CN101775750A - A clear pulp production process for realizing complete comprehensive utilization and removing three wastes - Google Patents
A clear pulp production process for realizing complete comprehensive utilization and removing three wastes Download PDFInfo
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- CN101775750A CN101775750A CN201010100362A CN201010100362A CN101775750A CN 101775750 A CN101775750 A CN 101775750A CN 201010100362 A CN201010100362 A CN 201010100362A CN 201010100362 A CN201010100362 A CN 201010100362A CN 101775750 A CN101775750 A CN 101775750A
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Images
Abstract
The invention aims to provide a clear pulp production process for realizing complete comprehensive utilization and removing three wastes. The method is characterized in that the traditional lagged production process for evaporating black liquor, reclaiming boiler burned alkali, causticizing white liquor, reclaiming lime and discharging the pollution in the pollution treatment of three-level biochemical treatment for middle waste water (three wastes of pulp comprise waste water, waste gas and waste sludge) is eliminated; the plant material is completely used to remove three-waste emission of the pulp and increase five by-products such as lignin biological glue and the like to achieve the good effect on pollution treatment with benefit for treating pollution and making money; and the rubbish-free and zero-emission clear pulp production is realized. Therefore, the pulp enterprise becomes a water-saving large enterprise from a water consuming large enterprise, becomes an environment-friendly large enterprise from a pollution discharging large enterprise, positively and actively treats the pollution from the passive treatment and becomes a comprehensive utilization model from a resource consuming large enterprise.
Description
Technical field
The present invention relates to a kind of pulping and paper-making industry to raw-material comprehensive utilization, particularly realize the paper stuff cleaning manufacturing technique method of 100% comprehensive utilization and the elimination three wastes.
Background technology
One, who does not fully utilize pulping and paper-making raw material 100% in the world:
The problem that the pulping and paper-making industry is serious in the world at present is to waste material of vegetable origin greatly, because pulping and paper-making just utilizes the cellulose in the plant material, and cellulose only accounts for 40%～54% in plant material, all the other are that lignin accounts for 20%～30%, hemicellulose accounts for 10%～25%, ash content accounts for 0.15%～6%, other composition major part in the slurrying production process all goes out of use except that cellulose, go out of use in the pulp-making waste-water or in alkali reclaims, be sent in the boiler and burned, that is to say, the pulping and paper-making industry has only been utilized the plant material resource of half, and second half has been wasted; Annual more than 400,000,000 ton of the paper pulp of producing in the whole world, wherein 50% is the regenerated paper pulp that utilizes waste paper to make for raw material; Also have 200,000,000 tons to be to be the new paper pulp of raw material processing with plant.Average by 1 ton of finished product paper pulp calculating of 2.5 tons of plant material processing, the annual whole world will consume 500,000,000 tons of plant resourceses, if with timber is that pulping raw material calculates, annual pulping and paper-making industry will consume 7.5 billion cubic meter timber, be equivalent to cut down every year 2000 ten thousand hectares virgin forest, and half about 3.75 hundred million side Mi Mucai wherein have been wasted, and this is an astonishing huge waste how!
Two, who fails social effects of pollution in the world---and " three wastes " of pulping and paper-making realize zero-emission:
Pulping and paper-making " three wastes " is meant waste water, waste gas, useless three disposals of pollutants of mud.Because what present pulp production was in the world mainly used is chemical method, wherein mainly is alkaline process, sulfate process, sulphite process; No matter the employ pulp-making method all will produce a large amount of waste liquids, contain big weight organic compounds and inorganic compound in the waste liquid, contain higher chemical oxygen demand COD
CrWith biochemical oxygen demand (BOD) BOD
5Contamination index.Though these waste liquids all pass through black liquor and carry that dense, alkali reclaims, white liquid causticization, middle-stage wastewater is through air supporting method, the precipitation method, the filtration method of physical method; The flocculence of chemical method, oxidizing process, reducing process; Three grades of biochemical treatments such as the activated sludge process of biological method, biofiltration process, its disposal of pollutants is still a huge numeral, report according to the annual report in 2003,2004,2005,2006 of Chinese paper industry, the quantity of wastewater effluent of this several years pulping and paper-making industries is respectively 31.9 hundred million tons, 31.8 hundred million tons, 36.7 hundred million tons, 43.5 hundred million tons, account for 17%～18% of Chinese industrial total amount of sewage discharge, wherein 4 years chemical oxygen demand CODs
CrDischarge capacity is respectively 163.9 ten thousand tons, 152.6 ten thousand tons, 159.7 ten thousand tons, 182.2 ten thousand tons, accounts for Chinese industrial COD respectively
Cr35.3%, 29.8%, 32.4%, 33.6% of total release, the sewage discharge of pulping and paper-making industry has occupied the umber one, is modern society's last one big public hazards!
What each big enterprises in pulp and paper industry of the whole world was generally applied at present is " alkali recovery " production technology: the processing method that earlier black liquor vaporizing is concentrated, sends to these cover systems such as burning boiler, alkali recovery, white liquid causticization, lime recovery, complex process as same seat chemical plant, white liquid causticization and lime reclaim the fixed gas that also will produce a large amount of reducibility sulfuration thing TRS, the alkali recovery boiler burns will produce ground caustic dust pollution boiler room surrounding space, and the chimney of boiler will be discharged a large amount of harmful hydrogen sulfide (H every day
2S), sulfur dioxide (SO
2) and methyl mercaptan (CH
2Pernicious gas such as SH), the heavenwards discharging that 24 hours every days are not left alone without help pollutes the atmosphere; Discharge of harmful gases is the second largest social effects of pollution of slurrying industry!
