CN1131350C - Alkali recovery process for black liquor of straw pulp - Google Patents
Alkali recovery process for black liquor of straw pulp Download PDFInfo
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- CN1131350C CN1131350C CN 01126588 CN01126588A CN1131350C CN 1131350 C CN1131350 C CN 1131350C CN 01126588 CN01126588 CN 01126588 CN 01126588 A CN01126588 A CN 01126588A CN 1131350 C CN1131350 C CN 1131350C
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- black liquor
- alkali
- electrodialysis
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Abstract
The present invention relates to an alkali recovery technology for black liquor of straw pulp. Firstly, steamed black liquor is diffused and dialyzed, the obtained diluted alkali liquor is used as electrolytic liquor of a cathode chamber in the process of electrodialysis. Electrodialysis uses a single-anode membrane to separate an anode chamber and a cathode chamber. The present invention uses a circulation type flow path, the black liquor is circulated by the anode chamber, and the diluted alkali liquor is circulated by the cathode chamber; the electrodialysis process is carried out at normal temperature and normal pressure, additional DC voltage is from 8 to 10 volts, electric current strength is controlled at 1A, electrode gaps are 2cm, and the concentration of the diluted alkali liquor of the cathode chamber is controlled between 0.015 and 0.050 mol/l; after thickened recovery alkali is obtained, the acid separation, the biochemical treatment and the electrocatalytic oxidation treatment of black liquor after electrodialysis are carried out. The present invention uses a novel fluorine membrane with low cost, improves the alkali recovery rate and reduces energy consumption, and the present invention has good application prospect.
Description
Technical field:
The present invention relates to a kind of new technology of straw pulp black liquor alkali recycling, adopting increased black liquor diffusion dialysis processing procedure before electrodialysis, realize the continuity of alkali recovery process, improved alkali recovery efficiency.Belong to Environmental Technology and electrochemical field.
Background technology:
The paper industry wastewater discharge is big, wherein contains a large amount of celluloses, lignin and suitable chemicals, and oxygen demand is big, is the pollution sources that people gaze at, and it can cause the heavy damage of whole water pollution and ecological environment.Wherein the pollution of black digestion liquid is the most serious, accounts for 90% of whole industrial pollution caused by paper manufacturing.At present, the common method of handling this class waste water both at home and abroad has traditional Silvola recovery, acid-precipitation method, flocculation sedimentation and Anaerobic Treatment method.The high load capacity that adopts traditional Silvola recovery not only can reduce black liquor greatly pollutes, BOD can reduce 80%～85%, can also reclaim heat energy, chemicals, reduce cost, increase economic benefit, but it is raw pulp that China adopts herbaceous plant such as wheat straw, straw, balloonflower root, reed, Chinese alpine rush and bagasse mostly, it is big that the straw pulp black liquor of its generation has viscosity, calorific value is low, characteristics such as burning difficulty; In addition, silicon content height in the straw pulp, easy fouling blocking pipeline during evaporation, therefore traditional burning alkali reclaiming method can not be effectively with its processing.Acid out and flocculating setting are because need add acid and flocculant, and cost is very high, and the lignin effect of settling during acid out is very poor.Because Na in the black liquor
+To CH
4Bacterium has toxic and side effect, and high concentration sulfide also has adverse effect to anaerobe, and in addition, lignin is difficult to degraded, therefore, generally is not suitable for straw pulp black liquor is directly carried out Anaerobic Treatment.
