U.S. patent number 3,760,815 [Application Number 05/104,459] was granted by the patent office on 1973-09-25 for preparation of reconstituted tobacco.
This patent grant is currently assigned to Philip Morris Incorporated. Invention is credited to Edward J. Deszyck.
United States Patent |
3,760,815 |
Deszyck |
September 25, 1973 |
PREPARATION OF RECONSTITUTED TOBACCO
Abstract
Tobacco parts are treated with ammonium salts of organic acids,
added or formed in situ, in the presence of ammonium hydroxide to
obtain an alkaline pH, to release tobacco pectins and form calcium
and/or magnesium salts with the organic anions. The pectins act as
a binding agent and together with the treated tobacco and
precipitated salts constitute a mix that may be cast or otherwise
treated to form a reconstituted tobacco product.
Inventors: |
Deszyck; Edward J. (Richmond,
VA) |
Assignee: |
Philip Morris Incorporated (New
York, NY)
|
Family
ID: |
22300591 |
Appl.
No.: |
05/104,459 |
Filed: |
January 6, 1971 |
Current U.S.
Class: |
131/309; 131/353;
131/352 |
Current CPC
Class: |
A24B
15/12 (20130101) |
Current International
Class: |
A24B
15/00 (20060101); A24B 15/12 (20060101); A24b
003/14 () |
Field of
Search: |
;131/2,15,17,140-144 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Rein; Melvin D.
Claims
The invention claimed is:
1. The method of forming a tobacco smoking product which
comprises,
a. combining water, tobacco and a reagent selected from the group
consisting of
1. ammonium salts of carboxylic acids and
2. ammonium hydroxide and a carboxylic acid
wherein the carboxylic acid is selected from the group of monobasic
fatty acids of six to 18 carbon atoms, polybasic acids of two to 12
carbon atoms and mixtures thereof,
b. adding sufficient ammonium hydroxide to bring said slurry to a
pH of 9 to 10,
c. releasing the tobacco pectins and forming insoluble calcium and
magnesium carboxylates by holding said slurry at a temperature of
about 25.degree. to 110.degree. C. for about one-half to 24 hours
while maintaining said pH at 9 to 10 through the addition of
ammonia, and
d. drying the components of said slurry to form a homogeneous
tobacco smoking product.
2. The method of claim 1, wherein the tobacco of step (a) is in
finely divided form.
3. The method of claim 1, wherein said reagent comprises a
polycarboxylic acid of two to 12 carbon atoms and ammonium
hydroxide.
4. The method of claim 1, wherein said reagent comprises a
monocarboxylic fatty acid having six to 18 carbon atom and ammonium
hydroxide.
5. The method of claim 1, wherein said reagent comprises ammonium
salts of said mono and polycarboxylic acids.
6. The method of claim 1, wherein the reaction is carried out in
the presence of ammonium cations and organic acid anions derived
from acids of the group consisting of oxalic, citric, malic,
sebacic, tartaric, mellitic, vanillic, gluconic, stearic, lauric,
oleic, linoleic and linolenic acids.
7. The method of claim 3, wherein the carboxylic acid is citric
acid.
8. The method of claim 4, wherein the carboxylic acid is oleic
acid.
9. The method of claim 5, wherein the salt is ammonium citrate.
10. The product produced by the process of claim 1.
Description
BACKGROUND OF THE DISCLOSURE
The preparation of reconstituted tobacco or tobacco material
generally produced in sheet form makes use of waste or scrap
tobacco parts or dust normally bound together by providing an
adhesive to give the product coherence. Various adhesives or
binding agents have been used or proposed for this purpose, many of
them being cellulose or other non-tobacco derivatives. Improvements
in binding agents have led to the use of adhesive material derived
from tobacco, notably tobacco pectins. These substances, and
methods for utilizing them, are described in U.S. Pat. Nos.
