CN109022491B - Coupling resource utilization process of livestock manure hydrogen alkane fermentation - Google Patents
Coupling resource utilization process of livestock manure hydrogen alkane fermentation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
- C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F3/00—Fertilisers from human or animal excrements, e.g. manure
- C05F3/02—Guano
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
本发明公开了禽畜粪污氢烷发酵耦合资源化工艺，通过全混合厌氧反应器加厌氧膜生物反应器两相氢烷发酵系统，一级厌氧对水解菌及酸化菌筛选驯化，同时产生氢气及有机酸和二氧化碳。二级发酵内乙酸营养型及氢营养型产甲烷菌得以充足底物进行高效代谢。再采用厌氧消化液三电极电解流控回收磷酸铵镁和鸟粪石。本发明相比较于传统的厌氧沼气生产，本系统产生的氢烷气体热值高更，进一步提升了禽畜粪便资源能源回用率。同耦合工艺针对消化液中富磷富氮进行三电极电解，牺牲阳极离子化镁棒，产生高效农肥(鸟粪石)的同时对消化液进一步降解。
The invention discloses a technology for coupled resource utilization of poultry and livestock manure hydrogen alkane fermentation. Through a two-phase hydrogen alkane fermentation system of a fully mixed anaerobic reactor and an anaerobic membrane bioreactor, the first-stage anaerobic process is used to screen and domesticate hydrolyzing bacteria and acidifying bacteria. At the same time, hydrogen and organic acids and carbon dioxide are produced. In the secondary fermentation, acetic and hydrogenotrophic methanogens can efficiently metabolize sufficient substrates. The three-electrode electrolytic fluid control of anaerobic digestion solution is used to recover magnesium ammonium phosphate and struvite. Compared with the traditional anaerobic biogas production, the present invention has a higher calorific value of the hydrogen alkane gas produced by the system, and further improves the energy recycling rate of livestock manure resources. The co-coupling process conducts three-electrode electrolysis for phosphorus-rich and nitrogen-rich digestive juice, sacrificing anode ionized magnesium rods, producing high-efficiency agricultural fertilizer (struvite), and further degrading the digestive juice.
Description
Technical Field
The invention belongs to the technical field of biology, and relates to a technology for recycling livestock and poultry manure by hydrogen alkane fermentation coupling.
Background
How to efficiently treat the livestock and poultry excrement with huge yield becomes a difficult problem concerning the environment and the human health. Although the biogas fermentation has a great economic market prospect at home and abroad, the methane content is low in the biogas fermentation process of the livestock manure, the heat value is low, and the promotion of the livestock manure recycling is limited by the technical bottlenecks of substrate/product inhibition, low organic matter conversion rate, liquid nitrogen and phosphorus digestion pollution and the like. The invention discloses a novel coupling process for CSTR + AnMBR two-phase hydrogen alkane fermentation-electrolysis flow control magnesium ammonium phosphate production and tail water one-stage anaerobic ammonia oxidation treatment, which is based on a microecological synergistic regulation response stress mechanism and aims at solving the problems of improving the conversion rate, improving the biogas heat value and recycling resources. The digestion and sewage absorption, the recovery of high-purity hydrogen alkane and nitrogen and phosphorus and the standard-reaching drainage of digestive juice are realized. And the livestock manure is complex, the integral metabolism of the functional flora in the hydrogen alkane fermentation is easy to fluctuate, the reaction activity is easy to be inhibited, and the hydrogen alkane is low in yield and purity due to low synergistic metabolic activity. Meanwhile, the anaerobic digestion solution has high discharge of nitrogen, phosphorus, odor and the like, which restrict the recycling efficiency. The yield and purity of the hydrogen alkane need to be fundamentally improved, and the problems of substrate/product inhibition in the fermentation process and the discharge of the purified digestive juice which reaches the standard are solved. Constructing a new technology of recycling the HYTHANE, recycling N.P and realizing clean drainage of digestive juice, and mastering an inhibition mechanism and a microecological stress resistance mechanism in the fermentation process is the foundation for realizing high-efficiency clean production of the HYTHANE from the livestock and poultry manure. The improvement of the hydrogen alkane conversion rate and the system metabolic stability greatly improves the livestock manure fermentation economic effect, realizes the high-efficiency hydrogen alkane production technology, and solves the practical problems of the agricultural and animal husbandry solid waste recycling technology bottleneck, really benefiting the nation and the people and urgently waiting to be solved.
The prior art has poor treatment effect on the livestock and poultry manure, has the problems of easy inhibition, low conversion rate, liquid nitrogen and phosphorus digestion pollution and the like. The invention can improve the hydrogen alkane conversion rate and the system metabolic stability, greatly improves the livestock manure fermentation economic effect, and realizes the high-efficiency hydrogen alkane production technology.
