CN100462139C - Method of preparing transition metal modified activated carbon for eliminating harmful substance - Google Patents
Method of preparing transition metal modified activated carbon for eliminating harmful substance Download PDFInfo
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Abstract
The making of transitional metal modified active carbon gets copper, ferrous iron and nickel to make into water solution, adding the above three solutions to 50-80 mush active carbon, through dipping, drying and baking in 300-500deg.C inert atmosphere for 4-5 hours, cooling to get the active carbon. The copper, ferrous iron and nickel water solution selects cupric nitrate, ammonium ferric sulfate, and nickel nitrate. The dipping sequence is ferrous salt, nantokite and nickel water solution. It is based on the quantity of the active carbon to decide the weight of water solution, baking for 1-2 hours in 100-120deg.C before baking in inert atmosphere. It can effectively remove hazardous material.
Description
Technical field
The invention belongs to the adsorbent technical field, particularly a kind of method of preparing transition metal modified activated carbon.
Background technology
Along with constant development of economy, the continuous improvement of modern resident living and condition of work, the time of staying of people in indoor environment is growing, and room air pollution causes people's extensive concern day by day to health effects.Interrelated data shows, the city indoor environment is owing to be subjected to the pollution of various chemistry and biotic factor, as a rule, pollution level is also more serious than outdoor, especially indoor in typical place, as be positioned at the building (office building, market and dwelling house etc.) and the newly-decorated room of urban transportation major trunk roads both sides.
Typical indoor air pollutants have formaldehyde, nitrogen oxide, ammonia, benzene series thing, carbon monoxide and other TOVC (TVOC) etc.Wherein, formaldehyde is a kind of colourless irritative gas soluble in water, can absorb through respiratory tract, and its 40% aqueous solution-formalin can absorb through alimentary canal.Long-term contact low dosage formaldehyde can cause chronic respiratory disease, women's paramenia, pregnancy syndrome, causes that neonate's physique reduces, chromosome abnormality, even causes nasopharyngeal carcinoma.High-concentration formaldehyde is all toxic to nervous system, immune system, liver etc.Formaldehyde also has teratogenesis, carcinogenesis.Nitrogen oxide (NOx) is common air pollutants, is often referred to nitric oxide (NO) and nitrogen dioxide (NO
2).The NOx of variable concentrations can have different detrimental effects to the human lung, and is bigger to the harmfulness of Pulmonary Function in Children and respiratory system.Ammonia is colourless and have the gas of intense stimulus smell, it is a kind of alkaline matter, tissue to contact has corrosion and spread effect, can make histone sex change, tissue fat saponification, destroy cell membrane, so mainly the upper respiratory tract to human body has stimulation and corrosiveness, can weaken the resistance of human body to disease.Ammonia enters blood by alveolar after being inhaled into lung easily, combines with hemoglobin, destroys fortune oxygen function, when serious pulmonary edema, ARDS etc. can take place.Also can cause cardiac arrest and breath stopped during excessive concentration by the reflex of trigeminal neuralgia tip.Benzene and derivative thereof are published as the organic pollution with " three cause " effect by the World Health Organization, skin, mucous membrane there is spread effect, can cause that dermatitis, mucosal bleeding, blood platelet and white blood cell reduce, bring out anaemia and leukaemia, cause the nervous centralis spasm, cause metabolic disturbance etc.Benzene is stronger to the male sex to women's hazard ratio, and the women of child-bearing age suck benzene for a long time can cause menstrual disorder, and when the women in pregnancy period contacted benzene, the incidence of disease of complications of pregnancy can significantly increase, even can cause the fetus birth defect.Carbon monoxide (CO) is a kind of gas of colorless and odorless, results from the imperfect combustion of any carbon atoms material.It combines with erythrin rapidly with 250 times oxygen combining powers after being absorbed by the human lung, forms COHB.The general symptom that it produces human body is that headache, fatigue and motoricity descend.When COHB concentration surpasses 60%, can cause the people to go into a coma even death.