3,353,541; 3,409,026; 3,499,454 and others. The patents describe
the release of pectins and pectinic substances from the tobacco
parts for subsequent redeposit on the same or other tobacco parts
as adhesives to bind them into a coherent sheet or other form. The
pectin release is carried out by the use of special agents which
act by removing the divalent metal cross-links, essentially calcium
and magnesium by a number of methods, for example, a method
utilizing additive substances which remove the divalent metal ions
by forming relatively insoluble salts; a method which removes the
ions by an additive causing a chelating or sequestering action; or
by another method which acidifies the system with an acid and
produces soluble salts of Ca and Mg, which can be washed out,
leaving the pectins in the insoluble acid form, but which then
requires an alkalinizing step to solubilize the pectins. These
methods made possible the separation of the pectins from the
insoluble portions of tobacco, generally without separation of the
released pectins, leaving these and other components of the
pectin-releasing step combined in the aqueous slurry which is then
cast into a final reconstituted tobacco product.
As a consequence of such prior methods, ash-forming agents that are
added or formed from such additives usually remain in the product.
These retained additives, left in the tobacco, may affect the
flavor, ash color, and other properties of the product. Such
ash-forming ingredients, moreover, may increase the delivery of
total particulate matter (TPM) in the smoke. The present invention
is an improvement in the production of a reconstituted tobacco in
that the release of tobacco pectins in situ may be accomplished
without the addition of ash-forming inorganic salts or acids, while
at the same time, enhancing the flavor and aroma of the smoke.
SUMMARY OF THE INVENTION
According to the present invention, selected monobasic organic
acids of six to 18 carbon atoms or polybasic acids of two to 12
carbon atoms and ammonium hydroxide or ammonium salts of such
acids, are added to tobacco parts as cross-links destroying agents.
The latter additives or components thereof, are volatilized in
subsequent drying operations, or are burned in smoking to produce
principally the same products that arise from combustion of tobacco
without additives, namely, carbon dioxide, water, ammonia, and the
like, so that ash appearance and, more importantly, TPM delivery
are substantially unchanged. Smoking of the products has shown the
flavor to be acceptable, and sometimes enhanced and novel, mild
rather than harsh, with no undesirable foreign notes. The sheet
produced is pliable and plastic, and added plasticizer (e.g.,
triethylene glycol) may be reduced or eliminated.
DESCRIPTION OF THE INVENTION
The process comprises the treatment of the tobacco parts,
preferably in finely divided form, with an aqueous solution or
suspension of selected organic acids with ammonium hydroxide or the
ammonium salt of one or more of these acids, in the presence of
excess ammonium hydroxide.
The treatment of the tobacco in the presence of these ammonium
salts and ammonium hydroxide results in the release of the
pectinaceous components from the tobacco in the form of ammonium
pectates. The original pectinaceous components, with may be termed
protopectins, consist essentially of calcium and/or magnesium salts
of polygalacturonic acid, the divalent metallic atoms acting as
cross-links between the galacturonic chains, these being destroyed
in the reaction.
When the pectins are released as ammonium pectates, the calcium
and/or magnesium cations form substantially water-insoluble salts
with the anionic groups, particularly when the pH is in the
alkaline range. These insoluble salts, together with the ammonium
pectates acting as binding agents, are combined with the treated
tobacco and are extruded, cast or otherwise formed into a
reconstituted tobacco product which may then be processed in known
manner to produce the desired form of smoking product.
The organic acids that are selected are unsubstituted aliphatic or
aromatic mono or polycarboxylic acids or such acids having only
hydroxy and lower alkoxy groups as substituents. In other words,
the acids should consist only of carbon, hydrogen and oxygen.
Meeting these qualifications, the monocarboxylic acids preferred
are fatty acids having six to 18 carbon atoms while the preferred
polycarboxylic acids are those having two to 12 carbon atoms.
These acids should have the general characteristic of forming
calcium or magnesium salts that, under the conditions of treatment,
particularly in an alkaline environment well above pH 8, preferably
pH 9 to 10, are substantially insoluble in the aqueous medium. As a
component of the final tobacco product, these salts either
volatilize off, or alternatively, break down during the combustion
of the tobacco to calcium or magnesium carbonates, carbon dioxide,
water and, in fact, the same elements normally released when
untreated tobacco is burned. Since there are ammonium components
also present, either as ammonium pectates or substantially trace
amounts of free ammonia or ammonium hydroxide, ammonia gas is
volatilized out either before the product is smoked, that is during
the drying step, or certainly during the combustion. The end result
is that the combustion of the treated tobacco produces the same
type of ash as would be produced from the combusion of tobacco that
had not been treated and was free of additives.
