EP1190137B1 - Verfahren zum auftrennen lignocellulosehaltiger biomasse - Google Patents

Verfahren zum auftrennen lignocellulosehaltiger biomasse Download PDF

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Publication number
EP1190137B1
EP1190137B1 EP00925193A EP00925193A EP1190137B1 EP 1190137 B1 EP1190137 B1 EP 1190137B1 EP 00925193 A EP00925193 A EP 00925193A EP 00925193 A EP00925193 A EP 00925193A EP 1190137 B1 EP1190137 B1 EP 1190137B1
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EP
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Prior art keywords
lignin
alkanolamine
extraction
cellulose
steam
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Expired - Lifetime
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EP00925193A
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German (de)
English (en)
French (fr)
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EP1190137A1 (de
Inventor
Ties Karstens
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Cerdia Produktions GmbH
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Rhodia Acetow GmbH
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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
    • D21C1/00—Pretreatment of the finely-divided materials before digesting
    • D21C1/02—Pretreatment of the finely-divided materials before digesting with water or steam
    • 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 present invention relates to a method for separating lignocellulose-containing Biomass, in particular from wood or grain straw, in the essential components in the form of lignin, hemicellulose and cellulose.
  • the disadvantages of classic pulp processes are mainly the high water requirement, the large content of organic substances in the wastewater and the relatively high operating costs. The latter are not least due to the ancillary companies to process the Alkali and the wastewater or waste streams.
  • the conventional process there is no separation without the use of sulfur-containing compounds of lignin; this is associated with odor nuisance.
  • the classic Wood pulping processes (sulfate, sulfite, Milox) are among the lignin chemically cleaving and mainly dissolving the cleavage products (lignin sulfonic acids).
  • the formacell process is mainly the lignin dissolving and only slightly splitting process.
  • ASAM and Organocell are combined Method.
  • the ASAM process in particular requires a complicated one Chemical recovery system.
  • a method of dissolving the lignin would have the advantage that the lignin and others By-products could easily be separated.
  • a disadvantage of using steam is that additives do not or can only be supplied in the steam with great technical effort. Much more The biomass must be in contact with the substances to be used before the steam explosion brought what is generally with a poor distribution or with a higher dosage is linked. This also applies analogously to the steam refining process (Steam digestion process with subsequent mechanical fibering), which with less high-tension steam works (10 - 15 bar) and mechanical for fraying Devices used.
  • Cereal straw is also of particular interest as a starting material, as in the USA 125 million tons of wheat straw in Europe and even 170 million tons a year attack. In many countries - especially in Asia (e.g. China) and in Africa - there are a lack of wood as a raw material for the production of pulp, so one on the use of straw is instructed.
  • Known reprocessing methods are for example the steam explosion or soda pulping (pulping) Straw.
  • the former method is a relatively complex mechanical construction and does not solve the problem of the clean separation of cellulose and lignin.
  • the Fibrillation is never entirely complete, which is what refiners add, especially but requires a high dilution of the fiber suspension down to 2%.
  • alkanolamines to remove lignin from lignocelluloses was first developed by Elton Fisher and R.S. Bower (J. Am. Chem. Soc. 63 (1941) 1881-1883). In the 1970s, monoethanolamine was used as an additive processed to sodium hydroxide solution for wood digestion (keywords: alkaline pulping in aqueous alcohols and amines, acceleration of soda delignification, sulfur free delignification). This should reduce or even replace the sulphurous ones Chemicals are made possible.
  • DE-A-2803465 describes a method for producing cellulose from plants Fiber raw materials by digestion with organic solvents, the Fiber raw materials during a pretreatment first the hemicelluloses and others extractable components are withdrawn.
  • US-A-4259151 discloses a process for producing cellulose powder from woody material and a device for performing the method.
  • a process for pulping is disclosed of raw lignocellulosic materials, especially for the production of alpha cellulose and other valuable products, described as a treatment agent at least 70% by weight alkylolamine is used.
  • the treatment is done by boiling under pressure between room temperature and 200 ° C for 4 to 20 Hours.
  • NaOH can also be used.
  • the treatment agent separated, the pulp obtained with dilute inorganic acid washed and bleached. The separation into the individual components achieved in this way However, the pulp is completely inadequate and the quality obtained is not satisfactory.
  • the invention is therefore based on the object of a method for fractionation of lignocellulose-containing biomass, in which the addressed Disadvantages of the prior art are largely eliminated.