Main harmful components are divided into two classes according to sampling and analytical method in the cigarette smoke: gaseous substance and granule phase substance matter.Main harmful components have ammonia, 4 kinds of aromatic amines (1-amido naphthalene, 2-amido naphthalene, 3-amido biphenyl, 4-amido biphenyl), benzo [a] pyrene, 8 kinds of group compounds of aldehydes and ketones (formaldehyde, acetaldehyde, acetone, methacrylaldehyde, propionic aldehyde, crotonaldehyde, methyl ethyl ketone, butyraldehyde), hydrogen cyanide, 7 heavy metal species (Ni, Pb, Cd, Cr, As, Se, Hg), nitrogen oxide (NO, NOBB
XBB), CO, tar, 7 kinds of phenolic compounds (phenol, catechol, resorcinol, hydroquinones, o, m, the p-methylphenol), 4 grow tobacco peculiar N-nitrosamine (NNN, NNK, NAB, NAT), 8 kinds of volatile organic components (pyridine, quinoline, 1,3-butadiene, isoprene, acrylonitrile, benzene, toluene and styrene).Wherein, NNN, the NNK in benzo [a] pyrene, the peculiar N-nitrosamine of tobacco is important carcinogen.
The control technology of indoor pollution mainly comprises: pollute source control technology, aeration technology, adsorption technology, photocatalysis oxidation technique and houseplant regulation technology etc.The characteristic of pollutant (as the chronicity that formaldehyde, benzene series thing, ammonia etc. discharge, the property at any time that NOx discharges) has determined the imperfection of only polluting from source control, also need be remedied by other measure; And aeration technology should satisfy the quality that resh air requirement when ventilating also will guarantee outdoor air simultaneously, can only play the dilution buffer effect, do not destroy pollutant, even outdoor air also may become new air pollution source sometimes; The application purpose of photocatalysis oxidation technique mainly is a deodorizing sterilizing, and this technology exists catalysqt deactivation and catalyst to solidify problems such as back catalytic efficiency reduction, therefore also is subjected to certain limitation in use.Therefore, adsorption technology is effective, adjustable, reliable control technology commonly used in the present room air pollution control.Environmental Protection Agency (USEPA) thinks that adsorption technology is another effective measures except that ventilation, pollution sources control aspect the control room air pollution, it can also make valuable raw material reclaim when removing pollutant.Common adsorbent has activated carbon granule, NACF, zeolite molecular sieve, adobe ore, activated alumina, silica gel etc. at present, above-mentioned adsorbent or exist adsorptive selectivity strong, based on physical absorption easy desorption (as active carbon), or be subjected to the easy inactivation of moisture effects (as silica gel), adsorption capacity not strong, or the higher and industrial mass manufacture difficulty of cost is bigger etc., is subjected to certain restriction in actual applications.
Aspect the cigarette harm reduction, more domestic research units have carried out the research that certain applications new technology and new material reduce harmful components in the cigarette smoke, as the technology that reduces free radical in the cigarette smoke, use the technology that contains the nano-noble metal catalysis material and reduce CO in the cigarette smoke, utilize the Modified NaY molecular sieve reduce the cigarette smoke harmful components technology, use technology that Chinese herbal medicine and natural botanical extraction liquid reduce cigarette harm, utilize nano composite oxide and mesic hole compound to reduce the technology etc. of cigarette smoke harmful components.Said method, because of some material price costliness, be difficult to preparation, or because of some technology harm reduction effect not very not obviously, promotional value is not high, or the industrial mass manufacture difficulty is bigger or the like, should be effective and fail really to be used widely and obtain.
Summary of the invention
The object of the invention is to provide a kind of industrialized method of preparing transition metal modified activated carbon that is easy to.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: eliminate the method for preparing transition metal modified activated carbon of harmful substance, comprise the steps: that (1) gets copper, water soluble salt ferrous and nickel is configured to the aqueous solution respectively; (2) 50-80 purpose active carbon is added in the perferrite solution, make active carbon absorb perferrite solution fully, then in 100-120 ℃ of oven dry 1-2 hours; (3) step (2) processed active carbon is added copper salt solution, make active carbon absorb copper salt solution fully, then in 100-120 ℃ of oven dry 1-2 hours; (4) step (3) processed active carbon is added nickel salt aqueous solution, make active carbon absorb nickel salt aqueous solution fully, then in 100-120 ℃ of oven dry 1-2 hours; Then in inert atmosphere in 300-500 ℃ of roastings 4-5 hours, cooling obtains transition metal modified active carbon.
Copper, water soluble salt ferrous and nickel are selected copper nitrate, iron ammonium sulfate, nickel nitrate respectively.
Is according to determining the metal oxide loading with the amounts of activated carbon, and then the water soluble salt quality of definite copper, ferrous and nickel, be configured to the aqueous solution respectively; Add the active carbon dipping, make active carbon absorb institute's water distribution solution fully; Then in 100-120 ℃ of oven dry 1-2 hours.
In the dipping process,, take out active carbon oven dry back repeated impregnations if active carbon can not all absorb the aqueous solution.
With the active carbon is carrier, and the metal oxide loading is 20-50% (wt/wt).
The metal oxide loading is 20-50% (wt/wt), and the mol ratio of the oxide of copper, ferrous and nickel is (1-2): (1-2): (1-2).
The present invention is carrier with the active carbon, is acceptor with the transition metal that contains unoccupied orbital, prepares transition metal modified activated carbon.The transition metal modified activated carbon cost that utilizes the present invention to prepare low (50,000 yuan/ton, make a self-control filtering material that is used for air cleaning, only need 25 gram modified activated carbons, only the modified activated carbon cost needs 1.25 yuan; Make a cigarette filter, needing needs to increase cost 0.2625 minute with 35.00 milligrams of modified activated carbons), absorption property is good; Preparation technology is simple, and does not need large-scale special equipment, helps industrialization promotion and uses.
The single tube catalytic reaction evaluating apparatus that adopts the design of Beijing Petroleum Chemical Engineering Institute to produce is estimated the absorption property of the transition metal modified activated carbon of the inventive method preparation.The method preparation that mist adopts CO and air to mix, the gas concentration of reactor inlet and outlet utilizes on-line gas chromatography to carry out online detection, testing result is estimated the absorption property of transition metal modified activated carbon with the clearance of harmful substance CO, the results are shown in table 1.
The influence of table 1 kinds of transition metals and composite CO absorption property to modified activated carbon thereof
* the active component loading is 30.0% (wt/wt)
Table 1 shows, the composite obvious adsorption capacity of transition metal modified activated carbon to CO that improved of transition metal.From detecting result of the test as can be known, to the power of CO adsorption capacity be: three kinds of transition metal modified activated carbons that transition metal is composite〉two kinds of composite transition metal modified activated carbons of transition metal〉single transition metal modified activated carbon.Simultaneously, from the data of table 1 as can be seen, when three kinds of composite transition metal ratios of transition metal are 1:1:1 (mol/mol/mol), absorption property the best of modified activated carbon, this may with since different transition metal coexist at carrier surface, interact easily, thereby its surface chemistry that influences each other is relevant with physical property.
Utilize the transition metal modified activated carbon of the inventive method preparation, pack in the round venting bags, and be installed on the commercially available ventilation fan gas passage with homemade fixed mount, make air cleaning unit (use choose conventional active carbon compare), measure air-polluting effect in the transition metal modified activated carbon decontamination chamber with quadrat method.Detect test and entrust environmental monitoring central station in Henan Province's to carry out, select the ventilation fan of 100mm internal diameter, the modified activated carbon consumption is 25g.Under close condition, 40 minutes (door and window is closed) of indoor circulation ventilation measured formaldehyde in indoor air, ammonia, benzene and TVOC, the results are shown in table 2.
Table 2 gained transition metal modified activated carbon of the present invention is eliminated the measurement result of room air pollution performance
As shown in Table 2, after the transition metal modified activated carbon filtration, formaldehyde in indoor air reduction by 75.6%, ammonia reduction by 78.4%, benzene reduction by 36.3%, TVOC reduce by 34.9%, four kinds of selected room air target contaminants all reduce significantly, and illustrate that prepared transition metal modified activated carbon has air-polluting performance in the good decontamination chamber.Simultaneously as can be seen, compare with commercially available conventional active carbon (formaldehyde reduction by 60.9%, ammonia reduction by 56.8%, benzene reduction by 12.7%, TVOC reduce by 15.9%), transition metal modified activated carbon has the ability of stronger decontamination chamber internal contamination.Analyze reason, may be relevant with its surperficial modification, promptly change Surface Physical and chemical property, make the absorption property of modified activated carbon and selection adsorption capacity that very big change all take place.
