CN102849676A - High-temperature water vapor pyrolysis-cracking-gasification device and method for solid fuel - Google Patents
High-temperature water vapor pyrolysis-cracking-gasification device and method for solid fuel Download PDFInfo
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Abstract
The invention relates to the comprehensive utilization field of a solid fuel, specifically to high-temperature water vapor pyrolysis-cracking-gasification device and method for the solid fuel. The method includes introducing the high-temperature water vapor generated by the combustion of O2 and H2 into the solid fuel for low-temperature pyrolysis, to separate out the volatile matter and obtain an oil gas product and pyrolysis semi-coke; performing thermal cracking to the oil gas product in hot state under the action of the high-temperature water vapor, and separating to obtain a lightweight product and a heavyweight component; gasifying the pyrolysis semi-coke and the heavyweight component under the action of oxygen-carrying high-temperature water vapor, to obtain water gas; and allowing the reaction between the water gas and water vapor, to obtain CO2 and H2, separating, storing the CO2, and using the H2 in power generation. The invention is characterized in that the high-temperature water vapor generated by hydrogen-oxygen combustion is used to provide heat; the oil gas product generated by the pyrolysis directly enters the thermal cracking reactor in hot state; higher-added value products, such as lightweight olefins and BTX, are obtained via the thermal cracking; and the clean and high-efficiency comprehensive utilization of the solid fuel is realized through fractional extraction.
Description
Technical field
The invention belongs to pyrolysis, thermo-cracking, the gasification comprehensive utilization field of solid combustion, particularly, the present invention relates to a kind of solid-fuelled high-temperature vapor pyrolysis-cracking-gasification installation and method.
Background technology
Carbonic solid fuels is processed through various thermal conversion process (such as burning, gasification, liquefaction and pyrolysis etc.) can obtain heat energy, electric energy, chemical or fuel, the working method of most industry is the material that the carbon raw materials such as coal, biomass is considered as single property, by single process it all is converted into single product.And the technique of coal direct liquefaction, indirect liquefaction, gasification mainly all is to obtain a kind of purpose product, and obtains the process more complicated of oil, gas product, and condition is harsh, invests higher.
Show that through fundamental research the solid fuel take coal as representative is comprised of organism and inorganics usually, thermolysis can occur and transform in organism wherein in heat-processed, generate organic product and gas, simultaneously residual semicoke.Obtain valuable chemical intermediate, oil fuel or combustion gas by the red-tape operati condition is can be selectively also as much as possible.
High volatile coal accounts for more than 80% in the coal resources of China, comprises about 13% brown coal, 42% sub-bituminous coal and 33% bituminous coal.Volatile matter is rich in the hydrocarbon structure that can be converted into high value chemical, large oil fuel and combustion gas in the coal, and directly burning or gasification mode cause volatile matter in the coal to be equal to solid ingredient in the coal, fail to realize the cascade utilization of resource, can cause the waste of the high value composition of coal resources, also can cause the Coal Chemical Industry Route of coal liquefaction gas long, efficient is low.Therefore, set up economically viable coal derived fuel and chemicals production route and become strategic challenge and the demand that coal in China is utilized industry.
There has been the history of decades in China to the research of pyrolysis and gasification technology, the units such as Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences, Beijing Coal Chemistry Inst., Coal Sciences General Inst., Dalian University of Technology, Chinese Academy Of Sciences Process Engineering Research Institute are at the low temperature pyrogenation of coal, and the aspects such as hydropyrolysis had been done a large amount of experimental studies.And, for achievement in research being pushed to industrial application, domestic expanding test even the type approval test that has carried out some Poly-generation.For example, the multiple-supplying technology that domestic many institutes are are researching and developing, wherein representational tetrad for process characteristic is: with the high-temp circulating ash of circular fluid bed as thermal barrier, generation pyrolysis after mixing with solid fuel, separated out volatilizable minute, isolated oil gas and combustion gas are collected; Isolated solid semicoke and circulating ash turn back in the boiler furnace together burns, heat production, generating, thereby the joint process of realization oil, coal gas, heat, electricity.
But, most of joint process, also there is more problem in the technique of not yet promotion and application, especially coproducing oil product.And adopting heat ash, recirculation system sand is that gained solid product semicoke and solid thermal carriers particle are the solid-solid blend state in the down-flow fluidized bed using ECT or fluidized bed pyrolysis technique of solid thermal carriers, and separating difficulty is larger, is difficult to obtain pure semicoke product; The coal-tar middle oil productive rate of gained pyrolysis product is lower, and the heavy tar component concentration is higher.In addition, these Poly-generation patterns all turn to the gas head with Single gas, and to satisfy the needs of composite part, the complicacy that this has not only increased system and technology causes the consumption of energy, and has increased CO by the ratio of carbon-hydrogen in the CO transformationreation adjustment raw gas
2Discharging.Reduce discharging requirement according to the world, need COB
2Separate, store.
