CN108865317B - Biomass carbon rod with high calorific value - Google Patents
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- CN108865317B CN108865317B CN201810666333.6A CN201810666333A CN108865317B CN 108865317 B CN108865317 B CN 108865317B CN 201810666333 A CN201810666333 A CN 201810666333A CN 108865317 B CN108865317 B CN 108865317B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
- C10L5/445—Agricultural waste, e.g. corn crops, grass clippings, nut shells or oil pressing residues
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/02—Treating solid fuels to improve their combustion by chemical means
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/02—Combustion or pyrolysis
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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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- 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
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a biomass carbon rod with high calorific value, which relates to the technical field of biological environmental protection, wherein corn straws are crushed to obtain corn straw powder, the corn straw powder is treated by a silane coupling agent solution, the treated corn straw powder is modified by a copolymer, and is carbonized by a pyrolysis furnace to obtain biomass carbon, and the biomass carbon is pressed to obtain the carbon rod; the biomass charcoal carbon rod prepared by the invention can enhance the combustion performance of the molded fuel, and the molded carbon rod can also have certain external force resistance, is not easy to break in the transportation or storage process, has less smoke and dust discharged in the combustion process, has less ash residue after combustion, has more stable combustion performance and strong anti-slagging capability, and can effectively reduce slagging corrosion in the straw combustion process.
Description
Technical Field
The invention belongs to the technical field of biological environmental protection, and particularly relates to a biomass carbon rod with a high calorific value.
Background
China is a big agricultural country, and according to statistics, about 6 to 7 hundred million tons of crop straws such as rice, wheat, corn and the like are generated every year. As agricultural production waste, the straws are usually directly incinerated, so that a large amount of smoke is generated, serious air pollution is caused, traffic accidents and even fire disasters are often caused, and the life of people is seriously influenced. Therefore, how to reasonably utilize the large amount of waste straws is a research hotspot not only in China but also in the world. At present, the domestic and foreign utilization of the waste straws mainly comprises the modes of returning to the field on site, fermenting and gasifying, generating electricity, producing biomass fuel and the like. Among them, the production of biomass fuel, especially shaped fuel, by using straw is one of the main development trends of straw application.
Disclosure of Invention
The invention aims to provide a biomass carbon rod with high calorific value aiming at the existing problems.
The invention is realized by the following technical scheme:
the utility model provides a biomass charcoal stick of high calorific value, smashes by maize straw, obtains maize straw powder, handles back with maize straw powder through silane coupling agent solution again, and the maize straw powder after will handling is through copolymer modification treatment again, passes through the pyrolysis oven carbomorphism and obtains biomass charcoal, and the charcoal gets the charcoal stick through the suppression again with biomass charcoal.
Further, the granularity of the corn straw powder is 50 meshes.
Further, the treatment of the corn straw powder by the silane coupling agent solution comprises the following steps: soaking the corn straw powder in 5.5% by mass of organosilane coupling agent solution in a water bath at 70 ℃ for 2 hours, filtering, and drying to constant weight.
Further, the preparation method of the copolymer comprises the following steps:
mixing ethyl orthosilicate and ethanol according to a mass ratio of 12: 3.3, adding the mixture into a reaction kettle, stirring at the rotating speed of 500r/min, then dropwise adding deionized water, wherein the molar ratio of the deionized water to the tetraethoxysilane is 15: 5.8, then adopting hydrochloric acid to adjust the pH of the reaction system to be 3.1, reacting for 1.8 hours at the constant temperature of 42 ℃ in a water bath, heating to 75 ℃, preserving the temperature for 3.5 hours to obtain colorless, transparent and stable sol, then dropwise adding an organic silicon monomer and deionized water, wherein the molar ratio of the organic silicon monomer to the tetraethoxysilane is 5: 1.4, the molar ratio of the deionized water to the organic silicon monomer is 2: 1.3, adjusting the pH value of the reaction system to 3.2 by adopting hydrochloric acid, keeping the temperature of the reaction system constant at 75 ℃ for 4 hours, and distilling the reaction system under reduced pressure to remove water and ethanol to obtain colorless, transparent and viscous copolymer liquid.
Further, the concentration of the hydrochloric acid is 1.2 mol/L.
Further, the copolymer is modified by mixing the copolymer with 30% ethanol solution by mass percent according to the weight ratio of 57-59 g: uniformly mixing 400ml of the raw materials, heating to 82 ℃, stirring at the rotating speed of 1500r/min for 2 hours to obtain a modified solution, mixing the modified solution with the mixed raw materials according to the proportion of 450 ml: 202g and 208g, then adding ammonium persulfate accounting for 1.4 percent of the mass of the mixed raw materials, stirring for 4 hours at the rotating speed of 150r/min in a water bath at 78 ℃, then filtering the mixed raw materials, and drying in vacuum to constant weight.
Further, the vacuum drying temperature is 40 ℃.
Further, the carbonization temperature of the pyrolysis furnace is 470-475 ℃.
Further, the carbonization time of the pyrolysis furnace is 1.6 hours.
Compared with the prior art, the invention has the following advantages: the carbon rod prepared by the invention has higher heat value, the heat value of the obtained biomass carbon is greatly improved by treating the corn straw powder with an organic silane coupling agent solution, then modifying the treated corn straw powder with a copolymer, and then carbonizing the modified corn straw powder, so that the utilization rate of resources is obviously improved, and when the mixed raw material modified by the copolymer is carbonized, the peanut shells and camphor trees are within the temperature range of 470-475 DEG CThe organic matters such as cellulose in the wood powder can be decomposed and carbonized more quickly and completely to generate a large amount of CO2The content of fixed carbon in gases such as CO and the like is correspondingly improved, so that the heat value after carbonization is correspondingly improved, and the biomass charcoal stick prepared by the method not only can enhance the combustion performance of the formed fuel and be pressed and formed, but also can have certain external force resistance, is not easy to break in the transportation or storage process, has less smoke and dust discharged in the combustion process, has less ash residue after combustion, has more stable combustion performance and strong anti-slagging capacity, and can effectively reduce slagging corrosion in the straw combustion process.
Detailed Description
Example 1
The utility model provides a biomass charcoal stick of high calorific value, smashes by maize straw, obtains maize straw powder, handles back with maize straw powder through silane coupling agent solution again, and the maize straw powder after will handling is through copolymer modification treatment again, passes through the pyrolysis oven carbomorphism and obtains biomass charcoal, and the charcoal gets the charcoal stick through the suppression again with biomass charcoal.
Further, the granularity of the corn straw powder is 50 meshes.
Further, the treatment of the corn straw powder by the silane coupling agent solution comprises the following steps: soaking the corn straw powder in 5.5% by mass of organosilane coupling agent solution in a water bath at 70 ℃ for 2 hours, filtering, and drying to constant weight.
Further, the preparation method of the copolymer comprises the following steps:
mixing ethyl orthosilicate and ethanol according to a mass ratio of 12: 3.3, adding the mixture into a reaction kettle, stirring at the rotating speed of 500r/min, then dropwise adding deionized water, wherein the molar ratio of the deionized water to the tetraethoxysilane is 15: 5.8, then adopting hydrochloric acid to adjust the pH of the reaction system to be 3.1, reacting for 1.8 hours at the constant temperature of 42 ℃ in a water bath, heating to 75 ℃, preserving the temperature for 3.5 hours to obtain colorless, transparent and stable sol, then dropwise adding an organic silicon monomer and deionized water, wherein the molar ratio of the organic silicon monomer to the tetraethoxysilane is 5: 1.4, the molar ratio of the deionized water to the organic silicon monomer is 2: 1.3, adjusting the pH value of the reaction system to 3.2 by adopting hydrochloric acid, keeping the temperature of the reaction system constant at 75 ℃ for 4 hours, and distilling the reaction system under reduced pressure to remove water and ethanol to obtain colorless, transparent and viscous copolymer liquid.
Further, the concentration of the hydrochloric acid is 1.2 mol/L.
Further, the copolymer is modified by mixing the copolymer with 30% ethanol solution by mass percent according to a ratio of 57 g: uniformly mixing 400ml of the raw materials, heating to 82 ℃, stirring at the rotating speed of 1500r/min for 2 hours to obtain a modified solution, mixing the modified solution with the mixed raw materials according to the proportion of 450 ml: 202g, adding ammonium persulfate accounting for 1.4 percent of the mass of the mixed raw materials, stirring for 4 hours in a water bath at 78 ℃ at the rotating speed of 150r/min, filtering the mixed raw materials, and drying in vacuum to constant weight.
Further, the vacuum drying temperature is 40 ℃.
Further, the carbonization temperature of the pyrolysis furnace is 470-475 ℃.
Further, the carbonization time of the pyrolysis furnace is 1.6 hours.
Example 2
The utility model provides a biomass charcoal stick of high calorific value, smashes by maize straw, obtains maize straw powder, handles back with maize straw powder through silane coupling agent solution again, and the maize straw powder after will handling is through copolymer modification treatment again, passes through the pyrolysis oven carbomorphism and obtains biomass charcoal, and the charcoal gets the charcoal stick through the suppression again with biomass charcoal.
Further, the granularity of the corn straw powder is 50 meshes.
Further, the treatment of the corn straw powder by the silane coupling agent solution comprises the following steps: soaking the corn straw powder in 5.5% by mass of organosilane coupling agent solution in a water bath at 70 ℃ for 2 hours, filtering, and drying to constant weight.
Further, the preparation method of the copolymer comprises the following steps:
mixing ethyl orthosilicate and ethanol according to a mass ratio of 12: 3.3, adding the mixture into a reaction kettle, stirring at the rotating speed of 500r/min, then dropwise adding deionized water, wherein the molar ratio of the deionized water to the tetraethoxysilane is 15: 5.8, then adopting hydrochloric acid to adjust the pH of the reaction system to be 3.1, reacting for 1.8 hours at the constant temperature of 42 ℃ in a water bath, heating to 75 ℃, preserving the temperature for 3.5 hours to obtain colorless, transparent and stable sol, then dropwise adding an organic silicon monomer and deionized water, wherein the molar ratio of the organic silicon monomer to the tetraethoxysilane is 5: 1.4, the molar ratio of the deionized water to the organic silicon monomer is 2: 1.3, adjusting the pH value of the reaction system to 3.2 by adopting hydrochloric acid, keeping the temperature of the reaction system constant at 75 ℃ for 4 hours, and distilling the reaction system under reduced pressure to remove water and ethanol to obtain colorless, transparent and viscous copolymer liquid.
Further, the concentration of the hydrochloric acid is 1.2 mol/L.
Further, the copolymer is modified by mixing the copolymer with 30% ethanol solution in a mass fraction of 59 g: uniformly mixing 400ml of the raw materials, heating to 82 ℃, stirring at the rotating speed of 1500r/min for 2 hours to obtain a modified solution, mixing the modified solution with the mixed raw materials according to the proportion of 450 ml: 208g, adding ammonium persulfate accounting for 1.4 percent of the mass of the mixed raw materials, stirring for 4 hours in a water bath at 78 ℃ at the rotating speed of 150r/min, filtering the mixed raw materials, and drying in vacuum to constant weight.
Further, the vacuum drying temperature is 40 ℃.
Further, the carbonization temperature of the pyrolysis furnace is 470-475 ℃.
Further, the carbonization time of the pyrolysis furnace is 1.6 hours.
Example 3
The utility model provides a biomass charcoal stick of high calorific value, smashes by maize straw, obtains maize straw powder, handles back with maize straw powder through silane coupling agent solution again, and the maize straw powder after will handling is through copolymer modification treatment again, passes through the pyrolysis oven carbomorphism and obtains biomass charcoal, and the charcoal gets the charcoal stick through the suppression again with biomass charcoal.
Further, the granularity of the corn straw powder is 50 meshes.
Further, the treatment of the corn straw powder by the silane coupling agent solution comprises the following steps: soaking the corn straw powder in 5.5% by mass of organosilane coupling agent solution in a water bath at 70 ℃ for 2 hours, filtering, and drying to constant weight.
Further, the preparation method of the copolymer comprises the following steps:
mixing ethyl orthosilicate and ethanol according to a mass ratio of 12: 3.3, adding the mixture into a reaction kettle, stirring at the rotating speed of 500r/min, then dropwise adding deionized water, wherein the molar ratio of the deionized water to the tetraethoxysilane is 15: 5.8, then adopting hydrochloric acid to adjust the pH of the reaction system to be 3.1, reacting for 1.8 hours at the constant temperature of 42 ℃ in a water bath, heating to 75 ℃, preserving the temperature for 3.5 hours to obtain colorless, transparent and stable sol, then dropwise adding an organic silicon monomer and deionized water, wherein the molar ratio of the organic silicon monomer to the tetraethoxysilane is 5: 1.4, the molar ratio of the deionized water to the organic silicon monomer is 2: 1.3, adjusting the pH value of the reaction system to 3.2 by adopting hydrochloric acid, keeping the temperature of the reaction system constant at 75 ℃ for 4 hours, and distilling the reaction system under reduced pressure to remove water and ethanol to obtain colorless, transparent and viscous copolymer liquid.
Further, the concentration of the hydrochloric acid is 1.2 mol/L.
Further, the copolymer is modified by mixing the copolymer with 30% ethanol solution according to a mass fraction of 58 g: uniformly mixing 400ml of the raw materials, heating to 82 ℃, stirring at the rotating speed of 1500r/min for 2 hours to obtain a modified solution, mixing the modified solution with the mixed raw materials according to the proportion of 450 ml: 205g, then adding ammonium persulfate accounting for 1.4 percent of the mass of the mixed raw materials, stirring for 4 hours in a water bath at 78 ℃ at the rotating speed of 150r/min, then filtering the mixed raw materials, and drying in vacuum to constant weight.
Further, the vacuum drying temperature is 40 ℃.
Further, the carbonization temperature of the pyrolysis furnace is 470-475 ℃.
Further, the carbonization time of the pyrolysis furnace is 1.6 hours.
Comparative example 1: the only difference from example 1 is that the corn straw powder was not treated with the organosilane coupling agent solution.
Comparative example 2: the only difference from example 1 is that the raw materials were not subjected to the copolymer modification treatment.
The carbon rod samples of the example and the comparative example with the same weight are placed in a mortar, crushed, dried at 105 ℃ for 2 hours, placed in a closed oxygen bomb of an instrument, and the heat value of the sample is calculated according to the rising of the water temperature caused by the sufficient combustion of the sample in oxygen:
TABLE 1
The contrast group is the corn straw powder before equal-mass carbonization;
as can be seen from Table 1, the carbon rod prepared by the method has higher heat value, the biomass carbon obtained by treating the corn straw powder with an organosilane coupling agent solution, modifying the treated corn straw powder with a copolymer, and carbonizing the modified corn straw powder has greatly improved heat value, so that the utilization rate of resources is obviously improved.
Claims (1)
1. A biomass carbon rod with high calorific value is characterized in that corn straws are smashed to obtain corn straw powder, the corn straw powder is treated by a silane coupling agent solution, the treated corn straw powder is modified by a copolymer, and then is carbonized by a pyrolysis furnace to obtain biomass carbon, and the biomass carbon is pressed to obtain the carbon rod; the granularity of the corn straw powder is 50 meshes; the corn straw powder is treated by a silane coupling agent solution to obtain the following components: soaking the corn straw powder in 5.5% by mass of an organosilane coupling agent solution in a water bath at 70 ℃ for 2 hours, filtering, and drying to constant weight; the preparation method of the copolymer comprises the following steps: mixing ethyl orthosilicate and ethanol according to a mass ratio of 12: 3.3 adding the mixture into a reaction kettle, stirring at the rotating speed of 500r/min, then dropwise adding deionized water, wherein the molar ratio of the deionized water to the tetraethoxysilane is 15: 5.8, then adopting hydrochloric acid to adjust the pH of the reaction system to be 3.1, reacting for 1.8 hours at the constant temperature of 42 ℃ in a water bath, heating to 75 ℃, preserving the temperature for 3.5 hours to obtain colorless, transparent and stable sol, then dropwise adding an organic silicon monomer and deionized water, wherein the molar ratio of the organic silicon monomer to the tetraethoxysilane is 5: 1.4, the molar ratio of the deionized water to the organic silicon monomer is 2: 1.3, adjusting the pH value of a reaction system to 3.2 by adopting hydrochloric acid, keeping the temperature at 75 ℃ for 4 hours, and distilling under reduced pressure to remove water and ethanol to obtain colorless transparent viscous copolymer liquid; the concentration of the hydrochloric acid is 1.2 mol/L; the copolymer modification treatment comprises the following steps of mixing the copolymer with 30% ethanol solution by mass percent according to a ratio of 57-59 g: uniformly mixing 400ml of the raw materials, heating to 82 ℃, stirring at the rotating speed of 1500r/min for 2 hours to obtain a modified solution, mixing the modified solution with the mixed raw materials according to the proportion of 450 ml: 202-208g, adding ammonium persulfate accounting for 1.4 percent of the mass of the mixed raw materials, stirring for 4 hours at the rotating speed of 150r/min in a water bath at 78 ℃, filtering the mixed raw materials, and drying in vacuum until the weight is constant; the vacuum drying temperature is 40 ℃; the carbonization temperature of the pyrolysis furnace is 470-475 ℃; the carbonization time of the pyrolysis furnace is 1.6 hours.
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| CN111944578B (en) * | 2020-08-26 | 2022-05-27 | 湖州民强新材料科技有限公司 | Preparation method of smokeless machine-made charcoal for barbecue |
| CN113881112A (en) * | 2021-11-03 | 2022-01-04 | 浙江树人学院（浙江树人大学） | Preparation method of biomass pyrolysis ash/corn starch biodegradable composite mulching film |
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