WO2000015056A1 - Improved method of treating tobacco to reduce nitrosamine content, and products produced thereby - Google Patents

Improved method of treating tobacco to reduce nitrosamine content, and products produced thereby Download PDF

Info

Publication number
WO2000015056A1
WO2000015056A1 PCT/US1999/020909 US9920909W WO0015056A1 WO 2000015056 A1 WO2000015056 A1 WO 2000015056A1 US 9920909 W US9920909 W US 9920909W WO 0015056 A1 WO0015056 A1 WO 0015056A1
Authority
WO
WIPO (PCT)
Prior art keywords
tobacco
air
content
less
nitrosamines
Prior art date
Application number
PCT/US1999/020909
Other languages
English (en)
French (fr)
Inventor
Jonnie R. Williams
Original Assignee
Star Scientific, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Star Scientific, Inc. filed Critical Star Scientific, Inc.
Priority to MXPA01002706A priority Critical patent/MXPA01002706A/es
Priority to BR9913700-3A priority patent/BR9913700A/pt
Priority to EP99948191A priority patent/EP1121026A4/en
Priority to CA002344063A priority patent/CA2344063C/en
Priority to APAP/P/2001/002097A priority patent/AP1461A/en
Priority to AU61420/99A priority patent/AU6142099A/en
Publication of WO2000015056A1 publication Critical patent/WO2000015056A1/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18Treatment of tobacco products or tobacco substitutes
    • A24B15/24Treatment of tobacco products or tobacco substitutes by extraction; Tobacco extracts
    • A24B15/241Extraction of specific substances
    • A24B15/245Nitrosamines
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18Treatment of tobacco products or tobacco substitutes
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18Treatment of tobacco products or tobacco substitutes
    • A24B15/22Treatment of tobacco products or tobacco substitutes by application of electric or wave energy or particle radiation
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B3/00Preparing tobacco in the factory
    • A24B3/18Other treatment of leaves, e.g. puffing, crimpling, cleaning

