CN114058479B - Carbon-negative-emission biological hydrogen alkane co-production fermentation system and method - Google Patents
Carbon-negative-emission biological hydrogen alkane co-production fermentation system and method Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 191
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 191
- 238000000855 fermentation Methods 0.000 title claims abstract description 83
- 230000004151 fermentation Effects 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 18
- -1 hydrogen alkane Chemical class 0.000 title claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 175
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 172
- 239000007789 gas Substances 0.000 claims abstract description 95
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000000746 purification Methods 0.000 claims abstract description 48
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 37
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 37
- 238000001514 detection method Methods 0.000 claims abstract description 31
- 230000000243 photosynthetic effect Effects 0.000 claims abstract description 18
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- 239000002184 metal Substances 0.000 claims description 35
- 241000894006 Bacteria Species 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
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Abstract
The invention discloses a bio-hydro-alkane co-production fermentation system and method with carbon-negative emission, comprising a dark-light combined hydrogen production device, a hydrogen quality detection system, a hydrogen purification device, a gas collection tank, an ultra-micro bubble nano device, a methane production device and a methane purification device, wherein the dark-light combined hydrogen production device is an integrated reactor, and a dark fermentation hydrogen production unit and a photosynthetic fermentation hydrogen production unit are arranged in the dark-light combined hydrogen production device. The low-quality hydrogen is introduced into a methanogenic phase, and carbon dioxide is reduced to generate methane under the action of methanobacteria, so that the process not only reduces the cost of hydrogen purification, but also improves the methane generation amount, and simultaneously, the high-quality hydrogen and the carbon dioxide trapped in the methane purification process are returned to a methanogenic reactor to be hydrogenated and converted into methane under the action of methanobacteria, and the combined system realizes the negative emission target of the carbon dioxide in the biomass anaerobic fermentation process.
Description
Technical Field
The invention belongs to the fields of carbon emission reduction and efficient clean energy utilization, and particularly relates to a bio-hydro-alkane co-production fermentation system and method with carbon emission reduction.
Background
With the proposal of 'carbon reaching peak, carbon neutralization' and the aim, the utilization of waste biomass resources is turning from importance to utilization scale to importance to utilization value; the economic value is changed from importance to environmental protection value and social value. The method for preparing hydrogen by using the waste biomass with large utilization amount and wide source as the raw material is one of effective ways for realizing the high-value utilization of the waste biomass, and provides a thinking for reducing the hydrogen production cost. The biological fermentation hydrogen production has mild reaction condition, simple process, wide raw material sources and diversified hydrogen production modes, and in the biological hydrogen production technology, the dark-light combined hydrogen production has higher substrate conversion rate, thereby being the most potential choice for developing the hydrogen production technology. However, in the biological hydrogen production process, hydrogen-producing microorganisms mainly utilize carbohydrate organic matters hydrolyzed by cellulose, but substances such as starch, protein and the like are not effectively utilized, and in addition, organic acid with a certain concentration is remained in fermentation tail liquid due to blocking of hydrogen production metabolism by accumulation of inhibitors in the hydrogen production fermentation process, so that substrate conversion in the fermentation process is hindered. Compared with hydrogen-producing microorganisms, methanogens have stronger metabolic capability, not only can utilize degradable cellulose, but also can utilize substances such as starch, protein and the like in straws, and have higher degradation capability, but the heat value of hydrogen is higher than that of methane, so that the single-phase fermentation limits the conversion of substrate energy, and the two types of microorganisms are utilized to perform hydrogen-producing and methane-producing fermentation, so that not only can high-heat-value combustible gas, namely biohydrogen alkane (about 20% of hydrogen and about 80% of methane) be obtained, but also the high-efficiency conversion of the substrate can be realized. The biohydrogen alkane gas has higher heating value compared with methane gas, and is safer to store and use than biohydrogen. From the microbial metabolism analysis, the biological anaerobic hydrogen production is equivalent to the acid and hydrogen production stage in the biological anaerobic methane production process, the separate operation of the acid and hydrogen production stage and the methane production stage is called two-phase anaerobic fermentation, and the two-phase anaerobic fermentation technology can remove antagonism among strains and has remarkable advantages in gas production, organic matter removal rate and system stability.
