CN102994122B - Low-rank coal quality-improving method and equipment - Google Patents
Low-rank coal quality-improving method and equipment Download PDFInfo
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Abstract
The invention relates to a low-rank coal quality-improving method and equipment; according to the method, a coal layer is heated to below 140 DEG C by a first gas heat carrier so as to obtain a water weight content of the dried low-rank coal of 5%-15% and to produce by-product gas; the coal layer temperature of the dried low-rank coal reaches 350-650 DEG C by a second gas heat carrier to obtain dust-containing gas and hot semicoke; the solid-phase substances of the dust-containing gas is separated from gas-phase substances to obtain powdered coal and the gas-phase substances; a part of the gas phase is combusted and supplements the first gas heat carrier or the second gas heat carrier; the other part of the gas phase is cooled to become cracking gas; the hot semicoke and the cracking gas in same space are cooled gradually by a gas cold carrier; heavy components in the cracking gas are precipitated and wrap on the surface of the hot semicoke cooled gradually; the semicoke is cooled by the by-product gas with a temperature of 200-300 DEG C to obtain wrapped semicoke and mixed gas; the cooled wrapped semicoke contacts the by-product gas with a temperature of 40-70 DEG C for water adsorption and surface oxidation and rehydration reaction of the wrapped semicoke so as to obtain a water weight content of the wrapped semicoke of 8-16%.
Description
Technical field
The present invention relates to a kind of novel low-rank coal method for upgrading and equipment thereof, particularly low-rank coal method for upgrading and the equipment thereof of the passivation of brown coal pyrolysis char and coal tar lighting coupling.
Background technology
China's brown coal reserves are abundant, and within 2010, brown coal output exceedes 300,000,000 tons, accounts for 10% of national coal production.The highly-efficient processing utilization of brown coal has become the problem that coal in China energy field is 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 on the other hand chemical reactivity too high, in air, very easily weathering and fragmentation, is unsuitable for long distance transportation and standing storage.Therefore, brown coal upgrading is the key link that brown coal utilize.In order to meet the requirement of different purposes to coal quality, brown coal Upgrading Processes is divided into dehydration upgrading, moulding upgrading and pyrolysis upgrading, wherein pyrolysis upgrading can be obtained semicoke, three kinds of primary products of coal tar oil and gas 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.It is hybrid that brown coal upgrading Technology can be divided into the outer heat of external-heat, internal heat type and interior heat according to type of heating; According to the difference of heating medium, there are two kinds of solid heat carrier method and air heat support methods; Operation conditions according to solid materials in reactor can be divided into rotating bed, fixed bed, fluidized-bed, air flow bed and bed (rotary kiln/kiln) technology etc. of rolling.
The Typical Representative of external brown improving quality of coal by pyrolysis packaged process mainly contains the Toscoal rotary kiln pyrolytic process of Oil Shale Corporation of America (The Oil Shale Corporation) exploitation; The LFC(Liquid FromCoal of U.S. shell mining (Shell Mining Company) company and the cooperative development of U.S. SGI company) technique; The ACCP(Advanced Coal Conversion Process of Western Energy Resources company exploitation) pyrolytic process; The fluid bed fast pyrolysis technique of Australian Union's science and industrial research institute (CSIRO) exploitation; The Lurgi-Ruhrgas(L-R that Germany Lurgi GmbH and U.S. Ruhrgas AG develop jointly) solid thermal carriers low temperature pyrogenation technique; And the Lurgi-Spuelgas(L-S of German Lurgi GmbH exploitation) technique etc.The unit of domestic research coal pyrolytic technique is numerous, and the technology that is more typically applicable to brown improving quality of coal by pyrolysis has multistage rotary kiln (MRF) pyrolytic process of Chinese coal scientific research Zong Yuan Beijing Coal Chemical Industry branch exploitation; The Guo Shu of Dalian University of Technology 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 pulls out head technique " (BT technique) of process engineering institute of the Chinese Academy of Sciences etc.
