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 PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
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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
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.
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| 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 |
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