CN103215056B - Method for improving semicoke pore structure - Google Patents
Method for improving semicoke pore structure Download PDFInfo
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- CN103215056B CN103215056B CN201310147411.9A CN201310147411A CN103215056B CN 103215056 B CN103215056 B CN 103215056B CN 201310147411 A CN201310147411 A CN 201310147411A CN 103215056 B CN103215056 B CN 103215056B
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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 semicoke production technology, particularly relate in coal low-temperature pyrolysis process, to the method that solid semicoke product pore texture improves.
Background technology
Pyrolysis of coal, be coal under isolated air or inert atmosphere continuous heating to comparatively high temps, there is series of physical change and chemical transformation, finally form the process of gaseous state (dry distillation gas), liquid (tar) and solid-state (coke) product.Pyrolysis of coal final temperature, 500 to 600 DEG C time, is low-temperature pyrolysis.Compare coal gasification and liquefaction, low-temperature pyrolysis technological process is simple, and processing conditions is gentle, can obtain semicoke, coal gas and tar by interlock system, realize partial gasification and the liquefaction of coal.
Semicoke, as the solid product of coal low-temperature pyrolysis, has a wide range of applications approach, comprises a series of Modern Coal-based Chemical industry processes such as burning, gasification.Form stage of semicoke at coal, namely devolatilization mainly generates in the process of hydrocarbon gas, and the reactivity of coal is high, and the time completing this section is also very short, and the semicoke that this section generates, and its gasification is subsequently then very slow.Therefore, in the design of reactor and industry gasification furnace, its volume depends primarily on the reactivity of semicoke.The reactive influence factor of char Gasification is very complicated, comprises the katalysis etc. of the metamorphic grade of coal, pyrolytical condition, semicoke microtexture, surface tissue and ash content.Large quantity research shows, half reactivity of coke and its pore texture closely related, as typical inhomogeneous reaction, semicoke surface pore structure has very material impact to gasification reaction, be in particular in that macropore in semicoke, mesopore directly determine the rate of diffusion of reactant in gasification reaction process and product, and then affect gasification reaction speed.Secondly, vaporized chemical and Jiaozhuo generating gasification reacts and be it is generally acknowledged and mainly carry out on the microporous activated point of semicoke, and increase semicoke micropore number, increase specific surface area are all conducive to the carrying out that char Gasification reacts.Therefore, can think to a certain extent, Pore Structure of Coal-char reaches all the more, and gasification activity is better.Therefore, find a kind of method to improve the pore texture of semicoke, then improve coke gasification reactivity and have important practical significance.
Summary of the invention
The object of the invention is improve the pore texture of semicoke by a kind of simple and effective means and increase its specific surface area, thus it is reactive to improve char Gasification, realizes the efficiency utilization of coal resources.
Traditional coal low-temperature pyrolysis be under isolated air or inert atmosphere, carry out coal pyrolysis to prepare semicoke.But the present invention surprisingly finds, at guarantee CO
2not react with semicoke generating gasification thus under losing the prerequisite of char yeild, at CO
2carry out the low-temperature pyrolysis of coal under atmosphere, significantly can improve the pore texture of semicoke, and increase the specific surface area of semicoke, thus improve the gasification activity of semicoke, realize the efficiency utilization of coal resources.
Usually, the gasification reaction generation starting temperature of Young Coal is substantially all more than 700 DEG C, and the low-temperature pyrolysis of coal is generally carried out between 500 ~ 700 DEG C.In this temperature range, semicoke almost can not with CO
2generating gasification is reacted, and this guarantees semicoke ultimate capacity can not because of CO
2the introducing of atmosphere is affected.
The present invention is by contrast CO
2prepare the difference of burnt sample in pore texture feature and specific surface area under preparing burnt sample and Ar atmosphere under atmosphere, repeat experiment in a large number and find, CO
2atmosphere is conducive to the growth of semicoke specific surface area and pore texture, has obvious reaming effect.
Therefore, the present invention proposes innovatively at CO
2coal low-temperature pyrolysis is carried out, the object can realize improving Pore Structure of Coal-char by the inventive method, increasing semicoke specific surface area under atmosphere.The inventive method only need change pyrolysis atmosphere, simple, Be very effective.
Accompanying drawing explanation
Fig. 1 carries out the specific surface area comparative result that coal low-temperature pyrolysis obtains semicoke under different atmosphere.
Fig. 2 carries out the total pore volume comparative result that coal low-temperature pyrolysis obtains semicoke under different atmosphere.
Fig. 3 carries out the micro pore volume comparative result that 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, with pressurization static bed pyrolysis oven for basic experiment means, utilize Xinjiang bituminous coal, respectively at CO
2under atmosphere and Ar atmosphere, prepare 8 groups of burnt samples with 0.1MPa, 0.5MPa, 1.0MPa, 1.5MPa tetra-synthesis pressure, the change of second close-burning structure of different atmosphere is investigated in contrast.
The detailed process that burnt sample preparation and sample well structural performance measure is as follows:
1) adopt sample quartering, after the fragmentation of Yining bituminous coal, grinding and screening, choose 5 ~ 6mm coal sample for the burnt sample of preparation;
2) accurately take coal sample 50g in step 1), add in vertical type pressurization tube furnace, according to the difference of the burnt atmosphere of system, pass into 1L/min CO
2or Ar gas, purge pressurization static bed pyrolysis oven 30 minutes, the air in emptying reactor, then control CO
2or Ar gas flow is 500ml/min;
3) regulate reactor pressure to experimental value, ensure that pyrolysis reactor internal pressure is stablized, and be set in 0.1MPa, 0.5MPa, 1.0MPa and 1.5MPa respectively;
4) with the temperature rise rate of 10K/min, coal sample sample is heated to 700 DEG C from room temperature, and keeps 30 minutes residence time, complete low-temperature pyrolysis experiment;
5) keep furnace pressure, gas flow constant, after question response device naturally cools to room temperature, experimental installation pressure release, takes out obtained burnt sample from pyrolysis oven, loads in sealing bag, in order to avoid ingress of air oxidation, then puts into moisture eliminator and preserves;
6) the burnt sample of selected part, is ground to below 0.2mm with agate mortar, sealing pack;
7) N is utilized
2adsorption experiment carries out semicoke aperture and specific surface test.
BET equation, BJH equation is utilized under calculating different atmosphere respectively, to prepare specific surface area and the total pore volume of semicoke, as shown in Figure 1 and Figure 2.As seen from the figure: under 0.1Mpa, the specific surface area preparing burnt sample under Ar atmosphere is 5.685m
2.g
-1, CO
2the specific surface area preparing burnt sample under atmosphere is 236.828 m
2.g
-1, be about 42 times of Ar atmosphere.In addition, CO under normal pressure
2preparing semicoke total pore volume under atmosphere is 4 times that Ar atmosphere prepares burnt sample.This fully shows, in pyrolysis of coal process, and CO
2atmosphere is grown Pore Structure of Coal-char and specific surface and is had strong promoter action, CO
2have and help increase semicoke specific surface area, then increase semicoke reactive behavior site, improve char Gasification reactive behavior.CO
2the specific surface area of semicoke under atmosphere, pore volume all reduce along with the increase of pressure, and this mainly because pressure increase can suppress pyrolysis of coal to produce the effusion of volatile matter, have impact on the reaming effect of semicoke.
Point out in background technology, it is generally acknowledged that vaporized chemical and Jiaozhuo generating gasification react main on the microporous activated point of semicoke, therefore the micro pore volume preparing semicoke sample under different atmosphere and synthesis pressure is investigated, as shown in Figure 3.Under normal pressure pyrolytical condition, CO
2preparing semicoke micropore cumulative volume under atmosphere is 42 times that Ar atmosphere prepares burnt sample, thus can prove CO
2promote semicoke structural development, contribute to the reaming of semicoke.
Claims (1)
1. improve a method for Pore Structure of Coal-char, it is characterized in that at CO
2under atmosphere, carry out the low-temperature pyrolysis of coal with the synthesis pressure 500 ~ 700 DEG C of 0.1MPa, to improve Pore Structure of Coal-char and to increase its specific surface area.
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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 |
| 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 |
| US7947155B1 (en) * | 2009-11-17 | 2011-05-24 | Green Liquid and Gas Technologies | Process and device for the pyrolysis of feedstock |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101580728B (en) * | 2009-06-10 | 2012-10-03 | 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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Patent Citations (5)
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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 |
| US7947155B1 (en) * | 2009-11-17 | 2011-05-24 | Green Liquid and Gas Technologies | Process and device for the pyrolysis of feedstock |
| 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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| Effect of Sodium on the Structure and Reactivity of the Chars Formed under N2 and CO2 Atmospheres;Xiaowei Liu et al.;《energy & fuels》;20111122;第26卷(第1期);第185页 摘要，第186页 2.2 半焦制备，第191页 4结论 * |
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