EP0584675B1 - Holzaufschluss mit Essigsäure unter Zusatz von Ameisensäuren - Google Patents
Holzaufschluss mit Essigsäure unter Zusatz von Ameisensäuren Download PDFInfo
- Publication number
- EP0584675B1 EP0584675B1 EP93113002A EP93113002A EP0584675B1 EP 0584675 B1 EP0584675 B1 EP 0584675B1 EP 93113002 A EP93113002 A EP 93113002A EP 93113002 A EP93113002 A EP 93113002A EP 0584675 B1 EP0584675 B1 EP 0584675B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- accordance
- acetic acid
- pulp
- lignocellulose
- pulping
- 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.)
- Expired - Lifetime
Links
Images
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 obtainable by this process Pulp and chemical pulp. With this procedure you can lignin and hemicelluloses can also be obtained.
- Formic acid has also been proposed as a means of digesting wood.
- wood chips were treated with formic or acetic acid in the first stage and hydrogen peroxide was added in the second stage and heated to 70 to 100 ° C.
- hydrogen peroxide was added in the second stage and heated to 70 to 100 ° C.
- 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).
- DE-A-38 30 993 relates to a method for Digestion of lignocellulose-containing material, which as a digestion medium according to a preferred Embodiment at least 90% by weight of a Contains solvent system, this 30 to 45% by weight of formic acid, 5 to 15% by weight of methanol or Includes ethanol and 40 to 60 wt% acetic acid.
- a Contains solvent system this 30 to 45% by weight of formic acid, 5 to 15% by weight of methanol or Includes ethanol and 40 to 60 wt% acetic acid.
- an alcohol is a mandatory component this digestion medium. This method enables low Kappa numbers, but requires facilities for Recovery of the alcohol used.
- the object of the invention is therefore a method for To provide pulp production, which on the one hand Enables pulps with significantly low residual lignin, on the other hand, however, with regard to its components is simply designed that the recovery of Alcohols can be avoided.
- This task is solved by a procedure for Obtaining pulp, lignin and hemicelluloses from Lignocelluloses by heating to 130 to 190 ° C below Pressure in one of primary alcohols and esters of Free formic acid with primary alcohols Digestion medium, the digestion medium consisting of 50 to 95 % By weight of acetic acid, 5 to 40% by weight of formic acid and up to Contains 45% by weight of water.
- Wood or annual plants can be used as starting lignocelluloses are used, preferably the Digestion temperature between 180 and 190 ° C.
- the concentration the 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 for the digestion solution is preferably 1: 1 to 1:12.
- the method can also for the extraction of lignin and hemicelluloses Lignocelluloses are used.
- the procedure can be done continuously and discontinuously, wherein in the case of a continuous process, the shredded lignocellulose entered in a pressure cooker by countercurrent of the digestion solution is extracted and the stove on the other side in leaves extra form continuously. You can for example 2 to 20 digestion vessels in a row be scolded.
- the Pulping and pulp washing process included in the methods of the invention can be used to remove the ingredients pre-extracted with a solvent and the digestion solution can add acetic anhydride and bleach will.
- the lignocelluloses are entered into the Digestion vessel with formic acid, acetic acid, acetic anhydride or impregnated their vapors. The impregnation can also with a solvent or its vapors, that forms an aceotrope with water.
- Lignins and hemicelluloses can be used, for example, to make glue be used.
- 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 SO 2 -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 is obtained by extracting it in countercurrent from the digestion solution and continuously leaving the cooker on the other side in extracted form.
- 2 to 20 digestion vessels can be connected in series.
- the Pulping and pulp washing process included in the methods of the invention can be used to remove the ingredients pre-extracted with a solvent and the digestion solution can add acetic anhydride and bleach will.
- the lignocelluloses are entered into the Digestion vessel with formic acid, acetic acid, acetic anhydride or impregnated their vapors. The impregnation can also with a solvent or its vapors, that forms an aceotrope with water,
- Lignins and hemicelluloses can be used, for example, to make glue be used.
- 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 SO 2 -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 acids are recovered by distillation so that the lignin and 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 one lower residual lignin content and improved properties.
- Table 1 shows that the addition of 10% by weight Formic acid under otherwise the same digestion conditions in spruce pulp a reduction in the kappa number of 15.6 to 3.6, corresponding to a lignin content of 2.5 0.5 causes, 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.
- Acetic acid 85% Acetic acid 85% + formic acid 10% Spruce poplar Misc. Spruce poplar Misc.
- GVZ mean the intrinsic viscosity Staudinger, DPW the degree of polymerization and R-10 the rest Pulp that is insoluble in 10% Na0H.
- the increase in R-10 values also evident from Table 1 in connection with the low xylose and mannose contents means lower hemicellulose levels with the addition of formic acid cellulose obtained and thus its suitability as starting materials (Chemical pulps) for the production of cellulose derivatives.
- the method according to the invention offers in particular Advantages in the production of cellulose acetate because the pre-swelling of the pulp in acetic acid before acetylation as well as an acetic acid recovery stage 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 condensations slow down increase. Compared to mineral acids appears as catalysts the selectivity of formic acid increases during lignin degradation. Formic acid also increases the solubility of Lignins in the exclusion medium.
- cellulose obtained is compared to that of conventional cellulose fundamentally simplified. While with the conventional Today, cellulose bleaching usually has five bleaching stages with oxygen, peroxide, ozone, sodium hydroxide solution and possibly chlorine dioxide are required for the bleaching of the process according to the invention two to three bleaching stages with small amounts of ozone in Acetic acid and / or peracetic acid sufficient.
- Spruce wood chips (20 ⁇ 35 ⁇ 5-6 mm) with a moisture content of 8% were with 6 times the amount by weight Poured 85% acetic acid containing 10% formic acid and heated in a rotary autoclave to 180 ° C for 2 hours (heating up time 40 min). Thereafter, by evaporating part of the Cooking liquor cooled to below 100 ° C, the pulp on a Nutsche squeezed out and washed with 85% acetic acid. Of the Filter cake was placed in a large beaker with a laboratory mixer whipped under 85% acetic acid and suction filtered again. The pulp obtained was splinter-free and had the properties specified in Table 1.
- the spruce pulp obtained with the addition of formic acid was washed on a nutsche with glacial acetic acid, to a consistency pressed from 35%, fluffed up in a coffee grinder for 30 seconds and then in a round bottom flask on a rotary evaporator gassed with a 3% ozone-oxygen mixture. After that the pulp was first washed with water and on a suction filter then washed with a 0.2% peracetic acid solution in water, pressed to 15% consistency, heated at 80 ° C for 1 h and finally washed with water on the suction filter.
- the bleached spruce pulp has the specified in Table 3 Characteristics.
- Wood chips (80 ⁇ 20 ⁇ 5 mm) of a six-year-old poplar (Populus nigra from the clone "Rapp") with a moisture content of 10% was mixed with six times the amount of an 85% acetic acid, which contained 10% formic acid, poured over and two Heated to 170 ° C in a rotary autoclave.
- the processing, The pulp was defibrated and washed as in Example 1 described 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 min 80 ° C, and then with 1.3% peracetic acid in 6.6 parts of water 120 min at 80 ° C.
- the properties of the bleached pulp are shown in Tab. 3.
- the pulp was bleached in two stages with peracetic acid, as described for poplar cellulose under 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 pulp obtained was worked up, defibred and washed in the same manner as in Example 1.
- the pulps were then free from splinters. Their residual lignin contents, degrees of whiteness and yields are shown in Table 2.
- a cooker is sufficient for the test phase (batch process, 25 t pulp / d) while for production 6 to 12 cookers can be connected in series (semi-continuous Process, maximum 300 t of pulp / d). Only by connecting several cookers in series an extraction of the wood chips according to the countercurrent principle possible 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.
- the H 2 O 2 is evenly distributed by pumping around the bleaching solution, the composition of which, with the exception of the H 2 O 2 , does not differ from the digestion solution.
- the active agent is peracetic acid, the formation of which is catalyzed by the formic acid present.
- the sorting consists of a post-defibrillation (separation), Rough sorting and cleaning.
- a mixing arm Slot sorter slot width about 0.4 mm, like a Pipe centrifuge and a hydrocyclone for cleaning suggested.
- the diffuser (thickener) must be very effective to be of a consistency of about 1%, which for the Sorting is required to come to at least 8% from which a consistency of about in a screw press 40% for ozone bleaching must be achieved.
- the cellulose washing takes place at the same time.
- a separate wash as with the conventional processes, is not necessary as no inorganic Digestion chemicals are to be washed out and the cooker leaving pulp hardly contains any lignin.
- the effectiveness the sorting can be done in series Improve pipe centrifugation or cyclones.
- 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. Way of the good Solubility of the ozone in acetic acid is a puffing up of the pulp is not required.
- Oxygen-ozone mixtures is explosion-proof Execution of the rotating drum required.
- the exhaust gases should be in a loop or a closed system being held.
- Ozone discharged with the pulp decomposes within a certain time.
- the pulp After ozone bleaching, the pulp still contains about 60% Digestion solution in an extraction tower (2.0 ⁇ 10 m) is displaced with butyl acetate. Because the swelling of the pulp in acetic acid is stronger than in butyl acetate, should be in the tower there are no constipation problems.
- the amount of butylacetate together with the digestion solution leaves the tower at the head should be about 60% of the dry weight of the pulp if the Wood moisture of the wood chips is 10% because then the subsequent distillation 20% water, based on Pulp weight as the aceotrope with butyl acetate Distillation column leaves in the upper part. Under these The butyl acetate would condition the mixed solution leave completely as an aceotrope while still 2.5% water remain in the digestion solution, which is undistilled flows back into the storage tank. Small amounts of Extract substances, furfural etc. remain in the digestion solution and do not disturb the information. A separation of the Formic acid is from acetic acid by distillation not mandatory. Changes in the composition of the digestion solution (see under A.) are by adding the in Compensate deficit existing component.
- 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 that of water, the pulp leaves the desolvent coating with 12% moisture and is then pressed in a press into sheets of 1 m 2 .
- the waste liquor leaving the stove contains 17% dissolved Lignin and hemicelluloses. Your focus on one 50% thick liquor takes place in a six-stage tube evaporator with pressure drop using the heat of condensation the vaporized digestion solution.
- the distillation column only serves to separate the with the chips of water entered from the digestion solution as an aceotrope with butyl acetate. After distillation the digestion solution flows undistilled into the storage tank. The capacity of the column is directed after the wood chips moisture. If this is 10%, so 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 m 3 of digestion solution + 0.6 m 3 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.
- 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.
- Formacell pulps are suitable for their high R10 value also for the production of cellulose derivatives.
- Tab. 4 also shows the improvements to the Formacell process compared to the previous Acetosolv process, which especially in a significant improvement in Delignification and increase in whiteness.
- Fig. 1 shows a comparison of the strengths (tear length and tear resistance) of Formacell and sulfate spruce pulp depending on the degree of grinding.
Landscapes
- 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)
Description
Essigsäure 85 % | Essigsäure 85 % + Ameisensäure 10 % | |||||
Fichte | Pappel | Misc. | Fichte | Pappel | Misc. | |
Kappazahl | 15,6 | 9,2 | 13,3 | 3,6 | 3,1 | 3,2 |
Ausbeute (%) | 49,0 | 50,1 | 48,5 | 46,8 | 50,3 | 48,2 |
Weißgrad (% ISO) | 20,3 | 20,0 | 25,9 | 28,0 | 34,7 | 33,8 |
GVZ (ml/g) | 1050,0 | 1005,0 | 1022,0 | 1179,0 | 849,5 | 1012,0 |
DPW | 3035,0 | 2850,0 | 2910,0 | 3490,0 | 2430,0 | 2870,0 |
Durchreißf. (cN) | 59,1 | 31,1 | 51,5 | 77,1 | 42,7 | 90,4 |
Berstfläche (m2) | 62,9 | 31,4 | 24,6 | 70,9 | 38,0 | 43,9 |
Reißlänge (km) | 10,3 | 7,5 | 5,2 | 11,4 | 7,3 | 8,1 |
R-10 (%) | 90,1 | 85,8 | 88,5 | 93,6 | 89,4 | 91,0 |
Mannose (%) | - | 2,3 | - | 0,5 | 1,2 | 0,2 |
Xylose (%) | - | 5,4 | - | 1,5 | 2,4 | 3,3 |
Glucose (%) | - | 92,3 | - | 94,2 | 93,5 | 96,2 |
Temperatur (°C) | 190 | 180 | 170 | |||||||||
Ameisensäure (%) | 5 | 10 | 15 | 20 | 5 | 10 | 15 | 20 | 5 | 10 | 15 | 20 |
Kappazahl | 7,2 | 5,3 | 5,6 | 14,6 | 14,5 | 11,2 | 7,8 | 7,1 | 39,9 | 25,4 | 14,5 | 7,1 |
Weißgrad (% ISO) | 27,9 | 29,9 | 28,7 | 24,4 | 22,6 | 25,8 | 26,3 | 27,0 | 19,8 | 22,5 | 24,6 | 27,6 |
Ausbeute (%) | 46,3 | 43,6 | 42,2 | 42,2 | 49,2 | 48,0 | 46,6 | 45,3 | 54,8 | 50,3 | 47,0 | 46,6 |
Eigenschaften der mit Ozon (Z) und Peressigsäure (Pa) gebleichten Zellstoffe beim Mahlgrad 20 SR | ||||||
Zellstoff | Bleichmittel | Menge (%) | Weißgrad (% ISO) | Reißlänge (km) | Berstfläche (m2) | Durchreißf. (cN) |
Fichte | Z/Pa | 0,6/1,3 | 84,3 | 9,315 | 52,5 | 76,7 |
Pa/Pa | 0,7/1,3 | 72,1 | 9,113 | 50,3 | 79,1 | |
Pappel | Pa/Pa | 0,7/1,3 | 83,4 | 6,68 | 28,8 | 46,0 |
Miscanthus | Pa/Pa | 0,7/1,3 | 83,0 | 6,933 | 35,6 | 89,6 |
Formacell | Sulfat | Acetosolv | |
Kappazahl | 3,6 | 30,6 | 15,6 |
Weißgrad (% 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 |
Ausbeute (%) | 46,8 | 47,4 | 49,0 |
Eigenschaften von Miscanthus-Zellstoffen, die nach drei verschiedenen Verfahren erhalten wurden | |||
Formacell | Soda | Acetosolv | |
Kappazahl | 3,2 | 27,2 | 13,2 |
Weißgrad (% ISO) | 33,8 | 26,6 | 25,9 |
GVZ (ml/g) | 1012 | 1010 | 1022,5 |
DP | 2870 | 2870 | 2910 |
R-10 | 91,0 | -- | 88,5 |
Ausbeute (%) | 48,2 | 54,6 | 48,5 |
Durchrf. (cN) | 90,4 | 63,2 | 51,5 |
Berstfl. (m2) | 43,9 | 41,2 | 24,6 |
Reißlänge (km) | 8,1 | 7,08 | 5,2 |
Claims (14)
- Verfahren zur Gewinnung von Zellstoffen, Lignin und Hemicellulosen aus Lignocellulosen durch Erhitzen auf 130 bis 190 °C unter Druck in einem von primären Alkoholen und Estern der Ameisensäure mit primären Alkoholen freien Aufschlußmedium, dadurch gekennzeichnet, daß das Aufschlußmedium 50 bis 95 Gew.% Essigsäure, 5 bis 40 Gew.% Ameisensäure und bis zu 45 Gew.% Wasser enthält.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Lignocellulose Holz oder eine Einjahrespflanze ist.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Feuchtgehalt der Lignocellulose durch eine Vorbehandlung bei erhöhter Temperatur oder durch Lösungsmitteldämpfe reduziert werden kann.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Gewichtsverhältnis der Lignocellulose zur Aufschlußlösung 1 : 1 bis 1 : 12 beträgt.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die zerkleinerte Lignocellulose kontinuierlich in einen Druckkocher eingetragen wird, in dem sie im Gegenstrom von der Aufschlußlösung extrahiert wird und den Kocher auf der anderen Seite in extrahierter Form kontinuierlich verläßt.
- Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß eine kontinuierliche Extraktion dadurch erreicht wird, daß 2 bis 20 Aufschlußgefäße hintereinandergeschaltet sind und die Aufschlußlösung die Lignocellulose im Gegenstrom extrahiert.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Zerfaserung des Zellstoffes eingeschlossen ist.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Waschprozeß des Zellstoffes in die kontinuierliche Extraktion eingeschlossen ist.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Lignocellulose mit einem Lösungsmittel zur Entfernung der Inhaltsstoffe vorextrahiert wird.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Aufschlußlösung Acetanhydrid zugegeben wird.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Aufschlußlösung ein Bleichmittel zugegeben wird.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Lignocellulose vor der Eingabe in das Aufschlußgefäß mit Ameisensäure, Essigsäure, Essigsäureanhydrid oder deren Dämpfen imprägniert wird.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Lignocellulose mit einem Lösungsmittel oder dessen Dämpfen imprägniert wird, das mit Wasser ein Aceotrop bildet.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Bleichen des Zellstoffs eingeschlossen ist.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4228171A DE4228171C2 (de) | 1992-08-25 | 1992-08-25 | Verfahren zur Gewinnung von Zellstoffen |
DE4228171 | 1992-08-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0584675A1 EP0584675A1 (de) | 1994-03-02 |
EP0584675B1 true EP0584675B1 (de) | 1998-10-28 |
Family
ID=6466358
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93113002A Expired - Lifetime EP0584675B1 (de) | 1992-08-25 | 1993-08-13 | Holzaufschluss mit Essigsäure unter Zusatz von Ameisensäuren |
Country Status (8)
Country | Link |
---|---|
US (1) | US6139683A (de) |
EP (1) | EP0584675B1 (de) |
JP (1) | JP3348387B2 (de) |
AT (1) | ATE172761T1 (de) |
CA (1) | CA2104765A1 (de) |
DE (2) | DE4228171C2 (de) |
ES (1) | ES2123600T3 (de) |
FI (1) | FI110695B (de) |
Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19516151A1 (de) | 1995-05-03 | 1996-11-07 | Sven Siegle | Verfahren zur Herstellung einer Pulpe aus zellulosehaltigem Material, die Pulpe selbst und deren Verwendung |
FR2770543B1 (fr) * | 1997-10-30 | 2000-05-05 | 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 |
FI116390B (fi) | 1998-05-05 | 2005-11-15 | Chempolis Oy | Menetelmä massan valmistamiseksi |
DE19856582C1 (de) * | 1998-12-08 | 2001-03-15 | Rhodia Acetow Ag | Verfahren zur Gewinnung von Chemiezellstoff aus Hackschnitzeln |
ES2209424T3 (es) * | 1999-05-06 | 2004-06-16 | Compagnie Industrielle De La Matiere Vegetale | Procedimiento de produccion de pasta de papel, ligninas, azucares y acido acetico mediante funcionamiento de material vegetal lignocelulosico en un medio de acido acetico/formico. |
TR200202805T2 (tr) * | 1999-10-15 | 2003-03-21 | Cargill Incorporated | Bitki tohumlarından yapılan fiberler ve kullanımları |
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 |
FR2885371B1 (fr) * | 2005-05-03 | 2007-08-03 | 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 |
US20080264588A1 (en) * | 2006-09-01 | 2008-10-30 | Masood Akhtar | Method of Making Medium Density Fiberboard |
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 |
FI123165B (fi) * | 2007-11-16 | 2012-11-30 | Jvs Polymers Oy | Menetelmä ja laitteisto jatkuvatoimiseksi biomassan molekyylien pilkkomiseksi |
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. |
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. |
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 |
BR112012014978A2 (pt) * | 2009-12-18 | 2016-04-05 | Shell Int Research | processo para a extração de açucares e/ou lignina de biomassa sólida compreendendo lignocelulose |
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 |
CN104245946A (zh) * | 2012-04-26 | 2014-12-24 | 阿彻丹尼尔斯米德兰德公司 | 用于制造糖浆和木质素部分的木质纤维素生物质的液体/液体分离 |
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 |
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 |
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 |
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 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB579669A (en) * | 1943-11-05 | 1946-08-12 | Stanley Charles Bate | Improvements in or relating to the production of cellulose |
US2601408A (en) * | 1947-08-29 | 1952-06-24 | Celanese Corp | Two-step digestion of wood with aliphatic acid |
US2645633A (en) * | 1949-11-14 | 1953-07-14 | Masonite Corp | Process for extraction of lignin |
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 |
SU821614A1 (ru) * | 1979-06-19 | 1981-04-15 | Белорусский Технологический Институт Им.C.M.Кирова | Способ получени целлюлозного полу-фАбРиКАТА |
EP0065984A1 (de) * | 1980-12-05 | 1982-12-08 | JORDAN, Robert K. | Pulpierung in ameisensäure |
DE3445132A1 (de) * | 1984-12-11 | 1986-06-12 | Nimz, Horst H., Prof.Dr., 2050 Hamburg | Holzaufschluss mit essigsaeure |
GB8721528D0 (en) * | 1987-09-14 | 1987-10-21 | Shell Int Research | Pulping lignocellulose-containing material |
EP0325890B1 (de) * | 1988-01-25 | 1993-06-09 | Acetocell GmbH & Co. KG | Verfahren zur Behandlung von Lignin enthaltender Cellulosemasse mit Ozon |
EP0325891A1 (de) * | 1988-01-25 | 1989-08-02 | Kunz Holding Gmbh & Co. Kg | Verfahren zur Gewinnung von gebleichtem Zellstoff |
FI85510C (fi) * | 1990-05-29 | 1992-04-27 | Kemira Oy | Foerfarande foer aotervinning av laegre alifatisk syra. |
EP0485150A1 (de) * | 1990-11-06 | 1992-05-13 | Biodyne Chemical Inc. | Aufschlussverfahren, Gewinnung von Lignin und Zusammensetzung daraus |
DE4107357C1 (de) * | 1991-03-08 | 1992-11-05 | Acetocell Gmbh & Co Kg, 7162 Gschwend, De | |
DE4107354C1 (de) * | 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 AT AT93113002T patent/ATE172761T1/de not_active IP Right Cessation
- 1993-08-13 EP EP93113002A patent/EP0584675B1/de not_active Expired - Lifetime
- 1993-08-13 ES ES93113002T patent/ES2123600T3/es not_active Expired - Lifetime
- 1993-08-13 DE DE59309094T patent/DE59309094D1/de not_active Expired - Fee Related
- 1993-08-24 CA CA002104765A patent/CA2104765A1/en not_active Abandoned
- 1993-08-24 JP JP23103793A patent/JP3348387B2/ja not_active Expired - Fee Related
- 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
Also Published As
Publication number | Publication date |
---|---|
US6139683A (en) | 2000-10-31 |
FI110695B (fi) | 2003-03-14 |
ES2123600T3 (es) | 1999-01-16 |
ATE172761T1 (de) | 1998-11-15 |
FI933729A0 (fi) | 1993-08-25 |
FI933729A (fi) | 1994-02-26 |
JPH06322682A (ja) | 1994-11-22 |
DE4228171A1 (de) | 1994-03-03 |
DE59309094D1 (de) | 1998-12-03 |
JP3348387B2 (ja) | 2002-11-20 |
DE4228171C2 (de) | 1995-06-14 |
CA2104765A1 (en) | 1994-02-26 |
EP0584675A1 (de) | 1994-03-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0584675B1 (de) | Holzaufschluss mit Essigsäure unter Zusatz von Ameisensäuren | |
DE19916347C1 (de) | Verfahren zum Auftrennen lignocellulosehaltiger Biomasse | |
DE2027319C3 (de) | Verfahren zur Herstellung von chemisch gut loslichem Zellstoff | |
DE2818320B2 (de) | Verfahren und Vorrichtung zur Behandlung von Holzhackschnitzeln | |
DE2022866A1 (de) | Verfahren zur Behandlung von zelluloseartigem Material | |
DE2945421C2 (de) | ||
DE69730233T2 (de) | Verfahren zur zellstoffherstellung durch einstufiges kochen mit ameisensaüre und wäsche mit perameisensaüre | |
DE3212767A1 (de) | Verfahren und reaktor zum kontinuierlichen aufschliessen von pflanzenfasermaterial | |
DE1299517B (de) | Verfahren zur Herstellung von abgebauten kristallinen Cellulosen | |
DD142562A5 (de) | Verfahren zum abbauen von lignocellulosematerialien | |
DE3518005A1 (de) | Sulfitaufschlussverfahren zur herstellung von zellstoff aus lignozellulosehaltigen materialien mit rueckgewinnung der aufschlusschemikalien | |
DE3445132C2 (de) | ||
WO2000034568A1 (de) | Verfahren zur gewinnung von chemiezellstoff aus hackschnitzeln | |
DE1249666C2 (de) | Verfahren zur gewinnung von zellstoff nach dem magnesiumbisulfitverfahren | |
DE2920731A1 (de) | Verfahren zur chemischen umwandlung von lignocellulose unter abtrennung von fasern davon | |
EP0325891A1 (de) | Verfahren zur Gewinnung von gebleichtem Zellstoff | |
EP0508064A1 (de) | Verfahren zur Delignifizierung von cellulosehaltigen Rohstoffen | |
DE3227843C2 (de) | ||
DE3423024A1 (de) | Holzaufschluss mit essigsaeure und chlorethanol | |
DE3239608A1 (de) | Verfahren zur herstellung von zellulosepulpe | |
EP0503304A1 (de) | Verfahren zur Delignifizierung von cellulosehaltigen Rohstoffen | |
DE3024420C2 (de) | ||
DE1517169C (de) | Verfahren zur Herstellung von chemo mechanischen Faserstoffen aus Holzschnitzel | |
DE1692857C3 (de) | Verfahren zum Herstellen eines Cellulosebreis | |
DE2439654C3 (de) | Verfahren zur Herstellung von Cellulose aus Siebpulpe |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT CH DE ES GB IT LI NL PT SE |
|
17P | Request for examination filed |
Effective date: 19940928 |
|
R17P | Request for examination filed (corrected) |
Effective date: 19940924 |
|
17Q | First examination report despatched |
Effective date: 19950126 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: EDELER, FRIEDRICH-WILHELM, DIPL.-ING. Owner name: SCHOENE, MARTIN, DR. DIPL.-HOLZWIRT Owner name: NIMZ, HORST H., PROF. DR. |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT CH DE ES GB IT LI NL PT SE |
|
REF | Corresponds to: |
Ref document number: 172761 Country of ref document: AT Date of ref document: 19981115 Kind code of ref document: T |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 59309094 Country of ref document: DE Date of ref document: 19981203 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19981118 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2123600 Country of ref document: ES Kind code of ref document: T3 |
|
ITF | It: translation for a ep patent filed |
Owner name: SOCIETA' ITALIANA BREVETTI S.P.A. |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 19981211 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20030709 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20030826 Year of fee payment: 11 Ref country code: CH Payment date: 20030826 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20030828 Year of fee payment: 11 Ref country code: AT Payment date: 20030828 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20030829 Year of fee payment: 11 Ref country code: ES Payment date: 20030829 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20030905 Year of fee payment: 11 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040813 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040813 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040814 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040814 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040831 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050214 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050301 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050301 |
|
EUG | Se: european patent has lapsed | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20040813 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: MM4A Free format text: LAPSE DUE TO NON-PAYMENT OF FEES Effective date: 20050214 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20050301 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050813 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20040814 |