ZA200610096B - Application of mesoporous molecular sieves as selective smoke filtration additives - Google Patents
Application of mesoporous molecular sieves as selective smoke filtration additives Download PDFInfo
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- ZA200610096B ZA200610096B ZA200610096A ZA200610096A ZA200610096B ZA 200610096 B ZA200610096 B ZA 200610096B ZA 200610096 A ZA200610096 A ZA 200610096A ZA 200610096 A ZA200610096 A ZA 200610096A ZA 200610096 B ZA200610096 B ZA 200610096B
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- South Africa
- Prior art keywords
- molecular sieve
- mesoporous molecular
- article
- filter element
- mcm
- Prior art date
Links
- 239000002808 molecular sieve Substances 0.000 title claims description 47
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims description 47
- 239000000654 additive Substances 0.000 title claims description 14
- 239000000779 smoke Substances 0.000 title description 28
- 238000001914 filtration Methods 0.000 title description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 87
- 239000000463 material Substances 0.000 claims description 38
- 235000019504 cigarettes Nutrition 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 24
- 230000000391 smoking effect Effects 0.000 claims description 24
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 241000208125 Nicotiana Species 0.000 claims description 8
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 230000009467 reduction Effects 0.000 description 25
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 24
- 238000012384 transportation and delivery Methods 0.000 description 20
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 19
- 239000012808 vapor phase Substances 0.000 description 17
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000000470 constituent Substances 0.000 description 9
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 150000002825 nitriles Chemical class 0.000 description 6
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 5
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 5
- 239000000796 flavoring agent Substances 0.000 description 5
- 235000019634 flavors Nutrition 0.000 description 5
- 239000013618 particulate matter Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 3
- 229940100603 hydrogen cyanide Drugs 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 229910020175 SiOH Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- JDPBLCQVGZLACA-UHFFFAOYSA-N benzo[a]perylene Chemical group C1=CC(C=2C3=CC=CC=C3C=C3C=2C2=CC=C3)=C3C2=CC=CC3=C1 JDPBLCQVGZLACA-UHFFFAOYSA-N 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- HKMTVMBEALTRRR-UHFFFAOYSA-N Benzo[a]fluorene Chemical compound C1=CC=CC2=C3CC4=CC=CC=C4C3=CC=C21 HKMTVMBEALTRRR-UHFFFAOYSA-N 0.000 description 1
- RAASUWZPTOJQAY-UHFFFAOYSA-N Dibenz[a,c]anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C3=CC=CC=C3C2=C1 RAASUWZPTOJQAY-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- PWPJGUXAGUPAHP-UHFFFAOYSA-N lufenuron Chemical compound C1=C(Cl)C(OC(F)(F)C(C(F)(F)F)F)=CC(Cl)=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F PWPJGUXAGUPAHP-UHFFFAOYSA-N 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002678 semianthracite Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
- A24D3/166—Silicic acid or silicates
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
Application of Mesoporous Molecular Sieves as
Selective Smoke Filtration Additives by
Rodney D. Schluter and
Lamar Perry
This international patent application claims Paris Convention priority to and benefit from, currently pending, U.S. Patent Application serial number 10/860,775, filed on 03 June 2004.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR
DEVELOPMENT
Not applicable.
REFERENCE TO A “SEQUENTIAL LISTING,” A TABLE, OR A COMPUTER
PROGRAM LISTING APPENDIX SUBMITTED ON A COMPACT DISC
Not applicable.
1. Field of the Invegtion :
The present invention relates to a smoking article having a filter element and/or smokable material containing a highly structured mesoporous molecular sieve, and more specifically, a smoking article having a filter element and/or smokable material containing a highly porous amorphous silica (hereinafter referred to as “MCM-41"), as the highly structured mesoporous molecular sieve for filtering vapor phase constituents in mainstream smoke.
2. Description of the Related Art
Typical smoking articles, such as cigarettes, have a cylindrical filter element axially aligned with a cylindrical tobacco-filled rod. The filter element, and even the tobacco-filled rod, incorporate various materials that work to remove particular components from the mainstream smoke. Often, these materials are non-selective, thereby removing desirable components from the mainstream smoke and resulting in an undesirable taste.
Certain cigarettes have filter elements which incorporate materials such as carbon.