Electrodialysis methods provides the possibility of alkali recycling straw pulp black liquor." electroosmose process is handled the experimental study that black liquid reclaims alkali " that Chen Changchun etc. write (Environmental Pollution and Control, 1997,19 (2): 7-10) introduced the employing electrodialysis and carried out the method that alkali recycles straw pulp black liquor.Black liquor circulates by the anode chamber, and sig water can precipitate and separates out by cathode chamber most of lignin that circulates.It is simple, easy to operate that single anode membrane electrodialysis has technological process, and equipment investment is few, is easy to automation, is not subjected to characteristics such as silicon interference.But the cathode chamber sig water direct reuse that reclaims is in production.But utilize the electrodialysis process black liquor to run into following problem through regular meeting: 1. alkali recovery and recovery concentration are low, and power consumption is higher; 2. electrode does not pass a test, easily consumes, and selects suitable anode material difficulty, frequent replacing, cleaning electrode, complex operation, expense height; 3. stifled groove, stifled film and polarization phenomena also often take place in the electrodialysis operation, have limited the practical ranges of this dialysis alkali recycling straw pulp black liquor.
Summary of the invention:
The present invention is directed to the above-mentioned deficiency of prior art straw pulping black liquor, design provides a kind of alkali of straw pulp black liquor to reclaim new technology, before electrodialysis, increase black liquor diffusion dialysis processing procedure, realize the continuity of alkali recovery process, and select novel electrode material and membrane material for use, make it to have the alkali recovery efficiency height, energy consumption is lower, stable advantage.
Technological process of the present invention mainly is made up of two links: diffusion dialysis process and electrodialytic process.The structure of diffusion dialysis device is made up of the alternate placement with amberplex of several dividing plates.The below of each chamber all is furnished with aeration tube, behind the bubbling air, promotes the diffuser efficiency of black liquor, and water inlet pipe is arranged at the bottom of each groove chamber, and oral area has drainpipe.The sig water that diffusion dialysis obtains is as the electrolyte of electrodialytic process cathode chamber, and the straw pulp black liquor of handling through diffusion dialysis can more easily obtain further acidifying in the electrodialytic process process, separate out lignin.
Electrodialytic process adopts two Room electrolytic cells, and is separated by single anode membrane.Black liquor circulates by the anode chamber, and sig water circulates by cathode chamber.Anode adopts graphite, iridium dioxide, the titanium base is coated with lead or titanium is coated with insoluble anodes such as ruthenium.Negative electrode adopts stainless steel electrode.The below, anode chamber is furnished with aeration tube, promotes the circulation and the diffusion of black liquor by the control aeration condition.Electrodialytic process carries out at normal temperatures and pressures, 8～10 volts of impressed DC voltages.Current strength is controlled at 1 peace.Interelectrode distance is 2cm, and cathode chamber sig water concentration is controlled at 0.015～0.050mol/L.
Diffusion dialysis is to utilize certain dialyser that the different solution of concentration is separated.Solute promptly is diffused into the low side of concentration from the high side of concentration by dialyser.When the concentration of film both sides reached balance, the dialysis process promptly stopped to carry out.Diffusion dialysis does not need electrode, only uses single kind of film, consumed power not, and operational administrative is simple.The dialyser that uses can be amberplex, hydrophobic fluorine film, hydrophilic fluorine film etc., wherein especially with the better effects if of hydrophilic fluorine film.Contain suitable NaOH in the straw pulp black liquor, the pH value is up to 11～13.Therefore can utilize diffusion dialysis recovery a part of alkali wherein.Adopt the circulating flow process of the general employing of the electrodialytic technology of single anode membrane, black liquor circulates by the anode chamber, and sig water circulates by cathode chamber.Under the DC electric field effect, Na
+Enter cathode chamber by anode membrane, with the OH of electrolysis generation
-Reclaimed alkali in conjunction with generating NaOH; Anode chamber's black liquor is because the H that electrolysis produces
+, constantly by acidifying, arriving to a certain degree, most of lignin is separated out precipitation.
Adopt alkali recovery process straw pulping black liquor of the present invention, black digestion liquid is suitable for carrying out immediately diffusion dialysis and handles, and the postpone black liquor will be unfavorable for the diffusion dialysis effect for a long time.In technological process of the present invention,, select novel hydrophobic fluorine film and insoluble iridium oxide anode for use by the control aeration condition, it is low to have solved alkali recovery preferably, the energy consumption height, problems such as the stifled film of selective membrane material and anode material difficulty and plugging have realized the continuity that alkali reclaims.