Definitions

  • the present invention relates to an improved method of treating tobacco to reduce the content of, or to prevent the formation of, harmful nitrosamines, which are normally found in tobacco.
  • the present invention also relates to tobacco products having low nitrosamine content.
  • cured tobacco products obtained according to conventional methods are known to contain a number of nitrosamines, including the harmful carcinogens N'-nitrosonornicotine (NNN) and 4-(N-nitrosomethylamino)-l-(3-pyridyl)-l-butanone (NNK). It is widely accepted that such nitrosamines are formed post-harvest, during the conventional curing process, as described further herein. Unfortunately, fresh-cut green tobacco is unsuitable for smoking or other consumption.
  • TSNAs tobacco-specific nitrosamines
  • TSNA tobacco-specific nitrosamine
  • Wiernik et al Certain aspects of Burton et al's 1993-94 study are reported in Wiernik et al, supra, at pages 54-57, under the heading "Modified Air-Curing.”
  • the Wiernik et al article postulates that subjecting tobacco leaf samples, taken at various stages of air-curing, to quick-drying at 70°C for 24 hours, would remove excess water and reduce the growth of microorganisms; hence, nitrite and tobacco- specific nitrosamine (TSNA) accumulation would be avoided.
  • Table II at page 56
  • Wiernik et al includes some of Burton et al's summary data on lamina and midrib nitrite and
  • the Wiernik et al article also discusses traditional curing of Skroniowski tobacco in Poland as an example of a 2-step curing procedure.
  • the article states that the tobacco is first air-cured and, when the lamina is yellow or brownish, the tobacco is heated to 65 °C for two days in order to cure the stem.
  • An analysis of tobacco produced in this manner showed that both the tobacco-specific nitrosamine (TSNA) and the nitrite contents were low, i.e., in the range of 0.6-2.1 micrograms per gram and less than 10 micrograms per gram, respectively.
  • TSNA tobacco-specific nitrosamine
  • TSNA tobacco-specific nitrosamine
  • nitrite contents 0.2 microgram per gram and less than 15 micrograms per gram, respectively, were obtained for tobacco subjected to air- curing in Poland.
  • tobacco leaves are generally cured according to one of three methods.
  • this variation of the flue curing process features the use of a heat exchanger and involves the burning of fuel and the passing of heated air through flue pipes in a curing barn. Accordingly, in this older version of the curing process, primarily radiant heat emanating from the flue pipes is used to cure the tobacco leaves. W ile a relatively low flow of air does pass through the curing barn, this process utilizes primarily radiant heat emanating from the flue pipes to cure the tobacco leaves within the barn. In addition, this process does not appreciate, and does not provide for, controlling the conditions within the barn to achieve prevention or reduction of TSNAs. This technique has been largely replaced in the United States by a different flue-curing process.
  • U.S. Patent No. 2,758,603 to Heljo discloses a process for treating tobacco with relatively low moisture levels (i.e., already cured tobacco) with radio frequency energy to accelerate the aging process.
  • relatively low moisture levels i.e., already cured tobacco
  • the patent states that the tobacco being treated is "green” tobacco, it is clear that the patent is using the term "green” in a non-conventional sense because the tobacco being treated therein is already cured (i.e., the tobacco is already dried). This is clearly evident from the disclosed moisture levels for the tobacco being treated in the Heljo patent. In fact, Heljo rehydrates the fully cured tobacco prior to the radio frequency treatment.
  • the term "green tobacco” refers to freshly harvested tobacco, which contains relatively high levels of moisture.
  • microwave energy to dry agricultural products has been proposed.
  • use of microwave energy to cure tobacco is disclosed in U.S. Patent No. 4,430,806 to Hopkins.
  • U.S. Patent No. 4,898,189 to Wochnowski teaches the use of microwaves to treat green tobacco in order to control moisture content in preparation for storage or shipping.
  • microwave energy is described to kill insect infestation of tobacco.
  • techniques using impregnation of tobacco with inert organic liquids for the purposes of extracting expanded organic materials by a sluicing means have been disclosed wherein the mixture was exposed to microwave energy.
  • microwave energy is disclosed as the drying mechanism of extruded tobacco-containing material (U.S. Patent No. 4,874,000).
  • U.S. Patent No. 3,773,055 Sturgis discloses the use of microwave to dry and expand cigarettes made with wet tobacco.
  • U.S. Patent No. 5,803,081 to Williams discloses a method of reducing the nitrosamine levels or preventing the formation of nitrosamines in a harvested tobacco plant using microwave energy.
  • Figure 1 illustrates a tobacco-curing apparatus according to the present invention.
  • FIG. 2 illustrates the air-handling device/heat exchanger system of the tobacco- curing apparatus according to the present invention.
  • the parameters that can be varied to control the conditions within the curing barn (or curing apparatus) during the curing process include humidity, rate of temperature change, temperature, the time of treatment of the tobacco, the airflow (through the curing apparatus or barn), CO level, CO 2 level, O 2 level, and the arrangement of the tobacco leaves.
  • one object of the present invention is to substantially eliminate or reduce the content of nitrosamines in tobacco intended for smoking or consumption by other means.
  • Another object of the present invention is to reduce the carcinogenic potential of tobacco products, including cigarettes, cigars, chewing tobacco, snuff and tobacco- containing gum and lozenges.
  • Still another object of the present invention is to substantially eliminate or significantly reduce the amount of tobacco-specific nitrosamines, including N'- nitrosonornicotine (NNN), 4-(N-nitrosomethylamino)-l-(3-pyridyl)-l-butanone (NNK), N'- nitrosoanatabine (NAT) and N'-nitrosoanabasine (NAB), in such tobacco products.
  • NNN N'- nitrosonornicotine
  • NNK 4-(N-nitrosomethylamino)-l-(3-pyridyl)-l-butanone
  • NAT N'- nitrosoanatabine
  • NAB N'-nitrosoanabasine
  • Another object of the present invention is to treat uncured tobacco at an appropriate time post-harvest so as to arrest the curing process without adversely affecting the tobacco's suitability for human consumption.
  • Another object of the present invention is to reduce the content of tobacco-specific nitrosamines by treating uncured tobacco in a controlled environment.
  • Yet another object of the present invention is to reduce the content of tobacco- specific nitrosamines, particularly NNN and NNK, and metabolites thereof in humans who smoke, consume or otherwise ingest tobacco in some form, by providing a tobacco product suitable for human consumption, which product contains a substantially reduced quantity of tobacco-specific nitrosamines, thereby lowering the carcinogenic potential of such product.
  • the tobacco product may be a cigarette, cigar, chewing tobacco or a tobacco-containing gum or lozenge.
  • Yet another object is to provide a novel curing barn (or curing apparatus) which is capable of providing tobacco suitable for human consumption, wherein the tobacco contains relatively low levels to zero tobacco-specific nitrosamines.
  • the above and other objects and advantages in accordance with the present invention can be obtained by a process for reducing the amount of or preventing the formation of nitrosamines in a harvested tobacco plant, comprising subjecting at least a portion of the plant, while said portion is uncured and in a state susceptible to having the amount of nitrosamines reduced or formation of nitrosamines arrested, to a controlled environment capable of providing a reduction in the amount of nitrosamines or prevention of the formation of nitrosamines, for a time sufficient to reduce the amount of or substantially prevent the formation of at least one nitrosamine, wherein said controlled environment is provided by controlling at least one of humidity, rate of temperature change, temperature, airflow, CO level, CO 2 level, O 2 level, and the arrangement of the tobacco leaves.