Exemplary cigarettes and filters are described in U.S. Patent Pub. No. 2003/0159703, to
Yang, etal, and U.S. Patent Pub. No. 2003/0154993, to Paine, Ill et al. Generally, surface area is inversely proportional to carbon particle size. If the particle size is too large, there maybe insufficient surface area to accomplish the desired filtration. This factor must be taken into careful consideration when selecting a particular carbon particle size. Also, filter elements which incorporate carbon often yield a metallic flavor during smoking. Carbon is often impregnated with a flavorant in an attempt to camouflage the metallic flavor and may actually block the pores, an impediment to filtration, and finding a preferred flavorant loading ! percentage is difficult and inefficient. Furthermore, filter elements which incorporate carbon vary in proportion of micropores to mesopores, where the term “microporous” generally refers to such materials having pore sizes of about 20A or less, while the term “mesoporous” generally refers to such materials with pore sizes of about 20-500A. Uniform pore size distribution is more favorable. By having a more uniform pore size distribution, more of the porosity can be assured to be in the mesoporous range (2-50nm), which is more effective at filtering smoke than microporous materials. A variety of pore sizes is more likely to filter a variety of compounds, and filters for specific analytes are more desirable.
A smoking article with a filter element capable of filtering vapor phase components that is efficient to produce and does not yield a metallic flavor is desired. Also, a filter element with a mesoporous molecular sieve that has uniform pore size is desired.
In view of known deficiencies associated with earlier smoking article filter elements, a smoking article with a mesoporous molecular sieve to filter vapor phase constituents from mainstream tobacco smoke is provided.
It has been found that a family of highly ordered mesoporous molecular sieves, manufactured by the Mobil Corporation and identified as M418, are useful in smoking article filter elements. M41S materials are non-crystalline surfactant templated silica having a narrow pore size distribution. MCM-41 is a highly porous surfactant templated silica gel belonging to the M41S family, and contains a highly organized hexagonal array of uniform pores with controllable diameters from about 15 A to about 100 A. The term “hexagonal” encompasses materials that exhibit mathematically perfect hexagonal symmetry and materials with significant observable deviations from perfection. MCM refers to Mobil Composition of
Matter or Mobil Crystalline Material, and was developed as a catalyst substrate by Mobil.
The surface chemistry of siliceous MCM-41 is comprised of silanol groups (SiOH), and may be synthesized using cetyltrimethylammonium chloride (CTACI), H,0, Na;O, and
Si0,. The formed MCM-41 may be utilized as a mesoporous molecular sieve in smoking articles. MCM-41 has a highly condensed surface with less SiOH groups than silica, and its uniqueness is in the shape it adopts by forming around a template which is subsequently removed. The use of mesopores as an absorbent is taught by U.S. Patent No. 5,580,370, to
Kuma, et al. Furthermore, MCM-41 has a large surface area, where the BET surface area is approximately 1000 m%g, and thus has a high sorption capacity. (‘BET” refers to Brunaur,
Emmett, and Teller, three scientists who optimized the theory for measuring surface areas.)
MCM-41 is effective for reducing levels of alcohols, aldehydes, ketones, nitriles, and naphthalene.
It is an object of the present invention to provide a smoking article with a filter element having a mesoporous molecular sieve, MCM-41. A preferred smoking article is a cigarette with MCM-41 disposed within the filter element.
It is another object to provide a smokable material in a smokable rod of the smoking article having the mesoporous molecular sieve, MCM-41. A preferred smoking article isa cigarette and a preferred smokable material is tobacco. In this embodiment, MCM+41 is disposed within the smokable material in the rod.
It is yet another object to provide the filter element and the smokable material in the smokable rod of the smoking article both having the mesoporous molecular sieve, MCM-41.
In this embodiment, MCM-41 is disposed within the filter element and throughout the smokable material in the rod.
It is still yet a further object to provide either or both the filter clement or the smokable material in the smokable rod of the smoking article having the mesoporous molecular sieve, MCM-41, in combination with charcoal, an ion-exchange resin, or both.
It is still yet another object to provide either or both the filter element or the smokable material in the smokable rod of the smoking article having an impregnated mesoporous molecular sieve, MCM-41. MCM-41 can be impregnated with copper oxide for greater HCN and HS reduction.
The aspects and advantages of the present invention will be better understood when the detailed description of the preferred embodiment is taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a graph showing total particulate matter normalized percentage reductions of various vapor phase analytes when utilizing MCM~41 in a cigarette filter.
FIG. 2 is a graph showing total particulate matter normalized percentage reductions of mainstream smoke carbonyls.
FIG. 3 is a graph showing selected vapor phase analytes percentage reductions of
MCM-41 and Sorbite.
FIG. 4 is a graph showing mainstream smoke carbonyl percentage reductions of
MCM-41 and Sorbite.
While this invention is susceptible of embodiments in many different forms, there are shown in the figures and will herein be described in detail, preferred embodiments of the invention with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention, and is not intended to limit the broad aspects of the invention to the embodiments illustrated. 16 The present invention provides for an article for smoking with a mesoporous molecular sieve, MCM-41, to filter vapor phase constituents from mainstream tobacco smoke. Vapor phase constituents to be filtered contact MCM-41 and are retained within the pores, thereby providing a separation of the undesirable constituents from the remainder of the vapor. MCM-41 is typically a black or white granular material with a density of =~0.3g/cm’ and a BET surface area of ~1000m?/g. Although pore wall thickness may vary,
MCM-41 typically has a uniform pore diameter of ~3.7nm, when cetyltrimethyl ammonium bromide is used.
