CN103588202A - Manufacturing method for active carbon/tourmaline composite material and product manufactured according to manufacturing method - Google Patents
Manufacturing method for active carbon/tourmaline composite material and product manufactured according to manufacturing method Download PDFInfo
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Abstract
The invention relates to a manufacturing method for an active carbon/tourmaline composite material and a product manufactured according to the manufacturing method. The active carbon/tourmaline composite material product which has an adsorption value larger than 100 ml/g to methylthionine chloride and an adsorption value larger than 950 mg/g to iodine can be obtained by mixing the following raw materials in percentage by weight: 53-97 percent of an active carbon precursor raw material, 1-34 percent of an organic matter assistant forming agent, 1-10 percent of tourmaline powder and 1-3 percent of a natural clay mineral raw material and then performing forming, drying, carbonization and activation. The product can be made into various shapes, is widely applied to adsorbing and degrading of formaldehyde, benzene and nitric oxides in air and toxic organic matters and heavy metal ions in a water body and has a wide application prospect.
Description
Technical field
The invention belongs to nonmetal solid material field, be specifically related to a kind of manufacture method of gac/tourmaline composite and the product making thereof.
Background technology
The mankind's production, life activity, made atmosphere, water body, soil be subject to more and more serious pollution.Chemical industry, papermaking, printing and dyeing, pharmacy, the industries such as agricultural chemicals give off a large amount of poisonous coloured sewage, make the surface water and groundwater in many places all be subject to pollution in various degree, as the underground water of the North China of China is subject to chromium, manganese, cadmium, the plumbous heavy-metal pollution that waits, Rice In Guangdong exceeds standard containing cadmium, some regional surface water are subject to phenol, phenyl ring, halohydrocarbon, ammonia nitrogen, nitrogen phosphorus, the pollution such as organophosphorus and organochlorine, there is a plurality of cancers village in Basin of Huaihe River, Taihu Lake, Jiangsu and Liaoning, marine site, Shandong, there is time and again blue-green algae or the red tide that algae excessive propagation causes in South China Sea, in the soil of some factories and miness peripheries, put aside Toxic of high density etc., directly threaten local people's orthobiosis and vegeto-animal existence, factory, vehicular emission volume of smoke, dust (PM2.5 suspended substance) and nitrogen, oxysulfide in atmosphere are exceeded standard again and again, the second half of last year is to this year, northern China has occurred that strong carcinogen polycyclic aromatic hydrocarbons, formaldehyde, benzene and other the various organic volatile content in the interior spaces such as serious haze weather ，Er family, office, motor vehicle is high again especially ...The topsoil atmosphere of " having difficulties at home and abroad ", various solids, water pollution are also deposited and ecotope is day by day impaired, unrepairable, and Sustainable development has been produced to serious restriction, and people's health has been formed to direct threat, and urgently strengthening is administered.
Gac is a kind of porousness, adsorptivity functional materials, the internal void structure of tool uniqueness and surfactivity functional group, stable chemical nature, acid-and base-resisting, heat-resisting, water insoluble and organic solvent, is widely used in the adsorptivity improvement of waste water, waste gas and the purification of soil, also for absorption, decolouring, deodorizing, refining, separated, the catalytic field of liquid phase, gas phase, be the critical function material of the industries such as food, medicine, chemical industry, electronics, mining and metallurgy, environmental protection.But there is following defect in gac at present: (1) great majority are powderies, though there is the product of a small amount of solid shape, intensity is low; (2) can only absorb polluted matter and can not degradation of contaminant, adsorb after saturated and lost efficacy, need manipulation of regeneration.If do not done manipulation of regeneration, the Toxic being adsorbed (as formaldehyde, benzene, heavy metal ion etc.) can cause secondary pollution; (3) regeneration difficulty, expense is larger; (4) work-ing life short, cost recovery is high, and easily produces secondary pollution after discarded.Therefore, be necessary to develop high strength, degradable Toxic, can realize the pressed active carbon from regeneration.
