Patent Grant
8701681
Various methods for reducing the amount of carbon monoxide in the mainstream smoke of a cigarette during smoking have been proposed.
Despite the developments to date, there remains an interest in improved and more efficient methods and compositions for reducing the amount of carbon monoxide in the mainstream smoke of a cigarette during smoking. Preferably, such methods and compositions should not involve expensive or time consuming manufacturing and/or processing steps. More preferably, it should be possible to catalyze or oxidize carbon monoxide along the length of the cigarette during smoking.
Cigarette wrappers, cut filler compositions, cigarettes, methods for making cigarettes and methods for smoking cigarettes that involve the use of an oxyhydroxide compound are provided. The oxyhydroxide compound is represented by MOOH where M is a metal selected from the group consisting of transition metals, rare earth metals, and mixtures thereof, and is capable of decomposing to form at least one product capable of acting as an oxidant for the conversion of carbon monoxide to carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide.
In one embodiment, a cigarette wrapper paper comprises a cellulosic component and a filler comprising an oxyhydroxide compound, wherein the oxyhydroxide compound is represented by MOOH where M is a metal selected from the group consisting of transition metals, rare earth metals, and mixtures thereof, and wherein during combustion of the cigarette wrapper paper, said oxyhydroxide compound is capable of decomposing to form at least one product capable of acting as an oxidant for conversion of carbon monoxide to carbon dioxide and/or as a catalyst for conversion of carbon monoxide to carbon dioxide.
A preferred cigarette wrapper paper comprises a cellulosic component and an oxyhydroxide compound, wherein the oxyhydroxide compound is represented by MOOH where M is a metal selected from the group consisting of Fe, Ti, and mixtures thereof, wherein during combustion of the cigarette wrapper paper, said oxyhydroxide compound is capable of decomposing to form at least one product capable of acting as an oxidant for conversion of carbon monoxide to carbon dioxide and/or as a catalyst for conversion of carbon monoxide to carbon dioxide, and wherein the oxyhydroxide compound and/or the product formed from the decomposition of the oxyhydroxide has an average particle size of greater than one micron to less than three microns.
Oxyhydroxide compounds include, but are not limited to: FeOOH, TiOOH, and mixtures thereof, with FeOOH being particularly preferred. Preferably, the oxyhydroxide compound is capable of decomposing to form at least one decomposition product, such as Fe2O3, TiO2, and mixtures thereof, that can convert carbon monoxide to carbon dioxide and is present in an amount effective to convert at least 15% of the carbon monoxide to carbon dioxide.
Cigarette wrappers, cut filler compositions, cigarettes, methods for making cigarettes and methods for smoking cigarettes are provided which involve the use of an oxyhydroxide compound that is capable of decomposing during smoking to form at least one product capable of acting as an oxidant for the conversion of carbon monoxide to carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide. The amount of carbon monoxide in mainstream smoke can be reduced, thereby also reducing the amount of carbon monoxide reaching the smoker and/or given off as second-hand smoke.
The term “mainstream” smoke refers to 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 cigarette during smoking of the cigarette. The mainstream smoke contains smoke that is drawn in through both the lit region of the cigarette, as well as through the cigarette paper wrapper.
The total amount of carbon monoxide present in mainstream smoke and formed during smoking comes from a combination of three main sources: thermal decomposition (about 30%), combustion (about 36%) and reduction of carbon dioxide with carbonized tobacco (at least 23%). Formation of carbon monoxide from thermal decomposition starts at a temperature of about 180° C., and finishes at around 1050° C., and is largely controlled by chemical kinetics. Formation of carbon monoxide and carbon dioxide during combustion is controlled largely by the diffusion of oxygen to the surface (ka) and the surface reaction (kb). At 250° C., ka and kb, are about the same. At 400° C., the reaction becomes diffusion controlled. Finally, the reduction of carbon dioxide with carbonized tobacco or charcoal occurs at temperatures around 390° C. and above. Besides the tobacco constituents, the temperature and the oxygen concentration are the two most significant factors affecting the formation and reaction of carbon monoxide and carbon dioxide.