The following examples are given for illustrative purposes only and are not to be deemed as limitative of the scope of the invention.
Example 1
MCM-41 ADSORPTIVE PROPERTIES
To evaluate the adsorptive properties of MCM-41, MCM-41 was tested in hand-made cavity filters and compared to semolina (inert flour granules used to simulate a granule-filled cavity). Hand-made cavity filters can be made by first removing the cellulose acetate (CA) filter of a cigarette. Shortened segments of CA on the tobacco and mouth end of the filter create a cavity to hold the granular material.
The MCM-41 sample sets were prepared according to usual synthesis procedure, except for minor modifications. MCM-41 was developed by Exxon/Mobil, but sample sets for experiment purposes were developed in the laboratory. Water, the surfactant cetyltrimethyl ammonium bromide (CTAB), and tetraethyl orthosilicate (TEOS) were mixed, in order, in a 250mL glass bottle until a cloudy white suspension was achieved. CTAB and
TEOS were combined with a surfactant:silica mole ratio of 1:2. The solution’s surfactant concentration, by total weight, equaled 25%. Concentrated sulfuric acid was added drop wise until the mixture changed to a clear liquid. The solution was stirred at approximately 400 rpm for .5 hours, and then placed under static autogenous conditions (121°C, 18psi) for 1 hour. The resulting ge! was removed from the autoclave and allowed to cool before being washed thoroughly with deionized water. The washed material was heated at 570°C for six to eight hours in air, resulting in a porous material with a BET surface area of =1 300mg.
Sample sets of cigarettes containing SOmg of a granular additive in a hand-made cavity filter were prepared using either MCM-41 synthesized as described above or semolina.
Each sample set was pressure drop selected to decrease smoke delivery variances. Samples were conditioned (65% relative humidity and 75°C for 48 hours) and analyzed for total measured vapor phase (TMVP), mainstream smoke (MSS) HCN, and MSS carbonyl deliveries.
Cigarettes with cavities containing 50mg of either semolina or MCM-41 were analyzed for TMVP smoke deliveries. TABLE A shows the results for selected vapor phase smoke compounds, comparing semolina with MCM-41:
TABLE A. Vapor Phase Smoke Analysis Data (uglcig) mun
Hydrogensuffide | 21.0 | ~~ 223 “Hydrogencyanide | 764 | 68.4 — Methanol | 795 | 304
Acetaldenyde | 6470 | 5361
Vinyichloride | 00 [00 i,3Butadiene | 556 | 542
Acetonitrile | 696 | 336
Propyleneoxide | 28 | 18 ~~ Acolein | 820 | = 458 — Fuan | 279 | 224
Propionaldehyde | 627 | 333
Acetone | 2285 | 911
Acrylonitile | 103 | = 60
Carbondisuide | 38 | 40 371.5 Propionttrle | 116 | 45 iButyradehyde | 184 | 100
Methacrylonitrile | 22 | 12 nButyrakdehyde | 65 | 35
Methylethylketone | 483 | 150
Crotonaldehyde | 126 | ~~ 68
Benzene | 351 | = 383
Styrene | 80 | 13
Total TMVP | 19361 | 14243
TMVP/TPM 147.8 112.1 g/mg
MCM-41 showed a greater reduction of analytes in the TMVP/TPM of 112.1pg/mg.
TMVP/TPM was higher with semolina (147.8pg/mg). FIG. 1 shows computed total particulate matter (TPM) normalized percentage reductions for various vapor phase constituents. These data suggest that the MCM-41 sample exhibited high filtration efficiencies for nitriles, ketones, and aldehydes when compared to the semolina control.
: Large percentage reductions were shown for the analytes Propionitrile (58%), Methanol (59%), Methyl Ethyl Ketone (66%), and Propionaldehyde (43%). Overall, TMVP deliveries were reduced by 24% when utilizing MCM-41.
Mainstream smoke (MSS) carbonyl deliveries for semolina and MCM-41 are compared in TABLE B:
TABLE B. MSS Carbonyl Deliveries (ug/cig) 276.4 Acolein | 1161 | 482
Butyraldehyde | 458 | 14.1 [Crotonaldehyde | 28.0 | 108
Formaldehyde | 657 | 344
Propionaideyde | 582 | 245 tl I ne mg
MCM-41 yielded less carbonyl in the mainstream smoke delivery than did semolina: 52.3pg/mg compared with 104.3pug/mg, respectively. TPM normalized percentage reduction for mainstream smoke carbonyls is shown in FIG. 2. The data indicates that the MCM-41 sample displayed an increased affinity for MSS carbonyls versus the semolina control. The
MCM-41 sample reduced mainstream smoke carbonyl deliveries by a total of 49% compared to the semolina sample, MCM-41 reductions above 50% were calculated, versus the control, for the analytes acrolein, acetone, butanone, and butyraldehyde. Measured formaldehyde deliveries, when using MCM-41, showed a 34% reduction versus semolina.
