CN1051063A - The continous processing system that black liquid is new - Google Patents
The continous processing system that black liquid is new Download PDFInfo
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- CN1051063A CN1051063A CN 89107711 CN89107711A CN1051063A CN 1051063 A CN1051063 A CN 1051063A CN 89107711 CN89107711 CN 89107711 CN 89107711 A CN89107711 A CN 89107711A CN 1051063 A CN1051063 A CN 1051063A
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Abstract
The present invention is applicable to the processing of black liquid (comprising the wood pulp papermaking black liquor, particularly is the black liquid of raw material with careless class).Native system has interactive new continous processing system for adopting ultrafiltration, electrodialysis, organically combination of biological treatment three.Can comprehensively reclaim in the black liquor about 80% lignin respectively and remove in the black liquor about 80% alkali (NaOH) and be reclaimed; organic matter is converted into biogas; reduce other organic matter and inorganic matter significantly, thereby can obtain significant environmental protection benefit and economic benefit.Native system adopt compact apparatus, easily supporting, investment is low, go up detective, convenient operation and management, the black liquor in medium and small paper mill is handled particularly economical.
Description
The invention belongs in the environmental improvement field, black liquid is carried out processed continuously system and equipment.
The present invention adopts ultrafiltration, electrodialysis, biological treatment organically to combine, and has interactive new continous processing system.
Through the update search (search report numbering 89239) and the manual information retrieval at Patent Office of the People's Republic of China search consultation place, the new black liquid treatment system of existing to being different from " evaporation and concentration-burning-causticization " method has checked in:
1, " electroosmose process comprehensive regulation black liquid of straw pulp paper-making " (sees " water technology " the 12nd the 2nd phase of volume, Wang Deshan; The comprehensive regulation of continent sub-farm, north paper waste) be directly reclaiming alkali without any pretreated black liquid, further handling through chemical coagulation (coagulation) again through single anode membrane (amberplex a kind of) electrodialysis plant.
The electrodialysis part of system of the present invention is to adopt yin, yang EDBM device to reclaim alkali.Before black liquid enters electrodialysis plant, earlier through ultrafiltration pretreatment; After the electrodialysis process again through uniting biological treatment.
2, " U, S, P-4,134,786 " is the method for purification to ox-hide paper plant waste water, is to add quaternary ammonium compound and active carbon and filtration in paper pulp and paper waste, add methyl alcohol etc. to reclaim lignin again; Need be furnished with active carbon regeneration and Methanol Recovery device in addition.
3, " U, S, P-4,490,257 " is the cleaning system to paper pulp chlorine bleach waste water, be waste water with the paper pulp chlorine bleach, purify through multi stage precipitation earlier, enter electrolysis unit then and handle, the electrolysis water outlet adds cationic polyelectrolyte and carries out chemical coagulation (coagulation); Handle through aerobic activated sludge process more at last.This method is not the processing black liquid.
4, Japan " special permission-clear 59-115795 " is the processing method to the paper pulp papermaking black liquor, is the draining of the steaming of sulfurous method slurrying being separated discharge opeing and washing procedure, earlier through ultrafiltration, then through culture yeasts and anaerobic bio-treated etc.
This method is not to be treatment system to alkaline pulping black liquor.
5, the black liquid wet cracking reaction is recycled and (is seen 102～103 pages of " several industrial wastewater treatment technology researchs of China " first fascicle paper-making industrial waste waters, Tianjin Light Industry College), be earlier through hygrochase reaction, sedimentation separation, again through evaporation and concentration, causticization recovery alkali etc. with the alkali straw pulp black liquor.
Hygrochase reaction in this method needs to carry out under 190～210atm, 350～370 ℃; And be equipped with evaporation and concentration and causticization equipment etc. in addition, and alkali recovery is more than 50%, organic removal rate is about 85%.
By above-mentioned update search, all find no the material that is same as black liquid treatment system of the present invention.
Papermaking is by slurrying and copy two main processes of paper and form.With the grass or the string of wooden class is that the pulping process of raw material has methods such as Mechanical Method, chemical method and both combine; It is alkaline process in the chemical method that China uses at present maximum.Operations such as the process of soda pulping process is got the raw materials ready, boiling, washing, screening, bleaching; The cooking waste liquor of alkaline process, Yin Sehei is so be called black liquid.(being designated hereinafter simply as black liquor).
Contain a large amount of organic matter (as the catabolite of lignin, carbohydrate and organic acid etc.) and inorganic matter (as various sodium salts and silicon compound etc.) in the black liquor, wherein the content of lignin is that the concentration of 20～50 grams per liters, alkali is that 8～35 grams per liters, CODcr value can reach that 100,000 mg/litre are above, colourity can be higher than 100,000 times (extension rates).As not treated direct discharging, meeting is contaminated environment extremely seriously.