Tourmalinite is a kind of natural Mineral with Polar Electricity, can produce negative ion, emitting far-infrared, dwindles water clusters, brine electrolysis, can increase substantially water dissolved oxygen amount (10 ~ 30%), reduce COD, itself has adsorptivity tourmalinite, can be by OH-and H
2o is oxidized to the OH hydroxyl radical free radical of extremely strong oxidisability etc., thereby aspect environment protection treating, bringing into play important effect: the negative ion that tourmalinite discharges, hydroxyl radical free radical can degradation of formaldehyde, the oxynitride in benzene and haze, negative ion has very strong antibacterial, anti-microbial effect to intestinal bacteria, staphylococcus aureus, be conducive to prevent that transmissible disease from occurring, and have deodorizing, mildew-resistant, anticorrosion and eliminate the effect of peculiar smell; Tourmalinite is to F
- , Cl
- and SO
4 2-, AsO
4 3, AsO
3 3deng all thering is absorption, the effect of concentrating, can absorbing copper, the heavy metal ion such as lead, zinc, chromium, cadmium being reduced, thus weaken the toxic of acid ion and heavy metal ion; Tourmalinite can increase the dissolved oxygen content in water body, the oxidation effectiveness of strengthening to organic pollutant; The far infrared rays of tourmalinite radiation, can dwindle water clusters and to organism produce fierce resonance and make it activation, contribute to pollutent collapse loose, clear up.For example utilize tourmalinite to the activation of organic oxidative function, the far infrared rays launched and collapse loose effect, can make the percent of decolourization of the blue BF-BR waste water from dyestuff of refined lattice element, Methyl Orange in Wastewater reach 100%; Tourmalinite also has good activation, collapses loose, Adsorption and decomposition ability carcinogens malachite green.
The DeR difference of the negative ion OH PARA FORMALDEHYDE PRILLS(91,95) of tourmalinite generation, oxynitride is as follows:
Tourmalinite and gac are compound, can solve to a certain extent gac can only adsorb can not degradation of contaminant problem, the adsorption function of tourmalinite itself also has enhancement to the adsorptivity of gac.
At present, many patented technologies are thermal treatment again after active carbon powder is mixed with tourmalinite.As patent CN200510045991 " porous ceramic matrix material functional ball and production technique thereof ", the method for making of a kind of tourmalinite and gac composite ceramics is provided, but it is raw material that this technique be take the gac having made, therefore there is the problem that twice firing energy consumption is higher with discharge, and tourmalinite is combined with C bad (than the combination of tourmalinite and newborn C), can spontaneous tar while not utilizing carbon raw material charing etc. the characteristic of binding agent, cause that product strength is poor, cost is high; Because charcoal absorption is strong, can adsorb the moisture of several times of himself weight, the adsorptive capacity of coal tar that plays the effect of furtherance shape, also up to 40%, so use CN200510045991 technology, is difficult to form with wet processing! More cannot prepare with wet method plastic process the product of complicated shape, particularly honeycombed product, and this technology also to consume a large amount of coal tar and guarantee to be shaped, cause cost up.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of technique is simple, the manufacture method of the gac/tourmaline composite of high absorbability and the product making thereof.
For solving above technical problem, technical scheme of the present invention is: a kind of manufacture method of gac/tourmaline composite, it is characterized in that: after by weight percentage 53 ~ 97% activated carbon precursor raw material, 1 ~ 34% organism class being helped binder, 1 ~ 10% tourmaline powder, 1 ~ 3% natural clay class raw mineral materials to mix, through being shaped, dry, charing, activation obtain to the adsorptive value of methylene blue is greater than 100ml/g, iodine sorption value is greater than 950mg/g, the pollutent being adsorbed is had to the matrix material of degradation capability.
Described activated carbon precursor raw material is the organic matter raw material that carbon content is high, comprises one or more in coal, bamboo wood byproduct, stalk, shell, plant processing waste residue, xylogen, coal tar, refinery coke, pitch, resin.
It is a kind of in coal tar, cellulose binder, grease or two kinds that described organism class helps binder.
Described cellulose binder is one or more in Xylo-Mucine (CMC), Vltra tears (HPMC), polyvinyl alcohol (PVA); Described grease is one or more in tung oil, soya-bean oil, rapeseed oil, Viscotrol C, sweet oil, glycerine; The content of described coal tar medium pitch is 25 ~ 65w%.
Described tourmaline powder is one or more in dravite, elbaite, iron tourmaline.
More than 90% particle diameter of described tourmaline powder is below 2 μ m.
Described natural clay class raw mineral materials is one or more in wilkinite, ball clay, rectorite leng, sepiolite, zeolite, attaclay, talc clay.
The technique of described charing, activation is: under nitrogen, argon gas class inert gas environment, carry out charing in 500 ~ 600 ℃, then passing into water vapour, CO
2under condition, in 800 ~ 900 ℃, activate.
The product that the manufacture method of above-mentioned matrix material makes, it is characterized in that: adopt extrusion molding technique to make cylindric, circular, cellular product, adopt rolling forming technology to make form of spherical particles product, adopt dry pressing technique to make tabular product.
