Method for extracting xylan compounds from comminuted wood components - Patents.com

Abstract

The present invention relates to a process for extracting xylan compounds from comminuted wood components using hot water extraction, which is carried out in a fixed bed reactor with rapid circulation.

Description

[Technical field]

[0001] The present invention relates to a method according to claim 1 for extracting xylan compounds from comminuted wood components. [Background technology]

[0002] Pentosan polysulfate (hereinafter abbreviated as PPS) is a semi-synthetic substance obtained in a multi-step process starting from raw materials of vegetable origin, in particular beech wood, and which can be used to treat various diseases.

[0003] The production and clinical application of PPS has been known in principle since 1944 and can be taken for example from publication CH 290145. The production processes as well as the influence on the specific product characteristics have been continuously improved and further developed over the decades, during which it has become clear that PPS with a specific molecular weight and the highest possible degree of functionalization is extremely well suited for pharmaceutical applications.

[0004] As of the mid-2000s, various partially very similar technical solutions have been published, which on the one hand focus on adjusting the desired molecular weight and on the other hand focus on increasing the degree of sulfation of PPS as much as possible. In this case, different methods of purification and treatment are used. These overcome different problems of different aspects of the process. However, all these methods are based on very similar strategies and often differ only in the choice of solvents used or the technical procedures used to purify the resulting intermediate or final products.

[0005] According to the known state of the art, xylan obtained from beech wood and not very specifically defined is converted into a raw product of sulfated xylan or raw PPS by conversion with chlorosulfonic acid in a solvent mixture of pyridine and dimethylformamide or a similar solvent or solvent mixture. The molar mass of the raw product is then adjusted to the required target value by acid, oxidation or a combined process. In a final step, the raw product adjusted in terms of molar mass is treated again in a solvent mixture with chlorosulfonic acid to obtain the actual target product.

[0006] Thus, in order to obtain the final product PPS with the desired molar mass and the desired degree of sulfation, at least three further obligatory process steps are required after the actual extraction of xylan from the wood components, which usually require further detailed steps such as purification, intermediate isolation and similar further intermediate processes, which make the known processes even more complicated. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Swiss Patent Application Publication No. 290145 Summary of the Invention [Problem to be solved by the invention]

[0008] The challenge is therefore to propose a method by which xylan can be obtained in a form that allows the subsequent generation of PPS to be carried out with a minimum number of steps. [Means for solving the problem]

[0009] This problem is solved by a method having the features of claim 1 for extracting xylan compounds from comminuted wood components.

[0010] A method for extracting xylan compounds, which can be converted to polysulfate pentosans by subsequent sulfation, using comminuted wood components and using hot water extraction is carried out according to the present invention in such a way that the hot water extraction is carried out in a pressure reactor system for heterogeneous reaction in a discontinuous operating mode.

[0011] In one configuration of the process, a mass of at least 3 kilograms, at most 15 kilograms, preferably at most 7 kilograms of aqueous extractant per kilogram of dry mass of the wood component is used in the hot water extraction.

[0012] In a further particular configuration of the method, the hot water extraction is carried out by bath circulation of the aqueous extractant in a pressure reactor system, the pressure reactor system being implemented as a fixed bed reactor.

[0013] Specifically, in a preferred mode of operation, hot water extraction with bath circulation is carried out by the following steps:

[0014] First, a reaction bed is created by filling the pressure vessel of the fixed bed reactor with the ground wood component. This reaction bed is then filled with an aqueous extractant, in particular water. The term "filled" in this context means that the water level of the aqueous extractant substantially corresponds to the water level of the reaction bed of ground wood component.

[0015] Thereafter, circulation of the entire amount of extractant through the extractant circuit for a defined duration takes place with a defined time profile of the temperature of the circulated extractant.

[0016] Finally, the entire amount of the extractant is finally removed from the fixed bed reactor, and then the dissolved xylan compounds within the volume of the extractant are isolated.

