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CN201309913Y - Device for producing and heating carbonic fuel gasifying agent - Google Patents

Device for producing and heating carbonic fuel gasifying agent Download PDF

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CN201309913Y
CN201309913Y CNU2008201233668U CN200820123366U CN201309913Y CN 201309913 Y CN201309913 Y CN 201309913Y CN U2008201233668 U CNU2008201233668 U CN U2008201233668U CN 200820123366 U CN200820123366 U CN 200820123366U CN 201309913 Y CN201309913 Y CN 201309913Y
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reactor
oxygen
air
fuel
gasification
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张鹏
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00Combustion technologies with mitigation potential
    • Y02E20/34Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery

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Abstract

产生和加热含碳燃料气化剂的装置属于含碳燃料的气化领域。本实用新型以化学链燃烧方式燃烧气化炉所产部分合成气,并将化学链燃烧的热量在换热网络中回收,在加入外来H2O和/或CO2的情况下,得到温度足够高、流量尽可能大的H2O和CO2混合气体作为气化剂使用;在气化剂热量不足,转化率过低时,通过氧分离器从含O2气体向气化剂传递O2。本实用新型得到的气化剂送往地面或地下气化炉与含碳燃料反应,得到不含N2的合成气。本实用新型通过调整气化剂组成,可按下游需要灵活调整合成气组成;整个气化过程CO2排放量低;对外界依赖少,气化系统开工正常后,可用含碳燃料气化得到的部分合成气燃烧供能持续进行生产,得到的中间物流便于低成本地向气化剂中掺入O2

Figure 200820123366

A device for generating and heating a carbon-containing fuel gasification agent belongs to the field of carbon-containing fuel gasification. The utility model burns part of the synthesis gas produced by the gasifier in the chemical chain combustion mode, and recovers the heat of the chemical chain combustion in the heat exchange network. In the case of adding external H 2 O and/or CO 2 , the obtained temperature is sufficient The mixed gas of H 2 O and CO 2 with high flow rate as large as possible is used as the gasification agent; when the heat of the gasification agent is insufficient and the conversion rate is too low, O 2 is transferred from the O 2 -containing gas to the gasification agent through the oxygen separator . The gasification agent obtained by the utility model is sent to the surface or underground gasification furnace to react with carbon-containing fuel to obtain synthesis gas without N2 . The utility model can flexibly adjust the synthesis gas composition according to downstream needs by adjusting the composition of the gasification agent; the CO 2 emission in the whole gasification process is low; there is less dependence on the outside world, and the gasification system can be obtained by gasification of carbon-containing fuels after the gasification system starts normally Part of the syngas is combusted to provide energy for continuous production, and the resulting intermediate stream facilitates the low-cost doping of O2 into the gasification agent.

Figure 200820123366

Description

The device of generation and heating carbonaceous fuel gasifying agent
Technical field
The utility model relates to the gasification of coal gasification and other carbonaceous fuels, and wherein said carbonaceous fuel comprises fossil oil, as coal, oil-sand, and biomass and organic domestic waste etc.
Background technology
The gasification of carbonaceous fuel is pointed to the carbonaceous fuel injection and is comprised O 2, H 2O, CO 2With the vaporized chemical of other materials, under certain temperature and pressure, make vaporized chemical and carbonaceous fuel generation physics and chemical reaction generate the technology of synthetic gas.
Turn to example with coal gas, cooking vaporized chemical with air is a kind of gasification mode cheaply, but contains more N in the synthetic gas 2, later use is had disadvantageous effect.With oxygen enrichment or pure O 2Cook vaporized chemical and then produce oxygen enrichment or pure O 2Cost higher.
With the coal is example, uses H 2O and CO 2Cook vaporized chemical and can not contained N 2Synthetic gas, the component of not firing in the synthetic gas is easy to separate.Especially adopt CO 2Cook vaporized chemical and can reduce CO in the coal gasification course 2Clean quantity discharged, help to protect environment.But, because H 2O and CO 2With the reaction of coal be thermo-negative reaction, so only use H 2O and CO 2When cooking vaporized chemical, except that pressurization hydrogasification technology, need the heat supply measure usually.
For example, number be CN1062329C at Granted publication, in the Chinese patent of " two-part coal underground gasifying technology " by name, obtain N in the air injection stage 2The synthetic gas that content is high, and heated up in the coal seam; Then utilize coal seam institute heat storage capacity to carry out water-gas reaction in the water filling steam stage, obtain N 2The synthetic gas that content is low.On open was on January 30th, 2007, and publication number is CN10112670A, then mentions with being O in the Chinese patent application of " a kind of coal underground gasifying technology " by name 2And CO 2Mixture be the O of vaporized chemical to inject 2With the coal partial oxidation, provide CO by oxidizing reaction 2Reduction reaction institute heat requirement.Pure in the method O 2Consumption is bigger.
2. burning chemistry chains
Burning chemistry chains refers to directly not utilize contain O 2Gas is combustion-supporting, and is to use the Sauerstoffatom combustion fuel in the oxygen carrier.This type systematic generally includes two reactors: air reactor and fuel reaction device also can be described as oxidation reactor and reduction reactor respectively.In the fuel reaction device, the oxygen carrier of oxidation state and fuel gas generation reduction reaction, this process is generally thermo-negative reaction or weak thermopositive reaction, and oxygen carrier is converted in the fuel reaction device and goes back ortho states; Also the ortho states oxygen carrier is sent the O in the air reactor usefulness feeding air back to 2Oxidation, this process are strong exothermal reaction.Oxygen carrier circulates between reactor to realize the transfer and the heat transmission of oxygen.
In the burning chemistry chains mode, fuel does not directly contact with air, just can not produce heating power type NO as long as temperature of reaction is not more than 1200 ℃ in air reactor x, the fuel burner products of combustion mainly is CO 2And water vapour, can obtain almost pure CO after removing wherein water vapour by condensation 2, can be simply and CO is realized on less energy-consumption ground 2Separation and capture, by with CO 2Seal up for safekeeping or utilize and to reduce CO effectively 2Quantity discharged.
A lot of reports about oxygen carrier preparation and test are arranged, and for example, people such as Ishida were published in " energy transforms and management " (Energy Conversion and Management) the 43rd phase article of 1469 to 1478 pages in 2002 and " adopt NiO/NiAl under 1200 ℃ 2O 4The test-results of particle circulation carrying out burning chemistry chains " (Experimental results ofchemical-looping combustion with NiO/NiAl 2O 41200 ℃ of particle circulation at) etc.
