CN106676572A - Paper-making dark liquid rough lignin extraction method and device based on wood ceramic electrode - Google Patents

Paper-making dark liquid rough lignin extraction method and device based on wood ceramic electrode Download PDF

Info

Publication number
CN106676572A
CN106676572A CN201710003728.3A CN201710003728A CN106676572A CN 106676572 A CN106676572 A CN 106676572A CN 201710003728 A CN201710003728 A CN 201710003728A CN 106676572 A CN106676572 A CN 106676572A
Authority
CN
China
Prior art keywords
chamber
anode
cathode chamber
valve
black liquor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710003728.3A
Other languages
Chinese (zh)
Other versions
CN106676572B (en
Inventor
孙德林
余先纯
盛利元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University of Forestry and Technology
Original Assignee
Central South University of Forestry and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University of Forestry and Technology filed Critical Central South University of Forestry and Technology
Priority to CN201710003728.3A priority Critical patent/CN106676572B/en
Publication of CN106676572A publication Critical patent/CN106676572A/en
Application granted granted Critical
Publication of CN106676572B publication Critical patent/CN106676572B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00Electrolytic production of organic compounds
    • C25B3/20Processes
    • C25B3/23Oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • C02F2001/46133Electrodes characterised by the material
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/46115Electrolytic cell with membranes or diaphragms

Abstract

The invention provides a paper-making dark liquid rough lignin extraction method based on a wood ceramic electrode. The method includes the steps that a porous ceramic filter plate and a cation exchange membrane are utilized to separate an electrolysis tank into an anode chamber, a buffering chamber and a cathode chamber; a porous wood ceramic material serving as the anode and a graphite material serving as the cathode are arranged in the anode chamber and the cathode chamber respectively; dark liquid and clear water are poured into the anode chamber and the cathode chamber respectively, electrolysis is performed in the condition of a low-voltage direct-current power source, and the anode is taken out every a period of time so that the lignin accumulated on a porous wood ceramic wafer can be collected; after take-out action is repeated multiple times, residual liquid in the anode chamber is exhausted, a NaOH solution concentrated in the cathode chamber is recycled, and hydrogen gas and oxygen gas generated in the electrolysis process are collected through gas guide-out pipes respectively. The extraction method is simple and practical, the anode cannot be consumed to cause secondary pollution, and the dark liquid treatment cost is lowered while the recycling rates of the lignin and the NaOH can be improved.

