CN101611927B - Catalyst capable of reducing carbon monoxide content in cigarette smoke, preparation method and application of same - Google Patents
Catalyst capable of reducing carbon monoxide content in cigarette smoke, preparation method and application of same Download PDFInfo
- Publication number
- CN101611927B CN101611927B CN2009103055895A CN200910305589A CN101611927B CN 101611927 B CN101611927 B CN 101611927B CN 2009103055895 A CN2009103055895 A CN 2009103055895A CN 200910305589 A CN200910305589 A CN 200910305589A CN 101611927 B CN101611927 B CN 101611927B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- cigarette
- preparation
- alumina carrier
- carbon monoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention belongs to the field of harm and tar reduction of cigarettes, and relates to a catalyst capable of reducing carbon monoxide content in cigarette smoke at normal temperature, and a preparation method and the application of the same. The method comprises the following steps that: directing agents with different structures are synthesized into mesoporous alumina with a high specific surface and a plurality of surface basic sites as a carrier of the catalyst, and nanometer metal catalytic active components are highly dispersed on the surface of the carrier by adopting different methods, such as a homogeneous deposition-precipitation method, a deposition-precipitation method, an ion exchange method and the like to prepare a mesoporous metal alumina catalyst. The specific surface of the catalyst is 100 to 400 m<2>/g; a pore size is 2.0 to 10.0 nm; the surface basicity of the mesoporous metal alumina catalyst is 0.01 to 0.08 mmol/g; pH of a surface isoelectric point (an IEP value) is 8 to 10; and the catalytic active components are nanometer metal. The catalyst of the invention can oxidate carbon monoxide to carbon dioxide completely at normal temperature and can selectively reduce the carbon monoxide content in the cigarette smoke by 10 to 30 percent when the catalyst is added to a filter candle of the cigarette.
Description
Technical field
The invention belongs to cigarette lowering harm and decreasing coking field, specifically, relate to a kind of catalyst and the preparation method and application that can reduce the cigarette smoke carbon monoxide content at normal temperatures.
Background technology
Discover that the harmful substances that mainly contains in the cigarette smoke comprises: the carbon monoxide in the flue gas gaseous substance, nitrogen oxide, methacrylaldehyde, volatile aromatics, hydrogen cyanide, volatile nitrosamine etc.; The radioactive element of the condensed-nuclei aromatics in the flue gas granule phase substance matter, phenols, nicotine, nitrosamine (especially tobacco-specific nitrosamine) and some heterocyclic compounds and trace etc.; And the free radical that all exists in mutually of gas phase and grain.Wherein, CO content and cigarette tar content in the flue gas gas phase are the highest, thereby also maximum to the harm of human body; Promptly combine with hemoglobin once sucking, its affinity is bigger more than 200 times than oxygen, causes human body anoxia; For the smoker, its evidence of coronary heart diseases is higher.Therefore, it is most important to the security that improves smoking property of cigarette how to select to reduce and eliminate in the cigarette smoke harmful components such as carbon monoxide, also receives people's attention day by day.
In the cigarette of burning; Nearly 30% carbon monoxide is to produce through the tobacco ingredient thermal decomposition; Nearly 36% carbon monoxide is to produce through the tobacco imperfect combustion, has at least 23% carbon monoxide at high temperature to generate
with carbon reduction reaction through carbon dioxide in addition
In recent years; People have carried out big quantity research aspect the CO burst size in reducing cigarette smoke, adoptable method mainly comprise to the cigarette tipping paper punching and increase mode such as cigarette paper natural permeable degree dilute flue gas concentration, add expanded cut tobacco or reconstituted tobacoo with reduce the pipe tobacco consumption, add combustion adjuvant make the pipe tobacco burning more fully, use composite filter tip to hold back CO and use catalyst that CO is converted into CO through absorption
2Deng.Early 1980s; The river, city of Japan is taken charge of clearly and has been invented a kind of porous material (like active carbon) filter tip [U.S.Patent 4414988] of Protoporphyrins compound solution of ferrous ion that contained the dipping chelating, can effectively remove CO, benzo [a] pyrene and derivative thereof etc. in the flue gas.Catalyst is added in the filter tip forming paper, also can it be loaded on the porous materials such as active carbon, molecular sieve, process composite filter tip [U.S.Patent, 4022223] then.BAT proposes in the mouth rod, to have added composite oxides M
2M ' RuO
6(M is a bivalent metal ion, and M ' is a trivalent rare earth metals, and the chemical valence of Ru is a pentavalent) [U.S.Patent, 4182348] can make the content of CO in the flue gas reduce by 15%～43%; The content of NO reduces by 36%～73%.It is CO that a kind of CO catalytic oxidation under low temperature has been invented by Britain Gallaher company
2Additives of filter tip [U.S.Patent; 4450245], crystallite (polycrystalline particle) form that this catalyst is made up of Cr, Sn, noble metal, transition metal and VI, VII, VIII family metal is dispersed in to heavens and processes in the whole pore system of carrier (molecular sieve, diatomite etc.); In addition; Carrier itself also can play catalytic action sometimes, and like this, this type catalyst often plays bifunctional effect.BP in 1980 has been reported catalyst [the UK Patent of load 6 wt%Cu and 0.5wt%Pd isoreactivity component on the 13X molecular sieve; 2042364A]; Be used for the CO oxidation of cigarette smoke; The CO conversion ratio can reach 76% when reaction temperature is 150 ℃, and the rising of reaction temperature or reduction all make catalyst activity reduction.1997, a United States Patent (USP) report [U.S.Patent, 5671758] was with V
2O
5, Mo
2O
3Or Rh
2This type such as O simple oxide adds in the filter tip on active carbon or other filtering material as catalyst cupport again, all can make the CO in the flue gas be oxidized to CO
2Loaded with nano metal oxide catalyst [CN1805694] on the high surface area carrier particle such as is reined at by KB section, makes an addition in pipe tobacco or the cigarette paper, it is said and can reduce the carbon monoxide content in the main flume.S Goethe Wan Nishiweili etc. can be incorporated into catalyst granules and form in employed tobacco pipe tobacco of cigarette and/or the cigarette paper, can reduce carbon monoxide and/or nitrogen oxide [CN101374429] in the main flume.Lv Gongxuan etc. have invented a kind of nano-noble metal catalyst [CN1460548] that reduces cigarette mainstream flue gas carbon monoxide burst size, are applied to can reduce in the cigarette carbon monoxide burst size 20-45% in the main flume.Zhu Jianhuas etc. have been invented a kind of mesoporous silicon based functional material [CN1460641] that contains rare earth metal or transition metal atoms, can reduce nitroso compound total content minimizing 30～47% in the cigarette smoke.Meng Zhaoyu etc. have invented a kind of cigarette filter tip with mesoporous silicon based molecular sieve (like MCM-41, the SBA-15 etc.) adsorbent of surface modification and preparation method thereof [CN101077223]; This adsorbent adds the composite tip stick of processing in the cigarette filter to can obviously reduce harmful substance contents such as the tar in the flue gas, low molecule aldehyde ketone, nitrosamine, condensed-nuclei aromatics, can improve the organoleptic quality of cigarette simultaneously.Recently, Philip Morris company announced relevant nano metal and oxide catalyst thereof and make an addition to pipe tobacco or cigarette paper in, can reduce the carbon monoxide content [U S Patent 7,243,658] in the main flume, [U S Patent; 7,228,862], [U S Patent, 7; 165,553], [U S Patent, 7,152; 609], [U S Patent, 7,011,096].Therefore, new material and the Study on new method and the exploitation that how to reduce CO content in smoke are the hot issues in this field always.