[0017] The method according to the invention is therefore based on the surprising discovery that the molecular weight distribution and further chemical and molecular properties can already be decisively influenced during the extraction of xylan if certain specific, later-described process parameters are observed during the bath circulation in a fixed-bed reactor, as a result of which the intermediate steps which would otherwise be required in the production of PPS from xylan can already be carried out, so to speak, one-handed during the extraction of xylan and therefore can be dispensed with entirely as specific process steps.

[0018] In an advantageous configuration of the process, after filling the reaction bed in the pressure vessel of the fixed-bed reactor with aqueous extractant, a swelling bath circulation after a subsequent total exchange of the extractant volume is carried out as an intermediate step.

[0019] This allows any initial contamination to be washed out of the reaction bed, without the actual extraction having taken place yet.

[0020] In an advantageous configuration of the invention, the circulation of the extractant volume is carried out in the following partial steps:

[0021] A first dissolution stage with a first temperature regime is carried out to increase the solubility of the xylan compounds, followed by a second dissolution stage with a second temperature regime to adjust the molecular weight and / or the degree of acetylation of the xylan compounds dissolved in the extractant. The two observed dissolution stages and temperature regimes are the decisive influencing parameters in this case for extracting xylans with the desired properties.

[0022] In one configuration of the method, a complete or partial exchange of the extractant is performed during the second dissolution stage to perform the fractional recovery of dissolved xylan compounds with different molecular weights and / or different degrees of acetylation.

[0023] Additionally, upon final removal of the entire amount of extractant and / or complete or partial exchange of the extractant, the extracted extractant can be directed through a lignin filtration unit, where the lignin portion is removed.

[0024] In the final removal of the total amount of extractant and / or in the complete or partial exchange of the extractant, a heat transfer device can be used to cool the extractant.

[0025] The heat transfer device may be an evaporator that utilizes the heat generated by the extractant, thereby further increasing the concentration of xylan in the extracted extractant.

[0026] Isolation of the xylan compounds dissolved in the withdrawn extractant volume is conveniently carried out by introduction of the extractant into an alcoholic volume followed by a precipitation reaction and final filtration.

[0027] Additionally, when the extractant is introduced into the alcohol volume, a stepwise increase in the ratio of the amount of extractant to the amount of alcohol can be carried out, whereby a fractional precipitation is carried out according to the molecular weight of the xylan compounds.

[0028] As far as temperature is concerned, heating of the aqueous extractant during the swelling bath circulation is carried out to a temperature of 100° C. to 150° C., and the extractant is circulated for a period of 10 to 90 minutes.

[0029] In the temperature regime in the dissolution stage, heating of the extractant to a target temperature of at least 150° C. and up to 210° C. is carried out in one embodiment, at which the extractant is circulated for at least 10 minutes and up to 50 minutes.

[0030] The extracted xylan compounds are suitably sulfated to polysulfate pentosans (PPS) in a basic polar solvent with sulfonic acid without the use of cosolvent power.

[0031] The invention is explained in more detail below on the basis of exemplary embodiments, the accompanying figures 1 to 8 serving for clarity, and the same reference numbers are used for identical parts or parts with the same action. [Brief description of the drawings]

[0032] [Figure 1] The main structure of a fixed-bed reactor for carrying out the method is shown. [Diagram 2] 4 shows a reactor in a further possible embodiment of the method. [Diagram 3] 1 shows an exemplary flow chart of an extraction process. [Figure 4] 1 shows an exemplary flow chart of an extraction process having an additional step, in particular a swelling step. [Diagram 5] 1 shows an exemplary temperature profile for an extraction process. [Figure 5a] 1 shows an exemplary size exclusion chromatogram. [Figure 6] Figure 2 shows the HPLC chromatogram of xylan obtained with the aid of an extraction process after acid hydrolysis. [Figure 7] 1 shows the 1H and 13C-NMR spectra of xylan obtained with the aid of the process according to the invention. [Figure 8] 1 shows an exemplary configuration of an extraction plant for carrying out the method according to the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0033] Figure 1 shows the main structure of a fixed-bed reactor for carrying out the method according to the invention. The fixed-bed reactor shown as an example in Figure 1 is constituted by a pressure-resistant reaction chamber with corresponding pressure-resistant reactor walls. In operation, it contains a pile of ground wood components 2 filled with a liquid extractant, in the case presented here extraction water 3. The extractant in this case only covers the pile slightly above its upper height and is continuously circulated in the subsequent extraction steps. The ground wood components then remain in place for the entire duration of the extraction process in the fixed-bed reactor, while the water volume as a whole is affected by its temperature, circulated, and part or all of its volume is replaced or taken out of the fixed-bed reactor.

