CN100500991C - Process for reclaiming and comprehensively utilizing waste digestion liquid of alkaline (or neutral) straw pulp generated by sodium sulfite method - Google Patents
Process for reclaiming and comprehensively utilizing waste digestion liquid of alkaline (or neutral) straw pulp generated by sodium sulfite method Download PDFInfo
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Abstract
A process for reclaiming the waste digestion liquid generated in making straw pulp by alkaline (or neutral) sodium sulfite method features that the said waste liquid is physically, chemically and biologically treated to separate out the lignosulfonate, oligose, volatile organic acid and sodium slat, and reclaim them for utilization. When they are used for pulping with combined chemical and chemico-mechanical pulps, the chemico-mechanical pulp waste liquid is effectively treated in the cross circulating mode, and a completely closed production system is constituted. Its advantages are low investment, reduced environmental pollution, and high economical effect.
Description
One, technical field
The present invention relates to pulping cooking waste liquor comprehensive utilization of resources technology, particularly a kind of alkalescence (or neutral) Arbiso process straw pulp reclaiming waste digestion liquid method of comprehensive utilization.
Two, background technology
Traditional combustion method alkali recovery technology is extensively adopted in the processing of chemical pulping cooking waste liquor at present.Facts have proved that production is successfully effective to wood pulp for it, and grass as raw material slurrying, particularly medium-sized and small enterprises are run into very big difficulty in practical application.From utilization of resources angle, firing method can not make the organic solid content in the cooking waste liquor be used adequately reasonably.Therefore, never be interrupted pulping cooking waste liquor comprehensive utilization of resources Study on Technology recent decades both at home and abroad, but also fail to form a cover economical and effective up to now, have the technical scheme of practical value.
Patented technology of the present invention is that the straw pulping paper-making cleaner production is carried out in the system research, a clearer production technology with key effect of developing.It is a kind of " modified form " pulping process between acid system and alkaline process that the exploitation of this technology is based on alkalescence (or neutral) inferior sodium method slurrying, compares the advantage with following several respects with traditional alkaline process (soda processes or sulfate process) pulping process:
1, paper pulp yield height increases by 6-8% (to raw material) than soda pulping process.Slurry easily floats, easily pulls an oar, easily washs, and pulp strength can compare favourably with sulfate process.
2, be easy to form chemical pulp and high yield machine slurry (sulfonation mechanical pulp SCMP or chemical heat defibrination CTMP) combination slurrying production system, thereby further increase substantially the fibrous raw material utilization rate and reduce the ambient pollution burden that slurrying is produced.
3, under the alkaline sodium sulfite conditions of cooking, the reducing end group of cellulose and hemicellulose (aldehyde radical) is by Na
2SO
3Be oxidized to carboxyl, play the effect that suppresses peeling reaction; And in the oxygen delignification process, can effectively prevent oxidative degradation under the alkali condition, thereby provide necessary advantage for implementing few chlorine bleach (ECF) or chlorine-free bleaching (TCF).
4, cooking waste liquor has the double characteristic of acid system and alkaline pulp black liquor, can use for reference some the maturation process technology of handling acid system and alkaline cooking liquid waste liquid that are applicable to simultaneously, realize comprehensive utilization of resources, and obtain than better economic benefit of traditional combustion method and environmental benefit.
More than first three bar in four advantages, except the anti-oxidant degradation characteristic that demonstrates in the oxygen delignification process is confirmed by we test, other all forms final conclusion already in the works of a lot of pulp technologies.Obviously if the 4th, also be that a most key energy is confirmed by patented technology of the present invention, then mean and adopt of the cleaner production of the inferior sodium method pulping process of alkalescence (or neutrality) to have Practical significance widely with the round Realization straw pulp.
Pulp and Paper Engineering National Key Laboratory of South China Science ﹠ Engineering University and light industry journey are doctor Wu Shubin, in his recent monograph (Wu Shubin writes paper industry water pollution control and the Environmental Science and Engineering publishing centre 2001.5.183-245 of improvement technology Chemical Industry Press), to the research of relevant reclaiming waste digestion liquid comprehensive utilization technique both at home and abroad in modern age, done comprehensive and systematic summary, can be used as useful background technology file and the reference of understanding, retrieval, examination patented technology of the present invention.
