U.S. patent number 3,889,689 [Application Number 05/279,857] was granted by the patent office on 1975-06-17 for method of treating tobacco with catalase and hydrogen peroxide.
This patent grant is currently assigned to Rosen Enterprise, Inc.. Invention is credited to William E. Rosen.
United States Patent |
3,889,689 |
Rosen |
June 17, 1975 |
Method of treating tobacco with catalase and hydrogen peroxide
Abstract
A method of treating tobacco is described which involves the use
of physical force to cause liquid containing catalase and hydrogen
peroxide to permeate the interstices of the tobacco where they are
reacted with each other in situ. Such reaction enhances properties
of the tobacco, and in certain cases the volume of the tobacco is
expanded. The physical force necessary to cause the treating
material penetration may take the form of rollers, flat pressure
means or continous expression means.
Inventors: |
Rosen; William E. (Lafayette
Hills, PA) |
Assignee: |
Rosen Enterprise, Inc.
(Lafayette Hills, PA)
|
Family
ID: |
26894025 |
Appl.
No.: |
05/279,857 |
Filed: |
August 11, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
198662 |
Dec 20, 1971 |
|
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|
Current U.S.
Class: |
131/293;
131/297 |
Current CPC
Class: |
A24B
3/182 (20130101); A24B 15/20 (20130101) |
Current International
Class: |
A24B
3/18 (20060101); A24B 15/00 (20060101); A24B
15/20 (20060101); A24B 3/00 (20060101); A24b
003/18 (); A24b 015/06 () |
Field of
Search: |
;131/143,17,140
;99/135 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Rein; Melvin D.
Attorney, Agent or Firm: Feldman; Stephen E.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of my co-pending
application Ser. No. 198,662, filed Dec. 20, 1971, now abandoned.
Claims
Having thus described my invention, I claim:
1. A method of treating tobacco to improve its flavor and expand
the tobacco, comprising the steps of substantially evenly
distributing on the surface of the tobacco catalase and a liquid
solution containing hydrogen peroxide, the amounts of catalase and
hydrogen peroxide being sufficient to mutually decompose each
other, and before significant reaction between these two components
obtaining, applying physical force in the form of pressure means
selected from the group comprising roller means, flat pressure
means, and continuous expression means to said tobacco to cause
catalase ahd hydrogen peroxide to permeate the interstices of the
tobacco, whereby the catalase and hydrogen peroxide react in situ
on and within the tobacco.
2. The method in accordance with claim 1, wherein the physical
force is removed from the tobacco prior to the completion of the
reaction of catalase and hydrogen peroxide, thereby allowing
volumetric expansion of the tobacco.
3. The method in accordance with claim 1, wherein a catalase
solution is first applied and then a hydrogen peroxide solution is
applied.
4. The method in accordance with claim 1, wherein a hydrogen
peroxide solution is first applied and then a catalase solution is
applied.
5. The method in accordance with claim 1, wherein step (1)
comprises applying a liquid solution containing both catalase and
hydrogen peroxide on the surface of the tobacco.
6. The method in accordance with claim 5, wherein the catalase is
delayed catalase.
7. The method in accordance with claim 1, wherein the tobacco is
uncured tobacco.
8. The method in accordance with claim 1, wherein the tobacco is
cured tobacco.
9. The method in accordance with claim 1, wherein the tobacco is
whole leaf tobacco.
10. The method in accordance with claim 1, wherein the tobacco is
tobacco lamina.
11. The method in accordance with claim 1, wherein the tobacco is
tobacco cut ribs and stems.
12. The method in accordance with claim 1, wherein the tobacco is
finished reconstituted tobacco sheet.
13. A method according to claim 1 wherein during the treatment of
the tobacco the moisture content of the tobacco does not exceed
about 46 weight percent of the tobacco.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method of treating tobacco, and more
particularly relates to a method for improving the quality of
tobacco and increasing its usefulness in the manufacture of smoking
products.
2. Description of the Prior Art
In my U.S. Pat. No. 3,612,065, the disclosure of which is
incorporated herein by reference and made a part hereof, I have
described a method of treating tobacco wherein a given amount of
catalase provided on said tobacco is reacted with a given amount of
hydrogen peroxide in contact therewith, the mutual decomposition of
catalase and hydrogen peroxide being effective to increase the
volume of the tobacco up to 20 percent. Other prior art methods of
treating tobacco to increase the volume thereof require the use of
expensive solvents and complex solvent recovery systems. Some
chemical solvents may affect the tobacco taste or leave a toxic
residue.
Tobacco quality is determined by various objective and subjective
factors, including the following:
1. Geographical source of the tobacco.
2. The portion of the tobacco plant used to form the tobacco
product.
3. The moisture content of the tobacco.
4. The resistance to crushing of the tobacco.
5. The flavor of the tobacco.
6. The aroma of the tobacco before and during smoking.
It is known that as a result of importing certain foreign tobaccos
importers and manufacturers are supplied with amounts of low
quality tobacco, including both stems and lamina. These products
may have a musty or ammoniacal odor and a sharp, peppery biting
taste.
It is also known that conventional tobacco curing and ageing
methods require from several months to several years in time in
order to obtain desirable changes in the appearance, taste and
aroma of the tobacco, as well as the smoke produced therefrom.
The less valuable forms of tobacco include the stems, ribs and
stalks of the plant. However, these forms may be utilized in
certain proportions for the production of acceptable smoking
products. For example, it is well known that cigars are often made
with a wrapper of one quality tobacco, a binder of another quality
tobacco and a filler of still another quality tobacco. Obviously,
the more less valuable tobacco product which can be incorporated
into a highly rated tobacco product, the greater are the economies
which may be expected. This same reasoning pertains to cigarettes
since such product is filled with shredded tobacco, which is much
more economically obtained from forms of tobacco such as stems,
ribs, stalks and scraps than from the more expensive forms of
tobacco.
