CS226707B2 - Method of processing lignin to be separated from cellulose and hemicellulose in lignocellulosic materials - Google Patents

Abstract

TITLE A METHOD OF RENDERING LIGNIN SEPARABLE FROM CELLULOSE AND HEMICELLULOSE IN LIGNOCELLULOSIC MATERIAL AND THE PRODUCT SO PRODUCED INVENTOR Edward A. DeLong Lignocellulosic material is packed in particulate form in a pressure vessel, steam is passed into the pressure vessel at a pressure of at least 500 psi to bring the lignocellulosic material to a temperature in the range 185 to 240.degree.C(preferably in the range 200 to 238.degree.C, more particularly 234.degree.C) in less than 60 seconds (preferably less than 45 seconds) to plasticize the lignocellulosic material. As soon as the material is plasticized it is extruded through a die to atmosphere where abrasion in the die and explosive decompression forms a particulate material like potting soil that rapidly sinks in water and from which the cellulose content is largely utilizeable, e.g. as a feed for ruminants. During extrusion the softened material is subjected to severe deformation and then severe mechanical shock thus fracturing the linkages between lignin, the hemicellulose and the cellulose. The temperature range and rapid rise thereto by the material substantially minimizes degradation of the fragile hemicellulose. The process according to the present invention converts lignocellulosic material into a substrate which is extremely easy to treat by enzymes, either as a feed for ruminant animals or for conversion to sugars and alcohols and for the solvent extraction of lignin.

Description

The invention relates to a process for treating lignin to a state separable from cellulose and hemicellulose in a lignocellulosic material by thermally softening the material in a pressure vessel. By lignin is meant lignin which is capable of separating from hemicellulose and cellulose by, for example, solvent extraction.

Field of the Invention The invention relates to a method of processing plant-derived materials, wherein plant-derived materials are organisms having a hard and soft stem, stem or stump structure, the organic components formed by photosynthesis. This material is commonly referred to as biomass.

Lignocellulosic materials of plant origin are formed in nature as three-dimensional constituents in which cellulosic, hemicellulosic and lignin polymers are intimately mixed into a complex structure whose nature varies from one plant species to another and also varies with the age of the individual plant species. Lignin is an amorphous three-dimensional polymer in which each macromolecule is made up of hundreds of phenylpropane units that are bound in different ways. This lignin, probably in a compound with hemicellulose, penetrates the cell walls into cellulosic microfibre structures and completely fills the spaces between the cells. X-ray crystallographic analysis suggests that since cellulose microfibers form a separate crystalline phase, lignin is more closely crosslinked with hemicellulosis than with alpha-cellulose.

- 3 '-

226 707

Dry cellulose of plant origin has. the softening temperature or the glass transition temperature at about 230 ° C and, due to its crystalline structure, this temperature is not greatly reduced by the presence of moisture. Conversely, hemicellulose and lignin of plant origin soften at a temperature ranging from 120 to 180 ° C. Since this material is non-crystalline in nature, the softening temperature of said components is varied with moisture content and tacao. Polymers of vegetable. These structures are interconnected by covalent bonds that can be compared to point welds, and it is these so-called point welds that they create. well known and persistent connections between lignin and hemcellulases. Plant. Character ·· V. point. the combined mixtures of macromireculum and vegetable origin. the thermal effect of the heat is determined by the behavior of the individual. cellulose components. Even though absorbed moisture decreases the conversion temperature of the yesophthalic components, it retains. material rigidity up to temperatures in the vicinity of 230 ° C. the spatial effect of cellulose backbone, which is not a plastif of cuboid molecules. waters ·

Lignocellulose mixture of vegetable origin. it constitutes a barrier to the effects of enzymatic rumen. атоП ^ у to break down cellulose. a. hemicenulozb to simple sugars. The lignocellulosic materials vary in their degree of cross-linking for improvement. digestibility

4,228,707 of these lignin-saccharide bonds, it is necessary to disrupt the chemical and / or physical forces.

With regard to the prior art, a process for the treatment of lignocellulosic material is disclosed in U.S. Patent 3,212,932, published on Oct. 19, 1965 entitled Selective Hyirolysis of Lignocellulosic Eaterals by R.W. Hesse, A.M. Thomsen, F. Porter and J.W. Anderson, in which a two-step hydrolysis process is described, wherein pentoses and hexoses are prepared in separate fractions of lignocellulose material, both of which may be used in feed feed mixtures or both may be used as desired. use these products separately for a variety of common purposes for which pentoses and hexoses are usually polluted. The aforementioned lignoceluozo eeterial which may. be selective for the process. Hydrolysis according to Hesse et al., various lignocellulosic coatings may be mixed, resulting from the process. plant growth, and mere! Waste by-products of all kinds of industrial origin are easily included in the above-mentioned raw material, corn husks, corn stalks and bagasse (which is an extracted sugar cane). Specifically, wood of a wide variety of tree species can be included in this material. The above-mentioned lignite weather meteorium does not require any special treatment before the desert. in the above procedure

No. 5,226,707 to Hess et al., Although this material can be crushed to finely divided particles if the material is no longer available in this state. In a preferred embodiment of the process, the wood may be used in the form of sawdust, wood shavings, thin chips in the form of flakes and the like.

In the first phase of the hydrolysis procedure of Hess et al., The lignocellulosic material is heated together with a first fraction of an aqueous liquid of such a nature and under such conditions that selectively the hydrolyzed content of 1: η1οε jakoυ1οζγ in the ligand gives rise to pentoses as desired final product. The premixed lignocrloite and the aqueous liquid mentioned above are fed to a suitable weaving vessel. The vessel may be a continuous or batch pressure reactor, which is provided with means for heating the batch to a predetermined temperature at a predetermined pressure. As mentioned above, this can be done by direct steam injection.

Inside the reactor, the pressure during which the conversion is carried out increases rapidly at a maximum rate to a value in the range of 0.69 MPa to 4.83 MPa, and preferably to a pressure in the range of 1 to 10 psi. 72 MPa to 4.14 MPa, the temperature being raised simultaneously to a value corresponding to saturated steam. These conditions are maintained within the reactor for a relatively short time, and this time is sufficient only to convert the hemmieluolysis content of the lignocrlulozr to pentoses, to a sufficient extent and selectively.

226 707 way. On average, this period ranges from 0.3 to 10 minutes, the time being essentially inversely related to the temperature used. This means that the higher the temperature, the shorter the processing time and vice versa.

As a result of the above process, products are obtained in liquid form which contain pentoses together with a small amount of volatile organic acids such as acetic acid together with residual mineral acid if the mineral acid has been introduced in the first phase. A first fraction of a solid residue which is substantially free of pentosanes and which consists predominantly of non-cleaved lignin and non-cleaved cellulose is also formed.

In a further phase of this process, the pressure is reduced before the liquid computer and the solid residue are separated as product. While the time required to reduce pressure has been very long in the prior art, that is, within a few hours, it is very important for the process of this patent that the value of this interval be kept at a low level to achieve a satisfactory result. For the above reason, and in the process of this patent, it basically uses an instantaneous pressure reduction, which is referred to in this patent as instantaneous expulsion. In the case where the continuous reactor is poauit, the time required for this instantaneous expulsion is about a few seconds. In the case where a batch reactor is charged, the batch reactor is charged. se

- 7 226 707 the interval required for the instantaneous expulsion is limited to a few minutes.

The above-mentioned rapid pressure reduction results in several significant effects. First, the hydrolytic reaction stops rapidly. That is, this measure minimizes the formation of hexoses resulting from cleavage of the cellular cell. This measure also minimizes the formation of lignin degraded products and also prevents the degradation of the desired sugars as products.

Second, some of the water present in the process is evaporated by this flash gas expulsion. The resulting steam can then advantageously be used for heat exchange with the material to be fed to the reactor.

Third, acetic acid, formic acid or other organic volatile components which can be formed as by-products of the above reaction are distilled off by said flash gas expulsion. In this way, a simultaneous separation operation is employed, in which a proportion of impurities is separated and removed from the reaction product.

