US3796222A - Method of making a smoking product from coffee bean hulls - Google Patents

Abstract

This disclosure relates to a smoking product derived from coffee bean hulls. Smoking compositions are described which contain coffee bean components alone or mixed with tobacco or non-tobacco substances. The hulls, which contain pectinaceous substances, are treated with reagents that attack the alkaline earth metal crosslinks causing the release of the coffee pectins. The latter acts as a binding agent and together with the treated hulls may be handled or used similarly to a tobacco product.

Description

Elite States atent [191 Deszyck METHOD OF MAKING A SMOKING PRODUCT FROM COFFEE BEAN HULLS [75] Inventor: Edward J. Deszyck, Richmond, Va.

[22] Filed: Mar. 17, 1971 [21] Appl. No.: 125,343

[52] US. Cl 131/2, 131/17, 131/140 C [51] Int. Cl. A24b 15/00, A24b 3/14 [58] Field of Search 131/2, 17, 15, 140-144 [56] References Cited UNITED STATES PATENTS 3,009,836 11/1961 Samfield et al. 1 31/17 AC 3,528,434 9/1970 Halter et a1 131/140 3,638,660 1/1972 Davis 131/2 3,429,316 2/1969 Hess 131/17 R 3,409,026 11/1968 Hind et al. 131/140 C FOREIGN PATENTS OR APPLICATIONS 368,764 10/1906 France l3l/2 Mar. 12, 1974 OTHER PUBLICATIONS The Evening Star, Aug. 27, 1963, page A 8 article entitled No Smoking Primary Examiner-Melvin Dv Rein [57] ABSTRACT This disclosure relates to a smoking product derived from coffee bean hulls. Smoking compositions are described which contain coffee bean components alone or mixed with tobacco or non-tobacco substances. The hulls, which contain pectinaceous substances, are treated with reagents that attack the alkaline earth metal cross-links causing the release of the coffee pectins. The latter acts as a binding agent and together with the treated hulls may be handled or used similarly to a tobacco product.

1 Claim, No Drawings METHOD OF MAKING A SMOKING PRODUCT FROM COFFEE BEAN HULLS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to the field of smoking compositions and more particularly, to smoking compositions prepared from non-tobacco ingredients.

2. Description of the Prior Art Various suggestions have been made from time to time to substitute or replace part of the tobacco in smoking articles for particular purposes.

Cigarette fillers and other tobacco products have often been described wherein some or all of the tobacco has been replaced by various substances, generally for the purposes of reducing costs or to give a smoke essentially free of nicotine where that is desired. However, few of these substitute ingredients provide a pleasant, flavorful smoke.

It is also known that reconstituted tobacco or tobacco material usually in the form of sheet and prepared from waste or scrap tobacco parts or dust may be used as a substitute for or may be blended with tobacco leaf by employing as a binder naturally occurring tobacco pectins. A number of patents describe such products, for example, various Hind et al. patents, notably U.S. Pat. Nos. 3,385,303, granted May 28, I968; U.S. Pat. No. 3,409,026, granted Nov. 5, 1968; U.S. Pat. No. 3,435,829, granted Apr. 1, 1969 and oth ers. While these patents describe products which provide satisfactory smoking articles, the basic desire or concept taught by these patents is to use only tobacco parts having, of course, the usual amount of nicotine and expected flavor normally found in tobacco.

SUMMARY OF THE INVENTION This invention relates to a smoking product and more particularly to smoking products which comprise coffee bean by-products and particular methods for making them.

One aspect of the invention is the manufacture of a smoking product utilizing the coffee bean hulls or different parts of the hulls after the coffee beans have been removed.

Another aspect of the invention is the preparation of a smoking composition in which various components of the coffee bean hulls are blended with either tobacco or non-tobacco substances to make a blended smoking product.

Still another aspect of the invention is the chemical treatment of coffee bean hulls and particularly components having pectinaceous elements to release the coffee pectins and to use such released pectins as a binding agent with the treated hulls or parts to form a sheet of smoking product.

DESCRIPTION OF THE INVENTION It has been discovered that a coffee product, and

particularly coffee bean hulls or specific parts thereof which are available as by-products from coffee processing, can be added to tobacco or even a nontobacco filler to provide a pleasant and unique flavor to the smoke without introducing additional nicotine thereto. In addition, as a substitute for tobacco, or as an added component to tobacco or other smoking materials, the use of coffee bean hulls in a smoking prodnot results not only in a relatively low cost product but a smoking product having a mild and enjoyable flavor.

