CN103725606A - Sequencing batch type biological hydrogen production reactor and use method thereof - Google Patents
Sequencing batch type biological hydrogen production reactor and use method thereof Download PDFInfo
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Abstract
The invention discloses a sequencing batch type biological hydrogen production reactor and a use method thereof, relating to a sequencing batch type biological hydrogen production reactor and application thereof. By adopting the sequencing batch type biological hydrogen production reactor, the problems that the utilization rate of a fermentation hydrogen production substrate is low and the biomass is easily lost when lignocellulose saccharification liquid is used as the substrate in an existing biological hydrogen production reactor are solved. The sequencing batch type biological hydrogen production reactor comprises a water inlet tank, a water inlet pump, a first time relay, a magnetic stirrer, a reactor main body, a water bath tank, a heating rod, a third time relay, a water outlet pump, a second time relay, a water outlet tank and a gas flow meter. The use method comprises the steps: adding a hydrogenogens liquid fermentation culture medium in the reactor main body, sealing after introducing nitrogen, and then inoculating a fermentation hydrogen production seed solution for hydrogen production fermentation. The sequencing batch type biological hydrogen production reactor disclosed by the invention is simple in structure, and convenient to operate; the lignocellulose saccharification liquid is used as the substrate and the utilization rate reaches above 90 percent, the specific hydrogen production rate reaches 1.7mol H2mol<-1>, and the maximum hydrogen production rate reaches 9.6mol H2L<-1>h<-1>.
Description
Technical field
The invention belongs to field of renewable energy technology, be specifically related to a kind of sequence batch (biological hydrogen production reactor and use thereof.
Background technology
Whole world fossil fuel storing amount reduces day by day, and the topsoil causing due to combustion of fossil fuel has caused the whole world to be faced with the energy and environment Double jeopardy simultaneously, and therefore finding the clean alternative energy is the inexorable trend that global energy is moved towards Sustainable development.In " the 12 national strategy new industry development program " of China in the face of this problem appearance, also explicitly point out: Devoting Major Efforts To Developing novel biological fuel, the industrialization that realizes renewable energy technologies is the most important thing of future source of energy development.Hydrogen is as a kind of novel energy carrier, and with its recoverable, cleanliness without any pollution and fuel value advantages of higher are more and more subject to people's favor.The manufacture method of hydrogen comprises: water electrolysis hydrogen production, and the hydrogen manufacturing of water-gas method, by synthetic gas and the natural gas hydrogen preparation of oil hot tearing, and biological hydrogen production etc.Plurality of advantages such as wherein bio-hydrogen production technology has mild condition, and energy consumption is little, and cost is low, green non-pollution, and its raw material sources are extensive, for the Sustainable development of Hydrogen Energy has brought hope, thereby receive much concern.
Lignocellulose biomass is renewable resources abundant, the most cheap on the earth, and the lignocellulose that the whole world produces by photosynthesis is every year up to 100,000,000,000 tons, and wherein 89% not yet by human use.The lignocellulose biomass of China is also very abundant, and being often only agricultural crop straw just has 700,000,000 tons, adds forestry fiber waste-material and the industrial fiber waste residue of enormous amount, and annual available lignocellulose biomass total amount can reach more than 2,000,000,000 tons.This clean alternative energy of renewable resources fermentation generation hydrogen by this enormous amount of lignocellulose has been the main trend of following hydrogen gas production.Yet lignocellulose is more difficult, by microorganism, directly utilized, generally need be after the step such as pre-treatment and saccharification obtain cellulose hydrolyte (comprising the soluble sugars such as pentose and hexose), then produce hydrogen by producing the fermentation of hydrogen microorganism.