Fourth, in the above-described flash gas expulsion, solid residue particles explode. By this measure, porous openings are created which allow more efficient processing of the material in the second hydrolytic phase.

- 8 22V 707

In the second phase, hydrolysis according to Hease et al. is used for this process in the second reactor more severe conditions than for the previous stage in the first stage reactor. The aim of this phase is to convert the cellulose to hexoses without bv causing undesirable lignin cleavage.

In view of the above, the liquid to solid ratio is kept within a wide range, practically from 1: 1 to 5: 1, and preferably from 1: 1 to 3: 1. The concentration of the mineral acid in the liquid treatment composition is maintained at a value in the range of 0.3 to 3.0% by weight.

In this process, the reactor is heated indirectly or preferably by direct steam injection until the pressure is in the range of 1.0 MPa to 6.21 MPa, and preferably from 2.76 MPa to 5.52 MPa. MPa, the temperature corresponding to saturated steam at this pressure.

The reactor is then maintained under these conditions for a time that is inverted to the temperature, i.e. the higher the temperature, the shorter the time and vice versa. During this period, which ranges from 0.3 minutes to 10 minutes, the cellulose content of the batch is converted in a substantially selective manner to hexoses, leaving a solid residue containing largely non-hydrolysed lignin.

226 707

With regard to this first phase, it should be noted that it is highly quenched in a sudden manner to evaporate excess water, further to distil off the organic volatile substances which may be present and, last but not least, to: The lignin residue may be physically modified and may be separated and more easily dispensed with.

For these reasons, the charge in the reactor is subjected to a flash gas expulsion which is carried out by continuously feeding the charge into a cyclone flash flash. In this way, the atmoosheric pressure in said material is reduced in a few seconds.

The vapor produced in the instantaneous expulsion apparatus is evacuated, the solid product formed being washed with water in the extract belonging to the second stage of the process. The result of processing in. this. of the extractor is that the hexose-containing liquid is removed from the cellulose containing the lignin residue, which recycle or being recycled.

Thereafter, the liquid is treated with a neutralizing substance, such as calcium carbonate and any auxiliary means for fittaation, further added with more water if necessary, and the resulting mixture is filtered.

- 10 226 707

The above procedure of Hess et al. is an important stage in solving this problem, but it has been found by the present inventors that hydrolysis, which serves to make pentoses and hexoses separable from lignin in the lignocellulosic material, works to account for the loss of the useful fraction of hemicellulosic substances present in the lignocellulosic material products of plant character. The acidic effect of hydrolysis required to cleave lignocellulose gradually decreases the fermentation value of hemicellulose, so that a high proportion of hemicellulose, which is indigestible to ruminants, becomes undesirable during the period required for hydrolysis.

The foregoing drawbacks of the prior art have resulted in the need to develop a process in which the accessibility of cellulose in the lignocellulosic material is increased while at the same time maintaining the fermentation values of hemicelluloses to a critical extent.

U.S. Pat. No. 3,667,961, published June 6, 1972, entitled " A method for improving the digestibility of ruminant feed by J.W. Algeo, and No. 3,817,786, published June 18, 1974, entitled "Apparatus for converting physical and complex structural bonds in natural ruminant feed into various less complex molecular structural bonds",

- 11 226 707 by J.W. Algeo, devices and processes are described in which ruminant feed is subjected to high pressure steam in a pressurized container and then this material is explosively released into the atmosphere into a centrally located vent whereupon the product is collected and stored. This final product is a spongy structure and is furthermore chalilkeeistic with its capacity to readily absorb water and digestive juices when ruminants are ingested. V. in the case of cellulosic feed materials such as bulk feed including hay, straw, and the like, as in the case of whole feed materials such as mud seed husks, rice husks, walnut shells, or chopped coffee material, the pressurized steam pressure The vessel is rapidly raised to a value in the range of 3.45 MPa to 6.9 MPa, and in this embodiment the temperature is in the range of about 243 ° C to 285 ° C. This process can be described as a thermo-mechanical process for processing lignosellulose materials. The process can also be applied to other materials, such as non-cellular staple feed, and the temperature of the vapors is between 177 ° C and 204 ° C.

The aforementioned Algeoai process undoubtedly greatly benefited from the practice of these processing methods, but the inventor has found that increasing the temperature of the material to a temperature in the range of 12 22β 707 ° C from j ° C to 285 ° C, used in the Algeo procedure, by a diminutive reduction in the fermentation value of the goat's cells. It follows from the foregoing that there is a requirement to develop a process for treating lignin into a cell separable from hemicellulose contained in a lignocellulosic material of plant origin, whereby some use of the product formed in this manner essentially preserves the fermentation value of hemicellulosis in this ma At the same time, the accessibility of alpha-cellulose is enhanced when enzymatic digestion is involved.

Pcd; A process for treating lignin to a separable cellulose and hemicellulosic state in a lignocellulosic material according to the present invention is to first fill a pressure vessel with a lignocellulosic material which is in a partially particulate form, the pressure vessel having a closed extrusion die. opening, followed by rapid filling of the pressure vessel with steam at a pressure ranging from 3.45 MPa to 4.83 MPa, wherein the lignocellulosic material is heated to a temperature ranging from 185 to 240 ° C, in an interval of less than 60 seconds, by thermally softening the lignocellulosic material, wherein when the lignocellulosic material is in the extrudable state, the extrusion die is opened, the lignocellulosic material is forced out of the pressure vessel into the atmosphere, leaving it in particulate form together with the lignin, which is also in particulate form. particle size in the range of 1 to

- 13 226 707

kron while simultaneously separating the lignin from the cellulose and the glue cellulose, optionally comprising filling the pressure vessel with lignocellulosic material, filling the pressure vessel with steam and extruding the lignocellulosic material under said conditions at least once.

In a preferred embodiment of the process of the invention, the lignocellulosic material is extruded onto the impact surface.

It is also advantageous if the pressure vessel is rapidly filled with steam, whereby the lignone is reduced. it is heated to a temperature in the range of from 00 to 238 ° C in an interval of less than 45 seconds.

An even more preferred embodiment is to quickly fill the bag container with steam, wherein the ignlo-cellulosic material is heated to 234 ° C in an interval of less than 45 seconds.

It is further preferred that, when repeating the phases of filling the pressure vessel with lignellulose material, filling the bag with steam and extruding the ainloceal cell material under said conditions, the temperature of the lignell cellulosic material is at most the same as in the first process.

The lignin is preferably extracted with a solvent

- 14 22В 707 of said particulate material exiting the otvoru extrusion orifice, the solvent selected from the group consisting of ethanol, methanol and acetone.

In this embodiment, it is preferred that the wet alcohol-insoluble material is separated from the particulate material by the alcohol before the lignin is extracted from the material by acetone.

Preferably, after extraction of the lignin wet in the organic solvent, the insoluble matter is separated from the lignin solvent by filtration in this embodiment.

Further, in this embodiment, it is advantageous to extract the water-soluble substances from the particulate material with water before the lignin has been extracted from the material by the solvent. _t

It is also advantageous to extract the water-soluble substances in this embodiment from the material with water only after the lignin has been extracted from the material with a solvent.

Alternatively, in the basic process, said hemicellulose is extracted from the lignocellulosic material by hydrolysis with water at a temperature above ambient temperature and below the boiling point, prior to filling the pressure vessel with the lignocellulosic material.

- 15 226 707

The lignocellulosic material to be treated according to the process of the present invention is preferably a wood mass, wherein the pressure vessel is rapidly filled with steam at a pressure of. from 3.45 MPa to 4.83 MPa, and preferably in the range from 4.14 MPa to 4.83 MPa.

It is further preferred that the lignocrluloo material to be treated according to the process of the present invention is an annual biomass, wherein the pressure vessel is rapidly filled with steam at a pressure ranging from 3.45 MPa to 4.14 MPa, preferably 3 bar. 79 MPa.

In a basic embodiment of the process of the present invention, it is further preferred that the lignocellulosic material in particulate form or in finely divided form is moistened with water when filled into a tank to a state of fiber saturation.