The anatomical and chemical structure of tobacco may be exemplified
by that of tobacco stems. Tobacco stem is herbaceous, consisting of
pith, primary xylem, vascular rays and cortex. It is poor in
collenchyma and rich in parenchyma, no cork being present. The
cells are rectangular and their walls are thickened by the
deposition of cellulose and pectin compounds. In cured stem all
cells shrink together because of the rapid moisture loss, thereby
reducing intracellular and intercellular space. However, the cells
contain a great number of pores which permit the passage of
gases.
It is accordingly an object of this invention to provide an
improved method for treating tobacco with catalase and hydrogen
peroxide.
It is another object of this invention to provide a method for
treating tobacco more thoroughly than heretofore with agents for
enhancing qualities of the tobacco.
It is another object of this invention to provide an improved
method of expanding the volume of tobacco.
SUMMARY OF THE INVENTION
The objects of this invention have been achieved by the process of
treating tobacco which comprises the steps of (1) evenly
distributing on the surface of the tobacco a liquid solution
containing catalase and a liquid solution containing hydrogen
peroxide and (2) applying physical force to said tobacco to cause a
portion of the hydrogen peroxide to permeate the interstices of the
tobacco, whereby the catalase and hydrogen peroxide react on and
within said tobacco. The selection of appropriate amounts of
catalase and hydrogen peroxide will cause these reatants to
mutually decompose. Where the physical force is removed from the
tobacco prior to completion of the reaction of catalase and
hydrogen peroxide, the gases produced by said reaction act to
expand the volume of the tobacco.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The essential feature of the process of this invention is the
carrying out of a reaction between catalase and hydrogen peroxide
from within the interstices of tobacco. By so doing, the effects of
said reaction are brought to bear more thoroughly on the tobacco
constituents than by any other process known to me. By this means,
I have been able to obtain increased expansion of tobacco and
excellent flavor and aroma enhancement.
It will readily be apparent that the order of applying the catalase
and hydrogen peroxide to the tobacco is not critical. A solution
containing catalase may first be applied, then a solution
containing hydrogen peroxide, or vice versa. Also, the catalase and
hydrogen peroxide may be applied in the same solution, in which
case a delayed catalase is preferred. Moreover, the catalase and
hydrogen peroxide, if applied from separate solutions may be forced
into the interstices of the tobacco at the same time, or one at a
time.
The physical force may be applied to the wetted tobacco in many
conventional ways such as by weighted flat plates, rollers,
presses, or continuous expression devices. In a preferred
embodiment of this invention, any excess liquid resulting from the
application of physical force to the tobacco is prevented from
again contacting the tobacco when the force is removed.
Since the catalase and hydrogen peroxide will mutually decompose
proportionate amounts of themselves with the production of nascent
oxygen, it is readily apparent that the physical force must be
applied in a timely manner in order that the optimum effect of such
reaction within the interstices of the tobacco is obtained. It is
believed that the flavor enhancement obtained by the process of
this invention is due to both sterilization of bacteria within the
tobacco and chemical changes in the tobacco brought about by
oxidation.
EXAMPLE 1
A 10 lb. sample of Pennsylvania cigar filler tobacco was treated by
spraying an aqueous catalase (4 ml. catalase/1 l. water) solution
onto the tobacco in an amount equal to 10 percent of the tobacco
weight, and then spraying onto the tobacco a 27 percent hydrogen
peroxide solution in an amount equal to 15 percent by weight of the
tobacco. This treated tobacco was dried at 150.degree. F. and made
into cigars. On smoking, these cigars had a foreign taste with no
noticeable improvement over the taste of control cigars, both
having an acrid, harsh taste. Some expansion of the tobacco was
noticed.
EXAMPLE 2
Example 1 was repeated, except that immediately after the spraying
of the hydrogen peroxide solution the tobacco was rolled with a
heavy roller for a few seconds. When the rolling was stopped, the
tobacco was seen to visibly expand to more than the volume of the
treated tobacco from Example 1 and upon smoking showed considerable
improvement in flavor over the control with a mildness that was
described as being neutral.
EXAMPLE 3
Poor quality Phillipine flue cured cigarette strips were treated by
spraying an aqueous catalase (4 ml. catalase/ 1 l. water) solution
onto the tobacco in an amount equal to 10 percent of the tobacco
weight, and then spraying onto the tobacco a 35 percent hydrogen
peroxide solution in an amount equal to 5 percent by weight of the
tobacco. This tobacco was dried and smoked with no noticeable
change in flavor over the control which flavor was called
undesirable to the industry by virtue of being overly sweet.
EXAMPLE 4
Example 3 was repeated, except that after the spraying of the
catalase solution the tobacco was rolled with a heavy roller for a
few seconds, and immediately after the spraying of the hydrogen
peroxide solution the tobacco was again rolled with a heavy roller
for a few seconds. Upon drying and smoking the overly sweet flavor
had become more neutral and the tobacco had greater expansion.
EXAMPLE 5
Ten lbs. of cigar stems were sprayed first with 5 percent be weight
of the tobacco of a 17 percent hydrogen peroxide solution and then
sprayed with an aqueous catalase (3 ml. catalase/ 1 l. water)
solution in an amount equal to 10 percent by weight of the tobacco.
The stems were dried and smoked, whereupon they retained the papery
acrid harsh flavor of the control. Some tobacco expansion over the
control was noted.
EXAMPLE 6
Example 5 was repeated except that after the catalase spraying the
stems were pressed by a flat weighted plate for a few seconds. This
tobacco was dried and smoked, the flavor being defined as neutral
and cigarette like. The tobacco had expanded more than the
resultant product of Example 5.
EXAMPLE 7
Shredded cigarette lamina of low quality is placed in the wide end
of a funnel having a central shaft with a helical screw surface
formed thereon which closely conforms to the funnel. As the shaft
is turned the tobacco is forced through the funnel being
alternately compressed and released from the funnel. Before being
forced through the funnel this tobacco is sprayed first with an
aqueous catalase solution (4 ml. catalase/ 1 l. water) in an amount
equal to 10 percent by weight of the tobacco and then sprayed with
a 12 percent hydrogen peroxide in an amount equal to 5 percent by
weight of the tobacco. After being forced through the expression
device the tobacco was dried and smoked, having a mild smooth
taste. The moisture content after expression was less than 22
percent.
