CN104891492A - Preparation method for activated carbon with medium pore radii - Google Patents
Preparation method for activated carbon with medium pore radii Download PDFInfo
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- CN104891492A CN104891492A CN201510330411.1A CN201510330411A CN104891492A CN 104891492 A CN104891492 A CN 104891492A CN 201510330411 A CN201510330411 A CN 201510330411A CN 104891492 A CN104891492 A CN 104891492A
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Abstract
The invention relates to a preparation method for activated carbon with medium pore radii, and solves the technical problem that the conventional preparation method is complex in technology and high in manufacturing cost. According to the preparation method, the activated carbon is prepared by processing one or more of the following raw materials: wood-based activated carbon, coconut shell-based activated carbon and coal-based activated carbon. The preparation method comprises the following specific steps: soaking one or more of the raw materials in an ethanol-water mixed solution; under the condition that a hydroxide is taken as a pore-enlarging agent, carrying out ultrasonic oscillation, and then carrying out washing and drying; under the protection of inert gas, carrying out calcination to obtain a product, namely the activated carbon. The pore radii (r) of the prepared activated carbon are larger than 2 nm and smaller than 50 nm. The preparation method provided by the invention can be widely applied to the field of preparation of the activated carbon with medium pore radii.
Description
Technical field
The present invention relates to battery material field, is a kind of preparation method of intermediate pore size gac specifically.
Background technology
Gac has excellent physics and chemistry stability, and flourishing pore structure and high loading capacity, be widely used in the relevant industries such as food, chemical industry, environment protection, pharmacy and new forms of energy.Particularly mesopore activated carbon (aperture 2nm<r<50nm) is in some new Application Areass, as in support of the catalyst, battery electrode, ultracapacitor, gas storage and biological medicine, is widely applied.Wherein the research and development of mesopore activated carbon in battery and ultracapacitor class energy storage electrode materials of high conductivity more and more receive publicity.
As the gac of energy storage material, must possess large specific surface area, because specific surface area is larger, the capacity of gac is higher, and specific storage and the specific energy of energy storage material are higher; Gac also should have abundant central hole structure simultaneously, if aperture is too little, as microvoid structure (r<2nm), the negatively charged ion radius of solution is large, then cannot spread micropore inside, cause the utilization ratio of gac to decline; Aperture is too large, the specific surface area of gac must be caused little, and structural strength is poor; Meanwhile, gac also should have excellent electroconductibility, and as energy storage electrode material, the electroconductibility of gac excellence significantly can reduce the internal resistance of cell, improves the capacity usage ratio of battery.Because energy storage material is in use along with discharge and recharge, i.e. electrochemical redox reaction, and the electrolytic solution of battery and electric capacity strong acid often, highly basic or various organic solvent, so gac must have excellent physics and chemistry stability.
Gac is made up of organic or inorganic carbonaceous material, conventional organic materials as coconut husk, rice husk, wood chip, bagasse and various marine algas etc., inorganic materials has mud coal, bituminous coal and brown coal etc., adopt various resin as resol, Synolac and polyacrylonitrile etc. in addition.The performance and application field of the gac adopting different material to obtain makes a big difference.The gac wherein adopting resol and polyacrylonitrile resin to prepare has the advantage that hole is flourishing and mesopore proportion is high, is used widely at battery and electric capacity field.But the carbon content of resol and polyacrylonitrile resin is low, energy consumption is large, and raw materials cost is high, causes the price of this kind gac to remain high always.The present invention adopts cocoanut active charcoal that is cheap and micropore prosperity, wood activated charcoal or bituminous coal gac are raw material, in oxyhydroxide ethanolic soln, reaming is carried out under hyperacoustic effect, and then through high temperature graphitization, obtain that specific surface area is large, mesopore proportion is high, the energy storage material gac of good conductivity.
As far back as the initial stage in 19th century, existing in a large number about the report of microporous activated carbon, gac is widely used in sugar-refining industry gradually.Mesopore activated carbon just has bibliographical information successively in 19 beginnings of the century in the end of the century 20.Nineteen ninety-five, the people such as Oya are published in the article on Carbon, have set forth employing cobalt catalytic activation method, have obtained mesoporous about 50% with resol, the about 200m of mesoporous surface area
2the activated carbon fiber of/g.1997, they adopted cocoanut active charcoal to be raw material, with glucose or glucosamine dipping, then high temperature carbonization, and activated with carbonic acid gas, pore volume 0.26 ~ 0.52cm in the gac made
3/ g, mesoporous surface area 97 ~ 372m
2the particle mesopore activated carbon of/g.