According to the invention, it is preferred that the lignocellulzo treatment to be treated is an annual plant substance, the pressure vessel being rapidly filled with clapping steam. 3.79 MPa, and after 40 seconds, the vapor pressure is rapidly increased to a pressure ranging from 3.45 MPa to 4.83 MPa, and the release pressure is released immediately after reaching of said higher pressure.

In the case where the said processed lignocelulo- 16 -

The 226707 material is a wood mass, wherein the pressure vessel is rapidly filled with 4.48 MPa steam, it is advantageous to increase the steam pressure rapidly to a higher pressure after about 40 seconds and then release the material by extrusion immediately upon reaching said higher pressure.

The solvent-extracted lignin may be present in particulate form, the particle size being in the range of 1 to 10 microns, having a purity of about 93% by weight, chemically readily reactive, thermoplastic, and similar in infrared spectrum. spectrum of the so-called natural lignin.

Advantages of the process of the invention include that the product obtained has the desired characteristics, i.e. a substantial proportion of the alpha-cellulose present in the lignocellulosic material is now present in a usable form, that is, a form useful for microorganisms, the values or hemicellulose content of the lignocellulosic material appears to be negligible. Therefore, the product obtained by the process of the present invention is useful as a ruminant feed, an enzyme for the preparation of sugars, and a material for conversion to alcohol using microbiological or chemical means or both.

- 17 226 707

Furthermore, the product obtained by the process of the invention has the advantageous properties that a major proportion of the sugars present in the hemicellulose can be removed from the material, for example by hot treatment, and a major proportion of the lignin is removable therefrom by solvent extraction, for example using ethanol, methanol. or acetone, leaving the cellulose-rich material as a residue, which can be used, for example, as a pulp in the cellulose derivative process, or can be directly dissolved using a suitable cellulose solvent.

As used herein, the term lignocellulosic material refers to materials of plant origin, such as oat waste, corn stalk, bagassa, wheat straw, rice straw, oat straw, barley and wood of various kinds, and particularly hardwood.

The nature of the process for treating lignin to a state separable from cellulose and hemicellulose according to the present invention will be further illustrated by the accompanying drawings, in which:

FIG. 1 is a side cross-sectional view of a pressure vessel having an extrusion die outlet for carrying out the process of the present invention; FIG. 2 is a graph showing the speed at which

228 707 releases the reducing sugar by hydrolysis from products obtained by extrusion. Figure 3 shows the graph of the enzymatic utilization of the fed-on substances, such as glucose, produced at different temperatures at which the lignocellulosic material is extruded; Figure 4 is a graph of the enzymatic utilization of the sugar content of the material prepared at different temperatures. Fig. 5 shows a flow diagram relating to solvent extraction of lignin from processed aspen pulp, Fig. 1 shows a flow diagram relating to solvent extraction of lignin from processed straw from barley. - * Fig. M shows flow diagram solvent extraction related to processed aspen wood or barley straw using acetone as solvent, and FIG. 1S is a flow diagram of acetone extraction of lignin originating, for example, from wood or straw.

FIG. 1 shows a pressure vessel 2 comprising a star-shaped extrusion die 4, an extrusion die 6

226 707 the end shutter 8 and the inlet openings 10 and χ2 for the steam.

The pressure vessel 2 comprises a bottle neck portion 14 which terminates through a die outlet 4, the pressure vessel also comprising passages 16 and 18 for thermometer probes (not shown).

The front end of the pressure vessel 2 'including the die outlet 4 also includes a flange 20 to which a curved impact tube 22 is tightly attached, the cross section of which gradually narrows downstream. This curved impact tube has an axial inlet sheet 24 which is also provided with a flange 26. Attached to this flange 26 is a pneumatic ram 28 which includes a die plug 30 mounted on a spindle 32 of said ram 26.

The rear end of said pressure vessel 2 is tightly connected to the remaining part by means of flanges 36 and 38, and this part comprises a filling end shutter 8, which is rotatably mounted on the hinge 40, and sealing is performed by the clamp 42.

In operation of this device, the filling end cap 8 opens and returns the flap 8 and the bag container 2 is filled with lignocell material in a comminuted form, wherein

-20 228 707 the die plug 512 is closed, closing the die outlet 4 · A rod (not shown) is used to fill the pressure vessel 2.

In a further stage of the process, the pressure vessel 2, which is completely filled with the lino-cellulosic material, is sealed at the location of the die end plug 30 by a pneumatic ram 28 and the end plug 8 is sealed to the rear end 34 by a clamp. 42. The bag is then filled with steam at a pressure of at least 3.45 MPa, and preferably at a pressure ranging from 3.45 MPa to 4.83 MPa, and at a temperature dossing to raise the temperature of the lignocellulosic material to a semi-humidifying temperature. in the range of from 185 to 240 ° C, and preferably at a temperature in the range of from 200 to 238 ° C, and particularly preferably at a temperature of 234 ° C, intervals of less than 60 seconds and preferably! at intervals of less than 45 seconds, whereby the hemagellucose fraction and the lignin fraction in the linocellular portion are injected into the vents 10 and 12 for supplying steam from a source (not shown). The temperature probes (not shown) in the passages 16 and 18 are used to monitor the temperature of the lignocellulosic material in the bag 2, which is necessary to see whether the aignocellusic maaeeia reaches. preselected temperatures.

As soon as the user and the user in the bag 2 reach the desired preselected temperature, the pneumatic rammer 28 is actuated, which releases the closure plug 30 or more immediately opens the die outlet. 4, which is opened to the atmosphere, wherein the lignocellulosic material is extruded through the die-like outlet 4 in the plasticized state and at the extrusion pressure, this material being J. sprayed into the atmosphere preferably at milliseconds intervals into the curved impact tube 22. This sudden release of the maaerial into the atmosphere causes extrusion of the ligrocellozo material in a plasticized state with a pressure in the preferred embodiment of the present invention ranging from 3.45 MPa to 4.83 MPa. The above process produces a particulate male that has the appearance of soil in a flower pot and which turns fingers brown, while at the same time having such a specific gravity that it falls like a stone in water.

The aforementioned curved impact tube is not essential to the apparatus for carrying out the process of the invention, but its advantage is that the extrusion force is used to further spread the lignocellulosic material in addition to the expansion that is achieved during extrusion.

One possible explanation of the effect of the process according to the invention is that the plasticized linaocellulosic material and thereby simultaneously the lignin, hemicellulose and cellulose are softened and in this way also weakened structurally, whereby during the extrusion the softened material is subjected to severe mechanical stress

· The impact of the lignocellulosic material at the same time as the pressure decreases, causing the lignocellulosic material to exit through the die at the same time as the pressure drops, that the weakened cleaved maternal material in this linnocellozoid material explodes, degrading the hemicluloose to a low como-constituent component while substantially degrading the major fibrous structure, thereby exposing a substantial proportion of the alpha-cellulose microfiber surface, which may advantageously be some cases of use of the product according to the invention attacked by a fermenting agent

The basic crystalline structure of the cellulose microfibers is retained. A high degree of lignin separation is achieved by the above process. When the process according to the invention is carried out at a temperature above the upper limit temperature of 243 ° C, the xylose component is likely to decompose. It should also be noted that the decomposition will cause toxicity to m-cr or c. One object of the present invention is to process alpha-cellulose into a state in which which would be highly accessible to m-cremation, which also has the effect of h / drolysis on herniceeuosis. It is obvious from the above that it is very important that the interval required to reach the desired temperature is not greater more than 1 minute, and even better if the interval is less than one minute

- 23 226 707 from 30 to 50 seconds. The pressure value is not critical as long as this pressure does not affect the time to reach an optimum temperature of 220 to 230 ° C. The process of the present invention may be repeated at least once at the same or lower temperature to provide additional yield or improved product closeability.

The detailed description of the further figures will be made in conjunction with specific examples of the process according to the invention.

