CN105329892A - Method for producing capacitive carbon from rice husks - Google Patents
Method for producing capacitive carbon from rice husks Download PDFInfo
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- CN105329892A CN105329892A CN201510822310.6A CN201510822310A CN105329892A CN 105329892 A CN105329892 A CN 105329892A CN 201510822310 A CN201510822310 A CN 201510822310A CN 105329892 A CN105329892 A CN 105329892A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/24—Alkaline-earth metal silicates
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a method for producing capacitive carbon from rice husks and belongs to the technical field of the biomass energy chemical industry. The method comprises the following steps: 1, the rice husks and a catalyst are mixed uniformly and subjected to pyrolysis, and pyrolytic gas and pyrolytic carbon are produced; 2, the pyrolytic gas and the pyrolytic carbon are subjected to constant-temperature catalytic decoking, volatile components of the pyrolytic carbon are reduced, and tar is pyrolysed into small molecules; 3, a horizontal reaction kettle is adopted and rotated, the pyrolytic carbon and alkali liquor are mixed uniformly, and a mixture is subjected to hot-pressing desilicication, washing and drying; 4, template carbon and an activator are ground, stirred at a high speed for homogenization and uniformly distributed; 5, a push type activation furnace is adopted, the heating rate and activation time are controlled, and an activation material is prepared; 6, the activation material is washed, pickled and washed to be neutral; 7, a product is dried, graded and packaged. The rice husks are adopted to produce the capacitive carbon, biomass is used for producing renewable energy sources and chemicals, the cost is low, the method is environment-friendly, a production process is safe and pollution-free, and large-scale production can be realized.
Description
Technical field
The invention belongs to biomass energy chemical technology field, particularly relate to a kind of preparation method of electric capacity charcoal.
Background technology
Renewable energy source replaces fossil energy to cause the extensive concern of whole world all circles.Along with the industrialized development such as electromobile, wind light generation with renewable energy source industrialization development, cause the great market demand to ultracapacitor and energy-storage battery.
Lead carbon battery is the state-of-the-art technology in lead acid cell field, and the development priority of Ye Shi international new forms of energy energy storage industry, has boundless application prospect.Energy-storage battery technology is one of gordian technique of restriction new forms of energy energy storage industry development.The energy storage fields such as photovoltaic plant energy storage, wind-powered electricity generation energy storage and peak load regulation network, require that battery has power density comparatively large, and the feature such as have extended cycle life and price is lower.
Electrode materials is one of important factor determining ultracapacitor performance, only develops high performance electrode materials and just can produce high performance ultracapacitor, just can produce high performance plumbous charcoal energy-storage battery.Porous carbon material due to have stable work-ing life, moderate price and extensive industrialization production basis and be widely used in ultracapacitor.
The quick industrialized development of ultracapacitor and derived product thereof, proposes high performance rigors to electric capacity charcoal used.Electric capacity Carbon Materials must have the characteristic such as high-ratio surface, high mesoporosity, high conductivity, high bulk specific gravity, high purity, high performance-price ratio.In addition, in use also will have good wetting property to electrolytic solution, and bubbing is few.Simultaneously environment for use difference (organic medium, acid medium, the alkaline media of gac in various device, what have is mixed into positive pole, what have is mixed into negative pole), very big difference is had to the index request of gac, therefore Carbon Materials is a class fine chemical product, with high content of technology, belong to high-tech product.
Current electric capacity charcoal is mainly by import, expensive, and import price is not at 30 to 80 ten thousand yuan/ton etc.It is the bottleneck that China's ultracapacitor and derived product thereof develop all the time that electric capacity charcoal is produced.
Under the promotion of Development of Electric Vehicles, the market of ultracapacitor and derivative energy storage device product thereof, by rapid expansion, also will increase day by day to the demand of electric capacity charcoal, and electric capacity charcoal must accelerate to domesticize becomes the common recognition of all circles in industry, urgently to be resolved hurrily.
Domesticly carry out a large amount of research and development around electric capacity charcoal Synthesis and applications, achieved many novelty patented technologies, for solid foundation has been established in China's electric capacity charcoal production domesticization.As: CN1203887 discloses a kind of preparation method of active carbon with superhigh specific surface area, is comparatively early to use rice husk to be raw material, and it is large that obtained gac has specific surface area, microvoid structure is flourishing, pore size distribution is narrow, the gac of high adsorption capacity, is extraordinary electrode materials.CN101759181A discloses a kind of production method of activated carbon for super capacitors, and be with various shell biolobic material for raw material, phosphoric acid is activator, and activation temperature is low, and without nitrogen protection, processing condition are loose.CN102849736A discloses a kind of activation method of Supercapacitor carbon, relates to the method for inflammable gas in burner hearth combustion heat-activated.It is take coal as raw material that CN102205962A discloses a kind of device and method preparing activated carbon material for electrochemical capacitor, and Microwave-assisted firing is even, preparation process is simple, and obtained gac is as electrochemical capacitor electrode material.CN102417179A discloses a kind of preparation method of activated carbon material for electrochemical capacitor, take Pericarppium arachidis hypogaeae as raw material, and potassium hydroxide is activator, and microwave reactor heat-activated, obtains activated carbon material for electrochemical capacitor.CN102730683A discloses the method that electrode material for super capacitor prepared by a kind of use cotton stalk matrix activated carbon material, first starting material cotton stalk floods with activator mix by the method after peeling is pulverized, then, after the technique such as activated process, washing, oven dry, the active carbon electrode material needed for ultracapacitor is obtained.CN103072986A discloses a kind of method that gradient constant-temperatureactivation activation method prepares cotton