In the process of preparing hydrogen by biological fermentation, the main components of generated gas are hydrogen and carbon dioxide, when the strain is in the logarithmic phase, the hydrogen at the stage of high generation rate and high concentration is called high-quality hydrogen, the hydrogen at other stages is low in concentration, the high concentration of carbon dioxide is called low-quality hydrogen, the low-quality hydrogen increases the cost and the working difficulty of hydrogen purification, meanwhile, in the methane fermentation process, the generated gas is mainly methane and carbon dioxide, and the gas obtained by purifying high-quality hydrogen, low-quality hydrogen or biological methane can be used as fuel, and the carbon dioxide is usually directly discharged, so that the method does not conform to the low-carbon and sustainable development strategy. By analyzing the biological anaerobic fermentation process, methane generation can be divided into two ways, namely, organic acid and other substances are decomposed into methane and carbon dioxide, and the carbon dioxide is reduced by hydrogen to form methane. Based on the method, if low-quality hydrogen is introduced into a methanogenic phase, carbon dioxide is reduced to generate methane under the action of methanobacteria, the process not only reduces the cost of hydrogen purification, but also improves the methane generation amount, and meanwhile, high-quality hydrogen and carbon dioxide trapped in the methane purification process are returned to a methanogenic reactor to be converted into methane through hydrogenation under the action of methanobacteria, so that the combined system achieves the negative emission target of carbon dioxide in the biomass anaerobic fermentation process. The hydrogen alkane is prepared through biomass multi-stage fermentation, and carbon capture and sealing are carried out, so that high-value utilization of crop straws and carbon negative utilization of biomass are realized.
Disclosure of Invention
In view of the above problems, the invention provides a bio-hydro-alkane co-production fermentation system and method with carbon-negative emission.
The utility model provides a bio-hydrogen alkane co-production fermentation system of negative carbon property emission, includes dark-light joint hydrogen production device, hydrogen quality detecting system, hydrogen purification device, gas collection jar, ultra-micro bubble nano device, methane production device, methane purification device, dark-light joint hydrogen production device is integrated reactor, and inside is equipped with dark fermentation hydrogen production unit and photosynthetic fermentation hydrogen production unit, dark-light joint hydrogen production device passes through metal collapsible tube with hydrogen quality detecting system and is connected, hydrogen quality detecting system passes through metal collapsible tube and connects hydrogen purification device, pass through metal collapsible tube connection between hydrogen quality detecting system and the hydrogen purification device.
Preferably, a 0.2 mu m acetate fiber membrane is arranged between the dark fermentation hydrogen production unit and the photosynthetic fermentation hydrogen production unit.
Preferably, the hydrogen quality detection system may comprise an on-line gas analyzer.
Preferably, the hydrogen quality detection system is connected with the hydrogen purification device through a gas flow pump.
Preferably, the hydrogen purification device comprises a solid/liquid impurity separator and a membrane separator.
Preferably, the gas separation membrane in the membrane separator of the hydrogen purification device is a graphene-like carbon-nitrogen separation membrane with the diameter of 0.51 nm.
Preferably, a polyimide hollow fiber composite membrane is adopted as a separation membrane in a membrane separator of the methane purification device.