Description of drawings:
Technical scheme for a better understanding of the present invention below is further described by accompanying drawing..
Fig. 1 is a process chart of the present invention.
As shown in the figure, the present invention adopts and carried out diffusion dialysis earlier before electrodialysis, further carries out conventional acid out, biochemical treatment and catalytic oxidation after the electrodialysis again and handles.In diffusion dialysis, alkali in the black liquor passes through the diffusion barrier dialysis in distilled water, distilled water becomes dilute alkaline soln after diffusion dialysis, electrolyte as the electrodialytic process cathode chamber, black liquor after the diffusion dialysis is carried out electrodialysis again, the sig water that obtains thus reclaims alkali as enrichment, is back to the recycling of paper making raw material place.To the black liquor acid out after the electrodialysis, add acid and reduce the pH value, make it to separate out a part of lignin on the one hand, make its acidity that reaches biochemical treatment on the other hand, carry out biochemical treatment.The waste water that flows out from biochemical treatment tank carries out after catalytic oxidation handles again, and the water that obtains just can discharge or reuse.
The schematic diagram of Fig. 2 single anode membrane electrodialysis process black liquid for the present invention utilizes.
As shown in the figure, electrodialysis adopts single anode membrane to be divided into anode chamber and cathode chamber, adopts circulating flow process, and the black liquor after the diffusion dialysis circulates by the anode chamber, and sig water circulates by cathode chamber.Under the DC electric field effect, Na
+Enter cathode chamber by anode membrane, with the OH of electrolysis generation
-Reclaimed alkali in conjunction with generating NaOH; Anode chamber's black liquor is because the H that electrolysis produces
+, constantly by acidifying, arriving to a certain degree, the lignin of most of acidifying is separated out precipitation.
The specific embodiment:
Embodiment 1
Strengthen at electronic peristaltic pump under the situation of circulation, black liquor carries out ion exchange membrane diffusion dialysis 100min earlier.The sig water that obtains is as the electrolyte of electrodialytic process cathode chamber, and the black liquor of handling through diffusion dialysis is being kept electrolysis 120min under the constant current 1A as the electrolyte of electrodialysis anode chamber, and wherein the electrode spacing of anode and cathode is 2cm.The result is as shown in table 1.
The result of black liquor is handled in table 1 ion exchange membrane diffusion dialysis and constant current
| Project | Raw black liquid | Diffusion dialysis 100min | Diffusion dialysis 100min+electrodialysis 120min | ||
| COD Cr(mg/L) | 37675.2 | 32400.67 | Clearance 14.0% | 36582.20 | Clearance 29.7% |
| Na +(g/L) | 7.68 | 6.996 | The rate of recovery 8.9% | 3.504 | The rate of recovery 54.4% |
Therefrom as can be seen, black liquor after diffusion dialysis, COD
CrClearance is 14%, and the NaOH rate of recovery is 8.9%, after the electrodialysis Combined Treatment, has reclaimed about 54.4% Na
+, and 29.7% COD is arranged
CrClearance.
After diffusion dialysis and electrodialysis, handle the COD of raw black liquid again through acid out, biochemical treatment and catalytic oxidation
CrBe reduced to 0.1360mg/L, reached the industrial wastewater discharge standard, and this water also can be used as the industrial water recycling.
In the science and engineering skill,, make and saved electric energy in the electrodialytic process herein, reduced sour consumption in the acid out owing to increased diffusion dialysis.
Embodiment 2
Strengthen at electronic peristaltic pump under the situation of circulation, black liquor carries out hydrophobic fluorine film diffusion dialysis 100min earlier.The sig water that obtains is as the electrolyte of electrodialytic process cathode chamber, and the black liquor of handling through diffusion dialysis is being kept electrolysis 120min under the constant current 1A as the electrolyte of electrodialysis anode chamber, and wherein the electrode spacing of anode and cathode is 2cm.The result is as shown in table 2.
