CN106676572B - The extracting method and device of black liquid rugose wood element based on woodceramics electrode - Google Patents
The extracting method and device of black liquid rugose wood element based on woodceramics electrode Download PDFInfo
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- C25B3/00—Electrolytic production of organic compounds
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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
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- 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
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- 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
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Abstract
The present invention provides a kind of extracting method of the black liquid rugose wood element based on woodceramics electrode, including electrolytic cell is divided into anode chamber, surge chamber and cathode chamber with filter plate of porous ceramic and cation-exchange membrane, porous woodceramics material is respectively set in anode chamber and cathode chamber as anode, graphite material as cathode, black liquor and clear water are injected separately into anode chamber and cathode chamber and are electrolysed under the conditions of low-voltage dc power supply, at regular intervals take out anode with balling-up porous woodceramics on piece lignin；After repeatedly taking-up action, the indoor raffinate of anode is drained, and recycle and be concentrated in the indoor NaOH solution of cathode, generated hydrogen and oxygen are then collected by gas eduction tube respectively in electrolysis.The extracting method is simple and practical, and will not consumable anode and cause secondary pollution, can also improve lignin and the rate of recovery of NaOH while reducing black liquor processing cost.
Description
Technical field
The present invention relates to the technical fields of black liquor extraction, and in particular, to one kind being 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 generate black liquid, main component it
As soon as being exactly to be dissolved alkali lignin out, about 20,000,000 tons of alkali wood is contained in 200,000,000 tons of black liquor that China generates every year
Quality.Lignin has having been widely used in industrial and agricultural production, therefore, extracted from black liquid lignin economical and
Field of environment protection is all of great significance.
The method of existing extraction lignin includes following several：
One, acid precipitation method.Acid precipitation method is also referred to as acid-precipitation method, is to use more one of method at present, 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, baking
Crystalloid rugose wood element is obtained after dry, used acid can be inorganic acid, can also be organic acid.
Two, ultrafiltration.Ultrafiltration is the membrane separation technique using pressure as motive force, i.e., under pressure, makes small point
Sub- solute and solvent pass through the special film of certain pore size, and prevent macromolecular solute from penetrating and staying in one side of film, to
So that macromolecular substances obtain the purifying of part.It, can in view of lignin is the high-molecular compound that molecular mass is 5-50ku
It is extracted from black liquid using ultrafiltration.
Three, flocculence.Since there are many colloidal substances in black liquid, there is colloidal nature under certain condition, because
The method that lignin deposit agent is added may be used in this, makes negatively charged lignin particle by the Cation adsorption of precipitating reagent,
To destroy the stability of colloid, achieve the purpose that make lignin that precipitation be precipitated.
Four, electrocoagulation and dialysis.Electrocoagulation refers under the action of impressed current, using iron or aluminum metal as sacrificial
Domestic animal anode and electrolysis when dissolve, to form Fe (OH)2、Al(OH)3It is agglomerated etc. metal oxide active not soluble in water
Body can play cohesion and suction-operated to the organic or inorganic object in liquid, and the cotton-shaped particle of formation settles and divided together
From；The titanium that sacrificed anticathode can also be used smaller does anode, can release with strong oxidizing property on electrolytic process, anode
Oxygen or chlorine, can make the organic matter in black liquor that strong oxidation decomposition occur.
Correspondingly, also all come with some shortcomings place in above-mentioned four kinds of methods, specific as follows：
(1) acid precipitation method：It needs that the strong acid such as sulfuric acid, phosphoric acid are added, and just has preferable recovery rate when pH reaches 2 or so,
Not only additive amount it is big, it is of high cost, there is the secondary pollution of residual acid, sulfuric acid can also generate salt, such as sulphur with the alkali in black liquor
Sour sodium, sodium phosphate etc. bring great inconvenience to the post-processing of black liquor.