A method for coproducing and fermenting biohydrogen and alkane with negative carbon emission comprises the following steps:
(1) Microbial fermentation to produce hydrogen: mixed bacteria consisting of hidden fermentation hydrogen-producing bacteria and photosynthetic hydrogen-producing bacteria, wherein a fermentation substrate is enzymatic hydrolysate of crop straws;
(2) Purification and splitting of hydrogen:
The hydrogen quality detection system feeds information back to the control system, and then the control system opens a gas flow pump in the direction of the hydrogen purification device, and gas is introduced into the hydrogen purification device through a metal hose to carry out purification, detection and diversion; the separated pure hydrogen flows to the gas collection tank through a metal hose under the action of a gas flow pump, and the separated carbon dioxide is introduced into the methane generating device through the metal hose under the action of the gas pump;
(3) And (3) performing biological anaerobic fermentation:
The fermentation temperature of the methane generating device is set to 35 ℃, the inoculation amount of methanogens is 20% (v/v), and gas generated from the methane generating device flows into the methane purifying device through a metal hose pipe under the action of a gas flow pump; the purified methane enters the gas tank through the metal hose under the action of the gas flow pump, and the separated carbon dioxide flows back to the methane generating device through the metal hose under the action of the gas flow pump.
Preferably, in (1), the dark fermentation unit is set at 35℃with a pH of 5.5-6.5 and an inoculum size of 20% (v/v), the photosynthetic fermentation unit is set at 35℃with an illumination of 3500lx, with a pH of 6.5-7 and an inoculum size of 20% (v/v).
Preferably, in the step (2), when the hydrogen quality detection system detects that the hydrogen concentration in the mixed gas is greater than 50%, the hydrogen quality detection system feeds back information to the control system, then the control system opens a gas flow pump which flows to the direction of the hydrogen purification device, the gas flow pump is used for introducing the pure hydrogen to the gas collection tank, the separated pure hydrogen flows to the methane generation device through a metal hose under the action of the gas flow pump, and the separated carbon dioxide is introduced to the methane generation device through the metal hose under the action of the gas pump; when the hydrogen quality detection system detects low-quality hydrogen, the hydrogen quality detection system feeds information back to the control system, and the control system turns on a gas flow pump for conveying the gas to the direction of the methane generating device and conveys the low-quality hydrogen to an ultra-micro bubble nano device in the methane generating device.
The invention has the beneficial effects that:
According to the invention, low-quality hydrogen is introduced into a methanogenic phase, and carbon dioxide is reduced to generate methane under the action of methanobacteria, so that the process not only reduces the cost of hydrogen purification, but also improves the methane generation amount, and simultaneously, high-quality hydrogen and carbon dioxide trapped in the methane purification process are returned to a methanogenic reactor to be converted into methane through hydrogenation under the action of methanobacteria, so that the combined system achieves the negative emission target of carbon dioxide in the biomass anaerobic fermentation process. The hydrogen alkane is prepared through biomass multi-stage fermentation, and carbon capture and sealing are carried out, so that high-value utilization of crop straws and carbon negative utilization of biomass are realized.
Drawings
Fig. 1 is a schematic structural view of the present invention.
FIG. 2 is a schematic diagram of a purification apparatus of the present invention.
Detailed Description
The following describes the aspects of the present invention in detail with reference to specific examples.
1-2, The bio-hydro-alkane co-production fermentation system with carbon-negative emission comprises a dark-light combined hydrogen production device 1, a hydrogen quality detection system 2, a hydrogen purification device 3, a gas collection tank 4, an ultra-micro bubble nano device 5, a methane production device 6 and a methane purification device 7. The device is an integrated reactor, a dark-light combined hydrogen production unit and a photosynthetic fermentation hydrogen production unit are arranged in the integrated reactor, the dark fermentation hydrogen production unit and the photosynthetic fermentation hydrogen production unit are separated by a 0.2 mu m acetate fiber membrane, the dark-light combined hydrogen production unit 1 is connected with a hydrogen quality detection system 2 through a metal hose, the hydrogen quality detection system 2 can comprise an online gas analyzer, the hydrogen quality detection system 2 is connected with a hydrogen purification device 3 through a gas flow pump and a metal hose, and the hydrogen quality detection system 2 is connected with the hydrogen purification device 3 and a methane production device through the metal hose.
The hydrogen purification device 3 is shown in fig. 2, and comprises a solid/liquid impurity separator 8 and a membrane separator 9, wherein mixed gas passes through the solid/liquid impurity separator to remove solid/liquid impurities mixed in the mixed gas, the mixed gas after preliminary purification enters the membrane separator, a graphite-like carbon-nitrogen separation membrane (purchased from the Kello membrane filtration equipment Co., ltd.) with the size of 0.51nm is adopted in the membrane separator, the temperature of the membrane separator is maintained at 27 ℃, the separated pure hydrogen flows to a gas collection tank through a metal hose under the action of a gas flow pump, the separated carbon dioxide is introduced into a methane production device through the metal hose under the action of the gas pump, the gas enters into methane production fermentation liquor after being micronized by the ultrasonic micro-nano device, and the contact probability of the carbon dioxide and the methane production bacteria is increased by the micronized gas, so that the fixed probability of the carbon dioxide is enhanced. When the hydrogen quality detection system detects low-quality hydrogen, the hydrogen quality detection system feeds information back to the control system, the control system turns on a gas flow pump for flowing gas to the direction of the methanogenic device, the low-quality hydrogen is conveyed to an ultra-micro bubble nano device in the methanogenic device through a metal hose, the contact probability of the gas and methanogenic bacteria is increased in ultrasonic micro, and the low-quality hydrogen is introduced to provide hydrogen for the methanogenic bacteria to reduce carbon dioxide.
The invention relates to a carbon-negative discharged biohydrogen alkane co-production fermentation method, which utilizes the system as described above and comprises the following steps:
(1) Microbial fermentation to produce hydrogen:
the technology of producing hydrogen by dark-light combination is adopted, the device for producing hydrogen by dark-light combination is an integrated reactor, a dark fermentation hydrogen producing unit and a photosynthetic fermentation hydrogen producing unit are arranged in the reactor, 0.2 mu m acetate fiber membrane is used for separating the dark fermentation hydrogen producing unit from the photosynthetic fermentation hydrogen producing unit (the acetate fiber membrane is purchased from Haining Ke Lo membrane filtration equipment Co., ltd.), the acetate fiber membrane can effectively separate the dark fermentation hydrogen producing bacteria from the photo-fermentation hydrogen producing bacteria, the respective space ecological position of the hydrogen producing bacteria is kept, and small molecular acid produced by the dark fermentation unit can permeate the photosynthetic hydrogen producing unit to be utilized by photosynthetic bacteria for producing hydrogen. The mixed bacteria of the hidden fermentation hydrogen-producing bacteria Paraclostridium, the Enterococcus and the Sporanaerobacter, the photosynthetic hydrogen-producing bacteria Rhodospirillum rubrum, rhodobacter capsulatus and Rhodopseudomonas palustris, the conditions of the hidden fermentation unit are 35 ℃, the pH is 5.5-6.5, the inoculation amount is 20% (v/v), the temperature of the photosynthetic fermentation unit is 35 ℃, the illumination is 3500lx, the pH is 6.5-7, the inoculation amount is 20% (v/v), and the fermentation substrate is the enzymatic hydrolysate of crop straws (the concentration is 10-15 g reducing sugar/L). The environmental temperature required in the hydrogen production fermentation process depends on solar energy to circulate hot water, and the illumination of the photosynthetic hydrogen production unit is partially from the sunlight transmitted by the optical fiber and partially provided by the LED lamp.