He did

The process according to the invention was carried out with the aid of the device shown in FIG. 1, the individual parts of the device having the following dimensions:

the inner diameter of the main part of the pressure vessel 2 was

190,5 mm,

- the smallest inside diameter of the bottle neck shape in the case of such a container was 82,4 mm,

- the length of the inner part of the pressure receptacle 2 was 1,14 m,

- the inside diameter of each steam inlet 10 and 12 was 19 mim,

- the inside diameter of the steam supply 11 was 50.8 mm,

the die port opening was shaped into a star shape with five equally spaced points, with a cross-sectional area of 11.6 wO '.

- 24 228 707

In the following tables δ. I to V, said temperature means the temperature of the material in the pressure vessel 2 at the time the closure plug 30 is removed, and the vapor pressure is the amount of steam in the pressure vessel 2 at this instant. Said time is the time interval in which the temperature of the lignocellozo material is raised to the temperature indicated, and then extrusion is carried out from the container 2. The tables below show the results of experiments according to the invention in comparison with the results of experiments carried out at temperatures higher than those used in the process according to the invention. In these experiments, the utilizability is determined in two ways, in vitro and in vivo, with ruminant microscopy and, in the latter case, by treatment with cellulase anzyme, the results obtained being shown in Tables I to V.

In all of the above tables, the same lignocellulosic material tested is labeled in the same way, for example, in each test, A denotes the same lignocellulosic ζ ^ γΙΙΙ, etc.

- 25 226 707

Μ)> о о

сб а Ή Р А> Ν

О

Оц

СО

О й Р • н>

а • н

> о> Р> 03 • п N

..XI Ό

Ф

Р со о β

ГЛ

what <0 co X> O trx O AND 1 A- m

β

what C0 and • β WHAT what • H what O m tr \ and O bunch m AND •with O AND AND AND cq nq what WHAT

• What about

β >> + AND N Φ O z-ч P 1—1 • 05 / and P > AND O O Φ and it O Λ • H 1 cR AND what • H «Ρ P AND 4-Z AND WHAT

x; > » ω N it O Z ~ 4 XI AND >> O 3 β AND • H Φ > сз > O 3 O 1 WHAT Pd 05 / i — 1 «Η Φ AND O WHAT 4Z

AND what 'Φ -P • H z-ч O β o AND Φ o Λ -P Φ what * - * CH and

00 AND kO O m 00 tcx O 4 » «* 44 ГЧ 4¾ in* · * 44 tr \ UTX H AND m kO AND <O AND it O- t- L \ AND b " it

00 AND <o r * 4 O- σχ , φ t- «4 «4 44 · * 44 4 » «4 «4 00 << n AND <O LÍA rq what WHAT cq m ro pq m pq rq ΓΌ

r4 O AND 00 CM AND AND AND CM AND r- m irx trx ČM t- rn CM CM AND CM CM CM CM AND CM

° 3 o> Сб Л4 'S'>

> ES3

Ф> β гл о d

P • H>

• H

Mar '05> O> P> ω • H

Ό

CO i-I

А

СО а я

o xi Ή β> 0

CO P β Φ g

0) С

O

WHAT Ό £? о «Η o

J3 ‘á

P

CO φ Eh> about it

I 3 —I Φ O

O во • H A

A 'CO -H £)

05 P 05 a

-and

AND

About d

• p <c and d o

Λ4

O A M í * <

гЪ

N * O

AND

AND

Ф

O

AND

CO ch A

Λ! And what about

o> Φ

And а φ a> o

Ф • o

O 3 I — I Ф P CO> o

AND

WHAT

N • H A • H P

AND

226 707

From the results shown in Table I, it is apparent that at temperatures above about 240 ° C, there is a marked decrease in the utilizability of the alpha-cellulose, and this represents approximately 65% of the monohydrate. generally, the carbohydrate carbohydrates present in the starting material, it is necessary to increase this carbohydrate.

The results of the analyzes are ukaszijí / see face. 4, where the sugar content in any units is plotted versus the temperature in ° C), that the alpha1011 has not been cleaved in this way, indicating that the loss in the in vitro utilizability of the rumen of the animals is due to some external factors .

Example 2

Cheirácká chaaaakterřika processed wood shavings.

The main objective of the process described below is to compare the effect of the process according to the invention under different reaction conditions. The experiments carried out were of an exploratory nature, the samples used being the same as in experiments A to D, and of exploratory significance. it also had aspen processing and barley straw processing, which were given to sheep in order to calibrate the test. These experiments include a wide range of reaction conditions. The results of the analyzes are shown in Tables II to IV.

As can be seen from the results of these experiments, it is evident that the samples can be classified into two categories:

226 707

- wood mass which has been processed by the process of the present invention at temperatures below 240 ° C (samples A, B and C),

wood material which has been processed at temperatures above 240 ° C (samples D and wood as feed).

The samples listed in the first kaΐegooii appear to be a better source of carbohydrate components than those in the second category, or O. the effect of the high temperatures that are used to prepare the products referred to as the second category will be manifested in. . .

extensive decomposition of pentozomes present in wood mass.

The preparation of samples A, B, C, D and wood material as feed was carried out by drying the samples at 105 ° C overnight to a constant height. These samples were extracted with water for 18 hours at 10 grams. The wood mass of the fibers was dried and then the extracted matter was recovered. The aqueous extract was diluted to a volume of 250 mL. analysis was then performed with aliquots of the extract.

The total carbohydrate content was determined by a colorimetric method with phenol and sulfuric acid, see M. Dubois et al. Anal. Chern.,. 28 (3), 350 (1965). The sugars were determined by Sornmoyi micromethod. I., pp. 380 (1962), Academic Prese, Inc. The total sugars content was determined by gas chromatography by hydrolysis by Tappi method T249 pm-75.

> N O гЧ

WHAT

Analysis of substances extracted by hot water (game cellulose) for aspen material * φ and A φ 14 я o Φ ai co eO o

O

I o H

Í o. O ÍX

P Ή a д • H

AND

Λ

O 05 CO o Pi & • H>

φ> φ> й £

• r4> ω what • H

Й

22B707

ir SR SR O σχ Λ ** OJ · * CM Q LT \ CM CM 00 r4 r4 4- + + +

XJ O> ф> Ф> й Ό хз by 1?

0> c0 (0

P o a

N> N

P ся>

>

>

й o

> what what> Ф and ♦ rl> 0) and what

> R ЪЯ '<R <R ř- 00 ir\ · » • 4 · * OJ CM rn O r4 гЧ r4 CM

> ф and й '05 co

O N and 05>

J-Э ώ о

P o and o 14

O • H <05 05 Й bO o • P ctf

1 o X4 'Ф f SR t- SR гЧ SR O SR r4 0 гЧ '05 £ сб О Й XÍ and + 05 / H £ Λ • 4 «4 · * • гЧ and о Й φ M · σ> 00 й • P P cn CM r4 ф о 0 ώ '05 • Р and О pq > гЧ 01 ф > а > N о 03 / Р O O 00 гЧ о Р гЪ Ή • b in* · * · * х: N1 гЧ M- xf м- * ф ri > О. 4ч Ф 0 0 : С0 О Й 0 • гЧ WITH 0 пз J3 гЧ -P ΧΌ СО О 0 '05 (J) C > О ♦ Н O WITH аЯ ъя ая м Р 14 > Ж and xí 0 Ф X3 O 3 Р о X! -Р r4 O гЧ хГ ЧО CM σ \ со '>> 05 / Сб а > 05 / '05 • w »* • 4 о q со Й • Η O oo гЧ and гЧ X) ig P й l · - 40 Lf \ -Р ф о о 05 / t <J Φ о ч ^> х: ω P а 05 / о 4D x> Φ 03 / XJ > XÍ Р O > а О XD ф ? я Х1 Р> > со 0 О 0 0 й 14 СО 0 о Р гЧ r4 со X Ф > ф 05 / '05 Ό ф О Р P • H й O Й о r4 O 00 O 01 14 Ή '05 гЧ Φ о CM гЧ ín > О • Р Ф О > со Pi P CM CM CM Ф й and • Р О 0 Ф 05 / 4Z > й Οι ф чО а со ЕЧ а ^r 0 о гЧ о о ф о л > 'Ф > О i й О P • гЧ > CU Р О · 05 / а 05 / С 0. Р со > й 14 0 ф Ф > 0 о 14 O 14 '4 and о Р and Ф O > XÍ о '0 > 0 • Р 05 / О > Ν о й гЧ • гЧ о O <í ra O й J4 Ф ф Pi > • о а N and 05 / > й > (0 4- N л > • о Л > 4 4-

