CN114921518A - Nano-microorganism co-production technology for coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane - Google Patents
Nano-microorganism co-production technology for coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane Download PDFInfo
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Abstract
The invention discloses a joint production technology of coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane nanometer microorganisms, which comprises the steps of injecting a nanometer expanding agent, a coal acid active agent, an expanding agent, liquid nitrogen or liquid carbon dioxide into a coal bed, dissolving, shrinking and expanding to build a nanometer and huge volume crack to communicate a space for permeation enhancement, displacing and desorbing coal bed gas, changing coal into powder and obtaining a huge activity space by the microorganisms; the hydrolytic zymophyte taking the extracellular nanoenzyme as the main component changes coal into nano coal slime, and the coal slime is sealed and muggy to form water gas; the traditional Chinese medicine hydrogen generation promoter, the coal slime and the water gas generate hydrogen; carbon monoxide is generated by the coal-derived carbon monoxide bacteria; the acetic acid is generated by the coal acetogenic bacteria taking the vinegar koji as the main material; under the action of an exothermic reaction heat gain and a coal gasification catalyst, stewing for 50 days, and allowing coal methanogens to organically and inorganic generate methane from coal slime, so that the simultaneous mining of coal bed gas, coal-to-hydrogen gas and coal-to-methane gas is realized; the ground absorbs harmful gases such as carbon monoxide, hydrogen sulfide and the like, and the ore sand is filled to prevent the ground from collapsing, so that the three gases are produced safely and environmentally.
Description
Technical Field
The invention relates to the technical field of coal mining, in particular to a nano-microorganism co-production technology for adsorbing gas, changing coal into hydrogen and changing coal into methane in a coal bed.
Background
Mendeleev proposed the extraction of energy-containing components in coal in 1888, and since the last 30 centuries, major coal-producing countries such as America, Germany, original Soviet Union, etc. have been actively researched. China began to carry out underground coal gasification tests in 1958. In 1980, more than ten mine areas such as Xuzhou, Tangshan and Shandong Xinwen were tested in sequence, and breakthrough of underground gasification from test to application was primarily realized. In 2007, the inner Mongolia Wulan cenbu shaft-free gasifier was successfully ignited. The first industrial gasification furnace is built in 2013 and put into trial production, and the single-furnace capacity is over 50 ten thousand square/day and is very unstable. The development of the mobile unit gasification technology was successful in 2014 8 months. The physical coal mining is changed into chemical coal mining. The coal is burned and gasified underground through a multistage reactor or a plurality of furnaces.
It is not popularized all over the world, and not popularized in China. The difficulty is:
firstly, the main idea of underground coal gasification is to burn underground coal in a controlled manner and generate combustible gas through the thermal and chemical actions on the coal. The reactor or the combustion furnace is actually built underground in a coal mine, and the reactor or the combustion furnace is a multi-stage reactor or a plurality of combustion furnaces. This concept determines that underground coal gasification is difficult to achieve.
Secondly, the existing coal-derived hydrogen producing bacteria, coal-derived carbon monoxide bacteria, coal-derived carbon dioxide bacteria, coal-derived acetic acid bacteria and coal-derived methane producing bacteria are only held by a few advanced researchers, are low in quantity and expensive, are difficult to realize industrial coal hydrogen production and methane production, and are high in cost.
Thirdly, it is difficult to make hydrogen producing bacteria, carbon monoxide producing bacteria, carbon dioxide producing bacteria, acetic acid producing bacteria and methane producing bacteria fully play a role without changing the coal into the nano-scale coal slime.
Fourth, coal seams without coal mine tunnels cannot be mined. The coal bed rock is particularly compact, the coal bed methane is absorbed in the pores of 0.5 nanometer, and the permeability is only 0.5 millidarcy. No activity space for coal-produced hydrogen bacteria, coal-produced carbon monoxide bacteria, coal-produced carbon dioxide bacteria, coal-produced acetic acid bacteria and coal-produced methane bacteria.
Fifthly, the hydrogen and methane production from coal must be carried out in a high-temperature reactor or a combustion furnace, but cannot be carried out at normal temperature.
Sixth, the ground collapses.
Seventh, no hydrogen-producing bacteria, carbon monoxide-producing bacteria, carbon dioxide-producing bacteria, acetic acid-producing bacteria, and methane-producing bacteria are added to the existing methane tank, and the methane tank does not play a due role.
Therefore, how to provide a simple, practical, safe and environment-friendly nano microorganism co-production technology for coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane, is a technical problem to be solved urgently by technical personnel in the field.
Disclosure of Invention
In view of this, the invention aims to provide a nano-microorganism coproduction technology for coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane, which can realize underground coal bed gas (adsorbed gas), coal slime to generate hydrogen gas and coal slime to generate methane gas, is safe and environment-friendly, and adopts three gases simultaneously, so as to solve the defects in the prior art;
in order to achieve the purpose, the invention adopts the following principle: injecting a nanometer expanding agent, a coal acid active agent and an expanding agent into the coal bed, dissolving, corroding and expanding to build a communicated pore space, improving permeability, and desorbing coal bed gas; the hydrolytic zymophyte changes coal into nano-particle coal slurry, and the coal slurry is sealed and slowly muggy to form water gas; inorganic and organic hydrogen generation by the coal hydrogen producing bacteria; carbon monoxide is generated by the coal-derived carbon monoxide bacteria; generating acetic acid by coal acetogenic bacteria; under the action of an exothermic reaction heat gain and a coal gasification catalyst, the coal methanogen can organically and organically generate methane from coal slime, so that the coal bed gas, the coal-to-hydrogen gas and the coal-to-methane gas can be simultaneously extracted. The ground absorbs harmful gases such as carbon monoxide, hydrogen sulfide and the like, and the ore sand is filled to prevent the ground from collapsing, so that the three gases are produced safely and environmentally.
Preferably, the coal seam nano expanding agent dissolves coal rocks to expand the pore diameter and increase permeability, and comprises the following components in percentage by mass: 1 to 8 percent of trichloroacetic acid and 1 to 10 percent of trichloroacetic acid carbitol, 5 to 10 percent of formic acid and 5 to 15 percent of sorbic acid ester or propionic acid triester, 5 to 15 percent of formic acid and 5 to 15 percent of sorbic acid ester, 1 to 10 percent of phosphoric acid and 1 to 10 percent of propionic acid triester or sorbic acid ester, 1 to 10 percent of dibutyl sulfamate or diethylene sulfamate, 1 to 15 percent of p-toluenesulfonic acid and 1 to 15 percent of diethylene tosylate or diethyl tosylate, 1 to 8 percent of propionic acid and 1 to 8 percent of dibutyl propionate or propionic acid triester, 5 to 10 percent of lactic acid and 5 to 10 percent of lactic acid triglyceride or tributyl lactate, 5 to 15 percent of oleic acid or isopropyl oleate or n-amyl oleate, 1 to 10 percent of citric acid or isoamyl citrate, and 5 to 30 percent of sulfuric acid or sorbic acid ester.
Preferably, the coal acid active agent comprises the following components in percentage by mass: 5 to 15 percent of hydrochloric acid, 5 to 30 percent of acetic acid, 2 to 15 percent of formic acid, 2 to 10 percent of sulfuric acid and 5 to 10 percent of phosphoric acid; the coal acid active agent can dissolve the ash content of the coal bed to enlarge the pore diameter and increase permeability;
preferably, the swelling agent comprises, by mass percent: 5 to 40 percent of urea, 0.5 to 30 percent of sodium bicarbonate, 0.5 to 15 percent of sodium carbonate, 0.5 to 15 percent of potassium bicarbonate, 0.5 to 15 percent of ammonium carbonate, 0.5 to 15 percent of ammonium bicarbonate, 1 to 5 percent of urease, 0 to 5 percent of cassia seed, 0 to 5 percent of oviductus ranae and 0 to 5 percent of monopotassium phosphate; and closing the well for 2 to 3 hours to ensure that the coal acid active agent and the expanding agent fully react to generate carbon dioxide to expand the pore size of more than micron and increase the permeability, so as to promote full formation of an expansion joint and provide a quick channel for injecting liquid nitrogen or liquid carbon dioxide.
