US3482578A - Preparation of smoking product from cellulosic material and processes in treatment thereof - Google Patents
Preparation of smoking product from cellulosic material and processes in treatment thereof Download PDFInfo
- Publication number
- US3482578A US3482578A US745133A US3482578DA US3482578A US 3482578 A US3482578 A US 3482578A US 745133 A US745133 A US 745133A US 3482578D A US3482578D A US 3482578DA US 3482578 A US3482578 A US 3482578A
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- US
- United States
- Prior art keywords
- nitrogen dioxide
- liquid nitrogen
- cellulosic material
- cellulosic
- reaction
- 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.)
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Classifications
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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
- smoking products is meant to refer to and to include filler material embodied in cigarettes, cigars and for use with pipes and the like, and mixtures thereof with various proportions of tobacco and including cigarette papers and wrapers used in the preparation of such cigars and cigarettes, and it includes cigarettes, cigars and the like products manufactured with such filler materials and wrappers.
- 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 and 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 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
- nitrogen compounds, quinones, ketones, aldehydes and unsaturates as otherwise have a tendency to impart undesirable aroma and taste as the smoking product is burned.
- the product before or after reduction can be subjected to additional oxidation with a dilute peroxide solution as a means for eliminating further groupings 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, strontium, preferably introduced to form the salt internally in the cellulosic derivative for purposes of providing desired 3,482,578 Patented Dec. 9, 1969 ashing characteristics.
- mineralizing agents such as oxalates, glycolates, diglycolates, lactates, pivalates or tannates of such metals as calcium, magnesium, lithium, potassium, barium, strontium
- the desired internal introduction is achieved by first wetting the cellulosic derivative with metal cation in dilute solution for absorption into the cellulosic derivative followed by exposure to the acid anion in solution to precipitate the metal salt in situ in the cellulosic material.
- the treated cellulosic derivatives can be further processed to improve the burning, glow and smoking characteristics by formulation to include a potassium salt, such as potassium oxalate or by the addition of 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 l% 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 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 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, straw, alpha-cellulose, flax, fibrous carbohydrates, seaweed carbohydrates, bamboo filaments, cotton filaments, hemp, refined paper, rice paper, filamentous gums and even plants and 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.
- wood pulp, straw, alpha-cellulose, flax, fibrous carbohydrates, seaweed carbohydrates, bamboo filaments, cotton filaments, hemp, refined paper, rice paper, filamentous gums and even plants and 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 01f.
- the object is to achieve selective oxidation of the cellulosic material to convert methylol groups, especially the methylol groups containing the C carbon, to carboxyl groups, preferably with better than conversion. There is no objection to further oxidation beyond by conversion of secondary hydroxyl groups as on C and C to monoand diketo groups so long as cleavage does not occur.
- Selective oxidation without degradation of the cellulosic material is difi'icult 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 lesser 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 re action medium is rendered relatively non-electrically conductive so that the presence of water in the reaction me dium will not result in attack or degradation of the cellulosic material to be oxidized and wherein 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.
- Pro-treatment with anhydrous liquid nitrogen dioxide offers a number of plus factors in that all of the anhydrous liquid nitrogen dioxide need not be removed from the cellulosic material since the cellulosic material is subsequently to be reacted for selective oxidation in the presence of liquid nitrogen dioxide.
- such lignins, waxes, oils, resins and the like organic substances as are extracted from the cellulosic raw material by the anhydrous liquid nitrogen dioxide, can be precipitated from solution by addition or dilution of the treating liquid with small amounts of aqueous medium followed by cooling. This then results in a purified liquid nitrogen dioxide which finds use as the reaction medium for the subsequent selective oxidation of the treated cellulosic raw material. For this purpose, it is not necessary to make use of such amounts of anhydrous liquid nitrogen dioxide as in the selective oxidation reaction for suspension of the cellulosic material therein.
- anhydrous liquid nitrogen dioxide used in pre-treatment to dissolve out waxes, lignins, oils, resins and the like impurities is employed in an amount within the range of five to fifty times the weight of the cellulosic raw material and preferably in an amount within the range of ten to twenty-five times the weight of the cellulosic raw material.
- Impurities dissolved in the anhydrous liquid nitrogen dioxide are rendered insoluble by the addition of water in an amount within the range of 0.5% to by weight of the liquid nitrogen dioxide and preferably in an amount within the range of 1% to 4% by weight. Cooling to a temperature of 5 C. to 0 C. is then employed until an acid liquor settles out, containing the organic impurities. When precipitation for separation of impurities is effected by the addition of water in the amounts described, the supernatant liquid can be used without further modification as the oxidizing medium for selective oxidation of the treated cellulosic material.
- an evaporation stage is very desirable to reduce loss of nitrogen dioxide.
- the post-treatment is carried out with substantially anhydrous liquid nitrogen dioxide employed in an amount'corresponding to 1 part by volume anhydrous liquid nitrogen dioxide to 0.5 to 5 parts by volume of the oxidized cellulosic material and preferably at a temperature between 5 C. and C. Temperatures below 5 C. are less capable of dissolving the acid liquor.
- recovery of the liquid nitrogen'dioxide used in the described post-treatment of the oxidized cellulosic material can be efl ected by the addition of aqueous medium followed by cooling to precipitate out an acid liquor containing dissolved impurities, preferably by the addition of water in amounts previously described.
- the resulting supernatant liquid can be used to make up all or part of the oxidizing medium for the selective oxidation reaction of the cellulosic raw material.
- anhydrous nitrogen dioxide is truly anhydrous is such that it contains substantially less water than the nitrogen dioxide at the end of the oxidation reaction.
