U.S. patent application number 10/202891 was filed with the patent office on 2004-01-29 for adsorbents for smoking articles comprising a non-volatile organic compound applied using a supercritical fluid.
Invention is credited to Thomas, Charles.
Application Number | 20040016436 10/202891 |
Document ID | / |
Family ID | 30769929 |
Filed Date | 2004-01-29 |
United States Patent
Application |
20040016436 |
Kind Code |
A1 |
Thomas, Charles |
January 29, 2004 |
Adsorbents for smoking articles comprising a non-volatile organic
compound applied using a supercritical fluid
Abstract
A surface-modified adsorbent and a process for making a
surface-modified adsorbent are provided. The process involves
providing an adsorbent and a non-volatile organic compound to a
vessel, adjusting the temperature and/or pressure to provide
supercritical conditions for a supercritical fluid, and introducing
the supercritical fluid into the vessel. The supercritical fluid
dissolves the non-volatile organic compound, and impregnates the
adsorbent with the non-volatile organic compound. The
surface-modified adsorbent can be used, for example, in cut filler
compositions, cigarette filters, and smoking articles. Methods for
making cigarette filters, cigarettes and for smoking a cigarette
comprising the surface-modified adsorbent are also provided. The
surface-modified adsorbents can be used to remove one or more
selected components from mainstream smoke, without removing other
components, such as those that contribute to flavor.
Inventors: |
Thomas, Charles; (Richmond,
VA) |
Correspondence
Address: |
Peter K. Skiff
BURNS, DOANE, SWECKER & MATHIS, L.L.P.
P.O. Box 1404
Alexandria
VA
22313-1404
US
|
Family ID: |
30769929 |
Appl. No.: |
10/202891 |
Filed: |
July 26, 2002 |
Current U.S.
Class: |
131/202 ;
131/203 |
Current CPC
Class: |
A24D 3/022 20130101;
A24D 3/163 20130101 |
Class at
Publication: |
131/202 ;
131/203 |
International
Class: |
A24D 001/04 |
Claims
What is claimed is:
1. A process for making a surface-modified adsorbent, said process
comprising: (i) providing at least one adsorbent and at least one
non-volatile organic compound to a vessel; (ii) adjusting
temperature and/or pressure to provide supercritical conditions in
said vessel for a supercritical fluid; and (iii) introducing the
supercritical fluid into the vessel, such that the supercritical
fluid dissolves the non-volatile organic compound, and wherein the
supercritical fluid with the dissolved non-volatile organic
compound impregnates the adsorbent to form a surface-modified
adsorbent.
2. The process of claim 1, wherein the adsorbent is selected from
the group consisting of: adsorbent carbon, activated carbon, silica
gel, alumina, polyester resins, zeolites or zeolite-like materials,
and mixtures thereof.
3. The process of claim 2, wherein the adsorbent is activated
carbon.
4. The process of claim 3, wherein the activated carbon comprises
at least about 80% micropores.
5. The process of claim 3, wherein the activated carbon has an
average particle size from about 6 mesh to about 300 mesh.
6. The process of claim 3, wherein the activated carbon has an
average particle size from about 0.2 mm to about 1 mm.
7. The process of claim 1, wherein the supercritical fluid is
selected from the group consisting of: carbon dioxide, n-propane,
n-butane, n-pentane, n-hexane, n-heptane, cyclohexane, ethanol,
toluene, acetone, methyl acetate, diethyl ether, dichloromethane,
dichlorodifluoromethane, trifluoromethane, carbon tetrachloride and
mixtures thereof.
8. The process of claim 7, wherein the supercritical fluid is
carbon dioxide.
9. The process of claim 1, wherein the non-volatile organic
compound is selected from the group consisting of: alkenes,
alkynes, cyclic and multicyclic hydrocarbons, aldehydes, ethers,
amides, esters, fatty acids, fatty acid esters, and mixtures
thereof.
10. The process of claim 9, wherein the non-volatile organic
compound is selected from the group consisting of: squalene,
squalane, phytol, sucrose octa-palmitic acid ester, and mixtures
thereof.
11. The process of claim 1, wherein the non-volatile compound is
capable of blocking pores in the adsorbent having an average size
greater than about 20 Angstroms.
12. The process of claim 11, wherein the non-volatile compound is
capable of blocking pores in the adsorbent having an average size
greater than about 10 Angstroms.
13. A surface-modified adsorbent, produced by a process comprising:
(i) providing at least one adsorbent and at least one non-volatile
organic compound to a vessel; (ii) adjusting temperature and/or
pressure to provide supercritical conditions in said vessel for a
supercritical fluid; and (iii) introducing the supercritical fluid
into the vessel, such that the supercritical fluid dissolves the
non-volatile organic compound, and wherein the supercritical fluid
with the dissolved non-volatile organic compound impregnates the
adsorbent to form a surface-modified adsorbent.
14. The surface-modified adsorbent of claim 13, wherein the
adsorbent is selected from the group consisting of: adsorbent
carbon, activated carbon, silica gel, alumina, polyester resins,
zeolite or zeolite-like materials, and mixtures thereof.
15. A surface-modified adsorbent useful as a cigarette filtration
agent wherein the adsorbent preferentially removes one or more
selected components from tobacco smoke while allowing components
that contribute to flavor to pass through the adsorbent, the
adsorbent including pores impregnated with a non-volatile organic
compound.
16. The surface-modified adsorbent of claim 15, wherein the
adsorbent comprises activated carbon having at least about 80%
micropores.
17. The surface-modified adsorbent of claim 15, wherein the
adsorbent comprises activated carbon having an average particle
size from about 6 mesh to about 300 mesh.
18. The surface-modified adsorbent of claim 15, wherein the
adsorbent comprises activated carbon having an average particle
size from about 0.2 mm to about 1 mm.
19. The surface-modified adsorbent of claim 15, wherein the
adsorbent has been prepared by (i) providing at least one adsorbent
and at least one non-volatile organic compound to a vessel; (ii)
adjusting temperature and/or pressure to provide supercritical
conditions in said vessel for a supercritical fluid; and (iii)
introducing the supercritical fluid into the vessel, such that the
supercritical fluid dissolves the non-volatile organic compound,
and wherein the supercritical fluid with the dissolved non-volatile
organic compound impregnates the adsorbent to form a
surface-modified adsorbent.
20. The surface-modified adsorbent of claim 19, wherein the
supercritical fluid is selected from the group consisting of:
carbon dioxide, n-propane, n-butane, n-pentane, n-hexane,
n-heptane, cyclohexane, ethanol, toluene, acetone, methyl acetate,
diethyl ether, dichloromethane, dichlorodifluoromethane,
trifluoromethane, carbon tetrachloride and mixtures thereof.
21. The surface-modified adsorbent of claim 15, wherein the
non-volatile organic compound is selected from the group consisting
of: alkenes, alkynes, cyclic or multicyclic hydrocarbons,
aldehydes, ethers, amides, esters, fatty acids, fatty acid esters,
and mixtures thereof.
22. The surface-modified adsorbent of claim 21, wherein the
non-volatile organic compound is selected from the group consisting
of: squalene, squalane, phytol, sucrose octa-palmitic acid ester,
and mixtures thereof.
23. The surface-modified adsorbent of claim 13, wherein the
non-volatile compound blocks pores in the adsorbent having an
average size greater than about 20 Angstroms.
24. The surface-modified adsorbent of claim 23, wherein the
non-volatile compound blocks pores in the adsorbent having an
average size greater than about 10 Angstroms.
25. A smoking article comprising a surface-modified adsorbent
according to claim 13.
26. The smoking article of claim 25, wherein the smoking article is
a cigarette.
27. The smoking article of claim 25, wherein the surface-modified
adsorbent is dispersed in smoking material.
28. The smoking article of claim 25, wherein the surface-modified
adsorbent is located in a filter.
29. The smoking article of claim 25, wherein the adsorbent is
selected from the group consisting of: adsorbent carbon, activated
carbon, silica gel, alumina, polyester resins, zeolite and
zeolite-like materials, and mixtures thereof.
30. The smoking article of claim 29, wherein the adsorbent is
activated carbon.
31. The smoking article of claim 30, wherein the activated carbon
comprises at least about 80% micropores.
32. The smoking article of claim 30, wherein the activated carbon
has an average particle size from about 6 mesh to about 300
mesh.
33. The smoking article of claim 30, wherein the activated carbon
has an average particle size from about 0.2 mm to about 1 mm.
34. The smoking article of claim 25, comprising from about 10 mg to
about 200 mg of the surface-modified adsorbent.
35. A cigarette filter comprising a surface-modified adsorbent
according to claim 13.
36. The cigarette filter of claim 35, wherein the adsorbent is
selected from the group consisting of: adsorbent carbon, activated
carbon, silica gel, alumina, polyester resins, zeolite or
zeolite-like materials, and mixtures thereof.
37. The cigarette filter of claim 36, wherein the adsorbent is
activated carbon.
38. The cigarette filter of claim 37, wherein the activated carbon
comprises at least about 80% micropores.
39. The cigarette filter of claim 37, wherein the activated carbon
has an average particle size from about 6 mesh to about 300
mesh.
40. The cigarette filter of claim 37, wherein the activated carbon
has an average particle size from about 0.2 mm to about 1 mm.
41. The cigarette filter of claim 35, comprising from about 10 mg
to about 200 mg of the surface-modified adsorbent.
42. A cut filler composition comprising a surface-modified
adsorbent according to claim 13.
