CN1720067A - Nano carbon ball for deodorization - Google Patents

Nano carbon ball for deodorization Download PDF

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Publication number
CN1720067A
CN1720067A CNA038257270A CN03825727A CN1720067A CN 1720067 A CN1720067 A CN 1720067A CN A038257270 A CNA038257270 A CN A038257270A CN 03825727 A CN03825727 A CN 03825727A CN 1720067 A CN1720067 A CN 1720067A
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nano carbon
carbon balls
metal
balls
shell
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CN100363060C (en
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宋俊烨
金钟润
朴承圭
俞宗成
朴容起
李哲伟
姜润锡
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LG H&H Co Ltd
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LG Household and Health Care Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A61L9/012—Deodorant compositions characterised by being in a special form, e.g. gels, emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A61L9/014—Deodorant compositions containing sorbent material, e.g. activated carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Abstract

The present invention provides a carbon nanoball for deodorization composed of porous carbon shells having a spherical hollow core. At least one metal selected from the group consisting of transition metal, oxidized transition metal and alkali metal salt is impregnated to the shell. This carbon nanoball for deodorization may adsorb various kinds of malodor substances together with good deodorizing capability. Thus, the carbon nanoball may give excellent deodorizing effects by capturing and resolving the malodor substances when it used as a deodorant for various daily necessaries or in houses, offices, industrial facilities and other various stinking circumstances.

Description

Be used for the deodorant Nano carbon balls
Technical field
The present invention relates to a kind of deodorant Nano carbon balls that is used for, more specifically, the present invention relates to a kind of Nano carbon balls of metal impregnation, this Nano carbon balls is made up of the porous carbon shell with spherical hollow, and is used to deodorization.
Background technology
Generally speaking, various bad smells are to produce from article of everyday use such as refrigerator, air-conditioning, diaper, sanitary pad, medicated cigarette, shoe chest, wardrobe and daily life place such as bedroom, washroom and garage.In addition, bad smell also can produce the waste gas from motor vehicles and commercial plant such as garbage disposal plant, waste water treatment plant and factory.The representative materials that produces bad smell is as follows: methanthiol, methyl sulfide, dimethyl disulfide, hydrogen sulfide, ammonia, trimethylamine, acetaldehyde, nitric oxide, nitrous oxide, styrene or the like.
Equally, in order to eliminate these bad smells, people have developed various deodorizer.
Recently, a kind of method that is used to prepare Nano carbon balls has been proposed, this Nano carbon balls by the porous carbon shell with spherical hollow form (Adv.Mater.2002,14, no.1, January4).This Nano carbon balls is compared with traditional active carbon deodorizer, and its advantage is to adsorb a greater variety of odorants.Yet this Nano carbon balls has certain limitation, promptly after it adsorbs a certain amount of odorant, just can not adsorb more odorant.In addition, there is a limited capacity in above-mentioned Nano carbon balls aspect deodorization.
Summary of the invention
In order to solve the above-mentioned shortcoming of prior art, therefore, the object of the present invention is to provide a kind of Nano carbon balls, this Nano carbon balls has fabulous deodoriging properties, and can adsorb multiple odorant.
To achieve these goals, the invention provides a kind of deodorant Nano carbon balls that is used for, this nanosphere comprises the porous carbon shell with spherical hollow, wherein, will be selected from least a metal impregnation in the group of being made up of transition metal, transition metal oxide and alkali metal salt in this shell.
Preferably, transition metal is to be selected from a kind of in the group of being made up of copper (Cu), ferrum (Fe), manganese (Mn), nickel (Ni), cobalt (Co), silver (Ag), gold (Au), vanadium (V), ruthenium (Ru), titanium (Ti), chromium (Cr), zinc (Zn) and palladium (Pd), and alkali metal salt is to be selected from by sodium bromide (NaBr), sodium iodide (NaI), potassium bromide (KBr), potassium iodide (KI) and potassium iodate (KIO 3) a kind of in the group formed.