The result of black liquor is handled in table 2 hydrophobic fluorine film diffusion dialysis and constant current
| Project | Raw black liquid | Diffusion dialysis 100min | Diffusion dialysis 100min+electrodialysis 120min | ||
| COD Cr(mg/L) | 37675.2 | 31533.9 | Clearance 16.3% | 25954.45 | Clearance 31.1% |
| Na +(g/L) | 7.68 | 6.65 | The rate of recovery 13.4% | 3.120 | The rate of recovery 59.3% |
Therefrom as can be seen, black liquor after diffusion dialysis, COD
CrClearance is 16.3%, and the NaOH rate of recovery is 13.4%, after the electrodialysis Combined Treatment, has reclaimed about 59.3% Na
+, and 31.1% COD is arranged
CrClearance.
Embodiment 3
Strengthen at electronic peristaltic pump under the situation of circulation, black liquor carries out hydrophilic fluorine film diffusion dialysis 100min earlier.The sig water that obtains is as the electrolyte of electrodialytic process cathode chamber, and the black liquor of handling through diffusion dialysis is being kept electrolysis 120min under the constant current 1A as the electrolyte of electrodialysis anode chamber, and wherein the electrode spacing of anode and cathode is 2cm.The result is as shown in table 3.
The result of black liquor is handled in table 3 hydrophilic fluorine film diffusion dialysis and constant current
| Project | Stoste | Diffusion dialysis 100min | Diffusion dialysis 100min+electrodialysis 120min | Remarks | |
| COD Cr(mg/L) | 37675.2 | 31182.24 | Clearance 17.2% | 25170.24 | Clearance 33.19% |
| Na +(g/L) | 7.68 | 6.530 | The rate of recovery 15.0% | 3.052 | The rate of recovery 60.26% |
Therefrom as can be seen, black liquor is through diffusion dialysis COD
CrClearance is 17.2%, the NaOH rate of recovery be 15.0% and the electrodialysis Combined Treatment after, reclaimed about 60% Na
+, COD
CrClearance is 33.19%.
Obtain thus: (1) diffusion dialysis has reduced the Na of about 14%-15%
+So, saved the power consumption of 14%-15%.Make this a part of alkali lye obtain recycling, saved paper making raw material.And in next step acid out process, saved sour consumption.(2) remove portion C OD and improved character such as viscosity with black liquor.(3) select multiple film for use, and found novel inexpensive fluorine film better effects if.
And prior art reclaims alkali to black liquor by single anode membrane electrodialysis methods, the rate of recovery is about 50%, and its result all obtains under the condition of power consumption.Under the contrast, better effects if of the present invention.
Claims (4)
1, a kind of alkali of straw pulp black liquor reclaims new technology, it is characterized in that earlier black digestion liquid being carried out diffusion dialysis, the sig water that obtains is re-used as the electrolyte of cathode chamber in the electrodialytic process, electrodialysis adopts single anode membrane to be divided into anode chamber and cathode chamber, adopt circulating flow process, black liquor circulates by the anode chamber, sig water circulates by cathode chamber, electrodialytic process carries out at normal temperatures and pressures, 8～10 volts of impressed DC voltages, current strength is controlled at 1A, and electrode spacing is 2cm, cathode chamber sig water concentration is controlled at 0.015～0.050mol/L, obtains again the black liquor after the electrodialysis being carried out acid out after enrichment reclaims alkali, biochemical treatment, catalytic oxidation is handled.
2, reclaim new technology as the alkali of the said a kind of straw pulp black liquor of claim 1, adopt aeration to promote the diffuser efficiency of black liquor when it is characterized in that described diffusion dialysis.
3, reclaim new technology as the alkali of the said a kind of straw pulp black liquor of claim 1, it is characterized in that described diffusion dialysis adopts hydrophilic fluorine film, hydrophobic fluorine film is adopted in electrodialysis.