22B 707

X Η

Ρ χ>

C0

Φ> φ TJ ο>

'Φ Μ,

Ci Ο ο

Ρ φ

Ρ 05> ο d Ρ X φ, Μ Φ Ρ '05

Ρ

Ν

3 ο Ρ> Ρ ο ⁸ β P what Ρ ο CLP1 β Ρ Ο Μ ο α • Η and > 0) Ρ 'and χο C < Ρ it · Η> ο • φ Ν Ρ > 05 / ο  ·> and Λ4 <5 ο Η d Whose Φ Α4 χ: Ο 3 ο ο

Ρ

Μ ο

Μ CM ϋ »Ή ό ο 3 ι

Τ5 φ «>

co ο d Ρ ο Βρ 5

TJ • Ρ Ρ> d ο 03 Λ! XI Ρ Ο φ 05 ο Φ

X Φ d Ο ISJ

£ R & М3 Μ * 00 · * • 4 · * kO ο ΙΓΧ CM ρ- rH Ρ

bR <R ižR t— 00 kO <уч Λ O Ο- LTk m · * CM OJ CM Okay

ϊ & <r ir t- LCk «4 л Ckl P kO > - •with ♦ * m -j .. CM O>

<CQ ο ο

X 05

Ό

Ο Ο>> Ρ α> a> d ï TJ X

3 Q 3 and O p I.E rH O Φ P ω Φ £ and 05 / 3 O X and O au P P P O 05 / β Whose Φ WHAT «Η O p P what ^r 3 05 / > φ and 3 and O O Whose I.E P X O P O P P Φ > N 3 and 3 O O > and CL O O Ρ d x Η 05 / ί >> O X Я P P ρ CL C < 5 P P O Φ Φ O I.E (SJ and X O '>> P P P P Whose d Φ O O xo and Whose P and I.E O φ O > 3 X d X! X φ P ^O Φ >} o a φ Whose O > O and O O X O d and 05 / '0 φ 05 / Ό > P O O φ N d d O φ from · ». x > P Op P O m ^r O P d P it. 05 / d P »3 05 / P ω Whose +5 P X O P r * 3 05 / > N Whose O WHAT P X X O 3 X 05 / Cl O 05 / what what "O 05 / P X5 O tSl O O P *; >> P • p> > O 3 > O > X O „Р O and X i — l Cl I.E <—1 φ P Φ & ϋ WHAT Whose O Ρ ÍM m

CO using the Tappi method 249T pm-75

228 707 о τ>

о>

л о гЧ

Ф -Р> О й

Р> 4 Ф

Л о '0 14 -Р' 0>

й

О> N

НЧ '>>

г-4

0S * 3 гЧо • н

0 <44

Лй ад

0о р н0 а о а х: о

ф гЧ

Ф О

40 4ř гЧ 00 · » • ч • ч 4R 40 О 40 ΙΪ4 CXJ СП м- сП гЧ гЧ

Г * 40 О О • ч • ч • ч «Ч • ч 04 / ГП ГП 04 / гЧ

σ> 04 / О Ш »Ч • ч • ч • ч 40 04 / гЧ гЧ · » 04 / 04 / 04 / ΟΊ

О 'xt с- 1ГЧ 00 ГЧ • ч г * л  ГЧ 04 / С \ 1 04 / гЧ о

О

IX й О IX) • п>

О о>> * г4 ω о η φ а> й й τι 14

N О Р

Ф 04

- 3i 226 707

The values of the five samples range from 3.6 to 4.1. This range is basically common for samples of wood components that are treated with high pressure steam (4 bar). Under the reaction conditions specified in the preamble, it is believed that the acetyl groups present in the wood mass are subject to hydrolysis to liberate acetic acid, which lowers the pH (i.e., increases acidity). Such increased acidity is present in the hydrolysis of the lignocellulosic material and increases the proportion of extractable material components in the water in said wood material.

It is apparent from the above procedures that 18 to 34% of the wood components have dissolved (see Table 11). Wood mass is normally made up of 2 to 3% water-soluble substances. The samples belonging to the first category (ie samples A, В and C) have a content of water extractable components ranging from 29.0 to 34.7%, while the samples belonging to the second category (ie samples D and wood material as feed) ) contain only 18.1 to 21.6% of these substances.

The lower percentage of water extractable substances listed for the second product category results from the decomposition of the carbohydrate material (pentose) due to the high reaction temperature.

In the case of samples belonging to the first category, the content of reducing sugars in the extract is approximately half of the total carbohydrate content (see Table III). This fact suggests that the carbohydrate material present in the material

- 32 226 707 has an average degree of polymerisation of 2. In the case of the samples referred to in the second category, the sugar content in the extraction is almost the same as the total sachsaud content. This suggests that the total proportion of soluble Sachaaidic material was converted to monomers.

Gas chromatographic analysis of sugars present in the components extracted with water is given in Table IV.

All test samples are approximately the same. hexoz (i.e. mairnose, oalactose, olucose), but samples D and wood mass feed much less pentos (i.e. arabinoses and xyloza) than other samples that were processed at lower temperatures. These results indicate that at a temperature ranging from 238 ° C to 246 ^° C there is a so-called transformation point, or range of conversion, within which the pentozone is cleaved. Above this temperature, the pentoses are cleaved by mild furfural. It follows from the above that wood fibers processed above this transformation temperature mma! a smaller fraction of the components extracted with water than the samples treated below the aforementioned metering point, since the furfural formed by the decomposition of the penteses is read in the explosive phase of the process according to the invention. The decomposition of hexoses does not appear to be problematic for the above-mentioned test temperatures, mainly because these hexoses are much more stable to thermal decomposition.

The decomposition of pentoses above the aforementioned conversion point decreases

226. 707 quantities of sugars available to be reduced by about 10%, based on the weight of the wood material to be treated. From the analyzes of the water-soluble extracts, it is clear that the above-mentioned conversion point, respectively. above this conversion point temperature, only 2 to 3.% of the fiber is composed of soluble carbohydrates (i.e., samples D and wood material as feed), but below this transition point temperature is 10 to 14% of the fiber content consisting of soluble carbohydrates (i.e., samples A, B and C). .

This sugar loss is caused by the cleavage of xyloza and γγιbinose. This 10% loss of carbohydrate material in the wood mass is also reported by other studies. The wood material as feed (processed at 246 ° C) was analyzed with the result that it was found to contain 33.8% of reducing sugars in the final state after utiizzing for 24 hours with the aid of Trihhoderaa viride cellulase, all other wood mass samples (processed below 238 ° C) have a reducing sugar content ranging from 42.8% to 47.4%. Sample D was not tested this way.

The treated wood mass samples are hydrolyzed with 2N sulfuric acid at a temperature of 100 ° C to determine whether a chemical method can be used to correlate the closability and the release rate of the components during hydrolysis. The results of these tests are shown in the graph of Figure 2, in which the percentages of reducing sugar are calculated per rank of dry product (RS).

34,226,707 versus time in minutes (TM).

In Fig. 2, the single graphs are:

X ----- χ. is sample A in Table IV • Δ ------- Δ is B in a ^ tw ^ lwIV

O - * - * - o is - sample C in Table V + - ------ + is vvooek D in a table XV, and a - O is wood material as feed (aspen) in Table IV.

Samples D and wood material as feed have values of reducing sugars somewhat lower than the other three samples, probably because the strands in the two samples are decomposed and are no longer available for hydrolysis. The difference in the final value of the reducing sugars content (at 2 hour interval) and the rate of sugar release indicates that if the wood pulp fiber is exposed to approximately the same cellulose (i.e. the acid availability of each fiber is approximately the same for all samples) ). Since this accessibility of cellulose is approximately the same, it can be assumed that the fibrillation of the fibers will also be the same, but this is not necessarily true as the access of the cellulosic enzyme to the cellulose. Cellulose fiber can be much more restricted than. it's with the acid.