[0034] In this respect, it must be clearly emphasized that the fixed bed reactor used in the method described herein is not operated as a flow reactor. This means, in particular, that the reaction bed of wood components is not continuously flowed through by the continuously renewed extractant. Rather, in the individual extraction steps described further below, the extractant, i.e. the extraction water, initially added and charged in each case always remains the same and is not renewed itself, at least during the individual process steps.

[0035] In this way, in the process according to the invention with bath circulation of the extractant, it is basically possible to use a smaller water-to-wood ratio compared to known flow systems, for example 4 liters of extraction water per kilogram of wood, since, excluding the dead volumes associated with the plant, in principle only such an amount of extraction water is required to fill the voids in the pile of comminuted wood material. This reduces the extraction volume to be subsequently processed for the same absolute yield of xylan per kg of wood, which gives several hundred to several thousand liters in known flow systems, to an extraction volume of about 60 liters per kg of xylan in the process according to the invention with bath circulation.

[0036] Furthermore, the mode of operation of extraction by bath circulation of the extractant allows the target product properties to be adjusted in the entire volume of the extract, and not just in the portions occurring temporarily as in conventional flow processes. Thus, over the entire extraction cycle, the method according to the invention does not give a product with the specific time-averaged properties of the portions occurring at different times in the flow process, but rather a single product with a single set of precisely determinable properties.

[0037] In principle, the method according to the invention does not necessarily require the withdrawal and reintroduction of the extraction water from the fixed-bed reactor during the extraction process. Such withdrawal is only necessary in so far as the extraction water can be easily thermostated in this case and thus a uniform thermostation of the reactor can be achieved over the entire cross section. Furthermore, the flow associated with the circulation process makes it possible to achieve a very efficient mixing of the comminuted wood components with the extractant, thus facilitating the transfer of xylan from the solid extraction product into the liquid extractant.

[0038] In principle, the mixing of the extraction product with the extractant and the temperature regulation of the total amount of water located in the reactor can also be achieved in other ways. Thus, the extraction product and the extractant can be kept in motion by a stirrer or any other mechanical conveying device located in the reactor, and can be temperature-regulated by a temperature regulation device, i.e. a heating system, located in the reactor itself. However, in this system, the small amount of liquid required for the extraction corresponding to the method according to the invention is only feasible with great technical efforts in the case of wood components. The reason for this is that a small amount of water leads to the fact that the entire mixture corresponds to a highly swollen, dripping, wet solid material rather than a stirrable liquid.

[0039] As an alternative to stirred reactors, it is also possible to mix the extraction product and the extractant by moving the entire reaction system, as well as to regulate the temperature by a heating system arranged in the reactor itself. However, moving a pressure reactor of a corresponding size is significantly more complicated than recirculating only a portion of the liquid. In principle, such reactors are quite technically feasible, in particular as so-called tumble reactors.

[0040] In the example shown in Fig. 1, the temperature regulation of the extraction water 3 is carried out by an extractant circuit 4 which includes a corresponding temperature regulation device, in particular a heating system. At the same time, a continuous mixing movement of the extractant with the mass of ground wood components is achieved by the flow of the extractant circuit.

[0041] The fixed bed reactor has a filler opening 5 for the injection of the ground wood components, which is suitably located at the top of the reactor vessel. At the bottom, an outlet opening 6 is provided which can serve for the introduction or withdrawal of the extraction water 3 in the example presented here.

[0042] In the lateral region of the fixed bed reactor, a second outlet opening is provided, which likewise serves for the circulation of the extractant.

[0043] The fixed bed screen 8 prevents the crushed wood components from being pushed out through the outlet opening 6 and at the same time forms a solid support for the fixed bed of wood components. Complementary to this fixed bed screen, the support and fixation of the crushed wood components can be improved by a suitable geometric realization of the reactor vessel itself. A reactor model suitable for this purpose is realized to be conical in the lower region, so that a screen can be realized which is significantly smaller in cross section and therefore more mechanically stable. At the same time, the flow characteristics are also improved.

[0044] The temperature regulation of the volume of extraction water 3, i.e. extractant, can be carried out in the fixed bed reactor shown here in such a way that the extractant is introduced under pressure into the fixed bed reactor via a first outlet opening 6. This allows the extractant to flow uniformly through the wood components 2 accumulated on the fixed bed screen, thus providing continuous mixing. The extractant leaves the fixed bed reactor via outlet opening 7, is externally temperature regulated and immediately returns to the fixed bed reactor via outlet opening 6.

[0045] During operation of the fixed bed reactor, the packing openings 5 ​​are closed. The entire reactor has an overpressure inside. The walls of the fixed bed reactor are therefore implemented as pressure walls.

[0046] If the extractant, i.e. the extraction water 3, is intended to be totally or partially removed from the fixed bed reactor, its removal takes place via the outlet opening 6. The collected extraction water 3 comprises the extracted xylan and can be further treated accordingly.

[0047] Figure 2 shows a further embodiment of a reactor for carrying out the method according to the invention. However, the reactor presented here is not a fixed bed reactor, but rather the reaction bed is continuously stirred. The reactor here also comprises a packing opening 5 in the upper region. This opening is also closed during operation of the reactor. Also, in the embodiment shown here the reactor has an overpressure during operation.

[0048] In addition, a stirring unit 9 is arranged in the inner region of the fixed bed reactor of one variant shown here, which in the example presented here comprises a stirring drive 10 and a stirring rod assembly 11 with a stirring propeller 12. This keeps the reaction bed of ground wood components 2 and extraction water 3 in permanent motion and circulation within the fixed bed reactor.

[0049] However, stirred systems are in principle technically more complex and therefore more expensive. Thus, for example, expensive sealing systems are required in the area of ​​the stirrer in the case of the pressures required for hot water extraction. At the same time, a reactor system with bath circulation is more advantageous in its simpler design in the process provided here, since a fundamentally larger reactor (pressure vessel) is required.

[0050] In the example shown in Fig. 2, the temperature regulation of the extraction water 3, and therefore of the bath arranged in the reactor, is not carried out by an extractant circuit passing through the exterior of the reactor, but by heat exchange with the environment occurring through the reactor wall, for example the surrounding heat bath or a subsequent heating circuit. For this reason, the embodiment shown in Fig. 2 has heat exchanger surfaces 13 shown diagrammatically. These are thermally coupled to external heating and / or cooling devices, corresponding circuits and temperature regulation devices, etc.

[0051] The extraction process is explained below by way of example. To this end, Fig. 3 shows an exemplary flow chart of the extraction process in its simplest configuration, Fig. 4 a flow chart including additional sub-steps, and Fig. 5 an exemplary specific temperature profile.

[0052] In the process described below as an example for obtaining xylan, the problem is essentially hot water extraction. The first important innovation compared to known processes of hot water extraction is the use of a specific type of reactor in combination with a special operating mode of the extraction, as already mentioned above.

[0053] For the mode of treatment described here, a fixed-bed reactor with bath circulation is used. This means that the wood to be extracted is placed in a pressure vessel in the form of wood chips, and the extractant water is circulated through this bed of wood chips, allowing the extractant to be heated, cooled, renewed or withdrawn as required. A crucial aspect of this mode of operation is the circulation of the extractant (bath circulation). This bath circulation, on the one hand, offers the possibility of intervention allowing the tuning of the xylan properties, and on the other hand, makes it possible to keep the volume of the extractant relatively low.

[0054] Furthermore, it is possible to achieve a specific temperature profile during cycling, which allows for the tailoring of both the molar mass and the degree of acetylation of the extracted xylan.

