WO2024009260A1 - Method for the recovery of ellagic acid from industrial pulp mill streams - Google Patents
Method for the recovery of ellagic acid from industrial pulp mill streams Download PDFInfo
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- WO2024009260A1 WO2024009260A1 PCT/IB2023/057001 IB2023057001W WO2024009260A1 WO 2024009260 A1 WO2024009260 A1 WO 2024009260A1 IB 2023057001 W IB2023057001 W IB 2023057001W WO 2024009260 A1 WO2024009260 A1 WO 2024009260A1
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- Prior art keywords
- ellagic acid
- effluent
- previous
- acid
- precipitate
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Links
- 229920002079 Ellagic acid Polymers 0.000 title claims abstract description 136
- AFSDNFLWKVMVRB-UHFFFAOYSA-N Ellagic acid Chemical compound OC1=C(O)C(OC2=O)=C3C4=C2C=C(O)C(O)=C4OC(=O)C3=C1 AFSDNFLWKVMVRB-UHFFFAOYSA-N 0.000 title claims abstract description 136
- ATJXMQHAMYVHRX-CPCISQLKSA-N Ellagic acid Natural products OC1=C(O)[C@H]2OC(=O)c3cc(O)c(O)c4OC(=O)C(=C1)[C@H]2c34 ATJXMQHAMYVHRX-CPCISQLKSA-N 0.000 title claims abstract description 136
- 229960002852 ellagic acid Drugs 0.000 title claims abstract description 136
- 235000004132 ellagic acid Nutrition 0.000 title claims abstract description 136
- FAARLWTXUUQFSN-UHFFFAOYSA-N methylellagic acid Natural products O1C(=O)C2=CC(O)=C(O)C3=C2C2=C1C(OC)=C(O)C=C2C(=O)O3 FAARLWTXUUQFSN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000011084 recovery Methods 0.000 title claims abstract description 14
- 238000010411 cooking Methods 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 34
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000004061 bleaching Methods 0.000 claims abstract description 21
- 238000002425 crystallisation Methods 0.000 claims abstract description 17
- 230000008025 crystallization Effects 0.000 claims abstract description 17
- 239000012978 lignocellulosic material Substances 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 230000003750 conditioning effect Effects 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229920003023 plastic Polymers 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 7
- -1 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 238000003913 materials processing Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000001143 conditioned effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 abstract description 15
- 238000002955 isolation Methods 0.000 abstract description 12
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- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 7
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- 239000000843 powder Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 239000000284 extract Substances 0.000 description 18
- 239000013078 crystal Substances 0.000 description 12
- 244000166124 Eucalyptus globulus Species 0.000 description 11
- 239000012632 extractable Substances 0.000 description 9
- 229920005610 lignin Polymers 0.000 description 9
- 235000000346 sugar Nutrition 0.000 description 9
- 150000008163 sugars Chemical class 0.000 description 8
- 239000005388 borosilicate glass Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002655 kraft paper Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229920001968 ellagitannin Polymers 0.000 description 5
- 229910052500 inorganic mineral Chemical class 0.000 description 5
- 239000011707 mineral Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920001732 Lignosulfonate Polymers 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000012611 container material Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 235000019357 lignosulphonate Nutrition 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920001864 tannin Polymers 0.000 description 3
- 235000018553 tannin Nutrition 0.000 description 3
- 239000001648 tannin Substances 0.000 description 3
- 235000004936 Bromus mango Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 235000011511 Diospyros Nutrition 0.000 description 2
- 244000236655 Diospyros kaki Species 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 240000007228 Mangifera indica Species 0.000 description 2
- 235000014826 Mangifera indica Nutrition 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 244000294611 Punica granatum Species 0.000 description 2
- 235000014360 Punica granatum Nutrition 0.000 description 2
- 235000009184 Spondias indica Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229920001461 hydrolysable tannin Polymers 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000010903 primary nucleation Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 235000017399 Caesalpinia tinctoria Nutrition 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 230000010736 Chelating Activity Effects 0.000 description 1
- 208000017667 Chronic Disease Diseases 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 235000004692 Eucalyptus globulus Nutrition 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 239000004117 Lignosulphonate Substances 0.000 description 1
- 241000218922 Magnoliophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000219492 Quercus Species 0.000 description 1
- 241001092459 Rubus Species 0.000 description 1
- 241001412171 Rubus corchorifolius Species 0.000 description 1
- 240000007651 Rubus glaucus Species 0.000 description 1
- 235000011034 Rubus glaucus Nutrition 0.000 description 1
- 235000009122 Rubus idaeus Nutrition 0.000 description 1
- 241000388430 Tara Species 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001088 anti-asthma Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003178 anti-diabetic effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000002555 anti-neurodegenerative effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000000924 antiasthmatic agent Substances 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 229940005513 antidepressants Drugs 0.000 description 1
- 239000003472 antidiabetic agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229940088623 biologically active substance Drugs 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 239000002537 cosmetic Substances 0.000 description 1
- 238000005384 cross polarization magic-angle spinning Methods 0.000 description 1
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- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 230000002178 gastroprotective effect Effects 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000002634 lipophilic molecules Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/40—Separation, e.g. from natural material; Purification
Definitions
- the present invention relates the isolation of ellagic acid from streams of the lignocellulosic materials processing industries, preferably in streams of cellulosic pulp mills, which may have applications in several areas, such as chemical technology and health .
- Ellagic acid is found dissolved in cooking liquors and bleaching effluents during the chemical processing of wood into pulp. Due to its polyphenolic and polyaromatic character, ellagic acid is a substance with unique chemical and bioactive properties, known for its antioxidant and chelating activities, attracting growing interest for technical and biomedical applications (e.g., possible antibacterial, antifungal, antiviral, anti-inflammatory, hepato- cardioprotective, chemopreventive, anti-neurodegenerative, antiasthmatic, anti-diabetic, gastroprotective and properties similar to antidepressants, among others) .
- the present invention relates to a method for the recovery of ellagic acid from industrial streams of cellulosic pulp mills, or streams from other lignocellulosic materials processing industries, comprising the following steps: a) Collecting a stream effluent and adjusting its pH between 0.1 and 14, and temperature between 1 and 100°C for subsequent conditioning; b) Conditioning of the effluent for a time between 0.1 and 720 hours in a container having a surface area-to-volume ratio between 0.1 and 100 irT 1 and made of a material selected from metal derivatives, glass, or plastics, which are suitable for the crystallization of ellagic acid, wherein the effluent is conditioned at the pH and temperature adj usted in the previous step; c ) Separation of the ellagic acid-containing precipitate obtained in the previous step via crystallization, wherein the separation is carried out by centrifugation or any other separation technique suitable for the purpose ; d ) Successive washing of the separated ellagic
- the industrial stream is an effluent from acid sulphite processes , such as cooking liquors or bleaching line effluents .
- step a ) is carried out after removing nonprocessed suspended matter .
- step b ) is carried out at conditioning temperatures between 60 and 80 ° C when the effluent is cooking liquor .
- step b ) is carried out at conditioning temperatures between 20 and 40 °C when the effluent is an alkaline bleaching effluent .
- the pH of the effluent in step a ) is adj usted between 2 and 5 .
- the conditioning time is above 720 hours .
- the container is made of glass with a percentage of borosilicate , between 65 and 80% of silica and between 8 and 25% of boron trioxide .
- the container is made of plastic such as polyethylene terephthalate or high-density polyethylene .
- the container is made of metal derivatives, such as variants of stainless steel.
- the surface area-to-volute ratio is above 100 nt 1
- step d) is carried out using acidified water comprising HC1 between 0.1 and 20% v/v.
- Ellagic acid (EA) ( Figure 1) belongs to the class of extractable polyphenols (tannins) widely distributed among dicotyledonous species (Quideau and Feldman, 1996) .
- EA extractable polyphenols
- Héau and Feldman a group of extractable polyphenols
- ETs ellagitannins
- ETs are secondary metabolites of higher plants and act as part of the defence mechanism against microbial and animal attacks due to their astringent capacity and ability to form complexes with proteins and polysaccharides (Quideau and Feldman, 1996) .
- Hydrolysable tannins have long been known for their use in leather tanning processes (Quideau and Feldman, 1996) .
- the growing interest in these compounds is mainly associated with the consumption and development of new products with benefits for human health, linked to the antioxidant properties of phenolics (Wu et al., 2004) .
- EA has been the subject of several scientific studies (Al-Sayed and El-Naga, 2015; Nguyen et al. , 2017) .
- EA and ETs may also have applications linked to advanced materials, such as polymeric materials (Reitze et al., 2001) , chelating reagents (Przewloka and Shearer, 2002) , ion exchange resins (Zhang and Chen, 1988) , materials for electrochemical devices (Goriparti et al. , 2013) , among others.
- advanced materials such as polymeric materials (Reitze et al., 2001) , chelating reagents (Przewloka and Shearer, 2002) , ion exchange resins (Zhang and Chen, 1988) , materials for electrochemical devices (Goriparti et al. , 2013) , among others.
- Marketed EA products are produced essentially from natural plants, fruits and agricultural residues, since the organic synthesis results in low yields and can compromise the biological activity of EA due to failures in the chemoselectivity, regioselectivity and stereoselectivity of the process
- EA eucalypt leaves
- tara CN107827900A
- pomegranate peel CN1803801A
- mango seed CN107163059A
- blackberry branches and leaves CN106913639A
- flower galls CN105175427A
- raspberry KR20170135744A
- eucalypt leaves CN105132179A
- many other natural sources Koponen et al. , 2007; Okuda et al. , 2009.
- EA examples include oxidative synthesis from ETs containing gallic acid and its water-soluble esters (US5231193A; EP0390107A2) or by a combination of alkaline hydrolysis and oxidation (CN105753880A) .
- EA methyl derivatives of EA and glycosides of both form part of the tannin extracts of Eucalyptus , Quercus , Acacia and Castanea species, among other angiosperms (Fengel and Wegener, 1989) . Since these woods are used in cooking processes to produce cellulosic pulp, they can also be considered a great source of EA. In fact, EA is present in different industrial streams from the production of kraft pulps (Costa et al., 2014) and sulphite pulps (Rodrigues et al. , 2018) .
- EA and its derivatives are obtained by extraction with a certain organic solvent, with mixtures of organic solvents (Quideau and Feldman, 1996) , with mixtures of organic solvents with water or, more recently, using ionic liquids (IL) (Chowdhury et al. , 2010) .
- IL ionic liquids
- EA recovery approaches are limited to extraction with poorly water-mixable organic solvents such as ethyl acetate (Alexandri et al. , 2016) or ethyl ether (Llano et al. , 2015) .
- Purification of EA is normally carried out by multi-step processes and may involve chromatographic and recrystallization steps, among other separation techniques.
- the present invention aims to recover ellagic acid from industrial streams of cellulosic pulp mills, or streams from other lignocellulosic materials processing industries, such as cooking liquors and bleaching line effluents.
- Ellagic acid (EA) in the free form or linked to sugars by ester linkage (ET) is present in wood subjected to a delignification (cooking) process in the production of pulp for paper or other cellulose-based products.
- the cooking process consists of degradation and removal of lignin together with other components of the wood, thus releasing the cellulosic fibers (Evtuguin 2016) .
- the present invention relates to a method for recovering ellagic acid from an industrial stream of cellulosic pulp mills, or a stream from other lignocellulosic materials processing industries, comprising the following steps: a) Collecting a stream effluent and adjusting the pH between 0.1 and 14, and temperature between 1 and 100°C for subsequent conditioning; b) Conditioning of the effluent for a time between 0.1 and 720 hours in a container made of a material selected from metal derivatives, glass or plastics which are suitable for the crystallization of ellagic acid, wherein the effluent is conditioned at the pH and temperature adjusted in the previous step; c) Separation of the ellagic acid-containing precipitate obtained in the previous step via crystallization, wherein the separation is carried out by centrifugation or any other separation technique suitable for the purpose; d) Successive washing of the separated ellagic acid-containing precipitate with water and separation of the precipitate by centrifugation or any other separation technique suitable for the purpose
- the industrial stream from cellulosic pulp mills, or stream from other lignocellulosic materials processing industries is an effluent from acid sulphite processes, such as cooking liquors or bleaching line effluents.
- step a) is carried out after removing nonprocessed suspended matter.
- step b) is carried out at a conditioning temperature between 60 and 80°C when the effluent is cooking liquor. In another embodiment, step b) is carried out at a conditioning temperature between 20 and 40°C when the effluent is an alkaline bleaching effluent. In one embodiment, the pH of the effluent in steps a) is adjusted between 0.1 and 14. In another embodiment, the pH of the effluent in step a) is adjusted between 2 and 5.
- step b) occurs with an effluent conditioning time comprised between 0.1 and 720 hours. In another embodiment, the conditioning time is above 720 hours.
- the container used in step b) is made of a material selected from, but not limited to: metal derivatives, such as variants of stainless steel; as well as glass, mainly with a large percentage of borosilicate, between 65 and 80% of silica (SiO2) and between 8 and 25% of boron trioxide (B2O3) ; plastic such as polyethylene terephthalate or high-density polyethylene; or other materials that have chemical and/or physical similarities, providing the same conditions suitable to promote selective crystallization of ellagic acid.
- metal derivatives such as variants of stainless steel
- glass mainly with a large percentage of borosilicate, between 65 and 80% of silica (SiO2) and between 8 and 25% of boron trioxide (B2O3)
- plastic such as polyethylene terephthalate or high-density polyethylene
- other materials that have chemical and/or physical similarities providing the same conditions suitable to promote selective crystallization of ellagic acid.
- step d) is a step of successive washing of the ellagic acid-containing precipitate with water, which however does not qualify as a specific purification step.
- the number of washes and the amount of water used will depend on the effluent used and isolation conditions.
- step d) is carried out using acidified water comprising HC1 between 0.1 and 20% v/v, which can also be used for metal and other concomitants removal.
- acidified water comprising HC1 between 0.1 and 20% v/v, which can also be used for metal and other concomitants removal.
- the number of washing cycles and the amount of water used in it depend on the effluent used and the conditions for isolating the ellagic acid.
- Step d) is influenced by the surface area-to-volume ratio (S/V) of the container used for processing, being preferred the use of containers with S/V values between 0.1 and 100 (nt 1 ) to increase the number of nucleation centres during ellagic acid crystallization.
- the S/V ratio can be above 100 (nV 1 ) .
- ellagic acid is obtained in powder form with purity ranging between 20 and 99% , without further purification, depending on the stream used and isolation conditions .
- EA is completely soluble in alkaline cooking liquors ( kraft black liquor pH is around 11 ) and very little soluble in acid sulphite cooking liquors (pH of SO2 solution is around 3 ) . Due to the symmetrical chemical structure ( Figure 1 ) and low solubility in water, EA easily forms crystals that can be recovered from the medium. This phenomenon occurs in a relatively simple way in the liquor from cooking with acid sulphite and the crystals formed are contaminated to a much lesser extent by components readily soluble in water ( lignosulphonates , sugars and their derivatives , organic acids and neutral extractables , among others ) .
- the amount and purity of EA will also depend on the pH and temperature of the liquor, the crystallization time and the contact material with the liquor at the time of crystallization .
- Another determining factor for the dynamics of the EA crystallization process is associated with the surface area-to- volume ( S/V) ratio of the container used as a crystallizer .
- S/V surface area-to- volume
- S/V surface area-to-volume ratio of the container used for processing the cooking liquor.
- EA crystals are molecular aggregates that form intermolecular bonds under the appropriate thermodynamic conditions. These processes for crystallization and precipitation are dominated by primary nucleation around vessel walls. Therefore, the crystallization rate is dependent on the contact area and the type of material in the container. For the same material, e.g. , glass ( Figure 3) , an increase in S/V ratio leads to greater precipitation of EA from the acid sulphite cooking liquor without apparently significant change in the final purity of the precipitate. At least in the S/V range of 0.5-2.0 (im 1 ) a logarithmic dependence of the amount of liquor precipitate versus the same time (120 hours) and the same temperature (20°C) was observed.
- the remaining contaminants are essentially low sulfonated lignin, extractable compounds and mineral/organic salts ( Figure 6) .
- the main ones are magnesium (400-500 ppm) , potassium (300-400 ppm) and calcium (100-200 ppm) salts. It is also important to point out that after the isolation of EA from the liquor, the latter can be returned to the conventional pulp manufacturing process and used for energy and reagent recovery.
- alkaline extracts from bleaching kraft pulps are less suitable for the isolation of EA than alkaline extracts from acid sulphite pulps.
- the effluent from the alkaline extract after pulp treatment with acid sulphite, has a pH close to 10 and must be acidified for the precipitation of EA to occur.
- acidification below pH 4 leads to non-selective co-precipitation of the various constituents of the extract (extractable substances, lignin removed from the pulp, hemicelluloses and beta-cellulose, among others) , which does not allow a selective isolation of the target product.
- the adjustment of pH 5 of the liquor (slightly below pKa of EA) , at temperature 20-40°C, allows the collection of a precipitate with a reasonable content of EA ( Figure 7) .
- the drop in the exposure temperature of the alkaline extract below 20°C showed a drastic drop in EA content in the precipitate (less than 10% at a temperature of 10°C with 24h of exposure) .
- Due to a strong dilution of the alkaline extract in the pulp mill the amount of EA recovered, considering comparable conditions , is considerably lower than that obtained from the cooking liquor ( Figure 2 ) .
- the degree of purity of EA in the alkaline extract precipitate is also lower than that obtained from the cooking liquor .
- the precipitation dynamics of the alkaline extract acidified to pH 5 in a way, is similar to that of the cooking liquor , however the maximum level of precipitated EA is reached more rapidly ( Figure 7 ) .
- Ellagic acid is a biologically active substance and is intended as a raw material for the pharmaceutical , cosmetic, food and chemical industries .
- the formed precipitate was separated from the extract by decantation followed by centrifugation.
- the amount of dry residue of the precipitate was 0.150 g with an EA content of 25% according to GC-MS analysis.
- the residue was washed successively 5 times with water at 20°C (5 x 3 ml) , first with water acidified with HC1 to pH 2 and then with distilled water, for a total of approx. 100 cm 3 per 1g of precipitate, centrifuging the sample after each wash.
- the precipitate washed with water was dried at 30 °C in the vacuum oven, obtaining in the end a dry precipitate of 0.090 g with an EA content of 39% detected by GC- MS analysis using the quantitative method by the standard response factor .
- Figure 1 shows the chemical structure of ellagic acid with the numbering of the carbon atoms.
- Figure 2 shows the content of ellagic acid (EA) in the precipitate from industrial acid sulphite cooking liquor (liquor A sample) from E. globulus wood, collected at different exposure times, in a borosilicate glass container with a ratio surface area/volume (S/V) of 0.67 (nt 1 ) at temperatures of 6 and 20°C.
- EA ellagic acid
- Figure 3 shows the content of ellagic acid (EA) in a precipitate of industrial acid sulphite cooking liquor (sample of liquor B) from E. globulus wood, collected at different exposure times, in borosilicate glass containers with the ratios surface area/volume (S/V) of 0.67 and 0.73 (nt 1 ) at a temperature of 20°C ( Figure 3A) .
- S/V surface area/volume ratio
- Figure 5 shows the effect of exposure temperature of acid sulphite industrial liquor (liquor D sample) from E. globulus wood, in a borosilicate glass container with S/V 0.63 (nV 1 ) , on the amount of precipitate and acid content ellagic acid (EA) in a precipitate before and after washing with water.
- Figure 6 represents the composition of unwashed and water washed precipitates.
- the precipitates were obtained by exposing acid sulphite industrial liquor (liquor E sample) from E. globulus wood in a borosilicate glass vessel with S/V 0.63 (nt 1 ) for 72h at a temperature of 85 °C.
- Figure 7 shows the content of ellagic acid (EA) in the unwashed and water-washed precipitate of the alkaline extract (sample Al) from the extraction stage (E) of the E-O-P bleaching of acid sulphite industrial pulp of E. globulus wood, collected at different exposure times, in a borosilicate glass container with a surface area-to-volume ratio (S/V) of 0.67 (im 1 ) at a temperature of 20°C.
- S/V surface area-to-volume ratio
- Figure 9 shows the CP-MAS 13 C NMR spectra of the precipitate, unwashed and washed with water, and ellagic acid (EA) standard.
- CN 107827900A 13.11.2017; Liu Hongwei, Yang Minhua, Yang Yanming, Liu Fan, Gong Hai, Zhu Qingqing; Method for preparing ellagic acid from tara pod.
- EP 0390107A2 ; 03.10.1990; Kiyoshi Mizusawa, Yasuhiko Imai, Katsumi Yuasa, Hirokazu Koyama, Nobuyuki Yamaji, Shigehiro Kataoka; Tetsuya Oguma; Process for producing ellagic acid.
- Evtuguin DV Sulphite Pulping.
- Lignocellulosic fibers and wood handbook renewable materials for today's environment; Belgacem NM, Pizzi A, (Eds) , Wiley-Scrivener Publishing, 1st ed. (2016) , 225 - 244.
- Przewloka SR Shearer BJ
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Abstract
The present invention refers to a method for the recovery of ellagic acid from streams of lignocellulosic materials manufacturing industries, preferably from cellulosic pulp mill streams, such as cooking liquors and bleaching line effluents. The method consists in the isolation of ellagic acid via crystallization from industrial streams. The method is based on the crystallization of ellagic acid from saturated aqueous solutions at pH values lower than the pKa of the target product. The method is applicable to any type of industrial stream of processing lignocellulosic materials, such as the production of cellulosic pulp, preferably in acid sulphite pulp mill streams. Ellagic acid is recovered in the form of a yellowish powder from chemical wood processing plants that contain derivatives of this acid in their composition. The purity of the recovered ellagic acid can reach 95% without further purification, depending on the effluents used and isolation conditions.
Description
MILL STREAMS"
Technical Domain of the Invention
The present invention relates the isolation of ellagic acid from streams of the lignocellulosic materials processing industries, preferably in streams of cellulosic pulp mills, which may have applications in several areas, such as chemical technology and health .
Ellagic acid, along with other components, is found dissolved in cooking liquors and bleaching effluents during the chemical processing of wood into pulp. Due to its polyphenolic and polyaromatic character, ellagic acid is a substance with unique chemical and bioactive properties, known for its antioxidant and chelating activities, attracting growing interest for technical and biomedical applications (e.g., possible antibacterial, antifungal, antiviral, anti-inflammatory, hepato- cardioprotective, chemopreventive, anti-neurodegenerative, antiasthmatic, anti-diabetic, gastroprotective and properties similar to antidepressants, among others) .
Summary of the invention
The present invention relates to a method for the recovery of ellagic acid from industrial streams of cellulosic pulp mills, or streams from other lignocellulosic materials processing industries, comprising the following steps: a) Collecting a stream effluent and adjusting its pH between 0.1 and 14, and temperature between 1 and 100°C for subsequent conditioning; b) Conditioning of the effluent for a time between 0.1 and 720 hours in a container having a surface area-to-volume ratio between 0.1 and 100 irT1 and made of a material selected from metal derivatives, glass, or plastics, which are suitable for the crystallization of ellagic acid, wherein the effluent is
conditioned at the pH and temperature adj usted in the previous step; c ) Separation of the ellagic acid-containing precipitate obtained in the previous step via crystallization, wherein the separation is carried out by centrifugation or any other separation technique suitable for the purpose ; d ) Successive washing of the separated ellagic acid-containing precipitate with water and separation of the precipitate by centrifugation or any other separation technique suitable for the purpose ; e ) Drying the obtained ellagic acid product .
In one embodiment , the industrial stream is an effluent from acid sulphite processes , such as cooking liquors or bleaching line effluents .
In one embodiment , step a ) is carried out after removing nonprocessed suspended matter .
In one embodiment , step b ) is carried out at conditioning temperatures between 60 and 80 ° C when the effluent is cooking liquor .
In one embodiment , step b ) is carried out at conditioning temperatures between 20 and 40 °C when the effluent is an alkaline bleaching effluent .
In one embodiment , the pH of the effluent in step a ) is adj usted between 2 and 5 .
In one embodiment , the conditioning time is above 720 hours .
In one embodiment , the container is made of glass with a percentage of borosilicate , between 65 and 80% of silica and between 8 and 25% of boron trioxide .
In one embodiment , the container is made of plastic such as polyethylene terephthalate or high-density polyethylene .
In one embodiment, the container is made of metal derivatives, such as variants of stainless steel.
In one embodiment, the surface area-to-volute ratio is above 100 nt1
In one embodiment, step d) is carried out using acidified water comprising HC1 between 0.1 and 20% v/v.
Background of the invention and state of the art
Ellagic acid (EA) (Figure 1) belongs to the class of extractable polyphenols (tannins) widely distributed among dicotyledonous species (Quideau and Feldman, 1996) . In plants, EA is mostly found in the composition of so-called hydrolysable tannins, where EA is esterified to sugars, resulting in a wide variety of structures also known as ellagitannins (ETs) . Like other tannins, ETs are secondary metabolites of higher plants and act as part of the defence mechanism against microbial and animal attacks due to their astringent capacity and ability to form complexes with proteins and polysaccharides (Quideau and Feldman, 1996) . Hydrolysable tannins have long been known for their use in leather tanning processes (Quideau and Feldman, 1996) . However, currently, the growing interest in these compounds is mainly associated with the consumption and development of new products with benefits for human health, linked to the antioxidant properties of phenolics (Wu et al., 2004) . In fact, due to the mitigating and/or preventive effects in several chronic diseases linked to oxidative stress, including cancer, cardiovascular diseases and neurodegenerative pathologies, EA has been the subject of several scientific studies (Al-Sayed and El-Naga, 2015; Nguyen et al. , 2017) . In addition to food and biomedical applications, EA and ETs may also have applications linked to advanced materials, such as polymeric materials (Reitze et al., 2001) , chelating reagents (Przewloka and Shearer, 2002) , ion exchange resins (Zhang and Chen, 1988) , materials for electrochemical devices (Goriparti et al. , 2013) , among others. Marketed EA products are produced essentially from natural plants, fruits and agricultural residues, since the
organic synthesis results in low yields and can compromise the biological activity of EA due to failures in the chemoselectivity, regioselectivity and stereoselectivity of the process (Quideau and Feldman, 1996) .
Thus, several methods have been registered to produce EA, such as: tara (CN107827900A) , pomegranate peel (CN1803801A) , mango seed (CN107163059A) , blackberry branches and leaves (CN106913639A) , flower galls (CN105175427A) , raspberry (KR20170135744A) , eucalypt leaves (CN105132179A) and many other natural sources (Koponen et al. , 2007; Okuda et al. , 2009) .
Examples of known methods of producing EA include oxidative synthesis from ETs containing gallic acid and its water-soluble esters (US5231193A; EP0390107A2) or by a combination of alkaline hydrolysis and oxidation (CN105753880A) .
At the same time, EA, methyl derivatives of EA and glycosides of both form part of the tannin extracts of Eucalyptus , Quercus , Acacia and Castanea species, among other angiosperms (Fengel and Wegener, 1989) . Since these woods are used in cooking processes to produce cellulosic pulp, they can also be considered a great source of EA. In fact, EA is present in different industrial streams from the production of kraft pulps (Costa et al., 2014) and sulphite pulps (Rodrigues et al. , 2018) . It should be noted that, despite the pulp sector being a prospective source of EA derivatives, no viable solutions have so far been proposed for their recovery from industrial effluents. There are few publications that aim to isolate the EA from the eucalypt wood acid sulphite cooking liquor (Llano et al. , 2015; Alexandri et al. , 2016) .
Mostly, EA and its derivatives are obtained by extraction with a certain organic solvent, with mixtures of organic solvents (Quideau and Feldman, 1996) , with mixtures of organic solvents with water or, more recently, using ionic liquids (IL) (Chowdhury et al. , 2010) . As for the industrial streams in the pulp and paper industry, EA recovery approaches are limited to extraction with
poorly water-mixable organic solvents such as ethyl acetate (Alexandri et al. , 2016) or ethyl ether (Llano et al. , 2015) . Purification of EA is normally carried out by multi-step processes and may involve chromatographic and recrystallization steps, among other separation techniques.
It should be noted that despite the aforementioned approaches in the production and isolation of EA, conventional extraction methods are not very selective, being affected by the great diversity of ET structures, a wide variety of plant sources and difficult purification, leading to low yields of EA, contaminations and excessive costs. Consequently, the need arises to develop alternative technologies, more efficient in terms of yield and energy cost and less polluting, to produce EA of superior purity and on a large scale, ideally from sources that do not compete with the food processing industry.
Description of the invention and embodiments
The present invention aims to recover ellagic acid from industrial streams of cellulosic pulp mills, or streams from other lignocellulosic materials processing industries, such as cooking liquors and bleaching line effluents.
Ellagic acid (EA) in the free form or linked to sugars by ester linkage (ET) is present in wood subjected to a delignification (cooking) process in the production of pulp for paper or other cellulose-based products. The cooking process consists of degradation and removal of lignin together with other components of the wood, thus releasing the cellulosic fibers (Evtuguin 2016) . During cooking, carried out at high temperature (130-170°C) , in an alkaline medium (such as the kraft process) or in an acid medium (such as the sulphite process) , a predominant part of EA is dissolved in the cooking liquor, while the other portion is present in the stream of raw pulp still submitted to bleaching (Rodrigues et al. , 2018) . Thus, there is a possibility of EA recovery from the cooking liquor or bleaching line effluents.
The present invention relates to a method for recovering ellagic acid from an industrial stream of cellulosic pulp mills, or a stream from other lignocellulosic materials processing industries, comprising the following steps: a) Collecting a stream effluent and adjusting the pH between 0.1 and 14, and temperature between 1 and 100°C for subsequent conditioning; b) Conditioning of the effluent for a time between 0.1 and 720 hours in a container made of a material selected from metal derivatives, glass or plastics which are suitable for the crystallization of ellagic acid, wherein the effluent is conditioned at the pH and temperature adjusted in the previous step; c) Separation of the ellagic acid-containing precipitate obtained in the previous step via crystallization, wherein the separation is carried out by centrifugation or any other separation technique suitable for the purpose; d) Successive washing of the separated ellagic acid-containing precipitate with water and separation of the precipitate by centrifugation or any other separation technique suitable for the purpose ; e) Drying the obtained ellagic acid product.
In one embodiment, the industrial stream from cellulosic pulp mills, or stream from other lignocellulosic materials processing industries, is an effluent from acid sulphite processes, such as cooking liquors or bleaching line effluents.
In one embodiment, step a) is carried out after removing nonprocessed suspended matter.
In one embodiment, step b) is carried out at a conditioning temperature between 60 and 80°C when the effluent is cooking liquor. In another embodiment, step b) is carried out at a conditioning temperature between 20 and 40°C when the effluent is an alkaline bleaching effluent.
In one embodiment, the pH of the effluent in steps a) is adjusted between 0.1 and 14. In another embodiment, the pH of the effluent in step a) is adjusted between 2 and 5.
In one embodiment, step b) occurs with an effluent conditioning time comprised between 0.1 and 720 hours. In another embodiment, the conditioning time is above 720 hours.
In one embodiment, the container used in step b) is made of a material selected from, but not limited to: metal derivatives, such as variants of stainless steel; as well as glass, mainly with a large percentage of borosilicate, between 65 and 80% of silica (SiO2) and between 8 and 25% of boron trioxide (B2O3) ; plastic such as polyethylene terephthalate or high-density polyethylene; or other materials that have chemical and/or physical similarities, providing the same conditions suitable to promote selective crystallization of ellagic acid.
In one embodiment, step d) is a step of successive washing of the ellagic acid-containing precipitate with water, which however does not qualify as a specific purification step. The number of washes and the amount of water used will depend on the effluent used and isolation conditions.
In one embodiment, step d) is carried out using acidified water comprising HC1 between 0.1 and 20% v/v, which can also be used for metal and other concomitants removal. The number of washing cycles and the amount of water used in it depend on the effluent used and the conditions for isolating the ellagic acid.
Step d) is influenced by the surface area-to-volume ratio (S/V) of the container used for processing, being preferred the use of containers with S/V values between 0.1 and 100 (nt1) to increase the number of nucleation centres during ellagic acid crystallization. In one embodiment, the S/V ratio can be above 100 (nV1) .
In the end of the method, ellagic acid is obtained in powder form with purity ranging between 20 and 99% , without further purification, depending on the stream used and isolation conditions .
1 . Recovery of EA from cooking liquors
Given the low pKa ( 5 . 4 -6 . 8 ) , EA is completely soluble in alkaline cooking liquors ( kraft black liquor pH is around 11 ) and very little soluble in acid sulphite cooking liquors (pH of SO2 solution is around 3 ) . Due to the symmetrical chemical structure ( Figure 1 ) and low solubility in water, EA easily forms crystals that can be recovered from the medium. This phenomenon occurs in a relatively simple way in the liquor from cooking with acid sulphite and the crystals formed are contaminated to a much lesser extent by components readily soluble in water ( lignosulphonates , sugars and their derivatives , organic acids and neutral extractables , among others ) . Therefore , it is possible to select the conditions for the recovery of the EA from the acid sulphite cooking liquor . Similarly, acidification of kraft cooking liquor to pH 1-5 also leads to the formation of EA crystals , but these are easily contaminated with poorly soluble liquor components at low pH values , which co-precipitate ( e . g . , kraft lignin and hemicelluloses , extractables , among others ) resulting in a complex mixture that requires extensive purification . Therefore , acid sulphite liquors are the most suitable effluents for the recovery of EA . In addition to the amount of EA in the processed wood and, therefore , its concentration in the acid sulphite cooking liquor , the amount and purity of EA will also depend on the pH and temperature of the liquor, the crystallization time and the contact material with the liquor at the time of crystallization . Another determining factor for the dynamics of the EA crystallization process is associated with the surface area-to- volume ( S/V) ratio of the container used as a crystallizer . The natural pH of the sulphite liquor, after elimination of free SO2 ( 2-3 ) , meets the necessary conditions for the crystallization of EA, while a pH greater than 5 will be harmful . The concentration of EA in liquor until saturation can be increased with its pre
evaporation. The dynamics of crystal agglomerates formation in the Eucalyptus acid sulphite cooking liquor at pH 2.6 and low temperatures shows that the largest fraction of EA is formed in the first 1-5 days, following a slower dynamic later (Figure 2) . Although decreasing the crystallization temperature to 6°C leads to an increase in the precipitated matter in the liquor, the EA content in this material is lower than that found at the temperature of 20°C. This fact is due to the competitive process of crystal formation or accelerated precipitation of other components of the liquor. In fact, chemical analysis of the precipitate showed the co-precipitation of aldonic acids in the form of 5-lactones, sugars, low degree sulfonated lignin, different extractable compounds, and mineral salts. The dynamics of EA crystal formation at 20°C was higher than that observed at 6°C, reaching the maximum level more quickly (Figure 2) .
Another factor that influences the intensity of EA crystal formation is the surface area-to-volume (S/V) ratio of the container used for processing the cooking liquor. EA crystals are molecular aggregates that form intermolecular bonds under the appropriate thermodynamic conditions. These processes for crystallization and precipitation are dominated by primary nucleation around vessel walls. Therefore, the crystallization rate is dependent on the contact area and the type of material in the container. For the same material, e.g. , glass (Figure 3) , an increase in S/V ratio leads to greater precipitation of EA from the acid sulphite cooking liquor without apparently significant change in the final purity of the precipitate. At least in the S/V range of 0.5-2.0 (im1) a logarithmic dependence of the amount of liquor precipitate versus the same time (120 hours) and the same temperature (20°C) was observed.
Given the importance of the primary nucleation process of EA in contact with the container, it is logical that the origin of material in the container is a determining factor in the dynamics and purity of the precipitate. This fact becomes evident when comparing EA precipitation of the liquor at the same temperature
(25°C) and during the same time (72h) of exposure in containers of different materials but with similar geometries (S/V=0.5-0.6 (nr1) ) . Among the selected container materials (stainless steel, glass, polyethylene terephthalate (PET) and high-density polyethylene (HDPE) ) , plastics showed the highest degree of EA purity in the precipitate, while the precipitate with the highest amounts was recorded for the stainless-steel container (Figure
4) . Therefore, by modifying the container material in contact with the liquor, it becomes possible to change both the amount and the purity of EA in precipitate. It is notable that the way EA adhered to the wall of the container was quite different. Therefore, the greatest adherence to the container wall was observed for PET, stainless steel and to a much lesser extent for glass. As mentioned above, increasing the conditioning temperature of the liquor results in a lower amount of precipitate formed, however, at the same time increasing the purity of the EA crystals (Figure 2) . This tendency is explained by the greater capacity of EA to form crystals in relation to aldonic acids, sugars, and mineral/organic salts and by the greater solubility of lignin in liquors with high temperatures. Consequently, there is a gradual increase in EA purity in precipitates obtained at higher temperatures (Figure
5) . In particular, the purity increased considerably with temperatures around 60-80°C (Figure 5) . Evidently, due to the increased solubility of EA and the thermodynamics of crystallization, the amount of EA precipitated at temperatures above 80°C has a tendency to decrease, making it also difficult to operate at temperatures close to 100°C, at atmospheric pressure. The liquor precipitate obtained by the described method has, in addition to EA, aldonic acids, sugars, lignin, different extractable lipophilic compounds and mineral/organic salts in its composition (Figure 6) . A large part of these compounds can be washed off with water, thus significantly increasing the EA purity up to values close to 90% (Figure 5) . The remaining contaminants are essentially low sulfonated lignin, extractable compounds and mineral/organic salts (Figure 6) . Among the mineral compounds, the main ones are magnesium (400-500 ppm) , potassium (300-400 ppm) and calcium (100-200 ppm) salts.
It is also important to point out that after the isolation of EA from the liquor, the latter can be returned to the conventional pulp manufacturing process and used for energy and reagent recovery.
2. Recovery of EA from bleaching effluent
Other industrial streams that contain EA are bleaching effluents. In the case of the acid sulphite process, the first bleaching stage after washing the raw pulp is the alkaline extraction stage, which aims to purify the obtained pulp (Rodrigues et al., 2018) . The EA contained in the raw (unbleached) pulp, in this case, is extracted in an alkaline medium (pH> 11) and remains in the effluent. Bearing in mind that this stage does not use any oxidizing agent, it is possible to preserve the EA against degradation and isolate it from the alkaline effluent in higher amounts. In the case of bleaching kraft pulp, the first stages of bleaching are normally aimed at removing residual lignin with oxidative reagents that degrade the EA. Considering the lower amount of EA present in the washed kraft pulp streams than in the sulphite pulp streams (Rodrigues et al., 2018) and the existing bleaching practice, alkaline extracts from bleaching kraft pulps are less suitable for the isolation of EA than alkaline extracts from acid sulphite pulps.
The effluent from the alkaline extract, after pulp treatment with acid sulphite, has a pH close to 10 and must be acidified for the precipitation of EA to occur. However, acidification below pH 4 leads to non-selective co-precipitation of the various constituents of the extract (extractable substances, lignin removed from the pulp, hemicelluloses and beta-cellulose, among others) , which does not allow a selective isolation of the target product. At the same time, the adjustment of pH 5 of the liquor (slightly below pKa of EA) , at temperature 20-40°C, allows the collection of a precipitate with a reasonable content of EA (Figure 7) . The drop in the exposure temperature of the alkaline extract below 20°C showed a drastic drop in EA content in the precipitate (less than 10% at a temperature of 10°C with 24h of exposure) . Due to a strong dilution of the alkaline extract in
the pulp mill , the amount of EA recovered, considering comparable conditions , is considerably lower than that obtained from the cooking liquor ( Figure 2 ) . The degree of purity of EA in the alkaline extract precipitate is also lower than that obtained from the cooking liquor . At the same time , the precipitation dynamics of the alkaline extract acidified to pH 5 , in a way, is similar to that of the cooking liquor , however the maximum level of precipitated EA is reached more rapidly ( Figure 7 ) .
The increase in temperature to values above 40 °C causes the coprecipitation of the polysaccharides dissolved in the alkaline extract of the sulphite pulp, essentially beta-cellulose , thus making the isolation of EA difficult . The main contaminants present in the precipitate , obtained at pH 5 and temperature 30 ° C for 24 hours , are derived from extractable compounds and lignin . Washing the precipitate with water also increases the purity of EA isolated from the alkaline extract , however these values are much lower than those obtained from the acid sulphite cooking liquor ( Figure 2 ) . Thus , in order to obtain EA with a higher degree of purity, it is necessary to apply a specific purification process .
It is important to note that after the isolation of EA from the alkaline extract , the latter can be returned to the conventional pulp manufacturing process .
Ellagic acid is a biologically active substance and is intended as a raw material for the pharmaceutical , cosmetic, food and chemical industries .
Application examples
For a better understanding of the main points of the invention, examples of preferred procedures of the method are described below, which, however, are not intended to limit the final obj ective of the present invention .