(2) ultrafiltration：Although without addition strong acid, solute deposits or is adsorbed in use the surface of ultrafiltration membrane
On, it is blocked so as to cause fenestra, causes permeation flux to greatly reduce, service life is short, although surfactant can be utilized
Processing is modified to the surface of ultrafiltration membrane, but still is difficult to reach ideal state, especially in long-time, the feelings of continuous processing
Under condition.Meanwhile when the concentration of black liquor is higher, permeation flux smaller greatly affected extraction efficiency.
(3) flocculence：It needs that a large amount of flocculant is added 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, equally exist black liquor
Post-processing problem, while also can be more or less in the lignin extracted 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 using sacrificial anode as cost, not only consuming cost
Height can also increase new metal ion in black liquor, influence post-processing, although and using method sun of the Titanium as anode
Pole sacrifice is smaller, but titanium is expensive, and extraction cost is excessive, and the matched dialysis used equally exists Pore Blocking
The problem of.
Chinese patent CN02113761 discloses a kind of method electric osmose formula processing black liquid and recycle alkali and lignin,
Semi-permeable membrane is arranged in the tank house for the DC power supply electric field for having negative electrode and positive electrode in it, and tank house is divided into negative side
Clear water and black liquid are flowed separately through the electrolysis of the tank house and side of the positive electrode of negative side by the tank house of tank house and side of the positive electrode
Room, obtain the lye excluded from the tank house of negative side, is excluded from the tank house of side of the positive electrode in treatment fluid, addition chlorion sinks
Shallow lake agent obtains organic matter and clear water containing lignin through separation.The invention makes black liquor by alkalinity by adjusting the size of electric current
Become neutral or faintly acid, and the precipitation that precipitating reagent realizes lignin is added, does not solve the problems, such as lignin later purification, at
This is also still very high.
Chinese patent CN99106161 disclose it is a kind of using electrolytic hydrogenation process is prepared from black liquid hydrogenate it is wooden
Element method, in separated type electrolytic tank, make cathode with foam Pb, Pt makees anode, saturation calomel motor make reference electrode, with
N,N dimethylformamide and ethyl alcohol make electroanalysis solvent, water makees hydrogen supply dissolvent, tetrabutylammonium bromide makees supporting electrolyte, to wooden
Element carries out electrolytic hydrogenation.The present invention does not need catalyst, increases C/Hratio, reduces the softening point of extracting hydrogenated lignin, still
The solvent used is excessive, and cost is very high.
Invention content
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 issues of reason, the present invention provide it is a kind of it is simple and practical, of low cost, it is reusable and without introduce other substances from
The method and device of extracting lignose from papermaking black liquor.
Woodceramics are a kind of novel environmentally conscious materials, be by impregnated of thermosetting substance timber or other biomass
Material is formed through vacuum carburization.Woodceramics have good calorifics, electricity, magnetism characteristic, under the conditions of low temperature (150 DEG C or less)
Intensity height, large specific surface area, good in oxidation resistance, corrosion resistance are 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 set in pole room as anode, setting graphite material as cathode, black liquor and clear water are distinguished
Anode chamber and cathode chamber are injected, is electrolysed under the conditions of DC power supply, lignin is obtained from the porous woodceramics material of anode chamber.
Preferably, the electrolytic cell has additional surge chamber between anode chamber and cathode chamber, and porous by being arranged respectively
Ceramic filter plate and cation-exchange membrane separate surge chamber and anode chamber and cathode chamber.By the initial filter of filter plate of porous ceramic
It acts on, the impurity stopping state occurred on cation-exchange membrane greatly reduces.
Preferably, NaOH is added to increase electric conductivity into cathode chamber at electrolysis initial stage so that initial NaOH in cathode chamber
The concentration of solution reaches 0.1mol/L-0.2mol/L.
Preferably, it is provided with ultrasonic transducer in the surge chamber, is just opened at regular intervals in electrolytic process
A ultrasonic transducer is opened, the hole to ensure filter plate of porous ceramic and cation-exchange membrane is unimpeded.