Disclosure of Invention
The invention aims to provide a technology for recycling the livestock manure by hydrogen alkane fermentation coupling, and has the beneficial effect of improving the overall recycling efficiency of the livestock manure by two-stage anaerobic treatment. The first-stage anaerobic fermentation method has obvious effects of screening and domesticating hydrolytic bacteria and acidifying bacteria, degrading TS (total solids) and VS (volatile solids) and simultaneously generating hydrogen, organic acid and carbon dioxide. Acetic acid nutritional type and hydrogen nutritional type methanogens in the secondary fermentation can be sufficiently metabolized by substrates efficiently. Compared with the traditional anaerobic biogas production, the system has higher heat value of the hydrogen alkane gas, and further improves the energy recycling rate of the livestock manure resources. The same coupling technology carries out three-electrode electrolysis aiming at phosphorus and nitrogen enrichment in the digestive juice, sacrifices an anode ionized magnesium rod, generates high-efficiency agricultural fertilizer (struvite) and further degrades the digestive juice.
The technical scheme adopted by the invention is carried out according to the following steps:
step 1: the first-stage fully-mixed anaerobic reactor is subjected to high-temperature rapid hydrolysis, high-temperature acclimation of microorganisms is carried out, rapid stabilization of the first-stage reactor is realized by an organic load increasing method, and hydraulic retention time is controlled to ensure thorough hydrolysis;
step 2: the ammonia nitrogen hydrolysis yield and the hydrogen production and methane production are coordinated and controlled, the ammonia nitrogen concentration change in the digestive juice is monitored, and the ammonia nitrogen concentration is controlled within 6000mg/L of the inhibition threshold of hydrolytic bacteria and acidifying bacteria by adopting a food-micro ratio regulation strategy;
and step 3: the secondary anaerobic membrane bioreactor strengthens methane fermentation, rapidly degrades dissolved organic matters in primary anaerobic sludge, further hydrolyzes undegraded total solids, and realizes interception and enrichment of dominant functional bacteria and degradation of feces by regulating sludge retention time;
and 4, step 4: regulating and controlling a high-quality polytetrafluoroethylene hollow membrane component in the anaerobic membrane bioreactor, adopting a high-strength polytetrafluoroethylene hollow fiber membrane fixing component, and regularly cleaning the membrane by a configured backwashing pump;
and 5: the method comprises the steps of realizing in-situ purification of the biological biogas in an anaerobic membrane bioreactor, converting CO2 in situ, introducing gas generated by a primary anaerobic acid-producing hydrogen-generating reactor into the anaerobic membrane bioreactor through an air pump to establish a gas circulation path, converting carbon dioxide and hydrogen generated at one stage into methane gas through a hydrogenotrophic methanogen part enriched by secondary flow while realizing gas stripping, and realizing in-situ purification of the biological biogas in the reactor;
step 6: the first-stage anaerobic gas production rate is improved, and the vibration amplitude of the membrane filaments is increased through the established circulating gas path stripping;
and 7: controlling the hydrogen ratio in the hydrogen alkane component, and realizing the whole hydrogen alkane yield by controlling the circulating gas quantity of the primary anaerobic reactor and improving the secondary anaerobic methane production efficiency;
and 8: recycling struvite from anaerobic digestion solution by three-electrode electrolytic flow control;
and step 9: the operation method in the step 8 is as follows:
firstly, constructing a three-electrode electrolysis flow control system and optimizing the electrode plate electrolysis: building a three-electrode electrolytic current control system, setting the voltage between 5V and 25V by adopting a voltage-stabilizing constant-current device, and firstly adopting a static three-electrode reaction to realize the optimal control of the voltage and the current;
② electrolytic static Mg of magnesium bar/titanium-based anode-iron plate cathode2+Releasing and controlling a mechanism: the anode adopts a magnesium rod and a titanium substrate, and is optimized by an anode sacrificial methodMg2+Controlling the generation of struvite through magnesium ion control;
③ electrolysis catalysis mechanism and control-adaptive factor driving force-magnesium ammonium phosphate slow-release rule: refluxing the electrolyzed digestive fluid to the membrane reactor, and improving the biodegradability of the substances which are difficult to biodegrade after catalysis, thereby enhancing the hydrogen production efficiency of the alkane, wherein the proper control factors of the catalysis comprise the distance between the polar plates, the substrate modification material, the voltage and the current and the oxygenation speed;
fourthly, the optimized layout of the dynamic electrolytic flow control multi-polar plate and the recycling efficiency of magnesium ammonium phosphate are regulated and controlled: the optimized layout of the dynamic flow control multi-polar plate device realizes a system for stably producing magnesium ammonium phosphate with large water volume.
Further, the first-stage fully mixed anaerobic reactor in the step 1 is rapidly hydrolyzed at high temperature under the condition of 55 ℃.
Further, in the step 3, the methane fermentation is enhanced by the secondary anaerobic membrane bioreactor at the temperature of 35 ℃.
Further, in step 7, the hydrogen content in the HYTHANE component is controlled to be 10% to 15%.
Drawings
FIG. 1 is a schematic view of a process flow of fermentation coupling recycling of HYTHANE from livestock and poultry manure.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention discloses a process flow for fermenting, coupling and recycling livestock manure by hydrogen alkane, which is shown in figure 1 and comprises the following steps:
a full-mixed anaerobic reactor (CSTR) + anaerobic membrane bioreactor (AnMBR) two-phase hydrogen alkane fermentation system:
1) full-mixing anaerobic reactor CSTR high-temperature rapid hydrolysis.
