CN111979275A - Method for improving yield of coal-based biomethane by using waste organic matters - Google Patents
Method for improving yield of coal-based biomethane by using waste organic matters Download PDFInfo
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Abstract
The invention discloses a method for improving the yield of coal-based biomethane by using waste organic matters. According to the invention, through pretreatment and separation of easily degradable components in the waste organic matters and improvement of organic structures of wastes, the material interaction between the pretreatment product and coal is utilized, the degradation effect of microorganisms on the coal is promoted, and the yield of biological methane is increased, so that the energy shortage is effectively relieved, the energy structure is improved, the resource utilization of the waste organic matters is realized, and the process is green and environment-friendly.
Description
Technical Field
The invention relates to a method for improving the yield of coal-based biological methane by using waste organic matters, belonging to the field of coal conversion and methane yield improvement.
Background
Biological methane is an important component of existing coal bed gas, is found in all large coal bed gas fields in the world, and is a main source of coal bed gas in partial basins. Based on a formation mechanism of the coal bed methane, the microorganism coal bed gas production increasing technology increases the coal bed gas reserve and improves the physical properties of a coal reservoir by artificially accelerating the in-situ generation of the coal bed methane, thereby improving the productivity of a coal bed gas well, prolonging the service life of the gas well, enhancing the recovery ratio of the coal bed gas and realizing the yield increase of the coal bed gas.
However, the efficiency of coal conversion into biomethane is low, and the yield of biomethane is likely to be lower if the complex geological conditions of coal seams, coal abundance and low coal content, non-optimal pressure and temperature and other adverse factors are considered. This has led to very limited practical industrial applications of microbial enhanced coal bed gas. At present, only a few companies carry out industrial tests, and the methane yield increasing effect is not ideal. Therefore, how to enhance the anaerobic biodegradation efficiency of coal and improve the methane yield is one of the key problems which need to be solved urgently by the technology of increasing coal bed methane by microorganisms.
The complex and firm coal molecular structure is an important limiting factor for directly degrading coal by microorganisms, so that the microbial activity is difficult to rapidly promote in the initial stage of reaction, and only a small part of organic matters in the coal are converted into methane. Meanwhile, the coal is mainly composed of refractory aromatic compounds and is not easily utilized by microorganisms. Therefore, researchers propose that microbial flora and coal molecules are activated by adding a carbon source, microbial metabolism is accelerated, and biological methane yield is improved. As a mixed carbon source which is easy to be utilized by microorganisms, after waste organic matters are pretreated by anaerobic microorganisms, chemical reagents and physical means, the joint fermentation of solid/liquid products and coal inevitably has important influence on the process of methane generation, effectively promotes the biodegradation of the coal and improves the yield of methane. In addition, the problems of energy waste, environmental pollution and the like are effectively solved by recycling the waste organic matters.
Disclosure of Invention
The invention aims to provide a method for improving the yield of coal-based biomethane by using waste organic matters, which utilizes the pretreatment products of the waste organic matters to carry out combined fermentation with coal, promotes the biodegradation of the coal and improves the yield of the coal-based biomethane.
The method specifically comprises the following steps:
(1) crushing the waste organic matters by using a crusher;
(2) finishing the pretreatment of the waste organic matters in a pretreatment container;
pretreating the waste by using any one method of anaerobic microbial flora, chemical reagents or physical means;
(3) the solid phase product or the liquid phase product obtained by the pretreatment of the waste organic matters and the coal are subjected to combined anaerobic fermentation to promote the biodegradation of the coal and improve the yield of the coal-based biomethane.
In the method, the waste organic matters comprise straws rich in organic matters, kitchen waste, fertilizer, waste sludge or coal mine waste coal gangue.
