CN101440290B - Method for rapid medium-low temperature dry distillation of coal by using microwave - Google Patents
Method for rapid medium-low temperature dry distillation of coal by using microwave Download PDFInfo
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- CN101440290B CN101440290B CN 200810232680 CN200810232680A CN101440290B CN 101440290 B CN101440290 B CN 101440290B CN 200810232680 CN200810232680 CN 200810232680 CN 200810232680 A CN200810232680 A CN 200810232680A CN 101440290 B CN101440290 B CN 101440290B
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Abstract
The invention discloses a method for carbonizing low-temperature coal of low metamorphic coal. The method adopts a microwave generation device as a heating source with the frequency of microwave of between 0.3 and 300 GHz; and the low metamorphic coal is heated to the a temperature of between 300 and 800 DEG C and is subjected to low-temperature carbonization to generate semi-coke, tar and coal gas. The method selects coal with shallow metamorphic degree as a raw material, utilizes a microwave radiation type heating mode to rapidly and selectively heat a coal material, depends on the dielectric property of the coal material to convert microwave energy and produce heat, utilizes the function of microwave activated molecules and achieves the aim of rapidly pyrolyzing the low metamorphic coal, thereby obtaining the semi-coke, tar and the low-temperature carbonization coal gas. The method has rapid coal pyrolyzing speed, can effectively improve the content of valuable compositions in the carbonation coal gas and is favorable for effective and comprehensive reclaiming of the coal gas.
Description
Technical field
The invention belongs to the coal pyrolysis technical field, relate to a kind of method of middle low-temperature pyrolysis of low-disintegration coal kind, the method is mainly used in the low-disintegration coal pyrolysis and produces blue charcoal (semicoke), coal tar and low-temperature pyrolysis coal gas.Also can be used for coal drying, fuel-burning power plant and steam coal and enter the stokehold pre-treatment, extract the tar in coal and the valency gaseous constituent is arranged.
Background technology
Along with the day of oil, natural gas source is becoming tight, coal resources further develop, and especially the development of Filter Tuber For Clean Coal burning and coal chemical technology becomes the center of gravity of China's energy exploitation and application research gradually.
China is the country of coal more than one, scarce oil, few Sweet natural gas, and current coal in China is mainly as industries such as generating, coking and power.Usually require low-sulfur high-quality coal or coal (bottle coal, rich coal, coking coal and the lean coal used as coking).Although coal resources in China is abundanter, the high-quality coal resource only accounts for half left and right, and all the other are the low-disintegration coal resources such as brown coal, long-flame coal, bottle coal, non-caking coal.The young coals such as brown coal, long-flame coal, bottle coal, non-caking coal are high because of moisture, ash content is high, volatile matter is high, calorific value is low, often is taken as the inferior fuel steam coal; Add easy differentiation and spontaneous combustion, should not transport for long-distance, also just become the coal resource that is difficult to the strange land processing and utilization.
The young low-disintegration coal kind such as Jurassic Coal accounts for 40% left and right of coal resources in China reserves, and the peaceful sweet area of waiting is up to more than 70% in Jin, Shaanxi and Inner Mongolia.China produced 25.1 hundred million tons of coals in 2007, and fat coal accounts for 65%, and the low-disintegration coal output that reserves are larger is less.In addition, in the exploitation fat coal, its association low-quality coal resources cause coal resources waste because of synchronously extraction of Market Reasons.
Form and analysis of the molecular structure from ature of coal, Jurassic Coal is the coal of suitable comprehensive utilization.Jurassic Coal is rich in oil and adsorbed methane moisture etc., is all main raw materials of production Coal Chemical Industry product, and for the area that conventional water resources lacks, Jurassic Coal is good Coal Chemical Industry raw material.Jurassic Coal is high-volatile coal, its molecular structure can be regarded the combination of hard coal and oil gas molecule as, take suitable working method that the oil gas component separating in Jurassic Coal out (is similar to the resinous shale processing and utilization), can alleviate China's oil and Sweet natural gas disparities between supply and demand.The present invention also can be used for the deep processing of brown coal and resinous shale in addition.
