US3478752A - Cellulosic smoking product and method in the preparation of same - Google Patents
Cellulosic smoking product and method in the preparation of same Download PDFInfo
- Publication number
- US3478752A US3478752A US745134A US3478752DA US3478752A US 3478752 A US3478752 A US 3478752A US 745134 A US745134 A US 745134A US 3478752D A US3478752D A US 3478752DA US 3478752 A US3478752 A US 3478752A
- Authority
- US
- United States
- Prior art keywords
- reaction
- cellulosic
- weight
- cellulosic material
- nitrogen dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
Definitions
- smoking products is meant to refer to and to include filler material embodied in cigaretes, cigars and for use with pipes and the like, and mixtures thereof with various proportions of tobacco and including cigarette papers and wrappers used in the preparation of such cigars and cigarettes, and it includes cigarettes, Cigars and the like products manufactured with such filler materials and wrapper.
- a smoking product suitable for use in cigarettes, cigars or with pipes wherein the smoking product is prepared of relatively pure cellulosic materials subjected to selective oxidation with liquid nitrogen dioxide to convert preferably more than 90% of the methylol groups in the cellulosic molecule to yield a product which can be referred to as an oxycellulose or polyuronic acid.
- the oxidation reaction product is further processed by removal of liquid nitrogen dioxide by vaporization preferably by washing the oxidized cellulosic product with water and/or alcohol and/ or acetone or other solvent for removal of solubilized foreign material, including oils, waxes, latices and the like, which contribute undesirably to the taste and aroma when used as a smoking product in accordance with the practice of this invention.
- the oxidized and cleansed cellulosic derivative is further processed by a reduction reaction with borohydrides of an alkali or alkaline earth metal such as sodium or lithium borohydride for reduction of such nitrogen compounds, quinones, ketones, aldehydes and unsaturates as otherwise have a tendency to impart undesirable aroma and taste as the smoking product is burned.
- borohydrides of an alkali or alkaline earth metal such as sodium or lithium borohydride
- the product before or after reduction can be subjected to additional oxidation with a dilute peroxide solution as a means for eliminating further groupings United States Patent 0 3,478,752 Patented Nov. 18, 1969 ice which impart undesirable aroma or taste to the product.
- the resulting smoking product is then formulated with mineralizing agents such as oxalates, glycolates, diglycolates, lactates, pivalates or tannates of such metals as calcium, magnesium, lithium, potassium, barium or strontium, preferably introduced to form the salt internally in the cellulosic derivative for purposes of providing desired ashing characteristics.
- mineralizing agents such as oxalates, glycolates, diglycolates, lactates, pivalates or tannates of such metals as calcium, magnesium, lithium, potassium, barium or strontium
- the treated cellulosic derivatives can be further proc essed to improve the burning, glow and smoking characteristics by formulation to include a potassium salt, such as potassium oxalate or by the addition or rubidium or cesium in the form of compounds thereof in amounts within the range of 0.1% to 10% by weight but preferably less than 1% by weight, as described in the copending application Ser. No. 623,528, filed Mar. 16, 1967, and entitled Smoking Products and Process for Their Manufacture.
- a potassium salt such as potassium oxalate or by the addition or rubidium or cesium in the form of compounds thereof in amounts within the range of 0.1% to 10% by weight but preferably less than 1% by weight
- Smoke generators for improving the appearance of the smoke generated by the product can be introduced as by the introduction of various fatty acids, esters, ethers and the like and the aroma and pH characteristics can be achieved by the addition of volatilizable alkalyzing material such as ammonium oxalate, nicotine and the like.
- the resulting product is suitable for use as a smoking product alone or in admixture with tobacco to produce a smoking product having good taste, good aroma and good appearance.
- the features of this invention reside in the conversion of a cellulosic material to a product which is desirable for use in smoking and which finds wide acceptance as a smoking product from the standpoint of taste, aroma, appearance, burning characteristics and relative absence of harmful ingredients or undesirable reaction products.
- cellulosic raw material use can be made of various forms of cellulose, such as wood pulp, alphacellulose, flax, fibrous carbohydrates, straw, seaweed carbohydrates, bamboo filaments, cotton filaments, hemp, refined paper, rice paper, filamentous gums and even plants or plant leaves and the like fibrous materials from which non-carbohydrate components have been separated, all of which is hereinafter referred to as cellulosic material.
