CN113502210A - Carbon dioxide internal circulation biogas fermentation carbon reduction method - Google Patents
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 74
- 238000000855 fermentation Methods 0.000 title claims abstract description 71
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 68
- 230000004151 fermentation Effects 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000009467 reduction Effects 0.000 title claims abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 142
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 238000000746 purification Methods 0.000 claims abstract description 24
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000011736 potassium bicarbonate Substances 0.000 claims abstract description 10
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims abstract description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
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- 244000005700 microbiome Species 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- 239000005416 organic matter Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
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- 230000001737 promoting effect Effects 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
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- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
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- C12M47/00—Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
- C12M47/18—Gas cleaning, e.g. scrubbers; Separation of different gases
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Abstract
The invention relates to a carbon dioxide internal circulation biogas fermentation carbon reduction method, which is characterized by comprising the following steps: introducing marsh gas prepared by marsh gas preparation unit into marsh gas purification and separation unit, separating methane and carbon dioxide from marsh gas purification and separation unit, introducing the separated carbon dioxide gas into container filled with carbon dioxide absorption liquid to generate KHCO3Solution, KHCO produced3The solution is refluxed and input to a methane preparation unit. The invention realizes the fermentation of carbon dioxide in the methaneConversion in the system and promotion of methane yield and biogas quality, and is particularly suitable for dry anaerobic fermentation system to carry out CO2And (4) internal circulation.
Description
Technical Field
The invention belongs to the field of organic matter recycling, relates to a technology for promoting anaerobic fermentation of organic matters to produce methane and deeply reducing carbon emission of a biogas system, and particularly relates to a carbon dioxide internal circulation biogas fermentation carbon reduction method.
Background
The biogas fermentation technology is widely applied to the treatment process of organic solid waste and high-concentration organic wastewater, and the organic components are converted into biomass energy through the metabolism of anaerobic microorganisms, so that the method is an effective way for realizing the reduction, stabilization and resource treatment of the organic waste. According to the anaerobic fermentation theory, organic matters are converted into biogas through four stages of hydrolysis, acidification, hydrogen production, acetic acid production and methane production, wherein the anaerobic fermentation of complex organic matters has low gas production efficiency, and is not beneficial to the industrial popularization and application of fermentation technology. The conventional method for improving the fermentation efficiency of organic matters mainly comprises substrate pretreatment, process parameter optimization, mixed matrix fermentation and the like.
The methane is a combustible gas, has high comprehensive utilization value and can be used for cogeneration and centralized gas supply. The main components of the biogas are methane (50-75%)) and carbon dioxide (25-50%), and a small amount or trace amount of impurity gases such as hydrogen sulfide, water vapor, nitrogen, hydrogen, oxygen, etc. The main energy component of the biogas is methane, and necessary biogas purification and purification processes are required to reduce unsafe factors in the biogas conveying and utilizing process and reduce cost and equipment loss. The high-concentration methane-rich gas can be obtained by decarbonizing the methane, so that the application range of the methane is expanded to the modes of vehicle-mounted biogas or natural gas pipe network and the like. At present, a large number of mature technologies and processes are available for separating methane and carbon dioxide from flue gas and biogas, such as membrane separation, pressure swing adsorption, pressurized water washing, adsorption, chemical absorption, and the like. However, current biogas decarbonization technologies focus on methane recovery, while carbon dioxide is often treated as an exhaust gas and discharged, and there is less concern about carbon dioxide recovery and reuse. The content (30-50% by volume) of carbon dioxide in the biogas is second only to methane, and if the carbon is not effectively utilized, the carbon emission is increased, and the resource waste is caused.