Description of drawings
In following detailed description, these and other feature, aspect and the advantage of the preferred embodiment of the present invention have been carried out more comprehensively describing with reference to accompanying drawing.In the accompanying drawings:
Fig. 1 is that explanation is according to the sketch map that is used to prepare deodorization with the method for Nano carbon balls of the present invention; And
Fig. 2 and Fig. 3 illustrate deodorization according to the present invention with the deodorizing effect curve chart of Nano carbon balls to ammonia and methanthiol.
The specific embodiment
Hereinafter, embodiments of the invention are described, yet the present invention is not limited to following examples, and can makes amendment by different way within the scope of the invention.
Nano carbon balls of the present invention has and comprises the hollow and spherical carbon structure porous shell.For shell, dipping transition metal, transition metal oxide, alkali metal salt or its mixture.What form in the shell mesoporously not only can adsorb various odorants, can also chemisorbed and destroy odorant and in order to deodorization.This impregnated activated carbon that is used for 1999-80808 number disclosure of deodorant Nano carbon balls and Korea S's publication publication of the present invention is compared, and has better deodoriging properties.In other words, because activated carbon has micropore, when deodoring materials was flooded, these holes may get clogged and slacken its deodoriging properties.Yet because the deodorant Nano carbon balls that is used for of the present invention has mesoporously at shell, suchlike problem just can not occur.In addition,, obviously be different from impregnated activated carbon, so odorant floods between the deodoring materials with the shell inner surface and has enough times of contact because odorant is used for the hollow of deodorant Nano carbon balls and is hunted down of the present invention.In addition, when being dispersed into the outside by the catabolite that deodoring materials produced, Nano carbon balls of the present invention can prevent the secondary pollution that caused.
With reference to Fig. 1, will be used to prepare deodorization with the method for Nano carbon balls according to of the present invention
Embodiment is described in detail.
At first, preparation spherical silica core 1.Silica core 1 can be according to known Stober method (Stober, W.; Fink, A.; Bohn, E.J.Colloid Inter.Sci.1968,26,62) make by silica precursor such as quanmethyl silicate and tetraethyl orthosilicate.Preferred 10～1,000 nanometer (nm) of silica core core diameter.
Subsequently, in solvent, by utilizing silica precursor and surfactant, on the surface of silica core 1, generate shell 2, for example, this surfactant is the alkyl trimethoxysilane that is expressed as following Chemical formula 1, the alkyl triethoxysilane that is expressed as following Chemical formula 2, the alkyl trimethyl ammonium halide that is expressed as following chemical formula 3, the alkyl polyoxyethylene glycol that is expressed as following chemical formula 4 and the glycerol ethoxylate that is expressed as following chemical formula 5.
Chemical formula 1
R 1R 2R 3R 4Si(OCH 3) 3
In Chemical formula 1, R 1, R 2And R 3Be methyl, and R 4Be that carbon number is 12 to 22 alkyl.
Chemical formula 2
R 1R 2R 3R 4Si(OC 2H 5) 3
In Chemical formula 2, R 1, R 2And R 3Be ethyl, and R 4Be that carbon number is 12 to 22 alkyl.
Chemical formula 3
R 1R 2R 3R 4NX
In chemical formula 3, R 1, R 2And R 3Be methyl or ethyl independently, R 4Be that carbon number is 12 to 22 alkyl, and X is a halogen.
Chemical formula 4
R(OCH 2CH 2) nOH
In chemical formula 4, R is that carbon number is 12 to 22 alkyl, and n is the integer between 3 to 20.
Chemical formula 5
CH 2(CH 2O) n1HCH(CH 2O) n2HCH 2(CH 2O) n3H
In chemical formula 5, n 1, n 2And n 3Be the integer between 4 to 20 independently.
Secondly, the product with shell carries out selective filter, and carries out roasting under as 500～600 ℃, so that remove surface active agent composition.Then, obtain having the granule 10 of silica shell 3, wherein mesoporously form in the removal of surfactant position and have a specific size.Can recently control the size of mesoporous (mesoporous pore) and the thickness of shell by the kind and the molecule that change kinds of surfactants, silica precursor.Preferably, the porous carbon shell thickness is 50～500 nanometers.
Then, the monomer 11 that can form polymer injects in mesoporous in the shell as acrylonitrile, phenol formaldehyde (PF) and divinylbenzene.Monomer carried out polymerization to form carbon precursor and form the granule 10 that contain silica shell thereafter.Preferably, monomer utilizes polycondensation or Raolical polymerizable to carry out polymerization.In addition, in Raolical polymerizable, monomer fully mixes with radical initiator and injects the mesoporous of silica dioxide granule, then according to monomeric characteristic aggregation.At this moment, with regard to radical initiator, can use as azodiisobutyronitrile (AIBN), peroxide acetic acid butyl ester, benzoyl peroxide, acetyl peroxide and lauryl peroxide.This polyreaction is being known in the art, and preferably carries out polyreaction 12 hours under 60～130 ℃, contains the silicon dioxide structure of polymer with manufacturing.
Then, contain the silicon dioxide structure of polymer (or, carbon precursor), in nitrogen atmosphere, handle down, make silicon dioxide structure contain carbonized polymers 13 at about 1,000 ℃.Thereafter, by the silicon dioxide structure of hydrofluoric acid solution or sodium hydroxide/ethyl alcohol mixed solution etching carbonization, and obtain spheric Nano carbon balls 20 and porous carbon shell, this Nano carbon balls has spherical hollow 15.
Thereafter, according to the present invention, Nano carbon balls 20 is immersed in the solution of being made up of transition metal, transition metal oxide, alkali metal salt or its mixture, and at room temperature soaked 2～3 days, filtration and dry under 70～110 ℃ then is to obtain the Nano carbon balls of metal impregnation.With regard to the transition metal or transition metal oxide that can be used to flood shell, can use copper (Cu), ferrum (Fe), manganese (Mn), nickel (Ni), cobalt (Co), silver (Ag), gold (Au), vanadium (V), ruthenium (Ru), titanium (Ti), chromium (Cr), zinc (Zn) and palladium (Pd) or their oxide.With regard to alkali metal salt, also can use sodium bromide (NaBr), sodium iodide (NaI), potassium bromide (KBr), potassium iodide (KI) and potassium iodate (KIO 3).The metal of certain pickup can GOLD FROM PLATING SOLUTION belongs to concentration or time of penetration is controlled by changing, and preferably, is benchmark with the gross weight that is used for the deodorant Nano carbon balls, and tenor is 0.01～30wt% (weight).
Can provide one or more metals in the above-mentioned metal according to the Nano carbon balls of metal impregnation of the present invention.Therefore, according to the Nano carbon balls deodorizer that contains metal impregnation of the present invention, can prepare by different way or form according to bad smell or its usage.For example, deodorizer can contain Nano carbon balls, and this nanosphere may only flood a kind of metal, or floods two kinds of different kinds of metals, perhaps two or more metals.
Nano carbon balls according to metal impregnation of the present invention can be used to deodorization and eliminate multiple material odorous, as the indoor bad smell and the Nicotiana tabacum L. abnormal smells from the patient of washroom, kitchen or shoe chest in methanthiol, methyl sulfide, dimethyl disulfide, hydrogen sulfide, ammonia, trimethylamine, styrene, acetaldehyde, nitric oxide, nitrous oxide, the generation self-housing.Like this, it also has fabulous effect aspect bad smell of eliminating refrigerator, air-conditioning, air purifier, garage, automobile exhaust gas and human body.
In addition, to can carry out homodisperse according to the Nano carbon balls of metal impregnation of the present invention and adhere to a laminar bag or pad, it can be applied to like this such as the baby suffer from patient's the diaper of incontinence or the women with the such commodity that utilize this class material of sanitary pad.
Embodiment 1-4
Preparing spherical SiO 2 is to utilize tetraethyl orthosilicate to make as silica precursor according to known Stober method.At this moment, tetraethyl orthosilicate is added into and octadecyl trimethoxy silane (C 18-TMS) one react, filter then to obtain silica dioxide granule.Silica dioxide granule 550 ℃ of following heat treatments 5 hours, so that in the position of removal of surfactant, is formed the mesoporous of certain size.Then, divinylbenzene is fully mixed with radical initiator azodiisobutyronitrile (AIBN), inject the mesoporous of silica dioxide granule then,, comprise the silicon dioxide structure of polymer with formation then 130 ℃ of following polyreactions 12 hours.And then, the silicon dioxide structure that contains polymer in nitrogen atmosphere in 1,000 ℃ of following carbonization to form the complex of carbon/silicon dioxide.Subsequently, this carbon/silica composite is put into the inorganic structure of Fluohydric acid. with removal carbon/silica composite, thereby obtain a kind of Nano carbon balls, this Nano carbon balls has spherical carbon structure, and it contains hollow and the porous shell.