3.0Y X 35000), common forming paper utilize acetate silk (specification:, according to compound ratio=1:1.5 (that is: 10mm+15mm), rod length=100mm, the design specification of circumference=24.3mm entrusts Nantong, Jiangsu Province cigarette material factory to carry out the cigarette filter rod processing.In process of production, according to different modified activated carbon design additions, modified activated carbon is applied on the long tow of every section 15mm (numbering respectively according to the addition difference) equably produces the transition metal modified activated carbon composite filter, be used for the tipping test (filter stick of producing will seal preservation) of cigarette.Utilize the transition metal modified activated carbon composite filter of the different additions of producing, entrust Xinzheng, Henan Xinzheng cigar mill of tobacco group company on " Red-Flag Canal " cigarette, to carry out the cigarette tipping test.The cigarette of being produced is numbered respectively, and extraction does not simultaneously use " Red-Flag Canal " cigarette of modified activated carbon filter stick as detecting contrast.Experiment cigarette sample and contrast cigarette sample are carried out the check and analysis of harmful substance: cigarette smoke tar, CO burst size entrust national tobacco quality supervision and inspection center to measure; The peculiar N-nitrosamine of tobacco burst size entrusts Zhengzhou tobacco research institute to measure in the cigarette smoke.
The addition of transition metal modified activated carbon the results are shown in table 3 to the influence of CO adsorbance in the cigarette smoke in the composite filter tip.
Table 3 transition metal modified activated carbon addition is to reducing the influence of CO in the cigarette smoke
Annotate: 1#: acetate fiber filter tip contrast cigarette;
2#: the composite filter tip cigarette that adds 25mg/15mm transition metal modified activated carbon of the present invention;
3#: the composite filter tip cigarette that adds 35mg/15mm transition metal modified activated carbon of the present invention;
4#: the composite filter tip cigarette that adds 45mg/15mm transition metal modified activated carbon of the present invention.
As shown in Table 3, when transition metal modified active carbon addition increased to 35mg/15mm by 25mg/15mm, the CO decline ratio in the test cigarette smoke increased to 33.3% by 26.0%; But further increase the transition metal modified activated carbon addition to 45mg/15mm, the CO decline ratio in the test cigarette smoke is reduced to 28.7% by 33.3%.Therefore selecting 35mg/15mm is the addition of transition metal modified activated carbon at composite filter.
2, utilize the effect of composite filter tip in the cigarette harm reduction of transition metal modified activated carbon production to list in table 4.
Table 4 transition metal modified activated carbon addition is to reducing the influence of CO in the cigarette smoke
Annotate: 1#: acetate fiber filter tip contrast cigarette;
2#: the composite filter tip cigarette that adds 25mg/15mm transition metal modified activated carbon of the present invention.
Data in the table 4 show, compare with the contrast cigarette, the CO burst size has reduced 5.0mg/ and has propped up (33.3%) in the composite filter test cigarette 2# flue gas of transition metal modified activated carbon preparation, the TSNAs burst size has reduced 4.8ng/ and has propped up (35.2%), illustrates that transition metal modified activated carbon has the performance of harmful components in the good adsorption cigarette smoke; Also can find out simultaneously, the CO burst size has reduced 0.2mg/ and has propped up (1.3%) in the binary compound filter candle test cigarette 3# flue gas of conventional Preparation of Activated Carbon, the TSNAs burst size has reduced 1.9ng/ and has propped up (13.9%), illustrates that transition metal modified activated carbon has stronger adsorption capacity and adsorptive selectivity than conventional active carbon to harmful components in the cigarette smoke.
Used active carbon is decided woods adsorbent charcoal Co., Ltd by Luoyang in the test provides, and adopts crop straws for producing to form, particle diameter 50-80 order, and specific surface is: 230m
2/ gram.
The specific embodiment
According to physical chemistry monolayer adsorption theory,, get oxonium ion O if oxide is done the close individual layer of putting at carrier surface and arranged
2-Radius is 1.40
, then the area that molecule occupied of each oxide is:
(2×R
0 2-)
2×sin60°
＝(2×1.40×10
-10)
2×1/2×3
1/2
＝6.79×10
-20?m
2
1g active carbon (specific surface: 230m then
2/ g) surface is paved with the quality of one deck oxide and is:
230/(6.79×10
-20)×M
MO/No
＝230/(6.79×10
-20)×79.54/(6.023×10
23)
=0.447g (work as M=Cu, MO is a cupric oxide, and its molecular weight M=79.54, No are avogadros constant)
Utilize above-mentioned principle can calculate the theoretical monolayer dispersion amount of different oxides on 50-80 order active carbon, 5:(unit sees the following form: the g/g active carbon)
The theoretical monolayer dispersion amount of table 5 transition metal oxide on active carbon
| Active carbon (50-80 order, 230m 2/g) (g) | CuO (g) | NiO (g) | FeO (g) |
| 1 | 0.447 | 0.420 | 0.404 |
According to the amount that calculates required transition metal oxide, can extrapolate the use amount of different transition metal salts.
