CN112877369A - Method for preparing CNG, LNG and biological dry ice from biomass and livestock and poultry manure - Google Patents

Method for preparing CNG, LNG and biological dry ice from biomass and livestock and poultry manure Download PDF

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CN112877369A
CN112877369A CN202011638693.9A CN202011638693A CN112877369A CN 112877369 A CN112877369 A CN 112877369A CN 202011638693 A CN202011638693 A CN 202011638693A CN 112877369 A CN112877369 A CN 112877369A
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carbon dioxide
biogas
fermentation
dry ice
straws
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王强
朱建军
周月
张雁茹
鲁在利
吕英胜
周桓
张巍
乔志勇
刘森
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NATIONAL BIO ENERGY GROUP CO LTD
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    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

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Abstract

The invention belongs to the technical field of natural gas preparation, and particularly relates to a method for preparing CNG, LNG and biological dry ice from biomass and livestock and poultry manure, wherein the manure and straws are respectively pretreated and then mixed, a CSTR (continuous stirred tank reactor) technology is adopted for two-stage anaerobic fermentation at the medium temperature of 38 ℃, biogas slurry and biogas are produced after fermentation, and after dehydration and desulfurization of the biogas, a membrane separation technology is adopted, and an absorber removes carbon dioxide to ensure that the content of the carbon dioxide is less than 3%; purifying to make methane concentration reach above 99%, to obtain biological natural gas, and compressing to 10-25Mpa to prepare compressed biological natural gas or condensing and liquefying to produce liquefied natural gas; the carbon dioxide is absorbed from the marsh gas by a reversible carbon dioxide adsorbent, the carbon dioxide is released by the carbon dioxide adsorbent by changing the conditions, and the dry ice can be prepared by the steps of reducing the pressure and the temperature and the like. The invention can switch the process flow at any time according to market demands, correspondingly produce CNG, LNG or dry ice, utilize the existing resources, improve the utilization rate of biomass and solve the problem of environmental pollution.

Description

Method for preparing CNG, LNG and biological dry ice from biomass and livestock and poultry manure
Technical Field
The invention belongs to the technical field of natural gas preparation, and particularly relates to a method for preparing CNG, LNG and biological dry ice from biomass and livestock and poultry manure.
Background
The biogas refers to high-purity methane obtained by purifying biogas generated by anaerobic fermentation of biomass, and has wide application in industrial fuel, urban gas and power generation.
Dry ice refers to solid carbon dioxide, and gaseous carbon dioxide is condensed into colorless liquid under high pressure and then rapidly evaporated under low pressure. The method is widely applied to the fields of food and medicine, refrigeration and transportation, petrochemical industry, automobiles, ships and the like.
The biomass resources are rich, but the utilization rate is low, most straws are abandoned in the field to be burned, so that resource waste and environmental pollution are caused, meanwhile, livestock and poultry farms in China are numerous, the amount of produced excrement and sewage is large, the waste substances counted by tons cannot be effectively controlled, a large part of the waste substances are randomly discharged, and the waste substances permeate fields or rivers to pollute the living environment of people. At present, the problems of low utilization rate of straws and environmental pollution caused by waste straws are solved, the treatment and recycling of livestock and poultry breeding waste are accelerated, the environment is in the production and living environment of more than 6 hundred million rural residents, the energy revolution of rural areas is concerned, and the soil and land capability cannot be improved and the agricultural non-point source pollution can be well treated. Therefore, a biomass resource utilization method needs to be provided, biomass straws and livestock and poultry manure are used as raw materials, and high value-added utilization of the straws and the livestock and poultry manure is realized. At present, the research at home and abroad has reports of producing biogas by using biomass or livestock and poultry manure, but the reports of producing LNG, CNG and dry ice by jointly using the biomass and the livestock and poultry manure are not found.
After biomass is subjected to raw material pretreatment, anaerobic fermentation, purification processes such as filtration, biogas desulfurization, solid-liquid separation, membrane purification and compression and the like, impurities such as sulfur, carbon, water and the like in biogas components meet corresponding standard requirements, the biogas components are compressed by a compressor and enter a high-pressure jet flow liquefaction cold box for liquefaction, the product is LNG, the liquefied product does not enter the high-pressure jet flow liquefaction cold box for liquefaction after compression, and the product is CNG. At present, LNG and CNG process systems are two independent and separate systems, and the process is not easy to convert when the market changes.
Disclosure of Invention
The invention provides a method for preparing CNG, LNG and biological dry ice from biomass and livestock and poultry manure, and aims to realize preparation of natural gas and dry ice on the basis of fully utilizing the biomass and the livestock and poultry manure, and simultaneously carry out process switching on the natural gas according to market demands to produce CNG or LNG.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing CNG, LNG and biological dry ice from biomass and livestock and poultry manure is characterized by comprising the following steps:
s1, preprocessing: pretreating excrement and straws, and then respectively feeding the pretreated excrement and straws into a CSTR anaerobic fermentation tank;
pretreating excrement: after being scattered, the septic enters a septic tank through a grating for homogenizing and preheating treatment, then enters fermentation equipment for aerobic fermentation, is added with jade ramuscule, is rapidly decomposed within 1-2d, releases heat of 50-60 ℃, and then is fed with oxygen for the fermentation equipment through an air supply system, wherein the ventilation rate is 0.05-0.2 m3·(min·m3)-1Sufficiently fermenting and decomposing the excrement, maintaining for 5-7 days, and pumping the treated excrement to a CSTR anaerobic fermentation tank from an excrement feeding pool;
straw pretreatment: conveying the straws to a crusher to crush the straws, wherein the particle size of the crushed straws is less than 5cm, and then feeding the crushed straws into a hydrolysis acidification system, wherein the hydrolysis temperature is 50-70 ℃, and the hydrolysis time is 2-3 d;
s2, anaerobic fermentation: performing two-stage anaerobic fermentation process at medium temperature of 38 deg.C by CSTR technique, mixing in a full-wet reactor for wet anaerobic fermentation for 5-20 days, and conveying fermented material after fermentation treatment to a dry fermentation reactor for dry solid fermentation; a heating coil and a heat-insulating layer are arranged in the tank, a stirrer is arranged to ensure that the mass transfer and the heat transfer in the tank are uniform, and methane liquid are generated after fermentation;
s3, desulfurization and dehydration: the biogas adopts alkaline biological desulfurization to desulfurize and purify the biogas, the volume load of the biological desulfurization is controlled to be below 70-300 mg/(h.L), and water S is fed2-The concentration is 85-90mg/L, the dissolved oxygen is 1.3-2.5mg/L, and H in the methane is extracted2Reducing the S gas content to below 200pmm, removing water in the biogas through a cold-dry dehydrator, temporarily storing in a double-membrane dry gas storage cabinet, desulfurizing through a fine desulfurizing tower, and generating H in the biogas through anaerobic fermentation2S is reduced to below 15 ppm;
s4, solid-liquid separation: selecting a screw extruder to carry out solid-liquid separation on the fermented biogas slurry, returning the separated liquid to a temporary storage tank for storage, and conveying biogas residues to an organic fertilizer device for producing an organic fertilizer;
s5, preparing natural gas: adopting a membrane separation technology, and removing carbon dioxide by an absorber to ensure that the content of the carbon dioxide is less than 3 percent; purifying to make methane concentration reach above 99%, to obtain biogas, compressing to 10-25Mpa to prepare compressed biogas or condensing and liquefying to produce liquefied natural gas, and storing in a storage tank;
s7, preparation of dry ice: adsorbing carbon dioxide from biogas by using a reversible carbon dioxide adsorbent, changing conditions to enable the carbon dioxide adsorbent to release carbon dioxide, purifying to enable the purity to be higher than 99% and the moisture content to be lower than 0.1%, condensing to enter a compressor, controlling the temperature to be 2 ℃ to condense into liquid carbon dioxide, pressurizing to be more than 7Mpa, filling into a steel cylinder to obtain a liquid carbon dioxide product, enabling the liquid carbon dioxide to enter an expansion tank, reducing the pressure, cooling and expanding to obtain snowflake-shaped solid carbon dioxide, extruding snow powder into fine rods by using particle production equipment, cutting into particles, and finally extruding into finished dry ice.
Furthermore, the width of the gaps between the bars of the grid is 16-25 mm.
Compared with the prior art, the invention has the following beneficial effects:
the invention firstly pretreats the excrement and the straws respectively and then mixes the pretreated excrement and the straws for anaerobic fermentation, so that the removal rate of COD can be improved, and simultaneously, the yield of biogas is improved. The anaerobic fermentation adopts a two-stage anaerobic fermentation technology, wet anaerobic fermentation is firstly carried out, and then dry anaerobic fermentation is carried out, so that the efficiency of the dry anaerobic fermentation is improved. The biogas and the biogas slurry are produced after fermentation, and the biogas slurry is recycled or used for producing organic fertilizer after solid-liquid separation, thereby being beneficial to the recycling and harmless utilization of biomass and excrement. The biogas can be used for respectively preparing CNG and LNG according to different market demands, and when the natural gas is prepared, a membrane separation technology is adopted, and an absorber removes carbon dioxide to ensure that the content of the carbon dioxide is less than 3%; purifying to make methane concentration reach above 99%, to obtain biological natural gas, compressing to 10-25Mpa to prepare compressed biological natural gas or condensing and liquefying to produce liquefied natural gas, and storing in storage tank. The desulfurized biogas can also be used for preparing dry ice, carbon dioxide is adsorbed from the biogas by a reversible carbon dioxide adsorbent, the carbon dioxide adsorbent releases carbon dioxide under changed conditions, the purity is higher than 99 percent and the moisture content is lower than 0.1 percent through purification, the biogas enters a compressor through condensation, the biogas is condensed into liquid carbon dioxide at the temperature of 2 ℃, the liquid carbon dioxide is pressurized to more than 7Mpa and is filled into a steel cylinder to obtain a liquid carbon dioxide product, the liquid carbon dioxide enters an expansion tank and is subjected to pressure reduction, temperature reduction and expansion to become snowflake solid carbon dioxide, the snowflake powder is extruded into a fine rod by adopting particle production equipment, the fine rod is cut into particles, and finally the fine rod is extruded into the finished dry ice.
According to the invention, on the basis of preparing the biogas from the biomass and the excrement, the biogas is further processed into liquefied natural gas and biological dry ice, so that the utilization rate of the biogas is improved, the production benefit is further improved, the existing process is fully utilized according to market demands, resources are saved, the ecological cycle and the efficient utilization of the biomass are realized, and the problem of environmental pollution caused by a large amount of waste biomass is solved.
Drawings
FIG. 1 is a flow chart of a feces pretreatment process of a method for preparing CNG, LNG and biological dry ice from biomass and livestock feces;
FIG. 2 is a flow chart of a straw treatment process of a method for preparing CNG, LNG and biological dry ice from biomass and livestock and poultry manure;
FIG. 3 is a general process flow diagram of a method for preparing CNG, LNG and biological dry ice from biomass and livestock and poultry manure.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The method for preparing CNG, LNG and biological dry ice by using straws and cow dung comprises the following steps:
s1, preprocessing: pretreating cow dung and straws, and then respectively feeding into a CSTR anaerobic fermentation tank;
pretreating excrement: the cattle manure is scattered, enters a septic tank through a grating for homogenizing and preheating treatment, then enters a fermentation device for aerobic fermentation, is added with Yubajun bacteria, is rapidly decomposed within 1d, releases 50 ℃ of heat, and then is fed with oxygen for the fermentation device through an air supply system, wherein the ventilation rate is 0.05m3·(min·m3)-1Fully fermenting and decomposing the cow dung, maintaining for 5 days, pumping the treated cow dung to a CSTR anaerobic fermentation tank from a dung feeding pool, wherein the width of gaps among grid bars of a grid is 16 mm;
straw pretreatment: conveying the straws to a crusher to crush the straws, wherein the particle size of the crushed straws is less than 5cm, and then feeding the straws into a hydrolysis acidification system, wherein the hydrolysis temperature is 50 ℃ and the hydrolysis time is 2 d;
s2, anaerobic fermentation: performing two-stage anaerobic fermentation process at medium temperature of 38 deg.C by CSTR technique, mixing in a full-wet reactor for wet anaerobic fermentation for 5 days, and transferring fermented material after fermentation treatment to a dry fermentation reactor for dry solid fermentation; a heating coil and a heat-insulating layer are arranged in the tank, a stirrer is arranged to ensure that the mass transfer and the heat transfer in the tank are uniform, and methane liquid are generated after fermentation;
s3, desulfurization and dehydration: the biogas adopts alkaline biological desulfurization to desulfurize and purify the biogas, the volume load of the biological desulfurization is controlled to be 70 mg/(h.L), and S is fed2-The concentration is 85mg/L, the dissolved oxygen is 1.3mg/L, and H in the methane is extracted2Reducing the S gas content to below 200pmm, removing water in the biogas through a cold-dry dehydrator, temporarily storing in a double-membrane dry gas storage cabinet, desulfurizing through a fine desulfurizing tower, and generating H in the biogas through anaerobic fermentation2S is reduced to below 15 ppm;
s4, solid-liquid separation: selecting a screw extruder to carry out solid-liquid separation on the fermented biogas slurry, returning the separated liquid to a temporary storage tank for storage, and conveying biogas residues to an organic fertilizer device for producing an organic fertilizer;
s5, preparing natural gas: adopting a membrane separation technology, and removing carbon dioxide by an absorber to ensure that the content of the carbon dioxide is less than 3 percent; purifying to make methane concentration reach above 99%, to obtain biogas, compressing to 10Mpa to prepare compressed biogas or condensing and liquefying to produce liquefied natural gas, and storing in a storage tank;
s7, preparation of dry ice: adsorbing carbon dioxide from biogas by using a reversible carbon dioxide adsorbent, changing conditions to enable the carbon dioxide adsorbent to release carbon dioxide, purifying to enable the purity to be higher than 99% and the moisture content to be lower than 0.1%, condensing to enter a compressor, controlling the temperature to be 2 ℃ to condense into liquid carbon dioxide, pressurizing to be more than 7Mpa, filling into a steel cylinder to obtain a liquid carbon dioxide product, enabling the liquid carbon dioxide to enter an expansion tank, reducing the pressure, cooling and expanding to obtain snowflake-shaped solid carbon dioxide, extruding snow powder into fine rods by using particle production equipment, cutting into particles, and finally extruding into finished dry ice.
Example 2
The method for preparing CNG, LNG and biological dry ice by using straws and pig manure comprises the following steps:
s1, preprocessing: pretreating pig manure and straws, and then respectively feeding into a CSTR anaerobic fermentation tank;
pretreating excrement: after being scattered, the pig manure enters a septic tank through a grating for homogenizing and preheating treatment, then enters fermentation equipment for aerobic fermentation, is added with jade ramuscule, is rapidly decomposed within 2d, releases heat of 60 ℃, and then is fed with oxygen for the fermentation equipment through an air supply system, wherein the ventilation rate is 0.2m3·(min·m3)-1Sufficiently fermenting and decomposing the excrement, maintaining for 7d, pumping the treated excrement to a CSTR anaerobic fermentation tank from an excrement feeding pool, wherein the width of gaps among grid bars of a grid is 25 mm;
straw pretreatment: conveying the straws to a crusher to crush the straws, wherein the particle size of the crushed straws is less than 5cm, and then feeding the straws into a hydrolysis acidification system, wherein the hydrolysis temperature is 70 ℃, and the hydrolysis time is 3 d;
s2, anaerobic fermentation: performing two-stage anaerobic fermentation process at medium temperature of 38 deg.C by CSTR technique, mixing in a full-wet reactor for wet anaerobic fermentation for 20 days, and transferring fermented material after fermentation treatment to a dry fermentation reactor for dry solid fermentation; a heating coil and a heat-insulating layer are arranged in the tank, a stirrer is arranged to ensure that the mass transfer and the heat transfer in the tank are uniform, and methane liquid are generated after fermentation;
s3, desulfurization and dehydration: the biogas is desulfurized and purified by alkaline biological desulfurization, the volume load of the biological desulfurization is controlled to be below 300 mg/(h.L), and water S is fed2-The concentration is 90mg/L, the dissolved oxygen is 2.5mg/L, and H in the methane is extracted2Reducing the S gas content to below 200pmm, removing water in the biogas through a cold-dry dehydrator, temporarily storing in a double-membrane dry gas storage cabinet, desulfurizing through a fine desulfurizing tower, and generating H in the biogas through anaerobic fermentation2S is reduced to below 15 ppm;
s4, solid-liquid separation: selecting a screw extruder to carry out solid-liquid separation on the fermented biogas slurry, returning the separated liquid to a temporary storage tank for storage, and conveying biogas residues to an organic fertilizer device for producing an organic fertilizer;
s5, preparing natural gas: adopting a membrane separation technology, and removing carbon dioxide by an absorber to ensure that the content of the carbon dioxide is less than 3 percent; purifying to make methane concentration reach above 99%, to obtain biogas, compressing to 25Mpa to prepare compressed biogas or condensing and liquefying to produce liquefied natural gas, and storing in a storage tank;
s7, preparation of dry ice: adsorbing carbon dioxide from biogas by using a reversible carbon dioxide adsorbent, changing conditions to enable the carbon dioxide adsorbent to release carbon dioxide, purifying to enable the purity to be higher than 99% and the moisture content to be lower than 0.1%, condensing to enter a compressor, controlling the temperature to be 2 ℃ to condense into liquid carbon dioxide, pressurizing to be more than 7Mpa, filling into a steel cylinder to obtain a liquid carbon dioxide product, enabling the liquid carbon dioxide to enter an expansion tank, reducing the pressure, cooling and expanding to obtain snowflake-shaped solid carbon dioxide, extruding snow powder into fine rods by using particle production equipment, cutting into particles, and finally extruding into finished dry ice.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (2)

1. A method for preparing CNG, LNG and biological dry ice from biomass and livestock and poultry manure is characterized by comprising the following steps:
s1, preprocessing: pretreating excrement and straws, and then respectively feeding the pretreated excrement and straws into a CSTR anaerobic fermentation tank;
pretreating excrement: after being scattered, the septic enters a septic tank through a grating for homogenizing and preheating treatment, then enters fermentation equipment for aerobic fermentation, is added with jade ramuscule, is rapidly decomposed within 1-2d, releases heat of 50-60 ℃, and then is fed with oxygen for the fermentation equipment through an air supply system, wherein the ventilation rate is 0.05-0.2 m3·(min·m3)-1The excrement is fully fermented and decomposed to maintain the vitaminKeeping for 5-7d, and pumping the treated manure from the manure feeding pool to a CSTR anaerobic fermentation tank;
straw pretreatment: the straws are conveyed to a crusher to crush the straws, the particle size after crushing is less than 5cm, then the straws enter a hydrolysis acidification system, the hydrolysis temperature is 50-70 ℃, the hydrolysis time is 2-3d, and the treated straws are conveyed to a CSTR anaerobic fermentation tank;
s2, anaerobic fermentation: performing two-stage anaerobic fermentation process at medium temperature of 38 deg.C by CSTR technique, mixing in a full-wet reactor for wet anaerobic fermentation for 5-20 days, and conveying fermented material after fermentation treatment to a dry fermentation reactor for dry solid fermentation; a heating coil and a heat-insulating layer are arranged in the tank, a stirrer is arranged to ensure that the mass transfer and the heat transfer in the tank are uniform, and methane liquid are generated after fermentation;
s3, desulfurization and dehydration: the biogas adopts alkaline biological desulfurization to desulfurize and purify the biogas, the volume load of the biological desulfurization is controlled to be 70-300 mg/(h.L), and S is fed2-The concentration is 85-90mg/L, the dissolved oxygen is 1.3-2.5mg/L, and H in the methane is extracted2Reducing the S gas content to below 200pmm, removing water in the biogas through a cold-dry dehydrator, temporarily storing in a double-membrane dry gas storage cabinet, desulfurizing through a fine desulfurizing tower, and generating H in the biogas through anaerobic fermentation2S is reduced to below 15 ppm;
s4, solid-liquid separation: selecting a screw extruder to carry out solid-liquid separation on the fermented biogas slurry, returning the separated liquid to a temporary storage tank for storage, and conveying biogas residues to an organic fertilizer device for producing an organic fertilizer;
s5, preparing natural gas: adopting a membrane separation technology, and removing carbon dioxide by an absorber to ensure that the content of the carbon dioxide is less than 3 percent; purifying to make methane concentration reach above 99%, to obtain biogas, compressing to 10-25Mpa to prepare compressed biogas or condensing and liquefying to produce liquefied natural gas, and storing in a storage tank;
s7, preparation of dry ice: adsorbing carbon dioxide from biogas by using a reversible carbon dioxide adsorbent, changing conditions to enable the carbon dioxide adsorbent to release carbon dioxide, purifying to enable the purity to be higher than 99% and the moisture content to be lower than 0.1%, condensing to enter a compressor, controlling the temperature to be 2 ℃ to condense into liquid carbon dioxide, pressurizing to be more than 7Mpa, filling into a steel cylinder to obtain a liquid carbon dioxide product, enabling the liquid carbon dioxide to enter an expansion tank, reducing the pressure, cooling and expanding to obtain snowflake-shaped solid carbon dioxide, extruding snow powder into fine rods by using particle production equipment, cutting into particles, and finally extruding into finished dry ice.
2. The method for preparing CNG, LNG and biological dry ice from biomass and livestock and poultry manure according to claim 1, which is characterized in that: the width of gaps among the grid bars of the grid is 16-25 mm.
CN202011638693.9A 2020-12-31 2020-12-31 Method for preparing CNG, LNG and biological dry ice from biomass and livestock and poultry manure Pending CN112877369A (en)

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Application publication date: 20210601