In addition to the important effect of the ammonium salts and
excess ammonia in releasing tobacco pectins, as an added feature of
the invention, when organic acids are selected, or when ammonium
salts of the acids are selected, it is within the scope of the
invention to select such acids or salts as described above but
capable of providing a special flavor and aroma in addition to
releasing pectins and leaving unchanged the ash color or other
desired properties of the product. Thus, citric, malic or vanillic
acids or other flavor or aroma inducing acids with ammonium
hydroxide, or alternatively their ammonium salts, with excess
ammonia, when used for the release of pectins and water-insoluble
salts, will also produce an exceptionally flavorful smoke.
With respect to the longer-chain fatty acids, either saturated or
unsaturated, for example, stearic, oleic, linoleic or linolenic
acids or their ammonium salts, these provide not only a subtle
flavor characteristic of the smoke when used in the desired
concentration, but also possess a plasticizing effect that requires
little or no added plasticizers normally used in making a
reconstituted tobacco product. Thus, one may select the acid or
salt tobacco treating agent which, under the conditions of
operation, will act merely to release pectins as adhesive or
binding agents but whose ash-forming salts will not change the
flavor, ash color or other properties of the product, or achieve
the same results with the additional feature of producing a softer,
more plastic sheet, or again achieve the same results but have an
additional flavoring component.
The preferred acids that may be used in carrying out the process of
the invention are citric, malic, gluconic, oxalic, tartaric,
mellitic, vanillic, sebacic, lauric, stearic, oleic, linoleic or
linolenic acids. Particularly preferred acids are citric or malic
acids. As indicated previously, one may use a single acid or a
mixture of different acids.
Describing the invention in greater detail, tobacco plant parts,
usually waste or scrap tobacco parts in the form of flakes, shreds,
tobacco fines or dust, but preferably in finely divided form, is
slurried with an aqueous solution of an ammonium salt of a selected
organic acid or a mixture of such salts. The amount of added salt
may be in the range of about 0.0 to about 0.25 mols of salt per 100
grams of tobacco, but preferably in an amount of about 0.025 to
0.08 mols per 100 grams of tobacco. Additionally, sufficient
ammonium hydroxide must be added to reach an alkaline pH,
preferably from pH 9 to about pH 10.
During the reaction of pectin release and salt formation, the
slurry is maintained at a temperature of from about 25.degree. to
110.degree.C. for about one-half to 24 hours. Heating may not be
necessary since heat may be generated by the reaction taking place
in the treating vessel. While heating or cooking is being carried
out, more ammonia may be needed to maintain the alkaline pH. After
sufficient time has elapsed and when the reaction is substantially
completed, the tobacco slurry may be refined by use of a rapid or
high speed beater, followed by deaeration before casting, spraying,
roller-coating or the like in reconstituted tobacco forms such as
webs, sheets, fibers or other desired forms.
Instead of using ammonium salts as such, one may form these salts
in situ or at least have the desired anions and cations present by
using one or more organic acids and sufficient ammonium hydroxide,
usually in excess so as to result in an alkaline pH of pH 9 or
higher. In this case, one may add the same amount of acid as
indicated for the salt, namely, from about 0.0 to 0.25 mols of acid
for each 100 grams of tobacco with a more preferred range of 0.025
to 0.08 mols per 100 grams of tobacco. Sufficient ammonium
hydroxide is then added to result in the slurry achieving an
alkaline pH in the range of 9 to 10.
As an alternative to the use of added ammonium salts, or the use of
an added organic acid with ammonium hydroxide, it is possible under
certain circumstances to use the citric, malic, oxalic or tartaric
acid content of tobaccos containing these acids or salts of these
acids in sufficiently high concentration so that it would not be
necessary to add such acids to the tobacco slurry. In that case, it
would only be necessary to add sufficient ammonium hydroxide to
bring the pH of the aqueous tobacco slurry to pH 9 to 10 and
heating, following the same treatment as previously described.
Thus, ammonium pectins would be formed from the released pectins
and the calcium and magnesium cross-linking cations of the tobacco
protopectins would form salts with the acidic anions.
