CN1766227A - Processing mthod of white water from paper making - Google Patents
Processing mthod of white water from paper making Download PDFInfo
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- CN1766227A CN1766227A CN 200410086580 CN200410086580A CN1766227A CN 1766227 A CN1766227 A CN 1766227A CN 200410086580 CN200410086580 CN 200410086580 CN 200410086580 A CN200410086580 A CN 200410086580A CN 1766227 A CN1766227 A CN 1766227A
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- paper
- boiled water
- milipore filter
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 223
- 238000012545 processing Methods 0.000 title description 13
- 238000000034 method Methods 0.000 claims abstract description 63
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 31
- 238000011282 treatment Methods 0.000 claims abstract description 27
- 239000012528 membrane Substances 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000108 ultra-filtration Methods 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 230000001112 coagulating effect Effects 0.000 claims description 8
- 238000005345 coagulation Methods 0.000 claims description 8
- 230000015271 coagulation Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 238000005189 flocculation Methods 0.000 claims description 6
- 230000016615 flocculation Effects 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 235000012489 doughnuts Nutrition 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000701 coagulant Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 17
- 239000002351 wastewater Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000005188 flotation Methods 0.000 description 9
- 238000004537 pulping Methods 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 239000010893 paper waste Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000202567 Fatsia japonica Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000003673 groundwater Substances 0.000 description 1
- 150000004680 hydrogen peroxides Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
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- 239000006259 organic additive Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 239000003643 water by type Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a treatment method for paper-making white water, which comprises: treating residual white water with superficial air-float technique and with polyaluminium chloride and strong-cation polyacrylamide as flocculant and coagulant by special proportion to make SS of out water about 10mg/L and turbidity not larger than 15NTU and become primary recycling water, ultrafiltrating to remove all SS with turbidity not larger than 1NTU, and obtaining super recycling water. This invention can realize zero-discharge of paper-making white water in deed.
Description
Technical field
The plain boiled water that the present invention relates to field of papermaking is handled and reuse technology, and relating in particular to high-grade paper, speciality paper is the resource technology of residue plain boiled water in the paper manufacturing systems of product, maximally utilises plain boiled water and improves the plain boiled water reclamation rate realizing.
Background technology
Water resources crisis has become one of global focal issue; water is the main carrier that paper product is produced; in paper, a large amount of dischargings of the demand of clear water and waste water will be subjected to comprising the restriction of the each side of factors such as economy, environment along with the shortage of water resource.Can predict, in the near future, water can become the papermaking enterprise survival and development " bottleneck " soon, and the papermaking enterprise that especially is distributed in the big and medium-sized cities of surface water scarcity, groundwater storage deficiency will at first face this significant problem.
Paper-making effluent mainly comprises black liquor, middle section water, mthod of white water from paper making three major types.Pulping system with cleaning procedure as alternative soda processes traditional handicrafts such as " alkaline hydrogen peroxides steam bleaching integrated " after, the lower (＜60m of pulp-making waste-water discharge capacity
3/ ton slurry), its pollutional load is equivalent to about 50% of traditional handicraft, and advanced pulp and paper production only discharges to steam and floats waste water and mthod of white water from paper making.Float waste water with steaming and compare, mthod of white water from paper making mainly contains fiber fines, heteroproteose cell thing, chemical additive (as sizing material, filler, chemical assistant etc.), and composition is simple relatively, is the part of tool resource possibility in the paper waste.
Different paper machines and paper product thereof, slurry character etc., the plain boiled water of generation is different with the quantity of possibility reuse with approach, for example in the fine paper that with the production bank-note paper is representative was manufactured paper with pulp, the plain boiled water secondary circulatory system was generally all turning round.So, seek the white water loop technology of high reclamation rate and adopt more advanced technology that residue plain boiled water is carried out harmless treatment, and then pursue the mthod of white water from paper making zero-emission, and be the most important thing of paper waste treatment technology, have remarkable economical meaning and social effect in today of water scarcity.