Here with regard to the relevant background technology document of enumerating in this works do following some quote as proof:
1, The experimental results shows, particularly a year practical experience is proved that being used for hyperfiltration technique from acid polishing effluent isolated lignin sulfonate is economical and practical technology surplus the chemical fibre slurry factory ten of village by China cuts into a mountain.Its major technique feature is to make lignosulphonates and organic reducing sugar (monose) realize separating entirely, makes high-purity lignosulphonic acid salt product.And when hyperfiltration technique was directly used in alkaline sodium sulfite legal system pulp waste, what obtain was the lignosulphonates that contain big molecule compound sugar.Trace it to its cause is that the cellulose of stripping under acid conditions of cooking and hemicellulose degradation product the most all are hydrolyzed into monose and are dissolved in the waste liquid; And can only be degraded into polysaccharide or compound sugar in that the alkaline sodium sulfite conditions of cooking is next.Usually the lignosulphonates of degraded are more much bigger than the molecular weight of compound sugar, but because the inhomogeneity of their molecular weight distribution, cause the lignosulphonates of existing low relative molecular mass in molecular weight distribution 600-1500 scopes, the compound sugar of high molecular weight is arranged again.Therefore concerning alkaline sodium sulfite method pulping waste liquor,, the compound sugar in the waste liquid can obtain separation and purification effect as acid polishing effluent as long as being hydrolyzed into monose.
2, from other hyperfiltration technique is used for the result of study that the alkaline process black liquor separates alkali lignin, will further confirms above result, promptly can only obtain containing the alkali lignin goods of big molecule compound sugar.Owing to be difficult to it is hydrolyzed when compound sugar and alkali lignin coexistence, so ultrafiltration recovery alkali lignin technology will be very limited on using.The electroosmose process alkali recovery technology of mentioning as (183 pages) in this works (lignin is reclaimed in ultrafiltration, alkali is reclaimed in electrodialysis) that carried out pilot scale in Qingzhou, Shandong paper plant promptly stops production after being interrupted operation through 1 year.We think that electroosmose process reclaims alkali (the special electrodialysis process that is made of composite membrane and cation-exchange membrane), though there are shortcomings such as film valency height, power consumption height, weigh from the suitability for industrialized production angle that still to can yet be regarded as be a kind of technology with practical value.Reclaim the utilization system that alkali lignin is combined into the alkaline process black liquor with it and ultrafiltration, see it is feasible technically, in pilot scale, be that ultrafiltration reclaims lignin and can only make the low-purity alkali lignin goods that contain compound sugar, be difficult to form in a short time the approved product that adapts to by stranded main cause; The part compound sugar is trapped within the alkali lignin in addition, remaining polysaccharide and a small amount of monose will form the waste water of high BOD content after alkali is reclaimed in electrodialysis, its both unsuitable biofermentation utilization should not be back to use pulping system again, still need send into outside the factory Waste Water Treatment and handle.Therefore like this can not its economic benefit of instant playback, can not eliminate the technology that cooking waste liquor pollutes again fully and be difficult to accept for enterprise.Make this technology obtain good practicability and must solve separating entirely of alkali lignin and compound sugar, and form a utilization system that comprises compound sugar, this is difficult to accomplish concerning the alkaline process black liquor at present.
Edition with parallel text patent of invention technology, what obtain in ultra-filtration and separation is the high-purity lignosulphonates with extensive use approach; Electroosmose process (the common electrodialysis process that constitutes by the yin, yang amberplex, there are not problems such as power consumption height, film valency height in it) with oppose through liquid carry out the salt sugar from, saline solution becomes alkali lye through causticization and is used to prepare cooking liquor, liquid glucose makes high-purity single cell protein (or alcohol) through biofermentation, and parting liquid returns the slurrying production system as the extracting water.Here as can be seen, be both and use ultrafiltration and two kinds of membrane separation techniques of electrodialysis, but its effect and effect are distinct.
3, from Tianjin light industry institute papermaking research department and the cooperation of food system of South China Science ﹠ Engineering University, the result of study of utilizing imonium pulping waste liquor and acid system reed pulp waste liquid to produce mycoprotein is seen (244 pages), utilize saccharomycete cultivation single cell protein yield in imonium (with alkalescence or neutral inferior sodium) waste liquid low, separation difficulty is difficult to realize suitability for industrialized production.For this reason, they walk the technology path of saccharomycete and mould combination cultivation, and set about from the screening of strain excellent, filter out the novel bacterial that utilizes the waste liquid ability strong.We then are from the whole synthesis utilization, analyze the factor that is unfavorable for the saccharomycete growth and breeding that exists in the inferior waste liquor of sodium of alkalescence (or neutral), therefrom find out to make the inferior waste liquor of sodium of alkalescence (or neutral) be suitable for the technology approach of saccharomycetes to make fermentation.
