US3516416A - Method of preparing a smokable material - Google Patents
Method of preparing a smokable material Download PDFInfo
- Publication number
- US3516416A US3516416A US745221A US3516416DA US3516416A US 3516416 A US3516416 A US 3516416A US 745221 A US745221 A US 745221A US 3516416D A US3516416D A US 3516416DA US 3516416 A US3516416 A US 3516416A
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- United States
- Prior art keywords
- nitrogen dioxide
- reaction
- cellulosic material
- cellulosic
- liquid nitrogen
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- 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
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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
Definitions
- a method of forming a smoking product formed of cellulosic materials is disclosed in which one of the preliminary steps includes the selective oxidation of the cellulosic material with liquid nitrogen dioxide under conditions to effect substantial conversion of the C methylol groups.
- the nitrogen dioxide used in the oxidation is present in a ratio of 5 to 1000 parts by weight to one part of the cellulosic material and the reaction is carried out at a temperature of between and 65 C.
- the moist nitrogen dioxide is first rinsed out of the cellulose material with dry nitrogen dioxide.
- smoking products refers to and includes filler materials used in the production of cigarettes, cigars and for filling pipes and mixtures thereof with various proportions of tobacco and cigarette papers and wrappers used in the preparation of and which are burned during the smoking of sugh cigarettes, cigars and the like, and it includes the cigarettes, cigars and the like products manufactured thereof.
- the oxidation reaction product is further processed by removal of liquid nitrogen dioxide by vaporization and copious washing of the oxidized product with water and/ or alcohol for removal of solubilized foreign materials and decomposition of nitrites and nitrates, and/or treatment with solvents such as acetone for removal of oils, waxes, latices and the like which impart undesirable taste and odor when the product is 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 a hydride or borohydride of an alkali or alkaline earth metal, such as sodium or lithium borohydride, for reducing groupings which otherwise have a tendency to evoke unpleasant odors or taste as the product is burned.
- a reduction reaction with a hydride or borohydride of an alkali or alkaline earth metal, such as sodium or lithium borohydride, for reducing groupings which otherwise have a tendency to evoke unpleasant odors or taste as the product is burned.
- the product before or after being processed by the described reduction reaction can be subjected to oxidation with peroxide solutions as a means for eliminating further components which contribute undesirable aroma or taste to the burning product.
- the resulting oxidized and reduced cellulosic material is then formulated with mineralizing agents in the form of oxalates, glycolates, diglycolates, lactates, pivalates or tannates of such metals as calcium, magnesium, lithium, potassium, barium or strontium, preferably introduced internally in the cellulosic derivative for purposes of providing desirable ashing characteristics, although beneficial ashing characteristics of limited utility can be achieved by external application of such mineralizing agents.
- mineralizing agents in the form of oxalates, glycolates, diglycolates, lactates, pivalates or tannates of such metals as calcium, magnesium, lithium, potassium, barium or strontium, preferably introduced internally in the cellulosic derivative for purposes of providing desirable ashing characteristics, although beneficial ashing characteristics of limited utility can be achieved by external application of such mineralizing agents.
- the desired internal application of the mineralizing agents can be achieved by first wetting the fibers with a solution of the desired metallic ion for absorption into the cellulosic derivative, followed by exposure to a solution of the desired anion whereby the corresponding metal salt forms in situ within the cellulosic material.
- a potassium salt such as potassium oxalate
- rubidium or cesium compounds in amounts within the range of 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.
- Smoke generators can be added to increase the visual effect of the smoking product when burned.
- the resulting product is suitable for use as a smoking product alone or in admixture with tobacco to produce a smoking product having better taste and less undesirable ingredients.
- This application will be addressed to a process for treatment of the cellulosic material with liquid nitrogen dioxide to effect selective oxidation of methylol groups to carboxyl groups in forming an oxidized cellulosic derivative suitable for use in the preparation of a smoking product.
- 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 harmul ingredients or combustion products.