Plain boiled water reuse degree has bigger difference because of conditions such as the kind of the structure of paper grades, paper machine and the speed of a motor vehicle, slurry character, chemical additive and consumption different.Be raw material with recycled writing paper etc. or be in the paper manufacturing systems of major product, thereby higher water circulation rate can be arranged, the zero-emission of realization that has because its water quality requirement to industrial water is not high with corrugated paper etc.In based on the paper manufacturing systems of producing speciality paper, fine paper, plain boiled water reuse degree varies, residue plain boiled water is generally discharged by local environmental protection standard after treatment.The domestic advanced level of the plain boiled water ton paper discharge capacity of non-wood-fiber papermaking at present is 50～70m
3, abroad be 10～30m
3Be in the pulp and paper production of raw material production bank-note paper with the cotton linter, discharge capacity is very high, and actual ton paper plain boiled water discharge capacity has reached 400m
3About.
At present, the White Water Treatment technology mainly contains filtering technique, air supporting method, the precipitation method, flocculence, membrane separation technique etc., and the air supporting method has obtained leading position as the major technique of plain boiled water reuse and slurry recovery.Along with progress of research, membrane separation technique is introduced into the wastewater treatment of paper industry gradually with its known advantage, has replaced traditional filtering technique, so the method for maximum and generally acknowledged comparative optimization of studying in the industry concentrates on air supporting method and membrane separation technique aspect.
Though there is a large amount of research reports to show that membrane separation technique has entered industrial applications in the paper waste process field, but the research from each side also shows simultaneously, membrane separation technique (for example ultrafiltration, counter-infiltration etc.) is applicable to that mainly black liquor is handled and the processing of floating waste water is washed in the stage casing, and do not have advantage economically (referring to " membrane technology is used for the progress that paper waste is handled " of Li Zhijian etc. for the processing of paper machine white water, " Chinese papermaking ", 2003 22 the 1st phases of volume); " application of membrane separation technique on paper waste is handled " (" International Paper " 21 the 1st phases of volume) that Cao Bangwei etc. deliver are also introduced, membrane separation technique is applicable to handles all paper-making effluents except that wastewater from paper machine (plain boiled water), and the removal to bleaching effluent toxicity, colourity and suspended matter has positive effect especially.As seen there is certain particularity in the plain boiled water treatment technology, and whether membrane separation technique is suitable for also exists different opinions.
Reclaiming research for the processing of paper machine white water discloses, adopting super efficiency shallow air flotation is present optimal means, its main feature is to ss suspended solid clearance height, for example adopt the KROFTA flotation tank to handle and the SS of mthod of white water from paper making can be reduced to 45mg/L (referring to " Hunan papermaking " the 2nd phase in 2002 from 3234mg/L, Dang Chaohua, " simple analysis KROFT flotation tank "), its SS treatment effeciency can reach more than 98%.But there is particularity in the plain boiled water that some speciality papers for example produce in the production of bank-note paper, cheque paper etc. on form, and the character for reuse plain boiled water also has very high requirement in the sector paper production, introduces present air flotation technology simply and obviously can not satisfy demand of practical production.
At first be that paper machine speed is slow in some specialties and the high-grade paper production process, the plain boiled water generation is big; And compare with the plain boiled water of other paper kinds, the residue plain boiled water that bank-note paper production produces has also that fibre-bearing is tiny, titanium dioxide (TiO
2) characteristics such as amount is big, particle thin (0.15～0.45 μ m), concentration are low, the plain boiled water emulsus that is white in color, solid content is free settling not, so this class plain boiled water has tangible particularity, can not direct reuse, the difficulty of processing is also bigger.According to statistics, the ton paper displacement of domestic bank-note paper production is at 300～400m
3Between, wherein remain plain boiled water and account for more than 60%.The general SS of water outlet that the shallow air-floatation that adopts in paper is at present handled is at 20～50mg/L, and process object is mainly based on the high concentration paper machine white water, and its solid content is mainly based on fiber.The plain boiled water low for concentration, that turbidity is high, for example SS is about 100mg/L, and turbidity is up to the bank-note paper residue plain boiled water of 1000NTU, and used shallow air-floatation treatment process is difficult to be suitable for.On the other hand, the system that manufactures paper with pulp of some high-grade paper requires to be lower than 20mg/L to the SS of reuse plain boiled water (elementary reuse), introduces present air flotation technology simply and is difficult to reach.