In the red liquid fermentation manufacturing technique of traditional acid system (calcium sulfite), be the monose that is easily directly absorbed by saccharomycete as the organic sugar of carbon source.Solubility is very little at normal temperatures owing to calcium sulfite, can have only the SO of free state in the red liquid to the material of saccharomycete growth and breeding toxigenicity effect
2, therefore adopt vaporizing extract process to remove SO
2Become pretreatment process necessary in this technology.Organic sugar in the inferior sodium method waste liquid of alkalescence (or neutral) is the difficult compound sugar that is directly absorbed by the budding fungus microorganism, and the inorganic sodium that is dissolved in " superelevation " concentration in the waste liquid can produce serious toxicity inhibitory action to saccharomycetic growth and breeding.Therefore as long as the compound sugar in the inferior sodium method cooking waste liquor of alkalescence (or neutral) is hydrolyzed into monose, and remove inorganic sodium (being controlled in the safe level scope), can satisfy budding fungus growth of microorganism breeding condition and environment requirement.
What need mention at last is that Ammonium Sulfite Method belongs to alkalescence or monosulfite pulping, but because the not recyclable property of ammonium salt makes patented technology of the present invention to being subjected to certain limitation in its application.From round Realization slurrying cleaner production angle, changing ammonium salt is that sodium salt will be its optimal selection.
Three, summary of the invention
The present invention handles alkalescence (or neutral) Arbiso process straw pulp cooking waste liquor with physics, chemistry, biological combined method, sodium lignosulfonate in the waste liquid, compound sugar, VFA and sodium salt is separated also fully utilized.Thereby eliminate the severe contamination that pulping cooking waste liquor causes environment, obtain huge economic benefit simultaneously.When being used for chemical pulp and high yield machine slurry combination slurrying and producing, can making machine pulp waste in handling chemical pulp waste liquid process, be effectively addressed with simple intersection endless form, and constitute the combination slurrying production system of a Totally-enclosed-type.
Mainly comprise processes such as concentrated acidifying, enzymatic hydrolysis, ultra-filtration and separation, electrodialysis separation, biofermentation, causticization in the reclaiming waste digestion liquid comprehensive utilization process flow process, be described as follows in conjunction with the specific embodiment here:
1, concentrates acidifying
It is in order to guarantee the totally-enclosed operating water balance of pulping by cooking operation and cost-effective waste liquid to be fully utilized that the extract of cooking waste liquor is concentrated acidifying.Consider that from the cleaner production angle optimised process approach that waste liquid concentrates acidifying is to utilize boiler smoke directly to contact evaporation with waste liquid.Utilize fume afterheat to make waste liquid so on the one hand by 8-9m
3Be concentrated to 6-7m
3/ t air dried pulp absorbs CO in the flue gas simultaneously
2, SO
2And SO
3Following chemical reaction takes place Deng residual alkali and organic acid sodium salt in sour gas and the waste liquid:
2NaOH+CO
2→Na
2CO
3+H
2O↑
2NaOH+SO
2→Na
2SO
3+H
2O↑
2NaOH+SO
3→Na
2SO
4+H
2O↑
2RCOONa+SO
2+H
2O→Na
2SO
3+2RCOOH↑
2RCOONa+SO
3+H
2O→Na
2SO
4+2RCOOH↑
It is to adopt venturi evaporation discrete group assembly system as shown in Figure 2 to implement that waste liquid concentrates acidifying.This system mainly is made up of Venturi tube, cyclone separator and surface condenser.After boiler smoke enters the collapsible tube of Venturi tube, because caliber reduces to make flow velocity to accelerate gradually.Waste liquid radially sprays in throat, impacted by high velocity air and is atomized into countless fine particles, and fully mix with the high speed flue gas and to finish above-mentioned various chemical reactions.Because liquid grain diameter is little, surface area is big, and the very fast transmission feeding of the heat of high-temperature flue gas grain evaporates moisture rapidly.The flue gas, steam, VFA and the liquid grain fluid-mixing that diffuse out from Venturi tube are tangentially entering near the cyclone separator bottom position, then along inwall shape rising in the shape of a spiral.Adhered to flue dust and the solidification liquid grain is thrown on the wall under centrifugal action, under top spray profit wall waste liquid down, flow to bottom the separator, sent by filter.A part is sent into sedimentation basin and be sent to the enzymatic hydrolysis operation after clarification, and another part is sent the Venturi tube circulation again back to.Control concentrating spent liquor discharge rate can guarantee to make full use of fume afterheat and sour gas, and obtains concentrated acidifying (pH value 6.0-6.5) waste liquid of Cmax.
VFA and steam condense into aqueous solutions of organic acids after entering surface condenser, concentrate products such as can making the formic acid of purity more than 95%, acetate through further separating.
