CN104031834A - Hydrogen manufacturing method through photosynthetic bacterium continuous reaction - Google Patents
Hydrogen manufacturing method through photosynthetic bacterium continuous reaction Download PDFInfo
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Abstract
The invention relates to a hydrogen manufacturing method through a photosynthetic bacterium continuous reaction. According to the hydrogen manufacturing method through the photosynthetic bacterium continuous reaction, a photosynthetic bacterium continuous hydrogen manufacturing reaction device is adopted for thallus culturing and hydrogen manufacturing through the reaction. The device is composed of a reactor, a raffinate treating pond, a hydrogen collecting device, a high-concentration hydrogen generating culture solution box and a photosynthetic bacterium culturing device; according to thallus culturing and hydrogen manufacturing through the reaction, after photosynthetic bacteria are cultured in a multiplication mode till OD 660 nm reaches 1.6-1.9, four fifths to five sixths of a bacterium solution by volume is concentrated through a millipore filtering membrane III with the pore diameter smaller than or equal to 0.22 micrometer, the concentrated bacterium solution is injected into the reactor for photosynthetic hydrogen generation under regulation and control of a computer, and the bacterium solution not concentrated is added with a new culture solution and then continues to be cultured in a multiplication mode. A substrate is recycled, and other bacteria can not enter a reactor body due to membrane filtration, so that the influence on photosynthetic bacterium hydrogen generation by the other bacteria is avoided, and hydrogen generation efficiency and the use ratio of the substrate are improved.
Description
Technical field
The present invention relates to a kind of photosynthetic bacterium successive reaction hydrogen production process, especially a kind of method that adopts continuously producing hydrogen with photosynthetic bacteria reaction unit to carry out yeast culture and reaction product hydrogen.
Background technology
Being on the rise of the problem of environmental pollution causing along with continuous consumption and the life-time service thereof of fossil energy, the mankind will face very serious energy dilemma and environmental degradation.The calorific value of hydrogen is high, and combustion velocity is fast, produces water and renewable after releasing energy, and is therefore acknowledged as a kind of clean green energy resource.At present, the method for hydrogen mainly contains water electrolysis hydrogen production, chemical hydrogen manufacturing, biological hydrogen production etc., the advantages such as compared with other hydrogen production process, biological hydrogen production power consumption is low, pollute less, reaction conditions gentleness.Because hydrogen production with photosynthetic bacteria speed is fast, high, the available spectral range of capacity usage ratio is wide, thereby correlative study is many.
The existing mode of utilizing hydrogen production with photosynthetic bacteria has batch-type, semi continuous and continous way.The method of producing hydrogen due to batch-type and semi continuous has that gas production rate is little, gas production rate is low and the problem such as substrate utilization ratio is low, so the main method that adopts continuous hydrogen production at present.Existing photosynthetic bacteria hydrogen production method, a part is separated the cultivation of bacterial classification and product hydrogen, and a part combines yeast culture and thalline product hydrogen.Yeast culture and thalline are produced to hydrogen and combine and can ensure the stability of aerogenesis, improve hydrogen-producing speed.But, the growth medium of part photosynthetic bacterium is different with product hydrogen substratum, and growth medium is unfavorable for photosynthetic bacterium, therefore, yeast culture and thalline product hydrogen are combined, can cause a large amount of growth mediums to enter reactor and mix mutually with product hydrogen substratum, the hydrogen generation efficiency of photosynthetic bacterium is declined.And still there are many problems in existing continuous hydrogen manufacturing device.
Publication number is that CN202415545U discloses " a kind of continuously streamed microorganism ferment for hydrogen production device ", be composed in series by feed reservoir, wriggling fresh feed pump, fermentation reactor, NaOH reactor, gas flow dryer, gas meter, accumulator unit, in described fermentation reactor, be provided with agitator, the waste liquid outlet of fermentation reactor is connected with waste collection pond by wriggling discharging pump, is provided with microfiltration membrane in the bottom of described fermentation reactor.This device has been realized the object of continuous, efficient hydrogen manufacturing.But while adopting this device continuous hydrogen production, fermented waste fluid directly enters waste collection pond, reflux and repeat fermentation, cause a part of substrate directly to run off, reduce the utilization ratio of substrate.Meanwhile, this device lacks temperature regulating device, cannot ensure the temperature range of fermented liquid temperature in the efficient hydrogen manufacturing of microorganism.