In a word, though the wastewater processing technology in each stage of pulping and papermaking processes all has a lot of research reports, but all be at common paper manufacturing, realize the high reclamation rate or the zero-emission of plain boiled water, also need to handle more targetedly means in special paper manufacturing industry resemble the bank-note paper.
Summary of the invention
The invention provides a kind of processing method of mthod of white water from paper making, the plain boiled water after the processing can satisfy different reuse requirements, reaches the purpose of mthod of white water from paper making zero-emission, and this method is particularly useful for the resource technology of plain boiled water in the speciality paper production.
According to White Water Treatment method provided by the invention, comprise the process that adopts shallow air-floatation technical finesse mthod of white water from paper making: make plain boiled water under turbulent condition, form the polymerization co-mixing system with the aluminium polychloride coagulation, this co-mixing system is sent in the dissolved air water hybrid system of shallow air-floatation water purifier then, adding flocculation aid mixes with dissolved air water after 3～5 seconds and carries out Separation of Solid and Liquid, isolated clear water is collected and discharged in bottom, shallow air-floatation pond, become elementary recycle-water; Wherein, the addition of aluminium polychloride is 60～240mg/L, with coagulating time of plain boiled water at 40～80 seconds, flocculation aid is the epistasis cationic-type polyacrylamide, addition is 1～1.5% of an aluminium polychloride addition.
In fine paper, speciality paper production system, I and II white water loop system is arranged all generally.One-level circulation is meant and a part of plain boiled water denseer, that amount is also bigger of deviating from when the slurry of the constant portion of paper machine at first forms page generally directly enters high-order white water chest, and be used to then size mixing, this part plain boiled water is called enriched water, and residue is discharged.Secondary circulation is meant that plain boiled water participates in sizing mixing, pull an oar and is used for the additional water of pulping system, and this part plain boiled water is called pure water.Said pure water derives from the vacuum suction box of wet end, be by the l Water Paper page or leaf on the felt is carried out the vacuum dehydration that vacuum suction filter produces, generally speaking, the vacuum dehydration behind this part suction strainer at first enters the machine water pond, pumps into high-order white water chest then and participates in circulation.But pure water generally all has discharging in many fine paper production system, and especially the elder generation along with pulping process evolves, and the pulping system water consumption reduces in a large number, thus the pure water generates residue that makes the circulation of plain boiled water secondary.Therefore, realize this part remaining plain boiled water is all handled and utilization is one of characteristics of the present invention.
The front is mentioned, and this part residue plain boiled water is different with other plain boiled waters, and promptly it has that concentration is low, turbidity is high, fiber is tiny, titanium dioxide content height, the characteristics that discharge capacity is big.For example bank-note paper residue plain boiled water characteristic has:
Physical characteristic: mainly contain solid content, dissolubility and colloidality organic additive, solid content is based on fiber fines and titanium dioxide, and wherein titanium dioxide content accounts for about 40% of total solid, and the outward appearance milkiness state that is white in color is tasteless, not free settling;
Water quality: SS 40～150mg/L, COD 50～200mg/L, pH value about 7, turbidity 200～1000NTU.
The inventor gropes to find through overtesting, only use flocculant according to the shallow air-floatation processing method of routine, and do not use the epistasis cationic-type polyacrylamide as auxiliary agent, perhaps its dosage or dosage be not than not at that time, handle in the water outlet and contain tiny condensate, the turbidity height, the screenings layer instability that forms on the flotation tank face easily sunk.When epistasis cationic-type polyacrylamide dosage was excessive, screenings layer viscosity increased, and can influence skimming of screenings, simultaneously, causes heavy particle detachment in the mixture easily, and the SS content in the water outlet increases on the contrary.So aluminium polychloride and epistasis cationic-type polyacrylamide require to use simultaneously in the method for the present invention, add with the solution form of debita spissitudo, and the two ratio of batching is 100: 1～100: 1.5, be preferably 100: 1.Mix down and the crane span structure cohesion of flocculation aid through the blend effect of described flocculant and dissolved air water, realize the general SS of isolated plain boiled water about 10mg/L, turbidity≤15NTU, and guarantee to reach the requirement of SS≤20mg/L, can satisfy elementary reuse.
