WO2014189355A2 - Procédés de traitement de tourteau de palmiste - Google Patents

Procédés de traitement de tourteau de palmiste Download PDF

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Publication number
WO2014189355A2
WO2014189355A2 PCT/MY2014/000072 MY2014000072W WO2014189355A2 WO 2014189355 A2 WO2014189355 A2 WO 2014189355A2 MY 2014000072 W MY2014000072 W MY 2014000072W WO 2014189355 A2 WO2014189355 A2 WO 2014189355A2
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WIPO (PCT)
Prior art keywords
pkc
hydrolysate
process according
palm kernel
hydrolysed
Prior art date
Application number
PCT/MY2014/000072
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English (en)
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WO2014189355A3 (fr
Inventor
Julia BINTI IBRAHIM
Shwu Fun KUA
Norhafizi BIN HASHIM
Khairul Izwan BIN NAN
Christopher Kuok Weng OOI
Hirzun MOHD YUSOF
Harikrishna Kulaveerasingam
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Sime Darby Malaysia Berhad
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Application filed by Sime Darby Malaysia Berhad filed Critical Sime Darby Malaysia Berhad
Publication of WO2014189355A2 publication Critical patent/WO2014189355A2/fr
Publication of WO2014189355A3 publication Critical patent/WO2014189355A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/02—Monosaccharides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00—Production of fats or fatty oils from raw materials
    • C11B1/02—Pretreatment
    • C11B1/025—Pretreatment by enzymes or microorganisms, living or dead
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00—Production of fats or fatty oils from raw materials
    • C11B1/10—Production of fats or fatty oils from raw materials by extracting
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase

Definitions

  • the present disclosure relates generally to processes for the treatment of palm kernel cake. More particularly, the disclosure relates to processes for the enzyme catalysed hydrolysis of palm kernel cake and to products obtained thereby.
  • the fruit of the oil palm yields two distinct oils: palm oil, derived from the outer parts of the fruit, and palm kernel oil, derived from the seed of the fruit, or kernel.
  • the palm kernel contains a hypothetical oil content of approximately 50-55%.
  • high pressure expellers are used to extract the oil from the kernel, although solvent-based extraction processes can also be used.
  • the extraction process affords the palm kernel oil and, as the waste by-product, the "de-oiled" solid mass, or pulp, referred to as "palm kernel cake” (P C), or sometimes, palm kernel expeller” (PKE).
  • the PKC While the extraction process affords the majority of the oil present in the kernel a significant proportion of the oil is retained in the PKC (about 10% w/w).
  • the PKC also contains some protein and significant amounts of polysaccharides, including hemicelluloses, celluloses and pectins which make up the cell walls, as well as a high phosphorus to calcium ratio. PKC is therefore utilised as a high energy, high fibre feed supplement for ruminants.
  • a relatively low nutrition value and only average protein content, together with a poor amino acid profile means that PKC, on its own, is ever only a medium quality feed, ranked a little higher than copra cake but lower than fish meal and ground nut cake in its protein value.
  • PKC can be considered as a low value product.
  • the present disclosure describes processes which utilise an enzyme-catalysed hydrolysis of PKC.
  • the hydrolytic process employs one or more enzymes which advantageously breakdown, or degrade, the polysaccharide and/or protein components which comprise plant cell walls, releasing retained oil and, further, and also affording smaller saccharide molecules.
  • the present disclosure provides a process for obtaining one or more saccharides from palm kernel cake (PKC) comprising:
  • the present disclosure provides a process for extracting palm kernel oil from palm kernel cake (PKC) comprising:
  • the present disclosure provides a process for extracting palm kernel oil and obtaining one or more saccharides from palm kernel cake (P C) comprising:
  • the present disclosure provides a process for extracting palm kernel oil from palm kernel cake (PKC) comprising:
  • the PKC subjected to hydrolysis is expeller pressed, derived from the mechanical screw press oil extraction method. In some embodiments, the PKC is derived from solvent extraction methods.
  • the enzymes are dissolved or suspended in water to provide an enzymatic solution which is mixed with the PKC.
  • one or more enzymes capable of hydrolysing at least a portion of hemicellulose polysaccharides present in the PKC are used.
  • one or more enzymes capable of hydrolysing or degrading at least a portion of mannan present in the PKC are used.
  • the process employs at least mannanase.
  • one or more enzymes capable of hydrolysing or degrading other cell wall constituents such as celluloses, pectins and associated proteins are used, that is to say one or more of cellulases, pectinases and proteinases.
  • the hydrolysis process uses a mixture of at least two of mannanase, xylanase, cellulase, pectinase and protease.
  • the hydrolysis process is conducted using mannanase, xylanase, cellulase and pectinase, optionally together with protease.
  • Figure 1 schematically depicts an example of a process for the production of palm kernel oil and PKC which incorporates an enzymatic hydrolysis treatment of the first pressed palm kernel cake.
  • Figure 2 schematically depicts an example of a process for the preparation of mannose and palm kernel oil by enzymatic hydrolysis of PKC.
  • Palm kernel cake is the material retained after extraction of palm kernel oil from the palm kernel.
  • Two major processes are typically used; a high pressure screw press method (e.g. expeller press) or a solvent-based (e.g. hexane) extraction method.
  • the PKC produced by each method differs in the amount of palm kernel retained in the cake: 5-12% for expeller pressed PKC versus 0.5-3% for solvent extracted PKC.
  • the PKC subjected to enzymatic hydrolysis is that obtained after the first pressing of palm kernels through a high pressure expeller press (first pressed PKC).
  • the PKC subjected to enzymatic hydrolysis is that obtained after the second pressing of palm kernels through high pressure expeller press (second pressed P C).
  • the PKC is obtained from solvent-based (for example, hexane) extraction of palm kernel oil. It will be understood that the PKC as described herein may be PKC obtained from one or more such processes.
  • Reference to PKC includes the material obtained directly from the oil extraction process.
  • material may be further subjected to one or more further physical and/or chemical treatments prior to being subjected to enzymatic hydrolysis.
  • Such treatments may include one or more of milling, crushing, grinding, chopping or other process of communition, hydrothermal treatment, such as steam or hot liquid water treatment, and acid (e.g. sulphuric acid) or base (e.g. sodium hydroxide) treatment.
  • Pre-treating the PKC chemically or physically helps to alter the hemicellulose structure of the PKC. This causes the PKC to be more accessible to the enzymes. This in turns helps to increase yield of the saccharides and/or oil.