TABLE C shows a summary of mean polycyclic aromatic hydrocarbon (PAH) deliveries in particulate phase smoke:
TABLE C. The Mean Levels of PAHs for the Cigarette Samples
MCM-41
Naphthalene | 3656] 284.5 1272] 134.9
Phenanthrene | 1034] 113.7
Anthracene | 403] 43.6]
Fluorenthene | ~~ 587] 61.5
Benzofiuorene | 303] 32.0)
Benzolelpyrene | 37] 38]
BAP
Perylene | 08 0.7]
Dibenzanthracene | 02] 02
Benzoperylene | 11] 1.2
Total PAH (ng/cig 816.4 763.9
Puff Number 69] 68
EE ad we ng/mg 72.0 64.6
Sol I I ng/mg 0.51
When comparing the semolina with MCM-41, total particulate matter (TPM) normalized results suggest naphthalene deliveries were reduced by =29%. This effect may be due to the fact that naphthalene is the smallest and most volatile of the PAHs measured, demonstrating
MCM-41’s high affinity for small and volatile compounds. All other PAH compounds analyzed failed to show an appreciable affinity for the MCM-41 sample versus the control.
To summarize, the MCM-41 samples were found to be an effective adsorbent for select constituents found in mainstream smoke. Significant reductions were observed for nitrile, aldehyde, and ketone deliveries. In addition, PAH deliveries indicate reduction for naphthalene. MCM-41 has an affinity for molecules that form strong intermolecular bonds,
and theretore, no reductions were observed for the analytes 1,3-butadiene, isoprene, furan, and benzene. The MCM-41 samples exhibited high filtration efficiencies for nitriles, aldehydes, and ketones when compared to the semolina control. In addition, MCM-41 displayed selectivity for naphthalene.
Example 2
MCM-41 IN COMPARISON TO SORBITE AS A CIGARETTE FILTER ADDITIVE
To evaluate the filtration efficiency of MCM-41, MCM-41 and Sorbite, a coal-based activated carbon derived from semi-anthracite coal, available from Calgon Carbons, were placed in hand-made cavity filtered cigarettes, the properties of which are explained above, and the filtration efficiencies of both were compared. Semolina was utilized as a control.
The highly porous nature of MCM-41 invited the comparison to activated carbons, such as
Sorbite. The MCM—41 samples were prepared according to the above-stated method. Sorbite was used without modification.
Three sample sets were prepared with hand-made cavity filtered cigarettes. TABLE D 156 lists the filter additives and loadings for each sample:
TABLE D. Loading Amounts for Filter Components —E
The samples were pressure drop selected to diminish variances in aerosol deliveries. After conditioning, the samples were analyzed for total measured vapor phase (TMVP), polycyclic aromatic hydrocarbon (PAH), and mainstream smoke carbonyl (MSS carbonyl) deliveries.
All three samples were analyzed for TMVP. TABLE E lists vapor phase deliveries for each sample:
TABLE E. Vapor Phase Smoke Analysis Data (nglclg)
Sorbite/Semolina | MCM-41/Semolina 1,3-Butadiene
Acetaldehyde e274 | 6%2 | 5418 “Acetone | _ 2947 | 2165 | 1209
Acetonitrile 42 | ess | a62 “Morolein | _ 750 | soe | 434
Cherylontuile | 133 | 100 | 87 "Benzene | 589 | 318 | 412
Carbon Disulfide | __ 41 | 38 | 39
Crotonaldehyde __ | _ 216 | 63 | 83
Furan | #14 | ser | 388 “Hydrogen Cyanide _|__ 780 | 733 | 707
Hydrogen Sulfide | _ 200 | 151 | 199
Tlsoprene | 5514 | a2 | 4737 “Methacrylonitiie __|__ 25 | 15 | 13 “Methanol | 808 | 723 | = 348 "Methyl Ethyl Ketone | 684 | 320 | 171 ‘Propionaidehyde | 582 | 457 | 304
Proplonitlle | 138 | 81 | 52
PropyleneOxide | 38 | 38 | 30 ‘Styrene | _58 | 25 | 38
Toluene | 627 | 238 | 357
Vinyl Chloride Ba. | Ba | sa. \.Butyraldehyde __| 287 | 210 | 182
N-Butyraldehyde 8.7 5.3 4.4
TMVP 2273.1 1863.7 1648.7
TPM 12.6 12.8 12.5
TMVP/TPM 180.4 145.6 131.9
A direct comparison of the vapor phase data for MCM-41 and Sorbite reveals that, while activated carbons are a good general adsorbent for a broad range of analytes, MCM-41 is selective for the more polar analytes such as nitriles, aldehydes, ketones, and alcohols. This affinity for polar molecules can be explained by their strong intermolecular bonding with pendant hydroxide groups on the surface of the silica, and FIG. 3 displays the selectivity of
MCM-4L.