2, enzymatic hydrolysis
Solid content mainly is made up of organic matter and inorganic sodium in the cooking waste liquor after the concentrated acidifying.Except the lignosulphonates of degraded, also has multiple oligosaccharide substance in the organic matter.Wherein mainly contain the oligomeric sugar of cellulose degradation generation, low poly-pentose and the FOS that the hemicellulose degraded generates, and amount of starch degradation product (1.4 α glucoside) and pectin (poly methoxyl group galacturonic acid) etc.Usually the lignosulphonates of degraded are than big many of the molecular weight of compound sugar, but because the inhomogeneity of their molecular weight distribution, cause the lignosulphonates of existing low relative molecular mass in molecular weight 600-1500 scopes, and big molecule compound sugar is arranged again.Be not easy directly to be absorbed as compound sugar in addition, therefore consider, all need compound sugar is hydrolyzed, be about to compound sugar and be hydrolyzed into monose from lignin separation and purification and compound sugar biological utilisation angle by the budding fungus microorganism.
Traditional commercial run is to use strong acid to be hydrolyzed under High Temperature High Pressure, therefore need withstand voltage corrosion resistant equipment, and energy consumption is also bigger.Applied Biotechnology uses promptly that enzyme preparation is this to have a proteinaceous organic catalyst, because it has efficient catalytic effect and highly single-minded characteristic, hydrolysis is carried out at normal temperatures and pressures.
But come catalytic hydrolysis reaction appellation enzymatic hydrolysis usually with enzyme.The operation of enzymatic hydrolysis is fairly simple, put into hydrolytic tank with concentrating waste liquid after the acidifying, add acid levelling pH value 4.5-5, add an amount of cellulose complex enzyme again with agitating device, stir down slowly 2-3h at 40 ℃, reach 90% and can stop when above when measuring the monose conversion ratio.
3, ultra-filtration and separation
Use hyperfiltration technique, can be fully the lignosulphonates in the waste liquid after the hydrolysis and monose and sodium salt be separated.Because solid concentration height in the cooking waste liquor, lignosulphonates are the polymer colloid shape again, though waste liquid still inevitably remains with fine suspension through the preliminary treatment of necessity, therefore conventional plate and frame, spiral wound and doughnut formula ultrafilter all is difficult to guarantee the long-term stability operation of ultra-filtration and separation.Though it is good that tubular structure has a hydraulics, can prevent that concentration polarization and film from polluting by regulating flow stream velocity, can handle the high concentration colloidal solution that contains suspended matter, but exist the membrane area dress density of unit volume little, make and all more high shortcoming of operating cost.For separation, the purifying and concentrated of cost-effective realization lignosulphonates, we have developed a kind of suitable new type of plate frame CLB-X type ultrafilter as shown in Figure 3 voluntarily.
CLB-X type ultrafilter is the rectangle porous porous disc that milipore filter is arranged by some two sides cards, alternately is piled up composition with the flowing water channel partition that has certain width, thickness and be stained with the fish scale net.See its similar conventional plate and frame from assembling form, thus have sound construction, can bear high pressure, advantage such as unit volume membrane area dress density height, operating cost are low.Again like the tubular type ultrafiltration apparatus of many series connection, can effectively prevent therefore that concentration polarization and film from polluting from the waste liquid current, significantly improve the water flux of milipore filter.In the flowing water passage, add the fish scale net, make swiftly flowing waste liquid produce stronger turbulent flow stirring waste liquid full and uniformly, thereby improve the separating effect in the ultra-filtration process.Heat-insulation layer has all been set up in CLB-X type ultra filtration unit assembly outside, is suitable for operation under the high temperature, and this also all plays good action to increasing substantially of water flux.
According to the technological requirement of ultra-filtration and separation, should guarantee the separation fully of lignosulphonates in the waste liquid and highly purified, make waste liquid obtain to a certain degree concentrating simultaneously again, therefore adopted one-level as shown in Figure 4 to add the ultra-filtration and separation technological processes that water purifies for four sections.With pressure water pump hydrolysis is also passed through the waste liquid of in-depth filtration and micro porous filtration at pressure 0.8Mpa, pump into the water inlet of ultrafiltration apparatus under 60-70 ℃ of the liquid temperature, through the ultra filtration unit assembly of four series connection, the liquid of outflow is the high-purity lignosulphonic acid salting liquid of concentration more than 20%.Seeing through liquid is that monose and sodium salt mixed liquor are drawn by every porous porous disc, delivers to the electrodialysis separation circuit after compiling.