At present each big slurrying enterprise all effluxes amplification quantity mud at Xiang Chang every day, these mud all are the deposits in the pulping waste liquor processing procedure, a manufacturing enterprise that produces 100000 tons of paper pulp per year, to outwards discharge more than 6000 ton of mud every year on average, the mud discharging field of these factories has much has been piled into the mountain, a large amount of arable lands have been captured in accumulation all the year round, and these mud dischargings just become the third-largest social effects of pollution of slurrying industry!
Three, China is the country of a lack of water, per capita water resource only be the world per capita water resource 1/4th, existing more than 300 the city serious water shortage of China, because the restriction of lack of water, at least cause 2000～3,000 hundred million yuans economic loss every year for Chinese industrial, annual average lack of water 300～400 billion cubic meter water of agricultural, be exactly under this lack of water situation, the annual water consumption of the pulping and paper-making industry of China is up to 80 billion cubic meters, account for national water for industrial use gross weight 18.4%, on average about 130 cubic metres, the pulping and paper-making industry is again a water consumption rich and influential family to ton slurry water consumption thus.
Four, above-mentioned pulping and paper-making industry existing three big drawbacks: waste plant resources, three disposals of pollutants, water consumption are many, be on record, experts and scholars over more than 100 year in the industry are in constantly active research and exploitation, all in the eager pollution of effecting a radical cure pulp production by every means, also obtained a lot of actual effects really, made the COD in the discharge of wastewater of pulp production
Cr, BOD
5Index constantly descends, reach each state emission standard, but because traditional paper pulp manufacturing technique method can not get radical change, pollution treatment need strengthen production cost, institute is so that the efforts at environmental protection of paper pulp industry are in loath " passive pollution treatment " situation always, and much progress is difficult to realize thoroughly eliminate three big disposals of pollutants though have very.
Pulping and paper-making industry technology present situation as mentioned above, in order to eliminate the discharging of social effects of pollution " the paper pulp three wastes ", the inventor is on the basis of summing up forefathers' experience, the method of thinking with new of unremitting effort goes to seek new pollution treatment production technology, finally draw such conclusion: have only realization could thoroughly eliminate the useless mud of waste water and gas to the comprehensive utilization of pulping raw material 100%, have only thoroughly to eliminate to change traditional alkali recovery and three grades of biochemical " passive pollution treatment " methods of administering, the pulping and paper-making industry could obtain new vitality.
Summary of the invention
The purpose of this invention is to provide a kind of paper stuff cleaning manufacturing technique method of realizing 100% comprehensive utilization and eliminating the three wastes, it is characterized in that overthrowing traditional black liquor vaporizing, boiler burns alkali and reclaims, white liquid causticization, lime reclaims, middle-stage wastewater is done still blowdown of pollution treatment (the paper pulp three wastes: waste water of three grades of biochemical treatments, waste gas, useless mud discharging) backward manufacturing technique method, by plant material 100% comprehensive utilization is used for eliminating the paper pulp three waste discharge, increase by five class byproducts such as lignin biological glue, the optimum effect of " profitable pollution treatment " that the formation pollution treatment can also be earned money realizes the paper pulp cleaning production of no rubbish zero-emission! Make paper pulp enterprise become the water saving rich and influential family, become the environmental protection rich and influential family, become positive pollution treatment, become the comprehensive utilization model from waste resource rich and influential family from those moving unwilling pollution treatments from the blowdown rich and influential family from the water rich and influential family.
Purpose of the present invention and solve its technical problem underlying and adopt following technical measures to realize.
According to realization 100% comprehensive utilization of the present invention's proposition and the paper stuff cleaning manufacturing technique method of the elimination three wastes.It is characterized in that being used for eliminating the slurrying three waste discharge by 100% comprehensive utilization to pulping raw material, specific practice is to washing material waste water in the slurrying production process, (red) liquid is deceived in boiling, middle-stage wastewater, bleaching effluent carries out segmentation and holds back extraction and cleaning improvement, by preliminary treatment, the net filter, micro-filtration (MF), ultrafiltration (UF), the combination technique means of nanofiltration (NF), using sieve effect selectively extracts respectively from waste liquid, separate, concentrate various solid contents and organic compound and dirt, again it is delivered to the new product that economic worth is processed in different deep processing workshop sections (5) (6) (7) respectively; Waste water after being cleaned becomes clean water, do not recycle at all at this workshop section inner sealing and to efflux, wherein filter membrane can selectively pass through filter membrane with bleaching agent (hydrogen peroxide) with water with the main chemical agent (alkali or sulfate or acid) that is free in the waste liquid, reaches the recovery Recycling; Because the employed plant material kind of slurrying difference, the processing method difference, drop into catalytic decomposition and the used chemical agent difference of bleaching process, so waste liquid color of each section, concentration, the solute that is contained, solid content, the composition of soluble solids, content and relative molecular weight size thereof are all inequality, therefore when each section waste liquid is carried out purification treatment, suitably adjust aperture specification of netting filter and filter membrane and the stepping rank that net and film are set targetedly according to the actual conditions of waste liquid, segmentation purification treatment waste liquid process of the present invention also is applicable to the making beating waste water in the paper process and makes the purified treatment of paper plain boiled water.
Purpose of the present invention and solve its technical problem underlying and can also be applied to the following technical measures to achieve further.
The paper stuff cleaning manufacturing technique method of aforesaid realization 100% comprehensive utilization and the elimination three wastes, wherein said pretreatment process, be that the colloidal substance that postorder filter membrane cleaning procedure is had adverse effect or forms dirty mucous membrane easily that is contained in the waste liquid is removed, comprise and being removed after with chelating agent metal ion-chelants such as Cn, Fe, Mn, Mg, Ca being become stable complex compound; Silica is changed into water-fast silicic acid compound to be separated; To become sulfate reaction with alkali and saponified the separating that form by organic impuritiess such as resin, fat, pectin, tannin.