Preferably, the voltage of used DC power supply 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 cathode chamber for housing clear water and NaOH solution, the anode chamber and cathode chamber are equipped with sealing cover and are arranged close
Gas port in capping, and it is provided in the anode chamber the porous woodceramics material as anode, in the cathode chamber
It is provided with the graphite material as cathode, the anode chamber further includes that the black liquor flow in pipes communicated therewith is led with valve and thin phenol water
Go out pipeline and valve, the cathode chamber further includes the clear water flow in pipes communicated therewith and valve and NaOH recovery channels and valve.
Preferably, between the anode chamber and cathode chamber setting there are one surge chamber, and the surge chamber pass through it is porous
Ceramic filter plate and cation-exchange membrane are separated with anode chamber and cathode chamber respectively, and the surge chamber includes the buffering communicated therewith
Room waste liquid export 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 two sets or two sets or more and is serially connected use, by by preceding a set of extraction element
In thin phenol water export pipeline be connected with the black liquor flow in pipes in valve and rear a set of extraction element with valve with realization pair
The multipass of black liquor is handled, to obtain higher lignin extraction rate and the NaOH solution rate of recovery.
Contain a large amount of sodium lignin and hydroxide ion in black liquid.In electrolytic process, anode aoxidizes
Reaction generates oxygen and hydrogen ion, and the pH value of anode region is caused to reduce, sodium lignin can occur in acidic environment cohesion and
Precipitation, while generating free sodium ion；It, can be in the work of electric field since the sodium lignin being dissolved in black liquor carries negative electrical charge
It is dynamic with lower Ghandler motion on the sunny side, sodium lignin be deposited on after obtaining electronics anode surface and near, thus may be implemented wooden
The separation of element and black liquor.At the same time, reduction reaction occurs for cathode chamber, generates hydrogen and hydroxide ion, the sodium of anode region from
Son under the action of DC electric field to cathodic region is mobile and aggregation, with by cation-exchange membrane barrier cathodic region hydroxyl from
Son combines and generates the NaOH that can be recovered.
In entire electrolytic cell, sodium ion can pass through filter plate of porous ceramic and cation-exchange membrane to surge chamber and cathode
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.Simultaneously in order to fully ensure that the hole of filter plate of porous ceramic and cation-exchange membrane is unimpeded, installed in surge chamber
Ultrasonic transducer can clear up absorption in time and be deposited on filter plate of porous ceramic and be handed over cation by the vibration of ultrasonic wave
Change the substance on film.The ultrasonic transducer can start at any time as needed, will not be clashed with electrolytic process, both can be with
It works, can also work during taking out anode and collecting lignin during anode adsorbs 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 (recycling)
In conclusion the lignin in black liquor, by separation and Extraction, part water, which is electrolysed, obtains oxygen and hydrogen, and NaOH is molten
Liquid is concentrated recycling in cathodic region.At the same time, anode region is nascent since the oxidation and anode reaction of anode are generated
The oxidation of state oxygen, the oxidable partial organic substances (can be by the pollutant of oxidative degradation i.e. in black liquor) for decomposing anode region, together
When because of the precipitation of lignin and the oxygenolysis of organic matter, so that COD value, the coloration etc. for the waste liquid that anode region flows out is had certain journey
The reduction of degree, alleviates environmental pollution.
Technical solution provided by the invention has the advantages that：
1, the present invention during extraction without adding acid or other chemical reagent, without secondary pollution, reduce at
This while, is also conducive to the post-processing of electrolysis waste solution and the purification of lignin；
2, the present invention uses woodceramics as anode, and raw material sources are extensive, manufacture craft is simple and price is low
It is honest and clean, simultaneously as not will produce anode consumption, while cost is reduced, it is thus also avoided that secondary dirt caused by consumable anode
The problem of contaminating, decreasing Pore Blocking, even woodceramics electrode plate is damaged in use, disassembles
Electrode plate is alternatively arranged as boiler oil processing；
3, since used woodceramics material has porosity, possess huge specific surface area, and pore structure can
It can be adjusted as needed, which greatly improves the extraction efficiencies of the efficiency of electrolysis and lignin；
4, it is cleaned due to the use of filter plate of porous ceramic and with ultrasonic wave, not only compares polymer on service life
Film is long, and the case where can also reducing and reduce blocking, even if being blocked, the ceramic filter plate changed can also be burnt in Muffle furnace
It is reused after knot, cost can be greatly reduced；
5, extraction process whole process is pollution-free, and black liquor can be fully used, and other than the lignin of needs, anode generates
Oxygen, cathode production hydrogen and NaOH all fully recycled.
