US3577994A - Method for producing smoking product of oxidized cellulosic material - Google Patents
Method for producing smoking product of oxidized cellulosic material Download PDFInfo
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- US3577994A US3577994A US774064A US3577994DA US3577994A US 3577994 A US3577994 A US 3577994A US 774064 A US774064 A US 774064A US 3577994D A US3577994D A US 3577994DA US 3577994 A US3577994 A US 3577994A
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- Prior art keywords
- nitrogen dioxide
- cellulosic material
- liquid nitrogen
- gaseous nitrogen
- percent
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/10—Chemical features of tobacco products or tobacco substitutes
- A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
- A24B15/165—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes comprising as heat source a carbon fuel or an oxidized or thermally degraded carbonaceous fuel, e.g. carbohydrates, cellulosic material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
- C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
Definitions
- This invention relates to a smokable product produced of oxidized cellulosic materials and to a smoking product produced thereof.
- smoking product is meant to include filler material for use in cigarettes, cigars, pipe tobacco and the like, cigarette papers and wrappers used in the preparation of cigarettes, cigars and the like.
- Purified cellulosic materials have been found to be unsatisfactory for use as a smokable product because of the irritating acids and aldehydes which are evolved during pyroly- SIS.
- the oxidation reaction product is further processed by removal of nitrogen oxides by vaporization and washing and by extraction with one or more organic solvents to remove undesirable impurities, such as oils, waxes, latexes and aromatics which have been released as a consequence of treatment with nitrogen dioxide.
- the oxidized and cleansed oxycellulose is further processed by a reduction reaction with a boro hydride or an alkali or alkaline earth metal, such as sodium borohydride, for reduction of nitro groups, quinones, ketones and aldehydes which otherwise might have a tendency to impart undesirable aroma and taste to the smoking product, when burned, or to reduce the stability thereof during storage.
- a boro hydride or an alkali or alkaline earth metal such as sodium borohydride
- the product before or after reduction, can be subjected to additional oxidation with a dilute solution of peroxide further to eliminate groupings that contribute undesirable aroma or taste to the product.
- additional treatments naturally varies with the initial purity of the oxycellulose.
- the refined oxycellulose is then formulated with mineralizing agents, such as oxalates, glycolates, diglycolates, lactates, pivalates or tannates of the alkaline earth metals, preferably in a manner to form such salts internally of the oxycellulose fibrils.
- mineralizing agents such as oxalates, glycolates, diglycolates, lactates, pivalates or tannates of the alkaline earth metals, preferably in a manner to form such salts internally of the oxycellulose fibrils.
- mineralizing agents such as oxalates, glycolates, diglycolates, lactates, pivalates or tannates of the alkaline earth metals, preferably in a manner to form such salts internally of the oxycellulose fibrils.
- internal formation can be achieved by first forming the alkaline earth metal salt of the oxycellulose and then treating with a solution of the anion to precipitate the mineralizing salt in situ in the cellulosic material.
- the treated oxycellulose can be further formulated to improve buming, glow and smoking characteristics by the use of potassium, rubidium or cesium salts, such as the oxalates thereof, as described in the copending application Ser. No. 623,528, filed Mar. 16, 1967, and entitled Smoking Products and Process for their Manufacture.”
- Smoke generators for improving the appearance of the smoke from the smoking product can be introduced by way of fatty acids and the like and suitable aroma can be achieved by the addition of volatilizable alkalyzing materials, such as ammonium oxalate, urea and the like.
- FIG. 1 is a schematic elevational view of one system for treatment of paper strip
- FIG. 2 shows a modified strip treating system
- the concept of this invention resides in the treatment of the cellulosic material to effect oxidation with gaseous nitrogen dioxide in a manner to achieve reaction speeds equivalent or superior to high temperature reaction in liquid nitrogen dioxide under pressure, but without the hazards of explosion.
- cellulosic materia is meant to include various cellulose containing materials, such as alphacellulose, beta-cellulose, hydrocellulose, cotton, flax, hemp, wood, bamboo, rice straw, wheat straw, comcobs, cornsilk, ramie, bast, seaweed in various forms such as leaves, pulp, fibers and filaments from which the cellulosic material is separated, paper, shreds of paper and the like, all of which are relatively free of noncarbohydrate components.