The technology quality of brown coal pyrolysis process for upgrading depends on the quality of coal gas, coal tar and semicoke, and above-mentioned various technique obtains coal tar or coal gas when being intended to promote semicoke quality.From the above-mentioned each technique of pyrolysis temperature angle contrast, can find out: except ACCP technology, the pyrolysis temperature of other technology all exceedes 500 ℃, after the simple Passivation Treatment of gained semicoke product, is difficult for spontaneous combustion, and water absorbability also significantly improves.From the speed of heating, compare, the existing gas-particle heat transfer of fluidization that CSIRO adopts also has heat transfer admittedly, and pyrolysis rate is fast, and liquid yield will be significantly higher than other upgrading technology, but quality and workability are poor.
The quenching of former Encoal process using water spray Quench, causes water consumption to cause greatly, on the other hand semicoke Quench to burst apart and efflorescence 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, 300,000 tons/year of processing poweies.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, 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 most of technology, 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 exchanges or reaction are the process of relative low temperature, causes thus heat transfer temperature difference little, the utilization difficulty of tow taste heat, and process efficiency is low;
3) research that the mechanism to lignite semi-coke passivation, process conditions and through engineering approaches are amplified there is no to be carried out, and makes a whole set of technique 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 that steel-making coke strenth promotes, the technique of pyrolyzing coal tar passivation semicoke and semicoke original position Slow cooling is proposed, not only improve semicoke intensity, reduced the apparent chemistry of semicoke, and pyrolyzing coal tar original position lighting, 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, below 140 ℃, be dried, and make the moisture weight content of the dry rear low-rank coal obtaining 5% ~ 15%, and produce by-product gas; Pyrolysis step, by the second gaseous heat-carrier, make the coal seam temperature of the above-mentioned dry rear low-rank coal obtaining reach 350 ~ 650 ℃, obtain dusty gas and hot semicoke, after the solid matter of above-mentioned dusty gas is separation with gaseous substance, obtain fine coal and the gaseous substance of solid matter, a part for gaseous substance is supplemented and is become above-mentioned the first gaseous heat-carrier or above-mentioned the second gaseous heat-carrier after burning, and another part of gaseous substance becomes splitting gas after preliminary cooling; Wrap step, by progressively cooling above-mentioned hot semicoke and the above-mentioned splitting gas that is positioned at the same space of gas cold carrier, heavy constituent in above-mentioned splitting gas is separated out and is wrapped on progressively cooling hot semicoke surface, subsequently, above-mentioned semicoke is that the above-mentioned by-product gas of 200 ~ 300 ℃ is further cooling by temperature, obtains wrapping semicoke and mixed gas; With quenching passivation step, make further cooledly above-mentionedly to wrap the above-mentioned by-product gas that semicoke is 40 ~ 70 ℃ with temperature and directly contact, again adsorption moisture, wraps the surface oxidation of semicoke and rehydrated reaction, and making this moisture weight content that wraps semicoke is 8 ~ 16%.
In above-mentioned low-rank coal method for upgrading, preferably, above-mentioned the first gaseous heat-carrier and above-mentioned the second gaseous heat-carrier are all with CO
2with gaseous state H
2o is main ingredient, and above-mentioned the first gaseous heat-carrier is controlled at 140 ~ 240 ℃ in the temperature entering before drying step, and above-mentioned the second gaseous heat-carrier is controlled at 380 ~ 680 ℃ in the temperature entering before pyrolysis step.
In above-mentioned low-rank coal method for upgrading, preferably, the volume percent of the oxygen level of above-mentioned the 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 the first gaseous heat-carrier is less than or equal to 6%, is more preferably less than or equal to 5%, further preferably be less than 2～3%, more preferably in 1% left and right.
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 ℃/s.
In above-mentioned low-rank coal method for upgrading, preferably, the moisture weight content of the above-mentioned low-rank coal obtaining after dry is 6% ~ 10%, said temperature be the moisture weight content of above-mentioned by-product gas of 40 ~ 70 ℃ 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, above-mentioned, wrap in step, above-mentioned splitting gas is cooled to 250 ~ 300 ℃, is separated into the raw gas of gas phase and the coal tar of liquid phase, and 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 the liquid oils separating step of separating liquid oil from the above-mentioned mixed gas that wraps step generation.
