专利摘要:
The invention relates to a method for the selective separation of water from process liquids, characterized in that water is selectively deposited in the implementation of a bioprocess by means of a membrane module.
公开号:AT513378A4
申请号:T50508/2012
申请日:2012-11-13
公开日:2014-04-15
发明作者:Christoph Herwig;Arne Seifert
申请人:Tech Universität Wien;
IPC主号:
专利说明:

10 2012/50508 iRiinted: 14r11r2012
IUÜ04AI
Selective separation of water with simultaneous biomass and media component retention
The invention relates to a method for the selective separation of water from process liquids, characterized in that water is selectively deposited in the implementation of a bioprocess by means of a membrane module.
The development and improvement of C02-neutral energy production processes is a central theme in the 21st century. A promising technology in this context is the conversion of C02 and hydrogen (H2) to methane (CH4) and water (H20) by methanogenic archaea, as this biological process, using the reaction equation CO2 + 4 H2 = CH4 + 2 H2O, by its high conversion efficiency is characterized.
As the reaction stoichiometry shows, the formation of methane also produces water at the same time. Permanent removal of water is therefore necessary during continuous cultivation of hydrogenotrophic methanogenic archaea, even if no additional liquids are fed into the bioprocess. If this separation is achieved by a constant removal of fermentation broth, there is a loss of biomass and thus a reduction of catalytic activity and a loss of media components, such as salts, trace elements and vitamins. Selective removal of water while maintaining the biomass and media components is therefore more cost effective and optionally also leads to improved process performance by increasing the amount of catalytically active biomass. This selective separation of water can be achieved, for example, by membrane-based separation processes.
The invention thus comprises a method for the separation of water from process liquids, characterized in that water is selectively deposited when carrying out a bioprocess by means of a membrane module.
The selective separation of water from the fermentation broth brings significant advantages over the conventional constant removal of fermentation broth. For example, less medium is needed, which means less 2
TU004AT
Operating costs are necessary and the necessary supply and discharge lines can be dimensioned correspondingly smaller. Weather it comes to a lower hydraulic volume exchange in the process whereby less, with residues of media components, charged waste streams incurred.
For the purposes of this invention, selective separation of water means that essentially only water is separated during this separation, while the fermentation medium and the biomass are retained in the bioreactor. For example, the separated water contains no cells and / or media components. If water has to be added to the bioprocess, this separated water can optionally be added to the fermentation liquid again, which in turn results in lower operating costs.
Another aspect of the invention is the method described above, characterized in that the bioprocess is carried out continuously.
In principle, a continuous fermentation process is economically superior to batch fermentation, but its implementation requires that the cultured organisms grow and multiply rapidly and evenly, and that they are insensitive to the stirring and shearing forces that occur in a batch fermentation continuous fermentation could occur for a longer duration and thereby damage the biological catalyst.
Another aspect of the invention is the method described above, characterized in that biomass and / or media components are retained in the bioreactor.
Another aspect of the invention is the method described above, characterized in that the method is carried out at a dilution rate of 0.005 to 0.2 h " 1.
Another aspect of the invention is the method described above, characterized in that the membrane module is provided outside or inside the bioreactor. iPrinted: 14-11-2012 I UU04A! iEÖ14 3 102012/50508
As possible membrane modules, conventional membranes from any manufacturer such as Novasep, GE Osmonics, Hydranautics, Dow Water & Process Solutions, Toray, Koch Membrane Systems, Membrana, Polypore, Liquicell etc. are used. It is important that these membrane modules are temperature and / or chemically stable. In a preferred embodiment, a pervaporation module is used. However, it is also possible to install membranes in a holder produced especially for this application.
Another aspect of the invention is the method described above, characterized in that the bioprocess is conducted under anaerobic conditions.
Another aspect of the invention is the method described above, characterized in that additional water is formed during the bioprocess.
Another aspect of the invention is the method described above, characterized in that methanogenic archaea are cultured.
Another aspect of the invention is the method described above, characterized in that the methanogenic archaea are cultured in the bioprocess.
The methanogenic archaea are preferably selected from the group consisting of Methanobacteriales, Methanomicrobiaies, Methanopyraies, Methanococcales Methanosarcinales and Methanocellales.
A methanogenic microorganism which is naturally capable of producing methane is particularly suitable for any embodiment of the invention. Preferably, the methanogenic microorganism is a methanogenic archaebacterium comprising all members of the methanogenic archaeal domain, such as Methanobacterium alcaliphilum, Methanobacterium bryantii, Methanobacterium congolense, Methanobacterium defluvii, Methanobacterium espanolae, Methanobacterium formicicum, Methanobacterium ivanovii, Methanobacterium peaustre, Methanobacterium thermaggregans, Methanobacterium uiiginosum, Methano -brevibacter acididurans, methanobrevibacter arbor iphilicus, methanobrevibacter gottschalkii, methanobrevibacter olleyae, methanobrevibacter ruminantium, methanobrevibacter smithii, methanobrevibacter woesei, methanobrevibacter woiinii, methanothermobacter marburgensis, methanothermobacter thermoautotrophicus, jPrintöd: 14-11-2012 IE014 1102012/50508 IUOU4AI 4
Methanobacterium thermoautotrophicus, Methanothermobacter thermoflexus, Methanothermobacter thermophilics, Methanothermobacter wolfeii, Methanothermus sociabilis, Methanocorpusculum bavaricum, Methanocorpuscutum parvum, Methanoculleus chikuoensis, Methanoculteus submarinus, Methanogenium frigidum, Methanogenium liminatans, Methanogenium marinum, Methanosardna acetivorans, Methanosarcina barks, Methanosardna mazei, Methanosardna thermophila, Methanomicrobium mobile , Methanocaldococeus jannaschii, Methanococcus aeolicus, Methanococcus maripaludis, Methanococcus vannielii, Methanococcus voltaei, Methanothermococcus thermolithotrophicus and Methanopyrus candied.
Another aspect of the invention is the method described above, characterized in that methane is produced by the bioprocess.
Another aspect of the invention is the method described above, characterized in that the membrane module is temperature and / or chemically resistant.
Brief description of the figures:
FIG. 1 shows the experimental setup of the bioprocess plant.
Figure 2 shows the reactor volume, biomass concentration, total biomass and qCH4 during the first experiment.
Figure 3 shows the reactor volume, biomass concentration, total biomass and qCH4 during the second experiment.
FIG. 4 shows the transmembrane flow in the second experiment.
Examples:
The following examples are merely exemplary and are intended to better illustrate the invention disclosed herein. Changes and variations of the following examples within the scope of the present claims may be made.
To demonstrate the feasibility of pervaporation for the selective separation of water in biological processes, M. marburgensis was cultured continuously in a bioprocess reactor, with the bioprocess reactor being equipped with a bypass membrane module outside the reactor. The fermentation broth was iPrinted: 14-11-2012 £ 014 il 0 2012/50508 IUÜU4AI 5
Pumped continuously through the bypass, thus keeping the reactor volume constant by the continuous separation of water across the membrane module. During the bioprocess, the biomass concentration, the specific and volumetric productivity and the quality of the permeate were monitored to investigate the influence of the selective deposition of the water on the culture.
material and methods
Fermentation setup and media composition
All experiments were performed with Methanothermobacter marburgensis (strain DSM 2133) in a 10 L laboratory reactor (Biostat C +, Sartorius Stedim Biotech AG, Göttingen, Germany). M. marburgensis cultures were stored at 4 Ό and 0.5 bar overpressure of a H2 / CO2 atmosphere in pressure-tight bottles capped with a rubber gum. The gas phase was exchanged once a week by releasing the overpressure in the bottle and refilling with H2 / CO2 to a pressure of 0.5 bar. For fermentation, a slightly altered medium of beauty was used (Schoenheit et al, 1979). The following constituents per liter are present: 2.1 g NH 4 Cl, 6.8 g KH 2 PO 4, 3.6 g Na 2 CO 3, 0.09 g Titriplex 1.0.04 g MgCl 2 .6H 2 .0.01 g FeCl 2 .4H 2 O, O, 2 mg CoCI2 * 6H20,1,2 mg NiCI2 * 6H20, 0,2 mg NaMo04 * 2H20.
The same medium was added during the continuous cultivation, with an additional 100 μΙ / L of antifoam added.
To ensure anaerobic conditions in the reaction vessel, the entire system was flushed with a H2 / CO2 mixture for several minutes prior to inoculation.
For inoculation, 50 ml of the M. marburgensis stock solution per liter of medium was anaerobically transferred to the reactor using an anaerobic gas tight syringe.
The cultivation was carried out at 65 ° C and a stirrer speed of 1500 rpm. The pH was measured by a pH probe (Mettler Toledo GmbH, Vienna, Austria and Hamilton Bonaduz AG, Bonaduz, Switzerland) and by
Printed: 14-11-2012 I UUU4A I
[E014 e [102012/50508
The addition of a 1M (NH4) 2CO3 solution was kept constant at a value of 6.85 to compensate for acidification by microbial growth.
The oxidation-reduction potential (ORP) was measured by a redox probe (Mettler Toledo GmbH, Vienna, Austria) and was always below-300 mV. A 0.5 M Na 2 S 9H 2 O solution was used as the sulfur source and fed continuously into the reactor at a rate of 0.018 LL-1 d-1. The addition of lye and Na2S solution was recorded gravimetrically. The feed medium was measured using an analogous peristaltic pump (Preciflow, Lambda Laboratory Instruments, Zurich,
Switzerland). The flow rate was detected gravimetrically and kept constant by controlling the speed. The bioreactor volume was kept constant by separating the culture suspension via a dip tube using a peristaltic pump and controlled by the fixed weight of the reactor. The separated suspension was collected in a harvest bottle and its volume determined gravimetrically. All solutions were kept anaerobic by rinsing with N2 or H2 / CO2. To maintain the anaerobic conditions, all bottles were pressurized with 1 bar N2. Pure H2 and C02 were used as substrates for M. marburgensis. The gas flows were individually adjusted by means of a thermal mass flow controller (Brooks Instruments, Hatfield, USA).
Pervaporation For the selective separation of water, a conventional pervaporation module was used. The fermentation broth was therefore pumped at a constant flow rate of 20 L / h by means of a bypass over the membrane module located outside the reactor with a Quattroflow 150S pump (Quattroflow Fluid Systems GmbH Co. KG, Hardegsen-Hevensen, Germany) and the retentate returned to the reactor , The anaerobic conditions in the bypass were ensured for the entire process time. Continuous separation of water through the membrane was achieved by applying a vacuum of 100 mbar on the permeate side of the membrane module. The evaporated water was then condensed with a Lauda Alpha cryostat (LAUDA DR. R. WOBSER GMBH & CO KG, Lauda-Koenigshofen, Germany) at originally -8 ° C. The structure is shown in FIG. iPrinted:
14-11- I UUU4AI EÖ14 '7 10 2012/50508
Results and discussion
Figure 2 shows the effect of selective separation of water over a pervaporation module during the continuous cultivation of M. marburgensis. The total gassing was 0.5 wm at a H2: C02 ratio of 4: 1 in the reaction gas. Pervaporation was started at time 0.
The biomass concentration increased during the experiment from 3.73 to 4.65 g / L. At the same time, the specific methane production rate (qChU) decreased continuously due to a gas-limited culture. The separated permeate was a clear, transparent, aqueous liquid that differed significantly from the supernatant of the reaction broth after microfiltration, which had an intense yellow color. It can therefore be assumed that the media components were effectively withheld.
The experiment was repeated. The result is shown in FIG.
Unfortunately, the cryostat provided insufficient cooling performance and could not maintain a stable temperature. The temperature rose from -8 to 7 ° C in the first one and a half hours. As a result, the pervaporation module was discontinuously employed to allow the cryostat to cool from time to time (Figure 4). During the shutdown phases, the reactor volume was kept constant by means of a normal dip tube, with appropriate amounts of the fermentation broth being separated. This resulted in a slightly lower increase in biomass concentration during the experiment (4.05 g / L to 4.57 g / L) compared to the previous experiment.
The successful, selective separation of water from continuous cultures of M. marburgensis with pervaporation has been demonstrated. This had no negative impact on cultural performance. The biomass concentration was continuously increased during the experiments and the adapted transmembrane flux allowed a constant reactor volume. The permeate was a clear, aqueous liquid that differed markedly in color from the fermentation broth, which was otherwise separated on the permeate side by microfiltration. Furthermore, an effective retention of the media components could be shown.
权利要求:
Claims (11)
[1]
1. Process for the separation of water from process liquids, characterized in that water is selectively separated when a bioprocess is carried out by means of a membrane module.
[2]
2. The method according to claim 1, characterized in that the bioprocess is carried out continuously.
[3]
3. The method according to claim 1 or 2, characterized in that biomass and / or media components are retained in the bioreactor.
[4]
4. The method according to any one of claims 1 to 3, characterized in that the method is carried out at a dilution rate of 0.005 to 0.2 h'1.
[5]
5. The method according to any one of claims 1 to 4, characterized in that the membrane module is provided outside or inside the bioreactor.
[6]
6. The method according to any one of claims 1 to 5, characterized in that the bioprocess is conducted under anaerobic conditions.
[7]
7. The method according to any one of claims 1 to 6, characterized in that during the bioprocess additional water is formed.
[8]
8. The method according to any one of claims 1 to 7, characterized in that methanogenic archaea are cultivated.
[9]
9. The method according to claim 8, characterized in that the methanogenic archaea are selected from the group consisting of Methanobacteriales, Methanomicrobiales, Methanopyrales, Methanococcales, Methanosarcinales and Methanocellales.
[10]
10. The method according to any one of claims 1 to 9, characterized in that is produced by the bioprocess methane.
[11]
11. The method according to any one of claims 1 to 10, characterized in that the membrane module is temperature and / or chemically resistant.
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同族专利:
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法律状态:
2021-07-15| MM01| Lapse because of not paying annual fees|Effective date: 20201113 |
优先权:
申请号 | 申请日 | 专利标题
ATA50508/2012A|AT513378B1|2012-11-13|2012-11-13|Selective separation of water with simultaneous biomass and media component retention|ATA50508/2012A| AT513378B1|2012-11-13|2012-11-13|Selective separation of water with simultaneous biomass and media component retention|
EP13792316.5A| EP2919893B1|2012-11-13|2013-11-12|Selective removal of water by means of membrane processes in an anaerobic bioprocess|
PCT/EP2013/073587| WO2014076062A1|2012-11-13|2013-11-12|Selective removal of water by means of membrane processes in an anaerobic bioprocess|
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