Embodiment 1, method of preparing transition metal modified activated carbon, get iron ammonium sulfate 34.66 gram, copper nitrate 20.84 grams, nickel nitrate 25.72 grams by loading 20% (wt/wt) and be mixed with the aqueous solution respectively, with flooding 1 hour in the 50-80 purpose active carbon 100 gram adding ferrous sulfate aqueous ammoniums, take out active carbon in 100-120 ℃ of oven dry 1 hour; The active carbon that last step process is crossed added in the copper nitrate aqueous solution dipping 2 hours then, took out active carbon in 100-120 ℃ of oven dry 2 hours; The active carbon that last step process is crossed adds in the nickel nitrate aqueous solution dipping 2 hours to exchange and reaches balance again, takes out active carbon in 100-120 ℃ of oven dry 1 hour.Through the transition metal modified activated carbon of above-mentioned three step process in inert atmosphere in 300 ℃ of roastings 5 hours, cool off transition metal modified activated carbon.
In embodiment 2, the present embodiment, get iron ammonium sulfate 51.99 gram, copper nitrate 31.26 grams, nickel nitrate 38.57 grams by loading 30% (wt/wt) and be mixed with the aqueous solution respectively, with flooding 1 hour in the 50-80 purpose ` charcoal 100 gram adding ferrous sulfate aqueous ammoniums alive, take out active carbon and dried 1 hour in 100-120 ℃; The active carbon that last step process is crossed added in the copper nitrate aqueous solution dipping 2 hours then, took out active carbon in 100-120 ℃ of oven dry 2 hours; The active carbon that last step process is crossed adds in the nickel nitrate aqueous solution dipping 2 hours to exchange and reaches balance again, takes out active carbon in 100-120 ℃ of oven dry 1 hour.Through the transition metal modified activated carbon of above-mentioned three step process in inert atmosphere in 400 ℃ of roastings 5 hours, cool off transition metal modified activated carbon.Other are with embodiment 1.
In embodiment 3, the present embodiment, get iron ammonium sulfate 86.66 gram, copper nitrate 52.09 grams, nickel nitrate 64.68 grams by loading 50% (wt/wt) and be mixed with the aqueous solution respectively, with flooding 1 hour in the 50-80 purpose active carbon 100 gram adding ferrous sulfate aqueous ammoniums, take out active carbon in 100-120 ℃ of oven dry 1 hour; The active carbon that last step process is crossed added in the copper nitrate aqueous solution dipping 2 hours then, took out active carbon in 100-120 ℃ of oven dry 2 hours; The active carbon that last step process is crossed adds in the nickel nitrate aqueous solution dipping 2 hours to exchange and reaches balance again, takes out active carbon in 100-120 ℃ of oven dry 1 hour.Through the transition metal modified activated carbon of above-mentioned three step process in inert atmosphere in 500 ℃ of roastings 4 hours, cool off transition metal modified activated carbon.Other are with embodiment 1.
The xps testing result of products obtained therefrom of the present invention is found, has above-mentioned three kinds of elements in the sample, the results are shown in Table 6 (electron spectrometer adopts the Britain Axis Ultra of Kratos company x-ray photoelectron spectroscopy).
The xsp measurement result of table 6 activated carbon sample
Claims (7)
1. eliminate the method for preparing transition metal modified activated carbon of harmful substance, it is characterized in that comprising the steps: that (1) gets copper, water soluble salt ferrous and nickel is configured to the aqueous solution respectively; (2) 50-80 purpose active carbon is added in the perferrite solution, make active carbon absorb perferrite solution fully, then in 100-120 ℃ of oven dry 1-2 hours; (3) step (2) processed active carbon is added copper salt solution, make active carbon absorb copper salt solution fully, then in 100-120 ℃ of oven dry 1-2 hours; (4) step (3) processed active carbon is added nickel salt aqueous solution, make active carbon absorb nickel salt aqueous solution fully, then in 100-120 ℃ of oven dry 1-2 hours; Then in inert atmosphere in 300-500 ℃ of roastings 4-5 hours, cooling obtains transition metal modified active carbon.