Yet, have the mesoporous metal oxide Al catalysts of surface alkalinty and be used for reducing harmful substances such as cigarette smoke carbon monoxide with preparation and do not appear in the newspapers as yet.
Summary of the invention
The object of the invention aims to provide a kind ofly has the catalyst and the application of higher catalytic activity to removing CO in the flue gas.
An also purpose of the present invention aims to provide several kinds of above-mentioned Preparation of catalysts methods.
The invention provides a kind of catalyst that has the meso-porous alumina of surface alkalinty especially and contain nano metal, and be applied to reduce in the cigarette carbon monoxide burst size in the cigarette mainstream flue gas.
The objective of the invention is to realize in the following manner:
Catalyst of the present invention contains mesoporous alumina carrier and nano metal; Described mesoporous alumina carrier surface alkalinty position is: 0.01～0.08mmol [OH
-]/g, surperficial isoelectric point is pH=8～10.
The mesoporous alumina carrier specific surface of catalyst of the present invention is 100～400m
2/ g, the aperture is 2.0～10nm.
Said catalyst also contains one or more in rare earth metal, transition metal or their oxides.
Nano metal is selected from one or more among Au, Pt, the Pd.
Meso-porous alumina (Al of the present invention
2O
3) preparation method of carrier is:
The present invention is with shitosan, surfactant P123 (EO
20PO
70EO
20), in the softex kw (CTABr) one or more are as structure directing agent; With aluminum nitrate, aluminium secondary butylate etc. is the aluminium source, has prepared the meso-porous alumina (Al that has than high-ratio surface and more surface alkalinty position through hydrolysis, isolated by filtration, drying, roasting
2O
3) carrier.
At meso-porous alumina (Al
2O
3) also can mix in the preparation process of carrier and add rare earth compound and prepare.
With the above-mentioned meso-porous alumina (Al for preparing
2O
3) carrier; Adopt distinct methods such as the homogeneous deposition precipitation method, deposition-precipitation method and ion-exchange that nano metal catalytic active component (like one or more catalytic active component in the noble metals such as gold (Au), platinum Pt and palladium Pd) high degree of dispersion has been prepared the mesoporous metal oxide Al catalysts that contains nano metal in carrier surface.
The mesoporous metal oxide Al catalysts that contains of preparation is made an addition in cigarette filter rod or cigarette forming paper and the groove paper, be used for reducing cigarette mainstream flue gas carbon monoxide burst size.
The prepared catalyst of the present invention preferably contains one or more catalytic active component and rare earth metal or its oxide (like La, Ce etc.) in the noble metals such as gold (Au), platinum Pt or palladium Pd.
The mass content of nano metal particles is 0.01～2.5%, and nano metal particles is of a size of 2～10nm.
Preparation method's concrete steps of the present invention are following:
1, mesoporous Al
2O
3The preparation of carrier
With shitosan, P123 (EO
20PO
70EO
20) and softex kw (CTABr) in one or more be structure directing agent; With aluminum nitrate, aluminium secondary butylate etc. is the aluminium source; Add certain rare earth compound (like La; Ce etc.), prepared the meso-porous alumina (Al that has than high-ratio surface and more surface alkalinty position through steps such as hydrolysis, isolated by filtration, drying and roastings
2O
3) carrier.
2, method for preparing catalyst is:
(1) HAuCl is got in homogeneous deposition-precipitation method (HDP) preparation
4, H
2PtCl
2Or PdCl
2Solution and mesoporous Al
2O
3Carrier mixes, and slowly is heated to 70-80 ℃.Meanwhile add urea and transfer the pH=7 of solution, under this temperature, keep 3.5-4.5h.Filter, hot water (preferred 70-80 ℃) washing is used AgNO for several times
3(preferred 0.10mol/L) detects no Cl
-, 65-75 ℃ of following dry 8-10h.Calcine 0.5-1.5h down at 330-370 ℃ then, be cooled to normal temperature, use hydrogen reducing 0.5-1.5h down at 300-350 ℃ again.