- the cellulosic raw material use can be made of the various forms of cellulose, such as wood pulp, flax, straw, fibrous carbohydrates, seaweed carbohydrates, bamboo filaments, cotton filaments, filamentous gums, rayon, a1- phacellulose, refined paper, hemp, and even plants and plant leaves and the like fibrouse materials in which the cellulose components have been separated and purified. It is preferred to make use of a purified cellulose from which the various sugars, proteins, chlorophylls, colors, lignins, oils, waxes, resins and latices have been removed since these materials lend considerably to undesirable odors and taste from the smoking product.
- cellulose such as wood pulp, flax, straw, fibrous carbohydrates, seaweed carbohydrates, bamboo filaments, cotton filaments, filamentous gums, rayon, a1- phacellulose, refined paper, hemp, and even plants and plant leaves and the like fibrouse materials in which the cellulose components have been separated and purified. It is preferred to make use of a purified cellulose from which the various
- Purified cellulose is unsatifactory by itself for use in smoking, at least from the standpoint of taste, smell and burning characteristics. These undesirable properties are believed to stem from acids and aldehydes that are evolved upon pyrolysis of the cellulosic material. It has been found that these defects in pure cellulose can be greatly alleviated by conversion of the free methylol groups to carboxyl groups to produce a product which readily pyrolyzes by complete breakup of the molecule into water vapor and oxidation products of carbon such as carbon dioxide and low molecular weight compounds which readily volatilize.
- the object of this invention is to achieve a selective oxidation of the cellulosic material or carbohydrate to convert free methylol groups, especially the methylol group on the C carbon, to varboxyl groups, preferably with better than conversion.
- free methylol groups especially the methylol group on the C carbon
- varboxyl groups preferably with better than conversion.
- oxidizing agents such as peroxides, periodic acid, hypochlorites, permanganates, dichromates and the like.
- selective oxidation for use in the preparation of smoking products from such cellulosic materials or carbohydrates hereinafter referred to as cellulosic materials, can be achieved with nitrogen dioxide.
- Gaseous nitrogen dioxide has been found to be impractical for this purpose for the reason that the oxidation reaction is extremely slow and it is commercially impractical to stock the cellulosic material so as to permit complete access of the gaseous nitrogen dioxide, with the result that it is difficult to provide the desired rate of conversion and conversion is not uniform throughout the cellulosic material, thereby resulting in an undesirable product.
- the oxidation reaction is an exothermic reaction that is accompanied by the generation of heat which is not easily dissipated with gaseous nitrogen dioxide. As a result, hot spots can develop which lead to degradation and even confiagration of the cellulosic material.
- the acid liquor produced is relatively high boiling and as reaction proceeds, the carbohydrate is subjected to increasing concentration of adsorbent acid liquor which is degradative rather than adsorbed nitrogen dioxide which would not be degradative.
- liquid nitrogen dioxide gives an oxidation reaction that has the desired selectivity and that complete wet-out of the cellulosic material is achieved almost instantly whereby the oxidation reaction can take 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.
- liquid nitrogen dioxide when used in proportions suitable for the practice of this invention, operates as a quench immediately to dissipate heat generated by any localized exothermic reactions.
- the oxidation of preferably purified cellulosic materials is carried out by suspension of the cellulosic material in liquid nitrogen dioxide in the ratio of 1 part by weight cellulosic material to to 1000 parts by weight of liquid nitrogen dioxide and preferably 1 part by weight of cellulosic material to 25 to 50 parts by weight of liquid nitrogen dioxide, often referred to as N 0
- the reaction is carried out at a temperature within the range of to 65 C. At a temperature below 15 C., the rate of reaction is too slow for commercial practice and excessive amounts of hydrolytic cleavage is experienced. At reaction temperatures in excess of 65 C., the oxidation reaction becomes less specific and undesirable side reactions take place to produce excessive amounts of un desirable byproducts.
