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

Definitions

• the process comprising the acid hydrolysis of the beet pulp to release beet pectins, and at least an alkaline earth treatment thereafter to cause cross-linking of the pectins and forming a binding agent for the exhausted beet matrix.
• a demethylation step on the released pectins is carried out prior to the cross-linking reaction.
• the final slurry is then dried by known procedures to form a smoking product.
• the present invention relates to a new smoking material whereby a tailored smoking product is made from an inexpensive non-tobacco natural material and which is also free of many undesirable components and properties normally present in tobacco or earlier proposed tobacco substitutes.
• the new smoking material which may replace all or at least part of tobacco parts used in cigarettes or the like is derived from beet pulp. More particularly, it is obtained as a by-product of sugar beet processing after the sugar fractions have been extracted from the beets.
• the final product is a good tobacco substitute by virtue of its very low cost. It may be used alone or as a blending agent with tobacco. Additionally it can be used to give substantially unlimited control over pyrolysis and the pyrolysis products.
• exhausted or waste beet pulp in the form of dried beet cossettes are slurried in an aqueous medium with pectin releasing agents capable of hydrolyzing and solubilizing at least a portion of the pectinaceous content of the beets thereby releasing pectins from the beet pulp.
• the beet mixture at this point may be refined by comminuting the hydrolyzed product in order to shorten the beet fibers.
• the comminuted beet mixture including the hydrolysis product is preferably then reacted with monovalent, basic demethylation and saponification agents to replace methyl ester groups on the released pectins with more water-soluble reactive radicals to make them receptive to a following cross-linking reaction with divalent or trivalent cation compounds whereby the released pectins are cross-linked and precipitated from solution in 0 characteristics when the demethylating-saponificating reaction is utilized.
• the divalent or trivalent cross-linking ions should be present in higher concentration.
• the total aqueous reaction slurry, containing the products of reaction, the pectinaceous gels as binders or film-formers and the beet residues are extruded or laid down to produce a sheet by procedures which conserve water-solubles and are essentially similar to known methods used in forming reconstituted tobacco in dried form for subsequent production of a smoking filler.
• a preferred pH of the slurry before casting or other shaping should be in the neighborhood of about pH 5.5 to 6, if nicotine is part of the formulation, and since the mixture may be somewhat alkaline, a suitable organic acid, for example, citric acid may be used to bring the pH to the desired point and supply at the same time ions found in natural tobaccos. If the nicotine is omitted, pH adjustment is unnecessary. Additionally, one may add non-toxic salts, sugars, nontoxic plasticizers and if preferred, nicotine to the slurry prior to the shaping operation or these may be added at a later point after the final drying step, to yield specific and desirable properties to the final product.
• the hydrolysis step is first carried out on exhausted and dried sugar beet pulp cossettes, a waste product of sugar beet refining, in which the beets, containing protopectins, are cooked with an agent capable of releasing beet pectins.
• protopectins have been found to have substantial similarities to tobacco protopectins in that they are water insoluble and comprise polygalacturonic acid molecules complexed with various multivalent groups acting as molecular cross-linkers.
• the beet pectins that are released by the hydrolysis step are water-soluble and in the cooking step the insoluble beet protopectins are hydrolyzed to water-soluble fragments consisting mainly of arabans, galactans, acetic acid, and the aforesaid water-soluble pectins.
• the pectin-releasing agent utilized in the primary hydrolysis cooking step is a substance capable of reacting with and destroying the cross-links of the beet protopectins so that the pectins are capable of being released from the beet material.
• mineral acids are preferred and particularly those acids are preferred whose anions will produce non-toxic salts which are normally found in tobacco.
• those acids useful in the present invention are such non-toxic mineral acids as hydrochloric, sulfuric or phosphoric acids.
• Organic acids found in tobacco such as citric or malic acid are also useful. While acids are the preferred materials for releasing pectins, other acidic substances capable of releasing the pectins may be used.
• cation sequestering agents a preferred agent in this category being diammonium hydrogen phosphate (DAP).
• a pH in the range of about 1.0 to 6.0 is maintained, preferably in the range of about 1.5 to 4.5 or 5.0 at the start of the operation.
• the acidity may decrease from a highly acid point to a pH of about 3 or 4 but this will not affect the hydrolysis to any material extent.
• Proportions of pectin-releasing agent to the beet charge, namely redried beet cossettes, are in the range of about 1 to 4 parts to 100 parts by weight of beet material. It should be pointed out that one may use either single acids or a mixture of acids in the cooking operation.
• the cooking or hydrolysis step is carried out at a temperature from about 40C. to 110C., the lower temperature naturally requiring a longer period of time for the desired hydrolysis. At the higher temperature refluxing or a higher than atmospheric pressure is advisable.
• a preferred pectin-releasing operation is to cook a dilute aqueous acid beet pulp slurry at a pH of about 1.9 to 2.9 for l to 4 hours, but preferably for the longer period of time, at a temperature of about 70C. to 90C. under generally normal pressures.
• film-forming pectinaceous beet substances from the released pectins is carried out preferably by reacting the released pectins with monovalent and divalent cation compounds in that order.
• Oxides or hydroxides or even salts that are essentially basic may be used for demethylation and saponification.
• Monovalent compounds should be selected whose cations will supply the type normally found in tobacco and which are nevertheless capable of demethylating and saponifying the alkyl esters of the released pectins. As an example, and in order of decreasing cation preference, this would be potassium hydroxide, sodium hydroxide and ammonium hydroxide.
• strongly basic salts of these monovalent cations could be used instead of the hydroxides, as would be apparent to those skilled in the art.
• the speed of the demethylation step has been found to vary depending on the basicity of the reaction medium.
• alkali metal hydroxides are used in an amount which will provide a pH SOMEWHAT BELOW PH 12
• the demethylation has been found to be rapid at the greatest pH, for example, pH 9.5, moderate at pH 8.5, and very slow at pH 7.0-8.0.
• Completion of the demethylation reaction is signalled by a slowing of the rate of drop of pH when it is about pH 8.5.
• Control of the temperature in the neighborhood between 0 and 25C. is usually necessary to limit deteriorating (chain scission) of the pectins by the alkaline medium.
• the product is substantially demethylated, it is fairly stable. As an example, if one operates at a pH of about 9, with the temperature kept below 30C., the demethylation will take place satisfactorily in about 30 minutes.