Coffee bean hulls, after the coffee beans have been harvested and removed, comprise in general four components which may be identified from the outermost part to the inner lining as consisting of an outer rind or exocarp, a pulp or mesocarp, a parchment or endocarp, and the silver skin or chaff next to the coffee bean itself. In the dehulling of coffee bean pods, one method involves separation of the outer rind and the pulp from the beans, parchment and silver skins or chaff. The bean itself is then separated from the parchment and silver skins or chaff by known and generally mechanical procedures.

According to the present invention, any one or more of the coffee hull components in dried and comminuted form may be used as a tobacco substitute or replacement, or blended with other smoking substances to produce a desirable smoking product having a unique and satisfying flavor. As an example, one may blend the parchment or chaff from coffee bean hulls with tobacco to the extent of from 5 to 30 percent by weight of the tobacco. By doing so, the side stream smoke and the main stream smoke of the smoking article is modified to produce a pleasant smoking article. Cigarettes that have a papery side stream odor can be improved by using as part of the tiller coffee bean hull chaff, thus changing the side stream from papery or stemmy" to coffee-like, or more tobacco-like depending upon the particular proportions used, and the base character of the filler. 1

As another composition, one may mix as much as 20-25 percent by weight of coffee bean chaff with non-tobacco materials such as cellulose or hemicellulose and a known binding material such as used in the tobacco art to form a sheet which is then cast, dried and cut into typical particulate material similar in physical characteristics to smoking tobacco.

While the dried coffee bean hulls or selected components thereof may be used as a filler alone or as filler components without further treatment as described above, it is an advantageous and important aspect of the invention to chemically pretreat particular coffee bean hull components before using them in a smoking product. It has been found that the coffee bean hulls contain pectinaceous material which is concentrated in the outer rind, the pulp and the silver skins or chaff. The chemical treatment of these materials encompasses the use of certain pectin-releasing agents capable of breaking down the pectinaceous elements to release the pectins therefrom so that they may act as a pectin binder on the treated hulls. Anadvantage of releasing the pectins and depositing them on the treated hulls to bind them into a coherent sheet or other form is that there is no need for separation of the released pectins from the remaining components, rather the whole may be cast or otherwise used directly alone or in admixture with tobacco or other substances in a smoking article.

The naturally occurring pectins in the coffee bean parts, or what might more accurately be called here the protopectins, consist of calcium and/or magnesium salts of polymers of galacturonic acid, the divalent calcium and/or magnesium atoms acting as cross-links between acid chains thus making the polymers waterinsoluble. The coffee protopectins, for the purposes described here may be considered somewhat similar to tobacco protopectins, differing therefrom mainly in the degree of cross-linking and chain lengths. Thus, in

accordance with the present invention, a smoking product usable in a smoking article may be prepared from coffee bean hulls bonded together by pectins which had been released therefrom after destroying the protopectin cross-links by a chemical reaction.

In the chemical treatment step, the coffee bean hulls are reacted with an aqueous solution of a non-toxic reagent which is capable of reacting with and destroying the calcium and magnesium cross-links in the naturally occurring pectinaceous substances. After the calcium and magnesium cross-links are destroyed, the pectins are liberated sufficiently from the hulls to become available for use as a binder through the washing action of the treating solution. tl-le pectins are then dissolved or dispersed in solution, or are at least suffciently released from the interstices of the hull mass so that they form a coating on the surface thereof. Pectins which are dissolved or dispersed in the treating solutions, are thereafter precipitated or deposited from the solution, so that they become available for use as a binder material.

Describing the pectin-releasing procedure in greater detail, the release of the pectins from the coffee hulls or any of its pectinaceous containing components is achieved by treating them with a solution of a reagent capable of destroying the alkaline earth metal crosslinks holding the pectinaceous material. The reagents that are used are in part disclosed in U.S. Pat. Nos. 3,353,541, 3,409,026, 3,411,515 and 3,420,241, and include precipitating agents for the divalent cations binding the pectins which form relatively insoluble salts, or sequestering agents for the divalent ions, or agents which partially insolubilize and partially sequester the divalent ions, or acids which solubilize the divalent cations as soluble salts of calcium and magnesium and allow them to be washed out while leaving the pectins in the insoluble acid form. When employing the latter type of reagent, the slurry must subsequently be made alkaline so as to solubilize the pectins.

As one embodiment of the pectin-releasing step, an aqueous slurry of the pectinaceous coffee bean substances is contacted with a reagent having monovalent cations and mono or polyvalent anions, which acts by forming a precipitate with the calcium or magnesium ions. Such a reactant can be a monovalent metal salt of the formula M X wherein M is a monovalent inorganic cation, n is an integer having a value of l, 2, or 3 and X is an anion which may be monovalent or polyvalent, such that the calcium salt of the formula Ca,,X is essentially insoluble in the treating solution and p and q are integers corresponding to the functionality of X.

Monovalent cations which are effective include the alkali metals such as sodium, potassium and lithium, as well as the ammonium ion. The anion portion of the molecule may be COf, P POf, HPOf, H PQF, and the like. For example, the compound M X could be sodium carbonate, (Na CO since sodium is a monovalent inorganic cation and calcium carbonate is essentially water insoluble. Additional representative examples of precipitating agents are the orthophosphates, metaphosphates as well as the carbonates of sodium, potassium, lithium and ammonium. Specifically, for example, when ammonium orthophosphate is used, the

precipitate is calcium and/or magnesium ammonium phosphate. The concentration of the reagent may be from about 0.008 to about 0.40 mols, preferably from about 0.038 to about 0.27 mols per g of coffee material. The pH of this reaction should be between about 5.8 and about 10 and the temperature may be as high as 400 C. but should, preferably, be between about 25 C. and about C. and the reaction time from a period of about 1 minute to about 24 hours. Among the precipitating agents which may be employed are the alkali metal carbonates, for example, sodium carbonate and potassium carbonate, the alkali metal phosphates, particularly, the alkali metal orthophosphates and the ammonium orthophosphates, such as ammonium orthophosphate, sodium orthophosphate, ammonium dihydrogen orthophosphate, potassium dihydrogen orthophosphate, diammonium monohydrogen orthophosphate, disodium monohydrogen orthophosphate and dipotassium monohydrogen orthophosphate.

In a second embodiment of a pectin-releasing operation, a cross-link destroying reagent may be used which acts by sequestering the calcium or magnesium, thereby removing the calcium or magnesium atoms by forming a complex therewith. Suitable reagents of this type include any sequestering agent which will form a complex or chelate with the calcium and/or magnesium, thereby removing the calcium and/or magnesium and making themunavailable for recross-linking with the pectin. Illustrative of such sequestering agents are amino acids such as ethylenediamine tetraacetic acid, ethylenediamine N, N-diacetic acid, aminobarbituric acid, 2-aminobenzoic acid, beta-aminoethylphosphonic acid or beta-aminosulfinic acid. Various polyphosphates may also act as sequestering agents such as the tetrametaphosphates, hexametaphosphates and trimetaphosphates, pyrophosphates and tripolyphosphates, representative examples including sodium hexametaphosphate, tetrasodium pyrophosphate and pentasodium tripolyphosphate. Another good sequestering agent is nitrilotriacetic acid. Additionally, many naturally occurring amines and peptides are also effective as sequestering agents for calcium and/or magnesium, and of these, alanine, aspartic acid, glycine, glycyl-glycine, glutamic acid, serine, tyrosine and di-iodol-tyrosine are examples.

The reaction mechanism which occurs when a sequestering agent is employed is the formation of a calcium or magnesium chelate and these ions are no longer available to recombine with the pectic ions. The conditions for carrying out this type of reaction involve the maintenance of a pH between about 4 and about 10 and the temperature should, preferably, be between about 0 C. and about C. for a period of from about 1 minute to about 24 hours. A concentration of 0.015 to 0.20 mols of sequestering agent per 100 g of coffee material may be used.

A preferred type of precipitation which is described in substantial detail in my copending application, Ser. No. 104,459, filed Jan. 6, 1971, involves the use ofcertain organic acids together with ammonium hydroxide, a particularly preferred acid being citric acid which furnishes citrate ion capable of reacting with available cations to form calcium or magnesium citrates that are relatively water-insoluble. To obtain the desired reaction, it must be carried out under alkaline conditions, preferably using ammonium hydroxide in an amount to react with the citric acid to form ammonium citrate, and to provide an alkaline environment in the slurry mixture above about pH 8 and preferably about pH 9 or somewhat higher. About 0.025 to about 0.10 mols of citric acid and about 0.15 to about 0.50 mols of am- .monium hydroxide per 100 g of coffee material may be used. The temperature for this type of operation may be from about 25 to about 135 C. with the reaction carried out from about 5 minutes to about 24 hours.

A cross-link destroying reagent may also function partially as a precipitating reagent, in accordance with the first embodiment of this invention, and partially as a sequestering agent, in accordance with the second embodiment of this invention. This is a favorable type of reaction and the reagent that is preferred for this purpose is diammonium monohydrogen orthophosphate (DAP). The reagent is used in an amount of about 0.01 to about 0.40 mols per 100 g of coffee material and in an alkaline environment provided by adding a base, preferably ammonium hydroxide, the mixture being held in the neighborhood of about pH 7.1 to about pH 9.0. The temperature-time conditions for operating the cross-link precipitation-sequestering step with DAP involves holding the reaction mixture at a temperature of about 25 to about 90 C. for about 1 minute to about 24 hours.

In the third embodiment of pectin release, the crosslink destroying reagent comprises an acid treatment which forms the released but insoluble free pectic acid and relatively soluble salts of the cross-linking metals. Generally the acid is an inorganic acid, such as hydrochloric acid, phosphoric acid, sulfuric acid or a similar acid, which will form soluble calcium and magnesium salts. The acid may be employed as 0.025 N to 5.0 N solutions, but is preferably employed as 0.5 N to 1.0 N solutions. The exact dilution and amount to be employed will vary with the particular acid which is used, it only being necessary that sufficient acid be present to convert the calcium and magnesium present in the tobacco being treated to the calcium and magnesium salts of the acid. The acid treatment is preferably conducted at a temperature of from about l C. to about 50 C. The acid treatment comprises reacting the coffee hulls or parts with the acid until the resulting mixture has a pH of from about 1.0 to about 2.5 Preferably the pH is brought to from about 1.0 to about 1.7. This treatment will generally be conducted from about 10 minutes to about 24 hours, depending in part on the size of the coffee hull particles. The acid conditions which are necessary for this embodiment of the invention may be achieved by the use of ion exchange resins which may be used, with suitable recycling, to obtain the desired pH of the solution during treatment. The ion exchange resins may be used and regenerated'in accordance with the usual practices for such resins.

The mixture resulting from the inorganic acid treatment is generally followed by a water washing step. This water washing step is conducted at a temperature of from about to about 35 C. and, preferably, distilled water is employed. When this wash step is employcd, sufficient water should be used to remove the calcium and magnesium salts of the acids, which salts are formed in the above-described treatment; thus, there should be at least two volumes of water per volume of the mixture resulting from the acid treatment. The wash water is separated from the tobacco by any suitable means, for example, by conducting the wash in a centrifuge, filter press, or any other apparatus from which liquids can be substantially removed from solid materials.

In the above-described inorganic acid treatment, the pectic acid that is formed in the reaction is substantially insoluble. To bring it to a soluble form for release, it must be reacted with an alkaline material before it is in condition for release from the coffee hull cell structure. Thus, the acid treated pectins are placed in condition for release by bringing the mixture resulting from the acid treatment, and, preferably, after the water wash described above, to a pH of from about 5.0 to about 10.5 and, preferably, from about 6.3 to about 8.5, by the addition of an alkaline material. Suitable alkaline materials include ammonium hydroxide and alkali metal hydroxides, for example, sodium hydroxide, potassium hydroxide and lithium hydroxide, and alkali metal salts, such as sodium bicarbonate, sodium carbonate, sodium phosphate, and similar salts to convert the pectic acid to a soluble form. The alkaline material may be any water-soluble compound containing monovalent inorganic cation and capable of producing hydroxide ions when dissolved in water. The temperature of this step may be from about l C. to about 45 C., but is, preferably, from about 15 to about 35 C.

Another method for carrying out a pectin-release step which has been described in my previously mentioned application and which is adaptable to the treatment of coffee bean hulls or components thereof when these substances contain natural acids or salts in sufficient amounts to effect the desired reactions. By this method the protopectin cross-links may be removed or destroyed by merely adding an excess of ammonia to the coffee slurry, preferably in the form of ammonium hydroxide. The precise reactions taking place have not been established but it is believed that the natural citric acid, phosphates and sulfates, react with the calcium pectates when the pH is in the alkaline range, thus liberating the pectins as ammonium pectates in sufficient amount to act as a binder. Conditions for this type of operation involves the use of sufficient ammonium hydroxide to provide a pH in the slurry of about pH 7.8 to 10.0, preferably about pH 9, a temperature of 35 to 135 C., preferably about C. and a reaction time of 10 minutes to about 24 hours, preferably about 2 hours.

It should be mentioned that while the pectinreleasing operation is being carried out under conditions conducive to a satisfactory yield of released pectinaceous binding agent, it may be desirable or necessary to agitate or beat the slurry of coffee parts and reagent to facilitate the release of the pectins and if necessary to reduce the fibrous slurry to the desired consistency and fineness. A Valley beater or the like may be employed for this refining operation.

When the pectin-releasing operation is terminated and the coffee hull pectins have been liberated to the extent desired, the slurry may be sprayed, extruded or cast on a plate or moving belt to form a sheet of coffee bean solids with coffee pectins as a binder. While no additional materials need be added to the slurry before drying, other additives may be incorporated in the slurry if desired. For example, preservatives, or organic acids for flavor or aroma which may in themselves be of coffee origin, may be added. Plasticizers,

such as glycols and polyglycols, and humectants, such as glycerin, may also be added, if desired. In addition, the gel strength of the pectins can be regulated by partial precipitation to control such rheological properties as viscosity, fluidity and elasticity. Other additives or dispersants may be'added in small amounts to regulate slurrying qualities, provided, however, that such substances are not added in large enough quantities to adversely affect the flavor or aroma of the final product. Furthermore, the coffee pectins can be combined or augmented with water-soluble gums or waterdispersible gums commonly used as binders such as methyl cellulose, sodium carboxymethyl cellulose, guar gum, locust bean gum, or alginates, although it is preferred to minimize or eliminate such additions.

The final sheet product from treating the coffee bean hulls in accordance with the methods of the present invention may be dried and then cut into particulate material similar in physical form to ordinary smoking tobacco and so used, preferably mixed with tobacco leaf cut or shredded in the usual manner. While casting in sheet form is preferred, the product may be cast in blocks or as threads or other shapes, as desired.

In general, the coffee-derived smoking product of the invention may be used alone as a smoking product or blended with other smoking substances in a matrix pared using g. of bright stern insoluble solids and 500 ml water, then heated on the steam bath for 16 hours. Another slurry was prepared using 30g. of coffee bean hulls, 750 ml water, and concentrated Nl-LOH to bring the pH to 9.0. This was also heated on the steam bath for 16 hours. The two slurries were refined for approximately 15 minutes in a blender, and then combined and mixed thoroughly. The slurry was cast on a plate using a casting knife setting of 50 mils, dried, and doctored. The sheets were cut into filler, and cigarettes prepared by hand. The blended cigarette having both the coffee bean hull components and the bright stem insoluble solids when smoked resulted in amounts of from about 5.0% to about 70% by weight of the matrix filler whether that be a tobacco or a nontobacco material but preferably constituting from 15 to 50% by weight of the matrix.

As a smoking product filler it produces an acceptable smoke characterized by an unusaul and different flavor.

The following examples are illustrative:

EXAMPLE 1 A slurry was prepared using g. of unground coffee bean chaff (essentially silver skins) with 270 ml water, 3g. diammonium phosphate (DAP) and concentrated NH OH to adjust the pH to 9. The slurry was refined for 15 minutes in aWaring blender, heated at 90 C. for 1 hour, refined again for 5 minutes, and heated for another hour at 90 C. While hot the slurry was cast on a plate with a casting knife setting of 50 mils, steam dried, and doctored (i.e., peeled from the plate). The slurry pH at casting was 8.6.

The sheet was excellent in physical properties: weight 13.27 g/sq. ft., wet tensile coefficient 7.98 g/in./g/ sq. ft. On burning it resulted in a mild, pleasant, and somewhat sweet smoke. It was very similar to a bright leaf smoke.

EXAMPLE 2 Another slurry was prepared by using 30g. of coffee bean chaff, 350 ml water, and 3g. DAP. The pH was adjusted to 9.0 by addition of concentrated Nl-l.,OH. The slurry was heated at 90 C. for l hour, refined in a Waring blender for 5 minutes, and reheated for 1 hour. It was cast on a plate using a casting knife, set at 50 mils, dried, and doctored. This sheet had a pleasant odor.

EXAMPLE 3 A blend of bright tobacco stem water-insoluble solids was mixed with coffee bean chaff. The bright stem insoluble solids was prepared using a Valley beater until the freeness was below 100ml. A slurry was prein a milder and sweeter flavor than the flavor or the smoke from the control cigarette (100 percent bright stem insoluble solids).

EXAMPLE 4 Twenty grams of bright stem water-insoluble solids, 5g. coffee bean chaff and 500 ml water were slurried in a Waring blender. The pH was adjusted with concentrated NH OH to 9.0. The slurry was refined for 15 minutes, heated at C. for 1 hour, refined for another 15 minutes, heated for another hour. The slurry was cast on a plate using a casting knife setting of 50 mils, dried, and doctored. The sheet was cut into filler from which cigarettes were prepared. When smoked and compared with the control percent bright stem insoluble solids), the flavor was milder and sweeter than that of the control. No apparent foreign taste or odor was detected in the experimental cigarette.

EXAMPLE 5 A slurry was prepared using 47.5g of coffee bean chaff, 2.5g. DAP, 450 ml water, and concentrated NH OH to adjust the pH to 9.0. The slurry was refined for 15 minutes in a Waring blender, heated at 90 C. for 1 hour, refined again for 5 minutes, and heated for another hour at 90- C. While hot the slurry was cast on a plate using a casting knife with a setting of 50 mils, steam dried, and doctored. The slurry pH at casting was 9.0. A satisfactory sheet resulted: wet tensile coefficient 7.35g/in./g/sq. ft.; sheet weight .1 1.1 lg/sq. ft.

EXAMPLE 6 A slurry was prepared using 40.5g. of coffee bean chaff, 4.5g. DAP, 455 ml water, and sufficient concentrated NH OH to adjust the pH to 9.0. The slurry was refined for 10 minutes and heated for 1 hour at 90 C. While hot the slurry was cast on a plate with a casting knife setting of 50 mils, steam dried, and doctored. The slurry pH at casting was 8.8. A satisfactory sheet resulted: wet tensile coefficient 10.06g/in./g/sq. ft.; wt. 11.10g/sq. ft.

EXAMPLE 7 EXAMPLE 8 EXAMPLE 9 A slurry was prepared using 35g. of powdered coffee bean outer skins and pulp, g. of spent coffee grounds, 7.5g. citric acid, 450 ml water, and concentrated NH OH to a pH of 9.0. The slurry was heated for 1 hour at 90 C., refined in a Waring blender for 15 minutes and then reheated for 1 hour at 90 C. It was cast on a plate using a casting knife with a setting of 50 mils, steam dried, and doctored. A satisfactory product resulted: wet tensile coefficient -5.6- g/in./g/sq. ft.; weight 10.5g/sq. ft.

EXAMPLE 10 Four cigarette samples were prepared manually. The first, a control sample, was made entirely of commercial reconstituted filler. The remaining three cigarettes were made from mixtures of the same reconstituted filler and coffee beans chaffs in which the percentages of the coffee material were 10%, 20% and 30% by weight of the mixture, respectively.

When all four cigarettes were compared from the standpoint of their smoking characteristics, all three cigarettes which contained the coffee bean chaffs were found to be milder, sweeter and have a more agreeable flavor than the control sample. In addition, the cigarettes which contained 20 percent coffee material had a detectable main stream and side stream aroma of roasted coffee beans, and this aroma was even more distinct in the cigarette sample containing 30 percent coffee material. However, such aroma was not detectable in the control sample or the cigarette containing 10 percent coffee material,

The invention that is claimed is:

1. A smoking composition adapted to be used alone or admixed with tobacco consisting essentially of coffee bean hull constituents which have been comminuted and slurried with a reagent capable of destroying alkaline earth metal cross-links of natural coffee bean hull exocarp, mesocarp or chaff protopectins to release said protopectins and then cast and dried into