While not wishing to be bound by theory, it is believed that the oxyhydroxide compounds decompose under conditions for the combustion of the cut filler or the smoking of the cigarette to produce either catalyst or oxidant compounds, which target the various reactions that occur in different regions of the cigarette during smoking. During smoking there are three distinct regions in a cigarette: the combustion zone, the pyrolysis/distillation zone, and the condensation/filtration zone. First, the “combustion zone” is the burning region of the cigarette, produced during smoking of the cigarette, usually at the lit end of a cigarette. The temperature in the combustion zone ranges from about 700° C. to about 950° C., and the heating rate can go as high as 500° C./second. The concentration of oxygen is low in this region, since it is being consumed in the combustion of tobacco to produce carbon monoxide, carbon dioxide, water vapor, and various organics. This reaction is highly exothermic and the heat generated here is carried by gas to the pyrolysis/distillation zone. The low oxygen concentrations coupled with the high temperature in the combustion zone leads to the reduction of carbon dioxide to carbon monoxide by the carbonized tobacco. In the combustion zone, it is desirable to use an oxyhydroxide that decomposes to form an oxidant in situ, which will convert carbon monoxide to carbon dioxide in the absence of oxygen. The oxidation reaction begins at around 150° C., and reaches maximum activity at temperatures higher than about 460° C.
Next, the “pyrolysis zone” is the region behind the combustion zone, where the temperatures range from about 200° C. to about 600° C. This is where most of the carbon monoxide is produced. The major reaction in this region is the pyrolysis (i.e. the thermal degradation) of the tobacco that produces carbon monoxide, carbon dioxide, smoke components, and charcoal using the heat generated in the combustion zone. There is some oxygen present in this zone, and thus it is desirable to use an oxyhydroxide that decomposes to produce a catalyst in situ for the oxidation of carbon monoxide to carbon dioxide. The catalytic reaction begins at 150° C. and reaches maximum activity around 300° C. In a preferred embodiment, the catalyst may also retain oxidant capability after it has been used as a catalyst, so that it can also function as an oxidant in the combustion zone as well.
Finally, there is the “condensation zone”, where the temperature ranges from ambient to about 150° C. The major process in this region is the condensation/filtration of the smoke components. Some amount of carbon monoxide and carbon dioxide diffuse out of the cigarette and some oxygen diffuses into the cigarette. However, in general, the oxygen level does not recover to the atmospheric level.
In commonly-assigned U.S. Patent Application Publication 2003/0075193 entitled “Oxidant/Catalyst Nanoparticles to Reduce Carbon Monoxide in the Mainstream Smoke of a Cigarette”, and in commonly-assigned U.S. Patent Application Publication 2003/0188758 entitled “Use of Oxhydroxide Compounds for Reducing Carbon Monoxide in the Mainstream Smoke of a Cigarette”, various oxidant/catalyst nanoparticles are described for reducing the amount of carbon monoxide in mainstream smoke. The disclosures of these applications are hereby incorporated by reference in their entirety. While the use of these catalysts reduces the amount of carbon monoxide in mainstream smoke during smoking, it is further desirable to minimize or prevent contamination and/or deactivation of catalysts used in the cigarette filler, particularly over long periods of storage. One potential way of achieving this result is to use an oxyhydroxide compound to generate the catalyst or oxidant in situ during smoking of the cigarette. For instance, FeOOH decomposes to form Fe2O3 and water at temperatures typically reached during smoking of the cigarette, e.g. above about 200° C.
By “oxyhydroxide” is meant a compound containing a hydroperoxo moiety, i.e. “—O—O—H”. One example of oxyhydroxides include, but are not limited to: FeOOH, and TiOOH. Another example of oxyhydroxides include MOOH where M is a metal selected from the group comprising of, consisting of or consisting essentially of transition metals, rare earth metals, and mixtures thereof. For example, preferred metals include a group IVB or a group VIII metal. More preferably, the metal is selected from the group comprising of, consisting of or consisting essentially of Fe, Ti, and mixtures thereof.
Any suitable oxyhydroxide compound may be used, which is capable of decomposing, under the temperature conditions achieved during smoking of a cigarette, to produce compounds which function as an oxidant and/or as a catalyst for converting carbon monoxide to carbon dioxide. In a preferred embodiment, the oxyhydroxide forms a product that is capable of acting as both an oxidant for the conversion of carbon monoxide to carbon dioxide and as a catalyst for the conversion of carbon monoxide to carbon dioxide. It is also possible to use combinations of oxyhydroxide compounds to obtain this effect and/or to use oxyhydroxides in combination with other oxidants and/or catalysts, such as oxyhydroxide in combination with metal oxides, e.g., iron oxides. Preferably, the selection of an appropriate oxyhydroxide compound will take into account such factors as stability and preservation of activity during storage conditions, low cost and abundance of supply.