Recovery of ellagic acid from acid sulphite cooking liquor
2000 cm3 of eucalypt wood (Eucalyptus globulus) magnesium-based acid sulphite industrial cooking liquor, taken at the exit of the last evaporation effect (dry content ca . 14%) , with a temperature ca. 70°C and pH 2.3, were placed in a closed glass container with the S/V ratio ca. 0.5 (nu1) . After 96 hours of contact, the liquor was decanted, and the precipitate was separated by centrifugation. The amount of dry residue of the precipitate was 1.123 g with an EA content ca . 70% according to GC-MS analysis based on retention time and standard mass spectrum (Rodrigues et al. , 2018) . The residue was washed successively 5 times with water at 20°C (5 x 20 ml) , first with water acidified with HC1 to pH 2 and then with distilled water, for a total of ca. 100 cm3 per 1g of precipitate, centrifuging the sample after each wash. The precipitate washed with water was dried at 30°C in the vacuum oven, obtaining in the end a dry precipitate of 0.820 g with an EA content of 95% detected by GC-MS analysis using the quantitative method by the standard response factor. According to the data obtained by solid state 13C NMR (Figure 8) , during washing with water most of the sugar derivatives and a part of lignin were removed. In fact, the series of signals between 50 and 90 ppm (carbons from the lignin side chain and non-anomeric carbons from sugars and their derivatives) decreased significantly. The washed sample also revealed the presence of residual lignin (peak at 56 ppm attributed to methoxyl groups) , sugars and their derivatives (peak at 64 ppm attributed to methylol groups) and trace amounts of extractable compounds (weak signals in the region 10-30 ppm) . The precipitate showed the presence of EA crystals according to the X-ray dif f ractogram (Figure 9) , obtained and compared with the EA standard (Sigma- Aldrich®, h 96%, E2250, Saint Louis, USA) . The characteristic reflection of the EA crystals at 2028.2° (Figure 10) corresponding to the distance between the planes of the adjacent layers of EA (3.2 A) and the reflection at 20 20.6° corresponding to the distance between the planes of stacked molecules (4.3 A) , clearly approximates to the dimensions of the triclinic cell described above (Rossi et al., 1991) . Some discrepancies between the dif f ractogram signals of the precipitate and the standard are due
to the difference in molecular rearrangements, with the concomitant and eventual metallic complexes promoting a variety of different crystalline groups of isolated EA. The water-washed liquor precipitate also showed a 1H NMR spectrum in DMSO-d6 with a singlet at 5 7.45 (2H, ArH) and a broad singlet cantered at 5 10.65 (4H, Ph-OH) . These values are also in agreement with those described in the literature (Li et al. , 1999; Goriparti et al., 2013) .
Recovery of ellagic acid from bleaching effluent
2000 cm3 of industrial alkaline extract after the first stage of the E-O-P bleaching line (alkaline extraction-oxygen delignif ication-hydrogen peroxide bleaching) of acid sulphite pulp obtained from E. globulus wood by magnesium acid sulphite- based cooking, were collected from the washing press at a temperature of approximately 70°C in an HDPE container. The extract was rapidly cooled to a temperature of 50 °C and the initial pH of 10 was adjusted to 7 using 20% sulfuric acid (m/m) . After cooling to 20°C the extract was acidified again to pH 5.0 and placed in a glass vessel with an S/V ratio of 0.67 (nr1) . After 24 h of exposure at 20°C, the formed precipitate was separated from the extract by decantation followed by centrifugation. The amount of dry residue of the precipitate was 0.150 g with an EA content of 25% according to GC-MS analysis. The residue was washed successively 5 times with water at 20°C (5 x 3 ml) , first with water acidified with HC1 to pH 2 and then with distilled water, for a total of approx. 100 cm3 per 1g of precipitate, centrifuging the sample after each wash. The precipitate washed with water was dried at 30 °C in the vacuum oven, obtaining in the end a dry precipitate of 0.090 g with an EA content of 39% detected by GC- MS analysis using the quantitative method by the standard response factor .
Brief description of figures
For a better understanding of the key points of the invention, the figures that aim to demonstrate the preferred procedures of
the method are attached, which, however, do not intend to limit the final objective of the present invention.
Figure 1 shows the chemical structure of ellagic acid with the numbering of the carbon atoms.
Figure 2 shows the content of ellagic acid (EA) in the precipitate from industrial acid sulphite cooking liquor (liquor A sample) from E. globulus wood, collected at different exposure times, in a borosilicate glass container with a ratio surface area/volume (S/V) of 0.67 (nt1) at temperatures of 6 and 20°C.
Figure 3 shows the content of ellagic acid (EA) in a precipitate of industrial acid sulphite cooking liquor (sample of liquor B) from E. globulus wood, collected at different exposure times, in borosilicate glass containers with the ratios surface area/volume (S/V) of 0.67 and 0.73 (nt1) at a temperature of 20°C (Figure 3A) . The influence of the surface area-to-volume ratio (S/V) of borosilicate glass containers at a temperature of 20°C, for the same acid sulphite liquor, is represented in Figure 3B.
Figure 4 shows the influence of the container material on the content of the precipitate and on the ellagic acid (EA) content in a precipitate from acid sulphite industrial liquor (liquor C sample) from E. globulus wood, exposed for 72 hours, at room temperature ca. 25°C, in containers of similar geometry (S/V=0.4- 0.5 (nV1) ) . Designation of materials: borosilicate glass (glass) ; stainless steel (stainless) ; high density polyethylene (HDPE) and polyethylene terephthalate (PET) .
Figure 5 shows the effect of exposure temperature of acid sulphite industrial liquor (liquor D sample) from E. globulus wood, in a borosilicate glass container with S/V 0.63 (nV1) , on the amount of precipitate and acid content ellagic acid (EA) in a precipitate before and after washing with water.
Figure 6 represents the composition of unwashed and water washed precipitates. The precipitates were obtained by exposing acid
sulphite industrial liquor (liquor E sample) from E. globulus wood in a borosilicate glass vessel with S/V 0.63 (nt1) for 72h at a temperature of 85 °C.
Figure 7 shows the content of ellagic acid (EA) in the unwashed and water-washed precipitate of the alkaline extract (sample Al) from the extraction stage (E) of the E-O-P bleaching of acid sulphite industrial pulp of E. globulus wood, collected at different exposure times, in a borosilicate glass container with a surface area-to-volume ratio (S/V) of 0.67 (im1) at a temperature of 20°C.
Figure 8 shows the X-ray dif f ractograms of the precipitate from industrial acid sulphite liquor (sample of E liquor) of E. globulus wood obtained under conditions described in Figure 6 and the ellagic acid pattern (source Cu-Ka with =0.154 nm, in the range 20 2-40° and scan step width of 0.02° / per scan) .
Figure 9 shows the CP-MAS 13C NMR spectra of the precipitate, unwashed and washed with water, and ellagic acid (EA) standard.
References
Patents :
CN 107827900A; 13.11.2017; Liu Hongwei, Yang Minhua, Yang Yanming, Liu Fan, Gong Hai, Zhu Qingqing; Method for preparing ellagic acid from tara pod.
CN 1803801A; 14.01.2005; Yuan Qipeng, Lu Jingjing, Lu Miaomiao; Method for preparing ellagic acid by pomegranate rind.
CN 107163059A; 27.05.2017; Kang Chao, Duan Zhenhua, Luo Yanghe, Li Yan, Wu Shuzhen, Mo Fuwang, Deng Nianfang, Xie Wei, Su Hui, Lan Shuailiang; Preparation method for mango seed ellagic acid.
CN 10691369A; 28.12.2015; Tian Yiling, Li Baoguo, Ye Yajie, Zhang Xuemei, Gu Yuhong, Li Jun; Method for preparing ellagic acid concentrate by using branches and leaves of Rubus corchorifolius. CN 105175427A; 10.08.2015; Mao Yefu; Method and device for preparation of ellagic acid from gall flowers.
KR 20170135744A.08.12.2017 ; Kwon Sang Oh, Dong Yoon Kwak; Seungmin Kim, Kwon Seob Han; Extraction method of Rasberry extract containing ellagic acid and isolation method of ellagic acid.
US 5231193A; 27.07.1993; Kiyoshi Mizusawa, Yasuhiko Imai, Katsumi Yuasa, Hirokazu Koyama, Nobuyuki Yamaji, Shigehiro Kataoka, Tetsuya Oguma; Process for producing ellagic acid.
EP 0390107A2 ; 03.10.1990; Kiyoshi Mizusawa, Yasuhiko Imai, Katsumi Yuasa, Hirokazu Koyama, Nobuyuki Yamaji, Shigehiro Kataoka; Tetsuya Oguma; Process for producing ellagic acid.
CN 105753880A; 13.07.2016; Mao Yefu; Method for preparation of ellagic acid from persimmon and persimmon leaves.
Articles :
Alexandri M, Papapostolou H, Vlysidis A, Gardeli, et al. ; Extraction of phenolic compounds and succinic acid production from spent sulphite liquor; J. Chem. Technol. Biotechnol. (2016) , 91(11) : 2751-2760.
Al-Sayed E, El-Naga RN; Protective role of ellagitannins from Eucalyptus citriodora against ethanol-induced gastric ulcer in rats: Impact on oxidative stress, inflammation and calcitoningene related peptide. Phytomedicine (2015) , 22: 5-15.
Chowdhury SA, Vi ayaraghavan R, MacFarlane DR; Distillable ionic liquid extraction of tannins from plant materials; Green Chem. (2010) , 12: 1023-1028.
Costa EV, Lima DLD, Evtyugin DV, et al. ; Development and application of a capillary electrophoresis method for the determination of ellagic acid in E. globulus wood and in filtrates from E. globulus kraft pulp; Wood Sci. Technol. (2014) , 48: 99- 108.
Evtuguin DV; Sulphite Pulping. In: Lignocellulosic fibers and wood handbook: renewable materials for today's environment; Belgacem NM, Pizzi A, (Eds) , Wiley-Scrivener Publishing, 1st ed. (2016) , 225 - 244.
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Goriparti S, Harish MNK, Sampath S; Ellagic acid - a novel organic electrode material for high capacity lithium ion batteries; Chem. Commun. (2013) , 49: 7234.
Koponen JM, Happonen AM, Mattila PH, et al.; Contents of anthocyanins and ellagitannins in selected foods consumed in Finland; J. Agric. Food Chem. (2007) , 55: 1612-1619.
Li XC, Elsohly HN, Huff ord CD, et al.; NMR assignments of ellagic acid derivatives; Magn. Reson. Chem. (1999) , 37: 856-859.
Llano T, Alexandri M, Koutinas A, Gardeli C, et al. Liquid-liquid extraction of phenolic compounds from spent sulphite liquor; Waste Biomass Valor. (2015) , 6(6) : 1149-1159.
Nguyen DH, Seo UM, Zhao BT, et al. ; Ellagitannin and flavonoid constituents from Agrimonia pilosa Ledeb. with their protein tyrosine phosphatase and acetylcholinesterase inhibitory activities; Bioorg. Chem. (2017) , 72: 293-300.
Okuda T, Yoshida T, Hatano T, et al.; Ellagitannins renewed the concept of tannins. In: Chemistry and biology of ellagitannins; Quideau S, (Eds) ; World Scientific Publ. , Comp. , Singapore, (2009) , 1-54.
Przewloka SR, Shearer BJ; The further chemistry of ellagic acid II. Ellagic acid and water-soluble ellagates as metal precipitants; Holzf orschung (2002) , 56: 13-19.
Quideau S, Feldman KS; Ellagitannin Chemistry; Chem. Rev. (1996) , 96: 475-503.
Reitze JD, Przewloka SR, Shearer BJ; The further chemistry of ellagic acid I. Synthesis of tetramethylellagic acid and associated polymer precursors; Holzf orschung (2001) , 55: 171-175. Rodrigues PF, Evtyugin DD, Evtuguin DV, et al.; Extractive Profiles in the Production of Sulphite Dissolving Pulp from E. globulus; J. Wood Chem. Technol. (2018) , 38: 397-408.
Rossi M, Erlebacher J, Zacharias DE, et al.; The crystal and molecular structure of ellagic acid dihydrate: a dietary anticancer agent; Carcinogenesis (1991) , 12: 2227-2232.
Wu X, Gu L, Holden J, et al.; Development of a database for total antioxidant capacity in foods: a preliminary study; J. Food Compos. (2004) , Anal. 17: 407-422.
Zhang NZ, Chen YY; Synthesis of macroporous ellagitannic acid resin and its chelating properties for metal ions; J. Macromol. Sci. - Chem. (1988) , 25 (A) : 1455-1462.
Claims
1 . Method for the recovery of ellagic acid from industrial streams of cellulosic pulp mills , or streams from other lignocellulosic materials processing industries , comprising the following steps : a ) Collecting a stream effluent and adj usting its pH between 0 . 1 and 14 , and temperature between 1 and 100 °C for subsequent conditioning; b ) Conditioning of the effluent for a time between 0 . 1 and 720 hours in a container having a surface area-to-volume ratio between 0 . 1 and 100 nt1 and made of a material selected from metal derivatives , glass , or plastics , which are suitable for the crystallization of ellagic acid, wherein the effluent is conditioned at the pH and temperature adj usted in the previous step; c ) Separation of the ellagic acid-containing precipitate obtained in the previous step via crystallization, wherein the separation is carried out by centrifugation or any other separation technique suitable for the purpose ; d ) Successive washing of the separated ellagic acid-containing precipitate with water and separation of the precipitate by centrifugation or any other separation technique suitable for the purpose ; e ) Drying the obtained ellagic acid product .
2 . Method according to the previous claim, wherein the industrial stream is an effluent from acid sulphite processes , such as cooking liquors or bleaching line effluents .
3 . Method according to any of the previous claims , wherein step a ) is carried out after removing non-processed suspended matter .
4 . Method according to any of the previous claims , wherein step b ) is carried out at conditioning temperatures between 60 and 80 ° C when the effluent is cooking liquor .
5. Method according to any of the claims 1 to 3, wherein step b) is carried out at conditioning temperatures between 20 and 40°C when the effluent is an alkaline bleaching effluent.
6. Method according to any of the previous claims, wherein the pH of the effluent in step a) is adjusted between 2 and 5.
7. Method according to any of the previous claims, wherein the conditioning time is above 720 hours.
8. Method according to any of the previous claims, wherein the container is made of glass with a percentage of borosilicate, between 65 and 80% of silica and between 8 and 25% of boron trioxide .
9. Method according to any of the claims 1 to 7 , wherein the container is made of plastic such as polyethylene terephthalate or high-density polyethylene.
10. Method according to any of the claims 1 to 7 , wherein the container is made of metal derivatives, such as variants of stainless steel.
11. Method according to any of the previous claims, wherein the surface area-to-volute ratio is above 100 im1.
12. Method according to any of the previous claims, wherein step d) is carried out using acidified water comprising HC1 between 0.1 and 20% v/v.
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