- cellulose such as wood pulp, alphacellulose, flax, fibrous carbohydrates, straw, seaweed carbohydrates, bamboo filaments, cotton filaments, hemp, refined paper, rice paper, filamentous gums and even plants or plant leaves and the like fibrous materials from which non-carbohydrate components have been separated, all of which is hereinafter referred to as cellulosic material.
- Purified cellulose is unsatisfactory for use as a smoking product from the standpoint of taste, aroma and burning characteristics. This is believed to stem from the acids and aldehydes that are evolved upon pyrolysis of the cellulose. It has been found that many of the defects of pure cellulose can be greatly alleviated by conversion of the methylol groups to carboxyl groups to produce a product which readily pyrolyzes with complete breakup of the cellulosic molecule into Water vapor, and oxidation products of carbon, such as carbon dioxide and low molecular weight compounds which readily volatilize.
- the object is to achieve selective oxidation of the cellulosic material to convert methylol groups, primarily the methylol groups containing the C carton, to carboxyl groups, with better than 30% and preferably with better than 90% conversion. There is no objection to further oxidation beyond 100% by conversion of secondary hydroxyl groups as on C and C to monoand diketo groups so long as cleavage does not occur.
- Selective oxidation of cellulosic material without degradation of the cellulosic material is difiicult to achieve with oxidizing agents such as peroxides, hypochlorites, permanganates, dichromates and the like.
- oxidizing agents such as peroxides, hypochlorites, permanganates, dichromates and the like.
- such selective oxidation for use in preparation of a smoking product from such cellulosic materials can be achieved with nitrogen dioxide.
- liquid nitrogen dioxide yields an oxidation reaction that has the desired selectivity and that complete wetting of the cellulosic materials can be achieved almost instantaneously with liquid nitrogen dioxide with the result that the oxidation reaction takes place substantially uniformly throughout the cross-section of the cellulosic material and at a much more rapid rate whereby a more uniformly and more completely oxidized product is obtained in less time.
- liquid nitrogen dioxide when used in the proportions most suitable for the practice of this invention, operates as a quench immediately to dissipate heat generated by the exothermic reaction so as to avoid the formation of hot spots or non-uniformity in the reactions.
- the formulation to include aqueous medium in the reaction of liquid nitrogen dioxide operates also to adjust the specific gravity of the reaction medium in the direction towards the specific gravity of the cellulosic material whereby suspension of the cellulosic material in the reaction medium is easier to achieve and maintain. The result is a more rapid and uniform oxidation reaction of the cellulosic material to produce a better product at a more rapid rate.
- the concepts of this invention are addressed to the further discovery that when oxygen, or a molecular oxygen, or a molecular oxygen containing gas, such as air or oxygen enriched air, is bubbled through, or otherwise introduced into the reaction medium formulated of liquid nitrogen dioxide, with or without water, during the selective oxidation of the cellulosic material, and oxidized cellulosic material more desirable for use as a smoking product is obtained and the rate of oxidation of the cellulosic material is noticeably increased.
- oxygen, or a molecular oxygen, or a molecular oxygen containing gas such as air or oxygen enriched air
- the oxygen containing gas is capable of entering into the oxidation reaction of the cellulosic material in the presence of liquid nitrogen dioxide to enhance the desired selective oxidation.
- the oxygen is effective to convert nitrous acid that is formed to nitric acid in situ in the reaction and to reconvert nitric oxide that is formed to nitrogen dioxide, with corresponding reduction in undesirable by-product formation.
- One or more of the above reactions can take place markedly to improve the reaction rate and product.
- the amount of oxygen introduced or the feed flow rate is not critical since only a small amount of nitric oxide is produced at a fairly slow rate.
- the oxygen in the form of pure oxygen or air, is introduced in the weight ratio of 1 part by weight oxygen or 5 parts by weight air per 5 parts by weight of cellulosic material and it is preferred to introduce an amount of oxygen or air up to ten times the minimum or up to 10 parts by weight of oxygen or parts by weight of air per 5 parts by weight cellulosic material, over the total time of the reaction.