China is still with the main force of Coal Energy Source as energy industry at present, accounts for about 65～70%.Coal and some mink cell focuses such as coal tar, vacuum residuum etc. will discharge a large amount of CO when directly burning
2, certainly will cause the restriction of international carbon tax.Enter 21 century, China need to solve the problem that energy industrial mix is adjusted.Accelerate on the one hand water power, the development of the renewable energy sources such as wind energy, sun power; Need on the one hand progressively coal, heavy hydrocarbon to be converted into Hydrogen Energy, make the clean energies such as Hydrogen Energy and Sweet natural gas progressively replace most of share of present coal and oil.Therefore, the problem that changes hydrogen and clean energy in order to solve coal in the energy and heavy hydrocarbon is necessary the development of novel process is brought into schedule.
Summary of the invention
The object of the present invention is to provide a kind of solid-fuelled high-temperature vapor pyrolysis-cracking-gasification installation.
A further object of the present invention is to provide a kind of solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process.
According to solid-fuelled high-temperature vapor pyrolysis-cracking of the present invention-gasification process, said method comprising the steps of:
1) with O
2And H
2The high-temperature vapor that burning produces passes in the solid fuel, and solid-fuelled low temperature pyrogenation occurs, and separates out volatile matter, obtains pyrolysis oil gas product, obtains simultaneously pyrolysis char;
2) the pyrolysis oil gas product that step 1) obtains is hot to carry out thermo-cracking under the high-temperature vapor effect that passes into, obtain lighter products and heavy component after separating;
3) pyrolysis char and the step 2 that step 1) obtain) in the heavy component that obtains gasify taking under the effect of oxygen high-temperature vapor of passing into, obtain water-gas, discharge simultaneously slag;
4) with step 3) water-gas that obtains and the water vapour that passes into reaction, obtain CO
2And H
2, through separating the CO that obtains
2Seal the H that obtains up for safekeeping
2Be used for generating or turn back to step 1) the preparation high-temperature vapor.
According to solid-fuelled high-temperature vapor pyrolysis-cracking of the present invention-gasification process, described step 1) in solid fuel when being coal, should be the bituminous coal and the brown coal that contain than high volatile; Also may be extended to other solid fuel, such as oil-sand, biomass, resinous shale etc.If described solid materials pelletizing, its granularity are preferably 20～30 millimeters; If the material powdery, its granularity should be less than 3 millimeters.
According to solid-fuelled high-temperature vapor pyrolysis-cracking of the present invention-gasification process, described step 1) in by O
2And H
2The high-temperature vapor that burning produces, as required, its temperature control is at 1000～2000 ℃.
Described step 1) hydrogen for generation of ultrahigh-temperature water vapour in can be excessive slightly; The temperature of extracting volatile matter in the pyrolysis is 500～900 ℃, and pyrolytic reaction is normal pressure.
Heat scission reaction occurs in pyrolysis oil gas product hot described step 2) under the high-temperature vapor effect that is produced by the oxyhydrogen combustion controller, the thermo-cracking temperature should be controlled at 600～900 ℃.
Described step 3) temperature of gasification reaction should be higher than 1000 ℃, and pressure is 3～5MPa, and the vaporized chemical of generating gasification reaction is for taking the oxygen high-temperature vapor from oxygen-steam evaporator; The slag of discharging behind the gasification reaction is high-temperature liquid furnace slag.
In addition, the present invention also provides a kind of solid-fuelled high-temperature vapor pyrolysis-cracking-gasification installation, described device comprises: feeder 1, pyrolysis reactor 2 and vapourizing furnace 6, it is characterized in that described device also comprises: oxyhydrogen combustion controller 3, pyrolysis reactor 4, oxygen-steam evaporator 5, water-gas shift reactor 7 and condensation separator 8;
Pulverulent material or material pelletizing enter pyrolysis reactor 2, O through feeder 1
2And H
2The high-temperature vapor that generates at oxyhydrogen combustion controller 3 internal reactions passes in the pyrolysis reactor 2, and the low temperature pyrogenation of coal occurs, and separates out volatile matter, obtains pyrolysis oil gas product, obtains simultaneously pyrolysis char;
The hot pyrolysis reactor 4 that directly enters of described pyrolysis oil gas product, under the effect of the high-temperature vapor that is produced by oxyhydrogen combustion controller 3 internal reactions, the heat scission reaction of pyrolysis oil gas product occurs, be isolated to light olefin (C2-C6), BTX (triphen, i.e. benzene, toluene and dimethylbenzene) and heavy component;
Described pyrolysis char and heavy component enter vapourizing furnace 6, taking under the effect of oxygen high-temperature vapor of being produced by oxygen-steam evaporator 5, the gasification reaction of semicoke and heavy component occur, and obtain water-gas, and pass into water-gas shift reactor 7, obtain CO
2And H
2, the H that obtains
2Return in the oxyhydrogen combustion controller 3 and recycle, perhaps be directly used in generating; Described heavy component also can be used for hydrocracking to obtain Chemicals.