The paper stuff cleaning manufacturing technique method of aforesaid realization 100% comprehensive utilization and the elimination three wastes, wherein said net filter, be to be used for holding back solid granulates material the thickest in the waste liquid, but because the size of the solid granulates in each section waste liquid is different with classification, so select the mesh size size also different: the net filter in raw material processing workshop section mainly is to be used for holding back various impurity, tie at interior various plant material impurity comprising bark, blade of grass, seed, fringe, root, joint, mesh can be established 3～6 grades, and the mesh size size is from 5mm～0.2mm; In the net filter of boiling catalysis workshop section and paper pulp processing workshop section mainly is to be used for holding back in the spent pulping liquor body greater than the solid matter of 20 μ m, comprising flocculating into oarse-grained colloid, residual chelating material grains, residual tiny silt particle particle, the paper pulp raw material disintegrating slag that does not have decomposition to get well, mesh can be established 3～5 grades, and the mesh size size is from 0.5mm～0.02mm.
Aforesaid realization 100% comprehensive utilization and eliminate the paper stuff cleaning manufacturing technique method of the three wastes, wherein said micro-filtration (MF) is to hold back various feature dimensions in the waste liquid greater than the granule foreign of 0.1 μ m.Be mainly used in and remove bacterium, suspended solids and colloid, particulate, submicron in the waste liquid; The aperture of micro-filtration (MF) film can be set up 3～7 grades separately, and the membrane pore size size is from 10 μ m～0.1 μ m.Micro-filtration (MF) is a pressure-driven separation filter membrane, and operating pressure is at P=0.01～0.07MPa.Film body is electronegative, and the organic matter that has negative electrical charge is had repulsive interaction, and film will regularly clean and guarantee the film passband.
The paper stuff cleaning manufacturing technique method of aforesaid realization 100% comprehensive utilization and the elimination three wastes, wherein said ultrafiltration (UF), be selectively to hold back respectively, separate various feature dimensions in the waste liquid between 0.1 μ m～0.002 μ m, relative molecular weight is at 1000～1000000 solid content, wherein mainly be lignin organic compound and fiber fines heteroproteose cell, lignin in the plant material is after alkalization and sulfate sulfonation or bleaching oxidation, being lignin fragment shape is decomposed to separate out and is dissolved in the slurries, its relative molecular weight major part is between 2000～4500, the aperture of ultrafiltration (UF) film can be set up 2～5 grades separately, and the membrane pore size size is from 0.05 μ m～0.002 μ m.Ultrafiltration (UF) is a pressure-driven separation filter membrane, operating pressure P=0.1～0.7MPa, and the ultrafiltration film body is electronegative, and the organic matter that has negative electrical charge is had repulsive interaction, so be difficult for dirty mucous membrane, film will regularly clean and guarantee the film passband.
The paper stuff cleaning manufacturing technique method of aforesaid realization 100% comprehensive utilization and the elimination three wastes, wherein said nanofiltration (NF), be selectively to hold back, separate feature dimension at the small organic matter and the inorganic matter of the relative molecular weight between 2nm～0.8nm between 100～1000, wherein mainly hold back and isolate the carbohydrate of the pentosan class of small-molecular weight lignifying compound, hemicellulose, remaining high price zwitterion, and can remove 98% colourity in the waste water, COD
CrIndex is reduced to below the 30mg/L, and selectively allows catalyst alkali (NaOH) and bleaching agent hydrogen peroxide (H
2O
2) pass through the filter membrane recycling together in company with water.Nanofiltration (NF) membrane aperture can set up 1～2 grade separately, the membrane pore size size is from 1.5nm～0.8nm, nanofiltration (NF) is a pressure-driven separation filter membrane, operating pressure is P=0.5～1.8MPa, the nanofiltration film body is electronegative, organic matter and the anion solute that has negative electrical charge had repulsive interaction, so be difficult for dirty mucous membrane, film will regularly clean and guarantee the film passband.
The paper stuff cleaning manufacturing technique method of aforesaid realization 100% comprehensive utilization and the elimination three wastes, wherein said comprehensive utilization deep processing, be meant that the separation and Extraction of holding back is come out in waste liquid (water) decontamination process organic matter and inorganic matter do deep processing, obtain the additional byproduct of five classes: (one) lignin organic polymer chemical products: utilize the characteristics that have multiple functional group and active group in the molecular structure unit of lignin, will be from black (red) liquid, middle-stage wastewater, hold back the lignin organic compound of separating in the ultrafiltration of each workshop section of bleaching effluent (UF) operation and nanofiltration (NF) operation, to its deep processing of doing chemical modification or connecing the skill copolymerization, can process and comprise the lignin organic adhesion agent, lignin one phenolic resins, degradable polyurethane; The degradable lignin plastic mulch film of agricultural usefulness, degradable long-acting slow-release chemical fertilizer, soil conditioner; The concrete for building and the water reducer of cement mortar, reinforcing agent, impervious agent, stone material are cut grinding agent; The high temperature conditioning agent that oil exploitation is used, profit coagulant, heavy crude thinner, emulsifying agent, economic benefits and social benefits water shutoff agent, AS FILTRATION LOSS CONTROLLER; Coal water slurry dispersing agent; Surfactant; Medicinal hay-scented aldehyde (vanillic aldehyde); The sizing agent that paper industry is used, reinforcing agent, retention and drainage aid agent are at interior multiple lignin products; (2) carbohydrate of the poly-pentose of hemicellulose and cellulose peeling reflection is to be dissolved in the second class organic compound in the waste liquid, nanofiltration in each workshop section (NF) can be held back it and be separated, and can obtain the addition product of furfural, ethanol, xylitol and so on to its deep processing; (3) the compound silicic acid (H of the silica that extraction is separated to pretreatment process
2SiO
3) or calcium silicates (CaSiO
3) carry out chemical modification processing, can obtain silica gel, sodium metasilicate, active silica, hydrophobic silica, aerosil, Ludox; (4) to come out from the pretreatment process separation and Extraction by the resin the wood raw material, pectin, fat and tannin through and alkali or sulfate reflection form saponified, can therefrom obtain rosin, Tall oil and aliphatic acid through acidifying processing, wherein tannin extracts and can be processed into a kind of new environment-friendly macromolecular material---degradable tannin polyurethane; (5) from the sedimentation basin operation of washing material waste water the sediment contamination separated and the metal ion complex of from the micro-filtration of the net filter of the net filter of black (red) liquid and middle-stage wastewater and each workshop section, separating, all kinds of organic with inorganic colloid, impurity such as not decomposing good paper pulp plant disintegrating slag, various solid particle, submicron to be mixed to mix adhesive, be pressed into insulating brick for building with brick machine.
