EP0584675A1 - Délignification de bois à l'acide acétique avec addition d'acide formique - Google Patents
Délignification de bois à l'acide acétique avec addition d'acide formique Download PDFInfo
- Publication number
- EP0584675A1 EP0584675A1 EP93113002A EP93113002A EP0584675A1 EP 0584675 A1 EP0584675 A1 EP 0584675A1 EP 93113002 A EP93113002 A EP 93113002A EP 93113002 A EP93113002 A EP 93113002A EP 0584675 A1 EP0584675 A1 EP 0584675A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pulp
- digestion
- acetic acid
- lignocellulose
- acid
- 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.)
- Granted
Links
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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/003—Pulping cellulose-containing materials with organic compounds
Definitions
- the invention relates to a method for pulp production and bleached pulp and chemical pulp obtainable by this process. This procedure can also be used to obtain lignin and hemicelluloses.
- Formic acid has also been proposed as a means of digesting wood. So in one Two-stage process Wood chips treated with formic or acetic acid in the first stage and hydrogen peroxide added in the second stage and heated to 70 to 100 ° C. However, the amounts of hydrogen peroxide required for this are too high with regard to economical process management (Poppius et al., Paper and Timber 73 (2) 154-158 (1991).
- the object of the present invention is to provide a method for the production of cellulose, whereby cellulose with a significantly lower residual lignin is obtained.
- Wood or annual plants can be used as starting lignocelluloses.
- the digestion temperature is preferably between 130 and 190 ° C.
- the concentration of acetic acid in the digestion medium is preferably between 50 and 95% by weight, that of formic acid from 5 to 40% by weight and that of water below 50% by weight.
- the weight ratio of the lignocellulose to the digestion solution is preferably 1: 1 to 1:12.
- the method can also be used to obtain lignin and hemicelluloses from lignocelluloses.
- the process can be carried out continuously and batchwise, with the comminuted lignocellulose being introduced into a pressure cooker in the case of a continuous process is extracted in countercurrent from the digestion solution and on the other hand continuously leaves the digester in extracted form.
- 2 to 20 digestion vessels can be connected in series.
- the pulping of the pulp and the washing process of the pulp are included in the methods according to the invention.
- the lignocelluloses can be pre-extracted with a solvent to remove the ingredients, and acetic anhydride and bleaching agents can be added to the digestion solution.
- the lignocelluloses are impregnated with formic acid, acetic acid, acetic anhydride or their vapors before being introduced into the digestion vessel. The impregnation can also be carried out with a solvent or its vapors, which forms an aceotrope with water.
- the lignins and hemicelluloses which are also obtained with a high degree of purity, can be used, for example, for glue production.
- the process according to the invention has the advantage over the conventional processes for the production of cellulose that it does not use any inorganic pulping chemicals and therefore no SO2-containing waste gases or heavy metal-containing waste water are produced.
- the pulps can be bleached with ozone in acetic acid and / or hydrogen peroxide, whereby neither chlorine nor waste water containing heavy metals is formed.
- Formic and acetic acid are recovered by distillation, so that the lignin and the hemicelluloses do not need to be burned for chemical recovery.
- Another advantage is that the digestion temperature of about 10 ° C is lower than in the conventional methods, which significantly reduces energy costs.
- the pulp obtained according to the invention has a significantly lower residual lignin content and improved properties. From Table 1 it can be seen that the addition of 10% by weight of formic acid under otherwise similar pulping conditions results in a reduction in the Kappa number from 15.6 to 3.6, corresponding to a lignin content from 2.5 to 0.5, while the Yield drops only slightly.
- Tab. 1 compares the pulp properties after digestion (2h, 180 ° C, poplar and miscanthus 170 ° C) with 85% acetic acid and with 85% acetic acid and 10% formic acid.
- the strength properties of the pulps obtained with the addition of formic acid also increase significantly.
- Table 1 Acetic acid 85% Acetic acid 85% + formic acid 10% Spruce poplar Misc.
- GVZ mean the intrinsic viscosity according to Staudinger, DPW the degree of polymerization and R-10 the remaining pulp, which is insoluble in 10% NaOH.
- the increase in the R-10 values in connection with the low xylose and mannose contents also evident from table 1, means lower hemicellulose contents of the cellulose obtained with formic acid addition and thus its suitability as starting materials (chemical cellulose) for the production of cellulose derivatives.
- the process according to the invention offers advantages in particular in the production of cellulose acetate, because at the pre-swelling of the pulp in acetic acid before acetylation and an acetic acid recovery step are eliminated.
- the optimal formic acid concentration depends on the digestion temperature, the digestion time, the type of wood and the water content of the digestion medium. As can be seen from Table 2, at 190 ° C with 20% formic acid, the lignin condensation already prevails after 1 h, which is why in Table 1 a two-hour digestion with 10% formic acid was chosen at 180 and 170%.
- the acetic acid concentration in Tab. 2 is 85%.
- Formic acid increases the acidity of the digestion medium and thus the lignin breakdown, while the lignin condensation increases more slowly. Compared to mineral acids as catalysts, the selectivity of formic acid in lignin degradation appears to be increased. In addition, formic acid increases the solubility of the lignin in the exclusion medium.
- the chlorine-free bleaching of the cellulose obtained by the process according to the invention is fundamentally simplified compared to that of conventional cellulose.
- conventional bleaching usually uses five bleaching stages required with oxygen, peroxide, ozone, sodium hydroxide solution and possibly chlorine dioxide, two to three bleaching stages with small amounts of ozone in acetic acid and / or peracetic acid are sufficient for the bleaching of the process according to the invention.
- Spruce wood chips (20 x 35 x 5-6 mm) with a moisture content of 8% were poured with 6 times the amount by weight of 85% acetic acid, which contained 10% formic acid, and heated in a rotary autoclave at 180 ° C for 2 hours (heating time 40 min). Then part of the cooking liquor was evaporated to below 100 ° C., the fibrous material was pressed off on a suction filter and washed with 85% acetic acid. The filter cake was opened with a laboratory mixer in a large beaker under 85% acetic acid and suction filtered again. The pulp obtained was splinter-free and had the properties given in Table 1.
- the spruce pulp obtained with the addition of formic acid (Table 1) was washed on a suction filter with glacial acetic acid, pressed to a consistency of 35%, fluffed up in a coffee grinder for 30 seconds and then in a rotary flask on a rotary evaporator with a 3% ozone-oxygen mixture fumigated.
- the pulp was then washed on a suction filter first with water and then with a 0.2% peracetic acid solution in water, pressed to 15% consistency, heated at 80 ° C for 1 h and finally washed on the suction filter with water.
- the bleached spruce pulp has the properties shown in Table 3.
- Wood chips (80 x 20 x 5 mm) of a six-year-old poplar (Populus nigra from the clone "Rapp") with a moisture content of 10% were poured with six times the amount of 85% acetic acid, which contained 10% formic acid, and put in a rotary autoclave for two hours heated to 170 ° C.
- the pulp was worked up, defibred and washed as described in Example 1 for spruce pulp.
- the pulp properties are shown in Tab. 1.
- the pulp was bleached in two stages with peracetic acid, first with 0.7% in 6.6 parts of glacial acetic acid for 90 minutes at 80 ° C, and then with 1.3% peracetic acid in 6.6 parts of water for 120 minutes at 80 ° C .
- the properties of the bleached pulp are shown in Tab. 3.
- the pulp was bleached in two stages using peracetic acid, as described for poplar cellulose in Example 2.
- the properties of the bleached pulp can be found in Tab. 3.
- Spruce woodchips of the type specified in Example 1 were poured over with six times the amount of 85% acetic acid, which contained 5, 10, 15 or 20% formic acid in four batches, and were each heated to 190 ° C. in a rotary autoclave for 1 hour.
- the resulting pulps were worked up, defibred and washed in the same manner as in Example 1. After that, the pulps were splinter-free.
- Their residual lignin contents, degrees of whiteness and yields are shown in Table 2.
- Digestion solution acetic acid / water / formic acid (75:15:10) Temperature: 160-180 ° C Time: 1 - 2 h
- One cooker is sufficient for the test phase (batch process, 25 t of pulp / d), while 6 to 12 cookers are connected in series for production (semi-continuous process, maximum 300 t of pulp / d). Only by connecting several cookers in series is it possible to extract the wood chips according to the countercurrent principle with optimal use of the digestion solution.
- the wood chips are heated by pumping the digestion solution heated externally in heat exchangers.
- the first bleaching stage is carried out with 1 to 2% hydrogen peroxide in the cooker after the digestion has ended and the extract has been displaced by fresh digestion solution, 1 to 2 hours at 70 to 90 ° C.
- a uniform distribution of the H2O2 takes place by pumping around the bleaching solution, the composition of which, apart from the H2O2, does not differ from the digestion solution.
- the active agent is peracetic acid, the formation of which is catalyzed by the formic acid present.
- Sorting consists of post-defibrating (separation), rough sorting and cleaning.
- a slot sorter equipped with stirring arms, slot width about 0.4 mm, in the manner of a pipe centrifuge, and a hydrocyclone for cleaning are proposed.
- the diffuser (thickener) must be very effective in order to get from a consistency of about 1%, which is necessary for the sorting, to at least 8%, from which a consistency of about 40% for the ozone bleaching is achieved in a screw press got to.
- the cellulose washing takes place at the same time.
- a separate wash as in the conventional processes, is not necessary since no inorganic pulping chemicals have to be washed out and the pulp leaving the cooker hardly contains any lignin.
- the effectiveness of the sorting can be improved by several pipe centrifuges or cyclones connected in series.
- Ozone bleaching takes place in a rotary drum at 20 to 50 ° C and a consistency of about 40%, the residence time of the pulp should be at least 10 minutes, ozone amount about 0.5%, calculated on pulp. Because of the good solubility of the ozone in acetic acid, it is not necessary to fluff up the pulp.
- the pulp After ozone bleaching, the pulp still contains about 60% digestion solution, which is displaced in an extraction tower (2.0 ⁇ 10 m) with butyl acetate. Because the pulp swells more in acetic acid than in butyl acetate, there should be no clogging problems in the tower.
- the amount of butyl acetate that leaves the tower at the top together with the digestion solution should be about 60% of the dry weight of the pulp if the wood moisture content of the wood chips is 10%, because then in the subsequent distillation 20% water, based on the pulp weight, than Aceotropically with butyl acetate leaves the distillation column in the upper part. Under these conditions, the butyl acetate would completely leave the solution mixture as an aceotrope, while 2.5% water remained in the digestion solution, which flows back undistilled into the storage tank. Small amounts of extract substances, furfural etc. remain in the digestion solution and do not interfere with the digestion. A separation of the Formic acid from acetic acid by distillation is not required. Changes in the composition of the digestion solution (see under A.) must be compensated for by adding the component present in the deficit.
- the butyl acetate is exchanged for water with steam in a desolventizer.
- the consistency of the pulp is brought to about 40% by a screw press upstream of the desolventizer. Since the enthalpy of vaporization of the butyl acetate is only about 1/5 of that of the water, the pulp leaves the desolvent coating with 12% moisture and is then pressed in a press into sheets of 1 m2.
- the waste liquor leaving the stove contains 17% dissolved lignin and hemicelluloses. They are concentrated to a 50% thick liquor in a six-stage tube evaporator with a pressure gradient, using the heat of condensation of the evaporated digestion solution.
- the distillation column only serves to separate the water introduced with the chips from the digestion solution as an aceotrope with butyl acetate. After the water has been distilled off, the digestion solution flows undistilled into the storage tank.
- the capacity of the column depends on the wood chip moisture. If this is 10%, there are 200 kg of water per ton of pulp (together with approx 600 kg of butyl acetate).
- the digestion solution contains 15% water, 1.333 m3 of digestion solution + 0.6 m3 of butyl acetate would be required per ton of pulp. With a wood chips moisture of 20%, the amount doubles. It should therefore be considered whether the wood chips can be pre-dried, which would also be advantageous for the storage capacity of the wood chips. Drying the wood chips has no influence on the wood digestion using the Formacell process.
- All parts of the system that come into contact with the hot digestion solution must use steels that are corrosion-resistant to acetic acid / formic acid / water mixtures. This applies in particular to the cooker, the distillation column and the spray dryer.
- Tab. 4 compares the properties of unbleached spruce pulps obtained by the process according to the invention (Formacell process) with those of sulfate and acetosolv pulps.
- Table 4 Formacell sulfate Acetosolv Kappa number 3.6 30.6 15.6 Whiteness (% ISO) 28.0 24.8 20.3 GVZ (ml / g) 1179.5 902.2 1059.0 DP 3490 2470 3035 R-10 (%) 93.6 88.3 90.1 Yield (%) 46.8 47.4 49.0
- Formacell pulps are also suitable for the production of cellulose derivatives.
- Tab. 4 also shows the improvements of the Formacell process compared to the earlier Acetosolv process, which are mainly due to a significant improvement in delignification and an increase in whiteness.
- Fig. 1 shows a comparison of the strengths (tear length and tear strength) of Formacell and sulfate spruce pulp depending on the degree of grinding.
- Formacell spruce pulp While the tear length of Formacell spruce pulp is above the values of the sulfate pulp at all grades, the tear strength of the Formacell pulp is lower. Overall, the strength potential of the Formacell pulp is roughly comparable to that of the sulfate pulp.
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- Paper (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Processing Of Solid Wastes (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4228171 | 1992-08-25 | ||
DE4228171A DE4228171C2 (de) | 1992-08-25 | 1992-08-25 | Verfahren zur Gewinnung von Zellstoffen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0584675A1 true EP0584675A1 (fr) | 1994-03-02 |
EP0584675B1 EP0584675B1 (fr) | 1998-10-28 |
Family
ID=6466358
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93113002A Expired - Lifetime EP0584675B1 (fr) | 1992-08-25 | 1993-08-13 | Délignification de bois à l'acide acétique avec addition d'acide formique |
Country Status (8)
Country | Link |
---|---|
US (1) | US6139683A (fr) |
EP (1) | EP0584675B1 (fr) |
JP (1) | JP3348387B2 (fr) |
AT (1) | ATE172761T1 (fr) |
CA (1) | CA2104765A1 (fr) |
DE (2) | DE4228171C2 (fr) |
ES (1) | ES2123600T3 (fr) |
FI (1) | FI110695B (fr) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996035013A1 (fr) * | 1995-05-03 | 1996-11-07 | Sven Siegle | Procede de production de pulpe d'un materiau cellulosique, pulpe obtenue et son utilisation |
FR2770543A1 (fr) * | 1997-10-30 | 1999-05-07 | Michel Delmas | Procede de production de pate a papier, lignignes sucres et acide acetique par fractionnement de matiere vegetale lignocellulosique em milieu acide formique/acide acetique |
WO1999057364A1 (fr) * | 1998-05-05 | 1999-11-11 | Chempolis Oy | Procede de production de pate avec un melange d'acide formique et d'acide acetique utilise comme produit chimique de cuisson |
WO2000068494A1 (fr) * | 1999-05-06 | 2000-11-16 | Compagnie Industrielle Des Matieres Vegetales | Procede de production de pate a papier, lignines, sucres et acide acetique par fractionnement de matiere vegetale lignocellulosique en milieu acide formique/acide acetique |
WO2006117295A1 (fr) * | 2005-05-03 | 2006-11-09 | Compagnie Industrielle De La Matiere Vegetale | Installation permettant de mettre en oeuvre un procede de production de pulpe de papier, de lignines et de sucres et procede de production utilisant cette installation |
WO2008028183A1 (fr) * | 2006-09-01 | 2008-03-06 | Wisconsin Alumni Research Foundation | Procédé de production d'un panneau de fibres de moyenne densité |
WO2009092749A1 (fr) * | 2008-01-25 | 2009-07-30 | Compagnie Industrielle De La Matiere Vegetale Cimv | Procédé pour prétraiter un matériau lignocellulosique en vue de produire du bioéthanol, et procédé de production de bioéthanol |
EP2227590A1 (fr) * | 2007-11-16 | 2010-09-15 | JVS-Polymers Oy | Procédé et appareillage pour décomposer en continu des composants moléculaires de biomasse |
WO2011073284A1 (fr) * | 2009-12-18 | 2011-06-23 | Shell Internationale Research Maatschappij B.V. | Procédé pour l'extraction de sucres et de lignine à partir de biomasse solide comprenant de la lignocellulose |
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DE19856582C1 (de) * | 1998-12-08 | 2001-03-15 | Rhodia Acetow Ag | Verfahren zur Gewinnung von Chemiezellstoff aus Hackschnitzeln |
PT1238141E (pt) | 1999-10-15 | 2006-05-31 | Cargill Inc | Fibras de sementes de plantas e seu uso |
DE10057878A1 (de) * | 2000-11-21 | 2003-02-27 | Natural Pulping Ag I Ins | Verfahren zur Herstellung einer Pulpe aus cellulosehaltigem Material |
FI117633B (fi) * | 2000-12-29 | 2006-12-29 | Chempolis Oy | Kemikaalien talteenotto ja valmistus massan valmistuksen yhteydessä |
FI117632B (fi) * | 2001-07-13 | 2006-12-29 | Chempolis Oy | Menetelmä massan valmistamiseksi |
US20040118536A1 (en) * | 2002-12-20 | 2004-06-24 | Kimberly-Clark Worldwide, Inc. | Process for manufacturing a cellulosic paper product exhibiting reduced malodor |
AU2003904323A0 (en) * | 2003-08-13 | 2003-08-28 | Viridian Chemical Pty Ltd | Solvents based on salts of aryl acids |
FI121811B (fi) * | 2007-06-01 | 2011-04-29 | Upm Kymmene Corp | Uudet dispersiot ja menetelmä niiden valmistamiseksi |
DE102007036382A1 (de) * | 2007-07-31 | 2009-02-05 | Voith Patent Gmbh | Lignocellulosischer Faserstoff aus Einjahrespflanzen |
AU2015203453B2 (en) * | 2008-06-23 | 2016-09-22 | Compagnie Industrielle De La Matiere Vegetale Cimv | Method For Pretreating Plant Starting Material For The Production, From Sacchariferous And Lignocellulosic Resources, Of Bioethanol And Of Sugar, And Plant |
FR2932815B1 (fr) * | 2008-06-23 | 2015-10-30 | Cie Ind De La Matiere Vegetale Cimv | Procede de pretraitement de la matiere premiere vegetale pour la production, a partir de ressources sacchariferes et lignocellulosiques, de bioethanol et/ou de sucre, et installation. |
US8608970B2 (en) | 2010-07-23 | 2013-12-17 | Red Shield Acquisition, LLC | System and method for conditioning a hardwood pulp liquid hydrolysate |
US9228243B2 (en) | 2011-08-24 | 2016-01-05 | Red Shield Acquistion, LLC | System and method for conditioning a hardwood pulp liquid hydrolysate |
CN103131017B (zh) * | 2011-11-22 | 2016-03-16 | 济南圣泉集团股份有限公司 | 一种从木质纤维素生物质中提取木质素的工艺 |
CA2870829A1 (fr) * | 2012-04-26 | 2013-10-31 | Archer Daniels Midland Company | Separation liquide/liquide de biomasse lignocellulosique pour produire des sirops de sucre et des fractions de lignine |
CN103031764B (zh) * | 2012-12-25 | 2015-01-14 | 济南圣泉集团股份有限公司 | 一种由生物质原料制备纸浆并联产生物碳的方法 |
CN103898783B (zh) * | 2012-12-25 | 2016-02-10 | 济南圣泉集团股份有限公司 | 一种由生物质原料制备纸浆的工艺 |
CN103898784B (zh) * | 2012-12-25 | 2016-02-10 | 济南圣泉集团股份有限公司 | 一种生物质原料的综合利用工艺 |
JP6260947B2 (ja) * | 2013-04-30 | 2018-01-17 | 公立大学法人秋田県立大学 | 蛍光色素 |
CN112127192A (zh) * | 2019-06-24 | 2020-12-25 | 广州腾龙材料科技有限公司 | 复合脱色碱式增白剂及其制备方法与应用 |
CN112080015B (zh) * | 2020-09-22 | 2022-06-03 | 南京林业大学 | 一种高糖基高酰化高缩合型木质素及其制备方法与应用 |
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US3553076A (en) * | 1968-01-22 | 1971-01-05 | Weyerhaeuser Co | Non-catalytic process for the production of cellulose from lignocellulosic materials using acetic acid |
DE3830993A1 (de) * | 1987-09-14 | 1989-04-06 | Shell Int Research | Verfahren zum aufschliessen lignozellulosehaltigen materials |
WO1991018864A1 (fr) * | 1990-05-29 | 1991-12-12 | Kemira Oy | Procede de recuperation d'un acide aliphatique inferieur |
EP0503304A1 (fr) * | 1991-03-08 | 1992-09-16 | Acetocell GmbH & Co. KG | Procédé pour la délignification de matière première contenant de la cellulose |
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GB579669A (en) * | 1943-11-05 | 1946-08-12 | Stanley Charles Bate | Improvements in or relating to the production of cellulose |
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SU821614A1 (ru) * | 1979-06-19 | 1981-04-15 | Белорусский Технологический Институт Им.C.M.Кирова | Способ получени целлюлозного полу-фАбРиКАТА |
WO1982001902A1 (fr) * | 1980-12-05 | 1982-06-10 | Robert K Jordan | Pulpage a l'acide formique |
DE3445132A1 (de) * | 1984-12-11 | 1986-06-12 | Nimz, Horst H., Prof.Dr., 2050 Hamburg | Holzaufschluss mit essigsaeure |
ES2041828T3 (es) * | 1988-01-25 | 1993-12-01 | Acetocell Gmbh & Co. Kg | Procedimiento para el tratamiento de masa de celulosa conteniendo lignina, con ozono. |
EP0325891A1 (fr) * | 1988-01-25 | 1989-08-02 | Kunz Holding Gmbh & Co. Kg | Procédé pour obtenir une pâte de cellulose blanchie |
EP0485150A1 (fr) * | 1990-11-06 | 1992-05-13 | Biodyne Chemical Inc. | Procédés de lessivage, extraction de lignine et composition pour ces procédés |
DE4107354C1 (fr) * | 1991-03-08 | 1992-11-05 | Acetocell Gmbh & Co Kg, 7162 Gschwend, De |
-
1992
- 1992-08-25 DE DE4228171A patent/DE4228171C2/de not_active Expired - Fee Related
-
1993
- 1993-08-13 ES ES93113002T patent/ES2123600T3/es not_active Expired - Lifetime
- 1993-08-13 EP EP93113002A patent/EP0584675B1/fr not_active Expired - Lifetime
- 1993-08-13 DE DE59309094T patent/DE59309094D1/de not_active Expired - Fee Related
- 1993-08-13 AT AT93113002T patent/ATE172761T1/de not_active IP Right Cessation
- 1993-08-24 JP JP23103793A patent/JP3348387B2/ja not_active Expired - Fee Related
- 1993-08-24 CA CA002104765A patent/CA2104765A1/fr not_active Abandoned
- 1993-08-25 FI FI933729A patent/FI110695B/fi not_active IP Right Cessation
-
1995
- 1995-10-06 US US08/540,571 patent/US6139683A/en not_active Expired - Fee Related
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US2730444A (en) * | 1950-10-10 | 1956-01-10 | British Celanese | Production of cellulose |
US3553076A (en) * | 1968-01-22 | 1971-01-05 | Weyerhaeuser Co | Non-catalytic process for the production of cellulose from lignocellulosic materials using acetic acid |
DE3830993A1 (de) * | 1987-09-14 | 1989-04-06 | Shell Int Research | Verfahren zum aufschliessen lignozellulosehaltigen materials |
WO1991018864A1 (fr) * | 1990-05-29 | 1991-12-12 | Kemira Oy | Procede de recuperation d'un acide aliphatique inferieur |
EP0503304A1 (fr) * | 1991-03-08 | 1992-09-16 | Acetocell GmbH & Co. KG | Procédé pour la délignification de matière première contenant de la cellulose |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6183597B1 (en) | 1995-05-03 | 2001-02-06 | Natural Pulping Ag | Method of producing a pulp from cellulosic material using formic acid and hydrogen peroxide |
WO1996035013A1 (fr) * | 1995-05-03 | 1996-11-07 | Sven Siegle | Procede de production de pulpe d'un materiau cellulosique, pulpe obtenue et son utilisation |
FR2770543A1 (fr) * | 1997-10-30 | 1999-05-07 | Michel Delmas | Procede de production de pate a papier, lignignes sucres et acide acetique par fractionnement de matiere vegetale lignocellulosique em milieu acide formique/acide acetique |
WO1999057364A1 (fr) * | 1998-05-05 | 1999-11-11 | Chempolis Oy | Procede de production de pate avec un melange d'acide formique et d'acide acetique utilise comme produit chimique de cuisson |
US6562191B1 (en) | 1998-05-05 | 2003-05-13 | Chempolis Oy | Process for producing pulp with a mixture of formic acid and acetic acid as cooking chemical |
US7402224B1 (en) | 1999-05-06 | 2008-07-22 | Compagnie Industrielle De La Matiere Vegetale | Method for producing paper pulp, lignins, sugars and acetic acid by frantionation of lignocellulosic vegetable material in formic/acetic acid medium |
WO2000068494A1 (fr) * | 1999-05-06 | 2000-11-16 | Compagnie Industrielle Des Matieres Vegetales | Procede de production de pate a papier, lignines, sucres et acide acetique par fractionnement de matiere vegetale lignocellulosique en milieu acide formique/acide acetique |
EA012118B1 (ru) * | 2005-05-03 | 2009-08-28 | Компани Эндюстриель Де Ля Матьер Вежеталь | Установка для осуществления способа получения целлюлозы для производства бумаги, лигнинов и сахаров и способ получения, в котором используется такая установка |
FR2885371A1 (fr) * | 2005-05-03 | 2006-11-10 | Cie Ind De La Matiere Vegetale | Installation pour la mise en oeuvre d'un procede de production de pate a papier, de lignines et de sucres et procede de production au moyen d'une telle installation |
WO2006117295A1 (fr) * | 2005-05-03 | 2006-11-09 | Compagnie Industrielle De La Matiere Vegetale | Installation permettant de mettre en oeuvre un procede de production de pulpe de papier, de lignines et de sucres et procede de production utilisant cette installation |
US8157964B2 (en) | 2005-05-03 | 2012-04-17 | Compagnie Industrielle De La Matiere Vegetale | Installation for implementing a method for producing paper pulp, lignins and sugars and production method using such an installation |
AU2006243234B2 (en) * | 2005-05-03 | 2010-10-28 | Compagnie Industrielle De La Matiere Vegetale | Installation for implementing a method for producing paper pulp, lignins and sugars and production method using such an installation |
WO2008028183A1 (fr) * | 2006-09-01 | 2008-03-06 | Wisconsin Alumni Research Foundation | Procédé de production d'un panneau de fibres de moyenne densité |
US8123904B2 (en) | 2006-09-01 | 2012-02-28 | Wisconsin Alumni Research Foundation | Method of making medium density fiberboard |
EP2227590A4 (fr) * | 2007-11-16 | 2012-01-25 | Jvs Polymers Oy | Procédé et appareillage pour décomposer en continu des composants moléculaires de biomasse |
EP2227590A1 (fr) * | 2007-11-16 | 2010-09-15 | JVS-Polymers Oy | Procédé et appareillage pour décomposer en continu des composants moléculaires de biomasse |
WO2009092749A1 (fr) * | 2008-01-25 | 2009-07-30 | Compagnie Industrielle De La Matiere Vegetale Cimv | Procédé pour prétraiter un matériau lignocellulosique en vue de produire du bioéthanol, et procédé de production de bioéthanol |
FR2926824A1 (fr) * | 2008-01-25 | 2009-07-31 | Cie Ind De La Matiere Vegetale | Procede de pretraitement d'une matiere vegetale lignocellulosique en vue de la production de bioethanol. |
US8551747B2 (en) | 2008-01-25 | 2013-10-08 | Campagnie Industrielle de la Matiere Vegetale CIMV | Process for producing bioethanol from lignocellulosic plant raw material |
EA019155B1 (ru) * | 2008-01-25 | 2014-01-30 | Компани Эндюстриель Де Ля Матьер Вежеталь Кэмв | Способ получения биоэтанола из лигноцеллюлозного растительного исходного материала |
WO2011073284A1 (fr) * | 2009-12-18 | 2011-06-23 | Shell Internationale Research Maatschappij B.V. | Procédé pour l'extraction de sucres et de lignine à partir de biomasse solide comprenant de la lignocellulose |
Also Published As
Publication number | Publication date |
---|---|
US6139683A (en) | 2000-10-31 |
CA2104765A1 (fr) | 1994-02-26 |
FI933729A (fi) | 1994-02-26 |
ES2123600T3 (es) | 1999-01-16 |
DE4228171A1 (de) | 1994-03-03 |
FI933729A0 (fi) | 1993-08-25 |
FI110695B (fi) | 2003-03-14 |
DE59309094D1 (de) | 1998-12-03 |
EP0584675B1 (fr) | 1998-10-28 |
JPH06322682A (ja) | 1994-11-22 |
JP3348387B2 (ja) | 2002-11-20 |
DE4228171C2 (de) | 1995-06-14 |
ATE172761T1 (de) | 1998-11-15 |
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