stalk matrix activated carbon electrode materials, the method with cotton stalk for raw material, effectively control the ratio between big or middle, micropore by gradient constant-temperatureactivation activation method, form a kind of cotton stalk matrix activated carbon electrode materials of ultracapacitor with vesicular structure.CN103964433A discloses a kind of preparation method for electrode material for super capacitor coal mass active carbon, take brown coal as raw material, and zinc chloride is activator, and the gac of preparation can be used for the aspects such as electrode material for super capacitor.CN103408009A discloses a kind of preparation method by rice husk coproduction high-specific-capacitance active carbon and nano silicon.CN103601185A discloses a kind of carbohydrate polymer that utilizes and prepares the novel method of ultracapacitor with spherical porous carbon, certain density sugar soln is carried out under certain temperature and pressure hydro-thermal reaction synthesis of nano carbon ball, again by nano carbon microsphere and activator by certain mass than mixing, carry out activation treatment, prepare the spherical porous carbon of ultracapacitor.CN104150461A discloses a kind of environment-friendly preparation method thereof of rice husk base electric capacity Carbon Materials of multi-stage artery structure.The Carbon Materials with multi-stage artery structure is prepared by charing, soda boiling, activation.CN104401992A discloses a kind of method and the application thereof that take shell as raw material and prepare activated carbon for super capacitors.Feature be the activated material that obtains after washing, adopt mixing acid to remove impurity, then dry, then be warming up to 760-1000 DEG C of removing activated carbon surface functional group, effectively can suppress the inflatable problem of ultracapacitor, extend the cycle life of ultracapacitor.CN104649267A discloses a kind of preparation method based on making activated carbon for super capacitors, to forge front refinery coke and potassium hydroxide for raw material, its charcoal alkali ratio is made to be down to 3.5 by the mixed solvent impregnation technology of alcohol-water, reduce equipment corrosion, the gac simultaneously prepared has micro-pore distribution concentration, mesoporous controls at 20%-30%, and holes of products gap structure is effectively controlled.CN104150478A discloses the green circulatory technique that a kind of rice husk prepares activated carbon for super capacitors, is by charred rice husk, and high specific capacitance rice hull carbon is prepared in activation; Filtrate prepares nano silicon through hydrochloric acid precipitation, filtrate is carried out impurity elimination, concentrated, refining, electrolysis, obtains sig water, evaporation, crystallization obtain alkali, as reactivation process activator, evaporative process obtains water as bath water, realizes the recycle of alkali and water.CN104386691A discloses a kind of method preparing ultracapacitor hollow tubular gac with cotton, is take cotton as raw material, obtains ultracapacitor hollow tubular absorbent charcoal material through basic activated dose of admixture activation process.CN104591184A discloses a kind of preparation method of ultracapacitor shelly Mesoporous Carbon Materials, take petroleum pitch as carbon source, nano zine oxide is template, potassium hydroxide is activator, gained shelly Mesoporous Carbon Materials, as electrode for super capacitor material, has the advantages such as the high and good cycling stability of good rate capability, specific storage.CN104150481A discloses a kind of method simultaneously being prepared mesoporous activated carbon for supercapacitors material by two kinds of carbon sources, be with deliming after rice husk and sucrose be carbon source simultaneously, take phosphoric acid as activator, obtained mesoporous activated carbon for supercapacitors material.It is that the method for ultracapacitor with rich nitrogen porous carbon material prepared by raw material with brown coal that CN104817082A discloses a kind of, and be take brown coal as raw material, alkali metal hydroxide is activator, prepares the rich nitrogen porous carbon material of ultracapacitor.CN104803383A discloses a kind of method utilizing Leaf of Camphortree to prepare activated carbon for super capacitors, is take Leaf of Camphortree as raw material, obtains through acidleach, charing, activation treatment.CN104709905A discloses a kind of fused salt mixt that utilizes and prepares the method for activated carbon for super capacitors for activator; for raw material with pitch or coal tar; itself and fused salt mixt are mixed together evenly; under argon gas or nitrogen protection; mixture is placed in charring furnace carbonize, final product pulverizing washing is dry obtains product.
The electric capacity charcoal preparation that above patent is China provides fine active charcoal preparing process, applies provide advanced experimental data and criteria in application for gac in ultracapacitor.But experiment all completes at laboratory lab scale, and inevitably have some limitations, industrial implementation difficulty is larger.As:
1, starting material do not take experiment measure in carbonization process, cause carbide volatile content high, easily cause inflammable gas enrichment in activation system, cause production safety hidden danger, and the volatile matter remained in gac easily causes in use and occurs flatulence problem.
2, in laboratory, in alkali priming reaction process, generation sodium or potassium steam can be taken out of by rare gas element, and amount is few without danger.But in Industrial processes, produce a large amount of potassium or Sodium vapour, as processed not in time, meeting water after enrichment can set off an explosion, and easily causes industrial accident.
3, potassium or Sodium vapour, alkali steam is contained in tail gas, and hydrogen, carbon monoxide and small organic molecule inflammable gas, if do not processed, being easy to contaminate environment, there is the hidden danger of combustion explosion.
4, rice husk is containing 20wt% silicon-dioxide of having an appointment, and has natural nanostructure, after pyrolysis, with rice hull carbon template each other, there is the inherent advantage as electric capacity charcoal, but, the existence of silicon-dioxide just, when producing electric capacity charcoal, ash content is dropped to below 0.3wt%, difficulty is larger.In laboratory, disregard cost activation treatment and aftertreatment, can realize, but industrially how to realize being that rice husk produces one of gordian technique of electric capacity charcoal.
Therefore in the middle of prior art, urgently a kind of novel production technology scheme solves this problem.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of rice husk to produce the method for electric capacity charcoal, adopt rice husk to make electric capacity charcoal, use biomass production renewable energy source and chemical, low cost, environmental protection, and production process safety non-pollution, can be mass-produced.