Research abroad about energy storage material special-purpose activated charcoal is also few, and Japan and the research of the U.S. in this field are relatively early.Nineteen ninety-five, the people such as U.S. Takeshi M have just published article " development and current status of electric double-layer capacitors ", discuss the impact of activated carbon pore size on electric capacity.2000, Japan adopted ball milled to prepare epigranular (1 ~ 7 μm), specific surface area 1300 ~ 2100m
2/ g, be specifically designed to the gac producing double electric layers supercapacitor, its specific storage is more than 80F/g (No. 2000-182904, Japanese Patent Application Laid-Open).Subsequently, they have declared again the preparation technology of the gac with more high-ratio surface sum electroconductibility, and gordian technique is gac subsequent disposal graphitization technique (No. 2006-324183, Japanese Patent Application Laid-Open).At present, performance best electrode activity charcoal is that Japanese AIR-WATER Co., Ltd. adopts resol and poly styryl carbinol butyral mixture carborization to prepare granulated active carbon, and specific surface area is more than 3300m
2/ g, electroconductibility is more than 5S/cm, and faraday's electric capacity is up to 420F/g.But this gac is expensive, amount to Renminbi 2000 yuan/kg, but also as strategic materials, be only limitted in Japan sell.
The domestic research of the mesopore activated carbon about energy storage material is more late, only has minority at present about the pertinent literature preparing the special mesopore activated carbon of energy storage material.2002, the people such as the Meng Qing letter mesopore activated carbon that adopted vapor activation to prepare, specific surface area was by 760m
2/ g is increased to 1480m
2/ g, ratio capacitance adds 28.91%, but after activation 2h, the yield of gac is only 26.5%.Within 2008, Wang Yu newly waits people to adopt the bamboo charcoal of activated carbon with rich mesoporous to be raw material, and phosphoric acid activation, the gac specific surface area obtained is 1567m
2/ g, mesopore proportion reaches 47.18%.Ratio capacitance reaches 170F/g, and is applicable to heavy-current discharge, and under 1000mA/g current density, ratio capacitance is still up to 131F/g.Domestic mesopore activated carbon energy storage material is the earliest the application of Japanese Misshin Spinning Co., Ltd, application number: 03820034.1.2010, the people such as Deng Meigen adopted glucose high-pressure oxidation legal system for obtaining hemispherical mesopore activated carbon, and are applied to ultracapacitor, application number: 201010277238.0.Subsequently, the domestic research also paying attention to this field successively, 2013, the people such as Sun little Hong prepared one by micropore and mesopore composite activated carbon, specific surface area 2000-3500m
2/ g, aperture 0.7-5nm, can be widely used in battery and electric capacity field.
Summary of the invention
The present invention is solution existing intermediate pore size method for preparation of active carbon complex process, technical problem that cost of manufacture is high just, provides a kind of method relatively simple, lower-cost intermediate pore size method for preparation of active carbon.
The invention provides a kind of preparation method of intermediate pore size gac, its with one or more of wood activated charcoal, cocoanut active charcoal or coal mass active carbon for raw material, process from strand, its by raw material soaking in ethanol and water mixed solvent, oxyhydroxide is expanding agent, and after ultra-sonic oscillation, water washing is dried, calcine under protection of inert gas, obtain goods; The scope of intermediate pore size gac pore radius r is: 2nm<r<50nm.
Preferably, the particle diameter of wood activated charcoal, cocoanut active charcoal or coal mass active carbon is 100 ~ 325 orders.
Preferably, in ethanol and water mixed solvent, the mass percentage of ethanol is 45% ~ 25%.
Preferably, oxyhydroxide is one or several in sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrated barta.
Preferably, oxyhydroxide is one or both in potassium hydroxide or sodium hydroxide.
Preferably, the concentration of potassium hydroxide and lithium hydroxide is 1 ~ 1.5mol/L.
Preferably, rare gas element is one or several the mixing in nitrogen, argon gas and helium.