The specific surface area of described cylindric product is 869m
2/ g, mechanical abrasive wear resistance are 97%; The axial compression strength of described circular product is that 5.7mPa, specific surface area are 298m
2/ g, pore volume are 0.183ml/g; The surface-area of described cellular product is 352 m
2/ g, pore volume are that 0.211ml/g, X axis ultimate compression strength are 10.4mPa; The specific surface area of described form of spherical particles product is 312 m
2/ g, mechanical abrasive wear resistance are 93%; The specific surface area of described tabular product is 899m
2/ g.
The present invention has the following advantages in preparation technology and in product performance and result of use:
1, aspect preparation technology
(1), the present invention by carbon raw material and tourmalinite in preparing the charing of gac, reactivation process, completed once the sintered combined of the two, first carbon raw material charing, activation are made to gac with common, the technology that makes tourmalinite/active carbon ceramic with the charing of gac+tourmalinite, activation is again compared, reduced firing process one, energy consumption and discharge reduce near half;
(2) due to the low activated carbon precursor raw material production of adsorptivity, thus can with wet processing, prepare the product of complicated shape, as honeycombed product.Having avoided patent CN200510045991 " porous ceramic matrix material functional ball and production technique thereof ", is the limitation that raw material can not be used wet production because adopting the high gac of adsorptivity;
(3), utilize carbon raw material when charing, can decomposite the jellies such as tar, produce the characteristic of the newborn C of high reactivity, must not add or only need add a small amount of tar, can make product have higher mechanical strength and wear resistance;
(4), the compound such as tourmalinite institute iron content, calcium, magnesium, potassium, at high temperature can produce catalysis booster action to the carbonization-activation of carbon raw material, Si provides C-basic capsule solution key in carbon raw material charing, reactivation process, contribute to increasing specific surface area and aperture, in the application, tourmalinite can play the effect that is similar to chemical activation gac, and avoided conventional, with chemical method, prepare gac, need add ZnCl
2, the industrial chemicals of the costliness such as KOH, the deficiency that produces chemical pollution, need wash etc. the gac preparing;
(5) natural mineral that, contains nanoparticle (comprising wilkinite, ball clay, rectorite leng, sepiolite) and attaclay or talc clay, normal temperature all has good cohesiveness, plasticity-, contribute to press forming, rolling balling, sepiolite, attaclay or talc clay also have satiny property, extrusion molding (for example preparing ceramic honey comb) is had to active effect, and the nanoparticle that wilkinite, ball clay, rectorite leng, sepiolite contain has certain promoter action to low-temperature sintering;
2, aspect product performance and result of use
(1), activated carbon precursor raw material+tourmalinite tourmalinite/active carbon ceramic of making after charing, activation, than with the charing of gac+tourmalinite, activation makes tourmalinite/active carbon ceramic intensity, wear resistance is higher, not fragile in application;
(2), tourmalinite and gac compound after, the adsorptive power that gac is superpower, makes product can adsorb high density pollution thing in use; And tourmalinite is except helping absorption, more can make the organic pollutant being adsorbed be degraded, heavy metal ion is reduced, and the far infrared rays of tourmalinite radiation, can dwindle water clusters and organism is produced fierce resonance and makes it activation, and tourmalinite increases the dissolved oxygen in water body, can accelerate organic oxidation, cause pollutent to become and be easier to clear up, therefore can extend charcoal saturation time, reducing regeneration link even can not need regeneration.
Preparation method's technique of the present invention is simple, easy to implement, easy and simple to handle in sum, make superior, the stable performance of product performance, to the pollutent being adsorbed, have degradation capability, suitability strong, therefore there is fabulous economy and social value.
Embodiment
Embodiment 1
1, particle diameter 100 orders be take thin hardwood wood chip, xylogen dry to moisture be 7.5%, by the component of hard wood dust 72kg, xylogen 4.0kg, tourmaline powder 4.0kg, sepiolite 2.0kg, weigh, prepare burden, above-mentioned raw materials is poured in the kneader that can heat, start stirs evenly, evenly adding temperature is 90 ℃, asphalt content is 50% coal tar 18kg, under 90 ℃ of conditions, mixes 10min;
2, blank is added in extrusion machine, be squeezed into cylindric, coal tar in this process compound permeates equably to the organization internal of hardwood flour, the compositions such as the grease in coal tar, hardwood flour and lignin, have very large cohesiveness, wood powder are easy to compacted, from extrusion die orifice, extrude cylindrical molding, by the cutting knife near the setting of overflow mould periphery, cut off again, the work in-process that obtain, work in-process improve physical strength in air-dry mode;
3, by work in-process at N
2in carry out charing, carbonization time 90min, 550 ℃ of carbonization temperatures (constant temperature 30min), then use steam-activation treatment 120min at 800 ℃, obtain cylindric product.After testing, product is 199ml/g to the adsorptive value of methylene blue; Iodine sorption value 997mg/g; Specific surface area 869m
2 / g; Machinery abrasive wear resistance 97%.