The lignosulphonates concentrate that from final stage ultra filtration unit assembly, flows out; except being directly used in purposes such as ore dressing, oil well grouting material; usually also need it further is concentrated into 45-50% the spray-dried then solid product that contains more than 95% of making.Relative molecular mass is had the lignosulphonic acid product salt of requirement, and the ultrafilter that can select for use corresponding cutting relative molecular mass milipore filter to form adds the water purification process by the one-level multistage it is separated into the product of different relative molecular masses.To being used for to carry out lignosulphonates the product of chemical modification as purposes such as surfactant or synthetic resin, as change cation type, take off sulfonic acid, methylolation, carboxylated and graft copolymerization etc., under condition permission situation, also should behind the lignosulphonates that obtain 20% concentration, be finished.
Use CLB-X type ultrafilter will note carrying out daily cleaning and maintaining work, to guarantee the long-term stability operation of whole ultra-filtration and separation system.Should accomplish that continuously in service per tour time (8 hours) all will wash 5-10 minutes with seeing through liquid under 2-3Mpa pressure, when the obvious decline of discovery water flux can not be with general purging method recovery, use special-purpose irrigation to wash repeatedly in accordance with regulations.In long-time running, still can not recover water flux with irrigation as finding, or see through the liquid color and luster and deepen or become when mixing and immediately unit block to be swapped out, take apart on request,, find out damaged membrane module and more renew film with the careful film surface of cleaning every porous disc of polyurethane sponge libation at an ancient wedding ceremony irrigation.The assembly of having cleared up should be assembled immediately, and standby after filling with through liquid in the flowing water passage.
Adopt the ultra-filtration and separation technology, in separation and purifying, lignosulphonates are concentrated, 1/3 of the not enough evaporation operation of its dehydration expense.
4, electrodialysis separates
What flow out from ultrafilter is with Na through liquid
2SO
3And Na
2SO
4Be the sodium salt of main component and the mixed liquor of multiple organic monose, wherein about (the Na of sodium salt total content
2SO
3Meter) 16-17g/L.Experiment is learnt when sodium salt concentration and the saccharomycete growth and breeding is demonstrated the toxicity inhibitory action during greater than 4g/L, therefore when the applying biological fermentation method utilizes organic sugar, must carry out in advance the salt sugar from, the sodium salt content in the liquid glucose is dropped to (less than 3g/L) in the safe level scope.Certainly this also is necessary fully concerning the sodium salt causticization reclaims alkali.
Making sodium salt and non-electrolyte organic sugar effective Separation in the mixed liquor is electrodialysis.What we used here is the DSZ type electric dialyzator that designs voluntarily, and it is a kind of with homogeneous phase cation exchange film and alternately arrangement of anion-exchange membrane, presses the electrodialysis separator that four sections assembling modes of secondary are formed.Relevant process design parameter, the planar dimension, flow process length, film logarithm, operating voltage, each section current density and the operating current that comprise dividing plate and film, be to see through flow quantity, sodium salt content and require electrodialysis to separate the high salinity that allows in the back liquid glucose according to known, calculate and after repetition test is checked, draw by relevant formula, therefore have good applicability in actual use.Supporting rectifier all is provided with automatic frequently pole-reversing device, can guarantee that the electrodialysis piece-rate system is long-term, continuous, stable operation.
The operation of electrodialysis separation processes is the liquid that sees through that will be chilled to room temperature with water pump, flow is sent into electric dialyzator " light chamber " water inlet in accordance with regulations, meanwhile will (single chemical pulp can use screening the pulp plain boiled water when producing as " carrier fluid " of accepting sodium salt, then use change machine pulp-making effluent during with change machine slurry combinations produce through coagulating treatment) send into " dense chamber " water inlet, adjust rectifier operating voltage and operating current and be stabilized in the technological requirement scope.From the sugar juice that meets the salt content control criterion that is of the light chamber of final stage delivery port outflow, be sent to the biofermentation operation like this; From the outflow of dense chamber delivery port is that sodium salt solution is sent to the causticization operation.
In the electrodialysis piece-rate system, every introduction one coulomb electric charge will cause 1 gram equivalent anion and CATION to be moved in the dense chamber from light chamber, so per minute roughly is constant from the power consumption of one kilogram of sodium salt, is generally 0.6-0.8kwh/kg.
5, biofermentation
The applying biological fermentation method produces alcohol from acid polishing effluent or fodder yeast is a conventional process techniques, uses for reference this technology the liquid glucose behind the desalination is used adequately reasonably.The liquid glucose has here passed through ultrafiltration and electrodialysis twice separation and purification program, therefore has very high cleanliness, and this provides better growth and breeding condition for the budding fungus microorganism undoubtedly.It not only can use the high yield alcohol of schizosaccharomyces pombe fermenting and producing, also can ferment with candida utili, produces the high-purity single cell protein that people and animals can eat.