43. The cut filler composition of claim 42, wherein the adsorbent
is selected from the group consisting of: adsorbent carbon,
activated carbon, silica gel, alumina, polyester resins, zeolite
and zeolite-like materials, and mixtures thereof.
44. The cut filler composition of claim 43, wherein the adsorbent
is activated carbon.
45. The cut filler composition of claim 44, wherein the activated
carbon comprises at least about 80% micropores.
46. The cut filler composition of claim 44, wherein the activated
carbon has an average particle size from about 10 mesh to about 20
mesh.
47. The cut filler composition of claim 44, wherein the activated
carbon has an average particle size from about 0.2 mm to about 1
mm.
48. A method of making a cigarette filter, said method comprising:
(i) providing a surface-modified adsorbent according to claim 13,
and (ii) incorporating the surface-modified adsorbent into a
cigarette filter.
49. A method of making a cigarette, said method comprising: (i)
providing a cut filler to a cigarette making machine to form a
tobacco rod; (ii) placing a paper wrapper around the tobacco rod;
(iii) providing a cigarette filter according to claim 35; and (iv)
attaching the cigarette filter to the tobacco rod to form the
cigarette.
50. A method of making a cigarette, said method comprising: (i)
adding a surface-modified adsorbent according to claim 13 to a cut
filler; (ii) providing the cut filler comprising the
surface-modified adsorbent to a cigarette making machine to form a
tobacco rod; and (iii) placing a paper wrapper around the tobacco
rod to form the cigarette.
51. A method of smoking the smoking article of claim 26, said
method comprising lighting the cigarette to form smoke and drawing
the smoke through the cigarette, wherein during the smoking of the
cigarette, the surface-modified adsorbent preferentially removes
one or more selected components from mainstream smoke.
Description
FIELD OF INVENTION
[0001] The invention relates generally to surface-modified
adsorbents comprising a non-volatile organic compound, applied to
an appropriate substrate using a supercritical fluid, and processes
for producing same. More specifically, the invention relates to the
use of a surface-modified adsorbent for filters, in particular for
the selective filtration of selected components from mainstream
smoke, i.e. in a cigarette.
BACKGROUND
[0002] Cigarette filters, incorporating various materials that
mechanically, chemically and/or physically remove components of
mainstream cigarette smoke have the disadvantage of non-selectively
filtering components from mainstream smoke, even those components
that contribute to flavor. The result may be a cigarette with an
unsatisfactory taste.
[0003] For instance, carbon has been used to filter various
components from mainstream smoke. Several modified forms of
activated carbon has also been described, for example, in U.S. Pat.
Nos. 5,705,269; 4,062,368; 3,652,461; 3,217,715; and 3,091,550. In
addition, U.S. Pat. No. 6,117,810 describes activated carbon having
zeolite salts crystallized in the pores. However, achieving the
desired selectivity can be difficult. In addition, the production
of such modified activated carbon typically requires additional
processing steps, such as coating the activated carbon with
solutions, filtration, drying and/or crystallization. Further, such
methods are generally unsuitable to effectively impregnate the
adsorbent material, and thus do not penetrate the pores or interior
surfaces.
[0004] Thus, despite various developments in adsorbent and
filtration materials, what is needed in the art are effective and
inexpensive means for producing modified adsorbents, particularly
those suitable for use in smoking articles and cigarette filters.
Preferably, such adsorbents should preferentially remove selected
components from mainstream tobacco smoke, while maintaining other
components, such as those that contribute to flavor, for example.
In particular, such adsorbent materials should preferentially
adsorb selected components such as acrolein, hydrogen cyanide and
acrylonitrile.
SUMMARY
[0005] In one embodiment, the invention relates to a process for
making a surface-modified adsorbent. The process comprises (i)
providing at least one adsorbent and at least one non-volatile
organic compound to a vessel; (ii) adjusting temperature and/or
pressure to provide supercritical conditions in said vessel for a
supercritical fluid; and (iii) introducing the supercritical fluid
into the vessel, such that the supercritical fluid dissolves the
non-volatile organic compound, and wherein the supercritical fluid
with the dissolved non-volatile organic compound impregnates the
adsorbent to form a surface-modified adsorbent. Another embodiment
of the invention relates to the surface-modified adsorbent produced
by this process.
[0006] In another embodiment, the invention relates to a smoking
article comprising the surface-modified adsorbent described above.
A preferred smoking article is a cigarette. The surface-modified
adsorbent is dispersed in smoking material and/or is located in a
filter. Preferably, the smoking article comprises from about 10 mg
to about 200 mg of the surface-modified adsorbent.
[0007] In another embodiment, the invention relates to a cigarette
filter comprising the surface-modified adsorbent described above.
Preferably, the cigarette filter comprises from about 10 mg to
about 200 mg of the surface-modified adsorbent. In yet another
embodiment, the invention relates to a cut filler composition
comprising the surface-modified adsorbent described above.
[0008] Preferably, the adsorbent used in the invention is selected
from the group consisting of: adsorbent carbon, activated carbon,
silica gel, alumina, polyester resins, zeolite, and mixtures
thereof, with activated carbon being particularly preferred.
Preferably, the activated carbon has an average particle size from
about 0.2 mm to about 1 mm.
[0009] Preferably, the supercritical fluid is selected from the
group consisting of: carbon dioxide, n-propane, n-butane,
n-pentane, n-hexane, n-heptane, cyclohexane, ethanol, toluene,
acetone, methyl acetate, diethyl ether, dichloromethane,
dichlorodifluoromethane, trifluoromethane, carbon tetrachloride and
mixtures thereof, with carbon dioxide being particularly
preferred.
[0010] Preferably, the non-volatile organic compound is selected
from the group consisting of: alkenes, alkynes, aldehydes, ethers,
amides, esters, fatty acids, fatty acid esters, and mixtures
thereof, with squalene, squalane, phytol, sucrose octa-palmitic
acid ester, and mixtures thereof being particularly preferred. In a
preferred embodiment, the non-volatile compound is capable of
blocking pores in the adsorbent having an average size greater than
about 20 Angstroms, and more preferably the non-volatile compound
is capable of blocking pores in the adsorbent having an average
size greater than about 10 Angstroms.
[0011] An embodiment of the invention also relates to a method of
making a cigarette filter, said method comprising: (i) providing a
surface-modified adsorbent as described above, and (ii)
incorporating the surface-modified adsorbent into a cigarette
filter.
[0012] Another embodiment of the invention relates to a method of
making a cigarette, said method comprising: (i) providing a cut
filler to a cigarette making machine to form a tobacco rod; (ii)
placing a paper wrapper around the tobacco rod; (iii) providing a
cigarette filter comprising a surface-modified adsorbent as
described above; and (iv) attaching the cigarette filter to the
tobacco rod to form the cigarette. In yet another embodiment, the
invention relates to a method of making a cigarette, said method
comprising: (i) adding a surface-modified adsorbent as described
above to a cut filler; (ii) providing the cut filler comprising the
surface-modified adsorbent to a cigarette making machine to form a
tobacco rod; and (iii) placing a paper wrapper around the tobacco
rod to form the cigarette.
[0013] In yet another embodiment of the invention is provided a
method of smoking a smoking article that comprises a
surface-modified adsorbent as described above, said method
comprising lighting the smoking article to form smoke and inhaling
the smoke, wherein during the smoking of the cigarette, the
surface-modified adsorbent preferentially removes one or more
selected components from mainstream smoke.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Various features and advantages of the invention will become
apparent from the following detailed description of the preferred
embodiments thereof in connection with the accompanying drawings,
in which:
[0015] FIG. 1 is a partially exploded perspective view of a
cigarette incorporating one embodiment of the present invention
wherein folded paper containing the surface-modified adsorbent is
inserted into a hollow portion of a tubular filter element of the
cigarette.
[0016] FIG. 2 is partially exploded perspective view of another
embodiment of the present invention wherein the surface-modified
adsorbent is incorporated in folded paper and inserted into a
hollow portion of a first free-flow sleeve of a tubular filter
element next to a second free-flow sleeve.
[0017] FIG. 3 is a partially exploded perspective view of another
embodiment of the present invention wherein the surface-modified
adsorbent is incorporated in a plug-space-plug filter element.
[0018] FIG. 4 is a partially exploded perspective view of another
embodiment of the present invention wherein the surface-modified
adsorbent is incorporated in a three-piece filter element having
three plugs.
[0019] FIG. 5 is a partially exploded perspective view of another
embodiment of the present invention wherein the surface-modified
adsorbent is incorporated in a four-piece filter element having a
plug-space-plug arrangement and a hollow sleeve.
[0020] FIG. 6 is a partially exploded perspective view of another
embodiment of the present invention wherein the surface-modified
adsorbent is incorporated in a three-part filter element having two
plugs and a hollow sleeve.
[0021] FIG. 7 is a partially exploded perspective view of another
embodiment of the present invention wherein the surface-modified
adsorbent is incorporated in a two-part filter element having two
plugs.
[0022] FIG. 8 is a partially exploded perspective view of another
embodiment of the present invention wherein the surface-modified
adsorbent is incorporated in a filter element which may be used in
a smoking article.
[0023] FIG. 9 is comparison of the selectivity of two
surface-modified adsorbents in removing various components from
mainstream smoke.
