EP1180171B1 - Method for producing paper pulp, lignins, sugars and acetic acid by fractionation of lignocellulosic vegetable material in formic/acetic acid medium - Google Patents
Method for producing paper pulp, lignins, sugars and acetic acid by fractionation of lignocellulosic vegetable material in formic/acetic acid medium Download PDFInfo
- Publication number
- EP1180171B1 EP1180171B1 EP99916998A EP99916998A EP1180171B1 EP 1180171 B1 EP1180171 B1 EP 1180171B1 EP 99916998 A EP99916998 A EP 99916998A EP 99916998 A EP99916998 A EP 99916998A EP 1180171 B1 EP1180171 B1 EP 1180171B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acetic acid
- process according
- paper pulp
- mixture
- sugars
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 144
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 36
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 235000000346 sugar Nutrition 0.000 title claims abstract description 24
- 229920005610 lignin Polymers 0.000 title claims abstract description 23
- 229920001131 Pulp (paper) Polymers 0.000 title claims abstract description 17
- 150000008163 sugars Chemical class 0.000 title claims abstract description 17
- 238000005194 fractionation Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000005418 vegetable material Substances 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000012074 organic phase Substances 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000004061 bleaching Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims 3
- 239000007790 solid phase Substances 0.000 claims 1
- 235000011054 acetic acid Nutrition 0.000 abstract description 37
- 150000001243 acetic acids Chemical class 0.000 abstract description 6
- 150000004674 formic acids Chemical class 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 235000013311 vegetables Nutrition 0.000 abstract description 2
- 241000196324 Embryophyta Species 0.000 description 31
- 229960000583 acetic acid Drugs 0.000 description 30
- 239000002253 acid Substances 0.000 description 13
- 238000010411 cooking Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 241000609240 Ambelania acida Species 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000010905 bagasse Substances 0.000 description 9
- 239000010902 straw Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 240000006394 Sorghum bicolor Species 0.000 description 7
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 7
- 235000015927 pasta Nutrition 0.000 description 7
- 240000007594 Oryza sativa Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920002488 Hemicellulose Polymers 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012978 lignocellulosic material Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 240000000111 Saccharum officinarum Species 0.000 description 4
- 235000007201 Saccharum officinarum Nutrition 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 241000219146 Gossypium Species 0.000 description 2
- 240000005979 Hordeum vulgare Species 0.000 description 2
- 235000007340 Hordeum vulgare Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 description 2
- 240000006240 Linum usitatissimum Species 0.000 description 2
- 235000014676 Phragmites communis Nutrition 0.000 description 2
- 244000273256 Phragmites communis Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 235000019714 Triticale Nutrition 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- -1 allylic phenols Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000009120 camo Nutrition 0.000 description 2
- 235000005607 chanvre indien Nutrition 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 239000011487 hemp Substances 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 241000228158 x Triticosecale Species 0.000 description 2
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 241000209128 Bambusa Species 0.000 description 1
- 244000218454 Bambusa tulda Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000861223 Issus Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 241000209056 Secale Species 0.000 description 1
- 235000007238 Secale cereale Nutrition 0.000 description 1
- 244000062793 Sorghum vulgare Species 0.000 description 1
- IOYNQIMAUDJVEI-BMVIKAAMSA-N Tepraloxydim Chemical compound C1C(=O)C(C(=N/OC\C=C\Cl)/CC)=C(O)CC1C1CCOCC1 IOYNQIMAUDJVEI-BMVIKAAMSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003853 activation of bipolar cell growth Effects 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
Definitions
- the invention relates to a method for producing pulp paper, lignins, sugars and acetic acid from matter lignocellulosic plant constituting most of the plants annuals and perennials.
- the lignocellulosic materials of the invention are the whole plants or parts of these plants (stems, bark, %) or industrial co-products of food production (wheat straw, rice, barley) .; bagasse of sugar cane, bagasse of sorghum sugar .
- Pulp produced from plants perennials can be classified according to the technology used, their paper quality and the yield mass of obtaining relative to the initial plant material.
- the pulp quality of a paste is defined in relation to process of separating cellulosic fibers or defibration and compared to a series of physicochemical parameters the most important are the break length that translates the tensile strength, tear index and index burst. The higher these characteristics are, the better the quality of the dough produced.
- Processes for the production of quality paper pulp are essentially chemical in which the cellulosic fibers of the lignocellulosic plant material are cleared of cement plant, which binds them in plants, consisting of hemicelluloses (polymers of sugars with 5 or 6 carbons) and lignins (polymers of substituted allylic phenols) with a chemical action of hydrolysis in a basic aqueous or acidic medium concentrated, often in the presence of sulfur at different states oxidation.
- Formic acid B. BUCHOLZ and RK JORDAN Pulp and Paper, pp.102-104, 1983; MN. ERISMANN et al., Bioresource Technology, Vol. 47, p. 247 - 256, 1994
- MN. ERISMANN et al. Bioresource Technology, Vol. 47, p. 247 - 256, 1994
- This technology makes it possible to conserve silica contained in the plant in pulp, which is a important advantage when using annuals as raw material because the silica disrupts considerably, in the current industrial processes in the middle basic, recovery of mineral reagents.
- a variant of the process as under the name of process MILOX proceeds by cooking with formic acid in several stages in the presence of hydrogen peroxide which improves the delignification (K.POPPIUS - LEVLIN et al., Tappi Journal, Vol. 80, No. 9, p.215-221, 1997).
- Acetic acid can be used for the same purpose under pressure at higher temperatures (160 to 180 ° C) at concentrations in water of 50 to 90% (R. A. YOUNG and J.L. DAVIS, Holzforshung, Vol. 40, p. 99-108, 1986).
- the delignification is correct but the process requires a washing the paste with acetone to remove lignins precipitated on the dough.
- a variant of this process allows, with oxygen under pressure, reduce cooking times and improve the delignification (C. P. NETO and A. ROBERT, Holzforshung, Vol.46, p. 233-240, 1993), but it is at the origin of a partial depolymerization of cellulose by joint action pH and oxygen.
- bleaching technologies without chlorine of these pasta uses hydrogen peroxide in a basic medium, which leads to the adjustment of the silica in the form of silicate sodium causing significant problems when draining of pasta and recycling of reagents.
- the present invention aims to propose a new process for making pulp from plants annuals or perennials that lead to chemical pulps of good quality preserving in their structure the endogenous silica at atmospheric pressure.
- EP-A-0.584.675 it is taught a cellulose extraction process from lignocelluloces, by heating for 2 hours at high temperatures (170 ° C or 180 ° C) and under pressure in the presence of aqueous acetic acid and addition of formic acid.
- WO-A-95/21960 discloses a method of cooking of lignocellulosic materials, in particular of plants annuals) with a mixture of carboxylic acids, a compulsory step of pyrolysis.
- the invention is directed to a method which makes it possible to obtain these performance whatever the nature of the plants used and which is therefore particularly interesting in the case of annual plants to pave the way for new valuations, particularly in the case of cereal straw and bagasse of sugar cane, or sugar sorghum.
- the process according to the invention results from the observation surprising following: the addition of acetic acid to the acid formic can significantly increase the power solvating of the liquid organic phase thus defined vis-à-vis hemicelluloses and lignins without affecting the capacity acid hydrolysis of these biopolymers with formic acid. Of this way we avoid the degradation of cellulosic fibers which appears with concentrated formic acid alone in usual conditions of use, and therefore the paper quality of the pulp obtained.
- This property is particularly important since it is the main limiting factor in the use of chemical straw pasta, especially in fast paper whose speed they slow down.
- acetic acid preferably in molecular form, solubilizes lignins more easily thus released. This effect limits the reaction time and the possible formylations of the free hydroxyl groups of cellulose which degrade the paper qualities of the dough.
- the process allows a particularly valorization interesting annual plants, especially straws and bags, which are considered in the processes of manufacture of traditional chemical pasta as second-class products without much interest.
- the moisture of the material is initial lignocellulose content is less than or equal to 25% by weight of water relative to the dry matter.
- impregnation of the lower vegetable matter at least 30 ° C at the reaction temperature.
- the impregnation by immersion is performed for a period of 10 to 30 minutes in the formic acid / acetic acid mixture used during the fractionation reaction.
- Impregnation and the reaction of following splitting are conducted at the pressure atmospheric.
- the reaction of fractionation is conducted at a lower temperature or equal to the reflux temperature of the mixture.
- the liquid / solid mass ratio will preferably be between 4 and 11.
- the separation of the pulp from the organic phase at the end of cooking is preferably carried out by pressing.
- Another preferred embodiment provides for the washing the dough thus separated by an acid mixture formic acid and acetic acid or pure acetic acid. Dough rid of most of the lignin and sugar residues is then washed with hot water.
- Another preferred embodiment proceeds by cooking in at least two stages to improve the delignification, and thus the quality of the pasta.
- the first step is carried out in the presence of the mixture formic acid / acetic acid.
- the second step is performed after having separated the pulp produced at the first stage into presence of anhydrous acetic acid.
- the washes of the dough are made with acetic acid.
- a preferred embodiment provides for the control pH during washing in organic acid medium so that the paper pulp at ideal pH for ozone bleaching in 1 or 2 sequences, to a dryness of the dough of the order of 40 to 60%.
- Another preferred embodiment provides for the separation of formic acid and acetic acid by evaporation under vacuum, the separation of the entrained water, the recycling of formic and acetic acids in the proportions required, and the recovery of acetic acid and water in excess.
- Another mode of implementation provides the mixture lignins / sugars taken up in water, the suspension is filtered or centrifuged to separate the precipitated lignins from the phase aqueous sweet acid. The latter is concentrated by vacuum evaporation to recover sugars and recycle the condensation water.
- 38g of rice straw at 88% dry matter (33,5g of material dry matter) are brought into contact at ambient temperature (20 ° C) with a mixture containing 150g of pure formic acid and 150g pure acetic acid in a 2 liter reactor equipped with a central mechanical stirrer, an open refrigerant and a thermometer.
- the mechanical agitation is maintained during 15 minutes at room temperature which corresponds to the time impregnation.
- the suspension is brought to a temperature of 100 ° C. using a thermostatic heating bath in 35 minutes. This temperature is maintained level for 60 minutes. Dough is drained and separated by pressing then washed twice in the reactor with 150 ml of a formic acid / acidic mixture acetic in the proportions of the initial reaction for a duration of 10 minutes.
- the acidic washing solutions are separated from the dough by filtration and pressing, then the dough is washed with hot water to recover traces of residual acids. The dough is then washed with cold water until neutral.
- 38g of rice straw at 90% dryness (34.2g of material dry matter) are brought into contact at ambient temperature (20 ° C) with a mixture containing 210 g of pure formic acid and 90 g of acid pure acetic acid in a 2-liter reactor equipped with an agitator central mechanics, an open refrigerant and a thermometer. Mechanical agitation is maintained for 15 minutes at ambient temperature which corresponds to the time impregnation.
- the suspension is raised to a temperature of 85 ° C. average of a heating bath thermostated in 25 minutes. This temperature is maintained level for 60 minutes. Dough is drained and separated by pressing then washed twice in the reactor with 150 ml of a formic acid / acidic mixture acetic in the proportions of the initial reaction for a duration of 10 minutes.
- the acidic washing solutions are separated from the dough by filtration and pressing, then the dough is washed with hot water then in cold water.
- the resulting paste (30 g) is then placed in the presence in a closed static reactor allowing the diffusion of a 1% air / ozone mixture through a sintered material on which the paste at a pH of 3 to about 50% dryness.
- the bleaching is carried out in two sequences of gas-solid contact of 20 minutes. Between each sequence a wash to the water is performed.
- the mixture of formic and acetic acids obtained by evaporation of the solution of sugars and lignins contains water supplied by lignocellulosic raw materials.
- the separation of excess acetic acid into from the acetyl groups of the lignocellulosic material can then be done by simple rectification.
- Ethyl acetate is separated from water in a decanter and it is recycled at the top of the column.
- the acid mixture acetic acid / dehydrated formic acid is extracted at the bottom of column and can then be distilled in a column of rectification to recover excess acetic acid.
- the mixture sugars and lignins is treated with the water recovered during washing dough.
- Lignins precipitate and are separated by filtration then dried. 11.2 g of lignins are thus recovered. The sweet solution is then evaporated allowing recovery final mixture of sugars containing predominantly five-carbon sugars / carbons. The amount of sugars recovered is 19.1g.
- 38g sorghum bagasse with 88% dryness (33.5g of dry matter) are brought into contact at ambient temperature (20 ° C) with a mixture containing 220 g of pure formic acid and 90g of pure acetic acid in a 2-liter reactor equipped a central mechanical stirrer, an open refrigerant and a thermometer. The mechanical agitation is maintained during 30 minutes at room temperature which corresponds to the time impregnation.
- the suspension is brought to a temperature of 100 ° C. using a thermostatic heating bath in 30 minutes. This temperature is maintained level for 60 minutes. Dough is drained and separated by pressing then washed twice in the reactor with 150 ml of a formic acid / acidic mixture acetic in the proportions of the initial reaction for a duration of 10 minutes.
- the acidic washing solutions are separated from the dough by filtration and pressing, then the dough is washed with hot water to recover traces of residual acids. The dough is then washed with cold water until neutral.
- the pulp obtained is characterized by its degree medium viscosimetric polymerization (DPv).
- DPv degree medium viscosimetric polymerization
- the measure is performed using a capillary viscometer of the type "Cellulose Commission” which is used to determine the viscosity (in mPa.s) intrinsic to natural or regenerated cellulose (NF T 12-005).
- 38g of rice straw at 88% dryness (33,5g of material dry matter) are brought into contact at ambient temperature (20 ° C) with a mixture containing 220 g of pure formic acid and 90 g of acid pure acetic acid in a 2-liter reactor equipped with an agitator central mechanics, an open refrigerant and a thermometer. Mechanical agitation is maintained for 15 minutes at ambient temperature which corresponds to the impregnation time.
- the suspension is brought to a temperature of 100 ° C. using a thermostatic heating bath in 30 minutes. This temperature is maintained level for 60 minutes. Dough is drained and separated by pressing The dough undergoes a second cooking with glacial acetic acid (150 ml) at a temperature of 90 ° C for 30 minutes.
- the new paste obtained is drained, separated by pressed and washed three times with acetic acid (150 ml) 15 minutes for each wash at a temperature of 95 ° C.
- the acidic washing solutions are separated from the dough by filtration and pressing, then the dough is washed with hot water to recover traces of residual acids. The dough is then washed with cold water until neutral.
Abstract
Description
L'invention concerne un procédé de production de pâte à papier, lignines, sucres et acide acétique à partir de matière végétale lignocellulosique constituant l'essentiel des plantes annuelles et perennes.The invention relates to a method for producing pulp paper, lignins, sugars and acetic acid from matter lignocellulosic plant constituting most of the plants annuals and perennials.
On entend dans ce qui suit par plante annuelle toute plante ayant une vie végétative de l'ordre d'une année (céréales, graminées diverses, coton, chanvre, lin, sorgho, canne à sucre, roseaux,...) et par plante perenne des plantes dont le développement s'étend sur une période plus longue, (bambous, bois feuillus, bois résineux...)In the following, we mean by annual plant any plant with a vegetative life of about one year (cereals, grasses, cotton, hemp, flax, sorghum, sugar cane, reeds, ...) and per plant perennial plants whose development extends over a longer period, (bamboo, hardwood, softwood ...)
Les matières ligno-cellulosiques de l'invention sont les plantes entières ou des parties de ces plantes (tiges, écorces,...) ou des co-produits de filière industrielle de production à finalité alimentaire (paille de blé, riz, orge).; bagasse de canne à sucre, bagasse de sorgho sucrier...).The lignocellulosic materials of the invention are the whole plants or parts of these plants (stems, bark, ...) or industrial co-products of food production (wheat straw, rice, barley) .; bagasse of sugar cane, bagasse of sorghum sugar ...).
Les pâtes à papier produites à partir de plantes annuelles ou perennes peuvent être classées selon la technologie utilisée, leur qualité papetière et le rendement massique d'obtention par rapport à la matière végétale initiale.Pulp produced from plants perennials can be classified according to the technology used, their paper quality and the yield mass of obtaining relative to the initial plant material.
La qualité papetière d'une pâte se définit par rapport au procédé de séparation des fibres cellulosiques ou défibrage et par rapport à une série de paramètres physico-chimiques dont les plus importants sont la longueur de rupture qui traduit la résistance à la traction, l'indice de déchirure et l'indice d'éclatement. Plus ces caractéristiques seront élevées, meilleure sera la qualité de la pâte produite.The pulp quality of a paste is defined in relation to process of separating cellulosic fibers or defibration and compared to a series of physicochemical parameters the most important are the break length that translates the tensile strength, tear index and index burst. The higher these characteristics are, the better the quality of the dough produced.
On considère donc :
- les pâtes de basse qualité, dites mécaniques ou thermomécaniques, qui sont obtenues avec un rendement de l'ordre de 80 à 90 % par des procédés mécaniques ou thermomécaniques,
- les pâtes chimicothermomécaniques ou mi-chimiques de qualité moyenne, qui sont obtenues avec un rendement de l'ordre de 60 à 80 % par des procédés chimicothermomécaniques ou mi-chimiques,
- les pâtes chimiques de qualité supérieure qui sont obtenues avec un rendement de l'ordre de 40 à 50 % par des procédés chimiques.
- the low quality pasta, known as mechanical or thermomechanical, which is obtained with a yield of the order of 80 to 90% by mechanical or thermomechanical processes,
- medium-quality chemi-thermomechanical or semi-chemical pulps, which are obtained with a yield of the order of 60 to 80% by chemo-thermomechanical or semi-chemical processes,
- high quality chemical pulps which are obtained with a yield of the order of 40 to 50% by chemical processes.
Dans le cas des plantes annuelles, la nature particulière de la matière lignocellulosique ne permet pas toujours d'atteindre, même avec les procédés chimiques, des valeurs convenables de longueur de rupture (supérieures à 4000 mètres).In the case of annuals, the particular nature lignocellulosic material does not always allow to achieve, even with chemical processes, values Suitable breaking lengths (greater than 4000 meters).
Il faut rappeler que la longueur de rupture, caractéristique essentielle de la pâte à papier et du papier correspond à la longueur d'une bande uniforme de largeur quelconque supposée suspendue par une de ses extrémités se rompant sous l'effet de son propre poids. Cette longueur de rupture se calcule par la formule 106. RT/15 G.g dans laquelle :
- RT est la résistance à la rupture par traction exprimée en newton par mètre (norme NFQ 03 002)
- G est le grammage de la bande de papier exprimée en g/m2.
- g est l'accélération de la pesanteur (9.81 m/s2).
- RT is the tensile breaking strength expressed in newtons per meter (NFQ 03 002 standard)
- G is the grammage of the paper web expressed in g / m2.
- g is the acceleration of gravity (9.81 m / s 2 ).
Les procédés de production de pâtes à papier de qualité, susceptibles d'obtenir avec la plupart des végétaux des longueurs de rupture convenables, sont de nature essentiellement chimique dans lesquels les fibres cellulosiques de la matière végétale lignocellulosique sont débarrassées du ciment végétal, qui les lie dans les végétaux, constitué par des hémicelluloses (polymères de sucres à 5 ou 6 carbones) et de lignines (polymères de phénols allyliques substitués) par une action chimique d'hydrolyse en milieu aqueux basique ou acide concentré, souvent en présence de soufre à différents états d'oxydation.Processes for the production of quality paper pulp, likely to obtain with most plants suitable breaking lengths, are essentially chemical in which the cellulosic fibers of the lignocellulosic plant material are cleared of cement plant, which binds them in plants, consisting of hemicelluloses (polymers of sugars with 5 or 6 carbons) and lignins (polymers of substituted allylic phenols) with a chemical action of hydrolysis in a basic aqueous or acidic medium concentrated, often in the presence of sulfur at different states oxidation.
Ces procédés sont aujourd'hui mis en oeuvre dans l'essentiel des unités industrielles existant de par le monde.These processes are now used in most of the existing industrial units around the world.
Ils ont comme inconvénient majeur d'exiger des quantités considérables (environ 20 % en poids) de produits chimiques minéraux lors de la cuisson des végétaux pour faire la pâte à papier. Ces produits chimiques minéraux sont nécessairement, mais difficilement recyclés, et ils sont souvent à l'origine, à cause de la présence de soufre, d'odeurs nauséabondes.They have the major disadvantage of requiring considerable quantities (about 20% by weight) of products mineral chemicals when cooking plants to make pulp. These mineral chemicals are necessarily but hardly recycled, and they are often originally, because of the presence of sulfur, odors foul.
De plus, ces usines requièrent, pour répondre à des normes d'environnement simplement acceptables, d'énormes investissements et elles ne sont donc rentables que pour une taille critique élevée de l'ordre de 100 à 200 000 tonnes de pâte produite par an.Moreover, these factories require, in order to meet simply acceptable environmental standards, huge investments and they are therefore profitable only for a high critical size in the order of 100 to 200 000 tonnes of paste produced per year.
Une amélioration technologique a été obtenue en remplaçant tout ou partie l'eau, par un solvant organique du genre alcools, cétones, esters, qui permet de s'affranchir de l'usage du soufre, mais pas des réactifs basiques et donc des problèmes de recyclage de ces réactifs. Ces technologies dites "organosolves" qui exigent pressions élevées et entraínent des coûts de fonctionnement élevés ne se sont pas, pour ces raisons, encore développées industriellement.A technological improvement was achieved in replacing all or part of the water with an organic solvent alcohol, ketones, esters, which makes it possible to overcome the use of sulfur, but not basic reagents and therefore recycling problems of these reagents. These technologies say "organosolves" which require high pressures and lead to high operating costs were not, for these reasons, still developed industrially.
Dans cet ordre d'idée, d'autres technologies du même type utilisant des acides organiques pour à la fois hydrolyser les hémicelluloses et les lignines et pour libérer les fibres de cellulose ont été développées à l'échelle d'unités pilotes. Ces technologies permettent de s'affranchir totalement des réactifs minéraux ce qui est un avantage considérable.In this vein, other technologies of the same kind type using organic acids to both hydrolyze hemicelluloses and lignins and to release the fibers from cellulose have been developed at pilot scale. These technologies make it possible to completely get rid of reagents minerals which is a considerable advantage.