For realizing the suitability for industrialized production demand of lignocellulose biological hydrogen production, develop a kind of biological hydrogen production reactor of high hydrogen output and hydrogen-producing speed that keeps imperative, both at home and abroad researchist through study for many years the biological hydrogen production reactor of according to hydrogen-producing bacteria, the requirement of growth conditions having been designed different structure form as: Continuous Flow stirred-tank reactor and up flow anaerobic sludge blanket reactor, make hydrogen generation efficiency obtain large increase.But due to the complicacy (pentose that comprises hexose and the more difficult utilization of microorganism) of the composition of cellulose hydrolyte own, still there is the problem that biomass easily runs off, substrate utilization ratio is low in reactor, and the method for there is no meets the needs of suitability for industrialized production.Therefore develop efficient biological hydrogen production reactor, become the key that promotes the development of lignocellulose bio-hydrogen production technology.
Summary of the invention
The present invention seeks in existing biological hydrogen production reactor, to take lignocellulose saccharified liquid during as substrate in order to solve, fermentation and hydrogen production substrate utilization ratio is low, the problem that biomass easily runs off, and a kind of sequence batch (biological hydrogen production reactor and using method thereof are provided.
Sequence batch (biological hydrogen production reactor, comprises into water tank, intake pump, very first time rly., magnetic stirring apparatus, reactor body, water bath, heating rod, the 3rd time relay, goes out water pump, second time relay, water tank and gas meter; Described water inlet tank is communicated with the water-in at reactor body top by intake pump, the switch of very first time Control intake pump, reactor body outside is water bath, and water bath is arranged on magnetic stirring apparatus, and second time relay is controlled the switch of magnetic stirring apparatus; The bottom of described reactor body arranges magnetic force rotor, the water outlet at reactor body top is communicated with water tank by going out water pump, the 3rd time relay is controlled out the switch of water pump, in water bath, be provided with heating rod, gas outlet pipe and rising pipe are installed on reactor body top, and gas meter is arranged on gas outlet pipe.
Principle of work of the present invention is as follows:
By intake pump, the water-in by reactor body top pumps in reactor body hydrogenogens liquid fermentation medium in water inlet tank; In reactor body reaction zone, fermentative hydrogen-producing bacteria mixes under the stirring action of magnetic force rotor, the organism making full use of in substratum produces hydrogen, the hydrogen producing is discharged reactor body by gas meter, after reacting completely, second time relay is controlled magnetic stirring apparatus switch, staticly settle, the rising pipe by reactor body top pumps reactor body and enters in water tank by reacted fermented liquid then to go out water pump; Wherein intake, stir, precipitation, water outlet be by very first time rly., second time relay and the 3rd time relay are accurately controlled separately; Water bath is heated and is maintained reactor body reaction zone temperature by heating rod.
The using method of sequence batch (biological hydrogen production reactor, by following process implementation:
In reactor body, add hydrogenogens liquid fermentation medium, after passing into purity and be 99.99% nitrogen, seal, the inoculum size that is 10% according to volume ratio again access fermentation and hydrogen production seed liquor, in temperature, it is 60 ℃, stirring velocity is 130r/min, produces hydrogen fermentation under the condition that hydraulic detention time is 6-24h;
Wherein the add-on of the liquid fermentation medium of hydrogenogens described in step 1 accounts for 2/3rds of reactor body 10 cumulative volumes;
The every L of the liquid fermentation medium of hydrogenogens described in step 1 by the ammonium chloride of 1.0g, the dipotassium hydrogen phosphate of the sodium-chlor of 1.0g, 3g, the halfcystine of the potassium primary phosphate of 1.5g, 0.5g, the MgCl of 0.5g
26H
2the VITAMIN storage liquid of the Repone K of O, 0.2g, the yeast powder of 2g, the peptone of 2g, the micro-metals of 1ml storage liquid, 1ml, 0.1 ‰ (w/v) resazurin, the carbon source of 700mL and the water of surplus of 1ml are prepared from; Described micro-metals storage liquid is by 1.5g/L iron protochloride, 70mg/L zinc chloride, 6mg/L boric acid, 0.1g/L MnCl
24H
2o, 2mg/L CuCl
22H
2o, 0.19g/L CoCl
26H
2o, 24mg/L NiCl
26H
2o, 36mg/L Na
2mO
4h
2o, 15mg/L sodium wolframate and 15mg/L Na
2seO
45H
2o forms; Described VITAMIN storage liquid is by 50.0mg/L Thioctic Acid, 20.0mg/L vitamin H, 0.35g/L nicotinic acid, 5.0mg/L vitamin, 50.0mg/L para-amino benzoic acid, 20.0mg/L folic acid, 50.0mg/L calcium pantothenate, 1.0mg/L vitamins B
12form with 100.0mg/L pyridoxine hydrochloride; Described carbon source is lignocellulose saccharified liquid; Hydrogenogens in described fermentation and hydrogen production seed liquor is pyrolysis sugar anaerobic spore-bearing bacilli W16(Thermoanaerobacterium thermosaccharolyticum W16).
Advantage of the present invention is as follows:
1, sequence batch (biological hydrogen production reactor of the present invention is simple in structure, workflow is simple, easy to operate, can regulate hydraulic detention time according to producing hydrogen situation, and then raising utilizes the biological volume of holding of the biological hydrogen production reactor that lignocellulose saccharified liquid is substrate, avoid to greatest extent bacterial classification to run off, the biomass of high density is realized and is produced efficiently hydrogen performance.
2, the present invention can reach maximization by the utilization ratio of substrate, and substrate utilization ratio reaches more than 90%, the pentose of more difficult utilization in reactor can be utilized, thereby can greatly increase substrate utilization ratio, further reduces and produces hydrogen cost.
3, hydrogen yield of the present invention reaches 1.7mol H
2mol
-1substrate, high yield hydrogen speed reaches 9.6mmol H
2l
-1h
-1.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of sequence batch (biological hydrogen production reactor in the present invention, and wherein 1 represents water inlet tank, and 2 represent intake pump, 3 represent magnetic stirring apparatus, and 3-1 represents magnetic force rotor, and 4 express water pump, 5 express water tank, 6 represent second time relay, and 7 represent the 3rd time relay, and 8 represent heating rod, 9 represent gas meter, 10 represent reactor body, and 11 represent water bath, and 12 represent very first time rly.;
Fig. 2 is the product hydrogen efficacy curve figure of sequence batch (biological hydrogen production reactor in embodiment.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is described in conjunction with Fig. 1, sequence batch (biological hydrogen production reactor, comprises into water tank 1, intake pump 2, very first time rly. 12, magnetic stirring apparatus 3, reactor body 10, water bath 11, heating rod 8, the 3rd time relay 7, goes out water pump 4, second time relay 6, water tank 5 and gas meter 9; Described water inlet tank 1 is communicated with the water-in at reactor body 10 tops by intake pump 2, very first time rly. 12 is controlled the switch of intake pump 2, reactor body 10 outsides are water bath 11, water bath 11 is arranged on magnetic stirring apparatus 3, and second time relay 6 is controlled the switch of magnetic stirring apparatus 3; The bottom of described reactor body 10 arranges magnetic force rotor 3-1, the water outlet at reactor body 10 tops is communicated with water tank 5 by going out water pump 4, the 3rd time relay 7 is controlled out the switch of water pump, in water bath 11, be provided with heating rod 8, reactor body is provided with gas outlet pipe and rising pipe on 10 tops, and gas flow 9 is arranged on gas outlet pipe.
Embodiment two: present embodiment is different from embodiment one, described reactor body 10 tops are provided with upper cover, and upper cover perforate is respectively water-in, gas stream outlet and water outlet.Other step and parameter are identical with embodiment one.
Embodiment three: the using method of above-mentioned sequence batch (biological hydrogen production reactor, by following process implementation:
In reactor body 10, add hydrogenogens liquid fermentation medium, after passing into purity and be 99.99% nitrogen, seal, the inoculum size that is 10% according to volume ratio again access fermentation and hydrogen production seed liquor, in temperature, it is 60 ℃, stirring velocity is 130r/min, produces hydrogen fermentation under the condition that hydraulic detention time is 6-24h;
Wherein the add-on of the liquid fermentation medium of hydrogenogens described in step 1 accounts for 2/3rds of reactor body 10 cumulative volumes;
The every L of the liquid fermentation medium of hydrogenogens described in step 1 by the ammonium chloride of 1.0g, the dipotassium hydrogen phosphate of the sodium-chlor of 1.0g, 3g, the halfcystine of the potassium primary phosphate of 1.5g, 0.5g, the MgCl of 0.5g
26H
2the VITAMIN storage liquid of the Repone K of O, 0.2g, the yeast powder of 2g, the peptone of 2g, the micro-metals of 1ml storage liquid, 1ml, 0.1 ‰ (w/v) resazurin, the carbon source of 700mL and the water of surplus of 1ml are prepared from; Described micro-metals storage liquid is by 1.5g/L iron protochloride, 70mg/L zinc chloride, 6mg/L boric acid, 0.1g/L MnCl
24H
2o, 2mg/L CuCl
22H
2o, 0.19g/L CoCl
26H
2o, 24mg/L NiCl26H
2o, 36mg/L Na
2mO
4h
2o, 15mg/L sodium wolframate and 15mg/L Na
2seO
45H
2o forms; Described VITAMIN storage liquid is by 50.0mg/L Thioctic Acid, 20.0mg/L vitamin H, 0.35g/L nicotinic acid, 5.0mg/L vitamin, 50.0mg/L para-amino benzoic acid, 20.0mg/L folic acid, 50.0mg/L calcium pantothenate, 1.0mg/L vitamins B
12form with 100.0mg/L pyridoxine hydrochloride; Described carbon source is lignocellulose saccharified liquid; Hydrogenogens in described fermentation and hydrogen production seed liquor is pyrolysis sugar anaerobic spore-bearing bacilli W16(Thermoanaerobacterium thermosaccharolyticum W16).
In present embodiment, passing into purity and be 99.99% nitrogen object is the oxygen of getting rid of in reactor body.
In present embodiment, hydrogenogens is pyrolysis sugar anaerobic spore-bearing bacilli W16(Thermoanaerobacterium thermosaccharolyticum W16), the name that Thermoanaerobacterium thermosaccharolyticum W16 publishes in the < < International Journal of Hydrogen Energy > > of 6132 pages of the 33rd phase the 6124th – in 2008 is called in the article of " Dark fermentation of xylose and glucose mix using isolated Thermoanaerobacterium thermosaccharolyticum W16 " open.
The preparation method of the saccharified liquid of lignocellulose described in present embodiment, open in patent " a kind of method (patent No. is ZL201110253537.5; the applying date is on August 30th, 2011) of utilizing cellulose raw hydrogen producing ", the preparation of cellulose hydrolyte described in it, the i.e. preparation of the saccharified liquid of lignocellulose described in present embodiment.
Adopt following examples to verify beneficial effect of the present invention:
Embodiment:
In conjunction with Fig. 1, the present embodiment is described, sequence batch (biological hydrogen production reactor, comprises into water tank 1, intake pump 2, very first time rly. 12, magnetic stirring apparatus 3, reactor body 10, water bath 11, heating rod 8, the 3rd time relay 7, goes out water pump 4, second time relay 6, water tank 5 and gas meter 9; Described water inlet tank 1 is communicated with the water-in at reactor body 10 tops by intake pump 2, very first time rly. 12 is controlled the switch of intake pump 2, reactor body 10 outsides are water bath 11, water bath 11 is arranged on magnetic stirring apparatus 3, and second time relay 6 is controlled the switch of magnetic stirring apparatus 3; The bottom of described reactor body 10 arranges magnetic force rotor 3-1, the water outlet at reactor body 10 tops is communicated with water tank 5 by going out water pump 4, the 3rd time relay 7 is controlled out the switch of water pump, in water bath 11, be provided with heating rod 8, reactor body is provided with gas outlet pipe and rising pipe on 10 tops, and gas flow 9 is arranged on gas outlet pipe.
The principle of work of above-mentioned sequence batch (biological hydrogen production reactor is as follows:
By intake pump 2, the water-in by reactor body 10 tops pumps in reactor body 10 hydrogenogens liquid fermentation medium in water inlet tank 1; In reactor body 10 reaction zones, fermentative hydrogen-producing bacteria mixes under the stirring action of magnetic force rotor 3-1, the organism making full use of in substratum produces hydrogen, the hydrogen producing is discharged reactor body 10 by gas meter 9, after reacting completely, second time relay 6 is controlled the switch of magnetic stirring apparatus 3, staticly settle, the rising pipe by reactor body 10 tops pumps reactor body 10 and enters in water tank 5 by reacted fermented liquid then to go out water pump 4; Wherein intake, stir, precipitation, water outlet be by very first time rly. 12, second time relay 6 and the 3rd time relay 7 are accurately controlled separately; Water bath 11 maintains reactor body 10 reaction zone temperatures by heating rod 8 heating.
The using method of sequence batch (biological hydrogen production reactor, by following process implementation:
In reactor body 10, add hydrogenogens liquid fermentation medium, after passing into purity and be 99.99% nitrogen, seal, the inoculum size that is 10% according to volume ratio again access fermentation and hydrogen production seed liquor, in temperature, it is 60 ℃, stirring velocity is 130r/min, produces hydrogen fermentation under the condition that hydraulic detention time is 12h;
Wherein the add-on of the liquid fermentation medium of hydrogenogens described in step 1 accounts for 2/3rds of reactor body 10 cumulative volumes;
The every L of the liquid fermentation medium of hydrogenogens described in step 1 by the ammonium chloride of 1.0g, the dipotassium hydrogen phosphate of the sodium-chlor of 1.0g, 3g, the halfcystine of the potassium primary phosphate of 1.5g, 0.5g, the MgCl of 0.5g
26H
2the VITAMIN storage liquid of the Repone K of O, 0.2g, the yeast powder of 2g, the peptone of 2g, the micro-metals of 1ml storage liquid, 1ml, 0.1 ‰ (w/v) resazurin, the carbon source of 700mL and the water of surplus of 1ml are prepared from; Described micro-metals storage liquid is by 1.5g/L iron protochloride, 70mg/L zinc chloride, 6mg/L boric acid, 0.1g/L MnCl
24H
2o, 2mg/L CuCl
22H
2o, 0.19g/L CoCl
26H
2o, 24mg/L NiCl
26H
2o, 36mg/L Na
2mO
4h
2o, 15mg/L sodium wolframate and 15mg/L Na
2seO
45H
2o forms; Described VITAMIN storage liquid is by 50.0mg/L Thioctic Acid, 20.0mg/L vitamin H, 0.35g/L nicotinic acid, 5.0mg/L vitamin, 50.0mg/L para-amino benzoic acid, 20.0mg/L folic acid, 50.0mg/L calcium pantothenate, 1.0mg/L vitamins B
12form with 100.0mg/L pyridoxine hydrochloride; Described carbon source is lignocellulose saccharified liquid; Hydrogenogens in described fermentation and hydrogen production seed liquor is pyrolysis sugar anaerobic spore-bearing bacilli W16(Thermoanaerobacterium thermosaccharolyticum W16).
The preparation method of the saccharified liquid of lignocellulose described in the present embodiment, open in patent " a kind of method (patent No. is ZL201110253537.5; the applying date is on August 30th, 2011) of utilizing cellulose raw hydrogen producing ", the preparation of cellulose hydrolyte described in it, the i.e. preparation of the saccharified liquid of lignocellulose described in the present embodiment; What in the present embodiment, lignocellulose saccharified liquid adopted is maize straw saccharified liquid.
As shown in Figure 1, in the present embodiment, hydrogen yield reaches 1.7mol H
2mol
-1substrate, hydrogen-producing speed reaches 9.6mmol H
2l
-1h
-1, substrate utilization ratio reaches more than 90%.
Claims (3)
1. sequence batch (biological hydrogen production reactor, is characterized in that sequence batch (biological hydrogen production reactor comprises into water tank (1), intake pump (2), very first time rly. (12), magnetic stirring apparatus (3), reactor body (10), water bath (11), heating rod (8), the 3rd time relay (7), goes out water pump (4), second time relay (6), water tank (5) and gas meter (9); Described water inlet tank (1) is communicated with the water-in at reactor body (10) top by intake pump (2), very first time rly. (12) is controlled the switch of intake pump (2), reactor body (10) outside is water bath (11), it is upper that water bath (11) is arranged on magnetic stirring apparatus (3), and second time relay (6) is controlled the switch of magnetic stirring apparatus (3); The bottom of described reactor body (10) arranges magnetic force rotor (3-1), the water outlet at reactor body (10) top is communicated with water tank (5) by going out water pump (4), the 3rd time relay (7) is controlled out the switch of water pump, in water bath (11), be provided with heating rod (8), reactor body (10) is provided with gas outlet pipe and rising pipe on top, and gas flow (9) is arranged on gas outlet pipe.
2. sequence batch (biological hydrogen production reactor according to claim 1, is characterized in that described reactor body (10) top is provided with upper cover, and upper cover perforate is respectively water-in, gas stream outlet and water outlet.
3. the using method of sequence batch (biological hydrogen production reactor as claimed in claim 1, is characterized in that it is by following process implementation:
In reactor body (10), add hydrogenogens liquid fermentation medium, after passing into purity and be 99.99% nitrogen, seal, the inoculum size that is 10% according to volume ratio again access fermentation and hydrogen production seed liquor, in temperature, it is 60 ℃, stirring velocity is 130r/min, produces hydrogen fermentation under the condition that hydraulic detention time is 6-24h;
Wherein the add-on of the liquid fermentation medium of hydrogenogens described in step 1 accounts for 2/3rds of reactor body (10) cumulative volume;
The every L of the liquid fermentation medium of hydrogenogens described in step 1 by the ammonium chloride of 1.0g, the dipotassium hydrogen phosphate of the sodium-chlor of 1.0g, 3g, the halfcystine of the potassium primary phosphate of 1.5g, 0.5g, the MgCl of 0.5g
26H
2the VITAMIN storage liquid of the Repone K of O, 0.2g, the yeast powder of 2g, the peptone of 2g, the micro-metals of 1ml storage liquid, 1ml, 0.1 ‰ (w/v) resazurin, the carbon source of 700mL and the water of surplus of 1ml are prepared from; Described micro-metals storage liquid is by 1.5g/L iron protochloride, 70mg/L zinc chloride, 6mg/L boric acid, 0.1g/L MnCl
24H
2o, 2mg/L CuCl
22H
2o, 0.19g/L CoCl
26H
2o, 24mg/L NiCl
26H
2o, 36mg/L Na
2mO
4h
2o, 15mg/L sodium wolframate and 15mg/L Na
2seO
45H
2o forms; Described VITAMIN storage liquid is by 50.0mg/L Thioctic Acid, 20.0mg/L vitamin H, 0.35g/L nicotinic acid, 5.0mg/L vitamin, 50.0mg/L para-amino benzoic acid, 20.0mg/L folic acid, 50.0mg/L calcium pantothenate, 1.0mg/L vitamins B
12form with 100.0mg/L pyridoxine hydrochloride; Described carbon source is lignocellulose saccharified liquid; Hydrogenogens in described fermentation and hydrogen production seed liquor is pyrolysis sugar anaerobic spore-bearing bacilli W16(Thermoanaerobacterium thermosaccharolyticum W16).
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| CN112266848A (en) * | 2020-11-09 | 2021-01-26 | 河南农业大学 | Novel no pump formula inner loop formula photosynthetic biological hydrogen production reactor |
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| CN102286538A (en) * | 2011-08-30 | 2011-12-21 | 哈尔滨工业大学 | Method for producing hydrogen utilizing cellulose |
| CN103255182A (en) * | 2013-04-24 | 2013-08-21 | 中国科学技术大学 | Method and reaction system for simultaneously producing biogas and fatty acid |
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|---|---|---|---|---|
| CN106399384A (en) * | 2016-10-31 | 2017-02-15 | 哈尔滨工业大学 | Method for enhancing hydrogen production through lignocellulose fermentation by using bio-carrier immobilization |
| CN112266848A (en) * | 2020-11-09 | 2021-01-26 | 河南农业大学 | Novel no pump formula inner loop formula photosynthetic biological hydrogen production reactor |
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