The difference of the present invention and traditional pulp production is: abolished that traditional black (red) liquid evaporation and concentration, burning boiler (pernicious gases such as discharging ground caustic dirt, hydrogen sulfide, sulfur dioxide), alkali reclaim, white liquid causticization, lime reclaim, the pollution treatment manufacturing technique method that series such as three grades of biochemical treatments of middle-stage wastewater (blowdown mud, effluent) falls behind, above-mentioned traditional contamination governing method only spends not earn money, strengthen production cost, so factory's pollution treatment does not have enthusiasm; Use the application and make enterprise except that obtaining pulp product, increase by five class addition products such as lignin organic gel again, the economic benefit that pollution treatment can be enhanced about more than once to enterprise, and can thoroughly eliminate three waste discharge again, produces the production of no rubbish realization clean environment firendly; Compare with traditional black liquor burning and three grades of biochemical improvement methods, Tou Zi Minus lacks 10%, saves 50% land used, reduces production costs, increases by 200% economic benefit, reaches ecological, environmental protective.
In sum, realization of the present invention 100% comprehensive utilization and eliminate the paper stuff cleaning manufacturing technique method of the three wastes has above-mentioned many advantages, it be existing enterprises in pulp and paper industry development must be by direction.Promptly do not discharge dirty gas to airspace to the earth sewage effluent and mud yet, i.e. water saving has overall economic efficiency again, the field technology revolution for many years of the common expectation of pulping and paper-making industry institute at present really really is the manufacturing technique method of a novelty, creative advanced person and practicality.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can implement according to the content of specification, below with most preferred embodiment of the present invention and conjunction with figs. describe in detail as after.
The specific embodiment of the present invention is provided in detail by following examples and accompanying drawing thereof.
Description of drawings
Fig. 1 is the improvement waste liquid process flow diagram of the paper stuff cleaning manufacturing technique method of subsection harnessing devil liquor zero discharge of the present invention and comprehensive utilization.
1...... raw material processing workshop section
11...... wash material waste water
12...... net filter
13...... sedimentation basin
2...... boiling catalysis workshop section
21...... black (red) liquid
22...... preliminary treatment
23...... net filter
24...... micro-filtration (MF)
25...... ultrafiltration (UF)
26...... nanofiltration (NF)
3...... paper pulp processing workshop section
31...... middle-stage wastewater
32...... preliminary treatment
33...... net filter
34...... micro-filtration (MF)
35...... ultrafiltration (UF)
36...... nanofiltration (NF)
4...... bleachery
41...... bleaching effluent
42...... micro-filtration (MF)
43...... ultrafiltration (UF)
44...... nanofiltration (NF)
5...... comprehensive utilization deep processing workshop section
Extract processing workshop section 6...... reclaim
7...... brick machine workshop section
The specific embodiment
Below in conjunction with accompanying drawing and preferred embodiment, realization 100% comprehensive utilization that foundation the present invention is proposed and the specific embodiment, feature and its effect of eliminating the paper stuff cleaning manufacturing technique method of the three wastes, describe in detail as after.
See also shown in Figure 1, the present invention realizes 100% comprehensive utilization and eliminates production workshop sections 1,2,3,4 and three comprehensive utilization workshop section 5,6, the 7:(s one of the paper stuff cleaning manufacturing technique method of the three wastes comprising four generation waste water) raw material processing workshop section 1, the material waste water 11 of washing of being discharged becomes clean water 14 through netting after filter 12 and sedimentation basin 13 operations are handled, and clean water 14 is returned raw material processing workshop section 1 again and is recycled.(2) boiling catalysis workshop section 2, black (red) liquid 21 of being discharged becomes clean water 27 through preliminary treatment 22, net filter 23, micro-filtration 24, ultrafiltration 25, nanofiltration 26 operations after handling, and clean water 27 is returned boiling catalysis workshop section 2 again and is recycled.(3) paper pulp processing workshop section 3, the middle-stage wastewater 31 of being discharged becomes clean water 37 through preliminary treatment 32, net filter 33, micro-filtration 34, ultrafiltration 35, nanofiltration 36 operations after handling, and clean water 37 is returned paper pulp processing workshop section 3 again and is recycled.(4) bleachery 4, and the bleaching effluent 41 of being discharged becomes clean water 45 through micro-filtration 42, ultrafiltration 43, nanofiltration 44 operations after handling, and again clean water 45 is returned bleachery 4 and recycles.Three comprehensive utilization workshop sections: (one) comprehensive utilization deep processing workshop section 5, specially to holding back the lignin of collection, hemicellulose, carbohydrate carries out deep processing.(2) reclaim to extract processing workshop section 6, carry out deep processing to the silicon of holding back recovery and organic acid are saponified specially.(3) brick machine 7, specially being pressed into insulating brick for building behind some silt particles and the organic-inorganic impurity refuse mix.