[0055] The advantage of circulation compared to the linear flow-through of the extractant, also in the temperature profile according to need, arises from the fact that the actual extraction in the sense of improving solubility and adjusting molar mass and acetyl group content follows different reaction kinetics.Therefore, the decisive advantage compared to the static method without any flow is the increase in mass transfer from wood chips to the extractant.In addition, the static method requires an additional step to adjust the specific content of acetyl group.

[0056] The extraction process starts with a filling step A of a fixed-bed reactor 1, whereby the crushed wood material is first filled into the reactor to the intended level. In a filling step B immediately following, the crushed wood material is filled with a liquid extractant, i.e. in particular extraction water 3, until the water level substantially corresponds to the filling level of the crushed wood material or slightly covers the wood material. The pressure vessel of the reactor is filled, in particular with beechwood chips with a particle size of 0.75-16 mm, preferably 1-4 mm. Water is then added until the chips are covered.

[0057] The reaction bed thus produced is then circulated in a circulation step C, the circulation being carried out under the influence of a temporal temperature control T. An exemplary temperature profile is shown in FIG.

[0058] Fresh extraction water is heated, for example, to 130-150°C, preferably 135-145°C, in about 20 minutes and then circulated at this temperature for 60-100 minutes, preferably 70-90 minutes. This step helps to promote the solubility of xylan in the extraction water.

[0059] In this case, the temperature of the extraction water reaches above 130°C for the dissolution of xylan, but it is crucial to keep it below 150°C in order not to cause excessively high decomposition initially and to minimize the solubilization of lignin as an undesired contamination during the relatively long extraction times.

[0060] The extraction water is subsequently heated to 155-175°C, preferably 169-170°C, in about 10 minutes and then circulated at this temperature for 10-50 minutes, preferably 20-40 minutes. This step serves to solubilize additional xylan fractions in the extraction water. At the same time, the increase in temperature here increases the yield of xylan, and thus this step allows the molar mass of the target product to be adjusted. At the same time, the content of acetyl groups is reduced.

[0061] Three constraints are observed that are crucial in this case.

[0062] The first constraint is to first increase the temperature above 155 °C to increase the efficiency of the reduction of the molar mass of xylan and the division of acetyl groups, which can effectively affect the molar mass of extracted xylan and the degree of acetylation of extracted xylan.

[0063] A second constraint is to keep the temperature below 180° C. This keeps the undesirable solubilization of the glucans present in the wood, especially the cellulose fragments, as low as possible.

[0064] The third constraint is that the time for which the temperature of the extraction water exceeds 150°C is kept as short as possible and not too long in order to keep the solubilization of the lignin contained in the wood, and therefore its intrusion as an unwanted contamination, as low as possible.

[0065] Further partial steps can be carried out within the extraction step C.

[0066] FIG. 4 shows an exemplary flow chart of the extraction process with additional sub-steps.

[0067] Thus, in the extraction step C, it is possible, for example, to first carry out a dissolution step C1 and then to increase the temperature above 155° C. before the extraction water is completely or partially exchanged in an exchange step C2. In this way, individual xylan fractions differing either in molar mass or in content of acetyl groups can be obtained or a particular distribution can be achieved with regard to these parameters.

[0068] Finally, the entire extraction water 3 is removed from the fixed-bed reactor in step D and further processed. The reaction water 3 is in this case completely removed from the reactor. The xylan, now dissolved therein and whose molar mass and degree of acetylation have been adjusted, for example, by the preceding method steps, is now precipitated as a solid by being introduced into a 4-10-fold (v / v) excess of alcohol (methanol or ethanol). The solid portion is then separated by conventional filtration equipment, washed with alcohol and dried. It can now be utilized for the production of PPS.

[0069] Furthermore, FIG. 4 shows a further swelling and treatment step Q, which is also shown in FIG. 5. The swelling and treatment step consists in carrying out the swelling of the wood components with a subsequent exchange of extraction water after the filling step B according to the flow chart of FIG. 3. After the addition of the extraction water, the wood chips are swollen in step Q at room temperature for about 16 hours. Then, the circulation of the extraction water is started in step Q, which is heated to 100° C. in the course of one hour. After reaching a temperature of 100° C., the extraction water is removed from the circuit. The removed extraction water contains various contaminations that will not be described in further detail, but does not contain xylan and is therefore discarded. This swelling step increases the efficiency of the subsequent solubilization of xylan. At the same time, the purity of the target product, which is recognizable by its color, can be improved by discarding the extraction water. Following this swelling and treatment step Q thus carried out, the wood bulk is filled with fresh extraction water and the actual extraction step C begins.

[0070] Additionally, the removal of the extraction water from the reactor can be modified or supplemented, either independently or in combination therewith.

[0071] In step D1, the extracted water can be led through an activated carbon filter. This integration of an activated carbon filter, in particular at the outlet of the reactor, makes it possible to remove the lignin, which is inevitably extracted to a certain extent together with the xylan, already prior to the subsequent precipitation in alcohol. This makes it possible, on the one hand, to reduce the amount of alcohol subsequently required and, on the other hand, to increase the concentration of the extract without clogging the equipment used.

[0072] It is even possible to use an evaporator in step D2 instead of a heat exchanger to cool the extract at the outlet of the reactor for removal, so that the process heat of the extraction can be directly used to remove water from the extract solution and increase the concentration of the extract.

[0073] It is further possible to obtain different fractions with gradually different molar masses and very narrow molar mass distributions by gradually increasing the relationship of the aqueous extract to the alcohol during precipitation in step D3. Thus, preferably, xylans with high molar mass are precipitated in a low relationship, while even xylans with low molar masses can be increasingly precipitated as the amount of alcohol increases.

[0074] The xylans obtained by the above-mentioned method steps are characterized by a specific property profile. Thus, for example, the weight-average molar mass of the xylan can be adjusted in a targeted manner to values ​​between 1000 and 5000 g / mol. The simultaneous excellent reproducibility of the molar mass distribution represents an important advantage of the xylans obtained with the aid of the process described herein. These can be converted into PPS in one step.

[0075] Figure 5a shows the size-exclusion chromatogram of xylans obtained with the aid of the process described herein. It shows that mainly the weight-average molar mass of xylans can be adjusted in a targeted manner to values ​​between 1000 and 5000 g / mol, while at the same time a defined molar mass distribution can be achieved. The simultaneous excellent reproducibility of the molar mass distribution represents an important advantage of xylans obtained with the aid of the process described herein. In particular, they can be converted into PPS in one step.

[0076] 6 shows an exemplary HPLC chromatogram of xylan obtained with the aid of the process described herein after acid hydrolysis. Overall, the chromatogram shows that the obtained extract is characterized by a specific sugar composition with very good processability with respect to obtaining PPS.

[0077] In particular, the chromatogram shows a content of more than 85% of xylose, represented by the dominant signal at a retention time of 9.29 min. Furthermore, the new process control allows for good reproducibility, for example with regard to the end groups, represented by the signal at a retention time of 7.65 min as well as other accessory sugars. At the same time, the high recovery determined is a measure of the high purity of the xylan obtained, which is in particular almost free of lignin / lignin degradation products and other impurities, as can be derived in particular from Table 1.

[0078] [Table 1]

[0079] Furthermore, with the aid of NMR spectroscopy it can be shown that functional groups such as glucuronic acid and acetyl groups are present in specific amounts and are specifically attached.

[0080] Here, FIG. 7 shows an exemplary NMR spectrum, the upper figure showing the 1H NMR spectrum recorded in DO at a temperature of 300 K and a spectrometer frequency of 300 MHz, and the lower figure showing the 13C NMR spectrum. The dominant peaks in the 13C NMR spectrum at about 101.6, 76.3, 73.6, 72.6, and 62.9 indicate the basic structure of the β-(1->4)-D-xylopyranose backbone, while the peaks at about 96.5, 75.5, 69.1, 65.2, and 57.4 ppm show sporadic α-(1->4) substitution of the backbone with 4-O-Me-glucuronic acid. From the peak at about 62.4 ppm in the 13C NMR and the peak at 2.12 in the 1H NMR, the substitution with acetyl groups can be derived and quantified.

