U.S. patent number 3,703,177 [Application Number 05/063,648] was granted by the patent office on 1972-11-21 for smoking product and method of making same.
This patent grant is currently assigned to Philip Morris, Incorporated. Invention is credited to John D. Hind, Matthias F. Kelley, Jr..
United States Patent |
3,703,177 |
Hind , et al. |
November 21, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
SMOKING PRODUCT AND METHOD OF MAKING SAME
Abstract
A smoking product is prepared from waste beet pulp that may be
used alone or may be blended with any desired proportion of
tobacco. The process comprising the acid hydrolysis of the beet
pulp to release beet pectins, and at least an alkaline earth
treatment thereafter to cause cross-linking of the pectins and
forming a binding agent for the exhausted beet matrix. Preferably a
demethylation step on the released pectins is carried out prior to
the cross-linking reaction. The final slurry is then dried by known
procedures to form a smoking product.
Inventors: |
Hind; John D. (Richmond,
VA), Kelley, Jr.; Matthias F. (Bon Air, VA) |
Assignee: |
Philip Morris, Incorporated
(New York, NY)
|
Family
ID: |
22050585 |
Appl.
No.: |
05/063,648 |
Filed: |
August 13, 1970 |
Current U.S.
Class: |
131/359 |
Current CPC
Class: |
A24B
15/16 (20130101) |
Current International
Class: |
A24B
15/16 (20060101); A24B 15/00 (20060101); A24b
003/14 () |
Field of
Search: |
;131/2 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rein; Melvin D.
Claims
The invention claimed is:
1. The process for preparing a smoking product from sugar beet pulp
comprising the following sequence of steps:
a. cooking an aqueous slurry of extracted sugar beet pulp in
comminuted form with a hydrolyzing agent to release beet
pectins;
b. refinng the hydrolyzed product to shorten fibers and break up
fiber bundles;
c. addinto the refined slurry components an alkaline earth metal
cross-linking agent to cross-link the beet pectin molecules into a
gel-like binding substance; and then
d. forming a dried product from the slurry components.
2. The process of claim 1 in which the hydrolyzed and refined
product of step 9(b) is subjected to a demethylation step by
reacting the released beet pectins with an alkaline demethylating
agent.
3. The process of claim 2 in which the alkaline demethylating agent
is added before the addition of the alkaline earth metal
cross-linking agent.
4. The process of claim 2 in which the demethylating agent is added
together with the alkaline earth metal cross-linking agent.
5. The process of claim 2 in which the demethylating agent is at
least one of sodium and potassium hydroxide and the cross-linking
agent is at least one of calcium and magnesium oxide or
hydroxide.
6. A smoking product produced by the process comprising
a. cooking an aqueous slurry of extracted sugar beet pulp with a
hydrolyzing agent to reduce beet pectins;
b. adding to the cooked slurry a polyvalent metal cross-linking
agent to cross-link the sugar beet pectin molecules into a gel-like
binding substance; and then
c. forming a dried product from the slurry components.
7. A product according to claim 6, wherein the cooked slurry of
step (a) is comminuted to shorten fibers and break up fiber
bundles.
8. A product according to claim 6, wherein the cooked slurry of
step (a) IS SUBJECTED TO A DEMETHYLATION OR SAPONIFICATION STEP BY
REACTING THE SUGAR BEET PECTINS WITH AN ALKALINE DEMETHYLATING OR
SAPONIFICATING AGENT.
9. The product according to claim 8, wherein the cooked slurry of
step (a) is comminuted to shorten fibers and break up fiber bundles
prior to the addition of the demethylating or saponificating
agent.
10. A product according to claim 6 wherein the cross-linkng agent
is selected from the group consisting of cations of calcium and
magnesium ions.
11. A product according to claim 8 wherein the cross-linking agent
is selected from the group consisting of cations of calcium and
magnesium ions.
12. A product according to claim 6 wherein tobacco is present in
the dried product.
13. A product according to claim 8 wherein tobacco is present in
the dried product.