Preferably, the coal seam supercooling agent for liquid nitrogen is ester, ether, alcohol and amine with the melting point or the freezing point of below 70 ℃ below zero, and the refrigerant comprises the following components in percentage by mass: 10-30% of acetate (2-ethylbutyl acetate, 2-ethylhexyl acetate, methylcyclohexyl acetate and methyl acetoacetate), 10-20% of butyrate (butyl butyrate, amyl butyrate and isoamyl butyrate), 10-40% of isoamyl propionate, 10-40% of acrylate (2-ethylhexyl acrylate, ethyl methacrylate and butyl methacrylate), 10-30% of glyceride (triacetin and butyrate), 5-15% of ether (ethyl sulfide, diethylene glycol methyl ether or ethyl ether), 5-15% of isoamyl alcohol and 5-20% of N, N-diethylformamide.
Preferably, the coal bed supercooling agent for the liquid carbon dioxide is ester or ether with the melting point or the freezing point lower than minus 50 ℃, and the coal bed supercooling agent comprises the following components in percentage by mass: 10 to 40 percent of acetate (methyl isoamyl acetate, cyclohexyl acetate and benzyl acetate), 10 to 40 percent of methyl lactate, 10 to 40 percent of trimethyl phosphate, 10 to 40 percent of triethyl citrate, 10 to 30 percent of ether (diethylene glycol ethyl ether, diethylene glycol butyl ether, ethylene glycol dibutyl ether and ethylene glycol hexyl ether) and 5 to 20 percent of N, N-dimethylformamide.
Preferably, the hydrogen producing bacteria for coal comprise, by mass percent: 10 to 30 percent of hydrolytic zymocyte, 5 to 20 percent of active metal, 5 to 40 percent of acid activator or alkaline activator, 3 to 20 percent of traditional Chinese medicine hydrogen generation accelerant, exothermic reaction or 0.5 to 3 percent of thermite and 0.5 to 3 percent of coal gasification catalyst; the coal hydrogen producing bacteria take coal slime as a nutrient medium, and active metal and acidic activator or alkaline activator generate hydrogen organically and inorganically under the action of traditional Chinese medicine hydrogen generation promoter, exothermic reaction or thermite and coal gasification catalyst;
wherein, by mass percent, the active metal comprises: 0 to 5 percent of potassium, 0 to 5 percent of sodium, 0 to 5 percent of magnesium, 0 to 10 percent of aluminum, 5 to 15 percent of zinc and 15 to 35 percent of iron.
Preferably, the carbon monoxide producing bacteria for coal comprise the following components in percentage by mass: 10 to 30 percent of hydrolytic zymocyte, 10 to 20 percent of active metal oxide, 5 to 20 percent of acid activator, 5 to 20 percent of boric oxide or boric acid, and 3 to 10 percent of thermite; the coal-derived carbon monoxide bacteria take coal slime as a culture medium, active metal oxide as an accelerant and oxidizing acid or boric acid as a synthetic culture medium to generate carbon monoxide and hydrogen.
The coal-derived carbon dioxide bacteria comprise the following components in percentage by mass: 10 to 30 percent of hydrolytic zymocyte, 10 to 30 percent of active metal oxide, exothermic reaction or 3 to 10 percent of thermite and 1 to 5 percent of coal gasification catalyst; the carbon dioxide producing bacteria of coal use coal slime as a culture medium, active metal oxide and carbon monoxide as promoters to generate carbon dioxide; meanwhile, the expanding agent and the coal acid active agent can be used for inorganic rapid generation of carbon dioxide.
The coal acetogenic bacteria comprise the following components in percentage by mass: 5 to 20 percent of ethanol, 10 to 20 percent of sugar, 10 to 30 percent of vinegar yeast, 10 to 30 percent of distiller's yeast, 10 to 20 percent of tannase or tannase, 5 to 20 percent of pancreatin, 5 to 15 percent of acetobacter, 5 to 15 percent of clostridium and 0.5 to 5 percent of coal gasification catalyst; the acetic acid is generated by coal acetogenic bacteria, and the coal slime is used as a culture medium.
The methanogen coal comprises the following components in percentage by mass: 5 to 20 percent of bacteroides fragilis, 5 to 20 percent of clostridium histolyticum, 15 to 30 percent of EM probiotic raw bacteria, 15 to 40 percent of yeast, 5 to 20 percent of lactic acid bacteria, 5 to 20 percent of alkaline protease and 1 to 5 percent of coal gasification catalyst; the methanogen can catalyze carbon monoxide and hydrogen to generate methane, carbon dioxide and hydrogen to generate methane, and acetic acid and acetate to generate methane.
Preferably, the hydrolytic fermentation bacteria comprise the following components in percentage by mass: 5 to 30 percent of lipase, 5 to 30 percent of urease, 5 to 10 percent of bromelain, 2 to 10 percent of animal protein hydrolase, 5 to 20 percent of amylase, 5 to 15 percent of pectinase, 3 to 10 percent of lysozyme, 5 to 30 percent of bean curd enzyme, 5 to 30 percent of edible fungi, 5 to 10 percent of bean feeding enzyme, 5 to 10 percent of acid vegetable enzyme, 3 to 12 percent of neutral protease, 5 to 10 percent of acid protease, 3 to 10 percent of aspergillus niger, 2 to 10 percent of cellulase, 1 to 8 percent of glucanase, 0.5 to 5 percent of phospholipase, 1 to 10 percent of gelatinase, 0 to 5 percent of DNA enzyme and 0 to 10 percent of RNA enzyme; the hydrolytic fermentation tubes can ferment the coal into coal slime.
Preferably, the alkaline active agent comprises: 5 to 40 percent of sodium hydroxide, 5 to 40 percent of potassium hydroxide, 0.5 to 20 percent of calcium oxide, 0 to 10 percent of sodium hydrosulfite, 0 to 10 percent of basic carbonate, 0.5 to 10 percent of sodium fluoride, 0.5 to 10 percent of potassium fluoride, 0.5 to 10 percent of ammonium bifluoride and 0.5 to 10 percent of ammonium fluoride;
preferably, the traditional Chinese medicine hydrogen generation accelerant comprises the following components in percentage by mass: 10 to 30 percent of astragalus root, 5 to 20 percent of largehead atractylodes rhizome, 4 to 15 percent of liquorice, 4 to 25 percent of coconut meat and 15 to 30 percent of lily.
Preferably, the thermite comprises the following components in percentage by mass: 0 to 15 percent of aluminum, 0.5 to 10 percent of ferric oxide, 0.5 to 10 percent of ferroferric oxide, 0.5 to 10 percent of manganese dioxide, 0.5 to 10 percent of vanadium pentoxide, 0.5 to 10 percent of chromium oxide and 0 to 10 percent of cryolite;
the coal gasification catalyst comprises the following components in percentage by mass: 0 to 25 percent of Ni nickel, 5 to 10 percent of titanium dioxide, 5 to 10 percent of manganese dioxide, 5 to 10 percent of iron, 0 to 3 percent of nickel, 0 to 1 percent of rhodium and 0 to 1 percent of ruthenium.
Preferably, the exothermic reaction comprises: thermite reaction, acid-base neutralization reaction, reaction of active metal and water or acid, and dissolving of alkaline activator in water.