Subsequent to the release of the pectins, the entire reaction mix
may then be cast, extruded, sprayed or otherwise treated to
solidify the solids by procedures well known in the art, to form a
reconstituted tobacco product.
The following examples are illustrative.
Example 1
A slurry was prepared in a Waring blender from 50 g of tobacco dust
(-50 mesh), 450 ml. of water, 1.0 g of citric acid, and sufficient
aqueous ammonia to raise the pH to 9.5. The slurry was refined by
beating for 30 minutes, at which time the temperature had reached
90.degree. C. The viscosity had reached a maximum after five
minutes. No additional heat was applied. The slurry was deaerated
under vacuum on a steam bath (pH after cooling, 8.8). The hot
slurry was cast on steel plates by using a casting knife set at 50
mils, dried over a steam bath, and stripped from the plates. A
uniform, dense sheet without pinholes resulted. Its properties
were:
Weight - 14.9 g/sq. ft.
Wet tension coefficient - 1.74 g/in/g/sq. ft.
pH (sheet reslurried in 10 parts water) 5.4
Example 2
Portions of tobacco dust (-50 mesh) and water, 50 g and 450 ml.
respectively, were treated with additives and conditions as listed
in Table I, using a Waring blender for refining and a steam bath
for heating. Deaeration after refining was for 10 minutes except
the last run where 1 hr. heating took its place. Casting on steel
plates with a casting knife set at 50 mils, and drying produced
sheets with the properties listed in Table I.
Example 3
Tobacco dust (50 g, -50 mesh) and citric acid (7.5 g) were slurried
with 285 ml. water in a Waring blender. To the slurry concentrated
NH.sub.4 OH was added to pH 9.0 which was maintained during the
heating period. The slurry was heated to 95.degree. C in a steam
bath for 2 hours, and refined for 1 minute. The hot slurry was cast
on steel plates using a casting knife set at 35 mils, dried over a
steam bath and doctored off. pH of the cold slurry was 8.7, sheet
pH was 5.3. The sheet was satisfactory but it did have many fine
cracks.
Example 4
A slurry consisting of 1,019.4 lb. water, 174.8 lb. tobacco dust,
24.6 lb. citric acid, and 42 lb. of 30% NH.sub.4 OH was prepared in
a mixing tank. The temperature was maintained ##SPC1## at
67.degree. C, and the pH at 9.0. The slurry was passed through a
refiner three times and constantly recirculated for approximately 4
hours. The temperature of the slurry at the cast box was maintained
at 57.degree. C. Casting was done on a steel belt; pH of the cold
slurry was 9.2. A uniform, dense sheet resulted.
pH -- 5.4
Pendulum tensile -- 0.65 kg/in
Weight -- 14.4 g/sq. ft.
Water -- 12.9 percent
Folded tensile -- 0.32 kg/in
Wet tensile -- 10.1 g/in
Wet tensile coefficient -- 0.72 g/in/g/sq. ft.
Instron tensile -- 0.50 g/in/g/sq. ft.
Elongation -- 2.3 percent
Work to break -- 18.8 g-cm/sq. in.
The sheets were cut into filler and cigarettes were prepared for
smoke test comparison against a standard cigarette, as shown in
Table II below. For the smoke tests, 15 mm. filter tips were
attached to the cigarettes, and then 50 mm. of cigarettes smoked
for TPM and nicotine.
TABLE II
Cigarette with Control, Stand- Rod: Citric Acid Filler ard
Cigarette Length mm. 60 60 Circumference mm. 25.2 25.2 Weight
g/cigt 1.38 1.13 RTD*, in. water 0.7 1.0 Filler rod TPM, mg/cigt
35.3 40.8 Filler rod nicotine, mg/cigt 1.3 1.4 Puff count 14.2 11.2
TPM/puff mg. 2.49 3.64 Tobacco smoked, g 1.16 0.94 Per gram of
product smoked: TPM mg 30.5 43.4 Puff count 12.5 11.9 *Resistance
to draw.
This lower delivery in comparison with conventional filler is
preferable to a higher delivery.
Example 5
Sebacic acid (5 g), 50 g tobacco dust (-50 mesh), and 450 ml.