Embodiment 2
1,120 orders are dried to moisture lower than 3% with thin walnut shell flour, the component of pressing walnut shell flour 91.5kg, lignin powder 5.5kg, wilkinite 1.0kg, tourmaline powder 1.0kg weighs, batching, above-mentioned raw materials is poured in mixing machine, and start is stirred, and fully mixes, after about 10min, be sprayed into prepare in advance containing 10% PVA aqueous solution 10kg, continue to stir discharging after 15min, cross 24 mesh sieves, in enclosed space, spread out and display 24h, and stir once every 6 ~ 8h;
2, old blank is crossed after 24 mesh sieves, added in the mold cavity of Bidirectional-pressure type hydraulic machine, under 40MPa pressure, be slowly forced into after top pressure, pressurize 35s, slower release of pressure, obtain discoid work in-process; As mould upper and lower surface is carved with pattern, can suppress the base substrate with solid pattern;
3, dried work in-process are placed in to N
2in rare gas element, 500 ℃ of charings 1.5 hours, then passing under water vapor conditions, in 800 ℃ of activation 2 hours, obtaining iodine sorption value was 980.8mg/g, and methylene blue adsorption value is 109mL/g, and specific surface area can reach 899m
2the product of/g;
4, product is loaded onto to frame, can make art wall dish or mural painting, become the product that has environmental protection effect and artistic value concurrently.
Embodiment 3
1, by 200 orders with thin, moisture lower than 3% low ash content a little less than cohesiveness datong bitumite 90kg, tourmaline powder (be crushed to particle that particle diameter is less than 1 μ m account for 90wt% more than) 6.0kg, moisture lower than 3%, 325 orders with thin wilkinite 2.5kg, hydroxypropyl level methylcellulose gum powder 1.5kg, pack in mixing machine and fully mix, obtain blank; Take 0.65kg Xylo-Mucine simultaneously, be dissolved in the water of 12.35kg, be mixed with the aqueous solution containing CMC5%, as being configured as binding agent;
2, get the above-mentioned base powder of 10.0kg, evenly spray into 1.0kg mass concentration and be 5% sodium carboxymethyl cellulose solution, cross 24 mesh sieves, obtain particulate material.With oil press by particulate material briquetting, more broken, sieve, make the particle of 0.5mm left and right, as the master batch of rolling balling;
3, in granulating disc, pour seed into; machine; it is 5% sodium carboxymethyl cellulose solution that atomization sprays into concentration; evenly be sprinkled into the base powder having mixed; rolling balling, will spray water repeated multiple times to dusting technique, spherolite be rolled large to certain particle size; can from tablets press, unload work in-process and sieve, dry for standby.This operation approximately consumes 5% sodium carboxymethyl cellulose solution 12kg;
4, by work in-process at N
2in with the heat-up rate of 6 ℃/min, carry out charing, and at 600 ℃ of constant temperature 60min of temperature, then in steam atmosphere, activate, 850 ℃ of 8 ℃/min of heat-up rate, activation temperatures, constant temperature time 60min, obtains iodine sorption value 901mg/g, specific surface area 312 m
2ball shape active carbon/tourmalinite composite prod of/g, mechanical abrasive wear resistance 93%.
Embodiment 4
1, take 100 orders with thin ash content lower than 10% weak cohesiveness datong bitumite 71.5kg, tourmalinite 10.0kg, 325 orders are with thin ball clay 2.0kg, hydroxypropyl level methylcellulose gum 2.5kg, packs in ball mill and pulverizes, mixes 120min;
2, blank operation 1 being mixed is poured in kneader, machines, and stirs evenly after several minutes, and atomization sprays into 29.0kg water, after stirring, adds successively tung oil 5.0kg, glycerine 2.0kg, rape oil 7.0kg, continues to stir 15min; After discharging, add in vacuum deairing machine to extrude, rub and practice and homogenizing, degassed processing, be extruded into after mud section in airtight, moistening space more than old 24h;
3, the mud section after old is placed in to fluid pressure type vacuum-extruder wet method and extrudes into 60 object green honeycomb body, soon put into microwave oven and formalize, through pick post-drying, refine;
4, activated carbon bodies is carried out to charing by the heat-up rate of 3 ℃/min in argon gas, and in 600 ℃ of constant temperature 120min, then in water vapour, the heat-up rate with 6 ℃/min activates, and in 800 ℃ of constant temperature 120min, obtains specific surface area 352 m
2 / g, pore volume 0.211ml/g, the cellular product of X axis ultimate compression strength 10.4mPa.