[0081] As shown, the step of subsequent adjustment of the molar mass of the already extracted xylan, and thus also the second sulfate addition step, can be saved on the basis of the xylan obtained by the above-mentioned method: precisely, these steps can be carried out with the method according to the invention already during the extraction.

[0082] This therefore makes it possible to obtain in one step, starting from xylan extracted by the steps described herein, a PPS which is comparable in pharma- ceutical important parameters, in particular in terms of sulfate group content and molar mass, to the PPS obtained according to known methods.A decisive advantage of the method according to the invention is therefore the saving of these additional steps according to the state of the art.

[0083] 8 shows an exemplary configuration of an extraction plant for carrying out the method according to the invention, in particular with regard to downstream components for working up the extraction water. In the extraction plant shown here, the fixed bed reactor 1 is the crucial operating element, but secondary components are necessary.

[0084] The above-mentioned extractant circuit 4 includes a heat exchanger 14 for regulating the temperature of the extraction water 3 circulating in the circuit. In the temperature profile shown in FIG. 5, where the temperature of the extraction water increases monotonically in a single stage of the extraction process and does not decrease from time to time, the heat exchanger 14 operates exclusively as a heater for the circulating extraction water 3. For this purpose, the heat exchanger 14 is associated with an external temperature regulation circuit 14a, in which an external heating medium circulates. The regulation of the temperature in the extraction water 3 and the control of the temperature rise are regulated in the extractant circuit 4, for example via the flow rate of the extraction water 3 in the extractant circuit 4.

[0085] A circulation pump 15 serves to circulate the extraction water in the extractant circuit 4. The operation of this pump is controlled by a control unit, not shown here, and a temperature sensor (also not shown here) arranged in the extractant circuit records the current value of the temperature of the extraction water.

[0086] The extractant circuit is initially fed with fresh water via the feed valve 16. The extractant circuit is finally emptied after the extraction process by switching over the discharge valve 17. During the extraction process in the fixed-bed reactor 1, both the feed valve 16 and the discharge valve 17 are closed. However, a so-called fractionated drainage of the extraction water is possible. However, there is no continuous throughflow of the extractant from the feed valve 16 to the discharge valve 17. Therefore, no throughflow operation is explicitly performed.

[0087] During the withdrawal of the extraction water, the discharge valve 17 is opened. A circulation pump 15 pushes the extraction water out of the fixed bed reactor 1 through the open discharge valve 17 into a downstream withdrawal branch which, in the example presented here, comprises an activated carbon filter 18, an evaporator 19 and a heat exchanger 20, which here functions as a cooler.

[0088] The activated carbon filter, as described above, removes the lignin simultaneously extracted from the xylan solution in the extraction water. This separation of the lignin allows, on the one hand, to reduce the amount of alcohol and, on the other hand, to increase the concentration of the extract without clogging the equipment used.

[0089] The evaporator 19 serves to cool the exit extraction water: on the one hand, the water evaporated here can be directly used to deliver the released extraction heat, and on the other hand, the concentration of xylan dissolved in the extraction water is further increased by the reduction of the water portion.

[0090] In the example presented here, the outlet extract water is further cooled in a heat exchanger 20. The heat also released in the process can be used as waste heat or can be partly returned to the temperature regulation circuit 14a.

[0091] The extraction water leaves the take-off branch via outlet valve 21 and is sent to a subsequent processing station "precipitation" for precipitating and separating the xylan.

[0092] The method according to the invention has been described on the basis of exemplary embodiments. Further embodiments result from the dependent claims and are within the scope of the working knowledge. [Explanation of symbols]

[0093] 1 Fixed-bed reactor 2. Crushed wood components 3 Extract water 4 Extractant Circuit 5 Filler opening 6 Outlet opening 7 Outlet opening 8 Fixed Bed Screen 9 Mixing unit 10 Agitation drive unit 11 Stirring Rod Assembly 12 Stirring propeller 13 Heat exchange surface (outline) 14 Heat exchanger (heater) 14a Temperature control circuit 15 Circulation Pump 16 Supply valve 17 Exhaust valve 18 Activated carbon filter 19 Evaporator 20 Heat exchanger (cooler) 21 Outlet valve A. Filling step B. Steps to be fulfilled C Circulation Step C1 Lysis step C2 Replacement Steps D. Removal step and xylan separation D1 Activated Carbon Filter Treatment D2 Evaporator Cooling D3 Fractionated precipitation by stepwise addition of alcohol Q Swelling and processing steps

Claims

1. 1. A method for extracting xylan compounds from comminuted wood components using hot water extraction, which can be converted to polysulfate pentosans by subsequent sulfation, comprising: The hot water extraction is carried out in a pressure reactor system for heterogeneous reactions in a discontinuous operating mode, The hot water extraction is carried out by bath circulation of the aqueous extractant in a pressure reactor system, the pressure reactor system being implemented as a fixed bed reactor (1), The hot water extraction with bath circulation comprises: - creating a reaction bed by filling the pressure vessel of said fixed bed reactor (1) with said comminuted wood components (2); - filling the reaction bed with an aqueous extractant (3), in particular water; - circulation of the entire amount of extractant (3) through the extractant circuit (4) for a given duration and with a given time progression of the temperature of the circulated extractant (3); - finally removing the entire amount of the extractant from the fixed bed reactor (1) and then isolating the xylan compounds dissolved in the volume of the extractant; It is run by The circulation of the extractant (3) comprises the following partial steps: - carrying out a partial step of a first dissolution phase (C1) having a first temperature regime for increasing the solubility of said xylan compound, and - carrying out a partial step (C2) of a second dissolution stage having a second temperature regime for adjusting the molar mass and / or the degree of acetylation of said xylan compounds dissolved in said extractant; 23. A method comprising:

2. 2. The method according to claim 1, characterized in that a mass of at least 3 kilograms, at most 15 kilograms, preferably at most 7 kilograms of aqueous extractant per kilogram of dry mass of the wood component is used in the hot water extraction.

3. 3. The method according to claim 1 or 2, characterized in that after filling the reaction bed in the pressure vessel of the fixed bed reactor (1) with the aqueous extractant (3), a swelling bath circulation (Q) with a subsequent total exchange of the extractant is carried out as an intermediate step.

4. 4. The method according to claim 1, wherein during the second dissolution stage (C2), a complete or partial exchange of the extractant (3) is carried out and a fractional removal of dissolved xylan compounds having different molar masses and / or different degrees of acetylation is carried out.

5. 5. The method according to claim 4, characterized in that in the final removal of the total amount of extractant (3) and / or in the complete or partial exchange of the extractant (3), the discharged extractant is passed through a lignin filtration device with removal of the lignin portion.

6. 6. The method according to claim 4 or 5, characterized in that in the final removal of the total amount of the extractant and / or in the complete or partial exchange of the extractant (3), a heat transfer device is used to cool the extractant (3).

7. 7. The method of claim 6, wherein the heat transfer device is an evaporator that utilizes heat radiated by the extractant.

8. 8. The method according to any one of claims 1 to 7, characterized in that isolation of the xylan compounds dissolved in the removed amount of extractant (3) is carried out by introducing the extractant (3) into an alcohol followed by a precipitation reaction and a final filtration.

9. 9. The method according to claim 8, characterized in that when the extractant (3) is introduced into the alcohol, a stepwise increase in the relationship of the amount of extractant to the amount of alcohol is carried out, so that a fractional precipitation is carried out according to the molar mass of the xylan compounds.

10. 4. The method according to claim 3, characterized in that in the swelling bath circulation (Q) heating of the aqueous extractant (3) to a temperature between 100 °C and 150 °C is carried out and the extractant is circulated for a period of between 10 and 90 minutes.

11. 2. The method according to claim 1, characterized in that the temperature regime in the second dissolution stage (C2) is achieved by heating the extractant to a target temperature of at least 150° C. and up to 210° C., and the extractant (3) is circulated at this target temperature for at least 10 minutes and up to 50 minutes.

12. 12. The method according to any one of claims 1 to 11, characterized in that the extracted xylan compounds are sulfated to polysulfate pentosans (PPS) in a basic polar solvent with sulfonic acid without the use of cosolvent power.

Images