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WO2025160540A1 - Production d'amidon résistant de type 4 à l'aide d'un processus de modification chimique semi-sèche - Google Patents

Production d'amidon résistant de type 4 à l'aide d'un processus de modification chimique semi-sèche

Info

Publication number
WO2025160540A1
WO2025160540A1 PCT/US2025/013185 US2025013185W WO2025160540A1 WO 2025160540 A1 WO2025160540 A1 WO 2025160540A1 US 2025013185 W US2025013185 W US 2025013185W WO 2025160540 A1 WO2025160540 A1 WO 2025160540A1
Authority
WO
WIPO (PCT)
Prior art keywords
starch
pulse
product
dietary fiber
crosslinked
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.)
Pending
Application number
PCT/US2025/013185
Other languages
English (en)
Inventor
Maaran SUNTHARAMOORTHY
Jihong Li
Darrell CHENAULT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Archer Daniels Midland Co
Original Assignee
Archer Daniels Midland Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Archer Daniels Midland Co filed Critical Archer Daniels Midland Co
Publication of WO2025160540A1 publication Critical patent/WO2025160540A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/212—Starch; Modified starch; Starch derivatives, e.g. esters or ethers
    • A23L29/219—Chemically modified starch; Reaction or complexation products of starch with other chemicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/003—Crosslinking of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/02—Esters
    • C08B31/06—Esters of inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives

Definitions

  • the invention relates to the production of highly digestion resistant type RS4 starches useful as dietary fiber containing starch from pulse plants more particularly illustrated by the production of type 4 resistant pea starch by cross linking.
  • the invention relates to a semi-dry rather than wet slurry process for the production of RS4 starches from any starch source.
  • Starches generally contain three fractions based on digestibility: rapidly digestible starch (RDS), slowly digestible starch (SDS) and resistant starch (RS).
  • RDS rapidly digestible starch
  • SDS slowly digestible starch
  • RS resistant starch
  • RS is further classified as RS 1, RS2, RS3, RS4 and RS5 based on the physical and chemical structure and under food regulatory standards is included as part of dietary fiber.
  • RS4 type starch is chemically modified via crosslinking, esterification, transglycosylation, or hydroxypropylation. High levels of RS dietary fiber in food have been considered a powerful benefit to health.
  • Pulse starches are not typically purified and are mostly available as a byproduct of isolating other more valuable components form pulses such as protein and/or vegetable oils. Pulse starch byproducts come in the form of starch concentrates or crude starch in a yield typically greater than about 60% yield of the total starch present and a purity in the range of 60-85%. Native pulse starches contain a wide range of amylose content (20 -70%) and have limited functional properties, such as pasting stability, thermal/shear resistance, acid stability and product shelf life in food applications.
  • Patent US5855946 describes a process of making phosphorylated starch using a wet slurry process (40% solids content) using a mixture of sodium trimetaphosphate (STMP) and sodium tripolyphosphate (STPP) in the presence of sodium chloride or sulfate at basic pH and moderate heating.
  • STMP sodium trimetaphosphate
  • STPP sodium tripolyphosphate
  • Patent EP1961769 also disclose cross-linking starch in a wet slurry reaction
  • the conditions used were 36-44% solids, 5-16% of STMP or a combination of STMP and STPP (in the range of 5-16% STMP and 0.05-0.16% STPP as a percent of starch weight) with 0.1- 20% sodium sulfate or sodium chloride - again as a percent of starch weight), incubated at 30-50°C for 16-24 h.
  • the pH of slurry was adjusted to 11.5-12 by adding 25% sodium hydroxide.
  • the cross-linked starches had 0.2-0.8% phosphorus and 30-96% total dietary fiber.
  • CN102187996A/WO11111928 A2 discloses a method of preparing a crude crosslinked potato dietary fiber/starch product using a wet slurry of a potato starch by-product at 40-50% solid, 8-12% of mixture of STMP/STPP, 10-12% sulfate incubated at 40-55°C for 1- 6 h.
  • the disclosed method of preparation is a conventional slurry process using the byproduct from potato wet process.
  • RS4-Fiber Modified Starch Phosphate Di-Starch Phosphate
  • RS4-fiber phosphorylated starch
  • the phosphorylated starch was produced by a wet slurry reaction with cross-linking agents using either a high amylose maize starch slurry derived from corn wet milling or a re-slurry of the corn starch in water.
  • the produced RS4 fiber contains about 70-80% fiber (resistant starch) by the AO AC 991.43 method.
  • starch is typically modified in 30-50% starch slurry with 5-16% sodium trimetaphosphate (STMP), 0.05-0.16% sodium tripolyphosphate (STPP), 0.1-20% sodium sulfate at pH 11-12 and 3O-5O°C for 1-3 hours.
  • STMP sodium trimetaphosphate
  • STPP sodium tripolyphosphate
  • the chemically modified starch is further treated by heat treatment at moisture of 20-35% based on the weight of dry starch at 90-120°C for 1-4 hours.
  • the resulted modified, heat-moisture treated starch contains at least 70% TDF based on the weight of starch.
  • the present invention provides a novel processing technology that produces RS4 type of dietary fiber through chemical modification of starch with cross-linking reagents in a semidry state.
  • the invention is exemplified using a crude pea starch containing 60- 80% wt/wt starch obtained as a byproduct of processing pea starch to make protein concentrates, but is applicable to any pulse starch and is also applicable to forming resistant starches from more conventional grain and tuber sources.
  • the invented process is more economical and more sustainable - involving simple mixing with less usage of chemicals, water, and energy and high reaction efficiency compared to conventional wet slurry modification processes.
  • the invention may be called a dry or semi-dry starch processing method that involves a chemical reaction at 60% or higher solids content, addition of up to 10% mixture of cross-linking reagents (STMP/STPP at ratio of 99-100:0-1) at pH 11-12 adjusted with the sodium hydroxide solution, holding at ambient temperature for 4 to 24 hours, and then washing with water to remove excess chemical residues followed by centrifugation/filtration, drying and grinding.
  • the produced novel starch ingredient contains up to 0.6% phosphorus and up to 99 % total dietary fiber on a dry wt/wt basis.
  • a method of making a digestion resistant starch product comprises contacting a starch source comprised of at least 50% starch with a mixture of sodium tripolyphosphate (STPP) and sodium trimetaphosphate (STMP) at a temperature of at least 20°C and at a pH of 10 to 12.0 for a time sufficient to convert at least 70% of the starch in the starch source to digestion resistant starch wherein during the contacting, the moisture content of the contacted starch is 50% or less on a wt/wt basis.
  • STPP sodium tripolyphosphate
  • STMP sodium trimetaphosphate
  • a digestion resistant pulse starch product comprises 60-85% wt/wt of starch and 5-10% wt/wt protein, wherein at least 50% of the starch is crosslinked starch and the pulse product contains at least 60% dietary fiber on a wt/wt basis.
  • the dietary fiber includes non-starch polysaccharides present in the pulse starch and the crosslinked starch.
  • Figure 1 Is a graph showing the measured total dietary fiber content produced in a modified pea starch product of the present invention by reacting with the crosslinker mixture of STMP/STPPP at different concentrations relative to the weight of starch.
  • Figure 2 is a graph showing the effect of reaction time on the content of total dietary fiber content produced from reacting a crude pea starch product containing 70% wt/wt starch with 6% and 7% of crosslinker mixture of STMP/STPPP relative to the weight starch according to a method of the present invention. .
  • Figure 3 Is graph showing a linear relationship between total dietary fiber and amount of phosphorous content present in a modified pea starch of the present invention.
  • the present disclosure provides a novel technology to produce type 4 resistant (RS4) granular starches through chemical modification of pulse starch with cross-linking reagents in a semidry state.
  • “semidry state” means a solids content of 50-80% by weight with the remainder being water.
  • the disclosure is illustrated by use of a pea starch product, but is applicable to any starch product derived from a pulse plant, which includes peas, lentils and beans.
  • the process is applicable for use in making RS4 granular starches from conventionally isolated starch products from grain, tubers and roots.
  • a “starch product” is a product derived from a plant source that contains at least 50% starch on a dry solids weight/weight basis.
  • the process disclosed herein is economic and more sustainable than making RS4 type starches using a wet slurry process.
  • the present process involves simple mixing of components with less chemical, water, and energy usage and with higher reaction efficiency than conventional processes.
  • Such processes of the present invention are applicable to non- conventional starch sources such as pulse starches.
  • a crude pea starch product was used. Such a product was obtained by peas to obtain a whole pea flour and separating a protein enriched fraction from the pea flour to obtain the peas starch product.
  • a similar process could also be used with any pulse fruit where a starch enriched fraction having at least 50% wt./wt starch is produced as a byproduct of separating proteins or oils from the pulse.
  • the pulse starch product that results from such a separation has a composition of about 60 to 85% weight percent starch, about 4 to 30 weight percent fiber and about 5 to 15 weight percent protein.
  • the fiber content is typically below 25%.
  • the crude pea starch was mixed with cross-linking reagents (0-10% sodium trimetaphosphate (STMP)/sodium tripolyphosphate (STPP) at ratio of 99-100:0- 1 , starch base) in a commercial mixer by spraying a mixture of STMP/STPP and sodium hydroxide solution under onto the crude starch with continuous mixing.
  • the pH of the mixture was adjusted to 11-12 and the moisture content of the resulting mixture was adjusted to 30-40 % by adding 5 - 10 % sodium hydroxide solution.
  • the mixture was continuously mixed at a low speed for up to 24 hours and then thoroughly washed with water, centrifuged and dried to the final moisture below 10%.
  • Total dietary fiber (TDF) content in starch was measured by AOAC 991.43 method (AO AC Official Methods of Analysis Supplment March 1995) and the phosphorous content was measured using ICP spectroscopy.
  • Figure 1 shows the increase of total dietary fiber (TDF) content in a crude pea starch fraction (70% wt/wt starch) obtained by reacting the same with increasing crosslinker concentrations up to 10% (dry starch base) at 30-40% moisture, pH 10.5- 12 for a reaction time of 20 hours at ambient temperature with continuous mixing.
  • the results indicate that at a ratio of STMP/STPP to starch of 6% or greater over 90% of starch had been converted to resistant starch type 4 (RS4) useful as a dietary fiber.
  • RS4 resistant starch type 4
  • Figure 2 shows the effect of reaction time on the content of TDF in crude pea starch with 6% and 7% crosslinker, at a final moisture content of 40% at pH 11-12 for reaction of up to 20 hours at ambient temperature with continuous mixing.
  • the TDF content increased quickly at first 8 hours and then slowed down.
  • the amount of conversion of the starch to total dietary fiber essentially is maximized in 20 h reaction.
  • Phosphorous content in starch is a key indicator indicating the degree of starch crosslinking. As shown in Figure 3, the phosphorous content is lineally correlated to the amount of TDF produced in the modified pea starch.
  • Table 1 compares the TDF content present in a crosslinked crude pea starch prepared according to the foregoing semi-dry process to that prepared in a conventional wet slurry process where the reaction mixture contained the same crude pea starch at 35% solids wt/wt, with 10% sodium sulfate (starch base), pH 11-12, mixing for 3 h at 45°C.
  • the invented process had much higher reaction efficiency as indicated by TDF content compared to the slurry process.
  • Table 1 Comparison of semi-dry process and slurry process of crude pea starch.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Nutrition Science (AREA)
  • Food Science & Technology (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

L'invention concerne une nouvelle technologie qui produit un type RS4 d'amidons résistants par modification chimique d'amidons à l'aide de tripolyphosphate de sodium (STPP) et de trimétaphosphate de sodium (STMP), pour réticuler l'amidon dans un état semi-sec. Le processus de l'invention est économique et plus durable par simple mélange avec moins de produits chimiques, moins d'eau, une faible consommation d'énergie, et présente une efficacité de réaction élevée par comparaison avec des processus classiques de modification de suspension humide à l'aide d'amidons purifiés. L'invention est illustrée à l'aide d'un amidon de pois pour fabriquer un nouveau produit à base d'amidon de légumineuse comprenant 60 à 85 % p/p d'amidon et 5 à 10 % p/p de protéine, au moins 50 % de l'amidon étant de l'amidon réticulé et le produit à base de pois contenant au moins 60 % de fibres alimentaires sur une base p/p, mais étant applicable à des amidons de céréale, de racine, de tubercule ou d'autres amidons de légumineuse.
PCT/US2025/013185 2024-01-26 2025-01-27 Production d'amidon résistant de type 4 à l'aide d'un processus de modification chimique semi-sèche Pending WO2025160540A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202463625821P 2024-01-26 2024-01-26
US63/625,821 2024-01-26

Publications (1)

Publication Number Publication Date
WO2025160540A1 true WO2025160540A1 (fr) 2025-07-31

Family

ID=96545893

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2025/013185 Pending WO2025160540A1 (fr) 2024-01-26 2025-01-27 Production d'amidon résistant de type 4 à l'aide d'un processus de modification chimique semi-sèche

Country Status (1)

Country Link
WO (1) WO2025160540A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5855946A (en) * 1997-06-06 1999-01-05 Kansas State University Research Foundation Food grade starch resistant to α-amylase and method of preparing the same
US6664389B1 (en) * 1999-10-01 2003-12-16 National Starch And Chemical Investment Holding Coporation Highly resistant granular starch
US20050271793A1 (en) * 2004-06-04 2005-12-08 Manildra Milling Corporation A resistant starch and process for the production thereof
US20070219160A1 (en) * 2006-03-20 2007-09-20 Monika Okoniewska Process Tolerant Starch Composition with High Total Dietary Fiber Content
US20080207894A1 (en) * 2007-02-22 2008-08-28 National Starch And Chemical Investment Holding Corporation Crosslinking Reactions
US20100189843A1 (en) * 2009-01-23 2010-07-29 Wei Luke Xie Hydroxypropylated Starch as a Processing Aid to Improve Resistant Starch Total Dietary Fiber (TDF) Retention in Direct Expansion Extrusion Applications
US20200392256A1 (en) * 2018-02-22 2020-12-17 Sanwa Starch Co., Ltd. Starch with high dietary fiber content suitably usable in foods and beverages

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5855946A (en) * 1997-06-06 1999-01-05 Kansas State University Research Foundation Food grade starch resistant to α-amylase and method of preparing the same
US6664389B1 (en) * 1999-10-01 2003-12-16 National Starch And Chemical Investment Holding Coporation Highly resistant granular starch
US20050271793A1 (en) * 2004-06-04 2005-12-08 Manildra Milling Corporation A resistant starch and process for the production thereof
US20070219160A1 (en) * 2006-03-20 2007-09-20 Monika Okoniewska Process Tolerant Starch Composition with High Total Dietary Fiber Content
US20080207894A1 (en) * 2007-02-22 2008-08-28 National Starch And Chemical Investment Holding Corporation Crosslinking Reactions
US20100189843A1 (en) * 2009-01-23 2010-07-29 Wei Luke Xie Hydroxypropylated Starch as a Processing Aid to Improve Resistant Starch Total Dietary Fiber (TDF) Retention in Direct Expansion Extrusion Applications
US20200392256A1 (en) * 2018-02-22 2020-12-17 Sanwa Starch Co., Ltd. Starch with high dietary fiber content suitably usable in foods and beverages

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KADYAN SAURABH, SHARMA ADITYA, ARJMANDI BAHRAM H., SINGH PRASHANT, NAGPAL RAVINDER: "Prebiotic Potential of Dietary Beans and Pulses and Their Resistant Starch for Aging-Associated Gut and Metabolic Health", NUTRIENTS, M D P I AG, CH, vol. 14, no. 9, CH , pages 1726, XP093341626, ISSN: 2072-6643, DOI: 10.3390/nu14091726 *

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