- EXAMPLE 1 A highly purified commercial grade of wood pulp is first treated with equal parts by weight of anhydrous liquid nitrogen dioxide to effect solution of soluble lignins, waxes, oils, resins and the like materials which are soluble in the liquid nitrogen dioxide.
- the anhydrous liquid nitrogen dioxide is separated from the pulp. After water washing, the pulp is then formed in the conventional manner into a thin paper and shredded into strands of about 2 mm. width. The shredded paper is then introduced into a reaction vessel with one hundred times its weight of liquid nitrogen dioxide. Reaction is carried out for six to eight days at a temperature of about 20 C. and atmospheric pressure until at least of the methylol groups on C have been oxidized. During the reaction, a slow stream of air is passed through the nitrogen dioxide to convert any nitric oxide by-product back into nitrogen dioxide.
- the liquid reactant is then drained from the reaction vessel and the remaining oxidized cellulosic derivative is warmed under mild vacuum to volatilize otf nitrogen dioxide and the derivative is then copiously washed with aqueous medium for the removal of water solubles.
- the anhydrous liquid nitrogen dioxide used in the pretreatment of the cellulosic raw material is diluted with about 2% by weight of water and cooled to 5 C. to precipitate out lignins, waxes and the like insolubilized components in the form of an acid liquor.
- EXAMPLE 2 A highly purified Wood pulp is fabricated into thin paper, formed 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 pulp to 25 parts by weight of the liquid oxidizing medium. The reaction medium is heated to a temperature within the range of 25 to 40 C. and the reaction is carried out under a pressure of about 35 to 50 p.s.i. for 24 hours.
- the liquid oxidizing medium is separated from the oxidized cellulose reaction product and then the latter is treated with a volume of anhydrous liquid nitrogen dioxide corresponding to one-half the weight of the oxidized cellulosic material to dissolve out the solubilized lignins, waxes, oils and resins and their oxidized reaction products and to wash out the spent nitrogen dioxide.
- the anhydrous liquid nitrogen dioxide is separated from the treated oxidized cellulosic derivative and the latter is heated to volatilize 01f nitrogen dioxide and then it is washed copiously with water to remove water solubles, or preferably used forthwith in further treatment with mineralizing solutions.
- the anhydrous liquid nitrogen dioxide separated in the post-treatment of the oxidized cellulosic material can be diluted with a small amount of water within the range of 2% to 5% by weight and cooled to 5 C. whereby lignins, oils, waxes and resins dissolved in the anhydrous liquid nitrogen dioxide will be precipitated as an acid liquor to enable separation.
- the separated anhydrous liquid nitrogen dioxide can be used to form a part of the reaction medium used in the selective oxidation of more cellulosic raw material.
- EXAMPLE 3 Purified wood pulp is given a pre-treatment with an equal volume of anhydrous liquid nitrogen dioxide to dissolve out lignins, waxes, oils, resins and the like soluble materials.
- the anhydrous liquid nitrogen dioxide is separated from the treated pulp and diluted with 2% by weight of water and cooled to -5 C. to precipitate out waxes, lignins, oils and resins which separate as an acid liquor.
- the supernatant liquid from which the insolubles have been removed is then introduced with sufficient amounts of additional liquid nitrogen dioxide containing about 2% by weight of water into a reaction vessel with the pre-treated wood pulp in amounts corresponding to 1 part by weight of wood pulp to parts by weight of the liquid reaction medium.
- the oxidation reaction is carried out at a temperature of about 25 to C.
- the liquid reaction medium is drained from the reaction vessel for separation from the oxidized cellulosic material.
- the treated cellulosic material is subjected to a posttreatment with an equal volume of anhydrous liquid nitrogen dioxide further to dissolve out lignins, waves, oils and resins remaining in the cellulosic material and oxidized reaction products which may become soluble in the anhydrous liquid nitrogen dioxide,
- the anhydrous liquid nitrogen dioxide is sep arated from the cellulosic oxidation reaction product and it may be diluted with 2% by weight of water and cooled to -5 C. to precipitate out dissolved impurities extracted from the oxidized cellulosic material.
- the supernatant liquid from the post-treatment can be used as a part of the liquid oxidizing medium employed in the selective oxidation reaction of more cellulosic material.
- the post-treated oxidized cellulosic material is then heated to elevated temperature to volatilize gaseous oxides of nitrogen and then the material is copiously washed with water to remove water solubles, if desired.
- the product resulting from the treatments described in Examples 1 to 3 will exhibit improved smoking characteristics from the standpoint of taste and aroma as compared to the cellulosic material prior to the described treatments. It is preferred, however, further to process the oxidized cellulosic materials in the manner described in the aforementioned copending applications'to effect one or more additional processing steps, such as reduc tion with a borohydride to convert residual nitro groups to amino groups and/ or conversion of residual quinone,
- ketone, aldehyde and unsaturate groups and/ or to introduce one or more agents, such as mineralizing agents in the form of calcium oxalate and the like, smoke generating agents, neutralizing agents such as ammonium or amine salts, glow supporting agents and burning agents such as salts of potassium, cesium or rubidium, coloring agents and the like, all as described in the aforementioned copending applications.
- agents such as mineralizing agents in the form of calcium oxalate and the like, smoke generating agents, neutralizing agents such as ammonium or amine salts, glow supporting agents and burning agents such as salts of potassium, cesium or rubidium, coloring agents and the like, all as described in the aforementioned copending applications.
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Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US74513368A | 1968-07-16 | 1968-07-16 |
Publications (1)
Publication Number | Publication Date |
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US3482578A true US3482578A (en) | 1969-12-09 |
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ID=24995386
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US745133A Expired - Lifetime US3482578A (en) | 1968-07-16 | 1968-07-16 | Preparation of smoking product from cellulosic material and processes in treatment thereof |
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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 US745133A patent/US3482578A/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 |
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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 |