Take all factors into consideration alcohol and the complicated and simple complexity of single cell protein production process equipment and the market demand, a period of time still is earlier comparatively safe to produce feeding single cell protein at present or from now on.According to enterprise's production scale, can select batch (-type) or continuous fermentation process flow process for use.Accompanying drawing 5 is depicted as the manufacture order cell protein technological process of continuously fermenting that the above enterprises in pulp and paper industry of suitable 10kt/a adopts.In the liquid glucose storage tank, add an amount of phosphoric acid or phosphate in advance, pH value 4-4.5 (the nitric acid here and produce nitrate simultaneously as the nitrogenous source in the fermentation of candida utili bacterium) is adjusted with nitric acid in the back that stirs, and the candida utili strain liquid in seeding tank is sent into aseptic fermentation tank under 35-38 ℃ then.Compressed air through sterilizer is sent into continuously from the fermentation tank bottom air inlet, and the heat that fermentation produces is shifted out by the fermentation tank intercooler, makes fermentation temperature be stabilized in 37 ℃.Zymotic fluid after the fermentation takes out from fermentation tank continuously, enters storagetank through gas-liquid separator, and after centrifugation, drying, its product is the feeding single cell protein of high-purity.
This flow process can reach 70-80% to the utilization rate of total organic sugar in the liquid glucose, and the BOD clearance reaches more than 85%.Fermenting and producing itself does not produce any environmental pollution, is used as the extracting water through the isolated parting liquid of yeast centrifuge, and then returns utilization system again, therefore can make the organic glucide in the pulping waste liquor almost all obtain utilizing.
Containing 55-60% protein and a large amount of Cobastabs in the high-purity single cell protein, can be used for substituted fish meal and soybean protein, is the good protein batching of feed industry and aquaculture.
6, causticization
Through the sodium salt liquid that the dense chamber of electric dialyzator delivery port flows out, its main component is Na
2SO
3And Na
2SO
4, also have small amount of N a in addition
2CO
3, Na
2SiO
3And LCFA and soap etc.Lime is added in the saline solution, make sodium salt change into the process appellation causticization of NaOH, the chemical reaction that takes place in the sodium salt liquid is:
Na
2SO
3+Ca(OH)
2→2NaOH+CaSO
3↓
Na
2SO
4+Ca(OH)
2→2NaOH+CaSO
4↓
Na
2CO
3+Ca(OH)
2→2NaOH+CaCO
3↓
Na
2SiO
3+Ca(OH)
2→2NaOH+CaSiO
3↓
2RCOONa+Ca(OH)
2→2NaOH+Ca(RCOOH)
2↓
2RCOOH+Ca(OH)
2→H
2O+Ca(RCOOH)
2↓
The calcium base salt that generates comprises that long chain fatty acid calcium salt solubility at normal temperatures is all very low, helps sodium salt and changes into NaOH and remove LCFA.
Here the causticization in reclaiming with traditional combustion method alkali is different be saline solution concentration lower (12-18g/L), the also less (4m of salt liquid measure
3/ t air dried pulp), should adopt the simple and easy interruption causticization flow process shown in the accompanying drawing 6.Saline solution pumps into the interruption causticizer from storage tank, adds lime simultaneously in the bracketplant of causticizer, carries out causticizing reaction simultaneously in 90 ℃ of liquid temperature and lime slaking.Stop agitator after the end and be chilled to room temperature, open the direct pump-in pressure filter of causticizer bottom valve.Filtrate flows into lye tank (vat), in order to prepare cooking liquor again.Close the liquid in-out valve after filtering end, open the recoil water valve, use screening the pulp plain boiled water to pump into filter-press, be deposited on white clay on the filtering layer and be sent to filtration on the lime mud folter, washing, washing lotion and enter the diluted alkaline liquid bath in order to replenish the waste water that the wet feed preparation operation is discharged through the bottom.Filter cake can be made other comprehensive utilization (pigment, stuffing etc.) or landfill.
Adopt patented technology of the present invention, can produce high-purity sodium lignosulfonate 500-550kg, high-purity single cell protein 140-160kg, formic acid and acetate 70-90kg, NaOH 30-45kg from the cooking waste liquor that air dried pulp per ton produces, this will bring huge economic benefit for enterprise undoubtedly.
Patented technology of the present invention is equally applicable to the inferior sodium method wood pulp reclaiming waste digestion liquid comprehensive utilization of alkalescence (or neutral), obtains identical practical function with waste liquid of straw pulp.
Patented technology of the present invention is compared with traditional combustion method alkali recovery technology, obviously has following beneficial effect:
1, environmental effect is good.Cooking waste liquor is handled with slurrying production and is carried out in a closed cycle system.Solid content in the waste liquid almost all is utilized.It does not produce secondary pollution, but also helps to eliminate boiler smoke grit and SO
2, SO
3Pollution to atmospheric environment.