Preferably, the active metal oxide comprises, by mass percent: 0 to 5 percent of sodium oxide, 0 to 5 percent of potassium oxide, 0 to 15 percent of calcium oxide, 0.5 to 15 percent of magnesium oxide, 5 to 30 percent of aluminum oxide, 5 to 30 percent of zinc oxide and 0 to 15 percent of copper oxide.
The method for coproducing the coal bed adsorbed gas, the coal-to-hydrogen gas and the coal-to-methane nano-microorganisms comprises the following steps of injecting reagents with different mass proportions into an underground coal bed step by step:
(1) injection formula: 0.5 to 2 percent of coal bed nanometer expanding agent or 0.3 to 0.8 percent of hydrolytic zymophyte and the balance of water. The injection amount is 500 to 1000. The concentration was increased from 0.5% to 2%. The injection mode is as follows: the output is 0.5 square/min to 3.5 square/min, and the nanometer aperture is enlarged in a pulse mode.
(2) Injection formulation: 0.5 to 1.5 percent of coal acid active agent and the balance of water. The injection amount is 200 to 500. The injection mode is as follows: the pulse slow injection with the discharge capacity of 2.5 square/min to 3.5 square/min. Pulse-type expansion of micron pore size.
(3) Injection formula: 0.5 to 1.5 percent of coal seam nanometer expanding agent, or 0.3 to 0.8 percent of hydrolytic zymophyte and the balance of water. The injection amount is 20 to 50 square. The injection mode is as follows: the pulse slow injection with the displacement of 0.5 square/min to 3.5 square/min.
(4) Injection formula: 2 to 5 percent of expanding agent and the balance of water. The injection amount is 200 to 500. The injection mode is as follows: pulse injection with the discharge capacity of 3.5 square/min to 5.5 square/min. The pulsed expansion expands the fracture width and length. And closing the well for 2 to 3 hours to promote the swelling agent to fully swell and form seams.
(5) Injecting coal bed refrigerant of 90-99.9% of liquid nitrogen or liquid carbon dioxide into a place from 0.5 to 2, then injecting liquid nitrogen or liquid carbon dioxide into a place from 50 to 200 at a large discharge amount, then injecting coal bed refrigerant of 90-99.9% of liquid nitrogen or liquid carbon dioxide into a place from 0.5 to 1, then injecting coal bed refrigerant of 10% of liquid nitrogen or liquid carbon dioxide into a place from 20 to 10 (the balance being water), and closing the well for 2-3 days.
Since liquid nitrogen at 1 st side rapidly changes to gaseous nitrogen at 862.067 st side and liquid carbon dioxide at 1 st side rapidly changes to gaseous carbon dioxide at 545 st side, the liquid to gaseous state will expand dramatically. And (3) injecting coal seam supercooling agent before and after injecting the liquid nitrogen or the liquid carbon dioxide, aiming at preventing the liquid nitrogen or the liquid carbon dioxide from being blocked by freezing when meeting water in a shaft and preventing the liquid nitrogen or the liquid carbon dioxide from being violently expanded in the shaft, so that huge seams are caused by the violent expansion of the liquid nitrogen or the liquid carbon dioxide in the coal seam. And closing the well for 2-3 days so that the liquid nitrogen or the liquid carbon dioxide is fully and violently expanded in the coal bed. The injection of liquid nitrogen or liquid carbon dioxide has several unexpected effects: coal is organic matter, and is particularly easy to shrink and crack; the liquid nitrogen or the liquid carbon dioxide is changed into gas state to be expanded violently to form a giant joint; displacing methane gas; the coal is changed into coal dust through violent expansion, and a foundation is laid for accelerating the coal dust to be changed into coal slime through microorganisms.
(6) Injection formulation: 1 to 1.5 percent of hydrolytic zymocyte, 0.6 to 1 percent of coal-produced hydrogen bacteria, 0.5 to 0.8 percent of coal-produced carbon monoxide bacteria, 0.4 to 0.6 percent of coal-produced carbon dioxide bacteria and the balance of water. The injection amount is 200 to 500. The injection mode is as follows: the pulse slow injection with the discharge capacity of 3.5 square/min to 5.5 square/min.
(7) Injection formula: 0.8 to 1.2 percent of hydrolytic zymocyte, 0.6 to 1 percent of coal-derived hydrogen bacteria, 0.5 to 0.8 percent of coal-derived carbon monoxide bacteria, 0.4 to 0.6 percent of coal-derived carbon dioxide bacteria, 0.4 to 0.6 percent of coal-derived acetogenic bacteria and the balance of water. The injection amount is 200 to 500. The injection mode is as follows: the pulse slow injection with the discharge capacity of 3.5 square/min to 5.5 square/min.
(8) Injection formula: 0.6 to 1 percent of coal-derived hydrogen producing bacteria, 0.5 to 0.8 percent of coal-derived carbon monoxide bacteria, 0.4 to 0.6 percent of coal-derived carbon dioxide bacteria, 0.4 to 0.6 percent of coal-derived acetogenic bacteria, 0.4 to 0.6 percent of coal-derived methanogen bacteria and the balance of water. The injection amount is 200 to 500. The injection mode is as follows: the pulse slow injection with the discharge capacity of 3.5 square/min to 5.5 square/min.
(9) Injection formula: 0.5 to 0.8 percent of coal-derived hydrogen bacteria, 0.6 to 1 percent of coal-derived carbon monoxide bacteria, 0.4 to 0.6 percent of coal-derived carbon dioxide bacteria, 0.8 to 1.2 percent of coal-derived acetogenic bacteria, 1 to 1.5 percent of coal-derived methanogen bacteria and the balance of water. The injection amount is 200 to 500. The injection mode is as follows: the pulse slow injection with the discharge capacity of 3.5 square/min to 5.5 square/min.
(10) Injection formula: 1 to 1.5 percent of methanogen from coal and the balance of water. The injection amount is 200 square to 500 square. The injection mode is as follows: the pulse slow injection with the discharge capacity of 3.5 square/min to 5.5 square/min.
(11) 2% -5% potassium chloride 20 to 30 formula of displacement fluid. And closing the well for 15 to 20 days.
(12) Injecting 2-5% of alkaline active agent 200-1000.
(13) Injecting 2-5% of displacement liquid and 20-30 parts of potassium chloride. And closing the well for 25 to 30 days. And opening the well to produce hydrogen and methane.
In order to produce coal bed gas, hydrogen and methane gas safely and environmentally, ammonium chloride or ammonium sulfate and sodium hydroxide or potassium hydroxide aqueous solution are filled in an opening near a wellhead to absorb carbon monoxide, or the cultivated chlorophytum comosum absorbs sulfur dioxide and carbon monoxide; CuSO is filled in an opening near the wellhead 4 Absorbing hydrogen sulfide by the aqueous solution; the mineral rock is crushed into 20-mesh sand grains, and the nano fracturing fluid is used for carrying sand and injecting the sand into a filling gap to prevent the ground from collapsing.
The application of the coal bed adsorption gas and coal-to-hydrogen and coal-to-methane nanometer microorganism co-production technology in the methane tank comprises the following steps of injecting reagents with different mass proportions into the methane tank step by step:
(1) injection formula: 1 to 2.5 percent of hydrolytic zymocyte and the balance of water are stirred with coal powder and poured into a methane tank;
(2) injection formula: 0.5 to 1.5 percent of coal acidic active agent and the balance of water are poured into the methane tank;
(3) injection formula: 1 to 2.5 percent of hydrolytic zymophyte and the balance of water are stirred with coal powder and poured into a methane tank;
(4) injection formula: 2 to 5 percent of expanding agent and the balance of water are poured into the methane tank;
(5) injection formulation: 0.6 to 1 percent of hydrolytic zymocyte, 1 to 1.5 percent of coal hydrogen producing bacteria, 0.5 to 0.8 percent of coal carbon monoxide producing bacteria, 0.4 to 0.6 percent of coal carbon dioxide producing bacteria, 1 to 1.5 percent of coal methane producing bacteria and the balance of water are stirred with coal dust and poured into a methane tank;
(6) pouring 200-1000 parts of 2-5% alkaline active agent after 15-20 days;
(7) and after 25-30 days, opening the well to produce hydrogen and methane.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
novelty of the invention:
firstly, according to the combined action of inorganic gas production and organic gas production, the hydrogen producing bacteria, carbon monoxide producing bacteria, carbon dioxide producing bacteria, acetic acid producing bacteria and methane producing bacteria are prepared by using microbial bacteria or enzyme as main materials.
Secondly, preparing the coal hydrogen producing bacteria according to the tradition of Chinese folk food bacteria and Chinese medicinal bacteria; preparing coal-derived carbon monoxide bacteria, coal-derived carbon dioxide bacteria, coal-derived acetogenic bacteria and coal-derived methanogenic bacteria.
Thirdly, coal is changed into coal slime with nanometer size fraction (hereinafter referred to as coal slime) by using coal hydrolytic fermentation bacteria.
Fourthly, the coal bed nanometer expanding agent, the coal acid active agent and the expanding agent are used for permeation enhancement and desorption of coal bed gas, and a seepage activity space for various bacteria microorganisms is built in the coal bed.
Fifthly, a reactor or a combustion furnace is not built under the coal mine, high temperature is not needed, only the exothermic reaction reaches normal temperature, and the reaction is directly carried out in a gas-tight coal bed for fifty days, and the high temperature is changed with time to obtain hydrogen and methane. The methane gas can be produced by producing hydrogen gas from deep coal beds or thin coal beds, or by producing hydrogen gas from coal in methane tanks.
And sixthly, crushing the mineral rock into 20-mesh sand grains, and carrying sand with nano fracturing fluid to fill the void so as to prevent the ground from collapsing.
The invention has the innovativeness that:
firstly, building a microbial enzyme nano-scale coal slime activity space in a coal seam.
Injecting a coal seam nanometer expanding agent into the coal seam to ensure that the nanometer pores of the coal rock are open and throat-expanded, and the pore diameters of the micrometer, millimeter and centimeter are smooth; injecting coal acid active agent to erode the ash content of the coal bed, and further enlarging each level of pore gaps; the expansion agent is injected to react with the coal acid active agent to generate carbon dioxide, so that the seam is formed by violent expansion, and the permeability is greatly improved.
And (3) injecting coal seam supercooling agent before and after injecting the liquid nitrogen or the liquid carbon dioxide, aiming at preventing the liquid nitrogen or the liquid carbon dioxide from being blocked by freezing when meeting water in a shaft and preventing the liquid nitrogen or the liquid carbon dioxide from being violently expanded in the shaft, so that huge seams are caused by the violent expansion of the liquid nitrogen or the liquid carbon dioxide in the coal seam.
Dissolving a plurality of repeated joint making methods of through joint expansion, throat expansion, joint making by contraction and joint making by violent expansion, and building a huge communicated pore space, so that the coal bed gas is desorbed and the adsorbed gas is replaced, the high yield of the coal bed gas is obtained, the coal is pulverized, the microbial bacteria and the enzyme hydrolysis zymogens can comprehensively permeate all nanopores of the coal bed, and the coal is actively and quickly changed into coal slime.
Secondly, the hydrolytic zymophyte takes extracellular nano enzyme as a main component and has traditional edible enzyme and edible fungus in China, coal is changed into nano particle coal slime, and the nano particle coal slime is sealed and slowly heated for about 50 days to be changed into water gas.
Thirdly, the hydrogen producing bacteria of coal generates hydrogen through the inorganic generation of active metal and acid activator (inorganic acid); hydrogen is generated by the active metal and an acid activator (organic acid); the traditional Chinese medicine hydrogen generation promoter generates hydrogen; and generating hydrogen by the coal slime and the water gas.
Fourthly, coal-derived carbon monoxide bacteria pass through, and coal slime and active metal oxides generate carbon monoxide; the coal slime and the water gas generate carbon monoxide.
Fifthly, the coal acetogenic bacteria mainly take sugar, vinegar yeast and distiller's yeast which are commonly used in China and coal slime as a nutrient medium to generate acetic acid.
Sixthly, using the conventional low-price strains in China to generate methane from the coal slime at the temperature lower than 60 ℃ in an inorganic and organic manner without using rare and expensive strains. The method realizes the simultaneous mining of three gases, namely underground coal bed gas (adsorbed gas), coal slime hydrogen and coal slime methane, avoids the danger of gas explosion and simplifies the complex working procedures of coal mining. The ground absorbs harmful gases such as carbon monoxide, hydrogen sulfide and the like, and the ore sand is filled to prevent the ground from collapsing, so that the three gases are produced safely and environmentally.
The beneficial effects of the above technical scheme are:
the shallow coal reserves in China are 1 trillion and more tons, wherein 3317 trillion base reserves and 6872 trillion resources. The heat released from complete combustion of a ton of coal is converted to 795.5 square of natural gas.
Manual mining destroys the land directly by about 157 million hectares. About 2000 people need to be migrated per 1000 million tons of coal mined. The discharge amount of waste water and sewage of coal mines in China reaches 27.5 hundred million tons. Exhaust gas is discharged, and the atmospheric environment is damaged. 4500 million tons of washing gangue, 4000 million tons of coal washing wastewater and 200 million squares of coal slime are discharged every year in the coal washing country.
Coal is also present in 5000 m depth underground. Deep coal and thin coal layers can not be extracted manually.
The invention has practicability, realizes the simultaneous production of three gases of coal bed gas (adsorbed gas, often called as gas), coal-to-hydrogen gas and coal-to-methane gas, flows to the well bottom from the coal layer, flows to the well head from the well bottom, flows to a user, completely flows in a closed and controllable environment, has controllable harmful gas, prevents ground collapse due to ore sand filling, and is safe and environment-friendly to produce the three gases.
The combustion value of methane gas and hydrogen gas is very high. The gas is transported by pipeline. Deep coal and thin coal layers which cannot be mined artificially can be mined. After the invention realizes the industrialized exploitation, the energy of China is thoroughly solved in a strategic way, China will become the first export big country of coal bed methane gas all over the world, and any foreign strength cannot prevent the China from advancing.
Therefore, the invention has extremely high economic value, good social benefit, safety and environmental protection.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments; all other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The embodiment 1 of the invention discloses an experiment for injecting a 1% coal seam nanometer expanding agent into a rock core.
The formula of the coal seam nano expanding agent comprises the following components:
6% of carbitol trichloroacetate, 8% of formic acid, 10% of tricarballyl formate, 10% of phosphoric acid, 6% of pyriftalid, 6% of p-toluenesulfonic acid, 4% of diethyl p-toluenesulfonic acid, 4% of dibutyl propionate, 6% of propionic acid, 4% of tributyl lactate, 4% of oleic acid, 10% of n-pentyl oleate, 8% of isoamyl citrate and 14% of pyriftalid sulfate.
The coal rock core is placed in a core holder, 1% of coal bed nanometer expanding agent and the balance of water are injected according to the standard, the pore diameter and the permeability of coal rock nanometer pores change as shown in the following table, the pore diameter of the nanometer pores is increased after displacement, and the permeability is increased.
| Before displacement | After displacement | Increase in amount | |
| Nanopore 1 pore size, nm | 1531 | 1567 | 36 |
| Nanopore 2 pore diameter, nm | 680.9 | 681.9 | 1 |
| Nanopores 3 pore size, nm | 578.7 | 592.2 | 13.5 |
| Nanopores 4 Aperture, nm | 715.6 | 743.9 | 28.3 |
| Permeability, millidarcy | 0.05 | 1.25 | 1.2 |
Example 2
Example 2 of the present invention discloses permeability test results before and after coal core liquid nitrogen soaking as shown in the following table, and cracks develop after coal core liquid nitrogen soaking. Coal is an organic matter, and the shrinkage crack at-190 ℃ is extremely good, even completely broken. Liquid nitrogen at 1 st rapidly changes to gaseous nitrogen at 862.067 st, which is particularly good if the seam is formed by violent expansion.
Example 3
The embodiment 3 of the invention discloses that hydrolytic zymophyte turns coal into nano-scale (with the particle size of 75nm) coal slime.
The formula is as follows: 5g of hydrolytic zymophyte (0.5g of lipase, 0.5g of urease, 0.3g of bromelain, 0.5g of animal protein hydrolase, 0.4g of amylase, 0.3g of pectinase, 0.2g of lysozyme, 0.4g of fermented bean curd, 0.3g of neutral protease, 0.3g of acid protease, 0.3g of Aspergillus niger, 0.3g of cellulase, 0.3g of glucanase, 0.2g of phospholipase, 0.2g of gelatinase, 0.1g of DNase, 0.1g of RNase.) +60g of coal +135ml of water, homogenized and left to stand for 15 days. The particle size is 75nm, and the particle size is 200 meshes according to the number of quartz sand meshes.
Example 4
Embodiment 4 of the invention discloses a method for generating hydrogen and carbon monoxide by using hydrogen producing bacteria
19g coal slurry (example 1) +21g hydrogen producing bacteria for coal [ 2.5g hydrolytic fermentation bacteria (example 1) +5g active metal (2g zinc Zn, 3g iron Fe) +8g acidic activator [ 10g (31% hydrochloric acid), 3g acetic acid, 1.5g formic acid, 0.5g sulfuric acid, 1g phosphoric acid ] +2g hydrogen generation promoter for traditional Chinese medicine (0.4g radix astragali, 0.3g Atractylodis rhizoma, 0.5g licorice, 0.3g coconut meat, 0.5g lily), 2.5g thermite (0.5g FeO, 0.5g Fe3O4, 0.6g MnO2, 0.4g vanadium pentoxide V2O5, 0.4g chromium oxide Cr2O3, 0.5 g) + cryolite 1g coal gasification catalyst (0.4gNi Ni, 0.3g TiO2, 0.3g manganese dioxide +160 ml) water. And (4) stirring uniformly. And (4) loading into a micro reaction kettle.
First, the generation of hydrogen gas is detected
(1) After five minutes, gas produced by the micro reaction kettle passes through the clear lime water, and the lime water does not become turbid; (2) the solid changed from black to red copper by the glowing copper oxide; (3) the solid turns blue by anhydrous copper sulfate; (4) by clarifying the lime water, the lime water does not become cloudy.
The generation of hydrogen can be confirmed by detection. The reason is that hydrogen has reducibility, H2+ CuO ═ Cu + H2O, and black copper oxide turns red elemental copper after burning. Anhydrous copper sulfate has the property of changing into blue when meeting water.
Second step, detecting the formation of hydrogen and carbon monoxide
(1) After 10 days, the gas produced by the micro reaction kettle passes through the clear lime water, and the lime water becomes turbid; (2) clarifying the lime water until the lime water is not turbid; (3) the solid changed from black to red copper by the glowing copper oxide; (4) the solid turned blue by anhydrous copper sulfate; (5) by clarifying the lime water, the lime water becomes turbid.
The formation of hydrogen and carbon monoxide can be confirmed by detection. The reason is that hydrogen has reducing property, carbon monoxide also has reducing property of CO + CuO + Cu + CO2, black copper oxide turns into red elemental copper after being heated, and carbon dioxide turns lime water turbid.
Example 5
Embodiment 5 of the invention discloses a coal-derived carbon dioxide bacterium
The formula is as follows: 20g of coal slime (example 1) +28g of carbon dioxide producing bacteria for coal (15 g of hydrolytic zymogen (see example 1) +10g of active metal (see example 2) +2g of thermite (see example 2) +1g of coal gasification catalyst (see example 2)) +152ml of water, stirring uniformly and then filling into a miniature reaction kettle.
After 10 days, the gas produced by the micro reaction kettle is proved to generate carbon dioxide by clarifying lime water, and the lime water becomes turbid.
In addition, the formula: 20g of expanding agent (3.5g of urea +3g of sodium bicarbonate +2g of sodium carbonate +2g of potassium carbonate +1g of potassium bicarbonate +1g of ammonium carbonate +3g of ammonium bicarbonate +2g of urease +0.5g of cassia seed +0.5g of oviductus ranae +0.5g of potassium dihydrogen phosphate) +20g of coal acid activator (10g [ 31% hydrochloric acid ] +4g of acetic acid, +3g of formic acid +1.5g of phosphoric acid +1.5g of sulfuric acid) +60g of water. And (4) loading into a micro reaction kettle.
After 5 minutes, the gas produced by the micro reaction kettle is proved to generate carbon dioxide by clarifying lime water, and the lime water becomes turbid.
Example 6
Embodiment 6 of the invention discloses a coal-derived carbon monoxide bacterium
The formula is as follows: 12g coal slurry (example 1) +28g carbonous CO bacteria [ 2.5g hydrolytic ferments (example 1) +15g active metal oxide (2g sodium oxide +2g potassium oxide +0.5g calcium oxide +2g magnesium oxide +5g aluminium oxide +3g zinc oxide +0.5 copper oxide) +3g coal acid activator (example 3) +5g boric acid +2.5g thermite (see example 2) ] +160ml water. After being stirred evenly, the mixture is put into a miniature reaction kettle.
(1) After 20 days, gas produced by the micro reaction kettle passes through the clear lime water, and the lime water becomes turbid; (2) clarifying the lime water until the lime water is not turbid; (3) the solid changed from black to red copper by the glowing copper oxide; (4) the solid does not change color through anhydrous copper sulfate; (5) by clarifying the lime water, the lime water becomes turbid.
The formation of carbon monoxide can be confirmed by detection. The reason is that until carbon dioxide is absent, CO + CuO + CO is hot due to the reduction of carbon monoxide 2 The black copper oxide turns into red elemental copper after being burnt, and the lime water turns turbid by the carbon dioxide.
Example 7
Embodiment 7 of the invention discloses the generation of acetic acid by coal acetogenic bacteria
The formula is as follows: 20g of coal slurry (example 1) +15g of coalacetogenic bacteria [ 2g of brown sugar, 5g of vinegar koji, 3g of distillers yeast, 1g of tannase, 1g of pancreatin, 1g of acetobacter, 1g of clostridium, 1g of coal gasification catalyst (as in example 2) ] and 165ml of water. Placing the mixture into a micro reaction kettle for sealing.
Opening the switch of the micro reaction kettle after 15 days to make the micro reaction kettle have vinegar smell, adding ethanol into the effluent liquid, and slightly adding sulfuric acid for catalysis to obtain aromatic ethyl acetate. The liquid is ignited to produce gas which passes through anhydrous copper sulfate, and the solid turns blue; by clarifying the lime water, the lime water becomes turbid.
The detection proves that acetic acid is generated because the acetic acid has vinegar smell and reacts with ethanol under the catalysis of sulfuric acid to generate aromatic ethyl acetate. The anhydrous copper sulfate turns blue due to the moisture generated by the acetic acid ignition; the generated carbon dioxide makes the lime water cloudy.