- reaction temperature which is as high as practical but other factors limit the use of high temperatures.
- use is made of a temperature above C. and preferably within the range of to 45 C.
- reaction temperatures above 21 C. it is necessary to make use of a closed pressure system since the liquid nitrogen dioxide boils at 213 C. at atmospheric pressure.
- the pressure can vary from the vapor pressure of the liquid nitrogen dioxide at reaction temperature up to high pressures consistent with the ability of the apparatus to withstand such pressures. It is preferable, in batch processing, to permit a vapor space to exist, although this is generally not so in continuous processing of slurried material.
- the effects of temperature on pressure and reaction rate of shredded paper are found to be as follows. For example, at 21 C., one atmosphere of pressure is generated and four to eight days are required for conversion in a system containing 1 part by weight of cellulosic material per 50 parts by weight of liquid nitrogen dioxide. At 40 C., the pressure becomes 30 to 50 p.s.i., and better than 90% conversion can be achieved with the same materials in one day. At a temperature of 50 C., the pressure becomes 60 to 75 p.s.i., and the time is reduced to four to five hours. A shorter reaction time suitable for continuous processes can be achieved by operating at temperatures within the range of 45 to 65 C. and at autogenous pressure or higher.
- EXAMPLE 1 A highly purified commercial grade of wood pulp in the form of thin paper is shredded into strands of about 2 mm. width and immersed in approximately one hundred times its weight of liquid nitrogen dioxide at 20 C. Immersion continues for about five to ten days at this temperature until testing indicates that the carboxyl level of 92% to expressed as polyanhydroglucuronic acid content, is achieved. The testing involves washing in aqueous alcohol, drying, dissolving in excess standard alkali and then titrating back with standard acid solution. The alkali consumption is expressed as a percent content of polyanhydroglucuronic acid in the salt-free, water-free carbohydrate. It should be noted that a virtue of this method is that it measures by hydrolysis those carboxyl groups which may otherwise be temporarily hidden in the form of lactones and internal esters.
- the shredded material is then substantially freed of excess nitrogen dioxide by means of a warm stream of dry air. This is followed by soaking the oxidized cellulosic material in aqueous alcohol containing about by Weight oxalic acid for 15 to 30 minutes. Any carbonates, nitrates and nitrites of calcium, present in the oxidized cellulosic material, are thus converted to calcium oxalate, which is interspersed within the oxidized cellulosic material. In this form, the calcium oxalate functions as a mineralizing agent which contributes to the ash of the smoking product.
- the content of nitrite and nitrate by-products of the nitrogen dioxide reaction is reduced by hydrolysis during this soaking period and by discarding the solution after it has been drained from the cellulosic derivative.
- the treated cellulosic derivative can be subjected to an extraction by an organic solvent, such as acetone, to remove undesirable odor producing materials from the oxidized cellulosic product.
- an organic solvent such as acetone
- the cleansed and oxidized cellulosic material represents material more suitable for use as a smoking product than the purified cellulosic raw material
- EXAMPLE 2 With reference now to the flow diagram, dry cellulose is loaded into the reactor 1 through a door (not shown) at the top. A partial vacuum is drawn on the reactor by means of a water jet. A weighed amount of liquid nitrogen dioxide is transferred from the liquid nitrogen dioxide storage tank 2 for introduction into the reactor by means of a spray pipe 3 to counteract the heat of absorption of the nitrogen dioxide vapors. During transfer, the pressure equalizing line from the reactor to the storage tank is kept open until transfer is complete. An amount of liquid nitrogen dioxide corresponding to thirty times the weight of cellulosic material is introduced into the reaction system and this amount of liquid nitrogen dioxide is constantly recirculated from the drain 4 at the bottom of the reactor to the spray 3 at the top via the gear pump 5.
- the reaction mixture is heated and maintained at reaction temperature of 40 C. by a heat exchange fluid circulated from a reservoir 6 through the jacket 7 about the reactor and a vapor pressure of about 35 to 50 p.s.i.g. is conserved within the reactor.