Description

The extracting method and device of the black liquid rugose wood element based on woodceramics electrode
Technical field
The present invention relates to the technical field that black liquor is extracted, in particular it relates to a kind of be based on woodceramics The extracting method and device of the black liquid rugose wood element of electrode.
Background technology
Lignin is the second largest component in plant, pulping and papermaking processes produce black liquid, its main component it One is exactly to be dissolved alkali lignin out, and about 20,000,000 tons of alkali wood is just contained in 200,000,000 tons of black liquor that China produces every year Quality.Lignin has having been widely used in industrial and agricultural production, therefore, lignin is extracted from black liquid economical and Field of Environment Protection is all significant.
The existing method for extracting lignin includes following several:
First, acid precipitation method.Acid precipitation method is also referred to as acid-precipitation method, is to use one of more method at present, and its principle is to pass through Acid adding adjust black liquor pH value, make the sodium lignin conversion in black liquor for hydrogen lignin Precipitation, through filtering, washing, dry Crystalloid rugose wood element is obtained after dry, the acid for being used can be inorganic acid, or organic acid.
2nd, ultrafiltration.Ultrafiltration is the membrane separation technique with pressure as motive force, i.e., under pressure, make small point Sub- solute and solvent pass through the special film of certain pore size, and prevent macromolecular solute from passing through and stay in one side of film, so that So that macromolecular substances obtain the purifying of part.It is the macromolecular compound that molecular mass is 5-50ku in view of lignin, can Extracted from black liquid using ultrafiltration.
3rd, flocculence.Due to there are many colloidal substances in black liquid, under certain condition with colloidal nature, because This can make negatively charged lignin particulate by the Cation adsorption of precipitating reagent using the method for addition lignin deposit agent, So as to destroy the stability of colloid, the purpose for making lignin separate out precipitation is reached.
4th, electrocoagulation and dialysis.Electrocoagulation refers in the presence of impressed current, by the use of iron or aluminum metal as sacrificial Domestic animal anode and electrolysis when dissolve, to form Fe (OH)2、Al(OH)3Condensed etc. water insoluble metal oxide active Body, cohesion and suction-operated can be played to the organic or inorganic thing in liquid, and the cotton-shaped particle of formation is settled and divided together From;Anode can also be done using the less titanium of sacrificed anticathode, be can release with strong oxidizing property on electrolytic process, anode Oxygen or chlorine, can make organic matter in black liquor that strong oxidation decomposition occurs.
Correspondingly, also all come with some shortcomings part in above-mentioned four kinds of methods, specific as follows:
(1) acid precipitation method:Need to add the strong acid such as sulfuric acid, phosphoric acid, and just have preferable recovery rate when pH reaches 2 or so, Not only addition is big, high cost, the secondary pollution that there is residual acid, sulfuric acid can also generate salt, such as sulphur with the alkali in black liquor Sour sodium, sodium phosphate etc., the later stage treatment to black liquor bring great inconvenience.
(2) ultrafiltration:Although without adding strong acid, solute is deposited or adsorbed on the surface of milipore filter in use On, so as to cause fenestra to be blocked, cause permeation flux to greatly reduce, service life is short, although can utilize surfactant Surface to milipore filter is modified treatment, but still is difficult to reach preferable state, particularly in long-time, the feelings of continuous processing Under condition.Meanwhile, when the concentration of black liquor is higher, its permeation flux is smaller, greatly affected extraction efficiency.
(3) flocculence:Need to add substantial amounts of flocculant in processing procedure, a portion can be sent out with the alkali in black liquor Raw reaction, and another part can be dissolved in black liquor, although its harm is so big unlike acid precipitation method, but equally exists black liquor Later stage process problem, while also can be more or less in the lignin for extracting contain flocculant, this also can be to lignin Later purification causes trouble.
(4) electrocoagulation and dialysis:Although electrocoagulation is environmentally friendly, it is intended to sacrificial anode as cost, not only consuming cost Height, can also increase new metal ion, the treatment of influence later stage in black liquor, although and using Titanium as the method sun of anode Pole sacrifices smaller, but titanium is expensive, and extraction cost is excessive, and the matched dialysis for using equally exists Pore Blocking Problem.
Chinese patent CN02113761 discloses a kind of electric osmose formula treatment black liquid and the method for reclaiming alkali and lignin, It sets pellicle in the tank house of the dc source electric field for having negative electrode and positive electrode, and tank house is divided into negative side The tank house of tank house and side of the positive electrode, clear water and black liquid are flowed separately through the electrolysis of the tank house and side of the positive electrode of negative side Room, obtain exclude from the tank house of negative side alkali lye, from the tank house of side of the positive electrode exclude in treatment fluid, add chlorion to sink Shallow lake agent, organic matter and clear water of the separated acquisition containing lignin.The invention makes black liquor by alkalescence by adjusting the size of electric current It is changed into neutral or faintly acid, and adds precipitating reagent to realize the precipitation of lignin, without solving the problems, such as lignin later purification, into This is also still very high.
Chinese patent CN99106161 disclose it is a kind of is prepared from black liquid using electrolytic hydrogenation process hydrogenate it is wooden The method of element, it makees negative electrode, Pt and makees anode, saturation calomel motor to make reference electrode in separated type electrolytic tank, with foam Pb, with DMF and ethanol make electroanalysis solvent, water and make hydrogen supply dissolvent, TBAB to make supporting electrolyte, to wooden Element carries out electrolytic hydrogenation.The present invention does not need catalyst, increased C/Hratio, reduces the softening point of extracting hydrogenated lignin, but The solvent used is excessive, and cost is very high.
The content of the invention
In order to overcome, purity difference present in the above method, efficiency are low, consuming cost is high, service life is short, waste liquid difficulty The technical problem of reason, the present invention provide it is a kind of simple and practical, with low cost, reusable and need not introduce other materials from The method and device of extracting lignose from papermaking black liquor.