- Introduction of the oxygen containing gas can be made through an inlet in the bottom portion of the reaction vessel with distributors for dispersing the gas throughout the cross-section of the reaction medium whereby the gas rises in fine bubbles through the reaction medium and the cellulosic material contained therein.
- EXAMPLE 1 A highly purified commercial I grade of wood pulp, formed into thin paper, is shredded into strands of about 2 mm. width and immersed in approximately one hundred times its weight of liquid nitrogen dioxide. Reaction is carried out for six to eight days while maintaining the temperature of the reaction medium at about 20 C. and with the introduction of air through an inlet in the bottom of the reaction vessel covered with a screen of porous polyethylene for distribution of the air throughout the cross-section of the reactor and through which the air rises as fin-e bubbles. Air is introduced in an amount to provide parts of weight of air perpart by weight of cellulosic material until the reaction is completed (better than 90% conversion of methylol groups).
- the liquid reactant is then drained from the reaction vessel and the oxidized cellulosic derivative is washed with aqueous medium for removal of solubles and nitrogen dioxide from the oxidized product.
- EXAMPLE 2 A highly purified wood pulp, fabricated into a thin paper, is shredded into strands of about 2 mm. width and loaded into a pressure vessel with liquid nitrogen dioxide containing 2% by weight water and in which the liquid reaction medium is introduced in the ratio of 1 part by weight of pulp to 25 parts by weight of the liquid oxidizing medium.
- the reaction medium is heated to a temperature within the range of 40 to 45 C., and the reaction is carried out at its autogeneous pressure of about 50 p.s.i.
- one-fifth of the reaction medium is bled from the system and replaced with anhydrous nitrogen dioxide to compensate for the amount of water which is released during the oxidation reaction so as to maintain the water content in the reaction medium at about 2% by weight.
- reaction cycle which takes about 20 hours, oxygen is bubbled through the reaction mass to a total amount corresponding to about 1 part by weight of oxygen to 5 parts by weight of the cellulosic material.
- the oxygen is shut oil and the liquid reaction medium is drained from the reactor and the oxidized cellulose is first rinsed With anhydrous liquid nitrogen dioxide and then dried and then rinsed with water to remove solubles and residualv nitrogen acids.
- the cellulosic material is oxidized by an amount greater than 90%, when calculated on the basis of conversion of the C methylol group;
- EXAMPLE 3 Alpha-cellulose is suspended in a pressure vessel with one hundred times its weight of liquid nitrogen dioxide containing 1.5% by weight of water. The reaction medium within the vessel is maintained at 20 C.
- the product resulting from Examples 1 to 3 will be found to have improved smoking characteristics from the standpoint of taste and aroma, as compared to the cellulosic material prior to the described selective oxidation treatment.
- a mineralizing agent represented by calcium oxalate
- liquid oxidizing medium is present in the ratio of 5 to 1000 parts by weight of the liquid oxidizing medium per 1 part by weight of the cellulosic material.
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US74513468A | 1968-07-16 | 1968-07-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3478752A true US3478752A (en) | 1969-11-18 |
Family
ID=24995392
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US745134A Expired - Lifetime US3478752A (en) | 1968-07-16 | 1968-07-16 | Cellulosic smoking product and method in the preparation of same |
Country Status (1)
Country | Link |
---|---|
US (1) | US3478752A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3640285A (en) * | 1966-11-21 | 1972-02-08 | Sutton Res Corp | Cigarette paper and method for preparation |
US3908671A (en) * | 1973-12-12 | 1975-09-30 | Brown & Williamson Tobacco | Thermoplastic cigarette wrapper |
US4034764A (en) * | 1975-08-15 | 1977-07-12 | Philip Morris Incorporated | Smoking material and method for its preparation |
WO1993016110A1 (en) * | 1992-02-11 | 1993-08-19 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing polysaccharide-based plycarboxylates |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3007917A (en) * | 1953-04-02 | 1961-11-07 | Leon Simon | Production of oxycellulose material |
US3012412A (en) * | 1957-10-09 | 1961-12-12 | Muffly Glenn | Refrigerator humidity control |
CA702918A (en) * | 1965-02-02 | V. Kirkland Earl | Tobacco substitute | |
US3280636A (en) * | 1964-06-02 | 1966-10-25 | Victor T Tomberg | Bio-monitoring system |
US3309684A (en) * | 1964-06-09 | 1967-03-14 | Elliott H Kahn | Bio-instrumentation monitoring and display device |
US3343536A (en) * | 1964-08-27 | 1967-09-26 | United Aircraft Corp | Space suit heat exchanger with liquid boiling point control |
US3364200A (en) * | 1960-03-28 | 1968-01-16 | Johnson & Johnson | Oxidized cellulose product and method for preparing the same |
-
1968
- 1968-07-16 US US745134A patent/US3478752A/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA702918A (en) * | 1965-02-02 | V. Kirkland Earl | Tobacco substitute | |
US3007917A (en) * | 1953-04-02 | 1961-11-07 | Leon Simon | Production of oxycellulose material |
US3012412A (en) * | 1957-10-09 | 1961-12-12 | Muffly Glenn | Refrigerator humidity control |
US3364200A (en) * | 1960-03-28 | 1968-01-16 | Johnson & Johnson | Oxidized cellulose product and method for preparing the same |
US3280636A (en) * | 1964-06-02 | 1966-10-25 | Victor T Tomberg | Bio-monitoring system |
US3309684A (en) * | 1964-06-09 | 1967-03-14 | Elliott H Kahn | Bio-instrumentation monitoring and display device |
US3343536A (en) * | 1964-08-27 | 1967-09-26 | United Aircraft Corp | Space suit heat exchanger with liquid boiling point control |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3640285A (en) * | 1966-11-21 | 1972-02-08 | Sutton Res Corp | Cigarette paper and method for preparation |
US3908671A (en) * | 1973-12-12 | 1975-09-30 | Brown & Williamson Tobacco | Thermoplastic cigarette wrapper |
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 |
WO1993016110A1 (en) * | 1992-02-11 | 1993-08-19 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing polysaccharide-based plycarboxylates |
US5541316A (en) * | 1992-02-11 | 1996-07-30 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of polysaccharide-based polycarboxylates |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2170107A (en) | Process for bleaching tobacco | |
KR100385585B1 (en) | Steam rupture method of tobacco stem | |
US4143666A (en) | Smoking material | |
US3608560A (en) | Smokable product of oxidized cellulosic material | |
US2274649A (en) | Process for bleaching tobacco | |
US4079742A (en) | Process for the manufacture of synthetic smoking materials | |
SU493951A3 (en) | Method for increasing filling capacity of cut tobacco | |
US3640285A (en) | Cigarette paper and method for preparation | |
US2429567A (en) | Denicotinizing tobacco | |
US3478752A (en) | Cellulosic smoking product and method in the preparation of same | |
US3575177A (en) | Smoking product of cellulosic material subjected to a nitrogen dioxide oxidation and a mild oxidation with peroxide | |
US3447539A (en) | Oxidized cellulose smokable product including ashing ingredient | |
US3380458A (en) | Method for producing a cigarette with low tar yield | |
US3478751A (en) | Method for preparation of smoking product with selective reduction following selective oxidation | |
US3516416A (en) | Method of preparing a smokable material | |
US3556110A (en) | Method for producing a smoking product of cellulosic material | |
CN110477439B (en) | Sugar ester essence for heating non-burning cigarette, tobacco sheet and non-burning cigarette | |
US3491766A (en) | Preparation of smoking product of cellulose derivatives and process | |
US3643668A (en) | Oxidized cellulose smoking product composition | |
US3482578A (en) | Preparation of smoking product from cellulosic material and processes in treatment thereof | |
US3512536A (en) | Smoking material of oxidized cellulosic material and method of making same | |
US3556109A (en) | Method of making a smoking product of oxidized cellulosic materials containing ashing ingredients | |
US3608559A (en) | Process of introducing ashing ingredients into oxidized cellulose material intended as smoking product and product obtained thereby | |
US3612063A (en) | Oxidized cellulose smoking product | |
US3577994A (en) | Method for producing smoking product of oxidized cellulosic material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
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 |