CN104312601A - Preparation method of high-strength biomass carbonaceous fuel - Google Patents
Preparation method of high-strength biomass carbonaceous fuel Download PDFInfo
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- CN104312601A CN104312601A CN201410506376.XA CN201410506376A CN104312601A CN 104312601 A CN104312601 A CN 104312601A CN 201410506376 A CN201410506376 A CN 201410506376A CN 104312601 A CN104312601 A CN 104312601A
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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
-
- 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
- C01B32/354—After-treatment
- C01B32/382—Making shaped products, e.g. fibres, spheres, membranes or foam
-
- 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
- C01B32/354—After-treatment
- C01B32/384—Granulation
-
- 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
- C10B53/08—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form in the form of briquettes, lumps and the like
-
- 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
-
- 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
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
- C10B57/10—Drying
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
The invention relates to a preparation method of a high-strength biomass carbonaceous fuel. The preparation method comprises the following steps: crushing wood flour and peanut shells, drying, then adding a binder and performing extrusion forming by a thermoforming machine, wherein the forming pressure is 15-25Mpa and the forming temperature is 180-230 DEG C; and demolding, then placing into a carbonization furnace for carbonization, placing the prepared carbon fuel into a ZnCl2 solution with the mass fraction of 12%-25% for soaking, and further placing into an activation furnace for activation so as to prepare the high-strength biomass carbonaceous fuel after activation, wherein the activation temperature is 650-800 DEG C. By adopting the preparation method provided by the invention, the strength and density of the biomass carbonaceous fuel are improved, and the biomass carbonaceous fuel further has high calorific value, easiness in ignition, environmental friendliness, high burnout rate, relatively large specific surface area and porosity and strong adsorption performance, and can be widely used in the fields of metallurgy, environmental friendliness and life.
Description
Technical field
The invention belongs to chemical field, particularly relate to a kind of renewable energy resources, specifically the preparation method of a kind of high strength biomass carbonaceous fuel and gac.
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Background technology
China's biomass resource enriches, mainly based on forest and agricultural biomass.Be characterized in that energy density is low, distribution is not concentrated, and biomass waste is mainly used as family's fuel, animal-feed or buries to make fertilizer in the ground, and even directly burn, utilization ratio declines.Biomass moulding charing technology solves the problem, and effective one of method utilizing biomass resource, current biomass moulding charring process can be divided into two classes according to charing sequencing: a class first carbonizes aftershaping, and an other class is first shaping rear charing.The technical process first carbonizing aftershaping is: raw material-pulverizing-charing-interpolation binding agent-extrusion molding-drying-packaging.This molding mode raw fibre structure is damaged in carbonization process, so add some binding agents to make its extrusion molding, characteristic improves, and the energy expenditure in the mechanical wear of profiled part and extrusion process reduces.If not adding additives, accumulating and the use of forming blocks be ensured, then need larger pressure.The technical process of first shaping rear charing is: raw material-pulverizing drying-shaping-charing-cooling-packaging.The method that mostly employing first carbonizes aftershaping in the market prepares carbonaceous fuel, but this molding mode exists, and shaping heat is uneven, ratio of briquetting is low, quality difficulty or ease control, and intensity and density difference some, purposes is single.
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Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of preparation method of high strength biomass carbonaceous fuel, the preparation method of described this high strength biomass carbonaceous fuel will solve that forming method heat of the prior art is uneven, ratio of briquetting is low, frangible, quality difficulty or ease control, and the technical problem of intensity and density difference.
The preparation method of a kind of high strength biomass of the present invention carbonaceous fuel, comprises the following steps:
1) step of peanut capsomere is prepared for one, prepare in the step of peanut capsomere described, first Pericarppium arachidis hypogaeae is pulverized, choose the peanut capsomere of particle diameter within 1mm, peanut capsomere is placed in loft drier, dry 2 ~ 3 hours at the temperature of 102 ~ 105 DEG C, make the water ratio of peanut capsomere between 7%-10%;
2) also comprise the step that is prepared wood grain, prepare in the step of wood grain described, first wood chip is pulverized, choose the wood grain of particle diameter within 1mm, wood grain is placed in loft drier, dries 2 ~ 3 hours at the temperature of 102 ~ 105 DEG C, make the water ratio of wood grain between 7%-10%;
3) peanut capsomere and wood grain are mixed according to the ratio of 1:1, then to add massfraction be 13 ~ 15%.Modified-Starch Binder stir, the mass ratio of described peanut capsomere and the quality of wood grain and Modified-Starch Binder is 70 ~ 80:20 ~ 30, then by mixture through heat pressing forming machines extrusion molding, mold temperature is 180 ~ 230 DEG C, forming pressure is 15 ~ 25Mpa, carries out drying treatment and obtain shaping biomass carbonaceous fuel after the demoulding;
4) above-mentioned shaping biomass carbonaceous fuel is positioned over charring furnace and carries out charing process, temperature rise rate is 10 DEG C/min, carbonization temperature is 540 ~ 600 DEG C, in charring furnace, pass into nitrogen simultaneously, and be incubated 30 ~ 40min, then power-off, continues biomass carbonaceous fuel to be that protection gas naturally cools to room temperature with nitrogen, takes out carbonaceous fuel in stove;
5) above-mentioned carbonaceous fuel is put into the Zncl that massfraction is 12% ~ 25%
2soak in solution, soak 0.2 ~ 2 hour, and then put into activation furnace (retort furnace) and activate; continue in activation furnace to pass into nitrogen as protective gas; activation temperature is 650 ~ 800 DEG C, activates 2-4 hours, obtained high strength biomass carbonaceous fuel after washing and drying process.
Further, the preparation method of described Modified-Starch Binder is as follows: calculate according to 100g starch, gets 200ml water, is incubated to 50 ~ 65 DEG C and adds 100g starch, add the dense H of 2ml under agitation condition
2sO
4, 2gKMnO
4oxidation 0.6 ~ 1.5h, magnesium oxide or the ferric oxide of 100g water and 1g unslaked lime and 0.4g is added after fully oxidized 0.6 ~ 1.5h, then add the solution of 8gNaOH preparation, add 30g borax after gelatinization 15 ~ 30min, last moisturizing makes starch adesive massfraction reach 13 ~ 15%.
Further, pass in the process of nitrogen in charring furnace, activation furnace, the flow of gas is 150 ~ 300ml/min.In activation furnace, temperature rise rate will lower than the temperature rise rate in charring furnace, in case crack arrest line produces.
Concrete, described charring furnace and activation furnace can be all retort furnaces.
Present invention also offers a kind of method preparing gac; by above-mentioned obtained high strength biomass carbonaceous fuel through pulverizing, washing, dry or before washing first pickling obtain gac; gained gac is classified to sieve or after milled processed; obtain indefinite form granulated active carbon or powdered carbon, pack with suitable screen cloth.
Known through technical analysis, Pericarppium arachidis hypogaeae raw material ash rate wood chip ash content is slightly high, volatile matter is lower than wood chip, by two kinds of obtained composite biomass charcoals of mixing, can make up that Pericarppium arachidis hypogaeae ash content is high, wood chip volatile matter not enough, learn from other's strong points to offset one's weaknesses, have complementary advantages, the ash content of these two kinds of biomass is far smaller than coal, and shaping rear calorific value and medium ature of coal calorific value almost, then add binding agent and make carbonaceous combust molding in moulding process.
The present invention be easy to pulverize wood chip and Pericarppium arachidis hypogaeae for carbon source, the dry materials of particle diameter within 1mm is selected after wood chip and Pericarppium arachidis hypogaeae being pulverized, add binding agent through forming machine extrusion molding, put into charring furnace after the demoulding to carbonize, put into activation furnace to activate, invention increases intensity and the density of biomass charcoal, be applicable to communications and transportation, and calorific value is high, easily light, environmental protection burn-off rate is high, also there is larger specific surface area, porosity can have powerful absorption property, its powdered carbon screen cloth is packaged into gac bag, metallurgy can be widely used in, environmental protection, sphere of life.
The present invention compares with prior art, and its technical progress is significant.Utilization ratio of the present invention is high, outward appearance is more stable, and grain forming rate is high, solves the difficult problem that the rear percentage of damage of shaped fuel charing is high.
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Accompanying drawing explanation
?fig. 1 is the process flow sheet of the preparation method of a kind of high strength biomass carbonaceous fuel of the present invention.
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concrete embodiment
embodiment 1
First wood chip and Pericarppium arachidis hypogaeae are pulverized through pulverizer, the raw material that particle diameter is not more than 1mm is chosen with sieve, be placed in loft drier, dry at the temperature of 105 DEG C after 2 ~ 3 hours, make water ratio that it controls material 7-10%, calculate according to 100g starch, get 200ml water, insulation adds 100g starch to 60 DEG C, adds the dense H of 2ml under agitation condition
2sO
4, 2gKMnO
4oxidation 1h, the magnesium oxide (or ferric oxide) of 100g water and 1g unslaked lime and 0.4g is added after fully oxidized 1h, then the solution of 8gNaOH preparation is added, 30g borax is added after gelatinization 20min, the per-cent that last moisturizing makes starch adesive massfraction reach needs is 13%, above-mentioned raw materials 70%(is selected Pericarppium arachidis hypogaeae: wood chip=1:1) to mix with 30% starch adesive (starch quality mark 5.6%) and on forming machine, then after the compression moulding demoulding, carry out drying and processing obtain shaping biomass carbonaceous fuel, rod shape fuel after shaping is placed in retort furnace, temperature rise rate is selected to be 10 DEG C/min, be warming up to 540 DEG C to carry out and lead to nitrogen carrying out carbonization process, and be incubated 60min, then in stove, room temperature is naturally cooled to after power-off, take out charing fuel, by the packing of shaping charing sample plastics bag, sealing, be placed with in the drying basin of silica-gel drier stand-by, above-mentioned carbonaceous fuel is put into the Zncl that concentration is 15%
2soak as activator, activation furnace continues to pass into nitrogen as protective gas, in activation furnace, temperature rise rate will lower than the temperature rise rate in charring furnace, in case crack arrest line produces, activation temperature is 650 DEG C, activates 2-4 hours, obtained carbonaceous fuel, washing, drying gets final product or first pickling before washing, dry.
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embodiment 2
First wood chip and Pericarppium arachidis hypogaeae are pulverized through pulverizer, the raw material that particle diameter is not more than 1mm is chosen with sieve, be placed in loft drier, dry at the temperature of 105 DEG C after 2 ~ 3 hours, make water ratio that it controls material 7-10%, calculate according to 100g starch, get 200ml water, insulation adds 100g starch to 60 DEG C, adds the dense H of 2ml under agitation condition
2sO
4, 2gKMnO
4oxidation 1h, the magnesium oxide (or ferric oxide) of 100g water and 1g unslaked lime and 0.4g is added after fully oxidized 1h, then the solution of 8gNaOH preparation is added, 30g borax is added after gelatinization 20min, the per-cent that last moisturizing makes starch adesive massfraction reach needs is 14%, above-mentioned raw materials 72.5%(is selected Pericarppium arachidis hypogaeae: wood chip=1:1) to mix with 27.5% starch adesive (starch quality mark 5.0%) and on forming machine, then after the compression moulding demoulding, carry out drying and processing obtain shaping biomass carbonaceous fuel, rod shape fuel after shaping is placed in retort furnace, temperature rise rate is selected to be 10 DEG C/min, be warming up to 570 DEG C to carry out and lead to nitrogen carrying out carbonization process, and be incubated 60min, then in stove, room temperature is naturally cooled to after power-off, take out charing fuel, by the packing of shaping charing sample plastics bag, sealing, be placed with in the drying basin of silica-gel drier stand-by, above-mentioned carbonaceous fuel is put into the Zncl that concentration is 15%
2soak as activator, activation furnace continues to pass into nitrogen as protective gas, in activation furnace, temperature rise rate will lower than the temperature rise rate in charring furnace, in case crack arrest line produces, activation temperature is 700 DEG C, activates 2-4 hours, obtained carbonaceous fuel, washing, drying gets final product or first pickling before washing, dry.
embodiment 3
First wood chip and Pericarppium arachidis hypogaeae are pulverized through pulverizer, the raw material that particle diameter is not more than 1mm is chosen with sieve, be placed in loft drier, dry at the temperature of 105 DEG C after 2 ~ 3 hours, make water ratio that it controls material 7-10%, calculate according to 100g starch, get 200ml water, insulation adds 100g starch to 60 DEG C, adds the dense H of 2ml under agitation condition
2sO
4, 2gKMnO
4oxidation 1h, the magnesium oxide (or ferric oxide) of 100g water and 1g unslaked lime and 0.4g is added after fully oxidized 1h, then the solution of 8gNaOH preparation is added, 30g borax is added after gelatinization 20min, the per-cent that last moisturizing makes starch adesive massfraction reach needs is 14%, above-mentioned raw materials 75%(is selected Pericarppium arachidis hypogaeae: wood chip=1:1) to mix with 25% starch adesive (starch quality mark 4.4%) and on forming machine, then after the compression moulding demoulding, carry out drying and processing obtain shaping biomass carbonaceous fuel, rod shape fuel after shaping is placed in retort furnace, temperature rise rate is selected to be 10 DEG C/min, be warming up to 600 DEG C to carry out and lead to nitrogen carrying out carbonization process, and be incubated 60min, then in stove, room temperature is naturally cooled to after power-off, take out charing fuel, by the packing of shaping charing sample plastics bag, sealing, be placed with in the drying basin of silica-gel drier stand-by, above-mentioned carbonaceous fuel is put into the Zncl that concentration is 15%
2soak as activator, and then put into an activation furnace and activate, activation furnace continues to pass into nitrogen as protective gas, and in activation furnace, temperature rise rate will lower than the temperature rise rate in charring furnace, in case crack arrest line produces, activation temperature is 750 DEG C, activate 2-4 hours, obtained carbonaceous fuel, washing, drying gets final product or first pickling before washing, dry.
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Embodiment 4
First wood chip and Pericarppium arachidis hypogaeae are pulverized through pulverizer, the raw material that particle diameter is not more than 1mm is chosen with sieve, be placed in loft drier, dry at the temperature of 105 DEG C after 2 ~ 3 hours, make water ratio that it controls material 7-10%, calculate according to 100g starch, get 200ml water, insulation adds 100g starch to 60 DEG C, adds the dense H of 2ml under agitation condition
2sO
4, 2gKMnO
4oxidation 1h, the magnesium oxide (or ferric oxide) of 100g water and 1g unslaked lime and 0.4g is added after fully oxidized 1h, then the solution of 8gNaOH preparation is added, 30g borax is added after gelatinization 20min, the per-cent that last moisturizing makes starch adesive massfraction reach needs is 15%, above-mentioned raw materials 80%(is selected Pericarppium arachidis hypogaeae: wood chip=1:1) to mix with 20% starch adesive (starch quality mark 3.4%) and on forming machine, then after the compression moulding demoulding, carry out drying and processing obtain shaping biomass carbonaceous fuel, rod shape fuel after shaping is placed in retort furnace, temperature rise rate is selected to be 10 DEG C/min, be warming up to 650 DEG C to carry out and lead to nitrogen carrying out carbonization process, and be incubated 60min, then in stove, room temperature is naturally cooled to after power-off, take out charing fuel, by the packing of shaping charing sample plastics bag, sealing, be placed with in the drying basin of silica-gel drier stand-by, above-mentioned carbonaceous fuel is put into the Zncl that concentration is 15%
2soak as activator, and then put into an activation furnace and activate, activation furnace continues to pass into nitrogen as protective gas, and in activation furnace, temperature rise rate will lower than the temperature rise rate in charring furnace, in case crack arrest line produces, activation temperature is 800 DEG C, activate 2-4 hours, obtained carbonaceous fuel, washing, drying gets final product or first pickling before washing, dry.
Claims (4)
1. a preparation method for high strength biomass carbonaceous fuel, is characterized in that comprising the following steps:
1) step of peanut capsomere is prepared for one, prepare in the step of peanut capsomere described, first Pericarppium arachidis hypogaeae is pulverized, choose the peanut capsomere of particle diameter within 1mm, peanut capsomere is placed in loft drier, dry 2 ~ 3 hours at the temperature of 102 ~ 105 DEG C, make the water ratio of peanut capsomere between 7%-10%;
2) also comprise the step that is prepared wood grain, prepare in the step of wood grain described, first wood chip is pulverized, choose the wood grain of particle diameter within 1mm, wood grain is placed in loft drier, dries 2 ~ 3 hours at the temperature of 102 ~ 105 DEG C, make the water ratio of wood grain between 7%-10%;
3) peanut capsomere and wood grain are mixed according to the ratio of 1:1, add again massfraction reach be 13 ~ 15% Modified-Starch Binder stir, the mass ratio of described peanut capsomere and the quality of wood grain and Modified-Starch Binder is 70 ~ 80:20 ~ 30, then by mixture through heat pressing forming machines extrusion molding, mold temperature is 180 ~ 230 DEG C, forming pressure is 15 ~ 25Mpa, carries out drying treatment and obtain shaping biomass carbonaceous fuel after the demoulding;
4) above-mentioned shaping biomass carbonaceous fuel is positioned over a charring furnace and carries out charing process, temperature rise rate is 10 DEG C/min, carbonization temperature is 540 ~ 600 DEG C, in charring furnace, pass into nitrogen simultaneously, and be incubated 30 ~ 40min, then power-off, naturally cools to room temperature by biomass carbonaceous fuel in stove, takes out carbonaceous fuel;
5) above-mentioned carbonaceous fuel is put into the Zncl that massfraction is 12% ~ 25%
2soak in solution, soak 0.2 ~ 2 hour, and then put into activation furnace and activate, continue in activation furnace to pass into nitrogen as protective gas, activation temperature is 650 ~ 800 DEG C, activates 2-4 hours, obtained high strength biomass carbonaceous fuel after washing and drying.
2. the preparation method of a kind of high strength biomass carbonaceous fuel as claimed in claim 1, it is characterized in that: the preparation method of described Modified-Starch Binder is as follows: calculate according to 100g starch, get 200ml water, be incubated to 50 ~ 65 DEG C and add 100g starch, under agitation condition, add the dense H of 2ml
2sO
4, 2gKMnO
4oxidation 0.6 ~ 1.5h, magnesium oxide or the ferric oxide of 100g water and 1g unslaked lime and 0.4g is added after fully oxidized 0.6 ~ 1.5h, then add the solution of 8gNaOH preparation, add 30g borax after gelatinization 15 ~ 30min, last moisturizing makes starch adesive massfraction reach 13 ~ 15%.
3. the preparation method of a kind of high strength biomass carbonaceous fuel as claimed in claim 1, it is characterized in that, pass in the process of nitrogen in charring furnace, activation furnace, the flow of gas is 150 ~ 300ml/min.
4. prepare the method for gac for one kind; it is characterized in that: by high strength biomass carbonaceous fuel obtained for claim 1 through pulverizing, washing, dry or before washing first pickling wash again and obtain gac after drying; gained gac is classified to sieve or after milled processed; obtain indefinite form granulated active carbon or powdered carbon, pack with suitable screen cloth.
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