Carbon dioxide is an important substrate for the growth of methanogens, is a direct carbon source of methanogens hydrogenophils and is an indirect carbon source of methanogens acetoacidophiles, and the methanogens acetoacidophiles can also utilize the carbon dioxide to generate methane by virtue of the synergistic effect of the homoacetogens. Researches prove that the methane yield of medium-temperature anaerobic fermentation can be improved by introducing carbon dioxide into the anaerobic fermentation device, and the promotion effect of introducing high-purity carbon dioxide on the methane production of the kitchen waste is obviously higher than the effect of traditional methane backflow. However, as a new way to improve fermentation efficiency, this method requires consumption of a large amount of exogenous carbon dioxide, resulting in an increase in running costs.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the carbon dioxide internal circulation methane fermentation carbon reduction method which can realize the internal circulation of carbon dioxide, reduce the cost input of exogenous carbon dioxide, reduce the carbon emission of a methane system and increase the alkalinity and the stability of a fermentation system, thereby improving the methane conversion rate of organic matters and the potassium content of a methane fertilizer.
The above object of the present invention is achieved by the following technical solutions:
a carbon dioxide internal circulation biogas fermentation carbon reduction method is characterized in that: introducing marsh gas prepared by marsh gas preparation unit into marsh gas purification and separation unit, separating methane and carbon dioxide from marsh gas purification and separation unit, introducing the separated carbon dioxide gas into container filled with carbon dioxide absorption liquid to generate KHCO3Solution, KHCO produced3The solution is refluxed and input to a methane preparation unit.
Further: the carbon dioxide absorption liquid is KOH solution or K2CO3And (3) solution.
Further: the biogas preparation unit comprises a raw material pretreatment device and an anaerobic fermentation reactor, and the materials treated by the raw material pretreatment device are conveyed into the anaerobic fermentation reactor.
Further, the method comprises the following steps: a spraying and/or mixing device is arranged in the raw material pretreatment device or the anaerobic fermentation reactor, and the spraying device is used for realizing refluxing KHCO3Is uniformly dispersed.
Further: the biogas purification and separation unit comprises a biogas purification and storage device and a biogas separation device, a gas discharge end of the biogas purification and storage device is communicated with a gas input end of the biogas separation device, and a carbon dioxide gas discharge end and a methane discharge end are arranged on the biogas separation device.
The invention has the advantages and positive effects that:
1. the invention internally circulates the carbon dioxide-rich waste gas after the purification of the methane, realizes the recycling, reduces the carbon emission of the methane project, promotes the low-carbon production, and improves the purity and the application range of the methane.
2. The invention uses KOH or K2CO3Absorb carbon dioxide and further take KHCO3The solution is circulated, which has several advantages:
2.1 by KOH solution or K2CO3Solution absorption of CO2The absorption efficiency is high, the effect is stable, the adjustment is convenient, and the CO can be controlled by controlling the quality of the absorbent KOH2The reflux quantity is helpful to regulate and control CO according to the running condition of the reaction device2And (4) refluxing.
2.2 HCO in liquid form3 -Feeding CO into the reactor2The carbon stays in the reaction system for a longer time, and the contact time with the microorganism is increased. Introducing CO2With HCO3 -The reflux is formed, thereby avoiding CO caused by uneven material mixing in the dry fermentation process or too low gas-liquid mass transfer rate in the wet fermentation process2Quickly separate from the microbial reaction system and improve CO2The biotransformation efficiency of (1).
2.3KOH solution or K2CO3Complete absorption of CO by the solution2After that, KHCO is formed3HCO in solution3 -Not only is the carbon source for the autotrophic microorganisms in the fermentation device, but also has buffering capacity. For high concentration fermentation or dry fermentation systems with high C/N fermentation substrates (e.g., kitchen waste), HCO3 -The buffering capacity of the system strengthens the anti-rancidity capacity of the system, promotes smooth starting and stable operation of the system, and efficiently produces methane.
2.4KOH solution or K2CO3K in solution+Has fertility, and is added with KHCO3The fertilizer efficiency of the biogas fertilizer is increased, and the adding amount of the additional potassium fertilizer in the subsequent preparation of the organic fertilizer is reduced. The organic fertilizer is suitable for improving acid soil.
2.5 for possible presence of Na+Inhibited fermentation processes (e.g. kitchen waste fermentation), K+Adding into fermentation system can improve the fermentation of methane to Na+The tolerance of the compound plays a toxic antagonistic role.
Drawings
FIG. 1 is a process flow diagram of the system of the present invention;
FIG. 2 is a reference graph showing the methane yield control in the examples of the present invention.
Detailed Description
The structure of the present invention will be further described by way of examples with reference to the accompanying drawings. It is to be understood that this embodiment is illustrative and not restrictive.
The invention discloses a carbon dioxide internal circulation biogas fermentation carbon reduction method, and mainly relates to a biogas preparation system, a biogas purification and separation system and a carbon dioxide internal circulation system. The biogas preparation system is mainly used for producing biogas, receiving internally-refluxed carbon dioxide absorption liquid, and setting a corresponding raw material pretreatment process, a structure or a device according to the type of materials, the type of a reaction device and the requirement of improving the fermentation effect. The main device of the biogas purification and separation system is a separation device for methane and carbon dioxide, and corresponding purification devices are arranged according to different requirements of the separation device on inlet air. The carbon dioxide internal circulation system is provided with a function of pressurizing carbon dioxide and then feeding the carbon dioxide into KOH (potassium hydroxide) or an absorption container to form KHCO3Dissolving in water, and adding KHCO3Equipment and devices for adding the solution into a biogas preparation system, and the like.
Organic matters enter a methane preparation device to perform methane fermentation reaction, and the generated methane enters a methane purification and separation system through an exhaust pipeline. The biogas is pretreated to meet the air inlet requirement of the decarburization process, and the methane and the carbon dioxide are separated in the decarburization equipment. The high-concentration methane obtained by separation is comprehensively utilized. The carbon dioxide is connected to a carbon dioxide absorption device, namely KOH or KHCO is introduced3Absorbing in a container with KHCO3Is returned to the biogas preparation system.
The anaerobic fermentation device is a biochemical reactor for converting organic matters in fermentation raw materials into methane, contains relevant microorganisms participating in organic matter conversion and methane production and is in an environment condition suitable for methane production. The fermentation raw materials refer to high-concentration organic wastewater, organic solid wastes or other materials capable of producing methane through fermentation, and the invention has more remarkable promoting effect on high-concentration fermentation or dry fermentation of raw materials with insufficient alkalinity. If the fermentation raw material needs to be pretreated, a raw material pretreatment device is arranged, and the pretreatment mode mainly comprises the following steps: sorting, diluting, adjusting temperature, adjusting pH value, crushing solid, separating solid and liquid, and setting pretreatment process and equipment according to the requirement of the anaerobic fermentation device on feeding.
The biogas fermentation device comprises equipment or a structure for maintaining normal fermentation operation. The fermentation device or the raw material pretreatment device comprises a device for spraying or introducing the carbon dioxide alkaline absorption liquid.
The biogas purification and storage device in the biogas purification and separation unit is biogas pretreatment equipment, comprises biogas purification process equipment such as dehydration and desulfurization and biogas storage and adjustment equipment such as a gas holder, and is additionally provided with corresponding pressurization and impurity removal devices according to the intake requirements of different biogas decarburization processes.
It is required that the amount of newly introduced air or other foreign gases, which are not conducive to biogas fermentation, into the separated gas (carbon dioxide and methane) during the biogas pretreatment and purification process should be small.
In the biogas purification and separation unit, the methane and carbon dioxide separation device can realize effective separation of two gases.
The transmission pipeline and equipment of the carbon dioxide-rich gas are anti-corrosion devices; because carbon dioxide is easily dissolved in water, a pipeline in contact with liquid is prevented from flowing backwards or a sealed pressure-resistant pipeline drainage device is arranged.
Depending on the amount of carbon dioxide-rich gas collected, it can be fed continuously or intermittently to the biogas production plant.
In summary, the invention provides a novel biogas fermentation process flow, which is characterized in that carbon dioxide purified, decarbonized and separated from biogas is absorbed by alkali liquor and then flows back to a biogas fermentation system, so that the conversion of the carbon dioxide in the biogas fermentation system is realized, and the improvement of the methane yield and the biogas quality is promoted.
Invention patent [ CN 112920939A]A method for enhancing methane production by fermentation of biogas through integration of carbon dioxide by fermentation separation coupling is provided, wherein a carbon dioxide circulating system consisting of a reactor and a separation membrane system is constructed, and carbon dioxide is fixed and biotransformation is carried out through additional anaerobic bacteria liquid. CO adopted in the patent2The immobilization method is a biological method, which is different from the chemical absorption method used in this patent.
The invention patent [ CN102329672A ] separates methane and carbon dioxide in the marsh gas, which is mainly used for producing methane and carbon dioxide, but not improves the fermentation efficiency by internal circulation of carbon dioxide.
The invention patent [ CN101892267A ] discloses a biogas fermentation process with methane in-situ enrichment function, which extracts partial fermentation liquor, reduces the carbon dioxide content in the fermentation liquor by using methods of stripping and vacuum release of carbon dioxide, and then reflows to a fermentation reactor, wherein the biogas content of the reactor is increased to 85%. However, this method fails to reduce the emission of carbon dioxide and does not achieve the conversion of carbon dioxide to methane
The carbon reduction system for methane fermentation with internal circulation of carbon dioxide according to the present invention is further illustrated by the following specific examples:
example (b):
selecting an anaerobic fermentation reactor which is a 500L anaerobic bottle with an effective volume of 400mL, fermenting the kitchen waste with a fermentation substrate concentration of 35g-VS/L,inoculating sludge at 16.5g-VS/L, fermenting at 40 deg.C and initial pH of 7.0, introducing N2Anaerobic condition is created within 10min, and batch fermentation is carried out. Experimental groups: introducing the fermentation produced gas into a 5mL KOH absorption bottle with 1mol/L for excessive absorption to obtain CO2And (3) absorbing liquid, namely injecting the absorbing liquid into an anaerobic fermentation bottle, and uniformly mixing. Control group: without CO2And (4) refluxing.
The methane yield was determined starting from the injection of reflux absorption solution, see fig. 2. As shown in FIG. 2, absorption of CO by the lye2After internal reflux, the yield of methane was increased by 8%. The methane concentration in the biogas is between 58 and 65 percent in the quick biogas production stage and after the biogas production tends to be stable.
Although the embodiments of the present invention and the accompanying drawings are disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit of the invention and the scope of the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments and the accompanying drawings.
Claims (5)
1. A carbon dioxide internal circulation biogas fermentation carbon reduction method is characterized in that: introducing marsh gas prepared by marsh gas preparation unit into marsh gas purification and separation unit, separating methane and carbon dioxide from marsh gas purification and separation unit, introducing the separated carbon dioxide gas into container filled with carbon dioxide absorption liquid to generate KHCO3Solution, KHCO produced3The solution is refluxed and input to a methane preparation unit.
2. The carbon dioxide internal recycle biogas fermentation carbon reduction method according to claim 1, characterized in that: the carbon dioxide absorption liquid is KOH solution or K2CO3And (3) solution.
3. The carbon dioxide internal recycle biogas fermentation carbon reduction method according to claim 1, characterized in that: the biogas preparation unit comprises a raw material pretreatment device and an anaerobic fermentation reactor, and the materials treated by the raw material pretreatment device are conveyed into the anaerobic fermentation reactor.
4. The carbon dioxide internal recycle biogas fermentation carbon reduction method according to claim 3, characterized in that: a spraying and/or mixing device is arranged in the raw material pretreatment device or the anaerobic fermentation reactor and is used for realizing the refluxing KHCO3Is uniformly dispersed.
5. The carbon dioxide internal recycle biogas fermentation carbon reduction method according to claim 1, characterized in that: the biogas purification and separation unit comprises a biogas purification and storage device and a biogas separation device, a gas discharge end of the biogas purification and storage device is communicated with a gas input end of the biogas separation device, and a carbon dioxide gas discharge end and a methane discharge end are arranged on the biogas separation device.
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