Rice husk produces a method for electric capacity charcoal, it is characterized in that: comprise the following steps,
Step one, rice husk thermal decomposition
Choose rice husk, mix in the ratio that butt mass ratio is (100:1) ~ (100:5) with catalyzer after screening purification, pyrolysis tower is added through Dou Shi lift after mixing, adjustment enters the oxygen level of pyrolysis zone, pyrolysis section temperature is made to remain on 600 DEG C ~ 700 DEG C, pyrolysis 0.5h ~ 1.0h, rice husk is decomposed into pyrolysis gas and pyrolytic carbon;
The charing of step 2, constant temperature and catalytic cracking of tar
The pyrolysis gas of 600 DEG C ~ 700 DEG C obtained in described step one and pyrolytic carbon are continued descending along pyrolysis tower, keep constant temperature tar removing 0.5h ~ 1.0h, obtain without tar pyrolysis gas and pyrolytic carbon, enter pyrolysis tower water-cooled cooling section, be cooled to 300 DEG C ~ 350 DEG C, through cyclonic separator, high energy pyrolysis gas be separated with decoking pyrolytic carbon;
Step 3, pyrolysis gas combustion heat supplying
The high energy pyrolysis gas obtained in described step 2 is introduced gas fired-boiler burning, obtains Boiler High Pressure steam;
Prepared by step 4, template carbon
By the pyrolytic carbon obtained in described step 2, join in horizontal reacting still through spiral propeller, 5% sodium hydroxide or potassium hydroxide aqueous solution is added in the ratio of solid-to-liquid ratio 1:5, revolving horizontal reactor, by pyrolytic carbon and sodium hydroxide lye Homogeneous phase mixing, pass into the Boiler High Pressure steam obtained in described step 3, the pressure keeping Boiler High Pressure steam is 5 ~ 6 normal atmosphere, reaction 3h ~ 4h, keeps original pressure to take out mixed solution, mixed solution is pressed into No. 1 storage tank, solid-liquid separation is carried out through No. 1 whizzer, reclaim sodium silicate solution, remaining solid enters No. 2 storage tanks through travelling belt, 80 DEG C of purified tap waters are added in No. 2 storage tanks, stirring and dissolving 20 minutes, solid-liquid separation is carried out through No. 2 whizzers, the solid obtained enters No. 3 storage tanks through travelling belt, add 70 DEG C of purified tap waters, stirring and dissolving 20 minutes, solid-liquid separation is carried out through No. 3 whizzers, obtain solid and enter No. 4 storage tanks through travelling belt, add 60 DEG C of purified tap waters, stirring and dissolving 20 minutes, solid-liquid separation is carried out through No. 4 whizzers, be washed to ash oontent and be less than discharging after 8wt%, be dried to moisture and be less than 10wt%, obtain template carbon,
Step 5, pulverizing
By the template carbon of drying obtained in described step 4, be crushed to the particle diameter <10um of template carbon through micronizer mill;
Step 6, priming reaction
By the template carbon pulverized through pulverizer obtained in described step 5, with pulverizing for pulverous solid activating agent, be (1:2) ~ the ratio of (1:3) mixing in mass ratio, after stirrer mixing completely, be evenly distributed in casket body, join in activation furnace, under nitrogen and aqueous vapor shielded, adjustment temperature rise rate is 10 DEG C/min ~ 20 DEG C/min, be heated to 350 DEG C ~ 400 DEG C, keep the temperature 30min ~ 40min of 350 DEG C ~ 400 DEG C, continue to be warming up to 700 DEG C ~ 800 DEG C, adjustment fltting speed, priming reaction 50min ~ 80min, enter cooling saggar cooling 50min ~ 80min,
Step 7, discharging
To cool in described step 6 in tank that saggar is transferred under aqueous vapor shielded, make activated material in saggar continue to be cooled to and be less than 300 DEG C, add water-soluble material, washing and drying saggar;
Step 8, washing
Activated material in described step 7 is transferred to No. 1 plastics high-speed stirring pot, the ratio being 1:20 in solid-liquid ratio adds 80 DEG C of pure water, stirring and dissolving 20 minutes, through No. 1 plastic-coated whizzer solid-liquid separation, solid enters No. 2 plastics high-speed stirring pots through travelling belt, add 80 DEG C of pure water, stirring and dissolving 20 minutes, through No. 2 plastic-coated whizzer solid-liquid separation, solid enters No. 3 plastics high-speed stirring pots through travelling belt, adds 80 DEG C of pure water, stirring and dissolving 20 minutes, through No. 3 plastic-coated whizzer solid-liquid separation, obtain washing rear solid;
Step 9, filtered and recycled
Reclaimed by described step 8 three time washings, add aqua calcis and produce calcium carbonate and precipitated calcium silicate, filtered and recycled alkali lye in the solution reclaimed, adjustment alkali concn, returns the recycle of molten silicon operation;
Step 10, pickling
By in solid transfer to 1 enamel reaction still after the washing that obtains in described step 8, add 60 DEG C of aqueous solution containing 1wt% ~ 2wt%HCl in the ratio of solid-to-liquid ratio 1:20, stirring and dissolving 20 minutes, carries out solid-liquid separation through No. 1 titanizing whizzer; By in solid transfer to 2 enamel reaction still of centrifugal rear acquisition, add 60 DEG C of aqueous solution containing 1wt% ~ 2wt%HCl in the ratio of solid-to-liquid ratio 1:20, stirring and dissolving 20 minutes, carries out solid-liquid separation through No. 2 titanizing whizzers; By in solid transfer to 3 enamel reaction still of centrifugal rear acquisition, add 60 DEG C of ultrapure waters in the ratio of solid-to-liquid ratio 1:20, stirring and dissolving 20 minutes, carry out solid-liquid separation through No. 3 titanizing whizzers; By in solid transfer to 4 enamel reaction still of centrifugal rear acquisition, add 60 DEG C of ultrapure waters in the ratio of solid-to-liquid ratio 1:20, stirring and dissolving 20 minutes, through No. 4 titanizing whizzer solid-liquid separation; By in solid transfer to 5 enamel reaction still of centrifugal rear acquisition, add 60 DEG C of ultrapure waters in the ratio of solid-to-liquid ratio 1:20, stirring and dissolving 20 minutes, through No. 5 titanizing whizzer solid-liquid separation; By in solid transfer to 6 enamel reaction still of centrifugal rear acquisition, add 60 DEG C of ultrapure waters in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 6 titanizing whizzer solid-liquid separation; In solid transfer to 7 enamel reaction still of centrifugal rear acquisition again, add 60 DEG C of ultrapure waters in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 7 titanizing whizzer solid-liquid separation, obtain the wet basis gac that ash content is less than 0.3wt%;
Step 11, drying
The wet basis gac described step 10 obtained evenly is dispensed in enamel pallet, transfers in thermostatic drying chamber, and under the condition of 120 DEG C, dry 20h ~ 24h, treats that electric capacity charcoal moisture is less than 3wt%, discharging;
Step 12, selection by winnowing classification
Electric capacity charcoal step 11 described in step obtained is through micronizer mill selection by winnowing, be separated through 4 grades of cyclonic separators containing charcoal air-flow, ultrafine powder is reclaimed through sack cleaner, emptying tail gas after water film dedusting, collect the product that 4 grades of cyclonic separators are separated and the ultrafine powder reclaimed through sack cleaner respectively, produce the electric capacity charcoal product of one or more size distribution, put in storage through vacuum packaging respectively.
The rice husk chosen in described step one is the rice husk of water content 8% ~ 15%.
Keep constant temperature tar removing 0.5h ~ 1.0h that pyrolytic carbon is continued charing in described step 2 and be less than 3wt% for volatile matter, and the pyrolytic carbon catalytic decomposition pyrolysis gas of supported catalyst coal-tar middle oil be not condensation small molecules.