EXAMPLE 8
Ten lbs. of a cigar tobacco was prepared by cutting 4-5 inch strips
from the leaf. This tobacco was first sprayed with a 5 percent
portion of 907 ml. of an aqueous catalase solution (3 ml.
catalase/1 l. water), then sprayed with 907 ml. of a 6 percent
hdyrogen peroxide solution to wet the tobacco 20 percent above its
original moisture content, then sprayed with the remaining catalase
solution. The thus sprayed tobacco was rolled with a heavy roller
for a few seconds. The treated strips were bulked and placed in a
curing room for 20 days, where the temperature was controlled to
not more than 140.degree. F. The cured tobacco had a mild smooth
sweet flavor and the leaves had obviously expanded.
EXAMPLE 9
10 lbs. of a cut blend of domestically grown lamina filler having a
strong odor of ammonia and a sharp bite was obtained. This tobacco
was first steamed. Then a portion of 680 ml. of an aqueous catalase
solution (4 ml. catalase/1 l. water) was sprayed on the tobacco.
Then 680 ml. of a 25 percent hydrogen peroxide solution was sprayed
on the tobacco, followed by the remaining portion of the catalase
solution. Then the sprayed tobacco was pressed by a weighted flat
plate for several seconds, after which the tobacco was again
steamed. The moisture level of the tobacco was never more than 29
percent during this treatment and it was easily dried. The
resulting lamina when smoked had a smooth mild flavor and based on
filling capacity showed an increased volume of 90 percent.
EXAMPLE 10
10 lbs. of whole stems were obtained. This tobacco was treated by
(1) steaming well, (2) spraying with a portion of 907 ml. of an
aqueous catalase solution (4 ml. catalase/1 l. water), (3) spraying
with 907 ml. of 12 percent hydrogen peroxide, (4) spraying with the
remainder of the catalase solution, (5) rolling the tobacco with a
heavy roller for several seconds, (6) steaming well and (7) drying
in a drier. When the thus treated tobacco was cut, rolled and
smoked, it had a flavor which was sweeter and milder than a
control, and the volume thereof had expanded three times.
EXAMPLE 11
101 lbs. of cut rolled burley stems was obtained. This tobacco was
treated by (1) steaming well, (2) spraying with 680 ml. of an
aqueous catalase solution (5 ml. catalase/1 l. water), (3) spraying
with 680 ml. of 15 percent hydrogen peroxide solution, (4) rolling
the tobacco with a heavy roller for several seconds, (5) steaming
well, and (6) drying. Moistures did not exceed 30 percent during
the process and upon smoking the flavor of the stems was mild and
sweet. Expansion was 100 percent.
EXAMPLE 12
Cut stems were treated by wetting to a 40 percent moisture level
with a combined spray of 1 percent hydrogen peroxide solution and a
1 percent aqueous delayed catalase solution. The sprays were
combined above the tobacco and allowed to fall thereon. After
spraying this tobacco was rolled for several seconds with a heavy
roller, and then dried. The tobacco had a filling capacity of 150
per cent of control tobacco. Cigarettes were then made from this
tobacco.
The cigarettes were conditioned for 25 hours at 75.degree. F. and
60% relative humidity. Smoking was done in a laboratory conditioned
to 75.degree. F. and 60 R.H. The smoking system consisted of the
cigarette, a tared Cambridge filter assembly and a smoking machine
that produces a 35 ml. puff of 2 second duration at a rate of one
puff per minute. All cigarettes were smoked to a butt length of 3
mm longer than the tipping paper. Five cigarettes were smoked
through each Cambridge filter and the results calculated and
reported in terms of one cigarette.
Moisture was determined by gas chromatography according to a
procedure described in a paper entitled "Determination of Moisture
in Total Particulate Matter" by Schultz and Spears in Tobacco
Science, Vol. X, pp. 75-76 (1966).
As soon as the filter assembly had been weighed to determine total
particulate matter, it was opened and the filter holder was then
wiped with one-fourth of a Cambridge filter pad and this added to
the bottle. Ten ml. of dry dioxane-isopropanol 100:1) was measured
from an automatic burette into the serum bottle and the stopper
inserted. The bottle was shaken for 20 minutes on a Wrist Action
shaker.
A sample of 5 microliters was withdrawn with a Hamilton syringe
through the rubber serum cap and subjected to gas chromatography in
an Aerograph 90-p3 gas chromatograph. The moisture content of the
particulate matter was read from a calibration curve made by adding
known amounts of water to the solvent mixture. Cigarettes
conditioned at 75.degree. F. and 60% R.H. were treated in the same
manner and the average value of the moisture content subtracted
from the amounts found to get the net moisture content.
The balance of the solution for GlC moisture, plus the filter pad,
was transferred to a Griffith still and the nicotine determined by
the usual procedure of double distillation and reading at three
wave lengths in an ultraviolet spectrophotometer.
The results of these tests were as follows:
Total Particulate Control Moisture Nicotine Tar
______________________________________ 27.5 2.1 1.43 20.0 27.2 1.7
1.41 20.7 25.7 2.3 1.39 19.8 25.8 1.5 1.45 20.2 Average 26.6 1.9
1.42 20.2 25% puffed material in cigarette 9.2 2.1 .59 8.4 9.8 1.6
.70 8.5 10.5 2.2 .70 9.6 8.7 1.4 .52 8.2 Average 9.5 1.8 .63 8.4
75% puffed material in cigarette 4.1 2.1 .22 4.1 4.2 1.6 .30 4.0
5.2 2.2 .29 4.1 4.3 1.4 .21 3.8 Average 4.4 1.8 .25 4.0
______________________________________ Average number of puffs for
all groups was 10 Butt length 27mm Average pressure drop 6.1 inches
-
EXAMPLE 13
Separate lots of cut rolled tobacco stems were treated by first
spraying the tobacco thoroughly with a 3% by weight acqueous
hydrogen peroxide solution and then with an acqueous solution of
catalase, both solutions being applied at a rate of 250 ml. of
solution per pound of tobacco. The treated tobacco was then rolled
for several seconds with a heavy roller and then dried. Each lot
was blended with tobacco lamina to give 75% lamina/25% cut rolled
stems blends. Comparable blends of untreated cut rolled stems and
lamina were prepared as a control, and all of the blends made into
cigarette samples and tested as follows:
Table No. 1A
__________________________________________________________________________
UNTREATED TREATED REQUIRED C.R.S. 130 c/i C.R.S. 227 c/i C.R.S. 130
c/i C.R.S. 227
__________________________________________________________________________
c/i Moisture content before treatment % -- -- 18 18
__________________________________________________________________________
Used H.sub.2 O.sub.2 concentration % -- -- 3 5 10 3 5 10 Total
Moisture Content after H.sub.2 O.sub.2 application % -- -- 32.+-. 2
32.+-. 2 32.+-. 2 32.+-. 32.+-. 32.+-. 2 Total Moisture content
after Enzyma application (finished treatment) % -- -- 46.+-. 2
46.+-. 2 46.+-. 2 46.+-. 46.+-. 46.+-. 2 Used Drying Temp.
