WO2005094619A1 - Filtre a fumee de tabac - Google Patents

Filtre a fumee de tabac Download PDF

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Publication number
WO2005094619A1
WO2005094619A1 PCT/EP2005/003533 EP2005003533W WO2005094619A1 WO 2005094619 A1 WO2005094619 A1 WO 2005094619A1 EP 2005003533 W EP2005003533 W EP 2005003533W WO 2005094619 A1 WO2005094619 A1 WO 2005094619A1
Authority
WO
WIPO (PCT)
Prior art keywords
tobacco smoke
smoke filter
filter according
filter
active component
Prior art date
Application number
PCT/EP2005/003533
Other languages
German (de)
English (en)
Inventor
Gunther Peters
Inga Gurke
Christian Müller
Ludwig Riepert
Bernhard Lücke
Irene Pitsch
Michael Bartoszek
Hendrik Kosslick
Original Assignee
Reemtsma Cigarettenfabriken Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Reemtsma Cigarettenfabriken Gmbh filed Critical Reemtsma Cigarettenfabriken Gmbh
Priority to EP05716527A priority Critical patent/EP1729603A1/fr
Publication of WO2005094619A1 publication Critical patent/WO2005094619A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
    • A24D3/166—Silicic acid or silicates

Definitions

  • the invention relates to a tobacco smoke filter and a method for producing such a tobacco smoke filter.
  • Tobacco smoke filters are e.g. used in cigarettes to reduce the amount of condensate or other ingredients in tobacco smoke (e.g. nicotine).
  • tobacco smoke e.g. nicotine
  • many, often undesirable substances in tobacco smoke can pass through a conventional tobacco smoke filter unhindered or are at least not sufficiently retained in it.
  • Such substances are e.g. Hydrocyanic acid (HGN), carbonyls or methanol.
  • Claim 31 relates to a smoking product with such a tobacco smoke filter
  • claims 32 and 33 relate to methods for producing such a tobacco smoke filter.
  • a catalyst carrier is arranged in the tobacco smoke filter according to the invention in order to reduce tobacco smoke components.
  • the catalyst support is preferably provided with an active component.
  • reduction is to be understood here generally in the sense of “reduction” and not restricted in the sense of a chemical reduction reaction. The terminology is chosen so that a catalyst support together with an active component results in a complete catalyst (supported catalyst).
  • catalyst support used here is to be understood in a broad sense and is not intended to imply that the use of an active component is absolutely necessary.
  • tobacco smoke eg hydrogen cyanide
  • the catalyst support can also have several substances, in particular a mixture of different materials.
  • Solids with adsorptive and / or catalytic properties are particularly suitable as catalyst supports, ie also solids which are themselves catalytically active without an additional active component applied.
  • Suitable are e.g. solid metal oxides which have acidic or alkaline surface centers, or acidic or alkaline oxidic solids, in particular if they are suitable as carriers for metallic active components, or metal oxides with catalytically active surface centers which are suitable as carriers for metallic active components, or as Carriers of metallic active components suitable metal oxides.
  • the active component preferably has metallic active centers.
  • catalytically active metals which are present as metal or metal compound, for example in the form of particles with a size in the range from 1 nm to 100 n or in the range from 1 nm to 20 nm.
  • the active component can be, for example, gold, copper, palladium, platinum , Ruthenium or silver, but also mixtures of these metals.
  • a preferred active component is gold.
  • the preferred mass ratio of active component to catalyst support is in the range from 0.002 to 0.04. A good catalytic effect is shown in this area, while the costs for the catalyst are not yet too high.
  • the active component can advantageously be applied to the catalyst support in a precipitation process.
  • the precipitation can e.g. with sodium hydroxide solution (NaOH) or urea as a precipitant.
  • NaOH sodium hydroxide solution
  • a precipitation process has the advantage that disperse catalysts are formed.
  • the solid (catalyst support) is soaked in a solution which contains the active component; in the precipitation process, an active metal is precipitated as hydroxide with a suitable precipitant and is dispersed on the surface of the catalyst support by means of a chemisorption process.
  • the catalyst support has acidic or alkaline 'properties. Acidic properties are particularly preferred.