L'acide formique (B. BUCHOLZ et RK. JORDAN Pulp and Paper, p.102 - 104, 1983 ; MN. ERISMANN et al., Bioresource Technology, Vol. 47, p. 247 - 256, 1994) peut être utilisé et il permet de faire des pâtes à papier acceptables sans pression. Cette technologie permet de plus de conserver la silice contenue dans le végétal dans les pâtes à papier, ce qui est un avantage important quand on utilise les plantes annuelles comme matière première car la silice perturbe considérablement, dans les procédés industriels actuels en milieu basique, la récupération des réactifs minéraux.Formic acid (B. BUCHOLZ and RK JORDAN Pulp and Paper, pp.102-104, 1983; MN. ERISMANN et al., Bioresource Technology, Vol. 47, p. 247 - 256, 1994) can be used and it allows to make acceptable paper pulp without pressure. This technology makes it possible to conserve silica contained in the plant in pulp, which is a important advantage when using annuals as raw material because the silica disrupts considerably, in the current industrial processes in the middle basic, recovery of mineral reagents.
Une variante du procédé comme sous le nom de procédé MILOX procède par des cuissons à l'acide formique en plusieurs stades en présence d'eau oxygénée qui améliore la délignification (K.POPPIUS - LEVLIN et al. Tappi Journal, Vol. 80, N° 9, p.215 - 221, 1997).A variant of the process as under the name of process MILOX proceeds by cooking with formic acid in several stages in the presence of hydrogen peroxide which improves the delignification (K.POPPIUS - LEVLIN et al., Tappi Journal, Vol. 80, No. 9, p.215-221, 1997).
L'acide acétique peut être utilisé dans le même but sous pression à plus haute température (160 à 180°C) à des concentrations dans l'eau de 50 à 90 % (R. A. YOUNG et J.L. DAVIS, Holzforshung, Vol. 40, p. 99-108, 1986).Acetic acid can be used for the same purpose under pressure at higher temperatures (160 to 180 ° C) at concentrations in water of 50 to 90% (R. A. YOUNG and J.L. DAVIS, Holzforshung, Vol. 40, p. 99-108, 1986).
La délignification est correcte mais le procédé exige un lavage de la pâte à l'acétone pour éliminer les lignines précipitées sur la pâte.The delignification is correct but the process requires a washing the paste with acetone to remove lignins precipitated on the dough.
Une variante de ce procédé permet, avec l'oxygène sous pression, de réduire les temps de cuisson et d'améliorer la délignification (C.P. NETO et A. ROBERT, Holzforshung, Vol.46, p. 233-240, 1993), mais il est à l'origine d'une dépolymérisation partielle de la cellulose par l'action conjointe du pH et de l'oxygène.A variant of this process allows, with oxygen under pressure, reduce cooking times and improve the delignification (C. P. NETO and A. ROBERT, Holzforshung, Vol.46, p. 233-240, 1993), but it is at the origin of a partial depolymerization of cellulose by joint action pH and oxygen.
Une variante du procédé MILOX utilisant en deux stades de cuisson, l'acide acétique et l'eau oxygénée, a aussi été proposée à 160-170° C (K. POPPIUS - LEVLIN et al., Paper and Timber, Vol. 73 p. 154-158, 1991), mais elle n'apporte pas d'amélioration considérable.A variant of the MILOX process using two stages of cooking, acetic acid and hydrogen peroxide, has also been proposed at 160-170 ° C (K. POPPIUS - LEVLIN et al., Paper and Timber, Vol. 73 p. 154-158, 1991), but it does not bring considerable improvement.
L'acidité limitée de l'acide acétique a conduit à renforcer sa capacité d'hydrolyse par addition d'acide chlorhydrique (J.C. PARAJO et al, Holz als Roh und Verkstoff, Vol. 54, p. 119 -125, 1996) à 115°-130°C. L'abaissement de la température de réaction est la principale amélioration de la méthode qui a comme inconvénient majeur d'introduire des ions chlore dans le procédé (G. VASQUES al. Holzforshung, Vol. 49, n° 1, p. 69-73, 1995).The limited acidity of acetic acid has led to its hydrolysis capacity by addition of hydrochloric acid (J.C. PARAJO et al, Holz als Roh and Verkstoff, Vol. 54, p. 119 -125, 1996) at 115 ° -130 ° C. The lowering of the temperature of reaction is the main improvement of the method that has as a major disadvantage of introducing chlorine ions into the method (G. VASQUES, Holzforshung, Vol 49, No. 1, pp. 69-73). 1995).
Par ailleurs, il faut signaler que l'ensemble des technologies utilisant, en deux ou plusieurs stades, un acide organique et l'eau oxygénée générant in situ des peroxyacides sont détaillées dans la revue (N. LIEBERGOTT Pulp and Paper Canada, Vol. 97, n° 2, p. 45-48, 1996).Moreover, it should be noted that all technologies using, in two or more stages, an acid organic and hydrogen peroxide generating in situ peroxyacids are detailed in the journal (N. LIEBERGOTT Pulp and Paper Canada, Vol. 97, No. 2, p. 45-48, 1996).
Il faut ajouter que les technologies de blanchiment sans chlore de ces pâtes utilisent l'eau oxygénée en milieu basique, ce qui entraíne le réglage de la silice sous forme de silicate de sodium provoquant des problèmes importants lors de l'égouttage des pâtes et du recyclage des réactifs.It should be added that bleaching technologies without chlorine of these pasta uses hydrogen peroxide in a basic medium, which leads to the adjustment of the silica in the form of silicate sodium causing significant problems when draining of pasta and recycling of reagents.
La présente invention vise à proposer un nouveau procédé de fabrication de pâte à papier à partir de plantes annuelles ou perennes qui conduise à des pâtes chimiques de bonne qualité conservant dans leur structure la silice endogène à la pression atmosphérique.The present invention aims to propose a new process for making pulp from plants annuals or perennials that lead to chemical pulps of good quality preserving in their structure the endogenous silica at atmospheric pressure.
Dans le document EP-A-0.584.675, il est enseigné un procédé d'extraction de cellulose à partir de lignocelluloces, par chauffage pendant 2 h à hautes températures (170°C ou 180°C) et sous pression en présence d'acide acétique aqueux et ajout d'acide formique.In EP-A-0.584.675, it is taught a cellulose extraction process from lignocelluloces, by heating for 2 hours at high temperatures (170 ° C or 180 ° C) and under pressure in the presence of aqueous acetic acid and addition of formic acid.
Le document WO-A-95/21960 décrit un procédé de cuisson de matières lignocellulosiques, en particulier de plantes annuelles) avec un mélange d'acides carboxyliques, mettant en oeuvre une étape obligatoire de pyrolyse.WO-A-95/21960 discloses a method of cooking of lignocellulosic materials, in particular of plants annuals) with a mixture of carboxylic acids, a compulsory step of pyrolysis.
L'invention vise un procédé qui permet d'obtenir ces performances quelle que soit la nature des plantes utilisées et qui est donc particulièrement intéressant dans le cas des plantes annuelles pour ouvrir la voie à de nouvelles valorisations, notamment dans le cas des pailles de céréales et de la bagasse de canne à sucre, ou de sorgho sucrier. The invention is directed to a method which makes it possible to obtain these performance whatever the nature of the plants used and which is therefore particularly interesting in the case of annual plants to pave the way for new valuations, particularly in the case of cereal straw and bagasse of sugar cane, or sugar sorghum.
A cet effet le procédé de fabrication de pâte à papier,
lignines, sucres, et acide acétique conforme à l'invention se
caractérise en ce qu'il comprend les étapes successives
suivantes consistant à :
Le procédé selon l'invention résulte de la constatation surprenante suivante : l'addition d'acide acétique à l'acide formique permet d'augmenter considérablement le pouvoir solvatant de la phase organique liquide ainsi définie vis-à-vis des hémicelluloses et lignines sans affecter la capacité d'hydrolyse acide de ces biopolymères par l'acide formique. De cette façon on évite la dégradation des fibres cellulosiques qui apparaít avec l'acide formique concentré seul dans les conditions habituelles d'utilisation, et on préserve donc la qualité papetière de la pâte à papier obtenue.The process according to the invention results from the observation surprising following: the addition of acetic acid to the acid formic can significantly increase the power solvating of the liquid organic phase thus defined vis-à-vis hemicelluloses and lignins without affecting the capacity acid hydrolysis of these biopolymers with formic acid. Of this way we avoid the degradation of cellulosic fibers which appears with concentrated formic acid alone in usual conditions of use, and therefore the paper quality of the pulp obtained.
On obtient alors des pâtes résistantes qui se séparent aisément du milieu réactionnel et qui s'égouttent aisément pour cause de non relargage de la silice endogène.We then obtain resistant pasta that separates easily from the reaction medium and which drip easily to cause of non-release of the endogenous silica.
Cette propriété est particulièrement importante puisqu'elle est le principal facteur limitant de l'utilisation des pâtes chimiques de pailles notamment dans les machines à papier rapides dont elles ralentissent la vitesse.This property is particularly important since it is the main limiting factor in the use of chemical straw pasta, especially in fast paper whose speed they slow down.
Il faut souligner que les acides acétique et formique sont recyclés. Les pertes dans le procédé n'excédent pas 1 % en poids par tonne de pâte produite, ce qui est négligeable.It must be emphasized that acetic and formic acids are recycled. Losses in the process do not exceed 1% in weight per tonne of pulp produced, which is negligible.
Les mécanismes par lesquels l'acide formique et l'acide acétique agissent en synergie dans les premiers instants de la cuisson restent difficiles à expliquer.The mechanisms by which formic acid and acid acetic acid act in synergy in the first moments of the cooking remain difficult to explain.
Néanmoins on peut avancer comme hypothèse que, dans les conditions de mise en oeuvre conformément au procédé de l'invention, la faible hydratation du milieu liée à l'eau apportée par les matières lignocellulosiques initiales favorise la dissociation de l'acide formique, ce qui entraíne l'hydrolyse contrôlée du complexe hémicelluloses/lignines.Nevertheless it can be argued that in the conditions of implementation according to the method of the invention, the low hydration of the medium associated with the water supplied by the initial lignocellulosic materials promotes the dissociation of formic acid, which leads to hydrolysis controlled complex hemicelluloses / lignins.
Dans ces conditions l'acide acétique, préférentiellement sous forme moléculaire, solubilise plus aisément les lignines ainsi libérées. Cet effet permet de limiter le temps de réaction et les possibles formylations des groupes hydroxyles libres de la cellulose qui dégradent les qualités papetières de la pâte.Under these conditions, acetic acid, preferably in molecular form, solubilizes lignins more easily thus released. This effect limits the reaction time and the possible formylations of the free hydroxyl groups of cellulose which degrade the paper qualities of the dough.
La libération progressive d'acide acétique issue des groupes acétyles des hémicelluloses conforte cet effet, mais elle ne permet pas d'obtenir les performances observées dans le procédé par sa trop faible quantité par rapport à l'acide formique initiale.The gradual release of acetic acid from Acetyl groups of hemicelluloses support this effect, but it does not make it possible to obtain the performances observed in the process by its too small amount compared to the acid initial form.
Le procédé selon l'invention peut être mis en oeuvre à partir de plantes ou parties de plantes du genre :
- paille de céréales (blé, orge, seigle, avoine, triticale, riz,...),
- plantes annuelles (coton, chanvre, lin, roseaux...),
- plantes perennes (bambous, bois feuillus, bois résineux...),
- bagasse de canne à sucre, bagasse de sorgho sucrier.
- cereal straw (wheat, barley, rye, oats, triticale, rice, ...),
- annual plants (cotton, hemp, flax, reeds ...),
- Perennial plants (bamboos, hardwoods, softwoods, etc.),
- bagasse of sugar cane, bagasse of sorghum sugar.
Le procédé permet une valorisation particulièrement intéressante des plantes annuelles, notamment des pailles et des bagasses, qui sont considérées dans les procédés de fabrication de pâtes chimiques traditionnelles comme des produits de seconde catégorie sans grand intérêt.The process allows a particularly valorization interesting annual plants, especially straws and bags, which are considered in the processes of manufacture of traditional chemical pasta as second-class products without much interest.
On veille de préférence à ce que l'humidité de la matière lignocellulosique initiale soit inférieure ou égale à 25% en poids d'eau par rapport à la matière sèche.Preferably, the moisture of the material is initial lignocellulose content is less than or equal to 25% by weight of water relative to the dry matter.
On réalise de préférence un broyage de la matière première lignocellulosique de façon à la réduire en fragments ou copeaux de longueur sensiblement comprise entre 0,5 et 20 cm.It is preferably carried out a grinding of the material first lignocellulosic so as to reduce it to fragments or chips of length substantially between 0.5 and 20 cm.
Selon un premier mode de mise en oeuvre, on procède à une imprégnation préalable de la matière végétale inférieure d'au moins 30°C à la température de réaction. L'imprégnation par immersion est réalisée pendant une durée de 10 à 30 mn dans le mélange acide formique/acide acétique utilisé pendant la réaction de fractionnement. L'imprégnation et la réaction de fractionnement qui suit sont conduites à la pression atmosphérique.According to a first mode of implementation, we proceed to a prior impregnation of the lower vegetable matter at least 30 ° C at the reaction temperature. The impregnation by immersion is performed for a period of 10 to 30 minutes in the formic acid / acetic acid mixture used during the fractionation reaction. Impregnation and the reaction of following splitting are conducted at the pressure atmospheric.
On entend ici par fractionnement le processus de réaction connu habituellement sous le nom de cuisson qui, dans les conditions de l'invention, conduit, en plus de la pâte à papier, à des produits aisément séparables, ce qui n'est pas le cas dans la plupart des procédés classiques.Here we mean by fractionation the process of reaction usually known as cooking which in the conditions of the invention leads, in addition to the dough to paper, to readily separable products, which is not the case in most conventional processes.
Selon un autre mode de mise en oeuvre, la réaction de fractionnement est conduite à une température inférieure ou égale à la température de reflux du mélange.According to another embodiment, the reaction of fractionation is conducted at a lower temperature or equal to the reflux temperature of the mixture.
Le rapport massique liquide/solide sera préférentiellement compris entre 4 et 11.The liquid / solid mass ratio will preferably be between 4 and 11.
La séparation de la pâte à papier de la phase organique en fin de cuisson est effectuée de préférence par pressage.The separation of the pulp from the organic phase at the end of cooking is preferably carried out by pressing.
Un autre mode de mise en oeuvre préféré prévoit le lavage de la pâte ainsi séparée par un mélange d'acide formique et d'acide acétique ou d'acide acétique pur. La pâte débarrassée de l'essentiel des résidus de lignines et de sucres est ensuite lavée à l'eau chaude.Another preferred embodiment provides for the washing the dough thus separated by an acid mixture formic acid and acetic acid or pure acetic acid. Dough rid of most of the lignin and sugar residues is then washed with hot water.
Un autre mode de mise en oeuvre préféré procède par une cuisson en au moins deux étapes pour améliorer la délignification, et donc la qualité des pâtes.Another preferred embodiment proceeds by cooking in at least two stages to improve the delignification, and thus the quality of the pasta.