DETAILED DESCRIPTION
[0024] The invention provides a process for making a
surface-modified adsorbent, where a non-volatile organic compound
is applied to an adsorbent using a supercritical fluid. The
invention also relates to the surface-modified adsorbent produced
by this process, as well as smoking articles, cigarette filters,
cut filler compositions and methods which incorporate the
surface-modified adsorbent.
[0025] The surface-modified adsorbent can be used as a filtration
agent. In particular, the surface-modified adsorbents of the
invention could be used as filters for a smoking article to
preferentially remove one or more selected components from
mainstream smoke, while retaining other components, such as those
components that contribute to flavor. The term "mainstream" smoke
includes the mixture of gases passing down the tobacco rod and
issuing through the filter end, i.e. the amount of smoke issuing or
drawn from the mouth end of a smoking article during smoking of the
smoking article. The mainstream smoke contains smoke that is drawn
in through the lit region of the smoking article, possibly diluted
by air that is drawn in through the paper wrapper.
[0026] The surface-modified adsorbent is made by the following
process, where a supercritical fluid is used to dissolve a
non-volatile organic compound and impregnate the adsorbent with the
non-volatile organic compound. In the process, at least one
adsorbent and at least one non-volatile organic compound are
provided to a vessel. The temperature and/or pressure conditions
are adjusted to provide supercritical conditions in the vessel for
whichever supercritical fluid or mixture of supercritical fluids is
to be used. The supercritical fluid is introduced into the vessel,
and dissolves the non-volatile organic compound. By "dissolved" is
meant that the non-volatile organic compound is dispersed in the
supercritical fluid. By "non-volatile" is meant that the organic
compound will not pass into the vapor state and will remain a solid
or liquid at standard temperature and pressure.
[0027] The supercritical fluid carrying the dissolved non-volatile
organic compound impregnates the adsorbent, preferably carrying the
non-volatile organic compound into the pores of the adsorbent.
While it is not possible to penetrate the small pores of many
adsorbents using typical coating methods with solutions,
supercritical fluids have the benefit of having densities and
diffusivities similar to liquids but viscosities comparable to
gases, thereby permitting the non-volatile organic compound to
permeate the pores of the adsorbent, in a manner which could not
otherwise be achieved using conventional methods.
[0028] Moreover, in a preferred embodiment, when the supercritical
conditions are removed the supercritical fluid will simply sublime
or vaporize, thus leaving behind a surface-modified adsorbent,
which does not require further purification steps. Since the
organic compound is non-volatile, it will not evaporate or move
from the location where the supercritical fluid carried it, i.e.
into the pores of the adsorbent.
[0029] Typical adsorbents include any material that has the ability
to condense or hold molecules of other substances on its surface.
While not wishing to be bound by theory, adsorption is mainly
caused by London Dispersion Forces, a type of Van der Waals force,
which exists between molecules. The forces act within extremely
short ranges, and are additive. In gas phase adsorption, molecules
are condensed from the bulk phase within the pores of the activated
carbon. The driving force for adsorption is the ratio of the
partial pressure and the vapor pressure of the compound. In liquid
or solid phase adsorption the molecules go from the bulk phase to
being adsorbed in the pores in a semi-liquid or solid state.
[0030] Examples of adsorbents include adsorbent carbon, activated
carbon, silica gel, alumina, polyester resins, zeolite, and
mixtures thereof. Such adsorbents may be manufactured or prepared
using any suitable technique known in the art, or may be purchased
from commercial suppliers.
[0031] While even charcoal or graphite have some ability to adsorb
molecules, activated carbon is particularly preferred as an
adsorbent because activated forms of carbon generally have stronger
physical adsorption forces, and higher volumes of adsorbing
porosity.
[0032] A particularly preferred activated carbon is commercially
available from PICA USA, Inc., Truth or Consequences, N. Mex. The
activated carbon could also be manufactured by any suitable method
known in the art. Such methods include the carbonization of coconut
husk, coal, wood, pitch, cellulose fibers, or polymer fibers, for
example. Carbonization is usually carried out at high temperatures,
i.e. 200-800.degree. C. in an inert atmosphere, followed by
activation under reduced conditions. The activated carbon produced
could be in the form of granules, beads, monoliths, fragments,
powder or fibers.
[0033] In a preferred embodiment, granulated carbon typically
having particles ranging in size from 0.1 mm to about 5 mm is used,
or pelleted carbon having particles ranging in size from 0.5 mm to
about 5 mm is used. In a most preferred embodiment, carbon
particles ranging in size from about 0.2 to 1 mm are used. In terms
of Tyler screen mesh size, the carbon particles are preferably from
about 6 mesh to about 300 mesh, preferably 10 to 70 mesh, and more
preferably from about 14 to 35 mesh.
[0034] Carbon particles also have a distribution of micropores,
mesopores and macropores. The term "microporous" generally refers
to such materials having pore sizes of about 15 .ANG. or less while
the term "mesoporous" generally refers to such materials with pore
sizes of about 15-300 .ANG.. In a preferred embodiment, the
proportion of micropores to mesopores will be about 50:40. In
almost preferred embodiment, the pores of the activated carbon
comprise at least 80% micropores. The relative amounts of ratio of
micropores, mesopores and macropores will depend upon the selected
components from mainstream tobacco smoke that are to be targeted
and removed. Thus, the pore sizes and pore distribution can be
adjusted accordingly as needed for a certain application.
[0035] Another preferred material, which may be used as the
adsorbent is a zeolite. A zeolite is a porous crystalline material
predominantly comprised of aluminosilicate. Zeolite pores may be
more or less uniform and may have pore dimensions over a range of
sizes; the material may further comprise additional metals and
metal oxides. Synthetic zeolite materials may have more uniform
pore dimensions and a more ordered structure. Phosphate -containing
aluminosilicate analogs of zeolites are also known. Various zeolite
types are described, for example, in U.S. Pat. No. 3,702,886
(zeolite ZSM-5), U.S. Pat. No. 2,882,243 (zeolite A), U.S. Pat. No.
2,882,244 (zeolite X), U.S. Pat. No. 3,130,007 (zeolite Y), U.S.
Pat. No. 3,055,654 (zeolite K-G), U.S. Pat. No. 3,247,195 (zeolite
ZK-5), U.S. Pat. No. 3,308,069 (zeolite Beta), U.S. Pat. No.
3,314,752 (zeolite ZK-4). A source of natural zeolite in North
America is the St. Cloud Mining Company, Truth or Consequences, N.
Mex. Preferred zeolite materials include ZSM-5, Y-type zeolite and
clinoptilolite.
[0036] The adsorbent should be selected to have a sufficient
surface area to preferentially adsorb selected components from
cigarette smoke. While surface area is inversely proportional to
particle size, adsorbents having small particle size may pack
together too densely to permit mainstream smoke to flow through the
filter during smoking. If particle size is too large, there will be
insufficient surface area. Therefore, these factors should be
considered in selecting an absorbent having a particular particle
size.
[0037] The non-volatile organic component may further act as a
"solvent" to dissolve mainstream smoke components of the
appropriate solubility characteristics. The non-volatile organic
compound may be selected from organic compounds which effectively
react and immobilize selected components in mainstream smoke, i.e.
by ion exchange, hydrophobic interactions, chelation, and/or
chemically binding. Alternatively, the non-volatile organic
compound may block certain pores of the adsorbent thereby adjusting
the ability of the adsorbent to only adsorb components of a
particular size.
[0038] Suitable non-volatile organic compounds include, but are not
limited to: alkenes, alkynes, aldehydes, ethers, amides, esters,
fatty acids, fatty acid esters, and mixtures thereof. Squalene,
squalane, phytol, sucrose octa-palmitic acid ester, and mixtures
thereof are particularly preferred. In a preferred embodiment, the
non-volatile compound is capable of blocking pores in the adsorbent
having an average size greater than about 20 Angstroms, and more
preferably the non-volatile compound is capable of blocking pores
in the adsorbent having an average size greater than about 10
Angstroms. One or more non-volatile compounds may be used to
achieve a desired result. The amount of the non-volatile compound
that is provided will be adjusted through routine experimentation,
depending on the amount of non-volatile compound desired in the
final surface-modified adsorbent.
[0039] The non-volatile organic compound or mixture of non-volatile
organic compounds used in making the surface-modified adsorbent may
be chosen to target selected components in mainstream smoke, and
may be located either on the exterior and/or interior surfaces of
the adsorbent, or may be embedded within pores of the adsorbent.
The selection of adsorbent material and non-volatile organic
compound permit the preferential removal of one or more selected
components from mainstream smoke, while retaining other components,
such as those relating to flavor. Usually components relating to
flavor are of larger size and/or molecular weight, while smaller
components, such as light gases, various aldehydes and small
molecules may be targeted for removal. For example, in a preferred
embodiment, pores on the adsorbent greater than a particular
average size are blocked. However, the selectivity of the
surface-modified adsorbent can be fine tuned, particularly by the
selection of adsorbent material and non-volatile organic compound,
as well the choice of supercritical fluid. Such optimization can be
achieved using routine experimentation.
[0040] The supercritical fluid used in the invention may be any
suitable supercritical fluid which dissolves the non-volatile
organic compound under supercritical conditions. By supercritical
conditions is meant temperatures and pressures where the solvent is
in the supercritical state, i.e. in the gas phase at a sufficiently
high temperature that it cannot be liquified by an increase in
pressure. The critical temperatures and pressure can be determined
by routine experimentation or reference to books such as the "CRC
Handbook of Chemistry and Physics," 70.sup.th Edition, R. C. Weast
et al., Editors, CRC PRess, Inc., Boca Raton, Fla., 1989. Table A
lists critical temperatures and critical pressures for several
representative examples of fluids.