Description
BACKGROUND OF THE INVENTION
Smoking materials have often been described where some or all of
the tobacco was proposed to be replaced by various synthetic or
natural products. Included in such proposals, at least as far as
neutral products are concerned, were leaves from tress, vines or
shrubs, leafy garden vegetables or herbs and even common weeds or
grasses. In general, the primary purpose of trying such materials
as a smoking product has been either to reduce costs or more often
to find a substitute for a failing supply of tobacco caused by
war-time conditions. However, such experiments in the past failed
to yield a satisfactory smoking product capable of substituting for
natural tobacco materials.
Research has continued in seeking a tobacco substitute for various
other reasons. For example, not all the components naturally
present in tobaccos grown under different climates or growing
conditions yield a satisfactory product from a smoker's standpoint.
Some have different burning characteristics producing products of
combustion that unfavorably affect the smoke, and some may have an
unsatisfactory flavor or aroma or an undesirable amount of nicotine
content. Thus, the desire to eliminate unnecessary or undesirable
tobacco components which have no favorable effect on the smoke from
a taste and flavor aspect has led to a continued search for a
satisfactory tobacco substitute. Additionally, of course, is the
desire to find a low cost tobacco substitute.
The present invention relates to a new smoking material whereby a
tailored smoking product is made from an inexpensive non-tobacco
natural material and which is also free of many undesirable
components and properties normally present in tobacco or earlier
proposed tobacco substitutes.
The new smoking material which may replace all or at least part of
tobacoo parts used in cigarettes or the like is derived from beet
pulp. More particularly, it is obtained as a by-product of sugar
beet processing after the sugar fractions have been extracted from
the beets
The final product is a good tobacco substitute by virtue of its
very low cost. It may be used alone or as a blending agent with
tobacoo. Additionally it can be used to give substantially
unlimited control over pyrolysis and the pyrolysis products.
Describing broadly a general sequence of operations for obtaining
the desired product of the invention, exhausted or waste beet pulp
in the form of dried beet cossettes are slurried in an aqueous
medium with pectin releasing agents capable of hydrolyzing and
solubilizing at least a portion of the pectinaceous content of the
beets thereby releasing pectins from the beet pulp.
Following the hydrolysis, the beet mixture at this point may be
refined by comminuting the hydrolyzed product in order to shorten
the beet fibers. The comminuted beet mixture including the
hydrolysis product is preferably then reacted with monovalent,
basic dimethylation and saponification agents to replace methyl
ester groups on the released pectins with more water-soluble
reactive radicals to make them receptive to a following
cross-linking reaction with divalent or trivalent cation compounds
whereby the released pectins are cross-linked and precipitated from
solution in gel-like form. These cross-linked pectins are excellent
film-forming and binding agents for fibrous material, in this case,
the beet residues.
It should be pointed out that one may carry out the demethylation
or saponification and the cross-linking reaction separately,
simultaneously or even omit the initial demethylation step.
However, there is a notable improvement in handling properties as
well as b burning characteristics when the
demethylating-saponificating reaction is utilized. When both
monovalent and polyvalent additions are made, the divalent or
trivalent cross-linking ions should be present in higher
concentration.
After the reactions are completed and the newly cross-linked
pectinaceous film-forming components have been produced, the total
aqueous reaction slurry, containing the products of reaction, the
pectinaceous gels as binders or film-forms and the beet residues
are extruded or laid down to produce a sheet by procedures which
conserve water-solubles and are essentially similar to known
methods used in forming reconstituted tobacco in dried form for
subsequent production of a smoking filler.
Prior to shaping thproduct into the desired form, it is preferred
to adjust the pH of the mixture at this point and, in addition, to
supply desired substances to improve the general properties of the
final product so that a proper flavor and aroma as well as the
burning or combustion characteristics will approach that of a good
tobaco filler. Thus, a preferred pH of the slurry before casting or
other shaping should be in the neighborhood of about pH 5.5 to 6,
if nicotine is part of the formulation, and since the mixture may
be somewhat alkaline, a suitable organic acid, for example, citric
acid may be used to bring the pH to the desired point and supply at
the same time ions found in natural tobaccos. If the nicotine is
omitted, pH adjustment is unnecessary. Additionally, one may add
non-toxic salts, sugars, non-toxic plasticizers and if preferred,
nicotine to the slurry prior to the shaping operation or these may
be added at a later point after the final drying step, to yield
specific and desirable properties to the final product.