(2) Na is used in the deposition-precipitation method (DP) preparation
2CO
3Do precipitating reagent with HAuCl
4, H
2PtCl
2Or PdCl
2Solution is transferred to pH=7, under vigorous stirring, 1.0g mesopore metal oxide carrier added wherein, and reaction 3.5-4.5h, 70-80 ℃ of hot wash used AgNO for several times
3(preferred 0.10mol/L) detects no Cl
-, 65-75 ℃ of following dry 8-10h.Calcine 0.5-1.5h down at 330-370 ℃ then, be cooled to normal temperature, use hydrogen reducing 0.5-1.5h down at 300-350 ℃ again.。
(3) anion exchange method (DAE) preparation is with certain density HAuCl
4, H
2PtCl
2Or PdCl
2Solution and 1.0g mesopore metal oxide carrier mix, and stir 1-2h at normal temperatures.Filter,, and then with water washing for several times, use AgNO with ammoniacal liquor (20%V/V) washing three times
3(preferred 0.10mol/L) detects no Cl
-, 65-75 ℃ of following dry 8-10h.Calcine 0.5-1.5h down at 330-370 ℃ then, be cooled to normal temperature, use hydrogen reducing 0.5-1.5h down at 300-350 ℃ again.
Preferred HAuCl
4, H
2PtCl
2Or PdCl
2The mesoporous Al of solution concentration 9.71mmol/L and 1.0g
2O
3Carrier.
Adopt above 3 kinds of modes to prepare in the process of catalyst, can also add transition metal salt and mix with mesoporous alumina carrier.
3, application process of the present invention is:
(1) the catalyst compressing tablet, sieve, choose 20-80 order particle;
(2) 20-80 order catalyst granules is scattered in the diacetate fiber, processes the cigarette binary compound filter candle, contain catalyst 5-50mg in every cigarette filter rod, the composite filter cigarette is become cigarette.
(3) 20-80 order catalyst granules is coated cigarette forming paper and groove paper surface, contain catalyst 5-50mg in every cigarette, cigarette becomes cigarette.
The used mesoporous alumina carrier of the present invention is different from traditional mesoporous silicon based carrier; Be characterized in that carrier surface has abundant surface alkalinty position; The surface isoelectric point is high; Help the precious metal catalyst active components such as nanometer Au, Pt and Pd that load height is disperseed, and traditional mesoporous silicon based mesoporous carrier surface isoelectric point is low, is difficult to obtain nanometer Au, Pt and the Pd catalyst of high dispersive.In addition, be carrier with the meso-porous alumina of the present invention preparation, tenor is low in the metallic catalyst of preparation, and decentralization is high, and is higher to removing in the flue gas catalytic activity of CO.The prepared catalyst of the present invention also has the characteristics that can significantly reduce carbon monoxide content in the cigarette mainstream flue gas under the normal temperature, and removal efficiency can reach 10-30%; The present invention prepares simply, and easy to operate, cost is low.
Description of drawings
Accompanying drawing 1: meso-porous alumina (meso-Al of the present invention
2O
3-a) the 2.0%Au of load (HDP) catalyst TEM photo and goldc grains footpath distribution map.
Accompanying drawing 2: meso-porous alumina (meso-Al of the present invention
2O
3-b) the 2.0%Au of load (HDP) catalyst TEM photo and goldc grains footpath distribution map.
Accompanying drawing 3: meso-porous alumina (meso-Al of the present invention
2O
3-c) the 2.0%Au of load (HDP) catalyst TEM photo and goldc grains footpath distribution map.
Accompanying drawing 4: meso-porous alumina (meso-Al of the present invention
2O
3-d) the 2.0%Au of load (HDP) catalyst TEM photo and goldc grains footpath distribution map.
The specific embodiment
Following examples are intended to explain the present invention rather than to further qualification of the present invention.
Carrier meso-Al
2O
3-a's is synthetic: 6.078g touches plate agent P123 (EO
20PO
70EO
20) and 0.060g LaCl
3Be dissolved in together in the 25ml sec-butyl alcohol, stir adding 5.4ml aluminium secondary butylate down.After stirring 1h under the room temperature, with mixed liquor (the 1.14ml H of water and sec-butyl alcohol
2O/10ml sec-butanol) slowly be added dropwise to wherein, mixture consists of 0.01 La
3+: 1.0Al (Bu
sO)
3: 0.10EO
20PO
70EO
20: 3.0H
2O:15.5Bu
sOH.Mixture continues down to stir 48 hours at 45 ℃, filters, and drying, in air atmosphere, 500 ℃ of calcining 6h obtain product, are labeled as meso-Al
2O
3-a.Use low temperature N
2The adsorption-desorption method is measured meso-Al
2O
3The specific surface of-a is 325m
2/ g, pore volume are 0.93cm
3/ g, average pore size is 7.5nm; Use CO
2Temperature programmed desorption (CO
2-TPD) its surface alkalinty of method mensuration is 0.0369mmol [OH
-]/g; Carrier surface isoelectric point IEP is pH=8.4.
Certain amount of H AuCl is got in homogeneous deposition-precipitation method (HDP) preparation
4(concentration is 9.71mmol/L) and 1.0g carrier meso-Al
2O
3-a mixes, and slowly is heated to 70-80 ℃.Meanwhile add urea and transfer the pH=7 of solution, under this temperature, keep 4h.Filter, hot water (70-80 ℃) washing is used AgNO for several times
3(0.10mol/L) detect no Cl
-, 70 ℃ of following dry 8-10h.Calcine 1.0h down at 350 ℃ then, be cooled to normal temperature, use hydrogen reducing 1.0h down at 300-350 ℃ again, obtain catalyst A u/meso-Al
2O
3-a (HDP).Use low temperature N
2The adsorption-desorption method is measured Au/meso-Al
2O
3The specific surface of-a (HDP) is 258m
2/ g, pore volume are 0.49cm
3/ g, average pore size is 4.9nm; The average-size that adopts transmission electron microscope (TEM) to observe carrier surface nanometer Au particle is 4.4nm.(seeing accompanying drawing 1).
