutting, air-dry forming.
The volume ratio of conducting particles and inert particle is 1: 1, and positive plate is a graphite material, and negative plate is a stainless steel.
(4) water outlet after step (3) processing is added hydrogen peroxide, mix rapidly, carry out catalytic oxidation treatment.The hydrogen peroxide add-on is 100mg/L (30%), treatment time 60min;
(5) precipitation: the water outlet that step (4) is obtained adds alkali adjusting pH value to 8, enters settling tank, precipitation 20min, and supernatant liquor is discharged, and mud enters sludge sump.
Treatment effect is a CODcr clearance 67.8%, chroma removal rate 95.8%, SS clearance 95.2%.
Adopt method of the present invention to handle Eucalyptus chemimechanical pulp Chemical Pretreatment waste liquid, the waste liquid characteristic is CODcr:20200mg/L, colourity: 22700C.U., SS:1844mg/L.
(1) regulate chemimechanical pulp waste liquor PH value to 2, the lignin acidizing separation phenomenon takes place, the acid insoluble lignin in the waste liquid is separated out, and becomes solid precipitation or suspended substance.Acid out and sedimentary time are 90 minutes;
(2) supernatant liquor of step (1) post precipitation is filtered by 80 eye mesh screens, to reclaim the fiber fines in the waste liquid, the while filter and remove suspended substances;
(3) combined electrolysis is carried out in the water outlet after step (2) processing and handle, the extra electric field of combined electrolysis is the 25V voltage stabilized source after the rectification, and the combined electrolysis reaction times is 80min, and water outlet pH value is controlled to be 5, and by the aeration tube air feed, gas-water ratio is 3: 1 by air compressor machine;
Conducting particles is diameter 2mm, the columnar-shaped particle of height 1mm, columnar-shaped particle comprises the iron powder of 55% (mass percent, together following), 30% activated carbon, 8% Sulfite lignin, 3% clay, 1% cupric oxide, 2% zinc oxide, 1% nickel oxide, by mentioned component by cohere, extruder grain, cutting, air-dry forming;
Inert particle is diameter 2mm, and the columnar-shaped particle of height 1mm, columnar-shaped particle comprise the iron powder of 25% (mass percent, together following), 15% activated carbon, 48% clay, 8% Sulfite lignin; 1% cupric oxide, 2% zinc oxide, 1% nickel oxide, by mentioned component by cohere, extruder grain, cutting, air-dry forming.
The volume ratio of conducting particles and inert particle is 2: 1, and positive plate is a graphite material, and negative plate is a stainless steel.
(4) water outlet after step (3) processing is added hydrogen peroxide, mix rapidly, carry out catalytic oxidation treatment.The hydrogen peroxide add-on is 300mg/L (30%), treatment time 60min;
(5) precipitation: the water outlet that step (4) is obtained adds alkali adjusting pH value to 8.5, enters settling tank, precipitation 40min, and supernatant liquor is discharged, and mud enters sludge sump.
Treatment effect is a CODcr clearance 75.1%, chroma removal rate 97.5%, SS clearance 97.2%.
Adopt method of the present invention handle Eucalyptus, pine mixed chemical mechanical pulp (Eucalyptus: 45%, pine: 55%; Mass ratio) Chemical Pretreatment waste liquid, waste liquid characteristic are CODcr:21500mg/L, colourity: 17300C.U., SS:713mg/L.
(1) regulate chemimechanical pulp waste liquor PH value to 2.5, the lignin acidizing separation phenomenon takes place, the acid insoluble lignin in the waste liquid is separated out, and becomes solid precipitation or suspended substance.Acid out and sedimentary time are 75 minutes;
(2) supernatant liquor of step (1) post precipitation is filtered by 60 eye mesh screens, to reclaim the fiber fines in the waste liquid, the while filter and remove suspended substances;
(3) combined electrolysis being carried out in the water outlet after step (2) processing handles, the extra electric field of combined electrolysis is the 20V voltage stabilized source after the rectification, and the combined electrolysis reaction times is 60min, and water outlet pH value is controlled to be 4.5, by the aeration tube air feed, gas-water ratio is 3: 1 by air compressor machine;
Conducting particles is diameter 3mm, the columnar-shaped particle of height 2mm, columnar-shaped particle comprises the iron powder of 52.5% (mass percent, together following), 34% activated carbon, 5% Sulfite lignin, 5% clay, 1.5% cupric oxide, 1.5% zinc oxide, 0.5% nickel oxide, by mentioned component by mix, cohere, extruder grain, cutting, air-dry forming;
Inert particle is diameter 3mm, and the columnar-shaped particle of height 2mm, columnar-shaped particle comprise the iron powder of 25% (mass percent, together following), 20% activated carbon, 45% clay, 5% Sulfite lignin; 2% cupric oxide, 2% zinc oxide, 1% nickel oxide, by mentioned component by cohere, extruder grain, cutting, air-dry forming;
The volume ratio of conducting particles and inert particle is 1: 1, and positive plate is a graphite material, and negative plate is a stainless steel;
(4) water outlet after step (3) processing is added hydrogen peroxide, mix rapidly, carry out catalytic oxidation treatment.The hydrogen peroxide add-on is 200mg/L (30%), treatment time 60min;
(5) precipitation: the water outlet that step (4) is obtained adds alkali adjusting pH value to 8, enters settling tank, precipitation 30min, and supernatant liquor is discharged, and mud enters sludge sump.