  • the step of subjecting tobacco leaf to the controlled environment is carried out on a tobacco leaf or portion thereof after onset of yellowing in the leaf and prior to substantial accumulation of tobacco-specific nitrosamines in the leaf. It is also preferred that in the process of the invention, the step of subjecting the tobacco leaf to the controlled environment is carried out prior to substantial loss of the leafs cellular integrity. It is also preferred in accordance with the present invention that the tobacco leaf or a portion thereof is subjected to the controlled environment for a time sufficient to effectively dry the leaf, without any charring when heat is applied, so that it is suitable for human consumption.
  • the present invention also seeks to subject tobacco leaves to the controlled environment to prevent normal accumulation of at least one tobacco-specific nitrosamine, such as N'-nitrosonornicotine, 4-(N-nitrosomethylamino)-l-(3-pyridyl)-l-butanone, N'- nitrosoanatabine and N'-nitrosoanabasine.
  • the process of the invention further comprises treating the tobacco leaves, while in a state susceptible to having the content of at least one TSNA prevented or reduced, to microwave energy or other forms of high energy treatment.
  • the present invention in its broadest forms also encompasses a tobacco product comprising non-green tobacco suitable for human consumption and having a lower content of at least one tobacco-specific nitrosamine than conventionally cured tobacco.
  • the present invention relates to a novel curing barn which is capable of providing a controlled environment in which the formation of tobacco-specific nitrosamines can be prevented or reduced.
  • controlling the conditions means determining and selecting an appropriate humidity, rate of temperature change, temperature, time of treatment of the tobacco, airflow, CO level, CO 2 level, O 2 level, and arrangement of the tobacco leaves to prevent or reduce the formation of at least one TSNA.
  • a given set of ambient conditions it may be necessary to adjust, within the curing apparatus or barn, one or more of these parameters.
  • it is possible to prevent or reduce the formation of TSNAs by simply setting a high airflow through the curing apparatus or barn.
  • tobacco that has been "conventionally cured” is tobacco that has been air-cured or flue-cured, without the controlled conditions described herein, according to conventional methods commonly and commercially used in the U.S.
  • green tobacco means tobacco that is substantially uncured and is particularly inclusive of freshly harvested tobacco.
  • the present invention is founded on the discovery that a window exists during the tobacco curing cycle, in which the tobacco can be treated in a manner that will essentially prevent the formation of TSNA.
  • the precise window during which TSNA formation can be effectively eliminated or substantially reduced depends on the type of tobacco and a number of other variables, including those mentioned above.
  • the window corresponds to the time frame post-harvest when the leaf is beyond the fresh-cut or "green" stage, and prior to the time at which TSNAs and/or nitrites substantially accumulate in the leaf. This time frame typically corresponds to the period in which the leaf is undergoing the yellowing process or is in the yellow phase, before the leaf turns brown, and prior to the substantial loss of cellular integrity.
  • TSNA reduced by subjecting the tobacco to a controlled environment capable of providing a reduction in the amount of nitrosamines or prevention of the formation of nitrosamines, for a time sufficient to reduce the amount of or substantially prevent the formation of at least one nitrosamine, wherein said controlled environment is provided by controlling at least one of humidity, rate of temperature change, temperature, airflow, CO level, CO 2 level, O 2 level, and arrangement of the tobacco leaves.
  • This treatment of the tobacco essentially arrests the natural formation of TSNAs, and provides a dried, golden yellow leaf suitable for human consumption.
  • the treatment according to the present invention effectively arrests the natural TSNA formation cycle, thus preventing any further substantial formation of TSNA.
  • yellow or yellowing tobacco is treated in this fashion at the most optimal time in the curing cycle, the resulting tobacco product has TSNA levels essentially approximating those of freshly harvested green tobacco, while maintaining its flavor and taste.
  • the nicotine content of the tobacco product according to the present invention remains unchanged, or is substantially unchanged, by the treatment according to the present invention. Accordingly, the tobacco product of the present invention has relatively low contents of TSNAs, and yet the user of the tobacco product can experience the same sensations that are obtainable from using conventional tobacco products.
  • tobacco-specific TSNAs are formed primarily during the curing process. Specifically, it is believed that the amount of TSNAs in cured tobacco leaf is dependent on the accumulation of nitrites, which are formed during the curing process by reduction of nitrates to nitrites under conditions approaching an anaerobic (i.e., oxygen deficient) environment. The nitrites accumulate during the death of the plant cell. Experimental evidence suggests that the nitrites are formed by the micro flora on the surface of the leaf under conditions approaching an anaerobic environment. If, for example, conditions are made aerobic, the microbes will consume the oxygen in the atmosphere for their energy source, and thus, no nitrites will form.
  • nitrites Once nitrites are formed, however, they can then combine with various tobacco alkaloids, including pyridine-containing compounds, to form carcinogenic substances such as nitrosamines.
  • the combustion exhaust gases pass through the tobacco, thereby creating a condition approaching an anaerobic environment.
  • This conventional curing technique utilizes air that is normally recirculated within the curing barn and is often air having high humidity.
  • Conventional curing has been developed over time without any appreciation for subjecting tobacco to a controlled environment for the purpose of eliminating or reducing TSNAs. Accordingly, such conventional curing techniques do not provide suitable conditions (e.g., adequate oxygen flow) and fail to prevent an anaerobic condition in the vicinity of the tobacco leaves.
  • the tobacco leaves will emit carbon dioxide, which will further dilute the oxygen present in the curing environment.
  • the micro flora reduce nitrates to nitrites. Consequently,
  • TSNA are formed and become part of the tobacco product that is ultimately consumed by the tobacco user.
  • the present invention is applicable to the treatment of harvested tobacco, which is intended for human consumption.
  • Much research has been performed on tobacco, with particular reference to tobacco-specific nitrosamines (i.e., TSNAs).
  • Freshly harvested tobacco leaves are called "green tobacco” and contain no known carcinogens, but green tobacco is not suitable for human consumption.
  • the process of curing green tobacco depends on the type of tobacco harvested. For example, Virginia flue (bright) tobacco is typically flue-cured, whereas Burley and certain dark strains are usually air-cured.
  • the flue-curing of tobacco typically takes place over a period of five to seven days compared to about one to two or more months for air-curing.
  • flue-curing has generally been divided into three stages: yellowing (35-40°C) for about 36-72 hours (although others report that yellowing begins sooner than 36 hours, e.g., at about 24 hours for certain Virginia flue strains), leaf drying (40-57°C) for 48 hours, and midrib (stem) drying (57-75°C) for 48 hours. Many major chemical and biochemical changes begin during the yellowing stage and continue through the early phases of leaf drying.
  • the yellowing stage is carried out in a barn. During this phase the green leaves gradually lose color due to chlorophyll degradation, with the corresponding appearance of the yellow carotenoid pigments.
  • the yellowing stage of flue-curing tobacco is accomplished by closing external air vents in the barn, and holding the temperature at approximately 35°-37°C. The yellowing stage typically lasts about 3 to 5 days. After the yellowing stage, the air vents are opened, and the heat is gradually and incrementally raised. Over a period of about 5 to 7 days from the end of yellowing, the tobacco product is dried.
  • this process utilizes a somewhat controlled environment, but the controlled environment is insufficient to ensure the prevention or reduction of nitrosamines as in the present invention.
  • the process during the yellowing maintains the relative humidity in the barn at approximately 85%, limits moisture loss from the leaves, and allows the leaf to continue the metabolic processes that has begun in the field.
  • the goal of the flue-curing process is merely to obtain a dry product that has a lemon or golden orange color.
  • tobacco-specific nitrosamines are formed upon reaction of amines with nitrite-derived nitrosating species, such as NO 2 , N 2 O 3 and N 2 O 4 under acidic or anaerobic conditions. Wiernik et al discuss the postulated formation of TSNAs at pp.
  • Tobacco leaves contain an abundance of amines in the form of amino acids, proteins, and alkaloids.
  • the tertiary amine nicotine (referenced as (1) in the diagram below) is the major alkaloid in tobacco, while other nicotine-type alkaloids are the secondary amines nornicotine (2), anatabine (3) and anabasine (4).
  • Tobacco also generally contains up to 5% of nitrate and traces of nitrite.
  • TSNAs include NNAL (4-N-nitrosomethylamino)-l-(3-pyridyl)-l-butanol, 10), iso-NNAL (4-N-nitrosomethylamino)-4-(3-pyridyl)-l-butanol, 11) and iso-NNAC (4- (N-nitrosomethylamino)-4-(3-pyridyl)-butanoic acid, 12).
  • the formation of these TSNAs from the corresponding tobacco alkaloids is shown schematically below, using the designations 1-12 above (reproduced from Wiernik et al, supra, p. 44, and incorporated herein by reference):
  • nitrite and TSNA accumulate on air-curing at the time intervals starting after the end of yellowing and ending when the leaf turns completely brown, e.g., 2-3 weeks after harvest for certain air-cured strains, and approximately a week or so after harvest in flue-cured varieties. This is the time during which loss of cellular integrity occurs, due to moisture loss and leakage of the content of cells into the intercellular spaces. Therefore, there is a short window in time during air- curing when the cells have disintegrated, making the nutrition available for microorganisms. Wiernik et al have suggested that nitrite may then substantially accumulate as a result of dissimilatory nitrate reduction, thus rendering formation of TSNA possible.
  • the formation of nitrosamines in a harvested tobacco plant is substantially prevented or arrested by a process, comprising subjecting at least a portion of the plant, while said portion is uncured and in a state susceptible to having the amount of nitrosamines reduced or formation of nitrosamines arrested, to a controlled environment capable of providing a reduction in the amount of nitrosamines or prevention of the formation of nitrosamines, for a time sufficient to reduce the amount of or substantially prevent the formation of at least one nitrosamine, wherein said controlled environment is provided by controlling at least one of humidity, rate of temperature change, temperature, airflow, CO level, CO 2 level, O 2 level, and arrangement of the tobacco leaves.
  • non-green and/or yellow tobacco products can be obtained which are suitable for human consumption, and which have a lower content of at least one tobacco-specific nitrosamine than conventionally cured tobacco.
  • Green or fresh-cut tobacco is generally unsuitable for human consumption as noted above; "non-green” as used herein means the tobacco has at least lost the majority of chlorophyll, and includes without limitation partially yellow leaves, full yellow leaves, and leaves which have begun to turn brown in places.
  • the present invention is applicable to all strains of tobacco, including flue or bright varieties, Burley varieties, dark varieties, oriental/Turkish varieties, etc.
  • the airflow through the barn may vary on a case-by-case basis and may be dependent on the arrangement of the tobacco leaves to be treated (i.e., the degree of tobacco leaf surface exposure) and the size of the curing apparatus or barn
  • the minimum flow of air is preferably about ten percent higher than the flow of flue gas commonly used in the prior art.
  • other parameters e.g., humidity, temperature, etc.
  • the minimum flow of air may be about 70 CFM at 1" static pressure per cubic feet of curing apparatus or barn volume, more preferably 80 CFM at 1" static pressure per cubic feet of curing apparatus or barn volume.
  • the specific minimum flow of air needed for a given set of conditions may be determined on a routine basis given the disclosure of the present invention.
  • the humidity of the heated or unheated air is desirably controlled using a commercially-available dehumidifier or humidifier.
  • the heated or unheated air flow comprises dehumidifed air with a humidity level of less than about 85%, more preferably less than about 60%, most preferably less than about 50%.
  • the air is fresh outside air, while the heated air is substantially free from combustion exhaust gases including water vapor, carbon monoxide, and carbon dioxide.
  • the air may be recirculated as long as an anaerobic condition is avoided.
  • the temperature within the curing barn of the present invention may range from ambient (i.e., outside) temperature to as high as about 250°F or more, without charring the tobacco product. If heated air (i.e., convective heat) is used to accelerate the drying of the tobacco product, suitable temperatures may range anywhere from about 100°F to about
  • the optimum temperature within the curing barn can be determined for each case, depending on the overall conditions of the environment and the tobacco product being treated.
  • the determination of the time for treating the tobacco according to the process of the present invention can be determined by trial and error.
  • the treatment time may be from about 48 hours up to about 2 weeks.
  • the arrangement of the tobacco leaves is not critical, but it is advantageous to provide the highest exposed surface area for the tobacco leaves.
  • UV light While it is not essential, it may be desirable to expose the tobacco product to UV light, either simultaneously with, or separately from, the treatment described above. It is believed that this UV light exposure can further reduce the amount of TSNA accumulation.
  • the UV light can be supplied using "Germicidal Sterilamp” tubes obtained from Philips Lighting , wherein the light has wavelengths of between 100 and 280 nm.
  • the curing process as described above is preferable over microwave curing techniques because microwaving requires moist tobacco whereas the inventive curing process does not, it is within the scope of the present invention to further treat the tobacco product with microwave or other high energy treatment, as described in copending U.S. Applications Nos. 08/879,905 and 08/998,043, both of which are incorporated herein by reference.
  • This additional microwave or other high energy treatment is conveniently performed within the window of time in which it is possible to further prevent or reduce the formation of at least one TSNA. While Applications Nos. 08/879,905 and 08/998,043 are incorporated herein by reference, the preferred aspects of the microwaving or other high energy treatment are described below.
  • the process of this invention may further comprise a microwaving process for reducing the amount of or preventing formation of nitrosamines in a harvested tobacco plant, which microwaving process comprises subjecting at least a portion of the plant to microwave radiation, while said portion is uncured and in a state susceptible to having the amount of nitrosamines reduced or formation of nitrosamines arrested, for a sufficient time to reduce the amount of or substantially prevent formation of at least one nitrosamine. It is preferred that in this aspect of the process of the invention, the step of subjecting to microwave radiation is carried out on a tobacco leaf or portion thereof after onset of yellowing in the leaf and prior to substantial accumulation of tobacco-specific nitrosamines in the leaf.
  • the step of subjecting to microwave radiation is carried out prior to substantial loss of the leafs cellular integrity.
  • Using microwave energy eliminates the potential for activation of the microbes that cause TSNAs in tobacco, particularly in tobacco that has been rehydrated.
  • microwave radiation refers to electromagnetic energy in the form of microwaves having a frequency and wavelength typically characterized as falling within the microwave domain.
  • microwave generally refers to that portion of the electromagnetic spectrum which lies between the far-infrared region and the conventional radiofrequency spectrum.
  • the range of microwaves extends from a wavelength of approximately 1 millimeter and frequency of about 300,000 MHz to wavelength of 30 centimeters and frequency of slightly less than about 1,000 MHz.
  • the present invention preferably utilizes high power applications of microwaves, typically at the lower end of this frequency range.
  • microwaves due to a greater penetration, microwaves generally heat quickly to a depth several centimeters while heating by infrared is much more superficial.
  • commercial microwave apparatuses such as kitchen microwave ovens, are available at standard frequencies of approximately 915 MHz and 2450 MHz, respectively. These frequencies are standard industrial bands. In Europe, microwave frequencies of 2450 and 896 MHz are commonly employed. Under properly balanced conditions, however, microwaves of other frequencies and wavelengths would be useful to achieve the objects and advantages of the present invention.
  • Microwave energy can be generated at a variety of power levels, depending on the desired application.
  • Microwaves are typically produced by magnatrons, at power levels of 600-1000 watts for conventional kitchen-level microwave apparatuses (commonly at about 800 watts), but commercial units are capable of generating power up to several hundred kilowatts, generally by addition of modular sources of about 1 kilowatt.
  • a magnatron can generate either pulsed or continuous waves of suitably high frequency.
  • the applicator is a necessary link between the microwave power generator and the material to be heated.
  • any desired applicator can be used, so long as it is adapted to permit the tobacco plant parts to be effectively subjected to the radiation.
  • the applicator should be matched to the microwave generator to optimize power transmission, and should avoid leakage of energy towards the outside.
  • Multimode cavities microwave ovens
  • the applicator can be equipped with a mode stirrer (a metallic moving device which modifies the field distribution continuously), and with a moving table surface, such as a conveyor belt. The best results are attained by single leaf thickness exposure to microwave radiation, as opposed to stacks or piles of leaves.
  • the microwave conditions comprise microwave frequencies of about 900 MHz to about 2500 MHz, more preferably about 915 MHz and about 2450 MHz, power levels of from about 600 watts up to 300 kilowatts, more preferably from about 600 to about 1000 watts for kitchen-type applicators and from about 2 to about 75 kilowatts, more preferably from about 5 to about 50 kilowatts, for commercial multimode applicators.
  • the heating time generally ranges from at least about 1 second, and more generally from about 10 seconds up to about 5 minutes. At power levels of about 800-1000 watts the heating time is preferably from about 1 minute to about 214 minutes when treating single leaves as opposed to piles or stacks.
  • heating times would be lower, ranging from about 5 seconds up to about 60 seconds, and generally in the 10-30 second range at, say, 50 kilowatts, again for single leaves as opposed to piles or stacks.
  • an optimal microwave field density could be determined for any given applicator based on the volume of the cavity, the power level employed, and the amount of moisture in the leaves.
  • use of higher power levels will require less time during which the leaf is subjected to the microwave radiation.
  • the microwave radiation is preferably applied to the leaf or portion thereof for a time sufficient to effectively dry the leaf, without charring, so that it is suitable for human consumption. It is also preferred to apply the microwave radiation to the leaf or portion thereof for a time and at a power level sufficient to reduce the moisture content to below about 20 % by weight, more preferably about 10% by weight.
  • the microwave radiation is applied to the leaf or portion thereof for a time sufficient to effectively dry the leaf, without charring, so that it is suitable for human consumption.
  • the present invention further comprises a method for reducing the amount of or preventing formation of nitrosamines in a harvested tobacco plant, comprising subjecting at least a portion of the plant to radiation having a frequency higher than the microwave domain, while said portion is uncured and in a state susceptible to having the amount of nitrosamines reduced or formation of nitrosamines arrested, for a sufficient time to reduce the amount of or substantially prevent formation of at least one nitrosamine.
  • the step of subjecting to radiation having a frequency higher than the microwave domain is carried out on a tobacco leaf or portion thereof after onset of yellowing in the leaf and prior to substantial accumulation of tobacco-specific nitrosamines in the leaf.
  • the step of subjecting to such radiation is carried out prior to substantial loss of the leafs cellular integrity.
  • Preferred energy sources capable of producing such radiation include far-infrared and infrared radiation, UV (ultraviolet radiation), soft x-rays or lasers, accelerated particle beams such as electron beams, x-rays and gamma radiation.
  • such energy sources include, without limitation, far-infrared and infrared radiation having frequencies of about 10 12 to 10 14 Hz and wavelengths of 3 x 10 "4 to 3 x 10 "6 meters, ultraviolet radiation having frequencies of about 10 16 to 10 18 Hz and wavelengths of 3 x 10 "8 to 3 x 10 "10 meters, soft x-rays or lasers, cathode rays (a stream of negatively charged electrons issuing from the cathode of a vacuum tube perpendicular to the surface), x-rays and gamma radiation typically characterized as having frequencies of 10 21 Hz and higher at corresponding wavelengths.
  • radiation application times of less than one minute, preferably less than 30 seconds and even more preferably less than about ten seconds are needed when using such higher frequency radiation sources.
  • the exposure rate can be controlled to deliver the radiation dosage over time, if desired. For example, 1 megarad of radiation can be delivered instantaneously, or at a predetermined exposure rate.
  • it is prefened to use an amount of radiation which achieves at least a 50% reduction in TSNAs, in comparison to untreated samples.
  • the particular radiation dosages and exposure rate will depend on the particular equipment and type of radiation source being applied, as would be apparent to one of ordinary skill in the art, it is generally preferred to subject the tobacco samples to radiation of from about .1 to about 10 megarads, more preferably from about .5 to about 5 megarads, and more preferably from about .75 to about 1.5 megarads.
  • microwaving or other high energy treatment is conducted after subjecting the tobacco to the controlled environment of the present invention.
  • the treatment according to the present invention may be performed in conventional barns as well as large-scale processing centers capable of treating tens of acres of tobacco. It is also possible to perform the process of the present invention in any size, including miniature curing apparatuses or barns.
  • the treatment of the tobacco product according to the present invention using airflow and temperature control, would be similar to treating tobacco product using a convective heating air oven or treating the tobacco product using a clothes dryer.
  • the present invention relates to a tobacco product comprising cured non-green or yellow tobacco suitable for human consumption and having a content of at least one tobacco-specific nitrosamine selected from N'-nitrosonornicotine (NNN), 4-(N-nitrosomethylamino)-l-(3-pyridyl)-l-butanone (NNK), N'-nitrosoanatabine (NAT) and N'-nitrosoanabasine (NAB) which is less than about 50% by weight of the content of said at least one tobacco-specific nitrosamine in conventionally cured tobacco, more preferably less than about 75% by weight, most preferably less than about 95% by weight, without the use of organic solvent extraction.
  • NNN N'-nitrosonornicotine
  • NK 4-(N-nitrosomethylamino)-l-(3-pyridyl)-l-butanone
  • NAT N'-nitrosoanatabine
  • NAB N'-nitrosoanabasine
  • the NNN level of the tobacco product according to the present invention is typically less than about 0.05 ⁇ g/g
  • the combined NAT and NAB level is typically less than about 0.10 ⁇ g/g
  • the NNK level is typically less than about 0.05 ⁇ g/g
  • the combined TSNA level is typically less than about 0.16 ⁇ g/g, even as low as less than about 0.009 ⁇ g/g.
  • the tobacco product according to the present invention comprises cured non-green or yellow tobacco having a NNN content less than about 0.05 ⁇ g/g.
  • the tobacco product of the present invention comprises cured non-green or yellow tobacco having a combined NAT and NAB content of less than about 0.10 ⁇ g/g.
  • the tobacco product of the present invention comprises cured non-green or yellow tobacco having a NNK content of less than about 0.05 ⁇ g/g.
  • the present invention also contemplates tobacco product comprising cured non-green or yellow tobacco having a total TSNA content of less than about 0.16
  • the tobacco product of the present invention has a NNN level of less than about 0.05 ⁇ g/g, a combined NAT and NAB level of less than about 0.10
  • the tobacco product according to the present invention can be converted to various final tobacco products, including, but not limited to, cigarettes, cigars, chewing tobacco, snuff and tobacco-containing gum and lozenges.
  • the present invention is directed to an apparatus for curing tobacco products
  • an enclosed or substantially enclosed container comprising a base frame, optionally at least one wall, optionally a roof, and optionally a door; an air handling device capable of providing an air flow of at least about 70 CFM at 1" static pressure per cubic feet of apparatus volume, wherein said air flow is at least partially and at least temporarily in communication with the interior of said container; and a heat exchanger capable of providing at least about 1 , 100 BTU/hour per cubic feet of apparatus volume.
  • the container may be in the form of a mobile unit with transport means.
  • the container may be constructed to any suitable size typical of tobacco curing barns.
  • the container may have a width of about 120 inches, a depth of 60 inches, and a height of 82 inches. It is possible to provide a container that is significantly smaller or larger than this exemplified container size.
  • the container may be insulated.
  • the container may comprise means that are capable of receiving the tobacco products to be cured. Preferably, these means are arranged so that the tobacco product is exposed for optimal curing.
  • the air circulation within the container may be of a vertical or horizontal draft design, with the flow of air being in any suitable direction, with manually or automatically controlled fresh air dampers and weighted exhaust dampers.
  • the blower for the air handling device can have a blower rating of, e.g., about 100 CFM at 0.4 inch WC static pressure per cubic feet of apparatus volume.
  • the heat exchanger is preferably constructed of stainless steel.
  • the heat exchanger system is preferably supplied with a flame detector, ignitor wire, sensor cable, dual valve gas train and or air proving switch.
  • the burner setting can be variable. As mentioned previously, however, it is possible to carry out the process of the present invention without the use of any heat. That is, the process can be conducted using simply a sufficient flow of air.
  • the apparatus for curing the tobacco products uses air that is free from combustion exhaust gases, such as carbon monoxide and carbon dioxide.
  • combustion exhaust gases such as carbon monoxide and carbon dioxide.
  • Figure 1 shows a container (1) and an air handling device/heat exhanger system (2).
  • Fugure 2 shows the air handling device/heat exhange system (2) in greater detail. It can be seen from Figure 2 that the exhausts (3) of the heat exchanger system is far removed from the air intakes (4) to minimize the possibility of combustion exhaust gases being introduced into the curing apparatus. Further, unlike conventional curing barns, the curing apparatus of the present invention features an externalized air handling device/heat exchanger system.
  • TSNA TSNA
  • a GC vial a gentle stream of nitrogen and the GC standard (N-nitrosoguvacoline; 3.2 ppm) in acetonitrile was added prior to analysis.
  • the GC-TEA was calibrated with a standard TSNA mixture on a daily basis, before and after analyses of tobacco extracts.
  • Yellow tobacco leaf was finely diced with scissors and subjected to curing for 45 minutes at 167°F using convective heat in the form of a hot air stream substantially free from combustion exhaust gases. (A hot convection air oven was used for this purpose.)
  • the sample was rather moist, and therefore, a wet weight was taken and calculations were made to correct the TSNA content to dry weight basis. 75% of the leaf was moisture, and thus the wet weight was multiplied by 0.25 to obtain the dry weight.
  • Table 1 The results are tabulated in Table 1 below. Although the treatment was made only for 45 minutes, longer or shorter treatment times are envisioned depending on the conditions and the results desired.
  • the process of the present invention provides tobacco having substantially reduced amounts of TSNA.
  • Tobacco leaf was flue cured according to a predominant version of the conventional flue curing process in a curing barn. As is the common practice for such conventional flue- curing, the combustion exhaust gases were vented through the curing barn in this process. In this conventional flue curing process, tobacco was placed in a bam with relatively low flow of air and closed external air vents. The temperature was incrementally increased (about 0.5 to 1.5°F per hour) to about 130°F over a period of about 3 days. At this point (i.e., end of yellowing), the external air vents were opened, and the temperature was maintained at 130°F for about 24-36 hours.
  • Examples 3 and 4 provided very low levels of TSNA, especially NNN and NNK, even when microwaving was not used.
  • the curing process according to the present invention provided unexpectedly lower levels of TSNA as compared to a conventional curing process.
  • Example 7 This example illustrates the advantageous effects obtainable by practicing the present invention even under the most severe environmental conditions.
  • combustion exhaust gases were not allowed to flow into the barn.
  • Green tobacco was left in a curing bam according to the present invention for about 72 hours with the external air vent closed, but with recirculating air of about 25,000 CFM, and with heating of about 300,000 BTUs to provide a temperature of about 105° F.
  • the external air vents were opened and the air handling device was adjusted to provide virtually all fresh air flow of approximately 25,000 CFM (with only a minor amount of recirculating air), and the heat was increased to about 1,000,000 BTUs to provide a rapid temperature increase to about 140° F.
  • This treatment was continued for about 72 hours.
  • the "killing out” phase i.e., drying of the stems
  • Treatment continued for about 1-2 days.
  • the resulting tobacco product was tested for TSNAs according to the analytical technique described above. The levels for each individual nitrosamine were so low that they could not be detected.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Manufacture Of Tobacco Products (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/US1999/020909 1998-09-15 1999-09-15 Improved method of treating tobacco to reduce nitrosamine content, and products produced thereby WO2000015056A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
MXPA01002706A MXPA01002706A (es) 1998-09-15 1999-09-15 Metodo mejorado de tratamiento de tabaco para reducir el contenido de nitrosamina, y productos producidos mediante el mismo.
BR9913700-3A BR9913700A (pt) 1998-09-15 1999-09-15 Processo aperfeiçoado para tratamento de tabaco para reduzir teor de nitrosamina, e produtos produzidos dele
EP99948191A EP1121026A4 (en) 1998-09-15 1999-09-15 IMPROVED TOBACCO TREATMENT METHOD FOR LIMITING ITS NITROSAMINE CONTENT AND PRODUCTS OBTAINED THEREBY
CA002344063A CA2344063C (en) 1998-09-15 1999-09-15 Tobacco curing barn
APAP/P/2001/002097A AP1461A (en) 1998-09-15 1999-09-15 Tobbacco curing barn.
AU61420/99A AU6142099A (en) 1998-09-15 1999-09-15 Improved method of treating tobacco to reduce nitrosamine content, and products produced thereby

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10037298P 1998-09-15 1998-09-15
US60/100,372 1998-09-15

Publications (1)

Publication Number Publication Date
WO2000015056A1 true WO2000015056A1 (en) 2000-03-23

Family

ID=22279407

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/020909 WO2000015056A1 (en) 1998-09-15 1999-09-15 Improved method of treating tobacco to reduce nitrosamine content, and products produced thereby

Country Status (7)

Country Link
EP (1) EP1121026A4 (es)
AP (1) AP1461A (es)
AU (1) AU6142099A (es)
BR (1) BR9913700A (es)
CA (1) CA2344063C (es)
MX (1) MXPA01002706A (es)
WO (1) WO2000015056A1 (es)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6668839B2 (en) * 2001-05-01 2003-12-30 Jonnie R. Williams Smokeless tobacco product
EP1383400A1 (en) * 2001-05-01 2004-01-28 Jonnie R. Williams Smokeless tobacco product
US6805134B2 (en) 1999-04-26 2004-10-19 R. J. Reynolds Tobacco Company Tobacco processing
WO2006038558A1 (ja) * 2004-10-01 2006-04-13 Japan Tobacco Inc. バーレー種葉タバコの乾燥方法および該乾燥方法により乾燥したバーレー種葉タバコ
CN102008120A (zh) * 2010-10-29 2011-04-13 江苏科地现代农业有限公司 烟叶烤房
CN102232614A (zh) * 2010-04-21 2011-11-09 河南农业大学 一种密集烤房的烤烟方法
EP2384127A1 (en) * 2008-12-23 2011-11-09 Jonnie R. Williams Tobacco curing method
CN102415608A (zh) * 2011-11-17 2012-04-18 陕西省烟草公司延安市公司 天然气加热循环气流烟叶烘烤室
CN102511917A (zh) * 2011-11-30 2012-06-27 四川省烟草公司宜宾市公司 用于密集式烤房的烟叶烘烤方法
WO2014047333A1 (en) * 2012-09-19 2014-03-27 Lusso Marcos Fernando De Godoy METHODS OF REDUCING TOBACCO-SPECIFIC NITROSAMINES (TSNAs) AND/OR IMPROVING LEAF QUALITY IN TOBACCO
WO2015091880A1 (en) * 2013-12-18 2015-06-25 Philip Morris Products S.A Methods for reducing matrix-bound nicotine-derived nitrosamine ketone in tobacco plant material
CN105192871A (zh) * 2015-10-12 2015-12-30 罗朝三 烤烟房及烟叶烘烤工艺
EP3199039A4 (en) * 2014-10-24 2018-06-27 Japan Tobacco Inc. Oral tobacco composition and production method thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102599624B (zh) * 2012-03-20 2014-07-16 中国农业科学院烟草研究所 五段五对应烟叶烤香密集烘烤精准工艺
CN104013093B (zh) * 2014-06-20 2015-12-02 福建中烟工业有限责任公司 烟叶的烘烤方法
CN105962411B (zh) * 2016-06-21 2018-01-12 昆明理工大学 一种容量可调的节能密集烤房
CN112611129B (zh) * 2021-01-28 2022-08-23 湖北沄禾泽生态农业开发有限公司 一种压缩机梯次启动节能热泵烤烟烤房
CN113796557B (zh) * 2021-08-24 2022-12-27 中国烟草总公司郑州烟草研究院 一种烟叶动态控湿烘烤控制方法和控制系统

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2758603A (en) * 1950-10-24 1956-08-14 Heljo Runar Rafael Process and apparatus for curing tobacco
US4212634A (en) * 1978-06-05 1980-07-15 Harrington Manufacturing Company Auxiliary heating system for a bulk tobacco barn
US4355648A (en) * 1980-12-09 1982-10-26 Philip Morris, Incorporated Method of curing tobacco
US4470422A (en) * 1980-01-22 1984-09-11 Modsa (Proprietary) Limited Curing of tobacco leaf
US5515775A (en) * 1992-10-30 1996-05-14 Philip Morris Incorporated Apparatus for treatment of solid material
US5810020A (en) * 1993-09-07 1998-09-22 Osmotek, Inc. Process for removing nitrogen-containing anions and tobacco-specific nitrosamines from tobacco products

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3927683A (en) * 1974-10-15 1975-12-23 Powell Mfg Co Bulk curing burley tobacco with a seven day curing cycle
US4482315A (en) * 1983-09-12 1984-11-13 Day Harding W Bulk tobacco barn furnace

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2758603A (en) * 1950-10-24 1956-08-14 Heljo Runar Rafael Process and apparatus for curing tobacco
US4212634A (en) * 1978-06-05 1980-07-15 Harrington Manufacturing Company Auxiliary heating system for a bulk tobacco barn
US4470422A (en) * 1980-01-22 1984-09-11 Modsa (Proprietary) Limited Curing of tobacco leaf
US4355648A (en) * 1980-12-09 1982-10-26 Philip Morris, Incorporated Method of curing tobacco
US5515775A (en) * 1992-10-30 1996-05-14 Philip Morris Incorporated Apparatus for treatment of solid material
US5810020A (en) * 1993-09-07 1998-09-22 Osmotek, Inc. Process for removing nitrogen-containing anions and tobacco-specific nitrosamines from tobacco products

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1121026A4 *

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6805134B2 (en) 1999-04-26 2004-10-19 R. J. Reynolds Tobacco Company Tobacco processing
US7404406B2 (en) 1999-04-26 2008-07-29 R. J. Reynolds Tobacco Company Tobacco processing
EP1383400A4 (en) * 2001-05-01 2006-08-02 Regent Court Technologies Llc SMOKED TOBACCO PRODUCT
US6834654B2 (en) * 2001-05-01 2004-12-28 Regent Court Technologies, Llc Smokeless tobacco product
AP1510A (en) * 2001-05-01 2005-12-17 Jonnie R Williams Smokeless tobacco product.
EP1383400A1 (en) * 2001-05-01 2004-01-28 Jonnie R. Williams Smokeless tobacco product
US6668839B2 (en) * 2001-05-01 2003-12-30 Jonnie R. Williams Smokeless tobacco product
WO2006038558A1 (ja) * 2004-10-01 2006-04-13 Japan Tobacco Inc. バーレー種葉タバコの乾燥方法および該乾燥方法により乾燥したバーレー種葉タバコ
EP2384127A4 (en) * 2008-12-23 2013-12-25 Jonnie R Williams TOBACCO DRYING PROCESS
EP2384127A1 (en) * 2008-12-23 2011-11-09 Jonnie R. Williams Tobacco curing method
CN102232614A (zh) * 2010-04-21 2011-11-09 河南农业大学 一种密集烤房的烤烟方法
CN102232614B (zh) * 2010-04-21 2013-04-17 河南农业大学 一种密集烤房的烤烟方法
CN102008120A (zh) * 2010-10-29 2011-04-13 江苏科地现代农业有限公司 烟叶烤房
CN102415608A (zh) * 2011-11-17 2012-04-18 陕西省烟草公司延安市公司 天然气加热循环气流烟叶烘烤室
CN102415608B (zh) * 2011-11-17 2013-02-13 陕西省烟草公司延安市公司 天然气加热循环气流烟叶烘烤室
CN102511917A (zh) * 2011-11-30 2012-06-27 四川省烟草公司宜宾市公司 用于密集式烤房的烟叶烘烤方法
CN102511917B (zh) * 2011-11-30 2013-12-04 四川省烟草公司宜宾市公司 用于密集式烤房的烟叶烘烤方法
WO2014047333A1 (en) * 2012-09-19 2014-03-27 Lusso Marcos Fernando De Godoy METHODS OF REDUCING TOBACCO-SPECIFIC NITROSAMINES (TSNAs) AND/OR IMPROVING LEAF QUALITY IN TOBACCO
US9521863B2 (en) 2012-09-19 2016-12-20 Altria Client Services Llc Methods of reducing tobacco-specific nitrosamines (TSNAs) and/or improving leaf quality in tobacco
US10390556B2 (en) 2012-09-19 2019-08-27 Altria Client Services Llc Methods of reducing tobacco-specific nitrosamines (TSNAs) and/or improving leaf quality in tobacco
WO2015091880A1 (en) * 2013-12-18 2015-06-25 Philip Morris Products S.A Methods for reducing matrix-bound nicotine-derived nitrosamine ketone in tobacco plant material
CN105764359A (zh) * 2013-12-18 2016-07-13 菲利普莫里斯产品有限公司 用于减少烟草植物材料中结合基质的尼古丁衍生物亚硝胺酮的方法
RU2671616C1 (ru) * 2013-12-18 2018-11-02 Филип Моррис Продактс С.А Способы снижения количества связанного с матриксом никотинпроизводного нитрозаминкетона в растительном материале табака
EP3199039A4 (en) * 2014-10-24 2018-06-27 Japan Tobacco Inc. Oral tobacco composition and production method thereof
US10306914B2 (en) 2014-10-24 2019-06-04 Japan Tobacco Inc. Oral tobacco composition and production method thereof
CN105192871A (zh) * 2015-10-12 2015-12-30 罗朝三 烤烟房及烟叶烘烤工艺

Also Published As

Publication number Publication date
MXPA01002706A (es) 2002-04-08
CA2344063A1 (en) 2000-03-23
AU6142099A (en) 2000-04-03
AP1461A (en) 2005-09-02
CA2344063C (en) 2006-07-04
EP1121026A4 (en) 2002-01-16
BR9913700A (pt) 2001-06-05
AP2001002097A0 (en) 2001-03-31
EP1121026A1 (en) 2001-08-08

Similar Documents

Publication Publication Date Title
US6202649B1 (en) Method of treating tobacco to reduce nitrosamine content, and products produced thereby
CA2294130C (en) Method of treating tobacco to reduce nitrosamine content, and products produced thereby
CA2344063C (en) Tobacco curing barn
EP0967898B1 (en) Method of treating tobacco to reduce nitrosamine content, and products produced thereby
US6805134B2 (en) Tobacco processing
WO1998005226A9 (en) Method of treating tobacco to reduce nitrosamine content, and products produced thereby
US6311695B1 (en) Method of treating tobacco to reduce nitrosamine content, and products produced thereby
USRE38123E1 (en) Tobacco products having reduced nitrosamine content
MXPA99012047A (es) Metodo para tratar tabaco para reducir el contenido de nitrosamina y productos elaborados con el mismo
MXPA99001292A (es) Metodo para tratar tabaco para reducir el contenido de nitrosamina y productos producidos asi
BG65186B1 (bg) Метод за обработка на тютюн за намаляване на съдържанието на нитрозамини и продукти, получени по този метод
UA75021C2 (en) Method for tobacco processing by reducing the content of nitrosamine and a product obtained by this method
CZ9904636A3 (cs) Způsob zpracování tabáku

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
ENP Entry into the national phase

Ref document number: 2344063

Country of ref document: CA

Ref document number: 2344063

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: IN/PCT/2001/00291/MU

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/002706

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 1999948191

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1999948191

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1999948191

Country of ref document: EP