Described pyrolysis reactor 2 adopts simulation moving-bed pyrolysis reactor, in this simulation moving-bed pyrolysis reactor some beds are set, be provided with valve between each bed and the oxyhydrogen combustion controller 3, and each bed is provided with venting port, and described venting port is connected with the CO infrared radiation detection apparatus all.
Described pyrolysis reactor 2 adopts fluidized bed pyrolysis reactor or fixed-bed pyrolysis reactor, and the exhaust ports of described pyrolysis reactor is provided with the CO infrared radiation detection apparatus.
According to solid-fuelled high-temperature vapor pyrolysis-cracking of the present invention-gasification process, be characterized in utilizing the high-temperature vapor of oxyhydrogen combustion generation as the energy derive of pyrolysis, thermo-cracking, gasification, wherein, the hydrogen source of oxyhydrogen combustion can be excessive slightly, according to calculation of thermodynamics, if in the high-temperature vapor of burning, keep some hydrogen, can play the effect of dephenolize, desulfurization.
According to solid-fuelled high-temperature vapor pyrolysis-cracking of the present invention-gasification process, the oil gas product that pyrolysis obtains generates micromolecular light olefin (C2-C6), BTX (triphen) etc. by thermo-cracking and can be used as industrial chemicals; But mink cell focus hydrocracking generates the products such as gasoline, diesel oil; Can return vapourizing furnace gasification gas making take the contracting PAH as main heavy component; The venting port of pyrolysis reactor all is connected with infrared radiation detection apparatus, for detection of the CO concentration of outlet; The high temperature semicoke of discharge after solid fuel pyrolysis is finished reacts with the direct generating gasification of oxygen high-temperature vapor of taking that passes in vapourizing furnace, and is capable of reducing energy consumption.
According to solid-fuelled high-temperature vapor pyrolysis-cracking of the present invention-gasification process, in the water-gas converter, the CO by gasification reaction generates issues the reaction of unboiled water gas reforming, i.e. CO+H in the water vapour effect that passes into
2O=CO
2+ H
2, the generation of this reaction does not consume extra energy substantially; The water vapour of discharging in the technological process can be sent back to oxyhydrogen combustion controller recycling, and reacts for the water-gas converter, to save the hydrogen consumption; The high-temperature gas of discharging in the technological process can be used as high-grade waste heat recovery, the waste heat of recovery, and sub-fraction can be used to the solid materials that preheating enters pyrolysis reactor; Obtain H after char Gasification and the water gas shift reaction
2, can be used as on the one hand Hydrogen Energy and be used for generation technology, can be used as hydrogen source of the present invention on a small quantity on the one hand; The CO that generates simultaneously
2Can be reused, perhaps permanent envelope is stored in underground.
The present invention proposes a kind of solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process, the method is the heat that the high-temperature vapor that utilizes oxyhydrogen combustion to produce provides solid fuel pyrolysis, cracking, gasification; Separate out volatile matter through low temperature pyrogenation, obtain pyrolysis oil gas product and pyrolysis char; The oil gas product is with the hot pyrolysis reactor of directly sending into, and product obtains the higher products of added value such as light olefin (C2-C6), BTX (triphen) through condensation separation, improved simultaneously system efficiency; The heavy component that obtains returns vapourizing furnace, perhaps continues hydrocracking; The high temperature semicoke that pyrolysis obtains directly enters vapourizing furnace, has also improved system thermal efficiency; Pyrolysis char and heavy component obtain CO through the product after the gasification after water-gas transforms
2And H
2, be easy to separate, with CO
2Seal the minimizing carbon emission up for safekeeping, H
2Be used for generating; Finally realize to solid-fuelled grading extraction cleaning, efficiently comprehensive utilization.
