CN103214153B - Regenerative cycle and utilization method for papermaking deep-treatment wastewater - Google Patents
Regenerative cycle and utilization method for papermaking deep-treatment wastewater Download PDFInfo
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- CN103214153B CN103214153B CN201310184142.3A CN201310184142A CN103214153B CN 103214153 B CN103214153 B CN 103214153B CN 201310184142 A CN201310184142 A CN 201310184142A CN 103214153 B CN103214153 B CN 103214153B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 96
- 230000001172 regenerating Effects 0.000 title abstract 4
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- 239000012528 membrane Substances 0.000 claims description 22
- 238000004064 recycling Methods 0.000 claims description 17
- 238000005374 membrane filtration Methods 0.000 claims description 14
- 238000005345 coagulation Methods 0.000 claims description 13
- 230000015271 coagulation Effects 0.000 claims description 13
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound 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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound 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[Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,PD94bWwgdmVyc2lvbj0nMS4wJyBlbmNvZGluZz0naXNvLTg4NTktMSc/Pgo8c3ZnIHZlcnNpb249JzEuMScgYmFzZVByb2ZpbGU9J2Z1bGwnCiAgICAgICAgICAgICAgeG1sbnM9J2h0dHA6Ly93d3cudzMub3JnLzIwMDAvc3ZnJwogICAgICAgICAgICAgICAgICAgICAgeG1sbnM6cmRraXQ9J2h0dHA6Ly93d3cucmRraXQub3JnL3htbCcKICAgICAgICAgICAgICAgICAgICAgIHhtbG5zOnhsaW5rPSdodHRwOi8vd3d3LnczLm9yZy8xOTk5L3hsaW5rJwogICAgICAgICAgICAgICAgICB4bWw6c3BhY2U9J3ByZXNlcnZlJwp3aWR0aD0nODVweCcgaGVpZ2h0PSc4NXB4JyB2aWV3Qm94PScwIDAgODUgODUnPgo8IS0tIEVORCBPRiBIRUFERVIgLS0+CjxyZWN0IHN0eWxlPSdvcGFjaXR5OjEuMDtmaWxsOiNGRkZGRkY7c3Ryb2tlOm5vbmUnIHdpZHRoPSc4NS4wJyBoZWlnaHQ9Jzg1LjAnIHg9JzAuMCcgeT0nMC4wJz4gPC9yZWN0Pgo8dGV4dCB4PSczNS4wJyB5PSc1My42JyBjbGFzcz0nYXRvbS0wJyBzdHlsZT0nZm9udC1zaXplOjIzcHg7Zm9udC1zdHlsZTpub3JtYWw7Zm9udC13ZWlnaHQ6bm9ybWFsO2ZpbGwtb3BhY2l0eToxO3N0cm9rZTpub25lO2ZvbnQtZmFtaWx5OnNhbnMtc2VyaWY7dGV4dC1hbmNob3I6c3RhcnQ7ZmlsbDojM0I0MTQzJyA+QzwvdGV4dD4KPHRleHQgeD0nNTEuMCcgeT0nNTMuNicgY2xhc3M9J2F0b20tMCcgc3R5bGU9J2ZvbnQtc2l6ZToyM3B4O2ZvbnQtc3R5bGU6bm9ybWFsO2ZvbnQtd2VpZ2h0Om5vcm1hbDtmaWxsLW9wYWNpdHk6MTtzdHJva2U6bm9uZTtmb250LWZhbWlseTpzYW5zLXNlcmlmO3RleHQtYW5jaG9yOnN0YXJ0O2ZpbGw6IzNCNDE0MycgPnI8L3RleHQ+Cjwvc3ZnPgo= [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound 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- 229910002804 graphite Inorganic materials 0.000 claims description 2
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- 239000011133 lead Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
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[O-]Cl=O QBWCMBCROVPCKQ-UHFFFAOYSA-M 0.000 description 2
- 229910001919 chlorite Inorganic materials 0.000 description 2
- 229910052619 chlorite group Inorganic materials 0.000 description 2
- 230000001112 coagulant Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 150000002972 pentoses Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SFZGFKZXECLEFV-UHFFFAOYSA-N 3,4-dichloro-2-methylsulfanylphenol Chemical compound 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- 241000894006 Bacteria Species 0.000 description 1
- 206010006895 Cachexia Diseases 0.000 description 1
- 229960005069 Calcium Drugs 0.000 description 1
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- QLNJFJADRCOGBJ-UHFFFAOYSA-N Propanamide Chemical compound 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- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
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- 230000003851 biochemical process Effects 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound 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OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound 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[Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound 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Abstract
The invention discloses a regenerative cycle and utilization method for papermaking deep-treatment wastewater. The regenerative cycle and utilization method comprises the steps of chemical decalcification, filtration, electrolysis, biological aerated filter biochemical treatment, ultrafiltration and reverse osmosis. A chemical decalcification system can be used for effectively removing high-concentration calcium ions and magnesium ions in the papermaking deep-treatment wastewater, and the removal rate achieves 50%; the COD (chemical oxygen demand) is further reduced via nano-catalytic electrolysis; 70-85% of the papermaking deep-treatment wastewater can be regeneratively cycled and utilized via the treatment of the method disclosed by the invention, thus greatly reducing the water consumption index and the wastewater discharge index of per ton of paper, increasing the economic and technical indexes of enterprises, reducing the discharge of the wastewater, avoiding the pollution of the wastewater to environment, and reducing the waste of water resources; and the cost of the regenerated cycling water can be lower than the price of running water, so that the regenerative cycle and utilization method is economical, reasonable, and capable of generating good economic benefits.
