CN113025355A - Method for recycling livestock and poultry manure and straw - Google Patents
Method for recycling livestock and poultry manure and straw Download PDFInfo
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- CN113025355A CN113025355A CN202110301147.4A CN202110301147A CN113025355A CN 113025355 A CN113025355 A CN 113025355A CN 202110301147 A CN202110301147 A CN 202110301147A CN 113025355 A CN113025355 A CN 113025355A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1018—Biomass of animal origin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention provides a recycling method of livestock and poultry manure and straws, which particularly takes various biomasses such as livestock and poultry manure and straws and the like as raw materials, utilizes an auxiliary microwave pyrolysis technology, obtains uncondensed mixed gas as biogas under carrier gas and an auxiliary pyrolysis agent, obtains bio-oil after condensation, and the rest in a pyrolysis device is bio-carbon, reduces the use of fossil fuel by using the biogas and the bio-oil, and provides cheap and high-quality conversion materials for activated carbon; the method has the advantages that the pollution-free treatment of agricultural wastes is realized, and meanwhile, the waste is changed into valuable; three valuable products including biogas, bio-oil and biochar are obtained by adjusting the flow of carrier gas in different atmosphere environments and the mass ratio of the biomass raw material to the auxiliary pyrolysis agent; in addition, due to the high temperature in the microwave pyrolysis process, bacteria and worm eggs can be killed, antibiotics for livestock are degraded, heavy metals contained in livestock manure are passivated, disease hazards are greatly reduced, and the method is healthier and more environment-friendly.
Description
Technical Field
The invention belongs to the technical field of waste recycling and environmental protection, and particularly relates to a recycling method of livestock and poultry manure and straws.
Background
Currently, there are about 700 million breeding animals worldwide, and this number is expected to double by 2050. One of the main reasons is that the demand for food and pets is increasing with the increase of the population, which also leads to a sharp increase in the production of animal faeces. These reasons have prompted the need to identify effective fertilizer management methods. The utilization of biological wastes such as livestock and poultry manure as a source and the conversion of the biological wastes into other high-value products is one of effective ways for solving the problem.
The livestock and poultry manure comprises agricultural solid wastes generated in the livestock and poultry breeding industry process, such as cow manure, sheep manure, pig manure, chicken manure, goose manure, duck manure and the like, and also comprises solid wastes generated by other cultured animals such as horse manure and the like. Animal excrement contains abundant organic substances and N, P, K elements, and also can provide Ca, Mg, S and other minerals and trace elements required by crop growth, so that the animal excrement is one of important sources of plant fertilizers. However, the contents of antibiotics, heavy metal elements, germs, ova and other harmful substances in the livestock and poultry manure are relatively high, so that the livestock and poultry manure cannot be directly used. The main treatment mode is anaerobic fermentation, the efficiency is low, and toxic and harmful gases generated in the fermentation process can cause great harm to the atmospheric environment. If the livestock and poultry manure is directly discharged into the nature, a series of environmental problems such as water body pollution and the like can be caused, and even trace amount of heavy metal elements and veterinary antibiotics can cause damage to the environmental ecology and human health.
The straws are a general term of stems, leaves (ears) of mature crops, are rich in various elements such as N, P, K, Ca, Mg, Zn, Fe, Mn, Cu and the like and organic matters, and are a renewable biological resource with rich yield and wide application. A large amount of substances containing cellulose, such as various crop straws and the like, are produced in China every year, but the substances are used as feed less than 10 percent, and the rest are incinerated. In recent years, a large amount of straws are returned to the field for treatment under the promotion of governments, and the straw returning is a method for directly applying straws which are not suitable for being directly used as feed to soil or applying the straws after being piled up and decomposed. Although the straw returning field has the advantage of improving soil, the problems of increased pest and disease damage, fertilizer competition with crops, large nitrogen fertilizer consumption and the like are caused, the pesticide use amount is increased, the pesticide residue is high, the crop growth is limited, the yield is reduced, the quality is poor and the like. In addition, although various nutrient elements exist in the straws, the nutrient elements exist in a combined state, such as exist in lignin and hemicellulose structures, are difficult or cannot be absorbed by plants, and the effect of increasing the weight of the straws cannot be achieved. In addition, if the straw is on the soil surface or the plough layer, the root system can not be rooted into the soil after the seed germination, the root system can not absorb moisture and nutrients because the root system can not contact the soil for a long time, diseases, weak seedlings and the like can be caused, and the yield of crops is reduced. And the piled and decomposed straw substances are applied to the soil, so that labor and time are wasted, and the quality of the piled and decomposed straw substances cannot be guaranteed.
In conclusion, a comprehensive utilization approach of straw and livestock wastes which can not pollute the environment and can also prepare high value-added products is needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for recycling livestock and poultry manure and straws.
In order to achieve the above purpose, the solution of the invention is as follows:
a method for recycling livestock and poultry manure and straws comprises the following steps:
(1) pretreating livestock and poultry manure and straws, then performing microwave pyrolysis, and blowing carrier gas in different atmosphere environments and treating with an auxiliary pyrolysis agent to obtain biogas;
(2) condensing the biogas to obtain bio-oil;
(3) and (2) in the step (1), after the microwave pyrolysis process is finished, the solid residues left by the livestock and poultry manure and the straws are biochar.
Further, in the step (1), the pretreatment process comprises: and (3) chopping and drying the livestock and poultry manure and the straws.
Further, in the step (1), the carrier gas is selected from nitrogen or carbon dioxide, and the ventilation amount is 0.1-3.0L/min.
Further, in the step (1), the auxiliary pyrolysis agent is activated carbon, and the mass ratio of the livestock and poultry manure, the straws and the activated carbon is 0.5-2.0.
Further, in the step (1), the microwave frequency of the microwave pyrolysis is 1000-.
Further, in the step (1), the yield of the biogas is 4-40%.
Further, in the step (1), the biogas comprises 50-70% of carbon monoxide, 10-33% of carbon dioxide, 13-25% of methane and 1-4% of hydrogen.
Further, in the step (2), the yield of the bio-oil is 12-36%.
Further, in the step (3), the yield of the biochar is 10-80%.
Due to the adoption of the scheme, the invention has the beneficial effects that:
in the microwave pyrolysis process of the livestock and poultry manure and the straws, products comprising biogas, bio-oil and biochar are obtained by processing under the conditions of carrier gas and auxiliary pyrolysis agents in different atmospheres, so that waste is changed into valuable, the use of fossil fuel is reduced by using the biogas and the bio-oil, and the biochar provides a cheap and high-quality conversion material for activated carbon; in addition, due to the high temperature in the pyrolysis process, bacteria and worm eggs can be killed, and the disease harm is greatly reduced, so that the environment-friendly and healthy tea is more environment-friendly.
Drawings
FIG. 1 is a schematic flow chart of a method for recycling livestock and poultry manure and straw.
Detailed Description
The invention provides a method for recycling livestock and poultry manure and straws.
As shown in figure 1, the method for recycling the livestock and poultry manure and the straws comprises the following steps:
(1) and obtaining biogas: pretreating livestock and poultry manure and straws, then performing microwave pyrolysis in a microwave pyrolysis device, and blowing carrier gas and treating an auxiliary pyrolysis agent to generate gas to obtain biogas;
(2) and obtaining the biological oil: condensing the pyrolyzed biogas through a condenser to obtain bio-oil;
(3) and obtaining the biochar: in the step (1), after the microwave pyrolysis process is finished, the solid residues left in the livestock and poultry manure and the straws in the microwave pyrolysis device are biochar.
Wherein, in the step (1), the pretreatment process comprises the following steps: and (3) chopping and drying the livestock and poultry manure and the straws. After pretreatment, the mixture is stirred and evenly sent into a microwave pyrolysis device. Biomass of the present invention includes, but is not limited to, livestock manure and straw.
In the step (1), the carrier gas is selected from nitrogen or carbon dioxide, and the ventilation amount is 0.1-3.0L/min. The purpose of adding the carrier gas and the auxiliary pyrolysis agent is as follows: to ensure the stability and efficiency of the pyrolysis process while varying the yield of different products.
In the step (1), the auxiliary pyrolysis agent is activated carbon, and the mass ratio of the raw materials (the livestock and poultry manure and the straws) to the activated carbon is 0.5-2.0. The auxiliary pyrolysis agent can be used as a microwave absorbent or an additive with a catalytic effect.
In the step (1), the microwave frequency of the microwave pyrolysis can be 1000-3000MHz, preferably 2450 MHz; the pyrolysis temperature can be 300-700 ℃, preferably 350-550 ℃; the pyrolysis time may be 30-60min, preferably 40-60 min. At the same time, microwave-induced pyrolysis is more efficient than conventional external-heating pyrolysis. Microwave-assisted pyrolysis can induce a fixed effective volume to heat because the radiation of electromagnetic waves can penetrate the feedstock. Not only the problem of uneven heating is overcome, but also the whole energy consumption is reduced. In addition, microwave heating can also increase heating rate and selectivity, increasing the yield of a given product.
In the step (1), the biogas yield can be controlled to be 4-40%.
Wherein the biogas is gaseous product obtained after pyrolysis, mainly comprising CO and CO2、CH4And H2. 50-70% of carbon monoxide, 13-25% of methane, 10-33% of carbon dioxide and 1-4% of hydrogen. The heat value of the biogas is 12-16MJ/m3And compared with the biogas obtained by other ways, the biogas has strong competitiveness. The carbon monoxide content of the biogas is high, and the biogas is one of important raw materials used by Integrated Gasification Combined Cycle (IGCC). Furthermore, by increasing the pyrolysis temperature, the proportion of hydrogen in the synthesis gas can also be increased, thereby obtaining a conventional synthesis gas. Further producing products such as ammonia gas, methanol and the like, or carrying out processes such as Fischer-Tropsch synthesis, hydroxyl synthesis and the like, thereby having good flexibility and practicability.
In the step (2), the yield of the bio-oil can be controlled to be 12-36%.
The bio-oil is a liquid product generated by pyrolysis, is light brown and is slightly acidic; the pH value is about 4; mainly comprising C, H, O, N, S elements. Wherein C accounts for 40-50%, H accounts for 5-6%, O accounts for 30-40%, N accounts for 7-25%, and S only accounts for 0-0.5%. The calorific value of the bio-oil is mainly 17.5-23.8MJ/kg according to different components, although lower than that of diesel oil, the bio-oil has stronger competitive power compared with other products obtained from biomass. Besides being used as boiler fuel, the bio-oil can also be used for extracting and preparing chemicals. Through research, bio-oil has more than 300 kinds of organic substances, and many chemicals have higher added values. The biological oil is used as a raw material for extracting and preparing chemicals, and has potential market value. The biological oil as the fuel product of the biomass boiler can not be separated from chemicals by using the traditional steaming and spreading process, and can be extracted by adopting a rochon agent, separated by adding water and the like. The company of Canada uses carboxylic acid, ketone, phenol and aldehyde in the biological oil and lime to carry out calcium ion exchange reaction, and the prepared biological lime is used as a boiler desulfurizer. The experiment of the mixed combustion of the lime bio-oil, high-sulfur diesel oil and heavy oil on a small boiler proves that NO is generatedXEmission reduction 40%, S02The emission is reduced by 90%.
In the step (3), the yield of the biochar can be controlled to be 10-80%.
Biochar is a solid product obtained after pyrolysis, and is a product with very high carbon density. Compared with biochar obtained from other channels, the product has a high surface area/pore volume ratio (about 2300), is characterized by being dense and porous, and therefore has stronger adsorption capacity, oxidation resistance and biological decomposition resistance, and can be widely applied to soil improvement, fertilizer slow release agents, carbon sequestration and emission reduction and the like. The biochar can greatly improve the soil fertility, cultivate fertile high-carbon reservoir soil on barren soil, has the most direct effect of obviously improving the yield and quality of crops, and can indirectly reduce the application amount of chemical fertilizers, pesticides and other chemicals. The most important is that the carbon is effectively adsorbed and solidified in the biochar, thereby reducing the emission of greenhouse gases and the dependence on petroleum products. It is currently known that one ton of biomass can fix 0.726 ton of carbon dioxide. The biochar can be used as a soil structure improver or prepared into various carbon-based fertilizers, and has the effects of improving the soil quality, increasing the crop yield and improving the quality; or as a soil pollution remediation agent and the like, and has the effect of reducing pollution. The carbon sequestration of the soil can be increased by about 40 to 50 percent by directly returning the soil. In recent years, the function of biochar in solving the aspects of global ecological environment safety, agricultural sustainable development and the like is generally accepted and is known as 'black gold' by academic circles, and a plurality of countries establish special institutions to research the theory and application prospect of biochar.
The present invention will be further described with reference to the following examples.
Example 1:
the method for recycling the livestock and poultry manure and the straws comprises the following steps:
(1) and obtaining biogas: chopping and drying animal waste and straws, performing microwave pyrolysis in a microwave pyrolysis device at 2450MHz and 1KW power, and blowing nitrogen and treating with activated carbon to obtain CO and CO2、CH4、H2The biogas of (2);
(2) and obtaining the biological oil: condensing the pyrolyzed biogas through a condenser to obtain bio-oil;
(3) and obtaining the biochar: in the step (1), after the microwave pyrolysis process is finished, the solid residues left by the animal wastes and the straws in the microwave pyrolysis device are biochar.
In order to verify the ratio of the three products under different conditions, the nitrogen flow was fixed at 1.0L/min, and the ratio of the different products in the pyrolysis process at 350 ℃, 450 ℃ and 550 ℃ was analyzed by changing the mass ratio of the raw materials (animal waste, straw) and activated carbon.
Immediately after pyrolysis, the product was analyzed to yield ratios of three different products as shown in table 1.
TABLE 1 nitrogen flow fixed at 1.0L/min, product temperature distribution at different raw material to active carbon ratios
Table 2: when the nitrogen flow is fixed at 1.0L/min, the biogas components are distributed along with the temperature under different raw material and active carbon ratios
As can be seen from tables 1 and 2, by adjusting the mass ratio of the raw material to the activated carbon and the different microwave pyrolysis temperatures, the recycling method of the embodiment has the advantages of obtaining a plurality of products with different types and contents, and having different contents of each component in the biogas, so that the ratio of the products can be controlled by changing the conditions of the pyrolysis catalyst, and the method is flexible and controllable.
Example 2:
the method for recycling the livestock and poultry manure and the straws comprises the following steps:
(1) and obtaining biogas: chopping and drying animal waste and straws, performing microwave pyrolysis in a microwave pyrolysis device at 2450MHz and 1KW power, and blowing nitrogen and treating with activated carbon to obtain CO and CO2、CH4、H2The biogas of (2);
(2) and obtaining the biological oil: condensing the pyrolyzed biogas through a condenser to obtain bio-oil;
(3) and obtaining the biochar: in the step (1), after the microwave pyrolysis process is finished, the solid residues left by the animal wastes and the straws in the microwave pyrolysis device are biochar.
In order to verify the proportion of the three products under different conditions, the mass ratio of the raw material to the activated carbon is fixed to be 1:1, and the proportion of different products in the pyrolysis process under the environments of 350 ℃, 450 ℃ and 550 ℃ is analyzed by adjusting the flow rate of different nitrogen gases.
Immediately after pyrolysis, the product was analyzed to yield ratios of three different products as shown in table 3.
Table 3: the mass ratio of the raw materials to the active carbon is fixed at 1:1 hour, product temperature profile at different nitrogen flow
As can be seen from table 3, by adjusting the flow rate of the nitrogen gas, the recycling method of the embodiment has a large number of product types and different contents, and thus the proportion of the product can be controlled by changing the flow rate of the protective gas in the pyrolysis process, which is flexible and controllable.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.
Claims (9)
1. A method for recycling livestock and poultry manure and straws is characterized by comprising the following steps: which comprises the following steps:
(1) pretreating livestock and poultry manure and straws, then performing microwave pyrolysis, and blowing carrier gas and treating an auxiliary pyrolysis agent by the generated gas to obtain biogas;
(2) condensing the biogas to obtain bio-oil;
(3) and (2) in the step (1), after the microwave pyrolysis process is finished, the solid residues left by the livestock and poultry manure and the straws are biochar.
2. The recycling method according to claim 1, wherein: in the step (1), the pretreatment process comprises the following steps: and (3) chopping and drying the livestock and poultry manure and the straws.
3. The recycling method according to claim 1, wherein: in the step (1), the carrier gas is selected from nitrogen or carbon dioxide, and the ventilation amount is 0.1-3.0L/min.
4. The recycling method according to claim 1, wherein: in the step (1), the auxiliary pyrolysis agent is activated carbon, and the mass ratio of the livestock and poultry manure, the straws and the activated carbon is 0.5-2.0.
5. The recycling method according to claim 1, wherein: in the step (1), the microwave frequency of the microwave pyrolysis is 3000MHz in the range of 1000-.
6. The recycling method according to claim 1, wherein: in the step (1), the yield of the biogas is 4-40%.
7. The recycling method according to claim 1, wherein: in the step (1), the biogas comprises 50-70% of carbon monoxide, 10-33% of carbon dioxide, 13-25% of methane and 1-4% of hydrogen.
8. The recycling method according to claim 1, wherein: in the step (2), the yield of the bio-oil is 12-36%.
9. The recycling method according to claim 1, wherein: in the step (3), the yield of the biochar is 10-80%.
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| CN113854101A (en) * | 2021-09-12 | 2021-12-31 | 昆明理工大学 | Method for utilizing waste bacterium rods to realize soil formation of copper tailings |
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| CN113750917A (en) * | 2021-09-10 | 2021-12-07 | 刘建浩 | High-elasticity high-temperature-resistant aerogel and preparation method thereof |
| CN113750917B (en) * | 2021-09-10 | 2024-05-03 | 刘建浩 | High-elasticity high-temperature-resistant aerogel and preparation method thereof |
| CN113854101A (en) * | 2021-09-12 | 2021-12-31 | 昆明理工大学 | Method for utilizing waste bacterium rods to realize soil formation of copper tailings |
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