  • the catalyst support can, for example, titanium dioxide (Ti0 2 ), iron oxides (in particular ⁇ -Fe 2 0 3 ), aluminum oxide (A1 2 0 3 ), silicon dioxide (Si0 2 ), aluminum hydroxide, silicon hydroxide, zinc oxide (ZnO), magnesium oxide (MgO), hydrotalcite Zeolites (preferably of the types HY, H-Beta, H-ZSM5, and / or HY (D)), ion exchangers, carbonized ion exchangers, activated carbons or mixtures of such materials. Mixtures of different catalyst support materials can be useful, for example, to selectively achieve a reduction in the gas phase content for a number of given tobacco smoke components.
  • the catalyst support contains Al0 3 and Si0 2 .
  • this type of catalyst support also has water which, for example, as crystal water or as adsorbed surface water or in water releasing compounds can be present. At least the major part of the water can be measured as loss on ignition, whereby a material sample is first heated to 150 ° C and after reaching a constant weight to 950 ° C until the weight remains constant.
  • the water fraction measurable as loss on ignition is preferably in the range from 5% by weight to 30% by weight.
  • Other constituents of the catalyst support together preferably make up less than 0.4% by weight.
  • the weight ratio of A1 2 0 3 to Si0 2 is preferably in the range from 0.5 to 100, in particular in the range from 1.5 to 40, values from or in the range from 1.5 and 4 and 19 being particularly preferred.
  • Such a catalyst support has proven to be particularly effective in reducing tobacco smoke components, even without an additional active component.
  • a salt form can be used as the starting product, preferably an ammonium resin, which can be converted into H form by heating and / or acidification.
  • the catalyst support preferably has a pore size of at least 0.3 nm or at least 3 nm or at least 10 nm, a preferred upper limit of the pore size being 100 nm.
  • the pore size is an average pore diameter, as can be specified for circular or spherical pores.
  • the terms "pore size” and “pore diameter” are both common; In the following, "pore size” is mostly used.
  • the catalyst support can be in very different forms, for example as microfine dust with particle sizes in the range from 1 ⁇ m to 15 ⁇ m, as powder or granules with particle sizes in the range from 10 ⁇ m to 2.5 mm or in the form of fibers with diameters in the range from 1 ⁇ m to 100 ⁇ m.
  • a filter body extruded from catalyst carrier material is also conceivable, for example per, which preferably has the dimensions of a conventional tobacco smoke filter and can contain one or more longitudinal channels.
  • Mixed forms are also conceivable for the catalyst support, in particular mixed forms with components which are selected from the aforementioned forms.
  • the catalyst support has a granular structure, preferably more than 98% by weight of the catalyst support having a grain size of less than 150 ⁇ m.
  • the tobacco smoke filter according to the invention can be manufactured in different forms. Examples are monofilters, double filters, triple filters, quadruple filters, quintuple filters or in general multiple filters, core filters and recess filters.
  • a further possibility are chamber filters, also chamber filters in which catalyst carriers (with or without active component) are contained in one chamber. These types of filters are known in principle; however, it must be ensured that the catalyst carrier (possibly with active component) is introduced into the tobacco smoke filter (see below).
  • the tobacco smoke filter contains one or more extruded filter bodies which are extruded from the catalyst carrier (see above), such a filter body also being able to make up essentially the entire tobacco smoke filter.
  • the tobacco smoke filter according to the invention preferably has filter material in which catalyst support or catalyst support with active component is arranged to reduce tobacco smoke components.
  • the filter material can be present, for example, in the form of fibers, also continuous fibers or staple fibers, in the form of paper, also crimped paper, in the form of foil, also crimped foil, as a fleece, as an extruded foam or in a mixed form.
  • Suitable materials for the filter material are, for example, cellulose acetate, cellulose, polymers and polymer derivatives (in particular polyolefins, starch and starch derivatives) and natural fibers (preferably hemp, flax or tobacco). Mixed materials are also conceivable.
  • the catalyst carrier which is optionally provided with an active component, is introduced into the filter material.
  • the catalyst carrier can be sprinkled onto the filter material from a conveyor belt, or the catalyst carrier is mixed with the filter material in a drum.
  • EP 0 913 100 A2 describes a method and a device for applying substances to a filter material, which work according to this principle and can also be used if catalyst support is used as the substance.
  • the catalyst carrier can be introduced in pulses by means of an air nozzle into a strand of filter material.
  • the air nozzle opens coaxially into the strand of filter material. The principle of this method is explained in DE 100 10 176 AI.
  • a suspension of the catalyst support can also be applied to the filter material, with subsequent drying. It is also conceivable to introduce the catalyst carrier into the paper pulp when producing a filter material made of paper. Another possibility is to add the catalyst carrier in the spinning process of fibers if the filter material has fibers.
  • the catalyst carrier can be added in the extrusion process in the production of such a filter material.
  • WO 01/80973 AI describes a method in which substances are introduced into the pores of open-pore fibers of a filter material containing open-pore fibers, e.g. with the help of an electrostatic field. Such a method can also be applied to the catalyst carrier.
  • the catalyst support is spread between two nonwoven or paper webs. This is followed by a calendering and drying process.
  • the filter material is made from regenerated cellulose (e.g. "Lyocell"
  • the catalyst support which is optionally provided with an active component, can be added to the filter material during the extrusion of the fibers.
  • the tobacco smoke filter is preferably set up to selectively reduce specified tobacco smoke components, for example hydrocyanic acid (HCN), alcohols (in particular methanol) and / or carbonyls (in particular acrolein, diacetyl, 2-butanone and / or i-butyraldehyde).
  • HCN hydrocyanic acid
  • alcohols in particular methanol
  • carbonyls in particular acrolein, diacetyl, 2-butanone and / or i-butyraldehyde.
  • a catalyst support provided with gold as active component with A1 2 0 3 and Si0 2 or a catalyst provided with gold as active component are particularly suitable.
  • carrier with ZnO or hydrotalcite as a catalyst carrier with or without an active component.
  • catalyst supports with A1 2 0 3 and Si0 2 in particular with a weight ratio of Al 2 0 3 to Si0 2 of 1.5, or catalyst supports with zeolites, preferably of the HY type, are particularly suitable, in each case with or without active component.
  • the tobacco smoke filter according to the invention is particularly suitable for smoking products such as cigarettes, cigarillos or filter tubes (which are customary for making cigarettes yourself).
  • This example shows the effect of a catalyst carrier, which contains no additional active component, on tobacco smoke, namely on the mainstream smoke of cigarettes.
  • a 20-channel smoke machine from Borgwaldt (RM 20 / CS) was equipped with 20 cigarettes and optionally with a glass fiber filter of 92 mm (Cambridge filter) to separate the wet condensate.
  • the test cigarettes were previously conditioned according to ISO 3402. About 1000 mg of each sample from a catalyst support were weighed into a glass reactor with a frit bottom (inside diameter 3.6 cm). The entire gas phase of the 20 cigarettes flowed through the reactor from above during the smoking. When using the glass fiber filter, the reactor was positioned immediately behind the glass fiber filter.
  • a quantification was carried out for the following gas phase components: isoprene, acetaldehyde, propionaldehyde, furan, i-butyraldehyde, acetone, acrolein, 2-methylfuran, 2-butanone, methanol, benzene-, 3-buten-2-one, 2, 5 -Dimetylfuran ,.
  • Table 1 shows a summary of the results for various catalyst support materials. '' The percentage change in the content of the respective gas phase component relative to the comparison measurement with an empty reactor is given, for each catalyst support in the first column when using the glass fiber filter (CF) with separated wet condensate and in the second column without using the glass fiber filter if the Carrier materials the total smoke (Ges.-R.) were exposed. Trade names are used as an abbreviation for the catalyst support materials.
  • CF glass fiber filter
  • the material called "Siral 5" contains a mixture of Al2O3 (as boehmite) and Si0 2 in a weight ratio of 95 to 5 and was calcined at about 200 ° C to 300 ° C before use, resulting in a reduction in the original loss of ignition measurable water content of approx. 25% by weight led to a lower value.
  • a corresponding material, but calcined by the manufacturer at about 600 ° C, is sold by Sasol Germany GmbH under the name "Siralox 5/320".
  • Other components are carbon with about 0.2 wt .-%, Fe0 3 with about 0.01 wt .-% and Na 2 0 with about 0.005 wt .-%.
  • the bulk density is in the range from 450 to 650 g / l and the median particle size is approximately 50 ⁇ m.
  • a material sample is heated to 150 ° C at a temperature increase rate of 15 K / min and then, after the sample mass has not changed, at a temperature increase rate of approx. 40 K / min to 950 ° C. After reaching a constant mass, the loss on ignition is the difference to the initial mass of the sample.
  • the two "Puralox" materials are also distributed by Sasol Germany GmbH and essentially contain A1 2 0 3 . 98.7% by weight of the material have a grain size of less than 125 ⁇ m.
  • the catalyst carrier material "Kronos 1001" (Kronos International, Inc.) consists of at least 99% Ti0 2 with a density of 3.8 g / cm 3 (typical for anatase pigments) and a bulk density of 450 g / 1 to 700 g /1.
  • Siralox 1.5 / 250 contains Al 2 0 3 and Si0 2 in a weight ratio of 98.3 to 1.7 and water, the loss on ignition (see above) being 8.1% by weight.
  • the specific surface of the material is 248 m 2 / g, the bulk density is approx. 680 g /. 1 76.6% by weight of the material have a grain size of less than 90 ⁇ m.
  • Table 2 shows the results for various catalyst supports. In all cases, finely dispersed gold was used as the active component.
  • the catalyst supports “Siral 5", “Puralox” and “Kronos 1001" have already been explained in connection with Example 1.
  • Table 2 also contains results for the catalyst support zinc oxide (ZnO; prepared by precipitation from zinc nitrate hexahydrate and NaOH, then calcined at 250 ° C. for 3 hours).
  • a glass fiber filter (Cambridge filter) was always used in the measurements summarized in Table 2, so that the wet condensate was separated on this filter.
  • Table 2 shows the carrier effect for each catalyst support in the first column, ie the percentage change in the content of the corresponding gas phase component in relation to the comparison measurement when the reactor is empty.
  • a minus sign means, as in example 1, a decrease.
  • the catalyst effect in the respective second column is the percentage change relative to the respective measurement with a catalyst carrier alone, that is to say without an active component, and accordingly gives Table 2 Percentage change in the content of selected gas phase components in cigarette mainstream smoke (reactor model, with Cambridge Reg filter) for various catalyst support materials; Carrier effect: without active component; Catalyst effect: with gold active component (additional effect)
  • HY (D) -20 is a 20-minute dealuminated HY zeolite that was previously in the sodium form and by repeated ion exchange into the salt form, namely the ammonium form, and then by hydrothermal treatment or thermal decomposition 400 ° C was converted into the H form. By removing the aluminum atoms from the framework, the number of Brönsted centers was reduced. At the same time, the AI atoms removed from the scaffold form Lewis centers.
  • the catalyst supports or catalyst supports with active component gold listed in Table 4 bring about a high selective reduction of HCN.
  • the measurements were carried out analogously to Example 1. In some cases a Cambridge filter was used.
  • Hydrotalcites are layered Mg-Al double hydroxides in which the magnesium content is given in%.
  • the hydrotalcite Mg30 (550 ° C) contains 30% magnesium and was calcined at 550 ° C. With thermal treatment, hydrotalcites change to the amorphous state.
  • Mesoporous A1 2 0 3 has a pore diameter between 2 nm and 50 nm, here 10 nm.
  • the catalyst supports or catalyst supports with active component gold listed in Table 5 bring about a high selective reduction for carbonyls (ketones, aldehydes). The measurements were again carried out analogously to Example 1.
  • aldehydes acrolein, acetaldehyde, propionaldehyde and i-butyraldehyde;
  • ketones acetone, 2-butanone, 3-buten-2-one and diacetyl.
  • Al-MMS ' 100 is an aluminum-substituted mesoporous silicate molecular sieve with a pore diameter of 10 nm.
  • Active components of a catalyst are applied to support materials (catalyst support) by precipitation, as explained in the following example for the preparation of a gold / “Siral 5” supported catalyst.
  • a mixture consisting of 900 mg of tetrachloroauric acid, 450 ml of distilled water and 6 g of urea was added with stirring.
  • the reaction mixture was heated to 70 ° C. and stirred at 70 ° C. for 5 hours.
  • Lyocell fibers with 25% carbon were made by an extrusion process, such as described in DE 100 53 359 AI, the grain size of the activated carbon was less than 12 microns.
  • Example 1 The fibers were examined as in Example 1. The values for the gas phase lowering are listed in Table 6. The weight of the fibers was chosen so that the measurement is comparable to the values from Examples 1 to 5 and corresponds to a net weight of approximately 1000 mg of activated carbon.

