EP0584675B1 - Holzaufschluss mit Essigsäure unter Zusatz von Ameisensäuren - Google Patents

Holzaufschluss mit Essigsäure unter Zusatz von Ameisensäuren Download PDF

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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
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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
Application number
EP93113002A
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German (de)
English (en)
French (fr)
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EP0584675A1 (de
Inventor
Horst Harry Hermann Nimz
Martin Schöne
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EDELER, FRIEDRICH-WILHELM, DIPL.-ING.
NIMZ, HORST H., PROF. DR.
SCHOENE, MARTIN, DR. DIPL.-HOLZWIRT
Original Assignee
Edeler Friedrich-Wilhelm Dipl-Ing
Nimz Horst H Prof Dr
Schone Martin Dr Dipl-Holzwirt
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Application filed by Edeler Friedrich-Wilhelm Dipl-Ing, Nimz Horst H Prof Dr, Schone Martin Dr Dipl-Holzwirt filed Critical Edeler Friedrich-Wilhelm Dipl-Ing
Publication of EP0584675A1 publication Critical patent/EP0584675A1/de
Application granted granted Critical
Publication of EP0584675B1 publication Critical patent/EP0584675B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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.

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  • Paper (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (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)
EP93113002A 1992-08-25 1993-08-13 Holzaufschluss mit Essigsäure unter Zusatz von Ameisensäuren Expired - Lifetime EP0584675B1 (de)

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

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Country Status (8)

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US (1) US6139683A (fi)
EP (1) EP0584675B1 (fi)
JP (1) JP3348387B2 (fi)
AT (1) ATE172761T1 (fi)
CA (1) CA2104765A1 (fi)
DE (2) DE4228171C2 (fi)
ES (1) ES2123600T3 (fi)
FI (1) FI110695B (fi)

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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
DE60025265T2 (de) * 1999-10-15 2006-08-03 Cargill, Inc., Minneapolis Fasern aus pflanzensamen und verwendung
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
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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
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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.
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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 (en) * 2012-04-26 2013-10-31 Archer Daniels Midland Company Liquid/liquid separation of lignocellulosic biomass to produce sugar syrups and lignin fractions
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
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
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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Also Published As

Publication number Publication date
EP0584675A1 (de) 1994-03-02
DE4228171C2 (de) 1995-06-14
FI110695B (fi) 2003-03-14
DE4228171A1 (de) 1994-03-03
US6139683A (en) 2000-10-31
FI933729A (fi) 1994-02-26
CA2104765A1 (en) 1994-02-26
JPH06322682A (ja) 1994-11-22
FI933729A0 (fi) 1993-08-25
ATE172761T1 (de) 1998-11-15
DE59309094D1 (de) 1998-12-03
ES2123600T3 (es) 1999-01-16
JP3348387B2 (ja) 2002-11-20

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