, in order to flood as shown in table 1 below metal, will with Nano carbon balls that said method make in the metallic solution of 1N flood 50 hour, filter then and under 70 ℃, carry out drying, obtain the Nano carbon balls of metal impregnation so thereafter.
In the Nano carbon balls A～H of metal impregnation, A, D, E and the H of 0.01 gram are selected as embodiment 1～4 respectively.
Table 1
The impregnating metal type (impregnating metal content, %)
A Copper (1.3)+manganese (0.3)
B Nickel (3.1)+ferrum (0.8)
C Gold (0.8)+chromium (0.9)+palladium (0.8)
D Copper (3.1)+ferrum (0.8)+zinc (0.8)
E Potassium iodide (3.4)
F Silver (4.2)
G Cobalt (2.1)+potassium iodate (1.3)
H Vanadium (2.1)+ruthenium (0.3)+titanium (0.6)
In table 1, metal impregnation amount (%)=weight metal/Nano carbon balls weight * 100.
Comparative example 1
With method same as the previously described embodiments, prepare a kind of Nano carbon balls of not impregnating metal, and take by weighing 0.01 gram Nano carbon balls as a comparative example 1.
Comparative example 2
With method same as the previously described embodiments, prepare a kind of Nano carbon balls of not impregnating metal, and take by weighing 0.1 gram Nano carbon balls as a comparative example 2.
Comparative example 3
Take by weighing 0.1 gram activated carbon (producing) as a comparative example 3 by the Junsei of Japan.
Comparative example 4～8
Take by weighing traditional deodorizer 4-8 as a comparative example of the multiple commercialization of 0.1 gram.
Comparative example 9～12
By the activated carbon of four kinds of metal impregnations (Junsei of Japan produces) as a comparative example 9～12, the activated carbon of these metal impregnations contains respectively with the corresponding identical metal of embodiment 1～4 to be formed.
In order to assess deodorizing effect, trimethylamine, ammonia, methanthiol and acetaldehyde are used as odor source.At first, to put into 250 milliliters transparent vessel as the deodorizer of listed weight in the table 2 respectively, it is 0.1% benzole soln as the methanthiol content of 0.2 milliliter 0.1% ammonia, 0.07 milliliter 1% trimethylamine solution, 0.15 milliliter 1% acetaldehyde solution and 0.12 milliliter that this container contains odorant.Then, with this container of lid sealing, placed 30 minutes, this covers installs the detector tube that is used to measure the odorant residual volume.Then, the change color of gas by seeing through detector tube in the monitoring container and detector tube is measured the capacity of deodorizer.
The efficient of deodorizer (%) is calculated on the basis of result of calculation shown in blank assay and the table 2 according to following formula, and this blank assay is meant to have only odor source, and does not put deodorizer.
Odor removal efficient (%)=[(blank assay detector tube value (ppm)-measuring tube detected value (ppm))/(blank assay detector tube value (ppm))] * 100.
