FI120878B - Process for processing carbohydrate-containing raw material - Google Patents

Description

A process for processing a carbohydrate-containing raw material

The present invention relates to the processing of carbohydrate-containing raw materials. In particular, the present invention relates to a process for treating carbohydrates in the basic aqueous phase according to the preamble of claim 1 in the presence of a catalyst to produce an aqueous solution or dispersion which can be used as such or as a starting material for fiber-free applications.

The conversion of biomass into value-added products, in particular different forms of energy 10, has gained increasing attention as a means of replacing energy and other end products from fossil raw materials. For example, from conventional biofuels for transport (bioethanol, bio-ETBE, pure vegetable oil, biodiesel and bio-methane), bioethanol has a long proven track record and, in some cases, environmental benefits over fossil fuels.

15

Bioethanol can be made from a variety of renewable raw materials. It has traditionally been made from starches or sugar-containing crops, but in the future the focus will be on various raw materials rich in lignocellulose. Such materials include agricultural and forestry waste, by-products from the wood and forestry industry, municipal and industrial waste and energy crops. Alongside the expansion of the raw material base for bioethanol production and perhaps the economic aspects of production, the "second generation" raw materials (lignocelluloses) and the conversion technologies required to convert them into ethanol are expected to reduce the carbon footprint of bioethanol production.

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The conversion of biomass to ethanol requires biotechnology. In the chain of catalytic reactions, microorganisms (typically yeast) convert sugars (preferably glucose or sucrose) into ethanol and by-products such as carbon dioxide. In conventional bioethanol production, sugars are obtained simply by squeezing out sucrose-rich juice, for example, from crushed sugar cane and sugar beet. Alternatively, the starch is hydrolysed to a solution rich in glucose by cheap enzymes and moderate heat. However, the structure of lignocellulosic materials is much more complex, and the release of sugars requires much more stringent processing. Enzymes are typically selected from lignocellulose to carry out the major hydrolysis of the available polysaccharides. However, the lignocellulosic material must first be pre-treated in order for the enzymes to function effectively. Methods of disrupting or modifying the natural structure of lignocellulose are thus referred to as pretreatment methods. Several such methods are known in the art. These include steam blasting, with or without chemicals such as sulfuric acid, ammonia, etc., hot water treatment, mild acid hydrolysis, CaO treatment, wet oxidation, organic solvent treatment, ammonium treatment, etc.

The main difficulties with the existing techniques are the incomplete modification of the degradation / lignocellulosic material and the formation of toxic compounds during pre-treatment, which renders further processing less feasible and effective.

It is an object of the present invention to eliminate at least some of the foregoing problems in the art and to provide a novel process for processing carbohydrate-containing raw materials from various sources, for example, to provide a better starting material for ethanol production.

Another object of the present invention is to provide a process for the preparation of novel liquid compositions containing dissolved carbon-hydrates and lignin.

The invention is based on the principle of subjecting the raw material, optionally after homogenization and dispersion to a liquid, to a treatment in a basic aqueous medium in the presence of a catalyst and diacid. Examples of such catalysts include transition metal catalysts comprising copper in coordination with at least one aliphatic or aromatic nitrogen-releasing ligand. Such catalysts are capable of increasing the disruption of the structure of the lignocellulosic or cellulosic material.

According to the invention, the raw material is treated in an alkaline slurry in the presence of a catalyst to obtain a suspension of the solid and dissolved components, and the suspension, or at least a portion thereof, is recovered and subjected to further processing or separation of its components.

More specifically, the method of the present invention is characterized in what is set forth in the characterizing part of claim 1.

The present invention achieves considerable advantages. Thus, the present invention 5 provides a method for efficiently modifying lignocellulosic material to produce less toxic compounds, thereby reducing the problems associated with current pretreatment techniques. Carbohydrates obtained by the process described in the present invention are also more susceptible to hydrolysis, which makes further processing of plant material more feasible than the known methods.

10

The present invention provides a more efficient conversion of any lignocellulosic material (wood, straw, sugar cane waste, etc.) to a hydrolyzable form. The present invention also provides the separation of lignin from lignocellulosic materials and the dissolution of the lignin thus isolated in the aqueous phase.

15

The invention will now be examined in more detail with reference to the accompanying drawings and numerous non-limiting working examples.

Figure 1 is a bar graph showing enzymatic hydrolysis of a solid fraction with cellulose cartridges;

Fig. 2 is a graph showing the hydrolysability of alkaline-treated and steam-blasted spruce with cellulases; Figure 3 shows the hydrolysis of alkali-treated barley straw by cellulases;

Figure 4 is a (CE) electropherogram showing the acid composition of the three treatments basic filtrates described in Example 10 using semi-quantitative quantitation compared to standard mixtures; 30

Figure 5 is a similar electropherogram showing treatment of the standard described in Example 10 at various dilution ratios of the acid composition of the basic filtrate; and 4

Figure 6 is a schematic representation of the products obtained from the various steps and processes based on the present catalytic lignocellulosic pretreatment.