Modal chemical chain combustion apparatus mostly is circulating fluidized bed device in the bibliographical information, wherein air reactor is a lifting tubular type fluidized-bed reactor, inject air in the riser tube bottom, and adding is from the oxygen carrier granule of going back ortho states of fuel reaction device, the air oxygen carrier granule of carrying under one's arms upwards flows, simultaneously with the oxygen carrier granule oxidation and emit big calorimetric.In the gas-solid mixture process cyclonic separation at riser tube top, isolated gas is used for energy recovery, and solid sends back in the fuel reaction device by dipleg.In the fuel reaction device of bubbling bed form, feed fuel, oxygen carrier is reduced, the CO of generation 2And H 2The O mixed gas also reclaims oxygen carrier through cyclonic separation, passes through energy recovery again, obtains highly purified CO then after the condensation 2The ortho states oxygen carrier granule of going back in the fuel reaction device enters the air reactor bottom by an inclined tube, constitutes a complete oxygen carrier circulation.
3. system oxygen
Present industrial oxygenerating technology comprises deep cooling system oxygen, transformation or methods such as alternating temperature adsorption oxygen-preparation and membrane sepn system oxygen.
Wherein oxygen permeable membrane belongs to a kind of of membrane separation technique.Oxygen permeable membrane refers to optionally see through O 2, make O 2Film from the transmission of high density side direction lower concentration side.In the U.S. Pat P 6503296 of " film and using method thereof (Membrane and use thereof) " by name, then mentioned with oxygen permeable membrane from containing O 2Gas is to high H 2O and CO 2Oxygen permeable in the gas of dividing potential drop is then with enrichment O 2H 2O and CO 2Mixed gas is used to transform carbonaceous fuel, produces the method for synthetic gas.Ion migration type oxygen permeable membrane is a kind of oxygen tripping device of less energy-consumption, can obtain the very high O of purity 2, but at present used ion migration type oxygen permeable membrane generally all need just can reach practical unit surface oxygen infiltration rate being higher than under 600 ℃ the temperature, in most cases will reach more than 800 ℃.
Alternating temperature or omnibus control system are by selective adsorbent the difference of different components adsorptive power to be reached the separation purpose.Oxygen selective sorbent has carbonaceous molecular sieve and cyanogen cobalt coordination compound sorbent material, and the latter can be referring to the U.S. Pat P 5239098 of " solid-state cyanogen cobalt coordination compound (Solid state cyanocobalate complexes) " by name.
The utility model content
The utility model relates to the device that produces carbonaceous fuel gasifying agent, can be by being produced partial synthesis gas with burning chemistry chains mode combustion gasification stove, and the heat of burning chemistry chains is reclaimed in heat exchanger network, adding external H 2O and/or CO 2Situation under, obtain the H that temperature is enough high, flow is big as far as possible 2O and CO 2Mixed gas uses as vaporized chemical; In the vaporized chemical shortage of heat, transformation efficiency is crossed when hanging down, can be by oxygen separator from containing O 2Gas transmits O to vaporized chemical 2The vaporized chemical that obtains is sent to ground or underground gasification furnace and carbonaceous fuel reaction, is not contained N 2Synthetic gas.
Adopt the utility model can not contained N 2Synthetic gas; Form by adjusting vaporized chemical, can need to adjust synthetic gas flexibly by the downstream and form; Whole gasification CO 2Quantity discharged is low; Rely on to external world and lack, gasification system can continue to produce with the partial synthesis gas firing energy supply that carbonaceous fuel gasifying obtains after going into operation normally.Resulting intermediate stream is convenient to mix at low cost O in vaporized chemical 2
The utility model also can be used for underground gasification exploitation fossil oil, as coal, viscous crude, oil-sand etc.
Main purpose of the present utility model is to obtain not contain N 2Vaporized chemical, thereby can not contained N 2Synthetic gas.Do not contain N 2The synthetic gas major impurity be H 2O and CO 2, separation costs is far below N 2Separation costs.And be used for pure O at synthetic gas 2During burning, N under the high temperature 2Easily and O 2Reaction generates atmospheric polluting material NO x(oxynitrides) be not so contain N 2Synthetic gas burning environmental pollution few.
So target of the present utility model is to be cost to consume partial synthesis gas, produce temperature enough height, flow big as far as possible do not contain N 2Vaporized chemical; In addition, when the vaporized chemical transformation efficiency is not enough, preferably can also add O to vaporized chemical at low cost 2Improve transformation efficiency.
In the utility model, by adopting the burning chemistry chains system, in the fuel reaction device synthetic gas being converted into main component is H 2O and CO 2Gas, reduce oxygen carrier simultaneously; Also can inject external H in the fuel reaction device input logistics 2O and/or CO 2, so that carry heat more, and can be with external CO 2Send into and partly be converted into CO in the vapourizing furnace; Bubbling air in air reactor makes oxygen carrier oxidating, discharges the high temperature oxygen-denuded air from oxidation reactor; By oxygen carrier being circulated or fuel reaction device and air reactor intermittent type switch and realize the transmission of Sauerstoffatom at air and fuel room between fuel reaction device and air reactor; In addition, with the most of heat recuperation in the high temperature Poor oxygen gas in the input logistics of burning chemistry chains system, the most of heat that finally makes reaction and produced outputs in the fuel reaction device output logistics, and fuel reaction device output logistics enters vapourizing furnace as outer defeated vaporized chemical.The vaporized chemical that makes with the utility model device also can be used as the part of vapourizing furnace vaporized chemical, for example, allocates H again into 2Or O 2, or only be used for a certain gasifying stage, for example, only be used for coal carbonization and pyrolysis phase.