- Reaction is continued for approximately two days to effect conversion of 95% to 98% of the methylol groups.
- the contents are cooled by circulation of cold fluid through the jacket and the pressure equalizing line is opened so that the liquid nitrogen dioxide can be drained from the reactor for transfer to the auxiliary storage tank 8.
- the reaction mass in the reactor is rinsed first with dry liquid nitrogen dioxide from storage with return of the drainage to storage.
- the reactor is isolated from the system and residual nitrogen dioxide is removed first by vaporization under vacuum and then by flushing with air circulated through the reactor.
- the vapors are drawn from the reactor by means of a jet ejector and the nitrogen dioxide is removed from the vapors by scrubbing with alkali.
- the converted cellulosic material may then be transferred from the reactor for subsequent purposes, such as solvent extraction, peroxide treatment, reduction with borohydride, mineralizing with calcium oxalate, modification with potassium salts or salts of rubidium or cesium to adjust the burning rate, and modification for pH control, smoke generation and odor, and the like processing steps, as previously described and as more fully described in the aforementioned copending applications.
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
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- 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 |
---|---|---|---|
US74522168A | 1968-07-16 | 1968-07-16 |
Publications (1)
Publication Number | Publication Date |
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US3516416A true US3516416A (en) | 1970-06-23 |
Family
ID=24995763
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US745221A Expired - Lifetime US3516416A (en) | 1968-07-16 | 1968-07-16 | Method of preparing a smokable material |
Country Status (1)
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US (1) | US3516416A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3666750A (en) * | 1969-12-15 | 1972-05-30 | Johnson & Johnson | Hemostatic material |
US4034764A (en) * | 1975-08-15 | 1977-07-12 | Philip Morris Incorporated | Smoking material and method for its preparation |
US9635881B2 (en) | 2012-04-10 | 2017-05-02 | Swedish Match North Europe Ab | Smokeless tobacco composition comprising non-tobacco fibers and a method for its manufacture |
US20180179301A1 (en) * | 2016-12-27 | 2018-06-28 | Zhejiang University Of Science And Technology | Method of Preparing Oxidized Starch Haemostatic Material |
US10390557B2 (en) | 2013-10-09 | 2019-08-27 | Swedish Match North Europe Ab | Oral smokeless tobacco composition comprising liberated, delignified tobacco fibres and a method for its manufacture |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA702918A (en) * | 1965-02-02 | V. Kirkland Earl | Tobacco substitute | |
US3364200A (en) * | 1960-03-28 | 1968-01-16 | Johnson & Johnson | Oxidized cellulose product and method for preparing the same |
-
1968
- 1968-07-16 US US745221A patent/US3516416A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA702918A (en) * | 1965-02-02 | V. Kirkland Earl | Tobacco substitute | |
US3364200A (en) * | 1960-03-28 | 1968-01-16 | Johnson & Johnson | Oxidized cellulose product and method for preparing the same |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3666750A (en) * | 1969-12-15 | 1972-05-30 | Johnson & Johnson | Hemostatic material |
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 |
US9635881B2 (en) | 2012-04-10 | 2017-05-02 | Swedish Match North Europe Ab | Smokeless tobacco composition comprising non-tobacco fibers and a method for its manufacture |
US10390557B2 (en) | 2013-10-09 | 2019-08-27 | Swedish Match North Europe Ab | Oral smokeless tobacco composition comprising liberated, delignified tobacco fibres and a method for its manufacture |
US20180179301A1 (en) * | 2016-12-27 | 2018-06-28 | Zhejiang University Of Science And Technology | Method of Preparing Oxidized Starch Haemostatic Material |
US10618981B2 (en) * | 2016-12-27 | 2020-04-14 | Hangzhou Singclean Medical Products Co., Ltd. | Method of preparing oxidized starch haemostatic 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 |