.degree.F. -- -- 140.+-. 5 140.+-. 5 140.+-.5 140.+-. 140.+-.
140.+-.5 Moist. content after 48 hrs. conditioning at 76.degree.F.
-- 68% R.H. % 16.4 16.2 17.6 17.5 17.4 17.5 17.5 17.5 Compression
m/m 6.60 8.98 4.37 2.32 1.59 4.84 3.58 1.88 Column Height m/m 23.40
22.02 25.63 27.68 28.41 25.16 26.42 28.12 Used Quantity: g. of
C.R.S. 20 20 20 20 20 20 20 20 Expansion % -- -- 9.5 18.3 21.4 14.2
20 27.7
__________________________________________________________________________
Table 1B
__________________________________________________________________________
UNTREATED TREATED C.R.S. 130 c/i C.R.S. 227 c/i C.R.S. 130 c/i
C.R.S. 227 c/i Moisture content before treatment % -- -- 18 18 Used
H.sub.2 O.sub.2 concentration % -- -- 3 5 10 3 5 10 Total Moisture
Content after H.sub.2 O.sub.2 application % 32.+-. 2 32.+-. 2
32.+-. 2 32.+-. 32.+-. 32.+-. 2 Total Moist. content after Enzyma
application (finished treatment) % -- -- 46.+-. 2 46.+-. 2 46.+-. 2
46.+-. 46.+-. 46.+-. 2 Used Drying Temp. .degree.F. -- -- 140.+-. 5
140.+-. 5 140.+-.5 140.+-. 140.+-. 140.+-.5 Moisture content after
72 hrs. conditioning at 73.degree.-- 65% R.H. % 12.50 12.80 14.0
13.6 13.6 13.9 13.7 13.8 Compression Height MM 8.24 9.27 4.40 2.52
1.04 4.26 3.48 2.36 Column Height MM 21.76 20.23 25.60 27.48 28.96
25.74 26.52 27.64 Used Quantity of C.R.S. g. 15 15 15 15 15 15 15
15 Expansion % -- -- 17.6 23.3 33.1 27.2 31.1 36.6
__________________________________________________________________________
Table 1C
__________________________________________________________________________
Cigarettes Blends Cigarettes Blends Untreated Treated
__________________________________________________________________________
Cont. 25% Untr. Cont. 25% Untr. Cont. 25% Treat Cont. 25% Treat.
C.R.S. 130 c/i in C.R.S. 227 c/i in C.R.S. 130 c/i in C.R.S. 227
c/i in 75% Lamina only 75% Lamina only 75% Lamina only 75% Lamina
__________________________________________________________________________
only Moisture Content in CRS LAMINA CRS LAMINA CRS LAMINA CRS
LAMINA C.R.S. And Lamina at 18 16 18 16 18 16 18 16 Blending time %
Used H.sub.2 O.sub.2 Concentra- tion % -- -- -- -- 3 -- 3 -- Blends
Moist. Contents After 72 hrs. conditioning at 73.degree.F. 65% R.H.
14.3 14.4 14.6 14.4 Compression MM 5.98 5.84 2.92 2.96 Column
Height MM 24.02 24.16 27.08 27.04 Used Quantity of Blend: g. 20 20
20 20 Expansion % -- -- 13 12
__________________________________________________________________________
Table No. 2
__________________________________________________________________________
Samples Cgt. Wt. Moisture Diameter Compression Filling Expansion
Description g. % m/m m/m Index g. %
__________________________________________________________________________
Control 130 c/i 1.1570 14.00 7.93 5.54 1.0381 +9 Sample 130 c/i
Treated with 3% 1.1568 14.56 7.93 5.59 0.9404 H.sub.2 O.sub.2
Control 227 c/i 1.1582 14.20 7.98 5.52 1.0413 +8 Sample 227 c/i
Treated with 3% 1.1540 14.37 7.90 5.58 0.9563 H.sub.2 O.sub.2
__________________________________________________________________________
Table No. 3A ______________________________________ Sample P.D.
T.P.M. NICOTINE Description cm. mg. mg.
______________________________________ Control 130 c/i 12.2 20.87
0.91 Sample 130 c/i Treated with 3% 13.2 20.03 0.89 H.sub.2 O.sub.2
Control 227 c/i 11.3 22.57 1.07 Sample 227 c/i Treated with 3% 12.8
21.09 1.02 H.sub.2 O.sub.2
______________________________________
Table No. 3B
__________________________________________________________________________
Sample Cgt. wt. Moisture Cold Warm Collapsing Description g. %
Compression Compression Index m/m m/m m/m
__________________________________________________________________________
Control 130 c/i 1.1570 14.00 4.47 4.47 1.07 Sample 130 c/i Treated
with 3% H.sub.2 O.sub.2 1.1568 14.56 5.59 4.49 1.10 Control 227 c/i
1.1582 14.20 5.58 4.50 1.08 Sample 227 c/i Treated with 3% H.sub.2
O.sub.2 1.1540 14.37 5.52 4.42 1.10 Repeat Control 227 c/i 1.2400
14.3 5.42 4.35 1.07 Sample 227 c/i Treated with 3% H.sub.2 O.sub.2
1.160 14.2 5.64 4.53 1.11
__________________________________________________________________________
When cigarettes from the treated samples are smoked, a concrete
mild smooth sensation can be detected. This is surprising since cut
rolled stems as a cigarette filler is a very rich-in-cellulose
component which contributes directly to the organoleptic qualities
of smoke, and which when added to leaf tobacco normally gave the
smoke a harsh quality readily detected by the smoker. Referring to
Tables 1A, 1B and 1C, effective increases in filling values are
shown for the treated lots of cut rolled stems and their blends
with lamina. Results of blends made into machine made cigarettes
are shown in Table 2. Referring to Table 3A, smoking tests showed
no significant differences on T.P.M. and nicotine between the
treated cigarettes and the controls. Referring to Table 3B, no
significant differences between the collapsing indexes of the
treated cigarettes and the controls were found.