1TABLE A Critical Temperatures and Critical Pressures for Several
Fluids Fluid T.sub.c (.degree. C.) P.sub.c (atm.) carbon dioxide
31.3 72.9 n-propane 96.8 42 n-butane 152.0 37.5 n-pentane 196.6
33.3 n-hexane 234.2 29.9 n-heptane 267.1 27 cyclohexane 280.4 40
ethanol 243 63 toluene 320.8 41.6 acetone 235.5 47 methyl acetate
233.7 46.3 diethyl ether 192.6 35.6 dichloromethane 237 60
dichlorodifluoromethane 111.8 40.7 trifluoromethane 25.9 46.9
carbon tetrachloride 283.1 45
[0041] Supercritical fluids will preferably have densities and
diffusivities similar to liquids but viscosities comparable to
gases. For instance, preferred supercritical fluids will have
densities from about 0.2-0.9 g/mL, viscosities from about
0.2.times.10.sup.-3 to 1.0.times.10.sup.-3 poise, and diffusivities
from about 0.1.times.10.sup.-4 to about 3.3.times.10.sup.-4
cm.sup.2/sec.
[0042] Suitable supercritical fluids that may be used include, but
are not limited to: carbon dioxide, n-propane, n-butane, n-pentane,
n-hexane, n-heptane, n-cyclohexane, n-hexanol, ethanol, n-pentanol,
toluene, acetone, methyl acetate, diethyl ether, petroleum ethers,
and halogenated hydrocarbons. Examples of halogenated hydrocarbons
include, for example, dichloromethane, difluoroethane,
dichlorodifluoromethane, trifluoromethane and carbon tetrachloride.
Other suitable supercritical fluids or mixtures of supercritical
fluids that dissolve the non-volatile organic compound may also be
used.
[0043] In a preferred embodiment, supercritical carbon dioxide is
used. Carbon dioxide is superfluid above its critical temperature,
i.e. above about 31.3.degree. C., and above its critical pressure,
i.e. above about 70 atmospheres. Supercritical carbon dioxide is
inexpensive and non-toxic. In addition, it may be modified, i.e.
with HCl or NH.sub.3, to make the solvent more acidic or basic in
order, as needed to dissolve the non-volatile organic compound.
[0044] The length of time required to impregnate or form the
surface-modified adsorbent may be determined by routine
experimentation. Typical reaction times will generally be less than
about 60 minutes, more preferably less than about 30 minutes, and
most preferably less than about 15 minutes. For example,
impregnation with carbon dioxide in the supercritical state is
typically carried out at pressures from about 70 atmospheres to
about 1500 atmospheres, and at temperatures in the range of from
above about the critical temperature to about 120.degree. C. for
reaction times of about 15-20 minutes for most non-volatile organic
compounds.
[0045] Any suitable vessel that is capable of maintaining
supercritical conditions may be used. Such vessels are commercially
available. For instance, most vessels used for supercritical fluid
extraction may be used, with minor or no modifications.
[0046] The surface-modified adsorbents may be used in a variety of
applications, including smoking articles, cut filler compositions
and cigarette filters. Thus, in one embodiment, the invention
relates to a smoking article comprising surface-modified
adsorbents. The smoking article may be any article containing
smokeable material, such as a cigarette, a pipe, a cigar and a
non-traditional cigarette. Non-traditional cigarettes include, for
example, cigarettes for electrical smoking systems as described in
commonly-assigned U.S. Pat. Nos. 6,026,820; 5,988,176; 5,915,387;
5,692,526; 5,692,525; 5,666,976; and 5,499,636. The
surface-modified adsorbents may be located in a filter and/or
dispersed in the smoking material itself. An amount effective to
remove or lower the amount of one or more selected components in
mainstream smoke is used. Typical smoking articles will include
from about 10 mg to about 200 mg of the surface-modified
adsorbents, although the amount needed can also be determined
easily by routine experimentation and/or adjusted accordingly.
[0047] The invention further relates to cigarette filters
comprising the surface-modified adsorbents. Any conventional or
modified filter may incorporate the surface-modified adsorbents. In
one embodiment, the surface-modified adsorbent is incorporated into
or onto a support such as paper (e.g., tipping paper) that is
located along a filter portion of a cigarette. As will be
recognized by persons skilled in the art, such paper can be used,
for example, as a wrapper or a liner in the filter portion of the
cigarette. The surface-modified adsorbent can also be loaded onto a
support such as lightly or tightly folded paper inserted into a
hollow portion of the cigarette filter. The support is preferably
in the form of a sheet material such as crepe paper, filter paper,
or tipping paper. However, other suitable support materials such as
organic or inorganic cigarette compatible materials can also be
used.
[0048] FIG. 1 illustrates a cigarette 2 having a tobacco rod 4, a
filter portion 6, and a mouthpiece filter plug 8. As shown, a
surface-modified adsorbent can be loaded onto folded paper 10
inserted into a hollow cavity such as the interior of a free-flow
sleeve 12 forming part of the filter portion 6.
[0049] FIG. 2 shows a cigarette 2 having a tobacco rod 4 and a
filter portion 6, wherein the folded paper 10 is located in the
hollow cavity of a first free-flow sleeve 13 located between the
mouthpiece filter 8 and a second free-flow sleeve 15 . The paper 10
can be used in forms other than as a folded sheet. For instance,
the paper 10 can be deployed as one or more individual strips, a
wound roll, etc. In whichever form, a desired amount of
surface-modified adsorbent can be provided in the cigarette filter
portion by adjusting the amount of surface-modified adsorbent
coated per unit area of the paper and/or the total area of coated
paper employed in the filter (e.g., higher amounts of
surface-modified adsorbent can be provided simply by using larger
pieces of coated paper). In the cigarettes shown in FIGS. 1 and 2,
the tobacco rod 4 and the filter portion 6 are joined together with
tipping paper 14. In both cigarettes, the filter portion 6 may be
held together by filter overwrap 11.
[0050] The surface-modified adsorbent can be incorporated into the
filter paper in a number of ways. For example, the surface-modified
adsorbent can be mixed with water to form a slurry. The slurry can
then be coated onto pre-formed filter paper and allowed to dry. The
filter paper can then be incorporated into the filter portion of a
cigarette in the manner shown in FIGS. 1 and 2. Alternatively, the
dried paper can be wrapped into a plug shape and inserted into a
filter portion of the cigarette. For example, the paper can be
wrapped into a plug shape and inserted as a plug into the interior
of a free-flow filter element such as a polypropylene or cellulose
acetate sleeve. In another arrangement, the paper can comprise an
inner liner of such a free-flow filter element.
[0051] Alternatively, the surface-modified adsorbent is added to
the filter paper during the paper-making process. For example, the
surface-modified adsorbent can be mixed with bulk cellulose to form
a cellulose pulp mixture. The mixture can be then formed into
filter paper according to methods known in the art.
[0052] In another embodiment of the present invention, the
surface-modified adsorbent is incorporated into the fibrous
material of the cigarette filter portion itself. Such filter
materials include, but are not limited to, fibrous filter materials
including paper, cellulose acetate fibers, and polypropylene
fibers. This embodiment is illustrated in FIG. 3, which shows a
cigarette 2 comprised of a tobacco rod 4 and a filter portion 6 in
the form of a plug-space-plug filter having a mouthpiece filter 8,
a plug 16, and a space 18. The plug 16 can comprise a tube or solid
piece of material such as polypropylene or cellulose acetate
fibers. The tobacco rod 4 and the filter portion 6 are joined
together with tipping paper 14. The filter portion 6 may include a
filter overwrap 11. The filter overwrap 11 containing traditional
fibrous filter material and surface-modified adsorbent can be
incorporated in or on the filter overwrap 11 such as by being
coated thereon. Alternatively, the surface-modified adsorbent can
be incorporated in the mouthpiece filter 8, in the plug 16, and/or
in the space 18. Moreover, the surface-modified adsorbent can be
incorporated in any element of the filter portion of a cigarette.
For example, the filter portion may consist only of the mouthpiece
filter 8 and the surface-modified adsorbent can be incorporated in
the mouthpiece filter 8 and/or in the tipping paper 14.
[0053] FIG. 4 shows a cigarette 2 comprised of a tobacco rod 4 and
filter portion 6. This arrangement is similar to that of FIG. 3
except the space 18 is filled with granules of surface-modified
adsorbents or a plug 15 made of material such as fibrous
polypropylene or cellulose acetate containing the surface-modified
adsorbent. As in the previous embodiment, the plug 16 can be hollow
or solid and the tobacco rod 4 and filter portion 6 are joined
together with tipping paper 14. There is also a filter overwrap
11.
[0054] FIG. 5 shows a cigarette 2 comprised of a tobacco rod 4 and
a filter portion 6 wherein the filter portion 6 includes a
mouthpiece filter 8, a filter overwrap 11, tipping paper 14 to join
the tobacco rod 4 and filter portion 6, a space 18, a plug 16, and
a hollow sleeve 20. The surface-modified adsorbent can be
incorporated into one or more elements of the filter portion 6. For
instance, the surface-modified adsorbent can be incorporated into
the sleeve 20 or granules of the surface-modified adsorbent can be
filled into the space within the sleeve 20. If desired, the plug 16
and sleeve 20 can be made of material such as fibrous polypropylene
or cellulose acetate containing surface-modified adsorbent. As in
the previous embodiment, the plug 16 can be hollow or solid.