Abstract

L'invention concerne un filtre à fumée de tabac servant à réduire les composants de fumée de tabac. Selon l'invention, un support de catalyseur, pourvu d'un composant actif et faisant de préférence partie intégrante d'un catalyseur complet, est placé dans ce filtre. Ce support de catalyseur est introduit dans le matériau filtrant lors de la production d'un tel filtre à fumée de tabac.
PCT/EP2005/003533 2004-04-02 2005-04-04 Filtre a fumee de tabac WO2005094619A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05716527A EP1729603A1 (fr) 2004-04-02 2005-04-04 Filtre a fumee de tabac

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004016432.0 2004-04-02
DE102004016432 2004-04-02

Publications (1)

Publication Number Publication Date
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EP (1) EP1729603A1 (fr)
WO (1) WO2005094619A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005118133A3 (fr) * 2004-05-28 2006-04-27 British American Tobacco Co Articles et materiaux lies a l'usage du tabac
ES2293835A1 (es) * 2006-07-21 2008-03-16 Juan Guerrero Moles Catalizador mineralogico para el filtrado de humos y su proceso de fabricacion.
CN102396780A (zh) * 2011-07-12 2012-04-04 广西中烟工业有限责任公司 一种选择性减害卷烟及其制备方法
US9642394B2 (en) 2011-07-21 2017-05-09 British American Tobacco (Investments) Limited Porous carbon and methods of production thereof
CN107551831A (zh) * 2017-08-30 2018-01-09 山东大学 一种用于过滤烟草烟雾颗粒物的金属‑有机骨架纤维膜及其应用
US10070664B2 (en) 2014-07-17 2018-09-11 Nicoventures Holdings Limited Electronic vapor provision system

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102551206A (zh) * 2012-01-04 2012-07-11 安徽中烟工业有限责任公司 一种可降低卷烟主流烟气有害成分释放量的含层状双氢氧化物的卷烟滤嘴