In the coagulating process of above-mentioned plain boiled water, plain boiled water be the order through two blenders, be transferred simultaneously in the dissolved air water hybrid system that is pumped into the shallow air-floatation water purifier well-mixed.Concrete processing procedure can be: residue plain boiled water at first enters first blender by water tank, under turbulent condition, give birth to coagulating with the abundant hybrid concurrency of coagulant polymeric aluminium chloride, form the polymerization co-mixing system, in course of conveying (pipeline conveying) enter delivery pump after the mixing through second blender once more, send into by delivery pump in the dissolved air water hybrid system of shallow air-floatation water purifier, with before dissolved air water mixes, add flocculation aid epistasis cationic-type polyacrylamide, the crane span structure cohesion takes place under the mixing of dissolved air water then.In the whole coagulation process, aluminium polychloride was controlled at 40～80 seconds with residue time of reacting of plain boiled water, preferably 40-60 second, can be controlled at about 50 seconds.Realize that this process is three different transportation sections, has passed through strong turbulent mixture three times: be respectively first blender by being arranged on the transfer pipeline diverse location and second blender and finish with the delivery pump impeller that is arranged on apart from the suitable distance of second blender.Be appreciated that and will realize turbulent flow and satisfy the coagulating time, between the fed distance of the polymerization co-mixing system that can form for plain boiled water and aluminium polychloride and flow, the caliber by the definite suitable corresponding relation of measuring and calculating.Certainly can also take other any feasible method, prerequisite is to carry out under well-mixed state, and will be controlled in the reaction time 40～80 seconds.The crane span structure pool time of epistasis cationic-type polyacrylamide should be controlled at 3～5 seconds, that is to say, carried out Separation of Solid and Liquid under the effect at dissolved air water rapidly after the crane span structure aggregation takes place.The epistasis cationic-type polyacrylamide that the present invention uses is meant the cationoid type polyacrylamide polymers with higher ion degree, generally can select molecular weight at the polymerizate more than 1,500 ten thousand.
The shallow air-floatation treatment system mainly is made up of dissolved air water energy dissipating system, shallow air-floatation pond, center rotary system (comprise water-locator, cast aside mud device, clear water gathering-device), air dissolving system (comprising Gas dissolving pipe, high-pressure circulation pump, air compressor machine).Fully contact with the high density dissolved air water that passes through after energy dissipating is handled by the mixed system after the cohesion of epistasis cationic-type polyacrylamide crane span structure, form the co-mixing system of microbubble, agglomerate, water, agglomerate combines with microbubble, come-up forms the screenings layer in flotation tank, collect the back discharge by casting aside the mud device, isolate the clear water of agglomerate and in the pond, discharge in the collection of the bottom in pond by synchronous clear water gathering-device.This part clear water can be sent into clear water reserviors, as the elementary recycle-water in the circulatory system (it is following that SS has been reduced to 20mg/L).
The course of conveying of each stage fluid and method, and the concrete structure of shallow air-floatation water purifying processing system and operation can adopt known any viable means and method at present, and the present invention does not have particular determination.
According to process technology scheme of the present invention, binding film isolation technics in the plain boiled water recycling treatment can realize that 100% removes the SS in the plain boiled water, significantly reduces the plain boiled water turbidity, the final clear water that obtains can satisfy the requirement of senior recirculated water, and this also is one of outstanding feature of the present invention.Promptly, air supporting is handled isolated clear water and is adopted the milipore filter piece-rate system to carry out hyperfiltration treatment, used milipore filter is selected from: polysulfones and modification thereof or blend series ultrafiltration membrane, polyacrylonitrile and modification thereof or blend series ultrafiltration membrane, Kynoar and modification thereof or blend series ultrafiltration membrane or cellulose acetate series ultrafiltration membrane see through liquid and collect the back as senior recycle-water.