The invention has the advantages that:
1) compares with traditional solid thermal carriers type of heating, the present invention adopts the high-temperature vapor of oxyhydrogen combustion generation as the energy derive of pyrolysis, thermo-cracking, gasification, avoided that solid thermal carriers mix with solid-fuelled in the pyrolytic process, and the separation of solid product, can obtain pure semicoke product and be used for gasification, reduce the Operating Complexity of technique;
2) hydrogen source in the oxyhydrogen combustion generation high-temperature vapor can be excessive slightly, according to calculation of thermodynamics, if keep some hydrogen in the high-temperature vapor of burning, can play the effect of dephenolize, desulfurization, simplified follow-up purification process technique;
3) compare with traditional low temperature pyrogenation technique, the present invention extracts the volatile matter that obtains and directly carries out thermo-cracking under the effect at high-temperature vapour with hot through low temperature pyrogenation, not only simplified technique, and improved system thermal efficiency; Simultaneously, the hot cracked Chemicals that obtain, as, light olefin (C1-C6) and BTX (triphen) they are the higher product of added value, thereby have improved the overall output value of technique;
4) compare with gasifying process with traditional pyrolysis of coal, utilize this technology, coal can be converted into the hydrogen power generation technology, so that coal electricity industry obtains further living space and investment field.And technical process of the present invention is that CO is taken off in the pyrolysis of coal elder generation, gasification
2, Hydrogen Energy is used for generating, has the advantage of saving Coal Transport; And with the CO that discharges
2Seal up for safekeeping, utilize hydrogen power generation, have the advantage of carbon zero release.
Description of drawings
Fig. 1 is the solid-fuelled high-temperature vapor pyrolysis-cracking of the present invention-gasification installation synoptic diagram.
Fig. 2 is the solid-fuelled high-temperature vapor pyrolysis-cracking of the present invention-gasification schematic flow sheet.
The accompanying drawing sign
1, feeder 2, pyrolysis reactor 3, oxyhydrogen combustion controller
4, pyrolysis reactor 5, oxygen-steam evaporator 6, vapourizing furnace
7, water-gas shift reactor 8, condensation separator
Embodiment
Below in conjunction with accompanying drawing device of the present invention and embodiment are described further.
Solid-fuelled high-temperature vapor pyrolysis-cracking of the present invention-gasification installation, described device comprises: oxyhydrogen combustion controller 3, pyrolysis reactor 2 and pyrolysis reactor 4, feeder 1, oxygen-steam evaporator 5, vapourizing furnace 6, water-gas shift reactor 7 and condensation separator 8;
Pulverulent material or material pelletizing enter pyrolysis reactor 2, O through feeder 1
2And H
2Burning generation high-temperature vapor passes in the pyrolysis reactor 2 in oxyhydrogen combustion controller 3, and the low temperature pyrogenation of coal occurs, and separates out volatile matter, obtains pyrolysis oil gas product, obtains simultaneously pyrolysis char;
The hot pyrolysis reactor 4 that directly enters of described pyrolysis oil gas product, under the high-temperature vapor effect that is produced by oxyhydrogen combustion controller 3, the heat scission reaction of oil gas product occurs, and obtains light olefin (C2-C6), BTX (triphen) and heavy component after separating;
Described pyrolysis char and heavy component enter vapourizing furnace 6, taking under the effect of oxygen high-temperature vapor of being produced by oxygen-steam evaporator 5, the gasification reaction of pyrolysis char and heavy component occur, and obtain water-gas, and pass into water-gas shift reactor 7, obtain CO
2And H
2, the H that obtains
2Return in the oxyhydrogen combustion controller 3 and recycle, perhaps be directly used in generating; Described heavy component can also continue hydrocracking to obtain Chemicals.
Described pyrolysis reactor 2 adopts simulation moving-bed pyrolysis reactor, in this simulation moving-bed pyrolysis reactor some beds are set, be provided with valve between each bed and the oxyhydrogen combustion controller 3, each bed is provided with venting port, and described venting port all is connected with the CO infrared radiation detection apparatus.
Described pyrolysis reactor 2 adopts fluidized bed pyrolysis reactor or fixed-bed pyrolysis reactor, and the exhaust ports of described pyrolysis reactor is provided with the CO infrared radiation detection apparatus.