With catalyst A u/meso-Al
2O
3-a (HDP) compressing tablet, sieve, choose 40-60 order particle and be scattered in the diacetate fiber, process the cigarette binary compound filter candle, contain catalyst 40mg in every cigarette filter rod, the composite filter cigarette is become cigarette.Suction on Filtrona COA200 orthoscopic smoking machine (suction capacity 35ml/min); Measure the CO content in the cigarette smoke according to YC/T-30-1996 (non-scattering infrared method); Contrast with the cigarette that does not add catalyst; The result shows, compares with the contrast cigarette, and the prepared catalyst of the present invention can make CO content decline 15% in the main flume.
Deposition-the precipitation method (DP) preparation is with the meso-Al of preparation in the instance 1
2O
3-a is a carrier, with Na
2CO
3Be precipitating reagent, with HAuCl
4Solution (concentration is 9.71mmol/L) is transferred to pH=7, under vigorous stirring, with 1.0g carrier meso-Al
2O
3-a adds wherein, and reaction 4h filters, and hot water (70-80 ℃) washing is used AgNO for several times
3(0.10mol/L) detection does not have Cl
-, 70 ℃ of following dry 10h.Calcine 1.0h down at 350 ℃ then, be cooled to normal temperature, use hydrogen reducing 1.0h down at 300 ℃ again, obtain catalyst A u/meso-Al
2O
3-a (DP).Use low temperature N
2The adsorption-desorption method is measured Au/meso-Al
2O
3The specific surface of-a (DP) is 209m
2/ g, pore volume are 0.45cm
3/ g, average pore size is 4.7nm; The average-size of carrier surface nanometer Au particle is 4.9nm.
With catalyst A u/meso-Al
2O
3-a (DP) compressing tablet, sieve, choose 40-60 order particle and be scattered in the diacetate fiber, process the cigarette binary compound filter candle, contain catalyst 40mg in every cigarette filter rod, the composite filter cigarette is become cigarette.The method of pressing in the embodiment 1 is measured the CO content in the cigarette mainstream flue gas, contrasts with the cigarette that does not add catalyst, and the result shows, compares with the contrast cigarette, and the prepared catalyst of the present invention can make CO content decline 12% in the main flume.
Anion exchange method (DAE) preparation is with the meso-Al of preparation in the instance 1
2O
3-a is a carrier, is that HAuCl4 solution and the 1.0g carrier of 9.71mmol/L mixes with concentration, stirs 1.5h at normal temperatures.Filter, with ammoniacal liquor (20%V/V) washing three times, and then with water washing for several times, to detecting no Cl with AgNO3 (0.10mol/L)
-Dry 10h under 70 ℃ calcines 1.0h down at 350 ℃, is cooled to normal temperature, uses hydrogen reducing 1.0h down at 300 ℃ again, obtains catalyst A u/meso-Al
2O
3-a (DAE).Use low temperature N
2The adsorption-desorption method is measured Au/meso-Al
2O
3The specific surface of-a (DAE) is 300m
2/ g, pore volume are 0.87cm
3/ g, average pore size is 6.7nm; The average-size of carrier surface nanometer Au particle is 3.9nm.
With catalyst A u/meso-Al
2O
3-a (DAE) compressing tablet, sieve, choose 40-60 order particle and be scattered in the diacetate fiber, process the cigarette binary compound filter candle, contain catalyst 40mg in every cigarette filter rod, the composite filter cigarette is become cigarette.The method of pressing in the embodiment 1 is measured the CO content in the cigarette mainstream flue gas, contrasts with the cigarette that does not add catalyst, and the result shows, compares with the contrast cigarette, and the prepared catalyst of the present invention can make CO content decline 10% in the main flume.
Carrier meso-Al
2O
3-b's is synthetic: (a) 0.8g NaOH is dissolved in 4ml H
2Among the O, join in the 80ml triethanolamine, 120 ℃ down heating 5min under agitation the 21.8ml aluminium secondary butylate is added dropwise to wherein to remove water wherein, be heated to 150 ℃ and kept 10 minutes, this is a solution one; (b) under 60 ℃, 14.56g softex kw (CTABr) is dissolved in the 240ml water, this is a solution two; (c) keep 60 ℃ of constant temperature, under vigorous stirring, solution one is slowly joined in the solution two ageing 72h.Filter, use the absolute ethanol washing secondary, 30 ℃ of dryings, 500 ℃ of calcining 5h obtain product in the air atmosphere, are labeled as meso-Al
2O
3-b.Use low temperature N
2The adsorption-desorption method is measured meso-Al
2O
3The specific surface of-b is 302m
2/ g, pore volume are 0.78cm
3/ g, average pore size is 7.2nm; Use CO
2Temperature programmed desorption (CO
2-TPD) its surface alkalinty of method mensuration is 0.0606mmol [OH
-]/g; Carrier surface isoelectric point IEP is pH=9.4.
Prepare catalyst A u/meso-Al according to the homogeneous deposition precipitation method (HDP) among the embodiment 1
2O
3-b (HDP).Use low temperature N
2The adsorption-desorption method is measured Au/meso-Al
2O
3The specific surface of-b (HDP) is 310m
2/ g, pore volume are 0.48cm
3/ g, average pore size is 4.0nm; The average-size that adopts transmission electron microscope (TEM) to observe carrier surface nanometer Au particle is 3.2nm.(seeing accompanying drawing 2)
With catalyst A u/meso-Al
2O
3-b (HDP) compressing tablet, sieve, choose 40-60 order particle and be scattered in the diacetate fiber, process the cigarette binary compound filter candle, contain catalyst 40mg in every cigarette filter rod, the composite filter cigarette is become cigarette.The method of pressing in the embodiment 1 is measured the CO content in the cigarette mainstream flue gas, contrasts with the cigarette that does not add catalyst, and the result shows, compares with the contrast cigarette, and the prepared catalyst of the present invention can make CO content decline 26.4% in the main flume.