Description of the drawings
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached 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, without creative efforts, others are can also be obtained according to these attached drawings
Attached drawing, wherein：
Fig. 1 is the principle schematic of extracting method in the present invention；
Fig. 2 is the structural schematic diagram of the preferred embodiment of extraction element in the present invention；
In figure：The anode chamber of 1 accommodating black liquor, the cathode chamber of 2 accommodating clear water and NaOH solution, 3 surge chambers, 4 porous ceramics
Filter plate, 5 cation-exchange membranes, 6 sealing covers, 7 gas eduction tubes, 8 ultrasonic transducers；11 porous woodceramics pieces, 12 is black
Liquid flow in pipes and valve, 13 thin phenol waters export pipeline and valve, 14 titanium alloy electrodes folder, 21 graphite flakes, 22 clear water injection pipes
Road and valve, 23NaOH recovery channels and valve, 24 stainless steel electrodes folder, 31 surge chamber waste liquids export pipeline and valve.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that the described embodiments are merely a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts all other
Embodiment shall fall within the protection scope of the present 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
In the anode chamber 1 of accommodating black liquor and cathode chamber 2 for housing clear water and NaOH solution, the anode chamber 1 and cathode chamber 2 are equal
Equipped with sealing cover 6 and gas eduction tube 7, and be provided in the anode chamber 1 the porous woodceramics piece 11 as anode,
The graphite flake 21 as cathode is provided in the cathode chamber 2, the anode chamber 1 further includes the black liquor flow in pipes communicated therewith
With valve 12 and thin phenol water export pipeline and valve 13, the cathode chamber 2 further includes the clear water flow in pipes and valve communicated therewith
Door 22 and NaOH recovery channels and valve 23.
There are one surge chambers 3 for setting between the anode chamber 1 and cathode chamber 2, and the surge chamber 3 passes through porous ceramics
Filter plate 4 and cation-exchange membrane 5 are separated with anode chamber 1 and cathode chamber 2 respectively, and the surge chamber 3 is slow including what is communicated therewith
Room waste liquid export pipeline and valve 31 are rushed, ultrasonic transducer 8 is additionally provided in 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 is connect by titanium alloy electrode folder 14 with external circuits, and the graphite flake 21 passes through
Stainless steel electrode folder 24 is connect with external circuits.Due to containing a large amount of alkaline matter in black liquor, it to be used for the electrode of jointed anode
Folder is easy to that oxidation reaction occurs and corrodes, so titanium alloy material is selected, and the electrode holder for being used to connect cathode 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, collects so wooden
Plain the time it takes is relatively short, but the calorific value of electrode increases, and not only wastes a large amount of electric energy, also results in anode and more hold
Easy cracked phenomenon is considered often to expose anode to collect lignin, so the extraction element uses in addition
36V low-tension supplies below, and preferably 12-24V.
When the density of woodceramics itself reduces, specific surface area increases, the electron transport ability in electrolytic process
It is promoted, i.e., the adsorption capacity of lignin is increased, 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 the lower density the better, too low density influences whether the strong of electrode itself
Degree, and then its service life is influenced, so the porous woodceramics piece of proper density should be chosen as anode.