Up to now, ripe both at home and abroad and industrialized black liquor processing method is the method that black liquor-evaporation and concentration-burning-causticization reclaims alkali.But this method exists following problems:
1. only reclaim alkali, can not reclaim lignin; And can be used as the multiple raw material of industry, lignin is used.
2. need main equipments such as multi-stage evaporator, combustion furnace, investment cost is very high, and more medium and small paper mill is difficult to bear; And China's enterprises in pulp and paper industry great majority are small-sized paper mills of producing per year below 3000 tons at present.
3. particularly be the black liquor of raw material with the paddy and wheat grass, tiny because of the fiber of straw or like vegetable, lignin content is lower, ash content is many, silicone content is high; Evaporation, burning and the causticization of chemical recovery system are all affected adversely, and the easy fouling of evaporimeter, combustion heat value are low, and the rate of recovery of alkali is also not high.So,, be urgently to remain the problem further researched and solved to the processing and the recovery of straw pulp black liquor.China is thousands of at present is the medium and small paper mill of raw material with the paddy and wheat grass, owing to black liquor is not handled (comprise and fail to reclaim alkali), environment is caused severe contamination.The function of near the river the paper mill that has, river, lake, pool is lost, and people ' s health and hydrobiological growth and breeding are all endangered.
Thereby, press for a kind of new continous processing system that is different from existing by evaporation and concentration-burning-causticization method of invention, black liquid is handled and comprehensive the recovery; To the treatment system and the black liquor treatment system that is applicable to medium and small paper mill of straw pulp black liquor, more need especially.
The present invention has set up one organically to be combined by ultrafiltration-electrodialysis-biological treatment, and has interactive new black liquid continous processing system.Here it is to remove the black liquid of larger particles through screen filtration, reclaims lignin with ultrafiltration earlier, reclaims alkali with the electrodialysis dealkalize again, at last with the biological treatment decomposing organic matter.
Fig. 1 is technological process of the present invention and technology frame chart, among the figure 1,2 ... 7 connotation is:
1. black liquor
2.100～120 eye mesh screens are removed larger particles, ultrafiltration pretreatment
3. lignin, electrodialysis preliminary treatment are reclaimed in ultrafiltration
4. electrodialysis dealkalize, recovery alkali, biological treatment preliminary treatment
Anaerobism, the oxygen of holding concurrently, aerobicly unite biological treatment and decompose, remove organic matter and produce biogas
6. precipitation Separation of Solid and Liquid
7. processing water
Ultrafiltration part in the system in order to after reclaiming lignin, molecular cut off and being about 10,000 pollutant, will help follow-up electrodialysis process and biological treatment.The yin, yang ion-exchange membrane electrodialysis dealkalize of black liquor after ultrafiltration, recovery alkali, than directly carrying out electrodialysis without ultrafiltration, power consumption can reduce greatly; And as the pre-treatment of subsequent biological treatment.Reclaim lignin and the black liquor after the electrodialysis dealkalize through ultrafiltration, carry out a biological disposal upon again, than carrying out a biological disposal upon with raw black liquid, have more advantages, because lignin is to be difficult to biodegradablely, and the existence of a large amount of alkali more will make the microorganism in the biological treatment be difficult to growth and breeding.
1. the ultrafiltration part of system of the present invention adopts external pressure tubular type stainless steel combination ultrafiltration apparatus, and milipore filter is PS membrane, polyacrylonitrile film, and device and milipore filter all can be buied to environmental protection equipment factory or by market on request.
Black liquor is removed a bigger material impurity earlier through 100～120 purpose screen filtrations, enters ultrafiltration apparatus then.During ultrafiltration, in 2.5～4.0 kilograms per centimeter
2Under pressure, 40～60 ℃ of temperature, flux is 26～35 liters/meter
2Hour.Through hyperfiltration treatment, about 80% lignin in the recyclable black liquor.
When reclaiming lignin with ultrafiltration, need not heat (temperature can improve gradually during ultrafiltration) more need not add any chemical agent; And equipment miniaturization, stable, be easy to the management.
2, vertical yin, yang EDBM device (can be on request, provided or buied by market by environmental protection equipment factory) is provided the electrodialysis part of system of the present invention.Positive and negative electrode in the device is all titanium plating ruthenium web plate, and anode membrane is that PECM001 amberplex, cavity block are the PEAM203 amberplex, and electrode web plate and amberplex all can be buied by market.
Black liquor after ultrafiltration enters above-mentioned electrodialysis plant, current density be the 20-30 milliampere/centimetre
2Following, but 80% alkali (NaOH) in the dealkalize recovery black liquor.