Woodceramics, are a kind of new environmentally conscious materialses, are by impregnated of the timber of thermosetting substance or other biomass Material is formed through vacuum carburization.Woodceramics have good calorifics, electricity, magnetism characteristic, under the conditions of low temperature (less than 150 DEG C) Intensity is high, specific surface area is big, good in oxidation resistance, corrosion resistance strong, can be used as super electrode material, energy storage material, corrosion-resistant material Material and high-temperature-resistant filtering material etc..
A kind of extracting method of the black liquid rugose wood element based on woodceramics electrode, in the anode chamber of electrolytic cell and the moon Porous woodceramics material is respectively provided with pole room as anode, setting graphite material as negative electrode, black liquor and clear water are distinguished Injection anode chamber and cathode chamber, are electrolysed under the conditions of dc source, obtain wooden from the porous woodceramics material of anode chamber Element.
Preferably, the electrolytic cell has additional surge chamber between anode chamber and cathode chamber, and porous by setting respectively Ceramic filter plate and cation-exchange membrane separate surge chamber with anode chamber and cathode chamber.By the initial filter of filter plate of porous ceramic Effect, the impurity stopping state occurred on cation-exchange membrane greatly reduces.
Preferably, NaOH is added in the electrolysis initial stage is to cathode chamber to increase electric conductivity so that initial NaOH in cathode chamber The concentration of solution reaches 0.1mol/L-0.2mol/L.
Preferably, ultrasonic transducer is provided with the surge chamber, is just opened at regular intervals in electrolytic process A ultrasonic transducer is opened, it is unimpeded with the hole for ensureing filter plate of porous ceramic and cation-exchange membrane.
Preferably, the voltage of the dc source for being used is no more than 36V.
A kind of extraction element of the black liquid rugose wood element based on woodceramics electrode, includes the anode for housing black liquor Room and the cathode chamber for housing clear water and NaOH solution, the anode chamber and cathode chamber are equipped with closure and are arranged on close Gas port in capping, and porous woodceramics material as anode is provided with the anode chamber, in the cathode chamber Inside it is provided with as the graphite material of negative electrode, the anode chamber also includes the black liquor flow in pipes that communicates therewith and valve and dilute black Liquid derives pipeline and valve, the cathode chamber also include the clear water flow in pipes that communicates therewith and valve and NaOH recovery channels with Valve.
Preferably, a surge chamber, and the surge chamber are provided between the anode chamber and cathode chamber by porous Ceramic filter plate and cation-exchange membrane separate with anode chamber and cathode chamber respectively, and the surge chamber includes the buffering for communicating therewith Room waste liquid derives pipeline and valve.
Preferably, the aperture of the filter plate of porous ceramic is 0.2 μm -0.5 μm, and the aperture of the cation-exchange membrane is 0.05μm-0.1μm。
Preferably, it is additionally provided with ultrasonic transducer in the surge chamber.
Preferably, the extraction element is serially connected and used for two sets or more than two sets, by by preceding a set of extraction element In thin phenol water derive pipeline be connected right to realize with valve with the black liquor flow in pipes in valve and rear a set of extraction element The multipass treatment of black liquor, so as to obtain lignin extraction rate and the NaOH solution rate of recovery higher.
Contain substantial amounts of sodium lignin and hydroxide ion in black liquid.In electrolytic process, anode is aoxidized Reaction, generates oxygen and hydrogen ion, and causes the pH value of anode region to reduce, sodium lignin can occur in sour environment cohesion and Precipitation, while producing free sodium ion;Because the sodium lignin being dissolved in black liquor is with negative electrical charge, it can be in the work of electric field With it is lower on the sunny side Ghandler motion move, sodium lignin be deposited on after electronics is obtained the surface of anode and near, can thus realize wooden The separation of element and black liquor.At the same time, there is reduction reaction in cathode chamber, generate hydrogen and hydroxide ion, the sodium of anode region from Son in the presence of DC electric field to cathodic region move and assemble, with by cation-exchange membrane intercept cathodic region hydroxyl from Son is combined and generates the NaOH that can be recovered.
In whole electrolytic cell, sodium ion can pass through filter plate of porous ceramic and cation-exchange membrane to surge chamber and negative electrode Room is moved, and macromolecular substances (pollutant) are then isolated in anode chamber by ceramic filter plate, reduce the sky of cation-exchange membrane Hole plug.It is simultaneously unimpeded in order to fully ensure that the hole of filter plate of porous ceramic and cation-exchange membrane, installed in surge chamber Ultrasonic transducer, can in time clear up absorption and be deposited on filter plate of porous ceramic and be handed over cation by the vibration of ultrasonic wave The material changed on film.The ultrasonic transducer can start at any time as needed, will not be clashed with electrolytic process, both can be with Worked during anode absorption lignin, it is also possible to worked taking out during anode collects lignin.
Said extracted principle is referring to Fig. 1, and the electrode reaction equation of electrolytic process is as follows:
Anode region:
2H2O-4e-→O2↑+4H+
nH++nRONa→nNa++ nROH (lignin precipitation)
mH++mRCOONa→mNa++ mRCOOH (organic acid)
Cathodic region:
2H2O+2e-→H2↑+OH-
OH-+Na+(anode is moved into) → NaOH (recovery)
In sum, by separation and Extraction, part water is electrolysed and is obtained oxygen and hydrogen the lignin in black liquor, and NaOH is molten Liquid is concentrated recovery in cathodic region.At the same time, anode region is by coming into being that the oxidation and anode reaction of anode are generated The oxidation of state oxygen, the partial organic substances (pollutant of degraded can be oxidized in black liquor) of oxidable decomposition anode region, together When precipitation because of the lignin and oxidation Decomposition of organic matter, COD value, colourity of waste liquid that anode region flows out etc. is had certain journey The reduction of degree, alleviates environmental pollution.
The technical scheme that the present invention is provided has the advantages that:
1st, the present invention does not have secondary pollution without addition acid or other chemical reagent during extraction, is reducing into This while, also beneficial to the later stage treatment and the purification of lignin to electrolysis waste solution;
2nd, the present invention uses woodceramics as anode, and its raw material sources is extensive, manufacture craft simple and price is low It is honest and clean, simultaneously as anode will not be produced to consume, while reduces cost, it is thus also avoided that the secondary dirt that consumable anode is brought Dye, decreases the problem of Pore Blocking, even woodceramics battery lead plate has been damaged in use, disassembles Battery lead plate is alternatively arranged as boiler oil treatment;
3rd, by the woodceramics material for being used has porous, huge specific surface area is possessed, and pore structure can It is adjusted as needed, which greatly improves the efficiency and the extraction efficiency of lignin of electrolysis;
4th, due to being cleaned using filter plate of porous ceramic and with ultrasonic wave, polymer is not only compared on service life Film is long, can also reduce and reduce situation about blocking, even if being blocked, the ceramic filter plate changed can also burn in Muffle furnace Reused after knot, cost can be greatly reduced;
5th, extraction process whole process is pollution-free, and black liquor can be fully used, and in addition to the lignin for needing, anode is produced Oxygen, negative electrode production hydrogen and NaOH all fully reclaimed.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be to that will make needed for embodiment description Accompanying drawing is briefly described, it should be apparent that, drawings discussed below is only some embodiments of the present invention, for this For the those of ordinary skill of field, on the premise of not paying creative work, can also obtain other according to these accompanying drawings Accompanying drawing, wherein:
Fig. 1 is the principle schematic of extracting method in the present invention;
Fig. 2 is the structural representation of the preferred embodiment of extraction element in the present invention;
In figure:The cathode chamber of the anode chamber of 1 accommodating black liquor, 2 accommodating clear water and NaOH solution, 3 surge chambers, 4 porous ceramics Filter, 5 cation-exchange membranes, 6 closures, 7 gas eduction tubes, 8 ultrasonic transducers;11 porous woodceramics pieces, 12 is black Liquid flow in pipes and valve, 13 thin phenol waters derive pipeline and valve, 14 titanium alloy electrodes folder, 21 graphite flakes, 22 clear water ascending pipes Road and valve, 23NaOH recovery channels and valve, 24 stainless steel electrodes folder, 31 surge chamber waste liquids derive pipeline and valve.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on Embodiment in the present invention, it is all other that those of ordinary skill in the art are obtained under the premise of creative work is not made Embodiment, belongs to the scope of protection of the invention.
Referring to Fig. 1 and Fig. 2, a kind of extraction element of the black liquid rugose wood element based on woodceramics electrode, including with Cathode chamber 2 in the anode chamber 1 of accommodating black liquor and for housing clear water and NaOH solution, the anode chamber 1 and cathode chamber 2 are equal Be provided with closure 6 and gas eduction tube 7, and be provided with the anode chamber 1 porous woodceramics piece 11 as anode, It is provided with as the graphite flake 21 of negative electrode in the cathode chamber 2, the anode chamber 1 also includes the black liquor flow in pipes for communicating therewith Pipeline and valve 13 are derived with valve 12 and thin phenol water, the cathode chamber 2 also includes the clear water flow in pipes and valve that communicate therewith Door 22 and NaOH recovery channels and valve 23.
A surge chamber 3 is provided between the anode chamber 1 and cathode chamber 2, and the surge chamber 3 passes through porous ceramics Filter 4 and cation-exchange membrane 5 separate with anode chamber 1 and cathode chamber 2 respectively, and the surge chamber 3 includes that what is communicated therewith delays Rushing room waste liquid derives pipeline and valve 31, and ultrasonic transducer 8 is additionally provided with the surge chamber 3.
The aperture of the filter plate of porous ceramic 4 is 0.2 μm, and the aperture of the cation-exchange membrane 5 is 0.05 μm.
The porous woodceramics piece 11 presss from both sides 14 and is connected with external circuitses by titanium alloy electrode, and the graphite flake 21 passes through Stainless steel electrode folder 24 is connected with external circuitses.Due to containing substantial amounts of alkaline matter in black liquor, for the electrode of jointed anode Folder is easy to be there is oxidation reaction and corrodes, so from titanium alloy material, and the electrode holder for being used to connect negative electrode is not susceptible to Oxidation reaction, therefore use cheap stainless steel.
In general, the speed that lignin gathers in the state of high voltage and high current is more quicker, so collects wooden The time that element is spent is relatively short, but the caloric value of electrode increases, and not only wastes substantial amounts of electric energy, also results in anode and more holds Easily there is seminess, in addition in view of often to expose anode to collect lignin, so the extraction element is used The low-tension supply of below 36V, and preferably 12-24V.
When woodceramics density in itself is reduced, its specific surface area increases, the electron transport ability in electrolytic process Lifting, i.e., the adsorption capacity to lignin increases, therefore also to increase the quantity of graphite flake in cathode chamber to adapt to woodceramics The increase of the electron transport ability of electrode;But nor density is more low better, too low density influences whether electrode strong in itself Degree, and then its service life is influenceed, so the porous woodceramics piece of proper density should be chosen as anode.
Embodiment 1
(1) from the filter plate of porous ceramic 4 that aperture is 0.2 μm and cation-exchange membrane 5 that aperture is 0.05 μm, spiral shell is used Bolt and silica gel sealing ring seal to prevent fluid seepage;
(2) top of anode chamber 1 and cathode chamber 2 is sealed with closure 6, and is drilled with Φ respectively on closure The gas port and electrode-inserting holes of 30mm, during external diameter inserted into the gas port of closure 6 for the gas eduction tube 7 of Φ 30mm, use Raw material band or sealant sealing, and cause that two gas eduction tubes 7 are connected with two gas collectors respectively;
(3) by 1 specification be 300mm × 150mm × 20mm, density be 0.7g/cm3Porous woodceramics piece 11 and 1 Piece specification is clamped with titanium alloy clamp 14 and stainless steel fixture 24 respectively for the graphite flake 21 of 300mm × 150mm × 20mm, and is worn Cross electrode-inserting holes to be respectively arranged in anode chamber 1 and cathode chamber 2, with raw material band or sealant sealing;