Embodiment 1
(1) filter plate of porous ceramic 4 that aperture is 0.2 μm and the cation-exchange membrane 5 that aperture is 0.05 μm are selected, spiral shell is used
Bolt and silica gel sealing ring sealing are to prevent fluid seepage；
(2) anode chamber 1 and the top of cathode chamber 2 are sealed with sealing cover 6, and are drilled with Φ respectively on sealing cover
The gas eduction tube 7 that outer diameter is Φ 30mm is inserted into the gas port of sealing cover 6, uses by the gas port and electrode-inserting holes of 30mm
Raw material band or fluid sealant sealing, and two gas eduction tubes 7 are connected to two gas collectors respectively；
(3) it is 300mm × 150mm × 20mm, density 0.7g/cm by 1 specification3Porous woodceramics piece 11 and 1
The graphite flake 21 that piece specification is 300mm × 150mm × 20mm uses titanium alloy clamp 14 and stainless steel fixture 24 to clamp respectively, and wears
It crosses electrode-inserting holes to be respectively arranged in anode chamber 1 and cathode chamber 2, be sealed with raw material band or fluid sealant；
(4) in the ultrasonic transducer 8 that the bottom installation power of surge chamber 3 is 300W, frequency is 24kHz；
(5) black liquor is injected into via black liquor flow in pipes and valve 12 in anode chamber 1, and black liquor liquid level is kept to be pressed from both sides with titanium alloy
Vertical distance between tool 14 is 3cm (ensuring that the two does not contact), 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, is added in cathode chamber 2
NaOH so that the concentration of NaOH solution reaches 0.1mol/L in cathode chamber 2；
(6) anode of the conducting wire and low-voltage dc power supply that connect porous woodceramics piece 11 is connected, graphite flake will be connected
21 conducting wire and the cathode of low-voltage dc power supply connect；
(7) power on, start to be electrolysed, decomposition voltage 24V, electric current 2A are opened in electrolytic process every 20min
Ultrasonic transducer 8, time 5min clean intermediate filter plate of porous ceramic 4 and cation-exchange membrane 5 to prevent from blocking up
Plug, takes out porous woodceramics piece 11 every 40min, to collect the lignin for being attached to its surface；
(8) it repeats step (7) three times, while paying attention to controlling black liquor liquid level, black liquor and clear water are supplemented when liquid level reduces；
(9) after lignin extraction, the thin phenol water export pipeline for opening 1 bottom of anode chamber 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), passes through simultaneously
The NaOH recovery channels of 2 bottom of cathode chamber recycle NaOH solution with valve 23；
(10) after about 10 extractions, the solution retrogradation in surge chamber, can by surge chamber waste liquid export pipeline with
Valve 31 exports.
Embodiment 2
(1) filter plate of porous ceramic 4 that aperture is 0.2 μm and the cation-exchange membrane 5 that aperture is 0.05 μm are selected, spiral shell is used
Bolt and silica gel sealing ring sealing are to prevent fluid seepage；
(2) anode chamber 1 and the top of cathode chamber 2 are sealed with sealing cover 6, and are drilled with Φ respectively on sealing cover
The gas eduction tube 7 that outer diameter is Φ 30mm is inserted into the gas port of sealing cover 6, uses by the gas port and electrode-inserting holes of 30mm
Raw material band or fluid sealant sealing, and two gas eduction tubes 7 are connected to two gas collectors respectively；
(3) it is 300mm × 150mm × 20mm, density 0.6g/cm by 1 specification3Porous woodceramics piece 11 and 2
The graphite flake 21 that piece specification is 300mm × 150mm × 20mm uses titanium alloy clamp 14 and stainless steel fixture 24 to clamp respectively, and wears
It crosses electrode-inserting holes to be respectively arranged in anode chamber 1 and cathode chamber 2, be sealed with raw material band or fluid sealant；
(4) in the ultrasonic transducer 8 that the bottom installation power of surge chamber 3 is 500W, frequency is 26kHz；
(5) black liquor is injected into via black liquor flow in pipes and valve 12 in anode chamber 1, and black liquor liquid level is kept to be pressed from both sides with titanium alloy
Vertical distance between tool 14 is 3cm (ensuring that the two does not contact), 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, is added in cathode chamber 2