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, reception is as the low-rank coal of feed coal, be connected with above-mentioned pipeline of hot air furnace, the first gaseous heat-carrier providing by above-mentioned hotblast stove is heated to low order coal seam below 140 ℃, be dried, make the moisture weight content of low-rank coal 5% ~ 15%, obtain dried low-rank coal and produce by-product gas, and above-mentioned by-product gas is led to above-mentioned reactor and the above-mentioned quenching deactivator of wrapping, cracker, be arranged at the below of above-mentioned moisture eliminator, above-mentioned dried low-rank coal enters above-mentioned cracker under action of gravity, the second gaseous heat-carrier providing by above-mentioned hotblast stove makes coal seam temperature after drying reach 350 ~ 650 ℃, obtain dusty gas and hot semicoke, above-mentioned dusty gas separates the fine coal and the gaseous substance that obtain solid matter after entering above-mentioned cyclonic separator, a part for gaseous substance is supplemented above-mentioned the 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 enters above-mentioned wrapping after reactor under action of gravity, utilize pipeline that above-mentioned gas cold carrier and above-mentioned splitting gas are input to the above-mentioned reactor that wraps, by progressively cooling above-mentioned hot semicoke and above-mentioned splitting gas of gas cold carrier, heavy constituent in above-mentioned splitting gas is separated out and is wrapped on progressively cooling hot semicoke surface, subsequently, above-mentioned hot semicoke is that the above-mentioned by-product gas of 200 ~ 300 ℃ is further cooling by temperature, obtains wrapping semicoke and mixed gas, with quenching deactivator, the above-mentioned by-product gas that further cooled above-mentioned hot semicoke is 40 ~ 70 ℃ with temperature is directly contacted, adsorption moisture again, the moisture weight content that makes this semicoke is 8 ~ 16%.
In above-mentioned low-rank coal upgrading device, preferably also comprise the gas treating system being connected with above-mentioned moisture eliminator, above-mentioned by-product gas is leading to above-mentioned reactor and the above-mentioned quenching deactivator of wrapping after above-mentioned gas treatment system is processed.
In above-mentioned low-rank coal upgrading device, preferably also comprise and be connected to above-mentioned cyclonic separator and the above-mentioned interchanger wrapping between reactor, above-mentioned another part of above-mentioned gaseous substance becomes splitting gas through after above-mentioned interchanger preliminary cooling.
In above-mentioned low-rank coal upgrading device, preferably also comprise with above-mentioned and wrap the electric fishing storage that reactor is connected, above-mentioned mixed gas is isolated liquid oils through above-mentioned electric fishing storage.
In above-mentioned low-rank coal upgrading device, preferably also comprise with above-mentioned and wrap the air-seperation system that reactor is 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 ℃ passes into above-mentioned back segment.
According to the present invention, can synchronously realize pyrolysis char passivation and coal tar lighting, and the low-rank coal coal-char combustion characteristic of producing is better than common upgrading semicoke that process is produced, point of ignition is low, calorific value is high, combustion stability is good, in addition, intensity is large, the 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, take brown coal as example, disclose low-rank coal method for upgrading and equipment thereof.
As shown in Figure 1, as the brown coal of raw material, through feeding tube, enter moisture eliminator 11, meanwhile, hotblast stove 12 feeds to moisture eliminator 11 by gaseous heat-carrier, and gaseous heat-carrier heats the brown coal in moisture eliminator 11.Wherein, hotblast stove 12 is take oxygen and oil fuel, Sweet natural gas or the liquefied gas etc. of fuel are as raw material as a supplement, and oxygen reacts with postcombustion, generates with CO
2with gaseous state H
2o is the gaseous heat-carrier of main ingredient, for example CO
2volume percent be about 50%, gaseous state H
2the volume percent of O is about 50%, and in reaction release of heat, obtain having the gaseous heat-carrier of optimal temperature.In the present embodiment, the temperature (also referred to as " temperature in ") that gaseous heat-carrier enters before moisture eliminator 11 is controlled at 140 ~ 240 ℃ (such as 160 ℃, 180 ℃, 200 ℃, 220 ℃), thereby by the gaseous heat-carrier of this temperature, the temperature in the coal seam in moisture eliminator 11 is controlled at below 140 ℃.
Table 1
| Coal seam temperature | Lower than 80 ℃ | 80℃~140℃ | Exceed 140 ℃ |
| The dried moisture weight content in coal seam | 25%~35% | 5%~10% | The water yield is few |
| Have or not pyrolytic reaction | Nothing | Nothing | Pyrolytic reaction aggravation, separates out CO, CH4 etc. |
As shown above, coal seam temperature is controlled at below 140 ℃, can guarantees at utmost to remove the moisture in coal, and do not have pyrolytic reaction to occur.This is due to when brown coal temperature is during lower than 80 ℃, and the moisture removing is mainly free water and forms the water of weak hydrogen bond with coal, the original moisture of low-rank coal at least can be removed to weight percentage 25%～35%(such as 28%, 30%, 32%, 34%); And when scope at 80 ℃ ~ 140 ℃ of the temperature of brown coal, the moisture removing is mainly and coal surface forms the water of strong hydrogen bonding, now minimum can be by moisture removal to weight percentage 5% ~ 10%; And when the temperature of brown coal exceedes 140 ℃, the moisture removing is the moisture that remains the inherent water of the part that is difficult to remove and pyrolysis generation, and the generation of pyrolysis be can aggravate at this temperature, thereby a small amount of CO, CH from brown coal, started to separate out
4deng, sometimes have and reach the upper and lower CO of 200ppm, CH
4separate out.
In order to prevent brown coal involuntary ignition in drying process, requiring the volume percent of the oxygen level in gaseous heat-carrier is below 8%, such as being less than or equal to volume percent 6%, the volume percent of the oxygen level of preferred gas thermal barrier is 1 ~ 5%, further preferably be less than 2～3%, more preferably in 1% left and right.Thereby guaranteed the safety of brown coal in drying process.
Evenly tile in coal seam in moisture eliminator 11, the gaseous heat-carrier that enters moisture eliminator is 140 ~ 240 ℃, and coal seam in moisture eliminator is room temperature substantially before heated, so when gaseous heat-carrier from bottom to top passes coal seam, carry out heat exchange between the two, until coal seam is heated to below 140 ℃.So far, the most of moisture in brown coal is removed, and now, the moisture weight content of brown coal is in 5% ~ 15% level (such as 8%, 11%, 14%), preferably can reach 6% ~ 10%.And, in this process, can not cause the pyrolytic reaction of brown coal, this is mainly because low-rank coal generally at 350 ~ 600 ℃, low temperature pyrogenation occurs,, at 800 ~ 900 ℃, there is high temperature pyrolysis in warm solution in 600 ~ 800 ℃ of generations, and in the present embodiment, coal seam temperature is controlled at below 140 ℃, does not reach the temperature that pyrolytic reaction occurs.In this drying treatment, only have a small amount of CO and produce, the processing that still removes moisture of mainly carrying out, produces a large amount of gaseous state H
2o.
In above-mentioned drying process, the by-product gas of generation is mainly gaseous state H
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 processing such as dedusting, desulfurization in gas treating system.Dust-removal and desulfurizing herein is only processed need according to common technology, for example, can adopt whirlwind primary dust removing, subsequent configuration electric precipitation or bag-type dust.
Coal seam in moisture eliminator is by homogeneous heating to predefined Heating temperature for example after 140 ℃, and drying process finishes.Subsequently, the valve plate in the fuel dropping pipe between moisture eliminator and cracker 13 is opened, and the brown coal through super-dry in moisture eliminator enter cracker 13 under action of gravity.And, in order to guarantee that the high-temperature gas thermal barrier in cracker can contact with coal seam is full and uniform, dried brown coal need to be laid on the disk of cracker 13 equably, and according to the internal structure of cracker, coal seam be suitably controlled in the scope of 200 ~ 600 millimeters of thickness.