Reverting to the described sequence of steps for a clearer
understanding and for greater detail, the hydrolysis step is first
carried out on exhausted and dried sugar beet pulp cossettes, a
waste product of sugar beet refining, in which the beets,
containing protopectins, are cooked with an agent capable of
releasing beet pectins.
These protopectins have been found to have substantial similarities
to tobacco protopectins in that they are water insoluble and
comprise polygalacturonic acid molecules complexed with various
multivalent groups acting as molecular cross-linkers. The beet
pectins that are released by the hydrolysis step are water-soluble
and in the cooking step the insoluble beet protopectins are
hydrolyzed to water-soluble fragments consisting mainly or arabans,
galactans, acetic acid, and the aforesaid water-soluble
pectins.
The pectin-releasing agent utilized in the primary hydrolysis
cooking step is a substance capable of reacting with and destroying
the cross-links of the beet protopectins so that the pectins are
capable of being released from the beet material. For the
hydrolysis step mineral acids are preferred and particularly those
acids are preferred whose anions will produce non-toxic salts which
are normally found in tobacco. Among those acids useful in the
present invention are such non-toxic mineral acids as hydrochloric,
sulfuric or phosphoric acids. Organic acids found in tobacco such
as citric or malic acid are also useful. While acids are the
preferred materials for releasing pectins, other acidic substances
capable of releasing the pectins may be used. Additionally, as a
substitute for a mineral acid, one may use cation sequestering
agents, a preferred agent in this category being diammonium
hydrogen phosphate (DAP).
In the cooking step a pH in the range of about 1.0 to 6.0 is
maintained, preferably in the range of about 1.5 to 4.5 or 5.0 at
the start of the operation. During the cookign, the acidity may
decrease from a highly acid point to a pH of about 3 or 4 but this
will not affect the hydrolysis to any material extent. Proportions
of pectin-releasing agent to the beet charge, namely redried beets
cossettes, are in the range of about 1 to 4 parts to 100 parts by
weight of beet material. It should be pointed out that one may use
either single acids or a mixture of acids in the cooking operation.
In the latter case, and as an example of a preferred mixture of
acids that could be used for each pound of beet cossettes, one may
have about 3 to 4 g of H.sub.3 PO.sub.4, about 9 to 10 g. of
H.sub.2 SO.sub.4 and about 4 to 5 g of HCl
The cooking or hydrolysis step is carried out at a temperature from
about 40.degree.C. to 110.degree.C., the lower temperature
naturally requiring a longer period of time for the desired
hydrolysis. At the higher temperature refluxing or a higher than
atmospheric pressure is advisable. A preferred pectin releasing
operation is to cook a dilute aqueous acid beet pulp slurry at a pH
of about 1.9 to 2.9 for 1 to 4 hours, but preferably for the longer
period of time, at a temperature of about 70.degree.C. to
90.degree.C. under generally normal pressures.
The formation of film-forming pectinaceous beet substances from the
released pectins is carried out preferably by reacting the released
pectins with monovalent and divalent cation compounds in that
order. Oxides or hydroxides or even salts that are essentially
basic may be used for demethylation and saponification. Monovalent
compounds should be selected whose cations will supply the type
normally found in tobacco and which are nevertheless capable of
demethylating and saponifying the alkyl esters of the released
pectins. As an example, and in order of decreasing cation
preference, this would be potassium hydroxide, sodium hydroxide and
ammonium hydroxide. As previously mentioned, strongly basic salts
of these monovalent cations could be used instead of the
hydroxides, as would be apparent to those skilled in the art.
The speed of the demethylation step has been found to vary
depending on the basicity of the reaction medium. Thus, where
alkali metal hydroxides are used in an amount which will provide a
pH SOMEWHAT BELOW PH 12, the demethylation has been found to be
rapid at the greatest pH, for example, pH 9.5, moderate at pH 8.5,
and very slow at pH 7.0-8.0. Completion of the demthylation
reaction is signalled by a slowing of the rate of drop of pH when
it is about pH *.%. Control of the temperature in the neighborhood
between 0.degree. and 25.degree.C. is usually necessary to limit
deteriorating (chain scission) of the pectins by the alkaline
medium. However, once the product is substantially demethylated, it
is fairly stable. As an example, if one operates at a pH of about
9, with the temperature kept below 30.degree.C., the demethylation
will take place satisfactorily in about 30 minutes.
