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    • 专利摘要:
    PROCESS FOR THE PREPARATION OF Aqueous GLUCAN SOLUTIONS. The invention relates to a process for producing aqueous solutions of glucans with a main chain with B-1,3-glycosidic bonds and side groups linked in it by B-1,6-glycosidic bonds, fermenting strains of fungus that secrete said glucans in the fermentation broth in an aqueous culture medium, in which the separation of the glucans from the fermentation broth occurs by means of asymmetric filter membranes.
    公开号:BR112012014740B1
    申请号:R112012014740-4
    申请日:2010-12-13
    公开日:2020-10-27
    发明作者:Jörg Therre；Hartwig Voss；Julia Kristiane Schmidt；Tillmann Faust；Rajan Hollmann
    申请人:Basf Se；
    IPC主号:
    专利说明:

    The present invention relates to a process for the preparation of aqueous solutions of glucans with a β-1,3-5 glycosidically linked backbone and side groups with a β-1,6, glycosidic bond in them by fermentation of fungal strains, which they secrete the said glucans in the fermentation broth, in an aqueous culture medium, the separation of the glucans from the fermentation broth being carried out with the use of asymmetric filter membranes.
    In natural mineral oil deposits, mineral oil is present in the cavities of porous reservoir rocks that are isolated from the earth's surface by layers of impermeable cover. The cavities can be very thin, capillary, pore or similar cavities. Fine pore bottlenecks can, for example, have a diameter of only about 1 pm.
    In addition to mineral oil, including fractions of natural gas, the deposits comprise water with a greater or lesser salt content.
    In mineral oil production, a distinction is made between primary, secondary and tertiary production.
    In primary production, after the well has sunk in the deposit, the mineral oil seeps through the well through the well due to the autogenous pressure of the deposit. However, in general, only about 5 to 10% of the amount of mineral oil present in the deposit, depending on the type of deposit, can be extracted through primary production, after which the autogenous pressure is no longer sufficient for extraction.
    Secondary production is therefore used after primary production. In secondary production, additional wells are drilled in the formation that carries mineral oil, in addition to the wells used to produce mineral oil, the so-called production wells. Water and / or steam is forced into the tank through these so-called injection wells in order to maintain or increase the pressure again. Forcing into the water, the mineral oil is forced slowly through the cavities in the formation, starting from the injection well, towards the production well. However, this works only as long as the cavities are completely filled with oil and the water pushes the more viscous oil in front of it. As soon as the low viscosity water penetrates through the cavities, it flows from this moment along the path of least resistance, that is, through the resulting channel between the injection wells and the production wells, and no longer push the oil in front of her. As a rule, only about 30 to 35% of the amount of mineral oil present in the deposit can be extracted through primary and secondary production.
    It is known that mineral oil yield can be further increased by measures of tertiary oil production. Tertiary mineral oil production includes processes in which suitable chemicals are used as auxiliaries for oil production. These include the so-called "polymer flood". In a polymer flood, an aqueous solution of a polymer with a thickening effect is forced, instead of water, through the injection wells in the mineral oil tank. Forcing the polymer solution, the mineral oil is forced through the said cavities in the formation, starting with the injection well, in the direction of the production well, and the mineral oil is finally extracted through the production well. Due to the high viscosity of the polymer solution, which is adapted to the viscosity of the mineral oil, the polymer solution can no longer, or at least as easily, break the cavities as is the case with pure water.
    A multiplicity of different water-soluble polymers has been proposed for polymer flooding, that is, both synthetic polymers, such as, for example, polyacrylamides or copolymers comprising acrylamide and other monomers and also water-soluble polymers of natural origin.
    Thickening polymers suitable for tertiary production of mineral oil must satisfy numerous specific requirements. In addition to sufficient viscosity, the polymers must also be thermally very stable and retain their thickening effect even at high salt concentrations.
    An important class of polymers of natural origin for polymer flooding comprises branched homopolysaccharides obtained from glucose. Polysaccharides comprising glucose units are also referred to as glucans. Said branched homopolysaccharides have a backbone of β-1,3 glucose units attached, of which in statistical terms about every third unit has a β-1,6-glycosidic bond with an additional glucose unit. Aqueous solutions of such branched homopolysaccharides have advantageous physicochemical properties, 15 so that they are particularly suitable for polymer flooding.
    Homopolysaccharides of said structure are secreted by various fungal strains, for example, by the Basidiomycetes Schizophyllum commune, which exhibits filamentous growth and, during growth, secrete homopolysaccharide of said structure with a typical molecular weight 20 Mw of about 5 to about 25- 106 g / mol (common name schizophilane). Homopolysaccharides of said structure that are secreted by Sclerotium rolfsii can also be mentioned (common name: scleroglucans).
    It is important for polymer flooding that the aqueous polymer solution used for this purpose does not comprise absolutely any gel particles or other small particles. Even a small number of particles in dimensions in the micrometer range can block the fine pores in the formation of mineral oil and thus at least complicate or even interrupt the production of mineral oil. Polymers for tertiary mineral oil production should therefore have as small a proportion as possible of gel particles or other small particles.
    For use in polymer flooding, it is therefore important that solutions of said homopolysaccharides are substantially free of cells and cell fragments, since they otherwise block the formation of mineral oil, which complicates the extraction of mineral oil or even takes this is impossible. The so-called Millipore Filtration Ratio (MPFR value) can be used as a characteristic for good quality of a polymer solution. The way in which the filter resistance changes during the filtration of a solution is determined here.