Brown coal reach after cracker, and hotblast stove 12 is fed to high-temperature gas thermal barrier in cracker 13, make the gaseous heat-carrier of high temperature can directly contact the brown coal coal seam on disk, thereby carry out pyrolytic reaction.
The gaseous heat-carrier that hotblast stove 12 is transported in cracker 13 is high-temperature gas thermal barrier, identical with the component that is transported to the gaseous heat-carrier 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 being transported in moisture eliminator 11.The temperature of high-temperature gas thermal barrier herein need be controlled at 380 ~ 680 ℃, thereby makes coal seam temperature reach 350 ~ 650 ℃, and then low temperature pyrogenation reaction in occurring.In this process, although follow certain moisture to produce, thus brown coal have been carried out being dried thoroughly, and this is in when producing moisture and is carrying out middle low temperature pyrogenation reaction, so the moisture producing belongs to pyrolysis water, different from the drying and dehydrating process in moisture eliminator.
And when coal seam temperature reaches 350 ~ 650 ℃, the oxygen level of this high-temperature gas thermal barrier requires below 2～3%, to be preferably controlled at 0.5 ~ 2% in volume percent, especially preferably by Control for Oxygen Content lower than 0.5%.Thus, can guarantee the very easily high temperature drying brown coal of involuntary ignition, even under this pyrolysis atmosphere, the hazardous conditions such as spontaneous combustion and detonation can not occur yet.
In pyrolytic reaction process, in order to remove more up hill and dale moisture and to carry out sufficient pyrolytic reaction, the heating rate of brown coal need to be controlled to 5 ~ 100 ℃/s, the residence time by brown coal in cracker 13 is controlled at 15-30min(such as 18min, 21min, 24min, 27min), the residence time by high-temperature gas thermal barrier in cracker is controlled at 2-12min(such as 4min, 6min, 8min, 10min).
Wherein, by controlling the factors such as coal input quantity, thickness of coal seam, coal breakage amount, can obtain the residence time of required brown coal (solid phase); By controlling the factors such as air input, reactor voidage, top hole pressure, can obtain the residence time of required high-temperature gas thermal barrier (gas phase).And, by controlling the gas phase residence time and the solid phase residence time, can obtain accordingly required pyrolysis heating rate, thereby 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 situations 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 (℃) | 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 connecting two cyclonic separators 14, carries out, in the process of pyrolysis, producing a large amount of dusty gases in this cracker 13.Dusty gas enters respectively two cyclonic separators 14.Two cyclonic separators 14 are all by the solid phase in dusty gas and gas phase separation, and obtain fine coal after will solid phase reclaiming.One of them cyclonic separator 14 is sent into hotblast stove 12 by isolated gas phase via pipeline and is burnt, and is moisture eliminator 11 and cracker 13 heat supplies.This isolated gas phase includes CO, CH
4with a small amount of H
2, C
2h
2deng gas, after these inflammable gas oxidizing fires, obtaining main ingredient is CO
2with gaseous state H
2the Poor oxygen gas of O etc., release of heat heats gaseous heat-carrier simultaneously, thereby obtains the gaseous heat-carrier of optimal temperature.
Another cyclonic separator 14 is delivered to interchanger 23 by isolated gas phase, make it to obtain tentatively cooling, thereby can be utilized in wrapping reaction described later.The gas temperature producing in cracker is substantially at 400 ~ 550 ℃, tentatively cooling by this, can heat exchange to 350 ~ 400 ℃, thus in operation afterwards, be used.Thus, by two cyclonic separators are set, can make full use of the gaseous substance producing in pyrolytic reaction.In preliminary cooling, can also by-product middle pressure steam, and this middle pressure steam can be offered to power plant etc. and do thermal source heat exchange or heat supply etc., thereby further improve heat utilization rate.
In the present embodiment, two cyclonic separators 14 are connected with cracker 13 respectively, are relation in parallel each other, and its object is mainly the in addition dual utilization of gas that scission reaction is produced, and improve the utilization ratio of this gas.But in actual applications, also can according to produce the gas volume, dustiness of gas and to gas utilize object etc., making both is relation in parallel or series connection, and can be 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 according to actual needs quantity.
Brown coal, after the reaction in cracker, obtain semicoke.Still there is the hot semicoke of certain temperature under action of gravity, via being arranged on pyrolyzer and follow-up wrapping the fuel dropping pipe 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, thereby wrapping in reactor 15, wrap reaction.
Wrapping in reactor 15, adopt gas hot semicoke to be carried out cooling step by step as cold carrier.The gas cold carrier of introducing at the leading portion that wraps reactor 1, consists of the inactive gas from air-seperation system 22 (being mainly nitrogen).A part for the gas-phase product that cracker 13 produces is all passed into by preliminary cooling gas (also can be described as splitting gas) and above-mentioned nitrogen the leading portion that wraps reactor 15 through interchanger 23.
Wherein, splitting gas is from cracker 13 outputs, and initial temperature is about 400 ~ 550 ℃, tentatively cooling through interchanger 23, can heat exchange to 350 ~ 400 ℃, and recovery part heat, produce 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 air separation nitrogen and oxygen containing gas, and wherein, nitrogen gas supply wraps the leading portion of reactor 15, and oxygen-containing gas is supplied with hotblast stove 12.Nitrogen is wherein room temperature substantially, synchronizes and passes into the leading portion that wraps reactor 15 with splitting gas, splitting gas is exacerbated and is cooled to 250 ~ 300 ℃, and hot semicoke is carried out progressively cooling.When splitting gas is exacerbated when 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 can curding out at 280 ~ 350 ℃.
Wherein nitrogen, except can 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.
Above-mentioned gas cold carrier enters after the leading portion that wraps reactor 15, because splitting gas is by nitrogen condensation, so can wrap and react with hot semicoke.Described wrap reaction refer to, the temperature lower (normal temperature) of the nitrogen providing due to air-seperation system, so when splitting gas is condensed, the hot semicoke wrapping in reactor 15 also obtains cooling, making the heavy constituent in splitting gas, is mainly that bituminous matter is separated out and wrapped on progressively cooling hot semicoke surface.
Subsequently, from the by-product gas of gas treating system 21, after temperature regulates, be introduced into the back segment that wraps reactor 15, directly contact with the semicoke being wrapped, the temperature of this by-product gas should remain on 200 ~ 300 ℃, semicoke is obtained further cooling.
Subsequently, through the mixed gas wrapping after reactor, enter electric fishing storage 16, now, the bituminous matter as heavy constituent of approximately 45% volume percent in gas is separated out wrapping the reactor stage, and remaining is 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 separated out as liquid oils in electric fishing storage 16.
Electric fishing storage 16 isolated liquid oils from mixed gas is equivalent to except the lightweight coal tar after bituminous matter.Thereafter, mainly by CO
2, N
2with gaseous state H
2the residual gas of O composition is through torch burning, and discharge after the conventional process such as wet desulphurization are up to standard.
After wrapping reaction and finishing, open and wrap the valve of reactor 15, semicoke drops on transfer roller in action of gravity, by mechanical transmission band, sends into quenching deactivator 17.Semicoke with from gas treating system the by-product gas after temperature regulates, directly contact, the progressively cooling stable product lignite semi-coke that obtains, leaves after the gaseous combustion of quenching deactivator 17 emptying.
Because this by-product gas contains moisture, through the processing of gas treating system, its moisture weight content at 10-20%(such as 12%, 14%, 16%, 18%), temperature at 40 ~ 70 ℃ (such as 50 ℃, 60 ℃, can be by external heat exchanger indirect heat exchange method cooling or use normal temperature nitrogen direct heat exchange cooling so far temperature), the volumn concentration of oxygen is that 5-21%(is such as 8%, 11%, 14%, 17%).Thus, can guarantee that quenching deactivator 17 works under the state of the oxygen volume content lower than air, guarantee carrying out smoothly of passivation reaction, and be convenient to temperature control.Thereby can make semicoke that further passivation and rehydrated reaction occur, make upgrading semicoke again relapse the moisture in atmosphere, slowly reach nature saturated-water phase, now in semicoke, moisture weight content is about 8 ~ 16% left and right (such as 10%, 12%, 14%), thereby make semicoke be adapted at placing in air, and can transport for long-distance, and not there is not dieseling.
According to the embodiment of the present invention, above-mentioned, realize the lighting of coal tar original position in wrapping reactor 15, removed wherein most bituminous matter, and preliminary carried 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, improved semicoke strength and stability.Such operation can be avoided the involuntary ignition phenomenon of 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 common upgrading semicoke that process is produced, and point of ignition is low, calorific value is high, combustion stability is good, and in addition, intensity is large, the 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.
And the weight percent of saturated hydrocarbon content is below 6% in the coal tar in traditional technology, the weight percent of aromatic hydrocarbon content is below 40%, and the weight percent of nonhydrocarbon is 10% left and right, and bitum weight percent is 45% left and right.And according to the present invention, bituminous matter major part is separated out, liquid oils studies on asphaltene content can reach below 10%, so, take this liquid oils as raw material Hydrogenation is for petrol and diesel oil, cost, productive rate improves.
Claims (18)
1. a low-rank coal method for upgrading, is characterized in that, comprising:
Drying step, is that first gaseous heat-carrier of 140～240 ℃ is heated to coal seam below 140 ℃, to be dried by temperature in, makes the moisture weight content of the dry rear low-rank coal obtaining 5%～15%, and produces by-product gas;
Pyrolysis step, the second gaseous heat-carrier that is 380～680 ℃ by temperature makes the coal seam temperature of the described dry rear low-rank coal obtaining reach 350～650 ℃, obtain dusty gas and hot semicoke, after the solid matter of described dusty gas is separation with gaseous substance, obtain fine coal and the gaseous substance of solid matter, a part for gaseous substance is supplemented and is become described the first gaseous heat-carrier or described the second gaseous heat-carrier after burning, and another part of gaseous substance becomes splitting gas after preliminary cooling;
Wrap step, the gas cold carrier of room temperature is synchronizeed with described splitting gas and is passed into the leading portion in the space that wraps step, described gas cold carrier is first cooled to 250～300 ℃ by described splitting gas aggravation, the cooling described hot semicoke that is positioned at described space progressively again, thus, the surface at progressively cooling described hot semicoke is separated out and wrapped to the heavy constituent being exacerbated in the described splitting gas that is cooled to 250～300 ℃, subsequently, temperature is the back segment that the described by-product gas of 200～300 ℃ passes into the space that wraps step, directly contact with the semicoke being wrapped, further cooling described semicoke, obtain wrapping semicoke and mixed gas, with
Quenching passivation step, making to wrap the described by-product gas that semicoke is 40～70 ℃ with temperature described in further cooled directly contacts, again adsorption moisture, wraps the surface oxidation of semicoke and rehydrated reaction, and making this moisture weight content that wraps semicoke is 8～16%.
2. low-rank coal method for upgrading according to claim 1, is characterized in that:
Described the first gaseous heat-carrier and described the second gaseous heat-carrier are all with CO
2with gaseous state H
2o is main ingredient.
3. low-rank coal method for upgrading according to claim 1, is characterized in that:
The volume percent of the oxygen level of described the second gaseous heat-carrier is less than or equal to 2%,
The volume percent of the oxygen level of described the first gaseous heat-carrier is less than or equal to 6%.
4. 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 ℃/s.
5. low-rank coal method for upgrading according to claim 1, is characterized in that:
The moisture weight content of the described low-rank coal obtaining after dry is 6%～10%, described temperature be the moisture weight content of described by-product gas of 40～70 ℃ 10～20%, the volumn concentration of oxygen is 5-21%.
6. low-rank coal method for upgrading according to claim 1, is characterized in that:
Described gas cold carrier is nitrogen, and described heavy constituent is bituminous matter, and described low-rank coal is brown coal.