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* Cited by examiner, † Cited by third party
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US4182348A (en) * 1977-09-06 1980-01-08 B.A.T. Cigaretten-Fabriken Gmbh Removal of nitric oxide and carbon monoxide from tobacco smoke
BE881118A (fr) * 1979-01-12 1980-07-11 Gallaher Ltd Catalyseurs redox a deux composants et leur preparation
FR2446127A1 (fr) * 1979-01-12 1980-08-08 Gallaher Ltd Catalyseur d'oxydation a base de cuivre et son procede de fabrication
US4252687A (en) * 1978-01-20 1981-02-24 Gallaher Limited Catalysts
EP0658320A2 (fr) * 1993-12-14 1995-06-21 Rothmans International Services Limited Article à fumer et son élément filtrant
US5446003A (en) * 1993-01-12 1995-08-29 Philip Morris Incorporated Production of supported particulate catalyst suitable for use in a vapor phase reactor
EP0740907A1 (fr) * 1995-05-03 1996-11-06 F. J. Burrus SA Article à fumer
WO2002043514A1 (fr) * 2000-11-28 2002-06-06 Lorillard Licensing Company, Llc Article pour fumeur comportant une pompe sélective à co
WO2004110186A1 (fr) * 2003-06-13 2004-12-23 Philip Morris Products S.A. Catalyseur permettant de reduire le taux de monoxyde de carbone dans le flux principal de fumee d'une cigarette
WO2004110183A2 (fr) * 2003-06-13 2004-12-23 Philip Morris Products S.A. Association de particules catalytiques nanometriques et d'aluminosilicate pour la reduction du taux de monoxyde de carbone dans le flux principal de fumee d'une cigarette

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182348A (en) * 1977-09-06 1980-01-08 B.A.T. Cigaretten-Fabriken Gmbh Removal of nitric oxide and carbon monoxide from tobacco smoke
US4252687A (en) * 1978-01-20 1981-02-24 Gallaher Limited Catalysts
BE881118A (fr) * 1979-01-12 1980-07-11 Gallaher Ltd Catalyseurs redox a deux composants et leur preparation
FR2446127A1 (fr) * 1979-01-12 1980-08-08 Gallaher Ltd Catalyseur d'oxydation a base de cuivre et son procede de fabrication
US5446003A (en) * 1993-01-12 1995-08-29 Philip Morris Incorporated Production of supported particulate catalyst suitable for use in a vapor phase reactor
EP0658320A2 (fr) * 1993-12-14 1995-06-21 Rothmans International Services Limited Article à fumer et son élément filtrant
EP0740907A1 (fr) * 1995-05-03 1996-11-06 F. J. Burrus SA Article à fumer
WO2002043514A1 (fr) * 2000-11-28 2002-06-06 Lorillard Licensing Company, Llc Article pour fumeur comportant une pompe sélective à co
WO2004110186A1 (fr) * 2003-06-13 2004-12-23 Philip Morris Products S.A. Catalyseur permettant de reduire le taux de monoxyde de carbone dans le flux principal de fumee d'une cigarette
WO2004110183A2 (fr) * 2003-06-13 2004-12-23 Philip Morris Products S.A. Association de particules catalytiques nanometriques et d'aluminosilicate pour la reduction du taux de monoxyde de carbone dans le flux principal de fumee d'une cigarette

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005118133A3 (fr) * 2004-05-28 2006-04-27 British American Tobacco Co Articles et materiaux lies a l'usage du tabac
US8104484B2 (en) 2004-05-28 2012-01-31 British American Tobacco (Investments) Limited Smoking articles and smoking materials
ES2293835A1 (es) * 2006-07-21 2008-03-16 Juan Guerrero Moles Catalizador mineralogico para el filtrado de humos y su proceso de fabricacion.
CN102396780A (zh) * 2011-07-12 2012-04-04 广西中烟工业有限责任公司 一种选择性减害卷烟及其制备方法
US9642394B2 (en) 2011-07-21 2017-05-09 British American Tobacco (Investments) Limited Porous carbon and methods of production thereof
US10070664B2 (en) 2014-07-17 2018-09-11 Nicoventures Holdings Limited Electronic vapor provision system
CN107551831A (zh) * 2017-08-30 2018-01-09 山东大学 一种用于过滤烟草烟雾颗粒物的金属‑有机骨架纤维膜及其应用
CN107551831B (zh) * 2017-08-30 2021-02-23 山东大学 一种用于过滤烟草烟雾颗粒物的金属-有机骨架纤维膜及其应用

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