Description
Technical field
The present invention relates to a kind of papermaking deep and process the treatment process of waste water, particularly relate to a kind of recycling utilization method of the processing of the papermaking deep based on chemical decalcification technology, electrochemical techniques and membrane technique waste water.
Background technology
Paper-making effluent refers to the cooking waste liquor (claiming again black liquor, red liquid) that chemical pulping produces, the plain boiled water producing in the middle section water producing in pulp washing bleaching process and copy paper operation.General every production 1t sulfate pulp just has 1t organism and 400kg bases, sulfide to be dissolved in black liquor; Producing 1t sulfite pulp approximately has 900kg organism and 200kg oxide compound (calcium, magnesium etc.) to be dissolved in red liquid with sulfide.Waste liquid enters in rivers not only severe contamination water source, and causes a large amount of wastings of resources.Paper-making industry is traditional water rich and influential family, is also one of important source of pollution that cause water pollution.At present, the first place of China's paper-making industrial waste water quantity discharged and COD quantity discharged Jun Ju China all types of industries quantity discharged, paper industry is the most serious to the pollution of water surrounding, it is the matter of utmost importance of China's industrial pollution caused by paper manufacturing control still not, is also the matter of utmost importance that national trade effluent carries out processing up to standard and water saving.According to statistics, the above papermaking in county of China and county and paper products industry wastewater discharge account for 18.6% of national industrial total release, wherein process emission compliance amount and account for 49.3% of paper-making industrial waste water total release, in waste discharge, COD accounts for 44.0% of national industrial COD total release.Therefore, how eliminating that paper waste pollutes and make precious resources in waste liquid obtain utilizing is a job with great social effect and economic worth, should attach great importance to.Along with expanding economy, China faces the problem of shortage of fresh water, scarcity of raw material day by day, and on the other hand, water pollutes also more and more serious.In recent years, through unremitting effort in many ways, paper industry water prevention and cure of pollution have obtained certain achievement, although paper and paperboard production increase year by year, but reduced year by year of the COD in waste discharge.But the waste water that at present paper industry accounts for total emission volumn 50% not yet carries out processing up to standard, paper waste process after recycling few especially, therefore, paper waste prevention and cure of pollution and to recycle task also quite heavy.
Paper waste complicated component, biodegradability is poor, belongs to more unmanageable trade effluent, and its source and feature are:
1, cooking section waste liquid
Be the black liquor of alkaline process generation and the red liquid that acid polishing produces.Overwhelming majority paper mill adopts alkaline process and produces black liquor.In black liquor, contained pollutent has accounted for the more than 90% of industrial pollution caused by paper manufacturing total emission volumn, and has the characteristic of high density and difficult degradation, and its improvement is a great problem always.Main component in black liquor has 3 kinds, i.e. xylogen, poly-pentose and total alkali.Xylogen is the nontoxic natural high molecular substance of a class, has been widely used as industrial chemicals tool, and poly-pentose can be used as animal feed.