All three samples were also analyzed for mainstream smoke carbonyls with the deliveries listed in TABLE F:
TABLE F. MSS Carbonyl Deliveries (ug/cig) semolina_| Sorbite/Sem* | MCM41/Sem"
Acetaldehyde e415 | 5612 | 5398 ‘Acetone | 266.7 | 1642 | 1049
Butanone | 747 | 330 | 248 [Butyraldenyde | 408 | 198 | 185
Crotonaldehyde | 272 | 167 | 116 [Formaldehyde | 51.8 | 436 [| 401
Proplonaldehyde | 539 | 336 | 350 [Total Carbonyls | 12533 | 9366 | 8420 [Total Carbonyls/TPM | 99.5 | 732 | 67.4 *Sem= Semolina
TABLE F shows mainstream smoke carbonyl deliveries comparing semolina,
Sorbite/semolina, and MCM-41/semolina. MCM-41 delivered 842.0pg/cigarette total carbonyls, while Sorbite delivered more carbonyls: 936.6p.g/cigarette. FIG. 4 shows normalized percentage reductions for mainstream smoke carbonyls of MCM-41 and Sorbite.
These results were consistent with the results of the vapor phase analyses. Reductions observed for the surfactant templated silica were (at a minimum) comparable to reductions for the Sorbite samples. A few analytes, such as acetone and crotonaldehyde, had greater reductions.
Deliveries of polycyclic aromatic hydrocarbons (PAHs) were measured because of known reductions in naphthalene for samples containing MCM-41. TABLE G shows a complete list of PAH test results:
TABLE G. Polycyclic Aromatic Hydrocarbons (PAH) Analysis Data (pg/cig)
PAHS - FTC [ Semolina | Sorbite/Sem | MCM41/Sem
Anthracene | 408 | 414 | 421 (Benzofalpyrene | 62 | 62 | 62
Benzofelpyrene | 44 | 46 | 45 : (Benzofluorene | 285 | 287 | 308 ‘Benzoperylene | 12 | 12 | 12 (Chrysene______ | 188 | 190 | 194 [Fluoranthene | 470 | 458 [| 484
Fluorens | 1300 | 126.0 | 1315 (Naphthalene | 4530 | 198.0 | 271.0
Perylene | 06 | 08 | 06 111.0 1105 | 1110
Pyrene | 395 | 380 | 308
PAHS TPM 133 | 127 | 132
Total PAH | ©9049 | 6453 | 7320
Total PAH/TPM | 683 | 507 | 554
Total particulate matter (TPM) normalized reductions of naphthalene versus a semolina control for MCM-41 was ~40%, and for Sorbite was =54%. No other reductions in PAHs were observed. Although naphthalene is the smallest and most volatile of the PAH analytes measured, reductions in naphthalene are presumably due to its volatility and not its size. The pore diameter of MCM~41 is large relative to anthracene, the next smallest analyte measured, in which no reductions were observed. These numbers reflect the capacity of Sorbite to adsorb non-polar molecules.
To summarize, the MCM-41 sample was found to be more selective for polar smoke constituents and outperformed the Sorbite for the removal of nitriles, ketones, alcohols, and aldehydes. The Sorbite sample was more selective for non-polar smoke constituents such as benzene, toluene, styrene, isoprene, and naphthalene. MCM-41 can compliment Sorbite and other additives, such as an ion-exchange resin, as a co-additive.
EXAMPLE 3
COPPER OXIDE IMPREGNATED MCM-41
A sample of MCM-41 was prepared using the process as described in EXAMPLE 1.
Additionally, copper nitrate was introduced into the MCM-41 reaction solution with a concentration of 3% by weight. The resulting gel was calcined at 400°C, forming a copper oxide impregnated MCM-41 having the same high surface area and vapor phase capacity as pure MCM-41, but with the added ability to reduce hydrogen cyanide and hydrogen sulfide.
Compared to the semolina control as previously described, copper oxide impregnated MCM- 41 showed a 56% reduction in HCN ad a 35% reduction in HaS.
The foregoing detailed description is given primarily for clearness of understanding and no unnecessary limitations are to be understood therefrom, for modifications will become obvious to those skilled in the art upon reading this disclosure, and may be made without departing from the spirit of the invention and scope of the appended claims.
Claims (40)
1. A smoking article, comprising: a smokable material circumscribed with a wrapping material to form a smokable rod; and, an axially aligned filter element, wherein said filter element includes a mesoporous molecular sieve.