NaOH so that the concentration of NaOH solution reaches 0.2mol/L in cathode chamber 2；
(6) anode of the conducting wire and low-voltage dc power supply that connect porous woodceramics piece 11 is connected, graphite flake will be connected
21 conducting wire and the cathode of low-voltage dc power supply connect；
(7) power on, start to be electrolysed, decomposition voltage 20V, electric current 1.5A are opened in electrolytic process every 25min
A ultrasonic transducer 8 is opened, time 5min cleans intermediate filter plate of porous ceramic 4 and cation-exchange membrane 5 to prevent
It blocks, takes out porous woodceramics piece 11 every 50min, to collect the lignin for being attached to its surface；
(8) it repeats step (7) three times, while paying attention to controlling black liquor liquid level, black liquor and clear water are supplemented when liquid level reduces；
(9) after lignin extraction, the thin phenol water export pipeline for opening 1 bottom of anode chamber 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), passes through simultaneously
The NaOH recovery channels of 2 bottom of cathode chamber recycle NaOH solution with valve 23；
(10) after about 10 extractions, the solution retrogradation in surge chamber, can by surge chamber waste liquid export pipeline with
Valve 31 exports.
Embodiment 3
(1) filter plate of porous ceramic 4 that aperture is 0.2 μm and the cation-exchange membrane 5 that aperture is 0.05 μm are selected, spiral shell is used
Bolt and silica gel sealing ring sealing are to prevent fluid seepage；
(2) anode chamber 1 and the top of cathode chamber 2 are sealed with sealing cover 6, and are drilled with Φ respectively on sealing cover
The gas eduction tube 7 that outer diameter is Φ 30mm is inserted into the gas port of sealing cover 6, uses by the gas port and electrode-inserting holes of 30mm
Raw material band or fluid sealant sealing, and two gas eduction tubes 7 are connected to two gas collectors respectively；
(3) it is 300mm × 150mm × 20mm, density 0.5g/cm by 1 specification3Porous woodceramics piece 11 and 3
The graphite flake 21 that piece specification is 300mm × 150mm × 20mm uses titanium alloy clamp 14 and stainless steel fixture 24 to clamp respectively, and wears
It crosses electrode-inserting holes to be respectively arranged in anode chamber 1 and cathode chamber 2, be sealed with raw material band or fluid sealant；
(4) in the ultrasonic transducer 8 that the bottom installation power of surge chamber 3 is 500W, frequency is 28kHz；
(5) black liquor is injected into via black liquor flow in pipes and valve 12 in anode chamber 1, and black liquor liquid level is kept to be pressed from both sides with titanium alloy
Vertical distance between tool 14 is 3cm (ensuring that the two does not contact), and clear water injects cathode chamber 2 via clear water flow in pipes and valve 22
In, ensure that the liquid level of cathode chamber 2 is lower 3-5cm than the liquid level of anode chamber 1 by the osmosis of liquid, is added in cathode chamber 2
NaOH so that the concentration of NaOH solution reaches 0.1mol/L in cathode chamber 2；
(6) anode of the conducting wire and low-voltage dc power supply that connect porous woodceramics piece 11 is connected, graphite flake will be connected
21 conducting wire and the cathode of low-voltage dc power supply connect；
(7) power on, start to be electrolysed, decomposition voltage 16V, electric current 1A are opened in electrolytic process every 30min
Ultrasonic transducer 8, time 5min clean intermediate filter plate of porous ceramic 4 and cation-exchange membrane 5 to prevent from blocking up
Plug, takes out porous woodceramics piece 11 every 60min, to collect the lignin for being attached to its surface；
(8) it repeats step (7) twice, while paying attention to controlling black liquor liquid level, black liquor and clear water are supplemented when liquid level reduces；
(9) after lignin extraction, the thin phenol water export pipeline for opening 1 bottom of anode chamber 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), passes through simultaneously
The NaOH recovery channels of 2 bottom of cathode chamber recycle NaOH solution with valve 23；
(10) after about 10 extractions, the solution retrogradation in surge chamber, can by surge chamber waste liquid export pipeline with
Valve 31 exports.
