CN112551526A - Multistage utilization method of waste biomass - Google Patents
Multistage utilization method of waste biomass Download PDFInfo
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- CN112551526A CN112551526A CN202011566144.5A CN202011566144A CN112551526A CN 112551526 A CN112551526 A CN 112551526A CN 202011566144 A CN202011566144 A CN 202011566144A CN 112551526 A CN112551526 A CN 112551526A
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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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
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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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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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
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Abstract
The invention discloses a multistage utilization method of waste biomass, which comprises the following steps: the collected waste biomass is spirally squeezed, waste biomass with high water content can obtain biomass juice and biomass slag, waste biomass with low water content can obtain small-particle biomass slag, and slag-juice separation is integrally realized; carrying out ultrasonic and alcohol heat extraction on the waste biomass slag and the waste biomass juice, and mixing extracted liquid to obtain an extracting solution; drying and performing segmented pyrolysis on the extracted waste biomass slag to obtain biomass pyrolysis liquid and biomass pyrolysis carbon, and activating the pyrolysis carbon to obtain biomass activated carbon; the biomass pyrolysis liquid is further extracted to obtain a high value-added chemical; further extracting the extracting solution to obtain the biological pesticide raw material.
Description
Technical Field
The invention belongs to the technical field of waste biomass treatment, and particularly relates to a multistage utilization method of waste biomass.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Along with the rapid development of society, the demand of human beings on resources increases day by day, and while the available amount of primary energy is reduced, biomass resources gradually enter the research category of scientists due to the characteristics of large reserves, renewability and the like, such as crop straws, kitchen garbage, municipal domestic garbage and the like. Most of these biomass resources are left unused, discarded and wasted, and for example, waste biomass in kitchen garbage is complex in composition, is easy to decay, produces pathogens, pollutes air and groundwater, but has the potential as an "energy crop" and can produce high value-added chemicals through a thermal conversion process. There is no systematic method of formation for waste biomass utilization at present.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, it is an object of the present invention to provide a method for multi-stage utilization of waste biomass.
In order to solve the technical problems, the invention adopts the following technical scheme:
a multistage utilization method of waste biomass comprises the following steps:
the collected waste biomass is spirally squeezed, waste biomass with high water content can obtain biomass juice and biomass slag, waste biomass with low water content can obtain small-particle biomass slag, and slag-juice separation is integrally realized;
carrying out ultrasonic and alcohol heat extraction on the waste biomass slag and the waste biomass juice, and mixing extracted liquid to obtain an extracting solution;
drying and performing segmented pyrolysis on the extracted waste biomass slag to obtain biomass pyrolysis liquid and biomass pyrolysis carbon, and activating the pyrolysis carbon to obtain biomass activated carbon;
the biomass pyrolysis liquid is further extracted to obtain a high value-added chemical;
further extracting the extracting solution to obtain the biological pesticide raw material.
Compared with the prior art, the beneficial effects of the above one or more embodiments of the invention are as follows:
according to the invention, the squeezing process adopts spiral sectional treatment, waste biomass with high water content can effectively extract waste biomass juice, waste biomass with low water content can directly obtain waste biomass slag, and slag-juice separation is integrally realized; compared with the traditional biomass treatment mode, the harmful gas is subjected to primary treatment to form liquid gas condensed tar, so that the emission of polluted air in the production process is avoided, and the method has great popularization value; the solid product can be used for preparing biological compost, biological charcoal and the like, and the liquid product can be used for extracting chemicals with high added values; can be popularized to the treatment of organic solid wastes, and provides a new idea for the energy regeneration of biomass resources.
The process is based on the multi-stage utilization of the waste biomass, can effectively utilize the waste biomass, and reduces the pollution of similar solid wastes; the process adopts multi-stage screw pressing and double-sided pressing, can realize 'one-breaking, two-kneading, three-pressing and four-grinding', has more thorough grinding of biomass, realizes residue and juice separation integrally and efficiently, and can also adapt to various types of biomass; the extraction rate can be improved by ultrasonic extraction; the biomass slag is pyrolyzed in sections, so that the extraction efficiency of active ingredients is higher; the pyrolytic biochar can be used for preparing activated carbon; the pyrolysis liquid is used for extracting phenolic substances, can be used as botanical pesticides, and achieves the maximum economic benefit and social benefit.
Drawings
FIG. 1 is a graph of activated carbon adsorption hydrogen storage in an example of the present invention;
FIG. 2 is a flow diagram for multi-stage utilization of waste biomass according to an embodiment of the present invention;
fig. 3 is a schematic structural view of a spiral breaker according to an embodiment of the present invention.
The device comprises a main shaft, a first section of spiral teeth, a second section of spiral teeth, a third section of spiral teeth, a fourth section of spiral teeth and a rotating main shaft, wherein the main shaft comprises 1 part of spiral teeth, 2 part of spiral teeth, 3 part of spiral teeth, 4 part of spiral teeth, and 5 part of.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
As discussed in the background, there is little prior art that is specific to the treatment of waste biomass. The invention discloses a method for multistage utilization of waste biomass, which creatively provides the application of extraction-pyrolysis combination to the treatment of waste biomass, and has the advantages of more efficient treatment, simpler operation, more environment-friendly production and lower cost.
A multistage utilization method of waste biomass comprises the following steps:
the collected waste biomass is spirally squeezed, waste biomass with high water content can obtain biomass juice and biomass slag, waste biomass with low water content can obtain small-particle biomass slag, and slag-juice separation is integrally realized;
carrying out ultrasonic and alcohol heat extraction on the waste biomass slag and the waste biomass juice, and mixing extracted liquid to obtain an extracting solution;
drying and performing segmented pyrolysis on the extracted waste biomass slag to obtain biomass pyrolysis liquid and biomass pyrolysis carbon, and activating the pyrolysis carbon to obtain biomass activated carbon;
the biomass pyrolysis liquid is further extracted to obtain a high value-added chemical;
further extracting the extracting solution to obtain the biological pesticide raw material.
The high value-added chemicals are chemical raw material intermediates, such as phenols, and can be used for pesticide rectification, and the pyridines can be used as raw materials for synthesizing dyes, medicines and disinfectants, etc.
The ultrasonic treatment can complete the cavitation of plant cells under the condition of external energy input, so that the internal cell sap, chemical components and the like are easily released, and the later-stage alcohol-heat extraction is carried out, so that the effect is better. Moreover, the alcohol thermal reaction needs to be carried out under the heating condition, and the actual conditions include ultrasonic treatment, more complex heating equipment and higher cost.
In some embodiments, the waste biomass is a plant-based biomass such as: waste vegetable leaves, straws and the like.
In some embodiments, the screw press is divided into four stages, respectively:
a first stage: disconnecting the biomass and preparing for extrusion;
and a second stage: kneading biomass, and primarily squeezing;
a third stage: finely grinding the biomass and extracting vegetable juice;
a fourth stage: grinding the biomass and extruding vegetable residue.
In some embodiments, the grinding is stone-like grinding double-sided extrusion. The juice and slag yield is higher, the applicable waste biomass varieties are more, and the purpose of separating the residue and the juice is better achieved on the whole.
In some embodiments, the press-break apparatus comprises a spiral press-break core and a housing, the spiral press-break core being coaxially disposed inside the housing, the spiral press-break core comprising a rotating spindle and a first section of spiral teeth, a second section of spiral teeth, a third section of spiral teeth, and a fourth section of spiral teeth disposed on the rotating spindle;
the rotary main shaft comprises a constant-diameter section and an expansion section, the expansion section is of a structure which gradually shrinks from the middle part to two sides, and the constant-diameter section is connected with the minimum-diameter end of the expansion section;
the first section of spiral teeth and the second section of spiral teeth are sequentially arranged on the constant-diameter section along the axial direction, and the helix angle is 20-24 degrees; the third section of helical teeth and the fourth section of helical teeth are sequentially arranged on the expansion section along the axial direction, the helix angle is 28-32 degrees, and the third section of helical teeth cross the maximum diameter of the expansion section.
Further, the thread diameter of the second section of spiral teeth is smaller than that of the first section of spiral teeth.
Furthermore, the pitch of the third section of helical teeth is larger than that of the fourth section of helical teeth.
The working principle of the breaker is as follows: the squeezing spiral teeth are fixed on the rotating main shaft, the lead angle of the spiral teeth generates forward thrust, and the forward thrust and the external pressure breaking shell form a squeezing space, so that the contact surface of a spirally squeezed material and the material is small, the friction force is small, no blockage exists, no winding exists, and the squeezing efficiency can be improved.
The press screw is divided into four sections: the first section of helical teeth and the second section of helical teeth perform helical rough treatment on the waste biomass, and the helix angle is 22 degrees. The screw diameter of the first section of spiral teeth is larger than that of the second section of spiral teeth, the contact surface of materials is larger, the 'breaking' can be realized, the screw pitch of the second section of spiral teeth is smaller than that of the first section of spiral teeth, and the materials after the 'breaking' enter a smaller space to be 'kneaded'. The third section of helical teeth and the fourth section of helical teeth are subjected to fine processing, and the helix angle is larger and is 30 degrees. The screw pitch is also smaller, the extrusion space is smaller, and the two steps of pressing and grinding of the conventional breaker are finished.
In some embodiments, the extractant for the alcoholic thermal extraction is absolute ethanol. Compared with other organic solvents, the method has the advantages that the post-treatment is easier, the secondary recovery can be carried out by spiral evaporation, and the environmental pollution degree is lower.
Further, the mass ratio of the absolute ethyl alcohol to the vegetable residue is 1:0.8-1 during alcohol-heat extraction.
Further, the temperature of alcohol hot extraction is 75-80 ℃. Under the temperature condition, the ethanol is in a boiling state, the liquid ethanol can completely soak the solid, and the gaseous ethanol enables the system to form a pressurized state, thereby being beneficial to improving the extraction efficiency.
Further, the time of alcohol hot extraction is 2.5-3.5 h.
In some embodiments, the power of the sonication is 40-60W and the time of the sonication is 20-40 min.
In some embodiments, the pyrolysis conditions for staged pyrolysis of the waste biomass slag are: the flow rate is 200-210ml/min under the nitrogen atmosphere; the pyrolysis heating rate is 8-12 ℃/min, the pyrolysis final temperature is 700 ℃, and the holding time is 20 min.
In some embodiments, the activating agent for the pyrolytic carbon is KOH, the activation temperature is 650-750 ℃, and the activation time is 0.8-1.2 h.
In some embodiments, the extraction solvent of the biomass pyrolysis liquid is ethyl acetate. The active ingredient in the pyrolysis liquid is biological oil containing water, so that a water-insoluble extractant is selected for extraction.
Ethyl acetate is used as an extracting agent to realize the primary enrichment of organic matters; then placing the mixture in a rotary evaporator for solvent evaporation, and setting the evaporation conditions as follows: the evaporation temperature is 80 ℃, and the evaporation pressure is 0.01MPa, so that fine organic compounds are obtained, and high value-added chemicals can be extracted.
In some embodiments, the high value-added chemical is a phenolic organic compound that can be used to make organic pesticides.
In some embodiments, the waste biomass may be a plant-based biomass, such as corn stover, waste vegetable leaves, fallen leaves, and the like.
The invention will be further illustrated with reference to the following specific examples.
Example 1
In order to facilitate the actual operation, certain vegetable markets are selected to discard vegetable leaves.
The following experimental procedures were carried out:
as shown in fig. 2, the method for multi-stage utilization of waste biomass comprises the following steps: selecting waste Chinese cabbage biomass to carry out spiral four-section squeezing, "first breaking, second kneading, third pressing and fourth grinding", and carrying out residue and juice separation; one stage, cutting off the biomass and preparing for extrusion; second stage, kneading biomass, and primarily squeezing juice; three stages, finely grinding biomass, and extracting vegetable juice; four-stage, grinding the biomass and extruding vegetable residue;
and selecting absolute ethyl alcohol as an extraction liquid, carrying out ultrasonic treatment on the waste biomass residue and the waste biomass juice for 30min, wherein the power of an ultrasonic generator is 50W, the mass ratio of the extraction liquid to the extract is 1:1, carrying out an alcohol thermal reaction in a reaction kettle after the ultrasonic treatment, wherein the reaction temperature is 75 ℃, and the reaction time is 3 h. Mixing the extracted liquids to obtain an extracting solution;
then, carrying out vacuum drying on the extracted waste biomass slag for 24 hours to obtain dried waste biomass slag;
performing segmented pyrolysis on the dried biomass slag to obtain biomass pyrolysis liquid and biomass pyrolysis carbon, wherein the pyrolysis conditions are as follows: the nitrogen atmosphere, the flow is 205 ml/min; setting the pyrolysis rate at 10 ℃/min, the initial pyrolysis temperature at 60 ℃, keeping for 10 minutes, the final pyrolysis temperature at 500 ℃, and keeping for 20 minutes;
the biomass pyrolysis liquid can be used for extracting chemicals with high added values; and (3) activating the pyrolytic carbon at the activation temperature of 700 ℃ by using KOH as an activating agent to obtain the biomass activated carbon.
Then, a hydrogen adsorption experiment was performed on the activated carbon: the adsorption pressure is 0-80bar, the adsorption temperature is room temperature, and the adsorbed gas is pure H2(99.999%) and the adsorption time is 12 h.
Then, the sample waste biomass juice and the waste biomass pyrolysis liquid are subjected to GC/MS analysis, as shown in tables 1 and 2, and the multi-activated carbon is subjected to an adsorption experiment, as shown in FIG. 1.
TABLE 1 GC/MS analysis of spent biomass extracts (phenolic fraction)
TABLE 2 GC/MS analysis of spent biomass pyrolysis liquid (phenolic fraction)
Wherein, in the biomass extract, the palmitic acid accounts for about 14 percent, and the stearic acid accounts for about 7.5 percent, and the palmitic acid and the stearic acid are chemical intermediates with pesticide potential; in the waste biomass pyrolysis liquid, the content of phenolic substances which can be used as pesticides can reach more than 40 percent, which shows that the Chinese cabbage pyrolysis liquid has great potential as a botanical pesticide; when the activated carbon is subjected to adsorption test, the adsorption value can reach 40cm under the laboratory condition3/g STP。
It can be shown that the process can achieve a fractionated utilization of waste biomass.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive faculty, based on the technical solutions of the present invention.
Claims (10)
1. A multistage utilization method of waste biomass is characterized in that: the method comprises the following steps:
the collected waste biomass is spirally squeezed, waste biomass with high water content can obtain biomass juice and biomass slag, waste biomass with low water content can obtain small-particle biomass slag, and slag-juice separation is integrally realized;
carrying out ultrasonic and alcohol heat extraction on the waste biomass slag and the waste biomass juice, and mixing extracted liquid to obtain an extracting solution;
drying and performing segmented pyrolysis on the extracted waste biomass slag to obtain biomass pyrolysis liquid and biomass pyrolysis carbon, and activating the pyrolysis carbon to obtain biomass activated carbon;
the biomass pyrolysis liquid is further extracted to obtain a high value-added chemical;
further extracting the extracting solution to obtain the biological pesticide raw material.
2. The multistage utilization method of waste biomass according to claim 1, characterized in that: the waste biomass is plant biomass.
3. The multistage utilization method of waste biomass according to claim 1, characterized in that: the spiral squeezing is divided into four sections of squeezing which are respectively as follows:
a first stage: disconnecting the biomass and preparing for extrusion;
and a second stage: kneading biomass, and primarily squeezing;
a third stage: finely grinding the biomass and extracting vegetable juice;
a fourth stage: grinding the biomass and extruding vegetable residue;
further, the grinding is stone-like grinding double-sided extrusion.
4. The multistage utilization method of waste biomass according to claim 1, characterized in that: the extractant for alcohol heat extraction is absolute ethyl alcohol;
further, during alcohol-heat extraction, the mass ratio of the absolute ethyl alcohol to the vegetable residue is 1: 0.8-1;
further, the temperature of alcohol heat extraction is 70-80 ℃;
further, the time of alcohol hot extraction is 2.5-3.5 h.
5. The multistage utilization method of waste biomass according to claim 1, characterized in that: the power of ultrasonic treatment is 40-60W, and the time of ultrasonic treatment is 20-40 min.
6. The multistage utilization method of waste biomass according to claim 1, characterized in that: the pyrolysis conditions for carrying out the segmented pyrolysis on the waste biomass slag are as follows: the flow rate is 200-210ml/min under the nitrogen atmosphere; the pyrolysis heating rate is 8-12 ℃/min, the pyrolysis final temperature is 700 ℃, and the holding time is 20 min.
7. The multistage utilization method of waste biomass according to claim 1, characterized in that: the activating agent of the pyrolytic carbon is KOH, the activating temperature is 650-750 ℃, and the activating time is 0.8-1.2 h.
8. The multistage utilization method of waste biomass according to claim 1, characterized in that: the extraction solvent of the biomass pyrolysis liquid is ethyl acetate.
9. The multistage utilization method of waste biomass according to claim 1, characterized in that: the biological pesticide raw material is formamide, stearic acid or palmitic acid.
10. The multistage utilization method of waste biomass according to claim 1, characterized in that: the spiral breaking core comprises a rotating main shaft, and a first section of spiral teeth, a second section of spiral teeth, a third section of spiral teeth and a fourth section of spiral teeth which are arranged on the rotating main shaft;
the rotary main shaft comprises a constant-diameter section and an expansion section, the expansion section is of a structure which gradually shrinks from the middle part to two sides, and the constant-diameter section is connected with the minimum-diameter end of the expansion section;
the first section of spiral teeth and the second section of spiral teeth are sequentially arranged on the constant-diameter section along the axial direction, and the helix angle is 22-25 degrees; the third section of helical teeth and the fourth section of helical teeth are sequentially arranged on the expansion section along the axial direction, the helix angle is 28-32 degrees, and the third section of helical teeth spans the maximum diameter of the expansion section;
furthermore, the thread diameter of the second section of spiral teeth is smaller than that of the first section of spiral teeth;
furthermore, the pitch of the third section of helical teeth is larger than that of the fourth section of helical teeth.
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| CN102247966A (en) * | 2010-05-20 | 2011-11-23 | 许绍良 | Method of harmless and recycle treatment of garbage |
| US20110258914A1 (en) * | 2011-05-15 | 2011-10-27 | Avello Bioenergy, Inc. | Methods for integrated fast pyrolysis processing of biomass |
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