From the above results it is possible to draw conclusions summarized in the following points:

- 35 226 707

Processing of wood shavings with high pressure steam results in the hydrolysis of acetyl groups and degradation of the hemicellulose present in the wood mass, releasing acetic acid and uronic acid.

Processing of hardwood shavings by the extrusion process according to the invention yields 18 to 34% by weight of woody components which are extractable with hot water.

The soluble carbohydrate material is likely to be present in the form of monomers and dimers.

By the present invention it has been found that a temperature in the vicinity of 240 ° C appears to be a transformation point, above which a substantial decomposition of pentoses occurs.

- The pentose cleavage above this conversion point reduces the amount of sugars available for serviceability by approximately 10% by weight of the processed wood mass.

- The proportion of exposed cellulose on the surface of the exploded fiber appears to be roughly the same in all samples tested.

Example 3

In this example, attention was focused on the characteristics of the enzymatic usability of processed wood shavings,

The following Table V shows the results of the measurement of the enzymatic utilization of Trichoderma viride cellulase and the aqueous suspension of the product according to the invention.

<л гЧ

X)

СО •

40 • Н й

Ф д-> со

Я о

] 4]} д со> о о со

ÉH

Ω-.

N • гЧ -Р

СО о η гЧ ω -Р ф> о to • ri г И • И • Р 'Ф

О • Н -Р

Г ”Н

Ib Ф гЧ ω 'ib>

1 д I сб О, М ф > 2 о гЧ о N ад Л • No гЧ ♦ > ь • Н g-i • Р ф Р 2 о о ^Ч Ф Л4 сМ СО ^ч гЧ о • гЧ • о Д • гЧ -Р > о -Р со • Л4 Сб о and Р я Д л ю гЧ ф NJ Ф Рч • Р ч— *

>> 'Ό 1 о со tSJ о 2 гЧ Ф • гЧ ьо > Р Оч Г-Ч • гЧ ♦ >> -Р Я Ф , -М Я О о о Л4 м сб о • Р ’Гэ М ♦ гЧ ω д -Р Q • > о сб д Я я н £ 3 гЪ ф rR ю N -Р ф д Сб чР * ф >

^ гЧ д> о

СО СО • н л гЧ О ♦ Η 'Ό XI -Р &

со -Р о о i — 1 о

Ри (D

FH

-Р со ф н ^ч сб • Н

Р -Р со к;

- 36 228 707

xt 00 43 00 кО 00 О • ч <* »Ч • ч • ч • ч * о СМ 00 <č xf 40 СО xf xť xf 40 LCS см

сП СМ (X) см <п СМ О • ч • ч «Ч л «Ч Л • ч 1Г \ гЧ <п 40 40 L4 40 гЧ гЧ гЧ гЧ гЧ

xt CM CM xf- xt

CM

MCM st- vjC \ l CM

гЧ о гЧ 00 гЧ гЧ гЧ гЧ СМ гЧ 1> · cn xf СМ t> - сП • Μ- си СМ гЧ см см см г-Ч СМ ου

4 · <4 D

o ΛΙ what Ό fa

• гэ

О сб • г}

СО гЧ (О

О

The samples were processed twice

- 37 Enzymatic conditions for utilizability

Pulp density:

PH of the aqueous suspension i

Aqueous suspension temperature:

226 707% by volume of an aqueous suspension

0.5% by volume aqueous suspension

5.0 ° C

Incubation 1

Duration:

continuous mixing of hours (1 hour)

The graph in Figure 3 was constructed based on the results in Table V and this graph shows the dependence of the amount of reducing agents in the dry material in% by weight (RS%) such as glucose versus the temperature (TEMP ° C) at which the lignocellulosic material extruded.

The individual curves shown in the graph in Figure 3 mean:

after usability only usability before usability

The graph in FIG. 4 was constructed based on the results shown in Table V, showing the sugar content in any units (SC) of the post-enzymatic utilization, and the temperature (TEMP ° C) at which the lignocellulosic material is extruded.

The individual curves shown in the graph in Figure 4 mean:

- 38 _________. _______ hexozy ______________ pentozy

226 707 t

The graphs in Fig. 3 and Fig. 4 show the results that the yield of hexos remains unaffected by the temperature of the steam that the lignocellulosic material is displaced, the yield of pentos starting to decrease rapidly. to a temperature of greater than 240 ° C. These results agree very well with those obtained in previous experiments.

In Table V, Test F was performed twice at the two temperatures indicated, and as a result, this embodiment means an additional improvement in performance.

These tests showed that the girder hole ^p lo sectional ^{Ev -} 11.6 mm ² needs Ostu ^{p p p} u ccording to the invention very well. The shape of the die-hole is not important, but it should be noted that the star-shaped hole has been found to provide a sufficient circumference with respect to the cross-sectional area so that meehanic deformations occur sufficiently during extrusion while at the same time very good splitting of the transverse the bonds between lignne, cellulose and cellulose.

In a preferred embodiment of the process of the present invention, the temperature ranges from 200 to 234 ° C.

39, and a temperature of 234 ° C is particularly suitable.

226 707

Example 4

According to this embodiment, the following morphological analysis was carried out with the processed aspen wood and the barley straw of the previous example.

- freeze-drying to determine the moisture content of the samples while maintaining their structure,

- microscopic optical observation of these freeze-dried products, - extraction in hot water for 24 hours,

- stereotypical X-ray diffraction for the original product, for the freeze-dried product and for the extraction residue,

- observation of freeze-dried samples by means of a scanning electron microscope.

Freeze-drying was performed with the following samples:

Sample

Moisture content wood material from aspen

48.8 wt.

straw of "barley mass".

- 40 226 707

After freeze-drying, the dark brown color of each of these samples is cleared and sedentary reflections appear.

A strong and acidic odor is characteristic of carbonized sugars and carbohydrates.

Optical observations of freeze-dried samples using a microscope showed that the fibrous structure of cellulose

It is recognizable, but the fibers are clearly torn. Obviously, the fibers have been milled and shattered during processing according to the process of the invention. Their characteristics (lumen, division) are still visible. It is possible to distinguish the deciduous character of the wood used from the presence of wood vessels.

Extraction with 100 ° C water for 24 hours was carried out using a Soxhlet tube using a reflux condenser. After 24 hours extraction, the sample became transparent in the last cycle so that the extraction appeared complete.

Aspen wood mass 30.0% extracted

Barley straw 26.8% extracted

The characteristic smell of the samples was reduced in the extract samples, but the color was the same. Carbohydrates and lignin weak chains went into solution, but the rest contained much more

- 41 226 707 water-insoluble lignin at 100 ° C. Briefly, the remainder consisted of cellulose and long chains of hemiceeuloid and lineage, and the extract consisted of carbohydrates from hydrolysis of hemicceuloid, already carbonated sugars and trace lignin. The cold extracted solution was colored and also contained a large percentage of suspended solids.

X-ray analysis revealed that cellulose is present in crystalline form in the crude products, in the freeze-dried products and in the extract residues. This confirms the long cellulosic chains (in the form of more or less torn fibers after processing). · '

There was no significant difference between samples of treated aspen wood and barley straw.

Electron microscopy of freeze-dried products was obtained by scanning electron microscopy. One sample was shown in Table V and represented: wood material as feed (x 1350) wood material as feed (x 2640), straw as feed (x 63SO), and straw as feed (x 2760).

These micrographs demonstrate high accessibility of alpha-cellulose, as well as the degree of eignnoic scare, which

- 42 is a day of lignin spheres that are spread out. in that iattniálj.

Z 4br. 5 0¾ 8 ^ which represent. freeze-dried samples are found to be. the longitudinally torn fragments of the fibers observed thereon. Spherical. the particles, presumably lignin, are separated from the fibers and emitted by mixing in the form of small spheres, which occurs after processing according to the invention.