Solid-fuelled high-temperature vapor pyrolysis-cracking of the present invention-gasification process may further comprise the steps:
1) coal is broken, screening, the material that obtains is made briquet, perhaps pulverulent material; After the drying, send into feeder;
2) oxygen and excessive hydrogen in right amount or slightly, burning produces high-temperature vapor in the oxyhydrogen combustion controller, with the energy derive as low-temperature pyrolysis of coal and thermo-cracking and gasification;
3) in pyrolysis reactor, low-temperature pyrolysis of coal with the high-temperature vapor effect that is produced by oxyhydrogen combustion, occurs in pulverulent material or material pelletizing by feeder is sent into, separates out volatilizable minute, obtains pyrolysis oil gas product, obtains simultaneously pyrolysis char;
4) the hot high-temperature vapour pyrolysis reactor of directly sending into of pyrolysis oil gas product, hot cracked reaction, and reclaim light olefin (C2-C6) and BTX (triphen) etc. after the condensation separation as the high value added product of industrial chemicals; But heavy component hydrocracking generates the products such as gasoline, diesel oil; Can return vapourizing furnace gas making take the contracting PAH as main heavy component;
5) venting port of each bed of pyrolysis reactor all is connected on the CO infrared radiation detection apparatus, to detect the CO concentration of outlet; When CO concentration begins to raise, in time finish the pyrolysis reactor reaction, therefrom discharge the high temperature semicoke; And new material pushed pyrolysis reactor; The pyrolysis char of discharging is directly sent into vapourizing furnace;
6) in vapourizing furnace, high temperature semicoke and heavy component generate CO, H in the generating gasification reaction under the effect of oxygen high-temperature vapour of taking of oxygen/water steam generator generation
2, be admitted to subsequently in the water-gas shift reactor; The high temperature furnace slag of discharging simultaneously, this high temperature furnace slag can be used as high-grade waste heat and is recycled;
7) in water-gas shift reactor, water gas shift reaction, i.e. CO+H occur in CO under the water vapour effect that passes into
2O=CO
2+ H
2, obtain CO
2And H
2After separating, H
2Can be used as Hydrogen Energy and be used for generating, a small part can be used as hydrogen source of the present invention; CO after the separation
2Can be stored in by permanent envelope undergroundly, part also can obtain utilizing.
By the enforcement of this technology, from coal, can obtain oil, gas, heat, electricity, with the Technology that realizes that tetrad produces, finish simultaneously CO
2The requirement that reduces discharging.
Embodiment 1:
Raw material: a kind of higher bituminous coal of volatile matter that contains, the pelletizing particle diameter is the 20-30 millimeter
Characteristics: simulation moving-bed pyrolysis reactor
Implementation method:
To make the briquet of 20-30 mm in size behind the coal sample reduction, after the drying treatment, send into feeder.Briquet is sent in the bed of simulation moving-bed pyrolysis reactor (10 beds, each bed is controlled separately); At first open lowest layer valve, by oxygen and under the high-temperature vapor effect that the excessive hydrogen burning produces slightly pyrolysis is occuring from the oxyhydrogen combustion controller; In the reaction process, by being connected to the infrared radiation detection apparatus of pyrolysis reactor venting port, detect in real time the CO concentration of outlet; When CO concentration begins to raise, close this layer valve with stopped reaction, avoid the generating gasification reaction under the high-temperature vapor effect of semicoke pelletizing; Open simultaneously the valve of a bed, pass into high-temperature vapor and continue pyrolytic reaction, react to control in the pyrolyzer by the CO infrared radiation detection apparatus equally; Successively carry out pyrolysis, until the complete devolatilization of the briquet in the pyrolysis reactor; In time push new material and enter pyrolysis reactor; The volatile matter (650 ℃) of being discharged by pyrolysis reactor is by the hot pyrolysis reactor (750～850 ℃) of directly sending into, with the high-temperature vapor effect By Direct Pyrolysis from the oxyhydrogen combustion controller, obtain the high value added product that light olefin (C2-C6) and BTX (triphen) etc. are used as industrial chemicals through the condensation separation recovery; Return the vapourizing furnace gasification take the contracting PAH as main heavy component; The high temperature semicoke of discharging is admitted to vapourizing furnace, and (temperature is 1300 ℃, and pressure is 3MPa with the oxygen high-temperature vapor generating gasification reaction of taking from the oxygen/water steam generator in vapourizing furnace with heavy component.), generate CO, H
2The product gas that generates continues in water-gas shift reactor, and the water vapour generation water gas shift reaction with passing into obtains CO
2And H
2After separating, H
2Can be used as Hydrogen Energy and be used for generating, sub-fraction is returned the hydrogen source that produces high-temperature vapor as the oxyhydrogen combustion controller; The CO that separates
2Can be reused or permanent envelope is stored in underground; From the liquid high temperature furnace slag that vapourizing furnace is discharged, utilize the chilling heat transfer technology to recycle, a part can be used for the material in the preheating pyrolysis reactor.