EXAMPLE 14
A quantity of Virginia leaf tobacco was obtained. Certain leaves
were randomly selected and separated into two groups of leaves. The
first group was subjected a conventional flue curing process and
yellowed at 35.degree.C and 85% R.H. These leaves were then
progressively dried under gradually elevated temperatures to
78.degree.C over a 48 hour period. The second group of leaves was
treated by first spraying with simultaneously with a mixture of
0.5% by weight acqueous solutions of hydrogen peroxide and delayed
catalase. Before significant reaction occurred these treated leaves
were rolled for several seconds with a heavy roller. When no
further reaction was apparent, the tobacco of this group appeared
bright in color.
Following drying of the separate groups, samples were conditioned
for handling.
Prior to cigarette manufacture, tobacco from various leaf positions
within each group was composited and uniformly blended. Cigarettes
85mm in length were prepared using 32 cuts/inch. Cigarettes were
selected having the same draw resistance.
Smoking Procedure and Chemical Examination of the Smoke
The cigarettes were moisture equilibrated at 65% relative humidity
and 25.degree.C. The cigarettes prepared from the hydgrogen
peroxide-catalase process were selected to weigh 835 mg and the
cigarettes made from the conventionally cured tobacco were selected
to weigh 835 mg.
The two types of cigarettes were smoked mechanically on a Phipps
and Bird machine using Cambridge Filters for trapping the
particulate matter (puff volume 35 ml, puff duration 2 sec., puff
frequency 1 puff/min., butt length 23 mm). The determination of the
amount of total particulate matter and its water content were
performed according to the Coresta standard method No. 10. The
amount of nicotine was determined by the Coresta standard method
No. 12. The determination of phenol in the particulate matter which
accounts for 97 per cent of total smoke phenol value was
accomplished using a method of Williamson modified by Carlson,
which is based on spectroscopic determination (480nm) after
treatment of the separated acidic material with diazotized
p-nitroaniline. The results of these determinations are as
follows:
Flue Cured H.sub.2 O.sub.2 -Catalase
______________________________________ Weight of tobacco mg./cig.
835 835 Average number of puffs/cig. 9.0 9.0 Total particulate
matter TPM 48.9 15.1 Increase in filling capacity (% in sample) 50%
Nicotine m/cig. 3.4 .7 Phenol mg/cig. 345 97 Sugars (%) 9.68 15.2
______________________________________
EXAMPLE 15
Cut lamina was sprayed with a mixture of a 2% by weight acqueous
hydrogen peroxide solution and a 1.5% by weight acqueous catalase
solution ((having a delay of 3 minutes) up to 20% by weight
moisture level. This lamina was then rolled with a heavy roller for
several seconds and allowed to dry. The filling capacity of this
treated lamina was 990 milliliters. Cigarettes were made from the
untreated lamina and 75% treated lamina -- 25% untreated lamina and
25% treated lamina -- 75% untreated lamina, and tested as
follows:
Smoking Conditions and Collection of Tar
Twenty cigarettes were smoked for each set of determinations. These
were smoked to an approximate 23 mm butt length using a CSM-10
Smoking Machine. A 35ml puff of 2 seconds duration was taken once a
minute on each cigarette. The smoke was collected at room
temperature in 50ml. of vigorously stirred cyclohexane contained in
a 250 ml. flask. Addition of the smoke beneath the surface of the
cyclohexane was avoided to eliminate a possible pressure drop.
Collection of smoke in this manner was very efficient. During the
smoking of groups of 20 cigarettes no significant amount of
particulate matter deposited on a Cambridge filter which was placed
behind the collection flask in the smoking train.
After the smoke was collected, the cyclohexane solution was
transferred to a separatory funnel. The collection flask, stirrer,
and inlet tube were rinsed with alternate portions of 2.times.5 ml.
of 0.5 N sodium hydroxide and 3.times.5 ml of cyclohexane. After
removing the aqueous layer, the cyclohexane solution was extracted
with 3.times.5 ml. of 0.5 N sodium hydroxide followed by 1.times.5
ml. saturated NaCl sodium chloride. The extracts were combined and
backwashed with 2.times.5 ml. of cyclohexane. This base extract was
used to determine phenols. The combined cyclohexane solution was
extracted with 5.times.5 ml. of 0.5 N hydrochloric acid followed by
1.times.5 ml. of saturated sodium chloride. The extracts were
combined and backwashed with 2.5 ml of cyclohexane which was added
to the main cyclohexane solution. This acid extract was used for
the determination of nicotine.
The cyclohexane solution was next extracted with 5 ml. of methanol
water (4:1). After separation the methanol-water solution was
backwashed with 2.10 ml. and 4.5 ml. of cyclohexane which was added
to the main cyclohexane solution. The cyclohexane solution was next
extracted with 2.10 ml. and 6.5 ml. of nitromethane. These
nitromethane extracts were combined and the solution concentrated
to dryness using a rotary evaporator (bath temp. 45.degree.C;
press. 30 mm.). The residue was used for the determination of
benzo-a-pyrene.