2, middle section water
Effluent refers to the waste water that the boiling slurry after black liquid extraction is discharged in the processes such as screening, washing, bleaching, and color is deep yellow, accounts for 8%~9% of industrial pollution caused by paper manufacturing total emission volumn, ton slurry COD load 310kg left and right.Middle section water concentration is higher than sanitary sewage, and the ratio of BOD and COD is between 0.20 to 0.35, and biodegradability is poor, and organism is difficult to biological degradation and intractability is large.Organism in middle section water is mainly xylogen, Mierocrystalline cellulose, organic acid etc., taking solubility COD as main.Wherein, what environmental pollution was the most serious is the chlorine-contained wastewater producing in bleaching process, such as Chlorinated Bleaching waste water, hypo(chlorite)bleaching waste water etc.Hypo(chlorite)bleaching waste water mainly, containing trichloromethane, also contains other organic chlorides of kind more than 40, wherein taking various chlorinated phenols as at most, as dichloro-phenol, three chlorinated phenols etc.In addition, in bleaching waste liquor, containing toxic extremely strong carcinogenic substance Dioxins, ecotope and HUMAN HEALTH have been caused to serious threat.
3, plain boiled water
Plain boiled water is copy paper workshop section waste water, and it derives from paper machine room paper making process.Plain boiled water mainly contains fiber fines, filler, coating and lysed timber composition, and the sizing material, Wet Strength Resin, sanitas that add etc., and taking insoluble COD as main, biodegradability is lower, and its sanitas adding has certain toxicity.The plain boiled water water yield is larger, but its contained organic pollution load is well below black digestion liquid and middle-stage wastewater.Nearly all paper mill paper machine room has all adopted part or totally-enclosed system to reduce papermaking water loss now, saves power consumption, improves plain boiled water reclamation rate, reduces unnecessary plain boiled water discharge.
At present, mainly contain for the method for paper waste processing: physical filtering method, coagulant sedimentation, absorption method, advanced oxidation processes, By Bubble-floating Method, acid adding absorption process, catalytic oxidation, biochemical process etc., every kind of method all has relative merits separately.Because single treatment process is difficult to be effective, in practice, normally according to the practical situation that will process waste water, several method is combined with, typical production technique be by paper waste through physical treatment such as filtrations grade, then qualified discharge after biochemical treatment again after flocculation sediment.
Chinese patent CN101708927A discloses a kind of advanced treatment method for papermaking waste water little, oxidative degradation+flocculation sediment+sand filtration that technique is simple, pollutants removal rate is high, working cost is cheap of investing.COD < 70mg/L after the method is processed, BOD5 < 20mg/L, SS < 30mg/L.
Ecological Disposal and resource recycling that Chinese patent CN1420091 discloses a kind of paper waste utilize method, and it is to utilize ecological engineering technology, and paper mill wastewater carries out BOD in settling tank
5: COD
crratio adjustment, then enter the digestion of series connection anaerobic pond and facultative lagoon, COD is carried out in draining in equalizing tank
cr: N: after P ratio is adjusted, be distributed into many groups rainwash wetland in parallel by transmission & distribution water system, water outlet is better than the primary standard of paper industry Sewage Water Emissions, can stay through the storage of the aerobic pool, supplement the required clear water of equalizing tank, is back to rainwash wetland and carries out the degree of depth and process.The method has overcome paper waste trophic structure imbalance, the poor shortcoming of biodegradability, can stablize the Ecological Disposal and the resource recycling utilization that effectively realize paper waste.
Chinese patent CN101337752 discloses a kind of advanced treatment process for paper-making waste water, this technique comprises the following steps: the paper waste after secondary biochemical treatment is introduced to micro-aeration iron reduction bed, in micro-aeration iron reduction bed, load iron filings, paper waste carries out reduction reaction in micro-aeration iron reduction bed; By step 1. water outlet after treatment introduce in coagulation basin, in coagulation basin, add coagulating agent and coagulant aids, impel the particle aggregation in water; 2. step is carried out to mud-water separation in water outlet introducing settling tank after treatment; The water outlet of settling tank is introduced in filtering basin and filtered, and the water outlet after filtration, after sterilization and disinfection, is introduced reuse water pipe network; Sewage backwash water in mud in settling tank and filtering basin is introduced to sludge thickener, and after dehydration, outward transport is disposed; Meanwhile, the overflowing liquid in dehydration filtrate and sludge thickener is introduced in coagulation basin and is processed.Technique of the present invention is simple, good decolorizing effect and with low cost.