2. the method for preparing transition metal modified activated carbon of elimination harmful substance as claimed in claim 1 is characterized in that, copper, water soluble salt ferrous and nickel are selected copper nitrate, iron ammonium sulfate, nickel nitrate respectively.
3. the method for preparing transition metal modified activated carbon of elimination harmful substance as claimed in claim 1 or 2, it is characterized in that, is according to determining the metal oxide loading with the amounts of activated carbon, and then the water soluble salt quality of definite copper, ferrous and nickel, be configured to the aqueous solution respectively; Add the active carbon dipping, make active carbon absorb institute's water distribution solution fully; Then in 100-120 ℃ of oven dry 1-2 hours.
4. the method for preparing transition metal modified activated carbon of elimination harmful substance as claimed in claim 1 or 2 is characterized in that, in the dipping process, if active carbon can not all absorb the aqueous solution, takes out active carbon oven dry back repeated impregnations.
5. the method for preparing transition metal modified activated carbon of elimination harmful substance as claimed in claim 1 or 2 is characterized in that, is carrier with the active carbon, and the metal oxide loading is 20-50% (wt/wt).
6. the method for preparing transition metal modified activated carbon of elimination harmful substance as claimed in claim 3, it is characterized in that, the metal oxide loading is 20-50% (wt/wt), and the mol ratio of the oxide of copper, ferrous and nickel is (1-2): (1-2): (1-2).
7. the method for preparing transition metal modified activated carbon of elimination harmful substance as claimed in claim 4, it is characterized in that, the metal oxide loading is 20-50% (wt/wt), and the mol ratio of the oxide of copper, ferrous and nickel is (1-2): (1-2): (1-2).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8119555B2 (en) * | 2008-11-20 | 2012-02-21 | R. J. Reynolds Tobacco Company | Carbonaceous material having modified pore structure |
| GB201112539D0 (en) * | 2011-07-21 | 2011-08-31 | British American Tobacco Co | Porous carbon and methods of production thereof |
| CN102972864B (en) * | 2012-11-26 | 2014-05-07 | 浙江中烟工业有限责任公司 | Preparation method of catalyst for selectively reducing released amount of hydrogen cyanide in mainstream smoke of cigarette |
| CN103506074A (en) * | 2013-08-30 | 2014-01-15 | 蚌埠凤凰滤清器有限责任公司 | Transition metal modified active carbon capable of eliminating harmful materials and preparation method thereof |
| CN103785278B (en) * | 2014-02-19 | 2017-01-04 | 南京工业大学 | A kind of processing method and processing device system of organic amine waste gas |
| CN104841441B (en) * | 2015-04-08 | 2017-09-26 | 昆明理工大学 | The method for preparing catalyst of hydrolysis oxidation coupled method purification HCN a kind of and application |
| CN113796572B (en) * | 2021-09-30 | 2023-05-12 | 湖北中烟工业有限责任公司 | Carbonaceous heat source of carbon heating cigarette and preparation method thereof |
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| SU1054347A1 (en) * | 1982-07-26 | 1983-11-15 | Ленинградский Ордена Октябрьской Революции И Ордена Трудового Красного Знамени Технологический Институт Им.Ленсовета | Process for preparing dimethylsulfoxide |
| CN1692848A (en) * | 2005-06-20 | 2005-11-09 | 南京师范大学 | Modified active carbon fiber used as filtering material to lower toxic matter from cigartte, and its prepn. method |
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| GB1263258A (en) * | 1967-10-10 | 1972-02-09 | Exxon Research Engineering Co | Preparation of heterogeneous catalysts |
| SU1054347A1 (en) * | 1982-07-26 | 1983-11-15 | Ленинградский Ордена Октябрьской Революции И Ордена Трудового Красного Знамени Технологический Институт Им.Ленсовета | Process for preparing dimethylsulfoxide |
| CN1692848A (en) * | 2005-06-20 | 2005-11-09 | 南京师范大学 | Modified active carbon fiber used as filtering material to lower toxic matter from cigartte, and its prepn. method |
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