Speciality paper and some high-grade paper with anti-counterfeiting characteristic, especially the particularity of bank-note paper production technology, cause in residue plain boiled water, may containing a spot of as dissolubility pluronic polymers such as FX-76 (strong positive amide-type), PX-5, coagulation air-float is handled in the water outlet of back also can bring micro-cationic PAM and a certain amount of chlorion into, therefore, when implementing the film lock out operation, the treatment effect that must selection should reach high flux and high-recovery is not simultaneously again by the membrane material of these composition influences or pollution.Recover angle from the cleaning of separating effect and film and consider, the present invention can with the milipore filter suggestion be selected from polysulfones and modification or blend series ultrafiltration membrane.
Different with other waste water hyperfiltration film separating treatment, the White Water Treatment amount is big, requires film long service life and percolate flux big, reduces the Treatment for Reuse cost with this.So, for screening suitable membrane material, the inventor handles the coagulation air-float water outlet with PS film, polyacrylonitrile film, PS-PEK film respectively, determine that preferred milipore filter is PS-PEK doughnut blend film (polysulfones+polyphenylene oxide ketone), holding back the material relative molecular weight is 10000～70000 dalton, especially membrane aperture is the single skin milipore filter of 0.01～0.1 μ m, this film good hydrophilic property, and the anti-pollution ability is strong.In specific implementation process, can select the milipore filter of concrete specification according to the character of plain boiled water, for example 10000～30000 dalton, 30000～60000 dalton or 60000～70000 dalton etc.
From realizing and expand the feasibility angle of industrial applications, the present invention has also filtered out the cleaning restoration methods of advanced treating after the Pollution of Ultrafiltration Membrane.That is, running water cleans 5～10min → 2% citric acid and cleans 30～60min → 0.5M NaOH soaking and washing 90～120mi n → running water cleaning 15～30min.
Milipore filter piece-rate system of the present invention can be made up of circulation tank, delivery pump, ultrafiltration membrance filter device etc.Water after device filters after filtration enters the circulation tank, sends into the ultrafiltration membrance filter device by delivery pump, sees through liquid and has all removed SS, and turbidity≤1NTU is collected in another clear water reserviors, and for senior reuse, concentrate returns the air supporting treatment system.
According to preferred version of the present invention, reach the requirement of senior recycle-water in order to ensure the plain boiled water after separating through film, plain boiled water after air supporting is handled should be earlier through suitable filtration treatment, removing the flocculated particle that do not eliminated on a small quantity etc., thereby guarantee the water stabilization that enters film separation system by the air supporting treatment system.Filter the concrete operations of link and can adopt known method, for example rotating filter or other screen filtrations.
In a word, the outstanding feature that the White Water Treatment technology that the present invention proposes is compared with known paper-making effluent treating process is mainly reflected in two aspects: the one, and control aluminium polychloride (PAC) forms stable polymerization co-mixing system with the hybrid reaction condition of plain boiled water to guarantee it, simultaneously, determined the magnitude relation of using of PAC and PAM (cationic polyacrylamide), reached the purified treatment effect of low concentration plain boiled water to greatest extent, the processing water outlet can be used as elementary recycle-water and is used for the white water loop system; The 2nd, adopt the milipore filter isolation technics that water outlet is handled in air supporting and carried out advanced treating, especially selected good hydrophilic property, single skin PS-PEK milipore filter that the anti-pollution ability is strong, and determined that film pollutes and cleaned restoration methods.
Another technical characterstic of the present invention is to have adopted " shallow air-floatation+milipore filter " group technology grading recycle again to the residue plain boiled water of the plain boiled water secondary circulatory system in fine paper, the speciality paper production and after washing net plain boiled water and handling.Wherein adopt primary treatment, be that the water outlet that shallow air-floatation is handled can be used for substituting the vavuum pump cool circulation water and being used for pulping system (the present invention is called elementary reuse), particularly, 1. be used for the cold circulatory system of vavuum pump, substitute the clear water of former usefulness fully, enter the plain boiled water secondary circulatory system after the circulation; 2. be used for pulping system, substitute whole former clear water of using, after pulping system uses, enter waste water terminal processes facility with the pulp-making waste-water form.The hydro-peening water (the present invention is called senior reuse) of alternative wet end felt of the water after the ultrafiltration membrane technique advanced treating and roller nets such as fourdrinier wire, cylinder.And two processes can independently be provided with, and set treatment process according to the concrete condition in producing.In the production system of manufacturing paper with pulp of fine paper, speciality paper, clear water consumption maximum be the cleaning of various roller nets and felt, they generally finish by a high pressure and a low pressure spray pipe respectively.Water after ultrafiltration membrane treatment can be all or part of substitutes the clear water in this system, thereby makes the paper manufacturing systems water realize closed cycle (zero-emission truly).The present invention is applied in the bank-note paper production, and a ton paper plain boiled water discharge capacity reduces 200m
3, can realize the plain boiled water resource substantially, have significant environment, economy and society benefit.
The accompanying drawing summary
Fig. 1 is the process chart of the preferred embodiment of the invention.
The specific embodiment
Introduce realization of the present invention in detail below in conjunction with the drawings and specific embodiments, be intended to help the reader to understand technical spirit of the present invention and characteristics better, can not be considered as qualification the scope of the present invention.
Embodiment one
Handle the secondary circulation residue plain boiled water of plain boiled water from certain banknote paper plant.
1. handle the water yield and water quality
1. handle the water yield: 3000m
3/ d;
2. influent quality: SS40～150mg/L, COD50～200mg/L, pH value about 7.0, turbidity 200～1000NTU.
2. capital equipment disposes and technological parameter
1. first, second blender: φ 300mm, long 500mm;
2. shallow air-floatation water purifier: CQJ-6 type (Wuxi river and mountain engineering complete set of equipments Co., Ltd), φ 6m;
3. clarified water pump: 150FR-35 type, power 30KW, lift 35m, maximum stream flow 200m
3/ h;
4. white water pump: 100WD type, power 15KW, lift 15m, maximum stream flow 140m
3/ h;
5. dissolved air water reflux pump: IS80-50-250A type, power 18.5KW/22KW, lift 64.5m/80m, maximum stream flow 45m
3/ h;
6. cationic PAM dispensation apparatus: power 2.2KW, rotating speed 1420r/min, gearratio are 1: 11, and PAM is from MIT, molecular weight 〉=1,500 ten thousand dalton;
7. PAC dispensation apparatus: power 5.5KW, rotating speed 1440r/min, gearratio 1: 17, PAC is from Gongyi City, Henan plumage water-purifying material factory of shaking, Al
2O
3Content 〉=30%;
8. dosing pump: G5 type diaphragm metering pump, maximum stream flow 5.37L/h;
9. No. 1 clear water reserviors: 100m
3
3. processing procedure
1. the cationic PAM working concentration of PAC and epistasis is respectively 10% and 0.2%, and the PAC dosage is 120～140mg/L (to handle plain boiled water), and aluminium polychloride and the epistasis cationic polyacrylamide ratio of batching are 100: 1;
2. air dissolving system technological parameter: Gas dissolving pipe inlet pressure 〉=0.45Mpa, outlet pressure 〉=0.40Mpa; Compressed air pressure 0.65Mpa, air inflow 0.6～1.0m
3/ h;
3. coagulation and air supporting processing procedure system are referring to accompanying drawing 1, and blender 1 passes through pipeline connection with blender 2, and distance is about 5m, and blender 2 is about 30m with the distance of delivery pump, and delivery pump and epistasis cationic polyacrylamide add point apart from being about 15m.Plain boiled water at first is admitted to blender 1, and is in turbulent condition, adds PAC at the back segment top of blender 1,, adds PAC (aluminium polychloride) before plain boiled water flows out this blender that is, and the polymerization co-mixing system that plain boiled water and PAC form is with 120m
3The flow of/h is carried in ∮ 200mm pipeline, and keep this state through blender 2, be transferred then and be pumped into the shallow air-floatation pond, this process is through three strong turbulent mixture, reaction time is about 50 seconds, drop into PAM this moment, and controlling its cohesion crane span structure time is 3～5 seconds, enters the dissolved air water system after promptly 3～5 seconds.After agglomerate was separated, clear water entered clear water reserviors 1, and this clear water character is measured, and the results are shown in Table 1.
Shallow air-floatation result table under table 1. specific process conditions
| Import | Outlet | Δ SS % | Δ turbidity % | ||||
| SS (mg/L) | Turbidity (NTU) | The pH value | SS (mg/L) | Turbidity (NTU) | The pH value | ||
| 77 | 455 | 7.54 | 8 | 15 | 7.10 | 88.3 | 96.7 |
| Inflow: 125m 3/ h; Add dose: about PAC120～140mg/L, about the cationic PAM1.2～1.4mg/L of epistasis. | |||||||
| Annotate: 1. above-mentioned water quality is the nearly bimestrial instantaneous sampling average result of actual motion; 2. handle the water outlet fully recovering in pulping system and the cold circulating pump system of paper machine (elementary reuse). | |||||||
Embodiment two
Advanced treating is implemented in the air supporting water outlet that embodiment 1 obtains:
1. treating capacity: 25m
3/ d.
2. capital equipment
1. water tank (circulation tank) ∮ 600mm*1000mm;
2. circulating pump (stainless steel centrifugal pump), Q60～260L/min;
3. hyperfiltration membrane assembly: single skin structure PS-PEK hollow fiber ultrafiltration membrane, filling area 4m
2, membrane aperture 0.01～0.1 μ m promptly, holds back molecular weight of material 60000～70000;
4. control system 1 cover and water-in and water-out spinner flowmeter are 1 group.
3. processing procedure
Filter liquor behind water outlet (for example water outlet of embodiment 1) the process rotating filter device that air supporting is handled, with certain speed and pressure (inlet pressure 0.13～0.15Mpa, outlet pressure is that 0.10～0.12Mpa) end from the milipore filter separator enters, water and small-molecule substance see through film, promptly form and see through liquid, discharge and be collected into 2 li of clear water reserviors from seeing through the liquid outlet, macromolecular substances other end (concentrate outlet) from separator under the carrying of water flows out, and this a part of water is called concentrate.The flux of this piece-rate system is 50～70L/m
2H handles the rate of recovery and can reach more than 95%, promptly has only 5% concentrate to enter the air supporting treatment system.
4. milipore filter cleaning method
Cleaning the PS-PEK blend film according to following process can make membrane flux be recovered: running water cleans 5min → 2% citric acid and cleans 30min → 0.5M NaOH soaking and washing 90min → running water cleaning 30min.
5. water quality treatment the results are shown in Table 2.
Table 2.PS-PEK hollow fiber ultrafiltration membrane result table
| Project | SS(mg/L) | Turbidity (NTU) | COD(mg/L) | Total molten solid (mg/L) |
| Water inlet | 8 | 15 | 40～100 | 400～600 |
| Water outlet | 0 | ≤1 | 30～60 | 300～400 |
| Clearance (%) | 100 | ≥93 | 25～40 | 25～33 |
Water outlet after the hyperfiltration treatment can partly or entirely substitute the hydro-peening water of wet end felt and roller nets such as fourdrinier wire, cylinder.
Test example: the influence that coagulation condition is handled shallow air-floatation
Process of the test:
1) do not add any flocculant
2) only add PAC (aluminium polychloride)
3) only add PAM (epistasis cationic-type polyacrylamide)
4) add PAC and PAM simultaneously
Process of the test adopts the shallow air-floatation water purifier of embodiment 1, and for the test of only adding PAC or PAM, its dispensing point is sent into the dissolved air water mixing arrangement for the corresponding dispensing point among the embodiment 1 after the dispensing; The process of adding PAC and PAM simultaneously is with embodiment 1.The result sees table 3.