Example 8
Embodiment 8 of the invention discloses methane generation by methanogens of coal
The formula is as follows: 20g of coal slurry (example 1) +5g of coal-derived hydrogen-producing bacteria (example 2) +3g of coal-derived carbon dioxide bacteria (example 3) +4g of coal-derived carbon monoxide bacteria (example 4) +6g of coal-derived acetic acid bacteria (example 5) +18g of coal-derived methanobacteria [ 2g of Bacteroides fragilis +2g of Clostridium histolyticum +3gEM probiotic bacteria +5g of yeast +4g of lactic acid bacteria +1g of alkaline protease +1g of coal gasification catalyst (example 2) ] +144ml of water are placed in a micro-reactor and placed in a sealed manner for 30 days.
Firstly, opening a switch to ignite after 30 days of the micro reaction kettle, covering a dry beaker above the flame, and changing the ignited gas into blue through anhydrous copper sulfate if water drops appear; by clarifying the lime water, the lime water becomes turbid. Demonstrating the possibility of methane. Secondly, 10g of tert-butyl alcohol is added with 90g of water and stirred evenly, and then the mixture is put into a container. Reversely buckling the measuring cup on the tertiary butanol solution, introducing the gas generated by the methanogen in the coal into the measuring cup which is reversely buckled by the miniature steel pipe, draining water and collecting gas, and waiting for the gas generated by the methanogen in the coal to be slowly dissolved. And putting the core into a second micro reaction kettle, and pouring a tert-butyl alcohol solution in which the gas generated by the methanogen of coal is dissolved into the second micro reaction kettle to fill the second micro reaction kettle. Sealing, and freezing in refrigerator for two days. And taking out the core, and igniting for combustion. Covering a dry beaker above the flame, and if water drops appear, changing the ignited gas into blue through anhydrous copper sulfate; by clarifying the lime water, the lime water becomes turbid. The combustible glacial methane was demonstrated to burn.
Example 9
Embodiment 9 of the invention discloses a coal-to-hydrogen coal-to-methane co-production experiment.
Firstly, performing coal core displacement by using a coal bed nanometer expanding agent (abbreviated as A), wherein the coal core displacement is performed by using 5% KCl, 0.8% A and the flow rate of 0.2ml/min, 1% A and the flow rate of 0.5ml/min, 1.5% A and the flow rate of 0.2ml/min, 2% A and 0.5ml/min respectively as shown in a table, and the permeability is improved from 0.41 millidarcy to 10.31 millidarcy, so that the effect of the coal bed nanometer expanding agent is very good. The effect of the concentration increasing pulse displacement is shown in the table below.
And secondly, continuing the coal core displacement, injecting 5% of expanding agent, and then injecting 1% of coal acid active agent.
The formula of the expanding agent is as follows: 10% urea, 20% sodium bicarbonate, 5% sodium carbonate, 10% potassium carbonate, 5% potassium bicarbonate, 5% ammonium carbonate, 10% ammonium bicarbonate, 5% urease, 2% cassia seed, 3% oviductus ranae, and 5% KH 2 PO 4 And (3) potassium dihydrogen phosphate.
The formula of the coal acid active agent comprises the following components: 35% [ 31% hydrochloric acid ], 30% acetic acid, 15% formic acid, 10% sulfuric acid, 10% phosphoric acid.
The coal core is substantially loose pieces.
Thirdly, placing the loosened coal core fragments into a micro reaction kettle, adding 15g of hydrolytic zymocyte into the micro reaction kettle according to the formula in the embodiment 2, stirring evenly, and placing for 10 days. The coal core fragments are changed into coal slurry with the particle size of 75nm (200 meshes).
Fourthly, 21g of coal-derived hydrogen producing bacteria is added into a micro-reactor according to the formula of example 3, 28g of coal-derived carbon dioxide producing bacteria is added into the micro-reactor according to the formula of example 4, 28g of coal-derived carbon dioxide producing bacteria is added into the micro-reactor according to the formula of example 5, 15g of coal-derived acetic acid producing bacteria is added into the micro-reactor according to the formula of example 6, 18g of coal-derived methanogenic bacteria is added into the micro-reactor according to the formula of example 7, water is added, the mixture is stirred uniformly, and the micro-reactor is sealed and placed for 30 days. The test was carried out in the same manner as in example 3, and hydrogen gas was indicated. The test conducted in the same manner as in example 7 revealed methane gas.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention; various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention; thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (11)
1. The joint production technology of the coal bed adsorbed gas, the coal-to-hydrogen gas and the coal-to-methane nanometer microorganism is characterized in that the principle is as follows: injecting a coal bed nanometer expanding agent, a coal acid active agent and an expanding agent into a coal bed, dissolving, corroding and expanding to build a communicated pore space, improving permeability, and desorbing coal bed gas; injecting liquid nitrogen or liquid carbon dioxide under the condition of ensuring that a shaft does not freeze, shrinking and expanding to form a large seam, expanding fine coal powder, and replacing and adsorbing methane; the hydrolytic zymophyte turns coal into nano-particle coal slime, and the coal slime is sealed and slowly stuffy to form water gas; the coal hydrogen producing bacteria generate hydrogen in an inorganic and organic manner; carbon monoxide is generated by the coal-derived carbon monoxide bacteria; the coal acetogenic bacteria generate acetic acid; under the action of exothermic reaction heat gain and coal gasification catalyst, the coal methanogen can organically generate methane from coal slime, so that the coal bed gas, the coal-to-hydrogen gas and the coal-to-methane gas can be simultaneously produced. The ground absorbs harmful gases such as carbon monoxide, hydrogen sulfide and the like, and the ore sand is filled to prevent the ground from collapsing, so that the three gases are produced safely and environmentally.
2. The nano-microorganism coproduction technology of coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane gas as claimed in claim 1, wherein a coal bed nano expanding agent is used for dissolving coal rock nano-pore gaps to enlarge the roar and increase the permeability, a coal bed ash is used for dissolving a coal acid active agent to enlarge the pore size and increase the permeability, and an expanding agent is used for expanding the pore size and increase the permeability by more than micrometers; injecting a coal bed super-cooling agent to ensure that the front end of liquid nitrogen or liquid carbon dioxide of a shaft is not frozen, then injecting the liquid nitrogen or the liquid carbon dioxide for cold contraction and expansion to form a large seam, and then injecting the coal bed super-cooling agent to ensure that the rear end of the liquid nitrogen or the liquid carbon dioxide of the shaft is not frozen, so that coal is pulverized, coal bed adsorbed gas is desorbed, methane is replaced and adsorbed, and a huge space for enabling microorganisms to be fully active is constructed;
the coal seam nanometer expanding agent comprises the following components in percentage by mass: 1-8% of trichloroacetic acid and 1-10% of trichloroacetic acid carbitol, 5-10% of formic acid and 5-15% of sorbic acid ester or propionic acid triester, 5-15% of formic acid and 5-15% of sorbic acid ester, 1-10% of phosphoric acid and 1-10% of propionic acid triester or sorbic acid ester, 1-10% of dibutyl sulfamate or diethylene sulfamate, 1-15% of p-toluenesulfonic acid and 1-15% of diethylene p-toluenesulfonic acid or diethyl p-toluenesulfonic acid, 1-8% of propionic acid and 1-8% of dibutyl propionate or propionic acid triester, 5-10% of lactic acid and 5-10% of lactic acid triglyceride or tributyl lactate, 5-15% of oleic acid or isopropyl oleate or n-amyl oleate, 1-10% of citric acid or isoamyl citrate, and 5-30% of sulfuric acid or sorbic acid ester;
the coal acid active agent comprises the following components in percentage by mass: 5 to 15 percent of hydrochloric acid, 5 to 30 percent of acetic acid, 2 to 15 percent of formic acid, 2 to 20 percent of sulfuric acid and 5 to 10 percent of phosphoric acid;
the expanding agent comprises the following components in percentage by mass: 5 to 40 percent of urea, 0.5 to 30 percent of sodium bicarbonate, 0.5 to 15 percent of sodium carbonate, 0.5 to 15 percent of potassium bicarbonate, 0.5 to 15 percent of ammonium carbonate, 0.5 to 15 percent of ammonium bicarbonate, 1 to 5 percent of urease, 0 to 5 percent of cassia seed, 0 to 5 percent of oviductus ranae and 0 to 5 percent of monopotassium phosphate;
the coal seam refrigerant for liquid nitrogen is ester, ether, alcohol and amine with the melting point or the freezing point lower than minus 70 ℃, and comprises the following components in percentage by mass: 10-30% of acetate (acetic acid-2-ethyl butyl ester, acetic acid-2-ethylhexyl ester, methyl cyclohexyl acetate and methyl acetoacetate), 10-20% of butyrate (butyl butyrate, amyl butyrate and isoamyl butyrate), 10-40% of isoamyl propionate, 10-40% of acrylate (2-ethylhexyl acrylate, ethyl methacrylate and butyl methacrylate), 10-30% of glyceride (triacetin and butyrate), 5-15% of ether (ethyl sulfide, diethylene glycol methyl ether or ethyl ether), 5-15% of isoamyl alcohol and 5-20% of N, N-diethyl formamide;
the coal bed supercooling agent for the liquid carbon dioxide is ester or ether with the melting point or the freezing point lower than minus 50 ℃, and comprises the following components in percentage by mass: 10 to 40 percent of acetate (methyl isoamyl acetate, cyclohexyl acetate and benzyl acetate), 10 to 40 percent of methyl lactate, 10 to 40 percent of trimethyl phosphate, 10 to 40 percent of triethyl citrate, 10 to 30 percent of ether (diethylene glycol ethyl ether, diethylene glycol butyl ether, ethylene glycol dibutyl ether and ethylene glycol hexyl ether) and 5 to 20 percent of N, N-dimethylformamide.
3. The nano-microorganism coproduction technology of coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane according to claim 1, wherein hydrolytic zymogens are used for fermenting coal into coal slurry, and the coal slurry is sealed and slowly smoldered to form water gas;
the hydrolytic zymophyte comprises the following components in percentage by mass: 5 to 30 percent of lipase, 5 to 30 percent of urease, 5 to 10 percent of bromelain, 2 to 10 percent of animal protein hydrolase, 5 to 20 percent of amylase, 5 to 15 percent of pectinase, 3 to 10 percent of lysozyme, 5 to 30 percent of bean curd enzyme, 5 to 30 percent of edible fungi, 5 to 10 percent of bean food enzyme, 5 to 10 percent of acid vegetable enzyme, 3 to 12 percent of neutral protease, 5 to 10 percent of acid protease, 3 to 10 percent of aspergillus niger, 2 to 10 percent of cellulase, 1 to 8 percent of glucanase, 0.5 to 5 percent of phosphoesterase, 1 to 10 percent of gelatinase, 0 to 5 percent of DNA enzyme and 0 to 10 percent of RNA enzyme.
4. The nano-microorganism coproduction technology of coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane according to claim 1, characterized in that hydrogen is generated by using coal hydrogen-producing bacteria, hydrogen is generated by using active metal and acidic activator or alkaline activator in an inorganic manner, and hydrogen is generated by using traditional Chinese medicine hydrogen generation promoter, thermite for increasing heat and coal gasification catalyst for accelerating;
according to the mass percentage, the coal hydrogen producing bacteria comprise: 10 to 30 percent of hydrolytic zymocyte, 5 to 20 percent of active metal, 5 to 40 percent of acid activator or alkaline activator, 3 to 20 percent of traditional Chinese medicine hydrogen generation accelerant, 0.5 to 3 percent of thermite and 0.5 to 3 percent of coal gasification catalyst;
wherein, by mass percent, the active metal comprises: 0 to 5 percent of potassium, 0 to 5 percent of sodium, 0 to 5 percent of magnesium, 0 to 10 percent of aluminum, 5 to 15 percent of zinc and 15 to 35 percent of iron;
the alkaline active agent comprises the following components in percentage by mass: 5 to 40 percent of alkali, 5 to 40 percent of potassium hydroxide, 0.5 to 20 percent of quicklime, 0 to 10 percent of sodium hydrosulfite, 0 to 10 percent of basic carbonate, 0.5 to 10 percent of sodium fluoride, 0.5 to 10 percent of potassium fluoride and 0.5 to 10 percent of NH 4 HF，0.5％～10％(NH 4 ) 2 F；
The traditional Chinese medicine hydrogen generation accelerant comprises the following components in percentage by mass: 10 to 30 percent of astragalus, 5 to 20 percent of largehead atractylodes rhizome, 4 to 15 percent of liquorice, 4 to 25 percent of coconut meat and 15 to 30 percent of lily;
the thermite comprises the following components in percentage by mass: 0 to 15 percent of aluminum, 0.5 to 10 percent of FeO and 0.5 to 10 percent of Fe 3 O 4 ，0.5％～10％MnO 2 0.5 to 10 percent of vanadium pentoxide, 0.5 to 10 percent of chromium oxide and 0 to 10 percent of cryolite;
the coal gasification catalyst comprises the following components in percentage by mass: 10 to 25 percent of Ni nickel, 5 to 10 percent of titanium dioxide, 5 to 10 percent of manganese dioxide, 5 to 10 percent of iron, 0 to 3 percent of nickel, 0 to 1 percent of rhodium and 0 to 1 percent of ruthenium.
5. The nano-microorganism coproduction technology of coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane according to claim 1, characterized in that coal slime is used as a culture medium, active metal oxide is used as an accelerant, boron oxide or boric acid is used as a synthetic culture medium, and carbon monoxide and hydrogen are generated by using bacteria producing carbon monoxide from coal;
according to the mass percentage, the carbon monoxide producing bacteria comprise: 10 to 30 percent of hydrolytic zymocyte, 10 to 20 percent of active metal oxide, 5 to 20 percent of acid activator, 5 to 20 percent of boron oxide or boric acid and 3 to 10 percent of thermite;
the active metal oxide comprises the following components in percentage by mass: 0 to 5 percent of sodium oxide, 0 to 5 percent of potassium oxide, 0 to 15 percent of calcium oxide, 0.5 to 15 percent of magnesium oxide, 5 to 30 percent of aluminum oxide, 5 to 30 percent of zinc oxide and 0 to 15 percent of copper oxide.
6. The nano-microorganism coproduction technology of coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane according to claim 1, wherein the expanding agent and the coal acid activating agent act to inorganic rapidly generate carbon dioxide; coal slime is used as a culture medium, active metal oxide and carbon monoxide are used as promoters, and carbon dioxide is generated by using coal-derived carbon dioxide bacteria.
According to the mass percentage, the coal-derived carbon dioxide bacteria comprise: 10 to 30 percent of hydrolytic zymocyte, 10 to 30 percent of active metal oxide, 3 to 10 percent of thermite and 1 to 5 percent of coal gasification catalyst.
7. The nano-microorganism coproduction technology for coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane according to claim 1, characterized in that coal slime is used as a culture medium, and acetic acid is generated by using coal acetogenic bacteria
The coal acetogenic bacteria comprise the following components in percentage by mass: 5 to 20 percent of ethanol, 10 to 20 percent of sugar, 10 to 30 percent of vinegar yeast, 10 to 30 percent of distiller's yeast, 10 to 20 percent of tannase or tannase, 5 to 20 percent of pancreatin, 5 to 15 percent of acetobacter, 5 to 15 percent of clostridium and 0.5 to 5 percent of coal gasification catalyst.
8. The nano-microorganism coproduction technology of coal bed adsorbed gas, coal-to-hydrogen and coal-to-methane as claimed in claim 1, characterized in that methanogens are used to catalyze CO, CO and H under the action of exothermic reaction heat-gaining and coal gasification catalysts 2 Methane formation, catalysis of carbon dioxide and hydrogen H 2 Methane is generated, and acetic acid and acetate (sodium acetate, potassium acetate and ammonium acetate) are catalyzed to generate methane.
The methanogen coal comprises the following components in percentage by mass: 5 to 20 percent of bacteroides fragilis, 5 to 20 percent of clostridium histolyticum, 15 to 30 percent of EM probiotic raw bacteria, 15 to 40 percent of yeast, 5 to 20 percent of lactic acid bacteria, 5 to 20 percent of alkaline protease and 1 to 5 percent of coal gasification catalyst;
the exothermic reaction comprises: thermite reaction, acid-base neutralization reaction, reaction of active metal and water or acid, and dissolving of alkaline activator in water.
9. The application of the nano-microorganism coproduction technology of coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane in underground coal beds according to any one of claims 1 to 8 is characterized by comprising the following implementation steps of:
the first step is injecting the formula: 0.5-2% of coal seam nanometer expanding agent + or 0.3-0.8% of hydrolytic zymocyte + the balance of water, the injection amount is 500 to 1000, the concentration is increased from 0.5% to 2%, the injection mode is as follows: pulse type slow injection with the discharge capacity of 0.5 square/min to 3.5 square/min is carried out, and the nano aperture is enlarged in a pulse type;
the second step is to inject the formula: 0.5 to 1.5 percent of coal acid active agent and the balance of water, the injection amount is 200 to 500, and the injection mode is as follows: pulse type slow injection with the discharge capacity of 2.5 square/min to 3.5/min is carried out, and the micron aperture is enlarged in a pulse type;
the third step is to inject the formula: 0.5 to 1.5 percent of coal seam nanometer expanding agent + or 0.3 to 0.8 percent of hydrolytic zymocyte + the balance of water, the injection amount is 20 to 50, and the injection mode is as follows: pulse slow injection with the discharge capacity of 0.5 square/min to 3.5 square/min;
fourth step injection formula: 2 to 5 percent of expanding agent and the balance of water, the injection amount is 200 to 500, and the injection mode is as follows: pulse injection with the discharge capacity of 3.5-5.5/min, pulse expansion to expand the width and length of the crack, and closing the well for 2-3 hours;
fifthly, injecting coal seam refrigerant of 90% -99.9% of liquid nitrogen or liquid carbon dioxide from 0.5 square to 2 square, then injecting liquid nitrogen or liquid carbon dioxide from 50 square to 200 square with large discharge, then injecting coal seam refrigerant of 90% -99.9% of liquid nitrogen or liquid carbon dioxide from 0.5 square to 1 square, then injecting coal seam refrigerant of 10% of liquid nitrogen or liquid carbon dioxide from 20 square (the balance being water), and closing the well for 2-3 days;
the sixth step is injecting the formula: 1 to 1.5 percent of hydrolytic zymocyte, 0.6 to 1 percent of coal-derived hydrogen bacteria, 0.5 to 0.8 percent of coal-derived carbon monoxide bacteria, 0.4 to 0.6 percent of coal-derived carbon dioxide bacteria and the balance of water, wherein the injection amount is 200 to 500, and the injection mode is as follows: pulse type slow injection with the discharge capacity of 3.5 to 5.5 square/min;
the seventh step is injecting the formula: 0.8 to 1.2 percent of hydrolytic zymocyte, 0.6 to 1 percent of coal hydrogen producing bacterium, 0.5 to 0.8 percent of coal carbon monoxide producing bacterium, 0.4 to 0.6 percent of coal carbon dioxide producing bacterium, 0.4 to 0.6 percent of coal acetic acid producing bacterium and the balance of water, wherein the injection amount is 200 to 500, and the injection mode is as follows: pulse type slow injection with the discharge capacity of 3.5 to 5.5 square/min;
eighth step injection formulation: 0.6 to 1 percent of coal-derived hydrogen producing bacteria, 0.5 to 0.8 percent of coal-derived carbon monoxide bacteria, 0.4 to 0.6 percent of coal-derived carbon dioxide bacteria, 0.4 to 0.6 percent of coal-derived acetogenic bacteria, 0.4 to 0.6 percent of coal-derived methane producing bacteria and the balance of water, wherein the injection amount is 200 to 500, and the injection mode is as follows: pulse type slow injection with the discharge capacity of 3.5 to 5.5 square/min;
ninth step injection formulation: 0.5 to 0.8 percent of coal-derived hydrogen bacteria, 0.6 to 1 percent of coal-derived carbon monoxide bacteria, 0.4 to 0.6 percent of coal-derived carbon dioxide bacteria, 0.8 to 1.2 percent of coal-derived acetogenic bacteria, 1 to 1.5 percent of coal-derived methanogen bacteria and the balance of water, wherein the injection amount is 200 to 500, and the injection mode is as follows: pulse type slow injection with the discharge capacity of 3.5 to 5.5 square/min;
the tenth step is injecting the formula: 1% -1.5% of coal methanogen and the balance of water, the injection amount is 200 to 500, and the injection mode is as follows: pulse type slow injection with the discharge capacity of 3.5 to 5.5 square/min;
eleventh, injecting 2-5% potassium chloride of displacement liquid into the well for 20-30 times, and closing the well for 15-20 days;
twelfth, injecting 2-5% alkaline activator 200-1000 times;
and a thirteenth step of injecting 2-5% of potassium chloride as a displacement liquid into the well for 20-30 times, closing the well for 25-30 days, and opening the well to produce hydrogen and methane.
10. The application of the nano-microorganism coproduction technology of coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane according to any one of claims 1 to 8 on the ground, wherein the construction of the methane tank comprises the following implementation steps:
the first step is injecting the formula: 1 to 2.5 percent of hydrolytic zymocyte and the balance of water are stirred with coal powder and poured into a methane tank;
the second step is to inject the formula: 0.5 to 1.5 percent of coal acidic active agent and the balance of water are poured into the methane tank;
the third step is to inject the formula: 1 to 2.5 percent of hydrolytic zymophyte and the balance of water are stirred with coal powder and poured into a methane tank;
fourth step injection formula: 2 to 5 percent of expanding agent and the balance of water are injected into the methane tank;
the fifth step is injecting the formula: 0.6 to 1 percent of hydrolytic zymocyte, 1 to 1.5 percent of coal hydrogen producing bacteria, 0.5 to 0.8 percent of coal carbon monoxide producing bacteria, 0.4 to 0.6 percent of coal carbon dioxide producing bacteria, 1 to 1.5 percent of coal methane producing bacteria and the balance of water are stirred with coal dust and poured into a methane tank;
sixthly, pouring 2-5 percent of alkaline active agent 200-1000 after 15-20 days;
and seventhly, waiting for 25 to 30 days, and then opening the well to produce hydrogen and methane.
11. The nano-microorganism coproduction technology for coal bed adsorbed gas, coal-to-hydrogen gas and coal-to-methane according to claim 1, characterized in that an opening near a wellhead is filled with ammonium chloride or ammonium sulfate and sodium hydroxide or potassium hydroxide aqueous solution to absorb carbon monoxide, or cultivated chlorophytum comosum is used to absorb sulfur dioxide and carbon monoxide; CuSO is held near the well mouth by an opening 4 Absorbing hydrogen sulfide by the aqueous solution; crushing mineral rock into 20-mesh sand grains, and carrying sand with nano fracturing fluid to fill the void so as to prevent the ground from collapsing; the safe and environment-friendly production of three gases, namely coal-to-hydrogen gas and coal-to-methane gas, is realized.
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