(4) ultrasonic transducer 8 that the bottom installation power in surge chamber 3 is 300W, frequency is 24kHz;
(5) black liquor is injected into anode chamber 1 via black liquor flow in pipes and valve 12, keeps black liquor liquid level to be pressed from both sides with titanium alloy Vertical distance between tool 14 is 3cm (ensuring that the two is not contacted), and clear water injects cathode chamber 2 via clear water flow in pipes and valve 22 In, ensure that anode chamber 1, cathode chamber 2 are concordant with the liquid level in surge chamber 3 by the osmosis of liquid, added in cathode chamber 2 NaOH so that the concentration of NaOH solution reaches 0.1mol/L in cathode chamber 2;
(6) wire for connecting porous woodceramics piece 11 is connected with the positive pole of low-voltage dc power supply, graphite flake will be connected 21 wire is connected with the negative pole of low-voltage dc power supply;
(7) switch on power, start electrolysis, decomposition voltage is 24V, and electric current is 2A, opened every 20min in electrolytic process Ultrasonic transducer 8, the time is 5min, cleans the filter plate of porous ceramic 4 and cation-exchange membrane 5 of centre to prevent from blocking up Plug, takes out porous woodceramics piece 11 every 40min, and the lignin on its surface is attached to collect;
(8) repeat step (7) three times, while noting control black liquor liquid level, black liquor and clear water are supplemented when liquid level is reduced;
(9) after lignin extraction terminates, the thin phenol water derivation pipeline for opening the bottom of anode chamber 1 puts waste liquid with valve 13 Go out, then black liquor is refilled by black liquor flow in pipes and valve 12, and repeat the above steps (7) and step (8), while passing through The NaOH recovery channels of the bottom of cathode chamber 2 reclaim NaOH solution with valve 23;
(10) by after the extraction of about 10 times, the solution retrogradation in surge chamber, can by surge chamber waste liquid derive pipeline with Valve 31 is derived.
Embodiment 2
(1) from the filter plate of porous ceramic 4 that aperture is 0.2 μm and cation-exchange membrane 5 that aperture is 0.05 μm, spiral shell is used Bolt and silica gel sealing ring seal to prevent fluid seepage;
(2) top of anode chamber 1 and cathode chamber 2 is sealed with closure 6, and is drilled with Φ respectively on closure The gas port and electrode-inserting holes of 30mm, during external diameter inserted into the gas port of closure 6 for the gas eduction tube 7 of Φ 30mm, use Raw material band or sealant sealing, and cause that two gas eduction tubes 7 are connected with two gas collectors respectively;
(3) by 1 specification be 300mm × 150mm × 20mm, density be 0.6g/cm3Porous woodceramics piece 11 and 2 Piece specification is clamped with titanium alloy clamp 14 and stainless steel fixture 24 respectively for the graphite flake 21 of 300mm × 150mm × 20mm, and is worn Cross electrode-inserting holes to be respectively arranged in anode chamber 1 and cathode chamber 2, with raw material band or sealant sealing;
(4) ultrasonic transducer 8 that the bottom installation power in surge chamber 3 is 500W, frequency is 26kHz;
(5) black liquor is injected into anode chamber 1 via black liquor flow in pipes and valve 12, keeps black liquor liquid level to be pressed from both sides with titanium alloy Vertical distance between tool 14 is 3cm (ensuring that the two is not contacted), and clear water injects cathode chamber 2 via clear water flow in pipes and valve 22 In, ensure that anode chamber 1, cathode chamber 2 are concordant with the liquid level in surge chamber 3 by the osmosis of liquid, added in cathode chamber 2 NaOH so that the concentration of NaOH solution reaches 0.2mol/L in cathode chamber 2;
(6) wire for connecting porous woodceramics piece 11 is connected with the positive pole of low-voltage dc power supply, graphite flake will be connected 21 wire is connected with the negative pole of low-voltage dc power supply;
(7) switch on power, start electrolysis, decomposition voltage is 20V, and electric current is 1.5A, is opened every 25min in electrolytic process A ultrasonic transducer 8 is opened, the time is 5min, clean the filter plate of porous ceramic 4 and cation-exchange membrane 5 of centre to prevent Block, take out porous woodceramics piece 11 every 50min, the lignin on its surface is attached to collect;
(8) repeat step (7) three times, while noting control black liquor liquid level, black liquor and clear water are supplemented when liquid level is reduced;
(9) after lignin extraction terminates, the thin phenol water derivation pipeline for opening the bottom of anode chamber 1 puts waste liquid with valve 13 Go out, then black liquor is refilled by black liquor flow in pipes and valve 12, and repeat the above steps (7) and step (8), while passing through The NaOH recovery channels of the bottom of cathode chamber 2 reclaim NaOH solution with valve 23;
(10) by after the extraction of about 10 times, the solution retrogradation in surge chamber, can by surge chamber waste liquid derive pipeline with Valve 31 is derived.
Embodiment 3
(1) from the filter plate of porous ceramic 4 that aperture is 0.2 μm and cation-exchange membrane 5 that aperture is 0.05 μm, spiral shell is used Bolt and silica gel sealing ring seal to prevent fluid seepage;
(2) top of anode chamber 1 and cathode chamber 2 is sealed with closure 6, and is drilled with Φ respectively on closure The gas port and electrode-inserting holes of 30mm, during external diameter inserted into the gas port of closure 6 for the gas eduction tube 7 of Φ 30mm, use Raw material band or sealant sealing, and cause that two gas eduction tubes 7 are connected with two gas collectors respectively;
(3) by 1 specification be 300mm × 150mm × 20mm, density be 0.5g/cm3Porous woodceramics piece 11 and 3 Piece specification is clamped with titanium alloy clamp 14 and stainless steel fixture 24 respectively for the graphite flake 21 of 300mm × 150mm × 20mm, and is worn Cross electrode-inserting holes to be respectively arranged in anode chamber 1 and cathode chamber 2, with raw material band or sealant sealing;
(4) ultrasonic transducer 8 that the bottom installation power in surge chamber 3 is 500W, frequency is 28kHz;
(5) black liquor is injected into anode chamber 1 via black liquor flow in pipes and valve 12, keeps black liquor liquid level to be pressed from both sides with titanium alloy Vertical distance between tool 14 is 3cm (ensuring that the two is not contacted), and clear water injects cathode chamber 2 via clear water flow in pipes and valve 22 In, the liquid level of cathode chamber 2 3-5cm lower than the liquid level of anode chamber 1 is ensured by the osmosis of liquid, added in cathode chamber 2 NaOH so that the concentration of NaOH solution reaches 0.1mol/L in cathode chamber 2;
(6) wire for connecting porous woodceramics piece 11 is connected with the positive pole of low-voltage dc power supply, graphite flake will be connected 21 wire is connected with the negative pole of low-voltage dc power supply;