Above method all obtains reasonable effect to the processing of paper waste, but all exist the processing degree of depth inadequate, the middle water of producing also contains more pollutent, can only be applicable to some production technique not high to water specification of quality, and its purposes consumption is all restricted.Make paper waste regeneration, meet the water requirement of various processes, the particularly requirement of high quality water, must carry out deep purifying processing to it, as the waste water of biochemical gained is passed through to membrane filtration processing again through further purification, obtain pure water.Chinese patent 201010567041.0,201020635352.1 has been introduced papermaking deep processing waste water and has been adopted membrane filtration to carry out the method for recycling utilization, but in implementation process, find in paper waste that calcium ion content is up to 150~400 mg/L, produce a large amount of foulings, the regeneration of waste water is caused to serious difficulty.
Summary of the invention
The object of the invention is to in existing paper waste treatment process, existing cost is higher, usefulness is lower, waste water after treatment mostly is discharge, there is no the problems such as advanced treatment recycle, waste water resource, providing a kind of combines with membrane technique based on chemical decalcification technology, electrochemical techniques, cost is lower, usefulness is higher, makes it the recycling utilization method of the papermaking deep processing waste water that reaches recycle.
The recycling utilization method that a kind of papermaking deep of the present invention is processed waste water comprises the following steps:
(1) chemical decalcification
Second pond water outlet after papermaking biochemical treatment (being that papermaking deep is processed waste water) flows into coagulation basin through pipeline, under agitation first adds appropriate lime saturated solution adjust pH to 8.5~9.5, then add the Na of 300 ~ 600mg/L in coagulation basin by chemicals dosing plant
2cO
3, then add the FeSO of 5 ~ 10mg/L
4, then add Na
2cO
3anti-adjust pH to 8~9, finally add the polyacrylamide (PAM) of 2 ~ 3mg/L, after reacting completely, enter tube settler, carry out precipitate and separate, thereby remove papermaking deep and process calcium magnesium, the reduction water hardness in waste water, throw out (being mud) is sent in sludge sump through pump and pipeline, finally in sludge dehydration device, carries out filtering separation, and reclaiming calcium carbonate, waste water enters next step and filters;
(2) filter
Waste water after chemical decalcification is pumped into more medium filter or filtering separation is carried out in sand filtration, further except SS and colloid in anhydrating;
(3) electrolysis
Waste water after filtering is pumped into electrolysis machine electrolysis, and degraded organic macromolecule, removes colourity, improves the biodegradability of waste water, and the adjacent two interelectrode voltages of electrolysis machine are 2~12V, and current density is 10~320mA/cm
2;
(4) BAF biochemistry
Waste water after electrolysis enters BAF, by oxidation degradation effect, waste water is carried out to fast purification, obtains papermaking and purifies liquid waste;
(5) ultrafiltration
Biochemical BAF gained papermaking is purified liquid waste and carry out ultra-filtration filters, separate to obtain water-dialyzing and condensed water, water-dialyzing enters reverse-osmosis treated, and condensed water flow to recycle in the electrolysis machine of step (3) through back of pipeline;
(6) reverse osmosis
Ultrafiltration gained water-dialyzing pumps into osmosis filtration film system by high-pressure pump after security personnel filter, and separates to obtain water-dialyzing and condensed water through reverse osmosis membrane filtration, and water-dialyzing enters basin and obtains reuse water; A condensed water part separates through the reflux membrane filtration that circulates of condensed water topping-up pump, redundance discharge.
Described in step (3) electrolysis, electrolysis machine is provided with power supply and electrolyzer, and the electrode materials in described electrolyzer is the one in graphite, titanium, iron, aluminium, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano-catalytic noble electrode; The top layer of described nano-catalytic noble electrode is coated with the metal oxide inertia catalyst coatings that crystal grain is 10~35nm, and the substrate of described nano-catalytic noble electrode is titanium plate or plastic plate.
The molecular weight cut-off of the described ultrafiltration of step (5) is 1000~50000MWCO, working conditions is normal temperature~45 DEG C, described ultrafiltration is the one of immersion ultrafiltration, pillar ultrafiltration, tubular type ultrafiltration, spiral wound or plate-type hyperfiltration, the operating pressure of immersion ultrafiltration is-1~-50kPa, and the operating pressure of pillar ultrafiltration, tubular type ultrafiltration, spiral wound and plate-type hyperfiltration is 3~300kPa.