[0055] FIGS. 6 and 7 show further modifications of the filter
portion 6. In FIG. 6, cigarette 2 is comprised of a tobacco rod 4
and filter portion 6. The filter portion 6 includes a mouthpiece
filter 8, a filter overwrap 11, a plug 22, and a sleeve 20, and the
surface-modified adsorbent can be incorporated in one or more of
these filter elements. In FIG. 7, the filter portion 6 includes a
mouthpiece filter 8 and a plug 24, and the surface-modified
adsorbent can be incorporated in one or more of these filter
elements. Like the plug 16, the plugs 22 and 24 can be solid or
hollow. In the cigarettes shown in FIGS. 6 and 7, the tobacco rod 4
and filter portion 6 are joined together by tipping paper 14.
[0056] Various techniques can be used to apply the surface-modified
adsorbent to filter fibers or other substrate supports. For
example, the surface-modified adsorbent can be added to the filter
fibers before they are formed into a filter cartridge, e.g., a tip
for a cigarette. The surface-modified adsorbent can be added to the
filter fibers, for example, in the form of a dry powder or a slurry
by methods known in the art. If the surface-modified adsorbent is
applied in the form of a slurry (e.g., using a solvent that allows
the organic impregnate to remain on the adsorbate), the fibers are
allowed to dry before they are formed into a filter cartridge.
[0057] In another preferred embodiment, the surface-modified
adsorbent is employed in a hollow portion of a cigarette filter.
For example, some cigarette filters have a plug/space/plug
configuration in which the plugs comprise a fibrous filter material
and the space is simply a void between the two filter plugs. That
void can be filled with the surface-modified adsorbent of the
present invention. An example of this embodiment is shown in FIG.
3. The surface-modified adsorbent can be in granular form or can be
loaded onto a suitable support such as a fiber or thread.
[0058] In another embodiment of the present invention, the
surface-modified adsorbent is employed in a filter portion of a
cigarette for use with a smoking device as described in U.S. Pat.
No. 5,692,525, the entire content of which is hereby incorporated
by reference. FIG. 8 illustrates one type of construction of a
cigarette 100 which can be used with an electrical smoking device.
As shown, the cigarette 100 includes a tobacco rod 60 and a filter
portion 62 joined by tipping paper 64. The filter portion 62
preferably contains a tubular free-flow filter element 102 and a
mouthpiece filter plug 104. The free-flow filter element 102 and
mouthpiece filter plug 104 may be joined together as a combined
plug 110 with plug wrap 112. The tobacco rod 60 can have various
forms incorporating one or more of the following items: an overwrap
71, another tubular free-flow filter element 74, a cylindrical
tobacco plug 80 preferably wrapped in a plug wrap 84, a tobacco web
66 comprising a base web 68 and tobacco flavor material 70, and a
void space 91. The free-flow filter element 74 provides structural
definition and support at the tipped end 72 of the tobacco rod 60.
At the free end 78 of the tobacco rod 60, the tobacco web 66
together with overwrap 71 are wrapped about cylindrical tobacco
plug 80. Various modifications can be made to a filter arrangement
for such a cigarette incorporating a surface-modified adsorbent of
the invention.
[0059] In such a cigarette, a surface-modified adsorbent can be
incorporated in various ways such as by being loaded onto paper or
other substrate material which is fitted into the passageway of the
tubular free-flow filter element 102 therein. It may also be
deployed as a liner or a plug in the interior of the tubular
free-flow filter element 102. Alternatively, the surface-modified
adsorbent can be incorporated into the fibrous wall portions of the
tubular free-flow filter element 102 itself. For instance, the
tubular free-flow filter element or sleeve 102 can be made of
suitable materials such as polypropylene or cellulose acetate
fibers and the surface-modified adsorbent can be mixed with such
fibers prior to or as part of the sleeve forming process.
[0060] In another embodiment, the surface-modified adsorbent can be
incorporated into the mouthpiece filter plug 104 instead of in the
element 102. However, as in the previously described embodiments,
according to the invention, surface-modified adsorbents may be
incorporated into more than one component of a filter portion such
as by being incorporated into the mouthpiece filter plug 104 and
into the tubular free-flow filter element 102.
[0061] The filter portion 62 of FIG. 8 can also be modified to
create a void space into which the surface-modified adsorbent can
be inserted.
[0062] As explained above, surface-modified adsorbents can be
incorporated in various support materials. When the
surface-modified adsorbent is used in filter paper, the particles
may have an average particle diameter of 10 to 100 .mu.m,
preferably 40 to 50 .mu.m. When the surface-modified adsorbent is
used in filter fibers or other mechanical supports such as
plug-type plug cavities, larger particles may be used. Such
particles preferably have a Tyler screen mesh size from 10 to 60,
and more preferably from 14 to 35 mesh.
[0063] The amount of surface-modified adsorbent employed in the
cigarette filter by way of incorporation on a suitable support such
as filter paper and/or filter fibers depends on the amount of
constituents in the tobacco smoke and the amount of constituents
desired to be removed. As an example, the filter paper and the
filter fibers may contain from 10% to 50% by weight of the
surface-modified adsorbent.
[0064] An embodiment of the invention relates to a method of making
a cigarette filter, said method comprising: (i) providing a
surface-modified adsorbent as described above, and (ii)
incorporating the surface-modified adsorbent into a cigarette
filter. Any conventional or modified methods for making a filter
may be used to incorporate the surface-modified adsorbent.
[0065] Another embodiment of the invention relates to a method of
making a cigarette, said method comprising: (i) providing a cut
filler to a cigarette making machine to form a tobacco rod; (ii)
placing a paper wrapper around the tobacco rod; (iii) providing a
cigarette filter comprising a surface-modified adsorbent as
described above; and (iv) attaching the cigarette filter to the
tobacco rod to form the cigarette. In yet another embodiment, the
invention relates to a method of making a cigarette, said method
comprising: (i) adding a surface-modified adsorbent as described
above to a cut filler; (ii) providing the cut filler comprising the
surface-modified adsorbent to a cigarette making machine to form a
tobacco rod; and (iii) placing a paper wrapper around the tobacco
rod to form the cigarette.
[0066] Examples of suitable types of tobacco materials which may be
used include flue-cured, Burley, Maryland or Oriental tobaccos, the
rare or specialty tobaccos, and blends thereof. The tobacco
material can be provided in the form of tobacco lamina; processed
tobacco materials such as volume expanded or puffed tobacco,
processed tobacco stems such as cut-rolled or cut-puffed stems,
reconstituted tobacco materials; or blends thereof. The invention
may also be practiced with tobacco substitutes.
[0067] In cigarette manufacture, the tobacco is normally employed
in the form of cut filler, i.e. in the form of shreds or strands
cut into widths ranging from about {fraction (1/10)} inch to about
{fraction (1/20)} inch or even {fraction (1/40)} inch. The lengths
of the strands range from between about 0.25 inches to about 3.0
inches. The cigarettes may further comprise one or more flavorants
or other additives (e.g. burn additives, humectants, combustion
modifying agents, coloring agents, binders, etc.) known in the
art.
[0068] Techniques for cigarette manufacture are known in the art,
and may be used to incorporate the surface-modified adsorbent. The
resulting cigarettes can be manufactured to any desired
specification using standard or modified cigarette making
techniques and equipment. The cigarettes of the invention may range
from about 50 mm to about 120 mm in length. Generally, a regular
cigarette is about 70 mm long, a "King Size" is about 85 mm long, a
"Super King Size" is about 100 mm long, and a "Long" is usually
about 120 mm in length. The circumference is from about 15 mm to
about 30 mm in circumference, and preferably around 25 mm. The
packing density is typically between the range of about 100
mg/cm.sup.3 to about 300 mg/cm.sup.3, and preferably 150
mg/cm.sup.3 to about 275 mg/cm.sup.3.
[0069] In yet another embodiment of the invention is provided a
method of smoking a smoking article comprising a surface-modified
adsorbent as described above, said method comprising lighting the
smoking article to form smoke and inhaling the smoke, wherein
during the smoking of the cigarette, the surface-modified adsorbent
preferentially removes one or more selected components from
mainstream smoke.
[0070] "Smoking" of a cigarette means the heating or combustion of
the cigarette to form smoke, which can be inhaled. Generally,
smoking of a cigarette involves lighting one end of the cigarette
and inhaling the cigarette smoke through the mouth end of the
cigarette, while the tobacco contained therein undergoes a
combustion reaction. However, the cigarette may also be smoked by
other means. For example, the cigarette may be smoked by heating
the cigarette and/or heating using electrical heater means, as
described in commonly-assigned U.S. Pat. Nos. 6,053,176; 5,934,289;
5,934,289, 5,591,368 or 5,322,075, for example.
[0071] The practice of the invention is further disclosed in the
following examples, which should not be construed to limit the
invention in any way.
EXAMPLES
[0072] In the following examples, three surface-modified adsorbents
are prepared, and their adsorption profiles were studied. The
adsorbent used in the experiments was Pica G-277 Carbon, which is
commercially available from PICA USA, Inc., Truth or Consequences,
N. Mex.
[0073] A. 10% squalene on Pica G-277 Carbon. Carbon Dioxide
Treated
[0074] The surface-modified adsorbent was produced by placing in a
sealable high pressure vessel 50 mg Pica G-277 carbon and 55 mg
squalene (provided on a piece of filter paper). The vessel was
pressurized to about 400 atmospheres at about 50.degree. C.