The retorting technique of the middle low temperature pyrogenation of coal and separation and Extraction high added value oil gas composition is as the traditional coal conversion that meets the clean coal technology and utilize technology, and the reasonable utilization of coal resources in China is had great importance.
The dry distillation of coal (coal carbonization) is one of significant process of Coal Chemical Industry.Refer to coal heating under the condition of isolated air or control air capacity, decompose, generate the process of the products such as coke/semicoke (blue charcoal), coal tar, crude benzol, coal gas.Difference by the heating final temperature can be divided into three kinds: 900 ℃～1100 ℃ are high temperature carbonization, i.e. coking; 700 ℃～900 ℃ is medium temperature carbonization; 500 ℃～700 ℃ are low-temperature pyrolysis.
Dry distillation of coal process mainly experiences following variation: during higher than 100 ℃, the moisture in coal evaporates when the temperature of coal charge; When temperature is elevated to more than 200 ℃, disengage in conjunction with water in coal; Up to more than 350 ℃ the time, caking coal begins to soften, and further forms the plastic mass (this phenomenon does not occur for mud coal, brown coal etc.) of thickness; Separate out to 400 ℃～500 ℃ most of coal gas and tar, claim one time thermal decomposition product; At 450 ℃～550 ℃, thermolysis is proceeded, residue retrogradation and solidify to form semicoke (blue charcoal) gradually; Higher than 550 ℃, semicoke (blue charcoal) continues to decompose, and separates out remaining volatile matter (main component is hydrogen, methane etc.), and semicoke weightlessness is shunk simultaneously, forms crackle; Temperature is higher than 800 ℃, and the hardening of semicoke volume-diminished forms porous coke/semicoke or blue charcoal etc.When destructive distillation was carried out in the cell-type gas retort, thermal decomposition product and red-hot coke and high temperature furnace wall contacted, and second heat occurs decompose, and form second heat degradation production (coke-oven gas and other coking chemistry product).
In coal, the product of low-temperature pyrolysis is coke or semicoke (blue charcoal), coal tar oil and gas.
The productive rate of dry distillation of coal product and composition depend on raw material ature of coal, furnace structure and processing conditions (being mainly the processing condition such as temperature and time).Along with the difference of destructive distillation final temperature, dry distillation of coal product is also different.The black semicoke that middle low-temperature pyrolysis solid product is short texture (blue charcoal), gas yield is low, and tar yield is high; The high temperature carbonization solid product is the silver gray coke of compact structure, and gas yield is high and tar yield is low.The yield of medium temperature carbonization product is between low-temperature pyrolysis and high temperature carbonization.The coal gas main component that generates in dry distillation of coal process is hydrogen and methane, can be used as fuel or industrial chemicals.High temperature carbonization is mainly for the production of metallurgical coke, and the tar of gained is the mixture of aromatic hydrocarbons, heterogeneous ring compound etc., is the important sources of industrial acquisition aromatic hydrocarbons; Middle low-temperature pyrolysis coal tar contains more alkane than high temperature tar, is one of artificial petroleum important sources, can be used as oil fuel by the hydrogenation lighting.
At present domestic coal pyrolysis is produced blue charcoal (semicoke) technology and is mainly contained coal solid thermal carriers destructive distillation multi-production process, MRF pyrolytic process, STF pyrolytic technique, reaches take fluidized bed pyrolysis as basic circulating fluidized bed heat-power multi-production process take the thermoelectricity gas multi-production process of moving-bed as the basis, these methods are summed up and are mainly contained two large classes: external heating and synthesis by internal resistance electric melting, external heating is that outside utilizing coking chamber, furnace wall conducts heat to coal charge, although the gas quality that produces is stable, but it is inhomogeneous to conduct heat, pyrolysis time is longer, and production efficiency is relatively low; Synthesis by internal resistance electric melting utilizes thermal barrier directly coal charge to be conducted heat, and has the uniform advantage of heat transfer, but the coal gas that produces can be diluted, increase the coal gas amount, reduced the active constituent content of coal gas, unfavorable to the further comprehensive utilization of coal gas, and the pyrolysis rate of coal is low, and pyrolysis time is long.
Summary of the invention
The object of the invention is to, a kind of middle low-temperature coal carbonization method of low-disintegration coal kind is provided, the method pyrolysis of coal speed is fast, production efficiency is high, and coke, semicoke (blue charcoal) productive rate are high, and the tar yield is high, and the coal gas valuable content is high, and calorific value is high.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of middle low-temperature coal carbonization method of low-disintegration coal kind, it is characterized in that, the method adopts microwave generating apparatus as heat source, and microwave frequency is 0.3GHz～300GHz, the low-disintegration coal kind is heated to 300 ℃～800 ℃ carries out middle low-temperature pyrolysis, generate semicoke/blue charcoal, tar and coal gas.
Method of the present invention is to utilize the basic fine structure coupling of special wave band that microwave has and material to produce heat to heat, the intensification of coal charge is not to transmit by heat but complete by outfield and object interaction, it has selectivity, untouchable, globality, good uniformity, heat-up time is short, start and stop fast, easy to operate, energy utilization rate and heating efficiency are high, and safety and sanitation are pollution-free.
The coal that method of the present invention was suitable for is mainly some low rotten coals, as Jurassic Coal, brown coal, long-flame coal, bottle coal, non-caking coal, common electric coal etc., the coal charge particle diameter that present method is processed is between 0-300mm, and the several minutes coal charge just can be heated between 300 ℃～800 ℃, fully pyrolysis of the fugitive constituent in coal charge, generate at last blue charcoal or semicoke, the coal tar oil and gas.The method can be used for the pyrolytic process of low-disintegration coal, and proposes the deep processings such as tar and coal gas for the pre-treatment of coal in power plant, or is used for coking coal preheating or formed coke preparation, also can be used for the drying process of all coals and coke, blue charcoal (semicoke).Have flow process short, the cycle is short, and efficient is high, constant product quality, the characteristics that the comprehensive utilization of resources rate is high.Not only can greatly improve the pyrolysis rate of low-disintegration coal, and can effectively regulate the valuable component content in coal gas, be conducive to further comprehensive utilization and the recovery of coal gas.
Embodiment
The low-temperature coal carbonization method of low-disintegration coal kind of the present invention, coal charge is the more shallow coal of metamorphic grade, as Jurassic Coal, brown coal, long-flame coal, bottle coal, non-caking coal or oil-containing bottle coal etc., particle diameter is between 0～300mm, and the product of gained is blue charcoal (semicoke), coal tar oil and gas and carbon materials.
Embodiment of the present invention can be selected following several:
the first scheme: microwave generator is placed in coal heat decomposition stove carries out external heat outward, the pyrolysis of coal body of heater adopts the silica brick that can see through microwave, the refractory materials that the microwave oven such as magnesia brick or high alumina brick is suitable for is as furnace wall, add coal in furnace chamber, just can be heated between 300 ℃～800 ℃ by microwave generator in the process that the low-disintegration coal kind descends in furnace chamber, coal charge is carried out the heating of fast selective body, rely on the dielectric properties conversion microwave energy of coal charge self, produce heat, utilize the effect of microwave activation molecule, reach the purpose of low-disintegration coal fast pyrogenation, and in pyrolytic process, the material that the waste heat of coal gas is added after can making removes a part of mechanical water and molecular water, utilize fully heat energy, thereby obtain blue charcoal (semicoke), tar and low-temperature pyrolysis coal gas.
First scheme: microwave generating apparatus is placed in heating in coal heat decomposition stove, microwave generating apparatus can be made some special shapes according to the furnace binding needs, also microwave generator can be made a plurality of, be distributed in coal heat decomposition stove, the pyrolysis of coal body of heater is except building by laying bricks or stones with insulating brick, need add again one deck microwave isolated material outside body of heater, outside preventing that microwave leakage from coming out of the stove, the low-disintegration coal kind can be with dynamic or static form by microwave heating, thereby obtain blue charcoal (semicoke), tar and low-temperature pyrolysis coal gas.
The third scheme: microwave generating apparatus be placed in coal heat decomposition stove external heating mode all can, but before being placed in coal-fired electric generation furnace, be used for extracting fire coal high added value oil gas composition, all the other products can be used for generating.
Be below the embodiment that the contriver provides, the invention is not restricted to these embodiment.
Embodiment 1:
Get the Jurassic Coal that 50g comes from the somewhere, northern Shensi, granularity is 200mm, and its composition sees Table 1.Jurassic Coal is put into the reactor that adopts microwave heating, microwave frequency 0.3GHz～300GHz, 700 ℃ of heating final temperatures, pyrolysis 7min～30min, in pyrolytic process, derive the tar that produces in pyrolytic process, collect dry distillation gas and carry out sampling analysis after removing tar, the dry distillation gas composition sees Table 2, and blue charcoal analytical results sees Table 3.
The analytical results of table 1 raw coal
The analytical results of table 2 dry distillation gas
| N 2 | CO | CH 4 | CO 2 | H 2 | O 2 | C 2 |
| 2.59 | 16.19 | 21.31 | -- | 59.76 | 0.15 | 2.24 |
The analytical results of the blue charcoal of table 3 (semicoke)
Claims (1)
1. the quick dry distillation of coal method of the middle low temperature of a low-disintegration coal kind, it is characterized in that, with 50g, granularity is the Jurassic Coal in the somewhere, northern Shensi of 200mm, puts into the reactor that adopts microwave heating, microwave frequency 0.3GHz ~ 300GHz, 700 ℃ of heating final temperatures, pyrolysis 7min～30min is in pyrolytic process, derive the tar that produces in pyrolytic process, collect dry distillation gas and blue charcoal/semicoke after removing tar;
Wherein, the element of blue charcoal/semicoke comprises C
ad: 85.13%, H
ad: 1.22%, N
ad: 0.23%, O
ad: 2.2%;
The composition of dry distillation gas is: N
2: 2.59%, CO:16.19%, CH
4: 21.31%, H
2: 59.76%, O
2: 0.15%, C
2: 2.24%;
Described microwave generating apparatus is in the outer setting of coal heat decomposition stove, and the pyrolysis of coal body of heater adopts the silica brick that can see through microwave, and magnesia brick or high alumina brick are as furnace wall; Perhaps microwave generating apparatus is placed in coal heat decomposition stove, the pyrolysis of coal body of heater need add one deck microwave isolated material again in the body of heater outside except building by laying bricks or stones with insulating brick, prevent that microwave leakage from coming out of the stove outside.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011047446A1 (en) * | 2010-01-04 | 2011-04-28 | Rodolfo Antonio M Gomez | Advanced coal upgrading process for a power station |
| CN102199434B (en) * | 2011-04-13 | 2013-06-05 | 西安建筑科技大学 | Method for direct liquefaction residues of coal by utilizing microwaves quick pyrolysis |
| CN103946341B (en) * | 2011-08-01 | 2015-09-16 | 北欧生质能源公司 | Microwave quick flashing thermal splitting system and method thereof |
| CN102517058A (en) * | 2012-01-09 | 2012-06-27 | 河南理工大学 | Method for improving microwave pyrolysis rate of low-rank coal |
| CN102827621A (en) * | 2012-08-30 | 2012-12-19 | 西安建筑科技大学 | Method for producing semi-coke, oil tar and coal gas by adopting coal-coal gas microwave co-pyrolysis |
| CN103788969B (en) * | 2012-11-01 | 2016-08-03 | 中国石油化工股份有限公司 | A kind of coal and the group technology of petroleum refining side-product copyrolysis |
| RU2569013C1 (en) * | 2014-02-25 | 2015-11-20 | Владимир Владимирович Чертов | Lignite complex processing line and method |
| CN104962300B (en) * | 2015-06-24 | 2018-03-13 | 南京三乐微波技术发展有限公司 | Coal microwave destructive distillation equipment and its coal microwave destructive distillation processing method |
| WO2019155367A1 (en) * | 2018-02-06 | 2019-08-15 | Tata Steel Limited | A method for producing metallurgical coke from non-coking coal |
| CN108913177B (en) * | 2018-07-12 | 2021-07-06 | 中国科学院上海高等研究院 | Method and device for low-temperature removal of biomass pyrolysis tar based on microwave hot spots |
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| CN1940015A (en) * | 2006-07-10 | 2007-04-04 | 鲍涛 | Various microwave carbonized compound process |
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| Title |
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| 郭树才.煤的低温干馏.《煤化工工艺学》.化学工业出版社,2006, * |
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