Therefore, the utility model relates to a kind of device that produces and add thermogenesis and heating carbonaceous fuel gasifying agent, a burning chemistry chains system, gas blower; Heat exchanger network;
Described burning chemistry chains system comprises at least one fuel reaction device and at least one air reactor, all contains the used oxygen carrier of burning chemistry chains in fuel reaction device and the air reactor; Between fuel reaction device and air reactor, be provided with and make oxygen carrier round-robin oxygen carrier circulation device; The fuel reaction device is provided with the fuel inlet, the air reactor that insert synthetic gas from the outside and is provided with gas inlet, oxygen-denuded air outlet;
Perhaps described burning chemistry chains system comprises at least one reactor but also as the reactor of air reactor of not only having acted as a fuel; This reactor is provided with fuel inlet, gas inlet, the oxygen-denuded air outlet that inserts synthetic gas from the outside;
The oxygen-denuded air outlet) connects heat exchanger network; Blower export finally leads to gas inlet;
It is characterized in that:
Fuel reaction device or the above-mentioned reactor but also be provided with as the reactor of air reactor and be used for receiving H of not only having acted as a fuel from the outside 2O, CO 2Or the external vaporized chemical input aperture of the mixture of the two and defeated outward vaporized chemical outlet), vapourizing furnace is led in defeated outward vaporized chemical outlet;
Described heat exchanger network connects fuel inlet at least, external vaporized chemical input aperture, one of gas inlet; When heat exchanger network connected gas inlet, heat exchanger network connected blower export.
When the burning chemistry chains system comprises air reactor and fuel reaction device at least, by fuel inlet synthetic gas is fed the fuel reaction device, oxygen carrier in the reduction fuel reaction device produces H 2O, CO 2Mixed gas; The outside H that receives 2O, CO 2Or the external vaporized chemical of the mixture of the two is by external vaporized chemical input aperture (6) feeding fuel reaction device, with the H that produces in the reduction fuel reaction device 2O, CO 2Mixed gas together from outside defeated vaporized chemical outlet discharge; After air enters from gas inlet, the oxygen carrier in the oxidation air reactor, the oxygen-denuded air that produces simultaneously after heating leads to heat exchanger network from the oxygen-denuded air outlet; Oxygen carrier circulates between fuel reaction device and air reactor;
When described burning chemistry chains system (1) comprises at least one reactor but also during as the reactor of air reactor of not only having acted as a fuel; When this reactor move as reduction reactor earlier, oxygen carrier reach go back ortho states after, cut off synthetic gas, purge and displacement with external vaporized chemical, purge and discharge from outer defeated vaporized chemical outlet the displacement back, after fail vaporized chemical outside closing and export and external vaporized chemical input aperture; Open gas inlet and oxygen-denuded air outlet bubbling air then oxygen carrier is carried out oxidation operation, after oxygen carrier is heated up and accumulating heat and make oxygen carrier be warmed up to 900 ℃ to 1200 ℃ or oxygen carrier to reach oxidation state, closing air inlet openings, open external vaporized chemical input aperture and purge displacement, purge the displacement back from oxygen-denuded air outlet emptying; Close the oxygen-denuded air outlet, open fuel inlet and outer defeated vaporized chemical outlet then, begin to carry out restoring operation and utilize accumulation of heat to heat external vaporized chemical; The oxygen carrier temperature begins to descend during restoring operation, drops to 600 to 1100 ℃ or oxygen carrier up to temperature and reaches and go back ortho states; The above-mentioned steps circulation repeats;
Described heat exchanger network is one of following gas of preheating at least: what feed fuel inlet inserts synthetic gas from the outside, feeds the external vaporized chemical of external vaporized chemical input aperture; The air that leads to gas inlet from blower export; External vaporized chemical is outside H 2O, CO 2Or the two mixture.
Described heat exchanger network connects fuel inlet at least, external vaporized chemical input aperture, and one of gas inlet, the heat recuperation in the oxygen-denuded air that oxygen-denuded air outlet is discharged is in the input logistics of burning chemistry chains system; When heat exchanger network connected gas inlet, heat exchanger network connected blower export.The air of blower export enters air reactor or the reactor but also as the reactor of air reactor of not only having acted as a fuel after the heat exchanger network preheating.
Heat exchanger network is made of a series of interchanger, is used to make the oxygen-denuded air of oxygen-denuded air outlet discharge and the input logistics heat exchange of burning chemistry chains system.
In common burning chemistry chains system, a high-temperature gas acting generating or a vapour that general using is discharged.And in embodiment of the present utility model, in order to improve the entrained heat of vaporized chemical, by with the oxygen-denuded air of oxidation reactor discharge and the input logistics heat exchange of burning chemistry chains system, the entrained most of heat of oxygen-denuded air is got back in the burning chemistry chains system the final exhaust temperature reduction of the oxygen-denuded air of oxidation reactor discharge.Like this, just can there be more heat to output to the vaporized chemical that is produced from that side of fuel reaction device.Different with the heat exchange amount that injects external gasification dosage, synthetic gas calorific value and oxygen-denuded air and input logistics, the gasification agent temperature that finally obtains can reach more than 900 ℃, even can reach more than 1150 ℃ or higher, actual temp is determined with conversion reaction is temperature required.The input logistics of said here burning chemistry chains system comprises air, the synthetic gas of importing this system, contains H 2O and CO 2Gas, H wherein 2O is preferably the steam form, but also can comprise liquid water.Preferably the oxygen-denuded air of discharging with oxidation reactor comes the feeding air of heated oxide reactor, is preheating to more than 600 ℃ the feeding air of oxidation reactor or higher temperature.If the outside can not supply steam, the part heat in the then also optional oxygen-denuded air that air reactor is discharged is used for bleed steam.
In native system, be that oxygenant, synthetic gas are that the heat that burning chemistry chains produced of reductive agent is except partial loss with the air, the all burned generation gas of major part and add vaporized chemical and be carried in the vapourizing furnace, its heating effect roughly is equivalent to inject pure O having under the situation of certain thermosteresis to vapourizing furnace 2With the synthetic gas combustion heating, and inject a part of external H 2O and/or CO 2
The raising of fuel reaction actuator temperature can make fuel reaction device exhaust temperature higher, carries some heats more, still, also needs to inject other material to the fuel reaction device usually remaining heat is carried out, in order to avoid system's overtemperature.Herein with the H that is injected from this device outside 2O and CO 2Total molar content is that the mixture more than 80% is called external vaporized chemical.Inject external CO 2Can reduce CO 2Discharging.