  • the PKC subjected to enzymatic treatment may be in the form of meal, flakes, granules, pellets or any other suitable form.
  • the PKC has a size in the range of about mesh size 1 mm to about 10 mm, such as from about 1 mm to about 5 mm.
  • Hemicelluloses are a heterogeneous group of polysaccharides, which together with celluloses, pectins, and proteins are present in plant cell walls.
  • the group of polysaccharides known as hemicelluloses include polysaccharides having p-(l ⁇ 4)-linked backbones of glucose, mannose or xylose with an equatorial configuration, and include xyloglucans, xylans, mannans (including galactomannans) and glucomannans (including galactoglucomannans).
  • Xylans feature a backbone of p-(l ⁇ 4)-linked xylose residues
  • mannans feature a backbone predominantly of -(l ⁇ 4)-linked mannose units
  • glucomannans contain a backbone of glucose and mannose
  • xyloglucans contain a backbone of glucose with xylose-containing sidechains
  • polysaccharides contain a number of different sugar monomers. For instance, besides glucose, xylose, and mannose. which are sugar monomers present in the backbone of the polysaccharides, hemicelluloses can also include, monomers of galactose, rhamnose, fucose, glucouronic acid, and arabinose. Hemicelluloses contained within PKC, together with celluolses and pectins are therefore a potential source of mono-, di-, tri and/or higher oligo-saccharides.
  • Mannan represents one of the major constituent groups of hemicelluloses in P C (approximately 30-35%) and therefore represents a potential source of its constituent monosaccharide, mannose.
  • D-Mannose and its reduced alcohol, D-mannitol have a number of medical applications; for example, D-mannose as a treatment for urinary tract infections and D-mannitol as an osmotic agent and, treatment for cystic fibrosis.
  • Mannitol is industrially formed by hydrogenation of fructose syrup or purified fructose to yield a mixture of the isomers sorbitol and mannitol.
  • the present disclosure allows for the preparation of purified mannose, and through its subsequent conversion to mannitol, a potentially more economical process for the preparation of purified D-mannitol.
  • the saccharide recovered from the PKC is mannose, for example, D-mannose.
  • the processes described herein may be used to recover one or more other monosaccharides, for example: glucose, xylose, galactose, rhamnose, fucose, glucouronic acid, and arabinose.
  • disaccharides may be recovered. Some examples thereof include ⁇ 1 ⁇ 4 glucan, ⁇ 1 ⁇ 4 xylan, ⁇ 1 ⁇ 4 glucomannan and ⁇ 1 ⁇ 4 mannan.
  • the processes described herein subject the PKC to enzymatic hydrolytic treatment by contacting or mixing the PKC with one or more enzymes under aqueous conditions in order to degrade cell wall polysaccharides and, thereby allow for the recovery of palm kernel oil and/or and smaller saccharide units from the PKC.
  • the PKC, enzymes and water are mixed under appropriate hydrolysis conditions.
  • the enzymes are selected according to the saccharide or saccharides desired to be recovered.
  • the enzymes may be presented in the form of an aqueous mixture in which the enzymes are dissolved or dispersed in water, herein also referred to as an "enzyme solution" or "enzyme cocktail".
  • the water used in the enzymatic hydrolysis step is suitably purified, for example by reverse osmosis (RO).
  • one or more enzymes capable of hydrolytically cleaving one or more chemical bonds within a hemicellulose polysaccharide, e.g. mannan contained in the PKC are employed. Such enzymes may be referred to as hemicellulases.
  • Hemicellulases are a diverse group of enzymes which can be categorised according to the chemical bonds they cleave: glycoside hydrolases (GH), which hydrolyse glycosidic bonds within the polysaccharide, and carbohydrate esterases (CE), which hydrolyse ester linkages within the polysaccharide.
  • GHs can be further categorised according to whether the enzyme cleaves a bond within the polysaccharide backbone (endo-glycoside) or cleaves off a mono- or di- saccharide side chain (exo-glycoside).
  • hemicellulases contemplated herein include endo-P-l,4-xylanase, exo ⁇ -l,4-xylosidase, endo-P-l,4-mannanase, exo-p-1,4- mannosidase, a-arabinofuranosidase, endo-ce-L-l,5-arabinase, a-glucuronidase, a- galactosidase, ⁇ -glucosidase, endo-galactanasee, acetyl xylan esterase and acetyl mannan esterase and mixtures thereof.
  • one or more other enzymes which hydrolyse other components such as lignans, celluloses or proteins within the PKC may also be used.
  • Some non-limiting examples thereof include lignan hydrolysing enzymes (lignases) cellulose hydrolysing enzymes (cellulases, e.g. endo-l,4-p-glucanase, carboxymefhyl cellulase, endo-l,4-P-D-glucanase, P-l,4-glucanase, P-l,4-endoglucan hydrolase, exocellulosase and ⁇ -glucosidase), pectin hydrolysing enzymes (pectinases, e.g.
  • enzymes to cleave cell wall-linked proteins
  • Any such one or more enzymes, crude or purified, or mixtures thereof, are encompassed by the present disclosure.
  • Enzymes for use in the processes described herein are obtainable from microbial (e.g. fungal and bacterial) sources (e.g. Aspergillus and Tricoderma) and are commercially available.
  • Such enzymes may include a mixture of enzymes and have one or more modes of action and specificity and are commonly simply referred to as, for example, "hemicellulase”, “xylanase”, “cellulase”, “mannanase” etc.
  • hemicellulase typically comprises a mixture of hemicellulase enzymes, and, optionally, other enzymes, thus having multiple modes of action and specificity.
  • the processes disclosed herein may be used to extract and recover monosaccharides, disaccharides and/or other oligosaccharides from PKC.
  • the skilled addressee will be able to determine suitable enzymes and combinations thereof due to their mode of action and specificity according to the desired saccharide recovery.
  • the enzymes are selected to allow recovery of one or more monosaccharides.
  • the one or more enzymes are selected in order to recover the monosaccharide mannose. This may advantageously be achieved using one or more mannan degrading enzymes, i.e. mannanase. Further enzymes to degrade one or more other polysaccharides present in the PKC, including celluloses and pectins, as well as associated proteins may additionally be used.
  • the enzyme solution comprises a mixture of two or more of mannanase, cellulase, pectinase, xylanase and protease.
  • the enzyme solution comprises a mixture of three or four of mannanase, cellulase, pectinase, xylanase and protease. In still further embodiments, the enzyme solution comprises a mixture of mannanase, cellulase, pectinase, xylanase and protease.
  • the PKC is contacted with the enzyme or enzymes for a time and under conditions sufficient to effect at least partial degradation of the plant cell wall through hydrolysis of polysaccharide cell wall components of the PKC.
  • the skilled person will be able to determine appropriate conditions according to the desired saccharide to be recovered, including length of incubation period, temperature of incubation, pressure, pH conditions, quantity and combination of enzymes used and relative ratios of components.
  • the hydrolysis mixture comprising the PKC and enzyme solution may be agitated by stirring the mixture or, rocking or shaking the incubation vessel.
  • the hydrolysis can be performed under acidic, neutral or mildly basic conditions and may depend on and be adjusted as necessary by the addition of an appropriate acid or base according to the enzyme(s) used.
  • the skilled addresses will be able to determine suitable pH levels.
  • the hydrolysis is performed at a pH in the range of 3-8 such as pH 3-5, pH 5-7 or pH 7-8.
  • the hydrolysis may be performed at a pH of about 3, or 4, or, 5 or, 6, or 7, or 8.
  • the hydrolysis is performed at a pH of about 5.
  • the hydrolysis proceeds over a period of at least about 12 hours, more advantageously, at least about 24 hours, or from about 36 or 48 hours to about 72 hours, or even up to about 168 hours.
  • longer or shorter incubation periods may be utilised depending on other factors such as the types of enzymes and amount and thereof used, quantity of PKC being treated, incubation temperature etc.
  • the incubation may be carried out at any suitable temperature which allows for enzyme activity under the relevant aqueous conditions.
  • hydrolysis may be performed at a temperature in the range of about 20-80°C, such as in the range of about 25-75°C, or 40-60°C, for example about 45-55°C.
  • the incubation is performed at a temperature of about 50°C.
  • the ratio of PKC to aqueous enzymatic solution may depend on the nature of the enzymes and the concentration of enzymes in solution and may advantageously be anywhere from about 1 :1 to 1 :10 (w/v).
  • the ratio of PKC to aqueous enzymatic solution is such that the hydrolysis mixture is sufficiently concentrated to allow the process to proceed to the desired level of completion or near completion in the desired time frame.
  • the ratio of PKC to aqueous enzymatic solution is from about 1 :1 to about 1 :5, such as about 1 :2, 1 :3 or 1 :4. In further embodiments, the ratio is about 1 :3.
  • An effective amount of one or more enzymes includes an amount of enzyme(s) capable of hydrolysing polysaccharide and/or protein components of PKC.
  • the total enzyme amount employed will depend on a number of factors including the nature of the enzyme(s), the amount of PKC to be treated etc, but typically may be independently in the range of about 0.1-10% (w/w) of dry PKC weight for each enzyme type, for example an amount in the range of about 0.5% to about 3.0% (w/w) or in the range of about 0.5% (w/w) to about 1.5% (w/w).
  • each enzyme is independently added in an amount (based on dry PKC weight) of about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1 , 1.2, 1.3, 1.4, 1.5, 2.0, 2.5, 3.0 or 5.0% (w/w).
  • the PKC is mixed with a cocktail of enzymes, including at least mannase and pectinase.
  • a cocktail of enzymes including at least mannase and pectinase.
  • a mixture comprising mannase, cellulase, xylanase, pectinase and optionally protease, each independently in an amount of 0.5-3.0% (w/w) for example, 0.5-1.0% (w/w) on a dry PKC basis, in water, added to the PKC in a ratio of about 1 :3 to 1 :5 (PKC:water)
  • the mixture may be incubated for a period of from about 24 to 168 hours, such as from 24 to 72 hours, at a temperature in the range of about 40-60°C, for example about 45-55°C.
  • PKC hydrolysate refers to the aqueous phase containing dissolved or dispersed saccharide products produced by enzymatic hydrolysis, as well as palm kernel oil.
  • hydrolysed PKC also referred to herein as “kernel paste” refers to the paste-like PKC which remains after PKC has been subjected to enzymatic hydrolysis.
  • the PKC hydrolysate is separated from the hydrolysed PKC by any suitable means, including one or more of decantation, such as centrifugal decantation, centrifugation and filtration.
  • Centrifugal decantation may advantageously be carried out at any appropriate bowl speed, for example at a speed in the range of from about 2000 rpm to about 5000 rpm, such as 3000 rpm to about 4500 rpm, and at a suitable feed rate such as from about 4, 6, 8 or 1 OL/min.
  • the residual enzymes may be deactivated at a point after the hydrolysis step is complete.
  • Deactivation may be performed by heating the hydrolysate at a suitable temperature for an appropriate time, for example at 90-100°C for about 10-15 minutes.
  • the separated PKC hydrolysate may then be subjected to further process steps in order to recover one or more saccharides and/or palm kernel oil.
  • “recover” or “recovery” and variations thereof refer to the separation, isolation or purification of the desired component from the PKC, or PKC hydrolysate.
  • An exemplary process is depicted in Figure 2. Although the illustrated process specifies the separation of the specific saccharide mannose, the skilled person will understand that the illustrated process is amenable to modification for the production and recovery of other saccharides, depending on the enzymes used.
  • the process depicted in Figure 2 may be adapted to produce and recover any one or more of the other saccharides herein described.
  • the separated PKC hydrolysate may be further separated or clarified to separately afford an oil phase comprising the palm kernel oil and an aqueous saccharide-containing phase.
  • Suitable methods therefore are known in the art and may include use of a separator or clarifier apparatus, such as Clara20, (Alfa Laval), or solvent extraction.
  • the saccharide-containing aqueous phase may then be subjected to one or more further purification/separation steps, which may include one or more of filtration (e.g. one or more of bag filtration, tangential flow filtration, membrane filtration, including ultrafiltration, reverse osmosis and nanofiltration), ion exchange, including selective adsorption on ion exchange resins or molecular sieves and chromatography, such as simulated moving bed chromatography (SMBC).
  • filtration e.g. one or more of bag filtration, tangential flow filtration, membrane filtration, including ultrafiltration, reverse osmosis and nanofiltration
  • ion exchange including selective adsorption on ion exchange resins or molecular sieves
  • chromatography such as simulated moving bed chromatography (SMBC).
  • SMBC simulated moving bed chromatography
  • the aqueous saccharide-containing phase is subjected to the steps of filtration, decalcification, concentration, chromatography and crystallisation.
  • the separated oil-containing phase may also be separately subjected to appropriate purification steps.
  • deactivation may be effected by heating the hydrolysate for a time and at a temperature sufficient to deactivate the enzyme, for example about 90-100°C for about 10-15 mins.
  • the processes described herein may afford at least about 5% (w/w) or about 10% (w/w) palm kernel oil based on PKC. In some further embodiments, the processes described herein may yield up from about 10-20% (w/w), for example about 15% (w/w) palm kernel oil based on PKC. In some embodiments, the processes described herein may afford about 15-20% (w/w) mannose based on PKC. In further embodiments, the processes described herein may yield from about 20-30% (w/w) mannose based on PKC.
  • the separated hydrolysed PKC may also be subjected to further treatment to recover oil remaining in the hydrolysed PKC. Suitable processes therefore include solvent extraction such as with hexane.
  • the processes described herein may be used to obtain "purified” or "high purity” saccharides, such as mannose.
  • Reference to “purified” or “high purity” refers to a purity of at least about 90%, such as about 93% or 95%. In still further embodiments, this refers to a purity of at least about 97% or 99%. Purity may be determined by chromatographic methods.
  • the processes described herein may be incorporated into conventional oil extraction processes and thus may be performed on an industrial (kg) scale, such as on about 50, 100, 150, or 200 kg of PKC.
  • the resulting PKC may be optionally subjected to one or more pre-treatment processes as described herein and transferred to a hydrolytic reactor, such as a tank or other vessel, for enzymatic hydrolysis.
  • a hydrolytic reactor such as a tank or other vessel
  • PKC palm kernel cake type-crushed B
  • Table 4-1 List of enzymes used.

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Abstract

La présente invention porte d'une manière générale sur des procédés de traitement de tourteau de palmiste. L'invention concerne en particulier des procédés d'hydrolyse par catalyse enzymatique de tourteau de palmiste, et des produits obtenus par ces procédés.
PCT/MY2014/000072 2013-05-21 2014-04-24 Procédés de traitement de tourteau de palmiste WO2014189355A2 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115536711A (zh) * 2022-09-28 2022-12-30 北京新锐得生物科技有限公司 一种棕榈粕提取甘露糖的制备工艺

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MY174318A (en) * 2007-12-12 2020-04-07 Novozymes As Enzymatic degradation of biomass substrates comprising mannan

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SCHELLER, H.V.; ULVSKOV, P., ANNU. REV. PLANT BIOL., vol. 61, 2010, pages 263 - 289

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115536711A (zh) * 2022-09-28 2022-12-30 北京新锐得生物科技有限公司 一种棕榈粕提取甘露糖的制备工艺

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