The partially recycled alkali of electrodialysis of the present invention is compared with adopting " evaporation and concentration-burning-causticization " method straw pulping black liquor, and the rate of recovery of alkali can improve about 20%, and equipment miniaturization, reduced investment; Compare with adopting single anode membrane multi-electrode electrodialysis plant recovery alkali, save the power consumption of battery lead plate and minimizing electrode reaction, so the investment of device and power consumption all reduce; And alkali is reclaimed in single anode membrane multi-electrode electrodialysis of having reported, be not carry out black liquor pretreated, the amberplex of the lignin in the black liquor, impurity meeting severe contamination electrodialysis plant, not only influence the equipment operation, power consumption also must increase, and the present invention is owing to after black liquor passed through hyperfiltration treatment, carry out electrodialysis again and reclaim alkali, so power consumption is lower, reclaiming alkali per ton (in 100%NaOH) power consumption is about 2500 degree; Than directly black liquor is reclaimed alkali with electrodialysis, 500～1000 degree that economize on electricity per ton; Reclaim alkali than single anode membrane multi-electrode electrodialysis, can improve alkali recovery about 20%.
3. the biological treatment part of system of the present invention adopts anaerobism, double oxygen, aerobic three sections methods that combine.
Black liquid is through ultrafiltration recovery lignin with after alkali is reclaimed in electrodialysis, and wherein organic concentration is still quite high, can reach tens thousand of mg/litre, so need carry out Anaerobic Treatment earlier, hold concurrently oxygen, Aerobic Process for Treatment again.
Three sections biological treatment devices of system of the present invention are all the up-flow bacteria bed, and the sheet thorniness medium-soft plastic filler (provided or buied by market by environmental protection equipment factory) of lifting is provided in the bed.Three respectively by go out, water inlet pipe connect.Anaerobic filter bed is established recirculated water insulation skin for what seal, and recirculated water adopts external heating type (biogas that available anaerobic stages produces heats), and with automatic temp controller.Temperature is controlled at about 35 ℃.The bottom of aerobic and double oxygen bed is provided with microporous aeration device, external air compressor machine snorkel; Aerobic bed adopts the continuous aeration oxygen supply; Gas-water ratio is 1: 15～20; Double oxygen bed aeration every day 1～inferior each 2～4 minutes, is mainly and stirs and a small amount of oxygen supply.
Black liquor enters anaerobic filter bed after ultrafiltration and electrodialysis process, temperature be about 35 ℃ and volumetric loading be 3.7～4.9 kilograms of COD/ rice
3Under it the condition, the clearance of CODcr is about 60%; 1 kilogram of CODcr of every removal can produce 0.3～0.6 meter
3Biogas, the calorific value of biogas is higher than coal gas, so can be used as circulation insulation water heating and other using energy source.The water outlet of anaerobic filter bed enters hold concurrently oxygen bed and aerobic bed, is 8～10 kilograms of COD/ rice at the normal temperature and the oxygen bed volumetric loading of holding concurrently
3My god, the aerobic bed volumetric loading is 10～12 kilograms of COD/ rice
3Under it the condition, the CODcr value in the anaerobic bed water outlet can be removed about 50% again.
The water outlet of aerobic bed is carried out Separation of Solid and Liquid through the precipitation of routine.
Black liquor is through ultrafiltration, water outlet after electrodialysis, the three sections bio combined processing, its CODcr value has been reduced to below 5% of raw black liquid (the total clearance of CODcr that is whole system is more than 95%), can mix mutually with the very big middle-stage wastewater of quantity in the paper mill, handle by existing ripe middle-stage wastewater processing method.
The continous processing system that black liquid of the present invention is new, once to 1 with timber be the pulp mill of raw material and 2 with rice, wheat straw is that the black liquid in the paper mill of raw material is handled.
1. can comprehensively reclaim simultaneously lignin (80%), alkali (80%), biogas (0.3～0.6 meter of 1 kilogram of biogas that CODcr produces
3), reduce the CODcr value (total clearance be more than 95%) of waste water significantly.
Lignin can be used as the multiple raw material of industry, and the various lignin series of products that China has developed have: farm chemicals diluent, oil drilling mud thinner, color additive cement water reducing agent and feed addictive etc.
Alkali is important well sold and in short supply industrial chemicals, and the alkali of recovery can return and be used for paper mill pulping and digesting usefulness.
Biogas is recyclable, as the heating and the use of other energy of anaerobic bio-treated filter bed insulation water.
Thereby the continous processing system that black liquid of the present invention is new is handled black liquor, can obtain significant environmental benefit and economic benefit.
2. reclaiming the alkali system with " evaporation and concentration-burning-causticization " compares, the continous processing system that the present invention is new, device miniaturization, easily supporting, investment is low, go up detective, and stable, convenient operation and management, particularly economical to medium and small paper mill (pulp mill).
3. be specially adapted to rice wheat straw class is the black liquor processing in the paper mill (pulp mill) of raw material; Certainly also be applicable to timber the black liquor processing in the paper mill (pulp mill) that is raw material.
Claims (1)
- A kind of new employing hyperfiltration technique, electrodialytic technique and biologic treating technique, the continous processing system to black liquid is handled, reclaimed is characterized in that:1, sets up a ultrafiltration-electrodialysis-biological treatment three and organically combined, had interactive treatment system;2, its ultrafiltration part adopts stainless steel external pressure tubular type combination ultrafiltration apparatus, and milipore filter is PS membrane, polyacrylonitrile film, and black liquor filters the laggard ultrafiltration apparatus of going into through 100～120 eye mesh screens earlier, is 2.5～4.0 kilograms per centimeter at pressure 2Under 40～60 ℃ of temperature, flux is 26～35 liters/meter 2Hour;3, its electrodialysis part adopts vertical yin, yang EDBM device, and the positive and negative electrode in the device is all titanium plating ruthenium web plate, and cavity block is that PEAM203 amberplex, anode membrane are the PECM001 amberplex, and current density is 20～30 milliamperes/centimetre 2;4, its biological treatment part combines for anaerobism, the oxygen of holding concurrently, aerobic three sections biological treatments, and three sections biological treatment devices are all the up-flow bacteria bed, connects by going out water inlet pipe respectively; It is outer that the anaerobic bed of sealing is established the recirculated water insulation, and recirculated water is external heating type and has automatic temp controller that temperature is controlled at about 35 ℃; The bottom of aerobic and double oxygen bed is provided with microporous aeration device; Anaerobic bed moves about 35 ℃, 3.7～4.9 kilograms of COD/ rice of volumetric loading 3My god, hold concurrently oxygen and aerobic bed move at normal temperatures, and the volumetric loading of the oxygen bed of holding concurrently is 8～10 kilograms of COD/ rice 3My god, the volumetric loading of aerobic bed is 10～12 kilograms of COD/ rice 3My god.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89107711 CN1051063A (en) | 1989-10-14 | 1989-10-14 | The continous processing system that black liquid is new |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89107711 CN1051063A (en) | 1989-10-14 | 1989-10-14 | The continous processing system that black liquid is new |
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| Publication Number | Publication Date |
|---|---|
| CN1051063A true CN1051063A (en) | 1991-05-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89107711 Pending CN1051063A (en) | 1989-10-14 | 1989-10-14 | The continous processing system that black liquid is new |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476257B (en) * | 2009-02-16 | 2011-01-26 | 北京嘉禾木科技有限公司 | Method for extracting lignose from papermaking black liquor |
| CN102390903A (en) * | 2011-09-30 | 2012-03-28 | 蒲茂军 | Papermaking black liquid membrane treating method |
| CN102910785A (en) * | 2012-11-01 | 2013-02-06 | 广西大学 | Treatment method and device for high-concentration organic wastewater |
| CN103351068A (en) * | 2013-07-24 | 2013-10-16 | 宜宾海丝特纤维有限责任公司 | Pre-treatment technology of ultrafiltration for electrodialytic alkali recovery of black liquor in pulp manufacturing |
| CN105347606A (en) * | 2015-09-23 | 2016-02-24 | 郑州大学综合设计研究院有限公司 | Treatment process for methanol protein wastewater |
| CN106865892A (en) * | 2017-03-07 | 2017-06-20 | 轻工业环境保护研究所 | Reducing rules black liquor by wet method alkali reclaiming method |
-
1989
- 1989-10-14 CN CN 89107711 patent/CN1051063A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476257B (en) * | 2009-02-16 | 2011-01-26 | 北京嘉禾木科技有限公司 | Method for extracting lignose from papermaking black liquor |
| CN102390903A (en) * | 2011-09-30 | 2012-03-28 | 蒲茂军 | Papermaking black liquid membrane treating method |
| CN102910785A (en) * | 2012-11-01 | 2013-02-06 | 广西大学 | Treatment method and device for high-concentration organic wastewater |
| CN102910785B (en) * | 2012-11-01 | 2015-05-06 | 广西大学 | Treatment method and device for high-concentration organic wastewater |
| CN103351068A (en) * | 2013-07-24 | 2013-10-16 | 宜宾海丝特纤维有限责任公司 | Pre-treatment technology of ultrafiltration for electrodialytic alkali recovery of black liquor in pulp manufacturing |
| CN105347606A (en) * | 2015-09-23 | 2016-02-24 | 郑州大学综合设计研究院有限公司 | Treatment process for methanol protein wastewater |
| CN105347606B (en) * | 2015-09-23 | 2018-06-19 | 郑州大学综合设计研究院有限公司 | A kind of Methanol Protein waste water treatment process |
| CN106865892A (en) * | 2017-03-07 | 2017-06-20 | 轻工业环境保护研究所 | Reducing rules black liquor by wet method alkali reclaiming method |
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