Reverse osmosis membrane assembly in the described reverse osmosis of step (6) is rolled membrane module, and mould material is cellulose acetate film or composite membrane in organic membrane, and the molecular weight cut-off of mould material is 50~200MWCO, and entrance pressure can be 6.0~35.0bar, goes out to press to can be 4.5~33.5 bar.
The present invention had both overcome the defect of alone membrane filtration separating treatment or adsorption treatment high cost, the treatment effect that has overcome again conventional paper waste method is undesirable, the defects such as the contaminated wastewater environment of discharge, existing papermaking deep is processed to purification of waste water and recycle and reuse, compared with the prior art, there is following outstanding advantages:
(1) papermaking deep is processed waste water through processing, and 70%~85% can recycling utilization, has both reduced discharge of wastewater, avoid waste water environmental pollution, reduce again water resource waste, can also make the recirculated water cost of regeneration lower than tap water price, economical rationality, produces good economic benefit.
(2) can process the high-concentration Ca magnesium ion in waste water by effective elimination papermaking deep by chemical decalcification system, clearance reaches 50%, ensures that subsequent treatment process is smooth, steady running.
(3) further reduce COD by nano-catalytic electrolysis, the one, can make the reclamation rate of waste water improve, both reduced discharge of wastewater, avoid waste water environmental pollution, reduce again water resource waste; The 2nd, can kill the microorganisms such as bacterium in waste water, eradicate the biological pollution of subsequent ultrafiltration film and reverse osmosis membrane, significantly reduce the wash number of ultra-filtration membrane and reverse osmosis membrane, reduce the clean regeneration cost of film, improve the service efficiency of film, extend the work-ing life of film, reduce film replacement cost.
(4) significantly reduce water consumption index and the discharge of wastewater index of ton paper, improve business economic technical indicator.
The alleged papermaking deep of the present invention is processed waste water and is referred to paper waste second pond water outlet after traditional filtration, flocculation and biochemical treatment, reaches the waste water of more than three grades emission standard.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
The present invention is in the purification to papermaking deep processed waste water that composition, character and the existing processing scheme of existing papermaking deep processing waste water are goed deep into completing after the comparative study of system and the design of recycling utilization method, it uses by the combination of the methods such as chemical decalcification, electrolysis, membrane filtration, is particularly suitable for the useless water purification of papermaking deep processing and recycling utilization method thereby form one.
1 explanation the specific embodiment of the present invention with reference to the accompanying drawings.
Embodiment 1
500 ton per day papermaking deeps are processed the recycling utilization method of waste water.
It is as shown in table 1 after measured that described papermaking deep is processed waste water quality index.
Table 1 papermaking deep is processed the water-quality guideline of waste water
Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
1 | COD Cr | mg/L | 150 | 4 | Colourity | ? | 60 |
2 | SS | mg/L | 140 | 5 | Ca | mg/L | 200 |
3 | Specific conductivity | μS/cm | 1800 | 6 | Hardness | mmol/L | 4 |
(1) chemical decalcification
Papermaking deep is processed waste water and is flowed into coagulation basin through pipeline, under agitation first adds appropriate saturated lime solution adjust pH to 8.5, then add the Na of 600mg/L in coagulation basin by chemicals dosing plant
2cO
3, then add the FeSO of 10mg/L
4, then add Na
2cO
3anti-adjust pH to 8, finally add the polyacrylamide (PAM) of 2mg/L, after reacting completely, enter tube settler, carry out precipitate and separate, thereby remove papermaking deep and process calcium magnesium, the reduction water hardness in waste water, throw out (being mud) is sent in sludge sump through pump and pipeline, finally in sludge dehydration device, carries out filtering separation, and reclaiming calcium carbonate, waste water enters next step and filters;
(2) filter
Waste water after chemical decalcification is pumped into more medium filter and carry out filtering separation, further except SS and colloid in anhydrating;
(3) electrolysis
Waste water after filtering is pumped into electrolysis machine electrolysis, and degraded organic macromolecule, removes colourity, and improves the biodegradability of waste water, and the adjacent two interelectrode voltages of electrolysis machine are 2V, and current density is 10mA/cm
2;
(4) BAF biochemistry
Waste water after electrolysis enters BAF, by oxidation degradation effect, waste water is carried out to fast purification, obtains papermaking and purifies liquid waste;
(5) ultrafiltration
Biochemical BAF gained papermaking is purified liquid waste and carry out immersion ultra-filtration filters, separate to obtain water-dialyzing and condensed water, water-dialyzing enters reverse-osmosis treated, and condensed water flow to recycle in electrolysis machine through back of pipeline;
(6) reverse osmosis
Ultrafiltration gained water-dialyzing pumps into osmosis filtration film system by high-pressure pump after security personnel filter, and separates to obtain water-dialyzing and condensed water through reverse osmosis membrane filtration, and water-dialyzing enters basin and obtains reuse water; A condensed water part separates through the reflux membrane filtration that circulates of condensed water topping-up pump, redundance discharge.
Described immersion ultrafiltration working conditions is: normal temperature~45 DEG C, and operating pressure is-1~-50kPa; The membrane module of described reverse osmosis is rolled membrane module, and mould material is cellulose acetate film in organic membrane, and entrance pressure can be 6.0~45.0bar, goes out to press to can be 4.5~33.5 bar.
Above-mentioned ultrafiltration is immersion ultrafiltration, and ultrafiltration can be the one of immersion ultrafiltration, pillar ultrafiltration, tubular type ultrafiltration, spiral wound or plate-type hyperfiltration.
Reuse water water-quality guideline is as shown in table 2 after measured.
The water-quality guideline of table 2 reuse water
Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
1 | COD Cr | mg/L | 10 | 4 | Colourity | ? | 10 |
2 | SS | mg/L | ≤1 | 5 | Ca | mg/L | ≤1 |
3 | Specific conductivity | μS/cm | 100 | 6 | Hardness | mmol/L | 0.1 |
Embodiment 2
6000 ton per day papermaking deeps are processed the recycling utilization method of waste water.
It is as shown in table 3 after measured that described papermaking deep is processed waste water quality index.
Table 3 papermaking deep is processed the water-quality guideline of waste water
Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
1 | COD Cr | mg/L | 90 | 4 | Colourity | ? | 150 |
2 | SS | mg/L | 60 | 5 | Ca | mg/L | 160 |
3 | Specific conductivity | μS/cm | 1200 | 6 | Hardness | mmol/L | 2 |
(1) chemical decalcification
Papermaking deep is processed waste water and is flowed into coagulation basin through pipeline, under agitation first adds appropriate saturated lime solution adjust pH to 9.5, then add the Na of 300mg/L in coagulation basin by chemicals dosing plant
2cO
3, then add the FeSO of 5mg/L
4, then add Na
2cO
3anti-adjust pH to 9, finally add the polyphenyl propionic acid amide (PAM) of 2mg/L, after reacting completely, enter tube settler, carry out precipitate and separate, thereby remove papermaking deep and process calcium magnesium, the reduction water hardness in waste water, throw out (being mud) is sent in sludge sump through pump and pipeline, finally in sludge dehydration device, carries out filtering separation, and reclaiming calcium carbonate, waste water enters next step and filters;
(2) filter
Waste water after chemical decalcification is pumped into sand filtration strainer and carry out filtering separation, further except SS and colloid in anhydrating;
(3) electrolysis
Waste water after sand filtration is filtered pumps into electrolysis machine electrolysis, and degraded organic macromolecule, removes colourity, and improve the biodegradability of waste water, and the adjacent two interelectrode voltages of electrolysis machine are 6V, and current density is 320mA/cm
2;
(4) BAF biochemistry
Waste water after electrolysis enters BAF, by oxidation degradation effect, waste water is carried out to fast purification, obtains papermaking and purifies liquid waste;
(5) ultrafiltration
Biochemical BAF gained papermaking is purified liquid waste and carry out pillar ultra-filtration filters, separate to obtain water-dialyzing and condensed water, water-dialyzing enters reverse-osmosis treated, and condensed water flow to recycle in the electrolysis machine of step (3) through back of pipeline.
(6) reverse osmosis
Ultrafiltration gained water-dialyzing pumps into osmosis filtration film system by high-pressure pump after security personnel filter, and separates to obtain water-dialyzing and condensed water through reverse osmosis membrane filtration, and water-dialyzing enters basin and obtains reuse water; A condensed water part separates through the reflux membrane filtration that circulates of condensed water topping-up pump, redundance discharge.
Described tubular type ultrafiltration working conditions is: normal temperature~45 DEG C, and operating pressure is 3~300kPa; The membrane module of described reverse osmosis is rolled membrane module, and mould material is composite membrane, and entrance pressure can be 6.0~45.0bar, goes out to press to can be 4.5~33.5 bar.
