CN102849676B - 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 pyrolysis, thermo-cracking, the gasification comprehensive utilization field that the invention belongs to 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 and can be obtained heat energy, electric energy, chemical or fuel through various thermal conversion process (as burning, gasification, liquefaction and pyrolysis etc.), the working method of most industry is the material that the carbon raw material such as coal, biomass is considered as to single property, by single process, it is all converted into single product.And the technique of coal direct liquefaction, indirect liquefaction, gasification is all mainly to obtain a kind of object product, and obtain process more complicated oily, gas product, condition harshness, invests higher.
Show through fundamental research, the solid fuel taking coal as representative, is made up of organism and inorganics conventionally, and organism wherein thermolysis can occur in heat-processed and transforms, and generates organic product and gas, simultaneously residual semicoke.Obtain valuable chemical intermediate, oil fuel or combustion gas by red-tape operati condition is can be selectively also as much as possible.
In the coal resources of China, high volatile coal accounts for more than 80%, comprises approximately 13% brown coal, 42% sub-bituminous coal and 33% bituminous coal.In coal, volatile matter is rich in the hydrocarbon structure that can be converted into high value chemical, large oil fuel and combustion gas, and directly burning or gasification mode cause volatile matter in coal to be equal to the solid ingredient in 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, efficiency is low.Therefore, set up economically viable coal derived fuel and chemicals production route and become coal in China and utilize strategic challenge and the demand of 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 is pushed to industrial application, the domestic even type approval test of expanding test that has carried out some Poly-generation.For example, the multiple-supplying technology that domestic Duo Jia institute is is researching and developing, wherein representational tetrad for process characteristic is: using the high-temp circulating ash of circular fluid bed as thermal barrier, generation pyrolysis after mixing with solid fuel, separate out volatilizable point, isolated oil gas and combustion gas are collected; Isolated solid semicoke turns back in boiler furnace and burns together with circulating ash, 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 in the down-flow fluidized bed using ECT or fluidized bed pyrolysis technique that heat ash, recirculation system sand are solid thermal carriers, gained solid product semicoke and solid thermal carriers particle are solid-solid blend state, 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 heavy tar component concentration is higher.In addition, these Poly-generation patterns all turn to gas head with Single gas, and by the ratio of carbon-hydrogen in CO transformationreation adjustment raw gas, to meet 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
2discharge.Reduce discharging requirement according to the world, need be by COB
2separate, store.
China is still the main force using Coal Energy Source as energy industry at present, accounts for 65～70% left and right.When directly burning as coal tar, vacuum residuum etc., coal and some mink cell focuses will discharge a large amount of CO
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 to progressively coal, heavy hydrocarbon be converted into Hydrogen Energy on the one hand, make the clean energy such as Hydrogen Energy and Sweet natural gas progressively replace most of share of present coal and oil.Therefore, change the problem of hydrogen and clean energy in order to solve coal in the energy and heavy hydrocarbon, be necessary the development of novel process to bring 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-gasification process of the present invention, said method comprising the steps of:
1) by O
2and H
2the high-temperature vapor that burning produces passes in solid fuel, and solid-fuelled low temperature pyrogenation occurs, and separates out volatile matter, obtains pyrolysis oil gas product, obtains pyrolysis char simultaneously;
2) step 1) the pyrolysis oil gas product that obtains is hot under the high-temperature vapor effect passing into, carries out thermo-cracking, after separating, obtains lighter products and heavy component;
3) step 1) pyrolysis char and the step 2 that obtain) in the heavy component that obtains gasify taking under the effect of oxygen high-temperature vapor of passing into, obtain water-gas, discharge slag simultaneously;
4) by step 3) water-gas obtaining and the water vapour passing into reaction, obtain CO
2and H
2, through separating, the CO obtaining
2seal the H obtaining up for safekeeping
2for generating or turn back to step 1) prepare high-temperature vapor.