  • It should be the wooden components Hemicellulose, lignin and cellulose in as little contaminated as possible Form obtained separately from each other in order to further process this way to provide these raw materials.
  • It should be a sulfur and chlorine free Wood digestion process can be provided, which also works without sodium hydroxide and thus on complex recovery, exhaust air and wastewater treatment processes can do without.
  • chemical pulp production in time, chemical and energy-saving way carried out in a small decentralized unit can be.
  • Cellulose is said to be a never-dried pulp, i.e. with high accessibility, can be directly processed into cellulose derivatives. This is intended to manufacture of tailor-made according to the criteria of the individual chemical pulp processor Pulp inexpensive and also in the state of highest reactivity for further processing with an integrated processing chain from wood to cellulose derivative.
  • the method according to the invention enables lignocelluloses to be digested and be broken down into its components by first performing a pre-hydrolysis be subjected to treatment with water or steam, then the hydrolyzed hemicelluloses formed are extracted with aqueous media and then extracting the residue with alkanolamine to obtain a Cellulose raw material is subjected.
  • lignocellulose can be used for the teaching according to the invention, namely the Fractionation into the essential components of cellulose, polyoses and lignin used become.
  • Plant growth materials are lignocellulose-containing biomass various types, such as wood, oat husks, corn and grain stalks, bagasse, Straw of all kinds, such as wheat straw, rice straw and oat straw, are suitable.
  • wood it is usual, logs or industrial waste wood, preferably in shredded form, e.g. in the form of wood chips.
  • fibrous raw materials such as annual plants, are suitable for cutting shredded fibers. Crushed is preferred or shredded wood, in the form of hardwood, beech or softwood used.
  • the water content of the lignocellulose-containing biomass can be between that for fresh harvested lignocelluloses typical content of about 80% by mass, in particular 50 % By mass, and after intensive drying are also close to 0%.
  • the initial step of the method according to the invention comprises pre-hydrolysis the lignocellulose-containing biomass by treatment with water or steam.
  • the biomass can so-called steam explosion process, the application is also of the steam refining process possible.
  • Prehydrolysis of the To carry out biomass in mild conditions the goal of this The process step is to break down the hemicelluloses to such an extent that their subsequent separation as oligosaccharides by extraction with aqueous Media, such as washing with water, is easily possible.
  • the pre-hydrolysis is a well-known process step in the pulp industry, not dealt with here must be received. Cellulose and lignin should be as little as possible to be attacked.
  • the total breakdown of the hemicelluloses in the first step of Process i.e. the pre-hydrolysis
  • the pre-hydrolysis according to step a) can also be carried out to a small extent be performed. It is then pre-hydrolyzed to the extent that the hemicelluloses bound acids are cleavable and the cleaved according to step b) Acids are washed out. This plays in particular for the production of High yield pulp plays a role. Excess acids would come with the following Alkanolamine to be used react and thus lead to losses. So it can a minimum pre-hydrolysis may be sufficient.
  • a two-stage pre-hydrolysis can also be used to improve the effectiveness of the pre-hydrolysis at the same temperature and cooking conditions, but at higher Effectiveness, i.e. first steam and then hot water.
  • the straw can also be at about 150 ° C to 190 ° C, especially about Prehydrolyzed 170 ° C and then an extraction according to step c) elevated temperature below about 170 ° C, preferably below about 160 ° C, in particular at about 115 to 135 ° C to chemical pulp receive.
  • Sugar is obtained here by concentrating the pre-hydrolyzate, what a suitable further processing can follow.
  • the appropriate variant can be selected for the desired pulp quality.
  • the lignocellulose-containing biomass can be used Carrying out step a), i.e. pre-hydrolysis, acidic or alkaline Undergo pretreatment. This means a further increase in the yield desired products.
  • the raw material which is generally already well-fibred, with hot Water is treated to dissolve most of the degraded hemicellulose and separate.
  • the pre-hydrolyzed and softened biomass is thus extracted with an aqueous medium from the hydrolyzed hemicelluloses formed freed.
  • excess water is preferably squeezed out and hot washed. This can be followed by mechanical unraveling of the biomass, for example crushing in a refiner to the desired degree of division, which can be of great importance depending on the desired quality.
  • Mass (based on dry matter) adjusted to about 0.1: 1 1 to 4: 1.