Embodiment 5
1,take fineness 100 orders with thin low ash content Using Jiaozuo Anthracite Coal 53.0kg, tourmalinite 10.0kg, 325 orders with thin talc clay 1.5kg, rectorite leng 1.5kg, in ball mill, mix 120min, after discharging, pour in kneader and mix, the coal tar 34.0kg that adds while stirring asphalt content 32%, tar stirs 15min again and gets final product discharging after all adding, join immediately vacuum deairing machine and process, extrude into mud section, then in airtight, moistening space old 24h;
2, the mud section after old is packed in vacuum deairing machine, extrude into circular base substrate, after microwave setting, far-infrared rays drying, then cut into satisfactory shape and size;
3, base substrate is placed in to carbonization-activation stove, with N
2 for shielding gas, by the heat-up rate of 4 ℃/min, in 700 ℃ of constant temperature 90min, carry out charing processing, then with the heat-up rate of 6 ℃/min, in CO
2in atmosphere, at 850 ℃ of constant temperature 90min, activate, obtain circular tourmalinite/absorbent charcoal composite material, diameter 10mm, height 10mm, wall thickness 3.5mm product axial compression strength 5.7mPa, specific surface area 298m
2 / g, pore volume 0.183ml/g.
Claims (10)
1. the manufacture method of a gac/tourmaline composite, it is characterized in that: after by weight percentage 53 ~ 97% activated carbon precursor raw material, 1 ~ 34% organism class being helped binder, 1 ~ 10% tourmaline powder, 1 ~ 3% natural clay class raw mineral materials to mix, through being shaped, dry, charing, activation obtain to the adsorptive value of methylene blue is greater than 100ml/g, iodine sorption value is greater than 950mg/g, has the matrix material of degradation capability to being adsorbed pollutent.
2. the manufacture method of matrix material according to claim 1, it is characterized in that: described activated carbon precursor raw material is the organic matter raw material that carbon content is high, comprise one or more in coal, bamboo wood byproduct, stalk, shell, plant processing waste residue, xylogen, coal tar, refinery coke, pitch, resin.
3. the manufacture method of matrix material according to claim 1, is characterized in that: it is a kind of in coal tar, cellulose binder, grease or two kinds that described organism class helps binder.
4. the manufacture method of matrix material according to claim 3, is characterized in that: described cellulose binder is one or more in Xylo-Mucine (CMC), Vltra tears (HPMC), polyvinyl alcohol (PVA); Described grease is one or more in tung oil, soya-bean oil, rapeseed oil, Viscotrol C, sweet oil, glycerine; The content of described coal tar medium pitch is 25 ~ 65w%.
5. the manufacture method of matrix material according to claim 1, is characterized in that: described tourmaline powder is one or more in dravite, elbaite, iron tourmaline.
6. the manufacture method of matrix material according to claim 5, is characterized in that: more than 90% particle diameter of described tourmaline powder is below 2um.
7. the manufacture method of matrix material according to claim 1, is characterized in that: described natural clay class raw mineral materials is one or more in wilkinite, ball clay, rectorite leng, sepiolite, zeolite, attaclay, talc clay.
8. the manufacture method of matrix material according to claim 1, is characterized in that: described charing, activation
Technique be: under nitrogen, argon gas class inert gas environment, carry out charing in 500 ~ 600 ℃, then passing into water vapour, CO
2under condition, in 800 ~ 900 ℃, activate.
9. the product that the manufacture method of matrix material according to claim 1 makes, it is characterized in that: adopt extrusion molding technique to make cylindric, circular, cellular product, adopt rolling forming technology to make form of spherical particles product, adopt dry pressing technique to make tabular product.
10. the product that the manufacture method of matrix material according to claim 9 makes, is characterized in that: the specific surface area of described cylindric product is 869m
2/ g, mechanical abrasive wear resistance are 97%; The axial compression strength of described circular product is that 5.7mPa, specific surface area are 298m
2/ g, pore volume are 0.183ml/g; The surface-area of described cellular product is 352 m
2/ g, pore volume are that 0.211ml/g, X axis ultimate compression strength are 10.4mPa; The specific surface area of described form of spherical particles product is 312 m
2/ g, mechanical abrasive wear resistance are 93%; The specific surface area of described tabular product is 899m
2/ g.
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