The effect of injecting external vaporized chemical is: the vaporized chemical portability increases to the heat of vapourizing furnace; In addition,, can adjust the composition of final outer defeated vaporized chemical, form thereby adjust the resulting synthetic gas of carbonaceous fuel gasifying by flow and the composition of adjusting external vaporized chemical.The amount of injecting external vaporized chemical depends on the composition of the synthetic gas that supplies.If contained the H of 90% above volumetric molar concentration in the synthetic gas 2O, CO 2, then do not need to add in addition again H 2O and CO 2
The burning chemistry chains system comprises fuel reaction device and air reactor, and oxygen carrier wherein all is housed.Fuel reaction device wherein and air reactor promptly can be not interchangeable equipment, also can be interchangeable equipment, that is, same reactor both can serve as the fuel reaction device, can serve as the air reactor switchover operation again.Described interchangeable implication is meant all Link Ports of being furnished with fuel reaction device and air reactor on the reactor, different according to the degree of oxidation of inner oxygen carrier and charging can be used at act as a fuel respectively reactor or air reactor of different stage in operational cycle.
In the existing burning chemistry chains systems technology scheme that is used for combustion power generation, adopt circulating fluidized bed technique more, shortcoming is that equipment complexity, operation easier height, oxygen carrier wearing and tearing are big, the power consumption height.
For this reason, the utility model has also further proposed a kind of intermittent thermal storage type reactor of simple in structure, flexible and convenient operation, and in different steps, same reactor both can be used as the fuel reaction device and use, and also can be used as air reactor and use.This reactor is accumulation of heat and oxidation oxygen carrier during oxidizing reaction.After oxidation is finished, carry out reduction reaction with this reactor, it is too fast to keep the unlikely decline of oxygen carrier bed temperature with institute's heat storage capacity during reduction reaction, and by the gas of heating by reactor, the conduct gas temperature raising of defeated vaporized chemical outward that reactor is discharged.In the utility model, preferably adopt 2 to 4 intermittent thermal storage type reactors, can be used for alternately blocked operation.
The heat energy density of carrying with vaporized chemical sensible heat form is lower, so when the gasification carbonaceous fuel that volatile constituent is less, reactive behavior is lower, even gasification agent temperature reaches 1150 ℃, transformation efficiency still may be on the low side.The vaporized chemical transformation efficiency is crossed to hang down and can be made a large amount of CO 2And H 2O circulates in system, causes power consumption to raise.So, at fuel and H 2O and CO 2When reactive activity is relatively lower,, preferably when injecting vapourizing furnace, vaporized chemical adds a certain amount of O in order to cut down the consumption of energy 2, can make its gasification by oxidized carbon-containing fuel on the one hand, on the other hand also can the auxiliary H of heat supply 2O and CO 2Be converted into combustibleconstituents.
For this reason, in some embodiment of the utility model device, also comprised oxygen separator with the burning chemistry chains system, coupled.Described oxygen separator can be based on oxygen permeable membrane, also can be alternating temperature adsorptive type or other types.The utility model can obtain high temperature gasification agent stream, thus can utilize the vaporization agent temperature and with the O of air 2Concentration difference is mixed O at low cost 2Especially also have the pyritous airflow to use at the utility model, so be particularly suitable for adopting oxygen separator based on ion migration type oxygen permeable membrane.
In the oxygen separator based on oxygen permeable membrane, a side is that temperature contains O more than 600 ℃ 2Gas, opposite side is a vaporized chemical more than 600 ℃ by device institute of the present utility model products temperature, owing to both sides temperature enough height all, and has natural O 2Concentration difference is so understand some O 2From containing O 2Gas side is delivered in the outer defeated vaporized chemical.Here said temperature contains O more than 600 ℃ 2Gas has two kinds of selections, and a kind of is the oxygen-denuded air that the selective oxidation reactor outlet is discharged, and advantage is the temperature height, and shortcoming is O 2Concentration is lower; Another kind is the oxidation reactor feeding air of selecting to be preheating to more than 600 ℃, and advantage is O 2Concentration height, shortcoming are that temperature is low slightly.
In the oxygen separator of alternating temperature adsorptive type, preferred employing can be adsorbed at normal temperatures, and has the sorbent material of higher oxygen selective.During this type oxygen separator used, it was adsorbent bed to feed the normal temperature air cooling earlier, and makes adsorbents adsorb O 2Use external cold CO then 2The vaporized chemical purge vent; At last with external cold CO 2Vaporized chemical is respectively told a part with outer defeated vaporized chemical and is mixed, and by the adjustment blending ratio mixed gas temperature is reached and makes O on the sorbent material 2Fully after the temperature of desorption it is fed oxygen separator, adsorbent bed intensification also purges sorbent material, makes O 2Desorption; The O of desorption 2Flow out from oxygen separator with mixed gas, after remaining outer defeated vaporized chemical converges, be sent to vapourizing furnace.
The utility model effect
As previously mentioned, the burning chemistry chains system is used for combustion fuel to do the heating power merit usually, is used to drive turbine or sends out vapour, a small amount of CO of by-product 2And H 2The O mixed gas.And in the utility model, burning heat that synthetic gas produced all is used for producing and the heating and gasifying agent except that the portion of hot loss in the burning chemistry chains system, and used oxidizer is an air, but the burning generation as not containing N in the gas of vaporized chemical 2, the general effect that is reached roughly is equivalent to supply some pure O to vapourizing furnace indirectly 2, therefore can be less with or need not pure O 2Just do not contained N 2Synthetic gas.
According to preresearch estimates, at external vaporized chemical with H 2O is main, does not add pure O 2During the underground gasification brown coal, it is about 10% that the vaporized chemical per pass conversion can reach, perhaps at equal H 2Under the situation of O transformation efficiency, make required pure O in the vaporized chemical 2Volumetric molar concentration reduces about 4%.And can produce high temperature gasification agent stream and high temperature air stream in the device of the present utility model, and be fit to very much again by using ion migration type oxygen permeable membrane, oxygen absorbent etc., give in the vaporized chemical at low cost in the mode that does not need outer energizing quantity and mix pure O 2, make O in the vaporized chemical 2Volumetric molar concentration reaches 10% or higher, so can supply pure O outward fully 2And heat, only with the vaporized chemical generation in the utility model and heating unit and with it the simple oxygen separator of coupled just make vaporized chemical reach higher transformation efficiency.
So, adopt the utility model can not need to establish in addition special oxygenerator and just do not contained N 2Synthetic gas, thereby can significantly reduce the construction and the running cost of coal gasification apparatus.Especially in in-situ coal gasification, often external conditions is limited, and it is not long relatively that single place produces the time length, thus need especially a kind of simple, to the external conditions dependence less, the equipment device that is easy to move carries out gasification operation.