La première étape est effectuée en présence du mélange acide formique/acide acétique. La deuxième étape est effectuée après avoir séparé la pâte produite au premier stade en présence d'acide acétique anhydre. Les lavages de la pâte sont effectués à l'acide acétique.The first step is carried out in the presence of the mixture formic acid / acetic acid. The second step is performed after having separated the pulp produced at the first stage into presence of anhydrous acetic acid. The washes of the dough are made with acetic acid.
Un mode de mise en oeuvre préféré prévoit le contrôle du pH pendant le lavage en milieu acide organique pour que la pâte à papier soit au pH idéal pour le blanchiment par l'ozone en 1 ou 2 séquences, à une siccité de la pâte de l'ordre de 40 à 60 %.A preferred embodiment provides for the control pH during washing in organic acid medium so that the paper pulp at ideal pH for ozone bleaching in 1 or 2 sequences, to a dryness of the dough of the order of 40 to 60%.
Un autre mode de mise en oeuvre préféré prévoit la séparation de l'acide formique et de l'acide acétique par évaporation sous vide, la séparation de l'eau entraínée, le recyclage des acides formique et acétique dans les proportions requises, et la récupération de l'acide acétique et de l'eau en excès.Another preferred embodiment provides for the separation of formic acid and acetic acid by evaporation under vacuum, the separation of the entrained water, the recycling of formic and acetic acids in the proportions required, and the recovery of acetic acid and water in excess.
Un autre mode de mise en oeuvre prévoit le mélange lignines/sucres repris à l'eau, la suspension est filtrée ou centrifugée pour séparer les lignines précipitées de la phase aqueuse sucrée acide. Cette dernière est concentrée par évaporation sous vide pour récupérer les sucres et recycler l'eau de condensation.Another mode of implementation provides the mixture lignins / sugars taken up in water, the suspension is filtered or centrifuged to separate the precipitated lignins from the phase aqueous sweet acid. The latter is concentrated by vacuum evaporation to recover sugars and recycle the condensation water.
Le procédé de l'invention est illustré par les exemples qui suivent :The process of the invention is illustrated by the examples that follow :
38g de paille de riz à 88 % siccité (33,5g de matière sèche) sont mis en contact à température ambiante (20°C) avec un mélange contenant 150g d'acide formique pur et 150g d'acide acétique pur dans un réacteur de 2 litres équipé d'un agitateur mécanique central, d'un réfrigérant ouvert et d'un thermomètre. L'agitation mécanique est maintenue pendant 15 mn à la température ambiante qui correspond au temps d'imprégnation.38g of rice straw at 88% dry matter (33,5g of material dry matter) are brought into contact at ambient temperature (20 ° C) with a mixture containing 150g of pure formic acid and 150g pure acetic acid in a 2 liter reactor equipped with a central mechanical stirrer, an open refrigerant and a thermometer. The mechanical agitation is maintained during 15 minutes at room temperature which corresponds to the time impregnation.
La suspension est portée à la température de 100°C au moyen d'un bain chauffant thermostaté en 35 mn. Cette température est maintenue en palier pendant 60 mn. La pâte est égouttée et séparée par pressage puis lavée deux fois dans le réacteur par 150 ml d'un mélange acide formique/acide acétique dans les proportions de la réaction initiale pour une durée de 10 mn.The suspension is brought to a temperature of 100 ° C. using a thermostatic heating bath in 35 minutes. This temperature is maintained level for 60 minutes. Dough is drained and separated by pressing then washed twice in the reactor with 150 ml of a formic acid / acidic mixture acetic in the proportions of the initial reaction for a duration of 10 minutes.
Les solutions acides de lavage sont séparées de la pâte par filtration et pressage, puis la pâte est lavée à l'eau chaude pour récupérer les traces d'acides résiduels. La pâte est ensuite lavée à l'eau froide jusqu'à neutralité.The acidic washing solutions are separated from the dough by filtration and pressing, then the dough is washed with hot water to recover traces of residual acids. The dough is then washed with cold water until neutral.
Les caractéristiques mécaniques de la pâte obtenue sont
les suivantes :
38g de paille de riz à 90% de siccité (34,2g de matière sèche) sont mis en contact à température ambiante (20°C) avec un mélange contenant 210g d'acide formique pur et 90g d'acide acétique pur dans un réacteur de 2 litres équipé d'un agitateur mécanique central, d'un réfrigérant ouvert et d'un thermomètre. L'agitation mécanique est maintenue pendant 15 mn à la température ambiante ce qui correspond au temps d'imprégnation.38g of rice straw at 90% dryness (34.2g of material dry matter) are brought into contact at ambient temperature (20 ° C) with a mixture containing 210 g of pure formic acid and 90 g of acid pure acetic acid in a 2-liter reactor equipped with an agitator central mechanics, an open refrigerant and a thermometer. Mechanical agitation is maintained for 15 minutes at ambient temperature which corresponds to the time impregnation.
La suspension est portée à la température de 85°C au moyen d'un bain chauffant thermostaté en 25 mn. Cette température est maintenue en palier pendant 60 mn. La pâte est égouttée et séparée par pressage puis lavée deux fois dans le réacteur par 150 ml d'un mélange acide formique/acide acétique dans les proportions de la réaction initiale pour une durée de 10 mn.The suspension is raised to a temperature of 85 ° C. average of a heating bath thermostated in 25 minutes. This temperature is maintained level for 60 minutes. Dough is drained and separated by pressing then washed twice in the reactor with 150 ml of a formic acid / acidic mixture acetic in the proportions of the initial reaction for a duration of 10 minutes.
Les solutions acides de lavage sont séparées de la pâte par filtration et pressage, puis la pâte est lavée à l'eau chaude puis à l'eau froide.The acidic washing solutions are separated from the dough by filtration and pressing, then the dough is washed with hot water then in cold water.
Les caractéristiques mécaniques de la pâte obtenue sont
les suivantes :
La pâte obtenue (30g) est ensuite mise en présence dans un réacteur statique fermé permettant la diffusion d'un mélange air/ozone à 1% à travers un fritté sur lequel repose la pâte à un pH de 3 à environ 50 % de siccité.The resulting paste (30 g) is then placed in the presence in a closed static reactor allowing the diffusion of a 1% air / ozone mixture through a sintered material on which the paste at a pH of 3 to about 50% dryness.
Le blanchiment est effectué en deux séquences de contact gaz-solide de 20 mn. Entre chaque séquence un lavage à l'eau est effectué.The bleaching is carried out in two sequences of gas-solid contact of 20 minutes. Between each sequence a wash to the water is performed.
L'indice de blancheur mesuré à l'aide du spectrophotomètre ELREPHO 2000 selon la norme NFQ 03039 passe de 28,1 photovolts pour la pâte brute à 68,2 photovolts pour la pâte blanchie dans ces conditions.The whiteness index measured with the spectrophotometer ELREPHO 2000 according to NFQ 03039 standard from 28.1 photovolts for the raw paste to 68.2 photovolts for the bleached dough under these conditions.
Le mélange d'acides formique et acétique obtenu par évaporation de la solution de sucres et de lignines contient l'eau apportée par les matières premières lignocellulosiques.The mixture of formic and acetic acids obtained by evaporation of the solution of sugars and lignins contains water supplied by lignocellulosic raw materials.
Cette eau est séparée du mélange d'acides par
distillation azéotropique à l'aide d'un tiers corps qui peut être :
La séparation de l'acide acétique en excès en provenance des groupes acétyles de la matière lignocellulosique peut alors être effectuée par simple rectification.The separation of excess acetic acid into from the acetyl groups of the lignocellulosic material can then be done by simple rectification.
Dans ces conditions, 100g de paille de riz correspondant sensiblement à trois essais identiques dans les conditions expérimentales décrites ci-dessus apportent environ 10g d'eau au milieu réactionnel. La phase liquide organique contient sensiblement 880g d'acides acétique et formique et 9,5g d'eau. Elle est traitée par 109g d'acétate d'ethyle.L'azéotrope acétate d'éthyle - eau (P. éb. 70,4°C sous 760 mm Hg, concentration en eau : 8,2 % en poids) est extrait en tête de colonne à distiller et condensé.Under these conditions, 100g of corresponding rice straw substantially to three identical tests under the conditions described above bring about 10g of water in the reaction medium. The organic liquid phase contains appreciably 880g of acetic and formic acids and 9.5g of water. It is treated with 109 g of ethyl acetate.Azeotrope acetate of ethyl-water (bp 70.4 ° C at 760 mm Hg, concentration in water: 8.2% by weight) is extracted at the top of the distillation column and condensed.
L'acétate d'éthyle est séparé de l'eau dans un décanteur et il est recyclé en tête de colonne. Le mélange acide acétique/acide formique déshydraté est extrait en pied de colonne et peut être ensuite distillé dans une colonne de rectification pour récupérer l'acide acétique en excès.Ethyl acetate is separated from water in a decanter and it is recycled at the top of the column. The acid mixture acetic acid / dehydrated formic acid is extracted at the bottom of column and can then be distilled in a column of rectification to recover excess acetic acid.
Les acides formique et acétique sont ensuite recyclés vers la cuisson en proportions convenables.Formic and acetic acids are then recycled to cooking in proper proportions.
Après évaporation des acides organiques, le mélange sucres et lignines est traité avec l'eau récupérée lors du lavage de la pâte.After evaporation of the organic acids, the mixture sugars and lignins is treated with the water recovered during washing dough.
Les lignines précipitent et sont séparées par filtration puis séchées. 11,2g de lignines sont ainsi récupérées. La solution sucrée est ensuite évaporée ce qui permet la récupération finale du mélange de sucres contenant majoritairement des sucres à cinq atomes/carbones. La quantité de sucres récupérée est de 19,1g.Lignins precipitate and are separated by filtration then dried. 11.2 g of lignins are thus recovered. The sweet solution is then evaporated allowing recovery final mixture of sugars containing predominantly five-carbon sugars / carbons. The amount of sugars recovered is 19.1g.
38g de bagasse de sorgho à 88 % de siccité (33,5g de matière sèche) sont mis en contact à température ambiante (20°C) avec un mélange contenant 220g d'acide formique pur et 90g d'acide acétique pur dans un réacteur de 2 litres équipé d'un agitateur mécanique central, d'un réfrigérant ouvert et d'un thermomètre. L'agitation mécanique est maintenue pendant 30 mn à la température ambiante qui correspond au temps d'imprégnation.38g sorghum bagasse with 88% dryness (33.5g of dry matter) are brought into contact at ambient temperature (20 ° C) with a mixture containing 220 g of pure formic acid and 90g of pure acetic acid in a 2-liter reactor equipped a central mechanical stirrer, an open refrigerant and a thermometer. The mechanical agitation is maintained during 30 minutes at room temperature which corresponds to the time impregnation.
La suspension est portée à la température de 100°C au moyen d'un bain chauffant thermostaté en 30 mn. Cette température est maintenue en palier pendant 60 mn. La pâte est égouttée et séparée par pressage puis lavée deux fois dans le réacteur par 150 ml d'un mélange acide formique/acide acétique dans les proportions de la réaction initiale pour une durée de 10 mn.The suspension is brought to a temperature of 100 ° C. using a thermostatic heating bath in 30 minutes. This temperature is maintained level for 60 minutes. Dough is drained and separated by pressing then washed twice in the reactor with 150 ml of a formic acid / acidic mixture acetic in the proportions of the initial reaction for a duration of 10 minutes.
Les solutions acides de lavage sont séparées de la pâte par filtration et pressage, puis la pâte est lavée à l'eau chaude pour récupérer les traces d'acides résiduels. La pâte est ensuite lavée à l'eau froide jusqu'à neutralité. The acidic washing solutions are separated from the dough by filtration and pressing, then the dough is washed with hot water to recover traces of residual acids. The dough is then washed with cold water until neutral.
La pâte à papier obtenue est caractérisée par son degré de polymérisation moyen viscosimétrique (DPv). La mesure est effectuée à l'aide d'un viscosimètre à capillaire du type "Commission de la Cellulose" qui sert à déterminer la viscosité (en mPa.s) intrinsèque de la cellulose naturelle ou régénérée (NF T 12-005). La valeur observée est liée au degré de polymérisation par la relation DPv = (0,75 (954 logv - 325)) 1,105 dans laquelle v est la viscosité mesurée, soit donc pour la pâte de bagasse de sorgho sucrier obtenue dans les conditions expérimentales décrites ci-dessus un DPv = 1680 caractéristique d'une pâte de bonne qualité.The pulp obtained is characterized by its degree medium viscosimetric polymerization (DPv). The measure is performed using a capillary viscometer of the type "Cellulose Commission" which is used to determine the viscosity (in mPa.s) intrinsic to natural or regenerated cellulose (NF T 12-005). The observed value is related to the degree of polymerization by the relation DPv = (0.75 (954 logv-325)) 1,105 where v is the measured viscosity, so for bagasse sugar sorghum paste obtained in experimental conditions described above a DPv = 1680 characteristic of a good quality dough.
38g de paille de riz à 88 % de siccité (33,5g de matière sèche) sont mis en contact à température ambiante (20°C) avec un mélange contenant 220g d'acide formique pur et 90g d'acide acétique pur dans un réacteur de 2 litres équipé d'un agitateur mécanique central, d'un réfrigérant ouvert et d'un thermomètre. L'agitation mécanique est maintenue pendant 15 mn à la température ambiante qui correspond au temps d'imprégnation.38g of rice straw at 88% dryness (33,5g of material dry matter) are brought into contact at ambient temperature (20 ° C) with a mixture containing 220 g of pure formic acid and 90 g of acid pure acetic acid in a 2-liter reactor equipped with an agitator central mechanics, an open refrigerant and a thermometer. Mechanical agitation is maintained for 15 minutes at ambient temperature which corresponds to the impregnation time.
La suspension est portée à la température de 100°C au moyen d'un bain chauffant thermostaté en 30 mn. Cette température est maintenue en palier pendant 60 mn. La pâte est égouttée et séparée par pressage La pâte subit une deuxième cuisson par l'acide acétique glacial (150 ml) à une température de 90° C pendant 30 mn.The suspension is brought to a temperature of 100 ° C. using a thermostatic heating bath in 30 minutes. This temperature is maintained level for 60 minutes. Dough is drained and separated by pressing The dough undergoes a second cooking with glacial acetic acid (150 ml) at a temperature of 90 ° C for 30 minutes.
La nouvelle pâte obtenue est égouttée, séparée par pressage et lavée trois fois à l'acide acétique (150 ml) pendant 15 mn pour chaque lavage à une température de 95° C.The new paste obtained is drained, separated by pressed and washed three times with acetic acid (150 ml) 15 minutes for each wash at a temperature of 95 ° C.
Les solutions acides de lavage sont séparées de la pâte par filtration et pressage, puis la pâte est lavée à l'eau chaude pour récupérer les traces d'acides résiduels. La pâte est ensuite lavée à l'eau froide jusqu'à neutralité.The acidic washing solutions are separated from the dough by filtration and pressing, then the dough is washed with hot water to recover traces of residual acids. The dough is then washed with cold water until neutral.
Le degré de polymérisation de la pâte de sorgho sucrier mesuré dans les conditions de l'exemple n° 3 a une valeur : DPv = 2360 particulièrement élevée, caractéristique d'une pâte à papier de qualité supérieure.The degree of polymerization of sugar sorghum pulp measured under the conditions of Example No. 3 has a value: DPv = 2360 particularly high, characteristic of a paste paper of superior quality.
Claims (17)
- Process for producing paper pulp, lignins, sugars and acetic acid, characterized in that it comprises the following successive steps consisting in:(i) placing the annual or perennial plants, used partially or totally, which constitute the lignocellulose-based starting raw material, in contact with a mixture of formic acid containing at least 5% of acetic acid by weight, which is brought to a reaction temperature of between 50°C and 115°C;(ii) next, separating at atmospheric pressure the solid fraction constituting the paper pulp from the organic phase, especially containing in solution the starting formic acid and acetic acid, solubilized monomeric and polymeric sugars, lignins and acetic acid derived from the initial plant raw material; the said process also involving a preliminary step consisting in(iii) preimpregnating the plant material at atmospheric pressure and at a temperature at least 30°C below the reaction temperature.
- Process according to Claim 1, characterized in that the paper pulp obtained then undergoes one or more additional phases of being placed in contact with acetic acid at between 50°C and 115°C.
- Process according to Claim 1 or 2, characterized in that the moisture content of the initial lignocellulose-based material is less than or equal to 25% by weight of water relative to the solids.
- Process according to any one of Claims 1 to 3, characterized in that the lignocellulose-based raw material is ground so as to reduce it to fragments or chips substantially of between 0.5 and 20 cm in length.
- Process according to any one of Claims 1 to 4, characterized in that the impregnation by immersion is performed for a period of from 10 to 30 minutes in the formic acid/acetic acid mixture used during the fractionation reaction.
- Process according to any one of Claims 1 to 5, characterized in that the fractionation reaction is performed at a temperature below or equal to the reflux temperature of the mixture.
- Process according to any one of Claims 1 to 6, characterized in that the liquid/solid mass ratio is between 4 and 11.
- Process according to any one of Claims 1 to 7, characterized in that the contact time between the plant material, the formic acid and the acetic acid is between 1 hour and 2 hours.
- Process according to any one of Claims 1 to 8, characterized in that the solid phase constituting the paper pulp is separated from the organic liquid phase by pressing.
- Process according to any one of Claims 1 to 9, characterized in that the paper pulp is washed with a mixture of formic acid and acetic acid in the reaction proportions.
- Process according to any one of Claims 1 to 10, characterized in that the washing is performed using anhydrous acetic acid.
- Process according to any one of Claims 1 to 11, characterized in that the paper pulp obtained is washed with hot water.
- Process according to any one of Claims 1 to 12, characterized in that the treatment after washing is performed so as to maintain the paper pulp, at a dryness of between 40% and 60%, at a pH allowing optimum bleaching with ozone in one or more sequences.
- Process according to any one of Claims 1 to 13, characterized in that the formic acid and the acetic acid are separated from the pulps, the lignins and the sugars by evaporation under vacuum.
- Process according to any one of Claims 1 to 14, characterized in that the formic acid/acetic acid/water mixture is treated so as to allow the recycling of the acetic acid/formic acid mixture at the desired concentration, the recovery of the acetic acid obtained from the starting cellulose-based material, and the separation of the excess water.
- Process according to any one of Claims 1 to 15, characterized in that the liquid/sugars mixture is taken up in water and then filtered to separate the precipitated lignins from the acidic liquid aqueous phase.
- Process according to any one of Claims 1 to 16, characterized in that the sugars dissolved in the aqueous phase are separated from the said aqueous phase by evaporation of the water under vacuum.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/FR1999/001071 WO2000068494A1 (en) | 1999-05-06 | 1999-05-06 | Method for producing paper pulp, lignins, sugars and acetic acid by fractionation of lignocellulosic vegetable material in formic/acetic acid medium |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1180171A1 EP1180171A1 (en) | 2002-02-20 |
EP1180171B1 true EP1180171B1 (en) | 2003-10-08 |
Family
ID=9541421
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP99916998A Expired - Lifetime EP1180171B1 (en) | 1999-05-06 | 1999-05-06 | Method for producing paper pulp, lignins, sugars and acetic acid by fractionation of lignocellulosic vegetable material in formic/acetic acid medium |
Country Status (8)
Country | Link |
---|---|
US (1) | US7402224B1 (en) |
EP (1) | EP1180171B1 (en) |
AT (1) | ATE251689T1 (en) |
AU (1) | AU3528699A (en) |
DE (1) | DE69912007T2 (en) |
DK (1) | DK1180171T3 (en) |
ES (1) | ES2209424T3 (en) |
WO (1) | WO2000068494A1 (en) |
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FR2960888A1 (en) * | 2010-06-08 | 2011-12-09 | Cie Ind De La Matiere Vegetale Cimv | PROCESS FOR SEPARATING LIGNINS AND SUGARS FROM AN EXTRACTION LIQUEUR |
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-
1999
- 1999-05-06 EP EP99916998A patent/EP1180171B1/en not_active Expired - Lifetime
- 1999-05-06 DK DK99916998T patent/DK1180171T3/en active
- 1999-05-06 US US10/490,555 patent/US7402224B1/en not_active Expired - Lifetime
- 1999-05-06 WO PCT/FR1999/001071 patent/WO2000068494A1/en active Application Filing
- 1999-05-06 ES ES99916998T patent/ES2209424T3/en not_active Expired - Lifetime
- 1999-05-06 AT AT99916998T patent/ATE251689T1/en not_active IP Right Cessation
- 1999-05-06 AU AU35286/99A patent/AU3528699A/en not_active Abandoned
- 1999-05-06 DE DE69912007T patent/DE69912007T2/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2960888A1 (en) * | 2010-06-08 | 2011-12-09 | Cie Ind De La Matiere Vegetale Cimv | PROCESS FOR SEPARATING LIGNINS AND SUGARS FROM AN EXTRACTION LIQUEUR |
WO2011154293A1 (en) | 2010-06-08 | 2011-12-15 | Compagnie Industrielle De La Matiere Vegetale - Cimv | Process for the separation of lignins and sugars from an extraction liquor |
RU2563675C2 (en) * | 2010-06-08 | 2015-09-20 | Компани Эндюстриель Де Ля Матьер Вежеталь-Симв | Process for separation of lignins and sugars from extraction liquor |
US9388207B2 (en) | 2010-06-08 | 2016-07-12 | Compagnie Industrielle De La Matiere Vegetable—Cimv | Process for the separation of lignins and sugars from an extraction liquor |
US9580588B2 (en) | 2012-07-17 | 2017-02-28 | Compagnie Industrielle De La Matiere Vegetale | Use of a lignin for the mechanical reinforcement of an elastomer, and elastomer thus reinforced |
US10160823B2 (en) | 2013-06-26 | 2018-12-25 | Compagnie Industrielle De La Matiere Vegetale-Cimv | Phenolic resin obtained by polycondensation of formaldehyde, phenol and lignin |
Also Published As
Publication number | Publication date |
---|---|
ES2209424T3 (en) | 2004-06-16 |
DE69912007D1 (en) | 2003-11-13 |
DK1180171T3 (en) | 2004-02-16 |
US7402224B1 (en) | 2008-07-22 |
DE69912007T2 (en) | 2004-06-24 |
AU3528699A (en) | 2000-11-21 |
ATE251689T1 (en) | 2003-10-15 |
WO2000068494A1 (en) | 2000-11-16 |
EP1180171A1 (en) | 2002-02-20 |
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