- cellulose containing materials such as alphacellulose, beta-cellulose, hydrocellulose, cotton, flax, hemp, wood, bamboo, rice straw, wheat straw, comcobs, cornsilk, ramie, bast, seaweed in various forms such as leaves, pulp, fibers and filaments from which the cellulosic material is separated, paper, shreds of paper and the like, all of which are relatively free of noncarbohydrate components.
- gaseous nitrogen dioxide for selective oxidation of cellulose is the rapid release of heat of absorption and the heat generated by the exothermic oxidation reaction when the cellulosic material is first exposed to gaseous nitrogen dioxide.
- Such localized heat effects can initiate conflagration of the material as well as generation of high pressures.
- the level of oxidation is not improved by any appreciable extent with the use of moist gaseous nitrogen dioxide as compared to dry gaseous nitrogen dioxide or with the use of cellulosic material having a certain amount of moisture as compared to dry cellulosic material.
- the level of oxidation is improved somewhat by the presence of moisture in the paper or other cellulosic material.
- an asymptotic level of 19 percent oxidation was achieved with the dried paper after 30 minutes of exposure to gaseous nitrogen dioxide as compared to an asymptotic level of 27 percent oxidation before the reaction became negligible.
- Termination of the oxidation reaction at such relatively low levels stems from the exposure for reaction of the outermost portions of the cellulosic material and the relative inability of the oxidation to proceed in the innermost regions beyond the reacted phase, perhaps because of the inability of the gaseous nitrogen dioxide to gain access to such regions or because of other interfering factors arising in the oxidized cellulosic product. This condition seems to be aggravated by the shrinkage of the cellulosic fibers due to the heat generated during the initial reaction.
- the level of selective oxidation of cellulosic materials with gaseous nitrogen dioxide can be markedly increased by wetting the cellulosic material with liquid nitrogen dioxide prior to exposure to gaseous nitrogen dioxide. While it is preferred to effect the exposure of the cellulosic material to gaseous nitrogen dioxide while the cellulosic material is still wet with liquid nitrogen dioxide, the marked improvement in level and uniformity of oxidation is achieved if a drying out period exists between the liquid treating step and the oxidation reaction with gaseous nitrogen dioxide. This can be illustrated by the following example:
- EXAMPLE I Purified cellulose paper, in strip form, was dipped in liquid nitrogen dioxide at ambient temperature and atmospheric pressure and allowed to dry until it had a dry appearance. Thereafter, the paper was exposed to gaseous nitrogen dioxide at 70 C. at atmospheric pressure. A rapid reaction, similar to that obtained with liquid nitrogen dioxide under pressure and at 70 C. was obtained. A level of oxidation of about 25 percent was obtained in about minutes before the rate of oxidation leveled off.
- EXAMPLE 2 Purified cellulosic paper was first dipped to wet the fibers in liquid nitrogen dioxide containing l percent by weight of water and then the cellulosic material wet with the liquid nitrogen dioxide was exposed to gaseous nitrogen dioxide at 100 C. After 7 minutes of exposure, an oxidation level of 44 percent conversion of the methylol groups was achieved. This is to be compared to only 11 percent conversion when treatment is carried out with the same materials and under the same conditions with dry liquid nitrogen dioxide.
- Cigarette wrapping paper containing calcium carbonate as filler was treated with gaseous nitrogen dioxide at 70 C. without first wetting the paper with liquid nitrogen dioxide and also after first wetting the paper with liquid nitrogen dioxide. Conversions were measured by first fixing the calcium carbonate with oxalic acid to form the corresponding calcium oxalate, titrating the oxycellulose with sodium hydroxide solution and calculating the percent conversion after allowing for the calcium oxalate content, as calculated from an ash determination.
- the repeated cycling of the cellulosic material through a station for wetting with liquid nitrogen dioxide and then through a station for reaction with the hot gaseous nitrogen dioxide is capable of arrangement for a continuous operation and/or for use with substantially endless strips of paper or other cellulosic material which can be cycled any number of times through the same stations or separately aligned stations to provide a continuous operation for selective oxidation of the cellulosic material until the desired level of conversion is achieved.
- Treatment with liquid nitrogen dioxide can be carried out with the liquid nitrogen dioxide at a temperature within the range of l to 21 C. at normal pressure and at higher temperatures commensurate with the boiling point temperature of liquid nitrogen dioxide at such pressure. In a continuous cycle of operation, it is preferred to work at about normal pressure and at a temperature of about l5 C. to minimize the escape of fumes into the atmosphere.