Following the demethylation or simultaneously therewith, or even in
place of the demethylation step, the released pectins in the beet
slurry are changed to film-forming gels by means of a cross-linking
reaction of the carboxylic acid groups of the pectins with
multivalent cation oxides, hydroxides or their equivalent such as
highly basic salts, of calcium or magnesium. As was mentioned
before, the demethylation requires and alkaline condition.
Cross-linking, in general, can occur at any pH above 3.0, but
usually occurs most readily in the region between pH 5.0 and 9.0.
The use of a multivalent cross-linking ion is an essential cation
in the process of forming a final product.
Conditions for carrying out the cross-linking step on the released
pectins are a pH in the range of about pH 5.0 to 9.0 supplied by
adding basic compounds if necessary. The cross-linking reaction
will proceed smoothly at temperatures preferably between 0.degree.
and 100.degree.C. and more preferably at a temperature between
20.degree. and 60.degree.C.
After the completion of the cross-linking and precipitation of the
film-forming gels, the slurry is essentially ready for casting or
extrusion as a sheet or other shaping operation assuming it has
those components deemed desirable which are normally associated
with the production of a satisfactory smoking product. In general,
however, a better product is achieved if the slurry after the
cross-linking step, is brought to a pH in the neighborhood of about
pH 5 to 6. This may require the addition of an acid, and preferably
an organic acid that desirably also supplies ions normally found in
most tobaccos. Such an acid may be citric, maleic or other lower
aliphatic carboxylic acids, or where there is a need for more
inorganic ion, a mineral acid could be used. The carboxylic acids
added may also act as plasticizing agents.
Other substances may be added to the beet product prior to the
casting or extrusion step to improve processing, to effect a
desirable change in color, flavor or aroma, or to improve
particular combustion characteristics such as ash content. Thus,
plasticizers in addition to the above-mentioned acids may be
incorporated into the slurry, such as tobacco extracts obtained by
leaching tobacco parts with solvents, glycerine, or di or
preferably triethylene glycol. These plasticizers may constitute
from 1 to 10 parts by weight of plasticizer per 100 parts by weight
of bee pulp.
Where flavor and aroma is to be adjusted, sugars, particularly
crude brown sugar or invert sugar or its components may be added in
an amount of from 1 to 50 parts by weight to 100 parts of beet
pulp. These materials additionally act as plasticizers.
Special flavors may also be added and these may be present in an
amount up to about 3 parts by weight to 100 parts by weight of beet
pulp. Such flavorants might be cocoa shell, carbo bean, deer's
tongue and many others commonly used in the toacco art. Other
additives, such as colorants and nicotine may be incorporated in
the final product in amounts depending on the effects desired.
After the substances described above are added for the desired or
special characteristics to the treated beet slurry, the pH is again
adjusted if necessary to pH %" AND THE SLURRY CAST OR EXTRUDED BY
ANY OF THE PROCESSES KNOWN IN THE ART. Casting on a metal belt or
the like for forming and drying is a preferred procedure but this
is not the only way the product may be treated before final
shredding as a smoking filler. Various other procedures, similar to
those used in preparing reconstituted tobacco could be used for
producing a sheet or extrusion in a variety of shapes.
It has been found that the beet pulp product processes well in
casting to form a sheet. Sheet material has been produced with good
tensile strength, for example, 0.7 to 1.0 kg./in. at 15 percent
moisture and in shredded form has the filling power equal to that
of conventional reconstituted tobaccos. The product may thus be
used alone as a smoking filler or may be incorporated with tobacco
in any desired amount or proportion.
The invention is further illustrated by the following examples:
EXAMPLE 1
Ingredients Extracted, dried sugar beet cossettes 55 g. Water 755
ml. H.sub.3 PO.sub.4 0.46 g. H.sub.2 SO.sub.4 1.22 g. HCl 0.58 g.
NaOH 0.42 g. KOH 3.07 g. CaO, powder 3.19 g. MgO, powder 0.80 g.
Invert sugar 24.4 g. Triethylene glycol (TEG) 13.2 g. Flavors 5.0
g. Nicotine 1.25 g.
The beet pulp was cooked in the solution of mineral acids in water
for four hours at about 80.degree.C. and then the slurry was
refined in a Waring Blender for one-half hour. The slurry was
stirred while the additives were introduced in sequence: first the
hydroxides in solution, then the powdered oxides. As the divalent
metal cross-linked pectins were precipitated, the agitation was
increased to disperse them. Next citric acid was added until the pH
was approximately 5.7. Sugar, TEG, and flavors were added. A CHECK
WAS MADE TO INSURE THAT THE PH had not risen above 6.0. Finally the
nicotine was stirred in.
The slurry was cast on a moving steel belt at a thickness of 25
mils, dried and removed from the belt. The sheet processed well.
Tensile strength at 15 percent moisture content was about 0.8
kg./in. width. When cut as filler, the product had fillinpower
equivalent to that of conventional reconstituted product.
Cigarettes were made from a blend of 30 parts by weight of this
product with 70 parts of a commercial all-leaf filler. Expert
smokers judged this to be an acceptable filler in flavor and lack
of harshness.
EXAMPLE 2
Ingredients Extracted, dried sugar beet cossettes 55.0 g. Water 750
ml. Hydrochloric acid (37% aqueous) 4 to 6 ml. Ca.sub.3
(PO.sub.4).sub.2 11.2 g. Invert sugar 26.4 g. Triethylene glycol
(TEG) 13.2 g.
After the beet pulp was suspended in the water, the pH was adjusted
to 2.5 to 3.0 and kept there during the cook by addition of HCl
After a four hour cook, the slurry was refined by one-half hour
treatment in a Waring Blender. The slurry was stirred in the
blender while the tricalcium phosphate was added and agitation
continued to ensure uniform dispersion of the solid phosphate. The
sugar and TEG were added and the slurry was used to lay down 25 mil
sheets on glass plates. These were dried and removed to be cut and
used as filler. In this case, there would be only a small amount of
cross-linking due to the reaction of the free acid groups naturally
present in beet pectin. The film was not strong when wet. Though it
was used satisfactorily for cigarettes made by hand, in commercial
cigarette making processes, it would be likely to break up to short
shreds or dust.
EXAMPLE 3
Ingredients Dried extracted sugar beet pulp 334.4 g. Water 11.4
liters Diammonium phosphate (DAP) 30.4 g. Invert sugar 228.0 g.
Citric acid 79.0 g. Triethylene glycol 12.2 g. Potassium hydroxide
10.0 g. Calcium hydroxide 26.4 g.
All ingredients except the pulp and Ca(OH).sub.2, were dissolved in
the water. The pulp was added in a Valley beater to the solution
and beating was continued 2 1/2 hours. Then the powdered
Ca(OH).sub.2 was added with beating. The final pH was 5.6. Sheet
was cast on stainless steel plate at a casting blade setting of 50
mils, air dried overnight, doctored from the plate, conditioned at
60 percent, relative humidity, and shredded into cigarette
filler.
Sheet prepared similarly from washed burley tobacco stems was used
as control. Expert smokers found cigarettes made from the two
materials generally equivalent, with the beet pulp product slightly
but not significantly preferred.
EXAMPLE 4
Ingredients Exhausted sugar beet pulp 1360 g. tc 17 liters H.sub.3
PO.sub.4 10.5 g. H.sub.2 SO.sub.4 27.8 g. HCl 13.2 g. NaOH 9.5 g.
KOH 69.5 g. Ca(OH).sub.2 96.0 g. Mg(OH).sub.2 26.1 g. Invert sugar
554 g. TEG 300 g. Dry flavors 113 g. Nicotine 38.4 g.
The acids and pulp were mixed with the water in a Cowles dissolver,
cooked four hours at about 80.degree.C. The slurry was refined in a
Sprout-Waldron 12 inch non-pressurized refiner for three passes.
The Cowles dissolver was used to introduced the monovalent
hydroxides, then the divalent hydroxides, followed by beating.
Citric acid was added to bring pH to 5.7. The invert sugar, TEG and
the dry flavors were added, then the pH was rechecked to make sure
it was not over 6.0. Nicotine was finally added. The slurry was
cast on a moving steel belt at 25 mils, dried, peeled off and used
for filler.
* * * * *