Meso-Al with preparation among the embodiment 4
2O
3-b is a carrier, prepares catalyst A u/meso-Al according to deposition-precipitation method (DP) among the embodiment 2
2O
3-b (DP).Use low temperature N
2The adsorption-desorption method is measured Au/meso-Al
2O
3The specific surface of-b (DP) is 259m
2/ g, pore volume are 0.54cm
3/ g, average pore size is 4.0nm; The average-size of carrier surface nanometer Au particle is 4.2nm.
With catalyst A u/meso-Al
2O
3-b (DP) compressing tablet, sieve, choose 40-60 order particle and be scattered in the diacetate fiber, process the cigarette binary compound filter candle, contain catalyst 40mg in every cigarette filter rod, the composite filter cigarette is become cigarette.The method of pressing in the embodiment 1 is measured the CO content in the cigarette mainstream flue gas, contrasts with the cigarette that does not add catalyst, and the result shows, compares with the contrast cigarette, and the prepared catalyst of the present invention can make CO content decline 23.5% in the main flume.
Meso-Al with preparation among the embodiment 4
2O
3-b is a carrier, prepares catalyst A u/meso-Al according to anion exchange method (DAE) among the embodiment 3
2O
3-b (DAE).Use low temperature N
2The adsorption-desorption method is measured Au/meso-Al
2O
3The specific surface of-b (DAE) is 305m
2/ g, pore volume are 0.59cm
3/ g, average pore size is 4.3nm; The average-size of carrier surface nanometer Au particle is 3.5nm.
With catalyst A u/meso-Al
2O
3-b (DAE) compressing tablet, sieve, choose 40-60 order particle and be scattered in the diacetate fiber, process the cigarette binary compound filter candle, contain catalyst 40mg in every cigarette filter rod, the composite filter cigarette is become cigarette.The method of pressing in the embodiment 1 is measured the CO content in the cigarette mainstream flue gas, contrasts with the cigarette that does not add catalyst, and the result shows, compares with the contrast cigarette, and the prepared catalyst of the present invention can make CO content decline 19.3% in the main flume.
Carrier meso-Al
2O
3-c's is synthetic: with 4.60g Al (NO
3)
39H
2O be dissolved in 20ml go dried up in, then this solution is slowly joined the 50mlCH that contains the 1.50g shitosan
3In the COOH solution (5%V/V), under vigorous stirring, kept one hour.And then this solution slowly is added in 800ml (50%V/V) ammonia spirit, under vigorous stirring, kept one hour.Filter normal temperature dry 72 hours down then.550 ℃ of calcinings obtained product in 1.5 hours in the air atmosphere, were labeled as meso-Al
2O
3-c.Use low temperature N
2The adsorption-desorption method is measured meso-Al
2O
3The specific surface of-c is 271m
2/ g, pore volume are 0.48cm
3/ g, average pore size is 4.9nm; Use CO
2Temperature programmed desorption (CO
2-TPD) its surface alkalinty of method mensuration is 0.0503mmol [OH
-]/g; Carrier surface isoelectric point IEP is pH=9.2.
Prepare catalyst A u/meso-Al according to the homogeneous deposition precipitation method (HDP) among the embodiment 1
2O
3-c (HDP).Use low temperature N
2The adsorption-desorption method is measured Au/meso-Al
2O
3The specific surface of-c (HDP) is 292m
2/ g, pore volume are 0.47cm
3/ g, average pore size is 4.5nm; The average-size that adopts transmission electron microscope (TEM) to observe carrier surface nanometer Au particle is 3.6nm, sees accompanying drawing 3.
With catalyst A u/meso-Al
2O
3-c (HDP) compressing tablet, sieve, choose 40-60 order particle and be scattered in the diacetate fiber, process the cigarette binary compound filter candle, contain catalyst 40mg in every cigarette filter rod, the composite filter cigarette is become cigarette.The method of pressing in the embodiment 1 is measured the CO content in the cigarette mainstream flue gas, contrasts with the cigarette that does not add catalyst, and the result shows, compares with the contrast cigarette, and the prepared catalyst of the present invention can make CO content decline 24.3% in the main flume.
Meso-Al with preparation among the embodiment 7
2O
3-c is a carrier, prepares catalyst A u/meso-Al according to deposition-precipitation method (DP) among the embodiment 2
2O
3-c (DP).Use low temperature N
2The adsorption-desorption method is measured Au/meso-Al
2O
3The specific surface of-c (DP) is 259m
2/ g, pore volume are 0.54cm
3/ g, average pore size is 4.0nm; The average-size of carrier surface nanometer Au particle is 4.2nm.
With catalyst A u/meso-Al
2O
3-c (DP) compressing tablet, sieve, choose 40-60 order particle and be scattered in the diacetate fiber, process the cigarette binary compound filter candle, contain catalyst 40mg in every cigarette filter rod, the composite filter cigarette is become cigarette.The method of pressing in the embodiment 1 is measured the CO content in the cigarette mainstream flue gas, contrasts with the cigarette that does not add catalyst, and the result shows, compares with the contrast cigarette, and the prepared catalyst of the present invention can make CO content decline 22.1% in the main flume.
Meso-Al with preparation among the embodiment 7
2O
3-c is a carrier, prepares catalyst Pt-Au/meso-Al according to the homogeneous deposition precipitation method (HDP) among the embodiment 1
2O
3-c (HDP) catalyst (Pt: Au atomic ratio=1: 1).With catalyst Pt-Au/meso-Al
2O
3-c (HDP) compressing tablet, sieve, choose 40-60 order particle and be scattered in the diacetate fiber, process the cigarette binary compound filter candle, contain catalyst 40mg in every cigarette filter rod, the composite filter cigarette is become cigarette.The method of pressing in the embodiment 1 is measured the CO content in the cigarette mainstream flue gas, contrasts with the cigarette that does not add catalyst, and the result shows, compares with the contrast cigarette, and the prepared catalyst of the present invention can make CO content decline 25.1% in the main flume.