- Treatment in the gaseous phase can be carried out at a temperature within the range of 30 to 120 C. and preferably at a temperature within the range of to 100 C.
- liquid nitrogen dioxide having up to about 4 percent by weight water although the amount of water can be raised to 8 percent when the cellulosic material is in the form of cotton. It is preferred to make use of liquid nitrogen dioxide having a water content within the range of 0.5 percent to 1.5 percent by weight of water.
- the pressure can be varied over a fairly wide range within the confines of the pressure-temperature curve for nitrogen dioxide. It is preferred, however, to operate at a pressure at or slightly below atmospheric pressure so that leakage will be inward instead of outward from the reaction chamber. Oxygen or an oxygen containing gas can be introduced for admixture with the gaseous nitrogen dioxide for purposes of regenerating nitrogen dioxide from the nitric oxide formed of the consumed nitrogen dioxide, thereby to maintain the level of nitrogen dioxide concentration in the reaction gases.
- a glass lined vessel 10 partially filled with liquid nitrogen dioxide 12 with an open space above the liquid level which becomes filled with gaseous nitrogen dioxide 14 at elevated temperature.
- Substantially continuous strips of paper 16 can be trained about resistant rollers 18 for continuous travel of the strip of paper in a sinuous path between the liquid portion at the bottom and the gaseous portion thereabove to provide a number of cycles of first wetting with liquid nitrogen dioxide and then exposure to gaseous nitrogen dioxide until the desired level of conversion has been achieved.
- the entrance and exit ducts for the paper strip can be provided in the form of Teflon lined slits.
- the strip of paper introduced in a system of the type described might, for practical purposes, first pass through the gaseous phase into the liquid phase to effect the prewet. Under such circumstances, it is desirable to have the paper pass through the gaseous phase as quickly as possible whereby the liquid phase can operate as a quench for temperature control.
- the strip of paper can be drawn through an elongate tubular member through which hot gaseous nitrogen dioxide is circulated with occasional spraying of the strip with liquid nitrogen dioxide at predetennined spaced intervals.
- Another technique for exposure to gaseous nitrogen dioxide with intermittent wetting with liquid nitrogen dioxide embodies the displacement of a strip of paper through a chamber filled with hot gaseous nitrogen dioxide 22 with rollers 24,
- liquid nitrogen dioxide with which the cellulosic material is wet contains water in an amount up to 4 percent by weight.
- liquid nitrogen dioxide with which the cellulosic material is wet contains water in an amount within the range of 0.5 percent to 1.5
- the sequence of steps of wetting relatively pure cellulosic material with nitrogen dioxide, and then reacting the cellulosic material which has been wet with liquid nitrogen dioxide with gaseous nitrogen dioxide is carried out by passing a strip of cellulosic material in a sinuous path about roller's within a chamber saturated with hot gaseous nitrogen dioxide, refrigerating at least some of the rollers to condense gaseous nitrogen dioxide on the periphery thereof to wet strip as it is passed thereabout.
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- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
Claims (12)
- 2. The method as claimed in claim 1 in which the gaseous nitrogen dioxide reaction is carried out at elevated temperature.
- 3. The method as claimed in claim 2 in which the reaction is carried out at a temperature within the range of 30* to 220* C.
- 4. The method as claimed in claim 1 in which the reaction with gaseous nitrogen dioxide is carried out at a pressure of about atmospheric pressure to slightly less than atmospheric pressure.
- 5. The method as claimed in claim 1 in which the liquid nitrogen dioxide with which the cellulosic material is wet contains water in an amount up to 4 percent by weight.
- 6. The method as claimed in claim 1 in which the liquid nitrogen dioxide with which the cellulosic material is wet contains water in an amount within the range of 0.5 percent to 1.5 percent by weight.
- 7. The method as claimed in claim 1 in which the liquid nitrogen dioxide is at a temperature within the range of -1* to 21* C.
- 8. In the method of rapidly and uniformly selectively oxidizing cellulosic material for use in the preparation of a smokable product, the sequence of steps of wetting relatively pure cellulosic material with nitrogen dioxide, drying the cellulosic material after so wetting it and then wetting it and then reacting the cellulosic material which has been wet with liquid nitrogen dioxide with gaseous nitrogen dioxide.
- 9. The method as claimed in claim 8 which comprises repeating the cycle a number of times until the desired level of conversion of methylol groups has been achieved.
- 10. The method as claimed in claim 9 in which the cycle is repeated until more than 90 percent of the methylol groups have been converted by oxidation.
- 11. In the method of rapidly and uniformly selectively oxidizing cellulosic material for use in the preparation of smokable product, the sequence of steps of wetting relatively cellulosic material with nitrogen dioxide, and then reacting the cellulosic material which has been wet with liquid nitrogen dioxide with gaseous nitrogen dioxide, the said reaction being carried out in a vessel partially filled with nitrogen dioxide whereby liquid nitrogen dioxide is in the bottom portion of the vessel and the space above the liquid nitrogen dioxide is filled with gaseous nitrogen dioxide and in which a strip of cellulosic material is continuously advanced for alternate immersion in the liquid and exposure to the vapor.
- 12. In the method of rapidly and uniformly selectively oxidizing cellulosic material for use in the preparation of a smokable product, the sequence of steps of wetting relatively pure cellulosic material with nitrogen dioxide, and then reacting the cellulosic material which has been wet with liquid nitrogen dioxide with gaseous nitrogen dioxide with gaseous nitrogen dioxide, the said reaction being carried out in an elongate tubular member having a number of spray positions, through which a strip of cellulosic material is pulled, passing gaseous nitrogen dioxide through the tubular member, and intermittently spraying the strip with nitrogen dioxide.
- 13. In the method of rapidly and uniformly selectiveLy oxidizing cellulosic material for use in the preparation of a smokable product, the sequence of steps of wetting relatively pure cellulosic material with nitrogen dioxide, and then reacting the cellulosic material which has been wet with liquid nitrogen dioxide with gaseous nitrogen dioxide, the said reaction is carried out by passing a strip of cellulosic material in a sinuous path about roller''s within a chamber saturated with hot gaseous nitrogen dioxide, refrigerating at least some of the rollers to condense gaseous nitrogen dioxide on the periphery thereof to wet strip as it is passed thereabout.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US77406468A | 1968-11-07 | 1968-11-07 |
Publications (1)
Publication Number | Publication Date |
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US3577994A true US3577994A (en) | 1971-05-11 |
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Application Number | Title | Priority Date | Filing Date |
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US774064A Expired - Lifetime US3577994A (en) | 1968-11-07 | 1968-11-07 | Method for producing smoking product of oxidized cellulosic material |
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US (1) | US3577994A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4034764A (en) * | 1975-08-15 | 1977-07-12 | Philip Morris Incorporated | Smoking material and method for its preparation |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2448892A (en) * | 1945-01-01 | 1948-09-07 | Eastman Kodak Co | Oxidation of cellulose |
US2537979A (en) * | 1949-11-25 | 1951-01-16 | Ethicon Suture Lab Inc | Oxidized cellulose suture |
US3461879A (en) * | 1967-06-30 | 1969-08-19 | Celanese Corp | Oxidized cellulose tobacco substitute composition |
-
1968
- 1968-11-07 US US774064A patent/US3577994A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2448892A (en) * | 1945-01-01 | 1948-09-07 | Eastman Kodak Co | Oxidation of cellulose |
US2537979A (en) * | 1949-11-25 | 1951-01-16 | Ethicon Suture Lab Inc | Oxidized cellulose suture |
US3461879A (en) * | 1967-06-30 | 1969-08-19 | Celanese Corp | Oxidized cellulose tobacco substitute composition |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4034764A (en) * | 1975-08-15 | 1977-07-12 | Philip Morris Incorporated | Smoking material and method for its preparation |
US4143666A (en) * | 1975-08-15 | 1979-03-13 | Philip Morris Incorporated | Smoking material |
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Legal Events
Date | Code | Title | Description |
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AS | Assignment |
Owner name: GALLAHER LIMITED, STATELESS Free format text: CHANGE OF NAME;ASSIGNOR:WATLING FIFTY-ONE LIMITED;REEL/FRAME:003858/0227 Effective date: 19810220 Owner name: GALLAHER LIMITED, STATELESS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HERGALL (1981) LIMITED;REEL/FRAME:003858/0222 Effective date: 19810306 Owner name: GALLAHER LIMITED Free format text: CHANGE OF NAME;ASSIGNOR:WATLING FIFTY-ONE LIMITED;REEL/FRAME:003858/0227 Effective date: 19810220 Owner name: GALLAHER LIMITED Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:HERGALL (1981) LIMITED;REEL/FRAME:003858/0222 Effective date: 19810306 |