(7) switch on power, start electrolysis, decomposition voltage is 16V, and electric current is 1A, opened every 30min in electrolytic process Ultrasonic transducer 8, the time is 5min, cleans the filter plate of porous ceramic 4 and cation-exchange membrane 5 of centre to prevent from blocking up Plug, takes out porous woodceramics piece 11 every 60min, and the lignin on its surface is attached to collect;
(8) repeat step (7) twice, while noting control black liquor liquid level, black liquor and clear water is supplemented when liquid level is reduced;
(9) after lignin extraction terminates, the thin phenol water derivation pipeline for opening the bottom of anode chamber 1 puts waste liquid with valve 13 Go out, then black liquor is refilled by black liquor flow in pipes and valve 12, and repeat the above steps (7) and step (8), while passing through The NaOH recovery channels of the bottom of cathode chamber 2 reclaim NaOH solution with valve 23;
(10) by after the extraction of about 10 times, the solution retrogradation in surge chamber, can by surge chamber waste liquid derive pipeline with Valve 31 is derived.
The specific data after the completion of relevant parameter and electrolysis in above three embodiment, see the table below 1.
Table 1
From table 1 it follows that the extracting method provided using the present invention and device, not only can effectively in black liquor Lignin extracted, and can also reclaim most NaOH, reduce COD value, realize black liquor is recycled while Alleviate environmental pollution.In addition, under conditions of safety and cost is considered, electric current during electrolysis is bigger with voltage, lignin Extraction rate is faster, and the amount of the lignin for finally extracting is also bigger, and the COD value and alkali recovery of decline also accordingly increase.
Embodiment 4
By the extraction element series connection in 2 sets of embodiments 1, will before thin phenol water in a set of extraction element derive pipeline and valve Black liquor flow in pipes in door 13 and rear a set of extraction element is connected with valve 12 so that the raffinate after being electrolysed in anode chamber 1 It is imported into the 2nd set of identical device, while being added equivalent to raffinate mass fraction 20% in the cathode chamber 1 of the covering device Clear water, be electrolysed again.By aforesaid operations, can farthest extract lignin and reclaim NaOH, and can make COD value significantly declines, and specific data are as follows:
(1) in black liquor rugose wood element recovery rate up to 93.2% or so, wherein containing Vinsol up to 88.9%;
(2) volume is 1m3Black liquor in can extract 12~16kg rugose woods element, energy consumption is 8.7kwh/kg;
(3) COD declines 83.9%;
(4) alkali recovery is up to 86.7%;
The standard of direct discharge can be met after the pressurized hyperfiltration treatment of raffinate after 2 times are electrolysed, follow-up row is reduced The link for the treatment of is put, not only environmental protection but also cost has been reduced.
Comparative example 1 --- replace porous woodceramics piece with titanium web plate as anode
(1) from the filter plate of porous ceramic 4 that aperture is 0.2 μm and cation-exchange membrane 5 that aperture is 0.05 μm, spiral shell is used Bolt and silica gel sealing ring seal to prevent fluid seepage;
(2) top of anode chamber 1 and cathode chamber 2 is sealed with closure 6, and is drilled with Φ respectively on closure The gas port and electrode-inserting holes of 30mm, during external diameter inserted into the gas port of closure 6 for the gas eduction tube 7 of Φ 30mm, use Raw material band or sealant sealing, and cause that two gas eduction tubes 7 are connected with two gas collectors respectively;
(3) by 1 specification be 300mm × 150mm × 1.5mm, grid specification for 2mm × 3mm titanium web plate and 1 Specification is clamped with titanium alloy clamp 14 and stainless steel fixture 24 respectively for the graphite flake 21 of 300mm × 150mm × 20mm, and is passed through Electrode-inserting holes are respectively arranged in anode chamber 1 and cathode chamber 2, with raw material band or sealant sealing;
(4) ultrasonic transducer 8 that the bottom installation power in surge chamber 3 is 300W, frequency is 24kHz;
(5) black liquor is injected into anode chamber 1 via black liquor flow in pipes and valve 12, keeps black liquor liquid level to be pressed from both sides with titanium alloy Vertical distance between tool 14 is 3cm (ensuring that the two is not contacted), and clear water injects cathode chamber 2 via clear water flow in pipes and valve 22 In, ensure that anode chamber 1, cathode chamber 2 are concordant with the liquid level in surge chamber 3 by the osmosis of liquid, added in cathode chamber 2 NaOH so that the concentration of NaOH solution reaches 0.1mol/L in cathode chamber 2;
(6) wire for connecting titanium web plate is connected with the positive pole of low-voltage dc power supply, leading for graphite flake 21 will be connected Line is connected with the negative pole of low-voltage dc power supply;
(7) switch on power, start electrolysis, decomposition voltage is 24V, and electric current is 2A, a ultrasonic wave is opened at interval of 20min Transducer 8, the time is 5min, cleans the filter plate of porous ceramic 4 and cation-exchange membrane 5 of centre to prevent from blocking, at interval of 120min takes out titanium web plate, and the lignin on its surface is attached to collect;
(8) repeat step (7) three times, while noting control black liquor liquid level, black liquor and clear water are supplemented when liquid level is reduced;
(9) after lignin extraction terminates, the thin phenol water derivation pipeline for opening the bottom of anode chamber 1 puts waste liquid with valve 13 Go out, then black liquor is refilled by black liquor flow in pipes and valve 12, and repeat the above steps (7) and step (8), while passing through The NaOH recovery channels of the bottom of cathode chamber 2 reclaim NaOH solution with valve 23;
(10) by after the extraction of about 10 times, the solution retrogradation in surge chamber, can by surge chamber waste liquid derive pipeline with Valve 31 is derived.
Specific data after the completion of relevant parameter in comparative example 1 and embodiment 1 and electrolysis are inserted into table 2.
Table 2
From Table 2, it can be seen that in the case where phase homogenous quantities lignin is extracted, the time that comparative example 1 is consumed And average energy consumption is much larger than embodiment 1;Therefore, the side of lignin electroextraction is carried out as anode with titanium web plate , there is the defect that extraction efficiency is low, average energy consumption is big in method poor practicability.
The preferred embodiments of the present invention are the foregoing is only, scope of patent protection of the invention is not thereby limited, for For those skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention, it is every Any improvement made using description of the invention and accompanying drawing content or equivalent, are directly or indirectly used in other correlations Technical field, all should be included within the scope of the present invention.