Determination of Phenols
The base extract was steam distilled. Approximately 500 ml. of
distillate was collected and discarded. The contents of the
distillation flask were allowed to cool and then acidified with 50
ml. of 20% sulfuric acid and again steam distilled. The distillate
(180ml.) was acidified and extracted with 6.50 ml. of purified
ether. The ether extracts were combined and extracted with 2.5 ml.
of saturated sodium bicarbonate solution. The ether solution was
dried over anhydrous sodium sulfate and concentrated to less than 1
ml. by distillation through a 13 cm. Vigreux column at atmospheric
pressure. This concentrated ether solution was transferred to a 1
ml. volumetric flask and diluted to volume. This solution was used
to determine phenols by gas chromatography, using a Barber-Coleman
Selecta 5000 system with a model 5043 electrometer and a flame
ionization detector. A 2m.times.1/8 in. s.s. column packed with
100-120 mesh Parapak Q was used.
The operating parameters were: nitrogen carrier gas flow 25
ml./min; air and hydrogen gas flows, 300 ml. and 27 ml./min
respectively; column, injector and detector temperatures,
230.degree., 250.degree., and 270.degree.C, respectively. The
electrometer settings were: sensitivity, 10.sup.10 amps and
attenuation, 2. An Infotronics Digital Readout System, Model CRS-11
HSB, was used to determine peak areas. The settings on the
integrator were: tracking rate, 3 up--10 down; threshold level,
0.05; trip, 4; slope sensitivity, 1; and filter frequency, 1.
The concentration of Phenol, o-cresol, and m- and/or p-cresol was
determined from the ratio of their individual peak areas to the
area of o-chlorophenol which served as an interanal standard. An
aliquot of a standard solution containing 2 mg. of o-chlorophenol
was added to the cyclohexane solution immediately after the smoke
was collected. The relative response and retention time of the
phenols to o-chlorophenol were determined from a standard solution
containing phenol, o-, m-, p-cresol and o-chlorophenol.
Determination of Nicotine
This procedure is a modification of that described by Ogg for the
determination of nicotine in smoke particulate matter collected on
a Cambridge Filter. The acid extract and 10 ml. of 0.5 N
hydrochloric acid were steam distilled until 300-400 ml. of
distillate was collected, which was discarded. After the acidic
solution in the distillation flask had been allowed to cool, 30 ml.
of a 30% sodium hydroxide solution, saturated with sodium chloride,
was added. The resulting solution was then steam distilled until
approximately 400 ml. of distillate was collected. In this second
distillation the distillate was collected under the surface of 50
ml. of 0.5 N hydrochloric acid contained in a 500 ml. volumetric
flask. After the volume of the distillate was adjusted to 500 ml.
with distilled water, a 25 ml. aliquot was diluted to 100 ml. with
0.05 N hydrochloric acid. The absorbance of this solution was read
at 236 mu, 259 mu, and 282 mu Milligrams of nicotine per cigarette,
N, was calculated using the formula:
N = A.sub.259 - (A.sub.236 + A.sub.282)/2/0.3213 .times. b,
where A.sub.236, A.sub.259 and A.sub.282 are the absorbances at the
indicated wavelengths and B is the pathlength of the cell in
cm.
Determination of Benzo-a-pyrene
The residue from the nitromethane-soluble fraction was dissolved in
approximately 20 ml. of benzene, placed on a 2.5 cm. column
containing 5 grams of silicic acid and the column was eluted with
250 ml. of benzene which was collected in a single portion. This
procedure removed the bulk of the polar chromophoric material. The
eluant which contained the benzo-a-pyrene and other aromatic
hydrocarbons was concentrated to dryness using a rotary evaporator
(bath temp. 45.degree.C, press 30mm.). The weight of this residue
is reported as the nitromethane fraction. After the residue was
weighted it was taken up in approximately 0.1 ml. cyclohexane and
applied as a series of spots, forming a 12 cm. streak, to a
20.times.20 cm alumina thin-layer plate. Reference spots of
authentic benzo-a-pyrene were placed 1.5 cm from each end of the
streak. After the plate was developed in ethyl etherpentane, the
band containing benzo-a-pyrene was located by examining the plate
under UV light and was transferred to a 15 ml. centrifuge tube. The
benzo-a-pyrene was desorbed with 4.times.4 ml. methanol. The four
solutions were combined and concentrated to approximately 0.1 ml.
and chromatogrammed on a 20% acetylated cellulose thin-layer plate.
After the plate was developed in ethanol-toluene-water (17:4:1),
the benzo-a-pyrene band was transferred to a 15 ml. centrifuge tube
and recovered by desorbing with 4.times.4 ml. of methanol. All
methanol solutions were pooled, concentrated to approximately 0.3
ml., and filtered through a small cotton plug into a volumetric
flask. After dilution to 2 or 5 ml. the fluorescence spectrum of
the solution was obtained, using an Aminco-Bowman
Spectrofluorometer set at an excitation wavelength of 380 mu. The
fluorescence maximum at 405 mu. was read and the concentration of
benzo-a-pyrene was determined with a standard curve.
Determination of Total Particulate Matter
Total particulate matter was determined from five cigarettes
essentially as described by Ogg. The cigarettes were smoked to a 23
mm. rather than a 30 mm. butt length.
Determination of Burn Temperature
Temperature measurements were made using a 0.012 inch diameter
Pt/Pt --13% R.H. thermocouple connected in series with a reference
junction (0.degree.C) to a potentiometer type recorder. The
thermocouple was inserted approximately 25mm. into the free end of
the cigarette which was held in a Cambridge filter holder. The burn
temperature was recorded as the point of maximum recorder response
as the combustion zone passed over the thermocouple junction. For
each determination 10 cigarettes were smoked, using a standard
smoking cycle, and the values averaged.
______________________________________ Puffed samples control
______________________________________ 75% 25% Average 2/cig. (g)
1.17 1.17 1.17 Percent moisture 10.0 12.1 12.1 No. puff/20 cig. 218
218 218 Average Burn temp (.degree.C) 497 668 878 Analysis of Cig.
Smoke per cig. Wet TPM (mg) 7.0 20.3 29.8 Dry TPM (mg) 4.2 17.1
28.2 Nicotine (mg) .09 .87 1.40 Benzo-a-pyrene (mg) .61 7.3 11.5
Phenol (mg) 3 54 83 o-cresol (mg) .7 8 15 m-, p-, cresol (ug) 5 24
35 Total phenols (ug) 10 78 133 per 100 ml. smoke Dry TPM (mg) .52
4.2 7.8 nicotine (mg) .53 .21 0.37 Benzo-a-pyrene (mg) .005 1.9 3.0
Phenol (ug) .03 14 22 o-cresol (ug) .04 2 4 m, p-cresol (ug) .02
7.5 9 Total Phenols (ug) .05 20 35
______________________________________
EXAMPLE 16
A mixture of equal parts of a 0.5% by weight aqueous hydrogen
peroxide solution and a 0.5% by weight aqueous catalase (2 min.
delay) solution was prepared. To this solution was added an equal
amount of ethanol. Cut lamina was wetted thoroughly by a spray of
this hydrogen peroxide-catalase-alcohol solution. The wet lamina
was then rolled for several seconds with a heavy roller and then
subjected to an air stream at a temperature of 100.degree.F for 2
minutes. The material was then dried in a vacuum drier for 15
minutes. The dried tobacco product had a filling capacity of 1,020
milliliters. Cigarettes were made from this treated tobacco in
varying proportions with respect to the control tobacco. Each
cigarette contained 1 gram of tobacco and was 85 mm. in length. All
of the cigarettes then were tested by smoking in a constant volume
smoking machine using the following conditions: -- puff volume, 35
ml.; puff duration, 2 sec.; puff frequency, 1 per min.
Tests were then made of the tobacco smoke to determine the presence
of ethane, ethylene, methanol, acetaldehyde, acetonitrile, acrolein
and acetone in the smoke composition.
Moisture determinations were performed by a modification of the
Carl Fischer Method and with the Ohaus Moisture Balance, both of
which gave comparable values.
Temperature measurements were made using a Pt/Pt -- 13% R.H.
thermocouple of either 0.001 or 0.002 in. diameter. For combustion
temperature measurements, the thermocouple was inserted
perpendicular to the longitudinal axis of the cigarette at a point
15mm. from the front end. The results of these tests were as
follows:
Mol % ______________________________________ Burn Temp. CO Methane
Ethane Ethylene ______________________________________ 100% P.T.*
480C .87 0.02 .0008 .0001 75% P.T. 510 .98 0.05 .0012 .0005 50%
P.T. 580 1.10 0.09 .0123 .0025 25% P.T. 670 2.20 0.15 .0319 .0149
control 849 3.00 0.43 .0805 .0389
______________________________________ *puffed tobacco
Mcg./l.
__________________________________________________________________________
Acetal- Aceto- Acro- Burn Temp. Methanol dehyde nitrile lein
Acetone
__________________________________________________________________________
100% P.T. 480C 4.1 7.2 .09 .08 2.1 75% P.T. 510 7.4 10.7 2.40 1.50
4.2 50% P.T. 580 10.2 14.6 3.82 2.81 8.0 25% P.T. 670 18.3 24.2
6.91 4.32 12.5 control 849 36.1 74.0 14.32 9.21 40.6
__________________________________________________________________________
Sampling Procedures
All analytical data were obtained on the fifth puff of the
cigarette. The puffing sequence was controlled by a preset timer
(Dual-Trol), such that the interval between puffs was 60 seconds
and the duration of the puff 2 seconds. Lighting the cigarette
constituted the first puff. A fresh Cambridge filter was used for
each cigarette to separate the particulate phase from the vapor
phase.
For colorimetric analysis reagent solution was injected into a
dismantled collection flask with a syringe. The flask stopcocks
were then closed, and the flask inserted into a wet ice-bath and
connected to the smoking machine manifold. At the end of the fourth
puff, the sample flask was opened to the manifold and evacuated.
After 45 seconds, the stopcock on the vacuum line was closed and
after 60 seconds, a puff of smoke was automatically puffed into the
flask during the second interval. The flask was then closed,
removed, and its contents thoroughly shaken prior to colorimetric
analysis.
For gas chromatographic analysis aliquots of the smoke gas were
extracted from the manifold by means of sampling values and
admitted immediately into the carrier gas stream of the
chromatographic column. The volume of gas admitted to the column
was regulated by the length of loops on the sampling values.
Determinations were based on measurements of peak heights; peaks
were characterized by retention time comparisons and chromatography
with standard mixtures of known compounds. Methane and CO -- 10 ft.
and 0.25 in. o.d. column of 40-60 mesh molecular sieve 13x; flow
rate 125 ml/min. ambient column temperature; thermal conductivity
detection. Acrolein, acetonitrile, acetaldehyde, acetone and
methanol-10 ft. .times. 0.125 in. o.d. column of Polypak 11; flow
rate 45 ml./min., column temperature programmed from 50 - 170 c. at
3.5/min. and from 170 - 225 C. at 2.8/min., hydrogen flame
detection.
EXAMPLE 17
Cut lamina was wetted thoroughly by spraying with a mixture of
equal parts of 0.5% aqueous solution of hydrogen peroxide and
isopropanol. This lamina was then rolled for several seconds with a
heavy roller and then immersed in liquid nitrogen. Upon removal
from the liquid nitrogen the lamina was wetted with a 0.5% aqueous
solution of catalase and then rolled again for several seconds.
This material was then vacuum dried for 10 minutes. Measurement of
the filling capacity of the thus dried tobacco showed 805
milliliters. Fifteen experimental cigarettes were made using 35% of
this treated tobacco and 65% cut lamina control. These experimental
cigarettes were compared with 15 commercial Kool cigarettes by
smoking each in lots of five cigarettes each. The CO content of the
mainstream smoke was determined Smoking conditions were as
specified by the current Federal Trade Commission regulation,
2-sec. 35-ml. puffs at 1 minute intervals in a laboratory
controlled to 75%F. and 60% Rh. The following data were obtained:
Carbon Monoxide mg./liter Vol. %
______________________________________ Kool commercial Lot 1 59 5.2
Lot 2 58 5.1 Lot 3 60 5.3 Average 59 5.2 Experimental Lot 1 22 1
Lot 2 22 1 Lot 3 22 1 Average 22 1
______________________________________
The average reduction in CO effected by the puffed tobacco process
using 35% puffed material in these cigarettes is 80%.