2, economic benefit height.When realizing that alkali reclaims, lignin, compound sugar, VFA are that the commercial form with high added value is utilized, and these commodity produce under the low consumption condition, therefore can create huge economic benefit for enterprise.
3, investment is little, and equal production-scale gross investment only is 1/5 of a firing method chemical recovery system.Technological operation is simple, has good operability and exploitativeness.It is not subjected to the production-scale restriction of enterprise, as a clearer production technology with key effect, will promote pulping and papermaking industry, the particularly medium-sized and small enterprises with the grass as raw material pulping and paper-making to realize cleaner production and sustainable development effectively.
4, be no problem in market sale as the high-purity single cell protein of byproduct, alcohol, formic acid, acetate etc.To the utilization of high-purity lignosulphonates with sell and also to have some unfavorable factors at present; But from the ecological environment angle, exploitation lignin and lignin goods have far reaching significance and bright prospects.Abundant this resource of can growing of reasonable use lignin; not only help to change the environmental situation of pulping and papermaking industry; help saving and protecting limited petroleum resources, also will develop towards modern clean pulping process, produce far-reaching positive impact for promoting China's pulping and papermaking industry.
5, the foundation of the diversification production and operation mechanism of reclaiming waste digestion liquid comprehensive utilization, help to alleviate behind pulping and papermaking industry common the price great fluctuation process, particularly China joined WTO owing to reduce the impact that the wood pulp import tariff may cause significantly to medium-sized and small enterprises.
Four, description of drawings
Fig. 1 is a straw pulp reclaiming waste digestion liquid comprehensive utilization process flow process.
Fig. 2 is the waste liquid evaporation piece-rate system.
1. sedimentation basins among the figure, 2. Venturi tube, 3. collapsible tube, 4. trunnion, 5. anemostat, 6. cyclone separator, 7. profit wall waste liquid, 8. float trap, 9. surface condenser, 10. air-introduced machine, 11. chimneys, 12. organic acid storage tanks, 13. waste liquid pools, 14. filters, 15. circulating pumps.
Fig. 3 is CLB-X type ultrafilter membrane module structure schematic diagram.
Plate frame structure membrane module 1. sees through the liquid delivery port among the figure, 2. waste liquid inlet, 3. porous porous disc, 4. nylon cloth, 5. milipore filter, 6. water stream channel dividing plate, 7. other plate, 8. compression bar, 9. tie bolt, 10. concentrated solution outlet of fiberglass.
Water stream channel dividing plate 1. charging apertures among the figure 2. see through hole, 3. concentrated solution outlet, 4. water stream channel, 5. fish scale net.
Fig. 4 is that four sections of one-levels add the technological process of water purification ultra-filtration and separation.
1. enzymatic hydrolysis grooves among the figure, 2. water pump, 3. deep layer filter tank, 4. millipore filter, 5. pressure water pump, 6. ultrafilter.
Fig. 5 is the continuously ferment practical operation flow process of manufacture order cell protein of sugar juice.
1. liquid glucose storage tanks among the figure, 2. water pump, 3. seeding tank, 4. condenser, 5. airlift fermentor, 6. gas-liquid separator, 7. yeast storage tank, 8. centrifuge, 9. vapour seasoning machine, 10. finished product case, 11. sterilizers, 12. air compressors.
Fig. 6 is simple and easy interruption causticization operating process.