Meso-Al with preparation among the embodiment 7
2O
3-c is a carrier, and certain amount of H AuCl is got in homogeneous deposition-precipitation method (HDP) preparation
4(concentration is 9.71mmol/L) and Cu (NO
3)
2Mixed solution, incipient impregnation carrier meso-Al
2O
3-c slowly is heated to 70-80 ℃.Meanwhile add urea and transfer the pH=7 of solution, under this temperature, keep 4h.Filter, hot water (70-80 ℃) washing is used AgNO for several times
3(0.10mol/L) detect no Cl
-, 70 ℃ of following dry 8-10h.Calcine 1.0h down at 350 ℃ then, be cooled to normal temperature, use hydrogen reducing 1.0h down at 300-350 ℃ again, obtain catalyst A u-Cu/meso-Al
2O
3-c (HDP).
With catalyst A u-Cu/meso-Al
2O
3-c (HDP) compressing tablet, sieve, choose 40-60 order particle and be scattered in the diacetate fiber, process the cigarette binary compound filter candle, contain catalyst 40mg in every cigarette filter rod.The method of pressing in the embodiment 1 is measured the CO content in the cigarette mainstream flue gas, contrasts with the cigarette that does not add catalyst, and the result shows, compares with the contrast cigarette, and the prepared catalyst of the present invention can make CO content decline 28.7% in the main flume.
Embodiment 11
Au/meso-Al with preparation among the embodiment 7
2O
3-c catalyst compressing tablet, sieve, choose the forming paper surface that 40-60 order particle is coated cigarette paper, roll into cigarette, contain catalyst 20mg in every cigarette.The method of pressing in the embodiment 1 is measured the CO content in the cigarette mainstream flue gas, contrasts with the cigarette that does not add catalyst, and the result shows, compares with the contrast cigarette, and the prepared catalyst of the present invention can make CO content decline 20.9% in the main flume.
Embodiment 12
Carrier meso-Al
2O
3-d's is synthetic: 3.038g touches plate agent P123 (EO
20PO
70EO
20) and 0.030g LaCl
3Be dissolved in together in the 12.5ml sec-butyl alcohol, be configured to solution 1; Under the vigorous stirring 1.0g shitosan is dissolved in 30ml CH
3In the COOH solution (5%V/V), wiring solution-forming 2.Under the stirring at room, with mixed liquor (the 1.14ml H of water and sec-butyl alcohol
2O/10ml sec-butanol) slowly be added dropwise in the mixed solution of solution 1 and solution 2, continue to stir 48 hours down, filter at 45 ℃, drying, in air atmosphere, 500 ℃ of calcining 6h obtain product, are labeled as meso-Al
2O
3-d.Use low temperature N
2The adsorption-desorption method is measured meso-Al
2O
3The specific surface of-d is 290m
2/ g, pore volume are 0.76cm
3/ g, average pore size is 7.0nm; Use CO
2Temperature programmed desorption (CO
2-TPD) its surface alkalinty of method mensuration is 0.0467mmol [OH
-]/g; Carrier surface isoelectric point IEP is pH=8.9.
(HDP) prepares catalyst A u/meso-Al according to the homogeneous deposition-precipitation method among the embodiment 1
2O
3-d (HDP).Use low temperature N
2The adsorption-desorption method is measured Au/meso-Al
2O
3The specific surface of-a (HDP) is 236m
2/ g, pore volume are 0.54cm
3/ g, average pore size is 5.3nm; The average-size that adopts transmission electron microscope (TEM) to observe carrier surface nanometer Au particle is 4.9nm, (seeing accompanying drawing 4).
With catalyst A u/meso-Al
2O
3-d compressing tablet, sieve, choose 40-60 order particle and be scattered in the diacetate fiber, process the cigarette binary compound filter candle, contain catalyst 40mg in every cigarette filter rod, the composite filter cigarette is become cigarette.The method of pressing in the embodiment 1 is measured the CO content in the cigarette mainstream flue gas, contrasts with the cigarette that does not add catalyst, and the result shows, compares with the contrast cigarette, and the prepared catalyst of the present invention can make CO content decline 20% in the main flume.
Embodiment 13
Meso-Al with preparation among the embodiment 4
2O
3-b is a carrier, and (HDP) prepares mesoporous Al according to the homogeneous deposition-precipitation method in the embodiment 1
2O
3-b carrier surface load Au and Pt alloy catalyst are got certain amount of H AuCl
4And H
2PtCl
21 (atomic ratio)) and 1.0g carrier meso-Al (concentration is respectively 9.71mmol/L to solution, Au: Pt=1:
2O
3-b mixes, and slowly is heated to 70-80 ℃.Meanwhile add urea and transfer the pH=7 of solution, under this temperature, keep 4h.Filter, hot water (70-80 ℃) washing is used AgNO for several times
3(0.10mol/L) detect no Cl
-, 70 ℃ of following dry 8-10h.Calcine 1.0h down at 350 ℃ then, be cooled to normal temperature, use hydrogen reducing 1.0h down at 300-350 ℃ again, obtain catalyst A u-Pt/meso-Al
2O
3-b (HDP).Use low temperature N
2The specific surface that the adsorption-desorption method is measured catalyst is 293m
2/ g, pore volume are 0.47cm
3/ g, average pore size is 4.5nm, the average-size of carrier surface nanometer Au particle is 3.8nm.With catalyst A u-Pt/meso-Al
2O
3-b compressing tablet, sieve, choose 40-60 order particle and be scattered in the diacetate fiber, process the cigarette binary compound filter candle, contain catalyst 40mg in every cigarette filter rod, the composite filter cigarette is become cigarette.The method of pressing in the embodiment 1 is measured the CO content in the cigarette mainstream flue gas; Contrast with the cigarette that does not add catalyst; The result shows, compares with the contrast cigarette, and the Au-Pt nanocatalyst of the meso-porous alumina load that the present invention is prepared can make CO content decline 26% in the main flume.