For the purpose of the present invention, the term "fiber applications" refers to applications in which the carbohydrate raw material is converted into products based on a fiber (self-supporting) network. The term "fiberless applications" is used to mean all other applications.

As explained above, the present invention is based on the observation that lignocellulosic material is degraded / modified in aqueous alkaline solutions in the presence of O 2 containing atmosphere in the presence of certain transition metal complexes (described below).

Similar catalytic processes have previously been used in the manufacture of pulp, but it has not been suggested in the art that these catalytic processes may be used as a pre-treatment in the manufacture of products other than paper pulp.

According to a preferred embodiment, the raw material consists of a carbohydrate material, for example material comprising cellulose, hemicellulose, lignin or combinations thereof. Optionally, the raw material may be present in a fibrous state, as is the case with cellulosic and lignocellulosic materials.

The raw material may be derived from biomass, including, for example, wood, pulp, agricultural and industrial by-products, forest and thinning waste; agricultural waste such as straw, sugar cane waste, olive-residue waste; energy crops such as reed canary grass, willow, broom millet, 25 Miscanthus; peat; cane waste and sea biomass. Municipal and industrial wastes, in particular organic, solid or liquid wastes, may also be used and may be selected from refuse derived fuel (RDF); waste from sawmills, waste from plywood, furniture and other mechanical forest industries; and sludges (including industrial and municipal waste).

30

According to a preferred embodiment, the raw materials of the present process include wood, fibrous pulp, recycled fibers, straw, agricultural, social and industrial wastes and similar compositions containing carbohydrates.

5

The raw material, usually a slightly moisture-containing solid, is typically homogenized, optionally in water, and slurried. The resulting slurry preferably has a consistency of from about 0.1% to about 75%, in particular from about 1% to about 15% by weight, based on the weight of the aqueous or aqueous solution or suspension.

5

The carbohydrate material is disintegrated in the slurry at least partially to produce an aqueous suspension comprising solids and dissolved ingredients. At least a portion of the aqueous suspension is recovered, and at least a portion of the recovered suspension is used for non-fibrous applications.

A suitable pretreatment solution capable of disintegrating the lignocellulosic material may be formed by mixing the copper salt or oxide with the nitrogen-containing organic compound in the aqueous solution / dispersion.

The solution or dispersion is basic, which means in practice that it contains, optionally in addition to the catalyst, a basic substance in the aqueous liquid phase.

The solution initially has a pH of at least 8, preferably at least 12. The temperature is typically about 50-150 ° C. The treatment can be carried out in air or in oxygen gas or in oxygen enriched air. The pressure may be reduced, but is typically ambient (normal) pressure or excess pressure up to about 50 bar (abs.); the oxygen partial pressure is preferably about 1 to 20 bar (abs.). Treatment times may range from 0.1 to 24 hours, preferably from about 10 minutes to about 20 hours.

The basic substance of the solution is selected from the group consisting of alkali metal and alkaline earth metal hydroxides and 25 carbonates and bicarbonates.

The transition metal catalyst comprises a catalyst containing a nitrogen-containing ligand (s). The catalyst is one which is capable of increasing the disruption of the structure of the lignocellulosic or cellulosic material. The inert metal catalyst preferably comprises 30 copper co-ordinated with at least one nitrogen-releasing ligand. The catalyst may comprise a copper ion coordinated with one or more nitrogen donor ligands. Preferably, the copper ion is coordinated with the nitrogen atoms of at least a portion of the nitrogen-containing organic compound having a structure wherein 6 at least two nitrogen atoms are spaced apart through a carbon chain having 1 to 4 carbon atoms, preferably 2 carbon atoms.

In one embodiment, the nitrogen-containing organic compound has a general structure selected from structure

R1 (R ^ m ^ NJCR'R4]! _4 JNL. (R5) nR6 I

wherein each substituent R 1 to R 6 independently represents hydrogen, an alkyl, alkenyl, alkynyl, alkoxy or hydroxyl group which is optionally substituted, or two of said substituents together with the nitrogen atom to which they are attached form an alicyclic or aromatic cyclic group comprising 1 to 6 carbon atoms; 3 rings, each ring having 5 to 15 7 ring members, optionally containing at least one additional heteroatom selected from N, O and S, m and n independently being 0 or 1, and _ represents a single bond or a double bond.

The substituents may be selected from hydroxy, oxo, carboxy, carbonyl, sulfonyl, sulfoxy-20, amido, nitro and / or amino groups.

Such groups may increase the water solubility of the ligands. It is also possible to provide substituents which increase the solubility in nonpolar media. Examples of such substituents are formed from hydrocarbyl radicals such as aliphatic and aromatic groups, especially linear or branched alkyl, alkenyl and alkynyl groups and aryl groups.