• the released pectins in the beet slurry are changed to film-forming gels by means of a cross-linking reaction of the carboxylic acid groups of the pectins with multivalent cation oxides, hydroxides or their equivalent such as highly basic salts, of calcium or magnesium.
• the demethylation requires an alkaline condition.
• Cross-linking in general, can occur at any pH above 3.0, but usually occurs most readily in the region between pH 5.0 and 9.0.
• the use of a multivalent cross-linking ion is an essential cation in the process of forming a final product.
• Conditions for carrying out the cross-linking step on the released pectins are a pH in the range of about pH 5.0 to 9.0 supplied by adding basic compounds if necessary.
• the cross-linking reaction will proceed smoothly at temperatures preferably between 0 and C. and more preferably at a temperature between 20 and 60C.
• the slurry After the completion of the cross-linking and precipitation of the film-forming gels, the slurry is essentially ready for casting or extrusion as a sheet or other shaping operation assuming it has those components deemed desirable which are normally associated with the production of a satisfactory smoking product. In general, however, a better product is achieved if the slurry after the cross-linking step, is brought to a pH in the neighborhood of about pH 5 to 6. This may require the addition of an acid, and preferably an organic acid that desirably also supplies ions normally found in most tobaccos. Such an acid may be citric, maleic or other lower aliphatic carboxylic acids, or where there is a need for more inorganic ion, a mineral acid could be used. The carboxylic acids added may also act as plasticizing agents.
• plasticizers in addition to the above-mentioned acids may be incorporated into the slurry, such as tobacco extracts obtained by leaching tobacco parts with solvents, glycerine, or di or preferably triethylene glycol. These plasticizers may constitute from I to 10 parts by weight of plasticizer per 100 parts by weight of beet pulp.
• sugars particularly crude brown sugar or invert sugar or its components may be added in an amount of from 1 to 50 parts by weight to 100 parts of beet pulp. These materials additionally act as plasticizers.
• Special flavors may also be added and these may be present in an amount up to about 3 parts by weight to 100 parts by weight of beet pulp.
• Such flavorants might be cocoa shell, carob bean, deers tongue and many others commonly used in the tobacco art.
• Other additives, such as colorants and nicotine may be incorporated in the final product in amounts depending on the effects desired. 7
• the pH is again adjusted if necessary to pH 5-6 and the slurry cast or extruded by any of the processes known in the art. Casting on a metal belt or the like for forming and drying is a preferred procedure but this is not the only way the product may be treated before final shredding as a smoking filler.
• Various other procedures, similar to those used in preparing reconstituted tobacco could be used for producing a sheet or extrusion in a variety of shapes.
• EXAMPLE 1 Ingredients Extracted, dried sugar beet cossettes Water The beet pulp was cooked in the solution of mineral acids in water for four hours at about 80C. and then the slurry was refined in a Waring Blender for one-half hour. The slurry was stirred while the additives were introduced in sequence: first the hydroxides in solution, then the powdered oxides. As the divalent metal crosslinked pectins were precipitated, the agitation was increased to disperse them. Next citric acid was added until the pH was approximately 5.7. Sugar, TEG, and flavors were added. A check was made to insure that the pH had not risen above 6.0. Finally the nicotine was stirred in.
• the slurry was cast on a moving steel belt at a thickness of 25 mils, dried and removed from the belt. The sheet processed well. Tensile strength at 15 percent moisture content was about 0.8 kg./in. width. When cut as filler, the product had filling power equivalent to that of conventional reconstituted product.
• Cigarettes were made from a blend of 30 parts by weight of this product with 70 parts of a commercial all-leaf filler. Expert smokers judged this to be an acceptable filler in flavor and lack of harshness.
• the pH was adjusted to 2.5 to 3.0 and kept there during the cook by addition of HCl.
• the slurry was refined by one-half hour treatment in a Waring Blender. The slurry was stirred in the blender while the tricalcium phosphate was added and agitation continued to ensure uniform dispersion of the solid phosphate.
• the sugar and TEG were added and the slurry was used to lay down 25 mil sheets on glass plates. These were dried and removed to be cut and used as filler. In this case, there would be only a small amount of cross-linking due to the reaction of the free acid groups naturally present in beet pectin. The film was not strong when wet. Though it was used satisfactorily for cigarettes made by hand, in commercial cigarette making processes, it would be likely to break up to short shreds or dust.
• EXAMPLE 3 Ingredients Dried extracted sugar beet pulp 334.4 g. Water 11.4 liters Diammonium phosphate (DAP) 30.4 g. lnvert sugar 228.0 g. Citric acid 79.0 g. Triethylene glycol 12.2 g. Potassium hydroxide 10.0 g. Calcium hydroxide 26.4 g.
• DAP Diammonium phosphate
• Sheet prepared similarly from washed burley tobacco stems was used as control. Expert smokers found cigarettes made from the two materials generally equivalent, with the beet pulp product slightly but not significantly preferred.
• EXAMPLE 4 ingredients Exhausted sugar beet pulp 1360 g Water 17 liters H 1 0. 10.5 g. H 27.8 g. HCl 13.2 g. NaOH 9.5 g. KOH 69.5 g. Ca(OH) 96.0 g. Mg(OH) 26.1 g. lnvert sugar 554 g. TEG 300 g. Dry flavors 113 g. Nicotine 38.4 g.
• the acids and pulp were mixed with the water in a Cowles dissolver, cooked four hours at about 80C.
• the slurry was refined in a Sprout-Waldron 12 inch non-pressurized refiner for three passes.
• the Cowles dissolver was used to introduce the monovalent hydroxides, then the divalent hydroxides, followed by beating.
• Citric acid was added to bring pH to 5.7
• the invert sugar, TEG and the dry flavors were added, then the pH was rechecked to make sure it was not over 6.0. Nicotine was finally added.
• the slurry was cast on a moving steel belt at 25 mils, dried, peeled off and used for filler.
• step 9b The process of claim 1 in which the hydrolyzed and refined product of step 9b is subjected to a demethylation step by reacting the released beet pectins with an alkaline demethylating agent.
• demethylating agent is at least one of sodium and potassium hydroxide and the cross-linking agent is at least one of calcium and magnesium oxide or hydroxide.
• a smoking product produced by the process comprising a. cooking an aqueous slurry of extracted sugar beet pulp with a hydrolyzing agent to reduce beet pectins;
• step (a) wherein the cooked slurry of step (a) is comminuted to shorten fibers and break up fiber bundles.
• step (a) is subjected to a demethyla tion or saponification step by reacting the sugar beet pectins with an alkaline demethylating or saponificating agent.
• step (a) is comminuted to shorten fibers and break up fiber bundles prior to the addition of the demethylating or saponificating agent.
• cross-linking agent is selected from the group consisting of cations of calcium and magnesium ions.
• cross-linking agent is selected from the group consisting of cations of calcium and magnesium ions.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Manufacture Of Tobacco Products (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)