1. saline solution storage tanks among the figure, 2. water pump, 3. lime bracketplant, 4. simple and easy causticizer, 5. agitator, 6. water pump, 7. liquid flowing valve, 8. filter-press, 9. fluid valve, 10. inlet valve, 11. flowing water Valves, 12. water pump, 13. lime mud folters, 14. diluted alkaline liquid pools, 15. white water chests, 16. alkali lye ponds
Claims (3)
1. alkalescence or neutral sodium sulfite method straw pulp reclaiming waste digestion liquid method of comprehensive utilization comprise to concentrate the process that acidifying, enzymatic hydrolysis, ultra-filtration and separation, electrodialysis separation, biofermentation and causticization are formed:
Utilize boiler smoke, with cooking waste liquor by 8-9m
3Be concentrated to 6-7m
3/ t air dried pulp under the acidic gas in flue gas effect, makes the pH value of waste liquid drop to 6.0-6.5, and the effumability organic acid is separated from waste liquid simultaneously;
Waste liquid after the concentrated acidifying adds acid and adjusts pH value 4.5-5, adds cellulose complex enzyme again, at 40 ℃ of slow down stirring 2-3h, the monose conversion ratio is reached more than 90%;
With pressure water pump with hydrolysis and through the waste liquid of deep layer and micro porous filtration, at hydraulic pressure 0.8Mpa, 60-70 ℃ of water inlets that pump into ultrafilter of liquid temperature, ultra filtration unit assembly through four series connection, what flow out is concentration 20% lignosulphonic acid sodium solution, in order to produce the lignin base product of various different purposes, seeing through liquid is that monose and sodium salt mixed liquor are sent to the electrodialysis separation circuit;
To be chilled to the liquid that sees through of room temperature with water pump, flow is sent into the light chamber water inlet of electric dialyzator in accordance with regulations, to send into dense chamber water inlet as " carrier fluid " of accepting sodium salt simultaneously, adjusting rectifier operating voltage and operating current is stabilized in the technological requirement scope, from the outflow of the light chamber of final stage delivery port is the sugar juice that meets the salt content control criterion, be sent to the biofermentation operation, the sodium salt solution that flows out from dense chamber delivery port is sent to the causticization operation;
In sugar juice, add phosphoric acid or phosphate in advance, stir evenly the back and adjust pH value 4-4.5 with nitric acid, candida utili strain liquid in seeding tank is sent into aseptic fermentation tank under 35-38 ℃ then, zymotic fluid after the fermentation takes out from fermentation tank continuously, through centrifugation, drying, make feeding single cell protein, parting liquid is used as the extracting water, returns utilization system again;
The sodium salt liquid pump is gone into to be interrupted causticizer, simultaneously in the lime hanging basket of causticizer, add lime, carry out causticizing reaction simultaneously in 90 ℃ of liquid temperature and lime slaking, stop to stir and being chilled to room temperature after the end, through pressure filtration, aqueous slkali is reused for the preparation cooking liquor, and the washing lotion of washing white clay is admitted to the water system of getting the raw materials ready.
2. alkalescence according to claim 1 or neutral sodium sulfite method straw pulp reclaiming waste digestion liquid method of comprehensive utilization, it is characterized in that, as " carrier fluid " of accepting sodium salt in the electrodialysis separation, when producing, uses single chemical pulp the screening the pulp plain boiled water after purifying; Then use change machine pulp-making effluent during with change machine slurry combinations produce, thereby constitute a Totally-enclosed-type combination slurrying production system through coagulating treatment.
3. alkalescence according to claim 1 or neutral sodium sulfite method straw pulp reclaiming waste digestion liquid method of comprehensive utilization is characterized in that, the wood pulp cooking waste liquor is replaced the straw pulp cooking waste liquor, can obtain identical practical function.
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| CN101250568B (en) * | 2008-04-14 | 2011-07-20 | 大连工业大学 | Method for purifying lignin from paper-making black liquor by fermentation process |
| CN101781006A (en) * | 2010-03-03 | 2010-07-21 | 天津科技大学 | New method for improving flocculation treatment effect of high yield pulp waste liquid by using surplus sludge |
| CN101768887B (en) * | 2010-03-17 | 2012-12-26 | 山东和润浆纸有限公司 | Circular utilization method of straw in pulping and papermaking processes |
| CN102140261A (en) * | 2011-01-18 | 2011-08-03 | 延边石岘白麓纸业股份有限公司 | Method for preparing dye dispersing agent based on sulfite pulping waste liquid and dye combination |
| CN102493251B (en) * | 2011-12-01 | 2015-05-20 | 中国科学院过程工程研究所 | Papermaking red liquor sugar component using method |
| FI129114B (en) * | 2012-03-12 | 2021-07-15 | Upm Kymmene Corp | A method and a system for treating liquid flows at a chemical pulp mill |
| CN103253838B (en) * | 2013-06-14 | 2014-08-06 | 波鹰(厦门)科技有限公司 | Recycling device used for papermaking advanced treatment wastewater and based on chemical decalcification |
| CN104071938B (en) * | 2014-07-08 | 2015-10-28 | 日照弗尔曼新材料科技有限公司 | The combination treatment method of black liquid and water glass tail gas |
| CN104232494A (en) * | 2014-09-03 | 2014-12-24 | 稼禾生物股份有限公司 | Method for producing saccharomycete and organic fertilizer mother solution by utilizing papermaking black liquor |
| CN107055924A (en) * | 2017-05-24 | 2017-08-18 | 广西碧清源环保科技有限公司 | Ceramic membranous system and its handling process for Sewage |
| CN114763680B (en) * | 2021-01-15 | 2024-01-30 | 中国石油天然气股份有限公司 | Method for removing lignin from lignocellulose raw material |
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