The specific data after the completion of relevant parameter and electrolysis in above three embodiments, see the table below 1.
Table 1
From table 1 it follows that using extracting method provided by the invention and device, it not only can be effectively in black liquor
Lignin extract, and can also recycle most NaOH, reduce COD value, realize black liquor is recycled while
Alleviate environmental pollution.In addition, considering safety and under conditions of cost, the electric current and voltage when electrolysis are bigger, lignin
Extraction rate is faster, and the amount of the lignin finally extracted 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, i.e., by the thin phenol water export pipeline and valve in preceding a set of extraction element
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 input into the 2nd set of identical device, while being added in the cathode chamber of the covering device 1 and being equivalent to raffinate mass fraction 20%
Clear water, be electrolysed again.By aforesaid operations, lignin and recycling NaOH can be extracted to the greatest extent, and can make
COD value significantly declines, and specific data are as follows：
(1) recovery rate of rugose wood element is up to 93.2% or so in black liquor, wherein containing Vinsol up to 88.9%；
(2) volume is 1m3Black liquor in can extract 12~16kg rugose woods element, energy consumption 8.7kwh/kg；
(3) COD declines 83.9%；
(4) alkali recovery is up to 86.7%；
The standard that direct emission can be met after the pressurized hyperfiltration treatment of raffinate after 2 electrolysis, reduces follow-up row
Put the link of processing, not only environmental protection but also reduce cost.
Comparative example 1 --- use titanium web plate to replace porous woodceramics piece as anode
(1) filter plate of porous ceramic 4 that aperture is 0.2 μm and the cation-exchange membrane 5 that aperture is 0.05 μm are selected, spiral shell is used
Bolt and silica gel sealing ring sealing are to prevent fluid seepage；
(2) anode chamber 1 and the top of cathode chamber 2 are sealed with sealing cover 6, and are drilled with Φ respectively on sealing cover
The gas eduction tube 7 that outer diameter is Φ 30mm is inserted into the gas port of sealing cover 6, uses by the gas port and electrode-inserting holes of 30mm
Raw material band or fluid sealant sealing, and two gas eduction tubes 7 are connected to two gas collectors respectively；
(3) by 1 specification is 300mm × 150mm × 1.5mm, grid specification is 2mm × 3mm titanium web plate and 1
The graphite flake 21 that specification is 300mm × 150mm × 20mm uses titanium alloy clamp 14 and stainless steel fixture 24 to clamp respectively, and passes through
Electrode-inserting holes are respectively arranged in anode chamber 1 and cathode chamber 2, are sealed with raw material band or fluid sealant；
(4) in the ultrasonic transducer 8 that the bottom installation power of surge chamber 3 is 300W, frequency is 24kHz；
(5) black liquor is injected into via black liquor flow in pipes and valve 12 in anode chamber 1, and black liquor liquid level is kept to be pressed from both sides with titanium alloy
Vertical distance between tool 14 is 3cm (ensuring that the two does not contact), 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, is added in cathode chamber 2
NaOH so that the concentration of NaOH solution reaches 0.1mol/L in cathode chamber 2；
(6) anode of the conducting wire and low-voltage dc power supply that connect titanium web plate is connected, leading for graphite flake 21 will be connected
The cathode of line and low-voltage dc power supply connects；
(7) power on, start to be electrolysed, decomposition voltage 24V, electric current 2A open a ultrasonic wave at interval of 20min
Energy converter 8, time 5min clean intermediate filter plate of porous ceramic 4 and cation-exchange membrane 5 to prevent from blocking, at interval of
120min takes out titanium web plate, to collect the lignin for being attached to its surface；
(8) it repeats step (7) three times, while paying attention to controlling black liquor liquid level, black liquor and clear water are supplemented when liquid level reduces；
(9) after lignin extraction, the thin phenol water export pipeline for opening 1 bottom of anode chamber 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), passes through simultaneously
The NaOH recovery channels of 2 bottom of cathode chamber recycle NaOH solution with valve 23；
(10) after about 10 extractions, the solution retrogradation in surge chamber, can by surge chamber waste liquid export pipeline with
Valve 31 exports.