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Country Status (13)

Cited By (12)

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Citations (3)

• 1970
  • 1970-08-13 US US63648A patent/US3703177A/en not_active Expired - Lifetime
• 1971
  • 1971-06-11 CA CA115,429A patent/CA949414A/en not_active Expired
  • 1971-07-01 FR FR7124149A patent/FR2101531A5/fr not_active Expired
  • 1971-07-08 BE BE769726A patent/BE769726A/xx unknown
  • 1971-07-19 FI FI2044/71A patent/FI54854C/fi active
  • 1971-07-20 JP JP46053649A patent/JPS5025559B1/ja active Pending
  • 1971-07-28 GB GB3550771A patent/GB1337489A/en not_active Expired
  • 1971-07-30 NL NL7110560A patent/NL7110560A/xx not_active Application Discontinuation
  • 1971-08-06 ES ES393964A patent/ES393964A1/es not_active Expired
  • 1971-08-09 SE SE7110147A patent/SE395598B/xx unknown
  • 1971-08-12 NO NO03007/71A patent/NO126895B/no unknown
  • 1971-08-12 DE DE19712140507 patent/DE2140507A1/de active Pending
  • 1971-08-13 CH CH1191071A patent/CH547610A/xx not_active IP Right Cessation

Patent Citations (3)

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