In addition, destructive distillation and pyrolysis that vaporized chemical composition that device of the present utility model is exported and temperature also are suitable for carbonaceous fuel very much are also than the hydrogasification that is more suitable for carbonaceous fuel.
Description of drawings
Device schema when Fig. 1 comprises at least one fuel reaction device 2 and at least one air reactor 3 for burning chemistry chains system 1 in the utility model.
Fig. 2 is the utility model embodiment 1 used intermittent thermal storage type structure of reactor synoptic diagram.
Fig. 3 is the utility model embodiment 2 device synoptic diagram.
Fig. 4 is the utility model embodiment 3 device synoptic diagram.
Embodiment
Specific implementation method in the utility model comprises with the lower section:
(1) in a burning chemistry chains system that comprises air reactor and fuel reaction device, vapourizing furnace is produced partial synthesis gas feed the fuel reaction device, oxygen carrier in the reduction fuel reaction device produces H 2O and CO 2Mixed gas; Inject H to the fuel reaction device 2O and CO 2Total mol concentration is greater than 80% external vaporized chemical; Contain H after the heating 2O and CO 2Mixed gas be sent to vapourizing furnace as outer defeated vaporized chemical; Described fuel reaction device and air reactor both can be interchangeable, also can be not interchangeable;
(2) with air bubbling air reactor after the heat exchanger network preheating, the oxygen carrier in the oxidation air reactor produces temperature simultaneously at the oxygen-denuded air more than 800 ℃;
(3) oxygen carrier is circulated between fuel reaction device and air reactor, or switch fuel reaction device and air reactor off and on;
(4) oxygen-denuded air that oxidation reactor is discharged feeds heat exchanger network, reclaims heat with the input logistics heat exchange of burning chemistry chains system, and the final exhaust temperature of the oxygen-denuded air that oxidation reactor is discharged is reduced to below 350 ℃; The input logistics of described burning chemistry chains system is selected from air, synthetic gas and the external vaporized chemical of input burning chemistry chains system;
In another specific embodiments in using the utility model, except that the above (1) arrives the step of (4), can further include to adding O in the vaporized chemical 2Step.Specific implementation method can adopt one of two kinds of methods:
Add O 2Measure 1:
Outer defeated vaporized chemical noted earlier is fed in the oxygen permeable membrane type oxygen separator, and a side that enters oxygen permeable membrane is with the O that comes from the oxygen permeable membrane infiltration 2Be sent to vapourizing furnace after the mixing again; Make one temperature at the O that contains more than 600 ℃ 2The opposite side of gas stream oxygen permeable membrane in oxygen separator, wherein said temperature is at the O that contains more than 600 ℃ 2Gas is the oxygen-denuded air that enters preceding preheated air of air reactor or air reactor discharge;
Add O 2Measure 2:
It is adsorbent bed and make adsorbents adsorb O to feed the normal temperature air cooling in an oxygen separator that oxygen selective sorbent is housed 2Then the hot and cold vaporized chemical of part is formulated as the required temperature of oxygen desorption, feeds adsorbent bed intensification, purge and make O 2Desorption, gained contains O 2Vaporized chemical stream with its besides the gas transmission agent be sent to vapourizing furnace.
Below in conjunction with Fig. 1 to the explanation of bulking property in addition of the utility model embodiment.
The device of generation and heating carbonaceous fuel gasifying agent comprises a burning chemistry chains system 1 in the utility model, described burning chemistry chains system 1 further comprises at least one fuel reaction device 2 and at least one air reactor 3, all contains the used oxygen carrier of burning chemistry chains in fuel reaction device 2 and the air reactor 3; Described fuel reaction device 2 and air reactor 3 both can be interchangeable, also can be not interchangeable; When fuel reaction device 2 and air reactor 3 are not interchangeable, there is the oxygen carrier circulation device that oxygen carrier is circulated between fuel reaction device 2 and air reactor 3;
Fuel reaction device 2 is provided with fuel inlet 4, fails vaporized chemical outlet 5, external vaporized chemical input aperture 6 outward, and wherein fuel inlet 4 inserts synthetic gas from the outside, and defeated outward vaporized chemical outlet 5 is towards vapourizing furnace, and external vaporized chemical input aperture 6 receives H from the outside 2O and CO 2Total mol concentration is greater than 80% external vaporized chemical;
Air reactor 3 is provided with gas inlet 7, oxygen-denuded air outlet 8;
Device of the present utility model also comprises gas blower 9 and heat exchanger network 10, and gas blower 9 outlet airs finally lead to the gas inlet 7 of air reactor 3; Heat exchanger network 10 high temperature side logistics comprise the oxygen-denuded air of discharging from the oxygen-denuded air outlet 8 of air reactor 3, in heat exchanger network 10, export 8 expellant gas temperature from oxygen-denuded air and reduce, and final exhaust temperature is lower than 350 ℃, preferably is lower than 200 ℃.
The cold side logistics of heat exchanger network 10 is the input logistics of burning chemistry chains system 1, and the input logistics of described burning chemistry chains system can select to import air, synthetic gas and the external vaporized chemical of burning chemistry chains system 1.
At least a portion cold side logistics of preferred heat exchanger network 10 adopts the air from gas blower 9.In the case, the temperature that the air after the preheating advances before the gas inlet 7 is more than 600 ℃, and is preferred more than 800 ℃.
Above-mentioned heat exchanger network 10 can be made of a series of interchanger.Press heat exchange temperature section branch, maximum operating temperature more than 900 ℃ the time used interchanger can adopt and switch heat regenerator or ceramic thermal wheel, maximum operating temperature can adopt high temperature heat pipe heat exchanger when being 950 ℃ to 500 ℃, the interchanger of types such as gentle low temperature heat pipe heat exchanger, plate-fin heat exchanger in can adopting when maximum operating temperature is lower than 600 ℃.In order to prevent the high temperature damage equipment, can establish the water filling heat sink at interchanger high temperature side inlet, damage heat-exchange equipment to prevent overtemperature.The explanation of this section heat exchanging network 10 does not have limited only for exemplifying.
In an embodiment of the present utility model, described burning chemistry chains system 1 comprises one or more interchangeable intermittent thermal storage type reactors, both can be used as fuel reaction device 2 at same reactor of different operating stage and has used, and also can be used as air reactor 3 and uses.An oxygen carrier bed is arranged in the reactor.
This intermittent thermal storage type reactor circulates to switch in the mode of hocket oxidation operation and restoring operation and uses.For single reactor, described circulation blocked operation step refers to:
(1) reactor that moves as reduction reactor, at the oxygen carrier bed temperature is arrived design minimum operation temperature, or reach the oxygen carrier bed also behind the ortho states, cut off the inlet synthetic gas, if necessary, the oxygen carrier bed is purged and displacement for some time with external vaporized chemical, sweep gas is discharged from vaporized chemical outlet 5, purges to close vaporized chemical after qualified and export 5 and external vaporized chemical input aperture 6.Open gas inlet 7 and oxygen-denuded air then and export 8 bubbling airs the oxygen carrier bed is carried out oxidation operation, the oxygen carrier bed is heated up and accumulate heat, the highest oxygen carrier bed that makes is warmed up to 1200 ℃.
(2) after the oxygen carrier bed was warmed up to 1200 ℃ or oxygen carrier bed and reaches oxidation state, closing air inlet openings 7 was opened external vaporized chemical input aperture 6 and is purged displacement, purges substitution gas and can export 8 emptying from oxygen-denuded air.Replace and close oxygen-denuded air outlet 8 after qualified, open fuel inlet 4 and vaporized chemical outlet 5 then, begin to carry out restoring operation.The oxygen carrier bed temperature begins to descend during restoring operation, reaches and goes back ortho states up to reaching design minimum operation temperature or oxygen carrier bed.
Above step (1) and (2) cycle alternation carry out.Oxygen carrier bed service temperature variation range is 600 ℃ to 1200 ℃, and preferably between 900 ℃ to 1200 ℃, wherein designing maximum operating temperature is 900 ℃ to 1200 ℃, and design minimum operation temperature is 600 to 1100 ℃.Wherein to reach the judgement symbol of oxidation state be that O2 concentration begins to rise quickly in oxygen-denuded air outlet 8 oxygen-denuded airs of discharging to the oxygen carrier bed, reaches certain value, for example more than 10% volumetric molar concentration; The concentration that the oxygen carrier bed reaches inflammable gas in the outer defeated vaporized chemical that the judgement symbol of going back ortho states is vaporized chemical outlet 5 discharges begins to rise quickly, reaches certain value, for example, and more than 2% volumetric molar concentration.Concrete numeral is different and different with operating parameters with used oxygen carrier type, type of reactor.Said oxidation state is at most of oxygen carrier in the oxygen carrier bed with going back ortho states.
By in the intermittent thermal storage type reactor, adding heat storage, interior oxygen carrier bed temperature variation range of reactor operational cycle is narrowed down in 300 ℃.Heat storage can adopt the solid particulate form of sneaking into the oxygen carrier bed, as not containing the Al of oxygen carrier 2O 3Particle also can adopt the form of accumulation of heat structure, for example uses Heat Storing Wall or other can accumulate the device of heat.Sneak into the inertia propping material when certainly, preparing oxygen carrier also can more.
In an embodiment of the present utility model, adopt 2 above intermittent thermal storage type reactors, can in two reactors, carry out the reduction and the oxidation operation of oxygen carrier bed respectively simultaneously, realize the production of semi continuous by mutual switching.3 above reactors of preferred employing, wherein 1 reactor can be standby, so just can rotate operations such as reactor overhaul, feeds in raw material under the situation of not interrupting the downstream gasification.More for a long time, can make more serialization of production process at reactor platform number by the switching of different series, parallel array modes.
In another embodiment of device of the present utility model, the intermittent thermal storage type reactor can be the single device operation, produces vaporized chemical off and on, still, because this operating method can't provide high temperature gasification agent stream and high temperature to contain O simultaneously 2Gas stream is difficult to carry out the aforementioned O of adding 2 Measure 1.
The effect that adopts the intermittent thermal storage type reactor to reach is that device structure is simple, easy handling and maintenance, and the power consumption that is used for the transportation flow oxidizing gases is low, and the oxygen carrier wearing and tearing are little, and the solid dust generation is few, and the oxygen carrier loss is low.Be particularly suitable for making the skid-mounted equipment of being convenient to move, make things convenient for field usage.
Embodiment 1
" 1200 ℃ are adopted NiO/NiAl down by aforementioned documents 2O 4The test-results of burning chemistry chains is carried out in particle circulation " described in method, preparation NiO/NiAl 2O 4Oxygen carrier granule.In oxygen carrier granule, mix particle diameter and make the approaching Al that does not contain Ni of oxygen carrier granule 2O 3Particle is to improve bed thermal capacity.Then with oxygen carrier granule and Al 2O 3The particulate mixture intermittent thermal storage type reactor of packing into.
In the present embodiment, adopt 3 intermittent thermal storage type reactors.In operation, an intermittent thermal storage type reactor carries out restoring operation, and an intermittent thermal storage type reactor carries out oxidation operation, and an intermittent thermal storage type reactor is standby.
Used intermittent thermal storage type structure of reactor as shown in Figure 2.The intermittent thermal storage type reactor be one have the awl end cylinder, the fire-resistant heat-storing material of liner., there is a spouted inlet mouth 11 at the awl end, and there is a bubbling air inlet sparger 12 at conical surface place.Wherein bubbling air inlet sparger 12 can be selected any known form for use, as sieve plate, and dendritic distribution pipe etc.Here the form of Cai Yonging is the distribution tubular type, specifically is the inlet manifold is divided into 16 arms, is connected on the conical surface on equally distributed 16 holes.Bubbling air inlet sparger 12 all links to each other with aforementioned gas inlet 7 with pipeline by valve respectively with spouted inlet mouth 11.Bubbling air inlet sparger 12 also links to each other with external gasification agent inlet with fuel inlet 4 with pipeline by valve.The intermittent thermal storage type reactor head has a cyclonic separator 13, constructs with high temperature material, is used for sending the oxygen carrier bed back to after the dust separation with gas.Cyclonic separator 13 outlets link to each other with oxygen-denuded air outlet 8 with outer defeated vaporized chemical outlet 5 respectively with valve through corresponding pipeline.The intermittent thermal storage type reactor also has a bottom discharge openings 14 and a top feeding mouth 15, and sidewall has an inspection manhole 16.
During oxidation operation, the air part after the preheating enters from bubbling air inlet sparger 12, with bubbling mode and oxygen carrier reaction; Air after another part preheating enters from spouted inlet mouth 11, is used to make the bed circulation, makes the uniform purpose of bed temperature to reach.Enter heat exchanger network 10 from cyclonic separator 13 outlet expellant gas and reclaim heat.
Oxidation proceeds to reactor temperature and reaches 1200 ℃, or after the exhaust oxygen level reaches more than 10%, stops to inject air, injects external vaporized chemical, and bed and air line are purged displacement, closes oxygen-denuded air outlet 8 then, and oxidation operation is finished.
In the restoring operation, only by 12 air inlets of bubbling air inlet sparger, institute's air inlet body is the mixture of synthetic gas and external vaporized chemical.By reduce oxygen carrier bed and heating and gasifying agent in the bubbling mode, bed temperature reduces gradually.Treat that bed temperature is reduced to 900 ℃, or produce that the combustibleconstituents volumetric molar concentration reaches at 2% o'clock in the outer defeated vaporized chemical, stop to inject fuel, only inject external vaporized chemical bed and fuel are purged displacement, close external vaporized chemical input aperture 6 and outer defeated vaporized chemical outlet 5 then.Carry out the oxidation operation of next cycle.Above-mentioned oxidation operation and restoring operation are alternately switched semi continuous ground by 2 above intermittent thermal storage type reactors and are carried out.
In another embodiment of the present utility model, fuel reaction device 2 and air reactor 3 are not interchangeable flow reactor.Contain oxygen carrier granule in described fuel reaction device 2 and the air reactor 3.The combination of, gravity transfer differential pressure mode of movement air conveying by adopting or these modes circulates oxygen carrier granule between fuel reaction device 2 and air reactor 3.
If the low excessively phenomenon of vaporized chemical transformation efficiency then needs to add O in vaporized chemical 2Here can adopt oxygen permeable membrane type oxygen separator, by containing O 2O in the gas 2Infiltration give in the outer defeated vaporized chemical from outer defeated vaporized chemical outlet 5 and add O 2The described O that contains 2Gas is optional enter before the air reactor gas inlet 7 preheated air or from the high temperature oxygen-denuded air of oxygen-denuded air outlet 8.
Embodiment 2
As shown in Figure 3, oxygen separator 17 is the equipment of dress oxygen permeable membrane 18 in, oxygen permeable membrane is two portions with space segmentation in the oxygen separator 17, from a flow through side of oxygen permeable membranes in the oxygen separator 17 of the outer defeated vaporized chemicals of fuel reaction device 2 outer defeated vaporized chemicals outlets 5, is sent to vapourizing furnace then; From gas blower, the opposite side of oxygen permeable membrane of flowing through of the air inversion after heat exchanger network 10 preheatings, and then advance the gas inlet 7 of air reactor 3.The side here is a logical concept, and physical device is a multilayer film sandwich structure.Before defeated outside vaporized chemical advances oxygen separator 17, can establish a diversion three-way valve 19, can make the outer defeated vaporized chemical of part walk around oxygen separator 17,, can adjust gasification side O by adjusting diversion three-way valve 19 2Concentration.
Used oxygen permeable membrane is an ion migration type oxygen permeable membrane.Vaporized chemical side design temperature is 900 to 1150 ℃, and the air side design temperature is 700 to 850 ℃.Membrane area is by gasification side O 2Concentration reaches the design of 10% volumetric molar concentration.
In addition, can also adopt oxygen selected adsorbent temperature swing adsorption system to give in the vaporized chemical and add O as oxygen separator 17 2Can separate unit batch operation oxygen separator, also can adopt many oxygen separators to replace blocked operation.Oxygen separator 17 is for O with the air 2Gas, defeated in addition vaporized chemical, external vaporized chemical or the mixture of the two are the desorption sweeping gas.The shortcoming of this method is resulting O 2In can be mixed with more N 2So, preferably after having adsorbed, purge with cold external vaporized chemical earlier and remove most of N 2, and then intensification makes O 2Desorption.The specific embodiments of this type oxygen separator is as follows:
Embodiment 3
As shown in Figure 4, adorn solid-state oxygen selective sorbent 20 in the oxygen separator 17, the gasification agent inlet that oxygen separator 17 is provided with the gas inlet that is connected to air source, waste gas drain, links to each other with defeated vaporized chemical pipeline outside the burning chemistry chains system with external vaporized chemical pipeline, and the oxygenousization agent that links to each other with the outer defeated vaporized chemical pipeline that removes vapourizing furnace exports.Here be air source with the blower export air.Have the oxygen separator 17 of two interchangeable operations.During operation, feed air in one of them oxygen separator, cool off adsorbent bed and make adsorbents adsorb O from gas blower 2, the later air of adsorb oxygen directly is discharged into atmosphere through the waste gas drain; Then use earlier in another oxygen separator from the cold external vaporized chemical purging of extraneous gas agent pipeline and discharge through the waste gas drain, close the waste gas drain then, feed the mixture of the external vaporized chemical of part and a small amount of high temperature gasification agent that chemical chain combustion apparatus produces, make mixture temperature reach 120 ℃ by adjusting cold and hot vaporized chemical proportioning, to heat adsorbent bed and to make adsorbent O 2Desorption enters vaporized chemical stream.The resulting O that contains 2Vaporized chemical stream flows out from oxygenousization agent outlet, is sent to vapourizing furnace after this device produces it besides the gas transmission agent converges.
When device of the present utility model was used for the fossil fuel gasification, the implantation temperature of described vaporized chemical also was subjected to the restriction of vaporized chemical inlet tolerable temperature.Usually, if the gas injection temperature reaches more than 320 ℃, just need to adopt specially designed high temperature gas injection port.For example, adopt the sleeve pipe form, interior pipe is a high-temperature resistant tube, and outer tube and interior ligament then play heat-blocking action.If in the circular clearance, feed cold air, then can play the cooling outer tube.