Treatment effect is a CODcr clearance 69.2%, chroma removal rate 96.4%, SS clearance 96.1%.
Claims (2)
1. a composite electrolytic reactor is separated into a plurality of grooves unit by dividing plate (7), is provided with the mixture of conducting particles (3) and inert particle (4) in each groove unit, and conducting particles (3) is (1～2) with the volume ratio of inert particle (4): 1; The unitary both sides of each groove are provided with positive plate (6) and negative plate (11) respectively, positive plate (6) and negative plate (11) opposing parallel, and each groove unit bottom is provided with back up pad (5), aeration tube (9), recoil water pipe (8) and blow-off pipe (10);
It is characterized in that: described conducting particles (3) is diameter 2～4mm, the columnar-shaped particle of height 1～3mm, by percentage to the quality, conducting particles (3) by the nickel oxide of 50～55% iron powder, 30～35% activated carbon, 5～8% Sulfite lignin, 3～5% clay, 1～2% cupric oxide, 1～2% zinc oxide and 0.5～1% by mix, cohere, extruder grain, cutting, air-dry forming;
Described inert particle (4) is diameter 2～4mm, the columnar-shaped particle of height 1～3mm, by percentage to the quality, inert particle (4) by the nickel oxide of 20～25% iron powder, 15～20% activated carbon, 45～50% clay, 5～8% Sulfite lignin, 1～2% cupric oxide, 1～2% zinc oxide and 0.5～1% by mix, cohere, extruder grain, cutting, air-dry forming;
The material of described positive plate (6) is a graphite, and the material of negative plate (11) is a stainless steel.
2. an application rights requires 1 described composite electrolytic reactor to handle the method for chemical machinery pulp-making effluent, it is characterized in that may further comprise the steps and processing condition:
(1) lignin acidizing separation: regulate pH value to 2～2.5 of chemical machinery pulp-making effluent, precipitate 1～1.5 hour;
(2) fiber recovery and suspended substance are handled: the supernatant liquor of post precipitation is filtered by 50～80 eye mesh screens;
(3) combined electrolysis is handled: the screen cloth filtered solution is carried out combined electrolysis handle, the extra electric field of combined electrolysis is the 15～25V voltage stabilized source after the rectification, and the combined electrolysis reaction times is 40～80min, and water outlet pH value is controlled to be 4～5, by the aeration tube air feed, gas-water ratio is 3: 1 by air compressor machine;
(4) catalytic oxidation treatment: the water outlet after step (3) processing is added hydrogen peroxide, carry out catalytic oxidation treatment;
(5) precipitation: the water outlet that step (4) is obtained adds alkali adjusting pH value to 8～8.5, enters settling tank, precipitation 20～40min, and supernatant liquor is discharged, and mud enters sludge sump.
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| CN101838074B (en) * | 2010-05-18 | 2012-05-09 | 华南理工大学 | Method for degrading nitrobenzene waste water by polyphase electrocatalytic oxidation-Fenton coupling process and reactor thereof |
| CN102583910B (en) * | 2012-03-28 | 2013-10-30 | 淄博高汇化工有限公司 | Method for treating waste water in multi-stage catalytic oxidation and microelectrolysis method |
| CN102659290B (en) * | 2012-05-25 | 2013-12-25 | 中国林业科学研究院林产化学工业研究所 | Method for advanced treatment of high-concentration chemi-mechanical pulp effluent by catalytic oxidation |
| CN102910768B (en) * | 2012-10-23 | 2013-12-25 | 王麒钧 | Multi-stage runner type waste water treating device and waste water treating method |
| CN103193301B (en) * | 2013-04-27 | 2014-07-30 | 国电环境保护研究院 | Electrochemical reactor for processing nitrogenous organic wastewater, and application and processing method thereof |
| CN103253741B (en) * | 2013-05-10 | 2014-01-01 | 山东大学 | Method for preparing anti-hardening granular ceramic iron-carbon micro-electrolysis filler from industrial wastes |
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| CN107487908A (en) * | 2017-08-15 | 2017-12-19 | 广东博地环境工程有限公司 | One kind fluidisation pole plate electric flocculation reactor and its method of work |
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| CN1153843A (en) * | 1996-09-10 | 1997-07-09 | 刘友会 | Alkali process for treating black liquor |
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