Claims (10)

1. it is a kind of based on woodceramics electrode black liquid rugose wood element extracting method, it is characterised in that in electrolytic cell Porous woodceramics material is respectively provided with anode chamber and cathode chamber as anode, setting graphite material as negative electrode, by black liquor Anode chamber and cathode chamber are injected separately into clear water, are electrolysed under the conditions of dc source, from the porous woodceramics material of anode chamber On obtain lignin.
2. extracting method according to claim 1, it is characterised in that the electrolytic cell increases between anode chamber and cathode chamber Surge chamber is provided with, and respectively by setting filter plate of porous ceramic and cation-exchange membrane by surge chamber and anode chamber and cathode chamber Separate.
3. extracting method according to claim 2, it is characterised in that NaOH is added in the electrolysis initial stage is to cathode chamber to increase Plus electric conductivity so that the concentration of initial NaOH solution reaches 0.1mol/L-0.2mol/L in cathode chamber.
4. extracting method according to claim 3, it is characterised in that be provided with ultrasonic wave transducer in the surge chamber Device, is switched on a ultrasonic transducer at regular intervals in electrolytic process, with ensure filter plate of porous ceramic and sun from The hole of proton exchange is unimpeded.
5. the extracting method according to claim 1-4 any one, it is characterised in that the voltage of the dc source for being used No more than 36V.
6. it is a kind of based on woodceramics electrode black liquid rugose wood element extraction element, it is characterised in that including for holding Put anode chamber (1) and the cathode chamber (2) for housing clear water and NaOH solution, the anode chamber (1) and the cathode chamber of black liquor (2) gas port for being equipped with closure (6) and being arranged on closure (6), and be provided with as sun in the anode chamber (1) The porous woodceramics material (11) of pole, it is provided with as the graphite material (21) of negative electrode, the sun in the cathode chamber (2) Pole room (1) also includes that the black liquor flow in pipes for communicating therewith derives pipeline and valve (13) with valve (12) and thin phenol water, described Cathode chamber (2) also includes the clear water flow in pipes for communicating therewith and valve (22) and NaOH recovery channels and valve (23).
7. extraction element according to claim 6, it is characterised in that set between the anode chamber (1) and cathode chamber (2) Be equipped with a surge chamber (3), and the surge chamber (3) by filter plate of porous ceramic (4) and cation-exchange membrane (5) respectively with Anode chamber (1) and cathode chamber (2) separate, and the surge chamber (3) derives pipeline and valve including the surge chamber waste liquid for communicating therewith (31)。
8. extraction element according to claim 7, it is characterised in that the aperture of the filter plate of porous ceramic (4) is 0.2 μm -0.5 μm, the aperture of the cation-exchange membrane (5) is 0.05 μm -0.1 μm.
9. extraction element according to claim 8, it is characterised in that be additionally provided with ultrasonic wave in the surge chamber (3) Transducer (8).
10. the extraction element according to any one in claim 6-9, it is characterised in that the extraction element is two sets Or more than two sets be serially connected and use, pipeline and valve (13) and latter are derived by by the thin phenol water in preceding a set of extraction element Black liquor flow in pipes in set extraction element is connected to realize that the multipass to black liquor is processed, so as to obtain higher with valve (12) Lignin extraction rate and the NaOH solution rate of recovery.
CN201710003728.3A 2017-01-04 2017-01-04 The extracting method and device of black liquid rugose wood element based on woodceramics electrode Active CN106676572B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710003728.3A CN106676572B (en) 2017-01-04 2017-01-04 The extracting method and device of black liquid rugose wood element based on woodceramics electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710003728.3A CN106676572B (en) 2017-01-04 2017-01-04 The extracting method and device of black liquid rugose wood element based on woodceramics electrode