Described step 6 activation furnace is pusher activation furnace, and 8 ~ 12 temperature-controlled areas established by activation furnace, controlled respectively by housing, adjust each warm area heating rate and temperature; Front 1 ~ 5 warm area of activation furnace is heating zone, and adjustment 2 ~ 4 warm area temperature are 350 DEG C ~ 450 DEG C, and the activator of melting penetrates into template carbon surfaces externally and internally, drive away air in hole, homogenizing priming reaction; After activation furnace, 6 ~ 12 warm areas are constant temperature region of activation.
Activation furnace in described step 6 is provided with cooling zone at body of heater tail end, and indirect water-cooling is cooled to casket surface temperature and is less than 200 DEG C.
Soak time in described step 6 referred in the constant temperature region of activation residence time.
Activator in described step 6 is sodium hydroxide or potassium hydroxide; Wherein, the mass ratio of described template carbon and sodium hydroxide is 1:2.5, and temperature of reaction is 700 DEG C, and the reaction times is 60 minutes; The mass ratio of described template carbon and potassium hydroxide is 1:3, and temperature of reaction is 750 DEG C, and the reaction times is 70 minutes.
In the protection gas of described step 6, the ratio of nitrogen and water vapour is reacted by the sodium that produces in priming reaction or potassium steam and water vapour the reaction requirement amount generating sodium hydroxide or potassium hydroxide and is regulated.
The tail gas produced in described step 6 reactivation process is through water film dedusting, and water cycle uses the alkali lye reclaimed in tail gas, and cleaning of off-gas introduces boiler combustion.
The Large stone electric capacity charcoal that described step 12 apoplexy is selected is for energy-storage battery or power cell, and small particle size electric capacity charcoal is used for ultracapacitor or lithium ion battery.
By above-mentioned design, the present invention can bring following beneficial effect: a kind of rice husk produces the method for electric capacity charcoal, adopts rice husk to make electric capacity charcoal, use biomass production renewable energy source and chemical, low cost, environmental protection, and production process safety non-pollution, can be mass-produced.
Further beneficial effect of the present invention is:
1, in pyrogenic processes, rice husk and catalyzer are evenly blended, contribute to reducing the coal-tar middle oil molecular weight of pyrolysis molecule, and catalysis rice husk water vapour participates in pyrolytic reaction, improve the energy density of pyrolysis gas, contribute to producing high-energy biomass Sweet natural gas.
2, in constant temperature charing and catalytic cracking of tar operation, under the effect of catalyzer, the further pyrolysis of the fugitive constituent in pyrolytic carbon, reduce fugitive constituent, pyrolytic tar, under the effect of charcoal supported catalyst, is cracked into small molecules further, avoid tar condensing blocking pipe, and improve fuel gases calorific value.
3, at silicon charcoal separation circuit, use horizontal rotary reactor, be conducive to pyrolytic carbon and alkali lye Homogeneous phase mixing, reduce solid-to-liquid ratio, hot pressing desiliconization, increase modulus of water glass.
4, after silicon charcoal is separated, charcoal is washed three times, remove free water glass or potassium silicate, avoid dried cake, affect template carbon quality.
5, before activation, template carbon is crushed to required particle diameter, is conducive to and activator Homogeneous phase mixing, is conducive to priming reaction, avoid the finished product crushing process after pickling to introduce iron contamination, avoid pulverizing that activated carbon capillary is subsided simultaneously, affect product quality and performances.
6, before activation, template carbon and solid alkali pulverizing, height are mixed conjunction, uniform distribution, ensures that activation environment is consistent, uniform activation.
7, in reactivation process, pass into part water vapour as shielding gas, in time external with effusion casket sodium or potassium element gas-phase reaction, avoid sodium or potassium enrichment, meets water and blast and wait danger.
8, the sodium contained in tail gas or potassium element gas, alkali steam, absorb through Water Membrane Dedusting System, recycle of alkali liquor, recycle.
9, the tail gas introducing boiler combustion through water film dedusting is combustion-supporting, avoids causing danger and contaminate environment.
10, after activation; first lower the temperature through indirect water-cooling at activation furnace afterbody; after coming out of the stove; be transferred in the box tank of steam protection by casket body rapidly, under steam protection, activated material is cooled to less than 300 DEG C; add the molten material of hot water again; be separated with casket body, avoid pore volume chilling to shrink, avoid being oxidized in atmosphere.
11, after activated material stripping casket body, be transferred to plastics high-speed stirring pot, add hot water and charcoal high-speed stirring is broken up three times, wash three times, remove free water glass and alkali, avoid microlith to exist, be conducive to electric capacity charcoal ash content and reduce.
12, use aqueous hydrochloric acid, pickling 2 times, dissolve and remove any metal-salt that may exist and oxide compound, do not generate any insoluble salt simultaneously.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated:
Fig. 1 is the operation steps schematic flow sheet that a kind of rice husk of the present invention produces the method for electric capacity charcoal.
Embodiment
A kind of rice husk as shown in Figure 1 produces the method for electric capacity charcoal, comprises the following steps, and 1, a kind of rice husk produces the method for electric capacity charcoal, concrete steps are as follows:
(1) rice husk thermal decomposition
First will be that (100:1) ~ (100:5) ratio mixes with catalyzer in butt mass ratio through screening purification rice husk, pyrolysis tower is added through Dou Shi lift, adjustment enters the oxygen level of pyrolysis zone, pyrolysis section temperature is made to remain on 600 DEG C ~ 700 DEG C, pyrolysis 0.5h ~ 1.0h, rice husk is decomposed into pyrolysis gas and pyrolytic carbon;
(2) constant temperature charing and catalytic cracking of tar
The pyrolysis gas of 600 DEG C ~ 700 DEG C obtained in step (1) and pyrolytic carbon are continued descending along pyrolysis tower, keep constant temperature tar removing 0.5h ~ 1.0h, newly-generated enters pyrolysis tower water-cooled cooling section without tar pyrolysis gas and pyrolytic carbon, be cooled to 300 DEG C ~ 350 DEG C, through cyclonic separator, high energy pyrolysis gas is separated with decoking pyrolytic carbon;
(3) pyrolysis gas combustion heat supplying
The high-energy fuel gas obtained in step (2) is directly introduced gas fired-boiler burning, production high pressure steam;
(4) template carbon preparation
By the pyrolytic carbon obtained in step (2), join in horizontal reacting still through spiral propeller, 5% sodium hydroxide (or potassium hydroxide) aqueous solution is added in the ratio of solid-to-liquid ratio 1:5, revolving horizontal reactor, make pyrolytic carbon and alkali lye Homogeneous phase mixing, pass in step (3) and obtain Boiler Steam, vapor pressure is kept to be 5 ~ 6 normal atmosphere, react 3 ~ 4 hours, discharging with pressure, mixed solution is pressed into No. 1 storage tank, through No. 1 whizzer solid-liquid separation, reclaim water glass (or potassium silicate) solution, solid enters No. 2 storage tanks through travelling belt, add 80 DEG C of purified tap waters, stirring and dissolving 20 minutes, through No. 2 whizzer solid-liquid separation, solid enters No. 3 storage tanks through travelling belt, add 70 DEG C of purified tap waters, stirring and dissolving 20 minutes, through No. 3 whizzer solid-liquid separation, solid enters No. 4 storage tanks through travelling belt, add 60 DEG C of purified tap waters, stirring and dissolving 20 minutes, through No. 4 whizzer solid-liquid separation, be washed to ash oontent and be less than 8wt%, discharging, be dried to moisture and be less than 10wt%, produce template carbon,
(5) pulverize
By the dry template carbon of producing in step (4), pulverize as particle diameter <10um through micronizer mill,
(6) priming reaction
By the template carbon pulverized through pulverizer of producing in step (5), with the solid activating agent pulverized as powder, and to mix for (1:2) ~ (1:3) ratio in mass ratio, height stirs blended homogenizing; Be evenly distributed in container, be sequentially added in activation furnace, under nitrogen and aqueous vapor shielded, adjustment temperature rise rate is 10 DEG C/min ~ 20 DEG C/min, heat temperature raising 350 DEG C ~ 400 DEG C constant temperature 30min ~ 40min, then be warming up to 700 DEG C ~ 800 DEG C, adjustment fltting speed, priming reaction 50min ~ 80min, enters cooling zone cooling 50min ~ 80min;
(7) discharging
Cooling saggar in step (6) is transferred in aqueous vapor shielded lower flume, makes activated material in saggar continue to be cooled within 300 DEG C, add water-soluble material, washing and drying saggar, recycle;
(8) wash
Activated material in step (7) is transferred to No. 1 plastics high-speed stirring pot, 80 DEG C of pure water are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 1 plastic-coated whizzer solid-liquid separation, solid enters No. 2 plastics high-speed stirring pots through travelling belt, add 80 DEG C of pure water, stirring and dissolving 20 minutes, through No. 2 plastic-coated whizzer solid-liquid separation, solid enters through travelling belt that No. 3 plastics are high stirs pot, adds 80 DEG C of pure water, stirring and dissolving 20 minutes, through No. 3 plastic-coated whizzer solid-liquid separation, obtain washing rear solid;
(9) filtered and recycled
Reclaimed by three washingss in step (8), add aqua calcis and produce calcium carbonate and precipitated calcium silicate, filtered and recycled alkali lye, adjustment alkali concn, returns the recycle of molten silicon operation;
(10) pickling
By in solid transfer to 1 enamel reaction still after the washing that obtains in step (8), 60 DEG C of aqueous solution containing 1wt% ~ 2wt%HCl are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 1 titanizing whizzer solid-liquid separation, again by solid transfer to 2 enamel reaction still, 60 DEG C of aqueous solution containing 1wt% ~ 2wt%HCl are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 2 titanizing whizzer solid-liquid separation, again by solid transfer to 3 enamel reaction still, 60 DEG C of ultrapure waters are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 3 titanizing whizzer solid-liquid separation, again by solid transfer to 4 enamel reaction still, 60 DEG C of ultrapure waters are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 4 titanizing whizzer solid-liquid separation, again by solid transfer to 5 enamel reaction still, 60 DEG C of ultrapure waters are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 5 titanizing whizzer solid-liquid separation, again by solid transfer to 6 enamel reaction still, 60 DEG C of ultrapure waters are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 6 titanizing whizzer solid-liquid separation, again by solid transfer to 7 enamel reaction still, 60 DEG C of ultrapure waters are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 7 titanizing whizzer solid-liquid separation, prepare the wet basis gac that ash content is less than 0.3wt%,
(11) dry
Step (10) is obtained wet basis gac be evenly dispensed in enamel pallet, transfer in thermostatic drying chamber, 120 DEG C of dry 20h ~ 24h, be dried to electric capacity charcoal moisture <3wt%, discharging;
(12) selection by winnowing classification
Electric capacity charcoal step (11) produced is through micronizer mill selection by winnowing, be separated through 4 grades of cyclonic separators containing charcoal air-flow, ultrafine powder is reclaimed through sack cleaner, tail gas is emptying after water film dedusting, collect the product that 4 grades of cyclonic separators are separated and the ultrafine powder reclaimed through sack cleaner respectively, produce the electric capacity charcoal product of different-grain diameter distribution, put in storage through vacuum packaging respectively.
Rice husk raw aqueous 8% ~ 15% described in step (1), need not be dry, and moisture is wherein as hydrogen source during catalyse pyrolysis.
Step (1) and the catalyzer described in step (2) are sodium hydroxide or potassium hydroxide.
Descending together with the pyrolysis gas that obtains in step (1) and pyrolytic carbon are continued along pyrolysis tower described in step (2), keep isothermal reaction to be continued by pyrolytic carbon to carbonize for volatile matter is less than 3wt%, the pyrolytic carbon catalytic decomposition pyrolysis gas of supported catalyst is coal-tar middle oil is simultaneously not condensation small molecules;
In step (4), wash 3 times with purified tap water, the water glass that removing is free and alkali, make the ash content of template carbon be less than 8wt%.Template carbon fouling when avoiding drying, the mobility of impact and purity.
Activation furnace described in step (6) is pusher activation furnace, and all activated materials synchronously push away and move back.
8 ~ 12 temperature-controlled areas established by activation furnace described in step (6), controlled respectively by housing, adjust each warm area heating rate and temperature.
Front 1 ~ 5 warm areas of activation furnace feed end described in step (6) are heating zone, and adjusting 2 ~ 4 warm area temperature is 350 DEG C ~ 450 DEG C, and the activator uniformly penetrating of melting, to template carbon surfaces externally and internally, drives away air in hole, homogenizing priming reaction; After activation furnace, 6 ~ 12 warm areas are constant temperature region of activation.
Activation furnace described in step (6) is provided with cooling zone at body of heater tail end, and indirect water-cooling is cooled to casket surface temperature and is less than 200 DEG C.
Soak time described in step (6) referred in the constant temperature region of activation residence time.
Activator described in step (6) is sodium hydroxide or potassium hydroxide.
In step (6), the mass ratio of described template carbon and sodium hydroxide is 1:2.5, and temperature of reaction is 700 DEG C, and the reaction times is 60 minutes.
In step (6), the mass ratio of described template carbon and potassium hydroxide is 1:3, and temperature of reaction is 750 DEG C, and the reaction times is 70 minutes.
In protection gas described in step (6), water vapour content reacts according to the sodium produced in priming reaction or potassium steam and water vapour the ratio that the reaction requirement amount adjustment generating sodium hydroxide or potassium hydroxide protects nitrogen and water vapour in gas.
In step (6), the tail gas produced in described reactivation process is through water film dedusting, and water cycle uses the alkali lye reclaimed in tail gas, and cleaning of off-gas introduces boiler combustion.
In step (12), the Large stone electric capacity charcoal that described selection by winnowing goes out is preferred for energy-storage battery or power cell, and small particle size electric capacity charcoal is preferred for ultracapacitor or lithium ion battery.
The following examples describe in further detail of the present invention.
Embodiment 1
(1) will be that 100:3 ratio mixes with sodium hydroxide in butt mass ratio through screening purification rice husk, pyrolysis tower is added through Dou Shi lift, adjustment induced draft fan rotating speed, control the oxygen level entering pyrolysis zone, pyrolysis section temperature is made to remain on 650 DEG C, pyrolysis 1.0 hours, the catalyzed pyrolysis of rice husk is pyrolysis gas and pyrolytic carbon;
(2) pyrolysis gas of 650 DEG C obtained in step (1) and pyrolytic carbon are continued descending along pyrolysis tower, keep constant temperature tar removing 1.0 hours, newly-generated enters pyrolysis tower water-cooled cooling section without tar pyrolysis gas and pyrolytic carbon, be cooled to 300 DEG C, be separated through cyclonic separator, producing calorific value is 2100 kilocalorie pyrolysis gas and containing volatile matter 2wt% pyrolytic carbon;
(3) pyrolysis gas combustion heat supplying
The high-energy fuel gas obtained in step (2) is directly introduced gas fired-boiler burning, production high pressure steam;
Embodiment 2
Change catalyzer is potassium hydroxide, and all the other conditions are as embodiment 1, and producing calorific value is 2200 kilocalorie pyrolysis gas and containing volatile matter 1.5wt% pyrolytic carbon;
Embodiment 3
By the pyrolytic carbon obtained in embodiment 1, join in horizontal reacting still through spiral propeller, 5% aqueous sodium hydroxide solution is added in the ratio of solid-to-liquid ratio 1:5, revolving horizontal reactor, make pyrolytic carbon and alkali lye Homogeneous phase mixing, pass in embodiment 1 and obtain Boiler Steam, vapor pressure is kept to be 5 normal atmosphere, react 3 hours, discharging with pressure, mixed solution is pressed into No. 1 storage tank, through No. 1 whizzer solid-liquid separation, reclaim sodium silicate solution, solid enters No. 2 storage tanks through travelling belt, add 80 DEG C of purified tap waters, stirring and dissolving 20 minutes, through No. 2 whizzer solid-liquid separation, solid enters No. 3 storage tanks through travelling belt, add 70 DEG C of purified tap waters, stirring and dissolving 20 minutes, through No. 3 whizzer solid-liquid separation, solid enters No. 4 storage tanks through travelling belt, add 60 DEG C of purified tap waters, stirring and dissolving 20 minutes, through No. 4 whizzer solid-liquid separation, be washed to ash oontent and be less than 8wt%, discharging, be dried to moisture and be less than 10wt%, the template carbon produced is pulverized as particle diameter <10um through micronizer mill,
Embodiment 4
By the template carbon pulverized through pulverizer of producing in embodiment 3, and pulverize as the sodium hydroxide of powder, and in mass ratio for 1:2.5 ratio mixes, height stirs blended homogenizing 20 minutes; Be evenly distributed in casket body, be sequentially added in activation furnace, under nitrogen and aqueous vapor shielded (wherein water vapour is carried secretly by nitrogen and passed through body of heater with 7.5L/min flow velocity), adjustment temperature rise rate is 10 DEG C/min, heat temperature raising 350 DEG C ~ 400 DEG C keeps 40 minutes, then is warming up to 700 DEG C, adjustment fltting speed, priming reaction 60 minutes, enters cooling zone and lowers the temperature 60 minutes;
Embodiment 5
By the template carbon pulverized through pulverizer of producing in embodiment 3, and pulverize as the potassium hydroxide of powder, and in mass ratio for 1:3 ratio mixes, height stirs blended homogenizing 20 minutes; Be evenly distributed in casket body, be sequentially added in activation furnace, under nitrogen and aqueous vapor shielded, adjustment temperature rise rate is 10 DEG C/min, heat temperature raising 350 DEG C ~ 400 DEG C keeps 40 minutes, then enters 750 DEG C of region of activations, adjustment fltting speed, priming reaction 70 minutes, enters cooling zone and lowers the temperature 70 minutes;
Embodiment 6
(1) being transferred to cooling saggar in embodiment 5 in aqueous vapor shielded lower flume, making activated material in saggar continue to be cooled within 300 DEG C, adding water-soluble material, washing and drying saggar, recycle;
(2) activated material in step (1) is transferred to No. 1 plastics high-speed stirring pot, 80 DEG C of pure water are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 1 plastic-coated whizzer solid-liquid separation, solid enters No. 2 plastics high-speed stirring pots through travelling belt, add 80 DEG C of pure water, stirring and dissolving 20 minutes, through No. 2 plastic-coated whizzer solid-liquid separation, solid enters through travelling belt that No. 3 plastics are high stirs pot, adds 80 DEG C of pure water, stirring and dissolving 20 minutes, through No. 3 plastic-coated whizzer solid-liquid separation, obtain washing rear solid;
(3) reclaimed by three washingss in step (2), add aqua calcis and produce calcium carbonate and precipitated calcium silicate, filtered and recycled alkali lye, adjustment alkali concn, returns the recycle of molten silicon operation;
(4) by solid transfer to 1 enamel reaction still after the washing that obtains in step (2), 60 DEG C of aqueous solution containing 3.5wt%HCl are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 1 titanizing whizzer solid-liquid separation, again by solid transfer to 2 enamel reaction still, 60 DEG C of aqueous solution containing 3.5wt%HCl are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 2 titanizing whizzer solid-liquid separation, again by solid transfer to 3 enamel reaction still, 60 DEG C of ultrapure waters are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 3 titanizing whizzer solid-liquid separation, again by solid transfer to 4 enamel reaction still, 60 DEG C of ultrapure waters are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 4 titanizing whizzer solid-liquid separation, again by solid transfer to 5 enamel reaction still, 60 DEG C of ultrapure waters are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 5 titanizing whizzer solid-liquid separation, again by solid transfer to 6 enamel reaction still, 60 DEG C of ultrapure waters are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 6 titanizing whizzer solid-liquid separation, again by solid transfer to 7 enamel reaction still, 60 DEG C of ultrapure waters are added in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 7 titanizing whizzer solid-liquid separation, produce wet basis gac,
Embodiment 7
(1) embodiment 6 step (4) is obtained wet basis gac to be evenly dispensed in enamel pallet, transfer in thermostatic drying chamber, 120 DEG C of dryings 24 hours, produce electric capacity charcoal product; Electric capacity charcoal productive rate 60.03%, moisture content 0.5wt%, ash content 0.18wt%, methylene blue adsorption value 532mg/g, water system ratio capacitance 210F/g.
(2) selection by winnowing classification
Electric capacity charcoal step (1) produced is through air-flow winnowing machine selection by winnowing, be separated through 4 grades of cyclonic separators containing charcoal air-flow, fine powder is reclaimed through sack cleaner, tail gas is emptying after water film dedusting, collect the product that 4 grades of cyclonic separators are separated and the ultrafine powder reclaimed through sack cleaner, produce the electric capacity charcoal product of different-grain diameter distribution, put in storage through vacuum packaging respectively.
Embodiment 8
Third time washings in embodiment 6 step (2) is reclaimed, the ratio being 1:1 in the mol ratio of sodium carbonate and water glass adds aqua calcis, precipitated chalk and Calucium Silicate powder, filtered and recycled alkali lye, naoh concentration is 5.1wt%, in alkali lye, alkali recovery reaches 73%, returns the recycle of molten silicon operation.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (10)
1. rice husk produces a method for electric capacity charcoal, it is characterized in that: comprise the following steps,
Step one, rice husk thermal decomposition
Choose rice husk, mix in the ratio that butt mass ratio is (100:1) ~ (100:5) with catalyzer after screening purification, pyrolysis tower is added through Dou Shi lift after mixing, adjustment enters the oxygen level of pyrolysis zone, pyrolysis section temperature is made to remain on 600 DEG C ~ 700 DEG C, pyrolysis 0.5h ~ 1.0h, rice husk is decomposed into pyrolysis gas and pyrolytic carbon;
The charing of step 2, constant temperature and catalytic cracking of tar
The pyrolysis gas of 600 DEG C ~ 700 DEG C obtained in described step one and pyrolytic carbon are continued descending along pyrolysis tower, keep constant temperature tar removing 0.5h ~ 1.0h, obtain without tar pyrolysis gas and pyrolytic carbon, enter pyrolysis tower water-cooled cooling section, be cooled to 300 DEG C ~ 350 DEG C, through cyclonic separator, high energy pyrolysis gas be separated with decoking pyrolytic carbon;
Step 3, pyrolysis gas combustion heat supplying
The high energy pyrolysis gas obtained in described step 2 is introduced gas fired-boiler burning, obtains Boiler High Pressure steam;
Prepared by step 4, template carbon
By the pyrolytic carbon obtained in described step 2, join in horizontal reacting still through spiral propeller, 5% sodium hydroxide or potassium hydroxide aqueous solution is added in the ratio of solid-to-liquid ratio 1:5, revolving horizontal reactor, by pyrolytic carbon and sodium hydroxide lye Homogeneous phase mixing, pass into the Boiler High Pressure steam obtained in described step 3, the pressure keeping Boiler High Pressure steam is 5 ~ 6 normal atmosphere, reaction 3h ~ 4h, keeps original pressure to take out mixed solution, mixed solution is pressed into No. 1 storage tank, solid-liquid separation is carried out through No. 1 whizzer, reclaim sodium silicate solution, remaining solid enters No. 2 storage tanks through travelling belt, 80 DEG C of purified tap waters are added in No. 2 storage tanks, stirring and dissolving 20 minutes, solid-liquid separation is carried out through No. 2 whizzers, the solid obtained enters No. 3 storage tanks through travelling belt, add 70 DEG C of purified tap waters, stirring and dissolving 20 minutes, solid-liquid separation is carried out through No. 3 whizzers, obtain solid and enter No. 4 storage tanks through travelling belt, add 60 DEG C of purified tap waters, stirring and dissolving 20 minutes, solid-liquid separation is carried out through No. 4 whizzers, be washed to ash oontent and be less than discharging after 8wt%, be dried to moisture and be less than 10wt%, obtain template carbon,
Step 5, pulverizing
By the template carbon of drying obtained in described step 4, be crushed to the particle diameter <10um of template carbon through micronizer mill;
Step 6, priming reaction
By the template carbon pulverized through pulverizer obtained in described step 5, with pulverizing for pulverous solid activating agent, be (1:2) ~ the ratio of (1:3) mixing in mass ratio, after stirrer mixing completely, be evenly distributed in casket body, join in activation furnace, under nitrogen and aqueous vapor shielded, adjustment temperature rise rate is 10 DEG C/min ~ 20 DEG C/min, be heated to 350 DEG C ~ 400 DEG C, keep the temperature 30min ~ 40min of 350 DEG C ~ 400 DEG C, continue to be warming up to 700 DEG C ~ 800 DEG C, adjustment fltting speed, priming reaction 50min ~ 80min, enter cooling zone, saggar cooling 50min ~ 80min,
Step 7, discharging
To cool in described step 6 in tank that saggar is transferred under aqueous vapor shielded, make activated material in saggar continue to be cooled to and be less than 300 DEG C, add water-soluble material, washing and drying saggar;
Step 8, washing
Activated material in described step 7 is transferred to No. 1 plastics high-speed stirring pot, the ratio being 1:20 in solid-liquid ratio adds 80 DEG C of pure water, stirring and dissolving 20 minutes, through No. 1 plastic-coated whizzer solid-liquid separation, solid enters No. 2 plastics high-speed stirring pots through travelling belt, add 80 DEG C of pure water, stirring and dissolving 20 minutes, through No. 2 plastic-coated whizzer solid-liquid separation, solid enters No. 3 plastics high-speed stirring pots through travelling belt, adds 80 DEG C of pure water, stirring and dissolving 20 minutes, through No. 3 plastic-coated whizzer solid-liquid separation, obtain washing rear solid;
Step 9, filtered and recycled
Reclaimed by described step 8 three time washings, add aqua calcis and produce calcium carbonate and precipitated calcium silicate, filtered and recycled alkali lye in the solution reclaimed, adjustment alkali concn, returns the recycle of molten silicon operation;
Step 10, pickling
By in solid transfer to 1 enamel reaction still after the washing that obtains in described step 8, add 60 DEG C of aqueous solution containing 1wt% ~ 2wt%HCl in the ratio of solid-to-liquid ratio 1:20, stirring and dissolving 20 minutes, carries out solid-liquid separation through No. 1 titanizing whizzer; By in solid transfer to 2 enamel reaction still of centrifugal rear acquisition, add 60 DEG C of aqueous solution containing 1wt% ~ 2wt%HCl in the ratio of solid-to-liquid ratio 1:20, stirring and dissolving 20 minutes, carries out solid-liquid separation through No. 2 titanizing whizzers; By in solid transfer to 3 enamel reaction still of centrifugal rear acquisition, add 60 DEG C of ultrapure waters in the ratio of solid-to-liquid ratio 1:20, stirring and dissolving 20 minutes, carry out solid-liquid separation through No. 3 titanizing whizzers; By in solid transfer to 4 enamel reaction still of centrifugal rear acquisition, add 60 DEG C of ultrapure waters in the ratio of solid-to-liquid ratio 1:20, stirring and dissolving 20 minutes, through No. 4 titanizing whizzer solid-liquid separation; By in solid transfer to 5 enamel reaction still of centrifugal rear acquisition, add 60 DEG C of ultrapure waters in the ratio of solid-to-liquid ratio 1:20, stirring and dissolving 20 minutes, through No. 5 titanizing whizzer solid-liquid separation; By in solid transfer to 6 enamel reaction still of centrifugal rear acquisition, add 60 DEG C of ultrapure waters in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 6 titanizing whizzer solid-liquid separation; In solid transfer to 7 enamel reaction still of centrifugal rear acquisition again, add 60 DEG C of ultrapure waters in the ratio of 1:20, stirring and dissolving 20 minutes, through No. 7 titanizing whizzer solid-liquid separation, obtain the wet basis gac that ash content is less than 0.3wt%;
Step 11, drying
The wet basis gac described step 10 obtained evenly is dispensed in enamel pallet, transfers in thermostatic drying chamber, and under the condition of 120 DEG C, dry 20h ~ 24h, treats that electric capacity charcoal moisture is less than 3wt%, discharging;
Step 12, selection by winnowing classification
Electric capacity charcoal step 11 described in step obtained is through micronizer mill selection by winnowing, be separated through 4 grades of cyclonic separators containing charcoal air-flow, ultrafine powder is reclaimed through sack cleaner, emptying tail gas after water film dedusting, collect the product that 4 grades of cyclonic separators are separated and the ultrafine powder reclaimed through sack cleaner respectively, produce the electric capacity charcoal product of one or more size distribution, put in storage through vacuum packaging respectively.
2. a kind of rice husk according to claim 1 produces the method for electric capacity charcoal, it is characterized in that: the rice husk chosen in described step one is the rice husk of water content 8% ~ 15%.
3. a kind of rice husk according to claim 1 produces the method for electric capacity charcoal, it is characterized in that: keep constant temperature tar removing 0.5h ~ 1.0h that pyrolytic carbon is continued charing in described step 2 and be less than 3wt% for volatile matter, and the pyrolytic carbon catalytic decomposition pyrolysis gas of supported catalyst coal-tar middle oil be not condensation small molecules.
4. a kind of rice husk according to claim 1 produces the method for electric capacity charcoal, it is characterized in that: described step 6 activation furnace is pusher activation furnace, and 8 ~ 12 temperature-controlled areas established by activation furnace, controlled respectively by housing, adjust each warm area heating rate and temperature; Front 1 ~ 5 warm area of activation furnace is heating zone, and adjustment 2 ~ 4 warm area temperature are 350 DEG C ~ 450 DEG C, and the activator of melting penetrates into template carbon surfaces externally and internally, drive away air in hole, homogenizing priming reaction; After activation furnace, 6 ~ 12 warm areas are constant temperature region of activation.
5. a kind of rice husk according to claim 1 produces the method for electric capacity charcoal, and it is characterized in that: the activation furnace in described step 6 is provided with cooling zone at body of heater tail end, indirect water-cooling is cooled to casket surface temperature and is less than 200 DEG C.
6. a kind of rice husk according to claim 1 produces the method for electric capacity charcoal, it is characterized in that: the soak time in described step 6 referred in the constant temperature region of activation residence time.
7. a kind of rice husk according to claim 1 produces the method for electric capacity charcoal, it is characterized in that: the activator in described step 6 is sodium hydroxide or potassium hydroxide; Wherein, the mass ratio of described template carbon and sodium hydroxide is 1:2.5, and temperature of reaction is 700 DEG C, and the reaction times is 60 minutes; The mass ratio of described template carbon and potassium hydroxide is 1:3, and temperature of reaction is 750 DEG C, and the reaction times is 70 minutes.
8. a kind of rice husk according to claim 1 produces the method for electric capacity charcoal, it is characterized in that: in the protection gas of described step 6, the ratio of nitrogen and water vapour is reacted by the sodium that produces in priming reaction or potassium steam and water vapour the reaction requirement amount generating sodium hydroxide or potassium hydroxide and regulated.
9. a kind of rice husk according to claim 1 produces the method for electric capacity charcoal, it is characterized in that: the tail gas produced in described step 6 reactivation process is through water film dedusting, and water cycle uses the alkali lye reclaimed in tail gas, and cleaning of off-gas introduces boiler combustion.
10. a kind of rice husk according to claim 1 produces the method for electric capacity charcoal, it is characterized in that: the Large stone electric capacity charcoal that described step 12 apoplexy is selected is for energy-storage battery or power cell, and small particle size electric capacity charcoal is used for ultracapacitor or lithium ion battery.
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