Preferably, ultrasonic frequency is 50 ~ 60Hz, and duration of oscillation is 1 ~ 2 hour, power density 1 ~ 2W/cm
2.
Preferably, calcining the temperature adopted is 1700 ~ 2000 DEG C, is incubated 1.5 hours.
The present invention selects raw material to be wood activated charcoal, cocoanut active charcoal and coal mass active carbon, because these three kinds of gacs are cheap, and wide material sources, and there is abundant microvoid structure, can mesopore activated carbon be obtained by suitable reaming.Wherein the carbon content of wood activated charcoal and coal mass active carbon is higher and have good structural strength, is less likely to occur to pulverize in subsequent ultrasonic process, is more conducive to further deep processing.
This gac is mainly used in energy storage material field, and its particle diameter should limit to some extent.The particle diameter of the gac adopted is 50 ~ 1000 orders, if the order number of gac is too little, namely particle diameter is too large, and the electrode film layer thickness of lithium ion battery and ultracapacitor often requires below 100 microns, and the particle of obvious single gac can not be greater than 100 microns; And particle diameter is too large, tap density is large, and for forming same conductive network, the amount of the gac of needs is more, causes unnecessary waste.Equally, the order number of gac can not be too large, and namely particle diameter can not be too little; This is because particle diameter is too little, the specific surface area of gac is corresponding to be reduced, and then the amount of charge causing its surface to adsorb reduces, and the activated carbon surface tension force that particle diameter is too little is large, causes its dispersion more difficult.Therefore the particle diameter of gac is 50 ~ 1000 orders, and wherein 100 ~ 325 orders are best.
The expanding method that the present invention adopts is that physics (ultrasonic wave) and chemistry (oxyhydroxide corrosion) act on simultaneously, and its advantage is that reaming speed is fast, and aperture is controlled and with low cost.According to ultrasonic wave principle, under the vibration of high frequency mechanical wave, the molecule of liquid is subject to the transmission of hyperacoustic energy, interaction of molecules and produce a large amount of bubbles, these bubbles constitute cavatition, energy accumulating, to bubbles burst when certain degree, produces huge energy and whole activated carbon capillary fragmentation is formed mesopore.And oxyhydroxide dissolves in the solution and just plays corrosive nature to activated carbon surface along with solution diffusion, this all requires that the micropore of gac must be able to, by soaked with liquid, soak more abundant, and effect is better.Obviously, the selection of this liquid is very important.It must have very low surface tension and less molecular weight.Surface tension is too low, cannot the surface of wetting activity charcoal, and molecular weight is too large, and its volume is too large, cannot diffuse in the micropore (r<2nm) of gac.The molecular weight of water is 18, meets the demands, but the surface tension of water is up to 72 × 10
-3newton/centimetre (25 DEG C), fully cannot infiltrate activated carbon capillary.The small-molecular-weight organic solvent of the overwhelming majority, as methyl alcohol, ethyl acetate, tetrahydrofuran (THF) and acetonitrile etc. all have lower surface tension, but have certain toxicity, and expensive (comparing with aqueous phase).So the present invention adopts hypotoxic organic solvent-ethanol; Its molecular weight 46, molecular volume is little, can infiltrate through in activated carbon capillary completely; And the surface tension of ethanol is only 22.8 × 10
-3newton/centimetre (25 DEG C).But its price is also higher, thus select ethanol and water mixed solvent more suitable.Second alcohol and water can complete miscibility, also considerably reduces the surface tension of water, as its surface tension of 50% aqueous ethanolic solution is only 28 × 10 simultaneously
-3newton/centimetre (25 DEG C) are 1/3 of water.Meanwhile, the oxyhydroxide of the overwhelming majority can dissolve in ethanol, and solubleness is larger, if potassium hydroxide solubleness is in ethanol 36.2g (25 DEG C).And ethanol also helps the organism (ash content) in lytic activity carbon surface and micropore, be conducive to the specific surface area and the minimizing impurity that improve gac.
Because second alcohol and water can complete miscibility, therefore the present invention adopts ethanol/water mixing solutions as solvent.The content of ethanol can be 100% ~ 15% (wt), and wherein ethanol content is that 45% ~ 25% (wt) is best.The content of ethanol is high, and the surface tension of solution is little, good penetrability, excellent to organism solvability, but solvent cost can be caused high, and dehydrated alcohol is 8000 ~ 9000 yuan/ton, and deionized water only 200 ~ 300 yuan/ton, the combustibility of ethanol also should be avoided to cause production safety hidden danger simultaneously.Ethanol content is few, and cost is low, but the surface tension of solvent is large, and poor permeability, organism dissolving power is weak.Consider, ethanol content is that 45% ~ 25% (wt) is best.
The expanding agent of gac is a lot, the most frequently used and be the most simply water vapour, and its shortcoming is that reaming efficiency is slow, and only to form micropore.Potassium permanganate is the strongest to the corrodibility of gac, and reaming speed is fast and the aperture obtained is large, but its reaction product is solid-state Manganse Dioxide remains in activated carbon surface, aftertreatment more complicated.Zinc chloride is also a kind of relatively conventional expanding agent, react gentleer controlled, shortcoming be the too slow and consumption of speed of response greatly, cost is high.Therefore, the present invention adopts oxyhydroxide as expanding agent.Wherein, the effect of sodium hydroxide and potassium hydroxide is best, and cheap, can also recycle, even if a small amount of waste liquid aftertreatment only need neutralize through simple hydrochloric acid.The concentration of expanding agent is very significant to reaming speed and pore size influences.Concentration is too low, too light to the corrodibility of gac, reaming DeGrain, and concentration is too high, and reaming speed is fast, and aperture is too large, and cause specific surface area to reduce, the internal structure even destroying gac time serious makes its efflorescence and cannot use.The concentration of potassium hydroxide and sodium hydroxide is that 0.1 ~ 3mol/L all can play reaming effect.Particularly when concentration is 0.5 ~ 2mol/L, reaming speed is moderate, and reaction 4-6h, the activated carbon pore size obtained meets the requirements.What deserves to be explained is, adopt the aqueous ethanolic solution of potassium hydroxide and sodium hydroxide as reaming liquid, collect after target product mesopore activated carbon through 300 order filter cloth press filtrations, again through 2000 order filter-cloth filterings, 0 DEG C of low temperature crystallization filters, again suitably after hydrogen make-up sodium oxide and potassium hydroxide, above-mentioned reaming liquid can recycle, and this is not only cost-saving also reduces environmental pollution.
Traditional gac chambering process is all the oxyhydroxide and the gac ground and mixed that adopt solid, then more than 700 DEG C elevated-temperature seal reactions.Simple and the technology maturation of this gac chambering process is stablized, but energy consumption is very large, and oxyhydroxide utilization ratio is very low and cannot recycling use.And temperature and concentration are too low, slowly, therefore the present invention adopts ultrasonic activation to reaming speed.Under normal temperature condition, the reaming of gac in hydroxide solution, can be realized.As mentioned before, lower molecular weight and capillary ethanol water permeation enter in the micropore of gac, oxyhydroxide in solution and the especially intrapore ash content of the ash content of gac, and activated carbon surface carboxylate radical (-COOH), there is acid-base neutralisation reaction in hydroxyl (-OH) and aldehyde radical (-CHO), makes them change-COO into
-,-O
-with-CHO
-, thus surface is with negative charge.Then under hyperacoustic effect, form a large amount of cavitation bubble, this bubble break to gac formed enormous impact, cause activated carbon capillary surfaces collapse to be destroyed, micropore is extended and form mesopore, and the tiny activated carbon granule surface of formation of simultaneously caving in is because with negative charge, electrostatic repulsion makes it temporarily suspend in the solution, along with ultrasonic carrying out, the flowing of liquid and taken out of hole, can not form precipitation and block.In sum, ultrasonic effect is mainly the reaction of the ash content accelerating oxyhydroxide and gac and cavitation is impacted and realizes reaming.Under the acting in conjunction of Physical (ultrasonic wave) and chemical method (oxyhydroxide), the reaming speed of activated carbon capillary is very fast, can avoid the pyroreaction that traditional technology adopts completely, and energy efficient and security increase substantially.
Reaming speed and pore size is regulated by regulating hyperacoustic frequency and power density.Generally speaking, under the condition that amplitude is identical, the vibrational energy of an object is directly proportional to vibrational frequency.This means, hyperacoustic frequency is higher, energy is more, number of bubbles is more, bubble is less, but the surging force of single isolated bubbles fragmentation weakens, and therefore high frequency ultrasound is specially adapted to the cleaning of small-particle dirt and does not destroy its workpiece surface, low-frequency ultrasonic waves is then widely used in fragmentation, as cytoclasis often adopts 20 ~ 25Hz.For gac reaming, ultrasonic frequency is too low, and bubble impact power is strong, and whole activated carbon granule will be caused to be shattered and efflorescence, and gac is destroyed and cannot use; Frequency is too high, does not have the effect that broken reaming and acceleration oxyhydroxide and ash content are reacted.Therefore the ultrasonic frequency adopted is 40 ~ 60Hz, and wherein ultrasonic frequency is that 50 ~ 55Hz effect is best.
Hyperacoustic power density is also very remarkable on the impact of reaming.In aqueous, hyperacoustic power density=transmitted power/emtting area, as power density>=0.3W/cm
2, ultrasonic wave can produce a very large pressure in a liquid, and fluid molecule drawing crack is become cavitation nucleus.Form a cavity close to vacuum thus, it breaks when ultrasonic wave pressure oppositely reaches maximum, and the intense impact will produced at body surface.This being broken by countless tiny cavitation bubble and the shock wave phenomenon produced is called " cavitation " phenomenon.Too little power density cannot produce cavitation effect.Therefore, power density is at 0.3 ~ 4kW/cm
2can cavatition be realized and realize the reaming of gac.Power density is too large, can be shatter by gac, and power density is too little, and reaming speed is too slow, even activated carbon capillary cannot be expanded as mesopore time serious.
The ultra-sonic oscillation time also directly affects the size of activated carbon pore size.After determining ultrasonic frequency and power density, the ultra-sonic oscillation time is longer, and aperture is larger, and hole is longer, and vice versa.In sum, hyperacoustic frequency, power density and ultrasonic time are interactional.In conjunction with the feature of 3 factors, we select relatively lower ultrasonic frequency, avoid frequency too high and cause gac to be shattered; Meanwhile, suitably improve hyperacoustic power density, improve reaming speed, be conducive to like this shortening pore-enlargement, energy efficient and running cost, improve productive rate.Therefore, hyperacoustic frequency is 50 ~ 55Hz, and duration of oscillation is 1 ~ 2 hour, power density 1 ~ 1.5W/cm
2shi Xiaoguo is best.
In order to improve the electroconductibility of gac, need to be carried out high temperature graphitization.Gac belongs to agraphitic carbon, structurally microcrystalline carbon is irregular alignment, therefore its electroconductibility is poor, in high temperature environments, the carbon atom in gac can realize molecular transposition, becomes the plane grid of hexagonal carbon atom, and then form the graphite microcrystal of a large amount of conductivity excellences, mutually overlap between them, form conductive network, thus improve the electroconductibility of gac.But, during high temperature, because activated carbon surface has a large amount of carbon atoms, will oxidized (burning) and become carbonic acid gas or carbon monoxide, therefore greying must be carried out under protection of inert gas.The rare gas element adopted is nitrogen, and one or several the mixing in argon gas and helium, wherein adopting the cost of nitrogen minimum, is only 1/20 of argon gas cost.Calcining temperature is the most remarkable on the impact of gac greying, and temperature is too low, and carbon atom is not active, is not enough to the plane grid forming hexagonal carbon atom, and for the gac of bigger serface, 1500 DEG C can realize carbon atom and reset and greying; Temperature is too high, the serious greying of gac and volumetric shrinkage, causes hole excessive, even complete collapse time serious, and the too high energy consumption that causes of temperature is too large, and when 2100 DEG C, gac shrinking percentage is higher, and has occurred powder phenomenon-tion.Therefore, the calcining temperature of employing is 1500 ~ 2100 DEG C, insulation 1 ~ 4h.Calcination time is comparatively large on the impact of the greying of gac, and when calcining temperature is lower than 1500 DEG C, gac cannot greying, calcining temperature does not affect, and temperature higher than 2100 DEG C time, even if calcination time is shorter, gac also can seriously efflorescence and cause properties significantly to decline.In sum, when calcining temperature be 1700 ~ 2000 DEG C best, insulation 1.5 ~ 2h.
Beneficial effect of the present invention is: first, adopts the ethanol/water solution of oxyhydroxide as expanding agent, micropore is expanded as mesopore; Tradition adopts the aqueous solution, and its surface tension is large, is difficult to infiltrate through in the micropore of gac, cannot not be realized reaming by the micropore of solution soaking; With traditional expanding agent as zinc chloride, phosphoric acid, water vapour is compared with potassium permanganate, oxyhydroxide is gentleer with the reaction of gac, be not easy cause overreaction and cause aperture excessive, and the solubleness of oxyhydroxide in second alcohol and water is very large, remove and recovery process simple.Secondly, adopt ultrasonic assistant reaction, in conventional carbon micropore, often cover one deck organism, in hyperacoustic effect, in the dissolved hydrogen oxide solution that they can be very fast, can Reaction time shorten, increase the specific surface area of gac; Simultaneously under hyperacoustic effect, micropore caves in the formation mesopore that breaks.Finally, adopt the method for protection of inert gas by quick for gac micro crystal graphite, improve the specific conductivity of gac.Compared with traditional mesopore activated carbon preparation method, adopt inexpensive gac to be raw material, significantly reduce costs; Adopt ultrasonic wave and oxyhydroxide activation method, preparation technology is simple, and equipment is few and reaming speed fast, and mesopore proportion is high, and specific surface area is large, and energy consumption is low.
Accompanying drawing explanation
Fig. 1 is the XRD spectra before and after wood activated charcoal greying of the present invention;
Fig. 2 is 240,000 times of stereoscan photographs of the wooden mesopore activated carbon of the present invention 325 order;
Fig. 3 is 240,000 times of stereoscan photographs of the wooden mesopore activated carbon of the present invention 120 order;
Fig. 4 is the XRD spectra before and after coal mass active carbon greying of the present invention;
Fig. 5 is 240,000 times of stereoscan photographs of the present invention 100 order ature of coal mesopore activated carbon;
Fig. 6 is 240,000 times of stereoscan photographs of the present invention 300 order ature of coal mesopore activated carbon.
Embodiment
Embodiment 1
500g wood activated charcoal, 325 orders, specific surface area 1850 ~ 1910m
2/ g, is immersed in 35% aqueous ethanolic solution of 1.5L, and concentration of potassium hydroxide is 1mol/L, stirs after 10 minutes, proceeds in ultrasonic cleaner, regulates ultrasonic frequency 50Hz, ultrasonic power 1W/cm
2, after time 1h, suction filtration, washes with 2L, wash altogether 5 times, after 100 DEG C of forced air drying 2h, proceed in tubular type retort furnace, first vacuumize, then continue to pass into nitrogen, be then rapidly heated to 1700 DEG C, after insulation 1.5h, naturally cooling can obtain the mesopore activated carbon of high conductivity.
The granularity of gac is that 300 ~ 400 orders account for more than 92.7%, 300 orders of total amount and account for 1.4%, accounts for 5.9% (mensuration of GB/T 12496.2-1999 wood activated charcoal test method-size-grade distribution) below 400 orders; Specific surface area is 2733m
2/ g, improves about 50%, after active carbon powder compression moulding, and its resistivity 2.41 × 10
-3Ω m (four point probe Instrument Measuring Resistivity of Carbon Products), specific pore volume amasss 1.42ml/g, mean pore size 9.65nm, and middle pore volume accounts for total hole volume 61.3% (low temperature liquid nitrogen method).Fig. 1 is the x-ray diffractometer test result before and after gac greying, " steamed bun shape " absorption peak is all there is in curve 1 and curve 2 2theta=19 ° and 45 °, this is the charateristic avsorption band of amorphous gac, and there is sharp-pointed absorption peak at 22 ° in curve 2, this is graphite (002) crystal face charateristic avsorption band, which illustrate after high-temperature activation, gac inside defines graphite microcrystal.Fig. 2 is scanning electronic microscope 240,000 times of microscopic appearances of gac.
Embodiment 2
500g wood activated charcoal, 120 orders, specific surface area 1530m
2/ g, is immersed in 45% aqueous ethanolic solution of 1.5L, and concentration of potassium hydroxide is 1.5mol/L, stirs after 10 minutes, proceeds in ultrasonic cleaner, ultrasonic frequency 50Hz, ultrasonic power 1.5W/cm
2, after ultrasonic time 2h, suction filtration, with 2L water/each, is washed till neutrality, after 100 DEG C of forced air drying 2h, proceeds in tubular type retort furnace, first vacuumize, then pass into nitrogen, be then rapidly heated to 2000 DEG C, after insulation 1.5h, and naturally cooling.
The granularity of gac is that 100 ~ 150 orders account for more than 94.8%, 100 orders of total amount and account for 0.8%, accounts for 4.4% (mensuration of GB/T 12496.2-1999 wood activated charcoal test method size-grade distribution) below 400 orders; Specific surface area is 2530m
2/ g, resistivity 1.73 × 10
-3Ω m (four point probe Instrument Measuring Resistivity of Carbon Products), specific pore volume amasss 2.17ml/g, mean pore size 14.25nm, and middle pore volume accounts for total hole volume 71.4% (low temperature liquid nitrogen method).Fig. 3 is scanning electronic microscope 50000 times of microscopic appearances of gac.
Embodiment 3
500g coal mass active carbon, 100 orders, specific surface area 1360m
2/ g, is immersed in 25% aqueous ethanolic solution of 1.5L, and concentration of potassium hydroxide is 1mol/L, stirs after 10 minutes, proceeds in ultrasonic cleaner, ultrasonic frequency 50Hz, ultrasonic power 1.5W/cm
2, after ultrasonic time 2h, suction filtration, with 2L water/each, is washed till neutrality, after 100 DEG C of forced air drying 2h, proceeds in tubular type retort furnace, first vacuumize, then pass into nitrogen, be then rapidly heated to 2000 DEG C, after insulation 1.5h, and naturally cooling.
The granularity of gac is that 80 ~ 120 orders account for more than 95.1%, 100 orders of total amount and account for 1.9%, accounts for 4.4% (mensuration of GB/T 12496.2-1999 wood activated charcoal test method-size-grade distribution) below 120 orders; Specific surface area is 2530m
2/ g, resistivity 0.28 × 10
-3Ω m (four point probe Instrument Measuring Resistivity of Carbon Products), specific pore volume amasss 1.33ml/g, mean pore size 19.64nm, and middle pore volume accounts for total hole volume 53.2% (low temperature liquid nitrogen method).Fig. 4 is the x-ray diffractometer test spectrogram before and after gac greying, and Fig. 5 is scanning electronic microscope 50000 times of microscopic appearances of gac.
Embodiment 4
500g coal mass active carbon, 300 orders, specific surface area 1640m
2/ g, is immersed in 45% aqueous ethanolic solution of 1.5L, and concentration of potassium hydroxide is 1mol/L, stirs after 10 minutes, proceeds in ultrasonic cleaner, ultrasonic frequency 60Hz, ultrasonic power 2W/cm
2, after ultrasonic time 2h, suction filtration, with 2L water/each, is washed till neutrality, after 100 DEG C of forced air drying 2h, proceeds in tubular type retort furnace, first vacuumize, then pass into nitrogen, be then rapidly heated to 2000 DEG C, after insulation 1.5h, and naturally cooling.
The granularity of gac is that 270 ~ 325 orders account for more than 90.1%, 300 orders of total amount and account for 2.6%, accounts for 7.3% (mensuration of GB/T 7702.2-1999 ature of coal granulated active carbon test method-size-grade distribution) below 325 orders; Specific surface area is 2520m
2/ g, resistivity 0.13 × 10
-3Ω m (four point probe Instrument Measuring Resistivity of Carbon Products), specific pore volume amasss 2.61ml/g, mean pore size 17.46nm, and middle pore volume accounts for total hole volume 67.2% (low temperature liquid nitrogen method).
Claims (9)
1. the preparation method of an intermediate pore size gac, its with one or more of wood activated charcoal, cocoanut active charcoal or coal mass active carbon for raw material, process from strand, it is characterized in that described raw material soaking in ethanol and water mixed solvent, oxyhydroxide is expanding agent, and after ultra-sonic oscillation, water washing is dried, calcine under protection of inert gas, obtain goods; The scope of described intermediate pore size gac pore radius r is: 2nm<r<50nm.
2. the preparation method of intermediate pore size gac according to claim 1, is characterized in that the particle diameter of described wood activated charcoal, cocoanut active charcoal or coal mass active carbon is 100 ~ 325 orders.
3. the preparation method of intermediate pore size gac according to claim 1, is characterized in that in described ethanol and water mixed solvent, and the mass percentage of ethanol is 45% ~ 25%.
4. the preparation method of intermediate pore size gac according to claim 1, is characterized in that described oxyhydroxide is one or several in sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrated barta.
5. the preparation method of intermediate pore size gac according to claim 4, is characterized in that described oxyhydroxide is one or both in potassium hydroxide or sodium hydroxide.
6. the preparation method of intermediate pore size gac according to claim 5, is characterized in that the concentration of described potassium hydroxide and lithium hydroxide is 1 ~ 1.5mol/L.
7. the preparation method of intermediate pore size gac according to claim 1, is characterized in that rare gas element is one or several the mixing in nitrogen, argon gas and helium.
8. the preparation method of intermediate pore size gac according to claim 1, it is characterized in that ultrasonic frequency is 50 ~ 60Hz, duration of oscillation is 1 ~ 2 hour, power density 1 ~ 2W/cm
2.
9. the preparation method of intermediate pore size gac according to claim 1, is characterized in that calcining the temperature adopted is 1700 ~ 2000 DEG C, is incubated 1.5 hours.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836747A (en) * | 2016-03-21 | 2016-08-10 | 邵武市金寿活性炭有限公司 | Spherical activated carbon and preparation method thereof |
| CN107051383A (en) * | 2017-04-27 | 2017-08-18 | 农玉金 | A kind of preparation method of carbon material for sewage disposal |
| CN107215871A (en) * | 2017-06-30 | 2017-09-29 | 海南大学 | A kind of preparation method of activated carbon for super capacitors |
| CN107973296A (en) * | 2017-11-28 | 2018-05-01 | 福建省鑫森炭业股份有限公司 | A kind of large aperture activated carbon and preparation method thereof |
| CN110465180A (en) * | 2019-08-23 | 2019-11-19 | 江苏瑞丰科技实业有限公司 | A kind of preparation of high-performance air cleaning honeycomb module material |
| CN111908469A (en) * | 2020-07-13 | 2020-11-10 | 宁夏新龙蓝天科技股份有限公司 | Preparation method of special adsorption activated carbon |
| CN113428857A (en) * | 2021-07-14 | 2021-09-24 | 海南大学 | Preparation method of isovolumetric impregnated activated carbon |
| CN114229843A (en) * | 2021-12-24 | 2022-03-25 | 贵州重力科技环保有限公司 | Method for activating and regenerating waste activated carbon after harmless treatment of waste mercury catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836747A (en) * | 2016-03-21 | 2016-08-10 | 邵武市金寿活性炭有限公司 | Spherical activated carbon and preparation method thereof |
| CN107051383A (en) * | 2017-04-27 | 2017-08-18 | 农玉金 | A kind of preparation method of carbon material for sewage disposal |
| CN107051383B (en) * | 2017-04-27 | 2020-06-05 | 台州中知英健机械自动化有限公司 | Preparation method of carbon material for sewage treatment |
| CN107215871A (en) * | 2017-06-30 | 2017-09-29 | 海南大学 | A kind of preparation method of activated carbon for super capacitors |
| CN107215871B (en) * | 2017-06-30 | 2019-11-22 | 海南大学 | A kind of preparation method of activated carbon for super capacitors |
| CN107973296A (en) * | 2017-11-28 | 2018-05-01 | 福建省鑫森炭业股份有限公司 | A kind of large aperture activated carbon and preparation method thereof |
| CN110465180A (en) * | 2019-08-23 | 2019-11-19 | 江苏瑞丰科技实业有限公司 | A kind of preparation of high-performance air cleaning honeycomb module material |
| CN111908469A (en) * | 2020-07-13 | 2020-11-10 | 宁夏新龙蓝天科技股份有限公司 | Preparation method of special adsorption activated carbon |
| CN113428857A (en) * | 2021-07-14 | 2021-09-24 | 海南大学 | Preparation method of isovolumetric impregnated activated carbon |
| CN114229843A (en) * | 2021-12-24 | 2022-03-25 | 贵州重力科技环保有限公司 | Method for activating and regenerating waste activated carbon after harmless treatment of waste mercury catalyst |
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