Publications (2)

Publication Number Publication Date
CN106676572A true CN106676572A (en) 2017-05-17
CN106676572B CN106676572B (en) 2018-10-02

Family

ID=58849182

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710003728.3A Active CN106676572B (en) 2017-01-04 2017-01-04 The extracting method and device of black liquid rugose wood element based on woodceramics electrode

Country Status (1)

Country Link
CN (1) CN106676572B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109455797A (en) * 2018-12-29 2019-03-12 东莞职业技术学院 A kind of non-preparation facilities and preparation method thereof for drinking strong basicity electrolytic ionic water
CN112405739A (en) * 2020-11-05 2021-02-26 江西中竹生物质科技有限公司 Preparation method of sodium lignosulfonate
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

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1106767A (en) * 1994-02-07 1995-08-16 胡扬五 Apparatus for treatment of black liquor
CN1459420A (en) * 2002-05-21 2003-12-03 四川川投博士创新科技开发有限公司 Method of treating papermaking black liquid and recovery alkali and lignin using electroosmosis method
CN201952262U (en) * 2010-10-26 2011-08-31 施冬梅 Ultrasonic-assisted electrodialysis equipment
CN103183403A (en) * 2011-12-31 2013-07-03 南开大学 Antibiotic pharmaceutical wastewater processing method and device
US20140034508A1 (en) * 2012-07-04 2014-02-06 Johannes-Gutenberg-Universität Mainz Process for the preparation of vanillin
CN103922445A (en) * 2014-03-10 2014-07-16 苏州科技学院相城研究院 Micro-nano hierarchical porous carbon electrode and preparation method and application
CN104178777A (en) * 2014-07-18 2014-12-03 广西大学 Method for recovering sodium hydroxide by combining lignin extraction from pulping alkaline waste liquid with electrolysis

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1106767A (en) * 1994-02-07 1995-08-16 胡扬五 Apparatus for treatment of black liquor
CN1459420A (en) * 2002-05-21 2003-12-03 四川川投博士创新科技开发有限公司 Method of treating papermaking black liquid and recovery alkali and lignin using electroosmosis method
CN201952262U (en) * 2010-10-26 2011-08-31 施冬梅 Ultrasonic-assisted electrodialysis equipment
CN103183403A (en) * 2011-12-31 2013-07-03 南开大学 Antibiotic pharmaceutical wastewater processing method and device
US20140034508A1 (en) * 2012-07-04 2014-02-06 Johannes-Gutenberg-Universität Mainz Process for the preparation of vanillin
CN103922445A (en) * 2014-03-10 2014-07-16 苏州科技学院相城研究院 Micro-nano hierarchical porous carbon electrode and preparation method and application
CN104178777A (en) * 2014-07-18 2014-12-03 广西大学 Method for recovering sodium hydroxide by combining lignin extraction from pulping alkaline waste liquid with electrolysis

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
涂建华等: "炭化温度对木质陶瓷性能和结构的影响", 《材料热处理学报》 *
盛利元等: "隔膜电解法处理草浆黑液", 《中南工业大学学报》 *
钟飞等: "单阳膜电渗析处理草浆黑液碱回收的研究", 《南京航空航天大学学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109455797A (en) * 2018-12-29 2019-03-12 东莞职业技术学院 A kind of non-preparation facilities and preparation method thereof for drinking strong basicity electrolytic ionic water
CN112405739A (en) * 2020-11-05 2021-02-26 江西中竹生物质科技有限公司 Preparation method of sodium lignosulfonate
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

Also Published As

Publication number Publication date
CN106676572B (en) 2018-10-02

Similar Documents

Publication Publication Date Title
CN105523668B (en) A kind of PCB nitrogen-containing wastewaters Zero discharge treatment method and device
CN106587472B (en) A kind of recycling recoverying and utilizing method of the electroplating wastewater containing palladium
CN103668305B (en) A kind of guide plate type microorganism electrolysis cell of built-in multi-electrode system and using method thereof
CN104909526B (en) Device for removing heavy metals in sludge by using electro-dynamic method and synchronously and deeply dehydrating sludge
CN106676572B (en) The extracting method and device of black liquid rugose wood element based on woodceramics electrode
CN109607746A (en) A kind of device of the Novel electro-Fenton based on carbon membrane, method and its application
CN208791261U (en) A kind of Electro Sorb coupling extension active carbon handles the device of micro- pollution bitter
CN207330597U (en) A kind of continuous electric desalination water treatment facilities
CN106115858B (en) A kind of efficient electrochemical waste water treatment device and its control method and application
CN212770375U (en) River sediment processing system
CN212222679U (en) Wastewater recycling treatment system based on flow electrode
CN206970371U (en) A kind of casing processes sewage-treatment plant
CN202729860U (en) On-line circulating water chlorination sterilization device
CN202499779U (en) Nickel-containing washing water treatment equipment
CN201809207U (en) Novel electrolysis reactor
CN114517302B (en) Device and method for coupling lithium extraction and hydrogen production of electrically-assisted photocatalytic lithium iron phosphate waste
CN206476851U (en) A kind of recycling recycling and processing device containing golden electroplating wastewater
CN216038978U (en) Device for producing high-purity hydrogen by electrolyzing water
CN204097576U (en) Secondary brine rectification device
CN218665515U (en) High concentration refractory organic waste water electrolytic oxidation preprocessing device
CN215628354U (en) Device for extracting lithium element from waste lithium ion battery
CN113463133B (en) Electrochemical device, application thereof and method for recycling metal in industrial wastewater
CN217104083U (en) Coupling seawater desalination hydrogen production system based on renewable energy power generation
CN209792230U (en) Removal device for organic pollutants in industrial waste salt
WO2023030551A1 (en) Seawater non-desalination in-situ direct electrolysis hydrogen production method, apparatus, and system

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant