CA1212573A - Process of separating polysaccharide-containing meals into high protein and low protein fractions - Google Patents
Process of separating polysaccharide-containing meals into high protein and low protein fractionsInfo
- Publication number
- CA1212573A CA1212573A CA000457865A CA457865A CA1212573A CA 1212573 A CA1212573 A CA 1212573A CA 000457865 A CA000457865 A CA 000457865A CA 457865 A CA457865 A CA 457865A CA 1212573 A CA1212573 A CA 1212573A
- Authority
- CA
- Canada
- Prior art keywords
- organic liquid
- guar
- fractions
- meal
- protein
- 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
Links
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23J—PROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
- A23J1/00—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites
- A23J1/12—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites from cereals, wheat, bran, or molasses
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23J—PROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
- A23J1/00—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites
- A23J1/14—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites from leguminous or other vegetable seeds; from press-cake or oil-bearing seeds
- A23J1/142—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites from leguminous or other vegetable seeds; from press-cake or oil-bearing seeds by extracting with organic solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
- C08B37/0093—Locust bean gum, i.e. carob bean gum, with (beta-1,4)-D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from the seeds of carob tree or Ceratonia siliqua; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
- C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Emergency Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Food Science & Technology (AREA)
- Botany (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Jellies, Jams, And Syrups (AREA)
- Cosmetics (AREA)
- Peptides Or Proteins (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Polysaccharide-containing particles, such as guar gum meal, are separated into high protein and low protein fractions by dispersing and suspending the particles in an organic liquid which has a density between those of the fractions to be separated The particles which partition in the organic liquid according to their density, are isolated and dried.
Polysaccharide-containing particles, such as guar gum meal, are separated into high protein and low protein fractions by dispersing and suspending the particles in an organic liquid which has a density between those of the fractions to be separated The particles which partition in the organic liquid according to their density, are isolated and dried.
Description
PROCESS OF SEPARATING POLYSACCHARIDE-CONTAINING
I MEALS INTO HIGH PROTEIN AND LOW PROTEIN FRACTIONS
_ ¦ Numerous polysaccharide-containing meals exist as physi-cal mixtures of high protein and low protein particles ! For many uses, a separation into low protein and high protein fractions is advantageous. Examples of such meals are polygalactomannan-con taining meals such as carob bean meal and guar bean meal as well ' as tamarind bean meal, tara bean mea1, wheat, rye and maize meals.
Il The object of this invention is the separation of the polysaccharide~containing meals into high protein and low protein fractions. The so obtained high protein fractions are particular-ily suited as prôtein-enriched foods. The low protein fractions, on the other hand, have technological advantages compared to the , starting materials, particularly when used as thickening agents.
I The preferred meals for conducting the separation pro-;lcess are those which contain polygalactomannans, such as guar bean meal and locust bëan meal with guar bean meal being most preferred.
';However, other meals can be processed in analogous manner and ~ separated into the desired high protein and low protein fractions.
Guar bean meal is produced from the endosperm of the guar seed. Guar seed contains about 35~ endosperm. The guar endo~
sperm is obtained by mechanically separating the endosperm from husks and seedlings and is contaminated by small amounts of husk j residues and seedling meal. The commercial products are produced by grinding this endosperm to varying degrees of fineness and then putting the so ground endosperm through sieves of corresponding sizes. The kind of physical and mechanical preliminary and subse-I quent treatments will then determine the quality and fineness of ~Ithe products marke~ed usually in meal form, t lll The morphology of ~uar seed shows that the seedling and ~ithe embryonal root are completely surrounded by the endosperm.
The periphery of the en~osperm consists of an aleuron-like cell llayer practically insoluble in water which contains about 25%
protein. This cell layer and the water-insoluble cell walls, husks and seedling residues are the reason for the inability,so far, of producing completely clear, water-soluble products.
The endosperm itself consists mainly of water-soluble llpolygalactomannans which during germination of the seed serve as llfood for the growing plant.
The mechanically separated guar endosperm, called guar ~splits, is characterized by its gum content (polygalactomannan content). The gum content is here defined as the difference be-l tween 100 weight percent and the sum of the percentage amounts of water, protein and components not hydrolyzable by acid (A.I.R. -!'- acid-insoluble residue). This gum content varies with most commercial guar splits between 78 and 86 weight percent. The ¦Iprotein content is mostly between 3.8 and 6.0 weight percent, and the A.I.R. content between 1.7 and 3.6 weight percent. The water I content of the splits fluctuates between 8.0 and 12.0 weight per-cent. Guar polygalactomannans in small concentrations with water form highly viscous solutions. One weight percent solutions of commercial guar bean meal in water give viscosities of about ji3,000 to 6,000 mPa.s.
l l ¦ Guar products are often subjected to extremely fine ,grinding in order to eliminate as much as possible the troubling ¦effect of the water-insoluble components. For use in the textile industry, for example, the particles should be smaller than 50~ m I
llso that they can pass through the stencils and cause no misprints. !
30 ¦1 It was now found that these undesirable water-insoluble Il ,
I MEALS INTO HIGH PROTEIN AND LOW PROTEIN FRACTIONS
_ ¦ Numerous polysaccharide-containing meals exist as physi-cal mixtures of high protein and low protein particles ! For many uses, a separation into low protein and high protein fractions is advantageous. Examples of such meals are polygalactomannan-con taining meals such as carob bean meal and guar bean meal as well ' as tamarind bean meal, tara bean mea1, wheat, rye and maize meals.
Il The object of this invention is the separation of the polysaccharide~containing meals into high protein and low protein fractions. The so obtained high protein fractions are particular-ily suited as prôtein-enriched foods. The low protein fractions, on the other hand, have technological advantages compared to the , starting materials, particularly when used as thickening agents.
I The preferred meals for conducting the separation pro-;lcess are those which contain polygalactomannans, such as guar bean meal and locust bëan meal with guar bean meal being most preferred.
';However, other meals can be processed in analogous manner and ~ separated into the desired high protein and low protein fractions.
Guar bean meal is produced from the endosperm of the guar seed. Guar seed contains about 35~ endosperm. The guar endo~
sperm is obtained by mechanically separating the endosperm from husks and seedlings and is contaminated by small amounts of husk j residues and seedling meal. The commercial products are produced by grinding this endosperm to varying degrees of fineness and then putting the so ground endosperm through sieves of corresponding sizes. The kind of physical and mechanical preliminary and subse-I quent treatments will then determine the quality and fineness of ~Ithe products marke~ed usually in meal form, t lll The morphology of ~uar seed shows that the seedling and ~ithe embryonal root are completely surrounded by the endosperm.
The periphery of the en~osperm consists of an aleuron-like cell llayer practically insoluble in water which contains about 25%
protein. This cell layer and the water-insoluble cell walls, husks and seedling residues are the reason for the inability,so far, of producing completely clear, water-soluble products.
The endosperm itself consists mainly of water-soluble llpolygalactomannans which during germination of the seed serve as llfood for the growing plant.
The mechanically separated guar endosperm, called guar ~splits, is characterized by its gum content (polygalactomannan content). The gum content is here defined as the difference be-l tween 100 weight percent and the sum of the percentage amounts of water, protein and components not hydrolyzable by acid (A.I.R. -!'- acid-insoluble residue). This gum content varies with most commercial guar splits between 78 and 86 weight percent. The ¦Iprotein content is mostly between 3.8 and 6.0 weight percent, and the A.I.R. content between 1.7 and 3.6 weight percent. The water I content of the splits fluctuates between 8.0 and 12.0 weight per-cent. Guar polygalactomannans in small concentrations with water form highly viscous solutions. One weight percent solutions of commercial guar bean meal in water give viscosities of about ji3,000 to 6,000 mPa.s.
l l ¦ Guar products are often subjected to extremely fine ,grinding in order to eliminate as much as possible the troubling ¦effect of the water-insoluble components. For use in the textile industry, for example, the particles should be smaller than 50~ m I
llso that they can pass through the stencils and cause no misprints. !
30 ¦1 It was now found that these undesirable water-insoluble Il ,
- 2 -ll lZ1~5'73 endosperm cell formations, which can contain up to 25 weight per-¦cent protein, and the husk residues of commercial guar products l can be removed in large part, if not completely, by separation in _ an organic liquid, chloroform for example, from the inner endo- ¦
Isperm. The separation of the guar meal particles into high ¦protein and low protein fractions is conducted by suspending the ¦particles in a liquid, the density of which is between those of ~the particles to be separated~ The particles separate into layers, ! the separated~layers are isolated and the liquid is removed.
,I The separation of the inner endosperm cell formations from the water-insoluble seed particles is based on the different specific weights of the various cell kinds. The seedling of the guar seed has a density of about 1290-1350 kg/m3, whereas the husk l~and the larger part of the endosperm (including aleuron-like cell Illayer) have a density of about 1490-1510 kg/m3 (at a water content of about 10%). The density of the fraction containing the aleuron-;-like cell layer varies between about 1300 and about 1450 kg/m .
' The density of chloroform is 1470 kg/m3~at 20C. and ~I lies thus between these fractions. By suspending the guar meal in chloroform/ the lighter rich-in~protein components rise to the top and the poor-in-protein~inner endosperm meal settles at the bottom.~
The separation into layers of different densities takes ¦
place as a function of time. Through simple tests, the optimal lltime conditions and organic liquids for a given starting material and the particular requirements can be determined.
The separation takes place according to the Stokes' Law which says:
Isperm. The separation of the guar meal particles into high ¦protein and low protein fractions is conducted by suspending the ¦particles in a liquid, the density of which is between those of ~the particles to be separated~ The particles separate into layers, ! the separated~layers are isolated and the liquid is removed.
,I The separation of the inner endosperm cell formations from the water-insoluble seed particles is based on the different specific weights of the various cell kinds. The seedling of the guar seed has a density of about 1290-1350 kg/m3, whereas the husk l~and the larger part of the endosperm (including aleuron-like cell Illayer) have a density of about 1490-1510 kg/m3 (at a water content of about 10%). The density of the fraction containing the aleuron-;-like cell layer varies between about 1300 and about 1450 kg/m .
' The density of chloroform is 1470 kg/m3~at 20C. and ~I lies thus between these fractions. By suspending the guar meal in chloroform/ the lighter rich-in~protein components rise to the top and the poor-in-protein~inner endosperm meal settles at the bottom.~
The separation into layers of different densities takes ¦
place as a function of time. Through simple tests, the optimal lltime conditions and organic liquids for a given starting material and the particular requirements can be determined.
The separation takes place according to the Stokes' Law which says:
- 3 -I, ~ 2~S~3 V = _ X . g (~ k ~ d ~ Il X = ~ ~ k L ~ k ~ d) ~
V = creaming or settling rate in m/s k = dynamic viscosity of the con~inuous phase (the organic liquid) in Pa.s.
~g = acceleration due to gravity in m/s2 ~ k = density of the continuous phase in kg/m d = density of the disperse phase (the solid) in kg~m3 Depending on the nature of the starting material, a more ;or less clear intermediate layer results from which, if need be, further solids can be obtained.
By an appropriate choice of the density difference be-I!tween the continuous phase and ~he disperse phase, the rates of separation of the various fractions and their amounts can be regulated as desired.
Il The following organic liquids and/or organic liquid mixtures, which at 20C. have a density of about 1460 to about 1480 kg/m , can be used, for example, for the separation of guar ' meals:
Il a) trichloroethylene, density = 1480 kg/m, i b) mixture of 87 volume percent trichlorotrifluoro-ethane and 13 volume percent 2-propanol, density =
~ I 1477 kg/m3, ,, I
c) mixture of 51 volume percent tetrachloroethylene and 49 volume percent trichloroethane,density =
~ 1460 kg/m .
l Suitable mixture~, for example, from two o:r more of the .~
5 ~3 following organic liquids can likewise be used for the separation:
l Tetrachloromethane 1595 kg/m ¦I Trichloroethylene 1466 kg/m3 I ~ichloromethane 1320 k~/m3 I Trichloropropane 1390 kg/m3 Trichloroethane 1325 kg/m Toluene ~ Il 866 kg/m Tetrachlorodifluoroethane f 1634 kg/m3 ¦ Heavy gasoline 760-785 kg/m3 I~The above enumerated examples are given by way of example only, those skilled in this art being able to readily compile further organic liquid mixtures that have the desired densities.
The organic liquids or organic liquid mixtures useful in , this invention are those which are liquid at room temperature, I i.e., 20-30C., which are non-solvents for the polysaccharide--containing meals and which contain no groups which are reactive with polysaccharide-containing meals under the reaction conditions j of the process of this invention. Such organic liquids or liquid mixtures have densities of about 1290 to about 1500 kg/m3 at 20C.
2G I'The organic liquids are used in the amounts of about l to about 10l jand, preferably, 1.4 to about ~, parts by weight per part of poly- !
saccharide-containing material.
I To implement the process of the present invention, the I material to be separated is generally suspended in the organic ~liquid under stirring and left standing until separation occurs.
Following that, the upper layer is removed, the remainder stirred up again and again left standing~ After the second separation, !
the upper layer is removed. The settled lower layer is stirred ¦¦up and drained off, separated by centrifugation from the organic lliquid and dried.
,1 ', _ 5 _ l ~
Il ~2~
Density separations of commercial guar bean meals of different qualities gave the follo~ing fraction amounts ~weight percent):
Inner Endosperm Upper ` Name of Product Meal Layer Loss Guar ~SA-200/50 (Meyhall Chemical AG) 75 24 Guar CSAA M 225 (Meyhall Chemical AG) 61 36 3 Guar CSAA M lO0 (Meyhall Chemical AG) 70 27 3 . . _ _ .
A 1 weight percent solution of the so obtained lnner endosperm meal has a viscosity of 7000-~000 mPa.s. Guar products of such a high viscosity h~d not been obtainable in the trade up till now.
; Joined to the aleuron-like upper layer are still cells that contain water-soluble polygalactomannans. Consequently, the upper fraction can be used to form solutions which have viscosi-i~ties of 2000-3000 mPa.s at l weight percent in water. This fraction can thus be used as starting material for thickeners for l the paper and textile industries.
0 Through a density separation with organic liquid mix-tures permitted for use in foods or by a complete removal of the orsanic liquid used from the separated fraction, thickeners for the food industry can be obtained which give solutions with up to j ~0% higher viscosities than those obtained with commercially lavailable guar products. This, in turn, will allow reduced amounts of starting materials.
¦ The unmodified inner endosperm meals obtained in accord-ance with the process of the invention are excellently suited as inexpensive thickeners for the textile industry (carpet printing, ~0 spacedyeing), since their solutions are clearer, thus contain less *Trade mark ~,~
'~
12~ ~573 ¦undissolved portions, and furthermore have with equal concentra-lltion a higher viscosity than commercia:Lly sold guar products.
¦¦This permits saving in the amount of t~lickeners required. Thick-_~ eners of this kind have in 1 weight percent solution, at 25C. and 20 RPM as measured in a Brookfield Viscosimeter RVT, a viscosity that is at least 20% higher than that of a corresponding solution ¦
of the starting products.
The inner endosperm fraction can be depolymerized easier l~than the conventional not fractionated guar bean meals, e.~., by ~lalkaline oxidation and other depolymerization reactions (enzy-matically, thermally, acid decomposition).
Guar derivatives can be made from the inner endosperm fraction obtained according to the invention. The aqueous solu-tions of such derivatives have at a low degree of substitution I considerably improved clearness and high viscosity.
Cationic derivatives of the inner endosperm fraction give practically clear water solutions with viscosities up to 4000 mPa.s in 1~ concentration. Corresponding hydroxypropylated ilor carboxymethylated guar derivatives give likewise solutions of 1l high viscosity and clearness. Phosphate esters of the inner endo-!, sperm fraction also show improved properties in respect to color and clearness of the solutions as compared to the commercially sold phosphate esters of guar bean meal.
I The invention will now be e~plained ~ore fully by several examples. The examples relate to the batchwise production of guar products; however, other meals can be similarly separated I
and modified. The said processes can also be carried out continu-l ously, in closed cycle.
~I The percentages are always in percent by weight, unless otherwise indicated. The viscosity always refers to 1 weight S~3 percent solutions at 25C., as measured with a Brookfield viscosi l meter RVT at 20 RPM.
l l _ EXAMPLE 1 To 12 liters (1.) of trichloroethylene were added with stirring 4.625 kilograms (kg.) of guar bean meal, type CSA 200/50 ¦
obtained from Meyhall Chemical AG. The guar bean meal was thor-lloughly dispersed in the trichloroethylene and was left standing I'for 30 minutes. The rich-in-protein particles which floated to the top were separated and filtered under vacuum. The inner endo-sperm meal which settled to the bottom was also recovered by fil-' tering off the trichloroethylene.
" The separated fractions were then dried at 60-70C. in I a hot air oven. The upper layer fraction weighed 1.072 kilograms, the lower layer 3.510 kilograms. The loss of product was 1%.
~ Ij Three additional runs were conducted using the same ; I materials and conditions. The results of all of these runs are I listed in Table 1. The density of the upper fractions were 1300-I -1450 kg./m3, the densities of the lower fractions were 1484-1507 kg./m3.
Tables 2 and 3 show the viscosities of aqueous solutions~
of the lower layers and the upper layers compared to that of the starting material and the analyses (water content, protein content land A.~.R. content) of the fractions after separation and organic ¦liquid removal.
!
,l '7 I
l l ¦ ~ TABLE 1 ~ , ¦l Run No.
IGuar bean meal kg. 4.625 7.583 7.583 7.5831 Trichloroethylene 1. 12 20 20 20 Inner endosperm ; - kg. 3.510 5.682 5.668 5.600 ~Upper layer kg. r.O72 1.755 1.903 1.928 I Organic liquid in product 1. 1.7 1.8 1.8 1.8 li prior to drying 1' ,Loss product % 1 2 0 .
,l TABLE 2 1 ~ Starting Inner Endosperm of Runs l! Material 1 2 3 4 ! Viscosity, 20 RPM, i 25C., 1% in Water ~
after 1 hour ~ 5500 - 6750 ~ 6850 6850 6900 i! after 24 hours 5800 6900 7000 7000 7000 hot dissolved~ ; 6940 7320 7210 6950 pH 6.6 6.6 6.7 6.7 Water Content 9.0 7.4 8.0 7.8 5.6 Protein Content 3.8 1.9 1.6 1.6 1.6 .
IA.I.R. Content 2.2 1.5 1.4 1.2 1.3 - - -Il .1 l~ !
!
1~ 9 I
?,5'7~ -Starting Upper I,ayer of Runs I Material 1 2 3 4 _ IViscosity, 20 RPM
25C., 1% in Water after l hour5500 242020202020 2340 after 24 hours 5800 24502070 2160 2380 pH 6.~6.9 7.0 6.9 I,Water Content 9.0 7.07.4 6.8 7.2 I Protein Content 3.8 9.4 10.4 10.8 9.7 'A.I.R. Content 2.2 3.43.6 3.4 3.2 Il EXAMPLE 2 Il 600 g guar bean meal CSA-200/50 (Meyhall) were suspended ¦'in 2336 g trichloroethylene. To investigate the effect of time on the quality of separation, the settled fractions were recovered llby filtration and drying at 50-60C. after 25, 30, 35 and 150 minutes.
¦; Thefractions were characterized microscopically and by the viscosities of their 1% solutions (based on lO weight percent water content). The solutions were dissolved at 86-89C. during , lllO minutes, and the viscosity measured at 25C; The table below shows the results:
l l S~7~?, i I Settling Amount Settled ! Time in in g Viscosity Microscopic j Fraction Minutes 10% Water Content mPa.s Analysis 1 25 179.1 7900 Pure inner endosperm ! ?. 30 132.8 7650 Pure inner ¦ endosperm 1 3 35 122.1 6800 Isolated aleuron--like cell formations
V = creaming or settling rate in m/s k = dynamic viscosity of the con~inuous phase (the organic liquid) in Pa.s.
~g = acceleration due to gravity in m/s2 ~ k = density of the continuous phase in kg/m d = density of the disperse phase (the solid) in kg~m3 Depending on the nature of the starting material, a more ;or less clear intermediate layer results from which, if need be, further solids can be obtained.
By an appropriate choice of the density difference be-I!tween the continuous phase and ~he disperse phase, the rates of separation of the various fractions and their amounts can be regulated as desired.
Il The following organic liquids and/or organic liquid mixtures, which at 20C. have a density of about 1460 to about 1480 kg/m , can be used, for example, for the separation of guar ' meals:
Il a) trichloroethylene, density = 1480 kg/m, i b) mixture of 87 volume percent trichlorotrifluoro-ethane and 13 volume percent 2-propanol, density =
~ I 1477 kg/m3, ,, I
c) mixture of 51 volume percent tetrachloroethylene and 49 volume percent trichloroethane,density =
~ 1460 kg/m .
l Suitable mixture~, for example, from two o:r more of the .~
5 ~3 following organic liquids can likewise be used for the separation:
l Tetrachloromethane 1595 kg/m ¦I Trichloroethylene 1466 kg/m3 I ~ichloromethane 1320 k~/m3 I Trichloropropane 1390 kg/m3 Trichloroethane 1325 kg/m Toluene ~ Il 866 kg/m Tetrachlorodifluoroethane f 1634 kg/m3 ¦ Heavy gasoline 760-785 kg/m3 I~The above enumerated examples are given by way of example only, those skilled in this art being able to readily compile further organic liquid mixtures that have the desired densities.
The organic liquids or organic liquid mixtures useful in , this invention are those which are liquid at room temperature, I i.e., 20-30C., which are non-solvents for the polysaccharide--containing meals and which contain no groups which are reactive with polysaccharide-containing meals under the reaction conditions j of the process of this invention. Such organic liquids or liquid mixtures have densities of about 1290 to about 1500 kg/m3 at 20C.
2G I'The organic liquids are used in the amounts of about l to about 10l jand, preferably, 1.4 to about ~, parts by weight per part of poly- !
saccharide-containing material.
I To implement the process of the present invention, the I material to be separated is generally suspended in the organic ~liquid under stirring and left standing until separation occurs.
Following that, the upper layer is removed, the remainder stirred up again and again left standing~ After the second separation, !
the upper layer is removed. The settled lower layer is stirred ¦¦up and drained off, separated by centrifugation from the organic lliquid and dried.
,1 ', _ 5 _ l ~
Il ~2~
Density separations of commercial guar bean meals of different qualities gave the follo~ing fraction amounts ~weight percent):
Inner Endosperm Upper ` Name of Product Meal Layer Loss Guar ~SA-200/50 (Meyhall Chemical AG) 75 24 Guar CSAA M 225 (Meyhall Chemical AG) 61 36 3 Guar CSAA M lO0 (Meyhall Chemical AG) 70 27 3 . . _ _ .
A 1 weight percent solution of the so obtained lnner endosperm meal has a viscosity of 7000-~000 mPa.s. Guar products of such a high viscosity h~d not been obtainable in the trade up till now.
; Joined to the aleuron-like upper layer are still cells that contain water-soluble polygalactomannans. Consequently, the upper fraction can be used to form solutions which have viscosi-i~ties of 2000-3000 mPa.s at l weight percent in water. This fraction can thus be used as starting material for thickeners for l the paper and textile industries.
0 Through a density separation with organic liquid mix-tures permitted for use in foods or by a complete removal of the orsanic liquid used from the separated fraction, thickeners for the food industry can be obtained which give solutions with up to j ~0% higher viscosities than those obtained with commercially lavailable guar products. This, in turn, will allow reduced amounts of starting materials.
¦ The unmodified inner endosperm meals obtained in accord-ance with the process of the invention are excellently suited as inexpensive thickeners for the textile industry (carpet printing, ~0 spacedyeing), since their solutions are clearer, thus contain less *Trade mark ~,~
'~
12~ ~573 ¦undissolved portions, and furthermore have with equal concentra-lltion a higher viscosity than commercia:Lly sold guar products.
¦¦This permits saving in the amount of t~lickeners required. Thick-_~ eners of this kind have in 1 weight percent solution, at 25C. and 20 RPM as measured in a Brookfield Viscosimeter RVT, a viscosity that is at least 20% higher than that of a corresponding solution ¦
of the starting products.
The inner endosperm fraction can be depolymerized easier l~than the conventional not fractionated guar bean meals, e.~., by ~lalkaline oxidation and other depolymerization reactions (enzy-matically, thermally, acid decomposition).
Guar derivatives can be made from the inner endosperm fraction obtained according to the invention. The aqueous solu-tions of such derivatives have at a low degree of substitution I considerably improved clearness and high viscosity.
Cationic derivatives of the inner endosperm fraction give practically clear water solutions with viscosities up to 4000 mPa.s in 1~ concentration. Corresponding hydroxypropylated ilor carboxymethylated guar derivatives give likewise solutions of 1l high viscosity and clearness. Phosphate esters of the inner endo-!, sperm fraction also show improved properties in respect to color and clearness of the solutions as compared to the commercially sold phosphate esters of guar bean meal.
I The invention will now be e~plained ~ore fully by several examples. The examples relate to the batchwise production of guar products; however, other meals can be similarly separated I
and modified. The said processes can also be carried out continu-l ously, in closed cycle.
~I The percentages are always in percent by weight, unless otherwise indicated. The viscosity always refers to 1 weight S~3 percent solutions at 25C., as measured with a Brookfield viscosi l meter RVT at 20 RPM.
l l _ EXAMPLE 1 To 12 liters (1.) of trichloroethylene were added with stirring 4.625 kilograms (kg.) of guar bean meal, type CSA 200/50 ¦
obtained from Meyhall Chemical AG. The guar bean meal was thor-lloughly dispersed in the trichloroethylene and was left standing I'for 30 minutes. The rich-in-protein particles which floated to the top were separated and filtered under vacuum. The inner endo-sperm meal which settled to the bottom was also recovered by fil-' tering off the trichloroethylene.
" The separated fractions were then dried at 60-70C. in I a hot air oven. The upper layer fraction weighed 1.072 kilograms, the lower layer 3.510 kilograms. The loss of product was 1%.
~ Ij Three additional runs were conducted using the same ; I materials and conditions. The results of all of these runs are I listed in Table 1. The density of the upper fractions were 1300-I -1450 kg./m3, the densities of the lower fractions were 1484-1507 kg./m3.
Tables 2 and 3 show the viscosities of aqueous solutions~
of the lower layers and the upper layers compared to that of the starting material and the analyses (water content, protein content land A.~.R. content) of the fractions after separation and organic ¦liquid removal.
!
,l '7 I
l l ¦ ~ TABLE 1 ~ , ¦l Run No.
IGuar bean meal kg. 4.625 7.583 7.583 7.5831 Trichloroethylene 1. 12 20 20 20 Inner endosperm ; - kg. 3.510 5.682 5.668 5.600 ~Upper layer kg. r.O72 1.755 1.903 1.928 I Organic liquid in product 1. 1.7 1.8 1.8 1.8 li prior to drying 1' ,Loss product % 1 2 0 .
,l TABLE 2 1 ~ Starting Inner Endosperm of Runs l! Material 1 2 3 4 ! Viscosity, 20 RPM, i 25C., 1% in Water ~
after 1 hour ~ 5500 - 6750 ~ 6850 6850 6900 i! after 24 hours 5800 6900 7000 7000 7000 hot dissolved~ ; 6940 7320 7210 6950 pH 6.6 6.6 6.7 6.7 Water Content 9.0 7.4 8.0 7.8 5.6 Protein Content 3.8 1.9 1.6 1.6 1.6 .
IA.I.R. Content 2.2 1.5 1.4 1.2 1.3 - - -Il .1 l~ !
!
1~ 9 I
?,5'7~ -Starting Upper I,ayer of Runs I Material 1 2 3 4 _ IViscosity, 20 RPM
25C., 1% in Water after l hour5500 242020202020 2340 after 24 hours 5800 24502070 2160 2380 pH 6.~6.9 7.0 6.9 I,Water Content 9.0 7.07.4 6.8 7.2 I Protein Content 3.8 9.4 10.4 10.8 9.7 'A.I.R. Content 2.2 3.43.6 3.4 3.2 Il EXAMPLE 2 Il 600 g guar bean meal CSA-200/50 (Meyhall) were suspended ¦'in 2336 g trichloroethylene. To investigate the effect of time on the quality of separation, the settled fractions were recovered llby filtration and drying at 50-60C. after 25, 30, 35 and 150 minutes.
¦; Thefractions were characterized microscopically and by the viscosities of their 1% solutions (based on lO weight percent water content). The solutions were dissolved at 86-89C. during , lllO minutes, and the viscosity measured at 25C; The table below shows the results:
l l S~7~?, i I Settling Amount Settled ! Time in in g Viscosity Microscopic j Fraction Minutes 10% Water Content mPa.s Analysis 1 25 179.1 7900 Pure inner endosperm ! ?. 30 132.8 7650 Pure inner ¦ endosperm 1 3 35 122.1 6800 Isolated aleuron--like cell formations
4 150 25.2 4400 As fraction 3, plus isolated husX residue 459.2 , . . . .
The table shows that the achievable viscoslty drops as the sett-ling time increases.
; EXAMPLE 3 .
7.5 kg. guar bean meal CSA-200/50 (Meyhall) with a water ~content of 9% were suspended under vigorous stirring in a mixture ~ of 17.4 1, trichlorotrifluoroethane (Freon*R 113) and 2.6 1.
3 2-propanol, the density of the mixture being 1477 kg./m3.
I In this test, the following fractions were obtained:
Fraction Weight No. Characterization (10% Water) Viscositv 1%
1 upper layer 1.457 kg. (not determined) , ~rich-in-protein) 5li 2 middle layer 0.686 kg. (not determined) (rich-in-protein to poor-in-protein) 3 lower layer 5.401 kg. 7600 mPa.s (poor-in-protein) 1 ~ .
O l ~ *Trade mark I
, , 1 ~2~73 ~': L'L' ~
ll 15 kg. guar inner endosperm meal from Example 1 (vis- ¦
_ cosity ca. 7600 mPa.s) were reacted in a nitrogen atmosphere with 3.32 kg. sodium hydroxide in the presence of 16 g sodium tetra- I
borate decahydrate at a total weight content of about 40% at 65C.¦
for a period of 60 minutes. After ~ooling to 45C., the alkaline product was partially neutralized with 2.40 kgO 80% acetic acid, which had previously been diluted with 0~60 kg. water and 1.00 kg.l l2-propanol. After a further cooling to room temperature, 3.35 kg. !
glycidyl trimethylammonium chloride which had been previously diluted with 3.60 kg. water were added. After heating to 65C., the reaction was continued at this temperature for a period of one hour. Following that, the reaction product was cooled to 45C.
I Thereafter, for purposes of neutralization, 1.27 kg. acetic acid, ¦Idiluted with 1.00 kg. methanol, were added. The byproducts of the ¦ reaction mixture were either extracted with methanol or the mix-I ture was dried directly.
¦I The purified product dissolved rapidly with a pH of 5.0 , in water and gave a clear water solution. Such a product is Illexcellently suited for use as hair conditioner ln transparent 1 .
!I shampoos.
With this process, products with a DS of 0.10 to 0.14 I~can be produced which as 1% solutions have viscosities of up to 4000 mPa.s.
EXAMPL~ 5 100 g guar inner endosperm meal from Exarnple 1 were carboxymethylated in the usual manner with sodium rnonochloro-l l , acetate and sodium hydroxide. After the reaction, the product was dried and then ground.
carboxymethyl guar with a DS of 1.6 to 1.8 according to this example gave clear aqueous solutions and shows at 8% con-icentration a viscosity of 24,000 mPa.s (measured with a Brookfield*
'RV~' viscosimeter at 20 RPM, spindle 6, 25C.).
The product was readily, i.e., without clumps, dispersi-~ble and dissolved immediately at a p~ below 10.
EXA~PLE 6 ;
1.06 moles inner guar endosperm meal from Example 1 were carboxymethylated with 0.21 mole sodium monochloroacetate and 0.50 mole sodium hydroxide at a water content of the reaction mixture of 40.5~ at 65C. under nitrogen. Following that, the alkaline reaction product was partially neutralized with 0.15 mole phos-phoric acid, diluted with 0.5 mole methanol, and the product was dried at 80C. and then ground.
The so obtained product had as a 1% aqueous solution a viscosity of 3000 ~Pa.s, at a pH of 9.4. The substitution degree was~about 0.16 EXAMPL~ 7 ~ .
ii j 200~g guar inner endosperm meal, obtained as in Example ¦1, were mixed in a laboratory kneader with a solution of 10 ml NaOH 30~, diluted with 100 ml water. This solution was added drop by drop within a period of seven minutes and at room tempera-~ ture. After completion of the addition, mixing was contlnued for O llanother 3 minutes in order to assure thorough mixing oE the i *Trade mark ,~ , Ii ¦!
components. Following that, a solution of 6 ml 30% hydrogen ¦ peroxide and 20 ml water was slowly aaded within a period of 4 I minutes and during heating to 70C. thoroughly mixed with the _ alkaline guar inner endosperm meal. During heating and also during the depolymerization at 70C., the kneader remained closed.
The depolymerization lasted about 60 minutes. After this time, the hydrogen peroxide had disappeared, and the reaction mixture 1, l was neutralized after cooling to 50C. with 5 ml 85% H3P04, ¦Idiluted with 20 ml isopropanol.
1, The product was then dried at 80C. to a water content of ca. 10% and then ground.
I The so obtainedl almost white product dissolved rapidly ; in cold water.
I; The viscosity of a 4% solution was ca. 4500 mPa.s I (measured with a sroOkfield RVT, spindle 4, 20 RPM, 25C.).
The product is well suited as textile printing thick-ener. When printing on polyester, a print paste containing 3~ of ¦'the product gives the same results as a conventional guar product in a concentration of 5-6~.
I The product is furthermore extremely thermally stable.
If the air-dry product is subjected during three days to a heat treatment at 60C., it loses only 18% of its thickening power, while commercially sold products can with this treatment lose up to 60% of their thickening power.
200 g inner guar endosperm meal (viscosity ca. 7000 mPa.s) were mixed with a solution of 60 ml 30% NaOH, 36 ml 85%
~ H3P04 and 100 ml water d~ring 10 minutes. The phosphate solution ~ - 14 -(cooled to 25C.) was added in drops during a period of 13 minutes.
Following that, the procedure as described in United States Patent I,No. 4,320,226 was followed.
I The so obtained slightly alkaline, slightly cream-col-jored and dispersible product dissolved at a neutral pH rapidly ! in cold water.
¦¦ The viscosity of a 2~ solution was ca. loo mPa.s.
EXA~IPLE 9 .: .
2500 g guar inner endosperm meal from Example 1 were mixed drop by drop with a solution of 265 ml 30% NaOH, 2.5 g borax and 1300 ml water in a reactor. After addition of the solution was completed, the reactor was closed and the air expelled by nitrogen. The reaction temperature was adjusted by indirect heat~
ing to 70-75C., and 565 g propylene oxide gas wereintroduced during the course of an hour. After a further reaction of 10 minutes, the product was dried at 80C. in a drying chamber and then ground.
Such a hydroxypropyl guar derivative had in 1~ aqueous solution a viscosity of about3000mPa.s, based on 10~ water con-tent of the product.
75 g JBKM FLEUR M 175 ~carob bean meal of Meyhall Chemical AG) were suspended under stirring in 294 g trichloro-ethylene.
After 30 minutes, the settled and the floating fractions were separated and recovered by filtration and subsequent drying *Trade mark l l ~''`,ID~ !i 1~:1L"5'7~ ~
at 70C.
The weights of the two fractions and their protein con-~ tents (6.25 x N content) illustrate the separation by the process _ I of the invention: -5Fraction ~eight (g) Protein (~) Raw product 75.00 6.3 ¦Upper layer 2.85 41.7 ILower layer 71.45 i 4.9 jl EXAMPLE 11 I
75 g of wheat extract meal type 405 were suspended under stirring in 294 g trichloroethylene.
' After 30 minutes, the settled and the floating fractions, were separated and recovered by filtration and drying at 70C.
The weights of the two fractions and their protein con-I tents (6.25 x N content) were as follows:
IlFraction Weight (g) Protein (%) ,Raw product 75.00 ca. 10.0 Upper layer 10.21 24.2 Lower layer 62.87 7.9 I, ~
¦ EXAMPLE 12 ,, When 500 g Raw Guar Meal (Guar-Keimlingsmehl plus husk plus endosperm fragments) were suspended in 1000 ml trichloro-l ethylene and 70 ml crystal oil (heavy gasoline), clensity of the mixture 1420 kg./m3, the following fractions after a separation li , 1 ` i !
~ .. ! c. 5 ~ ~
.,, time of 5 minutes were obtained:
In Wt. %
_ . I
FractionA.I.R. Fat ~ Protein Ash . . . _ _ , _ ca. 50% upper layer 11.4n.m. 5.7 57.7 4.8 13-15% middle layer 8.8 1.0 5.6 57.8 5.9 ca. 30% lower layer 37.6 1.0 3.5 11.6 4.4 Raw guar meal22.3 4.3 8.5 40.1 5.0 _ !
In.m.: not measured.
I . I
I When 1000 g tamarind bean meal were extracted ~for I degreasing) in 2000'ml trichloroethylene at 52C. and then left 'standing as suspension during 21 hours at 20C., three layers are formed:
¦ Fraction ~ Weight (g) Protein % H~0 % I
~,Upper iayer 92 68.7 7.4 Middle layer 55 n.m. n.m.
I,Lower layer `713 11.0 6.5 IStarting material 1000 12.9 ' 7.5 . ~
'n.m.: not measured.
The upper layer contains aleuron grains with a diameter of about 4 ~m and aleuron accumulations with a diameter of about 30 ~m.
.
,1 - 17 - ~
I
lZ1~5'~3 The clearness of the aqueous solutions of the various products obtained by the process described above was measured by I light transmission at 500 nm with a cell of 1 cm optical path.
The concentration of the solutions was 0.5 wt. %, not considering ' the water contentO The stated transmission in % represents a mean value of three determinations.,"-The ~learness of the solu-'tions of guar inner endosperm derivatives as obtained from the 10 l preceding examples is, as shown in the following table, clearly ~~better than that of solutions of commercial guar derivatives.
, _ I' /
/
/
, ' /
1l /
~' /
1. / ~
,, .
.~
i3 Il .
il , ' E z~
,! 3 ~
~1 o CO cr Cl ~) N 1~ 1~ ~1 Ct:) ~7 0 0 0 O
E~ O ~ O a~ c~ co In r--l N a~ ~ O
' ~0\o` ~
E~ .
a~
a ; ~u ~ E
O ~ 0 ~ OO O O O OO U~ ~ ~ ~ ~ ~ U~
N ~
a, I a ) U C~) ~,) H O ~ O ~) H O
O h O
OS~ S I h Q) 1~ 0 1~ rV ~ C) N~ ~~ ell tl~ 3 'h 3 rr~ u~ O O O 0 r~ H ~1 h ~ h I ~ ~u ~ 1~ .c o~
~ t) P~ ::~ o ~ .Y
~ O ~) h h S~ L~. U 3 3 x ~ ~ N ~ r~
, Pi O ~ J H O O O ~¢ h )~ O
" ~ H H H ~ O ~J ~) ~ Ll~:1 ~ ~ r~ ~
~ 1 1 1 1 ~ UU 1 ~,) 5~ ~rr, tO ~
I .
The table shows that the achievable viscoslty drops as the sett-ling time increases.
; EXAMPLE 3 .
7.5 kg. guar bean meal CSA-200/50 (Meyhall) with a water ~content of 9% were suspended under vigorous stirring in a mixture ~ of 17.4 1, trichlorotrifluoroethane (Freon*R 113) and 2.6 1.
3 2-propanol, the density of the mixture being 1477 kg./m3.
I In this test, the following fractions were obtained:
Fraction Weight No. Characterization (10% Water) Viscositv 1%
1 upper layer 1.457 kg. (not determined) , ~rich-in-protein) 5li 2 middle layer 0.686 kg. (not determined) (rich-in-protein to poor-in-protein) 3 lower layer 5.401 kg. 7600 mPa.s (poor-in-protein) 1 ~ .
O l ~ *Trade mark I
, , 1 ~2~73 ~': L'L' ~
ll 15 kg. guar inner endosperm meal from Example 1 (vis- ¦
_ cosity ca. 7600 mPa.s) were reacted in a nitrogen atmosphere with 3.32 kg. sodium hydroxide in the presence of 16 g sodium tetra- I
borate decahydrate at a total weight content of about 40% at 65C.¦
for a period of 60 minutes. After ~ooling to 45C., the alkaline product was partially neutralized with 2.40 kgO 80% acetic acid, which had previously been diluted with 0~60 kg. water and 1.00 kg.l l2-propanol. After a further cooling to room temperature, 3.35 kg. !
glycidyl trimethylammonium chloride which had been previously diluted with 3.60 kg. water were added. After heating to 65C., the reaction was continued at this temperature for a period of one hour. Following that, the reaction product was cooled to 45C.
I Thereafter, for purposes of neutralization, 1.27 kg. acetic acid, ¦Idiluted with 1.00 kg. methanol, were added. The byproducts of the ¦ reaction mixture were either extracted with methanol or the mix-I ture was dried directly.
¦I The purified product dissolved rapidly with a pH of 5.0 , in water and gave a clear water solution. Such a product is Illexcellently suited for use as hair conditioner ln transparent 1 .
!I shampoos.
With this process, products with a DS of 0.10 to 0.14 I~can be produced which as 1% solutions have viscosities of up to 4000 mPa.s.
EXAMPL~ 5 100 g guar inner endosperm meal from Exarnple 1 were carboxymethylated in the usual manner with sodium rnonochloro-l l , acetate and sodium hydroxide. After the reaction, the product was dried and then ground.
carboxymethyl guar with a DS of 1.6 to 1.8 according to this example gave clear aqueous solutions and shows at 8% con-icentration a viscosity of 24,000 mPa.s (measured with a Brookfield*
'RV~' viscosimeter at 20 RPM, spindle 6, 25C.).
The product was readily, i.e., without clumps, dispersi-~ble and dissolved immediately at a p~ below 10.
EXA~PLE 6 ;
1.06 moles inner guar endosperm meal from Example 1 were carboxymethylated with 0.21 mole sodium monochloroacetate and 0.50 mole sodium hydroxide at a water content of the reaction mixture of 40.5~ at 65C. under nitrogen. Following that, the alkaline reaction product was partially neutralized with 0.15 mole phos-phoric acid, diluted with 0.5 mole methanol, and the product was dried at 80C. and then ground.
The so obtained product had as a 1% aqueous solution a viscosity of 3000 ~Pa.s, at a pH of 9.4. The substitution degree was~about 0.16 EXAMPL~ 7 ~ .
ii j 200~g guar inner endosperm meal, obtained as in Example ¦1, were mixed in a laboratory kneader with a solution of 10 ml NaOH 30~, diluted with 100 ml water. This solution was added drop by drop within a period of seven minutes and at room tempera-~ ture. After completion of the addition, mixing was contlnued for O llanother 3 minutes in order to assure thorough mixing oE the i *Trade mark ,~ , Ii ¦!
components. Following that, a solution of 6 ml 30% hydrogen ¦ peroxide and 20 ml water was slowly aaded within a period of 4 I minutes and during heating to 70C. thoroughly mixed with the _ alkaline guar inner endosperm meal. During heating and also during the depolymerization at 70C., the kneader remained closed.
The depolymerization lasted about 60 minutes. After this time, the hydrogen peroxide had disappeared, and the reaction mixture 1, l was neutralized after cooling to 50C. with 5 ml 85% H3P04, ¦Idiluted with 20 ml isopropanol.
1, The product was then dried at 80C. to a water content of ca. 10% and then ground.
I The so obtainedl almost white product dissolved rapidly ; in cold water.
I; The viscosity of a 4% solution was ca. 4500 mPa.s I (measured with a sroOkfield RVT, spindle 4, 20 RPM, 25C.).
The product is well suited as textile printing thick-ener. When printing on polyester, a print paste containing 3~ of ¦'the product gives the same results as a conventional guar product in a concentration of 5-6~.
I The product is furthermore extremely thermally stable.
If the air-dry product is subjected during three days to a heat treatment at 60C., it loses only 18% of its thickening power, while commercially sold products can with this treatment lose up to 60% of their thickening power.
200 g inner guar endosperm meal (viscosity ca. 7000 mPa.s) were mixed with a solution of 60 ml 30% NaOH, 36 ml 85%
~ H3P04 and 100 ml water d~ring 10 minutes. The phosphate solution ~ - 14 -(cooled to 25C.) was added in drops during a period of 13 minutes.
Following that, the procedure as described in United States Patent I,No. 4,320,226 was followed.
I The so obtained slightly alkaline, slightly cream-col-jored and dispersible product dissolved at a neutral pH rapidly ! in cold water.
¦¦ The viscosity of a 2~ solution was ca. loo mPa.s.
EXA~IPLE 9 .: .
2500 g guar inner endosperm meal from Example 1 were mixed drop by drop with a solution of 265 ml 30% NaOH, 2.5 g borax and 1300 ml water in a reactor. After addition of the solution was completed, the reactor was closed and the air expelled by nitrogen. The reaction temperature was adjusted by indirect heat~
ing to 70-75C., and 565 g propylene oxide gas wereintroduced during the course of an hour. After a further reaction of 10 minutes, the product was dried at 80C. in a drying chamber and then ground.
Such a hydroxypropyl guar derivative had in 1~ aqueous solution a viscosity of about3000mPa.s, based on 10~ water con-tent of the product.
75 g JBKM FLEUR M 175 ~carob bean meal of Meyhall Chemical AG) were suspended under stirring in 294 g trichloro-ethylene.
After 30 minutes, the settled and the floating fractions were separated and recovered by filtration and subsequent drying *Trade mark l l ~''`,ID~ !i 1~:1L"5'7~ ~
at 70C.
The weights of the two fractions and their protein con-~ tents (6.25 x N content) illustrate the separation by the process _ I of the invention: -5Fraction ~eight (g) Protein (~) Raw product 75.00 6.3 ¦Upper layer 2.85 41.7 ILower layer 71.45 i 4.9 jl EXAMPLE 11 I
75 g of wheat extract meal type 405 were suspended under stirring in 294 g trichloroethylene.
' After 30 minutes, the settled and the floating fractions, were separated and recovered by filtration and drying at 70C.
The weights of the two fractions and their protein con-I tents (6.25 x N content) were as follows:
IlFraction Weight (g) Protein (%) ,Raw product 75.00 ca. 10.0 Upper layer 10.21 24.2 Lower layer 62.87 7.9 I, ~
¦ EXAMPLE 12 ,, When 500 g Raw Guar Meal (Guar-Keimlingsmehl plus husk plus endosperm fragments) were suspended in 1000 ml trichloro-l ethylene and 70 ml crystal oil (heavy gasoline), clensity of the mixture 1420 kg./m3, the following fractions after a separation li , 1 ` i !
~ .. ! c. 5 ~ ~
.,, time of 5 minutes were obtained:
In Wt. %
_ . I
FractionA.I.R. Fat ~ Protein Ash . . . _ _ , _ ca. 50% upper layer 11.4n.m. 5.7 57.7 4.8 13-15% middle layer 8.8 1.0 5.6 57.8 5.9 ca. 30% lower layer 37.6 1.0 3.5 11.6 4.4 Raw guar meal22.3 4.3 8.5 40.1 5.0 _ !
In.m.: not measured.
I . I
I When 1000 g tamarind bean meal were extracted ~for I degreasing) in 2000'ml trichloroethylene at 52C. and then left 'standing as suspension during 21 hours at 20C., three layers are formed:
¦ Fraction ~ Weight (g) Protein % H~0 % I
~,Upper iayer 92 68.7 7.4 Middle layer 55 n.m. n.m.
I,Lower layer `713 11.0 6.5 IStarting material 1000 12.9 ' 7.5 . ~
'n.m.: not measured.
The upper layer contains aleuron grains with a diameter of about 4 ~m and aleuron accumulations with a diameter of about 30 ~m.
.
,1 - 17 - ~
I
lZ1~5'~3 The clearness of the aqueous solutions of the various products obtained by the process described above was measured by I light transmission at 500 nm with a cell of 1 cm optical path.
The concentration of the solutions was 0.5 wt. %, not considering ' the water contentO The stated transmission in % represents a mean value of three determinations.,"-The ~learness of the solu-'tions of guar inner endosperm derivatives as obtained from the 10 l preceding examples is, as shown in the following table, clearly ~~better than that of solutions of commercial guar derivatives.
, _ I' /
/
/
, ' /
1l /
~' /
1. / ~
,, .
.~
i3 Il .
il , ' E z~
,! 3 ~
~1 o CO cr Cl ~) N 1~ 1~ ~1 Ct:) ~7 0 0 0 O
E~ O ~ O a~ c~ co In r--l N a~ ~ O
' ~0\o` ~
E~ .
a~
a ; ~u ~ E
O ~ 0 ~ OO O O O OO U~ ~ ~ ~ ~ ~ U~
N ~
a, I a ) U C~) ~,) H O ~ O ~) H O
O h O
OS~ S I h Q) 1~ 0 1~ rV ~ C) N~ ~~ ell tl~ 3 'h 3 rr~ u~ O O O 0 r~ H ~1 h ~ h I ~ ~u ~ 1~ .c o~
~ t) P~ ::~ o ~ .Y
~ O ~) h h S~ L~. U 3 3 x ~ ~ N ~ r~
, Pi O ~ J H O O O ~¢ h )~ O
" ~ H H H ~ O ~J ~) ~ Ll~:1 ~ ~ r~ ~
~ 1 1 1 1 ~ UU 1 ~,) 5~ ~rr, tO ~
I .
Claims (10)
1. A process for separating polysaccharide-containing particles into high protein and low protein fractions which com-prises dispersing and suspending said particles in an organic liquid or mixture of organic liquids, the density of which is be-tween those of the fractions to be separated, allowing the frac-tions to separate into separate layers, isolating the separated layers and removing the organic liquid.
2. The process of claim 1 wherein the polysaccharide--containing particles are polygalactomannan meals.
3. The process of claim 2 wherein the polysaccharide--containing meal is guar gum meal.
4. The process of claim 1 wherein the organic liquid has a density of about 1290 to about 1500 kg./m3 at 20°C.
5. The process of claim 1 wherein the organic liquid is used in the amount of about 1 to about 10 parts by weight per 1 part by weight of the polysaccharide containing particles.
6. A process for separating guar gum meal into high protein and low protein fractions which comprises dispersing and suspending the guar gum meal in an organic liquid or mixture of organic liquids having a density of about 1460 to about 1480 kg./m3 at 20°C., allowing the fractions to separate into separate layers, isolating the separated layers and removing the organic liquid.
7. The process of claim 6 wherein about 1.4 to about 4 parts by weight of organic liquid are used per 1 part by weight of guar gum meal.
8. The process of claim 6 wherein the organic liquid is trichloroethylene.
9. The process of claim 6 wherein the organic liquid is a mixture of 87 volume percent trichlorotrifluoroethane and 13 volume percent 2-propanol.
10. The process of claim 6 wherein the organic liquid is a mixture of 51 volume percent trichloroethylene and; 49 volume percent trichloroethane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3649/83-7 | 1983-07-01 | ||
| CH3649/83A CH666790A5 (en) | 1983-07-01 | 1983-07-01 | METHOD FOR SEPARATING POLYSACCHARIDE-CONTAINING FLOURS IN PROTEIN-LOW AND LOW-PROTEIN FRACTIONS. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1212573A true CA1212573A (en) | 1986-10-14 |
Family
ID=4260535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000457865A Expired CA1212573A (en) | 1983-07-01 | 1984-06-29 | Process of separating polysaccharide-containing meals into high protein and low protein fractions |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0130946B1 (en) |
| JP (1) | JPS6054646A (en) |
| CA (1) | CA1212573A (en) |
| CH (1) | CH666790A5 (en) |
| DE (1) | DE3470656D1 (en) |
| GB (1) | GB2142636B (en) |
| IN (1) | IN162625B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4758282A (en) * | 1986-02-15 | 1988-07-19 | Degussa Aktiengesellschaft | Process for dry cationization of galactomannans |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0146911B1 (en) * | 1983-12-29 | 1989-05-17 | Diamalt Aktiengesellschaft | Derivatives of polysaccharides from cassia tora, and their application |
| NL9300536A (en) * | 1993-03-25 | 1994-10-17 | Brinkers Margarinefab | Protein-containing margarine product |
| EP0884330A1 (en) | 1997-06-12 | 1998-12-16 | Meyhall AG | Process for producing pure guar seed flour |
| NO20160674A1 (en) * | 2016-04-19 | 2017-10-20 | Ewos Innovation As | Fish feed |
| EP3235385A1 (en) | 2016-04-19 | 2017-10-25 | Can Technologies, Inc. | Feed compositions containing faecal binder materials |
| WO2023119575A1 (en) * | 2021-12-23 | 2023-06-29 | 太陽化学株式会社 | Cosmetic composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2767167A (en) * | 1953-07-06 | 1956-10-16 | Gen Mills Inc | Process of reducing the viscosity of gums |
| US3712883A (en) * | 1970-02-03 | 1973-01-23 | Gen Mills Inc | Carboxyalkyl ethers of galactomannan gums |
| US3869438A (en) * | 1973-03-16 | 1975-03-04 | Us Agriculture | Process for isolating oil-seed proteins using liquid fluorocarbons |
| US4011393A (en) * | 1975-04-28 | 1977-03-08 | Celanese Corporation | Polygalactomannan gum formate esters |
| US4074043A (en) * | 1976-03-15 | 1978-02-14 | General Mills Chemicals, Inc. | Purification of tamarind gum |
-
1983
- 1983-07-01 CH CH3649/83A patent/CH666790A5/en not_active IP Right Cessation
-
1984
- 1984-06-27 DE DE8484810316T patent/DE3470656D1/en not_active Expired
- 1984-06-27 EP EP84810316A patent/EP0130946B1/en not_active Expired
- 1984-06-29 CA CA000457865A patent/CA1212573A/en not_active Expired
- 1984-06-29 GB GB08416619A patent/GB2142636B/en not_active Expired
- 1984-06-30 JP JP59136421A patent/JPS6054646A/en active Granted
-
1985
- 1985-02-15 IN IN127/DEL/85A patent/IN162625B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4758282A (en) * | 1986-02-15 | 1988-07-19 | Degussa Aktiengesellschaft | Process for dry cationization of galactomannans |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2142636A (en) | 1985-01-23 |
| GB2142636B (en) | 1988-03-16 |
| IN162625B (en) | 1988-06-18 |
| CH666790A5 (en) | 1988-08-31 |
| EP0130946B1 (en) | 1988-04-27 |
| EP0130946A2 (en) | 1985-01-09 |
| EP0130946A3 (en) | 1985-05-15 |
| JPS6054646A (en) | 1985-03-29 |
| JPH0150387B2 (en) | 1989-10-30 |
| GB8416619D0 (en) | 1984-08-01 |
| DE3470656D1 (en) | 1988-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5633032A (en) | Process of preparing cereal extracts | |
| US2801955A (en) | Process for extraction of hemicellulose | |
| US4269975A (en) | Preparation of guar gum | |
| JPH02222658A (en) | Grain fiber and making thereof | |
| CA1212573A (en) | Process of separating polysaccharide-containing meals into high protein and low protein fractions | |
| AU596008B2 (en) | Novel starch and products produced therefrom | |
| WO2018038055A1 (en) | Method for producing dry product of dispersible bacterial cellulose and method for producing bacterial cellulose dispersion | |
| Tang et al. | Cationic oxidized microporous rice starch: Preparation, characterization, and properties | |
| RU2119758C1 (en) | Method for production of cellulose-containing grain extract | |
| KR20050094470A (en) | A nonionic cellulose ether and its use | |
| US2647064A (en) | Method of improving the cold-water solubility of a fibrous cellulose ether | |
| US6162906A (en) | Clarified konjac glucomannan | |
| US4074043A (en) | Purification of tamarind gum | |
| US6190462B1 (en) | Method for dewatering starch | |
| WO2001005838A1 (en) | Process for drying reticulated bacterial cellulose without co-agents | |
| AU715312B2 (en) | Method for improving the exploitability and processability of guar endosperm and products obtained using said method | |
| US2720464A (en) | Method of preparing cold-water-soluble powdered cellulose ethers | |
| Xie et al. | Laboratory procedure to wet‐mill 100 g of grain sorghum into six fractions | |
| CA1087451A (en) | Process for the treatment of comminuted oats | |
| EP1399486B1 (en) | Method for producing starch or starch-containing products from starch-containing plant raw materials | |
| CN1101407C (en) | Process for producing pure guarseed flour | |
| EP1505077A1 (en) | Alkaline wet milling of corn grain | |
| JPH061801A (en) | Process for cationing nongranular polysaccharide | |
| CA1123432A (en) | Cold-water soluble tamarind gum | |
| JPH0678667A (en) | Preparation of fermented milk powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |