CN103937514B - Low-rank coal quality improvement method and low-rank coal quality improvement equipment - Google Patents
Low-rank coal quality improvement method and low-rank coal quality improvement equipment Download PDFInfo
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Abstract
The invention relates to a low-rank coal quality improvement method and low-rank coal quality improvement equipment. The method comprises the following steps: heating a coal layer to less than 140 DEG C by a first gas heat carrier, enabling the water content of dried low-rank coal to be 10%-15%, and generating byproduct gas; heating the coal layer temperature of the dried low-rank coal to 350-650 DEG C by a second gas heat carrier to obtain dust gas and hot semicoke, separating a solid-phase substance from a gas-phase substance of the dust gas to obtain powdered coal and the gas-phase substance, and cooling part of a gas phase to form pyrolysis gas; gradually cooling the hot semicoke and the pyrolysis gas in same space by a gas cooling carrier, separating out heavy components from the pyrolysis gas, wrapping the surface of the gradually cooled hot semicoke with the heavy components, and cooling the semicoke by the byproduct gas with temperature of 200-300 DEG C to obtain wrapped semicoke and mixed gas; enabling the cooled wrapped semicoke to be in contact with the byproduct gas with temperature of 40-70 DEG C, adsorbing water, performing surface oxidization and rehydration reaction on the wrapped semicoke, and enabling the water content of the wrapped semicoke to be 8%-16%.
Description
The application be to the applying date be on December 10th, 2012, application number is 201210530124.1, denomination of invention is the divisional application that " low-rank coal method for upgrading and equipment " this patent application is made.
Technical field
The present invention relates to a kind of novel low-rank coal method for upgrading and equipment thereof, particularly the low-rank coal method for upgrading that is coupled with coal tar lighting of brown coal pyrolysis char passivation and equipment thereof.
Background technology
China's brown coal rich reserves, within 2010, brown coal output is more than 300,000,000 tons, accounts for 10% of national coal production.The highly-efficient processing of brown coal utilizes the problem having become coal in China energy field and shown great attention to.
Because the brown coal coalforming period is short, its water yield, oxygen level and fugitive constituent are high, and total water is up to 20-60%.Cause calorific value low on the one hand, be unsuitable for direct burning; Cause chemical reactivity too high on the other hand, very easily weathering and fragmentation, is unsuitable for long distance transportation and standing storage in atmosphere.Therefore, brown coal upgrading is the key link that brown coal utilize.In order to satisfied different purposes is to the requirement of coal quality, brown coal Upgrading Processes is divided into dehydration upgrading, shaping upgrading and pyrolysis upgrading, wherein pyrolysis upgrading can obtain semicoke, coal tar oil and gas three kinds of primary products simultaneously, is considered to the effective ways of brown coal comprehensive utilization.
The brown improving quality of coal by pyrolysis research history of existing nearly 30 years.Brown coal upgrading Technology can be divided into the outer heat of external-heat, internal heat type and interior heat hybrid according to type of heating; Solid heat carrier method and air heat support methods two kinds is had according to the difference of heating medium; Rotating bed, fixed bed, fluidized-bed, air flow bed and rolling bed (rotary kiln/kiln) technology etc. can be divided into according to the operation conditions of solid materials in reactor.
The Typical Representative of external brown improving quality of coal by pyrolysis packaged process mainly contains the Toscoal rotary kiln pyrolytic process that Oil Shale Corporation of America (The Oil Shale Corporation) develops; The LFC(Liquid FromCoal of shell mining (Shell Mining Company) company of the U.S. and the cooperative development of SGI company of the U.S.) technique; The ACCP(Advanced Coal Conversion Process of Western Energy Resources company exploitation) pyrolytic process; The fluid bed fast pyrolysis technique that Australian Union's science and industrial research institute (CSIR O) develop; The Lurgi-Ruhrgas(L-R that Germany Lurgi GmbH and U.S. Ruhrgas AG develops jointly) solid thermal carriers low temperature pyrogenation technique; And the Lurgi-Spuelgas(L-S of German Lurgi GmbH exploitation) technique etc.The unit of studies in China coal pyrolysis technology is numerous, multistage rotary kiln (MRF) pyrolytic process that the technology being more typically applicable to brown improving quality of coal by pyrolysis has Chinese coal scientific research Zong Yuan Beijing Coal Chemical Industry branch to develop; Dalian University of Technology Guo Shu just waits brown coal solid heat carrier method destructive distillation (DG) technique of people's research and development; The low-rank coal pyrolytic process that Firing Shenhua Coal liquefaction chemical research institute is developing; Chinese Academy of Sciences's Shanxi coalification and " coal plug technique " (the BT technique) etc. of process engineering institute of the Chinese Academy of Sciences.
The technology quality of brown coal pyrolysis process for upgrading depends on that the quality of coal gas, coal tar and semicoke, above-mentioned various technique obtain coal tar or coal gas while being intended to promote semicoke quality.As can be seen from the above-mentioned each technique of pyrolysis temperature angle contrast: except ACCP technology, the pyrolysis temperature of other technology is all more than 500 DEG C, and not easily spontaneous combustion after the simple Passivation Treatment of gained semicoke product, water absorbability also significantly improves.Compare from the speed of heating, the existing gas-particle heat transfer of fluidization that CSIR O adopts also has and admittedly conducts heat, and pyrolysis rate is fast, and liquid yield will be significantly higher than other upgrading technology, but quality and workability poor.
Former Encoal technique adopts the quenching of water spray Quench, causes water consumption to cause semicoke Quench to burst apart and efflorescence greatly, on the other hand on the one hand.The mass-producing brown coal upgrading project of domestic unique operation is the LFC brown coal process for upgrading of Datang Xilin Hot, belongs to middle low-temperature pyrolysis brown coal process for upgrading, processing power 300,000 tons/year.But the upgraded brown coal disintegrating slag ratio of this project construction is large, long distance transportation is difficult, and product is mainly for surrounding area Industrial Boiler.