As a specific example of the present ligands, it should be mentioned that the nitrogen-containing organic compound may be a heterocyclic compound comprising two or more nitrogen-ring or fused-ring rings. Nitrogen-containing rings may be selected from rings derived from pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, isoindole, indazole, purine, quinoline and quinoxaline.

7

According to a particularly preferred embodiment, the nitrogen-containing organic compound contains the structure N-C-C-N (phenanthroline, bipyridine, cf. formulas A-B), and the treatment is carried out in a basic solution (Na 2 CO 3, NaOH, K 2 CO 3, NaHCO 3, KOH, etc.).

5

KK CuD

\ / \ / N N

'"= N N ^ 7

Formulas A and B

One particularly preferred embodiment comprises copper phenanthroline [Cu (II) -1,10-phenanthrolinate].

The catalyst concentration is from about 0,00001 to 10%, in particular from about 0,0001 to 0.01%, based on the weight of the liquid composition including the raw material and the liquid phase.

During treatment, about 5% to about 85% by weight of the crude material is soluble, and at least part of it is present in the aqueous phase of the aqueous suspension.

The treatment suspension contains solids and dissolved components; wherein the cellulose-20 loose is present as a polymer while most of the hemicellulose is partially or completely hydrolyzed / degraded. Lignin is mainly dissolved; the pectins are intact, and small molecule degradation products (e.g. acids) are also present.

The recovered material is used to produce carbohydrates selected from mono-saccharides, disaccharides, oligosaccharides and polysaccharides, alcohol compounds, lignin, chemicals and nanoparticles and nanofiber crystals.

For this purpose, the recovered portion, i. either the solid, the liquid portion, or the mixture of excipients and liquid, is subjected to a further treatment step selected from mechanical treatments, chemical treatments and enzymatic treatments, or combinations thereof, in particular hydrolysis, fermentation and oxidation and combinations thereof, optionally as an additional combination. prior or subsequent mechanical treatments.

In particular, the recovered material may also be subjected to a second treatment to increase the yield or concentration of carbohydrates, chemicals, lignin or nanoparticles or nanofibers. Extended hydrolysis of polysaccharides and oligosaccharides increases the yield of monosaccharides. Monosaccharides such as xylose and glucose and galactose can be used to make ethanol by fermentation.

Numerous combinations of treatment and fermentation can be used. One preferred embodiment involves the conversion of cellulose (and hemicellulose) to ethanol, which comprises either separate hydrolysis and fermentation (SHF) or simultaneous saccharification and fermentation (SSF). The latter alternative may be performed by simultaneous sugaring and hemicellulose fermentation (SSHF), also referred to as simultaneous sugaring and co-fermentation (SSCF).

In general, these embodiments can be applied to produce any chemicals that can be prepared by fermentation from monosaccharides such as ethanol, lactic acid, sugars, acetic acid and the like.

20

To produce ethanol, the fermentation step is carried out in the presence of a fermenting microorganism capable of fermenting the major lignocellulosic carbohydrates (sugars) such as hexoses and pentoses. Typically, the fermenting organism is capable of producing ethanol from the major lignocellulose-based sugars at a temperature of 30-70 ° C.

Examples of suitable organisms include:

Yeasts: Saccharomyces cerevisiae, including genetically engineered strains such as VTT strain B-03339, Pichia stipitis, Candida shehatae, Hansenulapolymorpha,

Pachysolen tannophilus, Brettanomyces naardenensis, Pichia segobiensis, P-dii Guillermo, P. naganishii, Candida tenuis, C. albicans, C. tropicalis, C. maltosa, C., Torres, Metschnikowia bicuspidata M. zobelii, Sporopachydermia quercuum, Wingea Roberts .

9

Bacteria: Zymomonas mobilis, Escherichia coli (strain (s) of genetically modified organisms (GMOs), Klebsiella oxytoca (strain of GMOs),

Fungi: Fusarium oxysporum, Candida millerii, C. tropicalis, C. parapsilosis, Petromyces 5 albertensis, Debaromyces hansenii, Cellulomonas cellulans, Corynebacterium sp., Serratia marcescens.

According to another embodiment, illustrated in the right hand flowchart of Figure 6, the resulting suspension of solids and dissolved components 10 is subjected to a liquid separation step to provide a liquid phase containing dissolved polymers (lignin, sugar oligomers, pectins, etc.) and other solvents. These can be recovered as such and / or refined.

Thus, at least a portion of the liquid portion may be recovered and subjected to further treatment to precipitate at least some amount of dissolved carbohydrate material or lignin.

The solid phase remaining after separation of the liquid consists mainly of cellulose. It can be used for cellulose hydrolysis to obtain sugar monomers or as a starting material for the recovery of nanoparticles and other nanostructures. In one embodiment, the solid phase is treated as a fermentation substrate as described above.

Accordingly, the present invention also encompasses a process for converting a cellulose or lignocellulosic feedstock, with the aim of modifying all or part thereof, into a matrix material having non-fibrous applications and applications based on the formed solid fraction nanoparticles or nanostructures. - optionally separating a fraction from the raw material and excluding it from further processing, - possibly further homogenizing, 30 - subjecting the raw material to treatment in the presence of a nitrogen-releasing ligand and a catalyst containing copper ion, fractions, - the material or at least part of it is recovered, 10 - possibly subjected to further processing of the modified material or part thereof, and - the recovered material is used in various applications.

The following examples illustrate the invention.

5

Example 1

In one embodiment of the invention, spruce chips (5% dry weight / weight) are suspended in a solution of 130 mg / l CuSO4, 300 mg / 11,10-phenanthroline and 20 g / l Na2CO3. The solution is mechanically stirred under 10 atmospheres of O 2 and kept at 100 ° C for 20 hours. The reaction gives a suspension of a solid and solution fractions suitable for further processing according to the examples below.

Example 2 15

In another embodiment of the invention, spruce chips (5% dry weight / weight) are suspended in a solution of 130 mg / L CuSO 4, 260 mg / 11,1-bipyridine and 20 g / L Na 2 CO 3. The solution is mechanically stirred under 10 atmospheres of O 2 and kept at 100 ° C for 20 hours. The reaction gives a suspension of a solid and solution fractions suitable for further processing according to the examples below.

Example 3 This Example illustrates ethanol production from catalytically pretreated coniferous wood according to Example 25 using enzymatic pre-hydrolysis prior to fermentation.

Spruce chips (4.9% dry weight / weight) were catalytically pretreated as in Example 1. The prehydrolysis was carried out directly in the pretreatment solution by adding commercial enzyme preparations and adjusting the temperature to 45 ° C and pH 5.0. The enzyme preparations used were 30 Celluclast 1.5 FG (10 FPU / g dry weight) and Novozym 188 (P-glucosidase dose 100 nkat / g dry weight). After 4 hours, the prehydrolyzate was tempered to 30 ° C and inoculated with a yeast strain (VTT-B-03339) to a concentration of 1 g / L (dry weight) suspended in nutrients with 10% (Yeast Nitrogen Base) YNB (pre-hydrolyzate).

11

The fermentation was carried out at 30 ° C in water trap bottles using slow agitation (100 rpm).

Fermentation using enzymatic pre-hydrolysis after alkaline catalytic treatment yielded an ethanol concentration of 8.8 g / L in 118 hours. As a result, ethanol can be produced from alkaline-catalyzed coniferous wood using enzymatic pre-hydrolysis prior to fermentation.

Example 4 10

The preparation of ethanol from catalytically pretreated conifers is described using simultaneous saccharification and fermentation (SSF).

Six chips (4.9% dry weight / wt) were suspended in a solution of 240 mg / l Cu-15 CO 4 * 5H 2 O, 350 mg / l 1,10-phenanthroline and 10 g / l NaOH. The solution was mechanically stirred at 10 atmospheres of O 2 and held at 100 ° C for 20 hours. Simultaneous saccharification and fermentation were performed directly in the pretreatment solution by adding commercial enzyme preparations and adjusting the temperature to 45 ° C and pH 5.0. The commercial enzyme preparations used were Celluclast 1.5 FG (10 FPU / g dry weight) and Novozym 188 (β-20 glucosidase dose 100 nkat / g dry weight). Yeast (strain VTT-B-03339) at 1 g / l (dry weight) was inoculated immediately after addition of the enzyme. It was suspended before inoculation with nutrients with 10% (v / v) YNB (Yeast Nitrogen Base) (pre-hydrolyzate). Hydrolysis and fermentation were performed at 30 ° C in water trap bottles using slow agitation (100 rpm).

25

Simultaneous saccharification and fermentation (SSF) after basic catalytic treatment gave an ethanol content of 6.6 g / l in 117 hours.

12

Example 5

Six chips (4.9% dry weight / wt) were suspended in a solution of 240 mg / l Cu-SO4 * 5H2O, 350 mg / l 1,10-phenanthroline and 10 g / lNaOH. The solution was mechanically stirred at 10 atmospheres of CL and held at 100 ° C for 20 hours.

The base-catalyzed material was filtered and the solid fibrous solid was washed with water. The carbohydrate composition of the washed solid fraction was analyzed by HPLC for monosaccharides after acid hydrolysis (Puis et al., 1985; Tenkanen and Siika-aho, 2000). Results 10 show that after the alkaline catalytic treatment a solid fraction with a high glucose content and thus a high cellulose content was obtained (Table 1).

Table 1. Carbohydrate composition (% by dry weight) obtained by HPLC after acid hydrolysis of the washed catalysts with alkaline catalysts.

15 __ __Excatalysically treated six, washed fiber rhamnose __ <0.10% _ arabinose__0.47% _ galactose__0.27% _ glucose__82.0% _ xylose__4.15% _ mannose__9.18% _ monosaccharides__96.3% _ in polysaccharides__86,6%

Example 6

The washed solid fraction obtained by the alkaline catalytic treatment was enzymatically hydrolyzed to 20 monosaccharides (from Example 5). The solid fraction was suspended in 50 mM sodium acetate buffer pH 5 at 10 mg / ml. The enzymatic reaction was initiated by the addition of commercial cellulase Celluclast 1.5L FP 10 FPU / g dry weights of commercial Novozym 188 100 nkat / g dry weight. The suspensions were incubated at 45 ° C with magnetic stirring for 24 hours.

The release of reducing sugars was analyzed during the hydrolysis reaction and the results are shown in Figure 1. The amount of reducing sugars was determined by an assay based on the reduction of 2-hydroxy-3,5-dinitrobenzoic acid (Bemfeld, 1955).

25 5 13

As shown in Figure 1, 90% of the carbohydrates in the base-treated solid fraction were hydrolyzed enzymatically within 24 hours. The results show that the basic catalytic treatment gave a solid fraction with high hydrolysis.

Example 7 The object of this experiment was to compare the hydrolyzability of a base catalyzed material with a steam blast treated spruce. Steam blasting is a cutting-edge technology for pretreating ligno-10 cellulosic material for ethanol production.

The base-catalyzed material of Example 1 was filtered and washed with water. After the catalytic treatment, 53% of the treated wood remained as a fibrous solid. The carbohydrate composition of the washed solid fraction was analyzed by HPLC for mono-15 saccharides after acid hydrolysis (Puis et al., 1985; Tenkanen and Siika-aho, 2000) (Table 2).

Table 2. Carbohydrate composition (% by dry weight) obtained by HPLC after acid hydrolysis of alkaline catalyzed washed fibers 20 __ __Basic catalytically treated six, washed fiber rhamnose __ <0.10% _ arabinose__0.61% _ galactose__0.61% _0.61% _glucose__0.61% _0.61% _ mannose__12.1% _ monosaccharides__97.5% _ as polysaccharides__87.6% _

The washed solid fractions obtained by alkaline catalytic treatment or by steam blasting were enzymatically hydrolyzed to the monosaccharides. Steam blasting was performed according to Ohgren et al. (2006) by impregnation with 2.5% SCM and steam pretreatment at 210 ° C for 5 min. The solid fractions were suspended in 50mM sodium acetate buffer pH 5 at 10 mg / ml. The enzymatic reaction was initiated by the addition of Celluclast 1.5L FP at 5 FPU / g and Novozym 188 at 50 nkat / g dry weight. The suspensions were incubated at 14 ° C to 45 ° C with magnetic stirring for 48 hours. The release of reducing sugars was analyzed during hydrolysis reactions (Bemfeld, 1955).

The results are shown in Figure 2.

5

As is evident, alkali-treated spruce was hydrolyzed with enzymes more efficiently than steam blasted spruce: both the rate of hydrolysis and the level of hydrolysis at the end of the reaction were higher.

Example 8

The base-catalyzed materials prepared according to Example 1 were filtered and the solid fractions washed with water. The composition of the solid fraction was analyzed by HPLC to monosaccharides after acid hydrolysis (Puis et al., 1985; Tenkanen and Siika-aho, 2000).

Table 3. Solid fractions monosaccharide composition (% dry weight)

Base Catalyst- Base Catalyst- Base Catalyzed Base Cured Salted Salted Seed (Without Barley Straw (Ilkwood, Washed Barley Straw, Washed Catalyst), Man Catalyst Solids Washed Solids), Washed _____ Material__Solid__ <0.1 __ <0.1 __ <0.1_ arabinose__0 ^ 6__2J__frO__fr9_ galactose__0 ^ 6__0 / 1__frO__0 ^ 2_ glucose__79__63__52__60_ xylose__4 ^ 9__27,8__6 /) __ 24,3_ mannose__12,1__0 / 7__11,1 __ <0,1 0.1 __ <0.1 __ <0.1_ monosaccharides _97__94__71_ 87 as polysaccharides _88__84__64_ 78 solid fraction 56 39 82 61 (% in original) _____

The filtrate was analyzed by HPLC as such after hydrolysis with the enzyme mixture (Buchert et al., 1993; Tenkanen et al., 1997; Tenkanen and Siika-aho, 2000). By this method, no monosaccharides were detected in the filtrate.

20 15

By acid hydrolysis, the oligosaccharides present in the filtrate could be analyzed by HPLC (Table 4).

Table 4. Solubilization of Sugars in Alkaline Catalytic Treatments Analyzed by Acid Hydrolysis and HPLC (% of Original Sugars).

Six, Base-Barley Straw, Six-Comparison Barley-Comparison Talented Hand Catalyst (Base Treatment (Base Treatment 20 Treatment 20 H Without Treatment With Catalyst ___20 h__Catalyst)) _

Ramnoosi__22__0__32__0_

Arabinoosi__41__30__18__40_

Galaktoosi__25__22__12__43_

Glukoosi__03__03__03__1J_

Ksyloosi__28__12__10__13_

Maunoosi__6J__0__13__0_

Fruktoosi__0__0__0__0_

Monosaccharides 4.8__53 ____ 7J_

Example 9 The purpose of this experiment was to determine the hydrolysability of barley catalyzed treated barley straw.

The alkali-treated barley straw was filtered and washed with water. After the catalytic treatment, 38% of the treated wood remained as a fibrous solid. The carbohydrate composition of the washed solid-15 fraction is shown in Example 8.

The washed solid fraction of barley straw obtained by alkaline catalytic treatment was enzymatically hydrolyzed to the monosaccharides. The solid fractions were suspended in 50 mM sodium acetate buffer pH 5 at 2 mg / ml. The enzymatic reaction was initiated by addition of Celluclast 20 1.5L FP at 5 FPU / g and Novozym 188 at 50 nkat / g dry weight. The suspensions were incubated at 45 ° C with magnetic stirring for 72 hours. The release of reducing sugars was analyzed during hydrolysis reactions (Bemfeld, 1955). The results are shown in Figure 3.

16

As a result, the carbohydrates in the base-treated barley oil were completely hydrolyzed to the monosaccharides within 72 hours by enzymatic hydrolysis. Therefore, mother liquor treatment is an effective way to improve the hydrolysis of barley straw and spruce.

Example 10 The purpose of this experiment was to recover the lignin from the dissolved fraction after treatment of the six chips with a catalyst (a standard sample was produced by the method described in Example 1, a standard 5 hour sample, except for a reaction time of 5 (65 mg / l CuSO 4, 150 mg / l 1,10-phenanthroline)).

The filtered solutions obtained from the basic catalytic treatments of spruce were precipitated by acidification to pH 2.5 with hydrochloric acid. The precipitates were collected by centrifugation and washed repeatedly with water, pre-adjusted to pH 2.5 and freeze-dried.

Three chips processing conditions were used. The yields of precipitates are given in Table 5.

20 Table 5. Yield of precipitated lignin ___ G / l% by dry weight ^ Standard 3.51 7.55_ “** Standard 5 h 1.05 2.25_” 1Standard lA cat 1.90 4.08_ * 46 g dry wood / 1, 0.25 M NaOH, 48.6 mg CuSO 4 * 5H 2 O, 70 mg phenanthroline at 100 ° C, 20 h, 10 atm O 2 25 ** 46 g dry wood / 1, 0.25 M NaOH, 48 , 6 mg CuSO 4 * 5H 2 O, 70 mg phenanthroline at 200 ° C, 5 h, 10 atm O 2 46 g dry wood / 1, 0.25 M NaOH, 24.3 mg CuSO 4 * 5 H 2 O, 35 mg phenanthroline 30 10 ° C, 20 h, 10 atm 02 5 17

Example 11 The object of this experiment was to recover pectic substances from the solubilized fraction after the alkaline catalytic treatment of the chips.

The lignin is oxidized and cleaved under basic catalytic treatment conditions to release the polysaccharides initially bound to the solution (Laine and Tamminen 2002). Analysis of the filtrates in Example 8 showed that treatment of the filtrate with a mixture of hydrolyzing enzymes affecting the main polysaccharides in the wood could release only small amounts of monosaccharides, whereas non-selective acid hydrolysis released monosaccharides derived from pectic substances.

The pectic substances are water soluble and thus remain in the filtrate after lignin precipitation. They may possibly be recovered by ultrafiltration.

15

Example 12 The purpose of this experiment was to recover small molecule organic acids from the dissolved fraction after alkaline catalytic treatment of hexagonal chips.

20

Lignin and, to some extent, carbohydrates are cleaved to small molecule organic acids under alkaline catalytic treatment conditions. after precipitation of lignin and ultrafiltration of pectic substances by ultrafiltration, the small molecule organic acids remain in solution and can be recovered by distillation or by selective complexation. The acid composition of the filtrate is shown in capillary electrophoresis (CE) electrogram in Figure 4.

The acetic and glycolic acids elute in parallel and require separate analysis for complete analysis. Dilution improves separation to some extent, indicating that both components are present, whereas analysis at higher concentrations reveals the presence of small amounts of malonic and succinic acids (Figure 5).

Figure 5 shows the acid compositions of the basic filtrate of the standard treatments described in Example 10 with varying dilution ratios.

5 18

The total acid concentration in the standard sample after removal of lignin was analyzed by potentiometric titration of 0.18 M. When used at 40 g / mol at a typical acid weight, this corresponds to 7.3 g / l and 15.7% by weight in wood.

Example 13

Base Catalytic Treatment as Pretreatment for Nanoparticles 10 The base catalytically treated material from wood and / or barley straw was filtered and the solid fibrous fraction was washed with deionized water. The washed solid fraction obtained by the alkaline catalytic treatment was further processed into nanoparticles.

Nanoparticles were also formed during basic catalytic treatment and can be detected in the filtrate.

Example 14

A summary of the plurality of process steps is given below in the schematic representation of two slightly different embodiments in Figures 6a and 6b. The first embodiment (Figure 6a) illustrates the various steps and products obtained as a sugar monomer for carbohydrates during processing, and the second (Figure 6b) describes the processing of cellulose into monomers, including the intermediate liquid separation step. The catalytic pretreatment process described in Examples 1 and 2 is referenced in the figures by reference numerals 3 and 13, respectively.

In the embodiment of Fig. 6a, carbohydrate raw materials such as those discussed above, usually solids with a low moisture content, are first passed to a homogenization step 1 where the materials can be dispersed in a liquid, for example water. Thereafter, the slurry thus obtained is subjected to a catalytic pretreatment 3 in which the slurry is mixed with the catalyst and, if necessary, with a base to adjust the pH of the slurry. High pressure and temperature are used. The result is a suspension of solids and dissolved constituents. Most, if any, feed cellulose is still present as a polymer, while most hemicelluloses are partially or fully hydrolyzed / digested. The lignin is mostly dissolved while the pectins are intact. The solids and dissolved polymer moieties typically also contain some small molecule degradation products, such as acids.

The suspension is subjected to a further treatment which is illustrated in the drawing by enzymatic treatment, for example by enzymatic hydrolysis. However, as explained above, further processing can involve a number of different processing steps, including not only chemical processing but also mechanical and physical processing. After any hydrolysis, most of the cellulose and hemicellulose is hydrolyzed to monomers, while the pectins are still intact. Naturally, the effluent contains small molecule degradation products (acids) and lignin in suspended or dissolved form.

In another embodiment, illustrated in Figure 6b, the raw material (e.g., cellulose 15 lozenge) is homogenized, if desired, and slurried. The slurry is subjected to a catalytic treatment 12 similar to that of Figure 6a. The resulting suspension contains both solids and dissolved ingredients and is passed to a liquid separation step 14 where the liquid phase is separated from the solid. The solid phase, consisting mainly of cellulose, can then be subjected to further treatment as described in connection with the process of Figure 62. As a result, most of the cellulose is present in hydrolysis effluent in the form of monomers.

The liquid phase can be separately processed to separate and recover the dissolved polymers (lignin, sugar oligomers, pectins, etc.) and other dissolved molecules, including various degradation products.

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reference Publications

Bemfeld, P (1955) Amylases, a and b. Colowick SP and Kaplan NO (eds) Methods of Enzymology, Vol. 1, Academic Press, NY, p. 149-158.

Buchert, J, Siika-aho, M, Pere, J, Valkeajarvi, Aja Viikari L (1993) Quantitative determination of wood-derived soluble oligosaccharides by HPLC. Biotechnol. Techn. 7, 785 -790.

10 Puls, J., Poutanen, K., Kömer, H.-U. and Viikari, L. (1985) Biotechnical utilization of wood carbohydrates after steaming pretreatment. Appl. Microbiol. Biotechnol. 22, 416-423.

Tenkanen, M. and Siika-aho, M. (2000) An α-glucuronidase of Schitzophyllum commune acting on polymeric xylan. J. Biotechnol., 78: 2, 149-161.

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Tenkanen, M., Makkonen, M., Perttula, M., Viikari, L. and Teleman, A. (1997) Action of Tricoderma reesei mannanase on galactoglucomannan in pine kraft pulp. J. Biotechnol. 55, 191-204.

20 Laine, C, Tamminen, T. Origin of carbohydrates dissolved during oxygen delignification of birch and pine kraft pulp, Journal of Nordic Pulp and Paper Research 17: 2 (2002) 168-171.

Ohgren, K., Rudolf, A., Galbe, M., and Zacchi, G. (2006) Fuel ethanol production from steam-25 pretreated com stover using SSF at higher dry matter content. Biomass & Bioenergy 30, 863 - 869.

Claims (26)

A process for processing a carbohydrate-containing raw material, characterized in that 5. the raw material is subjected to a treatment carried out with an alkaline substance in an aqueous medium in the presence of O 2 to break down at least part of the raw material, wherein an aqueous suspension is obtained containing solids and dissolved constituents, - at least a portion of the aqueous suspension is utilized, and - at least a portion of the collected suspension is used for fiber-free applications, wherein the carbohydrate-containing raw material is subjected to a first treatment. the presence of a transition metal catalyst formed by a copper ion and a nitrogen-donating ligand, the copper ions being coordinated with a nitrogen-containing organic compound's nitrogen atoms, the compound having a structure where at least two nitrogen atoms are spaced apart from each other carbon chain with 1-4 carbon atoms your. Process according to claim 1, characterized in that the carbohydrate-containing raw material is selected from the group of carbohydrate-containing biomasses consisting of wood, agri-cultural and industrial lateral flows, energy plants, such as willow, pipe flakes, germfruhirs and Miscanthus, as well as bagasse, sea biomass . Process according to claim 1 or 2, characterized in that the raw material is treated at a consistency of about 0.1 - 75% (w / w), preferably about 1 - 15% of the dry weight. Method according to any of claims 1-3, characterized in that about 5 - 90% of the weight of the raw material is dissolved, and at least part of it is utilized in the form of the aqueous suspension of the aqueous suspension. A process according to any one of claims 1-4, characterized in that the recovered material is used for the preparation of carbohydrates selected from the group consisting of monosaccharides, disaccharides, oligosaccharides and polysaccharides or chemicals selected from the group consisting of alcohols, lignin and extracts. 26 6. A process according to any of claims 1-4, characterized in that the recovered material is used for the preparation of nanoparticle or nanofiber crystal structures or other nanoscale structures consisting of substances selected from the group 5 comprising carbohydrates, lignin and extracts. . 7. A process according to any one of claims 1-6, characterized in that the recovered material is subjected to a further treatment step selected from the group comprising fractionation, mechanical treatments, chemical treatments, enzymatic treatments and combinations thereof. Process according to any of claims 1-7, characterized in that the recovered material is subjected to a further treatment step by hydrolysis, fermentation or oxidation or combinations thereof. 15 Method according to any of claims 1-8, characterized in that the recovered material is subjected to a second treatment to increase the yield of carbohydrates, chemicals, lignin, nanoparticles, nanofibrous crystals, nanofibrils or nanofibers. Process according to any of claims 1-9, characterized in that at least part of the solid part of the modified material is used. 11. A process according to claim 10, characterized in that the solid part is subjected to simultaneous sugaring and fermentation to prepare a fermentation product selected from the group consisting of ethanol, lactic acid, sugar acids, acetic acid and acetic acid, which can be prepared by fermentation from monosaccharides. Process according to claim 10, characterized in that the solid part is subjected to separate sugaring and fermentation to prepare a fermentation product selected from the group of chemicals which can be prepared by fermentation from monosaccharides, in particular ethanol, lactic acid and sugar acids. 27 13. A process according to claim 11 or 12, characterized in that a portion of the liquid portion is utilized and subjected to sugaring and fermentation possibly together with the recovered portion of the solid portion. A process according to any of claims 1-13, characterized in that at least part of the liquid portion is utilized and subjected to further processing to recover at least some of the dissolved carbohydrate material or lignin. Process according to any of the preceding claims, characterized in that the raw material is treated with the alkaline substance in aqueous liquid phase. Process according to any of the preceding claims, characterized in that the raw material is treated with the alkaline substance at a pH of at least 8, preferably at least 12. Process according to any of the preceding claims, characterized in that the raw material is treated with the alkaline material at a temperature of 50-150 ° C. A process according to any of the preceding claims, characterized in that the alkaline substance is selected from the group consisting of alkali metal and alkaline earth metal hydroxides and carbonates and bicarbonates. Process according to any of the preceding claims, characterized in that the transition metal catalyst comprises a homogeneous catalyst. 25 20. A process according to any of the preceding claims, characterized in that the transition metal catalyst is capable of more effectively breaking the structure of the lignocellulosic or cellulose material. A process according to any of the preceding claims, characterized in that the transition metal catalyst comprises a transition metal ion which is coordinated with an aliphatic or aromatic amine. 28 A process according to any of the preceding claims, characterized in that a nitrogen-containing organic compound has a structure in which at least two nitrogen atoms are separated from each other by a carbon chain with two nitrogen atoms. A process according to claim 21 or 22, characterized in that the nitrogen-containing organic compound is a heterocyclic compound comprising two or a plurality of fused or ring-assembled nitrogen-containing rings. The process according to claim 23, characterized in that the nitrogenous rings are selected from rings derived from pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, isoindole, indazole, purine, quinoline and quinoxaline. . Process according to claim 23 or 24, characterized in that the catalyst is copper phenanthroline [Cu (II) -1,1-phenanthrolinate]. 15 26. A process according to claim 21 or 22, characterized in that aliphatic or aromatic amine c has a general structure selected from the structure R1 (R2) nUiiN ^ [CR3R4] m_N R6 is independently hydrogen, an alkyl, alkenyl, alkynyl, alkoxy or hydroxyl group which is optionally substituted, or two of said substituents together with an intermediate nitrogen atom form an alicyclic or aromatic ring comprising 1 to 3 rings , each ring having 5-7 ring members and optionally containing at least one additional heteroatom selected from heteroatoms N, O and S, m and n being independently 0 or 1, and ". refers to a single or double bond.