Supercritical carbon dioxide was introduced, which dissolved the
squalene. The supercritical carbon dioxide with the dissolved
squalene, then impregnated the carbon with the squalene. After
about 15-20 minutes, the vessel was opened, and the supercritical
fluid sublimed. The non-volatile squalene was present on the
surface and within the pores of the activated carbon. The amount of
squalene adsorbed on the carbon is determined by measuring the
weight gain of the carbon before and after the experiment.
[0075] B. 10% squalene on Pica G-277 Carbon, Hexane Treated
[0076] The surface-modified adsorbent was produced by coating 50 mg
Pica G-277 carbon with a solution of squalene dissolved in hexane
to deposit squalene on the surface of the carbon. The squalene
coated carbon was heat treated at 60.degree. C. to drive off the
hexane and leave the squalene on the surface of the carbon. The
coated carbon was placed in a sealable high pressure vessel
pressurized to about 400 atmospheres at 50.degree. C. and
supercritical carbon dioxide was introduced to drive the squalene
into the pores of the carbon. After about 15-20 minutes, the vessel
was opened and the supercritical fluid sublimed. The non-volatile
squalene was present on the surface and within the pores of the
activated carbon.
[0077] C. 43% squalene on Pica G-277 Carbon. Carbon Dioxide
Treated
[0078] The surface-modified adsorbent was produced using the same
procedure as above in (A), except using 73 mg of squalene starting
material.
[0079] D. Adsorption Profiles
[0080] About 50 mg of the surface-modified adsorbents were placed
in a plug-space-plug filter of a 1R4F reference cigarette smoked in
a smoking machine, and the levels of various constituents in the
mainstream smoke of the cigarette were measured using a GC-mass
spectrometer. The surface-modified adsorbents were measured
relative to a control containing about 50 mg of Pica G-277
carbon.
[0081] The results of the experiments are summarized in Tables 1
through 16, below. The percentage total delivery is given with
respect to a 1R4F reference cigarette. The average standard
deviation is given as "% Rsd."
2 TABLE 1 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. hydrogen cyanide puff 1 0 0 0 32% 0
1 1 21% hydrogen cyanide puff 2 1 1 1 4% 1 2 1 64% hydrogen cyanide
puff 3 2 2 2 12% 1 3 2 60% hydrogen cyanide puff 4 3 3 3 7% 2 5 3
57% hydrogen cyanide puff 5 3 3 3 7% 3 7 5 53% hydrogen cyanide
puff 6 4 3 4 9% 4 7 5 41% hydrogen cyanide puff 7 4 4 4 2% 2 7 5
84% hydrogen cyanide puff 8 5 4 4 6% 5 8 6 31% % Total Delivery VS
1R4F 22 21 22 3% 18 39 29 52% 10% Squalene on 50 mg Pica G 43%
Squalene on 50 mg Pica G 277 SF CO.sub.2 treated (55 mg) 277 SF
CO.sub.2 treated (73 mg) Run 1 Run 2 Avg. % Rsd. Run 1 Run 2 Avg. %
Rsd. hydrogen cyanide puff 1 0 1 1 44% 0 1 1 24% hydrogen cyanide
puff 2 1 3 2 63% 3 2 3 8% hydrogen cyanide puff 3 2 4 3 62% 5 4 4
12% hydrogen cyanide puff 4 2 5 4 51% 6 5 6 14% hydrogen cyanide
puff 5 3 6 4 34% 7 6 7 11% hydrogen cyanide puff 6 4 6 5 32% 7 8 7
3% hydrogen cyanide puff 7 3 7 5 55% 8 9 8 10% hydrogen cyanide
puff 8 6 8 7 24% 12 9 10 24% % Total Delivery VS 1R4F 21 39 30 42%
48 43 46 8%
[0082]
3 TABLE 2 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. ethane puff 1 3 3 3 17% 3 4 3 25%
ethane puff 2 7 7 7 3% 7 11 9 34% ethane puff 3 12 12 12 4% 8 12 10
27% ethane puff 4 14 12 13 11% 9 15 12 32% ethane puff 5 14 14 14
1% 13 14 13 4% ethane puff 6 16 16 16 1% 9 12 11 23% ethane puff 7
16 20 18 16% 18 15 16 13% ethane puff 8 17 22 20 19 14 14 14 2% %
Total Delivery VS 1R4F 99 106 103 5% 81 98 89 13% 10% Squalene on
50 mg Pica G 43% Squalene on 50 mg Pica G 277 SF CO.sub.2 treated
(55 mg) 277 SF CO.sub.2 treated (73 mg) Run 1 Run 2 Avg. % Rsd. Run
1 Run 2 Avg. % Rsd. ethane puff 1 3 2 3 30% 2 5 4 53% ethane puff 2
8 8 8 4% 8 8 8 4% ethane puff 3 10 12 11 15% 11 11 11 1% ethane
puff 4 10 13 12 16% 13 10 11 20% ethane puff 5 14 13 13 3% 12 11 12
5% ethane puff 6 13 13 13 2% 13 13 13 1% ethane puff 7 13 13 13 1%
15 11 13 21% ethane puff 8 14 14 14 1% 15 13 14 9% % Total Delivery
VS 1R4F 85 89 87 3% 89 82 85 6%
[0083]
4 TABLE 3 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. propadiene puff 1 3 5 4 46% 6 10 8
29% propadiene puff 2 4 4 4 4% 9 14 11 38% propadiene puff 3 4 4 4
3% 7 9 8 17% propadiene puff 4 6 4 5 22% 6 9 8 37% propadiene puff
5 6 5 6 18% 6 10 8 31% propadiene puff 6 8 7 8 17% 5 8 7 28%
propadiene puff 7 10 8 9 17% 6 10 8 40% propadiene puff 8 11 8 10
21% 7 11 9 35% % Total Delivery VS 1R4F 52 44 48 11% 53 80 66 29%
10% Squalene on 50 mg Pica G 43% Squalene on 50 mg Pica G 277 SF
CO.sub.2 treated (55 mg) 277 SF CO.sub.2 treated (73 mg) Run 1 Run
2 Avg. % Rsd. Run 1 Run 2 Avg. % Rsd. propadiene puff 1 7 12 10 39%
24 21 22 8% propadiene puff 2 10 13 12 19% 14 12 13 12% propadiene
puff 3 9 10 9 6% 7 7 7 5% propadiene puff 4 9 10 9 12% 8 6 7 22%
propadiene puff 5 9 9 9 5% 6 7 7 3% propadiene puff 6 8 9 9 8% 8 8
8 3% propadiene puff 7 8 11 9 16% 9 7 8 16% propadiene puff 8 10 11
10 7% 10 8 9 20% % Total Delivery VS 1R4F 70 86 78 14% 86 75 81
10%
[0084]
5 TABLE 4 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, Hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. 1,3-butadiene puff 1 1 2 1 58% 1 2 2
62% 1,3-butadiene puff 2 1 1 1 50% 1 3 2 71% 1,3-butadiene puff 3 1
1 1 53% 1 2 2 60% 1,3-butadiene puff 4 1 1 1 7% 1 3 2 64%
1,3-butadiene puff 5 1 1 1 36% 2 4 3 50% 1,3-butadiene puff 6 1 2 1
33% 2 4 3 41% 1,3-butadiene puff 7 1 2 2 17% 3 5 4 46%
1,3-butadiene puff 8 2 2 2 14% 4 7 5 37% % Total Delivery VS 1R4F 8
13 10 32% 14 30 22 50% 10% Squalene on 50 mg Pica G 43% Squalene on
50 mg Pica G 277 SF CO.sub.2 treated (55 mg) 277 SF CO.sub.2
treated (73 mg) Run 1 Run 2 Avg. % Rsd. Run 1 Run 2 Avg. % Rsd.
