CN103588202B - A kind of manufacture method of gac/tourmaline composite and obtained product thereof - Google Patents
A kind of manufacture method of gac/tourmaline composite and obtained product thereof Download PDFInfo
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Abstract
The present invention relates to a kind of manufacture method of gac/tourmaline composite and obtained product thereof, by weight percentage by the activated carbon precursor raw material of 53 ~ 97%, the organism class help forming agent of 1 ~ 34%, the tourmaline powder of 1 ~ 10%, after the natural clay class raw mineral materials mixing of 1 ~ 3%, through being shaped, dry, charing, activation obtains and is greater than 100ml/g to the adsorptive value of methylene blue, having high absorbability and having the gac/tourmaline composite product of degradation capability of 950mg/g is greater than to iodine sorption value, product can be made into various shape, be widely used in the formaldehyde in absorption degradation air, benzene, oxynitride, and toxic organic compound and heavy metal ion in water body, have broad application prospects.
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 obtained product thereof.
Background technology
The production of the mankind, life activity, made air, 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 pollution that the surface water and groundwater in many places is all subject in various degree, underground water as the North China of China is subject to chromium, manganese, cadmium, lead waits heavy-metal pollution, 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 multiple cancer village in Basin of Huaihe River, Taihu Lake, Jiangsu and Liaoning, marine site, Shandong, there is the blue-green algae that algae excessive propagation causes or red tide time and again in South China Sea, Toxic putting aside high density etc. in the soil of some factories and miness peripheries, directly threaten the orthobiosis of local people and vegeto-animal existence, factory, vehicular emission volume of smoke, dust in air (PM2.5 suspended substance) and nitrogen, oxysulfide are exceeded standard again and again, the second half of last year is to this year, there is serious haze weather in northern China, and strong carcinogen polycyclic aromatic hydrocarbons, formaldehyde, benzene and other the various volatile organic content in the interior spaces such as family, office, motor vehicle remains high especially ...The topsoil atmosphere of " having difficulties at home and abroad ", various solid, water pollution to deposit and ecotope is day by day impaired, unrepairable, create serious restriction to Sustainable development, constitute direct threat, urgently strengthen improvement to the health of people.
Gac is a kind of porousness, adsorptive functional material, the internal pore structure of tool uniqueness and surface-active functional group, stable chemical nature, acid-and base-resisting, heat-resisting, water insoluble and organic solvent, is widely used in waste water, the adsorptivity improvement of waste gas and the purification of soil, also for the absorption of liquid phase, gas phase, decolouring, deodorizing, refining, be separated, catalytic field, 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 saturated after namely lost efficacy, need manipulation of regeneration.If do not done manipulation of regeneration, secondary pollution can be caused by the Toxic (as formaldehyde, benzene, heavy metal ion etc.) adsorbed; (3) regeneration difficulty, expense is larger; (4) work-ing life is short, and cost recovery is high, and easily produces secondary pollution after discarding.Therefore, be necessary development high strength, degradable Toxic, the pressed active carbon of regeneration certainly can be realized.
Tourmalinite is a kind of natural Mineral with Polar Electricity, can produce negative ion, emitting far-infrared, reduces water clusters, brine electrolysis, and can increase substantially the dissolved oxygen amount (10 ~ 30%) of water, reduce COD, tourmalinite itself has adsorptivity, can by OH-and H
2o is oxidized to the OH hydroxyl radical free radical etc. of extremely strong oxidisability, thus in environment protection treating, important effect is played: the negative ion of tourmalinite release, hydroxyl radical free radical can oxynitride in degradation of formaldehyde, benzene and haze, negative ion has very strong antibacterial, anti-microbial effect to intestinal bacteria, staphylococcus aureus, be conducive to preventing 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, there is absorption, the effect of concentrating, can the heavy metal ion such as absorbing copper, 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, strengthens the oxidation effectiveness to organic pollutant; The far infrared rays of tourmalinite radiation, can reduce water clusters and produce fierce resonance to organism and make it activation, contribute to pollutent collapse loose, clear up.Such as utilize tourmalinite to organic oxidative function, the activation of far infrared rays of launching and collapse loose effect, Yardang landform waste water from dyestuff can be made, the percent of decolourization of Methyl Orange in Wastewater reaches 100%; Tourmalinite also has good activation to carcinogens malachite green, collapses loose, Adsorption and decomposition ability.