Above-mentioned raw material processing workshop section 1 is meant the raw material processing to paper pulp, when will be to timber peeling, section, cleaning during for raw material with timber; When being raw material, want the dedusting of limit, blank limit, limit to clean with careless straw, the wherein main impurity of waste water 11 that this workshop section discharged is not have peace and quiet bark, the broken leaf of the disintegrating slag of knaur or careless straw, root, fringe, the impurity of seed and silt particle and so on, also be mingled with a little metallo-plastics and so on impurity sometimes, waste water 11 can be retained down most vegetable fault wherein through net filter 12 and give boiler and do fuel, the net filter is divided into five grades, mesh size is respectively 5mm, 2.5mm, 1mm, 0.5mm, 0.2mm, net filter back waste liquid passes through sedimentation basin 13 again, just some silt particles and metal impurities can be removed, the clean water 14 of post precipitation is returned materials processing workshop section 1 again and is recycled.
Above-mentioned boiling catalysis workshop section 2 is meant that raw material are done high-temperature catalytic extracts cellulosic paper pulp preliminary working, wherein catalysis process has multiple, alkaline process, sulfate process, sulphite process, acid system, organic solvent method are arranged, no matter how, the denseest black (red) liquid 21 is discharged in the capital, major part all is organic compound, fiber heteroproteose cell and the cellulosic carbohydrate of part that is decomposed because of the peeling reflection in the solute of these dopes, propolis, starch, fat, tannin, pectin by quaternization form saponified; Small part is an inorganic matter in addition, comprising the calcium in the raw material, magnesium, iron, manganese, metal ions such as copper, silica (many in the forage), inorganic impurity in the industrial water, free alkali, salt, these black (red) liquid 21 at first will be done preliminary treatment 22, the metal ion that to deceive in (red) liquid becomes stable complex compound to remove away with the chelating agent complexing again, the saponified removing that suspends is gone out, when raw material is wheat straw and straw, silica wherein must be removed, remove silica a variety of methods are arranged, carbon dioxide process is arranged, lime method, the sodium aluminate method, bioanalysis, wherein more effectively in rotary spherical digester, adding an amount of AHM (a kind of is the helping agent of main component with the aluminium oxide), it can be completely becomes water-fast silicic acid class compound with silicon dioxde reaction in the raw material, and is easier to be eliminated, because these materials can form inorganic colloid in waste liquid, it can quick dirty mucous membrane, influences membrane flux; Waste liquid after preliminary treatment 22 is handled enters net filter 23, five grades of the descending rows in the hole of net filter 23, mesh size is respectively 0.4mm, 0.2mm, 0.1mm, 0.05mm, 0.02mm, perform and lower gear between the ratio of pore size preferably be no more than 2 times, be difficult for dirty glutinous net like this, the net filter 23 at this position mainly is to hold back some flocculated colloid particles in the waste liquid, residual complex compound particle, small silt particle particle, there is not to decompose good plant disintegrating slag, impurity such as plant joint knot crushed particles, net filter 23 is exactly for micro-filtration 24 provides condition, will separate above the solid content impurity of 20 μ m.Waste liquid carries out the transition to micro-filtration 24 from net filter 23, and its size of holding back solid content is dwindled more, and micro-filtration 24 is divided into 7 grades, and membrane pore size is respectively 10 μ m, 5 μ m, 2.5 μ m, 1 μ m, 0.5 μ m, 0.25 μ m, 0.1 μ m.Micro-filtration 24 can be with the solid particle of feature dimension in the waste liquid greater than 0.1 μ m, submicron, organic colloid, microbial bacterial, enzyme, worm's ovum, vitamin, protein are removed and are separated, micro-filtration 24 films are selected the film body material that has negative electrical charge for use, film will be selected the acid and alkali-resistance material for use, micro-filtration 24 is diffusion barriers of pressure-driven, operating pressure for not influencing continuous production, the replacement equipment of a standby cover microfiltration equipment when cleaning film in P=0.01～0.07MPa scope.The waste water of handling through micro-filtration 24 changes ultrafiltration 25 immediately over to, and ultrafiltration 25 is divided into 5 grades, and membrane pore size is respectively 0.05 μ m, 0.025 μ m, 0.01 μ m, 0.005 μ m, 0.002 μ m, can hold back and separate the material of relative molecular weight between 1000～1000000.From ultrafiltration 25 beginnings, a large amount of useful organic compounds are lignin especially, there is the relative molecular weight of alkaline lignin, sulfonated lignin, acid lignin, neutral lignin, these lignins all to diminish, wherein the relative molecular weight more than 80% is between 2000～4500, because the native lignin in the raw material is alkalized and sulfuration or oxidation after the strand of lignin is destroyed fragments into the lignin fragment and separate out, the milipore filter in different apertures, the solid content that can selectively separate different molecular weight can reclaim fiber fines and use.The film body of ultrafiltration 25 is electronegative, the organic matter that has negative electrical charge in the waste liquid had repulsive force, so the organic matter solid content is difficult for dirty mucous membrane, ultrafiltration 25 is pressure-driven diffusion barriers, operating pressure is at P=0.1～0.7MPa, want a standby cover ultrafiltration apparatus in the production, the alternate device during for the cleaning film.Waste water enters nanofiltration 26 operations again from ultrafiltration 25 operations, nanofiltration 26 is selectively to hold back to separate various feature dimensions at the small solute of the relative molecular weight between 0.8nm～2nm between 100～1000, wherein mainly be from waste liquid, to extract the pentosan of the lignifying compound of isolating some small-molecular weights, hemicellulose and carbohydrate, remaining high price anion and high-valence cationic, make in the waste water colourity remove 98%, COD
CrIndex is reduced to below the 30mg/L, and selectively allow main chemical agent alkali and sulfate let pass to pass through membrane filtration with water, realize recycling, 2 grades of nanofiltrations 26 minutes, membrane pore size be respectively 1.5nm, 0.8nm,, specifically can also can select 1 grade or 2 grades for use according to the different situations of the solute of waste liquid.The nanofiltration film body will be selected for use and have negative electrical charge, and it can produce repulsive force to the organic matter of negative electrical charge, reduce dirty mucous membrane, nanofiltration 26 is pressure-driven diffusion barriers, operating pressure is wanted a standby cover nanofiltration equipment at P=0.5～1.8MPa in the production, can guarantee continuous production.Time cleaning frequency of filter membrane equipment will be determined according to the actual production actual measurement, promptly will clean film as long as the filtration flux of film reduces by 10%.Handle the back through nanofiltration 26 and deceive (red) liquid 21 and become clear water 27, turn back to boiling catalysis workshop section 2 and recycle and do not efflux.
Above-mentioned paper pulp processing workshop section 3, be meant the slurry that extracts after black (red) liquid through washing, shove, discongest, waste water general designation middle-stage wastewater 31 that the process of defibrination, screening is discharged, it is ejusdem generis that the wood pulp after the boiling of these waste water and last process is deceived (red) liquid 21.But it is a lot of that the end falls in the solute concentration in the waste liquid, COD in black (red) liquid 21 waste liquids of wood pulp
CrContent can reach 17000～22000mg/L, the COD in the straw pulp black liquor 21
CrContent can reach 23000～28000mg/L, and the COD in the middle-stage wastewater 31
CrContent can only reach about 2000～4000mg/L, even so, middle-stage wastewater 31 is also wanted and black (red) liquid 21 is same will pass through that preliminary treatment 32, net filter 33, micro-filtration 34, ultrafiltration 35, nanofiltration 36 these operations, middle-stage wastewater 31 is become clean water 37 to be turned back to paper pulp processing workshop section 3 and recycles the COD in the clean water 37
CrContent can be reduced to 30mg/L.Satisfy manufacturing technique requirent fully.
Few many of the waste liquid that contained solute concentration and colourity all go up several workshop section and discharged in the bleaching effluent 41 of above-mentioned bleachery 4, bleaching effluent 41 does not have bigger solid particle, therefore needn't do preliminary treatment and net filter again, and directly handle with micro-filtration 42, again after ultrafiltration 43, nanofiltration 44 handled, clean water 45 can reach the same clean-up performance of a few road workshop sections and turn back to bleachery 4 and recycle and do not efflux.
Above-mentioned comprehensive utilization deep processing workshop section 5, be meant and from ultrafiltration 25,35,43 and nanofiltration 26,36,44 operations, comprise alkali lignin by the lignifying compound of separation and Extraction, sulfuration lignin, acid lignin, neutral lignin, concentrate the chemical modification of carrying out of classification, chemistry connects the deep processing of methods such as skill copolymerization, can be by the height of the market demand and product economy value, selectively process lignin organic polymer chemical products, comprising the organic adhesive of the lignin of green, lignin one phenolic resins, degradable polyurethane; The degradable lignin plastic mulch film of agricultural usefulness, degradable long-acting slow-release chemical fertilizer, soil conditioner; The concrete for building and the water reducer of cement mortar, reinforcing agent, impervious agent, stone material are cut grinding agent; The high temperature conditioning agent that oil exploitation is used, profit coagulant, heavy crude thinner, emulsifying agent, economic benefits and social benefits water shutoff agent, AS FILTRATION LOSS CONTROLLER; Coal water slurry dispersing agent; Surfactant; Medicinal hay-scented aldehyde (vanillic aldehyde); The sizing agent that paper industry is used, reinforcing agent, retention and drainage aid agent are at interior multiple lignin products.Organic matters such as hemicellulose poly-pentose that will separation and Extraction goes out from nanofiltration 26,36,44 and carbohydrate carry out deep processing and obtain products such as furfural, ethanol, xylitol.
Processing workshop section 6 is extracted in above-mentioned recovery, is products such as the silicic acid that will extract from pretreatment process 22,32 or the calcium silicates waterglass that is processed into economical and practical value, various silica gel, active silica, hydrophobic silica, aerosil, Ludox, electron level silicic acid potassium, si molecular sieves.That extracts from preliminary treatment 22,32 is saponified, form after alkalizing by propolis, fat, pectin, tannin, carry out sour processing and can obtain the product that rosin, Tall oil and aliphatic acid etc. have economic worth saponified, tannin can be processed into the tannin polyurethane.
Above-mentioned brick machine workshop section 7 is meant the sediment contamination that precipitation obtains from raw material waste water 11 and reaches the metal ion complex of separating in the micro-filtration 24,34,42 from net filter 23,33, all kinds of organic and inorganic colloids, there is not to decompose good paper pulp disintegrating slag, plant joint knot fragment, impurity such as various solid particles, submicron mix stirring, add binding agent, be pressed into the insulating brick of architectural usefulness, whole refuses are all utilized, make processing raw material that pulping and paper-making factory comes in all become product export, there is not the drop discarded object, real round Realization cleaner production.
Each above-mentioned manufacturing procedure constitutes realization 100% comprehensive utilization of the present invention and eliminates the paper stuff cleaning manufacturing technique method of the three wastes, concerning technical staff of the same trade now, all have a lot of saving graces, and certain creative and progressive, eliminating the black liquor vaporizing of overthrowing present pulping and paper-making industry widespread usage completely concentrates, boiler burns alkali and reclaims, white liquid causticization, lime reclaims, middle-stage wastewater will be through waste liquid (water) processing method of complicated backwardness such as three grades of biochemical treatments, three-waste pollution and garbage emission have been eliminated, realize 100% comprehensive utilization and paper pulp cleaning environmental protection production, using water wisely has increased byproduct and has improved economic benefit.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any type of restriction, anyly be familiar with this professional designer and may utilize the technology contents of above-mentioned announcement to be changed or be modified to the equivalent embodiment of equivalent variations, but every do not break away from realization of the present invention 100% comprehensive utilization and eliminate the three wastes paper stuff cleaning manufacturing technique method substance or according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong to the scope of technical solution of the present invention.
Claims (7)
1. the paper stuff cleaning manufacturing technique method realizing 100% comprehensive utilization and eliminate the three wastes is characterized in that being used for eliminating the slurrying three waste discharge by 100% comprehensive utilization to pulping raw material; Specific practice is that washing in the slurrying production process expected waste water (11), (red) liquid (21) is deceived in boiling, middle-stage wastewater (31), bleaching effluent (41) carries out segmentation and holds back extraction and cleaning improvement, by preliminary treatment (22) (32), net filter (12) (23) (33), micro-filtration (MF) (24) (34) (42), ultrafiltration (UF) (25) (35) (43), the combination technique means of nanofiltration (NF) (26) (36) (44), using sieve effect selectively extracts respectively from waste liquid, separate, concentrate various solid contents and organic compound and dirt, again it is delivered to the new product that economic worth is processed in different deep processing workshop sections (5) (6) (7) respectively; Waste water after being cleaned becomes clean water (14 ((27) (37) (45), do not recycle at all at this workshop section inner sealing and to efflux, wherein filter membrane can selectively pass through filter membrane with bleaching agent (hydrogen peroxide) with water with the main chemical agent (alkali or sulfate or acid) that is free in the waste liquid, reaches the recovery Recycling; Because the employed plant material kind of slurrying difference, the processing method difference, drop into catalytic decomposition and the used chemical agent difference of bleaching process, so waste liquid color of each section, concentration, the solute that is contained, solid content, the composition of soluble solids, content and relative molecular weight size thereof are all inequality, therefore when each section waste liquid is carried out purification treatment, suitably adjust aperture specification of netting filter and filter membrane and the stepping rank that net and film are set targetedly according to the actual conditions of waste liquid, segmentation purification treatment waste liquid process of the present invention also is applicable to the making beating waste water in the paper process and makes the purified treatment of paper plain boiled water.
2. the paper stuff cleaning manufacturing technique method of realization 100% comprehensive utilization according to claim 1 and the elimination three wastes, wherein said pretreatment process (22) (32), be will be contained in the waste liquid the postorder filter membrane purified the colloidal substance that adverse effect is arranged or form dirty mucous membrane easily remove, comprise and being removed after with chelating agent metal ion-chelants such as Cn, Fe, Mn, Mg, Ca being become stable complex compound; Silica is changed into water-fast silicic acid compound to be separated; Saponified the separating that will form by organic impurities such as resin, fat, pectin, tannin and alkali or sulfate reaction.
3. according to realization 100% comprehensive utilization of claim 1 and the paper stuff cleaning manufacturing technique method of the elimination three wastes, wherein said net filter (12) (23) (33), be to be used for holding back solid granulates material the thickest in the waste liquid, but because the size of the solid granulates in each section waste liquid is different with classification, so select the mesh size size also different: the net filter (12) in raw material processing workshop section (1) mainly is to be used for holding back various impurity, comprising bark, blade of grass, seed, fringe, root, the joint knot is at interior various plant material impurity, mesh can be established 3～6 grades, and the mesh size size is from 5mm～0.2mm; Mainly be to be used for holding back in the spent pulping liquor body in net filter (23) (33) of boiling catalysis workshop section (2) and paper pulp processing workshop section (3) greater than the solid matter of 20 μ m, comprising flocculating into oarse-grained colloid, residual chelating material grains, residual tiny silt particle particle, there is not to decompose good paper pulp raw material disintegrating slag, mesh can be established 3～5 grades, and the mesh size size is from 0.5mm～0.02mm.
4.
According to realization 100% comprehensive utilization of claim 1 with eliminate the paper stuff cleaning manufacturing technique method of the three wastes, wherein said micro-filtration (MF) (24) (34) (42) is to hold back various feature dimensions in the waste liquid greater than the granule foreign of 0.1 μ m; Be mainly used in and remove bacterium, suspended solids and colloid, particulate, submicron solid content in the waste liquid; The aperture of micro-filtration (MF) film can be set up 3～7 grades separately, and the membrane pore size size is from 10 μ m～0.1 μ m; Micro-filtration (MF) is a pressure-driven separation filter membrane, and operating pressure is at P=0.01～0.07MPa, and film body is electronegative, and the organic matter that has negative electrical charge is had repulsive interaction, and film will regularly clean and guarantee the film passband.
5.
According to realization 100% comprehensive utilization of claim 1 and the paper stuff cleaning manufacturing technique method of the elimination three wastes, wherein said ultrafiltration (UF) (25) (35) (43), be selectively to hold back respectively, separate the relative molecular weight of various feature dimensions between 0.1 μ m～0.002 μ m in the waste liquid at 1000～1000000 solid content, wherein mainly be lignin organic compound and fiber fines heteroproteose cell, lignin in the plant material is after alkalization and sulfate sulfonation or bleaching oxidation, being lignin fragment shape is decomposed to separate out and is dissolved in the slurries, its relative molecular weight major part is between 2000～4500, the aperture of ultrafiltration (UF) film can be set up 2～5 grades separately, and the membrane pore size size is from 0.05 μ m～0.002 μ m; Ultrafiltration (UF) is a pressure-driven separation filter membrane, operating pressure P=0.1～0.7MPa, and the ultrafiltration film body is electronegative, and the organic matter that has negative electrical charge is had repulsive interaction, so be difficult for dirty mucous membrane, film will regularly clean and guarantee the film passband.
6.
According to realization 100% comprehensive utilization of claim 1 and the paper stuff cleaning manufacturing technique method of the elimination three wastes, wherein said nanofiltration (NF) (26) (36) (44), be selectively to hold back, separate feature dimension at the small organic matter and the inorganic matter of the relative molecular weight between 2nm～0.8nm between 100～1000, wherein mainly hold back and isolate the carbohydrate of the pentosan class of small-molecular weight lignifying compound, hemicellulose, remaining high price zwitterion, and can remove 98% colourity in the waste water, COD
CrIndex is reduced to below the 30mg/L, and selectively allows catalyst alkali (NaOH) and bleaching agent hydrogen peroxide (H
2O
2) pass through the filter membrane recycling together in company with water; Nanofiltration (NF) membrane aperture can set up 1～2 grade separately, the membrane pore size size is from 1.5nm～0.8nm, nanofiltration (NF) is a pressure-driven separation filter membrane, operating pressure is P=0.5～1.8MPa, the nanofiltration film body is electronegative, organic matter and the anion solute that has negative electrical charge had repulsive interaction, so be difficult for dirty mucous membrane, film will regularly clean and guarantee the film passband.
7.
According to realization 100% comprehensive utilization of claim 1 and the paper stuff cleaning manufacturing technique method of the elimination three wastes, wherein said comprehensive utilization deep processing (5) (6) (7), be meant that the separation and Extraction of holding back is come out in waste liquid (water) decontamination process organic matter and inorganic matter do deep processing, obtain the additional byproduct of five classes: (one) lignin organic polymer chemical products: utilize the characteristics that have multiple functional group and active group in the molecular structure unit of lignin, will be from black (red) liquid (21), middle-stage wastewater (31), hold back the lignin organic compound of separating in ultrafiltration (UF) (25) (35) (43) operation of each workshop section of bleaching effluent (41) and nanofiltration (NF) (26) (36) (44) operation, to its deep processing of doing chemical modification or connecing the skill copolymerization, can process and comprise organic lignin adhesive, lignin one phenolic resins, degradable polyurethane; The degradable lignin plastic mulch film of agricultural usefulness, degradable long-acting slow-release chemical fertilizer, soil conditioner; The concrete for building and the water reducer of cement mortar, reinforcing agent, impervious agent, stone material are cut grinding agent; The high temperature conditioning agent that oil exploitation is used, profit coagulant, heavy crude thinner, emulsifying agent, economic benefits and social benefits water shutoff agent, AS FILTRATION LOSS CONTROLLER; Coal water slurry dispersing agent; Surfactant; Medicinal hay-scented aldehyde (vanillic aldehyde); The sizing agent that paper industry is used, reinforcing agent, retention and drainage aid agent are at interior multiple lignin products; (2) carbohydrate of the poly-pentose of hemicellulose and cellulose peeling reflection is to be dissolved in the second class organic compound in the waste liquid, nanofiltration in each workshop section (NF) (26) (36) (44) can be held back it and be separated, and can obtain the addition product of furfural, ethanol, xylitol and so on to its deep processing; (3) the compound silicic acid (H of the silica that extraction is separated to pretreatment process (22) (32)
2SiO
3) or calcium silicates (CaSiO
3) carry out chemical modification processing, can obtain silica gel, sodium metasilicate, active silica, hydrophobic silica, aerosil, Ludox; (4) to come out from pretreatment process (22) (32) separation and Extraction by the resin the wood raw material, pectin, fat and tannin through and alkali or sulfate reflection form saponified, can therefrom obtain rosin, Tall oil and aliphatic acid through acidifying processing, wherein tannin extracts and can be processed into a kind of new environment-friendly macromolecular material---degradable tannin polyurethane; (5) from sedimentation basin (13) operation of washing material waste water (11) sediment contamination separated and the metal ion complex of from the micro-filtration (24) (34) (42) of the net filter (33) of the net filter (23) of black (red) liquid (21) and middle-stage wastewater (31) and each workshop section, separating, all kinds of organic with inorganic colloid, impurity such as not decomposing good paper pulp plant disintegrating slag, various solid particle, submicron to be mixed to mix adhesive, be pressed into insulating brick for building (7) with brick machine.
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| CN102516559A (en) * | 2011-12-01 | 2012-06-27 | 中国科学院过程工程研究所 | High value transformation method of classification and separation of lignin sulfonate in red liquor |
| CN103613688A (en) * | 2013-11-22 | 2014-03-05 | 河北科技大学 | Extraction method and quaternarization modification method for semi-cellulose in waste viscose fiber production liquor |
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| CN113048854A (en) * | 2021-02-08 | 2021-06-29 | 天津大学 | Automatic measuring device and measuring method |
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