2. The article of claim 1, wherein said mesoporous molecular sieve is disposed within said filter element.
3. The article of claim 1, wherein said filter element includes a plurality of filter cavities, wherein one or more of said filter cavities includes a mesoporous molecular sieve.
4. The article of claim 1, wherein said mesoporous molecular sieve is MCM-41.
S. The article of claim 1, wherein said mesoporous molecular sieve is a surfactant templated silica gel having an organized hexagonal array of uniform pores.
6. The article of claim 5, wherein said uniform pores have diameters of from about 15A to about 100A.
7. A smoking article, comprising: a smokable material circumscribed with a wrapping material to form a smokable rod; and, an axially aligned filter element, wherein said smokable material includes a mesoporous molecular sieve, said mesoporous molecular sieve being disposed within said smokable rod.
8. The article of claim 7, wherein said wrapping material is coated with said mesoporous molecular sieve.
9. The article of claim 7, wherein said mesoporous molecular sieve is MCM441.
10. The article of claim 7, wherein said mesoporous molecular sieve is a surfactant templated silica gel having an organized hexagonal array of uniform pores.
11. The article of claim 10, wherein said uniform pores have diameters of from about 15A to about 100A.
12. A smoking article, comprising: a smokable material circumscribed with a wrapping material to form a smokable rod; and, an axially aligned filter element, wherein said smokable material, said wrapping material, and said filter element include a mesoporous molecular sieve, said mesoporous molecular sieve being disposed within said smokable material and said filter element and coated on said wrapping material.
13. The article of claim 12, wherein said mesoporous molecular sieve is MCM-41.
14. The article of claim 12, wherein said mesoporous molecular sieve is a surfactant templated silica gel having an organized hexagonal array of uniform pores
15. The article of claim 14, wherein said uniform pores have diameters of from about 15A to about 100A.
16. A cigarette, comprising: a tobacco rod with a filter element attached thereto; and a mesoporous molecular sieve.
17. The cigarette of claim 16, wherein said mesoporous molecular sieve is disposed within said filter element.
18. The cigarette of claim 16, wherein said filter element includes a plurality of filter cavities. .
19. The cigarette of claim 18, wherein one or more of said filter cavities includes said mesoporous molecular sieve.
20. The cigarette of claim 16, wherein said filter element is attached in axial alignment with a tobacco-filled smokable rod, said smokable rod including said mesoporous molecular sieve disposed therein.
21. The cigarette of claim 20, wherein said filter clement and said smokable rod are circumscribed with a wrapping paper, said wrapping paper coated with said mesoporous molecular sieve.
22. The cigarette of claim 16, wherein said mesoporous molecular sieve is MCM-41.
23. The cigarette of claim 16, wherein said mesoporous molecular sieve is a surfactant templated silica gel having an organized hexagonal array of uniform pores.
24. The cigarette of claim 23, wherein said uniform pores have diameters from about 15A to about 100A.
25. A smoking article, comprising: a smokable material circumscribed with a wrapping material to form a smokable rod; and, an axially aligned filter element, wherein said smoking article includes a mesoporous molecular sieve and a plurality of additives.
26. The article of claim 25, wherein said mesoporous molecular sieve and said additives are disposed within said smokable material.
57. The article of claim 25, wherein said mesoporous molecular sieve and said additives are disposed within said filter element.
28. The article of claim 25, wherein said mesoporous molecular sieve and said additives are disposed within said smokable material and said filter element.
29. The article of claim 25, wherein said filter clement includes a plurality of filter cavities, and wherein one or more of said filter cavities includes said mesoporous molecular sieve and said additives.
30. The article of claim 25, wherein said mesoporous molecular sieve is MCM-41.
31. The article of claim 25, wherein said mesoporous molecular sieve is a surfactant templated silica gel having an organized array of uniform pores.
32. The article of claim 31, wherein said uniform pores have diameters from about 15A to about 100A.
33. The article of claim 25, wherein one of said additives is an activated carbon.
34. The article of claim 33, wherein said activated carbon is a Sorbite.
35. The article of claim 25, wherein one of said additives is an ion-exchange resin.
36. A smoking article, comprising: a smokable material circumscribed with a wrapping material to form a smokable rod; and, an axially aligned filter element, wherein said smoking article includes a mesoporous molecular sieve impregnated with copper oxide.
37. The article of claim 36, wherein said mesoporous molecular sieve impregnated with copper oxide is disposed within said smokable material.
38. The article of claim 36, wherein said filter element includes said mesoporous molecular sieve impregnated with copper oxide disposed therein.
39. The article of claim 36, wherein said filter element is comprised of a plurality of filter cavities, and wherein one or more of said filter cavities includes said mesoporous molecular sieve impregnated with copper oxide.