Above-mentioned ultrafiltration is tubular type ultrafiltration.Ultrafiltration can be the one of immersion ultrafiltration, pillar ultrafiltration, tubular type ultrafiltration, spiral wound or plate-type hyperfiltration.
Reuse water water-quality guideline is as shown in table 4 after measured.
The water-quality guideline of table 4 reuse water
Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
1 | COD Cr | mg/L | 6 | 4 | Colourity | ? | 5 |
2 | SS | mg/L | ≤1 | 5 | Ca | mg/L | ≤1 |
3 | Specific conductivity | μS/cm | 80 | 6 | Hardness | mmol/L | 0.05 |
Embodiment 3
20000 ton per day papermaking deeps are processed the recycling utilization method of waste water.
It is as shown in table 5 after measured that described papermaking deep is processed waste water quality index.
Table 5 papermaking deep is processed the water-quality guideline of waste water
Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
1 | COD Cr | mg/L | 120 | 4 | Colourity | ? | 80 |
2 | SS | mg/L | 120 | 5 | Ca | mg/L | 200 |
3 | Specific conductivity | μS/cm | 1500 | 6 | Hardness | mmol/L | 1.2 |
(1) chemical decalcification
Papermaking deep is processed waste water and is flowed into coagulation basin through pipeline, under agitation first adds appropriate saturated lime solution adjust pH to 9, then add the Na of 500mg/L in coagulation basin by chemicals dosing plant
2cO
3, then add the FeSO of 8mg/L
4, then add Na
2cO
3anti-adjust pH to 8.5, finally add the polyacrylamide (PAM) of 3mg/L, after reacting completely, enter tube settler, carry out precipitate and separate, thereby remove papermaking deep and process calcium magnesium, the reduction water hardness in waste water, throw out (being mud) is sent in sludge sump through pump and pipeline, finally in sludge dehydration device, carries out filtering separation, and reclaiming calcium carbonate, waste water enters next step and filters;
(2) filter
Waste water after chemical decalcification is pumped into more medium filter and carry out filtering separation, further except SS and colloid in anhydrating;
(3) electrolysis
Waste water after filtering is pumped into electrolysis machine electrolysis, and degraded organic macromolecule, removes colourity, and improves the biodegradability of waste water, and the adjacent two interelectrode voltages of electrolysis machine are 12V, and current density is 200mA/cm
2;
(4) BAF biochemistry
Waste water after electrolysis enters BAF, by oxidation degradation effect, waste water is carried out to fast purification, obtains papermaking and purifies liquid waste;
(5) ultrafiltration
Biochemical BAF gained papermaking is purified liquid waste and carry out tubular type ultra-filtration filters, separate to obtain water-dialyzing and condensed water, water-dialyzing enters reverse-osmosis treated, and condensed water flow to recycle in step (3) electrolysis machine through back of pipeline;
(6) reverse osmosis
Ultrafiltration gained water-dialyzing pumps into osmosis filtration film system by high-pressure pump after security personnel filter, and separates to obtain water-dialyzing and condensed water through reverse osmosis membrane filtration, and water-dialyzing enters basin and obtains reuse water; A condensed water part separates through the reflux membrane filtration that circulates of condensed water topping-up pump, redundance discharge.
Described tubular type ultrafiltration working conditions is: normal temperature~45 DEG C, and operating pressure is 3~300kPa; The membrane module of described reverse osmosis is rolled membrane module, and mould material is composite membrane, and entrance pressure can be 6.0~45.0bar, goes out to press to can be 4.5~33.5 bar.
Above-mentioned ultrafiltration is tubular type ultrafiltration.Ultrafiltration can be the one of immersion ultrafiltration, pillar ultrafiltration, tubular type ultrafiltration, spiral wound or plate-type hyperfiltration.
Reuse water water-quality guideline is as shown in table 6 after measured.
The water-quality guideline of table 6 reuse water
Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
1 | COD Cr | mg/L | 8 | 4 | Colourity | ? | 6 |
2 | SS | mg/L | ≤1 | 5 | Ca | mg/L | ≤1 |
3 | Specific conductivity | μS/cm | 60 | 6 | Hardness | mmol/L | 0.06 |
Above are only the specific embodiment of the present invention, but design concept of the present invention is not limited to this, allly utilizes this design to carry out the change of unsubstantiality to the present invention, all should belong to the behavior of invading protection domain of the present invention.