According to solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process of the present invention, described step 1) in solid fuel while being coal, should be containing compared with the bituminous coal of high volatile and brown coal; Also may be extended to other solid fuel, as oil-sand, biomass, resinous shale etc.If described solid materials pelletizing, its granularity is preferably 20～30 millimeters; If material powdery, its granularity should be less than 3 millimeters.
According to solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process of the present invention, described step 1) in by O
2and H
2the high-temperature vapor that burning produces, as required, its temperature control is at 1000～2000 DEG C.
Described step 1) in can be excessive slightly for generation of the hydrogen of ultrahigh-temperature water vapour; The temperature of extracting volatile matter in pyrolysis is 500～900 DEG C, and pyrolytic reaction is normal pressure.
Described step 2) in hot pyrolysis oil gas product issue heat-dissipating scission reaction in the high-temperature vapor effect being produced by oxyhydrogen combustion controller, thermo-cracking temperature should be controlled at 600～900 DEG C.
Described step 3) temperature of gasification reaction should be higher than 1000 DEG C, and pressure is 3～5MPa, and the vaporized chemical of generating gasification reaction is to take oxygen high-temperature vapor from oxygen-steam evaporator; The slag of discharging after 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 generating in the interior reaction of oxyhydrogen combustion controller 3 passes in pyrolysis reactor 2, and the low temperature pyrogenation of coal occurs, and separates out volatile matter, obtains pyrolysis oil gas product, obtains pyrolysis char simultaneously;
The hot pyrolysis reactor 4 that directly enters of described pyrolysis oil gas product, under the effect of the high-temperature vapor being produced by the interior reaction of oxyhydrogen combustion controller 3, there is the heat scission reaction of pyrolysis oil gas product, 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 obtaining
2return in oxyhydrogen combustion controller 3 and recycle, or 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, between each bed and oxyhydrogen combustion controller 3, be provided with valve, and each bed is provided with venting port, and described venting port is all connected with 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 CO infrared radiation detection apparatus.
According to solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process of the present invention, be characterized in utilizing high-temperature vapor that oxyhydrogen combustion the produces energy derive as pyrolysis, thermo-cracking, gasification, wherein, the hydrogen source of oxyhydrogen combustion can be excessive slightly, according to calculation of thermodynamics, if retain some hydrogen in the high-temperature vapor of burning, can play the effect of dephenolize, desulfurization.
According to solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process of the present invention, 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; Mink cell focus can hydrocracking generate the products such as gasoline, diesel oil; Can return to vapourizing furnace gasification gas making taking contracting PAH as main heavy component; The venting port of pyrolysis reactor is all connected with infrared radiation detection apparatus, for detection of the CO concentration of outlet; The high temperature semicoke of discharge after solid fuel pyrolysis completes reacts with the direct generating gasification of oxygen high-temperature vapor of taking passing in vapourizing furnace, capable of reducing energy consumption.
According to solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process of the present invention, in water-gas converter, the CO being generated by gasification reaction, issues raw water gas shift reaction, i.e. CO+H in the water vapour effect passing into
2o=CO
2+ H
2, the generation of this reaction does not consume extra energy substantially; The water vapour of discharging in technological process, can be sent back to oxyhydrogen combustion controller recycling, and react for water-gas converter, to save hydrogen consumption; The high-temperature gas of discharging in technological process, can be used as high-grade waste heat recovery, the waste heat of recovery, and sub-fraction can be used to preheating and enter the solid materials of pyrolysis reactor; After char Gasification and water gas shift reaction, obtain H
2, can be used as Hydrogen Energy for generation technology on the one hand, what one side was a small amount of can be used as hydrogen source of the present invention; The CO simultaneously generating
2can be reused, or 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 to utilize the high-temperature vapor of oxyhydrogen combustion generation that the heat of solid fuel pyrolysis, cracking, gasification is provided; Separate out volatile matter through low temperature pyrogenation, obtain pyrolysis oil gas product and pyrolysis char; Oil gas product is with the hot pyrolysis reactor of directly sending into, and product obtains the higher product of added value such as light olefin (C2-C6), BTX (triphen) through condensation separation, has improved system efficiency simultaneously; The heavy component obtaining returns to vapourizing furnace, or continues hydrocracking; The high temperature semicoke that pyrolysis obtains directly enters vapourizing furnace, has also improved system thermal efficiency; Pyrolysis char and the heavy component product after gasification obtains CO after water-gas transforms
2and H
2, be easy to separate, by CO
2seal minimizing carbon emission up for safekeeping, H
2for generating; Finally realize to solid-fuelled grading extraction clean, comprehensive utilization efficiently.
The invention has the advantages that:
1) compared 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, avoid solid thermal carriers in pyrolytic process to mix with solid-fuelled, and the separation of solid product, can obtain pure semicoke product for gasification, reduce the Operating Complexity of technique;
2) hydrogen source that oxyhydrogen combustion produces in high-temperature vapor can be excessive slightly, according to calculation of thermodynamics, if retain some hydrogen in the high-temperature vapor of burning, can play the effect of dephenolize, desulfurization, simplified follow-up purification process technique;
3), compared with traditional low temperature pyrogenation technique, the present invention extracts the volatile matter obtaining and directly under the effect at high-temperature vapour, carries out thermo-cracking with hot through low temperature pyrogenation, not only simplified technique, and improved system thermal efficiency; Meanwhile, the hot cracked Chemicals that obtain, as, light olefin (C1-C6) and BTX (triphen) they are the product that added value is higher, 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 hydrogen power generation technology, make coal electricity industry obtain further living space and investment field.And technical process of the present invention is the first pyrolysis of coal, the de-CO of gasification
2, Hydrogen Energy, for generating, has advantages of the Coal Transport of saving; And by the CO of discharge
2seal up for safekeeping, utilize hydrogen power generation, there is the advantage of carbon zero release.
Brief description of the drawings
Fig. 1 is the solid-fuelled high-temperature vapor pyrolysis-cracking-gasification installation of the present invention schematic diagram.
Fig. 2 is the solid-fuelled high-temperature vapor pyrolysis-cracking-gasification of the present invention schematic flow sheet.
Accompanying drawing mark
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-gasification installation of the present invention, 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
2in oxyhydrogen combustion controller 3, burning generation high-temperature vapor passes in pyrolysis reactor 2, and the low temperature pyrogenation of coal occurs, and separates out volatile matter, obtains pyrolysis oil gas product, obtains pyrolysis char simultaneously;
The hot pyrolysis reactor 4 that directly enters of described pyrolysis oil gas product, under the high-temperature vapor effect being produced by oxyhydrogen combustion controller 3, there is the heat scission reaction of oil gas product, after separating, obtain light olefin (C2-C6), BTX (triphen) 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 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 obtaining
2return in oxyhydrogen combustion controller 3 and recycle, or 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, between each bed and oxyhydrogen combustion controller 3, be provided with valve, each bed is provided with venting port, and described venting port is all connected with 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 CO infrared radiation detection apparatus.
Solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process of the present invention comprises the following steps:
1), by coal fragmentation, screening, the material obtaining is made briquet, or pulverulent material; After dry, send into feeder;
2) oxygen and excessive hydrogen in right amount or slightly, in oxyhydrogen combustion controller, burning produces high-temperature vapor, using the energy derive as low-temperature pyrolysis of coal and thermo-cracking and gasification;
3), in pyrolysis reactor,, with the high-temperature vapor effect being produced by oxyhydrogen combustion, there is low-temperature pyrolysis of coal in the pulverulent material of sending into by feeder or material pelletizing, separates out volatilizable point, obtains pyrolysis oil gas product, obtains pyrolysis char simultaneously;
4) the hot high-temperature vapour pyrolysis reactor of directly sending into of pyrolysis oil gas product, hot cracked reaction, and after condensation separation, reclaim the high value added product as industrial chemicals such as light olefin (C2-C6) and BTX (triphen); Heavy component can hydrocracking generate the products such as gasoline, diesel oil; Can return to vapourizing furnace gas making taking contracting PAH as main heavy component;
5) venting port of each bed of pyrolysis reactor, is all connected on CO infrared radiation detection apparatus, to detect the CO concentration of outlet; In the time that CO concentration starts to raise, finish in time pyrolysis reactor reaction, therefrom discharge high temperature semicoke; And new material is pushed to pyrolysis reactor; The pyrolysis char of discharging is directly sent into vapourizing furnace;
6), in vapourizing furnace, high temperature semicoke reacts with the generating gasification under the effect of oxygen high-temperature vapour of taking that heavy component produces at oxygen/water steam generator, generates CO, H
2, be admitted to subsequently in water-gas shift reactor; The high temperature furnace slag of simultaneously discharging, this high temperature furnace slag can be used as high-grade waste heat and is recycled;
7), in water-gas shift reactor, under the water vapour effect passing into, there is water gas shift reaction, i.e. CO+H in CO
2o=CO
2+ H
2, obtain CO
2and H
2; After separating, H
2can be used as Hydrogen Energy for generating, a small part can be used as hydrogen source of the present invention; CO after separation
2can be stored in by permanent envelope underground, part also can be utilized.
By the enforcement of this technology, from coal, can obtain oil, gas, heat, electricity, the Technology of producing to realize tetrad completes CO simultaneously
2the requirement reducing discharging.
Embodiment 1:
Raw material: a kind of containing the higher bituminous coal of volatile matter, pelletizing particle diameter is 20-30 millimeter
Feature: simulation moving-bed pyrolysis reactor
Implementation method:
To after coal sample reduction, make the briquet of 20-30 mm in size, after drying treatment, send into feeder.Briquet is sent in the bed of simulation moving-bed pyrolysis reactor (10 beds, each bed is controlled separately); First open lowest layer valve, issuing heat-dissipating solution from oxyhydrogen combustion controller by oxygen and the high-temperature vapor effect that excessive hydrogen burning produces slightly; In 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; In the time that CO concentration starts to raise, close this layer of valve with stopped reaction, avoid the generating gasification reaction under high-temperature vapor effect of semicoke pelletizing; Open the valve of a bed simultaneously, pass into high-temperature vapor and continue pyrolytic reaction, react to control in pyrolyzer by CO infrared radiation detection apparatus equally; Successively carry out pyrolysis, until the complete devolatilization of briquet in pyrolysis reactor; Push in time new material and enter pyrolysis reactor; The volatile matter (650 DEG C) of being discharged by pyrolysis reactor is by the hot pyrolysis reactor (750～850 DEG C) of directly sending into, with the high-temperature vapor effect By Direct Pyrolysis from oxyhydrogen combustion controller, reclaim the high value added product that obtains light olefin (C2-C6) and BTX (triphen) etc. and be used as industrial chemicals through condensation separation; Return to vapourizing furnace gasification taking contracting PAH as main heavy component; The high temperature semicoke of discharging is admitted to vapourizing furnace, reacts that (temperature is 1300 DEG C, and pressure is 3MPa together with heavy component in vapourizing furnace with the oxygen high-temperature vapor generating gasification of taking from oxygen/water steam generator.), generate CO, H
2; The product gas generating continues in water-gas shift reactor, and the water vapour generation water gas shift reaction with passing into, obtains CO
2and H
2; After separating, H
2can be used as Hydrogen Energy for generating, sub-fraction is returned to the hydrogen source that produces high-temperature vapor as oxyhydrogen combustion controller; The CO separating
2can be reused or permanent envelope is stored in underground; The liquid high temperature furnace slag of discharging from vapourizing furnace, utilizes chilling heat transfer technology to recycle, and a part can be used for the material in preheating pyrolysis reactor.
Embodiment 2
Raw material: a kind of containing the higher brown coal of volatile matter, particle diameter is less than 3 millimeters
Feature: fluidized bed pyrolysis reactor
Implementation method:
By below coal sample reduction to 3 millimeter, after drying treatment, send into feeder; Then material is sent in fluidized bed pyrolysis reactor; Issuing heat-dissipating solution from oxyhydrogen combustion controller by oxygen and the high-temperature vapor effect that excessive hydrogen burning produces slightly; 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 high-temperature vapor effect.The hot pyrolysis reactor of directly sending into of volatile matter of being discharged by pyrolyzer, the high-temperature vapor effect generation cracking with from oxyhydrogen combustion controller, obtains light olefin and BTX product; Return to vapourizing furnace gasification gas making taking contracting PAH as main heavy component; The high temperature semicoke of discharging, after intermediate bunker pressurization, is directly sent into vapourizing furnace; In vapourizing furnace, semicoke reacts generation CO, H with the oxygen high-temperature vapor generating gasification of taking from oxygen/water steam generator together with heavy component
2; The product gas generating continues in water-gas shift reactor, and the water vapour generation water gas shift reaction with passing into, obtains CO
2and H
2; Through separating, H
2can be used as Hydrogen Energy for generating, a part is returned to the hydrogen source that generates high-temperature vapor as oxyhydrogen combustion controller; CO after separation
2sealed up for safekeeping or recycled; The liquid high temperature furnace slag of discharging from vapourizing furnace, utilizes chilling heat transfer technology to recycle; A part is used for the material in preheating pyrolyzer.
Embodiment 3
Raw material: a kind of containing the higher bituminous coal of volatile matter, pelletizing particle diameter is 20～30 millimeters
Feature: fixed-bed pyrolysis reactor
Implementation method:
To after coal sample reduction, make the briquet of 20 mm in sizes, after drying treatment, send into feeder; Then briquet is sent into (parallel two pyrolysis reactors, are used alternatingly) in fixed-bed pyrolysis reactor; With issue heat-dissipating solution from oxyhydrogen combustion controller by oxygen and the high-temperature vapor effect that excessive hydrogen produces by burning slightly; In reaction process, by being connected to the infrared radiation detection apparatus of pyrolyzer venting port, detect the CO concentration of outlet; In the time that CO concentration starts to raise, stop reacting in this pyrolyzer, to avoid semicoke to react with high-temperature vapor generating gasification; Conversion valve makes high-temperature vapor pass through another pyrolysis reactor, and new material is carried out to pyrolysis; Meanwhile, last pyrolyzer is discharged 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 oxyhydrogen combustion controller, obtains light olefin and BTX; Return to vapourizing furnace gasification gas making taking contracting PAH as main heavy component; The high temperature semicoke of discharging is directly sent into vapourizing furnace, and in vapourizing furnace, semicoke reacts generation CO, H with the oxygen high-temperature vapor generating gasification of taking from oxygen/water steam generator together with heavy component
2; The gaseous product generating continues in water-gas shift reactor, obtains CO with the water vapour generation water gas shift reaction passing into
2and H
2; Through separating, H
2as Hydrogen Energy, for generating, a part is returned to the hydrogen source that produces high-temperature vapor as oxyhydrogen combustion controller; CO after separation
2sealed up for safekeeping or recycled; The liquid high temperature furnace slag that vapourizing furnace is discharged, utilizes chilling heat transfer technology to recycle; A part is used for the material in preheating pyrolyzer.
Embodiment 4
Raw material: a kind of containing the higher resinous shale of volatile matter, pelletizing particle diameter is 20～30 millimeters
Feature: simulation moving-bed pyrolysis reactor
Implementation method:
By making the pelletizing of 20 mm in sizes after the fragmentation of resinous shale sample, after drying treatment, send into feeder.Then resinous shale pelletizing is sent in the bed of simulation moving-bed pyrolysis reactor (10 beds, each bed is controlled separately); First open lowest layer valve, issuing heat-dissipating solution from oxyhydrogen combustion controller by oxygen and the high-temperature vapor effect that excessive hydrogen burning produces slightly; In reaction process, by being connected to the infrared radiation detection apparatus of pyrolyzer venting port, detect in real time the CO concentration of outlet; In the time that CO concentration starts to raise, close this layer of valve to stop pyrolytic reaction, avoid pelletizing generating gasification reaction under high-temperature vapor effect; Open a bed valve simultaneously, pass into high-temperature vapor and continue pyrolytic reaction, pass through CO infrared radiation detection apparatus to control the reaction in pyrolyzer with method; Successively carry out pyrolysis, until the complete devolatilization of resinous shale pelletizing in pyrolysis reactor pushes away in time new material and enters pyrolysis reactor.The hot volatile matter of being discharged by pyrolysis reactor is directly sent into pyrolysis reactor, with the high-temperature vapor effect By Direct Pyrolysis from oxyhydrogen combustion controller, reclaims and obtains the product such as light olefin and BTX; Return to vapourizing furnace gas making taking contracting PAH as main heavy component; The high temperature semicoke of discharging is admitted to vapourizing furnace, and in vapourizing furnace, semicoke reacts generation CO, H with the oxygen high-temperature vapor generating gasification of taking from oxygen/water steam generator together with heavy component
2; The product gas generating continues in water-gas shift reactor, and the water vapour generation water gas shift reaction with passing into, obtains CO
2and H
2; After separating, H
2as Hydrogen Energy, for generating, sub-fraction is returned to the hydrogen source that produces high-temperature vapor as oxyhydrogen combustion controller; The C0 separating
2can be reused or permanent envelope is stored in underground; The liquid high temperature furnace slag of discharging from vapourizing furnace, utilizes chilling heat transfer technology to recycle; A part is as the material in thermal source preheating pyrolyzer.
In addition, adopt the method for method of the present invention and prior art to process feed coal, the output value specifically obtaining 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 tons/year, 7000kcal/ kilogram of (volatile matter 25% of standard thermal value of coal, fixed carbon 60%) in the volatile matter that extracts containing methane 10%, light olefin 15%, BTX15% (8500 yuan/ton), electric explant price is 0.15 yuan/degree:
1, in the gas phase of extracting, contain 10% methane (methane enters gas distributing system, 3000 yuan): 1000 × 25% × 10% × 3000 (ten thousand yuan/year)=7.5 hundred million yuan/year;
2, in tar, change light olefin 15% and BTX15% (8500 yuan/ton) into: 1000 × 25% × 30% × 8500 (ten thousand yuan/year)=63.75 hundred million yuan/year
3, fixed carbon semicoke 60%, the heavy component that returns to vapourizing furnace accounts for 50% of tar, after gasification, utilize improved IGCC generating, 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
(electricity)=11,500,000,000 yuan/year, total annual value of production=7.5 (Sweet natural gas)+63.75 (light olefin and BTX)+43.86
If when 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 be all 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 the output value is: hundred million yuan/year of 1,000 ten thousand tons × 1000 kgs/tonne × 7000kcal/kg × 44.2%/859.8 × 0.15=54.0 (can avoid carbon tax problem).
3, directly adopt ultra supercritical power generation, the benefit of acquisition:
Conversion efficiency of thermoelectric 40%, the output value is: hundred million yuan/year of 1,000 ten thousand tons × 1000 kgs/tonne × 7000kcal/kg × 40%/859.8 × 0.15=48.8; If when conversion efficiency of thermoelectric is 45%, annual value of production is 55.0 hundred million yuan/year (after for some time, may need to pay carbon tax).
Can see by data above, by method of the present invention, solid fuel be carried out to comprehensive disposal and utilization, utilize the high-temperature vapor that oxyhydrogen combustion produces to provide heat for solid fuel pyrolysis, cracking, gasification; Separate out volatile matter through low temperature pyrogenation, obtain pyrolysis oil gas product and pyrolysis char; Oil gas product is with the hot pyrolysis reactor of directly sending into, and product obtains the higher product of added value such as light olefin (C2-C6), BTX (triphen, i.e. benzene, toluene and dimethylbenzene) through condensation separation, has improved system efficiency simultaneously; The heavy component obtaining returns to vapourizing furnace, or continues hydrocracking; The high temperature semicoke that pyrolysis obtains directly enters vapourizing furnace, has also improved system thermal efficiency; Pyrolysis char and the heavy component product after gasification obtains CO after water-gas transforms
2and H
2, be easy to separate, by CO
2seal minimizing carbon emission up for safekeeping, H
2for generating.By method and apparatus of the present invention, finally realize solid-fuelled grading extraction, clean, comprehensive utilization efficiently, obtains considerable economic benefit.
Finally it should be noted that above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although the present invention is had been described in detail with reference to embodiment, those of ordinary skill in the art is to be understood that, technical scheme of the present invention is modified or is equal to replacement, do not depart from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (7)
1. solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process, is characterized in that, said method comprising the steps of:
1) by O
2and H
2the high-temperature vapor that burning produces passes in solid fuel, and solid-fuelled low temperature pyrogenation occurs, and separates out volatile matter, obtains pyrolysis oil gas product, obtains pyrolysis char simultaneously;
2) step 1) the oil gas product that obtains carries out heat scission reaction under the high-temperature vapor effect passing into, and after separating, obtains lighter products and heavy component;
3) step 1) pyrolysis char and the step 2 that obtain) in the heavy component that obtains gasify taking under the effect of oxygen high-temperature vapor of passing into, obtain water-gas, discharge slag simultaneously;
4) by step 3) water-gas obtaining reacts with the water vapour passing into, and obtains CO
2and H
2, through separating, the CO obtaining
2seal the H obtaining up for safekeeping
2for generating or turn back to step 1) prepare high-temperature vapor;
Described step 1) middle O
2and H
2the high-temperature vapor temperature that burning generates is 1000～2000 DEG C;
Described step 1) in the low temperature pyrogenation of the coal temperature of separating out volatile matter be 500～900 DEG C;
Described step 2) in the temperature of heat scission reaction be 600～900 DEG C;
Described step 3) in gasification temperature higher than 1000 DEG C.
2. solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process according to claim 1, is characterized in that, by described step 2) in the heavy component that obtains for hydrocracking.
3. solid-fuelled high-temperature vapor pyrolysis-cracking-gasification process according to claim 1, is characterized in that described step 1) in solid fuel be containing high bituminous coal, brown coal, oil-sand, biomass or the resinous shale of volatile matter.
4. 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. a 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), passed in pyrolysis reactor (4) by the high-temperature vapor that in oxyhydrogen combustion controller (3), reaction produces, there is the heat scission reaction of pyrolysis oil gas product, and obtain lighter products and heavy component after condensation separator (8);
Described semicoke and heavy component enter vapourizing furnace (6), and the oxygen water vapour of taking being 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 water-gas shift reactor (7) and react with water vapour, obtain CO
2and H
2, the H obtaining
2turn back in oxyhydrogen combustion controller (3) and recycle, or be directly used in generating.
6. solid-fuelled high-temperature vapor pyrolysis-cracking-gasification installation according to claim 5, 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, between each bed and oxyhydrogen combustion controller (3), are provided with valve; Each bed is provided with venting port, and described venting port is all connected with CO infrared radiation detection apparatus.
7. solid-fuelled high-temperature vapor pyrolysis-cracking-gasification installation according to claim 5, 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 CO infrared radiation detection apparatus.
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| CN105586067B (en) * | 2014-10-21 | 2018-04-24 | 中国科学院过程工程研究所 | Oxyhydrogen combustion method directly heats the device and method of oil pyrolysis hydrocarbon |
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