40. The article of claim 36, wherein said mesoporous molecular sieve impregnated with copper oxide is disposed within said smokable material and said filter element.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/860,775 US20050268925A1 (en) | 2004-06-03 | 2004-06-03 | Application of mesoporous molecular sieves as selective smoke filtration additives |
Publications (1)
| Publication Number | Publication Date |
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| ZA200610096B true ZA200610096B (en) | 2008-07-30 |
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ID=34967712
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| ZA200610096A ZA200610096B (en) | 2004-06-03 | 2006-12-01 | Application of mesoporous molecular sieves as selective smoke filtration additives |
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| US (1) | US20050268925A1 (en) |
| EP (1) | EP1750530A1 (en) |
| CN (1) | CN101010013A (en) |
| AR (1) | AR050414A1 (en) |
| BR (1) | BRPI0511750A (en) |
| CA (1) | CA2567295A1 (en) |
| GT (1) | GT200500131A (en) |
| PA (1) | PA8635701A1 (en) |
| PE (1) | PE20060071A1 (en) |
| RU (1) | RU2337596C1 (en) |
| SV (1) | SV2005002133A (en) |
| TW (1) | TW200614926A (en) |
| UY (1) | UY28928A1 (en) |
| WO (1) | WO2005120261A1 (en) |
| ZA (1) | ZA200610096B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7479098B2 (en) | 2005-09-23 | 2009-01-20 | R. J. Reynolds Tobacco Company | Equipment for insertion of objects into smoking articles |
| ES2301392B1 (en) | 2006-11-07 | 2009-06-09 | Universidad De Alicante | TOBACCO-CATALYST BLENDS FOR REDUCTION OF TOXIC COMPOUNDS PRESENT IN TOBACCO SMOKE. |
| US8186360B2 (en) * | 2007-04-04 | 2012-05-29 | R.J. Reynolds Tobacco Company | Cigarette comprising dark air-cured tobacco |
| EP2537427B1 (en) | 2008-05-21 | 2016-08-17 | R.J. Reynolds Tobacco Company | Cigarette filter having composite fiber structures |
| US8613284B2 (en) | 2008-05-21 | 2013-12-24 | R.J. Reynolds Tobacco Company | Cigarette filter comprising a degradable fiber |
| US8079369B2 (en) | 2008-05-21 | 2011-12-20 | R.J. Reynolds Tobacco Company | Method of forming a cigarette filter rod member |
| US8434498B2 (en) | 2009-08-11 | 2013-05-07 | R. J. Reynolds Tobacco Company | Degradable filter element |
| US20120000481A1 (en) | 2010-06-30 | 2012-01-05 | Dennis Potter | Degradable filter element for smoking article |
| CN101934234B (en) * | 2010-09-13 | 2012-07-04 | 中南大学 | Mesoporous molecular sieve catalyst for catalytic cracking of waste plastics as well as preparation method and application thereof |
| US8973588B2 (en) | 2011-07-29 | 2015-03-10 | R.J. Reynolds Tobacco Company | Plasticizer composition for degradable polyester filter tow |
| US20130167849A1 (en) | 2011-12-28 | 2013-07-04 | Balager Ademe | Method of tipping for smoking article |
| US20130167851A1 (en) | 2011-12-28 | 2013-07-04 | Balager Ademe | Method of filter assembly for smoking article |
| US20160073686A1 (en) | 2014-09-12 | 2016-03-17 | R.J. Reynolds Tobacco Company | Tobacco-derived filter element |
| US10226066B2 (en) | 2016-03-07 | 2019-03-12 | R.J. Reynolds Tobacco Company | Rosemary in a tobacco blend |
| CN106858717A (en) * | 2017-04-10 | 2017-06-20 | 滁州卷烟材料厂 | The filter tip of carbonyls in a kind of selectivity reducing cigarette fume |
| CN113576027A (en) * | 2021-08-25 | 2021-11-02 | 上海烟草集团有限责任公司 | Composite filter stick for reducing propionaldehyde in cigarette smoke and cigarette |
| CN113558290A (en) * | 2021-08-26 | 2021-10-29 | 上海烟草集团有限责任公司 | Method for reducing acetone in cigarette smoke |
| CN114669272A (en) * | 2022-02-24 | 2022-06-28 | 昆明理工大学 | Adsorbent for synergistically removing dust, hydrogen fluoride and hydrogen chloride in copper smelting flue gas and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3338246A (en) * | 1964-05-04 | 1967-08-29 | Union Carbide Corp | Smoking tobacco preparation |
| US3292636A (en) * | 1964-05-04 | 1966-12-20 | Union Carbide Corp | Smoking tobacco preparation |