Hydrogen peroxide, utilized in accordance with the process of this
invention will not leave toxic residues in the tobacco. Moreover,
it is well known that hydrogen peroxide is used medically as a
sterilizer and in many food products to eliminate bacteria and
other organisms. Also in accordance with the process of this
invention, catalase and hydrogen peroxide are mutually decomposed,
leaving no amount of either reactant. Peroxide-catalase treatment
of milk for cheesemaking is known, as is peroxidase-catalase
treatment of liquid egg products.
The fact that flavor of tobacco may be enhanced by the process of
this invention is believed to be due to the fact that the extremely
large amount of nascent oxygen evolved upon decomposition of
hydgrogen peroxide acts to oxidize substances within the tobacco as
well as to expand the tobacco. The resulting milder, smoother
tastes are considered to be the consequence of a breakdown of
polysaccharide chains such as starch and cellulose composed of
glucose residues which are the main constituents of the cell walls
of the tobacco leaf.
It will be apparent that there is no theoretical limit on the
amounts of hydrogen peroxide and catalase used, since the process
of this invention is shown to be effective at levels at least as
low as 0.5% by weight concentrations. Increased mutually
decomposing amounts of catalase and hydrogen peroxide bring about
greater recognized effects, such as expansion, but the upper limits
of catalase and hydrogen peroxide are only economic.
It will moreover be appreciated that advantages accrue to the
process of this invention when the hydrogen peroxide is made more
concentrated from an aqueous solution while it is on and within the
tobacco. Examples of the means for accomplishing this concentration
are contacting the peroxide wetted tobacco with cold gaseous or
liquid nitrogen, heated air, ultraviolet radiation and/or vacuum
drying.
Once the hydrogen peroxide has been concentrated it is then
contacted by catalase in its normal or delayed form in order to
puff the tobacco. Various inhibitors can be used to delay the
catalase including citric acid and alcohol.
The advantages of concentrating the hydrogen peroxide are one of
economy and efficiency. For instance, a lesser concentration of
peroxide may be used to wet the tobacco, but when concentrated can
double or triple in strength. The greater the strength of the
peroxide, the greater the expansion of the tobacco when contacted
with catalase. Also concentrated peroxide will mix better with the
catalase when contacted in that there is less water present
creating a maximum of the treating materials. This helps to
eliminate excess moisture and insures quicker drying. Furthermore,
the peroxide will penetrate down into the tobacco and concentrate
in the cells so that when catalase hits the tobacco surface the
reaction will spread down into the tobacco expanding it to its
maximum.
The method of applying the nitrogen and alcohol is by spraying or
immersion or other feasible methods or by passing an air stream
over the tobacco as in the case of heated air.
It is also possible although not a preferred method to first treat
the tobacco with nitrogen gas or liquid, alcohol or heated air. The
hydrogen peroxide may then be applied. It will then concentrate
although not as efficiently. The tobacco may also be treated by a
series of treatments of either the nitrogen liquid or gas, alcohol,
heated air, ultraviolet light, or vacuum drying. For instance, the
tobacco may be sprayed with liquid nitrogen, then soaked in
hydrogen peroxide, then contacted with catalase and then heated air
passed over it.
The tobacco may also be treated with hydrogen peroxide by spraying,
immersed in nitrogen and contacted with catalase and then vacuum
dried.
The tobacco may be sprayed with hydrogen peroxide, vacuum dried to
concentrate, and then contacted with catalase.
The tobacco may also be treated with a mixture of hydrogen peroxide
and delayed catalase placed on the tobacco with alcohol as a
carrier. This tobacco will then be contacted with heated air under
140.degree. to concentrate the peroxide and volatilize the alcohol.
The catalase already present in the mixture will then react with
the concentrated peroxide.
The tobacco may also be treated with hydrgen peroxide and alcohol
and sprayed with liquid nitrogen to concentrate, contacted with
catalase and then vacuum dried.
Another method of treatment is to freeze the hydrogen peroxide on
the tobacco and then contact it with liquid nitrogen to stabilize
and concentrate the hydrogen peroxide. The tobacco will then be
contacted with catalase to reactivate the hydrogen peroxide and
then dried with heated air.
The alcohols used may be of the type that is non-toxic for use on
tobacco such as ethanol, isopropanol and butanol.
While I have disclosed the use of the process of this invention
with respect to various naturally occurring forms of tobacco, such
as leaf, stems and ribs, it will be readilly apparent that a
finished product such as reconstituted tobacco sheet may likewise
be treated in accordance with the process of this invention to
achieve the desirable advantages thereof.
EXAMPLE 18
A finished homogenized tobacco sheet is sprayed with equal parts of
a 27 per cent by weight aqueous hydrogen peroxide solution and an
aqueous catalase (4 ml catalase/1 water) solution in order to
increase the moisture content of the sheet by 20 per cent of its
weight. The wet sheet is immediately pressed with a heavy roller in
order to cause the solutions to penetrate interstices of the sheet.
The sheet was then dried. After drying the sheet was found to be
more porous than originally and a cigarette incorporating the
shredded sheet was judged to be milder than a cigarette
incorporating untreated sheet.
One advantage gained by treating reconstituted tobacco sheet by the
process of this invention is the sufficient modification of the
tobacco flavor to enable a smoking article to be produced utilizing
solely reconstituted tobacco sheet as filler. This is an important
industrial factor since the amounts of reconstituted tobacco sheet
utilized in commercial American cigarettes rose to a level of 15
per cent of the total filler in 1964.
Additionally, many forms of reconstituted tobacco sheet are formed
with high densities. By use of the process of this invention,
finished reconstituted tobacco sheet may be provided at a lower
density than heretofore allowing more air penetration of the
tobacco article and therefore lower burn temperature. It has also
been observed that lower density sheet may become stronger with
respect to the liklihood of tearing when used to wrap or bind
cigars or cigarettes. Moreover, such products have increased
hygroscopicity, leading to products with longer shelf lives and
stability.
* * * * *