H.sub.2 O were slurried in a Waring blender. Concentrated NH.sub.4
OH was added to raise pH to 9.5. The slurry was refined for 30
minutes during which period the temperature was raised to
90.degree. C. After the refining, the slurry was heated on a steam
bath in order to deaerate. It was then cast on stainless steel
plates using a casting knife with 50 mils setting. To dry the
product the plates were placed over a steam bath. The sheets were
doctored.
Sheet weight - 14.9 g/sq. ft.
Wet tensile coefficient - 4.99 g/in/g/sq. ft.
Example 6
Mellitic acid (5 g), 50 g tobacco dust (-50 mesh), and 450 ml.
H.sub.2 O were slurried in a Waring blender. Concentrated NH.sub.4
OH was added to adjust pH to 9.5. The slurry was heated oon a steam
bath for one hour, then refined for 10 minutes, and finally heated
for another hour. The slurry was then cast on stainless steel
plates using a casting knife with setting at 50 mils. The sheets
were dried over a steam bath and doctored.
Sheet weight - 12.70 g/sq. ft.
Wet tensile coefficient - 13.39 g/in/g/sq. ft.
Example 7
Ten grams oleic acid, 50 g tobacco dust, and 450 ml. H.sub.2 O were
slurried in a Waring blender. pH was adjusted to 9.0 with
concentrated NH.sub.4 OH. The slurry was heated at 90.degree. C.
over a steam bath for 1 hour, refined for 5 minutes, and again
heated for an hour. The slurry was cast on stainless steel plates
using a casting knife set at 50 mils, dried over a steam bath and
doctored. The product was soft and plastic.
Sheet weight - 13.39 g/sq. ft.
Wet tensile coefficient - 7.84 g/in/g/sq. ft.
Ammonium oleate (10.6 g) may be used in place of the oleic acid in
the above example, and using sufficient ammonium hydroxide to
obtain a pH of 9. The heating, refining and casting are described
above. The product is the equivalent of that given in the
example.
Example 8
Vanillic acid (8.4 g), 50 g tobacco dust and 450 ml. H.sub.2 O were
slurried in a Waring blender. pH was adjusted to 9.3 with
concentrated NH.sub.4 OH. The slurry was heated for 2 hours at
90.degree. C. in a steam bath, refined for 10 minutes, and
deaerated for 15 minutes. The slurry was cast on stainless steel
plates using a casting knife set at 50 mils, dried over a steam
bath and doctored. The product had a subtle sweet aroma. Cigarettes
prepared from this product when smoked had a subtle vanilla flavor
both in the main and side streams.
Sheet weight - 15.0 g/sq. ft.
Wet tensile coefficient - 1.47 g/in/g/sq. ft.
pH of product - 5.3
Example 9
Ammonium sebacate (6 g) and 50 g (-50 mesh) of tobacco dust were
slurried in 450 ml. H.sub.2 O in a Waring blender. The pH was
adjusted to pH 9.0 with concentrated NH.sub.4 OH. The slurry was
brought to 90.degree. C. and held at that temperature for 1 hour.
It was refined for 30 minutes and then heated on a steam bath to
deaerate for about 30 minutes. The slurry was cast on stainless
steel plates using a casting knife set at 50 mils, then dried over
a steam bath and doctored. The product had similar characteristics
to the product of Example 5.
Example 10
Eighty pounds of tobacco dust having a pH of 5.7, 12 lb. 8 oz.
concentrated NH.sub.4 OH, and 454 lb. H.sub.2 O were placed in a
vat with steam coils and circulating pump. The slurry was heated to
about 90.degree. C. for one hour while being constantly circulated
during the heating. The slurry was recycled through refiners for
about 45 minutes. The temperature was maintained at about
90.degree. C. and additional NH.sub.4 OH was added to maintain pH
at 9.0. When refining was completed the total solids were 17
percent and the viscosity approximately 8,000 centipoises at 21/2
RPM, spindle D, using Brookfield wire T-form spindle. A portion of
the slurry after deaeration was hand cast on stainless steel plates
at 50 mils, using a casting knife.
Hand Cast Product:
Sheet weight - 20.32 g/sq. ft.
Wet tensile coefficient - 1.28 g/in/g/sq. ft.
* * * * *