Claims (3)
1. papermaking deep is processed a recycling utilization method for waste water, and it comprises the following steps:
(1) chemical decalcification
After papermaking biochemical treatment, second pond water outlet flows into coagulation basin through pipeline, in coagulation basin, under agitation first adds appropriate lime saturated solution adjust pH to 8.5~9.5 by chemicals dosing plant, then adds the Na of 300 ~ 600mg/L
2cO
3, then add the FeSO of 5 ~ 10mg/L
4, then add Na
2cO
3anti-adjust pH to 8~9, finally add the polyacrylamide (PAM) of 2 ~ 3mg/L, after reacting completely, enter tube settler, carry out precipitate and separate, thereby remove papermaking deep and process calcium magnesium, the reduction water hardness in waste water, throw out is sent in sludge sump through pump and pipeline, finally in sludge dehydration device, carries out filtering separation, and reclaiming calcium carbonate, waste water enters next step and filters;
(2) filter
Waste water after chemical decalcification is pumped into more medium filter or filtering separation is carried out in sand filtration, further except SS and colloid in anhydrating;
(3) electrolysis
Waste water after filtering is pumped into electrolysis machine electrolysis, and degraded organic macromolecule, removes colourity, improves the biodegradability of waste water, and the adjacent two interelectrode voltages of electrolysis machine are 2~12V, and current density is 10~320mA/cm
2described electrolysis machine is provided with power supply and electrolyzer, electrode in described electrolyzer is the one in graphite, titanium, iron, aluminium, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano-catalytic noble electrode, the top layer of nano-catalytic noble electrode is coated with the metal oxide inertia catalyst coatings that crystal grain is 10~35nm, and the substrate of described nano-catalytic noble electrode is titanium plate or plastic plate;
(4) BAF biochemistry
Waste water after electrolysis enters BAF, by oxidation degradation effect, waste water is carried out to fast purification, obtains papermaking and purifies liquid waste;
(5) ultrafiltration
Biochemical BAF gained papermaking is purified liquid waste and carry out ultra-filtration filters, separate to obtain water-dialyzing and condensed water, water-dialyzing enters reverse-osmosis treated, and condensed water flow to recycle in the electrolysis machine of step (3) through back of pipeline;
(6) reverse osmosis
Ultrafiltration gained water-dialyzing pumps into osmosis filtration film system by high-pressure pump after security personnel filter, and separates to obtain water-dialyzing and condensed water through reverse osmosis membrane filtration, and water-dialyzing enters basin and obtains reuse water; A condensed water part separates through the reflux membrane filtration that circulates of condensed water topping-up pump, redundance discharge.
2. a kind of papermaking deep according to claim 1 is processed the recycling utilization method of waste water, it is characterized in that: the molecular weight cut-off of the described ultrafiltration of step (5) is 1000~50000MWCO, working conditions is normal temperature~45 DEG C, described ultrafiltration is the one of immersion ultrafiltration, pillar ultrafiltration, tubular type ultrafiltration, spiral wound or plate-type hyperfiltration, the operating pressure of immersion ultrafiltration is-1~-50kPa, and the operating pressure of pillar ultrafiltration, tubular type ultrafiltration, spiral wound and plate-type hyperfiltration is 3~300kPa.
3. a kind of papermaking deep according to claim 1 is processed the recycling utilization method of waste water, it is characterized in that: the reverse osmosis membrane assembly in the described reverse osmosis of step (6) is rolled membrane module, mould material is cellulose acetate film or composite membrane in organic membrane, the molecular weight cut-off of mould material is 50~200MWCO, entrance pressure is 6.0~35.0bar, and going out to press is 4.5~33.5 bar.
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CN103992013B (en) * | 2014-06-09 | 2015-06-10 | 江苏德鑫环保科技有限公司 | Method and equipment for treating high-concentration refractory chemical wastewater |
CN105060626B (en) * | 2015-08-03 | 2017-06-20 | 浙江兴舟纸业有限公司 | A kind of processing method of papermaking factory production waste water |
CN105000727A (en) * | 2015-09-02 | 2015-10-28 | 波鹰(厦门)科技有限公司 | Oil-field wastewater treating and recycling device |
CN106495351A (en) * | 2016-12-15 | 2017-03-15 | 孙澳 | A kind of high concentration wastewater treatment method that refining process is produced |
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