WO2018011789A1 - Matériaux polymères superabsorbants produits à partir d'un matériau végétal vert débarrassé de sa chlorophylle - Google Patents

Matériaux polymères superabsorbants produits à partir d'un matériau végétal vert débarrassé de sa chlorophylle Download PDF

Info

Publication number
WO2018011789A1
WO2018011789A1 PCT/IL2017/050774 IL2017050774W WO2018011789A1 WO 2018011789 A1 WO2018011789 A1 WO 2018011789A1 IL 2017050774 W IL2017050774 W IL 2017050774W WO 2018011789 A1 WO2018011789 A1 WO 2018011789A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
chlorophyllized
dry
plant
plant biomass
Prior art date
Application number
PCT/IL2017/050774
Other languages
English (en)
Inventor
Mircea Dan Bucevschi
Original Assignee
Hinoman Ltd
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 Hinoman Ltd filed Critical Hinoman Ltd
Publication of WO2018011789A1 publication Critical patent/WO2018011789A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/32—Proteins, polypeptides; Degradation products or derivatives thereof, e.g. albumin, collagen, fibrin, gelatin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/40—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing ingredients of undetermined constitution or reaction products thereof, e.g. plant or animal extracts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3021—Milling, crushing or grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C08L89/005—Casein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4856—Proteins, DNA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/68—Superabsorbents

Definitions

  • This invention relates in general to superabsorbent materials and methods for making them.
  • Absorbent materials for water and aqueous media including fluids secreted by the human body, are known. These materials are polymeric powders, granules, microparticles or fibers. Upon contact with aqueous systems, they swell by absorbing the liquid phase into their structure, without dissolving in it. A “hydrogel” is polymeric material after it has absorbed water. If the water absorbency is greater than 100 g water / g dried polymer the material is called “superabsorbent" polymer (SAP).
  • SAP superabsorbent polymer
  • PCT Pat. Appl. Pub. No. WO2007/115169 which is hereby incorporated by reference in its entirety, discloses a superabsorbent polymer that is a composite of a carboxylic- containing synthetic polymer and a biopolymer.
  • the biopolymer is a protein obtained from soybeans or from animal sources.
  • Plants represent a renewable resource that produces biomass that can be used either directly for such uses as food or energy generation or indirectly as a source of raw materials that can be converted into any number of products such as adhesives, fibers, bioplastics, products used in the cosmetic industry, drugs, biofuels, etc.
  • Vegetable biomass derived from plants is a composite material and comprises a wide diversity of organic and inorganic compounds. The proportions of the different chemical constituents of the biomass depend on the particular plant from which it is derived and the part of the plant that is used.
  • Green plant biomass That portion of plant biomass that derives from the parts of the plant that contain chlorophyll is known as "green plant biomass.”
  • Green juice processing uses fresh wet biomass and subjects it to mechanical operations to extract a liquid phase called “green juice” and a solid phase called “green pellet,” each of which is then processed separately.
  • Plant extract processing produces a suspension by contact between wet or dry plant biomass and a liquid medium that can be aqueous or non-aqueous, followed by separation into a liquid phase called “plant extract” and a solid phase called “plant pellet,” each of which is then processed separately.
  • U.S. Pat. No. 3,173,309 discloses a method for producing a nutrient from unicellular green Chlorella algae.
  • the algae are cultured for 72 to 96 hours.
  • the supply of reducible carbon is then removed from the medium and the pH of the culture is adjusted until it is in the range from 8.0 to 8.5.
  • the culture is then agitated by introduction of oxygen and decolorized by exposure to artificial white light having an intensity in excess of 5000 foot candles.
  • the chlorophyll and chlorophyll-like compounds are destroyed and the product is collected, preferably by centrifugation.
  • the algae are then dried , preferably by lyophilization. This process yields a fluffy white or light tan powder of bland flavor and odor which may be used directly as a food supplement.
  • U.S. Pat. No. 4,334,024 discloses a method for preparing crystalline ribulose 1.5-bis- phosphate carboxylase from plant material that comprises grinding a sample of plant material with a suitable buffer solution; filtering the solution; adding to the solution, while stirring, sufficient quantities of polyethylene glycol (PEG) having a molecular weight in the range from 5000 to 7000 to bring the PEG to a final concentration of between 5% and 15% (w/v); discarding the precipitate; storing the solution for about 1 to 8 hours; collecting and washing the crystals formed during the storage period; and lyophilizing the crystals.
  • PEG polyethylene glycol
  • Effiong et al. (2009) discloses a method of producing a water-soluble antimicrobial agent / food preservative from duckweed (Lemna pauciscostata).
  • Duckweed was cultured in and then harvested from outdoor concrete tanks. The harvested plant material was rinsed with clean water and evenly spread on a mosquito net-sized mesh to dry and thereafter dried in a forced air oven at 65 °C for 48 hours before being ground to a powder. The powder was exhaustively extracted with 95% ethanol and sterile distilled water at room temperature for 2 days.
  • Rusoff et al. (1980) discloses a method of treating duckweed.
  • Duckweed was dried in the sun and then mixed with 12 times its weight of 0.5 N NaOH to bring the pH to above 8.5.
  • the mixture was placed in a blender and homogenized for 60 s.
  • the juice was then squeezed out of the homogenate through a double layer of cheesecloth and clarified by centrifugation at 2000 rpm, and the protein was precipitated from the supernatant by acidifying to pH 3.65 with 0.1 N HC1.
  • the acidified suspension was heated to 75 °C to coagulate the soft gelatinous protein which was then refrigerated overnight.
  • the supernatant was siphoned off and the precipitated protein was separated from the liquid portion by centrifugation at 2,000 rpm. It was subsequently frozen in thin layers in pans and dried in a Virtis freeze-dryer at -40 °C.
  • the chlorophylls, other pigments, and lipids were removed from the concentrate with boiling acetone in a Soxhlet apparatus.
  • the concentrate was dried in a desiccator.
  • the protein concentrate can also be obtained from washed fresh duckweed. Instead of alkalinizing with NaOH, anhydrous ammonia was bubbled through the biomass to a pH of over 8.5. The alkalinized duckweeds were then treated as described above.
  • Victoria Gonzalez Lopez et al (2010) and Xiangliang Pan et al. (2010) disclose additional methods for treatment of green biomass.
  • the biomass was recovered by centrifugation (2,200g, 5 min), washed with a 1% (w/v, g/ 100 mL) aqueous NaCl solution, centrifuged again and freeze-dried.
  • the dry biomass was analyzed immediately or stored at 22 °C for up to 10 days prior to analysis.
  • the following pretreatment methods were tested: (i) suspension in lysis buffer; (ii) ultrasonication at high power for 10 minutes using a commercial sonic bath in lysis buffer; (iii) milling for 5 minutes with a pestle and mortar without grinding elements prior to suspension in lysis buffer; and (iv) milling for 5-min with a pestle and mortar in presence of an inert ceramic powder, the grinding particles prior to suspending in the lysis buffer.
  • Pietryczuk A. et al. (2009) discloses a different method of soluble protein extraction from duckweed.
  • Fresh W. arrhiz (0.1 g) was filtered and homogenized, water-soluble proteins extracted by exposing the homogenized plant material overnight to 0.1 M NaOH at 4 °C, and the amount of water-soluble protein extracted then determined.
  • Al-Amoudi et al. (2009) disclose a method for preparation of a dry algal material.
  • Algae (100 g) were extracted with methanol in a Soxhlet apparatus for 8 h.
  • the extract was concentrated under reduced pressure at 60 °C, filtered, washed with distilled water, and stored in the dark at 4 °C.
  • Fractionation of extracts by centrifugation yielded two fractions (Fl and F2).
  • Fractions were extracted with MeOH-CHCl 3 .
  • the residue was then sequentially extracted with MeOH-CHCl 3 and the final volume was measured and noted as fraction (F2). Samples of each fraction were tested for their hydrolyzed chemical composition.
  • the mixture of NaOH and pellets was kept at room temperature for 1 h with occasional manual shaking and then centrifuged at 21 °C, 15,000g for 20 minutes. The second supernatants were combined with the first ones and the pellets were discarded. The final volume of the extract was between 2.0 and 9.0 mL.
  • the pH of the supernatant was decreased from 12 or 7 to 4 progressively by addition of 1M HC1 in order to obtain the pi value of the majority of the proteins.
  • the paste obtained after precipitation and centrifugation was freeze-dried and then stored at room temperature.
  • tangential ultrafiltration was performed using a pilot-scale tangential-flow filtration unit. A membrane in PES with a molecular weight cut-off of 300 kDa and 0.1 m surface of filtration was used for the separation. Ultrafiltration was carried out at room temperature under a fixed transmembrane pressure of 1.5 bar. Approximately 5L of raw material (supernatant from extractions at pH 7 or pH 12) were concentrated five times by tangential ultrafiltration.
  • RPPRM-WS water- soluble protein-rich concentrate
  • the biomass is treated with chemicals that are used as cell wall lysis agents, which remain as an impurity in the resulting RPPRM-WS.
  • the level of impurities remaining in the RPPRM-WS is very difficult to control, and the impurities can have the effect of making the RPPRM-WS unusable for further processing or for use as a starting material for synthesis of new products.
  • the present invention is designed to meet this long-felt need.
  • the present invention discloses a method for production of a superabsorbent polymeric material that is a composite of a synthetic polymer that comprises carboxyl groups and a biopolymer obtained from dechlorophyllized green biomass, particularly dechlorophyllized green biomass derived from aquatic plants.
  • step of producing an aqueous mixture of water-soluble protein concentrate from plant biomass comprises: (a) obtaining dry de-chlorophyllized plant matter from said plant biomass; (b) treating said dry de-chlorophyllized plant matter with water, thereby at least partially dissolving water-soluble protein content of said dry de- chlorophyllized plant matter and preparing an aqueous suspension of said dry de- chlorophyllized plant matter; (c) separating said aqueous suspension of said dry de- chlorophyllized plant matter into a first neutral extract and a wet solid; and (d) drying said first neutral extract, thereby yielding a water-soluble protein concentrate.
  • step of producing an aqueous mixture of water-soluble protein concentrate from plant biomass comprises: (a) washing said wet solid with water, thereby producing a second neutral extract; (b) concentrating said second neutral extract; and, (c) drying said second neutral extract, thereby yielding additional water-soluble protein concentrate, i.e. a second crop of said water-soluble protein concentrate.
  • step of producing an aqueous mixture of water-soluble protein concentrate from plant biomass comprises: (a) washing said wet solid with water, thereby producing a second neutral extract; and (b) combining said first neutral extract and said second neutral extract prior to said step of drying said first neutral extract, thereby producing a combined neutral extract; wherein said step of drying said first neutral extract comprises drying said combined neutral extract, thereby yielding a water-soluble protein concentrate.
  • said plant biomass is obtained from aquatic plants.
  • said plant biomass is obtained from aquatic plants selected from the group consisting of algae, microalgae, and duckweed.
  • said plant biomass is obtained from duckweed.
  • said duckweed is selected from the group consisting of Lemna gibba, Spirodela polyrrhiza, Spirodela punctuata, Wolffia arrhiza, Wolffia columbiana, and Wolffia globosa.
  • step of obtaining dry de-chlorophyllized plant matter comprises: (a) drying said plant biomass, thereby producing dried plant biomass; (b) grinding said dried plant biomass, thereby producing ground dried plant biomass; (c) extracting chlorophyll from said ground dried plant biomass, thereby producing de-chlorophyllized plant matter; and (d) drying said de-chlorophyllized plant matter, thereby obtaining dry de-chlorophyllized plant matter.
  • step of obtaining dry de-chlorophyllized plant matter comprises drying said plant biomass in the absence of light at a temperature not exceeding 50 °C.
  • step of obtaining dry de-chlorophyllized plant matter comprises drying said plant biomass in the absence of light at a temperature not exceeding 45 °C.
  • step of obtaining dry de-chlorophyllized plant matter comprises drying said plant biomass in the absence of light at a temperature not exceeding 40 °C.
  • step of grinding said dried plant biomass comprises grinding said dried plant biomass in a ball mill. In some preferred embodiments of the invention, wherein said step of grinding said dried plant biomass comprises grinding said dried plant biomass at a temperature not exceeding 30 °C.
  • step of grinding said dried plant biomass comprises grinding said dried plant biomass to a powder characterized by a maximum particle diameter of 200 ⁇ . In some preferred embodiments of the invention, said step of grinding said dried plant biomass comprises grinding said dried plant biomass to a powder characterized by a maximum particle diameter of 150 ⁇ . In some especially preferred embodiments of the invention, said step of grinding said dried plant biomass comprises grinding said dried plant biomass to a powder characterized by a maximum particle diameter of 100 ⁇ .
  • step of treating said dry de-chlorophyllized plant matter with water comprises treating for 2 - 12 hours.
  • said step of treating said dry de-chlorophyllized plant matter with water comprises treating for 3 - 8 hours.
  • step of treating said dry de-chlorophyllized plant matter with water comprises treating for 4 - 6 hours.
  • step of treating said dry de-chlorophyllized plant matter with water comprises treating dry de-chlorophyllized plant matter with water in a plant matter/water ratio of 5:95 by weight on a dry matter basis.
  • step of treating said dry de-chlorophyllized plant matter with water comprises treating dry de-chlorophyllized plant matter with water in a plant matter/water ratio of 10:90 by weight on a dry matter basis.
  • said step of treating said dry de-chlorophyllized plant matter with water comprises treating dry de-chlorophyllized plant matter with water in a plant matter/water ratio of 20:80 by weight on a dry matter basis.
  • said step of treating said dry de-chlorophyllized plant matter with water comprises treating dry de-chlorophyllized plant matter with water at a temperature of in the range of 20 - 80 °C.
  • said step of treating said dry de-chlorophyllized plant matter with water comprises treating dry de-chlorophyllized plant matter with water at a temperature of in the range of 30 - 70 °C. In some especially preferred embodiments of the invention, said step of treating said dry de-chlorophyllized plant matter with water comprises treating dry de-chlorophyllized plant matter with water at a temperature of in the range of 40 - 60 °C.
  • step of washing said wet solid with water comprises washing with successive aliquots of water until an aliquot is produced that is characterized by a concentration of dissolved material of less than 0.1% by weight.
  • step of concentrating said second neutral extract comprises concentrating said second neutral extract until said neutral extract is characterized by a dissolved solid content of not less than 10%.
  • step of concentrating said second neutral extract comprises concentrating said second neutral extract until said neutral extract is characterized by a dissolved solid content of not less than 5%.
  • step of concentrating said second neutral extract comprises concentrating said second neutral extract until said neutral extract is characterized by a dissolved solid content of not less than 3%.
  • said step of drying said wet solid comprises drying said wet solid in a hot air dryer at a temperature of between 75 °C and 85 °C.
  • said step of drying said wet solid comprises drying said wet solid until said wet solid is characterized by a moisture content of less than 15%.
  • said step of drying said wet solid is followed by a step of grinding said dry fibrous material.
  • said step of grinding comprises grinding until said dry fibrous material is characterized by a maximum particle diameter of less than 1 mm.
  • It is a further object of this invention to disclose a superabsorbent swellable polymeric material comprising a composite of a water-soluble protein concentrate derived from de- chlorophyllized green plant biomass and a copolymer comprising carboxyl groups, wherein said superabsorbent swellable polymeric material is produced by the method as defined in any of the above.
  • FIGs. 1A and IB present schematic illustrations of methods for derivatizing and activating, respectively, protein concentrates herein disclosed;
  • FIG. 2 presents a schematic illustration of chemical processing of protein concentrates herein disclosed to form non-food materials
  • FIG. 3 presents results of tangential flow filtration of a neutral extract solution prepared by water treatment of dry de-chlorophyllized plant material at 50 °C for 4 hours;
  • FIG. 4 presents the relationship between the solution concentration and the reduced viscosity for a solution of the protein concentrate of the present invention.
  • FIG. 5 presents experimental results of measurements of rheological properties of gels produced from the protein concentrate of the present invention.
  • the superabsorbent materials of the instant invention comprise a synthetic carboxyl- containing polymer and a biopolymer obtained from concentrated protein plant materials.
  • concentrated protein plant materials can be produced from any kind of green plant biomass.
  • the plant biomass is harvested from aquatic environments (marine or fresh water).
  • the biomass is harvested from algae or duckweeds.
  • duckweeds are used as the source of the plant biomass.
  • duckweed of genus Woljfia is used, and in the most preferred embodiments, the source of the biomass is Woljfia globosa.
  • Typical proximate analyses of the chemical composition of some common duckweed species are given in Table 1. All concentrations are given as percentages. The crude protein content was calculated as 6.25 x the nitrogen content, and the carbohydrate content as 100 minus the sum of the moisture, fat, fiber, and ash.
  • the inventive process uses dry de-chlorophyllized plant matter, which can be prepared by any method known in the art.
  • the dry de-chlorophyllized plant matter is prepared according to the following protocol.
  • raw plant biomass preferably fresh
  • Any method for drying the biomass known in the art can be used.
  • the drying is done in the dark.
  • the drying is done at a fairly low temperature, preferably below 50 °C, more preferably below 45 °C, and most preferably below 40 °C.
  • the dried raw plant biomass is then ground.
  • the grinding is preferably performed in a ball mill, and preferably below 30 °C.
  • the dried raw biomass is ground to a powder having a maximum particle diameter of 200 ⁇ .
  • the dried raw biomass is ground to a powder having a maximum particle diameter of 150 ⁇ .
  • the dried raw biomass is ground to a powder having a maximum particle diameter of 100 ⁇ .
  • the chlorophyll can be removed from the ground dried raw biomass by any method known in the art. In preferred embodiments of the invention, it is extracted by Soxhlet extraction under vacuum using a water-miscible organic solvent.
  • the organic solvent is one that is not poisonous to humans.
  • a food-grade solvent is used.
  • the chlorophyll is extracted using ethanol as the solvent.
  • the de-chlorophyllized plant material is dried to remove the solvent used to extract the chlorophyll.
  • the dried de-chlorophyllized plant material is treated with water, preferably demineralized water with a conductance of less than 4 ⁇ 8. Enough water is added to the de- chlorophyllized plant matter to produce an aqueous suspension.
  • the suspension comprises a plant matter/water ratio of 5 : 95 by weight on a dry matter basis.
  • the suspension comprises a plant matter/water ratio of 10 : 90 by weight on a dry matter basis.
  • the suspension comprises a plant matter/water ratio of 20 : 80 by weight on a dry matter basis.
  • the plant material is kept in contact with the water for a predetermined time.
  • this treatment lasts between 2 and 12 hours. In some more preferred embodiments of the invention, this treatment lasts between 3 and 8 hours. In the most preferred embodiments of the invention, this treatment lasts between 4 and 6 hours.
  • the temperature of the suspension is maintained between 20 °C and 80 °C during the treatment. In more preferred embodiments of the invention, the temperature of the suspension is maintained between 30 °C and 70 °C during the treatment. In the most preferred embodiments of the invention, the temperature of the suspension is maintained between 40 °C and 60 °C during the treatment.
  • the suspension is separated, preferably by centrifugation, most preferably by 5000 g centrifugation, into a liquid fraction and a wet solid fraction.
  • the liquid fraction also known as the neutral extract, contains water soluble protein (RPPRM-WS) extracted from the plant material during the treatment with water.
  • RPRM-WS water soluble protein
  • the solid fraction of this first neutral extract is in the range 0.5 - 2.5%.
  • the solid fraction of the neutral extract is in the range 1 - 3%.
  • the solid fraction of the neutral extract is in the range 5 - 10%.
  • the wet solid fraction remaining after removal of the liquid fraction also known as the crude neutral fraction, comprises de-chlorophyllized fiber.
  • the wet solid is washed with water and the washing water separated from the wet solid fraction (e.g. by 5000 g centrifugation at 10 °C) to produce a second neutral extract.
  • the washing is performed three times at a fiber : water ratio of 1:3 by volume.
  • the washing is performed with multiple aliquots of water applied in succession until the supernatant washing water has a dissolved solids content of less than 0.1%.
  • the neutral extracts are concentrated, preferably by evaporation in vacuo (typically at a pressure of 40 mbar and a temperature of 40 °C).
  • the first and second neutral extracts are combined prior to the step of concentrating them.
  • the neutral extracts are concentrated until the dissolved solids reach a predetermined minimum concentration. In some embodiments of the invention, this concentration is at least 3%. In some preferred embodiments of the invention, it is at least 5%. In some more preferred embodiments of the invention, it is at least 10%.
  • the concentrated neutral extract is then dried. Any method of drying known in the art can be used. In preferred embodiments, spray drying or freeze drying is used.
  • the resulting solid mass is generally in powder form and comprises a concentrate of the water-soluble protein from the de-chlorophyllized plant material.
  • the wet solid fraction comprising fibrous material from which water-soluble protein has been extracted, is dried following the washing with water. In typical embodiments, it is dried in a hot air oven at a temperature of about 75 °C - 85 °C. In preferred embodiments, the drying is performed until the moisture content falls below a predetermined level. In particularly preferred embodiments, the wet solid fraction is dried until the moisture content is less than 15%.
  • the dried fibrous material can then be ground, preferably to a granular mass with particles having a maximum diameter of less than 1 mm, and stored for other uses.
  • the protein concentrate produced by this method is a water-soluble composition comprising a mixture of substances. Typically, the average molecular weight is less than 12,000 Dalton; in preferred embodiments, the average molecular weight is less than 8,000 Dalton.
  • the protein in the concentrate can be seen to have at least partially undergone a conformational transition from random coil to rod when a dilute solution (0.5 - 1.5% protein concentrate) is prepared at 25 °C.
  • the water-soluble protein concentrate can be used as raw materials for obtaining end products with novel three-dimensional configurations that can be based on covalent or non- covalent bonds.
  • FIGs. 1A, IB, and 2 present schematic illustrations of method of derivatizing, activating, and chemical processing, respectively, of wholly water-soluble protein-rich plant-containing raw materials (RPPRM-WS).
  • RPRM-WS wholly water-soluble protein-rich plant-containing raw materials
  • Non-limiting examples include aqueous environments and organic solvents at temperatures that are typically between 20 °C and 80 °C.
  • Non-limiting examples chemical transformations that can be performed on the protein concentrates of the instant invention include nucleophilic substitution, addition reactions, and free radical polymerization.
  • the biomass starting material used was obtained from the duckweed species Woljfia globosa cultivated by Hino-man Ltd. (Israel). The plants were harvested, washed with demineralized water to remove dirt and foreign materials, and dried in a current of warm (40 °C) air using an Ezidri Ultra FD 1000 air dryer obtained from Food Dehydrators (Israel).
  • the superabsorbent polymeric material is then prepared.
  • separate aqueous mixtures are prepared of (a) a synthetic copolymer that comprises carboxylic groups; an inorganic salt; and a water-soluble concentrate produced from green plant biomass as described above.
  • the aqueous mixture of the synthetic polymer is mixed with the inorganic salt solution, and the aqueous mixture of the protein concentrate is then added, thereby forming an aqueous mixture (solution or suspension) of polymeric material.
  • the polymeric material is then dried. Crosslinking (preferably thermal crosslinking) of the dried polymeric material yields the desired superabsorbent swellable material.
  • the resulting suspension was mixed for 4 hours at 50 °C, cooled to room temperature, and discharged from the extraction reactor, after which it was separated by vacuum filtration using a Buchner funnel and polyester net with a pore diameter of 100 microns.
  • the separation produced 360 ml of extract solution (neutral extract) and 146 g of insoluble wet solid.
  • the neutral extract solution was found to contain 1.92 g of dissolved solids, as evaluated by a gravimetric method performed on 10 ml aliquots of the solution (average of 3 replicates).
  • the solution was dried at 105°C for 4 hours using an oven with forced-air convection.
  • the remaining solution of extract was freeze-dried by using a lyophilizer (FreeZone, Labconco). 1.89 g of solid "Rich Plant Protein Raw Material- Water Soluble" (RPPRM-WS-1) was obtained.
  • RPPRM-WS-1 Sufficient RPPRM-WS-1 was added to water buffered to a predetermined pH to make up a 0.5% solution. The components were centrifuged to 5,000 g at a temperature of 20 °C. The RPPRM-WS-1 completely dissolved over the entire pH range 2 - 12.
  • the average molecular mass of the protein concentrate was determined using tangential flow filtration (TFF) by dilution at constant volume using a Minimate TFF apparatus obtained from Pall. For this purpose has been prepared a solution of RPPRM-WS- 1 of 0.5% concentration in demineralized water using as medium a filter membrane of 12 kDa. Reference is now made to FIG. 3, which presents the results obtained from the application of TFF. The TFF results indicate the protein concentrate comprises water soluble compounds with average molecular mass lower than 12,000 Da. [0084] A viscosimetric method was used to confirm the coil-rod conformational transition [Tsujita Y. et al 1979.,Mark J.E. 2007].
  • red function on concentration are shown in FIG. 4. These results demonstrated that the coil to rod conformational transition had indeed occurred.
  • the RPPRM-WS materials of the present invention were used to produce superabsorbant polymers (hereinafter referred to as "Bio-SAP").
  • the protein concentrate (RPPRM-WS-1) was prepared as described in Example 1 above.
  • ISOBAM-18 isobutylene- maleic anhydride copolymer; see FIG. 5A) obtained from Kuraray Co. was used as the crosslinking agent, and the synthesis was performed according to the protocol disclosed in PCT Pat. Appl. Pub. No. WO2007/115169.
  • a polymer/crosslinker ratio of 90: 10 (dry basis) was used in the presence of ammonia which provides a 70% degree of neutralization of the synthetic polymer.
  • Rheological properties of the gel were measured as a function of the ratio of protein concentrate to ISOBAM-18.
  • Properties of bio-SAP gels produced from RPPRM-WS-1 and ISOBAM-18 were compared with analogous gels made from commercially available proteins and ISOBAM-18, and with analogous gels made from RPPRM-WS-1 and other polysaccharides.
  • Swelling was measured as a function of different swelling media types: distilled water (DW); tap water (TW); salt water 0.9% (SW); milk (3% fat); simulated human sweat (SHS); simulated wound fluids (SWF); simulated saliva (SS); simulated gastric fluids (SGF).
  • the simulated fluids were prepared according to literature procedures (Marques 2011).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Animal Behavior & Ethology (AREA)
  • Medicinal Chemistry (AREA)
  • Epidemiology (AREA)
  • Analytical Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Hematology (AREA)
  • Polymers & Plastics (AREA)
  • Botany (AREA)
  • Dispersion Chemistry (AREA)
  • Biochemistry (AREA)
  • Zoology (AREA)
  • Peptides Or Proteins (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

L'invention concerne un procédé de production d'un matériau superabsorbant à partir d'un polymère synthétique et d'une biomasse végétale dérivée d'un concentré protéique soluble dans l'eau. Ce procédé consiste à préparer un mélange aqueux d'un copolymère comprenant des groupes carboxyliques ; à préparer une solution aqueuse d'un sel inorganique ; à préparer un mélange aqueux d'un concentré de protéines soluble dans l'eau dérivé d'une biomasse végétale verte ; à mélanger ledit mélange aqueux dudit polymère synthétique avec ladite solution de sel inorganique pour former un mélange polymère synthétique-sel inorganique ; à ajouter ledit mélange aqueux dudit concentré de protéines soluble dans l'eau audit mélange polymère synthétique-sel inorganique pour former un mélange aqueux de matériau polymère ; à sécher ledit matériau polymère ; et à réticuler thermiquement ledit matériau polymère pour former un matériau polymère expansible superabsorbant. L'invention porte également sur le matériau superabsorbant produit par le procédé.
PCT/IL2017/050774 2016-07-11 2017-07-10 Matériaux polymères superabsorbants produits à partir d'un matériau végétal vert débarrassé de sa chlorophylle WO2018011789A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201662360480P 2016-07-11 2016-07-11
US62/360,480 2016-07-11

Publications (1)

Publication Number Publication Date
WO2018011789A1 true WO2018011789A1 (fr) 2018-01-18

Family

ID=60952911

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IL2017/050774 WO2018011789A1 (fr) 2016-07-11 2017-07-10 Matériaux polymères superabsorbants produits à partir d'un matériau végétal vert débarrassé de sa chlorophylle

Country Status (1)

Country Link
WO (1) WO2018011789A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007115169A2 (fr) * 2006-03-30 2007-10-11 Gelesis, Inc. Matières polymères utilisées comme agent de remplissage de l'estomac et leur préparation
WO2011078671A1 (fr) * 2009-12-22 2011-06-30 Nizo Food Research B.V. Procédé d'isolement d'une préparation de rubisco déchlorophyllée à partir d'une substance végétale

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007115169A2 (fr) * 2006-03-30 2007-10-11 Gelesis, Inc. Matières polymères utilisées comme agent de remplissage de l'estomac et leur préparation
WO2011078671A1 (fr) * 2009-12-22 2011-06-30 Nizo Food Research B.V. Procédé d'isolement d'une préparation de rubisco déchlorophyllée à partir d'une substance végétale

Similar Documents

Publication Publication Date Title
RU2618329C2 (ru) Способ получения гидрогелей
ES2789649T3 (es) Una formulación bioestimulante para mejorar el crecimiento vegetal y usos de la misma
EA011709B1 (ru) Способ получения пектинового продукта, содержащего волокна, пектиновый продукт и его применение
Bagde et al. Extraction of pectin from orange peel and lemon peel
Zelencova et al. Chitin extraction and chitosan production from Chilopoda (Scolopendra cingulata) with identification of physicochemical properties
Rocha et al. Effect of pH on the flaxseed (Linum usitatissimum L. seed) mucilage extraction process
DE60105984T2 (de) Carboxyl-modifiziertes superabsorbierendes proteinhaltiges hydrogel
Adekanmi et al. Different processing sequential protocols for extraction, quantification and characterization of chitosan from cray fish
CA2339978C (fr) Procede pour obtenir des alginates hautement purifies
Ewerton de Oliveira et al. The cooling of blends in water supports durable, thermo-responsive, and porous gelatin-polyphenolic tannin assemblies with antimicrobial activities
JP2011026272A (ja) 桑由来１−デオキシノジリマイシンの抽出方法
US20190144497A1 (en) Concentrated protein materials from de-chlorophyllized aquatic plant biomass
Yang et al. High-pressure homogenization combined with alcohol treatment is effective in improving the sensory and techno-functional characteristics of Chlorella pyrenoidosa
TW201929878A (zh) 幾丁質以及化學製備幾丁質及／或幾丁聚醣之方法
WO2018011789A1 (fr) Matériaux polymères superabsorbants produits à partir d'un matériau végétal vert débarrassé de sa chlorophylle
CN103768654A (zh) 一种水溶性丝素粉及其制备方法
WO2018011788A1 (fr) Coacervats à partir d'une biomasse végétale aquatique déschlorophylisée
Elangovan et al. Extraction, characterization and biological activity of Galactomannan rich endosperm of Borassus flabellifer (Linn.) suitable for biofabrication of tissue scaffolds
RU2658701C1 (ru) Способ получения свекловичного пектина
Choi et al. Dissolution, crystallilnity, and mechanical properties of silk sericin from Sericinjam silkworm cocoons.
WO2019045643A1 (fr) Production de matériaux de type nitrigel à partir de déchets de soja
SE543429C2 (en) Method of preparing plant protein based absorbent material and absorbent material thus produced
Mikhailova et al. Stability of hyaluronan-pectic gel particles in the conditions of the artificial gastrointestinal environment
JP4378477B2 (ja) 成形材料及びその製造方法
US11685794B1 (en) Method of industrial extraction of alginates from brown seaweed of the family sargassaceae of the order fucales

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17827115

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17827115

Country of ref document: EP

Kind code of ref document: A1