All in all, current brown coal upgrading technology major part both domestic and external is in experimental study and industrial Qualify Phase, there is no precedent and the experience of large-scale engineeringization application.There is process system complexity in technology to major part, system operation reliability is low, brown coal upgrading cost is high, the environmental pollution problem such as heavily.Its major cause comprises:
1) due to the particular attribute of coal solid materials, in Practical Project, the formation of coal dust (dirt) and control be laboratory even pilot-plant test platform scale cannot verify;
2) brown coal pyrolysis temperature is low, and various heat exchange or reaction are the process of relative low temperature, causes heat transfer temperature difference little thus, the utilization difficulty of tow taste heat, and process efficiency is low;
3) research of amplifying the mechanism of lignite semi-coke passivation, process conditions and through engineering approaches there is no to be carried out, and makes whole set process limited in ripening degree and business promotion.
Summary of the invention
In order to overcome these shortcomings, present inventor uses for reference the theory of polarization (delayed coking) in mink cell focus processing and the thinking of steel-making coke strenth lifting, the technique of pyrolyzing coal tar passivation semicoke and semicoke original position Slow cooling is proposed, not only increase semicoke intensity, reduce the apparent chemistry of semicoke, and the lighting of pyrolyzing coal tar original position, reach the dual purpose of semicoke passivation and coal tar lighting, kill two birds with one stone.
The invention provides a kind of low-rank coal method for upgrading, it comprises: drying step, by the first gaseous heat-carrier, coal seam is heated to less than 140 DEG C, carries out drying, makes the moisture weight content of the dry rear low-rank coal obtained 10% ~ 15%, and produces by-product gas; Pyrolysis step, the coal seam temperature of the low-rank coal above-mentioned drying being obtained afterwards by the second gaseous heat-carrier reaches 350 ~ 650 DEG C, obtain dusty gas and hot semicoke, after the solid matter of above-mentioned dusty gas is separated with gaseous substance, a part for the isolated gaseous substance of described dusty gas becomes splitting gas after preliminary cooling; Wrap step, the above-mentioned hot semicoke and above-mentioned splitting gas that are positioned at the same space is progressively cooled by gas cold carrier, heavy constituent in above-mentioned splitting gas is separated out and is wrapped the hot semicoke surface progressively cooled, subsequently, the above-mentioned by-product gas that above-mentioned semicoke is 200 ~ 300 DEG C by temperature cools further, obtains wrapping semicoke and mixed gas; With quenching passivation step, make cooledly above-mentionedly to wrap the above-mentioned by-product gas that semicoke and temperature are 40 ~ 70 DEG C and directly contact further, again adsorption moisture, carries out wrapping the surface oxidation of semicoke and rehydrated reaction, makes this moisture weight content wrapping semicoke be 8 ~ 16%.
In above-mentioned low-rank coal method for upgrading, preferably, above-mentioned first gaseous heat-carrier and above-mentioned second gaseous heat-carrier are all with CO
2with gaseous state H
2o is main ingredient, and the temperature of above-mentioned first gaseous heat-carrier before entering drying step controls at 140 ~ 240 DEG C, and the temperature of above-mentioned second gaseous heat-carrier before entering pyrolysis step controls at 380 ~ 680 DEG C.
In above-mentioned low-rank coal method for upgrading, preferably, the volume percent of the oxygen level of above-mentioned second gaseous heat-carrier is less than or equal to 2%, preferably in 0.5 ~ 2%, more preferably, below 0.5%, the volume percent of the oxygen level of above-mentioned first gaseous heat-carrier is less than or equal to 6%, is more preferably less than or equal to 5%, preferably be less than 2 ~ 3% further, more preferably about 1%.
In above-mentioned low-rank coal method for upgrading, preferably, in above-mentioned pyrolysis step, the thickness in above-mentioned coal seam is 200 ~ 600 millimeters, and the heating rate in above-mentioned coal seam is in the scope of 5 ~ 100 DEG C/s.
In above-mentioned low-rank coal method for upgrading, preferably, the moisture weight content of the low-rank coal that above-mentioned drying obtains afterwards 6% ~ 10%, said temperature be the moisture weight content of the above-mentioned by-product gas of 40 ~ 70 DEG C 10 ~ 20%, the volumn concentration of oxygen is 5-21%.
In above-mentioned low-rank coal method for upgrading, preferably, above-mentioned gas cold carrier is the nitrogen under room temperature, and above-mentioned heavy constituent is bituminous matter, and above-mentioned low-rank coal is brown coal.
In above-mentioned low-rank coal method for upgrading, preferably, wrap in step above-mentioned, above-mentioned splitting gas is cooled to 250 ~ 300 DEG C, and be separated into the raw gas of gas phase and the coal tar of liquid phase, above-mentioned raw gas comprises CO, CH
4, H
2and CO
2, above-mentioned coal tar comprises stable hydrocarbon, aromatic hydrocarbon, non-hydrocarbon and asphaltene.
In above-mentioned low-rank coal method for upgrading, preferably, also comprise from the above-mentioned liquid oils separating step wrapping separating liquid oil the mixed gas of step generation.
The present invention also provides a kind of low-rank coal upgrading device, comprises hotblast stove, moisture eliminator, cracker, the first cyclonic separator, the second cyclonic separator, wraps reactor and quenching deactivator, wherein,
Hotblast stove, provides the gaseous heat-carrier of differing temps to described moisture eliminator and described cracker;
Moisture eliminator, receive the low-rank coal as feed coal, be connected with described pipeline of hot air furnace, low order coal seam is heated to less than 140 DEG C by the first gaseous heat-carrier provided by described hotblast stove, carry out drying, make the moisture weight content of low-rank coal 5% ~ 15%, obtain dried low-rank coal and produce by-product gas, and wrap reactor and described quenching deactivator described in being led to by described by-product gas;
Cracker, be arranged at the below of described moisture eliminator, described dried low-rank coal enters described cracker under gravity, the second gaseous heat-carrier provided by described hotblast stove makes coal seam temperature after drying reach 350 ~ 650 DEG C, obtain dusty gas and hot semicoke, described dusty gas enters the first cyclonic separator and described second cyclonic separator respectively, fine coal and the gaseous substance of solid matter is all obtained after separation, wherein be separated through described first cyclonic separator the gaseous substance obtained after burning, supplement described first gaseous heat-carrier or the second gaseous heat-carrier that become in described hotblast stove, be separated through described second cyclonic separator the gaseous substance obtained and become splitting gas after preliminary cooling,
Wrap reactor, be arranged at the below of described cracker, after wrapping reactor described in described hot semicoke enters under gravity, utilize pipeline described gas cold carrier and described splitting gas are input to described in wrap reactor, described hot semicoke and described splitting gas is progressively cooled by gas cold carrier, heavy constituent in described splitting gas is separated out and is wrapped the hot semicoke surface progressively cooled, subsequently, the described by-product gas that described hot semicoke is 200 ~ 300 DEG C by temperature cools further, obtains wrapping semicoke and mixed gas; With
Quenching deactivator, make further cooled described in wrap the described by-product gas that semicoke and temperature are 40 ~ 70 DEG C and directly contact, adsorption moisture again, makes the moisture weight content of this semicoke be 8 ~ 16%.
The present invention also provides a kind of low-rank coal upgrading device, and it comprises hotblast stove, moisture eliminator, cracker, cyclonic separator, wraps reactor and quenching deactivator, and wherein, hotblast stove, provides the gaseous heat-carrier of differing temps to above-mentioned moisture eliminator and above-mentioned cracker, moisture eliminator, receive the low-rank coal as feed coal, be connected with above-mentioned pipeline of hot air furnace, low order coal seam is heated to less than 140 DEG C by the first gaseous heat-carrier provided by above-mentioned hotblast stove, carry out drying, make the moisture weight content of low-rank coal 10% ~ 15%, obtain dried low-rank coal and produce by-product gas, and above-mentioned by-product gas is led to above-mentionedly wrap reactor and above-mentioned quenching deactivator, cracker, be arranged at the below of above-mentioned moisture eliminator, above-mentioned dried low-rank coal enters above-mentioned cracker under gravity, the second gaseous heat-carrier provided by above-mentioned hotblast stove makes coal seam temperature after drying reach 350 ~ 650 DEG C, obtain dusty gas and hot semicoke, the fine coal and the gaseous substance that obtain solid matter is separated after above-mentioned dusty gas enters above-mentioned cyclonic separator, a part for gaseous substance supplements above-mentioned first gaseous heat-carrier or the second gaseous heat-carrier that become in above-mentioned hotblast stove after burning, another part of gaseous substance becomes splitting gas after preliminary cooling, wrap reactor, be arranged at the below of above-mentioned cracker, above-mentioned hot semicoke enter under gravity above-mentioned wrap reactor after, utilize pipeline above-mentioned gas cold carrier and above-mentioned splitting gas to be input to and above-mentionedly wrap reactor, above-mentioned hot semicoke and above-mentioned splitting gas is progressively cooled by gas cold carrier, heavy constituent in above-mentioned splitting gas is separated out and is wrapped the hot semicoke surface progressively cooled, subsequently, the above-mentioned by-product gas that above-mentioned hot semicoke is 200 ~ 300 DEG C by temperature cools further, obtains wrapping semicoke and mixed gas, with quenching deactivator, the above-mentioned by-product gas that further cooled above-mentioned hot semicoke and temperature are 40 ~ 70 DEG C is directly contacted, and adsorption moisture again, makes the moisture weight content of this semicoke be 8 ~ 16%.
In above-mentioned low-rank coal upgrading device, preferably also comprise the gas treating system be connected with above-mentioned moisture eliminator, above-mentioned by-product gas above-mentionedly wraps reactor and above-mentioned quenching deactivator leading to after the process of above-mentioned gas treatment system.
In above-mentioned low-rank coal upgrading device, preferably also comprise and be connected to above-mentioned cyclonic separator and the above-mentioned interchanger wrapped between reactor, above-mentioned another part of above-mentioned gaseous substance becomes splitting gas after the preliminary cooling of above-mentioned interchanger.
In above-mentioned low-rank coal upgrading device, preferably also comprise and the above-mentioned electric fishing storage wrapping reactor and be connected, above-mentioned mixed gas isolates liquid oils through above-mentioned electric fishing storage.
In above-mentioned low-rank coal upgrading device, preferably also comprise and the above-mentioned air-seperation system wrapping reactor and be connected, from air, isolate the nitrogen as above-mentioned gas cold carrier.
In above-mentioned low-rank coal upgrading device, preferably the above-mentioned reactor that wraps is divided into leading portion and back segment, and above-mentioned gas cold carrier and above-mentioned splitting gas pass into above-mentioned leading portion, and said temperature is that the above-mentioned by-product gas of 200 ~ 300 DEG C passes into above-mentioned back segment.
In above-mentioned low-rank coal upgrading device, preferred described cyclonic separator comprises the first cyclonic separator and the second cyclonic separator that are cascaded.
According to the present invention, synchronously can realize pyrolysis char passivation and coal tar lighting, and the low-rank coal coal-char combustion characteristic of producing is better than semicoke that common grading process produces, point of ignition is low, calorific value is high, combustion stability is good, in addition, intensity is large, not spontaneous combustion of transporting for long-distance.And product liquid oil studies on asphaltene content is extremely low, and added value is large, and product price is high, and follow-up deep processing is convenient, economical.
Accompanying drawing explanation
Fig. 1 is low-rank coal method for upgrading schematic flow sheet of the present invention.
Nomenclature
11: moisture eliminator
12: hotblast stove
13: cracker
14: cyclonic separator
15: wrap reactor
16: electric fishing storage
17: quenching deactivator
21: gas treating system
22: air-seperation system
23: interchanger
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details.In the present embodiment, for brown coal, disclose low-rank coal method for upgrading and equipment thereof.
As shown in Figure 1, the brown coal as raw material enter moisture eliminator 11 through feeding tube, and meanwhile, gaseous heat-carrier is fed to moisture eliminator 11 by hotblast stove 12, and gaseous heat-carrier heats the brown coal in moisture eliminator 11.Wherein, hotblast stove 12 is with oxygen and the oil fuel of fuel, Sweet natural gas or liquefied gas etc. are for raw material as a supplement, and oxygen and postcombustion react, and generate with CO
2with gaseous state H
2o is the gaseous heat-carrier of main ingredient, such as CO
2volume percent be about 50%, gaseous state H
2the volume percent of O is about 50%, and release of heat in the reaction, obtain the gaseous heat-carrier with optimal temperature.In the present embodiment, the gaseous heat-carrier temperature (also referred to as " temperature in ") entered before moisture eliminator 11 controls at 140 ~ 240 DEG C (such as 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C), thus the temperature in the coal seam in moisture eliminator 11 is controlled below 140 DEG C by the gaseous heat-carrier of this temperature.
Table 1
| Coal seam temperature | Lower than 80 DEG C | 80℃～140℃ | More than 140 DEG C |
| The dried moisture weight content in coal seam | 25%～35% | 5%～10% | The water yield is few |
| With or without pyrolytic reaction | Nothing | Nothing | Pyrolytic reaction is aggravated, and separates out CO, CH4 etc. |
As shown above, coal seam temperature is controlled below 140 DEG C, can ensure at utmost to remove the moisture in coal, and not have pyrolytic reaction to occur.This is due to when brown coal temperature is lower than 80 DEG C, and the moisture removed mainly free water and form the water of weak hydrogen bond with coal, can at least be removed to weight percentage 25% ~ 35%(such as 28%, 30%, 32%, 34% by the original moisture of low-rank coal); And when the temperature of brown coal is when the scope of 80 DEG C ~ 140 DEG C, the moisture removed mainly forms the water of strong hydrogen bonding with coal surface, now minimum can by moisture removal to weight percentage 5% ~ 10%; And when the temperature of brown coal is more than 140 DEG C, the moisture removed is then the moisture that residue is difficult to the inherent water of the part that removes and pyrolysis and produces, and the generation of pyrolysis can be aggravated at this temperature, thus from brown coal separate out a small amount of CO, CH
4deng, sometimes have and reach 200ppm upper and lower CO, CH
4separate out.
In order to prevent brown coal involuntary ignition in drying process, the volume percent of the oxygen level in requirement gaseous heat-carrier is less than 8%, such as be less than or equal to volume percent 6%, the volume percent of the oxygen level of preferred gas thermal barrier is 1 ~ 5%, preferably be less than 2 ~ 3% further, more preferably about 1%.Thus ensure that the safety of brown coal in drying process.
Evenly tile in coal seam in moisture eliminator 11, the gaseous heat-carrier entering moisture eliminator is 140 ~ 240 DEG C, and the coal seam in moisture eliminator is room temperature substantially before being heated, so when gaseous heat-carrier is from bottom to top through coal seam, carry out heat exchange between the two, until coal seam is heated to less than 140 DEG C.So far, the most of moisture in brown coal is removed, and now, the moisture weight content of brown coal is in the level (such as 8%, 11%, 14%) of 5% ~ 15%, preferably can reach 6% ~ 10%.And, in the process, the pyrolytic reaction of brown coal can not be caused, this is mainly owing to generally there is low temperature pyrogenation at 350 ~ 600 DEG C in low-rank coal,, there is high temperature pyrolysis at 800 ~ 900 DEG C in warm solution in occurring at 600 ~ 800 DEG C, and in the present embodiment, coal seam temperature is controlled below 140 DEG C, do not reach the temperature that pyrolytic reaction occurs.In this drying treatment, only have a small amount of CO and produce, the process still removing moisture mainly carried out, produces a large amount of gaseous state H
2o.
In above-mentioned drying process, the by-product gas mainly gaseous state H of generation
2the Poor oxygen gas such as O and a small amount of CO.Subsequently, by-product gas enters gas treating system 21, and carries out the process such as dedusting, desulfurization in gas treating system.Dust-removal and desulfurizing process herein only need be carried out according to usual technology, such as, can adopt whirlwind primary dust removing, subsequent configuration electric precipitation or bag-type dust.
Coal seam in moisture eliminator is heated properly to the Heating temperature preset such as 140 DEG C, and drying process terminates.Subsequently, the valve plate in the fuel dropping pipe between moisture eliminator and cracker 13 is opened, and enters cracker 13 under gravity in moisture eliminator through the brown coal of super-dry.And, in order to ensure that the high-temperature gas thermal barrier in cracker can contact with coal seam is full and uniform, need dried brown coal to be laid in equably on the disk of cracker 13, and according to the internal structure of cracker, coal seam is suitably controlled in the scope of 200 ~ 600 mm of thickness.
After brown coal reach cracker, high-temperature gas thermal barrier is fed in cracker 13 by hotblast stove 12, makes the gaseous heat-carrier of high temperature directly can contact brown coal coal seam on disk, thus carries out pyrolytic reaction.
Hotblast stove 12 gaseous heat-carrier be transported in cracker 13 is high-temperature gas thermal barrier, identical with the component of the gaseous heat-carrier be transported in moisture eliminator, is also to generate with CO after oxygen in hotblast stove and postcombustion oxidizing fire
2with gaseous state H
2o is the Poor oxygen gas of main ingredient.But the temperature of this high-temperature gas thermal barrier is different from the gaseous heat-carrier be transported in moisture eliminator 11.The temperature of high-temperature gas thermal barrier herein need control at 380 ~ 680 DEG C, thus makes coal seam temperature reach 350 ~ 650 DEG C, and then low temperature pyrogenation reaction in occurring.In this process, although produce with certain moisture, thus carried out drying thoroughly to brown coal, this carries out middle low temperature pyrogenation reaction while being in and producing moisture, so the moisture produced belongs to pyrolysis water, different from the drying and dehydrating process in moisture eliminator.
Further, when coal seam temperature reaches 350 ~ 650 DEG C, the oxygen level of this high-temperature gas thermal barrier requires in volume percent less than 2 ~ 3%, preferably controls 0.5 ~ 2%, especially preferred by Control for Oxygen Content lower than 0.5%.Thereby, it is possible to ensure the high temperature drying brown coal of very easily involuntary ignition, even if under this pyrolysis atmosphere, also the hazardous condition such as spontaneous combustion and detonation can not be there is.
In pyrolytic reaction process, in order to remove moisture more up hill and dale and carry out sufficient pyrolytic reaction, the heating rate of brown coal is needed to control at 5 ~ 100 DEG C/s, the residence time of brown coal in cracker 13 is controlled at 15-30min(such as 18min, 21min, 24min, 27min), the residence time of high-temperature gas thermal barrier in cracker is controlled at 2-12min(such as 4min, 6min, 8min, 10min).
Wherein, the residence time of required brown coal (solid phase) can be obtained by controlling the factors such as coal input quantity, thickness of coal seam, coal breakage amount; The residence time of required high-temperature gas thermal barrier (gas phase) can be obtained by controlling the factors such as air input, reactor voidage, top hole pressure.Further, by controlling the gas phase residence time and the solid phase residence time, required pyrolysis heating rate can be obtained accordingly, thus obtain target product, particularly the output of splitting gas and composition.
Below, table 2 represents the pyrolysis product of a kind of brown coal in different pyrolysis situation and the weight percent of output thereof.
Table 2
Table 3 represents the volume percent content of the component of coal gas in table 2.
Table 3
| Temperature (DEG C) | H2 | CH4 | CO | CO2 | C2H4 | C2H6 | CmHn | N2 |
| 550 | 20.1 | 24.2 | 23.7 | 24.2 | 1.3 | 2.9 | 5.6 | 0.5 |
| 600 | 25.6 | 23.3 | 20.1 | 22.7 | 1.8 | 2.4 | 2.4 | 0.8 |
| 650 | 33.7 | 21.6 | 17.8 | 19.5 | 2.4 | 1.9 | 4.5 | 0.7 |
Cracker 13 is connected to two cyclonic separators 14, carries out, in the process of pyrolysis, producing a large amount of dusty gas in this cracker 13.Dusty gas enters two cyclonic separators 14 respectively.Two cyclonic separators 14 all by the solid phase in dusty gas and gas phase separation, and obtain fine coal after solid phase being reclaimed.Isolated gas phase is sent into hotblast stove 12 via pipeline and is burnt by one of them cyclonic separator 14, is moisture eliminator 11 and cracker 13 heat supply.This isolated gas phase includes CO, CH
4with a small amount of H
2, C
2h
2deng gas, obtaining main ingredient after these inflammable gas oxidizing fires is CO
2with gaseous state H
2the Poor oxygen gas of O etc., release of heat heats gaseous heat-carrier simultaneously, thus obtains the gaseous heat-carrier of optimal temperature.
Isolated gas phase is delivered to interchanger 23 by another cyclonic separator 14, makes it tentatively to be cooled, thus can be utilized described later wrapping in reaction.The gas temperature produced in cracker at 400 ~ 550 DEG C, is tentatively cooled by this substantially, can heat exchange to 350 ~ 400 DEG C, thus to be used in operation afterwards.Thus, by arranging two cyclonic separators, the gaseous substance produced in pyrolytic reaction can be made full use of.In preliminary cooling, can also by-product middle pressure steam, and this middle pressure steam can be supplied to power plant etc. and do thermal source heat exchange or heat supply etc., thus improve heat utilization rate further.
In the present embodiment, two cyclonic separators 14 are connected with cracker 13 respectively, are parallel relationship each other, and its object is mainly the gas in addition dual utilization produced scission reaction, improves the utilization ratio of this gas.But in actual applications, also can, according to producing the gas volume of gas, dustiness and utilizing object etc. to gas, make both for relation that is in parallel or series connection, and can using two cyclonic separators 14 as one-level, two-stage dust removal equipment.The quantity of cyclonic separator is not defined as two yet, can increase and decrease quantity according to actual needs.
Brown coal, after the reaction in cracker, obtain semicoke.Still there is the hot semicoke of certain temperature under gravity, via being arranged on pyrolyzer and the follow-up fuel dropping pipe wrapped between reactor, by operating devices such as the valve plates in unlatching fuel dropping pipe, what be slipped to that fuel dropping pipe bottom UNICOM wraps reactor 15, thus wrapping in reactor 15, carry out wrapping reaction.
Wrapping in reactor 15, adopting gas to cool step by step hot semicoke as cold carrier.At the gas cold carrier that the leading portion wrapping reactor 1 is introduced, be made up of the inactive gas (being mainly nitrogen) from air-seperation system 22.A part for the gas-phase product that cracker 13 produces is all passed into above-mentioned nitrogen the leading portion wrapping reactor 15 by the gas (also can be described as splitting gas) tentatively cooled through interchanger 23.
Wherein, splitting gas is after cracker 13 output, and initial temperature is about 400 ~ 550 DEG C, tentatively cools through interchanger 23, can heat exchange to 350 ~ 400 DEG C, and recovery part heat, produces middle pressure steam.But in this process, there will not be the separation of cracked gas.
Above-mentioned air-seperation system 22 is for becoming nitrogen and oxygen containing gas by air separation, wherein, nitrogen gas supply wraps the leading portion of reactor 15, oxygen-containing gas supply hotblast stove 12.Nitrogen is wherein room temperature substantially, synchronously passes into the leading portion wrapping reactor 15, splitting gas is exacerbated and is cooled to 250 ~ 300 DEG C, and progressively cool hot semicoke with splitting gas.When splitting gas is exacerbated cooling, it is generally separated into gas phase (raw gas) and liquid phase (coal tar).Raw gas main component has CO, CH
4, H
2, CO
2deng; Coal tar main body of oil has stable hydrocarbon, aromatic hydrocarbon, nonhydrocarbon, bituminous matter etc.The degree of each component is relevant with raw coal ature of coal, cracking temperature, speed etc.And its studies on asphaltene generally then can curding out at 280 ~ 350 DEG C.
Wherein nitrogen is except cooling splitting gas, makes it outside condensing air liquid phase separation, also as fire fighting gas, plays the effect of fire-fighting protection, and it is with low cost, safety is easy to get.
After above-mentioned gas cold carrier enters the leading portion wrapping reactor 15, because splitting gas is by nitrogen condensation, so reaction can be wrapped with hot semicoke.Describedly wrap reaction and refer to, due to the temperature lower (normal temperature) of the nitrogen that air-seperation system provides, so while splitting gas is condensed, the hot semicoke wrapped in reactor 15 is also cooled, make the heavy constituent in splitting gas, mainly bituminous matter is separated out and is wrapped the hot semicoke surface progressively cooled.
Subsequently, from the by-product gas of gas treating system 21, after temperature regulates, be introduced into the back segment wrapping reactor 15, directly contact with by the semicoke wrapped, the temperature of this by-product gas should remain on 200 ~ 300 DEG C, and semicoke is cooled further.
Subsequently, the mixed gas after wrapping reactor enters electric fishing storage 16, and now, the bituminous matter as heavy constituent of about 45% volume percent in gas is wrapping the precipitation of reactor stage, and remaining is then CO, CH substantially
4, stable hydrocarbon and aromatic hydrocarbon etc., wherein CO, CH
4go Combustion of Hot Air Furnace, other stable hydrocarbon and aromatic hydrocarbon etc. are then separated out as liquid oils in electric fishing storage 16.
Electric fishing storage 16 isolated liquid oils from mixed gas is equivalent to the light tar after except bituminous matter.Thereafter, primarily of CO
2, N
2with gaseous state H
2the residual gas of O composition through torch burning, and discharges after the conventional process such as wet desulphurization are up to standard.
Wrap after reaction terminates, open the valve wrapping reactor 15, semicoke is fallen on transfer roller under gravity, sends into quenching deactivator 17 by mechanical transmission band.Semicoke directly contacts with the by-product gas from gas treating system and after temperature regulates, and progressively cooling obtains stable product lignite semi-coke, emptying after leaving the gaseous combustion of quenching deactivator 17.
Because this by-product gas contains moisture, through the process of gas treating system, its moisture weight content is at 10-20%(such as 12%, 14%, 16%, 18%), temperature is at 40 ~ 70 DEG C (such as 50 DEG C, 60 DEG C, so far temperature is cooled by the cooling of external heat exchanger indirect heat exchange method or the direct heat exchange of use nitrogen at room), the volumn concentration of oxygen is 5-21%(such as 8%, 11%, 14%, 17%).Thereby, it is possible to ensure that quenching deactivator 17 works under the state of the oxygen volume content lower than air, ensure carrying out smoothly of passivation reaction, and be convenient to temperature control.Thus can make semicoke that further passivation and rehydrated reaction occur, upgrading semicoke is made again to relapse moisture in atmosphere, slowly reach nature saturated-water phase, now in semicoke, moisture weight content is about about 8 ~ 16% (such as 10%, 12%, 14%), thus make semicoke be applicable to placing in atmosphere, and can transport for long-distance, and there is not dieseling.
According to the embodiment of the present invention, achieve the lighting of coal tar original position above-mentioned wrapping in reactor 15, be stripped of wherein most bituminous matter, and preliminary carry out semicoke passivation; In quenching deactivator 17, carry out semicoke original position Slow cooling, comprise the surface oxidation of semicoke and rehydrated reaction, reduce the apparent chemically reactive of semicoke, improve semicoke strength and stability.Such operation can avoid the involuntary ignition phenomenon concentrating passivating process to cause because of semicoke, and emergency processing cost is low, simple to operate.
Thus, the low-rank coal coal-char combustion characteristic of production is better than semicoke that common grading process produces, and point of ignition is low, calorific value is high, combustion stability is good, and in addition, intensity is large, not spontaneous combustion of transporting for long-distance.And product liquid oil studies on asphaltene content is extremely low, and added value is large, and product price is high, and follow-up deep processing is convenient, economical.
Further, in the coal tar in traditional technology, the weight percent of saturated hydrocarbon content is less than 6%, and the weight percent of aromatic hydrocarbon content is less than 40%, and the weight percent of nonhydrocarbon is about 10%, and bitum weight percent is about 45%.And according to the present invention, bituminous matter major part is separated out, liquid oils studies on asphaltene content can reach less than 10%, so with this liquid oils for raw material Hydrogenation is for petrol and diesel oil, cost reduces, and productive rate improves.
Claims (24)
1. a low-rank coal method for upgrading, is characterized in that, comprising:
Drying step, is heated to less than 140 DEG C by the first gaseous heat-carrier by coal seam, carries out drying, makes the moisture weight content of the dry rear low-rank coal obtained 10% ~ 15%, and produces by-product gas;
Pyrolysis step, the coal seam temperature of the low-rank coal described drying being obtained afterwards by the second gaseous heat-carrier reaches 350 ~ 650 DEG C, obtains dusty gas and hot semicoke, and a part for the isolated gaseous substance of described dusty gas becomes splitting gas after preliminary cooling;
Wrap step, the described hot semicoke and described splitting gas that are positioned at the same space is progressively cooled by gas cold carrier, heavy constituent in described splitting gas is separated out and is wrapped the hot semicoke surface progressively cooled, subsequently, the described by-product gas that described semicoke is 200 ~ 300 DEG C by temperature cools further, obtains wrapping semicoke and mixed gas; With
Quenching passivation step, make further cooled described in wrap the described by-product gas that semicoke and temperature are 40 ~ 70 DEG C and directly contact, again adsorption moisture, carries out wrapping the surface oxidation of semicoke and rehydrated reaction, makes this moisture weight content wrapping semicoke be 8 ~ 16%.
2. low-rank coal method for upgrading according to claim 1, is characterized in that:
Described first gaseous heat-carrier and described second gaseous heat-carrier are all with CO
2with gaseous state H
2o is main ingredient, and the temperature of described first gaseous heat-carrier before entering drying step controls at 140 ~ 240 DEG C, and the temperature of described second gaseous heat-carrier before entering pyrolysis step controls at 380 ~ 680 DEG C.
3. low-rank coal method for upgrading according to claim 1, is characterized in that:
The volume percent of the oxygen level of described second gaseous heat-carrier is less than or equal to 2%,
The volume percent of the oxygen level of described first gaseous heat-carrier is less than or equal to 6%.
4. low-rank coal method for upgrading according to claim 3, is characterized in that:
The volume percent of the oxygen level of described second gaseous heat-carrier in 0.5 ~ 2%,
The volume percent of the oxygen level of described first gaseous heat-carrier is less than or equal to 5%.
5. low-rank coal method for upgrading according to claim 4, is characterized in that:
The volume percent of the oxygen level of described second gaseous heat-carrier below 0.5%,
The volume percent of the oxygen level of described first gaseous heat-carrier is less than 2 ~ 3%.
6. low-rank coal method for upgrading according to claim 5, is characterized in that:
The volume percent of the oxygen level of described first gaseous heat-carrier is about 1%.
7. low-rank coal method for upgrading according to claim 1, is characterized in that:
In described pyrolysis step, the thickness in described coal seam is 200 ~ 600 millimeters, and the heating rate in described coal seam is in the scope of 5 ~ 100 DEG C/s.
8. low-rank coal method for upgrading according to claim 1, is characterized in that:
Described temperature be the moisture weight content of the described by-product gas of 40 ~ 70 DEG C 10 ~ 20%, the volumn concentration of oxygen is 5-21%.
9. low-rank coal method for upgrading according to claim 8, is characterized in that:
Described gas cold carrier is the nitrogen under room temperature, and described heavy constituent is bituminous matter, and described low-rank coal is brown coal.
10. low-rank coal method for upgrading according to claim 1, is characterized in that:
Wrap in step described, described splitting gas is cooled to 250 ~ 300 DEG C, and be separated into the raw gas of gas phase and the coal tar of liquid phase, described raw gas comprises CO, CH
4, H
2and CO
2, described coal tar comprises stable hydrocarbon, aromatic hydrocarbon, non-hydrocarbon and asphaltene.
11. low-rank coal method for upgrading according to claim 10, is characterized in that:
Also comprise from the described liquid oils separating step wrapping separating liquid oil the mixed gas of step generation.
12. 1 kinds of low-rank coal upgrading devices, is characterized in that, comprise hotblast stove, moisture eliminator, cracker, the first cyclonic separator, the second cyclonic separator, wrap reactor and quenching deactivator, wherein,
Hotblast stove, provides the gaseous heat-carrier of differing temps to described moisture eliminator and described cracker;
Moisture eliminator, receive the low-rank coal as feed coal, be connected with described pipeline of hot air furnace, low order coal seam is heated to less than 140 DEG C by the first gaseous heat-carrier provided by described hotblast stove, carry out drying, make the moisture weight content of low-rank coal 5% ~ 15%, obtain dried low-rank coal and produce by-product gas, and wrap reactor and described quenching deactivator described in being led to by described by-product gas;
Cracker, be arranged at the below of described moisture eliminator, described dried low-rank coal enters described cracker under gravity, the second gaseous heat-carrier provided by described hotblast stove makes coal seam temperature after drying reach 350 ~ 650 DEG C, obtain dusty gas and hot semicoke, described dusty gas enters the first cyclonic separator and described second cyclonic separator respectively, fine coal and the gaseous substance of solid matter is all obtained after separation, wherein be separated through described first cyclonic separator the gaseous substance obtained after burning, supplement described first gaseous heat-carrier or the second gaseous heat-carrier that become in described hotblast stove, be separated through described second cyclonic separator the gaseous substance obtained and become splitting gas after preliminary cooling,
Wrap reactor, be arranged at the below of described cracker, after wrapping reactor described in described hot semicoke enters under gravity, utilize pipeline described gas cold carrier and described splitting gas are input to described in wrap reactor, described hot semicoke and described splitting gas is progressively cooled by gas cold carrier, heavy constituent in described splitting gas is separated out and is wrapped the hot semicoke surface progressively cooled, subsequently, the described by-product gas that described hot semicoke is 200 ~ 300 DEG C by temperature cools further, obtains wrapping semicoke and mixed gas; With
Quenching deactivator, make further cooled described in wrap the described by-product gas that semicoke and temperature are 40 ~ 70 DEG C and directly contact, adsorption moisture again, makes the moisture weight content of this semicoke be 8 ~ 16%.
13. low-rank coal upgrading devices as claimed in claim 12, is characterized in that:
Also comprise the gas treating system be connected with described moisture eliminator, described by-product gas wraps reactor and described quenching deactivator described in leading to after described gas treating system process.
14. low-rank coal upgrading devices as claimed in claim 13, is characterized in that:
Also comprise and be connected to described second cyclonic separator and the described interchanger wrapped between reactor, be separated through described second cyclonic separator the gaseous substance obtained becomes splitting gas after the preliminary cooling of described interchanger.
15. low-rank coal upgrading devices as claimed in claim 14, is characterized in that:
Also comprise and the described electric fishing storage wrapping reactor and be connected, described mixed gas isolates liquid oils through described electric fishing storage.
16. low-rank coal upgrading devices as claimed in claim 15, is characterized in that:
Also comprise and the described air-seperation system wrapping reactor and be connected, from air, isolate the nitrogen as described gas cold carrier.
17. low-rank coal upgrading devices as claimed in claim 16, is characterized in that:
The described reactor that wraps is divided into leading portion and back segment, and described gas cold carrier and described splitting gas pass into described leading portion, and described temperature is that the described by-product gas of 200 ~ 300 DEG C passes into described back segment.
18. 1 kinds of low-rank coal upgrading devices, is characterized in that, comprise hotblast stove, moisture eliminator, cracker, cyclonic separator, wrap reactor and quenching deactivator, wherein,
Hotblast stove, provides the gaseous heat-carrier of differing temps to described moisture eliminator and described cracker;
Moisture eliminator, receive the low-rank coal as feed coal, be connected with described pipeline of hot air furnace, low order coal seam is heated to less than 140 DEG C by the first gaseous heat-carrier provided by described hotblast stove, carry out drying, make the moisture weight content of low-rank coal 10% ~ 15%, obtain dried low-rank coal and produce by-product gas, and wrap reactor and described quenching deactivator described in being led to by described by-product gas;
Cracker, be arranged at the below of described moisture eliminator, described dried low-rank coal enters described cracker under gravity, the second gaseous heat-carrier provided by described hotblast stove makes coal seam temperature after drying reach 350 ~ 650 DEG C, obtain dusty gas and hot semicoke, the fine coal and the gaseous substance that obtain solid matter is separated after described dusty gas enters described cyclonic separator, a part for gaseous substance supplements described first gaseous heat-carrier or the second gaseous heat-carrier that become in described hotblast stove after burning, another part of gaseous substance becomes splitting gas after preliminary cooling,
Wrap reactor, be arranged at the below of described cracker, after wrapping reactor described in described hot semicoke enters under gravity, utilize pipeline described gas cold carrier and described splitting gas are input to described in wrap reactor, described hot semicoke and described splitting gas is progressively cooled by gas cold carrier, heavy constituent in described splitting gas is separated out and is wrapped the hot semicoke surface progressively cooled, subsequently, the described by-product gas that described hot semicoke is 200 ~ 300 DEG C by temperature cools further, obtains wrapping semicoke and mixed gas; With
Quenching deactivator, make further cooled described in wrap the described by-product gas that semicoke and temperature are 40 ~ 70 DEG C and directly contact, adsorption moisture again, makes the moisture weight content of this semicoke be 8 ~ 16%.
19. low-rank coal upgrading devices as claimed in claim 18, is characterized in that:
Also comprise the gas treating system be connected with described moisture eliminator, described by-product gas wraps reactor and described quenching deactivator described in leading to after described gas treating system process.
20. low-rank coal upgrading devices as claimed in claim 18, is characterized in that:
Also comprise and be connected to described cyclonic separator and the described interchanger wrapped between reactor, described another part of described gaseous substance becomes splitting gas after the preliminary cooling of described interchanger.
21. low-rank coal upgrading devices as claimed in claim 18, is characterized in that:
Also comprise and the described electric fishing storage wrapping reactor and be connected, described mixed gas isolates liquid oils through described electric fishing storage.
22. low-rank coal upgrading devices as claimed in claim 18, is characterized in that:
Also comprise and the described air-seperation system wrapping reactor and be connected, from air, isolate the nitrogen as described gas cold carrier.
23. low-rank coal upgrading devices as claimed in claim 18, is characterized in that:
The described reactor that wraps is divided into leading portion and back segment, and described gas cold carrier and described splitting gas pass into described leading portion, and described temperature is that the described by-product gas of 200 ~ 300 DEG C passes into described back segment.
24. low-rank coal upgrading devices as claimed in claim 18, is characterized in that:
Described cyclonic separator comprises the first cyclonic separator and the second cyclonic separator that are cascaded.
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| CN105018119B (en) * | 2014-04-30 | 2018-09-04 | 肖自江 | Hot low temperature downlink pyrolysis oven outside fine coal oil shale powder |
| CN105018118B (en) * | 2014-04-30 | 2018-05-11 | 肖自江 | Fine coal oil shale powder low temperature pyrogenation method and the vertical downlink low temperature pyrogenation stove of outer heat |
| CN103939158B (en) * | 2014-05-09 | 2015-10-07 | 湖南华银能源技术有限公司 | A kind of low-order coal purification power generation system |
| CN106929045A (en) * | 2015-12-30 | 2017-07-07 | 北京三聚环保新材料股份有限公司 | A kind of coking process of biomass |
| CN108218653B (en) * | 2016-12-21 | 2023-11-07 | 中国石化集团四川维尼纶厂 | Method for producing acetylene and synthesis gas by partial oxidation of hydrocarbon |
| CN107118785B (en) * | 2017-04-21 | 2019-08-16 | 太原理工大学 | The self-heating of low-order coal-spontaneous combustion process energy utilization method |
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