Relevant parameter in comparative example 1 and embodiment 1 and the specific data after the completion of electrolysis are inserted into table 2.
Table 2
From Table 2, it can be seen that in the case where extracting phase homogenous quantities lignin, 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
Method poor practicability, the defect that there are extraction efficiencies is low, average energy consumption is big.
The foregoing is merely the preferred embodiment of the present invention, are not intended to limit the scope of patent protection of the present invention, for
For those skilled in the art, the invention may be variously modified and varied.Within the spirit and principles in the present invention, every
Using any improvement or equivalent replacement made by description of the invention and accompanying drawing content, directly or indirectly it is used in other relevant
Technical field should all be included within the scope of the present invention.
Claims (10)
1. a kind of extracting method of the black liquid rugose wood element based on woodceramics electrode, which is characterized in that in electrolytic cell
Porous woodceramics material is respectively set in anode chamber and cathode chamber as anode, setting graphite material as cathode, by black liquor
It is injected separately into anode chamber and cathode chamber with clear water, is electrolysed under the conditions of DC power supply, the porous woodceramics material from anode chamber
On obtain lignin.
2. extracting method according to claim 1, which is characterized in that the electrolytic cell increases between anode chamber and cathode chamber
Equipped with surge chamber, and respectively by the way that filter plate of porous ceramic and cation-exchange membrane is arranged by surge chamber and anode chamber and cathode chamber
It separates.
3. extracting method according to claim 2, which is characterized in that NaOH is added into cathode chamber to increase at electrolysis initial stage
Add 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, which is characterized 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. extracting method according to any one of claims 1-4, which is characterized in that the voltage of used DC power supply
No more than 36V.
6. a kind of extraction element of the black liquid rugose wood element based on woodceramics electrode, which is characterized in that including being used to hold
Set the anode chamber (1) of black liquor and the cathode chamber (2) for housing clear water and NaOH solution, the anode chamber (1) and cathode chamber
(2) gas port for being equipped with sealing cover (6) and being arranged on sealing cover (6), and be provided with as sun in the anode chamber (1)
The porous woodceramics material (11) of pole is provided with graphite material (21) as cathode, the sun in the cathode chamber (2)
Pole room (1) further includes that the black liquor flow in pipes communicated therewith exports pipeline and valve (13) with valve (12) and thin phenol water, described
Cathode chamber (2) further includes the clear water flow in pipes communicated therewith and valve (22) and NaOH recovery channels and valve (23).
7. extraction element according to claim 6, which is characterized in that set between the anode chamber (1) and cathode chamber (2)
Set there are one 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) includes the surge chamber waste liquid export pipeline and valve communicated therewith
(31)。
8. extraction element according to claim 7, which is characterized 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, which is characterized in that be additionally provided with ultrasonic wave in the surge chamber (3)
Energy converter (8).
10. according to the extraction element described in any one of claim 6-9, which is characterized in that the extraction element is two sets
Or two sets or more be serially connected use, by the way that the thin phenol water in preceding a set of extraction element is exported pipeline and valve (13) and latter
Black liquor flow in pipes in set extraction element is connected with valve (12) to realize that the multipass to black liquor is handled, higher to obtain
Lignin extraction rate and the NaOH solution rate of recovery.
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| CN112405739B (en) * | 2020-11-05 | 2022-07-22 | 江西中竹生物质科技有限公司 | Preparation method of sodium lignosulfonate |
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| CN1059643C (en) * | 1994-02-07 | 2000-12-20 | 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 |
| CN103183403B (en) * | 2011-12-31 | 2014-07-16 | 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 |
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