CN102786994A - Method for preparing methane-rich gas through autocatalytic gasification of biomass - Google Patents
Method for preparing methane-rich gas through autocatalytic gasification of biomass Download PDFInfo
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Abstract
The invention aims to provide a method for preparing methane-rich gas through cyclic utilization of alkali/alkaline earth metals contained in biomass for autocatalytic pyrolysis and autocatalytic pressurized gasification of the biomass. According to the method, water quenching is carried out on biomass ash so as to cyclically extract alkali/alkaline earth metals in the biomass ash, and the alkali/alkaline earth metals are sprinkled on and dipped in biomass; the biomass containing the alkali/alkaline earth metals undergoes autocatalytic pyrolysis at a low temperature of 280 to 320 DEG C at first, then a pyrolysis gas product enters into a combustion reactor and burns together with solid particles separated from a gasification reactor so as to supply heat for the process of pyrolysis, a pyrolysis solid product enters into the gasification reactor and undergoes autocatalytic pressurized gasification in a steam/oxygen atmosphere, hydrogen-rich gas is separated from crude synthetic gas produced in gasification and is returned to the pressurized gasification reactor, and the pyrolysis solid product is subjected to hydrogasification at the same time. With the method provide by the invention, biomass can be used for preparing methane-rich gas with low tar content, and high gasification efficiency is obtained. The method has the advantages of simple operation, less water consumption, strong technological adaptability and easy operation.
Description
Technical field
The present invention relates to biomass energy Transformation Application technical field, relate in particular to the contained alkali/alkaline earth metal of a kind of biomass recycle self and carry out the method that autocatalysis pyrolysis and autocatalysis pressurized gasification prepare methane-rich gas.
Technical background
China has the huge agricultural-forestry biomass resource of reserves, utilizes the gasifying biomass synthol to substitute exhausted day by day fossil oil and has extensive market prospects.The utilization of biomass energy mainly is divided into direct utilization and (conversion) utilization indirectly, and the trans-utilization of biomass energy comprises that mainly thermochemistry transforms and the biochemical conversion utilization.In general, the time that the thermochemistry conversion process needs is short, efficient is high, mainly comprises direct burning, pyrolysis and gasification etc.Gasifying biomass is the transformation technology of a high-efficiency cleaning, and making the conversion of biomass obtain staple by means of the effect of vaporized chemical is CO, H
2, CO
2And CH
4Gas, gasification technology and subsequent technique coupling can be used for generating, heat supply, cogeneration or synthesis of chemicals.Gasifying biomass can with bulky, energy density is low, biomass material nonflammable or that efficiency of combustion is low be converted into energy density higher, be suitable for the geseous fuel that stores, transport and use; Improve energy utilization quality and utilising efficiency greatly, widened the scope of utilizing of biomass energy simultaneously.
Influence because of factors such as biomass self structure characteristic and operating procedure parameters unavoidably can produce a large amount of tar in biomass gasification process, can cause problems such as obstruction, fouling in the subsequent technique.Tar can be removed through quadratic method, and like physics method, high-temperature cracking method and catalystic pyrolysis, but the subsequent disposal technology all can increase running cost or increase the complex equipments degree.If can in gasification, reduce the output of tar; Make it be converted into the combustible gas physical efficiency and improve gasifying biomass efficient greatly; A lot of now researchs are devoted to Biomass Catalytic Gasification to reduce the output of tar; As adopt rhombspar, Wingdale, and nickel-base catalyst etc. join in the gasifying reactor as the bed material, but have the easy inactivation of catalyzer and reclaim the phenomenon of difficulty.
The synthetic gas that gasifying biomass produces is formed the influence that receives reactor drum, gasifying medium, operating parameters etc.Gasifying biomass obtains that methane content need be with H generally all below 10% in the synthetic gas
2It is synthetic to carry out methanation reaction after being adjusted into 3 with the CO mol ratio, and intermediate demand carries out complicated purification and adjustment process.Simultaneously methanation reaction is strong exothermic process, and the thermotolerance and the reactor drum heat exchange of catalyzer required than higher, and catalyzer is easily because of multiple factor inactivations such as poisoning, carbon distribution, sintering in the methanation.Gasify in the process of synthesizing methane whole, the complex process running cost is high, and energy efficiency is lower.If can in gasification, improve the output of methane can reduce in the subsequent technique in purification, adjustment and the building-up process to the pressure of catalyzer and reactor drum, more help improving efficiency of energy utilization.