Raw material: a kind of higher brown coal of volatile matter that contain, particle diameter is less than 3 millimeters
Characteristics: fluidized bed pyrolysis reactor
Implementation method:
With below the coal sample reduction to 3 millimeter, send into feeder after the drying treatment; Then material is sent in the fluidized bed pyrolysis reactor; By oxygen and under the high-temperature vapor effect that the excessive hydrogen burning produces slightly pyrolysis is occuring from the oxyhydrogen combustion controller; By being connected to the infrared radiation detection apparatus of pyrolyzer venting port, detect in real time the CO concentration of outlet, the mean residence time by adjusting coal dust is to avoid semicoke generating gasification reaction under the high-temperature vapor effect.By the hot pyrolysis reactor of directly sending into of volatile matter that pyrolyzer is discharged, the high-temperature vapor effect generation cracking with from the oxyhydrogen combustion controller obtains light olefin and BTX product; Return vapourizing furnace gasification gas making take the contracting PAH as main heavy component; The high temperature semicoke of discharging is directly sent into vapourizing furnace after the intermediate bunker pressurization; In vapourizing furnace, semicoke and heavy component react generation CO, H with the oxygen high-temperature vapor generating gasification of taking from the oxygen/water steam generator together
2The product gas that generates continues in water-gas shift reactor, and the water vapour generation water gas shift reaction with passing into obtains CO
2And H
2Through separating H
2Can be used as Hydrogen Energy and be used for generating, a part is returned the hydrogen source that generates high-temperature vapor as the oxyhydrogen combustion controller; CO after the separation
2Sealed up for safekeeping or recycled; From the liquid high temperature furnace slag that vapourizing furnace is discharged, utilize the chilling heat transfer technology to recycle; A part is used for the material in the preheating pyrolyzer.
Raw material: a kind of higher bituminous coal of volatile matter that contains, the pelletizing particle diameter is 20～30 millimeters
Characteristics: fixed-bed pyrolysis reactor
Implementation method:
To make the briquet of 20 mm in sizes behind the coal sample reduction, send into feeder after the drying treatment; Then briquet is sent into (parallel two pyrolysis reactors are used alternatingly) in the fixed-bed pyrolysis reactor; With pyrolysis occurs under the high-temperature vapor effect that is produced by burning by oxygen and excessive hydrogen slightly from the oxyhydrogen combustion controller; In the reaction process, by being connected to the infrared radiation detection apparatus of pyrolyzer venting port, detect the CO concentration of outlet; When CO concentration begins to raise, stop to react in this pyrolyzer, to avoid the reaction of semicoke and high-temperature vapor generating gasification; Conversion valve makes high-temperature vapor pass through another pyrolysis reactor, and new material is carried out pyrolysis; Simultaneously, last pyrolyzer is discharged the high temperature semicoke and is pushed new material; The volatile matter of being discharged by pyrolyzer is by the hot cracking reactor of directly sending into, and the high-temperature vapor effect generation cracking with from the oxyhydrogen combustion controller obtains light olefin and BTX; Return vapourizing furnace gasification gas making take the contracting PAH as main heavy component; The high temperature semicoke of discharging is directly sent into vapourizing furnace, and in vapourizing furnace, semicoke and heavy component react generation CO, H with the oxygen high-temperature vapor generating gasification of taking from the oxygen/water steam generator together
2The gaseous product that generates continues to obtain CO with the water vapour generation water gas shift reaction that passes in water-gas shift reactor
2And H
2Through separating H
2Be used for generating as Hydrogen Energy, a part is returned the hydrogen source that produces high-temperature vapor as the oxyhydrogen combustion controller; CO after the separation
2Sealed up for safekeeping or recycled; The liquid high temperature furnace slag that vapourizing furnace is discharged utilizes the chilling heat transfer technology to recycle; A part is used for the material in the preheating pyrolyzer.