7. low-rank coal method for upgrading according to claim 1, is characterized in that:
Described, wrap in step, described splitting gas is cooled and is separated into the raw gas of gas phase and the coal tar of liquid phase, and described raw gas comprises CO, CH
4, H
2and CO
2, described coal tar comprises stable hydrocarbon, aromatic hydrocarbon, non-hydrocarbon and asphaltene.
8. low-rank coal method for upgrading according to claim 7, is characterized in that,
Also comprise the liquid oils separating step of separating liquid oil from the described mixed gas that wraps step generation.
9. low-rank coal method for upgrading according to claim 3, is characterized in that:
The volume percent of the oxygen level of described the second gaseous heat-carrier is in 0.5～2%.
10. low-rank coal method for upgrading according to claim 3, is characterized in that:
The volume percent of the oxygen level of described the second gaseous heat-carrier is under 0.5%.
11. low-rank coal method for upgrading according to claim 1, is characterized in that:
The volume percent of the oxygen level of described the first gaseous heat-carrier is less than or equal to 5%
12. low-rank coal method for upgrading according to claim 11, is characterized in that:
The volume percent of the oxygen level of described the first gaseous heat-carrier is 2～3%
13. low-rank coal method for upgrading according to claim 11, is characterized in that:
The volume percent of the oxygen level of described the first gaseous heat-carrier is 1%.
14. 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, reception is as the low-rank coal of feed coal, be connected with described pipeline of hot air furnace, the temperature in providing by described hotblast stove is that first gaseous heat-carrier of 140～240 ℃ is heated to low order coal seam below 140 ℃, be dried, 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 described by-product gas is led to;
Cracker, be arranged at the below of described moisture eliminator, described dried low-rank coal enters described cracker under action of gravity, the temperature providing by described hotblast stove is that second gaseous heat-carrier of 380～680 ℃ makes coal seam temperature after drying reach 350～650 ℃, obtain dusty gas and hot semicoke, described dusty gas separates the fine coal and the gaseous substance that obtain solid matter after entering described cyclonic separator, a part for gaseous substance is supplemented described the 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, described hot semicoke wraps after reactor described in entering under action of gravity, utilize pipeline to wrap the leading portion of reactor described in the gas cold carrier in room temperature and described splitting gas are synchronously input to, described gas cold carrier is first cooled to 250～300 ℃ by described splitting gas aggravation, progressively wrap again the described hot semicoke of reactor described in cooling being positioned at, thus, the surface at progressively cooling described hot semicoke is separated out and wrapped to the heavy constituent being exacerbated in the described splitting gas that is cooled to 250～300 ℃, subsequently, temperature is the back segment that wraps reactor described in the described by-product gas of 200～300 ℃ passes into, directly contact with the semicoke being wrapped, further cooling described semicoke, obtain wrapping semicoke and mixed gas, with
Quenching deactivator, makes to wrap the described by-product gas that semicoke is 40～70 ℃ with temperature described in further cooled and directly contacts, adsorption moisture again, and the moisture weight content that makes this semicoke is 8～16%.
15. low-rank coal upgrading devices as claimed in claim 14, is characterized in that:
Also comprise the gas treating system being connected with described moisture eliminator, described by-product gas wraps reactor and described quenching deactivator described in leading to after described gas treating system is processed.
16. low-rank coal upgrading devices as claimed in claim 14, is characterized in that:
Also comprise be connected to described cyclonic separator and described in wrap the interchanger between reactor, described another part of described gaseous substance becomes splitting gas through after described interchanger preliminary cooling.
17. low-rank coal upgrading devices as claimed in claim 14, is characterized in that:
Also comprise with described and wrap the electric fishing storage that reactor is connected, described mixed gas is isolated liquid oils through described electric fishing storage.
18. low-rank coal upgrading devices as claimed in claim 14, is characterized in that:
Also comprise with described and wrap the air-seperation system that reactor is connected, from air, isolate the nitrogen as described gas cold carrier.
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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 | A method for producing acetylene and synthesis gas by partial oxidation of hydrocarbons |
| 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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