4, the alkali as the said a kind of straw pulp black liquor of claim 1 reclaims new technology, it is characterized in that graphite, iridium dioxide are adopted in described electrodialysis, the titanium base is coated with lead or titanium is coated with the ruthenium insoluble electrode as anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01126588 CN1131350C (en) | 2001-08-30 | 2001-08-30 | Alkali recovery process for black liquor of straw pulp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01126588 CN1131350C (en) | 2001-08-30 | 2001-08-30 | Alkali recovery process for black liquor of straw pulp |
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| CN1334376A CN1334376A (en) | 2002-02-06 |
| CN1131350C true CN1131350C (en) | 2003-12-17 |
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|---|---|---|---|
| CN 01126588 Expired - Fee Related CN1131350C (en) | 2001-08-30 | 2001-08-30 | Alkali recovery process for black liquor of straw pulp |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298637C (en) * | 2005-08-08 | 2007-02-07 | 南京工业大学 | Method for recycling sodium hydroxide from pigment containing alkali waste liquid |
| DE102009001512A1 (en) * | 2009-03-12 | 2010-09-16 | Evonik Degussa Gmbh | Production of high-purity suspensions containing precipitated silicas by electrodialysis |
| CN102107973B (en) * | 2011-01-20 | 2012-05-23 | 江阴东大新材料研究院 | Closed cyclic processing method for low-concentration acid wastewater during industrial production |
| CN102557189A (en) * | 2012-01-18 | 2012-07-11 | 长沙矿冶研究院有限责任公司 | Method for separating and recovering peracid and high arsenic from waste liquor obtained after arsenic is extracted from nickel-molybdenum ore smelting dust |
| CN103074796A (en) * | 2012-12-30 | 2013-05-01 | 山东天维膜技术有限公司 | Alkali recovery process for paper-making black liquid |
| CN103349909B (en) * | 2013-07-24 | 2015-07-01 | 宜宾海丝特纤维有限责任公司 | Post-processing method for squeezed alkali liquid in diffusion dialysis recycling viscose manufacture |
| CN103349913B (en) * | 2013-07-24 | 2015-04-22 | 宜宾海丝特纤维有限责任公司 | Novel alkali recovery technology during viscose fiber production |
| CN105463505A (en) * | 2015-11-25 | 2016-04-06 | 合肥科佳高分子材料科技有限公司 | Device and method for conducting diffusion dialysis and electrolysis electrodialysis integrated treatment on vanadium-alkali feed liquid in alkali method vanadium extraction process |
| CN105668889A (en) * | 2016-01-07 | 2016-06-15 | 浙江蓝极膜技术有限公司 | Process for recycling sulfuric acid and methylamine in sulfuric acid and methylamine salt wastewater through bipolar membrane electrodialysis method |
| CN105645644B (en) * | 2016-01-07 | 2018-06-08 | 浙江蓝极膜技术有限公司 | A kind of technique for recycling sulfuric acid in sulfur acid and sodium sulfate wastewater with two sections of diffusion dialysis, two sections of electrodialysis and Bipolar Membrane |
| CN106007113A (en) * | 2016-07-25 | 2016-10-12 | 大连佳瑞环保科技有限公司 | Treatment device and treatment method for circulating cooling water |
| CN113563605A (en) * | 2021-08-07 | 2021-10-29 | 木质素重庆科技有限公司 | Papermaking black liquor lignin separation and alkali recovery device and method |
| CN113481521B (en) * | 2021-08-07 | 2023-04-25 | 木质素重庆科技有限公司 | Continuous chlor-alkali industrial electrolysis alkali preparation device and method |
| CN115072897A (en) * | 2022-05-31 | 2022-09-20 | 光大环保技术研究院（南京）有限公司 | Electrodialysis membrane pollution prevention and treatment method and electrodialyzer |
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