Morphological analysis suggests that greater fiber accessibility due to the tearing and splitting of the secondary walls explains the increased enzymatic accessibility that occurs in the case of a soaked farmer according to the process of the invention. In fact, the fiber surface area of the fibers increases (splitting of the walls).

This cleavage is likely to occur as a result of the bursting of the middle lamella, with lignin being bleached. and in this way it is separated from the walls.

On the other hand, it should be noted that the microfibrous structure. and cellulose. The ratsatiniet is retained as can be the X-ray diffraction analysis diffraction pattern.

Example 1 and d · 5

226 707

The procedure of this example was carried out in order to turn gold into gold. elimination of lignin from processed aspen wood and barley straw, using ethyl alcohol, and in order to determine lignin yields in these extractions ·

According to the process shown in Fig. JT, treated wet aspen wood (55% ammonium moisture), which is labeled WAP, is divided equivalently into two subdivisions. Each subdivision is extracted three times with 95% alcohol (ethanol) at temperature. surroundings · Can also be used Slightly! as well as other similar solvents · The resulting mixture is continuously stirred in a plastic container using a centrifugal drmecaada · Extraction time and volume of ethanol used were as follows: 1 · Extraction: 12 0.5 · hours,

2 · extraction: 12 liters, 2 hours,

3 · extraction: 7 liters, 2 hours ·

The dark alcoholic extract (fraction # 1), which is designated F ^, is present in the form of wetted alcoholic solutes, which is filtered, centrifuged in a centrifuge and then iconified to a thick black solution. it is fresh ethanol and then extracted with about 500 ml of benzene in a separating funnel. This yields a crude fatty product (fraction # 5),

44 228 707 designated as Fg, a gray powder (fraction No. 7), designated as Fy, was obtained from the benzene and aqueous layers after an associated filtering.

About 3 liters of acetone are then added to the concentrated alcoholate extract, in a slow manner, and the alcohol extract is stirred up in the vessel. The mixture was allowed to stand overnight and then filtered to give a wet acetone. A soluble precipitate (fraction # 2), which is indicated as Fg. The acetone filtrate was then concentrated to a volume of about 1 liter. and then slowly added to 14 Ι ^ ΐη ^ water and the mixture is stirred in a plastic container. In a further embodiment of this embodiment, the water-insoluble precipitate (Fraction No. 3), referred to as Fj, is wintered and then extracted twice with a total volume of 5 liters per liter to obtain a smaller fraction of wax (Fraction No. 8) which is designated as Fg. The aqueous solution was then evaporated to a volume of about 1.5 liters and extracted with another 2 liters of ethyl acetate to give the ethyl acetate (fraction 5) fraction, which is referred to as F 1, and the fraction. ^ είάνε! ^! in water (fraction No. 4), referred to as F 1.

Originally, the wetness of the wet aspen wood material (WAP) was 3,252 grams and the dry weight of the dried ether in the oven was 1463 grams. The following table lists the commander for each fraction obtained in this process.

- 45 Table VI

Fractions Weight of dried material in the oven (G) Weight % of total weight of dry exploded wood from the oven Comment ^F 1 884.0 60.4 carbohydrate-rich fraction ^F 2 94.5 6.5 carbohydrate-rich fraction F, 272.5 12.6 lignin-rich fraction ^F 4 115.3 7.9 carbohydrate-rich fraction ^F 5 81.3 5.6 lignin-rich fraction ^F 6 14.6 1.0 ^F 7 0.6 0.04 ^F S 0.9 0.06

- 46 Example 6

226 707

According to this exemplary embodiment, a similar leaching process is carried out with treated moistened barley straw, this material being designated WBSP 'in Fig. 16.

In FIG. 10, the same fractions are designated with the same reference numerals as in FIG. 9 and in the foregoing description, and this description also applies to the process of FIG.

The initial wet moisture content of the barley product was

173.4 grams and the dry matter dry weight in the oven was 88.97 g.

The initial extraction was carried out in two steps, using 1000 ml of 95% ethanol in each step.

The concentrated alcohol extract (fraction # 1) of F-1 was concentrated to near dryness, then acetone was added to obtain fraction # 2 of Fg.

The acetone foil Fg, fraction # 2, was then concentrated to a volume of about 120 m, forming a precipitate, and the mixture was then added to 1.8 µl of water. The ethyl acetate soluble fraction # 3 Fj was extracted twice with ethyl acetate. The following table provides a commentary on each fraction obtained in the process of FIG. 10.

Table VII 226 707 Fractions Weight of dried material in the oven (g) Weight % of in the oven WBSP tot. asušen. Comment ^F i 55.76 65.3 carbohydrate-rich fraction ^F 2 7.67 9.1 carbohydrate-rich fraction b 11.53 13.6 lignin-rich fraction (93% purity) ^F 4. 5.32 6.3 carbohydrate-rich fraction ^F 5 4.32 5.1 lignin-rich fraction

- 48 228 707

In fractions 1, 2 and 4, lignin is likely to be present in very small. The infrared spectrum of these fractions has absorption chalal saccharides of carbohydrate-rich material. Fractions 3 and 4 are lignin-rich. The Klnsom lignin content in fraction 3 for barley straw is 92.9% and 78.1% for WAP, respectively. These fractions of infrared absorption chhlalktrittlky natural lignin. In conclusion, a very large fraction of the lignin content of the exploded methanol can easily be extracted with ethanol. The separation of lignin from cellulose and hermecellulose is probably due to the lignin depolymerization process of the invention.

Because ethano! and acetone is readily regenerable by performing the above-mentioned simple extraction, this method is very effective in obtaining lignin.

Example 7

In accordance with the process of the present invention, the cast iron can be separated from the two-layered glass complex after processing, for example, wood grain and straw. Another test was carried out with the intention to show that a larger subset of this natural lineage can be easily extracted with acetone.

This procedure was carried out according to FIG. In carrying out this experiment, 70.5 iram treated wet aspen wood

226,707 mass (55.4% moisture, weight of oven-dried 31.44 g), which is designated AW, is extracted three times with acetone. in a 500 ml beaker. 250 ml of acetone was used for each extraction phase. The mixture was stirred with a glass rod for about 5 minutes and then mixed. The third extract was clear and translucent in color. The extracts were combined and concentrated to a volume of about 150 ml in a rotary evaporator. In this way acetone-insoluble matter A1 and acetone-insoluble substance AS in fraction F F are obtained. At the end of the evaporation, great care must be taken to avoid overheating of the solution, which may cause precipitation of the lignin suspension and formation of a sticky mass. Concentrated extract. is then slowly poured into one liter of cold water (10 ° C) and then stirred in the vessel. The mixture of lignin and water is then passed through a slow flow and then dried at ambient temperature to give 6.55 dry powder of lignin, which is a water-insoluble precipitated material in the fraction of 20.8. % of the total dry oil which appears from the fraction Fj as a residue in water, i.e. the water-soluble number WS.

A similar extraction can be carried out with processed barley straw, which is designated BS. In this embodiment, 97.0% of the wet exploded BS material (50.0% moisture, 48.5% of the dried mass in the oven) was extracted three times with a total of 1050 milliliters. The extract thus obtained is

50 228 707 is concentrated to a volume of about 200 ml and then poured slowly into one liter of cold water. This procedure ae yielded 7.2 grams of dry lignin-rich powder, which is about 14.8% of the total dry mass of the material.

The ratio of solvent volume to material weight is selected randomly so that the mixture thus prepared is not too stiff to stir. A concentration of about 12 grams of DM / 100 milliliters of the liquid mixture is most likely diluted sufficiently for stirring with a glass rod. Since the extracted lignin is completely soluble in acetone and the leaching proceeds to a sufficient extent, a high degree of efficacy can be expected. However, equilibrium data for acetone extraction need to be established for this procedure, knowing the amount of solvent and the number of steps. Due to the presence of water in the exploded material, low molecular weight hemicellulose is also excluded. Other much smaller amounts of wax, phenolic substances and extracts are also extracted. The wax (AW only) remains in the lignin-rich fraction and represents less than 1% of the total material. Fig. 11 shows the leaching process AW and BS in summary.

The following table VIIIa lists the amounts of each fraction and the commentary on each fraction.

226,707 ¢ 0

Д1 rO co

Л) А>> Рч · Η чо н а 4-3-Ρ а ο ο Φ t> 4 a ό со Ο Φ й Μ ^{, Γ} 3 ¢ -4 o x4 'Φ> o ΛΙ r ~ í

Φ O • P o o Хч 'Ф а xo а со

-What about a

-p o

AND

Ф o Л4 co P Рч cO> o co cx.

CsJ

40 40 OJ O0 .WHAT *what + »Co Ό? 4 4-p 05 / • P а +3 05 / -P «5 -P what F*" xí • rT X! ti x: • H XI • H XI Whose x: ♦ H O ti O O ti O ti O O ti rO 05 / X) • H x> 03 / X) 03 / x> • H XJ WHAT X3 tL X5 X3 80 X5 φ O Φ 80 φ ϋ Φ O Φ φ O O 05 / O Ή O 05 / O 05 / O ♦ H O 05 / rM ω Λ5 r — 1 what Λ4 Φ You are Í-1 Ю It 05 / 05 / 05 / 05 / 05 / t. 05 / ti WHAT ti ti 05 / ti 05 / ti 05 / <H ti <4 ti Ph ti «Η ti 0i Whose ¢ -4 а

o XJ 'Φ and φ> O and co a

Ή> -P what> tsj o

and г — I '05 • H ti

CO • P CO a

О $

> о о а л ta> ф а ti ό5 ха а со hO> ω and Й 'CO xo а co

σ '. 00 O 00 00 > x> а * а% · • 4 · » а * m- O x · H xť CM M3 CM rH O r4 CM

O m O xť íí \ M- O • CM <* · * Λ ** · < O MD X * O t- CM

1 H CM

Pm pR • η £ ч

I-R

CM

Pm m Pm

I í

AND

I 'CO • H and Φ • P § <!

- 52 22b 707

Klason's lignin analysis of lignin-rich fractions suggests that these lignin-rich fractions contain about 93% lignin. For this reason, a minimum yield of about 90% yield of leaching of wood and straw with acetone can be expected in the treatment of the inventive material. The solvent used can be easily recovered with low requirements for the emitter to be supplied, making the process even more attractive. Another advantage of the process of the present invention is that the acetone-extracted material does not contain almost lignin, thereby substantially increasing the value for fermentation of the substrate or feed material.

Example 8

According to this embodiment, the procedure according to, vol. 1B showing a simplified technical diagram of the acetone extraction of lignin, for example, from treated wood or straw.

The processed material M is fed to the ES extractor and fresh FA-labeled acetone (ethanol or methanol) is introduced into the T tank. Acetone from tank T is then continuously fed into the extractor. The ES and the upper phase of these extractors are then fed into the first evaporator EV1, while the lower phase of these extractors ES flows to the first fiHi F1. the filtrate obtained from the first filter is fed to the first EV1 evaporator, while the remainder of the first F1 F1 is dried in an oven D to form a solid carbohydrate rich subsection S1.

- 53 226 707

The recovered acetone from this first evaporator EV1 and from dryer D is then recycled to tank T. The residue from the above first evaporator EV1 is mixed with water W in the precipitation vessel P. The mixture thus obtained is passed from the precipitation vessel P into a second flask F3, whereby a fraction rich in lignin and a purity of more than 90% is obtained by filtration. The remainder of the second flask F2 is then passed to a second evaporator EV2, where a sachaid-rich solution, designated S2, is obtained, while the vaporized products are sent from this apparatus to a dessillation unit, designated DU, where water W2 is separated from acetone, and the acetone thus obtained is recycled to a tank T.

The lignin obtained by the process according to the invention, by means of solvent extraction from the treated material, can be thermally dispersed and pressed as a lignin fiber, and this fibrous material can be reduced by applying heat to the carbon fibers. Carbon fibers prepared in this way can be used for example for air or water blowing.

Claims (16)

object of the invention 228 707 A method for treating lignin to a cell-separable and hemicellulosic state in a lignocellulosic material, characterized in that the pressure vessel is first filled with a lignocellulosic material which is in particulate wetted form, the pressure vessel having a closed extrusion die orifice, followed by Rapidly filling the pressure vessel with a pressure of 3 to 45 MPa to 4.83 MPa, wherein the lignocellulosic material is heated to a temperature ranging from 185 to 240 ° C, in an interval of less than 60 seconds, while thermally softening the lignocellulosic material wherein, when the lignocellulosic material is in the extrudable state, the extrusion die is opened, the lignocellulosic material is forced out of the pressure vessel into the atmosphere, leaving it in particulate form together with the lignin, which is also in particulate form having a particle size stic ranging from 1 to 10 microns while separating the lignin from the cellulose and hemicellulose, optionally adding the pressure vessel to the lignocellulosic material, filling 220, 707 pressure vessels by steam and extrusion of the indolible material at least once under the above conditions. 2. The method of claim 1, wherein the cellulosic malenial is extruded onto the impact surface. 3. Process according to claim 1, characterized in that the pressure vessel is rapidly filled with steam, wherein the lignocellulosic material is heated to a temperature ranging from 200 to 238 [deg.] C. in an interval of less than 45 seconds. 4. The method of claim 1, wherein said pressure vessel is rapidly filled with steam, wherein said lignocellulosic dipstick. heats to 234 ° P in less than 45 seconds. . 5. A method according to claim 1, characterized in that at S6 228 707 by repeating the phases of filling the pressure vessel with lignocellulosic material, filling the pressure vessel with steam and extruding the lignocellulosic material under said conditions, the temperature of the lignocellulosic material is at most the same as during the first processing in said manner. 6. The method of claim 1, wherein the lignin is extracted with a solvent from said particulate material exiting the extrusion orifice selected from the group consisting of ethanol, methanol and acetone. 7. The method according to claim 6, characterized in that the wet alcohol-insoluble matter is separated from the particulate material by means of alcohol before the lignin is extracted from the material with acetone. 8. The method of claim 6, wherein said method comprises: The extraction of lignin is separated from the lignin solvent by filtration of the wet insoluble organic material. 226 707 9. The method of claim 6, wherein the water-soluble matter is extracted from the particulate material with water before the lignin has been extracted from the material with a solvent. 10. The method of claim 6, wherein the water-soluble matter is extracted from the particulate material with water only after the lignin has been extracted from the material with a solvent. 11. The method of claim 1, wherein said hemicellulosis is extracted from the lignocellulosic material by hydrolysis with water at a temperature above ambient temperature and below the boiling point prior to filling the pressure vessel with the lignocellulosic material. Method according to claim 1, characterized in No. 228,707, wherein said lignocellulosic material is a wood mass, wherein the pressure vessel is rapidly filled with steam at a pressure in the range of 3.45 to 4.83 MPa, preferably in the range of 4.14 MPa to 4.83 MPa. 13. The method of claim 1, wherein said lignocellulosic material is an annual biomass, wherein the pressure vessel is rapidly filled with steam at a pressure ranging from 3.45 MPa to 4.14 MPa, preferably at 3 pressure. 79 MPa. 14. The method of claim 1, wherein the lignocellulosic material in particulate form or in finely divided form is moistened with water when filled into a pressure vessel to a fiber saturated state. 15. The method of claim 1 wherein said lignocellulosic material is an annual plant material, wherein the pressure vessel is rapidly filled with pressure steam. 226 707 And after 40 seconds, the vapor pressure is rapidly increased to a pressure in the range of 3.45 MPa to 4.83 MPa, and the material is then released by extrusion immediately upon reaching the higher pressure. 16. The method of claim 1, wherein said lignocellulosic material is a wood mass, wherein the pressure vessel is rapidly filled with 4.48 MPa vapor, after about 40 seconds the vapor pressure is rapidly increased to a higher pressure, and then the material is released by extrusion. immediately upon reaching said higher pressure.