Raw material: a kind of higher resinous shale of volatile matter that contains, the pelletizing particle diameter is 20～30 millimeters
Characteristics: simulation moving-bed pyrolysis reactor
Implementation method:
With making the pelletizing of 20 mm in sizes after the fragmentation of resinous shale sample, send into feeder after the drying treatment.Then the resinous shale pelletizing is sent in the bed of simulation moving-bed pyrolysis reactor (10 beds, each bed is controlled separately); At first open lowest layer valve, by oxygen and under the high-temperature vapor effect that the excessive hydrogen burning produces slightly pyrolysis is occuring from the oxyhydrogen combustion controller; In the reaction process, by being connected to the infrared radiation detection apparatus of pyrolyzer venting port, detect in real time the CO concentration of outlet; When CO concentration begins to raise, close this layer valve to stop pyrolytic reaction, avoid pelletizing generating gasification reaction under the high-temperature vapor effect; Open simultaneously a bed valve, pass into high-temperature vapor and continue pyrolytic reaction, pass through the CO infrared radiation detection apparatus with the reaction in the control pyrolyzer with method; Successively carry out pyrolysis, until the complete devolatilization of resinous shale pelletizing in the pyrolysis reactor in time pushes away new material and enters pyrolysis reactor.Directly sent into pyrolysis reactor by the hot volatile matter that pyrolysis reactor is discharged, with the high-temperature vapor effect By Direct Pyrolysis from the oxyhydrogen combustion controller, reclaim and obtain the products such as light olefin and BTX; Return vapourizing furnace gas making take the contracting PAH as main heavy component; The high temperature semicoke of discharging is admitted to vapourizing furnace, and in vapourizing furnace, semicoke and heavy component react generation CO, H with the oxygen high-temperature vapor generating gasification of taking from the oxygen/water steam generator together
2The product gas that generates continues in water-gas shift reactor, and the water vapour generation water gas shift reaction with passing into obtains CO
2And H
2After separating, H
2Be used for generating as Hydrogen Energy, sub-fraction is returned the hydrogen source that produces high-temperature vapor as the oxyhydrogen combustion controller; The C0 that separates
2Can be reused or permanent envelope is stored in underground; From the liquid high temperature furnace slag that vapourizing furnace is discharged, utilize the chilling heat transfer technology to recycle; A part is as the material in the thermal source preheating pyrolyzer.
In addition, adopt the method for method of the present invention and prior art that feed coal is processed, the output value that specifically obtains is as follows:
1, adopt method of the present invention to process the benefit of acquisition:
The inventive method---suppose parameter: feed coal: 1,000 ten thousand ton/years, contain methane 10%, light olefin 15% in the volatile matter that the standard thermal value 7000kcal/ kilogram (volatile matter 25%, fixed carbon 60%) of coal extracts, BTX15% (8500 yuan/tons), electric explant price is 0.15 yuan/degree:
1, contains 10% methane (methane enters gas distributing system, 3000 yuan) in the gas phase of extracting: 1000 * 25% * 10% * 3000 (ten thousand yuan/year)=7.5 hundred million yuan/year;
2, change light olefin 15% and BTX15% (8500 yuan/tons) in the tar into: 1000 * 25% * 30% * 8500 (ten thousand yuan/year)=63.75 hundred million yuan/year
3, the fixed carbon semicoke 60%, the heavy component that returns vapourizing furnace accounts for 50% of tar, utilize improved IGCC generating after the gasification, thermo-efficiency is 85%, combined cycle efficiency is 52%, 1kwh=859.8kcal the calorific value of pure carbon is ten thousand tons of 393.51kJ/mol:1000 * (60%+25% * 50%) * 85% * 1000 kg/tonne * (393.51 * 10
3/ (12 * 4.18))=43.86 hundred million yuan/year of 52%/859.8 * 0.15 yuan/degree
Total annual value of production=(electricity)=11,500,000,000,7.5 (Sweet natural gas)+63.75 (light olefin and BTX)+43.86 yuan/year
When if volatilization is divided into 15%, total annual value of production is: hundred million yuan/year of (electricity)=83.58,4.5 (Sweet natural gas)+38.25 (light olefin and BTX)+40.83.
2, be gasified totally and all be converted into hydrogen, utilize improved IGCC electrification technique as well as, the benefit of acquisition:
Gasification efficiency 85%, generating efficiency 52%, total thermoelectrical efficiency is 85% * 52%=44.2%, and then the output value is: hundred million yuan/year of 1,000 ten thousand tons * 1000 kg/tonnes * 7000kcal/kg * 44.2%/859.8 * 0.15=54.0 (can avoid the carbon tax problem).
3, directly adopt ultra supercritical power generation, the benefit of acquisition:
Conversion efficiency of thermoelectric 40%, then the output value is: hundred million yuan/year of 1,000 ten thousand tons * 1000 kg/tonnes * 7000kcal/kg * 40%/859.8 * 0.15=48.8; When if conversion efficiency of thermoelectric is 45%, annual value of production is 55.0 hundred million yuan/year (may need to pay carbon tax after for some time).
Can see by top data, by method of the present invention solid fuel be carried out comprehensive disposal and utilization, the high-temperature vapor that utilizes oxyhydrogen combustion to produce provides heat for solid fuel pyrolysis, cracking, gasification; Separate out volatile matter through low temperature pyrogenation, obtain pyrolysis oil gas product and pyrolysis char; The oil gas product is with the hot pyrolysis reactor of directly sending into, and product obtains the higher products of added value such as light olefin (C2-C6), BTX (triphen, i.e. benzene, toluene and dimethylbenzene) through condensation separation, improved simultaneously system efficiency; The heavy component that obtains then returns vapourizing furnace, perhaps continues hydrocracking; The high temperature semicoke that pyrolysis obtains directly enters vapourizing furnace, has also improved system thermal efficiency; Pyrolysis char and heavy component obtain CO through the product after the gasification after water-gas transforms
2And H
2, be easy to separate, with CO
2Seal the minimizing carbon emission up for safekeeping, H
2Be used for generating.By method and apparatus of the present invention, realize to solid-fuelled grading extraction that finally cleaning, efficiently comprehensive utilization obtain considerable economic benefit.
It should be noted that at last above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although with reference to embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, technical scheme of the present invention is made amendment or is equal to replacement, do not break away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (8)
1. solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process is characterized in that, said method comprising the steps of:
1) with O
2And H
2The high-temperature vapor that burning produces passes in the solid fuel, and solid-fuelled low temperature pyrogenation occurs, and separates out volatile matter, obtains pyrolysis oil gas product, obtains simultaneously pyrolysis char;
2) the oil gas product that step 1) obtains carries out heat scission reaction under the high-temperature vapor effect that passes into, obtain lighter products and heavy component after separating;
3) pyrolysis char and the step 2 that step 1) obtain) in the heavy component that obtains gasify taking under the effect of oxygen high-temperature vapor of passing into, obtain water-gas, discharge simultaneously slag;
4) with step 3) water-gas that obtains and the water vapour that passes into reaction, obtain CO
2And H
2, through separating the CO that obtains
2Seal the H that obtains up for safekeeping
2Be used for generating or turn back to step 1) the preparation high-temperature vapor.
2. described solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process according to claim 1 is characterized in that, with described step 2) in the heavy component that obtains be used for hydrocracking.
3. described solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process according to claim 1 is characterized in that described step 1) in solid fuel be to contain the high bituminous coal of volatile matter, brown coal, oil-sand, biomass or resinous shale.
4. described solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process according to claim 3 is characterized in that described solid fuel is powdered granule, or solid fuel is made bulk by powdery.
5. described solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process according to claim 1 is characterized in that,
Described step 1) O in
2And H
2The high-temperature vapor temperature that burning generates is 1000～2000 ℃;
Described step 1) to separate out the temperature of volatile matter be 500～900 ℃ for the low temperature pyrogenation of coal in;
Described step 2) temperature of heat scission reaction is 600～900 ℃ in;
Described step 3) gasification temperature is higher than 1000 ℃ in.
6. solid-fuelled high-temperature vapor pyrolysis-cracking-gasification installation, described device comprises: feeder (1), pyrolysis reactor (2) and vapourizing furnace (6), it is characterized in that described device also comprises: oxyhydrogen combustion controller (3), pyrolysis reactor (4), oxygen-steam evaporator (5), water-gas shift reactor (7) and condensation separator (8);
Solid fuel enters pyrolysis reactor (2), O through feeder (1)
2And H
2The high-temperature vapor that reaction generates in oxyhydrogen combustion controller (3) passes into pyrolysis reactor (2), and solid-fuelled low temperature pyrogenation occurs, and separates out volatile matter, obtains pyrolysis oil gas product and pyrolysis char;
Described pyrolysis oil gas product directly enters pyrolysis reactor (4), the high-temperature vapor that is produced by reaction in the oxyhydrogen combustion controller (3) passes in the pyrolysis reactor (4), the heat scission reaction of pyrolysis oil gas product occurs, and obtains lighter products and heavy component behind condensation separator (8);
Described semicoke and heavy component enter vapourizing furnace (6), and the oxygen water vapour of taking that is produced by oxygen-steam evaporator (5) passes into vapourizing furnace (6), and the gasification reaction of semicoke and heavy component occurs, and obtain water-gas; And pass in the water-gas shift reactor (7) and the water vapour reaction, obtain CO
2And H
2, the H that obtains
2Turn back in the oxyhydrogen combustion controller (3) and recycle, perhaps be directly used in generating.
7. the high-temperature vapor pyrolysis-cracking of solid fuel according to claim 6-gasification installation, it is characterized in that, described pyrolysis reactor (2) adopts simulation moving-bed pyrolysis reactor, in this simulation moving-bed pyrolysis reactor some beds are set, are provided with valve between each bed and the oxyhydrogen combustion controller (3); Each bed is provided with venting port, and described venting port all is connected with the CO infrared radiation detection apparatus.
8. solid-fuelled high-temperature vapor pyrolysis-cracking according to claim 6-gasification installation, it is characterized in that, described pyrolysis reactor (2) adopts fluidized bed pyrolysis reactor or fixed-bed pyrolysis reactor, and the exhaust ports of described pyrolysis reactor is provided with the CO infrared radiation detection apparatus.
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