| US3347245A (en) * | 1965-12-27 | 1967-10-17 | Edward J Hawkins | Filter cigarette |
| US3572348A (en) * | 1968-08-01 | 1971-03-23 | Liggett & Myers Inc | Tobacco composition |
| US3703901A (en) * | 1971-03-11 | 1972-11-28 | Liggett & Myers Inc | Tobacco composition |
| US4317460A (en) * | 1978-01-20 | 1982-03-02 | Gallaher Limited | Smoking products |
| FR2446127A1 (en) * | 1979-01-12 | 1980-08-08 | Gallaher Ltd | Supported redox catalysts contg. chemically bound copper - esp. useful as oxidn. catalysts in tobacco products (NL 15.7.80) |
| US5246689A (en) * | 1990-01-25 | 1993-09-21 | Mobil Oil Corporation | Synthetic porous crystalline material its synthesis and use |
| US5102643A (en) * | 1990-01-25 | 1992-04-07 | Mobil Oil Corp. | Composition of synthetic porous crystalline material, its synthesis |
| US5198203A (en) * | 1990-01-25 | 1993-03-30 | Mobil Oil Corp. | Synthetic mesoporous crystalline material |
| JP3233169B2 (en) * | 1992-05-03 | 2001-11-26 | 株式会社西部技研 | Element for total heat exchanger and method for producing the same |
| US5534368A (en) * | 1994-05-12 | 1996-07-09 | Morris; Jerry L. | Battery module |
| PT740907E (en) * | 1995-05-03 | 2002-05-31 | British American Tobacco Co | SMOKING PRODUCT |
| US20020166564A1 (en) * | 1997-12-19 | 2002-11-14 | Sung Michael T. | Silica resin filter for smoking articles |
| US6209547B1 (en) * | 1998-10-29 | 2001-04-03 | Philip Morris Incorporated | Cigarette filter |
| CA2359825C (en) * | 2000-10-26 | 2008-09-23 | Quanjie Liu | A mesoporous aluminum based molecular sieve and a process for the preparation of the same |
| FR2820342B1 (en) * | 2001-02-07 | 2003-12-05 | Inst Francais Du Petrole | PROCESS FOR THE PREPARATION OF ZEOLITHIC MEMBRANES SUPPORTED BY TEMPERATURE CONTROLLED CRYSTALLIZATION |
| US6563988B2 (en) * | 2001-04-25 | 2003-05-13 | Lightwave Microsystems Corporation | Optical apparatus and method having predetermined group velocity dispersion |
| MY135471A (en) * | 2002-01-09 | 2008-04-30 | Philip Morris Prod | Cigarette filter with beaded carbon |
| US20040020504A1 (en) * | 2002-03-15 | 2004-02-05 | Rothmans, Benson & Hedges Inc. | Low sidestream smoke cigarette with combustible paper having a modified ash |
| US8381738B2 (en) * | 2003-12-22 | 2013-02-26 | Philip Morris Usa Inc. | Composite materials and their use in smoking articles |
-
2004
- 2004-06-03 US US10/860,775 patent/US20050268925A1/en not_active Abandoned
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2005
- 2005-04-29 EP EP05743017A patent/EP1750530A1/en not_active Withdrawn
- 2005-04-29 BR BRPI0511750-0A patent/BRPI0511750A/en not_active IP Right Cessation
- 2005-04-29 WO PCT/US2005/015022 patent/WO2005120261A1/en active Application Filing
- 2005-04-29 CA CA002567295A patent/CA2567295A1/en not_active Abandoned
- 2005-04-29 RU RU2006146202/12A patent/RU2337596C1/en not_active IP Right Cessation
- 2005-04-29 CN CNA2005800182850A patent/CN101010013A/en active Pending
- 2005-05-24 PE PE2005000571A patent/PE20060071A1/en not_active Application Discontinuation
- 2005-05-27 UY UY28928A patent/UY28928A1/en not_active Application Discontinuation
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- 2005-06-01 GT GT200500131A patent/GT200500131A/en unknown
- 2005-06-02 TW TW094118086A patent/TW200614926A/en unknown
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- 2005-06-03 PA PA20058635701A patent/PA8635701A1/en unknown
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| TW200614926A (en) | 2006-05-16 |
| CN101010013A (en) | 2007-08-01 |
| PE20060071A1 (en) | 2006-02-12 |
| AR050414A1 (en) | 2006-10-25 |
| US20050268925A1 (en) | 2005-12-08 |
| EP1750530A1 (en) | 2007-02-14 |
| CA2567295A1 (en) | 2005-12-22 |
| RU2006146202A (en) | 2008-07-20 |
| WO2005120261A1 (en) | 2005-12-22 |
| UY28928A1 (en) | 2006-01-31 |
| PA8635701A1 (en) | 2006-10-13 |
| GT200500131A (en) | 2006-01-10 |
| RU2337596C1 (en) | 2008-11-10 |
| BRPI0511750A (en) | 2008-01-02 |
| SV2005002133A (en) | 2011-03-22 |
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