  • alkanolamines in particular all alkanolamines in question that are not due to alkyl groups on nitrogen are substituted. For example, from: N-methyl-monoethanolamine and N, N-dimethyl-monoethanolamine, since this has no effect on the extraction of the lignin show the wood.
  • the extraction according to the invention is preferably carried out under pressure, i.e. in one suitable autoclave or a continuous extractor. With an extraction under atmospheric pressure, e.g. with straw, equally good results can be achieved.
  • the hemicelluloses are released washed, if necessary crushed and suitably pretreated with ammonia Biomass with the water it contains, the extractant (s), for at least heated to a temperature between about 80 and 220 ° C for about 1 hour. It can also use solvents for the resulting lignin degradation components be present.
  • a continuous extraction is preferred over a batch mode of operation. This can be done by placing the biomass in a pressure reactor can flow through the preheated extractant or by doing this extracting material, the biomass, leads to the extractant in countercurrent. Both Variants have the advantage over the autoclave, i.e. stationary operation, that as a result of removing the degradation products with the extractant side reactions are largely excluded. In addition, with the same extraction effect with a lower liquor ratio of extractant to wood chips and work at a lower temperature. The solubility of Organosolv lignin in monoethanolamine is relatively high (250 g / liter).
  • the extraction is multi-stage, i.e. in at least two successive extractions with alkanolamine carried out.
  • the same total amount of alkanolamine is preferably used as used in a one-step extraction. This can effectively Countercurrent extraction takes place, since the shortest extraction times are realized become.
  • MEA Monoethanolamine
  • the alkanolamine extraction can be carried out at lower temperatures (approx. 100 to 120 ° C) be carried out when ammonia pretreatment is carried out. Despite the low temperatures, low kappa numbers are then obtained. Moreover side reactions are strongly suppressed.
  • the cellulose raw material is obtained.
  • the residue after distilling off the solvent can also be combined with the extract separated from the fibers. From this, water and the alkanolamine serving as extractant are separated by distillation, preferably vacuum distillation. Other separation processes which, as desired, lead to the concentration of the lignin extract - in extreme cases to dry matter - are also suitable here.
  • the lignin can also be separated off by adding a non-solvent to the solution of the lignin in alkanolamine.
  • the lignin precipitates in the form of solid particles and can be separated from the extraction agent alkanolamine by a suitable solid / liquid separation process, such as filtration, centrifugation, thin-layer evaporation or membrane separation processes.
  • the lignin can be separated off, for example, by introducing CO 2 into the lignin / alkanolamine extract, which is optionally concentrated and diluted with water or better with the wash water after the alkanolamine extraction.
  • a large part of the alkanolamine is recovered in pure form by concentration using thin-layer evaporation or a suitable other distillation method.
  • the rest of the alkanolamine is distilled after the water has been distilled off from the precipitation liquid after the lignin has been separated off, likewise in vacuo. Lignin precipitation is thus accomplished by introducing CO 2 and centrifuging.
  • the alkanolamine * CO 2 addition compound which forms with the CO 2 can be decomposed completely again into alkanolamine and CO 2 thermally or by injecting steam.
  • the residue consists of lignin, which is greatly degraded in its molecular weight and not chemically modified. This can therefore be used as a chemical raw material, eg for the production of thermosets or polyurethanes.
  • the degraded hemicelluloses are in aqueous solution or suspension and can also be used for further purposes.
  • the raw pulp has a kappa number of at most about 20, preferably below about 10 on. This corresponds to a lignin content of ⁇ 3 or ⁇ 1.5 mass% and represents an advantageous entry into bleaching.
  • a so-called “inclined screw reactor” can be used for the pre-hydrolysis, which is followed by a fiberization and washout that is customary in the production of "cmp" (see above).
  • the use of an inclined screw reactor for the pretreatment with NH 4 OH / alkanolamine is preferred, then an above-mentioned fiberization for the thorough lignin extraction in the form of countercurrent extraction.
  • these two steps result in a weakly lignin-containing, water-rich fraction which can be used several times, the lignin being concentrated, and in the second case a fraction with a high lignin content and alkanolamine-rich fraction.
  • FIG. 1 is the so-called pre-hydrolysis, for example in the form of the steam explosion or of the steam refining process, which is shown after extraction with an aqueous Medium leads to the separation of hemicelluloses.
  • ammonia treatment is optionally followed by ammonia treatment.
  • it is, for example, a so-called ammonia explosion.
  • FIG. 2 A variant of the alkanolamine extraction is shown in detail in FIG. 2. Here is a recycle circuit shown, the recovery of the solvent used or the extractant used. This variant allows an extremely economical mode of operation.
  • One advantage is initially in the fact that no sulfur-containing chemicals are used for the wood digestion become. Furthermore, chlorine-containing chemicals do not have to be used for bleaching become.
  • the so-called severity factor ie the integral the steam temperature and the exposure time
  • the so-called severity factor ie the integral the steam temperature and the exposure time
  • One of the advantages of the method according to the invention is that hemicelluloses and lignin in two different process stages, accordingly appropriate and specifically, be separated from the cellulose. This also means that the molecular weight of the cellulose does not decrease so much and the lignin content before Bleach is significantly lower than in the above-mentioned processes and also in the industrially introduced processes (sulfate and sulfite processes).
  • the steam used for the pre-hydrolysis of the hemicelluloses can be used for Preheat the extractor. It is used twice. The for that Fibrillating energy is also due to the strong softening of the Biomass very low after extraction. The fraying mostly takes place after the Pre-hydrolysis, in individual cases after the extraction step, without a significant Entry of mechanical energy must be accepted.
  • caustic soda as an extractant for lignin, as is the case after the steam explosion or the steam refining process is common.
  • the use of caustic soda in particular requires the construction and operation of so-called Recovery systems (recovery) in the pulp mills. Their size is first Line through the economically sensible operation only in certain dimensions of these ancillary systems.
  • the recovery consists of a simple vacuum distillation.
  • the alkanolamine * CO 2 addition compound which forms with the CO 2 can be decomposed completely again into alkanolamine and CO 2 thermally or by injecting steam. There is no need to recover sodium salts.
  • a simple pre-hydrolysis with water makes the alkanolamine extraction so effective that the raw pulp already has an ISO brightness of approx. 50%.
  • the alkanolamine extraction can also be carried out without pressure given the low water content of the straw, which allows the use of simple apparatus.
  • the biomass must also be of relatively the same size within relatively narrow limits, otherwise for digestion e.g. Larger wood chips are not sufficient in the cooking time are permeated by the white liquor.
  • the invention allows Extraction with an alkanolamine with significantly lower liquor ratios (about 3: 1) - especially in continuous operation. This has a positive effect the steam consumption during extraction and recovery.
  • the biomass according to the Pre-hydrolysis with steam with low mechanical energy consumption in suitable Refiners or defibrators machined so that during the subsequent extraction with Alkanolamine the effective duration is not affected by diffusion processes.
  • Additives to prevent the condensation of the lignin are also not necessary, which saves costs.
  • As a pretreatment with chemicals, as with exclusive Use of the steam explosion and steam refining process necessary is, there are no problems with their distribution. Accordingly points the method according to the invention has a very low reject rate (coarse wood components, which are not sufficiently frayed due to a lack of distribution).
  • the pre-hydrolysis can be carried out either for total degradation or only slightly Scope can be used, which gives another variation results.
  • a multi-stage alkanolamine extraction in the process according to the invention chosen instead of a single-stage, this alternative offers efficiency and efficiency of the process management further advantages.
  • the process according to the invention also improves the separation of sugar achieved by fiberization before or after the pre-hydrolysis. Furthermore is a two-stage pre-hydrolysis to improve the effectiveness of the pre-hydrolysis possible. Short dwell times and effective extraction of the broken down sugar result also less furfural formation
  • Continuous process control also has advantages: there is no need for displacement one process liquid through another, as is the case with classic pulping technology is necessary in stoves.
  • the exchange and washing processes are fewer in stoves effective and take a relatively long time.
  • the selectivity is in the displacement in practice so that there is undesirable mixing or blurring Transitions comes, so additional effort in recovery is required becomes.
  • Drying can be omitted if small, decentralized units work economically; this is possible with the method according to the invention. This will make the specific Invest and operating costs significantly reduced.
  • the method according to the invention also delivers higher yields than other chemical pulp processes; cold alkali extraction to achieve low hemicellulose residues is also not mandatory.
  • the bleaching of the product obtained is possible, for example, with peracetic acid a directly subsequent acetylation without changing solvents and one represents high cost savings.
  • the DP determination was carried out using the known Cuoxam method.
  • wood chips 40 g were in a mixture consisting of liquid ammonia, monoethanolamine and water (80 g: 40 g: 20 g) cooked in a pressure reactor at 140 ° C, then suddenly from the Unload reactor, washed and dried.
  • the kappa number was 143, according to the Alkaline extraction of Example 1 was kappa number 129.
  • N-methylmonoethanolamine and N, N-dimethylmonoethanolamine have no effect during the extraction, since the nitrogen is substituted by alkyl groups.
  • the lignin extraction is therefore significantly improved if an ammonia explosion has occurred.
  • adding MEA with the ammonia to the chips before the explosion does not have a positive effect compared to the NH 3 explosion without the addition of MEA.
  • the cumulative amounts of lignin extracted are given, expressed in% of the absolute lignin content, for row 1 (100 ° C), row 2 (140 ° C) and row 3 (170 ° C).
  • the extraction rate was approximately 45 ml per hour.
  • the apparatus used is a pressure-resistant chromatography column, which is compatible with the Wood chips were filled. This was indicated on the electrical heating tapes Brought temperatures; the temperatures were controlled by an electronic Regulation kept constant.
  • the monoethanolamine was using a high pressure pump (HPLC) preheated pumped through the wood chips. There were factions of 25 ml each, of which after dilution by a factor of 100 optical densities were measured.
  • the pre-hydrolysis conditions (heating time, duration, temperature, type and concentration of acid) can be adjusted in order to achieve the desired residual hemicellulose content.
  • the following table shows the status achieved in tests in a laboratory autoclave (heating-up time approx.
  • Acetic acid is not necessary for the complete pre-hydrolysis of hemicellulose in beech wood sufficient.
  • a hemicellulose content of ⁇ 3 mass% is for beech chips achievable without the addition of acid in the pre-hydrolysis.
  • the mannose content is below these conditions ⁇ 1%.
  • the ⁇ -cellulose content is ⁇ 96%, what chemical pulp is sufficient - except for acetylation pulp.
  • the one required for acetylation pulp Low xylose content ⁇ 2% by mass could, however, be sharper in beech wood Digestion conditions and in eucalyptus achieved with less harsh conditions become. A deterioration in the target sizes when switching to wood chips in original size was not found. They were in larger autoclaves Results even better.
  • the yield was 40%, the whiteness 50%.
  • Example 21 was repeated, but no prehydrolysis was carried out. The received one Whiteness was 22%.
  • the products obtained from the preceding examples were each based on By-products of monoethanolamine examined. It was found that the By-products of monoethanolamine, such as N-methyl-monoethanolamine, N, N-dimethyl-monoethanolamine, N-acetyl-monoethanolamine and N-formyl-monoethanolamine, did not occur or in one case using N-methyl-monoethanolamine only with a share of 0.3% (based on the analyzed MEA lignin extract) templates. The so-called head was used as the analysis method Space gas chromatography used.

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  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Treatment Of Sludge (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Processing Of Solid Wastes (AREA)
EP00925193A 1999-04-12 2000-04-11 Verfahren zum auftrennen lignocellulosehaltiger biomasse Expired - Lifetime EP1190137B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19916347A DE19916347C1 (de) 1999-04-12 1999-04-12 Verfahren zum Auftrennen lignocellulosehaltiger Biomasse
DE19916347 1999-04-12
PCT/EP2000/003212 WO2000061858A1 (de) 1999-04-12 2000-04-11 Verfahren zum auftrennen lignocellulosehaltiger biomasse

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EP1190137A1 EP1190137A1 (de) 2002-03-27
EP1190137B1 true EP1190137B1 (de) 2003-11-26

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Country Status (18)

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EP (1) EP1190137B1 (cs)
JP (1) JP2002541355A (cs)
CN (1) CN1208514C (cs)
AT (1) ATE255187T1 (cs)
AU (1) AU756976B2 (cs)
BR (1) BR0011169B1 (cs)
CA (1) CA2368872C (cs)
CZ (1) CZ298831B6 (cs)
DE (2) DE19916347C1 (cs)
ES (1) ES2213011T3 (cs)
NO (1) NO20014939L (cs)
NZ (1) NZ515051A (cs)
PL (1) PL203363B1 (cs)
PT (1) PT1190137E (cs)
RU (1) RU2220245C2 (cs)
SK (1) SK14392001A3 (cs)
WO (1) WO2000061858A1 (cs)
ZA (1) ZA200108406B (cs)

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WO2023047423A1 (en) * 2021-09-27 2023-03-30 Fuma Labs Private Limited Process for treatment of biomass for pulping and biorefinery applications

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