(2) Purification and splitting of hydrogen:
The main components of the generated gas in the hydrogen production stage are hydrogen and carbon dioxide, the generated gas is analyzed by an online gas analyzer for the content of each component in the gas, and the dark-light combined hydrogen production device is connected with the online gas device by a metal hose. The invention defines that the hydrogen concentration in the mixed gas is more than 50 percent and is called high-quality hydrogen, and the hydrogen concentration in the mixed gas is less than 50 percent and is called low-quality hydrogen. When the hydrogen quality detection system detects that the hydrogen concentration in the mixed gas is greater than 50%, the hydrogen quality detection system feeds information back to the control system, then the control system opens a gas flow pump which flows to the direction of the hydrogen purification device, the gas is introduced into the hydrogen purification device through a metal hose, and the hydrogen quality detection system is linked with the hydrogen purification device and the methane generating device through the metal hose. The system diagram of the hydrogen purification device is shown in fig. 2, firstly, mixed gas passes through a solid/liquid impurity separator to remove solid/liquid impurities mixed in the mixed gas, preliminary purification is carried out, the mixed gas after preliminary purification enters a membrane separator, a gas separation membrane in the membrane separator adopts a graphene-like carbon-nitrogen separation membrane (purchased from Haining Ke Lo membrane filtration equipment Co., ltd.) with the thickness of 0.51nm, the temperature of the membrane separator is maintained at 27 ℃, the separated pure hydrogen flows to a gas collection tank through a metal hose under the action of a gas flow pump, the separated carbon dioxide is introduced into a methane-producing device through the metal hose under the action of the gas pump, the gas enters into methane-producing fermentation liquor after being micronized by an ultrasonic micro-nano device, and the micronized gas increases the contact probability of the carbon dioxide and methane-producing bacteria, thereby enhancing the fixation probability of the carbon dioxide. When the hydrogen quality detection system detects low-quality hydrogen, the hydrogen quality detection system feeds information back to the control system, the control system turns on a gas flow pump for flowing gas to the direction of the methanogenic device, the low-quality hydrogen is conveyed to an ultra-micro bubble nano device in the methanogenic device through a metal hose, the contact probability of the gas and methanogenic bacteria is increased in ultrasonic micro, and the low-quality hydrogen is introduced to provide hydrogen for the methanogenic bacteria to reduce carbon dioxide.
(3) And (3) performing biological anaerobic fermentation:
The methane fermentation is carried out in a methane generating device, fermentation tail liquid is pumped into the methane generating device through a peristaltic pump after the hydrogen generating fermentation is finished, the fermentation temperature of the methane generating device is 35 ℃, the inoculation amount of methane generating bacteria is 20% (v/v), gas generated from the methane generating device flows into a methane purifying device through a metal hose pipeline under the action of a gas flow pump, the methane purifying device and the hydrogen purifying device have the same composition, as shown in figure 2, the difference is that a polyimide hollow fiber composite membrane (membrane density is 1.422kg/m < 3 >) (purchased from Haining Ke Gao membrane filter equipment Co., ltd.) is adopted as a separation membrane in the methane purifying device, the generated mixed gas firstly passes through a solid/liquid impurity purifying device and then enters a membrane separator, methane is trapped on the high pressure side of the membrane, carbon dioxide and other gases permeate into an enriching side through the membrane, the purified methane enters a gas tank through the metal hose under the action of the gas flow pump, and the separated carbon dioxide flows back into the methane generating device through the metal hose under the action of the gas flow pump, and also enters the methane generating device from the methane generating device through the membrane filter, and the ultrasonic substrate is adopted to increase the contact probability. In the carbon cycle angle analysis, biomass fixes carbon dioxide equal to carbon dioxide released in the degradation process by photosynthesis, and hydrogen, carbon dioxide and carbon dioxide purified and refluxed carbon dioxide in low-quality hydrogen are converted into methane under the action of methane bacteria by diversion of high-quality hydrogen and low-quality hydrogen in the hydrogen-producing fermentation process, so that the cost of hydrogen purification is reduced, the methane generation amount is improved, more importantly, the emission of carbon dioxide in the biological utilization process is reduced, hydrogen alkane is prepared by biomass multi-stage fermentation, carbon capture and sealing are carried out, and the high-value utilization of crop straws and the negative carbon utilization of biomass are realized.
Claims (8)
1. A negative carbon emission biological hydrogen alkane co-production fermentation system is characterized in that: the device comprises a dark-light combined hydrogen production device, a hydrogen quality detection system, a hydrogen purification device, a gas collection tank, an ultra-micro bubble nano device, a methane production device and a methane purification device, wherein the dark-light combined hydrogen production device is an integrated reactor, a dark fermentation hydrogen production unit and a photosynthetic fermentation hydrogen production unit are arranged in the integrated reactor, a 0.2 mu m acetate fiber membrane is arranged between the dark fermentation hydrogen production unit and the photosynthetic fermentation hydrogen production unit, the dark-light combined hydrogen production device is connected with the hydrogen quality detection system through a metal hose, the hydrogen quality detection system is connected with the hydrogen purification device through the metal hose, and the hydrogen quality detection system is connected with the methane production device through the metal hose;
the hydrogen purification device is respectively connected with the gas collection tank and the methane generating device through pipelines;
the methane generating device is sequentially connected with the methane purifying device and the gas collecting tank through pipelines, and the methane purifying device is also connected with the methane generating device through a return pipeline;
The fermentation tail liquid of the hydrogen production device is led into the methane production device through a metal hose, and the ultra-micro bubble nano device is positioned in the methane production device and is used for carrying out ultrasonic micro-treatment on gas led into the methane production device.
2. A carbon-negative discharged biohydrogen co-production fermentation system as defined in claim 1, wherein: the hydrogen quality detection system may include an online gas analyzer.
3. A carbon-negative discharged biohydrogen co-production fermentation system as defined in claim 1, wherein: the hydrogen quality detection system is connected with the hydrogen purification device through a gas flow pump.
4. A carbon-negative discharged biohydrogen co-production fermentation system as defined in claim 1, wherein: the hydrogen purification device comprises a solid/liquid impurity separator and a membrane separator.
5. A carbon-negative discharged biohydrogen co-production fermentation system as defined in claim 1, wherein: the gas separation membrane in the membrane separator of the hydrogen purification device is a graphene-like carbon-nitrogen separation membrane with the diameter of 0.51 nm.
6. A carbon-negative discharged biohydrogen co-production fermentation system as defined in claim 1, wherein: the separation membrane in the membrane separator of the methane purification device adopts a polyimide hollow fiber composite membrane.
7. A method of co-production fermentation of biohydro alkanes based on carbon-negative emissions of a co-production fermentation system according to any one of claims 1-6, comprising the steps of:
(1) Microbial fermentation to produce hydrogen: mixed bacteria composed of hidden fermentation hydrogen-producing bacteria and photosynthetic hydrogen-producing bacteria, wherein the fermentation substrate is crop straw
An enzymolysis liquid of the stalk;
(2) Purification and splitting of hydrogen:
when the hydrogen quality detection system detects that the hydrogen concentration in the mixed gas is greater than 50%, the hydrogen quality detection system feeds information back to the control system, then the control system opens a gas flow pump which flows to the direction of the hydrogen purification device, the gas flow pump is used for introducing the hydrogen purification device, the separated pure hydrogen flows to the gas collection tank through a metal hose under the action of the gas flow pump, and the separated carbon dioxide is introduced to the methane production device through the metal hose under the action of the gas pump; when the hydrogen quality detection system detects that the hydrogen concentration in the mixed gas is less than 50%, the hydrogen quality detection system feeds information back to the control system, the control system turns on a gas flow pump in the direction of gas flow to the methane generating device, and the mixed gas is directly conveyed to an ultra-micro bubble nano device in the methane generating device;
(3) And (3) performing biological anaerobic fermentation:
The fermentation temperature of the methane generating device is set to 35 ℃, the inoculation amount of methanogens is 20% (v/v), and gas generated from the methane generating device flows into the methane purifying device through a metal hose pipe under the action of a gas flow pump; the purified methane enters the gas collection tank through the metal hose under the action of the gas flow pump, and the separated carbon dioxide flows back to the methane generating device through the metal hose under the action of the gas flow pump.
8. The method for co-producing fermentation of biohydro-alkanes with carbon negative emission according to claim 7, wherein in (1), the dark fermentation unit is set to 35 ℃, the pH is 5.5-6.5, the inoculum size is 20% (v/v), the photosynthetic fermentation unit temperature is 35 ℃, the illumination is 3500lx, the pH is 6.5-7, and the inoculum size is 20% (v/v).
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