Claims (21)
1. a catalyst that reduces carbon monoxide content in the cigarette smoke is characterized in that, this catalyst contains mesoporous alumina carrier and nano metal; Described mesoporous alumina carrier surface alkalinty position is: 0.01～0.08mmol [OH
-]/g, surperficial isoelectric point is pH=8～10; Nano metal is selected from Au, Pt or Pd.
2. a kind of catalyst that reduces carbon monoxide content in the cigarette smoke according to claim 1 is characterized in that the specific surface of said mesoporous alumina carrier is 100～400m
2/ g, the aperture is 2.0～10nm.
3. a kind of catalyst that reduces carbon monoxide content in the cigarette smoke according to claim 1 and 2, said catalyst also contain one or more in rare earth metal or transition metal or their oxide.
4. a kind of catalyst that reduces carbon monoxide content in the cigarette smoke according to claim 1 and 2 is characterized in that, wherein to account for the mass content of catalyst be 0.01～2.5% to nano metal particles, and nano metal particles is of a size of 2～10nm.
5. the said a kind of Application of Catalyst method that reduces carbon monoxide content in the cigarette smoke of claim 1; It is characterized in that, with the catalyst compressing tablet, sieve, choose 20-80 order particle; The acetate fibres that is scattered in cigarette filter rod is intrafascicular; Process binary or ternary composite filter, the composite filter cigarette is become cigarette, contain catalyst 5-50mg in every cigarette filter rod.
6. the said a kind of Application of Catalyst method that reduces carbon monoxide content in the cigarette smoke of claim 1 is characterized in that, with the catalyst compressing tablet, sieve; Choose 20-80 order particle; Coat cigarette forming paper and groove paper surface, cigarette becomes cigarette, contains catalyst 5-50mg in every cigarette.
7. the described a kind of catalyst method that reduces carbon monoxide content in the cigarette smoke of preparation claim 1 is characterized in that, with HAuCl
4, H
2PtCl
2Or PdCl
2Solution and mesoporous alumina carrier mix, and slowly are heated to 70-80 ℃, meanwhile add the pH=7 that urea is transferred solution, under this temperature, keep 3.5-4.5h; Filter, hot wash is used AgNO for several times
3Detect no C1
-, 65-75 ℃ of following dry 8-10h; Calcine 1.0h down at 330-370 ℃ then, be cooled to normal temperature, use hydrogen reducing 0.5-1.5h down at 300-350 ℃ again; The preparation of described mesoporous alumina carrier may further comprise the steps: one or more in employing shitosan, surfactant P123, the softex kw are as structure directing agent; With aluminum nitrate or sec-butyl alcohol is the aluminium source, makes through hydrolysis, isolated by filtration, drying, roasting.
8. the preparation method of a kind of mesoporous alumina carrier according to claim 7 is characterized in that, also mixing is added with rare earth compound.
9. preparation method according to claim 7 is characterized in that HAuCl
4, H
2PtCl
2Or PdCl
2The concentration of solution is that 9.71mmol/L and mesoporous alumina carrier 1.0g mix.
10. preparation method according to claim 7 is characterized in that, with 70-80 ℃ of hot wash.
11. preparation method according to claim 7 is characterized in that, also adds transition metal salt and mixes with mesoporous alumina carrier.
12. the said a kind of catalyst method that reduces carbon monoxide content in the cigarette smoke of preparation claim 1 is characterized in that, uses Na
2CO
3Do precipitating reagent with HAuCl
4, H
2PtCl
2Or PdCl
2Solution is transferred to pH=7, under vigorous stirring, mesoporous alumina carrier added wherein, and reaction 3.5-4.5h, hot wash is used AgNO for several times
3Detect no Cl
-, 65-75 ℃ of following dry 8-10h.Calcine 0.5-1.5h down at 330-370 ℃ then, be cooled to normal temperature, use hydrogen reducing 0.5-1.5h down at 300-350 ℃ again; The preparation of described mesoporous alumina carrier may further comprise the steps: one or more in employing shitosan, surfactant P123, the softex kw are as structure directing agent; With aluminum nitrate or sec-butyl alcohol is the aluminium source, makes through hydrolysis, isolated by filtration, drying, roasting.
13. preparation method according to claim 12 is characterized in that, mesoporous alumina carrier also mixes and is added with rare earth compound.
14. preparation method according to claim 12 is characterized in that, HAuCl
4, H
2PtCl
2Or PdCl
2The concentration of solution is that 9.71mmol/L and mesoporous alumina carrier 1.0g mix.
15. preparation method according to claim 12 is characterized in that, with 70-80 ℃ of hot wash.
16. preparation method according to claim 12 is characterized in that, also adds transition metal salt and mixes with mesoporous alumina carrier.
17. prepare a kind of method that reduces the catalyst of carbon monoxide content in the cigarette smoke, it is characterized in that, with HAuCl
4, H
2PtCl
2Or PdCl
2Solution and mesoporous alumina carrier mix, and stir 1-2h at normal temperatures, filter, and with ammonia scrubbing for several times, and then with water washing for several times, use AgNO
3Detect no Cl
-, 65-75 ℃ of following dry 8-10h.Calcine 0.5-1.5h down at 330-370 ℃ then, be cooled to normal temperature, use hydrogen reducing 0.5-1.5h down at 300-350 ℃ again; The preparation of mesoporous alumina carrier may further comprise the steps: one or more in employing shitosan, surfactant P123, the softex kw are as structure directing agent; With aluminum nitrate or sec-butyl alcohol is the aluminium source, makes through hydrolysis, isolated by filtration, drying, roasting.
18. the preparation method of a kind of mesoporous alumina carrier according to claim 17 is characterized in that, also mixing is added with rare earth compound.
19. preparation method according to claim 17 is characterized in that, HAuCl
4, H
2PtCl
2Or PdCl
2The concentration of solution is that 9.71mmol/L and mesoporous alumina carrier 1.0g mix.