Publication number is that CN101538587B discloses " a kind of method and apparatus of continuously producing hydrogen with photosynthetic bacteria ".Described in it, method is method of fractional steps continuously producing hydrogen with photosynthetic bacteria, comprises two stages of yeast culture and fermentation and hydrogen production: photosynthetic bacterium and growth medium thereof are after multiplication culture, as the cell concentration OD after cultivation
660 nmreach at 1.5～2.0 o'clock, by volume, the bacterium liquid of 1/10～3/10 bacterium liquid total amount mixes and re-starts multiplication culture with photosynthetic bacterium growth substratum by refluxing, and all the other bacterium liquid carry out fermentation and hydrogen production after mixing with product hydrogen substrate again.The device adopting is made up of the yeast culture case of contacting successively, the blending bin of bacterium material and photosynthetic hydrogen production reactor three parts.The effect of yeast culture case is: adopt bactogen, for photosynthetic hydrogen production reactor provides the thalline supply of continous-stable.The effect of bacterium material blending bin is: fully mix with product hydrogen substrate cultivating the thalline in the logarithmic proliferation phase, reduce as far as possible air and introduce the inhibition that thalline is caused, and complete the acidity-basicity ph value of mixed bacteria liquid is adjusted, ensure that bacterium liquid pH value is within 6.8～7.2 scopes.The effect of photosynthetic hydrogen production reactor is: for the product hydrogen of photosynthetic bacterium provides needed illumination, temperature ambient conditions, make photosynthetic bacterium that fermenting substrate is converted into hydrogen, in order to improve hydrogen output, also can increase and stir at this.Yeast culture case, the blending bin of bacterium material and photosynthetic hydrogen production reactor are respectively as independently contacting partly and successively.Yeast culture case, the blending bin of bacterium material and photosynthetic hydrogen production reactor, as a global existence, are isolated into overall internal space in three spaces successively as yeast culture case, the blending bin of bacterium material and photosynthetic hydrogen production reactor.Along continuous straight runs, is isolated into overall internal space in three spaces that communicate or independently seal separately, wherein can overall space be isolated into by least two staggered dividing plates to three spaces that communicate.While adopting the method and apparatus hydrogen manufacturing of this invention, 7/10～9/10 Jun liquid mixes and produces hydrogen with product hydrogen substrate, cause the raised growth nutrient solution containing in bacterium liquid to mix with product hydrogen substrate, but growth medium is also unfavorable for hydrogen production with photosynthetic bacteria, even part hydrogen production with photosynthetic bacteria is had to restraining effect, therefore can cause the decline of hydrogen generation efficiency.Leftover materials in photosynthetic reactor are directly discharged from sewage draining exit, make photosynthetic bacterium in reactor along with leftover materials are also discharged from, cause the loss of photosynthetic bacterium, cause difficulty to maintaining the quantity of photosynthetic bacterium in reactor, also wasted a part of substrate, reduced the utilization ratio of substrate simultaneously.
Publication number is that CN101845387B discloses " a kind of continuous hydrogen production reactor with photosynthetic bacteria ", comprise housing, housing one end is provided with opening for feed and the other end is provided with discharge port, inner walls is alternately provided with upper traverse baffle and lower traverse baffle perpendicular to the flow direction of feed liquid, between the lower end of upper traverse baffle and shell bottom wall, be provided with gap, between the upper end of lower traverse baffle and housing top wall, be provided with gap, it is characterized in that: upper and lower traverse baffle all longitudinally arranges and housing is alternately divided into rising area and decline district, in the housing corresponding with rising area, is provided with means of illumination; Case top is also provided with collection and confinement of gases hole.This reactor arranges baffle in enclosure interior, and feed liquid is mixed completely in casing.But reactor used after for some time, and a part of photosynthetic bacterium can float the inwall at reactor, affects the light transmission of reactor, therefore needs, to reactor routine cleaning, to ensure its light transmission.And the reactor of this invention is as a whole, cannot split, and the inner baffle arranging increases the difficulty of cleaning reaction device.
In addition, current photosynthetic organism hydrogen generation reaction unit cannot avoid nutrient solution in reactor by living contaminants, is subject to the impact of miscellaneous bacteria, and the hydrogen generation efficiency of photosynthetic bacterium and substrate conversion efficiency all can reduce.And existing photosynthetic organism hydrogen generation reaction unit cannot solve following two problems that exist in the time collecting the hydrogen producing.If one does not compress storage to the hydrogen producing, need huge hydrogen-storing device; But when the hydrogen producing is compressed to storage, the internal pressure that produces the gas collection pipe between hydrogen reactor and compression pump declines, and causes the larger pressure difference of existence between gas collection pipe and reactor, make the nutrient solution in reactor flow into gas collection pipe.Two, in reactor, the hydrogen of generation makes to occur more vacuole in reactor head, and a part of vacuole can enter collecting pipe along with hydrogen, and collecting pipe is caused to corrosion, therefore needs to realize separating of collection hydrogen process and compression hydrogen process.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of this invention is to provide a kind of photosynthetic bacterium successive reaction hydrogen production process.
The present invention is achieved through the following technical solutions.
A kind of photosynthetic bacterium successive reaction hydrogen production process, described in it, method is to adopt continuously producing hydrogen with photosynthetic bacteria reaction unit to carry out yeast culture and reaction product hydrogen;
One end that described continuously producing hydrogen with photosynthetic bacteria reaction unit is reactor is communicated with raffinate treating pond, and is connected with the other end of reactor by wriggling liquid feeding pump; Be communicated with hydrogen collection device, high density product hydrogen nutrient solution case, Photosynthetic bacteria culturing device and PH conditioning agent case on the top of reactor; Be provided with constant temperature water tank at the outer bottom face of reactor and be communicated with solar water heater by fresh water pump; Fresh feed pump and fresh water pump are controlled by computer; Wherein reactor is to set gradually communication seals by feed liquor housing, transparent reaction housing and fluid housing to form, and is provided with millipore filtration I between feed liquor housing and reactor shell, between reactor shell and fluid housing, is provided with millipore filtration II; In reactor shell, be provided with agitator.。
Described yeast culture and reaction are that photosynthetic bacterium breeds to OD in cultivation
660 nmafter reaching 1.6～1.9, by volume 4/5～5/6 bacterium liquid is concentrated into bacterial concentration by the millipore filtration III of aperture≤0.22 μ m and reaches 2～3 times of original bacteria liquid concentration, the bacterium liquid after concentrated carries out photosynthetic hydrogen production and is stored in hydrogen collection device (5) at computer regulated lower injecting reactor; Unconcentrated bacterium liquid, adding after new nutrient solution, is proceeded multiplication culture.
Technique scheme, further additional technical feature is as follows.
Described hydrogen collection device is to be connected with air collector II by pond by air collector I; Air collector I and air collector II are communicated with respectively reactor, are communicated with compression pump and hydrogen container by hydrogen purification loft drier respectively.
Described Photosynthetic bacteria culturing device is to be communicated with incubator and concentrated case by pump, and in concentrated case, is provided with the millipore filtration III of aperture≤0.22 μ m apart from 4/5～5/6 casing length place of bacterium liquid entrance.
The material of described millipore filtration I, millipore filtration II and millipore filtration III is tetrafluoroethylene or polyethersulfone.
Described transparent reaction housing is to be made up of glass or resin material.
A kind of photosynthetic bacterium successive reaction hydrogen production process provided by the invention, compared with the conventional method, the miscellaneous bacteria that the millipore filtration of its reactor front portion makes to flow in the liquid in feed liquor housing cannot enter reactor shell; Therefore, ensureing in Photosynthetic bacteria culturing device in the not contaminated situation of photosynthetic bacterium, only need to use high-concentration culturing liquid and the PH conditioning agent after sterilizing, just can make not exist in reactor shell other microorganism except photosynthetic bacterium, avoid the impact of miscellaneous bacteria on hydrogen production with photosynthetic bacteria, and only to high-concentration culturing liquid and the sterilizing of PH conditioning agent, required energy consumption is less.The millipore filtration at reactor rear portion, for realizing separating of photosynthetic bacterium and effluent liquid, makes the quantity of photosynthetic bacterium in reactor remain stable, and this is conducive to ensure that reactor produces stability and the high efficiency of hydrogen; Meanwhile, reduce the consumption of microbial growth to substrate, thereby increased the efficiency that substrate conversion is hydrogen.
The raffinate that the inventive method flows out reactor rear portion, by raffinate treating pond, is removed after the material of inhibition hydrogen production with photosynthetic bacteria of photosynthetic bacterium metabolism generation, then is entered reactor by wriggling liquid feeding pump.Thereby improve the product hydrogen activity of photosynthetic bacterium, meanwhile, make unemployed substrate in raffinate again enter reactor participation reaction, improve substrate utilization ratio.
The hot water in solar water heater is passed into the constant temperature water tank that the outer bottom face of reactor arranges by the inventive method, make the temperature-stable of liquid in reactor in the temperature range of photosynthetic bacterium highly effective hydrogen yield, simultaneously, utilize free of contamination sun power by solar water heater, be conducive to energy-saving and emission-reduction.
The inventive method is by temperature, the PH of density, concentration of substrate and the liquid of photosynthetic bacterium in the real-time detection reaction device of proofing unit, and give computer signal feedback, make computer adjust in real time high density and produce the input of hydrogen nutrient solution, concentrated bacterium liquid, PH conditioning agent and hot water, thereby make to produce hydrogen condition always in optimum regime.
The inventive method adopts two air collectors in turn for collecting hydrogen, by the related valve in switch gas collection pipe and right compression conduit, can realize the object that collection and confinement of gases and gas compression are independent of each other, and makes pressurized gas not affect the pressure of collection and confinement of gases pipeline.Two air collectors, in turn for collecting hydrogen, have ensured that the successional while of collection and confinement of gases also provides plenty of time to pressurized gas.Adopt drainage to collect hydrogen, by the water row pump sump in air collector, after the hydrogen compression being full of in air collector is stored, air collector internal pressure declines, opening the valve that air collector is connected on pipeline with pond just can make air collector automatically refill water again, so that next gas collection uses, this method is simple to operate, can realize repetition gas collection.
The inventive method, by the millipore filtration III in concentrated case, separates photosynthetic bacterium and most of growth medium, has reduced the disadvantageous effect of growth medium to hydrogen production with photosynthetic bacteria; Meanwhile, the growth medium being separated is refilled to the propagation of incubator for photosynthetic bacterium, improve the utilization ratio of growth medium.
Brief description of the drawings
Fig. 1 is the structural representation of the continuously producing hydrogen with photosynthetic bacteria reaction unit that adopts of the inventive method.
Fig. 2 is the structural representation of reactor in Fig. 1.
Fig. 3 is the structural representation of feed liquor housing 25 in Fig. 2.
Fig. 4 is the structural representation of fluid housing 15 in Fig. 2.
Fig. 5 is the structural representation of reactor shell 26 in Fig. 2.
Fig. 6 is the vertical view of gas collection mouth 21 in Fig. 2.
Fig. 7: the structural representation of gas extractor 5 in Fig. 1.
Fig. 8: the structural representation of Photosynthetic bacteria culturing device 7 in Fig. 1.
In figure: 1: reactor; 2: raffinate treating pond; 3: constant temperature water tank; 4: solar water heater; 5: hydrogen collection device; 6: high density is produced hydrogen nutrient solution case; 7: Photosynthetic bacteria culturing device; 8:PH conditioning agent case; 9: fresh feed pump; 10: computer; 11: liquid feeding pump; 12: fresh water pump; 13: proofing unit; 14: agitator; 15: fluid housing; 16: millipore filtration I; 17: flange; 18: nut; 18: opening for feed; 19: opening for feed; 20: detect mouth; 21: collection and confinement of gases mouth; 22: fluid inlet; 23: liquid outlet; 24: millipore filtration II; 25: feed liquor housing; 26: reactor shell; 27: air collector I; 28: hydrogen container; 29: compression pump; 30: valve; 31: valve; 32: valve; 33: valve; 34: valve; 35: valve; 36: pond; 37: hydrogen purification loft drier; 38: air collector II; 39: millipore filtration III; 40: inlet; 41: liquid outlet; 42: liquid outlet; 43: fluid inlet; 44: incubator; 45: pump; 46: concentrated case.
Embodiment
First by the inlet 40 of the incubator 44 in the Photosynthetic bacteria culturing device 7 after sterilizing, the photosynthetic bacteria liquid that is 1:4 by volume ratio and growth medium inject incubator 44, carry out multiplication culture.Treat the cell concentration OD in incubator
660 nmafter reaching 1.6～1.9, by volume 4/5～5/6 bacterium liquid is delivered in concentrated case 46 with pump 45, millipore filtration III 39 by the concentrated interior aperture≤0.22 μ m apart from 4/5～5/6 casing length place of bacterium liquid entrance of case 46 concentrates, in the time that bacterial concentration is concentrated into 2～3 times of original bacteria liquid concentration, stop concentrating.The nutrient solution of separating is back in incubator 44 by fluid inlet 43, then adds new nutrient solution by inlet 40, continue multiplication culture photosynthetic bacterium, realize photosynthetic bacterium multiplication culture and concentrated continuous circulation.Then open liquid feeding pump 11 water is injected in feed liquor housing 25 by fluid inlet 22, enter into the water in feed liquor housing 25, then filter out miscellaneous bacteria by aperture≤0.22 μ m millipore filtration I 16 and go forward side by side in sterilized reactor shell 26.Then open computer 10, agitator 14 and proofing unit 13, the signal feeding back by proofing unit 13, high density is produced to the PH conditioning agent in high-concentration culturing liquid, the PH conditioning agent case 8 in hydrogen nutrient solution case 6 with the automatic control fresh feed pump 9 of computer 10 and the bacterium liquid after millipore filtration III 39 is concentrated injects in reactor shell 26 by opening for feed 19, and by the stirring of agitator 14, water in reactor shell, photosynthetic bacterium and nutrient solution are mixed, make the bacterial concentration OD in reactor shell 26
660 nmreach 0.2～0.5, the concentration of nutrient solution concentration stabilize in the time that photosynthetic bacterium normally produces hydrogen, pH value is stabilized in 6.5～7.5; Control fresh water pump 12 by 3 li of the constant temperature water tanks of the outer bottom face setting of the hot water injecting reactor 1 in solar water heater 4 by computer 10 simultaneously, the mixing liquid in reactor 1 is heated to 25～30 DEG C.Further, the photosynthetic bacterium in reactor shell 26 absorbs the nutritive substance producing in hydrogen nutrient solution and the luminous energy that sees through reactor shell 26 produced hydrogen, and the hydrogen of generation enters hydrogen collection device 5 by collection and confinement of gases mouth 21.The product hydrogen nutrient solution being utilized by photosynthetic bacterium enters fluid housing 15 after filtering out photosynthetic bacterium by aperture≤0.22 μ m millipore filtration II 24 again, after the material of the inhibition hydrogen production with photosynthetic bacteria producing while then flowing into by liquid outlet 23 the photosynthetic bacterium self-dissolving that raffinate treating pond 2 removes hydrogen production with photosynthetic bacteria process and Mortality, again in inflow reactor 1, participate in reaction by liquid feeding pump 11.
In the time that hydrogen enters hydrogen collection device 5, first open valve 33 and 35, close other valve of gas collector 5, hydrogen enters in air collector I 27 by valve 35, makes the valve 33 that passes through of the water in air collector I 27 flow into pond 36.After air collector I 27 is collected full hydrogen, valve-off 33 and 35, opens valve 32 and 34, uses air collector II 38 instead and collects hydrogen.Then open valve 31, after making hydrogen in air collector I 27 dry by hydrogen purification loft drier 37 purifying, compress in hydrogen container 28 with compression pump 29.Then valve-off 31, opening valve 33 makes the water in pond again fill air collector I 27, in the time that air collector II 38 is collected full hydrogen, use again air collector I 27 instead and collect hydrogen, and the hydrogen in air collector II 38 is stored in hydrogen container 28 with the compression of as above method, realize storage hydrogen continuously by gas collecting mode as above.
Claims (6)
1. a photosynthetic bacterium successive reaction hydrogen production process, described in it, method is to adopt continuously producing hydrogen with photosynthetic bacteria reaction unit to carry out yeast culture and reaction product hydrogen;
Described continuously producing hydrogen with photosynthetic bacteria reaction unit is that one end of reactor (1) is communicated with raffinate treating pond (2), and is connected with the other end of reactor (1) by wriggling liquid feeding pump (11); Be communicated with hydrogen collection device (5), high density product hydrogen nutrient solution case (6), Photosynthetic bacteria culturing device (7) and PH conditioning agent case (8) on the top of reactor (1); Be provided with constant temperature water tank (3) at the outer bottom face of reactor (1) and be communicated with solar water heater (4) by fresh water pump (12); Fresh feed pump (9) and fresh water pump (12) are controlled by computer (10); Wherein reactor (1) is to set gradually communication seals by feed liquor housing (25), transparent reaction housing (26) and fluid housing (15) to form, and be provided with millipore filtration I (16) between feed liquor housing (25) and reactor shell (26), between reactor shell (26) and fluid housing (15), be provided with millipore filtration II (24); In reactor shell (26), be provided with agitator (14);
It is that photosynthetic bacterium breeds to OD in cultivation that hydrogen is produced in described yeast culture and reaction
660 nmafter reaching 1.6～1.9, by volume 4/5～5/6 bacterium liquid is concentrated into bacterial concentration by the millipore filtration III (39) of aperture≤0.22 μ m and reaches 2～3 times of original bacteria liquid concentration, the bacterium liquid injecting reactor (1) under computer (10) regulation and control after concentrated carries out photosynthetic hydrogen production and is stored in hydrogen collection device (5); Unconcentrated bacterium liquid, adding after new nutrient solution, is proceeded multiplication culture.
2. photosynthetic bacterium successive reaction hydrogen production process according to claim 1, described in it, hydrogen collection device (5) is to be connected with air collector II (38) by pond (36) by air collector I (27); Air collector I (27) is communicated with respectively reactor (1), is communicated with compression pump (29) and hydrogen container (28) by hydrogen purification loft drier (37) respectively with air collector II (38).
3. photosynthetic bacterium successive reaction hydrogen production process according to claim 1, Photosynthetic bacteria culturing device described in it (7) is to be communicated with incubator (44) and concentrated case (46) by pump (45), and in concentrated case (46), is provided with the millipore filtration III (39) of aperture≤0.22 μ m apart from 4/5～5/6 casing length place of bacterium liquid entrance.
4. according to the photosynthetic bacterium successive reaction hydrogen production process described in claim 1 or 3, described in it, the material of millipore filtration I (16), millipore filtration II (24) and millipore filtration III (39) is tetrafluoroethylene or polyethersulfone.
5. photosynthetic bacterium successive reaction hydrogen production process according to claim 1, described in it, to produce the product hydrogen nutrient solution concentration in hydrogen nutrient solution case (6) be 3～5 times of the nutrient solution concentration of photosynthetic bacterium while normally producing hydrogen to high density.
6. photosynthetic bacterium successive reaction hydrogen production process according to claim 1, described in it, transparent reaction housing (26) is to be made up of glass or resin material.
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| CN109762723A (en) * | 2019-03-23 | 2019-05-17 | 武汉轻工大学 | A kind of device for photosynthetic bacteria culture |
| CN111500415A (en) * | 2020-04-27 | 2020-08-07 | 马尧顺 | Fermentation conversion reaction equipment for bioethanol bacterial liquid of microbial biomass fuel |
| CN116676165A (en) * | 2023-06-06 | 2023-09-01 | 上海勘测设计研究院有限公司 | Split type hidden fermentation biological hydrogen production reactor |
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