The negative ion OH PARA FORMALDEHYDE PRILLS(91,95) that tourmalinite produces, the DeR of oxynitride are as follows respectively:
Tourmalinite and gac compound, can solve that gac can only adsorb to a certain extent can not the problem of degradation of contaminant, and the adsorptivity of adsorption function to gac of tourmalinite itself also has enhancement.
At present, many patented technologies are thermal treatment again after being mixed with tourmalinite by active carbon powder.As patent CN200510045991 " porous ceramic matrix material functional ball and production technique thereof ", provide the method for making of a kind of tourmalinite and gac composite ceramics, but this technique with the gac made for raw material, therefore the problem having twice firing energy consumption higher with discharge, and tourmalinite and C in conjunction with bad (combination compared to tourmalinite and newborn C), do not utilize carbon raw material to carbonize time can the characteristic of the binding agent such as spontaneous tar, cause that product strength is poor, cost is high; Due to by force charcoal-stripped, the moisture of himself weight several times can being adsorbed, to playing the adsorptive capacity of the coal tar that furtherance shape acts on also up to 40%, so use CN200510045991 technology, being difficult to form with wet processing! More cannot prepare the product, particularly honeycombed product of complicated shape with wet method plastic process, and this technology also to consume a large amount of coal tar to guarantee shaping, causes 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 obtained product 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: by weight percentage by the activated carbon precursor raw material of 53 ~ 97%, 1 ~ 34% organism class help forming agent, 1 ~ 10% tourmaline powder, 1 ~ 3% the mixing of natural clay class raw mineral materials after, through being shaped, dry, charing, activation obtain and be greater than 100ml/g to the adsorptive value of methylene blue, iodine sorption value be greater than to 950mg/g, to the matrix material being had degradation capability by the pollutent adsorbed.
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.
Described organism class help forming agent is one in coal tar, cellulose binder, grease or two kinds.
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.
The particle diameter of described tourmaline powder more than 90% is less than 2 μm.
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: carbonize in 500 ~ 600 DEG C under nitrogen, argon gas class inert gas environment, then passing into water vapour, CO
2activate in 800 ~ 900 DEG C under condition.
The product that the manufacture method of above-mentioned matrix material is obtained, it is characterized in that: adopt extrusion molding technique to obtain cylindric, circular, cellular product, adopt rolling forming technology to obtain form of spherical particles product, adopt dry pressing technique to obtain tabular product.
The specific surface area of described cylindrical product is 869m
2/ g, mechanical abrasive wear resistance are 97%; The axial compression strength of described circular product is 5.7mPa, specific surface area is 298m
2/ g, pore volume are 0.183ml/g; The surface-area of described cellular product is 352 m
2/ g, pore volume are 0.211ml/g, X axis ultimate compression strength is 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 with in product performance and result of use:
1, in preparation technology
(1), carbon raw material and tourmalinite are being prepared in the charing of gac, reactivation process by the present invention, complete the sintered combined of the two once, with commonly first carbon raw material to be carbonized, activates obtained gac, compare with the technology of gac+tourmalinite charing, the obtained tourmalinite/active carbon ceramic of activation again, decrease one firing process, energy consumption reduces nearly half with discharge;
(2) due to the low activated carbon precursor raw material production of adsorptivity, therefore the product of complicated shape can be prepared with wet processing, as honeycombed product.Avoiding patent CN200510045991 " porous ceramic matrix material functional ball and production technique thereof ", the limitation of wet production can not be used because adopting the high gac of adsorptivity to be raw material;