Principal elements such as abundant nitrogen, phosphorus, potassium are arranged in the biomass, and inorganic elements can be enriched in the bottom ash usually behind the gasifying biomass, and also some gets in the flying dust, and the composition of ash comprises CaO, K
2O, P
2O
5, MgO, SiO
2, Na
2O, SO
3And a small amount of residue carbon, wherein the CaO massfraction be about 5～50%, K
2O content is 0.5～30%, MgO content is between 1～20%, Na
2O content is 0.2～5%, and these alkali/alkaline earth metals have advantages of high catalytic activity, and especially the katalysis of potassium in biomass pyrogenation gasification is not studied person's broad research and checking.Adopt the alkali/alkaline earth metal that biomass are contained self to do the generation that catalyzer can promote solid Jiao in the pyrolytic process, accelerate gasification reaction speed, reduce the coal-tar middle oil generation of gasification.Alkali/alkaline earth metal can promote the generation of micro-molecular gas in the biomass gasification process simultaneously, promotes H in the crude synthesis gas
2Increase and the reduction of CO content of content, improve H
2With the CO mol ratio, alleviated the pressure of gas ratio adjustment unit in the follow-up synthesizing methane technology.
Utilize catalytic gasification to reduce tar output and the more existing correlative studys of segmentation pyrolysis of gasified bio-matter at present.Patent CN101781579A discloses a kind of biomass gasification method and biomass gasifying furnace; Get into the vapourizing furnace gasification after sneaking into rhombspar and sea salt in the biomass material; Gasifying gas gets into combustion chamber second pyrolysis under rhombspar and sea salt effect; This process has reduced tar output, has improved the quality of combustible gas.Patent CN1608972A discloses a kind of biomass-gasifying hydrogen generating serial fluid bed apparatus and method; Adopt quicklime/magnesium oxide particle to make the bed material; Biomass are carried out the water vapour catalytic pyrolysis gasification; Quicklime/Natural manganese dioxide is converted into to get into behind the carbonate and returns gasifier bed after the burning bed calcining and recycle, and helps improving the productive rate of hydrogen.Patent CN101805638A discloses a kind of biomass gasification method; Dry thermal cracking, burning reduction, gas reforming are separately also carried out in same vapourizing furnace relatively continuously; The pyrolysis gaseous product is used for reforming, and pyrolysis Jiao is used for combustion heat supplying, finally can obtain clean high-quality gas.Patent ZL03133799.6 discloses the method that a kind of solid thermal carriers catalytic gasification biomass are produced hydrogen-rich gas, and catalytic gasification after biomass and the solid thermal carriers catalyst mix, catalyzer do not have the regeneration of switching continuously, and the gas tar content is few, and aerogenesis purity is high.Patent ZL200510043836.0 discloses a kind of low-tar biomass gasifying method and device, and biomass all get in the pyrolysis gasification reactor drum at 400～650 ℃ pyrolysis product incomplete oxidation takes place, and it is low to obtain the coal-tar middle oil content of gas.
Prepare focusing mostly on of methane about biomass aspect humidogene fermentation of materials or the supercritical water gasification.Patent CN101880558A discloses a kind of carbonaceous material and has come the method for production substitute natural gas through the methanation of synthetic gas, comprising purification, the H of synthetic gas
2With adjustment of CO ratio and methanation.Patent CN101851537A discloses a kind of method and apparatus for preparing synthetic natural gas.Patent CN201010634Y discloses a kind of biogas methanation catalytic unit.
Above-mentioned patent does not all relate to utilizes the contained alkali/alkaline earth metal catalyse pyrolysis of biomass self, catalytic gasification; The crude synthesis gas that reaching gasifies produces is isolated hydrogen-rich gas and is turned back in the gasifying reactor, makes the pyrolysis solid that the method that hydrogasification prepares methane-rich gas take place simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of biomass autocatalysis gasification to prepare the method for methane-rich gas.
The present invention extracts the alkali/alkaline earth metal in the lime-ash through the cindery mode of the cold biomass of shrend; And sprinkle impregnated in biomass; Contain the biomass autocatalysis pyrolysis under 280 ℃～320 ℃ low temperature earlier of alkali/alkaline earth metal; The pyrolysis gas product burns in combustion reactor and for pyrolytic process heat supply, pyrolysis solid product get into the autocatalysis pressurized gasification takes place in water vapour/oxygen atmosphere in the gasifying reactor; The isolated hydrogen-rich gas of crude synthesis gas that gasification produces turns back in the gasifying reactor, makes the pyrolysis solid that the method for hydrogasification take place simultaneously.Utilize these method biomass can be through preparing the methane-rich gas of low tar content from heat supply, autocatalysis, gasification efficiency be high, helps in the subsequent technique further synthetic natural gas.
For achieving the above object, the present invention has taked following technical scheme:
The inventive method may further comprise the steps:
(1) biomass are carried out the sprinkle immersion with the quenching liquid of gasification bottom ash and combustion ashes earlier, carry out drying then.
(2) dried biomass get into low-temperature catalysis thermal decomposition in the pyrolysis installation, adopt the flue gas indirect heating, obtain pyrolysis Jiao and pyrolysis gas, and the outlet flue gas is handled the back emptying through flue gas purification system;
(3) pyrolysis Jiao who biomass in the step (2) is produced in pyrolysis reactor sends into and in water vapour/oxygen atmosphere, carries out the pressurized catalysis gasification in the gasifying reactor; The gasification bottom ash is arranged in ash bucket; Obtain crude synthesis gas behind the exit gas separate solid particles thing, solid particulate matter gets into combustion reactor;
(4) crude synthesis gas that step (3) is obtained gets into gas separation unit, obtains methane-rich gas after the gas delivery, and part is rich in H
2Separated gas send into again in the step (3) in the pressure gasification reactor;
(5) pyrolysis gas that biomass in the step (2) is produced in pyrolysis reactor is sent into combustion reactor, obtains combustion ashes with the common burning of isolated solid particulate matter in the step (3), and the flue gas that burning produces is used for the biomass pyrolytic of step (2);
Combustion ashes in the gasification bottom ash of step (3) and the step (5) is discharged back water quenching, obtains quenching liquid after water separates admittedly, is used for step (1) sprinkle and soaks biomass.
The biomass source is an agriculture and forestry organic waste material in the step (1); Comprise agricultural crop straw; Farm crop shell, broken bamboo chip, wood powder etc.; Quenching liquid with gasification bottom ash and combustion ashes carries out the sprinkle immersion earlier, and biomass and quenching liquid mass ratio are controlled between 1:0.5～1:1, and the total mass mark of quenching potassium, sodium, calcium and magnesium in night is between 1%～10%; Dried biomass water cut is about 5～20%, and the mode biomass water ratio that adopts natural air drying is between 15%～20%, and the total mass mark of potassium, sodium, calcium and magnesium elements is between 1%～5%.Under this condition, contain metals ions such as abundant potassium, sodium, calcium in the quenching liquid, can be adsorbed in the biological particles through dipping and exsiccant mode, few with hourly water consumption, biomass are easy to drying.
In the step (2) biomass after air-dry are carried out pyrolysis in pyrolysis reactor, adopt 400 ℃～500 ℃ flue gas indirect heating, pyrolysis time is 10～40min, and the medial temperature in the pyrolysis reactor is 280 ℃～320 ℃.Most of semicellulose generation pyrolysis under this condition in the biomass; Mierocrystalline cellulose and xylogen are retained in the solid product basically; The existence of alkali/alkaline earth metal simultaneously can promote pyrolysis product further to be cracked into micro-molecular gas, promote the generation that solid is burnt; Biomass pyrolytic Jiao accounts for 55～70% of biomass quality, and pyrolysis gas accounts for 35～45% of biomass quality.Behind the smoke pre-heating air after the heat supply, the gas cleaning treatment process through a series of prior aries can reach standard limit of smog release.
Pyrolysis reactor is a prior art in the step (2); Medial temperature is about 280 ℃～320 ℃ in the pyrolysis reactor; The alkali/alkaline earth metal major part of under this temperature, flooding in the biomass is trapped in the solid product; The pyrolysis solid product gets into gasifying reactor and the reaction of water vapour generating gasification, and the pyrolysis gas product gets into combustion reactor and air combustion is the pyrolysis reactor heat supply.
Pyrolysis solid product in the said step (3) gets in the pressure gasification reactor; This gasifying reactor is a prior art; Generating gasification reaction in water vapour/oxygen atmosphere under the certain pressure effect, simultaneously with from gas separation unit, separate the hydrogen-rich gas generation hydrogasification of returning.The water vapour inlet temperature is 250 ℃～300 ℃, and pyrolysis mass ratio burnt and water vapour is between 0.3～2:1, and the oxygen excess coefficient is between 0.2～0.4, and reactor pressure is between 1～6MPa.Biomass pyrolytic Jiao is 5～30s the residence time in gasifying reactor, and temperature of reaction is between 700～850 ℃, and Outlet Gas Temperature adds hot water in the gas entering heat exchanger after going out and prepares water vapour between 600～650 ℃, and the gasification lime-ash enters in the ash bucket.Under this condition, biomass pyrolytic Jiao reacts with the water vapour generating gasification under the katalysis of alkali/alkaline earth metal, and alkali/alkaline earth metal can be accelerated the speed of reaction of biomass pyrolytic Jiao and water vapour, promotes the further cracking of macromole intermediate product, is converted into and is rich in H
2Reach a small amount of CO, CO
2, CH
4Middle calorific value gas.The gas that from gas separation unit, returns simultaneously is rich in H
2, H
2Content reaches more than 70%, and temperature is lower in the gasifying reactor, biomass pyrolytic Jiao and H under pressurized conditions
2Hydrogasification takes place simultaneously generate a large amount of CH
4, in the gasifying reactor exit end crude synthesis gas methane content more than 20%, H
2Content reaches more than 50%, CO and CO
2Content is lower.The solid particulate matter that the gasifying reactor exit end is taken out of by gas in this process gets into combustion reactor through cyclonic separator, and the quality of this solid particulate matter accounts for 5～15% of the burnt quality of import biomass pyrolytic.
Crude synthesis gas is at first removed CO in the step (4) in gas separation unit
2Gas is through selecting technology such as absorption method or membrane separation process with CH
4Separate with other gases, make the CH more than 80% in the crude synthesis gas
4Get in the final gaseous product, finally can obtain CH
4Content is at the methane-rich gas more than 40%.Isolated mixed gas staple is CO and H
2, about 40～60% get in the gasifying reactor again, and rest part stores for future use.
In the step (5); The solid particulate matter that pyrolysis gas product that is obtained by step (2) and step (3) cyclonic separation obtain gets in the combustion reactor; Under 600～800 ℃ of temperature, burn; The oxygen excess coefficient is between 1.1～1.4, and the flue gas that burning produces is used for the biomass pyrolytic heat supply of step (2).Under this condition, produce a spot of lime-ash.
In the step (6) in the bottom ash carbon content be lower than 3%, be rich in elements such as potassium, sodium, calcium and magnesium, its total mass mark is more than 10%, water miscible CaO, K during the water quenching
2O, MgO, Na
2O gets in the quenching liquid, makes quenching liquid be rich in Ca
2+, K
+, Mg
2+, Na
+Plasma.But liquid also can be made material of construction with the lime-ash sanitary landfill that obtains after lime-ash separates, and quenching liquid is used for step (1) and soaks biomass.Under this condition, lime-ash accounts for primordial matter quality 5～20%, and water loss is few.This technical process operation starting stage, alkali/alkaline earth metal enrichment circulation yield is few in the biomass, behind the quenching in the quenching liquid alkali/alkaline earth metal content lower, can in quenching liquid, suitably add K
2CO
3Improve its concentration, the total mass mark that makes quenching potassium, sodium, calcium and magnesium in night is between 1%～5%.
Compared with prior art, the present invention has following beneficial effect:
1. the present invention carries out low temperature pyrogenation earlier with biomass, with pyrolysis gas be used for the burning, the pyrolysis solid be used for the gasification, reduced the generation of tar dramatically.
2. the present invention takes the contained abundant alkali/alkaline earth metal of biomass recycle self, carries out catalyse pyrolysis and water vapour/oxygen gasified, reduces tar yield respectively two stages, accelerates gasification reaction speed, promotes micro-molecular gas to generate;
3. the present invention takes to isolate from the biomass raw synthetic gas and is rich in H
2Gas return in the gasifying reactor, make the biomass pyrolytic solid product that hydrogasification take place under pressurized conditions, help synthetic CH
4, finally improve the content of methane in the gas separation unit exit end gaseous product;
4. the present invention adopts the method for combustion reactor to the gasifying reactor indirect heating, can directly carry out air combustion, does not exist the cost that causes because of gas delivery to increase, and gaseous product is not by flue gas dilution simultaneously, and calorific value is higher;
5. the present invention adopts cold circulation extraction alkali/alkaline earth metal of shrend and sprinkle to get into the method for biomass again, and water loss is few, and is with low cost, simple to operate.
6. this invented technology flexibility is stronger, easy handling.
Description of drawings
Fig. 1 is a techniqueflow chart of the present invention.
Embodiment
Below further specify the present invention through embodiment.
Embodiment 1:
This instance utilizes a kind of biomass autocatalysis gasification to prepare the method for methane-rich gas, and its techniqueflow synoptic diagram is seen Fig. 1, and its process may further comprise the steps:
(1) being 1.6% pine powder with ash oontent carries out the sprinkle immersion with the quenching liquid of gasification bottom ash and combustion ashes, places outdoor natural air drying then.
(2) biomass after air-dry join carries out catalyse pyrolysis under 320 ℃ in the spiral pyrolysis installation, adopt the flue gas indirect heating, handles the back emptying through flue gas purification system behind the outlet smoke pre-heating air;
(3) pyrolysis Jiao who biomass in the step (2) is produced in spiral pyrolysis reactor sends into and carries out pressurized water steam/oxygen catalytic gasification in the fluidized bed gasification reactor; About 790 ℃ of temperature of reaction; The gasification bottom ash is arranged in ash bucket; Exit gas separates post-heating water through cyclonic separator and prepares water vapour, and obtains crude synthesis gas, gets into the combustion reactor burning from the isolated solid particulate matter of cyclonic separator;
(4) with carrying out CH behind the recovery of the crude synthesis gas in the step (3) heat
4Carry out gas delivery and obtain methane-rich gas, isolate the H that is rich in of gas
2, 40% separated gas gets in the gasifying reactor again;
(5) pyrolysis gas that biomass in the step (2) is produced in pyrolysis reactor is sent into combustion reactor, and with isolated solid particulate matter mixed firing in the step (3), the flue gas of generation is used for the biomass pyrolytic of step (2);
(6) bottom ash in step (3) and the step (5) is discharged back water quenching, and the quenching liquid that water obtains after separating admittedly is used for step (1) sprinkle and soaks biomass.
Pine powder carries out the sprinkle immersion with the quenching liquid of gasification bottom ash and combustion ashes earlier in the step (1), and biomass and quenching liquid mass ratio are controlled to be 1:1, and the total mass mark of potassium, sodium, calcium and magnesium is 2.5% in the quenching liquid.Place outdoor natural air drying then, air-dry artifact matter water ratio is 19.8%, and the potassium in the biomass, sodium, calcium and magnesium elements total content are 1.91%.
With pine powder pyrolysis in the spiral pyrolysis installation, adopt 450 ℃ flue gas indirect heating in the step (2), pyrolysis time is 40min, and medial temperature is 320 ℃ in the helical reactors, and producing the solid product quality is 57.6%, and pyrolysis gas accounts for 42.4% of biomass quality.Flue gas after the heat supply is through qualified discharge after the gas cleaning treatment process of a series of prior aries.
Pine pyrolysis Jiao in the said step (3) in gasifying reactor with water vapour/oxygen pressurized gasification; The water vapour inlet temperature is 260 ℃; The burnt ratio with water vapour of pine pyrolysis is 0.3, oxygen excess coefficient 0.25, and temperature of reaction is 800 ℃; Reaction pressure is 5MPa, from gas separation unit, returns H in the gas
2Volume content is 77.86%, the burnt about 20s of the residence time of pine pyrolysis, and Outlet Gas Temperature is 650 ℃, adds hot water in the gas entering heat exchanger after going out and prepares water vapour, the gasification lime-ash enters in the ash bucket, accounts for 6.2% of primordial matter quality.Gasifying reactor exit end gas CH
4Content is about 31.34%.
The crude synthesis gas that will gasify in the step (4) all feeds gas separation unit, adopts membrane separation technique to CH
4Separate, obtain that methane content is 46.47% in the methane-rich gas.Separated gas is rich in hydrogen, and 40% gets in the gasifying reactor again, and all the other store for future use.
The solid particulate matter of pyrolysis gas product and cyclonic separation burns in combustion reactor in the step (5), about 780 ℃ of temperature, and the oxygen excess coefficient is 1.5, and the flue gas that burning produces is used for the biomass pyrolytic of step (2).
Bottom ash water quenching in the step (6), potassium, sodium, calcium and magnesium elements total content are 3.32% in the quenching liquid through detecting.
Embodiment 2:
Being 10.10% straw powder with ash oontent carries out the sprinkle immersion with the quenching liquid of gasification bottom ash and combustion ashes, and biomass and quenching liquid mass ratio are controlled to be 1:0.8, and potassium, sodium, calcium and magnesium elements total content are 3.5% in the quenching liquid.Dry then to water ratio be 5.2%.With the pyrolysis in the spiral pyrolysis installation of straw powder, adopt 410 ℃ flue gas indirect heating, pyrolysis time is 15min, and medial temperature is about 290 ℃ in the helical reactors, and producing the solid product quality is 65.7%, and pyrolysis gas accounts for 34.3% of biomass quality.Straw Jiao in gasifying reactor with steam gasification, the water vapour inlet temperature is 280 ℃, the burnt ratio with water vapour of pyrolysis is 0.8; The oxygen excess coefficient is 0.35; Temperature of reaction is 725 ℃, and reaction pressure is 1.2MPa, from gas separation unit, returns H in the gas
2Volume content is 70.45%, and residence time 30s, Outlet Gas Temperature are 623 ℃, and the gasification lime-ash enters in the ash bucket, accounts for 14.36% of primordial matter quality, CH in the gasification crude synthesis gas body
4Volume content is 26.87%, through behind the membrane sepn, obtains that methane content is 42.09% in the methane-rich gas, has 60% to send in the pressure gasification reactor in the separated gas.About 650 ℃ of the solid particulate matter of pyrolysis gas product and cyclonic separation temperature of combustion in combustion reactor, oxygen excess coefficient are 1.3, and the flue gas that burning produces is used for aforementioned biomass pyrolytic.Gasification and burning bottom ash water quenching, potassium, sodium, calcium and magnesium elements total content are 4.78% in the quenching liquid through detecting.
Embodiment 3:
Being 16.32% rice straw powder with ash oontent carries out the sprinkle immersion with the quenching liquid of gasification bottom ash and combustion ashes, and biomass and quenching liquid mass ratio are controlled to be 1:0.5, dry then to water ratio be 10.7%, potassium, sodium, calcium and magnesium elements total content are 4.8%.With rice straw pyrolysis in the spiral pyrolysis installation, adopt 430 ℃ flue gas indirect heating, pyrolysis time is 10min, and medial temperature is about 300 ℃ in the helical reactors, and producing the solid product quality is 69.2%, and pyrolysis gas accounts for 30.8% of biomass quality.Rice Stalk Pyrolysis Jiao in gasifying reactor with water vapour/oxygen pressurized gasification, the water vapour inlet temperature is 300 ℃, the burnt mass ratio with water vapour of Rice Stalk Pyrolysis is 0.5; The oxygen excess coefficient is 0.2; Temperature of reaction is 760 ℃, and reaction pressure is 3MPa, from gas separation unit, returns H in the gas
2Volume content is 75.40%, residence time 20s, and Outlet Gas Temperature is 650 ℃, adds hot water in the gas entering heat exchanger after going out and prepares water vapour, the gasification lime-ash enters in the ash bucket, accounts for 19.47% of primordial matter quality.CH in the gasification crude synthesis gas body
4Volume content is 26.66%, through behind the membrane sepn, obtains that methane content is 55.78% in the methane-rich gas, and 50% sends in the gasifying reactor in the gas that is separated.The solid particulate matter of pyrolysis gas product and cyclonic separation burns in combustion reactor, and temperature is about 720 ℃, and the oxygen excess coefficient is 1.2, and the flue gas that burning produces is used for aforementioned biomass pyrolytic.Gasification and burning bottom ash water quenching, potassium, sodium, calcium and magnesium elements total content are 5.97% in the quenching liquid through detecting
Above-mentioned detailed description is to the specifying of possible embodiments of the present invention, and this embodiment is not in order to limiting claim of the present invention, does not allly break away from equivalence of the present invention and implements or change, all should be contained in the claim of the present invention.
Claims (10)
1. biomass autocatalysis gasification prepares the method for methane-rich gas, it is characterized in that may further comprise the steps:
(1) biomass are carried out the sprinkle immersion with the quenching liquid of gasification bottom ash and combustion ashes earlier, carry out drying then.
(2) dried biomass get into low-temperature catalysis thermal decomposition in the pyrolysis installation, adopt the flue gas indirect heating, obtain pyrolysis Jiao and pyrolysis gas, and the outlet flue gas is handled the back emptying through flue gas purification system;
(3) pyrolysis Jiao who biomass in the step (2) is produced in pyrolysis reactor sends into and in water vapour/oxygen atmosphere, carries out the pressurized catalysis gasification in the gasifying reactor; The gasification bottom ash is arranged in ash bucket; Obtain crude synthesis gas behind the exit gas separate solid particles thing, solid particulate matter gets into combustion reactor;
(4) crude synthesis gas that step (3) is obtained gets into gas separation unit, obtains methane-rich gas after the gas delivery, and part is rich in H
2Separated gas send into again in the step (3) in the pressure gasification reactor;
(5) pyrolysis gas that biomass in the step (2) is produced in pyrolysis reactor is sent into combustion reactor, obtains combustion ashes with the common burning of isolated solid particulate matter in the step (3), and the flue gas that burning produces is used for the biomass pyrolytic of step (2);
(6) combustion ashes in the gasification bottom ash of step (3) and the step (5) is discharged back water quenching, obtains quenching liquid after water separates admittedly, is used for step (1) sprinkle and soaks biomass.
2. biomass autocatalysis gasification according to claim 1 prepares the method for methane-rich gas; It is characterized in that: biomass and quenching liquid mass ratio are controlled between 1:0.5～1:1 in the described step (1), and the total mass mark of quenching potassium, sodium, calcium and magnesium in night is between 1%～5%.
3. biomass autocatalysis gasification according to claim 1 and 2 prepares the method for methane-rich gas; It is characterized in that: dry artifact matter water ratio is between 5%～20% in the described step (1), and the total mass mark of potassium, sodium, calcium and magnesium is between 1%～5% in the biomass.
4. biomass autocatalysis gasification according to claim 1 prepares the method for methane-rich gas, and it is characterized in that: the residence time in pyrolysis reactor of the biomass in the said step (2) is 10～40min, and medial temperature is 280 ℃～320 ℃.
5. biomass autocatalysis gasification according to claim 1 prepares the method for methane-rich gas, it is characterized in that: biomass pyrolytic mass ratio burnt and water vapour is between 0.3～2.0:1 in the said step (3), and the oxygen excess coefficient is between 0.2～0.4.
6. biomass autocatalysis gasification according to claim 1 prepares the method for methane-rich gas; It is characterized in that: temperature of reaction is between 700～850 ℃ in the middle gasifying reactor of said step (3); The residence time is between 5～30s, and vapor pressure is between 1～6MPa;
7. biomass autocatalysis gasification according to claim 1 prepares the method for methane-rich gas, and it is characterized in that: in the said step (4), have 40～60% parts to be admitted in the pressure gasification reactor in the separated gas, rest part stores for future use;
8. biomass autocatalysis according to claim 1 gasification prepare the method for methane-rich gas, it is characterized in that: the excess coefficient that burns in the combustion reactor in the said step (5) is between 1.1～1.4, between 600～800 ℃ of the temperature of combustion.
9. biomass autocatalysis gasification according to claim 1 prepares the method for methane-rich gas, it is characterized in that: the gasification bottom ash gets in the ash bucket in the said step (3), and carbon content is lower than 3% in the ash, and the total mass mark of potassium, sodium, calcium and magnesium is more than 10%.
10. biomass autocatalysis gasification according to claim 1 prepares the method for methane-rich gas, and it is characterized in that: said step adds K in (1) in quenching liquid
2CO
3Improve its concentration, the total mass mark that makes quenching potassium, sodium, calcium and magnesium in night is between 1%～5%.
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| CN103031157A (en) * | 2013-01-11 | 2013-04-10 | 华东理工大学 | Method for preparing hydrogen-rich gas by biomass charcoal |
| CN103146404A (en) * | 2013-03-27 | 2013-06-12 | 北京化工大学 | Process for pyrolyzing and gasifying forestry and agricultural waste by recycling catalyst |
| CN104789270A (en) * | 2015-01-16 | 2015-07-22 | 胜利油田胜利动力机械集团有限公司 | Biomass two-section type dry distillation gasification process and device |
| CN104830358A (en) * | 2015-04-30 | 2015-08-12 | 东南大学 | Apparatus for preparing hydrogen rich gas through grading gasification of biomasses, and method thereof |
| CN105602999A (en) * | 2015-11-13 | 2016-05-25 | 中国石油大学(北京) | System and method used for producing high-quality biological methane gas from biomass |
| CN105602628A (en) * | 2016-03-11 | 2016-05-25 | 浙江科技学院 | Device and method for producing high-heating-value synthesis gas in dry-distillation and gasification mode through biomass/coal |
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| CN110589760A (en) * | 2019-08-27 | 2019-12-20 | 华南农业大学 | Chemical chain gasification reforming device and method for controllably removing and adding alkali metal or alkaline earth metal |
| CN112080322A (en) * | 2020-09-16 | 2020-12-15 | 新奥科技发展有限公司 | Pulverized coal grading gasification system and method |
| CN112158805A (en) * | 2020-09-08 | 2021-01-01 | 新奥生物质能(天津)有限公司 | Method and system for preparing hydrogen by using biomass |
| CN112410075A (en) * | 2020-11-25 | 2021-02-26 | 新奥科技发展有限公司 | Coal catalytic gasification system and method |
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| CN112877084A (en) * | 2021-01-20 | 2021-06-01 | 西北大学 | Method for preparing oil-electricity-gas-heat from self-circulation oil-electricity balance domestic garbage |
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| CN115446097A (en) * | 2022-08-31 | 2022-12-09 | 北京工商大学 | Silicon-aluminum base alkali metal curing agent, preparation method thereof and method for inhibiting alkali metal volatilization in synergistic temperature range |
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| CN116040580A (en) * | 2023-01-13 | 2023-05-02 | 哈尔滨工业大学 | Method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass |
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| CN112410075A (en) * | 2020-11-25 | 2021-02-26 | 新奥科技发展有限公司 | Coal catalytic gasification system and method |
| CN112410075B (en) * | 2020-11-25 | 2022-03-04 | 新奥科技发展有限公司 | Coal catalytic gasification system and method |
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| CN112742336B (en) * | 2020-11-27 | 2022-12-02 | 中国煤层气集团有限公司 | Hydrocarbon gasification reactor |
| CN112877084A (en) * | 2021-01-20 | 2021-06-01 | 西北大学 | Method for preparing oil-electricity-gas-heat from self-circulation oil-electricity balance domestic garbage |
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| CN113060704A (en) * | 2021-03-30 | 2021-07-02 | 大连理工大学 | Organic solid clean and efficient hydrogen production device and method |
| CN113060704B (en) * | 2021-03-30 | 2023-05-12 | 大连理工大学 | Organic solid clean high-efficiency hydrogen production device and method |
| CN113322102A (en) * | 2021-05-27 | 2021-08-31 | 江苏大学 | System for preparing hydrogen-rich synthesis gas by biomass staged gasification |
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| CN115446097A (en) * | 2022-08-31 | 2022-12-09 | 北京工商大学 | Silicon-aluminum base alkali metal curing agent, preparation method thereof and method for inhibiting alkali metal volatilization in synergistic temperature range |
| CN115772424A (en) * | 2022-11-15 | 2023-03-10 | 华南农业大学 | Alkali lignin reinforced coal coke powder chemical chain cooperative gasification method |
| CN116040580A (en) * | 2023-01-13 | 2023-05-02 | 哈尔滨工业大学 | Method for preparing hydrogen by co-catalytic vaporization of internal and external metals of biomass |
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