Table 2
Deodorizer (weight) Deodorizing effect (%)
Ammonia Trimethylamine Acetaldehyde Methanthiol
Embodiment 1 Metal impregnation Nano carbon balls (0.01 gram) 78 87 63 90
Embodiment 2 Metal impregnation Nano carbon balls (0.01 gram) 98 94 47 93
Embodiment 3 Metal impregnation Nano carbon balls (0.01 gram) 89 92 54 98
Embodiment 4 Metal impregnation Nano carbon balls (0.01 gram) 88 86 58 92
Comparative example 1 Nano carbon balls (0.01 gram) 43 85 7 29
Comparative example 2 Nano carbon balls (0.1 gram) 80 84 40 91
Comparative example 3 Activated carbon (0.1 gram) 61 58 20 48
Comparative example 4 Beta-schardinger dextrin-(0.1 gram) 15 2 0 0
Comparative example 5 Copper chloride (98%, 0.1 gram) 68 85 4 84
Comparative example 6 Carbazole W7 MCT (0.1 gram) 60 9 12 0
Comparative example 7 Aluminum chloride (0.1 gram) 92 97 0 0
Comparative example 8 Zeolite (0.1 gram) 30 27 8 0
Comparative example 9 Metal impregnation activated carbon (0.01 gram) 76 67 34 68
Comparative example 10 Metal impregnation activated carbon (0.01 gram) 78 58 40 64
Comparative example 11 Metal impregnation activated carbon (0.01 gram) 69 66 47 72
Comparative example 12 Metal impregnation activated carbon (0.01 gram) 70 69 45 70
Can understand like this from table 2, according to embodiments of the invention, at four kinds of odor sources, compare with comparative example, even seldom amount only is 10% (0.01 gram) as consumption, deodorization promptly shows fabulous deodorizing effect with Nano carbon balls.In addition, also can understand like this from table 2, promptly the Nano carbon balls of metal impregnation is at above-mentioned four kinds of odor sources, and deodorizing effect improves about 20% or more.
Embodiment 5
With method preparation four kind metal impregnation Nano carbon balls identical with embodiment 1, metal concentration is as shown in table 3 below respectively.Then, preparation is used for the deodorization filtering agent of refrigerator, and this filtering agent is to utilize polyacrylic polymer to be binding agent, mixes above-mentioned 4 kinds of metal impregnation Nano carbon balls, and makes through further handling, and wherein binding agent accounts for 20% of filtering agent gross weight.In metal impregnation Nano carbon balls I～K, K is chosen as embodiment 5.
Comparative example 13
Comparative example 13 is equal to embodiment 5, and its difference is that the metal impregnation activated carbon is used to the Nano carbon balls in the alternate embodiment 5, and the metal impregnation activated carbon makes by the method for impregnating metal on activated carbon (Junsei of Japan produces).
Table 3
The kind of impregnating metal (pickup of metal, %)
I Copper (1.3)+manganese (0.3)
J Cobalt (2.1)+ferrum (0.8)+zinc (0.3)
K Potassium iodide (3.2)+copper (0.8)
In table 3, the pickup of metal (%)=weight metal/Nano carbon balls weight * 100
The deodorizing effect test is carried out according to listed experiment condition in the following table 4.
When the deodorizing effect test of carrying out ammonia, the deodorization filtering agent in embodiment 5 and the comparative example 13 is respectively got 0.5 gram, put into tubular reactor respectively.Then, ammonia flow is crossed each tubular reactor, then the concentration of waste gas is analyzed gained result such as table 5 and shown in Figure 2.
When the deodorizing effect test of carrying out methanthiol, the deodorizer in embodiment 5 and the comparative example 13 is respectively got 0.01 gram, puts into tubular reactor respectively.Then, methanthiol gas is crossed each tubular reactor, then the concentration of waste gas is analyzed gained result such as table 5 and shown in Figure 3.
At this moment, gas chromatograph or mass spectrograph are used as analyzer, and relative humidity is 50%.
Table 4
Odor source Adsorption temp (℃) Relative humidity (RH) Gas flow rate (ml/min) Adsorbance (gram) Initial vapor concentration (ppm)
Ammonia Room temperature 50％ 600 0.5 500
Methanthiol Room temperature 50％ 100 0.01 50
In order to analyze odor concentration, in comparative example and embodiment, exhaust gas concentration is compared measurement here.Based on ASTM D28 standard method of measurement, carry out the efficient of kinetic test with assessment carbon removal odorous substance.In breakthrough curve, flex point is defined as break through.