    Processes for the preparation of branched homopolysaccharides comprising glucose units linked to β-1,3 are known.
    EP 271 907 A2, EP 504 673 A1 and DE 40 12 238 A1 reveal processes for the preparation, that is, the preparation is carried out by batch fermentation of the fungus Schizophyllum commun with agitation and aeration. The culture medium substantially comprises glucose, yeast extract, potassium dihydrogen phosphate, magnesium sulfate and water. EP 271 907 A2 describes a process for isolating the polysaccharide, in which the culture suspension is first centrifuged and the polysaccharide is precipitated from the supernatant with isopropanol. A second process comprises pressure filtration followed by ultrafiltration of the obtained solution, with no details of the process having been revealed.
    "Udo Rau," Biosynthese, Produktion und Eigenschaften von extrazellulãren Pilz-Glucanon ", Habilitationsschrift, Technical University of Brunswick, 1997, pages 70 to 95", describes the preparation of schizophilan by continuous or batch fermentation. Schizophilane can be separated by cross-flow filtration (loc. Cit., Page 75). To separate the cell mass, several stainless steel membranes with pore diameters of 0.5 pm, 2 pm, 10 µm and 20 µm were tested. With 2 pm membranes, however, only small permeation rates were obtained with a solution that comprised 0.5 g / L of glucan and 0.5 g / L of dry biomass. In addition, hyphae fragments at a concentration of about 0.1 g / mL remained. A second stage of ultra-fine clarification is therefore proposed (loc. Cit., Page 94). Such a process is very complicated and, in addition, stainless steel membranes are very expensive.
    "Udo Rau, Biopolimers, Editor A. Steinbüchel, Volume 6, pages 63 to 79, WILEY-VCH Publishers, New York, 2002" describes the preparation of schizophilane by continuous or batch fermentation.
    Cross-flow centrifugation and microfiltration are recommended to recover the cell and schizophilan without cell fragment (loc. Cit., Page 78, section 10.1). For cross-flow microfiltration, the use of sintered stainless steel membranes with a pore size of 10 pm is proposed therein. The permeate thus obtained must, however, be purified again by means of diafiltration and, optionally, be further purified by means of cross-flow microfiltration (loc. Cit., Page 78, section 10.2). Such a process is very complicated and, in addition, stainless steel membranes are very expensive.
    "GIT Fachzeitung Labor 12/92, pages 1233 - 1238" describes a continuous preparation of branched β-1,3-glucans with cell recycling. First, cross-flow filtration through stainless steel membranes that has a pore size of 200 pm is proposed to separate branched β-1,3-glucans from the fermentation circulation. The polymer containing permeate obtained is, however, still contaminated with large quantities of the cell fragments and must subsequently be purified in a second step. Deep-bed filtration using a fiberglass deep-bed filter, three-stage pressure filtration and centrifugation are proposed for this purpose. As an additional process for the second purification stage, the authors have unsuccessfully investigated cross-flow filtration of ceramic membranes. As a result of their experiments, they came to the conclusion that cross-flow microfiltration is not suitable for cell separation from high viscosity culture suspensions containing mycelium. The permeate obtained is finally subsequently purified in a third stage of purification by means of diafiltration. A three-stage process like this, however, is very complicated and therefore unsuitable for an industrial production process.
    WO 03/016545 A2 discloses a continuous process for the preparation of scleroglucans using Sclerotium rolfsii. For purification, cross-flow filtration using stainless steel filters with a pore size of 20 pm with a transmembrane flow rate of at least 7 m / s is described. However, a 20 pm filter is not enough to separate very small particles.
    It is true that in principle the removal of fine particles can be improved by using thinner filter membranes. With a smaller pore size, however, filter membranes also increasingly retain glucans in an undesired manner, in particular fractions with very high molecular weights. In addition, thinner membranes require higher filter pressures and the risk that the fungus may be subjected to an excessive mechanical load, therefore, increases. Destruction and cell lysis must be avoided, and the polymer to be prepared will be contaminated thereby.
    In addition, for economic reasons, the concentration of aqueous glucan solutions obtained should be as high as possible, that is, first be able to use fermentation plants as small as possible and secondly to ensure as little transport effort as possible for transport aqueous glucan solutions from the production site to the site of use. For economic reasons, a concentration of at least 3 g / L of glucan should be attempted. Glucan solutions with such a high concentration have very high viscosity and, in addition, have a high structural viscosity. Such solutions are difficult to filter. The higher the concentration, the more difficult the filtration step is.
    It was an objective of the present invention to provide an economical process for the preparation of solutions of branched β-1, 3-glucans, where the solutions must have sufficient qualities for use in tertiary production of mineral oil. In addition to a high specific viscosity, the solutions should in particular have a content of cells and cell fragments as low as possible. With filtrates, MPFR filterability specification values <2.5 should be obtained with 1.2 pm Isopore filters.
    Thus, a process for the preparation of aqueous solutions of glucans with a β-l, 3-glycosidically linked main chain and side groups with a β-l, 6-glycosidic link therein was observed, the process comprising fermentation of fungal strains , which secrete glucans of said structure, in an aqueous culture medium, and subsequent separation of an aqueous solution of the glucan resulting from the aqueous fermentation broth comprising glucans and biomass by cross-flow microfiltration, asymmetric filter membranes comprising at least one layer of a support material and at least one separation layer being used for cross flow microfiltration, the pore size of the separation layer being from 1 pm to 10 pm and the pore size of the support material being from 5 pm to 100 pm pm, with the proviso that the pore size of the separation layer is at least 1 pm larger than the pore size of the support material, and the cross flow rate being from 0.2 m / s to 20 m / s and the transmembrane pressure being from 0.1 to 10 bar. List of figures
    Figure 1: Schematic diagram of a preferred filtration device.