Preferred oxyhydroxide compounds are stable when present in cigarette wrappers, e.g., cigarette paper or other paper used in the manufacture of smoking articles such as cigarettes, cut filler compositions or in cigarettes, at typical room temperature and pressure, as well as under prolonged storage conditions. Preferred oxyhydroxide compounds include inorganic oxyhydroxide compounds that decompose during smoking of a cigarette, to form metal oxides. For example, in the following reaction, M represents a metal:
2M—O—O—H→M2O3+H2O
Optionally, one or more oxyhydroxides may also be used as mixtures or in combination, where the oxyhydroxides may be different chemical entities or different forms of the same metal oxyhydroxides. A preferred oxyhydroxide compound is aluminum-free and includes FeOOH, TiOOH, and mixtures thereof, with FeOOH being particularly preferred. Another preferred oxyhydroxide compound includes MOOH where M is a metal selected from the group consisting of transition metals, rare earth metals, and mixtures thereof. For example, preferred metals include a group IVB or a group VIII metal. More preferably, the metal is selected from the group consisting of Fe, Ti, and mixtures thereof. Other preferred oxyhydroxide compounds include those that are capable of decomposing to form at least one product selected from the group consisting of metal oxides. For example, the decomposition product can include Fe2O3, TiO2, and mixtures thereof. Of course, one of ordinary skill in the art will appreciate that the decomposition product will depend upon the oxyhydroxide compound selected. Particularly preferred oxyhydroxides include FeOOH, particularly in the form of α-FeOOH (goethite); however, other forms of FeOOH such as γ-FeOOH (lepidocrocite), β-FeOOH (akaganeite), and δ′-FeOOH (feroxyhite) may also be used. The oxyhydroxide compound may be made using any suitable technique, or purchased from a commercial supplier, such as Aldrich Chemical Company, Milwaukee, Wis.
FeOOH is preferred because it produces Fe2O3 upon thermal degradation. Fe2O3 is a preferred catalyst/oxidant because it is not known to produce any unwanted byproducts, and will simply be reduced to FeO or Fe after the reaction. In addition, use of a precious metal can be avoided, as both Fe2O3 and Fe2O3 nanoparticles are economical and readily available. Moreover, Fe2O3 is capable of acting as both an oxidant for the conversion of carbon monoxide to carbon dioxide and as a catalyst for the conversion of carbon monoxide to carbon dioxide.
If desired, the cigarette wrapper can further include one or more optional metal oxides, such as iron oxides, may be used alone or in combination with other oxides or oxyhydroxides. A preferred metal oxide is iron oxide. More preferably, the metal oxide is γ-Fe2O3. The γ-Fe2O3 is in the form of particles having a particle size less than or equal to 1 micron, preferably having a particle size of less than or equal to 100 nanometers (nm). The metal oxide may additionally be mixed with or supported on a paper filler material, e.g., a filler material used in the production of paper. An example of a paper filler material is calcium carbonate, although other paper filler materials may be used such as TiO2, SiO2, Al2O3, MgCO3, MgO and Mg(OH)2 and mixtures thereof. The oxyhydroxide compound and optional metal oxide may be present in the paper at a total loading of up to 60 weight percent (wt. %) of the paper, preferably from 15 wt. % to 50 wt. %. When mixed with or supported on a paper filler material, the oxyhydroxide compound and optional metal oxide is present in the cigarette wrapper paper at a loading of up to 60 wt. % of the paper, preferably from 15 wt. % to 50 wt. %, and the ratio of wt. % iron oxide to wt. % paper filler in the cigarette wrapper paper is from 1:9 to 9:1, preferably from 1:4 to 4:1, more preferably about 1:1.
Table 1 shows results for cigarette parameters for cigarette paper having a filler loading of 30 wt. %, wherein a control cigarette has only CaCO3 filler in the paper. One sample has only FeOOH as the filler and one sample has a 50:50 mixture of FeOOH and CaCO3 as the filler. Also shown are parameters for cigarette paper using a 50:50 wt. % mixture of 3 nm Fe2O3/CaCO3 (calcined at 300° C.) (the Fe2O3 can be, for example, NANOCAT®) and a 50:50 wt. % mixture of 20 nm gamma Fe2O3/CaCO3 (noncalcined). The cigarettes are handmade using 35 g/m2 paper with 30% filler loading and having a permeability of the wrapper of 33 CU (CORESTA UNITS) (CORESTA, is defined as the amount of air, measured in cubic centimeters, that passes through one square centimeter of material in one minute at a pressure drop of 1.0 kilopascals). The values in Table 1 represent the average of 20 test samples.
The oxyhydroxide compounds (or the oxyhydroxide compounds and the optional materials described herein) can be incorporated into the cigarette paper during the manufacturing process. For example, the oxyhydroxide compounds can be incorporated in the wrapper through conventional papermaking processes. The oxyhydroxide compounds can be used as all or part of a filler material in the papermaking processes or can be distributed directly onto the wrapper, such as by spraying or coating onto wet or dry base web. In production of a smoking article such as a cigarette, the wrapper is wrapped around cut filler to form a tobacco rod portion of the smoking article by a cigarette making machine, which has previously been supplied or is continuously supplied with tobacco cut filler and one or more ribbons of wrapper.
A wrapper can be any wrapping surrounding the cut filler, including wrappers containing flax, hemp, kenaf, esparto grass, rice straw, cellulose and so forth. Optional filler materials, flavor additives, and burning additives can be included. When supplied to the cigarette making machine, the wrapper can be supplied from a single bobbin in a continuous sheet (a monowrap) or from multiple bobbins (a multiwrap, such as a dual wrap from two bobbins). Further, the wrapper can have more than one layer in cross-section, such as in a bilayer paper as disclosed in commonly-owned U.S. Pat. No. 5,143,098, issued to Rogers, the entire content of which is herein incorporated by reference.
The papermaking process can be carried out using conventional paper making equipment. An exemplary method of manufacturing paper wrapper, e.g., cigarette paper including oxyhydroxide compounds, comprises supplying the oxyhydroxide compounds and a cellulosic material to a papermaking machine. For example, an aqueous slurry (or “furnish”) including the oxyhydroxide compounds and the cellulosic material can be supplied to a head box of a forming section of a Fourdrinier papermaking machine. The aqueous slurry can be supplied to the head box by a plurality of conduits which communicate with a source, such as a storage tank.
The oxyhydroxide compounds can be supplied to the papermaking process in any suitable form, such as in the form of an aqueous slurry or in the form of a dry powder to be slurried during the papermaking process prior to addition to the head box. For example, the oxyhydroxide compounds can be produced on site as a slurry. The aqueous slurry containing the oxyhydroxide compounds can be used immediately or stored for future use. In a preferred embodiment, the head box is supplied with an aqueous slurry of furnish containing the oxyhydroxide compounds and cellulosic material used to form a web. Optionally, an aqueous slurry of furnish containing oxyhydroxide compounds and an aqueous slurry furnish of cellulosic material without oxyhydroxide compounds or with a different concentration of oxyhydroxide compounds can be supplied to separate head boxes or multiple head boxes.
An exemplary method deposits the aqueous slurry from the head box onto a forming section so as to form a base web of the cellulosic material and the catalyst modified web-filler. For example, in a typical Fourdrinier machine, the forming section is a Fourdrinier wire which is arranged as an endless forming wire immediately below the head box. A slice defined in a lower portion of the head box adjacent to the endless wire permits the aqueous slurry of oxyhydroxide compounds and cellulosic material from the head box to flow through the slice onto the top surface of the endless wire to form a wet base web. Optionally, the aqueous slurry can be deposited onto a support web that is retained within the paper. For example, a support web can be transported through the forming section of a papermaking machine and can be a foundation on which the aqueous slurry is deposited. The aqueous slurry dries on the Fourdrinier wire in the forming section to an intermediate web, which may still retain an aqueous component, and is further processed to form a paper sheet (e.g., finished web) with the support web embedded therein. The support web can be a conventional web, such as a flax support web, or can include a web with an incorporated oxyhydroxide compound. If the support web includes an oxyhydroxide compound, the incorporated oxyhydroxide compound can be directly supported on the support web.
After depositing the aqueous slurry onto the forming section, water is removed from the wet base web to form an intermediate web and, with additional processing such as further drying and pressing if necessary, forms a sheet of cigarette paper (e.g., finished web). The cigarette paper is subsequently taken up for storage or use, e.g. the cigarette paper is coiled in a sheet or roll.
As a further addition, the oxyhydroxide compounds can be used in other portions of the smoking article, e.g., cigarette, and the smoking article components, e.g., cut filler, second wrappers, tipping paper and so forth. For example, the oxyhydroxide compounds, as described above, may optionally be provided along the length of a tobacco rod by distributing the oxyhydroxide compounds on the tobacco or incorporating them into the cut filler tobacco using any suitable method. The oxyhydroxide compounds may be provided in the form of a powder or in a solution in the form of a dispersion, for example. In a preferred method, the oxyhydroxide compounds in the form of a dry powder are dusted on the cut filler tobacco. The oxyhydroxide compounds may also be present in the form of a solution or dispersion, and sprayed on the cut filler tobacco. Alternatively, the tobacco may be coated with a solution containing the oxyhydroxide compounds. The oxyhydroxide compounds may also be added to the cut filler tobacco stock supplied to the cigarette making machine or added to a tobacco rod prior to wrapping cigarette paper around the cigarette rod.
The oxyhydroxide compounds will preferably be distributed throughout the tobacco rod portion of a cigarette and, optionally, the cigarette filter. By providing the oxyhydroxide compounds throughout the entire tobacco rod, it is possible to reduce the amount of carbon monoxide throughout the cigarette, and particularly at both the combustion region and in the pyrolysis zone.
The amount of oxyhydroxide compound to be used may be determined by routine experimentation. Preferably, the product formed from the decomposition of the oxyhydroxide during combustion of the cut filler composition is present in an amount effective to convert at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% of the carbon monoxide to carbon dioxide. Preferably, the amount of the oxyhydroxide will be from about a few milligrams, for example, 5 mg/cigarette, to about 200 mg/cigarette. More preferably, the amount of oxyhydroxide will be from about 40 mg/cigarette to about 100 mg/cigarette.
In addition, the combinations of oxyhydroxide compounds containing a metal oxide disclosed herein can be used in a cut filler tobacco rod, or a cigarette similar to the disclosed uses of oxyhydroxide compounds, e.g., incorporated in cut filler, distributed along the tobacco rod length, distributed throughout the cigarette, used in powder form, or used in solution form.
One embodiment relates to a cut filler composition comprising tobacco and at least one oxyhydroxide compound, as described above, which is capable of acting as an oxidant for the conversion of carbon monoxide to carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide. Any suitable tobacco mixture may be used for the cut filler. Examples of suitable types of tobacco materials 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.
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 1/10 inch to about 1/20 inch or even 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, combustion modifying agents, coloring agents, binders, etc.) known in the art.
Another embodiment relates to a cigarette comprising a tobacco rod, wherein the tobacco rod comprises cut filler having at least one oxyhydroxide compound, as described above, which is capable of decomposing during smoking to produce a product that is capable of acting as an oxidant for the conversion of carbon monoxide to carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide. A further embodiment relates to a method of making a cigarette, comprising (i) adding an oxyhydroxide compound to a cut filler, wherein the oxyhydroxide compound is capable of decomposing during smoking to produce a product that is capable of acting as an oxidant for the conversion of carbon monoxide to carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide; (ii) providing the cut filler comprising the oxyhydroxide compound to a cigarette making machine to form a tobacco column; and (iii) placing a paper wrapper around the tobacco column to form a tobacco rod of the cigarette.
Techniques for cigarette manufacture are known in the art. Any conventional or modified cigarette making technique may be used to incorporate the oxyhydroxide compounds. The resulting cigarettes can be manufactured to any desired specification using standard or modified cigarette making techniques and equipment. Typically, the cut filler composition is optionally combined with other cigarette additives, and provided to a cigarette making machine to produce a tobacco column, which is then wrapped in cigarette paper, and optionally tipped with filters.
The cigarettes may range from about 50 mm to 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/cm3 to about 300 mg/cm3, and preferably 150 mg/cm3 to about 275 mg/cm3.
Yet another embodiment relates to methods of smoking the cigarette described above, which involve lighting the cigarette to form smoke and drawing the smoke through the cigarette, wherein during the smoking of the cigarette, the oxyhydroxide compound decomposes during smoking to form a compound that acts as an oxidant for the conversion of carbon monoxide to carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide.
“Smoking” of a cigarette means the heating or combustion of the cigarette to form smoke, which can be drawn through the cigarette. Generally, smoking of a cigarette involves lighting one end of the cigarette and drawing 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, 5,591,368 or 5,322,075, for example.
While various embodiments have been described, 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 claims appended hereto.
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.
This application claims priority under 35 U.S.C. §119 to U.S. Provisional Application No. 60/514,529 entitled USE OF OXYHYDROXIDE COMPOUNDS IN CIGARETTE PAPER FOR REDUCING CARBON MONOXIDE IN THE MAINSTREAM SMOKE OF A CIGARETTE, filed Oct. 27, 2003, the entire content of which is hereby incorporated by reference.
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| Number | Date | Country | |
|---|---|---|---|
| 20050155616 A1 | Jul 2005 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60514529 | Oct 2003 | US |