1,3-butadiene puff 1 1 3 2 53% 11 10 10 12% 1,3-butadiene puff 2 1
2 2 54% 9 8 9 8% 1,3-butadiene puff 3 1 2 2 52% 7 6 7 8%
1,3-butadiene puff 4 1 3 2 53% 8 6 7 19% 1,3-butadiene puff 5 2 3 3
37% 7 7 7 1% 1,3-butadiene puff 6 2 4 3 36% 10 10 10 1%
1,3-butadiene puff 7 3 5 4 25% 11 9 10 19% 1,3-butadiene puff 8 4 6
5 26% 12 10 11 14% % Total Delivery VS 1R4F 16 27 22 37% 75 65 70
10%
[0085]
6 TABLE 5 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. isoprene puff 1 0 1 0 50% 0 1 0 29%
isoprene puff 2 0 1 0 47% 0 1 0 46% isoprene puff 3 0 1 0 55% 0 0 0
26% isoprene puff 4 1 1 1 22% 0 2 1 74% isoprene puff 5 1 1 1 39% 1
2 1 64% isoprene puff 6 1 2 1 28% 1 2 1 62% isoprene puff 7 1 2 1
13% 1 3 2 67% isoprene puff 8 1 2 2 20% 1 4 3 76% % Total Delivery
VS 1R4F 6 9 8 28% 5 14 9 64% 10% Squalene on 50 mg Pica G 43%
Squalene on 50 mg Pica G 277 SF CO.sub.2 treated (55 mg) 277 SF
CO.sub.2 treated (73 mg) Run 1 Run 2 Avg. % Rsd. Run 1 Run 2 Avg. %
Rsd. isoprene puff 1 0 1 1 28% 3 2 3 10% isoprene puff 2 0 1 1 32%
4 3 3 10% isoprene puff 3 0 1 0 46% 3 2 3 15% isoprene puff 4 1 2 2
62% 9 7 8 20% isoprene puff 5 1 2 2 49% 9 8 9 11% isoprene puff 6 1
2 2 43% 11 11 11 3% isoprene puff 7 2 3 2 38% 12 12 12 3% isoprene
puff 8 2 3 3 17% 13 14 14 5% % Total Delivery VS 1R4F 8 15 11 38%
63 60 62 4%
[0086]
7 TABLE 6 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. formaldehyde puff 1 15 23 19 30% 12
33 23 65% formaldehyde puff 2 6 6 6 8% 6 15 10 63% formaldehyde
puff 3 2 4 3 41% 3 4 3 12% formaldehyde puff 4 3 2 3 23% 2 3 2 31%
formaldehyde puff 5 2 2 2 14% 2 2 2 17% formaldehyde puff 6 2 2 2
18% 2 1 2 30% formaldehyde puff 7 2 3 2 31% 2 1 2 28% formaldehyde
puff 8 1 1 1 9% 1 2 1 77% % Total Delivery VS 1R4F 33 44 38 21% 29
60 45 49% 10% Squalene on 50 mg Pica G 43% Squalene on 50 mg Pica G
277 SF CO.sub.2 treated (55 mg) 277 SF CO.sub.2 treated (73 mg) Run
1 Run 2 Avg. % Rsd. Run 1 Run 2 Avg. % Rsd. formaldehyde puff 1 15
23 19 30% 53 33 43 32% formaldehyde puff 2 6 7 7 12% 13 10 11 15%
formaldehyde puff 3 2 4 3 40% 6 4 5 28% formaldehyde puff 4 3 3 3
2% 3 3 3 12% formaldehyde puff 5 2 3 2 7% 3 1 2 56% formaldehyde
puff 6 3 1 2 60% 2 2 2 23% formaldehyde puff 7 2 2 2 30% 2 2 2 16%
formaldehyde puff 8 3 1 2 64% 3 1 2 65% % Total Delivery VS 1R4F 36
43 40 13% 85 56 70 29%
[0087]
8 TABLE 7 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. acetaldehyde puff 1 1 2 1 62% 1 2 2
57% acetaldehyde puff 2 1 2 2 28% 3 5 4 37% acetaldehyde puff 3 2 2
2 12% 4 6 5 31% acetaldehyde puff 4 3 2 2 11% 4 8 6 43%
acetaldehyde puff 5 3 3 3 2% 6 10 8 36% acetaldehyde puff 6 4 4 4
8% 7 10 9 23% acetaldehyde puff 7 5 5 5 6% 9 12 10 20% acetaldehyde
puff 8 7 6 7 10% 11 14 13 14% % Total Delivery VS 1R4F 26 26 26 1%
45 66 56 27% 10% Squalene on 50 mg Pica G 43% Squalene on 50 mg
Pica G 277 SF CO.sub.2 treated (55 mg) 277 SF CO.sub.2 treated (73
mg) Run 1 Run 2 Avg. % Rsd. Run 1 Run 2 Avg. % Rsd. acetaldehyde
puff 1 1 2 2 15% 6 6 6 1% acetaldehyde puff 2 3 3 3 21% 7 7 7 1%
acetaldehyde puff 3 4 5 5 20% 9 7 8 14% acetaldehyde puff 4 5 7 6
15% 10 8 9 17% acetaldehyde puff 5 7 8 8 8% 9 9 9 3% acetaldehyde
puff 6 8 9 9 4% 11 11 11 1% acetaldehyde puff 7 10 11 10 4% 13 11
12 11% acetaldehyde puff 8 12 13 13 6% 16 12 14 16% % Total
Delivery VS 1R4F 51 58 54 9% 81 71 76 9%
[0088]
9 TABLE 8 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. acrolein puff 1 0 1 1 71% 0 1 1 38%
acrolein puff 2 0 1 0 57% 0 1 1 60% acrolein puff 3 0 1 0 73% 1 1 1
29% acrolein puff 4 0 1 1 54% 0 1 1 141% acrolein puff 5 1 1 1 4% 1
1 1 25% acrolein puff 6 2 1 1 11% 1 2 1 25% acrolein puff 7 1 1 1
31% 1 3 2 68% acrolein puff 8 1 2 2 30% 2 4 3 58% % Total Delivery
VS 1R4F 6 8 7 28% 6 14 10 55% 10% Squalene on 50 mg Pica G 43%
Squalene on 50 mg Pica G 277 SF CO.sub.2 treated (55 mg) 277 SF
CO.sub.2 treated (73 mg) Run 1 Run 2 Avg. % Rsd. Run 1 Run 2 Avg. %
Rsd. acrolein puff 1 0 0 0 2% 4 3 4 13% acrolein puff 2 0 0 0 6% 5
4 4 12% acrolein puff 3 0 1 1 61% 5 4 5 16% acrolein puff 4 1 1 1
27% 7 4 5 29% acrolein puff 5 1 2 1 56% 7 7 7 1% acrolein puff 6 2
3 2 49% 8 8 8 8% acrolein puff 7 2 3 2 38% 10 8 9 12% acrolein puff
8 2 4 3 41% 11 9 10 16% % Total Delivery VS 1R4F 8 15 11 41% 56 47
51 13%
[0089]
10 TABLE 9 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. diacetyl puff 1 0 1 1 57% 0 1 0 34%
diacetyl puff 2 1 1 1 28% 0 1 1 38% diacetyl puff 3 1 1 1 40% 0 1 1
50% diacetyl puff 4 1 1 1 22% 1 1 1 66% diacetyl puff 5 1 1 1 26% 1
2 1 60% diacetyl puff 6 1 1 1 27% 1 2 1 54% diacetyl puff 7 1 2 1
45% 1 2 2 49% diacetyl puff 8 1 2 1 19% 1 2 2 58% % Total Delivery
VS 1R4F 6 10 8 31% 5 11 8 54% 10% Squalene on 50 mg Pica G 43%
Squalene on 50 mg Pica G 277 SF CO.sub.2 treated (55 mg) 277 SF
CO.sub.2 treated (73 mg) Run 1 Run 2 Avg. % Rsd. Run 1 Run 2 Avg. %
Rsd. diacetyl puff 1 00 1 1 22% 1 2 1 17% diacetyl puff 2 1 1 1 14%
3 3 3 1% diacetyl puff 3 1 1 1 47% 4 4 4 6% diacetyl puff 4 1 1 1
47% 5 5 5 9% diacetyl puff 5 1 1 1 32% 5 5 5 1% diacetyl puff 6 1 2
1 29% 6 6 6 8% diacetyl puff 7 1 2 1 20% 8 6 7 13% diacetyl puff 8
1 2 2 24% 8 7 8 11% % Total Delivery VS 1R4F 7 11 9 29% 42 38 40
7%
[0090]
11 TABLE 10 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. benzene puff 1 0 1 1 56% 1 1 1 21%
benzene puff 2 0 1 1 39% 0 1 1 59% benzene puff 3 0 1 1 51% 0 1 1
63% benzene puff 4 1 1 1 23% 0 1 1 73% benzene puff 5 1 1 1 31% 0 1
1 65% benzene puff 6 1 1 1 33% 0 1 1 62% benzene puff 7 1 1 1 36% 1
1 1 62% benzene puff 8 1 1 1 24% 1 2 1 72% % Total Delivery VS 1R4F
5 8 7 35% 4 9 6 61% 10% Squalene on 50 mg Pica G 43% Squalene on 50
mg Pica G 277 SF CO.sub.2 treated (55 mg) 277 SF CO.sub.2 treated
(73 mg) Run 1 Run 2 Avg. % Rsd. Run 1 Run 2 Avg. % Rsd. benzene
puff 1 1 1 1 44% 2 2 2 0% benzene puff 2 1 1 1 39% 3 3 3 12%
benzene puff 3 0 1 1 59% 4 3 3 16% benzene puff 4 1 1 1 53% 4 4 4
14% benzene puff 5 1 1 1 43% 4 4 4 2% benzene puff 6 1 1 1 37% 5 5
5 1% benzene puff 7 1 1 1 31% 6 6 6 3% benzene puff 8 1 2 1 26% 8 7
7 10% % Total Delivery VS 1R4F 5 10 7 40% 36 32 34 7%
[0091]
12 TABLE 11 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. toluene puff 1 0 10 0 40% 1 0 0 40%
toluene puff 2 0 1 1 42% 0 1 1 27% toluene puff 3 1 1 1 47% 0 1 1
50% toluene puff 4 1 1 1 49% 0 1 1 52% toluene puff 5 1 1 1 20% 0 1
1 62% toluene puff 6 1 1 1 35% 1 1 1 49% toluene puff 7 1 2 1 39% 1
1 1 60% toluene puff 8 1 2 1 34% 1 2 1 71% % Total Delivery VS 1R4F
5 9 7 38% 4 8 6 49% 10% Squalene on 50 mg Pica G 43% Squalene on 50
mg Pica G 277 SF CO.sub.2 treated (55 mg) 277 SF CO.sub.2 treated
(73 mg) Run 1 Run 2 Avg. % Rsd. Run 1 Run 2 Avg. % Rsd. toluene
puff 1 0 0 0 22% 0 0 0 15% toluene puff 2 0 1 1 41% 1 1 1 14%
toluene puff 3 0 1 1 52% 2 2 2 14% toluene puff 4 1 1 1 52% 3 2 2
14% toluene puff 5 1 1 1 50% 3 3 3 9% toluene puff 6 1 1 1 45% 3 3
3 10% toluene puff 7 1 1 1 29% 4 4 4 1% toluene puff 8 1 2 1 28% 6
5 5 13% % Total Delivery VS 1R4F 5 9 7 40% 23 20 21 10%
[0092]
13 TABLE 12 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. acrylonitrile puff 1 1 3 2 46% 4 8 6
40% acrylonitrile puff 2 2 6 4 68% 7 7 7 8% acrylonitrile puff 3 3
6 4 48% 8 9 9 5% acrylonitrile puff 4 3 6 4 38% 7 13 10 45%
acrylonitrile puff 5 0 1 0 43% 1 1 1 3% acrylonitrile puff 6 1 1 1
36% 1 1 1 64% acrylonitrile puff 7 1 1 1 48% 1 2 2 24%
acrylonitrile puff 8 1 2 1 34% 1 3 2 63% % Total Delivery VS 1R4F
12 25 18 48% 30 44 37 27% 10% Squalene on 50 mg Pica G 43% Squalene
on 50 mg Pica G 277 SF CO.sub.2 treated (55 mg) 277 SF CO.sub.2
treated (73 mg) Run 1 Run 2 Avg. % Rsd. Run 1 Run 2 Avg. % Rsd.
acrylonitrile puff 1 5 7 6 27% 8 9 9 8% acrylonitrile puff 2 7 8 8
13% 11 10 11 2% acrylonitrile puff 3 7 9 8 23% 14 11 12 21%
acrylonitrile puff 4 7 15 11 52% 14 12 13 10% acrylonitrile puff 5
0 1 1 41% 3 3 3 1% acrylonitrile puff 6 1 1 1 22% 4 4 4 8%
acrylonitrile puff 7 1 2 2 7% 5 5 5 2% acrylonitrile puff 8 1 2 2
27% 10 6 8 36% % Total Delivery VS 1R4F 30 46 38 30% 69 59 64
10%
[0093]
14 TABLE 13 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. methyl furan puff 1 0 0 0 51% 0 0 0
6% methyl furan puff 2 0 1 1 46% 0 1 1 57% methyl furan puff 3 1 1
1 49% 0 1 1 49% methyl furan puff 4 1 1 1 16% 1 1 1 54% methyl
furan puff 5 1 1 1 30% 1 2 1 75% methyl furan puff 6 1 2 1 30% 1 2
1 66% methyl furan puff 7 1 2 1 24% 1 2 2 54% methyl furan puff 8 1
2 2 24% 1 3 2 67% % Total Delivery VS 1R4F 6 10 8 30% 5 12 8 59%
10% Squalene on 50 mg Pica G 43% Squalene on 50 mg Pica G 277 SF
CO.sub.2 treated (55 mg) 277 SF CO.sub.2 treated (73 mg) Run 1 Run
2 Avg. % Rsd. Run 1 Run 2 Avg. % Rsd. methyl furan puff 1 0 1 0 32%
1 1 1 3% methyl furan puff 2 1 1 1 21% 3 3 3 19% methyl furan puff
3 1 1 1 33% 6 5 5 15% methyl furan puff 4 1 1 1 46% 7 6 6 11%
methyl furan puff 5 1 2 1 51% 7 7 7 2% methyl furan puff 6 1 2 1
44% 9 8 9 6% methyl furan puff 7 1 2 2 39% 11 10 10 8% methyl furan
puff 8 2 2 2 29% 12 11 11 6% % Total Delivery VS 1R4F 7 12 9 38% 56
50 53 8%
[0094]
15 TABLE 14 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. hydrogen sulfide puff 1 0 0 0 38% 0
0 0 4% hydrogen sulfide puff 2 2 2 2 8% 3 3 3 5% hydrogen sulfide
puff 3 2 3 2 26% 3 4 3 31% hydrogen sulfide puff 4 2 2 2 19% 4 7 5
37% hydrogen sulfide puff 5 3 3 3 3% 5 8 7 36% hydrogen sulfide
puff 6 4 4 4 9% 6 7 6 14% hydrogen sulfide puff 7 5 4 4 11% 7 8 8
11% hydrogen sulfide puff 8 4 5 5 8% 8 8 8 5% % Total Delivery VS
1R4F 22 22 22 0% 35 45 40 17% 10% Squalene on 50 mg Pica G 43%
Squalene on 50 mg Pica G 277 SF CO.sub.2 treated (55 mg) 277 SF
CO.sub.2 treated (73 mg) Run 1 Run 2 Avg. % Rsd. Run 1 Run 2 Avg. %
Rsd. hydrogen sulfide puff 1 0 0 0 40% 0 1 0 18% hydrogen sulfide
puff 2 2 3 2 28% 4 4 4 17% hydrogen sulfide puff 3 3 5 4 23% 9 7 8
21% hydrogen sulfide puff 4 5 6 5 7% 10 7 8 23% hydrogen sulfide
puff 5 6 7 7 3% 9 9 9 2% hydrogen sulfide puff 6 7 7 7 2% 9 11 10
14% hydrogen sulfide puff 7 9 8 8 7% 13 10 12 18% hydrogen sulfide
puff 8 10 10 10 4% 13 11 12 11% % Total Delivery VS 1R4F 43 45 44
3% 68 59 64 10%
[0095]
16 TABLE 15 50 mg Pica G-277 Carbon 10% Squalene on 50 mg Pica G
Control, PSP in a 1R4F 277, hexane treated (55 mg) Run 1 Run 2 Avg.
% Rsd. Run 1 Run 2 Avg. % Rsd. carbonyl sulfide puff 1 1 2 1 41% 2
3 3 23% carbonyl sulfide puff 2 3 4 4 12% 7 8 7 16% carbonyl
sulfide puff 3 5 6 6 13% 8 9 9 12% carbonyl sulfide puff 4 8 6 7
11% 9 13 11 28% carbonyl sulfide puff 5 9 8 8 4% 9 13 11 23%
carbonyl sulfide puff 6 12 10 11 9% 10 11 10 9% carbonyl sulfide
puff 7 14 12 13 10% 10 14 12 19% carbonyl sulfide puff 8 14 12 13
8% 11 13 12 9% % Total Delivery VS 1R4F 65 61 63 4% 66 84 75 17%
10% Squalene on 50 mg Pica G 43% Squalene on 50 mg Pica G 277 SF
CO.sub.2 treated (55 mg) 277 SF CO.sub.2 treated (73 mg) Run 1 Run
2 Avg. % Rsd. Run 1 Run 2 Avg. % Rsd. carbonyl sulfide puff 1 2 3 3
18% 5 5 5 4% carbonyl sulfide puff 2 6 7 7 13% 8 8 8 7% carbonyl
sulfide puff 3 8 10 9 15% 10 8 9 14% carbonyl sulfide puff 4 10 11
10 9% 11 8 9 20% carbonyl sulfide puff 5 11 12 11 8% 10 10 10 5%
carbonyl sulfide puff 6 12 12 12 2% 11 13 12 13% carbonyl sulfide
puff 7 13 13 13 0% 14 12 13 10% carbonyl sulfide puff 8 15 15 15 0%
15 13 14 13% % Total Delivery VS 1R4F 77 84 80 6% 84 78 81 6%
[0096]
17TABLE 16 Summary of Percentage Reduction of Various Compounds
Using Surface- Modified Adsorbents (rounded to nearest 5%) 50 mg
Pica G-277 10% Squalene on 10% Squalene on 43% Squalene on Carbon
50 mg Pica 50 mg Pica 50 mg Pica Control, PSP in a G277, CO.sub.2
G277 SF Hexane G277 SF CO.sub.2 1R4F treated treated treated
hydrogen cyanide 80 60 70 55 ethane 0 10 15 15 propadiene 50 35 20
20 1,3-butadiene 90 80 80 30 isoprene >90 >90 >90 40
formaldehyde 60 55 60 30 acetaldehyde 75 45 45 25 acrolein >90
>90 >90 50 diacetyl >90 >90 >90 60 beuzene >90
>90 >90 65 toluene >90 >90 >90 80 acrylonitrile 80
75 60 35 methyl furan >90 >90 >90 45 hydrogen sulfide 80
60 55 35 carbonyl sulfide 40 25 20 20
[0097] A comparison of some of the constituents is shown in FIG. 9
as well. As depicted, the control is compared against both the 10%
squalene on Pica G-277 carbon that was carbon dioxide treated and
the 43% squalene on Pica G-277 carbon that was carbon dioxide
treated. As shown by the chart, preferential selection of acrolein
over acetaldehyde and hydrogen cyanide over acrylonitrile is
achieved through the use of the surface-modified adsorbents. In
addition, increased adsorption of ethane is achieved by using the
surface-modified adsorbents, as compared to the untreated
carbon.
[0098] While the invention has been described with reference to
preferred embodiments, it is to be understood that variations and
modifications may be resorted to as will be apparent to those
skilled in the art. Such variations and modifications are to be
considered within the purview and scope of the invention as defined
by the claims appended hereto.
[0099] All of the above-mentioned references are herein
incorporated by reference in their entirety to the same extent as
if each individual reference was specifically and individually
indicated to be incorporated herein by reference in its
entirety.
* * * * *