20. preparation method according to claim 17 is characterized in that, with 20%V/V ammonia scrubbing three times.
21. preparation method according to claim 17 is characterized in that, also adds transition metal salt and mixes with mesoporous alumina carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103055895A CN101611927B (en) | 2009-08-13 | 2009-08-13 | Catalyst capable of reducing carbon monoxide content in cigarette smoke, preparation method and application of same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103055895A CN101611927B (en) | 2009-08-13 | 2009-08-13 | Catalyst capable of reducing carbon monoxide content in cigarette smoke, preparation method and application of same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101611927A CN101611927A (en) | 2009-12-30 |
| CN101611927B true CN101611927B (en) | 2012-04-25 |
Family
ID=41491967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009103055895A Active CN101611927B (en) | 2009-08-13 | 2009-08-13 | Catalyst capable of reducing carbon monoxide content in cigarette smoke, preparation method and application of same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101611927B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102578695A (en) * | 2010-06-22 | 2012-07-18 | 中国烟草总公司郑州烟草研究院 | Preparation method of one-dimensional gold nano material for reducing the CO (carbonic oxide) content of the cigarette smoke and application thereof |
| CN102059120A (en) * | 2010-12-02 | 2011-05-18 | 云南大学 | Transition metal oxide doped mesoporous alumina prepared with vegetable emulsions as templates and application 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 |
| US10130941B2 (en) | 2014-02-07 | 2018-11-20 | East China University Of Science And Technology | Methods, systems and catalysts for oxidizing carbon monoxide to carbon dioxide |
| CN104174357A (en) * | 2014-08-25 | 2014-12-03 | 云南中烟工业有限责任公司 | Preparation method of Ag(I)@beta molecular sieve for adsorbing low-concentration CO |
| CN108686653B (en) * | 2018-04-27 | 2021-01-22 | 郑州轻工业学院 | Preparation method and application of bimetallic nano-catalyst for reducing CO release amount of cigarette smoke |
| CN111715240B (en) * | 2020-07-22 | 2022-10-04 | 无锡尚好蓝图环保科技有限公司 | Rare earth metal oxide catalyst for degrading VOCs at low temperature and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007096785A2 (en) * | 2006-02-27 | 2007-08-30 | Philip Morris Products S.A. | Catalysts to reduce carbon monoxide such as in the mainstream smoke of a cigarette |
| CN101385975A (en) * | 2007-09-14 | 2009-03-18 | 湖南中烟工业有限责任公司 | Composite metal oxides and preparation method and use thereof |
-
2009
- 2009-08-13 CN CN2009103055895A patent/CN101611927B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007096785A2 (en) * | 2006-02-27 | 2007-08-30 | Philip Morris Products S.A. | Catalysts to reduce carbon monoxide such as in the mainstream smoke of a cigarette |
| WO2007096785A3 (en) * | 2006-02-27 | 2008-01-24 | Philip Morris Prod | Catalysts to reduce carbon monoxide such as in the mainstream smoke of a cigarette |
| CN101385975A (en) * | 2007-09-14 | 2009-03-18 | 湖南中烟工业有限责任公司 | Composite metal oxides and preparation method and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101611927A (en) | 2009-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101611927B (en) | Catalyst capable of reducing carbon monoxide content in cigarette smoke, preparation method and application of same | |
| US8104484B2 (en) | Smoking articles and smoking materials | |
| US7569510B2 (en) | Catalysts to reduce carbon monoxide such as in the mainstream smoke of a cigarette | |
| US6782892B2 (en) | Manganese oxide mixtures in nanoparticle form to lower the amount of carbon monoxide and/or nitric oxide in the mainstream smoke of a cigarette | |
| US7856992B2 (en) | Tobacco catalyst and methods for reducing the amount of undesirable small molecules in tobacco smoke | |
| CA2527551A1 (en) | Catalyst to reduce carbon monoxide in the mainstream smoke of a cigarette | |
| PL204274B1 (en) | PARTIALLY REDUCED NANOPARTICLE ADDITIVES for using to reduce the amount of carbon monoxide and/or nitric oxide present in mainstream smoke | |
| CN101947435A (en) | Chitosan polycation additive for reducing phenols in cigarette smoke | |
| CN101596015A (en) | Reduce additive of CO in smoke of cigarettes and its production and application | |
| US20050121045A1 (en) | Treatment of mainstream smoke constituents by use of oxygen storage and donor metal oxide oxidation catalyst | |
| CN102972864B (en) | Preparation method of catalyst for selectively reducing released amount of hydrogen cyanide in mainstream smoke of cigarette | |
| CN101804356B (en) | Catalyst for reducing the content of CO in cigarette smoke and preparation and application thereof | |
| CN101618350A (en) | Mesoporous alumina carrier capable of reducing content of carbon monoxide in cigarette smoke, preparation method and application thereof | |
| CN101992058B (en) | Mesoporous copper oxide-aluminum oxide adsorbing agent for reducing hydrogen cyanide content in main stream smoke of cigarette, and preparation and application | |
| WO2008018617A1 (en) | Cigarette filter | |
| CN109012606A (en) | A kind of MOF-Zn@molecular sieves compound material, preparation method and the application in cigarette | |
| CN100396374C (en) | Catalyst for reducing CO release guantity in main flow smove of cigarette, its preparation method and application | |
| JPS6322185B2 (en) | ||
| CN101999756A (en) | Absorbent for reducing hydrocyanic acid content of main stream smoke of cigarettes and use thereof | |
| CN112841717A (en) | Aromatized attapulgite based cigarette filter tip additive material as well as preparation method and application thereof | |
| JP4994919B2 (en) | Nitric oxide remover | |
| CN102499467B (en) | Additive for reducing quantity of carbon monoxide in smoke of cigarette and preparation method and application thereof | |
| CN101862037B (en) | Preparation method and application of hexagonal mesoporous monox coated nano-TiO2 composite material | |
| CN116251562A (en) | Nanoscale cerium oxide particle material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |