CN102094048A - Method and device for producing organic acid or alcohol by fermenting synthetic gas - Google Patents
Method and device for producing organic acid or alcohol by fermenting synthetic gas Download PDFInfo
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- CN102094048A CN102094048A CN201010572549XA CN201010572549A CN102094048A CN 102094048 A CN102094048 A CN 102094048A CN 201010572549X A CN201010572549X A CN 201010572549XA CN 201010572549 A CN201010572549 A CN 201010572549A CN 102094048 A CN102094048 A CN 102094048A
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Abstract
The invention relates to a method for producing organic acid or alcohol by fermenting synthetic gas, which comprises the following steps: (1) adding anaerobic bacteria capable of metabolizing CO, H2 and CO2 to produce organic acid or alcohol into a reactor filled with inert particles which are used as a vector; (2) introducing synthetic gas, which is composed of one or more of CO, H2 and CO2, into the reactor, enabling the vector to be in a fluidized state and keep the fluidized state, thoroughly mixing the anaerobic bacteria and the vector, and fermenting; and (3) adding a liquid culture medium into the reactor, and flushing the suspended anaerobic bacteria out of the reactor, so that the microbes attached to the surface of the vector form a biomembrane. The invention also provides a device for implementing the method. The invention fully utilizes the characteristic of high mass transfer efficiency of the solid/liquid internal circulation fluidized bed, and is assisted by the gas external circulation technology, thereby realizing high-efficiency conversion from synthetic gas into organic acid or alcohol.
Description
Technical field
The invention belongs to the microbial fermentation engineering field, is raw material with synthetic gas (carbon monoxide, hydrogen, carbonic acid gas) specifically, utilizes microbial fermentation to produce the method for organic acid or alcohol.
The invention still further relates to a kind of device that is used to realize aforesaid method.
Background technology
Synthetic gas is that a class is with carbon monoxide, carbonic acid gas and hydrogen are the mixed gas of main ingredient, it not only can be produced or be produced by light hydrocarbons such as Sweet natural gas and oil by the vaporization of solid fuels such as coal or coke, also can be by heavy oil through partial oxidation process production, simultaneously, biomass such as stalk, nutgrass flatsedge, agriculture and forestry organic waste material and city organic solid waste etc. all can be used as its raw materials for production, come source range extremely wide.As the energy fuel, synthetic gas also is important chemical industry basic material except that directly.The chemical production technical that with the synthetic gas is raw material synthetic ammonia, oxygenatedchemicals and hydro carbons etc. has all been put into commercial operation, but these technologies all adopt chemical process.In recent years, biological process comprehensive utilization synthetic gas has caused very big concern, especially by the microbiological anaerobic fermentation synthetic gas is changed into various useful fuel and chemical technology.Have slower speed of reaction although compare with chemical catalysis, specificity height, the cell that microorganism catalysis still has reaction conditions gentleness, a purpose product reclaim and regeneration easily, the proportion of composing of raw material CO and H2 is required low and distinct advantages such as catalyst vulcanization thing intoxicating phenomenon can not occur.
Yet the synthetic gas fermentation is the heterogeneous reaction process of a complexity, comprises the triphasic interactions of gas, liquid, solid such as gaseous substrate, nutrient solution and microorganism cells.Gaseous substrate need could arrive cell surface through the transmission of a plurality of steps and be absorbed by microorganism, thereby gas-liquid mass transfer is the main rate-limiting step of synthetic gas fermenting process, and owing to CO and H
2Solubleness in the aqueous solution is very low, makes this mass transfer limit seem more outstanding.In order to improve the gas-liquid mass transfer problem of synthetic gas fermenting process, except being optimized, can also explore from reactor design from the zymotechnique aspect.The synthetic gas fermentation reactor that is widely studied at present mainly contains continuous stirred tank reactor, trickle-bed reactor, bubbling column reactor, microvesicle aerobic reactor and composite hollow fiber membrane formula reactor etc.Wherein, continuous stirred tank reactor is most widely used in laboratory scale synthetic gas fermentation, its volume transmission quality coefficient (KLa) improves along with the increase of unit volume power of agitator (P/V) and empty tower gas velocity (Ug), but improving Ug can cause the transformation efficiency of gaseous substrate to reduce, and high P/V means that energy consumption increases, and this has just limited its application on technical scale to a certain extent.
The organism fluidization bed technique is set forth in the seventies in last century, it is characterized in that based on biomembrance process, has drawn the fluidization technology in the chemical industry operation, has greatly improved mass-transfer efficiency, is widely used in waste water treatment process.Biological fluidized bed is a carrier with less inert particles of a class such as sand, gac, coke, haydite, zeolite, magnet ring, granulated glass sphere, porous balls, make microorganism inhabit carrier surface, form the thin layer microbial film, liquid or gas-liquid mixture from bottom to top pass through bed with certain speed, make the carrier fluidisation, substrate is biological with suspending phase and adhere in continuous contact of biology mutually and degraded.In principle, the organism fluidization bed technique is that the microbial film by carrier surface works, but in liquid or gas-liquid mixture, be fluidized with carrier granule at the inside reactor microbial film, thereby it not only has the fixed biofilm growth characteristics but also have the suspension growth feature.These characteristics have overcome the susceptible to plugging problem of static bed biomembrane method; Simultaneously, the small-particle carrier provides huge surface-area for microbial immobilization, make the biomass concentration in the fluidized-bed improve, and the fluidization of biological particles can disperse bubble with cutting, make gas distribution more even, also promoted the continual renovation at microbial film and liquid or gas-liquid mixed interface, these have all greatly strengthened mass-transfer efficiency, have improved the stability of production efficiency and technology.
Summary of the invention
The method that the object of the present invention is to provide a kind of synthetic gas that ferments to produce organic acid or alcohol.
Another purpose of the present invention is to provide a kind of device of realizing aforesaid method.
For achieving the above object, fermentation synthetic gas provided by the invention is produced the method for organic acid or alcohol, and its key step is:
1) with energy metabolism CO, H
2And CO
2The anaerobic bacterium that produces organic acid or alcohol joins and is filled with the inert particle is in the reactor of carrier;
Organic acid or alcohol comprise: acetate, lactic acid, butyric acid, methyl alcohol, ethanol and butanols.
Energy metabolism CO, H
2And CO
2Produce the anaerobic bacterium of organic acid or alcohol, comprise: methylbutyric bacillus (Butyribacterium methylotropphicum), clostridium aceticum (Clostridiumaceticum), producing and ethanol clostridium (Clostridium autoethanogenum), carbonyl degraded clostridium (Clostridium carboxidivorans), Clostridium lentocellum (Clostridium lentocellum), Yang Shi clostridium (Clostridium ljungdahlii), Clostridium thermocellum (Clostridium thermocellum) and thermophilic acetate clostridium (Clostridium thermoaceticum), and any mutant strain that on their bases, carries out.
Carrier can be that particle diameter is one or more in the sand, gac, haydite, zeolite, granulated glass sphere, perlite, sepiolite, polypropylene, modified polyurethane, wire netting sponge particle, biozeolite of 0.1～50mm.
2) will be by CO, H
2And CO
2The synthetic gas of one or more compositions feed reaction vessel, make carrier reach fluidized state, and keep fluidized state, make anaerobic bacterium and carrier thorough mixing and ferment;
3) liquid nutrient medium is joined in the reaction vessel, the anaerobic bacterium that suspends is gone out reaction vessel, make microorganism form microbial film attached to carrier surface.Liquid nutrient medium is: NH
4Cl0.5-1.5g/L, NaCl 0.5-1.5g/L, MgCl
6H
2O 0.2-0.6g/L, KH
2PO
40.5-1.5g/L, K
2HPO
41.0-2.0g/L, Tryptone 1.5-2.5g/L, Yeast extract 0.5-1.5g/L, FeCl
36H
2O2.0-3.0mg/L, xylose 3-6g/L, Cysteine-HClH
2O 0.5-1.5g/L, pH 5.5-6.5.
The device that is used to realize aforesaid method provided by the invention, for the gentle extracorporeal circulation three-phase of solid-liquid internal recycle anaerobic fluidized bed; Wherein: the fluidized-bed bottom from bottom to top is respectively equipped with stopping valve (6), gas distributor (7) and liquid distributor (8), and Open Side Down for gas distributor, and the liquid distributor opening upwards; The reaction zone at middle part is three layers of concentric drums, ecto-entad is respectively chuck outer wall (10), urceolus (11) and inner core (13), the chuck outer wall links to each other with temperature controlling system (5) respectively at two ends up and down, inner core is fixed on the urceolus by back-up block (21) and adjusting screw (14), can regulate the relative height of inner core and urceolus by adjusting screw, be filled with carrier (12) in the inner core, carrier can be that particle diameter is the sand of 0.1～50mm, gac, haydite, zeolite, granulated glass sphere, perlite, sepiolite, polypropylene, modified polyurethane, wire netting sponge particle, in the biozeolite one or more; The top is by tilted plate separator (15), triphase separator (16) and overflow groove (17), the vergence direction of tilted plate separator swash plate is opposite with the opening direction of overflow groove, triphase separator is positioned at above the tilted plate separator, running through top cover also can be by setting nut adjustment height, its venting port direction is opposite with the overflow groove opening direction, and the venting port of fluidized-bed is positioned on the top cover.
Described device, wherein fluidized-bed is connected with the extraneous gas circulation supply system, consisting of of this extraneous gas circulation supply system: synthetic gas storage tank (1) is by air compressor (A), gas meter (F) and stopping valve (2) are connected to gas buffer jar (3), the side exit of gas buffer jar connects stopping valve (4), gas filter (S) and gas recycle pump (M1), the gas distributor (7) of gas being delivered to the fluidized-bed bottom enters fluidized-bed, the gas that comes out from fluidized-bed passes through stopping valve (19) and condensing tower (20) earlier by top interface backflow return-air body surge tank, and then realizes the outer circulation of gas; The gas buffer jar is provided with tensimeter (P1); Gas duct (22) is communicated between overflow groove (17) rising pipe and the outlet of fluidized-bed tail gas.
Described device, wherein fluidized-bed is connected with that substratum is supplied with and the product recovery system, and this substratum is supplied with and the consisting of of product recovery system: seeding tank (23) all links to each other with liquid distributor (8) through liquor pump (M2) with stopping valve (25) with culture tank (9) with stopping valve (24); The overflow groove (17) on bed top links to each other with vacuum breaker (18); Condensing tower (20) is connected on the gas path pipe behind the stopping valve (19), communicates with gas buffer jar (3).
Described device, wherein the chuck outer wall (10) of fluidized-bed is connected with temperature controlling system, the temperature of reaction in the control fluidized-bed.
Description of drawings
Fig. 1 is an internal recycle three-phase anaerobic fluidized bed reactor synoptic diagram of the present invention.
Description of symbols in the accompanying drawing:
1 synthetic gas storage tank, 2 stopping valve, 3 gas buffer jars, 4 stopping valve, 5 temperature controlling systems, 6 stopping valve, 7 gas distributors, 8 liquid distributors, 9 culture tanks, 10 chuck outer walls, 11 fluidized-bed urceolus, 12 carriers, 13 fluidized-bed inner cores, 14 adjusting screws, 15 tilted plate separators, 16 triphase separators, 17 overflow grooves, 18 vacuum breaker, 19 stopping valve, 20 condensing towers, 21 back-up blocks, 22 gas ducts, 23 seeding tanks, 24 stopping valve, 25 stopping valve, the M1 gas recycle pump, M2 liquor pump, CW cooling water inlet, CW ' cooling water outlet, P1 tensimeter, P2 tensimeter, the F gas meter, A air compressor, S gas filter.
Embodiment
The present invention has used for reference the organism fluidization bed technique of wastewater treatment, be applied to the microbial fermentation of synthetic gas after the improvement, and composite gas circulation technology, both guaranteed gas-liquid mass transfer efficiently, take into account effective utilization of unstripped gas again, realized the efficient conversion that the microbial fermentation synthetic gas is produced organic acid or alcohol.The present invention had both enriched the type of synthetic gas biological fermentation reactor, had also solved the technical barrier of synthetic gas fermentative Production organic acid or alcohol to a certain extent, helped promoting the development of China's energy-saving and emission-reduction and low-carbon economy.
With the biological fluidized bed is carrier, it is characterized in that by microorganism in the recycle system of sealing, by the fermentation in solid, liquid, gas three-phase circulation anaerobic fluidized-bed reactor, realizes from the synthetic gas to the organic acid or the efficient conversion of alcohol.
In recent years, based on the very big concern of the synthetic gas biological process of microbial fermentation comprehensive utilization having caused.Yet the synthetic gas fermentation is a heterogeneous reaction process, and gaseous substrate need could arrive cell surface through the transmission of a plurality of steps and be absorbed by microorganism, and because CO and H
2Solubleness in water is low, thereby gas-liquid mass transfer is the rate-limiting step of synthetic gas fermenting process.About the gas-liquid mass transfer of synthetic gas fermenting process, do not find a kind of both efficiently, economical again at present yet, and be easy to realize the method for industrial applications.In order to overcome these difficult points in the synthetic gas biological fermentation process, the present invention uses for reference the organism fluidization bed technique of wastewater treatment, developed a kind of method of utilizing biological fluidized bed fermentation synthetic gas to produce organic acid or alcohol, both guaranteed gas-liquid mass transfer efficiently, take into account effective utilization of unstripped gas again, realized the efficient conversion that the microbial fermentation synthetic gas is produced organic acid or alcohol.Its principal character is as follows:
1) the fermentation synthetic gas is produced organic acid or alcohol in three-phase circulation anaerobic fluidized-bed reactor.
2) three-phase circulation anaerobic fluidized-bed reactor, round-robin air-flow is a power beyond it, by the fluidized-bed main body, the extraneous gas circulation supply system, substratum is supplied with and product recovery system and temperature controlling system four parts composition.
3) bottom of fluidized-bed main body from bottom to top is respectively equipped with stopping valve, gas distributor and liquid distributor, and Open Side Down for gas distributor, and the liquid distributor opening upwards is convenient to the uniform distribution of gas and liquid, prevents situations such as vector aggregation or short circuit.The reaction zone at middle part is three layers of concentric drums, and ecto-entad is respectively chuck outer wall, urceolus and inner core.The chuck outer wall links to each other with temperature controlling system respectively at two ends up and down, the leavening temperature in the control fluidized-bed.Inner core is fixed on the urceolus by back-up block and adjusting screw, by the relative height that adjusting screw can be regulated inner core and urceolus, the fluidisation of regulating different carriers.Placement carrier in the inner core, carrier is that particle diameter is less, surface irregularity, the inert particle of porous and good biocompatibility.Urceolus Gao Jing: the diameter ratio is 3～10: 1.After fluidisation began, air-flow carried carrier and form the fluidization bed in inner core, and substratum-the carrier mixed solution is at the inner core upper reaches, and urceolus is dirty, constituted the solid-liquid internal recycle.The fluidized-bed top is made up of tilted plate separator, triphase separator, overflow groove and tensimeter.The angle of inclination of tilted plate separator swash plate (the little angle angle that swash plate and lower shoe face form) is 45 °～60 °, and vergence direction is opposite with the opening direction of overflow groove.Triphase separator is positioned at above the tilted plate separator, and the two tandem working has effectively been controlled the top liquid turbulence that air-flow causes, the loss of having stopped active carrier to greatest extent.Triphase separator runs through top cover also can be by setting nut adjustment height, to regulate the effective separation between synthetic gas, liquid nutrient medium and the carrier three-phase.The end opening subtended angle of triphase separator is 100 °～150 °.Triphase separator venting port direction is opposite with the overflow groove opening direction, and the venting port of fluidized-bed is positioned on the top cover, and this has also been avoided the influence of air-flow to overflow liquid.
4) in the extraneous gas circulation supply system, the synthetic gas storage tank is connected to the gas buffer jar by air compressor machine, gas meter and stopping valve, the side exit of gas buffer jar connects stopping valve, gas filter and gas recycle pump, the gas distributor of gas being delivered to the fluidized-bed bottom enters fluidized-bed, the gas that comes out from fluidized-bed passes through stopping valve and condensing tower earlier by top interface backflow return-air body surge tank, and then realizes the outer circulation of gas.The flow of adjustments of gas recycle pump, adjustable bed interior fluidized state.When synthetic gas is consumed, when the pressure of gas buffer jar was decreased to the emergent pressure that air compressor sets, the air compressor machine compressed synthesis gas entered the gas buffer jar.The gas buffer jar is provided with tensimeter.The gas duct that is communicated between the outlet of overflow groove rising pipe and fluidized-bed tail gas helps to eliminate the pressure of an internal gas pressure to overflow liquid.
5) in substratum supply and the product recovery system, seeding tank all links to each other with liquid distributor through liquor pump with stopping valve with culture tank with stopping valve, can directly send seed liquor or liquid nutrient medium to fluidized-bed by liquid distributor.After the substratum fermentation, enter the product recovery system through overflow groove and vacuum breaker.By regulating the flow of liquor pump, the residence time of may command liquid nutrient medium in fluidized-bed, can guarantee making full use of of each effective constituent in the substratum.Condensing tower is connected on the gas path pipe behind the top stopping valve, communicates with the gas buffer jar.Liquid collected in the condensing tower can contain certain density end product, also enters recovery system and carries out the product recovery.
Using three-phase circulation anaerobic fluidized-bed reactor described above to carry out synthetic gas fermentation production of organic acid or alcohol, is that those skilled in the art can realize.The invention has the advantages that it has utilized the high characteristics of solid-liquid Internal Circulating Fluidized Bed mass-transfer efficiency, and be aided with the gas external circulation process, both guarantee gas-liquid mass transfer efficiently, taken into account effective utilization of unstripped gas again, realized the efficient conversion that the microbial fermentation synthetic gas is produced organic acid or alcohol.The present invention had both enriched the type of synthetic gas biological fermentation reactor, had also solved the technical barrier of synthetic gas fermentative Production organic acid or alcohol to a certain extent, and it helps promoting the development of China's energy-saving and emission-reduction and low-carbon economy.
Elaborate by the following examples and in conjunction with the accompanying drawings, make those skilled in the art more fully understand the present invention, but the following description does not limit the present invention in any way.
Embodiment
See also shown in Figure 1, a kind of method of utilizing biological fluidized bed fermentation synthetic gas to produce organic acid or alcohol, it uses reactor to be three-phase circulation anaerobic fluidized-bed reactor, is made up of fluidized-bed main body, extraneous gas circulation supply system, substratum supply and product recovery system and temperature controlling system four parts.
The bottom of fluidized-bed main body from bottom to top is respectively equipped with stopping valve 6, gas distributor 7 and liquid distributor 8, and Open Side Down for gas distributor, and the liquid distributor opening upwards is convenient to the uniform distribution of gas and liquid, prevents situations such as vector aggregation or short circuit.The reaction zone at middle part is three layers of concentric drums, and ecto-entad is respectively chuck outer wall 10, urceolus 11 and inner core 13.The chuck outer wall links to each other with temperature controlling system 5 respectively at two ends up and down, temperature controlling system 5 mainly includes water route circulating line, temp probe, temperature regulator etc., wherein the water route circulating line is to link to each other at two ends up and down with the chuck outer wall, and temp probe insertion reaction device inside, be that temperature control head is connected to the fluidized-bed inner core shown in the accompanying drawing, the leavening temperature in the control fluidized-bed.Inner core is fixed on the urceolus by back-up block 21 and adjusting screw 14, by the relative height of adjusting screw with adjusting inner core and urceolus, thus the fluidisation of regulating different carriers.Inner core placement carrier 12, carrier are that particle diameter is less, surface irregularity, the inert particle of porous and good biocompatibility.The Gao Jing of urceolus: the diameter ratio is 3～10: 1, is designed to 7: 1 in the present embodiment.After fluidisation began, air-flow carried carrier and form the fluidization bed in inner core, and substratum-carrier mixed solution upper reaches in inner core passes through urceolus again to dirty, constituted the internal recycle of solid and liquid.The fluidized-bed top is made up of tilted plate separator 15, triphase separator 16, overflow groove 17 and tensimeter P2.The angle of inclination of tilted plate separator swash plate (the little angle angle that swash plate and lower shoe face form) is 45 °～60 °, is designed to 60 ° in the present embodiment, and vergence direction is opposite with the opening direction of overflow groove.Triphase separator is positioned at above the tilted plate separator, and the two tandem working has effectively been controlled the top liquid turbulence that air-flow causes, the loss of having stopped active carrier to greatest extent.Triphase separator runs through top cover also can be by setting nut adjustment height, to regulate the effective separation between synthetic gas, liquid nutrient medium and the carrier three-phase.The end opening subtended angle of triphase separator is 100 °～150 °, is designed to 120 ° in the present embodiment.Triphase separator 16 venting port directions are opposite with overflow groove 17 opening directions, and the venting port of fluidized-bed is positioned on the top cover, and this has also been avoided the influence of air-flow to overflow liquid.
In the extraneous gas circulation supply system, synthetic gas storage tank 1 is connected to gas buffer jar 3 by air compressor machine A, gas meter F and stopping valve 2, the side exit of gas buffer jar connects stopping valve 4, gas filter S and gas recycle pump M1, the gas distributor 7 of gas being delivered to the fluidized-bed bottom enters fluidized-bed, the gas that comes out from fluidized-bed passes through stopping valve 19 and condensing tower 20 earlier by top interface backflow return-air body surge tank 3, and then realizes the outer circulation of gas.The flow of adjustments of gas recycle pump M1, adjustable bed interior fluidized state.When synthetic gas is consumed, when the pressure of gas buffer jar was decreased to the emergent pressure (being designed to 0.3MPa in the present embodiment) that air compressor sets, the air compressor machine compressed synthesis gas entered the gas buffer jar.The gas buffer jar is provided with tensimeter P1.Gas duct 22 is communicated between overflow groove rising pipe and the outlet of fluidized-bed tail gas, and it helps to eliminate the pressure of fluidized-bed internal gas pressure to overflow liquid.
In substratum supply and the product recovery system, seeding tank 23 all links to each other with liquid distributor 8 through liquor pump M2 with stopping valve 25 with culture tank 9 with stopping valve 24, can directly send seed liquor or liquid nutrient medium to fluidized-bed by liquid distributor.After the substratum fermentation, enter the product recovery system through overflow groove 17 and vacuum breaker 18.By regulating the flow of liquor pump M2, the residence time of may command liquid nutrient medium in fluidized-bed, guarantee making full use of of each effective constituent in the substratum.Condensing tower 20 is connected on the gas path pipe behind the top stopping valve 19, communicates with gas buffer jar 3.Liquid collected in the condensing tower can contain certain density end product, also enters recovery system and carries out the product recovery.
Produce organic acid or ethanol with the three-phase circulation anaerobic fluidized-bed reactor synthetic gas that continuously ferments, its concrete operations are as follows:
1) to select gac for use be carrier to present embodiment, and producing and ethanol clostridium (Clostridiumautoethanogenum) is a fermentation strain, fluidized-bed urceolus diameter 100mm, inner diameter of steel flue 60mm, high 700mm.
2) add the gac that volume is 40ml in main body fluidized-bed inner core 13, install system and sterilize the main body fluidized-bed.
3) in seeding tank 23, use substratum: NH
4Cl 0.9g/L, NaCl 0.9g/L, MgCl
6H
2O0.4g/L, KH
2PO
40.75g/L, K
2HPO
41.50g/L, Tryptone 2.0g/L, Yeast extract1.0g/L, FeCl
36H
2O 2.5mg/L, xylose 5g/L, Cysteine-HClH
2O 0.75g/L, pH6.0 cultivates producing and ethanol clostridium seed (Clostridium autoethanogenum) 1L.
4) open reactor temperature control system 5, setting leavening temperature is 37 ℃; Open condensing tower 20.
5) open stopping valve 24, open liquor pump M2, in liquid distributor 8 pumped into the main body fluidized-bed, this moment, the flow of M2 pump was 2.4L/h with cultured seed liquid in the seeding tank 23, and gac is fluidisation not.
6) treat that seed liquor is full of the fluidized-bed inner/outer tube after, closing liquid pump M2 and stopping valve 24, open stopping valve 2, air compressor A compressed synthesis gas enters gas buffer jar 3 through gas filter S, open stopping valve 4,19 and gas recycle pump M1, synthetic gas enters fluidized-bed, regulates pump M1 flow, make the gac in the inner core be issued to fluidized state in the air-flow effect, this moment, the M1 flow was 5L/min.Adjust the height of triphase separator, make it effectively to separate synthetic gas, liquid nutrient medium and active carrier, do not have carrier to enter overflow groove again.When synthetic gas is consumed, when the pressure of gas buffer jar 3 was decreased to the 0.3MPa of setting, air compressor A compressed synthesis gas entered gas buffer jar 3 through gas filter S.
7) keep fluidized state 1h, make bacterium and carrier thorough mixing in the seed liquor.
8) open liquor pump M2 and stopping valve 25, the fresh sterilising medium in the culture tank 9 is pumped in the fluidized-bed, the flow of regulating liquor pump M2 is 0.3L/h, and the residence time of liquid nutrient medium in fluidized-bed this moment is about 2h.Than the liquid nutrient medium of short residence time(SRT), the bacterium that suspends can be gone out reactor, reduce the competition of substrate, help microbial growth attached to carrier surface, form microbial film.Nutrient solution after the fermentation enters the product abstraction process through overflow groove 17 and vacuum breaker 18.
9) fermentation 48h is after microbial film forms and stablizes, from vacuum breaker 18 samplings, detect nitrogen content wherein, according to the rate of consumption of nitrogen, adjust the flow of pump M2, as the rate of consumption of nitrogen less than 95%, then reduce the flow of M2, prolong the residence time of substratum, otherwise, augmented flow then, the nitrogen rate of consumption of overflow liquid is reached more than 95%, until fermentation ends.
More than be sub in conjunction with specific embodiments to further describing that the present invention did.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The scope of protection of present invention is defined by claim and equivalent thereof.
Claims (10)
1. the synthetic gas that ferments is produced organic acid or pure method, and its key step is:
1) with energy metabolism CO, H
2And CO
2The anaerobic bacterium that produces organic acid or alcohol joins and is filled with the inert particle is in the reactor of carrier;
2) will be by CO, H
2And CO
2The synthetic gas of one or more compositions feed reaction vessel, make carrier reach fluidized state, and keep fluidized state, make anaerobic bacterium and carrier thorough mixing and ferment;
3) liquid nutrient medium is joined in the reaction vessel, the anaerobic bacterium that suspends is gone out reaction vessel, make microorganism form microbial film attached to carrier surface.
2. method according to claim 1, wherein, described organic acid or alcohol comprise: acetate, lactic acid, butyric acid, methyl alcohol, ethanol and butanols.
3. method according to claim 1, wherein, described energy metabolism CO, H
2And CO
2Produce the anaerobic bacterium of organic acid or alcohol, comprise: methylbutyric bacillus (Butyribacteriummethylotropphicum), clostridium aceticum (Clostridium aceticum), producing and ethanol clostridium (Clostridium autoethanogenum), carbonyl degraded clostridium (Clostridiumcarboxidivorans), Clostridium lentocellum (Clostridium lentocellum), Yang Shi clostridium (Clostridium ljungdahlii), Clostridium thermocellum (Clostridium thermocellum) and thermophilic acetate clostridium (Clostridium thermoaceticum), and any mutant strain that on their bases, carries out.
4. method according to claim 1, wherein, described carrier is selected from one or more in sand that particle diameter is 0.1～50mm, gac, haydite, zeolite, granulated glass sphere, perlite, sepiolite, polypropylene, modified polyurethane, wire netting sponge particle, the biozeolite.
5. method according to claim 1, wherein, described liquid nutrient medium is: NH
4Cl0.5-1.5g/L, NaCl 0.5-1.5g/L, MgCl
6H
2O 0.2-0.6g/L, KH
2PO
40.5-1.5g/L, K
2HPO
41.0-2.0g/L, Tryptone 1.5-2.5g/L, Yeast extract 0.5-1.5g/L, FeCl
36H
2O2.0-3.0mg/L, xylose 3-6g/L, Cysteine-HClH
2O 0.5-1.5g/L, pH 5.5-6.5.
6. device of realizing the described method of claim 1, for the gentle extracorporeal circulation three-phase of solid-liquid internal recycle anaerobic fluidized bed; Wherein:
The fluidized-bed bottom from bottom to top is respectively equipped with stopping valve (6), gas distributor (7) and liquid distributor (8), and Open Side Down for gas distributor, and the liquid distributor opening upwards;
The reaction zone at middle part is three layers of concentric drums, ecto-entad is respectively chuck outer wall (10), urceolus (11) and inner core (13), the chuck outer wall links to each other with temperature controlling system (5) respectively at two ends up and down, inner core is fixed on the urceolus by back-up block (21) and adjusting screw (14), by the relative height that adjusting screw can be regulated inner core and urceolus, be filled with carrier (12) in the inner core;
The top is by tilted plate separator (15), triphase separator (16) and overflow groove (17), the vergence direction of tilted plate separator swash plate is opposite with the opening direction of overflow groove, triphase separator is positioned at above the tilted plate separator, running through top cover also can be by setting nut adjustment height, its venting port direction is opposite with the overflow groove opening direction, and the venting port of fluidized-bed is positioned on the top cover.
7. device according to claim 6, wherein, fluidized-bed is connected with the extraneous gas circulation supply system, the consisting of of this extraneous gas circulation supply system:
Synthetic gas storage tank (1) is connected to gas buffer jar (3) by air compressor (A), gas meter (F) and stopping valve (2), the side exit of gas buffer jar connects stopping valve (4), gas filter (S) and gas recycle pump (M1), the gas distributor (7) of gas being delivered to the fluidized-bed bottom enters fluidized-bed, the gas that comes out from fluidized-bed passes through stopping valve (19) and condensing tower (20) earlier by top interface backflow return-air body surge tank, and then realizes the outer circulation of gas; The gas buffer jar is provided with tensimeter (P1); Gas duct (22) is communicated between overflow groove (17) rising pipe and the outlet of fluidized-bed tail gas.
8. device according to claim 6, wherein, fluidized-bed is connected with that substratum is supplied with and the product recovery system, and this substratum is supplied with and the consisting of of product recovery system:
Seeding tank (23) all links to each other with liquid distributor (8) through liquor pump (M2) with stopping valve (25) with culture tank (9) with stopping valve (24); The overflow groove (17) on bed top links to each other with vacuum breaker (18); Condensing tower (20) is connected on the gas path pipe behind the stopping valve (19), communicates with gas buffer jar (3).
9. device according to claim 6, wherein, the chuck outer wall (10) of fluidized-bed is connected with temperature controlling system, the temperature of reaction in the control fluidized-bed.
10. device according to claim 6, wherein, described carrier is selected from one or more in sand that particle diameter is 0.1～50mm, gac, haydite, zeolite, granulated glass sphere, perlite, sepiolite, polypropylene, modified polyurethane, wire netting sponge particle, the biozeolite.
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Application publication date: 20110615 |