CN104069810A - Method for preparing activated charcoal from paper mill sludge and pine through co-pyrolysis - Google Patents
Method for preparing activated charcoal from paper mill sludge and pine through co-pyrolysis Download PDFInfo
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Abstract
The invention discloses a method for preparing activated charcoal from paper mill sludge and pine through co-pyrolysis. The method is characterized by comprising the following steps: (1) pretreating paper mill sludge; (2) airing and grinding pine sawdust; (3) fully mixing the sludge and the pine sawdust; (4) arranging the mixture in a pyrolyzing furnace feeding hopper, and performing constant temperature pyrolysis in an inert atmosphere; (5) heating for reacting at constant temperature until no gas is generated, and naturally cooling to room temperature, thereby obtaining charcoal; and (6) putting the charcoal into a sulfuric acid solution with the concentration of 2.5-3.5 mol/L, introducing nitrogen, reacting at the constant temperature of 500-600 DEG C for 20-40 minutes, and naturally cooling to room temperature, thereby obtaining the activated charcoal. The activated charcoal is prepared by a paper mill sludge and pine co-pyrolysis process, a sludge drying process is not needed, chemical components of adsorbents are improved, and a certain effect of activating the charcoal can be achieved by steam formed by moisture in the sludge at high temperature, so that the adsorption capacity of the charcoal is improved, and an ideal adsorption effect is obtained.
Description
Technical field
The present invention relates to environmental pollution improvement and agriculture and forestry organic waste material recycling field, specifically refer to a kind of method of utilizing paper mill sludge and pine copyrolysis to prepare active bio charcoal.
Background technology
Paper mill sludge is the end product generating because of wastewater treatment in paper-making process, according to statistics, 1 ton of recycled writing paper of every production, 700 tons, the mud that large appointment generation water content is 75%～85%, its composition mainly contains the high molecular organic matter such as hemicellulose, cellulose and lignin and flocculating agent, filler etc., and, containing heavy metal substance, not a kind of biomass resource.But paper mill sludge because its moisture content is higher, complicated component, intractability be larger, its disposal cost accounts for greatly the more than 50% of water treatment running gear expense, therefore, the handling problems of mud has become the bottleneck of constraint paper mill development, the mud producing not only takies a large amount of soils, and poisonous and harmful element wherein will produce serious influence to environment and the mankind.In paper mill sludge, become because containing abundant carbon the advantage of preparing charcoal, pyrolyzing sludge is prepared charcoal adsorbent and is utilized method to be widely studied as a kind of desirable recycling sludge.But because moisture percentage in sewage sludge is higher, traditional pyrolytic process need to be dried mud, has so not only increased the operation of Treatment of Sludge, has greatly improved especially the disposal cost of mud.In addition, ash contents a large amount of in mud butt also can remain in charcoal, thereby have a strong impact on performance and the adsorption effect of charcoal adsorbent.
Summary of the invention
Technical problem to be solved by this invention is to prepare the method for active bio charcoal for utilize paper mill sludge and the pine copyrolysis that it is good that the present situation of prior art provides a kind of absorption property, thereby makes the charcoal of preparation have desirable adsorption effect.
The present invention solves the problems of the technologies described above adopted technical scheme: this utilizes paper mill sludge and pine copyrolysis to prepare the method for active bio charcoal, it is characterized in that comprising the steps:
(1) paper mill sludge of learning from else's experience after mechanical dehydration carries out pretreatment, by deionized water, Sludge Surface impurity is cleaned, and obtains raw sludge;
(2) by collect pine sawdust after natural air drying, shatter and sieve, obtain pine sawdust;
(3) described raw sludge and described pine sawdust are fully mixed by the mass ratio of 9:1-1:9;
(4) mixture of step (3) gained is placed in to pyrolysis oven loading hopper, setting reaction temperature is 600-900 DEG C, until temperature reach set value and keep stable after, pass into nitrogen, raw material is evenly sent in pyrolysis oven, ensured to generate charcoal under oxygen free condition;
(5) keep the constant temperature of 600-900 DEG C during without γ-ray emission, to stop heating to reaction, obtain charcoal after naturally cooling to room temperature;
(6) gained charcoal in step (5) is put into the sulfuric acid solution that concentration is 2.5-3.5mol/L, pass into nitrogen, at 500-600 DEG C, constant temperature 20-40min; Then naturally cool to room temperature, obtain active bio charcoal;
The amount ratio of described charcoal and described sulfuric acid solution is 1:10-1:50, and wherein the unit of the quality of charcoal is gram, and the volume unit of sulfuric acid solution is milliliter.