    Figure 2: Schematic diagram of the apparatus used for the experiments and comparative experiments.
    With respect to the invention, the following can be stated specifically:
    Versed in the technique, they understand that “Glucans” are homopolysaccharides that are composed exclusively of glucose units. By means of the process according to the invention, a specific class of glucans is prepared, and in particular those which comprise a main chain of glucose units and β-1,3-glycically linked side groups with a β-1,6 bond glycosidics therein and comprising glucose units. Preferably, the side groups consist of a single β-1,6-glycosidically linked glucose unit, where in statistical terms each third main chain unit has a β-1,6-glycosidic bond in an additional glucose unit.
    Such fungal strains that secrete glucans are known to those skilled in the art. Examples include Schizophyllum commune, Sclerotium rolfsii, Sclerotium glucanicum, Monilinia fructigena, Lentinula edodes or Botrytis cinera. Suitable fungal strains are furthermore mentioned, for example, in EP 271 907 A2 and EP 504 673 A1, in each case in claim 1. Preferably, the fungal strains used are Schizophyllum communeou Sclerotium rolfsii and in particular preferably Schizophyllum commune, which secrete a glucan in which, in a backbone comprising β-1,3-glycosidically linked glucose units, in statistical terms, each third backbone unit has a β-1,6-glycosidic bond with an additional glucose unit, that is, glucan is preferably so-called schizophilane. Typical schizophilans have an average molecular weight Mw of about 5 to about 25-106 g / mol.
    In a first stage of the process, the fungi are fermented in a suitable aqueous culture medium. In the course of fermentation, fungi secrete the aforementioned class of glucans in the aqueous fermentation broth.
    Processes for the fermentation of such fungal strains are known in principle to those skilled in the art, for example, EP 271 907 A2, EP 504 673 Al, DE 40 12 238 Al, WO 03/016545 A2 and “Udo Rau,“ Biosynthese, Produktion und Eigenschaften von extrazellulãren Pilz-Glucanon ”, Habitations schr ift, Technical University of Brunswick, 1997”, which in each case also mentions an appropriate culture medium.
    According to the invention, fungi can be grown, for example, in an aqueous culture medium at a temperature of 15 ° C to 40 ° C, preferably from 25 to 30 ° C and, for example, at about 27 ° C, preferably with aeration and movement, for example, using a stirrer.
    In the process according to the invention, the fermentation should preferably run in such a way that the concentration of the glucans to be prepared is at least 3 g / L in the fermentation broth to be filtered. The upper limit in principle is not limited. It depends on the viscosity that can still be handled by the fermentation apparatus used in each case.
    Finally, an aqueous solution comprising glucans is separated by cross-flow microfiltration from the fermentation broth which comprises glucans and dissolved biomass (fungal cells and optionally constituent cell), an aqueous fermentation broth in which the biomass has a concentration greater than that remaining beforehand .
    In one embodiment of the process, fermentation is carried out in a fermentation vessel and the contents of the fermentation tank after fermentation are filtered according to the invention using asymmetric filter membranes.
    In a further embodiment of the invention, fermentation is carried out in a suitable plant that comprises at least one fermentation vessel. Fermentation broth is removed continuously or from time to time by means of a side stream, and an aqueous solution comprising glucans is separated by filtration by cross-flow microfiltration. The remaining aqueous fermentation broth in which the biomass has a higher concentration than beforehand can at least be partially recycled to the fermentation vessel.
    The cross-flow microfiltration process is known in principle to those skilled in the art and is described, for example, in "Melin, Rautenbach, Membranverfahren, Springer-Verlag, 3rd edition, 2007, page 309 to page 366". Here, “microfiltration ”Is understood by those skilled in the art as the removal of particles with a size of about 0.1 pm to about 10 pm.
    In cross-flow filtration, a stream of liquid to be filtered is applied, for example, by a suitable circulation pump, parallel to the membrane surface used as the filtration material. A liquid stream, therefore, continuously flows into the filter membrane, and the formation of deposits on the membrane surface is prevented or at least reduced in this way. In principle, all types of pump are suitable as the pump. Because of the high viscosity of the medium to be transported, however, in particular, positive displacement pumps and very particularly eccentric screw pumps and rotary piston pumps have been shown to be suitable.
    According to the invention, asymmetric filter membranes are used for cross-flow microfiltration. Asymmetric filter membranes consist of at least two different layers with different pore size, that is, at least one support layer and a separation layer. The support layer is relatively thick and has relatively large pores. It provides mechanical resistance to the filter membrane. At least one separation layer with pores thinner than the pores of the backing layer is applied to the backing layer. For example, mercury porosimetry can be used in a manner known in principle to measure pore size. Optionally, one or more intermediate layers can also be arranged between the separation layer and the support layer.
    Asymmetric membranes can be, for example, metal membranes or ceramic membranes. The asymmetric membranes used are preferably asymmetric ceramic membranes. Details of asymmetric ceramic membranes are described, for example, in "Melin, Rautenbach, Membranverfahren, Springer-Verlag, 3rd edition, 2007, page 51 to page 52".
    The ceramic or metallic membrane body is produced from the support material. Suitable forms of these membrane bodies are known to those skilled in the art and are chosen by those skilled in the art according to the design of the filter apparatus. They can be formed, for example, as a flat membrane or tubular membrane. Flat membranes are disk-like structures. Tubular membranes are tubular structures that have a channel (single channel membrane) or a plurality of channels (multichannel membrane). The internal diameter of the tubular membrane channels is, as a rule, from 1 mm to 25 mm, in particular from 2 mm to 12.5 mm. The channels do not need to be round, but irregular shapes, such as, for example, polygons with rounded tips, are also possible. The tubular membranes are, as a rule, from 0.1 m to 5 m in length, preferably from 0.5 to 2 m. Tubular membranes from 1 m to 1.2 m in length are commercially available. It is also possible that a plurality of tubular membranes are arranged one behind the other or parallel to each other, optionally also in different housings, so-called membrane modules.
    In the case of ceramic filter membranes, the support material consists of a porous inorganic material, such as, for example, alumina, silica, silicon carbide, zirconium oxide, titanium oxide or mixtures of these substances. In the case of metal membranes, sintered metal, such as, for example, stainless steel, Hastelloy, Inconell or titanium, is used as a support material. Combinations of material, for example, sintered metal supports and ceramic separation layers, are also possible. In the case of single channel membranes or flat membranes, the support material is usually 0.05 to 10 mm thick, preferably from 1 mm to 5 mm.
    The use of multichannel membranes is particularly preferred. In the case of multichannel membranes, the support material forms a mold, for example, a round or hexagonal mold, in which the aforementioned channels are conducted. The outside diameter of a molding like this for multichannel membranes is, as a rule, from 5 mm to 100 mm, preferably from 10 mm to 50 mm.
    In the process according to the invention for the preparation of glucans with a β-1, 3-glycosidically linked main chain and side groups with a solution of β-1, 6-glycosidic linked in them, the pore size of the support material is from 5 pm to 100 pm, preferably from 7 pm to 100 pm and in particular preferably from 10 pm to 60 pm.
    Said values are in each case the pore size D90. The term "D90 pore size" is known to those skilled in the art. It is determined from a distribution curve and pore size of the support material, the “pore size D90” with a pore size in which 90% of the pore volume of the material has a pore size <pore size D90. The pore size distribution of a material can be determined, for example, by means of mercury porosimetry and / or gas adsorption processes. These processes are known in principle to those skilled in the art and are described, for example, in the relevant standards ISO 15901-1 EN, ISO 15901-2 EN and ISO 15901-3 EN.
    Optionally, one or more intermediate layers can be applied to the support material. The backing layer or intermediate layers optionally present is or are followed by a separating layer. The average pore size of the separation layer is from 1 to 10 pm, preferably from 1 pm to 6 pm and in particular preferably from 2 pm to 5 pm. The values are, as previously described, size of 10 pores D90.
    The pore sizes of the support layer and the separation layer are chosen in each case by those skilled in the art so that the pore size of the support layer is at least 1 pm greater than that of the separation layer. Preferably, the pore size of the support layer is at least 5 pm larger than that of the separation layer, in particular preferably at least 10 pm and, for example, at least 20 pm.
    The separation layer and the intermediate layers may consist, for example, of alumina, silica, silicon carbide, zirconium oxide, titanium oxide, mixtures of these substances or metal alloys. It is not necessary for the separation layer, the intermediate layers and the support material to be produced from the same substances; often, precisely the combination of different substances is advantageous.
    The thickness of the intermediate layers optionally present is from 1 pm to 500 pm. The average thickness of the separation layer is, as a rule, from 1 pm to 50 pm, preferably from 5 pm to 200 pm. The intermediate layers have pore sizes that are between the respectively chosen pore size of the support material and the pore size of the separation layer.
    To carry out the process according to the invention, the asymmetric filter membranes are installed in suitable filter devices. Designs of suitable filter devices are known in principle to those skilled in the art. It is advantageous that the separating layer is present between the support material and the retentate space, without the invention being limited to that.
    Preferably, tubular membranes can be used to carry out the process according to the invention. In the case of tubular membranes, the retentate is preferably passed through the interior of the channel or channels, and the permeate thereby emerges through the walls of the support material in the permeate space. It is less preferable that the retentate is present outside the channel or channels and that the permeate is collected inside the channel or channels.
    Tubular membranes can be used as so-called single-channel elements. However, the use of multichannel elements is preferred. These elements have the advantage of a larger membrane area in combination with the same space requirement, simpler installation and consequently substantially lower capital costs. In the case of these membrane elements, however, the permeate must penetrate the total support body in order to emerge from the membrane element. In the case of substances with structural viscosity, the viscosity is particularly high at low flow rates, which takes the passage of a glucan solution through the most difficult support body. It was therefore assumed that, due to the long path and the more complicated flow of permeate through the support body, multichannel elements cannot be suitable for the filtration of schizophilane solutions.
    However, it was observed that, despite the high viscosity and structural viscosity property of the permeate, the use of multichannel elements is possible and a high permeate flow can be obtained even at low transmembrane pressures.
    According to the invention, the flow rate of the cross flow must be from 0.2 m / s to 20 m / s, preferably from 0.5 m / s to 7 m / s and in particular preferably from 1 m / s to 6 m / s s. A flow rate that is too low is disadvantageous since the membrane then quickly becomes blocked; due to the large amount of retentate to be circulated, a flow rate that is too high causes unnecessarily high costs.
    The transmembrane pressure is, as a rule, from 0.1 bar to 10 bar, preferably from 0.5 bar to 6 bar and most particularly from 1 bar to 4 bar.
    The temperature at which cross-flow microfiltration is carried out is not critical and is, as a rule, from 5 ° C to 150 ° C, preferably from 10 to 80 ° C and in particular preferably from 15 to 40 ° C. If the cells to be separated by filtration have to be killed, that is, for example, in processes with recycling of biomass, the temperature must be from 15 ° C to 40 ° C.
    A preferred embodiment of a filter unit to be used according to the invention is shown in figure 1. The preferred apparatus comprises a circulation pump P, a filter module F and a heat exchanger W. By means of pump P, the aforementioned cross flow of the liquid on the membrane surface arranged in the filter apparatus F is produced. The contents of the plant can be controlled by a thermostat using a W heat exchanger.
    The filter apparatus F consists of a housing in which a membrane is inserted as a partition. The housing is divided by the membrane into a so-called retentate space and a permeate space. The liquid that arrives from the P pump, referred to as food, is the glucan solution, which is contaminated with biomass. The feed enters the retentate space through at least one feed. A liquid stream, referred to as a concentrate, appears again from the retentate space through at least one discharge. The pressure in the retentate space is greater than the pressure in the permeate space. The pressure difference is referred to as transmembrane pressure. A portion of the feed stream passes through the membrane and is collected in the permeate space. This part of the passing liquid, referred to as permeate, is the glucan solution separated from the biomass.
    In a further embodiment of the invention, high shear forces can be obtained on the membrane surface using internal rotating components or by rotating the membrane itself. In this case, the term dynamic cross-flow filtration is also used. Apparatus for performing dynamic cross-flow microfiltration are known to those skilled in the art and can be purchased, for example, under the name module DynaMem from Buss-SMS-Cancler GmbH, Düren. Using a dynamic cross-flow microfiltration device like this, the asymmetric ceramic membranes described are used in a disk shape.
    The operating time of the membrane filtration plant can optionally be extended by regular backwashing with permeate. For this purpose, a pressure that is greater than the pressure in the retentate space is applied at regular intervals in the permeate space and a certain amount of permeate is forced back through the membrane in the retentate space for a defined time. This backwash can be carried out, for example, by forcing nitrogen into the permeate space, by a backwash pump or by using a piston system, sold, for example, under the name "BACKPULSE DECOLMATEUR BF 100" by Pall, Bad Kreuznach. Backwashing should be carried out at intervals of 1 minute to 5 hours, preferably at intervals of 2 minutes to 60 minutes, without wishing to limit the invention to this cycle of time. The amount of backwashed permeate is preferably in the range of 0.05 to 5 liters per m of the membrane area, but preferably in the range of 0.1 to 2 liters per m of the membrane area.
    Depending on the quality of the fermentation discharge used, it may be necessary to clean the used filter membranes at an appropriate time. The cleaning of the filter membranes can be carried out by treating the membranes with a suitable cleaning solution at a temperature of 20 ° C to 100 ° C, in particular from 40 ° C to 80 ° C. Acids (mineral acids, such as, for example, phosphoric acid, nitric acid, or organic acids, such as, for example, formic acid) can be used as a cleaning solution. The acid concentration is, as a rule, at a concentration of 1% by weight to 10% by weight. Better cleaning effects are usually achieved by using alkali (for example, sodium hydroxide solution, potassium hydroxide solution). The concentration of alkali used is 0.1% by weight to 20% by weight. By the addition of oxidizing substances, such as, for example, hydrogen peroxide, hypochlorite, in particular sodium hypochlorite, or peracetic acid, the cleaning effect can be substantially improved. The concentration of the oxidizing substances should be from 0.5% by weight to 10% by weight, in particular from 1% by weight to 5% by weight. The cleaning can in particular preferably be carried out with a mixture of hydrogen peroxide and alkali or hydrogen peroxide and hypochlorite. The cleaning of the membranes is carried out - during the plant shutdown - preferably in the state installed in the membrane filtration plant, with the help of a cleaning system in place (CIP system). It has been shown to be appropriate to perform the cleaning of the filter membranes as soon as an amount of 50 kg of permeate per m2 of membrane area to 5,000 kg of permeate per m of membrane area has been obtained, preferably of 50 kg of permeate per m2 of membrane area at 1,000 kg of permeate per
    By means of the process according to the invention, a solution of glucans with a β-1,3-glycosidically linked backbone and side groups with a β-1,6-glycosidic bonded in them which is suitable for tertiary production of mineral oil in a simple way.
    Asymmetric membranes used in accordance with the invention are economical. Due to the high permeate flow, the membrane plant requires low capital costs and low energy consumption. Asymmetric membranes have a long service life.
    The good quality of the product is evident from the good filtration properties, which are expressed by the low filtration ratio (MPFR value). The MPFR value of the product is 1.001 to 2.5, but in particular 1.01 to 2.0.
    The schizophilane yield, that is, the amount of schizophilane that can be recovered from the fermentation discharge, based on the amount of schizophilane present in the fermentation discharge, is 25% to 97%, in particular 30% to 95% and particularly much preferable from 50% to 93%.
    The glucan yield can optionally be increased by the diafiltration process using water, which is known to those skilled in the art.
    The following examples are intended to illustrate the invention in more detail: Determination of the filtration ratio (MPFR value)
    Measurement principle:
    In determining the Millipore filtration ratio (MPFR value), the amount of filtrate that flows through a defined filter is determined as a function of time. The MPFR value is determined according to the following formula (I) MPFR = (ti90g - 1170g) / (Í70g “Í50g) (I)> where the variables and the equation have the following meaning: ti90g = time in which 190 g of filtrate are obtained, ti70g = time in which 170 g of filtrate are obtained, Fog = time in which 70 g of filtrate are obtained, tsog = time in which 50 g of filtrate are obtained.
    Thus, in each case, the period of time that is required for each 20 g of filtrate to drain is determined, that is, in an initial and final moment in the filtration process, and the quotient is calculated from the two time periods. The higher the MPFR value, the greater the decrease in filtration speed with the increase in the duration of the filtration process. This indicates greater blockage of the filter, for example, by gels or particles.
    The MPFR value is determined by the following process: 1. Equipment a) Sartorius 16249 pressure filtration apparatus; filter diameter 47 mm; with 200 mL digestion cylinder (0i = 41 mm) b) Isopore 1.2 pm membrane; 0 47 mm; No. RTTP04700 c) Scale 2. Preparation of the glucan solution First, 50 g of a mixture of the glucan solution obtained by the experiments and ultrapure water are prepared, that is, in a ratio such that the concentration of the glucan is 1, 75 g / L. The mixture is stirred for 10 minutes and checked visually for homogeneity. If the mixture is still heterogeneous, further stirring is carried out until the mixture is homogeneous. The mixture is then made up to a total amount of 250 g with 200 g of ultrapure water. Then, stirring is performed for at least 1 hour for homogenization, after which the pH is adjusted to 6.0 with 0.1 M NaOH, and stirring is then carried out again for 15 minutes. The pH of 6.0 is checked again. The final concentration of glucan in the mixture is 0.35 g / L. 3. Conducting the filtration test The filtration test is carried out at room temperature (T = 25 ° C) at a pressure of 1.0 bar (compressed air or Na). - place the coarse support grid on the sieve tray - place the thin support grid on the sieve tray - place the membrane filter on top - insert the seal (O-ring) - screw the sieve tray and outlet tap on the cylinder - close the outlet tap - introduce 220 g (about 220 mL) of solution - screw the top cap onto the cylinder - attach to the air inlet tube - check the pressure and adjust to 1.0 bar - place a beaker on the scale under the filtration apparatus. Tarar. - open the outlet tap - the test is interrupted when no more filtrate emerges.
    Using the scale, the amount of filtrate is determined as a function of time. The mass indicated in each case can be read visually, but certainly also automatically and evaluated. Retention:
    Retention R is used to characterize the separation behavior of the membrane (cf. Melin, Rautenbach, loc. Cit., Page 6). R = 1 - (concentration of glucan in the permeate) at a time divided by the concentration of glucan in the retentate at this time.
    Since glucan is obtained as a permeate, retention should be as slow as possible. In the case of microfiltration, the retention is usually greater than 0%. Since the retention can change over time, an average retention over time is established as the characteristic.
    With the filter membranes used according to the invention, average retentions of less than 60% are obtained, in advantageous cases even less than 30%. This means that the glucan can be substantially recovered from the fermentation broth. Concentration factor:
    In the concentration of the fermentation broth, the MK concentration factor is an important quantity. It is defined as the ratio of the mass of the fermentation broth used at time zero divided by the mass of the fermentation broth at the end of the glucan isolation. The concentration factor should be as large as possible.
    With the process according to the invention, concentration factors up to 15, in advantageous cases even up to 30, can be obtained. Comparative example
    Filtration using a symmetric filter membrane
    The cross-flow filtration device used is shown in figure 2. It consisted of a stirred double-jacketed BI receiver with a volume of 120 liters, the eccentric screw pump Pl, the tube bundle heat exchanger W1, the valve pressure relief valve V1 and the two Fie F2 filter modules. The filter modules Fl and F2 were backwashed with permeate through the three-way valves V3 and V4 at intervals of 300 seconds in each case, in each case with 200 mL of permeate, and the nitrogen pressure was 7 bar. The content of the cross-flow filtration plant was cooled to 24 ° C through the double jacket of the BI container and the heat exchanger Wl.
    In filter modules F1 and F2, a symmetrical tubular membrane was used, that is, a 5 channel element from TAMI comprising ceramic ATZ (alumina / titania / zirconia). The D90 pore size of the membrane was 3.5 µm. The membrane had a symmetrical structure and had no separation layer or intermediate layers. The length of the membrane tube was 1 m and the outside diameter was 20 mm. The membrane area of a module element was 0.11 m2. The hydraulic diameter of a channel was 6 mm.
    Schizophyllum communefoi used for the experiments, that is, the schizophilane described in "Udo Rau, Biopolimers, editor A. Steinbüchel, W1LEY-VCH Publishers, Volume 6, pages 63 to 79" was prepared in a batch fermentation. fermentation was 96 hours, 99.6 kg of this fermentation broth (= feed) were introduced into the BI container (fig. 2) and circulated for 45 minutes at a pressure of 4 bar at a circulation rate of 7 m / h through the pump Pl. The contents of the container were analyzed and a content of 9.8 grams of schizophilane per liter was determined.
    The circulation rate was then adjusted to 5.1 m / h and a transmembrane pressure of 1.1 bar applied. The transmembrane flow was 5 m / s. The permeate emerging from the filter modules was collected and weighed. During the first 10 minutes of the experiment, 0.75 kg of permeate was obtained. This corresponds to a permeate flow of 20.4 kg / h / m. The transmembrane pressure was 2.9 bar. The filtration was operated for 16 hours and 6.18 kg of permeate were obtained at this time. In the last hour, it was possible to obtain only 5.4 g of permeate since the membranes were virtually blocked completely.
    The collected permeate was analyzed and a glucan content of 6.7 grams per liter was observed. The yield was therefore only 4%. The permeate MPFR value was 2.8 and the average glucan retention during the experiment was 32%. The concentration factor was only 1.07. Inventive Example 1
    Filtration using an asymmetric filter membrane
    Again, the cross-flow filtration apparatus described in example 1 was used. The filter modules Fl and F2 were backwashed with permeate through the three-way valves V3 and V4 at 120 s intervals in each case, in each case with 200 mL of permeate and the nitrogen pressure was 4 bar. The contents of the cross-flow filtration plant were cooled to 22 ° C by the double jacket of the BI container and the heat exchanger Wl.
    An asymmetric tubular membrane comprising SIC was used in filter modules F1 and F2, that is, a 37 channel element (model "CRYSTAR, Type FT 3000" by St. Gobain). The D90 pore size of the membranes was 3.0 µm. The D90 pore size of the support material was 30 µm. The length of the membrane tube was 1 m and the outer diameter was 32 mm. The membrane area of a module element was 0.42 m. The hydraulic diameter of a channel was 3.4 mm.
    The fermentation discharge described in example 1 was used for the experiments. 115 kg of this fermentation broth (= feed) were introduced into the BI container and circulated for 50 minutes at a pressure of □ 4 bar and a circulation rate of 7 m / h using the Pl pump. The contents of the container were analyzed and a content of 8.7 grams of schizophilane per liter was determined.
    Then, the circulation rate was adjusted to 4.1 m / h and a transmembrane pressure of 1.1 bar was applied. The transmembrane flow rate was 1.7 m / s. The permeate emerging from the filter modules was collected and weighed. 50 minutes after the beginning of the permeate removal, 25 kg of fermentation broth were added to vessel B1. 16 hours and 20 minutes after the beginning of the permeate removal, 40 kg of fermentation broth were added to the BI container and the circulation rate was adjusted to 6.5 m / h. So far, 77 kg of permeate have been obtained. This corresponds to an average permeate flow of 5.6 kg / m / h. After 20 hours since the beginning of the experiment, another 55 kg of fermentation broth were added to the Bl container. After 22.5 hours from the beginning of the experiment, 109 kg of permeate were collected in the permeate container. The permeate was analyzed.
    The MPFR value of the permeate in this first filtration step was 1.3. The schizophilane content was 6.9 grams per liter (average retention to date 26%) and the viscosity at 7 / s was 1,380 mPas.
    The collection container for the permeate has now been changed, an additional 20 kg of fermentation broth has been added to the B1 container and the filtration has been operated for an additional 19.5 hours. At this point, an additional 85 kg of permeate was obtained. This corresponds to an average permeate flow of 5.1 kg / h / m2.
    The permeate collected during the second filtration step was analyzed. The MPFR value was 1.2 and the schizophilane content was 7.8 grams per liter (average retention during the total experiment 29%) and the viscosity at 7 / s was 1,560 mPas.
    The yield during both filtration steps was therefore 64%. The concentration factor was 4.2. Discussion
    The values of the comparative example and the example are listed again in Table 1 below.
    Table 1
    The experiments show that the filtered product according to the invention comprises substantially less constituents that can block the 1.2 pm filter during the determination of the MPFR value. With the process according to the invention, the fermentation broth can be concentrated to a much greater value. The yield in the process according to the invention is substantially higher and, in addition, the retention in the example according to the invention using asymmetric filter membranes is substantially less than in the comparison using symmetric filter membranes. Inventive example 2
    Filtration using an asymmetric filter membrane
    Once again, the cross flow filtration apparatus described in example 1 was used. However, the apparatus was equipped, for backwashing the permeate, with two piston systems “BACKPULSE DECOLMATEUR BF 100” (see Figure 3, positions B3 and B4). The filter modules Fl and F2 were backwashed with permeate by means of ball valves V3 and V4 at intervals of 900 s in each case, in each case with 100 mL of permeate, and the nitrogen pressure was 10 bar.
    The two neighboring liners of the Bl container and the W1 heat exchanger were used to control the temperature of the content of the cross-flow filtration unit at 29 ° C to 30 ° C.
    An asymmetric tubular membrane comprising alumina was used in filter modules Fl and F2, that is, a 19-channel element (model “MEMBRALOX, Type EP 1940” by Pali). The D90 pore size of the membranes was 5.0 µm. The D90 pore size of the support material was 12 µm. The length of the membrane tube was 1,020 mm. The membrane tube is shaped like a hexagon with rounded corners, the distance between two opposite corners being 31 mm and the distance between two opposite edges being 28 mm. The membrane area of a module element was 0.24 m2. The diameter of a channel was 4 mm.
    The experiments were carried out with a prepared fermentation discharge described in the comparative example and containing 8.3 grams of schizophilane per liter. At the beginning of the experiments, 100 kg of this fermentation broth (= feed) were introduced into the Bl container, the circulation rate of the Pl pump was adjusted to 2.8 m / h and a transmembrane pressure of 0.9 bar. The transmembrane flow rate was 1.6 m / s. The permeate emerging from the filter modules was collected and weighed. 20 minutes after the beginning of the permeate removal, 41 kg of fermentation broth were added to the Bl container. 10 hours and 35 minutes after the beginning of the permeate removal, the transmembrane pressure increased to 1.8 bar. Permeate withdrawal was interrupted. So far, 100.6 kg of permeate have been obtained. This corresponds to an average permeate flow of 19.8 kg / m / h. The permeate was analyzed. The MPFR value of the permeate in this first filtration step was 1.7. The schizophilane content was 6.3 grams per liter.
    The permeate collection vessel has now been changed, an additional 107 kg of fermentation broth has been added to vessel B1 and the transmembrane pressure has been adjusted to 1.2 bar. After 7 hours and 55 minutes from the beginning of this second filtration step, 24.3 kg of permeate were recovered. This corresponds to an average permeate flow of 6.4 kg / m2 / h. The permeate analysis in this first filtration step gave an MPFR value of 1.6 and a schizophilane content of 7.4 grams per liter.
    The collection container for the permeate has now been changed and the filtration operated for an additional 15 hours. At this time, an additional 47.2 kg of permeate was obtained, the transmembrane pressure increased to 1.5 bar. The average permeate flow was 6.6 kg / h / m2. The permeate collected during the third filtration step was analyzed. The MPFR value was 2.2, the schizophilane content was 7.7 grams per liter.
    The glucan yield during the three filtration steps was 57%, the concentration factor was 3.3 and the retention was 28%.
    权利要求:
    Claims (11)
    [0001]
    1. Process for the preparation of aqueous solutions of glucans with a β-1, 3-glycosidically linked main chain and side groups with a β-1,6, glycosidic linked therein comprising the fermentation of fungal strains that secrete glucans from said structure, in an aqueous culture medium, and subsequent separation of an aqueous solution of the glucan resulting from the aqueous fermentation broth comprising glucans and biomass by cross-flow microfiltration, characterized by the fact that the concentration of glucans in the fermentation broth to be filtered is at minus 3 g / 1, where asymmetric filter membranes comprising at least one layer of a support material and at least one separation layer for cross-flow microfiltration are used, the pore size of the separation layer being 1 pm at 10 pm and the pore size of the support material being from 5 pm to 100 pm, with the proviso that the pore size of the support material is at least 1 pm larger than the size of pore of the separation layer, and the cross-flow flow rate being from 0.2 m / s to 20 m / s and the transmembrane pressure being from 0.1 to 10 bar.
    [0002]
    2. Process according to claim 1, characterized in that the pore size of the support material is at least 5 pm greater than the pore size of the separation layer.
    [0003]
    3. Process according to claim 1 or 2, characterized by the fact that fermentation is carried out at a temperature of 15 to 40 ° C with aeration and movement.
    [0004]
    4. Process according to claim 1, characterized by the fact that the fungal strains are Schizophyllum commune or Sclerotium rolfsii.
    [0005]
    Process according to any one of claims 1 to 4, characterized by the fact that asymmetric ceramic filter membranes are used.
    [0006]
    Process according to any one of claims 1 to 4, characterized in that asymmetric metal filter membranes are used.
    [0007]
    Process according to any one of claims 1 to 6, characterized by the fact that multi-channel elements are used as asymmetric filter membranes.
    [0008]
    Process according to any one of claims 1 to 7, characterized in that the asymmetric filter membranes are regularly backwashed.
    [0009]
    Process according to any one of claims 1 to 8, characterized by the fact that fermentation is carried out in a plant comprising at least one fermentation vessel, fermentation broth comprising biomass and glucan is removed from the plant by means of a side stream, an aqueous solution of glucans is separated by filtration through cross-flow microfiltration, at least part of the remaining fermentation broth comprising biomass being recycled to the fermentation vessel.
    [0010]
    10. Process according to any one of claims 1 to 9, characterized in that the membranes are cleaned at regular intervals with a mixture of hydrogen peroxide and alkali, with the proviso that cleaning is carried out in each case as once an amount of 50 kg of permeate per m2 of membrane area to 5,000 kg of permeate per m2 of membrane area has been reached since the previous cleaning.
    [0011]
    11. Process according to any one of claims 1 to 9, characterized in that the membranes are cleaned at regular intervals with a mixture of hypochlorite and alkali, with the proviso that cleaning is carried out in each case as soon as a quantity of 50 kg of permeate per m2 of membrane area to 5,000 kg of permeate per m2 of membrane area has been reached since the previous cleaning.
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    同族专利:
    公开号 | 公开日
    EA201290533A1|2013-01-30|
    US8574873B2|2013-11-05|
    US20110151517A1|2011-06-23|
    EP2513324A2|2012-10-24|
    AU2010341022A1|2012-07-19|
    ES2596656T3|2017-01-11|
    KR101773215B1|2017-08-31|
    EP2513324B1|2016-07-13|
    CA2784226A1|2011-07-14|
    WO2011082973A3|2011-09-15|
    TN2012000305A1|2013-12-12|
    BR112012014740A2|2017-09-26|
    KR20120120234A|2012-11-01|
    JP2013514067A|2013-04-25|
    AU2010341022A2|2012-09-13|
    CN102712943A|2012-10-03|
    MX2012006882A|2012-12-05|
    CA2784226C|2018-10-16|
    WO2011082973A2|2011-07-14|
    DK2513324T3|2016-11-07|
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    法律状态:
    2018-05-29| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-11-21| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2020-04-07| B09A| Decision: intention to grant|
    2020-10-06| B25D| Requested change of name of applicant approved|Owner name: WINTERSHALL DEA GMBH (DE) |
    2020-10-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    2020-10-27| B25A| Requested transfer of rights approved|Owner name: BASF SE (DE) |
    优先权:
    申请号 | 申请日 | 专利标题
    US28722409P| true| 2009-12-17|2009-12-17|
    EP09179716|2009-12-17|
    US61/287,224|2009-12-17|
    EP09179716.7|2009-12-17|
    PCT/EP2010/069518|WO2011082973A2|2009-12-17|2010-12-13|Method for producing homopolysaccharides|
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