Shallow air-floatation result under the different coagulation condition of table 3. (SS, COD unit are mg/L, turbidity unit NTU)
| Experimental condition | Influent quality | Effluent quality | ΔSS ％ | ||||||
| SS | The pH value | COD | Turbidity | SS | The pH value | COD | Turbidity | ||
| Do not add PAC, PAM | 58 | 8.12 | 85.9 | 372 | 41 | 8.23 | 66.7 | 234 | 29.7 |
| Only add PAC | 94 | 8.07 | 113 | 430 | 105 | 7.73 | 82.6 | 216 | -11.7 |
| Only add PAM | 76 | 7.65 | 112 | 543 | 34 | 7.78 | 54.2 | 184 | 55.2 |
| Add PAC, PAM | 77 | 8.20 | 103 | 455 | 9 | 7.79 | 50.1 | 15 | 88.3 |
As can be seen from the above results:
Do not add under the situation of any medicament, though can obtain certain air flotation effect, the SS clearance has reached 30%, and dialogue water purification effect is relatively poor, and especially not obvious to the removal effect of turbidity, outward appearance still is creamy white;
During polyaddition aluminium chloride, water outlet SS raises on the contrary to some extent, and this is because behind the solid content generation coagulating in aluminium polychloride and the plain boiled water, particle showed increased but particle is tiny, and particle proportion increases simultaneously, the difficult cause that is held up by microbubble;
When only adding PAM, the suspended matter generation coagulating in PAM and the plain boiled water, the fiber fines that proportion is little is built up into bulky grain by crane span structure, and it is big that particle diameter becomes, and after air supporting was handled, major part can be removed, but also had the TiO of quite a few
2Can not be built up by crane span structure etc. big proportion particle, therefore, SS has certain clearance, but delivery turbidity is still higher;
Add PAC and PAM simultaneously, can obtain good air flotation effect, the SS clearance can reach more than 88%, and turbidity is below 15NTU.
Claims (10)
1, the processing method of mthod of white water from paper making, comprise the process that adopts shallow air-floatation technical finesse mthod of white water from paper making: make plain boiled water under turbulent condition, form the polymerization co-mixing system with the aluminium polychloride coagulation, this co-mixing system is sent in the dissolved air water hybrid system of shallow air-floatation water purifier, adding flocculation aid 3-5 mixes with dissolved air water after second and carries out Separation of Solid and Liquid, isolated clear water is collected and discharged in bottom, shallow air-floatation pond, become elementary recycle-water; Wherein, the addition of aluminium polychloride is 60-240mg/L, with coagulating time of plain boiled water in 40-80 second, flocculation aid is the epistasis cationic-type polyacrylamide, addition is the 1-1.5% of aluminium polychloride addition.
2, the described method of claim 1, wherein, isolated clear water adopts the milipore filter piece-rate system to carry out hyperfiltration treatment, collecting through liquid becomes senior recycle-water, and used milipore filter is selected from: polysulfones and modification thereof or blend series ultrafiltration membrane, polyacrylonitrile and modification thereof or blend series ultrafiltration membrane, Kynoar and modification thereof or blend series ultrafiltration membrane or cellulose acetate series ultrafiltration membrane.
3, the described method of claim 2, wherein, used milipore filter is polysulfones and modification or blend series ultrafiltration membrane.
4, the described method of claim 3, wherein, used milipore filter is polysulfones-polyphenylene oxide ketone doughnut blend film, molecular cut off is 10000-70000 dalton.
5, claim 3 or 4 described methods, wherein, it is polysulfones-polyphenylene oxide ketone doughnut blend film of 0.01～0.1 micron that milipore filter is selected from membrane aperture.
6, claim 3 or 4 described methods, wherein, described milipore filter is the single skin structure.
7, claim 2 or 3 described methods, wherein, contaminated milipore filter can clean recovery in accordance with the following methods in proper order: running water cleans 5～10min, and 2% citric acid cleans 30～60min, 0.5MNaOH soaking and washing 90～120min, running water cleans 15～30min.
8, the described method of claim 1, wherein, in the coagulating process of plain boiled water, plain boiled water be the order through two blenders, be transferred simultaneously in the dissolved air water hybrid system that is pumped into the shallow air-floatation water purifier well-mixed.
9, the described method of claim 1, wherein, described mthod of white water from paper making is the residue plain boiled water of plain boiled water secondary circulation in the paper-making process.
10, claim 1 or 9 described methods, wherein, described mthod of white water from paper making is the residue plain boiled water of the plain boiled water secondary circulation in the bank-note paper manufacture process.
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