Preferably, the pine sawdust described in step (2) is crossed 30-50 mesh sieve.
Compared with prior art, the present invention adopts paper mill sludge and pine sawdust copyrolysis technique to prepare active bio charcoal, not only without drying sludge process, also improve the chemical constituent of adsorbent, and can utilize the steam that the moisture in mud at high temperature forms to play certain activation to charcoal, thereby the adsorption capacity that improves charcoal, has obtained desirable adsorption effect.
Brief description of the drawings
Fig. 1 is the electron scanning electromicroscopic photograph of the charcoal of preparation in embodiment 1.
Fig. 2 is the electron scanning electromicroscopic photograph of the charcoal of preparation in comparative example 1.
Fig. 3 is the electron scanning electromicroscopic photograph of the charcoal of preparation in comparative example 2.
Fig. 4 is the electron scanning electromicroscopic photograph of the charcoal of preparation in comparative example 3.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
Embodiment 1
(1) paper mill sludge of learning from else's experience after mechanical dehydration carries out pretreatment, by deionized water, Sludge Surface impurity is cleaned, and obtains raw sludge;
(2) by collect pine sawdust after natural air drying, shattered 40 mesh sieves;
(3) by gained paper mill sludge in step (1) and step (2) and pine sawdust in mass ratio for 2:3 fully mixes;
(4) mixture of step (3) gained is placed in to pyrolysis oven loading hopper, set reaction temperature be 850 DEG C, until temperature reach set value and keep stablize after, pass into nitrogen, raw material is evenly sent in pyrolysis oven, ensured to generate charcoal under oxygen free condition;
(5) set reaction temperature be under the condition of 850 DEG C continuous heating to reaction without γ-ray emission, stop heating, charcoal to be generated naturally cools to after room temperature, taking-up is weighed, and packs for subsequent use.
(6) get charcoal in step (5) and put into the sulfuric acid solution that concentration is 3mol/L, the ratio of charcoal and sulfuric acid solution is 1 gram: 30 milliliters; Pass into nitrogen, at 550 DEG C, constant temperature 30min; Then naturally cool to room temperature, obtain active bio charcoal.
(7) after the time to be activated finishes, stop heating, naturally cooling, taking-up material, can obtain active bio charcoal.
(8) get the middle gained active bio charcoal of 0.01g step (7) in 100mL conical flask, add 50mL concentration be 90mg/L containing Pb (II) solution, conical flask is put into constant temperature oscillator, under room temperature, with the speed oscillation absorption of 125rpm, after adsorption equilibrium, measure the residual quantity of Pb in solution (II), and calculated equilibrium adsorption capacity.
Active bio charcoal productive rate prepared by the present embodiment is 15.8%, and its electron scanning electromicroscopic photograph as shown in Figure 1.As seen from the figure, the charcoal fibre structure after activation obtains further fragmentation, and it is more unordered that pore distribution becomes, and it is more loose that structure becomes, and surface roughness obviously increases, thereby has improved its absorption property.The active bio charcoal specific area of preparation is 338.9m
2/ g, adsorption capacity is 976.7mg/g.
The computing formula of described charcoal productive rate is:
η＝W
1/W
0×100％
In formula: W
0for quality raw materials used before pyrolytic reaction (g); W
1for the quality (g) of gained charcoal after pyrolytic reaction; η is the productive rate of charcoal.
The mensuration of described charcoal specific area adopts JW-BK122W type specific surface and pore analysis instrument to measure.
The computing formula of described charcoal adsorption capacity is:
Q＝V×(C
0-C)/W
In formula: V is the volume (mL) of Pb (II) solution; C
0for adsorbing the concentration (mg/L) of Pb in front solution (II); C is the concentration (mg/L) of Pb (II) in the rear solution of absorption; W is the quality (g) of charcoal; Q is adsorption capacity (mg/g).
After described absorption, in solution, the mensuration of the concentration of Pb (II) adopts xylenol orange AAS.
Calculating and the detection method of following each embodiment and comparative example are same as described above.
Embodiment 2
(1) paper mill sludge of learning from else's experience after mechanical dehydration carries out pretreatment, by deionized water, Sludge Surface impurity is cleaned, and obtains raw sludge;
(2) by collect pine sawdust after natural air drying, shattered 40 mesh sieves;
(3) by gained paper mill sludge in step (1) and step (2) and pine sawdust in mass ratio for 1:9 fully mixes;
(4) mixture of step (3) gained is placed in to pyrolysis oven loading hopper, set reaction temperature be 600 DEG C, until temperature reach set value and keep stablize after, pass into nitrogen, raw material is evenly sent in pyrolysis oven, ensured to generate charcoal under oxygen free condition;
(5) set reaction temperature be under the condition of 600 DEG C continuous heating to reaction without γ-ray emission, stop heating, charcoal to be generated naturally cools to after room temperature, taking-up is weighed, and packs for subsequent use.
(6) get after the sulfuric acid solution activation that the charcoal in step (5) is 3mol/L through concentration, put into pyrolysis oven loading hopper, pass into nitrogen, regulating activation temperature is 550 DEG C, and soak time is 30min.The amount ratio of charcoal and sulfuric acid solution is 1 gram: 12 milliliters.
(7) after the time to be activated finishes, stop heating, naturally cooling, taking-up material, can obtain active bio charcoal.
(8) get the middle gained active bio charcoal of 0.01g step (7) in 100mL conical flask, add 50mL concentration be 90mg/L containing Pb (II) solution, conical flask is put into constant temperature oscillator, room temperature, with the speed oscillation absorption of 125r/min, after adsorption equilibrium, measure the residual quantity of Pb in solution (II), and calculated equilibrium adsorption capacity.
Embodiment 3
(1) paper mill sludge of learning from else's experience after mechanical dehydration carries out pretreatment, by deionized water, Sludge Surface impurity is cleaned, and obtains raw sludge;
(2) by collect pine sawdust after natural air drying, shattered 40 mesh sieves;
(3) by gained paper mill sludge in step (1) and step (2) and pine sawdust in mass ratio for 1:5 fully mixes;
(4) mixture of step (3) gained is placed in to pyrolysis oven loading hopper, set reaction temperature be 750 DEG C, until temperature reach set value and keep stablize after, pass into nitrogen, raw material is evenly sent in pyrolysis oven, ensured to generate charcoal under oxygen free condition;
(5) set reaction temperature be under the condition of 750 DEG C continuous heating to reaction without γ-ray emission, stop heating, charcoal to be generated naturally cools to after room temperature, taking-up is weighed, and packs for subsequent use.
(6) get after the sulfuric acid solution activation that the charcoal in step (5) is 3mol/L through concentration, put into pyrolysis oven loading hopper, pass into nitrogen, regulating activation temperature is 550 DEG C, and soak time is 30min.The amount ratio of charcoal and sulfuric acid solution is 1 gram: 20 milliliters.
(7) after the time to be activated finishes, stop heating, naturally cooling, taking-up material, can obtain active bio charcoal.
(8) get the middle gained active bio charcoal of 0.01g step (7) in 100mL conical flask, add 50mL concentration be 90mg/L containing Pb (II) solution, conical flask is put into constant temperature oscillator, room temperature, with the speed oscillation absorption of 125r/min, after adsorption equilibrium, measure the residual quantity of Pb in solution (II), and calculated equilibrium adsorption capacity.
Embodiment 4
(1) paper mill sludge of learning from else's experience after mechanical dehydration carries out pretreatment, by deionized water, Sludge Surface impurity is cleaned, and obtains raw sludge;
(2) by collect pine sawdust after natural air drying, shattered 40 mesh sieves;
(3) by gained paper mill sludge in step (1) and step (2) and pine sawdust in mass ratio for 1:1 fully mixes;
(4) mixture of step (3) gained is placed in to pyrolysis oven loading hopper, set reaction temperature be 900 DEG C, until temperature reach set value and keep stablize after, pass into nitrogen, raw material is evenly sent in pyrolysis oven, ensured to generate charcoal under oxygen free condition;
(5) set reaction temperature be under the condition of 900 DEG C continuous heating to reaction without γ-ray emission, stop heating, charcoal to be generated naturally cools to after room temperature, taking-up is weighed, and packs for subsequent use.
(6) get after the sulfuric acid solution activation that the charcoal in step (5) is 3mol/L through concentration, put into pyrolysis oven loading hopper, pass into nitrogen, regulating activation temperature is 550 DEG C, and soak time is 30min.The amount ratio of charcoal and sulfuric acid solution is 1 gram: 40 milliliters.
(7) after the time to be activated finishes, stop heating, naturally cooling, taking-up material, can obtain active bio charcoal.
(8) get the middle gained active bio charcoal of 0.01g step (7) in 100mL conical flask, add 50mL concentration be 90mg/L containing Pb (II) solution, conical flask is put into constant temperature oscillator, room temperature, with the speed oscillation absorption of 125r/min, after adsorption equilibrium, measure the residual quantity of Pb in solution (II), and calculated equilibrium adsorption capacity.
Embodiment 5
(1) paper mill sludge of learning from else's experience after mechanical dehydration carries out pretreatment, by deionized water, Sludge Surface impurity is cleaned, and obtains raw sludge;
(2) by collect pine sawdust after natural air drying, shattered 40 mesh sieves;
(3) by gained paper mill sludge in step (1) and step (2) and pine sawdust in mass ratio for 5:1 fully mixes;
(4) mixture of step (3) gained is placed in to pyrolysis oven loading hopper, set reaction temperature be 900 DEG C, until temperature reach set value and keep stablize after, pass into nitrogen, raw material is evenly sent in pyrolysis oven, ensured to generate charcoal under oxygen free condition;
(5) set reaction temperature be under the condition of 900 DEG C continuous heating to reaction without γ-ray emission, stop heating, charcoal to be generated naturally cools to after room temperature, taking-up is weighed, and packs for subsequent use.
(6) get after the sulfuric acid solution activation that the charcoal in step (5) is 3mol/L through concentration, put into pyrolysis oven loading hopper, pass into nitrogen, regulating activation temperature is 550 DEG C, and soak time is 30min.The amount ratio of charcoal and sulfuric acid solution is 1 gram: 50 milliliters.
(7) after the time to be activated finishes, stop heating, naturally cooling, taking-up material, can obtain active bio charcoal.
(8) get the middle gained active bio charcoal of 0.01g step (7) in 100mL conical flask, add 50mL concentration be 90mg/L containing Pb (II) solution, conical flask is put into constant temperature oscillator, room temperature, with the speed oscillation absorption of 125r/min, after adsorption equilibrium, measure the residual quantity of Pb in solution (II), and calculated equilibrium adsorption capacity.
Embodiment 6
(1) paper mill sludge of learning from else's experience after mechanical dehydration carries out pretreatment, by deionized water, Sludge Surface impurity is cleaned, and obtains raw sludge;
(2) by collect pine sawdust after natural air drying, shattered 40 mesh sieves;
(3) by gained paper mill sludge in step (1) and step (2) and pine sawdust in mass ratio for 9:1 fully mixes;
(4) mixture of step (3) gained is placed in to pyrolysis oven loading hopper, set reaction temperature be 850 DEG C, until temperature reach set value and keep stablize after, pass into nitrogen, raw material is evenly sent in pyrolysis oven, ensured to generate charcoal under oxygen free condition;
(5) set reaction temperature be under the condition of 850 DEG C continuous heating to reaction without γ-ray emission, stop heating, charcoal to be generated naturally cools to after room temperature, taking-up is weighed, and packs for subsequent use.
(6) get after the sulfuric acid solution activation that the charcoal in step (5) is 3mol/L through concentration, put into pyrolysis oven loading hopper, pass into nitrogen, regulating activation temperature is 550 DEG C, and soak time is 30min.The amount ratio of charcoal and sulfuric acid solution is 1 gram: 30 milliliters.
(7) after the time to be activated finishes, stop heating, naturally cooling, taking-up material, can obtain active bio charcoal.
(8) get the middle gained active bio charcoal of 0.01g step (7) in 100mL conical flask, add 50mL concentration be 90mg/L containing Pb (II) solution, conical flask is put into constant temperature oscillator, room temperature, with the speed oscillation absorption of 125r/min, after adsorption equilibrium, measure the residual quantity of Pb in solution (II), and calculated equilibrium adsorption capacity.
In embodiment 2 to embodiment 6, the productive rate of active bio charcoal is between 12-21%, and specific area is at 300-350m
2between/g, adsorption capacity is between 950-1000mg/g, and electron-microscope scanning structure and embodiment's 1 is similar.
Comparative example 1
(1) paper mill sludge of learning from else's experience after mechanical dehydration carries out pretreatment, by deionized water, Sludge Surface impurity is cleaned, and obtains raw sludge;
(2) by collect pine sawdust after natural air drying, shattered 40 mesh sieves;
(3) by gained raw sludge in step (1) and step (2) and pine sawdust in mass ratio for 2:3 mixes;
(4) mixture of step (3) gained is placed in to pyrolysis oven loading hopper, set reaction temperature be 850 DEG C, until temperature reach set value and keep stablize after, pass into nitrogen, raw material is evenly sent in pyrolysis oven, ensured to generate charcoal under oxygen free condition;
(5) set reaction temperature be under the condition of 850 DEG C continuous heating to reaction without γ-ray emission, stop heating, charcoal to be generated naturally cools to after room temperature, taking-up is weighed, and packs for subsequent use.
(6) get the middle gained charcoal of 0.01g step (3) in 100mL conical flask, add 50mL concentration be 90mg/L containing Pb (II) solution, conical flask is put into constant temperature oscillator, speed oscillation with 125rpm under room temperature is adsorbed, after adsorption equilibrium, measure the residual quantity of Pb in solution (II), and calculated equilibrium adsorption capacity.
Charcoal productive rate prepared by the present embodiment is 15.8%, and its electron scanning electromicroscopic photograph as shown in Figure 2.As seen from the figure, the fibrous gap structure of the charcoal rule being obtained by mud and pine sawdust pyrolysis is destroyed, has formed irregular projection, presents irregular loose structure.The charcoal specific area of preparation is 186.3m
2/ g, adsorption capacity is 536.5mg/g.
Comparative example 2
(1) paper mill sludge of learning from else's experience after mechanical dehydration carries out pretreatment, by deionized water, Sludge Surface impurity is cleaned, and obtains raw sludge;
(2) get the pure mud of certain mass in step (1) and be placed in pyrolysis oven loading hopper, set reaction temperature be 750 DEG C, until temperature reach set value and keep stablize after, pass into nitrogen, raw material is evenly sent in pyrolysis oven, ensured to generate charcoal under oxygen free condition;
(3) set reaction temperature be under the condition of 750 DEG C continuous heating to reaction without γ-ray emission, stop heating, charcoal to be generated naturally cools to after room temperature, taking-up is weighed, and packs for subsequent use.
(4) get the middle gained charcoal of 0.01g step (3) in 100mL conical flask, add 50mL concentration be 90mg/L containing Pb (II) solution, conical flask is put into constant temperature oscillator, room temperature, with the speed oscillation absorption of 125r/min, after adsorption equilibrium, measure the residual quantity of Pb in solution (II), and calculated equilibrium adsorption capacity.
Charcoal productive rate prepared by this comparative example is 10.2%, and its electron scanning electromicroscopic photograph as shown in Figure 3.As seen from the figure, the charcoal surface being obtained by pyrolyzing sludge is comparatively closely knit, has obvious clustering phenomena, space skewness, and top layer gap structure is not very abundant.Preparing charcoal specific area is 45.1m
2/ g, adsorption capacity is 129.8mg/g.
Comparative example 3
(1) by collect pine sawdust after natural air drying, shattered 40 mesh sieves;
(2) get the pine sawdust of certain mass in step (1) and be placed in pyrolysis oven loading hopper, set reaction temperature be 750 DEG C, until temperature reach set value and keep stablize after, pass into nitrogen, raw material is evenly sent in pyrolysis oven, ensured to generate charcoal under oxygen free condition;
(3) set reaction temperature be under the condition of 750 DEG C continuous heating to reaction without γ-ray emission, stop heating, charcoal to be generated naturally cools to after room temperature, taking-up is weighed, and equips for subsequent use.
(4) get the middle gained charcoal of 0.01g step (3) in 100mL conical flask, add 50mL concentration be 90mg/L containing Pb (II) solution, conical flask is put into constant temperature oscillator, room temperature, with the speed oscillation absorption of 125rpm, after adsorption equilibrium, measure the residual quantity of Pb in solution (II), and calculated equilibrium adsorption capacity.
Charcoal productive rate prepared by the present embodiment is 23.7%, its electron scanning electromicroscopic photograph as shown in Figure 4, as seen from the figure, the orifice throat ratio on the charcoal surface being obtained by pine sawdust pyrolysis is more smooth, regular, present fibrous gap structure, but the ablation of part micropore hole wall caves in, stop up space and crack.The charcoal specific area of preparation is 26.5m
2/ g, adsorption capacity is 75.8mg/g.
Claims (2)
1. utilize paper mill sludge and pine copyrolysis to prepare a method for active bio charcoal, it is characterized in that comprising the steps:
(1) paper mill sludge of) learning from else's experience after mechanical dehydration carries out pretreatment, by deionized water, Sludge Surface impurity is cleaned, and obtains raw sludge;
(2) by collect pine sawdust after natural air drying, shatter and sieve, obtain pine sawdust;
(3) described raw sludge and described pine sawdust are fully mixed by the mass ratio of 9:1-1:9;
(4) mixture of step (3) gained is placed in to pyrolysis oven loading hopper, setting reaction temperature is 600-900 DEG C, until temperature reach set value and keep stable after, pass into nitrogen, raw material is evenly sent in pyrolysis oven, ensured to generate charcoal under oxygen free condition;
(5) keep the constant temperature of 600-900 DEG C during without γ-ray emission, to stop heating to reaction, obtain charcoal after naturally cooling to room temperature;
(6) gained charcoal in step (5) is put into the sulfuric acid solution that concentration is 2.5-3.5mol/L, pass into nitrogen, at 500-600 DEG C, constant temperature 20-40min; Then naturally cool to room temperature, obtain active bio charcoal;
The amount ratio of described charcoal and described sulfuric acid solution is 1:10-1:50, and wherein the unit of the quality of charcoal is gram, and the volume unit of sulfuric acid solution is milliliter.
2. method according to claim 1, is characterized in that the pine sawdust described in step (2) crosses 30-50 mesh sieve.
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| CN106732361A (en) * | 2016-12-21 | 2017-05-31 | 福建师范大学 | A kind of preparation method of the sludge base charcoal of the paper powder that adulterates |
| CN108176359A (en) * | 2018-01-22 | 2018-06-19 | 济南大学 | A kind of preparation method of mixing waste charcoal |
| CN109575929A (en) * | 2018-11-28 | 2019-04-05 | 攀钢集团攀枝花钢铁研究院有限公司 | The method of the agent of heavy-metal contaminated soil complex repairation and its rehabilitating soil |
| CN109603759A (en) * | 2019-01-25 | 2019-04-12 | 太原理工大学 | Modification biological charcoal of Dye Adsorption and preparation method thereof |
| CN110302748A (en) * | 2019-05-05 | 2019-10-08 | 浙江清风源环保科技有限公司 | A kind of sludge base charcoal preparation method |
| CN112108118A (en) * | 2020-09-21 | 2020-12-22 | 黄河水利职业技术学院 | Magnetic biomass charcoal based on Fenton sludge and cellulose and preparation method and application thereof |
| CN113634229A (en) * | 2021-09-02 | 2021-11-12 | 浙江理工大学绍兴柯桥研究院有限公司 | Preparation method and application of biochar with selective adsorption-desorption capacity |
| CN114149004A (en) * | 2021-11-19 | 2022-03-08 | 中国电建集团环境工程有限公司 | Preparation method of activated carbon of municipal sludge coupled biomass and activated carbon module |
| CN114733480A (en) * | 2022-03-28 | 2022-07-12 | 上海园林绿化建设有限公司 | Modified biochar and preparation method thereof |
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| CN108176359A (en) * | 2018-01-22 | 2018-06-19 | 济南大学 | A kind of preparation method of mixing waste charcoal |
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| CN109603759A (en) * | 2019-01-25 | 2019-04-12 | 太原理工大学 | Modification biological charcoal of Dye Adsorption and preparation method thereof |
| CN110302748B (en) * | 2019-05-05 | 2022-04-05 | 浙江清风源环保科技有限公司 | Preparation method of sludge-based biochar |
| CN110302748A (en) * | 2019-05-05 | 2019-10-08 | 浙江清风源环保科技有限公司 | A kind of sludge base charcoal preparation method |
| CN112108118A (en) * | 2020-09-21 | 2020-12-22 | 黄河水利职业技术学院 | Magnetic biomass charcoal based on Fenton sludge and cellulose and preparation method and application thereof |
| CN112108118B (en) * | 2020-09-21 | 2023-04-25 | 黄河水利职业技术学院 | Fenton sludge and cellulose-based magnetic biomass charcoal and preparation method and application thereof |
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| CN114733480A (en) * | 2022-03-28 | 2022-07-12 | 上海园林绿化建设有限公司 | Modified biochar and preparation method thereof |
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| CN116082092B (en) * | 2023-01-12 | 2024-04-19 | 南开大学 | Preparation method of biochar, and method and application for returning tail vegetables to field |
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