(3), utilize carbon raw material decomposable asymmetric choice net when carbonizing discharge of the coke wet goods jelly, produce the characteristic of the newborn C of high reactivity, must not add or only need add a small amount of tar, product can be made to 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 being similar to chemical activation gac, and avoid and conventional prepare gac with chemical method, need ZnCl be added
2, industrial chemicals that KOH etc. is expensive, the deficiency that produces chemical pollution, need to wash etc. the gac prepared;
(5) natural mineral (comprising wilkinite, ball clay, rectorite leng, sepiolite), containing nanoparticle 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, have active effect to extrusion molding (such as preparing ceramic honey comb), the nanoparticle that wilkinite, ball clay, rectorite leng, sepiolite contain has certain promoter action to low-temperature sintering;
2, in product performance and result of use
(1), the tourmalinite/active carbon ceramic obtained after charing, activation of activated carbon precursor raw material+tourmalinite, than higher with gac+tourmalinite charing, the obtained tourmalinite/active carbon ceramic intensity of activation, wear resistance, not fragile in application;
(2), after tourmalinite and gac compound, the adsorptive power that gac is superpower, makes product can adsorb high density pollution thing in use; And tourmalinite is except can helping absorption, the organic pollutant by adsorbing more can be made to be degraded, heavy metal ion is reduced, and the far infrared rays of tourmalinite radiation, can reduce water clusters and produce fierce resonance to organism and make it activation, 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, and obtained product performance are superior, stable performance, strong to being had degradation capability, suitability by the pollutent adsorbed, and therefore has fabulous economy and social value.
Embodiment
Embodiment 1
1, particle diameter 100 order is dried to moisture as 7.5% with thin hardwood wood chip, xylogen, weigh by the component of hard wood dust 72kg, xylogen 4.0kg, tourmaline powder 4.0kg, sepiolite 2.0kg, prepare burden, above-mentioned raw materials is poured in the kneader that can heat, start stirs evenly, evenly adding temperature is 90 DEG C, asphalt content is the coal tar 18kg of 50%, under 90 DEG C of conditions, mix 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, cylindrical molding is extruded from extrusion die orifice, cut off by the cutting knife arranged near overflow mould periphery, the work in-process obtained, work in-process make physical strength improve in air-dry mode again;
3, by work in-process at N
2in carbonize, carbonization time 90min, carbonization temperature 550 DEG C (constant temperature 30min), then uses steam-activation treatment 120min at 800 DEG C, obtains cylindrical 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, weigh by the component of walnut shell flour 91.5kg, lignin powder 5.5kg, wilkinite 1.0kg, tourmaline powder 1.0kg, prepare burden, poured into by above-mentioned raw materials in mixing machine, 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, spread out in enclosed space and display 24h, and stir once every 6 ~ 8h;
2, after old blank being crossed 24 mesh sieves, add in the mold cavity of Bidirectional-pressure type hydraulic machine, under 40MPa pressure, after being slowly forced into top pressure, pressurize 35s, slower release of pressure, obtain discoid work in-process; As mould upper and lower surface is carved with pattern, then can suppress the base substrate with solid pattern;
3, dried work in-process are placed in N
2in rare gas element, 500 DEG C of charings 1.5 hours, then passing under water vapor conditions, in 800 DEG C 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 frame, art wall dish or mural painting can be made, become the product having environmental protection effect and artistic value concurrently.
Embodiment 3
1, by 200 orders with thin, moisture lower than 3% low ash content weak cohesiveness datong bitumite 90kg, tourmaline powder (be crushed to the particle that particle diameter is less than 1 μm and account for more than 90wt%) 6.0kg, moisture lower than 3%, 325 orders with thin wilkinite 2.5kg, hydroxypropyl level methylcellulose gum powder 1.5kg, load 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 the sodium carboxymethyl cellulose solution that 1.0kg mass concentration is 5%, cross 24 mesh sieves, obtain particulate material.With oil press by particulate material briquetting, more broken, sieve, the particle of obtained about 0.5mm, as the master batch of rolling balling;
3, in granulating disc, seed is poured into; machine; atomization sprays into the sodium carboxymethyl cellulose solution that concentration is 5%; evenly be sprinkled into the base powder 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 about consumes the sodium carboxymethyl cellulose solution 12kg of 5%;
4, by work in-process at N
2in carbonize with the heat-up rate of 6 DEG C/min, and at temperature 600 DEG C of constant temperature 60min, then to activate in steam atmosphere, heat-up rate 8 DEG C/min, activation temperature 850 DEG C, constant temperature time 60min, obtain iodine sorption value 901mg/g, specific surface area 312 m
2ball shape active carbon/tourmalinite the 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, and hydroxypropyl level methylcellulose gum 2.5kg, loads in ball mill and carry out pulverizing, mixing 120min;
2, pour in kneader by the blank that operation 1 mixes, machine, after stirring evenly several minutes, atomization sprays into 29.0kg water, after stirring, adds tung oil 5.0kg, glycerine 2.0kg, rape oil 7.0kg successively, continues to stir 15min; Namely add after discharging in vacuum deairing machine carry out extruding, rub practice and homogenizing, degassed process, to be extruded into after mud section old more than 24h in airtight, moistening space;
3, the mud section after old is placed in 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 carbonized by the heat-up rate of 3 DEG C/min in argon gas, and in 600 DEG C of constant temperature 120min, then activate with the heat-up rate of 6 DEG C/min in water vapour, in 800 DEG C of constant temperature 120min, obtain specific surface area 352 m
2 the cellular product of/g, pore volume 0.211ml/g, X axis ultimate compression strength 10.4mPa.
Embodiment 5
1,take fineness 100 order 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, 120min is mixed in ball mill, pour in kneader after discharging and mix, add the coal tar 34.0kg of asphalt content 32% while stirring, stir 15min after tar all adds again and get final product discharging, join vacuum deairing machine process immediately, extrude into mud section, then in airtight, moistening space old 24h;
2, the mud section after old is loaded 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 carbonization-activation stove, with N
2 for shielding gas, by the heat-up rate of 4 DEG C/min, in 700 DEG C of constant temperature 90min, carry out charing process, then with the heat-up rate of 6 DEG C/min, in CO
2in atmosphere, activate at 850 DEG C of constant temperature 90min, 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 gac/tourmaline composite, it is characterized in that: by weight percentage by the activated carbon precursor raw material of 53 ~ 97%, 1 ~ 34% organism class help forming agent, 1 ~ 10% tourmaline powder, 1 ~ 3% the mixing of natural clay class raw mineral materials after, through being shaped, dry, charing, activation obtain and be greater than 100ml/g to the adsorptive value of methylene blue, iodine sorption value be greater than to 950mg/g, to the matrix material being had degradation capability by absorb polluted matter.
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 coal, bamboo wood byproduct, stalk, shell, plant processing waste residue, xylogen, coal tar, refinery coke, pitch, one or more in resin.
3. the manufacture method of matrix material according to claim 1, is characterized in that: described organism class help forming agent is one in coal tar, cellulose binder, grease or two kinds.
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, Vltra tears, polyvinyl alcohol; 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: the particle diameter of described tourmaline powder more than 90% is less than 2 μm.
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: carbonize in 500 ~ 600 DEG C under nitrogen, argon gas class inert gas environment, then passing into water vapour, CO
2activate in 800 ~ 900 DEG C under condition.
9. the manufacture method of matrix material according to claim 1, it is characterized in that: described matrix material adopts extrusion molding technique to obtain cylindric, circular, cellular product, adopt rolling forming technology to obtain form of spherical particles product, adopt dry pressing technique to obtain tabular product.
10. the manufacture method of matrix material according to claim 9, is characterized in that: the specific surface area of described cylindrical product is 869m
2/ g, mechanical abrasive wear resistance are 97%; The axial compression strength of described circular product is 5.7MPa, specific surface area is 298m
2/ g, pore volume are 0.183ml/g; The surface-area of described cellular product is 352 m
2/ g, pore volume are 0.211ml/g, X axis ultimate compression strength is 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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