CA1282630C - Fibrous product - Google Patents
Fibrous productInfo
- Publication number
- CA1282630C CA1282630C CA000513465A CA513465A CA1282630C CA 1282630 C CA1282630 C CA 1282630C CA 000513465 A CA000513465 A CA 000513465A CA 513465 A CA513465 A CA 513465A CA 1282630 C CA1282630 C CA 1282630C
- Authority
- CA
- Canada
- Prior art keywords
- slurry
- solid
- mesh screen
- natural product
- product
- 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
- 239000002002 slurry Substances 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 73
- 230000008569 process Effects 0.000 claims abstract description 73
- 235000010582 Pisum sativum Nutrition 0.000 claims abstract description 44
- 229930014626 natural product Natural products 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000000047 product Substances 0.000 claims abstract description 27
- 240000004713 Pisum sativum Species 0.000 claims abstract description 18
- 235000021374 legumes Nutrition 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000012265 solid product Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 22
- 230000001590 oxidative effect Effects 0.000 claims description 19
- 239000001814 pectin Substances 0.000 claims description 18
- 239000011343 solid material Substances 0.000 claims description 18
- 229920001277 pectin Polymers 0.000 claims description 17
- 235000010987 pectin Nutrition 0.000 claims description 17
- 239000007844 bleaching agent Substances 0.000 claims description 15
- 239000007800 oxidant agent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 6
- 108090000623 proteins and genes Proteins 0.000 claims description 6
- 102000004169 proteins and genes Human genes 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical group 0.000 claims description 5
- 238000004061 bleaching Methods 0.000 claims description 5
- 235000000346 sugar Nutrition 0.000 claims description 5
- 150000008163 sugars Chemical class 0.000 claims description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 244000066764 Ailanthus triphysa Species 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 244000013123 dwarf bean Species 0.000 claims description 2
- 235000021278 navy bean Nutrition 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 239000004291 sulphur dioxide Substances 0.000 claims description 2
- 235000010269 sulphur dioxide Nutrition 0.000 claims description 2
- 235000013305 food Nutrition 0.000 abstract description 8
- 235000008429 bread Nutrition 0.000 abstract description 2
- 235000012459 muffins Nutrition 0.000 abstract description 2
- 235000015927 pasta Nutrition 0.000 abstract description 2
- 241000219843 Pisum Species 0.000 description 26
- 239000007858 starting material Substances 0.000 description 13
- 235000013312 flour Nutrition 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 239000000306 component Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 206010001497 Agitation Diseases 0.000 description 3
- 244000046052 Phaseolus vulgaris Species 0.000 description 3
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000013325 dietary fiber Nutrition 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 108010050181 aleurone Proteins 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/20—Reducing nutritive value; Dietetic products with reduced nutritive value
- A23L33/21—Addition of substantially indigestible substances, e.g. dietary fibres
- A23L33/22—Comminuted fibrous parts of plants, e.g. bagasse or pulp
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
- A23L11/00—Pulses, i.e. fruits of leguminous plants, for production of food; Products from legumes; Preparation or treatment thereof
- A23L11/05—Mashed or comminuted pulses or legumes; Products made therefrom
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Botany (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Mycology (AREA)
- Agronomy & Crop Science (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Beans For Foods Or Fodder (AREA)
Abstract
ABSTRACT A process for the preparation of a novel improved fibrous natural product comprising agitating an aqueous slurry of ground material from the outer seed coat of a legume, especially yellow or green field peas, to dis-solve water-soluble products, filtering the slurry and drying the solid product thus obtained to provide a novel fibrous natural product. The latter is useful as an ad-ditive for edible food products such as bread, muffins and pasta to increase the fibrous content thereof.
Description
X63~3 A NOVEL FIBROUS PRODUCT
~ his invention relates to novel improved fibrous nat-ural products and more particularly it relates to novel im-proved fibrous natural products which are prepared from leg-umes such as peas and beans. These novel products are use-ful as additives to edible food products such as bread, muf-fins and pasta.
It is known from Canadian Patent No. 1,111,708, issued November 3, 1981, that a fibrous product containing pea fibres can be obtained from the hulls of green field peas and such pea fibres have particle sizes in the range which pass a 20 mesh screen but do not pass an 80 mesh screen (U.S. Standard Sieve). Particularly preferred pea fibres have particle sizes which pass a 20 mesh screen but do not pass a 60 or 40 mesh screen, referred to as -20+60 or -20+40, respectively, mesh particles. It is also known from Canadian Patent No. 1,048,848, issued February 20, 1979, that a related fibrous product con-taining pea fibres can be obtained from yellow field peas. The pea fibres described in this known art were obtained from com-mercially available pea hulls solely by selection of particularpaxticle sizes and without any treatment of the hulls.
We have now found, and herein lies our invention, that the hulls of legumes, which we prefer to name as the outer seed coat of legumes, such as peas and beans, can be purified by our novel process to provide novel improved fibrous natural products.
We have named or described our novel fibrous natural products obtained from the process of our invention as concen-trated pea bran when prepared from the outer seed coat of peas.
The invention~ as claimed herein, is a process for the preparation of a novel improved fibrous natural product which comprises agitating an aqueous slurry of ground material from , ~
~ his invention relates to novel improved fibrous nat-ural products and more particularly it relates to novel im-proved fibrous natural products which are prepared from leg-umes such as peas and beans. These novel products are use-ful as additives to edible food products such as bread, muf-fins and pasta.
It is known from Canadian Patent No. 1,111,708, issued November 3, 1981, that a fibrous product containing pea fibres can be obtained from the hulls of green field peas and such pea fibres have particle sizes in the range which pass a 20 mesh screen but do not pass an 80 mesh screen (U.S. Standard Sieve). Particularly preferred pea fibres have particle sizes which pass a 20 mesh screen but do not pass a 60 or 40 mesh screen, referred to as -20+60 or -20+40, respectively, mesh particles. It is also known from Canadian Patent No. 1,048,848, issued February 20, 1979, that a related fibrous product con-taining pea fibres can be obtained from yellow field peas. The pea fibres described in this known art were obtained from com-mercially available pea hulls solely by selection of particularpaxticle sizes and without any treatment of the hulls.
We have now found, and herein lies our invention, that the hulls of legumes, which we prefer to name as the outer seed coat of legumes, such as peas and beans, can be purified by our novel process to provide novel improved fibrous natural products.
We have named or described our novel fibrous natural products obtained from the process of our invention as concen-trated pea bran when prepared from the outer seed coat of peas.
The invention~ as claimed herein, is a process for the preparation of a novel improved fibrous natural product which comprises agitating an aqueous slurry of ground material from , ~
- 2 - ~ ~ ~2G3~
the outer seed coat of a legume to dissolve water-soluble pro-ducts, filtering said slurry and drying the solid product thus obtained to provide a novel fibrous natural product.
According to a further feature of the invention, as claimed herein, we provide a process for the preparation of a novel improved fibrous natural product which comprises grind-ing material from the outer seed coat of a legume to a requi-site particle size, forming an aqueous slurry of the ground material and agitating said slurry to dissolve water-soluble products, filtering said slurry and drying the solid product to provide a novel fibrous natural product.
In yet a further feature of the invention, as claimed herein, we provide a process for the preparation of a novel improved fibrous natural product which comprises agitating an aqueous slurry of ground material from the outer seed coat of a legume to dissolve water-soluble products, filtering said slurry, suspending the solid material in water to form a sec-ond aqueous slurry and treatina said second slurry with an oxidizing or bleaching agent, filtering said second slurry ~0 and drying the solid product to provide a novel fibrous nat-ural product.
The material to be used as starting material in the pro-cess of this invention is the outer seed coat of the legume.
Legumes which are suitable for use in this inventive process are peas and beans such as yellow or green field peas, white beans, navy beans and soya beans. The crop, such as yellow or green field peas, is usually field dried prior to harvest-ing and during that time the outer seed coat may become con-taminated with soil and sand and perhaps soil borne bacteria.
It is desirable to remove this contaminating material in order to provide final products in the form of powders having a high level of dietary fibre, being substantially bland in flavour
the outer seed coat of a legume to dissolve water-soluble pro-ducts, filtering said slurry and drying the solid product thus obtained to provide a novel fibrous natural product.
According to a further feature of the invention, as claimed herein, we provide a process for the preparation of a novel improved fibrous natural product which comprises grind-ing material from the outer seed coat of a legume to a requi-site particle size, forming an aqueous slurry of the ground material and agitating said slurry to dissolve water-soluble products, filtering said slurry and drying the solid product to provide a novel fibrous natural product.
In yet a further feature of the invention, as claimed herein, we provide a process for the preparation of a novel improved fibrous natural product which comprises agitating an aqueous slurry of ground material from the outer seed coat of a legume to dissolve water-soluble products, filtering said slurry, suspending the solid material in water to form a sec-ond aqueous slurry and treatina said second slurry with an oxidizing or bleaching agent, filtering said second slurry ~0 and drying the solid product to provide a novel fibrous nat-ural product.
The material to be used as starting material in the pro-cess of this invention is the outer seed coat of the legume.
Legumes which are suitable for use in this inventive process are peas and beans such as yellow or green field peas, white beans, navy beans and soya beans. The crop, such as yellow or green field peas, is usually field dried prior to harvest-ing and during that time the outer seed coat may become con-taminated with soil and sand and perhaps soil borne bacteria.
It is desirable to remove this contaminating material in order to provide final products in the form of powders having a high level of dietary fibre, being substantially bland in flavour
3~
and which can be added to food products to increase dietary fibre levels without significantly detracting from the flav-our or texture of the food products.
The outer seed coat or skin of peas is a preferred starting material. The outer seed coat of peas is made up of an outer layer of palisade cells, a layer of hourglass cells, smaller parenchyma cells, aleurone cells and, finally, compressed layers of endosperm cells. The internal or remain-ing portion of the seed is generally referred to as the meat.
The raw starting material is generally in the form of whole or complete half pea shapes (split hollow spheres or rough hollow hemispheres) of the outer seed coat or skins of the pea seed mixed with fragments of spheres and pea cotyle-don chips or broken powder-like particles. This raw start-ing material is available from manufacturers or processors of split peas who process the pea seeds by splitting the seeds to remove the outer seed coat or skin and retain only the residual internal portion of the seed in the form of split peas (meat). If necessary, the raw starting material may be passed over a gravity type separator in order to sep-arate the denser pea cotyledon chips and other particles from the lighter, less dense outer seed coat pieces. ~fter such a gravitational separation treatment, the outer seed coat is low in density, fluffy in texture and fairly light in colour.
It is to be understood that the sizes of mesh screens referred to throughout this specification are to be interpre-ted as U.S. standard screen sizes. Thus, for example, 30 to 60 mesh screen size refers to sieve openings of 590 microns to 250 microns, an 80 mesh screen size refers to a sieve op-ening of 177 microns, a 150 mesh screen size refers -to a sieve opening of 104 microns and a 325 mesh screen size refers to a 12~3Z63~
sieve opening of 44 microns.
In order to increase the surface area of the outer seed coat starting material so as to effectively dissolve and remove undesirable components during the process, the dry cleaned outer seed coat may be reduced in size, for ex-ample, by means of a grinder. An air swept pulverizer or hammer mill may preferably be used to grind the outer seed coat to a powder. The impact of the hammers or beaters af-fects the components of the outer seed coat starting mater-ial to different degrees. The pure outer seed coat itselfis somewhat difficult to grind because of its fibrous nat-ure whereas any pea cotyledon chips present are more readily reduced to a fine powder. The ground outer seed coat mat-erial may then be separated by means of a cascading screen-ing system. Initially, the ground outer seed coat material may be sifted over vibratory screens or centrifugal screens using a 150 mesh screen to separate the finer powder, re-ferred to as pea flour, from the larger particle size pow-der. This pea flour contains varying amounts of fibre and protein depending upon the moisture content of the outer seed coat starting material and the settings of the grinder.
This pea flour may be used for treatment according to the process of this invention to provide a novel fibrous nat-ural product.
On the other hand, ground outer seed coat material having different particle sizes may also be used in the pro-cess of this invention. Thus, for example, ground outer seed coat material which passes through a 60 mesh screen is very suitable for use in the process of this invention. Rel-atively tough cellulosic fibrous material from the outer seedcoat tends to remain on a 60 mesh screen whereas softer fi-bres having higher contents of hemicellulose, pectins and gums are more readily ground and tend to pass through a 60 - 5 - ~ 3~
mesh screen. The actual particle size of the outer seed coat starting material may be varied according to the type of fi-brous natural product which it is desired to produce. The finer the particle size of the powder, i.e., ground outer seed coat material passing through a 100 mesh screen or a 150 mesh screen, to be used as starting material for the process of this invention, the softer the fibrous natural product will be which is prepared therefrom and such a product tends to be characterized by having a high water absorption. When the ground outer seed coat used as starting material is a powder having larger particle sizes, such as a powder which passes through a 60 mesh screen or a 40 mesh screen, the fi-brous natural product obtained therefrom tends to be a less soft fibrous product having a lower water absorption charac-teristic.
It is to be understood, therefore, that ground outer seed coat material to be used as starting material in this process may vary over a broad range of particle sizes and the particular range of particle size chosen to be used will be dependent upon the type of fibrous natural product re-quired. Thus, for example, ground outer seed coat material to be used as starting material may have particle sizes such that it may pass through any screen from about 20 mesh size to about 150 mesh size. Thus, different sizes of ground outer seed coat material to be used in this process may be (a) passes through 150 mesh screen, (b) passes through 100 mesh screen, (c) passes through 20 mesh screen but remains on a 150 mesh screen, (d) passes through a 30 to 60 mesh screen, preferably a 40 mesh screen, but remains on a 150 mesh screen, (e) passes through a 60 mesh screen but remains on an 80 mesh screen, and (f) passes through a 20 mesh screen but remains on a 60 mesh screen.
2~i3(~
Any oversized or too large particle size of ground outer seed coat material which is considered to be unsuit-able for the process of this lnvention may be recycled and returned to the grinder for regrinding to smaller particle size.
A conveniently sized ground outer seed coat material may be a powder passing through a 20 to 60 mesh screen (840 to 250 microns) and remaining on a 150 mesh screen (104 mi-crons) or it may be a powder passing through a 50 mesh screen (297 microns) and remaining on an 80 mesh screen (177 microns).
According to the process of this invention, the ground outer seed coat material is mixed with an excess of water to provide an aqueous slurry which is agitated to dissolve com-ponents, such as proteins and sugars, present in the ground material. The aqueous slurry used may be of the order of from about 2~ to about 20% by weight of solid, preferably from about 2~ to about 10% by weight of solid, and particularly from about 5% to about 6% by weight of solid, according to equipment available.
The slurry may be agitated at a temperature of from about 5C to about 40C, preferably from about 15C to about 25Cr more particularly at about 20C, and for a period of from about 2 minutes to about 10 minutes, preferably for from about 6 to about 8 minutes. It is desirable to avoid agita-tion of the slurry for too long a period in order to avoid dissolving certain soluble components present in the fibrous material such as pectins or gums.
It is also desirable to maintain the aqueous slurry at a pH below about 8.5 and preferably below about 7Ø The slurry tends to become darker coloured on increasing the pH
and it is therefore particularly useful to maintain the pH
within the range of from about 6.0 to about 6.5 when the ~.,'2~3Z630 slurry contains ground outer seed coat material from green or yellow peas. The pH of the slurry may be adjusted, if de-sired, by the addition of an appropriate amount of a weak acid such as citric acid or phosphoric acid to maintain a p~
range of from about 6.0 to about 6.5.
When agitation of the aqueous slurry is complete, the slurry is then filtered. A vibratory type screen may be used which may have a 325 mesh screen and the solid moist cake re-tained by the filter is then dried. Drying may be effectively carried out by passing the solid moist cake to a suitable dri-er such as a flash type (forced air) drier. The dried mater-ial thus obtained is a fibrous product which may have a mois-ture content of about 8% with a particle size of from about 150 mesh to about 30 to 50 mesh. In certain circumstances, it may be desirable to reduce the particle size to a maximum of 80 mesh size (177 microns) to reduce the apparent texture of the fibrous product. The dried powder may therefore be subjected to further grinding, for example, by use of an air swept pulverizer. The product thus obtained may then be ~0 screened over an 80 mesh screen using vibratory or centri-fugal type sifters to produce a fairly uniform product in the form of a powder. This powder is a fibrous natural product which we have named as concentrated pea bran in view of its preparation from the outer seed coat of pea seeds.
As a further valuable feature of the invention we have found that an additional processing stage may be included to provide an alternative type of novel fibrous natural product which may be desired for certain uses as an additive to food products. Thus, after the initia] agitation of the aqueous slurry and filtering to remove the aqueous filtrate contain-ing soluble products, the residual moist solid cake may then be reslurried in water and subjected to an oxidation or blea--~28Z63~
ching treatment.
This second slurry may conveniently be a 2% to 20% by weight slurry in water, preferably from about 2% to about 10%
by weight slurry in water, and more particularly, from about 5% to about 6% by weight slurry in water.
As a suitable oxidizing or bleaching agent there may be mentioned hydrogen peroxide or an alkali metal hypochlor-ite, such as sodium hypochlorite. ~he oxidizing or bleaching agent may be used at a concentration of from about 100 parts to about 200 parts per million (ppm). A preferred oxidizing or bleaching agent is hydrogen peroxide used at a concentra-tion of about 100 ppm. Other oxidizing or bleaching agents which may be used are, for example, an alkali metal sulphite or bisulphite such as sodium sulphite or sodium bisulphite, and sulphur dioxide. Treatment of the aqueous slurry with an oxidizing or bleaching agent may be carried out at a tempera-ture of from about 15C to about 30C, preferably from about 20C to about 25C with a residence time which may be from about 5 minutes to about 30 minutes. It is desirable to avoid ~0 too long a residence time because the aqueous slurry may tend to thicken. A preferred oxidizing or bleaching treatment in-volves agitating the slurry at about 25C for about 5 minutes.
As indicated above, it is desirable that the aqueous slurry be maintained at a pH below about 8.5 and preferably below about 7Ø A particularly useful pH is within the range of from about 6.0 to about 6.5 where using an aqueous slurry prepared from the outer seed coat of green or yellow peas.
Such a pH may be achieved by the addition of a weak acid such as citric acid or phosphoric acid to the aqueous slurry.
When the oxidizing or bleaching treatment is complete, the aqueous slurry is filtered, conveniently by use of a cen-trifuge, such as a decanter centrifuge. The moist solid cake .. .. .
- 9 - ~ 3X6~30 thus obtained is then dried, for example, by means of a flash type (forced air) drier. The product obtained generally has particle sizes of the order of from about 150 mesh to about 30 to 60 mesh.
When it is desired to reduce the particle size to ob-tain a more uniform size of product, the dried material may be ground by usingr for example, an air swept pulverizer.
This grinding produces a powder which may then be screened over 80 mesh screens (177 microns) using vibratory or centri-fugal type sifters. The generally uniform powdered productis a novel fibrous natural product which we describe as a concentrated pea bran and which is useful as an additive in a variety of food products where natural fibre is required.
The invention is illustrated by, but not limited by, the following Examples describing the process and the pro-ducts of the invention.
- 10 - ~8X~3~3 One thousand pounds of cleaned outer seed coat from yellow field peas are ground in a Jacobson hammer mill equipped with air conveyance for product removal. The powder is sifted across a 150 mesh screen using a Kason centrifugal sifter. The fine fraction passing through the 150 mesh screen is a variety of pea flour with a protein content of approxi-mately 22~ and a crude fibre content of approximately 11%.
The fine pea flour amounts to approximately 170 pounds. This pea flour is subjected to a process as described at the end of this Example.
The remaining powder retained on 150 mesh is sifted over a 40 mesh screen in a similar type of rotary or centri-fugal sifter. The material that passes through 40 mesh is gathered for further processing. The material retained on 40 mesh is returned to the grinder or hammer mill for further size reduction. Approxima-tely 750 pounds of material passes through the 40 mesh and 80 pounds is recycled to the grinder.
The 750 pounds of powder passing through the 40 mesh screen is mixed with 14,250 pounds of water to form a slurry in water containing 5% w/w solids. This slurry, having a p~I
of 6.8 r is agitated and held for an average residence time of 7 minutes at a temperature of 20C.
The slurry is then pumped to a Sweco brand vibratory screen fitted with a 325 mesh screen. Dissolved components are washed through the screen while the fibre fraction is collected as a solid wet filter cake. This solid cake of fibrous material weighs about 3,000 pounds and has a solids content of approximately 20%r i.e.~ it contains about 600 ~0 pounds of solid material.
The soli~ cake is passed to a flash type (forced air) 8X~3~
drier. The solid cake is dried to a moisture content of 8%
and then ground in an air swept pulverizer. The moisture content is thereby reduced to 5% and the powder is then sifted over a Kason type centrifugal sifter with an 80 mesh screen.
The oversized particles are recirculated to the feed entry to the flash type (forced air) drier where they provide some ad-ditional friability to the new feed cake entering the drier.
The 550 pounds of powder that passes through the 80 mesh screen is a novel fibrous natural product which we describe as "concentrated pea bran" and which is useful as an additive to a variet~ of food products.
The pea flour (approximately 170 pounds) is formed in-to an aqueous 5% w/w slurry and subjected to a similar type of treatment as indicated above. There is thus obtained a fibrous natural product (80 to lO0 pounds) as a dried powdered product which is a concentrated pea bran.
EXA~PLE 2 The process of Example l is repeated to the stage where there is obtained the solid wet cake of washed fibre weighing about 3,000 pounds and having a solids content of approximately 20~. An additional processing stage is then carried out as follows:
This washed fibrous material weighing about 3,000 pounds and containing about 600 pounds of solid material is added to 3,000 pounds of water containing phosphoric acid to provide a slurry of about 10% w/w having a pH of 6.5. To this slurry is added lO0 parts per million (ppm) of hydrogen peroxide and the slurry is agitated and maintained at 25~C for 5 minutes. The slurry is then centrifuged in a Sharples decanter centrifuge.
The liquid supernatant is stored for future use at the begin-ning of this process and the l,375 pounds of solid cake having a solids content of 40% is passed ~o a flash type (forced air) drier.
- 12 - ~2~2~
The solid cake is dried to a moisture content of 8 and then ground in an air swept pulverizer. The moisture content is thereby reduced to 5% and the powder is then sif-ted over a Kason type centrifugal sifter with an 80 mesh screen. The oversized particles are recirculated to the feed entry to the flash type (forced air) drier where they provide some additional friability to the new feed cake entering the drier. The 550 pounds of powder that passes throl~gh the 80 mesh screen is a novel fibrous product which we describe as "concentrated pea bran" and which is useful as an additive to a variety of food products.
.
~ . . . . .
and which can be added to food products to increase dietary fibre levels without significantly detracting from the flav-our or texture of the food products.
The outer seed coat or skin of peas is a preferred starting material. The outer seed coat of peas is made up of an outer layer of palisade cells, a layer of hourglass cells, smaller parenchyma cells, aleurone cells and, finally, compressed layers of endosperm cells. The internal or remain-ing portion of the seed is generally referred to as the meat.
The raw starting material is generally in the form of whole or complete half pea shapes (split hollow spheres or rough hollow hemispheres) of the outer seed coat or skins of the pea seed mixed with fragments of spheres and pea cotyle-don chips or broken powder-like particles. This raw start-ing material is available from manufacturers or processors of split peas who process the pea seeds by splitting the seeds to remove the outer seed coat or skin and retain only the residual internal portion of the seed in the form of split peas (meat). If necessary, the raw starting material may be passed over a gravity type separator in order to sep-arate the denser pea cotyledon chips and other particles from the lighter, less dense outer seed coat pieces. ~fter such a gravitational separation treatment, the outer seed coat is low in density, fluffy in texture and fairly light in colour.
It is to be understood that the sizes of mesh screens referred to throughout this specification are to be interpre-ted as U.S. standard screen sizes. Thus, for example, 30 to 60 mesh screen size refers to sieve openings of 590 microns to 250 microns, an 80 mesh screen size refers to a sieve op-ening of 177 microns, a 150 mesh screen size refers -to a sieve opening of 104 microns and a 325 mesh screen size refers to a 12~3Z63~
sieve opening of 44 microns.
In order to increase the surface area of the outer seed coat starting material so as to effectively dissolve and remove undesirable components during the process, the dry cleaned outer seed coat may be reduced in size, for ex-ample, by means of a grinder. An air swept pulverizer or hammer mill may preferably be used to grind the outer seed coat to a powder. The impact of the hammers or beaters af-fects the components of the outer seed coat starting mater-ial to different degrees. The pure outer seed coat itselfis somewhat difficult to grind because of its fibrous nat-ure whereas any pea cotyledon chips present are more readily reduced to a fine powder. The ground outer seed coat mat-erial may then be separated by means of a cascading screen-ing system. Initially, the ground outer seed coat material may be sifted over vibratory screens or centrifugal screens using a 150 mesh screen to separate the finer powder, re-ferred to as pea flour, from the larger particle size pow-der. This pea flour contains varying amounts of fibre and protein depending upon the moisture content of the outer seed coat starting material and the settings of the grinder.
This pea flour may be used for treatment according to the process of this invention to provide a novel fibrous nat-ural product.
On the other hand, ground outer seed coat material having different particle sizes may also be used in the pro-cess of this invention. Thus, for example, ground outer seed coat material which passes through a 60 mesh screen is very suitable for use in the process of this invention. Rel-atively tough cellulosic fibrous material from the outer seedcoat tends to remain on a 60 mesh screen whereas softer fi-bres having higher contents of hemicellulose, pectins and gums are more readily ground and tend to pass through a 60 - 5 - ~ 3~
mesh screen. The actual particle size of the outer seed coat starting material may be varied according to the type of fi-brous natural product which it is desired to produce. The finer the particle size of the powder, i.e., ground outer seed coat material passing through a 100 mesh screen or a 150 mesh screen, to be used as starting material for the process of this invention, the softer the fibrous natural product will be which is prepared therefrom and such a product tends to be characterized by having a high water absorption. When the ground outer seed coat used as starting material is a powder having larger particle sizes, such as a powder which passes through a 60 mesh screen or a 40 mesh screen, the fi-brous natural product obtained therefrom tends to be a less soft fibrous product having a lower water absorption charac-teristic.
It is to be understood, therefore, that ground outer seed coat material to be used as starting material in this process may vary over a broad range of particle sizes and the particular range of particle size chosen to be used will be dependent upon the type of fibrous natural product re-quired. Thus, for example, ground outer seed coat material to be used as starting material may have particle sizes such that it may pass through any screen from about 20 mesh size to about 150 mesh size. Thus, different sizes of ground outer seed coat material to be used in this process may be (a) passes through 150 mesh screen, (b) passes through 100 mesh screen, (c) passes through 20 mesh screen but remains on a 150 mesh screen, (d) passes through a 30 to 60 mesh screen, preferably a 40 mesh screen, but remains on a 150 mesh screen, (e) passes through a 60 mesh screen but remains on an 80 mesh screen, and (f) passes through a 20 mesh screen but remains on a 60 mesh screen.
2~i3(~
Any oversized or too large particle size of ground outer seed coat material which is considered to be unsuit-able for the process of this lnvention may be recycled and returned to the grinder for regrinding to smaller particle size.
A conveniently sized ground outer seed coat material may be a powder passing through a 20 to 60 mesh screen (840 to 250 microns) and remaining on a 150 mesh screen (104 mi-crons) or it may be a powder passing through a 50 mesh screen (297 microns) and remaining on an 80 mesh screen (177 microns).
According to the process of this invention, the ground outer seed coat material is mixed with an excess of water to provide an aqueous slurry which is agitated to dissolve com-ponents, such as proteins and sugars, present in the ground material. The aqueous slurry used may be of the order of from about 2~ to about 20% by weight of solid, preferably from about 2~ to about 10% by weight of solid, and particularly from about 5% to about 6% by weight of solid, according to equipment available.
The slurry may be agitated at a temperature of from about 5C to about 40C, preferably from about 15C to about 25Cr more particularly at about 20C, and for a period of from about 2 minutes to about 10 minutes, preferably for from about 6 to about 8 minutes. It is desirable to avoid agita-tion of the slurry for too long a period in order to avoid dissolving certain soluble components present in the fibrous material such as pectins or gums.
It is also desirable to maintain the aqueous slurry at a pH below about 8.5 and preferably below about 7Ø The slurry tends to become darker coloured on increasing the pH
and it is therefore particularly useful to maintain the pH
within the range of from about 6.0 to about 6.5 when the ~.,'2~3Z630 slurry contains ground outer seed coat material from green or yellow peas. The pH of the slurry may be adjusted, if de-sired, by the addition of an appropriate amount of a weak acid such as citric acid or phosphoric acid to maintain a p~
range of from about 6.0 to about 6.5.
When agitation of the aqueous slurry is complete, the slurry is then filtered. A vibratory type screen may be used which may have a 325 mesh screen and the solid moist cake re-tained by the filter is then dried. Drying may be effectively carried out by passing the solid moist cake to a suitable dri-er such as a flash type (forced air) drier. The dried mater-ial thus obtained is a fibrous product which may have a mois-ture content of about 8% with a particle size of from about 150 mesh to about 30 to 50 mesh. In certain circumstances, it may be desirable to reduce the particle size to a maximum of 80 mesh size (177 microns) to reduce the apparent texture of the fibrous product. The dried powder may therefore be subjected to further grinding, for example, by use of an air swept pulverizer. The product thus obtained may then be ~0 screened over an 80 mesh screen using vibratory or centri-fugal type sifters to produce a fairly uniform product in the form of a powder. This powder is a fibrous natural product which we have named as concentrated pea bran in view of its preparation from the outer seed coat of pea seeds.
As a further valuable feature of the invention we have found that an additional processing stage may be included to provide an alternative type of novel fibrous natural product which may be desired for certain uses as an additive to food products. Thus, after the initia] agitation of the aqueous slurry and filtering to remove the aqueous filtrate contain-ing soluble products, the residual moist solid cake may then be reslurried in water and subjected to an oxidation or blea--~28Z63~
ching treatment.
This second slurry may conveniently be a 2% to 20% by weight slurry in water, preferably from about 2% to about 10%
by weight slurry in water, and more particularly, from about 5% to about 6% by weight slurry in water.
As a suitable oxidizing or bleaching agent there may be mentioned hydrogen peroxide or an alkali metal hypochlor-ite, such as sodium hypochlorite. ~he oxidizing or bleaching agent may be used at a concentration of from about 100 parts to about 200 parts per million (ppm). A preferred oxidizing or bleaching agent is hydrogen peroxide used at a concentra-tion of about 100 ppm. Other oxidizing or bleaching agents which may be used are, for example, an alkali metal sulphite or bisulphite such as sodium sulphite or sodium bisulphite, and sulphur dioxide. Treatment of the aqueous slurry with an oxidizing or bleaching agent may be carried out at a tempera-ture of from about 15C to about 30C, preferably from about 20C to about 25C with a residence time which may be from about 5 minutes to about 30 minutes. It is desirable to avoid ~0 too long a residence time because the aqueous slurry may tend to thicken. A preferred oxidizing or bleaching treatment in-volves agitating the slurry at about 25C for about 5 minutes.
As indicated above, it is desirable that the aqueous slurry be maintained at a pH below about 8.5 and preferably below about 7Ø A particularly useful pH is within the range of from about 6.0 to about 6.5 where using an aqueous slurry prepared from the outer seed coat of green or yellow peas.
Such a pH may be achieved by the addition of a weak acid such as citric acid or phosphoric acid to the aqueous slurry.
When the oxidizing or bleaching treatment is complete, the aqueous slurry is filtered, conveniently by use of a cen-trifuge, such as a decanter centrifuge. The moist solid cake .. .. .
- 9 - ~ 3X6~30 thus obtained is then dried, for example, by means of a flash type (forced air) drier. The product obtained generally has particle sizes of the order of from about 150 mesh to about 30 to 60 mesh.
When it is desired to reduce the particle size to ob-tain a more uniform size of product, the dried material may be ground by usingr for example, an air swept pulverizer.
This grinding produces a powder which may then be screened over 80 mesh screens (177 microns) using vibratory or centri-fugal type sifters. The generally uniform powdered productis a novel fibrous natural product which we describe as a concentrated pea bran and which is useful as an additive in a variety of food products where natural fibre is required.
The invention is illustrated by, but not limited by, the following Examples describing the process and the pro-ducts of the invention.
- 10 - ~8X~3~3 One thousand pounds of cleaned outer seed coat from yellow field peas are ground in a Jacobson hammer mill equipped with air conveyance for product removal. The powder is sifted across a 150 mesh screen using a Kason centrifugal sifter. The fine fraction passing through the 150 mesh screen is a variety of pea flour with a protein content of approxi-mately 22~ and a crude fibre content of approximately 11%.
The fine pea flour amounts to approximately 170 pounds. This pea flour is subjected to a process as described at the end of this Example.
The remaining powder retained on 150 mesh is sifted over a 40 mesh screen in a similar type of rotary or centri-fugal sifter. The material that passes through 40 mesh is gathered for further processing. The material retained on 40 mesh is returned to the grinder or hammer mill for further size reduction. Approxima-tely 750 pounds of material passes through the 40 mesh and 80 pounds is recycled to the grinder.
The 750 pounds of powder passing through the 40 mesh screen is mixed with 14,250 pounds of water to form a slurry in water containing 5% w/w solids. This slurry, having a p~I
of 6.8 r is agitated and held for an average residence time of 7 minutes at a temperature of 20C.
The slurry is then pumped to a Sweco brand vibratory screen fitted with a 325 mesh screen. Dissolved components are washed through the screen while the fibre fraction is collected as a solid wet filter cake. This solid cake of fibrous material weighs about 3,000 pounds and has a solids content of approximately 20%r i.e.~ it contains about 600 ~0 pounds of solid material.
The soli~ cake is passed to a flash type (forced air) 8X~3~
drier. The solid cake is dried to a moisture content of 8%
and then ground in an air swept pulverizer. The moisture content is thereby reduced to 5% and the powder is then sifted over a Kason type centrifugal sifter with an 80 mesh screen.
The oversized particles are recirculated to the feed entry to the flash type (forced air) drier where they provide some ad-ditional friability to the new feed cake entering the drier.
The 550 pounds of powder that passes through the 80 mesh screen is a novel fibrous natural product which we describe as "concentrated pea bran" and which is useful as an additive to a variet~ of food products.
The pea flour (approximately 170 pounds) is formed in-to an aqueous 5% w/w slurry and subjected to a similar type of treatment as indicated above. There is thus obtained a fibrous natural product (80 to lO0 pounds) as a dried powdered product which is a concentrated pea bran.
EXA~PLE 2 The process of Example l is repeated to the stage where there is obtained the solid wet cake of washed fibre weighing about 3,000 pounds and having a solids content of approximately 20~. An additional processing stage is then carried out as follows:
This washed fibrous material weighing about 3,000 pounds and containing about 600 pounds of solid material is added to 3,000 pounds of water containing phosphoric acid to provide a slurry of about 10% w/w having a pH of 6.5. To this slurry is added lO0 parts per million (ppm) of hydrogen peroxide and the slurry is agitated and maintained at 25~C for 5 minutes. The slurry is then centrifuged in a Sharples decanter centrifuge.
The liquid supernatant is stored for future use at the begin-ning of this process and the l,375 pounds of solid cake having a solids content of 40% is passed ~o a flash type (forced air) drier.
- 12 - ~2~2~
The solid cake is dried to a moisture content of 8 and then ground in an air swept pulverizer. The moisture content is thereby reduced to 5% and the powder is then sif-ted over a Kason type centrifugal sifter with an 80 mesh screen. The oversized particles are recirculated to the feed entry to the flash type (forced air) drier where they provide some additional friability to the new feed cake entering the drier. The 550 pounds of powder that passes throl~gh the 80 mesh screen is a novel fibrous product which we describe as "concentrated pea bran" and which is useful as an additive to a variety of food products.
.
~ . . . . .
Claims (51)
1. A process for the preparation of a novel improved fibrous natural product which comprises agitating an aqueous slurry of ground solid material from the outer seed coat of a legume for only a period of time required to dissolve water-soluble proteins and sugars present in the solid material while retaining in the solid material pectins or gums present in the solid material, filtering said slurry to remove solid product containing said pectins or gums from said slurry, and drying the solid product containing said pectins or gums to provide a novel fibrous natural product containing said pec-tins or gums.
2. A process for the preparation of a novel improved fibrous natural product which comprises grinding solid mater-ial from the outer seed coat of a legume to a requisite part-icle size, forming an aqueous slurry of the ground material and agitating said slurry for only a period of time required to dissolve water-soluble proteins and sugars present in the solid material while retaining pectins or gums present in the solid material, filtering said slurry to remove solid product containing said pectins or gums from said slurry, and drying the solid product containing said pectins or gums to provide a novel fibrous natural product containing said pectins or gums.
3. A process for the preparation of a novel improved fibrous natural product which comprises agitating an aqueous slurry of ground material from the outer seed coat of a leg-ume for only a period of time required to dissolve water-soluble proteins and sugars present in the solid material while retaining in the solid material pectins or gums present in the solid material, filtering said slurry to remove solid material containing said pectins or gums from said slurry, suspending the solid material containing said pectins or gums in water to form a second aqueous slurry and treating said second slurry with an oxidizing or bleaching agent to oxidize or bleach the solid material while retaining in the solid material said pectins or gums, filtering said second slurry to remove solid product containing said pectins or gums from said second slurry, and drying the solid product containing said pectins or gums to provide a novel fibrous natural pro-duet containing said pectins or gums.
4. The process of claim 1, wherein the outer seed coat material is obtained from yellow or green field peas.
5. The process of claim 1, wherein the legume hull material is obtained from white beans, navy beans or soya beans.
6. The process of claim 1, wherein the outer seed coat material has a particle size which passes through a 30 to 60 mesh screen but does not pass through a 150 mesh screen.
7. The process of claim 1, wherein the outer seed coat material has a particle size which passes through a 40 mesh screen but does not pass through a 150 mesh screen.
8. The process of claim 1, wherein the outer seed coat material has a particle size which passes through a 60 mesh screen but does not pass through an 80 mesh screen.
9. The process of claim 1, wherein the slurry con-tains from about 2% to about 20% by weight of solid.
10. The process of claim 1, wherein the slurry con-tains from about 2% to about 10% by weight of solid.
11. The process of claim 1, wherein the slurry con-tains about 5% by weight of solid.
12. The process of claim 1, wherein the slurry is agitated at a temperature of from about 5°C to about 40 C.
13. The process of claim 1, wherein the slurry is agitated at a temperature of from about 15°C to about 25°C.
14. The process of claim 1, wherein the slurry is agitated at a temperature of about 20 C.
15. The process of claim 1, wherein the slurry is agitated for a period of from about 2 minutes to about 10 minutes.
16. The process of claim 1, wherein the slurry is agitated for a period of from about 6 minutes to about 8 minutes.
17. The process of claim 1, wherein the slurry is agitated at a temperature of about 20°C for a period of from about 6 minutes to about 8 minutes.
18. The process of claim 1, wherein the slurry is maintained at a pH of from about 6.0 to about 6.5.
19. The process of claim 1, wherein the slurry is maintained at a pH of from about 6.0 to about 6.5 by the addition of citric acid or phosphoric acid.
20. The process of claim 3, wherein the second slurry contains from about 5% to about 20% by weight of solid.
21. The process of claim 3, wherein the second slurry contains about 10% by weight of solid.
22. The process of claim 3, wherein the oxidizing or bleaching agent is an alkali metal hypochlorite, an alkali metal sulphite or an alkali metal bisulphite.
23. The process of claim 3, wherein the oxidizing or bleaching agent is sodium hypochlorite, sodium sulphite or sodium bisulphite.
24. The process of claim 3, wherein the oxidizing or bleaching agent is sulphur dioxide.
25. The process of claim 3, wherein the oxidizing or bleaching agent is hydrogen peroxide.
26. The process of claim 3, wherein the oxidizing or bleaching agent is used at a concentration of from about 100 parts to about 200 parts per million (ppm).
27. The process of claim 3, wherein the oxidizing or bleaching agent is used at a concentration of about 100 ppm.
28. The process of claim 3, wherein the oxidizing or bleaching agent is hydrogen peroxide which is used at a con-centration of about 100 ppm.
29. The process of claim 3, wherein the oxidizing or bleaching is carried out at a temperature of from about 15°C
to about 30°C.
to about 30°C.
30. The process of claim 3, wherein the oxidizing or bleaching is carried out at a temperature of from about 20°C
to about 25°C.
to about 25°C.
31. The process of claim 3, wherein the oxidizing or bleaching is carried out at a temperature of about 25°C for a period of about 5 minutes.
32. The process of claim 1, wherein the fibrous natu-ral product is dried by means of a flash type (forced air) drier.
33. The process of claim 1, wherein the fibrous natu-ral product is ground to a powder having a particle size which passes through a 30 to 50 mesh screen but does not pass through a 150 mesh screen.
34. The process of claim 1, wherein the fibrous natu-ral product is ground to a powder having a particle size which passes through an 80 mesh screen.
35. A process for the preparation of a novel improved fibrous natural product which comprises grinding material from the outer seed coat of a legume to a particle size which passes through a 20 mesh screen but does not pass through a 60 mesh screen, forming a 5% w/w aqueous slurry of the ground material and agitating said slurry at a temperature of about 20°C for a period of from about 6 to about 8 minutes to dis-solve water-soluble products, filtering said slurry through a 325 mesh screen, suspending the solid material in water to form a 10% w/w second slurry, treating said second slurry, with 10% ppm of hydrogen peroxide at a temperature of about 25°C for a period of about 5 minutes, filtering said second slurry and drying the solid product to provide a fibrous product.
36. The process of claim 35 wherein the legume is yellow or green field peas.
37. The process of claim 35 wherein the fibrous pro-duct is ground to a powder having a particle size which passes through an 80 mesh screen.
38. A process for the preparation of a fibrous pro-duct which comprises grinding material from the outer seed coat of a legume to a particle size which passes through a 20 mesh screen but does not pass through a 150 mesh screen, forming an aqueous slurry of the ground material and agitat-ing said slurry at a temperature of from about 5°C to about 40°C for a period of from about 2 to about 10 minutes to dis-solve water-soluble proteins and sugars present in the mater-ial while retaining pectins or gums present in the material, filtering said slurry to remove solid product from said slurry, and drying the solid product to provide a fibrous product.
39. A novel fibrous natural product when prepared by the process of claim 1, 2 or 3.
40. A novel fibrous natural product when prepared by the process of claim 4, 5 or 6.
41. A novel fibrous natural product when prepared by the process of claim 7, 8 or 9.
42. A novel fibrous natural product when prepared by the process of claim 10, 11 or 12.
43. A novel fibrous natural product when prepared by the process of claim 13, 14 or 15.
44. A novel fibrous natural product when prepared by the process of claim 16, 17 or 18.
45. A novel fibrous natural product when prepared by the process of claim 19, 20 or 21.
46. A novel fibrous natural product when prepared by the process of claim 22, 23 or 24.
47. A novel fibrous natural product when prepared by the process of claim 25, 26 or 27.
48. A novel fibrous natural product when prepared by the process of claim 28, 29 or 30.
49. A novel fibrous natural product when prepared by the process of claim 31, 32 or 33.
50. A novel fibrous natural product when prepared by the process of claim 34, 35 or 36.
51. A novel fibrous natural product when prepared by the process of claim 37 or 38.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000513465A CA1282630C (en) | 1986-07-10 | 1986-07-10 | Fibrous product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000513465A CA1282630C (en) | 1986-07-10 | 1986-07-10 | Fibrous product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1282630C true CA1282630C (en) | 1991-04-09 |
Family
ID=4133534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000513465A Expired - Lifetime CA1282630C (en) | 1986-07-10 | 1986-07-10 | Fibrous product |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1282630C (en) |
-
1986
- 1986-07-10 CA CA000513465A patent/CA1282630C/en not_active Expired - Lifetime
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