CN103215056A - Method for improving semicoke pore structure - Google Patents
Method for improving semicoke pore structure Download PDFInfo
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- CN103215056A CN103215056A CN2013101474119A CN201310147411A CN103215056A CN 103215056 A CN103215056 A CN 103215056A CN 2013101474119 A CN2013101474119 A CN 2013101474119A CN 201310147411 A CN201310147411 A CN 201310147411A CN 103215056 A CN103215056 A CN 103215056A
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Abstract
The invention discloses a method for improving a semicoke pore structure. The method specifically comprises a step of: under the premise that CO2 does not have gasifying reaction with semicoke and the semicoke yield is not lost, carrying out low-temperature carbonization in a CO2 atmosphere, so that the semicoal pore structure is obviously improved, the semicoal specific surface area is increased, the semicoal gasification reactivity is improved, and coal resources are efficiently utilized.
Description
Technical field
The present invention relates to pyrolysis of coal and produce the semicoke production technology, particularly relate in the coal low-temperature pyrolysis process, the method that solid semicoke product pore texture is improved.
Background technology
Pyrolysis of coal is that coal continues to be heated to comparatively high temps under secluding air or inert atmosphere, and a series of physical changes and chemical transformation take place, and finally forms the process of gaseous state (dry distillation gas), liquid (tar) and solid-state (coke) product.Pyrolysis of coal temperature eventually is low-temperature pyrolysis in the time of 500 to 600 ℃.Compare coal gasification and liquefaction, the low-temperature pyrolysis technological process is simple, the processing conditions gentleness, but interlock system gets semicoke, coal gas and tar, realizes the partial gasification and the liquefaction of coal.
Semicoke has application approach widely as the solid product of coal low-temperature pyrolysis, comprises a series of modern coalification commercial runs such as burning, gasification.Form stage of semicoke at coal, promptly devolatilization mainly generates in the process of hydrocarbon gas, coal reactive high, and the time of finishing this section is also very short, and the semicoke of this section generation, its gasification subsequently is then very slow.Therefore, in the design of reactor and industrial gasification stove, its volume depends primarily on the reactivity of semicoke.Semicoke gasification reaction influence factor is very complicated, comprises the katalysis etc. of metamorphic grade, pyrolytical condition, semicoke microtexture, surface tissue and the ash content of coal.Studies show that in a large number, semicoke is reactive closely related with its pore texture, as typical inhomogeneous reaction, semicoke surface pore structure has very material impact to gasification reaction, be in particular in that macropore in the semicoke, mesopore directly determine the reactant in the gasification reaction process and the rate of diffusion of product, and then influence gasification reaction speed.Secondly, vaporized chemical and Jiaozhuo be it is generally acknowledged mainly with the generating gasification reaction and are carried out on semicoke micropore active site, increases semicoke micropore number, increases the carrying out that specific surface area all helps the semicoke gasification reaction.Therefore, can think to a certain extent that the semicoke pore texture reaches all the more, gasification reaction is good more.Therefore, seek a kind of method, improve the coke gasification reactivity then and have important practical significance to improve the pore texture of semicoke.
Summary of the invention
The objective of the invention is to improve the pore texture of semicoke and increase its specific surface area, thereby improve the semicoke gasification reaction, realize the efficient utilization of coal resources by a kind of simple and effective means.
Traditional coal low-temperature pyrolysis is to carry out the pyrolysis of coal to prepare semicoke under secluding air or inert atmosphere.Yet the present invention is unexpected to be found, is guaranteeing CO
2Thereby do not lose under the prerequisite of char yeild, at CO with the reaction of semicoke generating gasification
2Carry out the low-temperature pyrolysis of coal under the atmosphere, can significantly improve the pore texture of semicoke, and increase the specific surface area of semicoke, thereby improve the gasification reaction of semicoke, realize the efficient utilization of coal resources.
Usually, starting temperature takes place substantially all more than 700 ℃ in young coal gasification reaction, and the low-temperature pyrolysis of coal is generally carried out between 500～700 ℃.In this temperature range, semicoke almost can not with CO
2The generating gasification reaction, this has just guaranteed that the semicoke ultimate capacity can be because of CO
2The introducing of atmosphere is affected.
The present invention is by contrast CO
2The difference of the burnt sample of preparation aspect pore texture characteristics and specific surface area under burnt sample of preparation and the Ar atmosphere under the atmosphere, a large amount of repeated experiments are found CO
2Atmosphere helps the growth of semicoke specific surface area and pore texture, has tangible reaming effect.
Therefore, the present invention proposes innovatively at CO
2Carry out the coal low-temperature pyrolysis under the atmosphere, can realize improving the purpose of semicoke pore texture, increase semicoke specific surface area by the inventive method.The inventive method only need change pyrolysis atmosphere and get final product, and simple, effect is remarkable.
Description of drawings
Fig. 1 carries out the specific surface area comparative result that the coal low-temperature pyrolysis obtains semicoke under different atmosphere.
Fig. 2 carries out the total pore volume comparative result that the coal low-temperature pyrolysis obtains semicoke under different atmosphere.
Fig. 3 carries out the micro pore volume comparative result that the coal low-temperature pyrolysis obtains semicoke under different atmosphere.
Embodiment
Below in conjunction with the drawings and specific embodiments the inventive method is explained in detail.
In order to verify the feasibility of the inventive method, be the basic experiment means with pressurization static bed pyrolysis oven, utilize Xinjiang bituminous coal, respectively at CO
2Under atmosphere and the Ar atmosphere, prepare 8 groups of burnt samples with 0.1MPa, 0.5MPa, four synthesis pressure of 1.0MPa, 1.5MPa, the variation of second close-burning structure of different atmosphere is investigated in contrast.
The detailed process that burnt sample preparation and sample well structural performance are measured is as follows:
1) adopts sample quartering, after the fragmentation of Yining bituminous coal, grinding and screening, choose 5～6mm coal sample and use for the burnt sample of preparation;
2) accurately take by weighing coal sample 50g in the step 1), add in the vertical pressurization tube furnace,, feed 1L/min CO according to the difference of the burnt atmosphere of system
2Or Ar gas, purging pressurization static bed pyrolysis oven 30 minutes, the air in the emptying reactor is controlled CO then
2Or the Ar gas flow is 500ml/min;
3) conditioned reaction device pressure guarantees that the pyrolysis reactor internal pressure is stable, and is set in 0.1MPa, 0.5MPa, 1.0MPa and 1.5MPa respectively to experimental value;
4) temperature rise rate with 10K/min is heated to 700 ℃ with the coal sample sample from room temperature, and keeps 30 minutes residence time, finishes the low-temperature pyrolysis experiment;
5) keep furnace pressure, gas flow constant, after the question response device naturally cooled to room temperature, the experimental installation pressure release was taken out the burnt sample that makes from pyrolysis oven, in the sealing bag of packing into, in order to avoid the ingress of air oxidation is put into moisture eliminator then and preserved;
6) the burnt sample of selected part is ground to below the 0.2mm with agate mortar, the sealing pack;
7) utilize N
2Adsorption experiment carries out semicoke aperture and specific surface test.
Utilize BET equation, BJH equation to calculate specific surface area and the total pore volume for preparing semicoke under the different atmosphere respectively, as shown in Figure 1 and Figure 2.As seen from the figure: under the 0.1Mpa, the specific surface area of the burnt sample of preparation is 5.685m under the Ar atmosphere
2.g
-1, CO
2The specific surface area of the burnt sample of preparation is 236.828 m under the atmosphere
2.g
-1, be about 42 times of Ar atmosphere.In addition, CO under the normal pressure
2Preparation semicoke total pore volume prepares 4 times of burnt sample under the atmosphere for Ar atmosphere.This fully shows, in the pyrolysis of coal process, and CO
2Atmosphere has strong promoter action, CO to semicoke pore texture and specific surface growth
2Have and help increase the semicoke specific surface area, increase semicoke reactive behavior site then, improve semicoke gasification reaction activity.CO
2The specific surface area of semicoke, pore volume are along with the increase of pressure all reduces under the atmosphere, and this mainly is because the pressure increase can suppress the effusion that pyrolysis of coal produces volatile matter, has influenced the reaming effect of semicoke.
Point out in the background technology, it is generally acknowledged vaporized chemical and Jiaozhuo with generating gasification reaction mainly on semicoke micropore active site, therefore the micro pore volume of preparation semicoke sample under different atmosphere and the synthesis pressure is investigated, as shown in Figure 3.Under the normal pressure pyrolytical condition, CO
2Preparation semicoke micropore cumulative volume prepares 42 times of burnt sample for Ar atmosphere under the atmosphere, thereby can prove CO
2Promote the semicoke structural development, help the reaming of semicoke.
Claims (2)
1. a method of improving the semicoke pore texture is characterized in that at CO
2Carry out the low-temperature pyrolysis of coal under the atmosphere, to improve the semicoke pore texture and to increase its specific surface area.
2. the method for improving the semicoke pore texture according to claim 1 is characterized in that described low-temperature pyrolysis temperature is 500～700 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016512A (en) * | 2014-06-10 | 2014-09-03 | 上海大学 | Method for treating copper-containing wastewater by utilizing spartina-alterniflora-loisel-based charcoal |
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| CN1291587A (en) * | 2000-09-05 | 2001-04-18 | 天津大学 | Process for preparing activated carbon to make electrode of super capacitor |
| CN101004977A (en) * | 2006-01-18 | 2007-07-25 | 中国科学院化学研究所 | Active carbon electrode material for super capacitor and its preparing method |
| CN101580728A (en) * | 2009-06-10 | 2009-11-18 | 中煤能源黑龙江煤化工有限公司 | Process technology for non-caking coal or weak caking coal |
| CN102040218A (en) * | 2011-01-19 | 2011-05-04 | 成都信息工程学院 | New method for producing active carbon by using biomass wastes |
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2013
- 2013-04-25 CN CN201310147411.9A patent/CN103215056B/en active Active
Patent Citations (6)
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| US4053285A (en) * | 1974-04-18 | 1977-10-11 | Occidental Research Corporation | Process for reducing the sulfide sulfur content of char with carbon dioxide and H2 O |
| CN1291587A (en) * | 2000-09-05 | 2001-04-18 | 天津大学 | Process for preparing activated carbon to make electrode of super capacitor |
| CN101004977A (en) * | 2006-01-18 | 2007-07-25 | 中国科学院化学研究所 | Active carbon electrode material for super capacitor and its preparing method |
| CN101580728A (en) * | 2009-06-10 | 2009-11-18 | 中煤能源黑龙江煤化工有限公司 | Process technology for non-caking coal or weak caking coal |
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| CN104016512A (en) * | 2014-06-10 | 2014-09-03 | 上海大学 | Method for treating copper-containing wastewater by utilizing spartina-alterniflora-loisel-based charcoal |
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