In the method, the process of pretreating the waste organic matters by the anaerobic microbial flora specifically comprises the steps of sterilizing a pretreatment container for 20-30 minutes at the temperature of not less than 121 ℃ before pretreatment; after cooling, placing the waste organic matters into a container, then injecting anaerobic microbial floras, and pretreating the waste organic matters for 4-12 days to obtain a pretreatment mixed solution; and carrying out solid-liquid separation, and respectively collecting a solid-phase product and a liquid-phase product. And finally, performing combined microbial anaerobic fermentation on the waste organic matter pretreatment solid/liquid products and coal respectively to generate methane.
Further, the anaerobic microbial flora used for the pretreatment is a hydrolytic microorganism. The ratio of the hydrolytic microorganisms to the waste organic matters is 10-15 mL to 1 g. The hydrolytic microorganism is selected from coal bed or water body sediment anaerobic habitat, comprising: bacillus, enterococcus, Acidobacterium, Desulfotomaculum, Proteus, Lactobacillus, Acetobacter, Aspergillus, Alternaria, Cladosporium, Pseudomonas aeruginosa, Clostridium, Enterobacter, Penicillium, and Acremonium.
In the method, the process of pretreating the waste organic matters by the chemical reagent specifically comprises the following steps: mixing a chemical reagent with the waste organic matters, stirring for 12-15 h by a magnetic stirrer at the temperature of 25-30 ℃ and the rotating speed of 600-700 r/min to obtain a pretreated mixed solution, then carrying out solid-liquid separation, and collecting a solid-phase product and a liquid-phase product. And finally, performing combined microbial anaerobic fermentation on the waste organic matter pretreatment solid/liquid products and coal respectively to generate methane.
Further, the chemical agents include: alkali NaOH or KOH or acid H2SO4Or HNO3Or peroxides H2O2Or CaO2In the chemical reagent, the mass concentration of the chemical reagent is 2-6%. The ratio of the chemical reagent to the waste organic matters is 10-15 mL to 1 g.
In the method, the process of pretreating the waste organic matters by a physical means specifically comprises the following steps: the waste organic matters are pretreated for 25-40 min by one of physical means of irradiation, ultrasonic wave or microwave pretreatment, a pretreated solid phase product is collected, and then the pretreated solid phase product and coal are subjected to combined anaerobic fermentation to generate methane.
Furthermore, gamma-ray irradiation is adopted in the irradiation pretreatment, and the irradiation dose is 1200-1500 kGy. The power of ultrasonic treatment is 120W, the time of ultrasonic action for 1 time is 1-2 s, and the intermittent time is 4-6 s. The microwave treatment adopts a low-power microwave oven with the power of 800-900W.
In the method, the microbial flora used in the step (3) combined anaerobic fermentation is a mixed flora of hydrolytic microorganisms and methanogenic bacteria, and the volume ratio of the hydrolytic microorganisms to the methanogenic bacteria is 4-6:1, so that a new microbial mixed flora is formed. The time of the combined anaerobic fermentation is 30-60 days.
Further, the methanogen group is selected from a coal bed or a water body sediment anaerobic habitat, and comprises: one or more of Methanobacterium manacilus, Methanophagus methylotrophus, Methanosarcina, Methanobacterium, and Methanophyllum.
The invention provides a method for improving the yield of coal-based biomethane by using waste organic matters on the ground. Firstly, making waste organic matters into powder by a pulverizer, and placing the powder in a waste organic matter pretreatment reaction container; finishing the pretreatment process according to the preset time, separating the pretreatment liquid-phase product from the pretreatment solid-phase product, and respectively placing the products in two different storage tanks; crushing raw coal by a coal mill, and placing the crushed raw coal in a coal storage tank; then the pulverized coal and the solid phase product or the pulverized coal and the liquid phase product are put in a biotransformation reactor containing microbial flora and nutrients to complete the combined anaerobic fermentation of the pretreated product and the coal; the pretreatment by physical means does not need solid-liquid separation, and the obtained solid product and coal are directly subjected to combined anaerobic fermentation; finally, the biogas is conveyed to a biogas storage tank through a pipeline.
The invention provides a method for improving the yield of coal-to-methane by using waste organic matters in a coal mine. Firstly, preparing waste organic matters into powder on the ground through a pulverizer, and placing the powder in a waste organic matter pretreatment reaction container; finishing the pretreatment process according to the preset time to obtain a waste organic matter pretreatment liquid-phase product; injecting the pretreatment liquid phase product, nutrient solution and microbial flora into the coal bed through a pre-drilled well under static pressure; completing in-situ combined anaerobic fermentation of waste organic matter liquid phase products and coal in a coal mine; and finally, conveying the biogas generated in the underground coal bed to a ground natural gas pipeline through a gas pipeline.
The invention has the beneficial effects that:
(1) according to the invention, anaerobic microbial flora, chemical reagents and physical means are utilized to pretreat the waste organic matters, easily degradable components in the waste organic matters are separated, and the degradation of the coal by microorganisms is promoted through the mutual stimulation between the pretreatment product of the waste organic matters and the coal, so that the yield of biomethane is increased, the energy shortage can be effectively relieved, and the energy structure is improved.
(2) The invention provides a novel waste organic matter utilization mode, which can realize resource utilization of waste organic matters and is green and environment-friendly in process.
Drawings
FIG. 1 is a schematic diagram of an exemplary process for surface utilization of waste organic pretreatment products to facilitate a coal bioconversion system.
FIG. 2 is a schematic diagram of an exemplary process for downhole utilization of waste organic pretreatment products to facilitate a coal bioconversion system.
FIG. 3 shows the change of methane production in the combined fermentation process of liquid-phase product of anaerobic microbial flora pretreated waste organic rice straw and coal, corresponding to example 1.
FIG. 4 shows the variation of methane production in the combined fermentation of solid/liquid phase product of chemical NaOH-pretreated waste organic rice straw and coal, corresponding to example 2.
FIG. 5 shows chemical reagent H2SO4The methane yield of the combined fermentation process of the solid/liquid phase product of the pretreated waste organic matter sweet sorghum straw and coal changes, corresponding to example 3.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
the method for promoting coal bioconversion by selecting liquid-phase products of anaerobic microbial flora pretreated waste organic matter straws comprises the following steps:
firstly, waste organic rice straws are made into powder by a pulverizer, and after anthracite coal samples are obtained from a target coal bed in a waterlogging basin, the coal samples are also pulverized.
And secondly, carrying out enrichment culture of anaerobic microbial flora.
And thirdly, taking 0.45 g of straw powder obtained in the first step, putting the straw powder into a 140 mL serum bottle which is subjected to sterilization treatment, and adding 3 mL of anaerobic microorganism flora and required nutrient substances. Then, the reaction flask was incubated at a temperature of 35 ℃ without shaking. And (4) performing anaerobic removal on the straws on the 4 th day, the 8 th day and the 12 th day of the pretreatment respectively to obtain liquid-phase products of the straws subjected to microbial pretreatment in different periods.
And fourthly, under the condition of providing nutrient components, performing combined fermentation on the pretreatment liquid-phase product obtained in the third step and the anthracite sample obtained in the first step at 35 ℃ respectively to realize biodegradation of coal and methane production. Methane production was monitored periodically during the combined fermentation.
The biological methane production is shown in FIG. 3. After the gas production experiment is finished, the liquid phase products obtained by pretreating straws for 4 days, 8 days and 12 days by anaerobic microorganisms and the methane yield of the combined fermentation of coal are 561.73 mu mol/g coal, 578.84 mu mol/g coal and 550.69 mu mol/g coal respectively.
Comparative example 1:
in this example, coal alone was fermented under the same other process conditions as in example 1. The biological methane production is shown in FIG. 3. In comparative example 1, the methane production after the completion of the culture was 38.67. mu. mol/g coal.
By comparing example 1 and comparative example 1, it was found that: after liquid phase products obtained by pretreating straws by anaerobic microbial floras at different times are fermented with coal in a combined manner, the yield of the biological methane is respectively increased by 1352.62%, 1396.87% and 1324.08%.
Example 2:
a solid/liquid phase product of waste organic rice straw pretreated by a chemical reagent NaOH with the concentration of 2% is selected to promote the coal bioconversion, and the method comprises the following steps:
firstly, making waste organic rice straws into powder by using a pulverizer, and pulverizing a coal sample for experiment after acquiring an anthracite coal sample in a target coal bed in a water-logging basin.
And secondly, preparing a NaOH solution with the mass concentration of 2%.
And thirdly, placing 2g of waste organic straw powder obtained in the first step into a pretreatment container filled with 30 mL of 2% NaOH solution, continuously stirring for 12 hours at the speed of 700 r/min by a magnetic stirrer at the temperature of 25 ℃, and stirring to obtain a mixed solution.
And fourthly, carrying out solid-liquid separation on the mixed solution obtained in the third step through a vacuum filtration device and a matched filter membrane, and collecting a solid-phase product and a liquid-phase product which are obtained after the pretreatment of the waste organic straws into corresponding experiment bottles.
And fifthly, under the condition of providing nutrient components, performing combined fermentation on the solid/liquid product obtained in the fourth step and the anthracite sample in the first step at 35 ℃ respectively to realize biodegradation of coal and methane production. Methane production was monitored periodically during the combined fermentation.
The biological methane production is shown in FIG. 4. After the gas production experiment is finished, the yield of methane produced by the joint fermentation of the solid-phase product obtained by pretreating the waste organic straw by using 2% NaOH and coal is 99.10 mu mol/g coal; the methane yield of the liquid phase product and the coal combined fermentation is 108.47 mu mol/g coal.
Comparative example 2:
in this example, coal alone was fermented and the other process conditions were the same as in example 2. The biological methane production is shown in FIG. 4. In comparative example 2, the methane production after the completion of the culture was 44.89. mu. mol/g coal.
By comparing example 2 and comparative example 2, it was found that: after the solid-phase product obtained by pretreating the waste organic straws with 2% NaOH is fermented together with coal, the yield of the biological methane is increased by 120.76%. After the liquid phase product is fermented together with coal, the yield of the biological methane is increased by 141.64%.
Example 3:
selecting 2% chemical reagent H2SO4The solid-phase/liquid-phase product of the pretreated waste organic matter sweet sorghum straw for promoting coal bioconversion comprises the following steps:
firstly, waste organic matter sweet sorghum straws are made into powder by a pulverizer, and after anthracite coal samples are obtained from a goal coal bed in a water-logging basin, the coal samples are also pulverized for carrying out experiments.
Secondly, preparing H with the mass concentration of 2%2SO4And (3) solution.
Thirdly, 2g of waste organic straw powder obtained in the first step is placed in a container containing 30 mL of 2% H2SO4In the solution pretreatment container, stirring is continuously carried out for 12 hours at the temperature of 25 ℃ by a magnetic stirrer at the speed of 700 r/min, and a mixed solution is obtained after stirring.
And fourthly, carrying out solid-liquid separation on the mixed solution obtained in the third step through a vacuum filtration device and a matched filter membrane, and collecting a solid-phase product and a liquid-phase product which are obtained after the pretreatment of the waste organic matter sweet sorghum straws in corresponding experiment bottles.
And fifthly, under the condition of providing nutrient components, performing combined fermentation on the solid/liquid product obtained in the fourth step and the anthracite sample in the first step at 35 ℃ respectively to realize biodegradation of coal and methane production. Methane production was monitored periodically during the combined fermentation.
The biological methane production is shown in FIG. 5. Gas production experiment knotAfter completion, 2% H2SO4The yield of methane produced by the joint fermentation of the solid-phase product obtained by pretreating the waste organic straws and coal is 100.90 mu mol/g coal; the yield of methane produced by the combined fermentation of the liquid phase product and the coal is 98.90 mu mol/g coal.
Comparative example 3:
in this example, coal alone was fermented under the same other process conditions as in example 3. The biological methane production is shown in FIG. 5. In comparative example 3, the methane production after the completion of the culture was 45.00. mu. mol/g coal.
By comparing example 3 and comparative example 3, it was found that: through 2% H2SO4After the solid-phase product obtained by pretreating the waste organic straws is fermented together with coal, the yield of the biological methane is increased by 124.22%. After the liquid phase product is fermented together with coal, the yield of the biological methane is increased by 119.78%.
Example 4:
the solid-phase product of the waste organic matter kitchen waste pretreated by physical means microwave is selected to promote coal biotransformation, and the method comprises the following steps:
firstly, waste organic kitchen waste is made into powder by a pulverizer, and after an anthracite coal sample is obtained from a target coal bed in an infiltration basin, the coal sample is also pulverized for carrying out an experiment.
And step two, placing 2g of the waste organic matter kitchen waste obtained in the step one in a low-power microwave oven for physical means pretreatment, wherein the power of the microwave oven is 800-.
And thirdly, putting the solid-phase product obtained in the second step into a corresponding experimental bottle.
And fourthly, performing combined fermentation on the solid-phase product obtained in the third step and the anthracite sample obtained in the first step at 35 ℃ under the condition of providing nutrient components to realize biodegradation of coal and methane production.
After the combined fermentation experiment is finished, the methane yield of the solid-phase product obtained by microwave pretreatment of the waste organic matter kitchen waste and coal combined fermentation is improved by 30.00 percent compared with that of single coal fermentation.
Claims (10)
1. A method for improving the yield of coal-based biomethane by using waste organic matters is characterized by comprising the following steps:
(1) crushing the waste organic matters by using a crusher;
(2) finishing the pretreatment of the waste organic matters in a pretreatment container;
pretreating the waste by using any one method of anaerobic microbial flora, chemical reagents or physical means;
(3) performing combined anaerobic fermentation on a solid-phase product or a liquid-phase product obtained by pretreating waste organic matters and coal to promote biodegradation of the coal and improve the yield of coal-based biomethane;
the waste organic matter comprises one of straw, kitchen waste, fertilizer, waste sludge or coal mine waste rich in organic matter, and the coal mine waste comprises coal gangue.
2. The method for improving the yield of coal-based biomethane by using waste organic matters according to claim 1, wherein the method comprises the following steps: in the step (2), the process of pretreating the waste organic matters by the anaerobic microorganism flora specifically comprises the following steps: before pretreatment, the pretreatment container is sterilized for 20-30 minutes at the temperature of not less than 121 ℃; after cooling, placing the waste organic matters into a container, then injecting anaerobic microbial floras, and pretreating the waste organic matters for 4-12 days to obtain a pretreatment mixed solution; carrying out solid-liquid separation, and respectively collecting a solid-phase product and a liquid-phase product; finally, respectively carrying out combined microbial anaerobic fermentation on the solid/liquid products of the pretreatment of the waste organic matters and coal to generate methane; the anaerobic microbial flora used for pretreatment is hydrolytic microorganisms; the ratio of the hydrolytic microorganisms to the waste organic matters is 10-15 mL to 1 g.
3. The method for improving the yield of coal-based biomethane by using waste organic matters according to claim 2, wherein the method comprises the following steps: the hydrolytic microorganism is selected from a coal bed or water body sediment anaerobic habitat and comprises: bacillus, enterococcus, Acidobacterium, Desulfotomaculum, Proteus, Lactobacillus, Acetobacter, Aspergillus, Alternaria, Cladosporium, Pseudomonas aeruginosa, Clostridium, Enterobacter, Penicillium, and Acremonium.
4. The method for improving the yield of coal-based biomethane by using waste organic matters according to claim 1, wherein the method comprises the following steps: in the step (2), the process of pretreating the waste organic matters by the chemical reagent specifically comprises the following steps: mixing a chemical reagent with the waste organic matter, and stirring for 12-15 h by a magnetic stirrer under the conditions that the temperature is 25-30 ℃ and the rotating speed is 600-; then carrying out solid-liquid separation, and collecting a solid-phase product and a liquid-phase product; and finally, performing combined microbial anaerobic fermentation on the waste organic matter pretreatment solid/liquid products and coal respectively to generate methane.
5. The method for improving the yield of coal-based biomethane by using waste organic matters as claimed in claim 4, wherein the method comprises the following steps: the chemical reagents include: one of alkali, acid or peroxide, wherein the mass concentration of the chemical reagent is 2-6%; the ratio of the volume of the chemical reagent to the mass of the waste organic matter is 10-15 mL:1 g;
the alkali is NaOH or KOH; the acid is H2SO4Or HNO3(ii) a The peroxide is H2O2Or CaO2。
6. The method for improving the yield of coal-based biomethane by using waste organic matters according to claim 1, wherein the method comprises the following steps: in the step (2), the process of pretreating the waste organic matters by a physical means specifically comprises the following steps: pretreating the waste organic matter for 25-40 min by one of physical means of irradiation, ultrasonic wave or microwave pretreatment, and collecting a pretreated solid-phase product; then performing combined anaerobic fermentation on the biomass and coal to generate methane;
the irradiation pretreatment adopts gamma-ray irradiation, and the irradiation dose is 1200-1500 kGy; the power of ultrasonic treatment is 120W, the time of ultrasonic action for 1 time is 1-2 s, and the intermittent time is 4-6 s; the microwave treatment adopts a low-power microwave oven with the power of 800-900W.
7. The method for improving the yield of coal-based biomethane by using waste organic matters according to claim 1, wherein the method comprises the following steps: the microbial flora used in the combined anaerobic fermentation in the step (3) is a mixed flora of a hydrolytic microbial flora and a methanogenic flora, and the volume ratio of the hydrolytic microbial flora to the methanogenic flora is 4-6:1, so that a new microbial mixed flora is formed; the time of the combined anaerobic fermentation is 30-60 days.
8. The method for improving the yield of coal-based biomethane by using waste organic matters as claimed in claim 7, wherein the method comprises the following steps: the hydrolytic microorganism is selected from a coal bed or water body sediment anaerobic habitat and comprises: one or more of Bacillus, enterococcus, Acidobacterium, Desulfotomaculum, Proteus, Lactobacillus, Acetobacter, Aspergillus, Alternaria, Cladosporium, Pseudomonas aeruginosa, Clostridium, Enterobacter, Penicillium, and Acremonium; the methanogen flora is selected from coal bed or water body sediment and comprises: one or more of Methanobacterium manacilus, Methanophagus methylotrophus, Methanosarcina, Methanobacterium, and Methanophyllum.
9. A method for improving the yield of coal-based biomethane by using waste organic matters on the ground is characterized by comprising the following steps: making waste organic matters into powder by a pulverizer, and placing the powder into a waste organic matter pretreatment reaction container; finishing the pretreatment process according to the preset time, separating the pretreatment liquid-phase product from the pretreatment solid-phase product, and respectively placing the products in two different storage tanks; crushing raw coal by a coal mill, and placing the crushed raw coal in a coal storage tank; then the pulverized coal and the solid phase product or the pulverized coal and the liquid phase product are put in a biotransformation reactor containing microbial flora and nutrients to complete the combined anaerobic fermentation of the pretreated product and the coal; the pretreatment by physical means does not need solid-liquid separation, and the obtained solid product and coal are directly subjected to combined anaerobic fermentation; finally, the biogas is conveyed to a biogas storage tank through a pipeline.
10. A method for improving the yield of coal-to-methane by using waste organic matters in a coal mine is characterized by comprising the following steps: firstly, preparing waste organic matters into powder on the ground through a pulverizer, and placing the powder in a waste organic matter pretreatment reaction container; finishing the pretreatment process according to the preset time to obtain a waste organic matter pretreatment liquid-phase product; injecting the pretreatment liquid phase product, nutrient solution and microbial flora into the coal bed through a pre-drilled well under static pressure; completing in-situ combined anaerobic fermentation of waste organic matter liquid phase products and coal in a coal mine; and finally, conveying the biogas generated in the underground coal bed to a ground natural gas pipeline through a gas pipeline.
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