And (3) performing high-temperature acclimation on the microorganisms at the temperature of 55 ℃. The quick stabilization of the first-stage reactor is realized by an organic load increasing method. The hydraulic retention time is controlled to ensure complete hydrolysis.
2) The ammonia nitrogen hydrolysis yield and the hydrogen and methane production are coordinately controlled.
And monitoring the ammonia nitrogen concentration change in the digestive juice, and controlling the ammonia nitrogen concentration within 6000mg/L of the inhibition threshold of the hydrolytic bacteria and the acidification bacteria by adopting a food-micro ratio control strategy.
3) The second-stage anaerobic membrane bioreactor AnMBR enhances methane fermentation.
Under the condition of 35 ℃, the functional bacteria are reasonably matched by adopting the technical means of feeding the functional bacteria, so that the abundance of each dominant bacteria in the membrane reactor is realized, and the cooperative metabolism of various microorganisms is further ensured. The second-stage anaerobic treatment can rapidly degrade dissolved organic matters in the first-stage anaerobic treatment, and can further hydrolyze undegraded total solids. The second-stage anaerobic treatment realizes interception and enrichment of dominant functional bacteria by regulating and controlling the sludge retention time, and realizes the function of efficiently degrading the feces.
4) Regulating and controlling a high-quality polytetrafluoroethylene hollow membrane component in an anaerobic membrane bioreactor (AnMBR).
The fixing component of the high-strength polytetrafluoroethylene hollow fiber membrane is adopted, so that the service life can be prolonged, and the membrane flux is ensured to a certain extent. The membrane is periodically cleaned by a back-flushing pump.
5) And realizing in-situ purification of the biological biogas in an anaerobic membrane bioreactor (ANMBR), and in-situ conversion of CO 2.
And gas generated by the primary anaerobic acidogenic hydrogen production reactor is introduced into the AnMBR through the gas pump to establish a gas circulation path. The carbon dioxide and the hydrogen generated at one stage are partially converted into methane gas through the hydrogenotrophic methanogen enriched by the secondary flow while the gas stripping is realized, and the in-situ purification of the biogas is realized in a reactor.
6) Membrane module optimization parameters of the membrane reactor.
The first-stage anaerobic gas production is improved, the membrane filament vibration amplitude is increased through the established circulating gas circuit stripping, the biofilm carrying time is effectively prolonged, the backwashing frequency is reduced, and the use of the membrane is prolonged. Optimizing the layout of the membrane component and the length of the membrane filaments, and ensuring the flux to realize parameter optimization of the membrane component.
7) A method for optimizing the yield of hydrogen alkane.
The hydrogen content in the hydrogen-methane component is controlled to be 10-15%, and the whole hydrogen-methane yield is realized by controlling the circulating gas quantity of the primary anaerobic reactor and improving the secondary anaerobic methane production efficiency.
8) And (4) performing three-electrode electrolytic flow control on the anaerobic digestion solution to recover the struvite.
1) Three-electrode electrolysis flow control system construction and polar plate electrolysis optimization
A three-electrode electrolytic flow control system is built, a voltage stabilizing constant current device is adopted, and the set voltage is between 5V and 25V. Firstly, a static three-electrode reaction is adopted to realize the optimal control of voltage and current.
2) Electrolytic static Mg of magnesium rod/titanium-based anode-iron plate cathode2+Control releasing mechanism
The anode adopts a magnesium rod and a titanium substrate, and Mg is optimized by an anode sacrificial method2+And (5) releasing and controlling. The generation of struvite is regulated and controlled by the release and control of magnesium ions.
3) Electrolytic catalysis mechanism and control-adaptive factor driving force-magnesium ammonium phosphate slow-release rule
And (3) refluxing the electrolyzed digestion solution to the membrane reactor, and improving the biodegradability of the difficultly biodegradable substances after catalysis. Thereby enhancing the efficiency of producing hydrogen alkane. The proper control factors of the catalysis include the distance between the polar plates, the substrate modification material, the voltage and the current, the oxygenation rate and the like.
4) Dynamic electrolytic flow control multi-polar plate optimization layout and magnesium ammonium phosphate recovery efficiency regulation
The optimized layout of the dynamic flow control multi-polar plate device realizes a system for stably producing magnesium ammonium phosphate with large water volume.
The invention constructs a new technology of hydrogen alkane recovery, N.P resource utilization and clean drainage of digestive juice, and the mastering of an inhibition mechanism and a microecological stress resistance mechanism in the fermentation process is the foundation of realizing high-efficiency clean production of the hydrogen alkane fermentation of the livestock and poultry manure.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not intended to limit the present invention in any way, and all simple modifications, equivalent variations and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the present invention.
Claims (4)
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| CN112679036A (en) * | 2020-12-03 | 2021-04-20 | 南京大学 | Method for synthesizing struvite fertilizer from biological wastewater |
| CN113354083B (en) * | 2021-07-12 | 2023-04-07 | 中国科学院生态环境研究中心 | Device and method for synchronously recycling struvite in anaerobic membrane biological sewage treatment |
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