Table 5
Deodorization reagent (weight) Odor source Deodorizing effect
Turning point (minute) Flex point place concentration (ppm)
Embodiment 5 Metal impregnation Nano carbon balls (0.5 gram) Ammonia 80～90 0
Comparative example 13 Metal impregnation activated carbon (0.5 gram) Ammonia 8～16 260
Embodiment 5 Metal impregnation Nano carbon balls (0.01 gram) Methanthiol 50～55 0
Comparative example 13 Metal impregnation activated carbon (0.01 gram) Methanthiol 3～6 3
From table 5, Fig. 2 and Fig. 3 as can be known, the deodorizer of embodiment 5 form with comparative example 13 in used traditional deodorizer compare and need the relative time of growing just can reach flex point.For ammonia, at the flex point place, ammonia can not detect in embodiment 5, but in comparative example 13, measurement concentration is 260ppm.For methanthiol, at the flex point place, in embodiment 5, methanthiol gas can not detect, but in comparative example 13, detectable concentration is 3ppm.Therefore, can understand like this these results, deodorizer of the present invention is compared with traditional deodorizer, when eliminating the such foul smell of for example ammonia and methanthiol, has better deodorancy performance.
Industrial applicibility
As mentioned above, metal impregnation Nano carbon balls of the present invention adsorbs multiple odorant, and shows good deodoriging properties.Therefore, Nano carbon balls of the present invention when being used as deodorizer, when being applied to the environment of multiple article of everyday use, living space, industrial site and other multiple generation stink, can show fabulous deodorizing effect aspect the odorant catching and dissolve.
The present invention is described in detail.It should be understood, however, that the above only is the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (4)

1. one kind is used for the deodorant Nano carbon balls, and described nanosphere comprises the porous carbon shell with spherical hollow, wherein, will be selected from least a metal impregnation in the group of being made up of transition metal, transition metal oxide and alkali metal salt in described shell.
2. the deodorant Nano carbon balls that is used for according to claim 1,
Wherein, described transition metal is to be selected from a kind of in the group of being made up of copper (Cu), ferrum (Fe), manganese (Mn), nickel (Ni), cobalt (Co), silver (Ag), gold (Au), vanadium (V), ruthenium (Ru), titanium (Ti), chromium (Cr), zinc (Zn) and palladium (Pd), and
Wherein, described alkali metal salt is to be selected from by sodium bromide (NaBr), sodium iodide (NaI), potassium bromide (KBr), potassium iodide (KI) and potassium iodate (KIO 3) a kind of in the group formed.
3. the deodorant Nano carbon balls that is used for according to claim 1 and 2,
Wherein, be benchmark with the described gross weight that is used for the deodorant Nano carbon balls, described metal impregnation amount is 0.01～30wt%.
4. the deodorant Nano carbon balls that is used for according to claim 1 and 2,
Wherein, described spherical hollow diameter is 10～1,000 nanometer, and described porous carbon shell thickness is 50～500 nanometers.
CNB038257270A 2002-12-27 2003-06-11 Nano carbon ball for deodorization Expired - Fee Related CN100363060C (en)

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KR1020020084983A KR100879202B1 (en) 2002-12-27 2002-12-27 Deodorant Carbon Nano-ball Using Acrylonitrile As A Carbon Precursor
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CN110054316A (en) * 2019-04-25 2019-07-26 郑水芝 A kind of black-odor riverway treatment process
CN114981211A (en) * 2020-01-17 2022-08-30 东洋制罐集团控股株式会社 Porous silica, deodorant, and method for producing deodorant

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* Cited by examiner, † Cited by third party
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KR100292140B1 (en) * 1999-04-08 2001-06-01 임창혁 Metal deposited active carbon having selective absorption capability for polar contaminants and preparation method thereof
JP2001172089A (en) * 1999-12-16 2001-06-26 Univ Waseda Silica-titania porous body
DE10055082A1 (en) * 2000-11-07 2002-05-16 Bosch Gmbh Robert Ceramic composite
JP4109952B2 (en) * 2001-10-04 2008-07-02 キヤノン株式会社 Method for producing nanocarbon material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110054316A (en) * 2019-04-25 2019-07-26 郑水芝 A kind of black-odor riverway treatment process
CN114981211A (en) * 2020-01-17 2022-08-30 东洋制罐集团控股株式会社 Porous silica, deodorant, and method for producing deodorant

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