Claims (4)

1.一种产生和加热产生和加热含碳燃料气化剂的装置,它包括:1. A device for generating and heating a carbon-containing fuel gasification agent, comprising: 一个化学链燃烧系统(1),鼓风机(9);换热网络(10);A chemical looping combustion system (1), blower (9); heat exchange network (10); 所述化学链燃烧系统(1)包括至少一个燃料反应器(2)和至少一个空气反应器(3),燃料反应器(2)和空气反应器(3)内都含有化学链燃烧所用载氧体;在燃料反应器(2)和空气反应器(3)之间设有使载氧体循环的载氧体循环装置;燃料反应器(2)设有从外部接入合成气的燃料入口(4)、空气反应器(3)设有空气入口(7)、贫氧空气出口(8);Described chemical looping combustion system (1) comprises at least one fuel reactor (2) and at least one air reactor (3), all contains the used oxygen carrier of chemical looping combustion in fuel reactor (2) and air reactor (3) body; between the fuel reactor (2) and the air reactor (3), an oxygen carrier circulation device for circulating the oxygen carrier is provided; the fuel reactor (2) is provided with a fuel inlet (4) for accessing syngas from the outside , The air reactor (3) is provided with an air inlet (7) and an oxygen-poor air outlet (8); 或者所述化学链燃烧系统(1)包括至少一个既作为燃料反应器又作为空气反应器的反应器;该反应器设有从外部接入合成气的燃料入口(4)、空气入口(7)、贫氧空气出口(8);Or the chemical looping combustion system (1) includes at least one reactor not only as a fuel reactor but also as an air reactor; the reactor is provided with a fuel inlet (4) and an air inlet (7) for accessing synthesis gas , oxygen-poor air outlet (8); 贫氧空气出口(8)连接换热网络(10);鼓风机(9)出口最终通往空气入口(7);The oxygen-poor air outlet (8) is connected to the heat exchange network (10); the blower (9) outlet finally leads to the air inlet (7); 其特征在于:It is characterized by: 燃料反应器(2)或上述既作为燃料反应器又作为空气反应器的反应器设有用于从外部接收H2O、CO2或二者的混合物的外来气化剂输入口(6)以及外输气化剂出口(5),外输气化剂出口(5)通往气化炉;The fuel reactor (2) or the above-mentioned reactor as both a fuel reactor and an air reactor is provided with an external gasification agent input port (6) for receiving H2O , CO2 or a mixture of the two from the outside and an external The gasifying agent outlet (5) for transporting the gasification agent, and the gasifying agent outlet (5) for the external transportation leads to the gasifier; 所述的换热网络(10)至少连接燃料入口(4),外来气化剂输入口(6),空气入口(7)之一;当换热网络(10)连接空气入口(7)时,换热网络(10)连接鼓风机(9)出口。The heat exchange network (10) is at least connected to the fuel inlet (4), the external gasification agent input port (6), and one of the air inlets (7); when the heat exchange network (10) is connected to the air inlet (7), The heat exchange network (10) is connected to the blower (9) outlet. 2.根据权利要求1的装置,所述既作为燃料反应器又作为空气反应器的反应器为间歇蓄热式反应器;所述间歇蓄热式反应器内装有蓄热体。2. The device according to claim 1, wherein the reactor which is used as both a fuel reactor and an air reactor is a batch heat storage reactor; a heat storage body is housed in the batch heat storage reactor. 3根据权利要求2的装置,其特征在于:所述间歇蓄热式反应器底部为锥形,锥底有一个喷动进气口(11),锥面上有一个鼓泡进气分布器(12)。3. The device according to claim 2, characterized in that: the bottom of the batch regenerative reactor is conical, and there is a spray air inlet (11) at the bottom of the cone, and a bubbling air inlet distributor (11) on the conical surface ( 12). 4.根据权利要求1的装置,其特征在于:进一步包括氧分离器(17);4. The device according to claim 1, characterized in that: further comprising an oxygen separator (17); 所述氧分离器(17)内装氧渗透膜(18),氧渗透膜将氧分离器(17)内空间分割为两部分;外输气化剂出口(5)连接氧分离器(17)内氧渗透膜的一侧后连接气化炉;空气入口(7)或贫氧空气出口(8)连接氧分离器(17)内氧渗透膜的另一侧。The oxygen permeable membrane (18) is installed in the oxygen separator (17), and the oxygen permeable membrane divides the inner space of the oxygen separator (17) into two parts; One side of the oxygen permeable membrane is connected to the gasifier; the air inlet (7) or the oxygen-poor air outlet (8) is connected to the other side of the oxygen permeable membrane in the oxygen separator (17).
CNU2008201233668U 2008-11-05 2008-11-05 Device for producing and heating carbonic fuel gasifying agent Expired - Lifetime CN201309913Y (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101392188B (en) * 2008-11-05 2012-05-02 张鹏 Method and apparatus for generating and heating carbonaceous fuel gasifying agent
CN103113917A (en) * 2013-02-18 2013-05-22 上海锅炉厂有限公司 Solid fuel chemical-looping gasification hydrogen production system and method
CN104169399A (en) * 2012-01-11 2014-11-26 Ifp新能源公司 Integrated method for the chemical-looping gasification and indirect combustion of solid hydrocarbon feedstocks
CN107964425A (en) * 2017-10-26 2018-04-27 哈尔滨理工大学 A kind of more gases catch chemical chain reaction device
CN110452738A (en) * 2019-08-20 2019-11-15 南京科技职业学院 Coal processing device and method
CN110923010A (en) * 2019-12-10 2020-03-27 中国科学院工程热物理研究所 Coal staged gasification method and device based on chemical looping combustion

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101392188B (en) * 2008-11-05 2012-05-02 张鹏 Method and apparatus for generating and heating carbonaceous fuel gasifying agent
CN104169399A (en) * 2012-01-11 2014-11-26 Ifp新能源公司 Integrated method for the chemical-looping gasification and indirect combustion of solid hydrocarbon feedstocks
CN103113917A (en) * 2013-02-18 2013-05-22 上海锅炉厂有限公司 Solid fuel chemical-looping gasification hydrogen production system and method
CN107964425A (en) * 2017-10-26 2018-04-27 哈尔滨理工大学 A kind of more gases catch chemical chain reaction device
CN110452738A (en) * 2019-08-20 2019-11-15 南京科技职业学院 Coal processing device and method
CN110923010A (en) * 2019-12-10 2020-03-27 中国科学院工程热物理研究所 Coal staged gasification method and device based on chemical looping combustion

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