CN102533340A - Method utilizing waste biomasses to prepare biogas - Google Patents
Method utilizing waste biomasses to prepare biogas Download PDFInfo
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Abstract
The invention discloses a method utilizing waste biomasses to prepare biogas. The method comprises the following steps: processing abandoned biomasses into semi-liquid slurry; carrying out steam gasification process for the semi-liquid slurry to obtain raw oil; and carrying out supercritical water gasification process for the raw oil to obtain biogas. The method of the invention adopts the waste biomasses as raw materials, so that the scope of sources is wide. A two-step gasification method is adopted, so that not only the rate of gasification of carbon in the abandoned biomasses can be increased but also clogging of tar carbon deposit can be avoided, and therefore continuous feeding can be realized.
Description
Technical field
The present invention relates to a kind of preparation method of biological flue gas, particularly a kind of method of utilizing abandoned biomass to prepare biological flue gas.
Background technology
Biomass are the various organisms that utilize atmosphere, water, soil etc. to produce through photosynthesis, and all the lived organic substances that can grow are commonly referred to as biomass, comprise plant, animal and mikrobe.Sensu lato biomass comprise all plants, mikrobe and are the animal of food and the waste of production thereof with plant, mikrobe; Generally include timber and forest industry waste, agricultural wastes, waterplant, oilseed plant, domestic waste and trade waste and movement; Have renewablely, pollute low and distribute characteristics such as extensive.The formation of biomass mainly comprises xylogen, Mierocrystalline cellulose and semicellulose, mainly contains elements such as carbon, hydrogen, oxygen and a spot of nitrogen, sulphur, contains certain ash content and moisture in addition.
Biomass energy be a kind of be the energy of carrier with biomass, be the important energy source that the mankind depend on for existence, be to be only second to coal, oil and natural gas and the energy that occupy the 4th of world energy sources total quantity consumed, in whole energy resource system, occupy critical role.The utilization of biomass energy mainly comprises approach such as direct burning, materialization conversion and biochemical conversion.The thing chemistry conversion of biomass is under certain temperature and condition, makes gasifying biomass, charing, pyrolysis and catalytic liquefaction, to produce gaseous fuel, liquid fuel and chemical substance.The biochemical transformations of biomass includes biomass-biogas conversion and biomass-ethanol conversion etc.; Biogas transform be organic substance in anaerobic environment, to produce a kind of through microbial fermentation be the flammable mixed gas (being biogas) of staple with methane, ethanol conversion is to utilize raw materials such as saccharic, starch and Mierocrystalline cellulose to process ethanol through fermentation.
Gasifying biomass is the thermochemical process that solid or liquid fuel is changed into geseous fuel, significant progress has been arranged in recent years, particularly in fields such as power generation and heat supplies.Prepare synthetic gas and mainly contain two technological lines by being rich in lignocellulose biomass, the one, by biomass gasified gas through reform, conversion prepares synthetic gas; The 2nd, make bio oil by biomass through quick cracking, again by preparing synthetic gas by gasifying biological oil.Article one, technological line combines sophisticated biomass gasification technology and the gas reforming converter technique that can use for reference petrochemical complex, and its technical difficulty is little, and development is comparatively ripe, is suitable for biomass and transforms preparing synthetic gas on a small scale on the spot.The second technological line can become resource dispersive biomass processing to concentrate after the bio oil and is transported to a ground, thereby realizes the large-scale production of biomass synthesis gas.
Yet, in the gasification of biomass, can produce under more tar and the normal temperature and can be condensed into liquid organic cpds, gathering of these materials can be stopped up, corrosion pipeline; Reduce gasification efficiency, therefore in biomass gasification process, often use catalyzer, in order to reduce reaction activity; Reduce the input of gasifying medium, reduce the tar generation, the adjustment gas composition; Improve the grade of small molecules inflammable gas, improve the biomass utilising efficiency.Catalyzer commonly used in the biomass gasification process comprises natural crystal; Though these catalyzer have certain katalysis, but still there are various shortcomings in basic metal and nickel-base catalyst; Can make polycyclic aromatic hydrocarbons type organic increase in the tar like natural crystal such as rhombspar etc.; Cause the tar behind the catalytic pyrolysis to be difficult to more remove, basic metal is difficult to satisfy to generate rich H to the reformation poor-performing of methane
2With the CO synthetic gas be the biogas metallization processes of purpose, the nickel catalyzator working conditions is harsh, costs an arm and a leg etc.
Granted publication number for the disclosure of the Invention of CN101239317B a kind of Catalysts and its preparation method that is used for dry gasification for moisture component of coke oven gas; The catalyzer of this invention is carrier with the manganese-cerium composite oxide; With in nickel, cobalt and the iron one or both is active ingredient, and as auxiliary agent, its specific surface area of the catalyzer that makes is big with alkali (soil) metal or REE; The reactive metal good dispersivity; And have characteristics such as the strong and open loop ability of long service life, carbon accumulation resisting ability is good, yet the catalyst component of this invention is complicated, preparation technology is loaded down with trivial details.
Compare with the atmospheric gasification process, supercritical water gasification has advantages such as homogeneous media, high solid transformation efficiency.Publication No. be CN102092681A disclosure of the Invention the CO of biomass gasifying hydrogen making in a kind of supercritical water
2Removing process, this technology is at first prepared catalyst solution and biomass slurry, injects charging basket separately respectively; Open high-pressure reactor, CO packs into
2Remove agent; Utilizing the double plunger HPP, is 1 with volume ratio: the interchanger that the catalyst solution of 10-20 and biomass slurry are sent into separately carries out preheating, sends into the mixing tank thorough mixing again; Fluid after mixing is pressed in the high-pressure reactor and reacts; The gas-liquid mixed product gets into gas-liquid separator separates, and hydrogen content can reach 60.8% in the gas of preparation, and carbon monoxide content is 23.7%, and methane content is 12.2%, and carbon dioxide content is 0%.Yet this method only adopts supercritical water gasification to handle, and temperature of reaction is high, pressure is big, the time is long, and process energy consumption is big, also can't solve problems such as tar carbon deposit obstruction simultaneously preferably.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of two step evaporating methods to prepare biological flue gas from abandoned biomass to the problem that above-mentioned prior art exists; Two step evaporating methods become thick oil with Wood Adhesives from Biomass earlier; Again thick oil gasization is prepared biological flue gas, not only energy consumption is low to adopt two step evaporating methods, and solution tar carbon deposit obstruction can be arranged; Thereby the realization continuously feeding helps the large-scale industrialization preparation.
In order to achieve the above object, one aspect of the present invention provides a kind of method of utilizing abandoned biomass to prepare biological flue gas, comprises as follows step in sequence:
A) abandoned biomass is processed into the semi-fluid slurry;
B) the semi-fluid slurry is carried out the water vapor gasification process and make thick oil;
C) thick oil is carried out the supercritical water gasification processing and make the coarse biometric combustion gas.
Wherein, steps A) comprise as follows step in sequence:
A1) abandoned biomass is carried out fragmentation, make the broken end of biomass;
A2) in the broken end of biomass, add first catalyzer, stir, obtain broken last compound;
A3) in broken last compound, add tap water, stir, be modulated into the semi-fluid slurry.
Wherein, steps A 1) described in abandoned biomass select in corn straw, corn cob, wood chip, forestry processing waste material, the wooden residue one or more.Particularly, the water ratio of said corn straw is 20-25%, and the water ratio of said corn cob is 25-40%, and the water ratio of said wood chip, forestry processing waste material is 15%-25%, and the water ratio of said wooden residue is 30-40%, like bagasse etc.
Particularly, steps A 1) described in the granularity at the broken end of biomass be the 20-40 order.
Wherein, steps A 2) weight proportion at first catalyzer and the broken end of biomass is 1.0-1.5 described in: 100, and said first catalyzer comprises carbonate and rare earth nitrate, the mol ratio of carbonate and rare earth nitrate is 10-20: 1, be preferably 16-18: 1.
Particularly, said carbonate is selected from alkaline carbonate or alkaline earth metal carbonate, and wherein said alkaline carbonate is selected from yellow soda ash or salt of wormwood, and said alkaline earth metal carbonate is selected from magnesiumcarbonate or lime carbonate; Said rare earth nitrate is selected from Lanthanum trinitrate or cerous nitrate.
Wherein, steps A 3) water ratio of semi-fluid slurry is 60-80% described in, and the water ratio in the control semi-fluid slurry can prepare different H
2The biological flue gas of/CO, wherein the water ratio in the semi-fluid slurry is big more, and the water vapor that produces in the gasification process process is many more, H in the biological flue gas
2Volume content high more.
Wherein, steps A) also comprise: under agitation condition, the semi-fluid slurry is preheated to 90-150 ℃, so that make the semi-fluid slurry and first catalyzer when carrying out the water vapor gasification process, can reach required temperature of reaction rapidly.
Particularly, step B) in the semi-fluid slurry sent into and carry out described water vapor gasification process in first reactor drum, the temperature of wherein controlling the water vapor gasification process is 200-300 ℃, is preferably 220-240 ℃; Absolute pressure is 6-12MPa, is preferably 10MPa; Treatment time is 15-40 minute.
Wherein, step C) comprise thick oil sent into second reactor drum after, in second reactor drum, add second catalyzer and carry out said supercritical water gasification and handle; Wherein controlling the supercritical water gasification treatment temp is 500-700 ℃, is preferably 600 ℃; Absolute pressure is 25-32MPa, is preferably 28MPa; Treatment time is 10-20 minute; Under the described conditions, water is in supercritical state, and gasification reaction is a homogeneous reaction, thereby reduces resistance to mass transfer, and ability rapid heating material reduces coke and generates, and improves the biological flue gas productive rate.
Particularly; The weight proportion at said second catalyzer and the broken end of biomass is 1.0-1.5: 100; Second catalyzer comprises carbonate, nickelous nitrate and rare earth nitrate; Wherein the mol ratio of carbonate, nickelous nitrate and rare earth nitrate is (10-20): (8-20): 1, be preferably (16-18): (8-12): 1.
Especially, said carbonate is selected from alkaline carbonate or alkaline earth metal carbonate, and wherein said alkaline carbonate is selected from yellow soda ash or salt of wormwood, and said alkaline earth metal carbonate is selected from magnesiumcarbonate or lime carbonate; Said rare earth nitrate is selected from Lanthanum trinitrate or cerous nitrate.
Wherein, also comprise step C) described in the coarse biometric combustion gas wash processing successively, catch that foam is handled and processed, make biological flue gas; Said washing is handled and is used for removing water vapor and other impurity of combustion gas, and the said foam of catching is handled and is used for removing the foam shape impurity greasy dirt that combustion gas is mingled with, and said processed is used for removing the moisture that combustion gas is mingled with.
Particularly, said washing is handled and in water wash column, is carried out, the temperature of water wash column≤45 ℃ wherein, and the outlet relative pressure is-0.03～-0.02MPa; The said foam of catching is handled and in the silk screen mist eliminator, to be carried out, the temperature of silk screen mist eliminator≤30 ℃ wherein, and the outlet relative pressure is-0.04～-0.035MPa; Said processed is carried out in dehydration tower, wherein dehydration tower outlet relative pressure be-0.05～-0.06MPa, temperature≤28 ℃, the moisture in the biological flue gas of preparation≤0.01%.
The present invention provides a kind of biological flue gas for preparing according to the method described above on the other hand.
Particularly, H in the said biological flue gas
2Volumn concentration is 26-36%, and the CO volumn concentration is 60-70%, CO
2Volumn concentration is 2-5%, CH
4Volumn concentration is 0.3-0.9%; The thermal value of biological flue gas reaches 46MJ/m
3
Especially, H in the biological flue gas of the present invention's preparation
2With the volume ratio of CO be 0.3-0.6: 1.
The present invention has the following advantages:
1, to adopt abandoned biomass be the feedstock production biological flue gas in the present invention, not only can turn waste into wealth, and reduces environmental pollution, saves production cost, and widened the range of application of abandoned biomass simultaneously, created higher economic worth;
2, the present invention adopts two step evaporating methods to prepare biological flue gas, and employed Preparation of Catalyst is simple, stable performance; Preparation technology need not raw material is carried out drying and dehydrating, and is simple to operate, energy consumption is low; Adopt the gasification of two steps to have in addition and solve the obstruction of tar carbon deposit, thereby realize continuously feeding, help the large-scale industrialization preparation;
3, the present invention adopts supercritical water to carry out gasification process, and gasification reaction is a homogeneous reaction, thereby reduces resistance to mass transfer, and ability rapid heating material reduces coke and generates, and improves the biological flue gas productive rate, and the carbon vaporization rate is up to 94-97% in the abandoned biomass;
4, preparation method of the present invention can prepare different H through regulating the water ratio of material in the gasification reaction
2The biological flue gas of/CO, wherein H
2With the volume ratio of CO be 0.3-0.6: 1, the biological flue gas of preparation is formed adjustable, applied range, the biological flue gas constant product quality, thermal value reaches 46MJ/m
3
Description of drawings
Fig. 1 prepares the process flow sheet of biological flue gas for the present invention.
The specific embodiment mode
Raw material used among the present invention is an abandoned biomass, comprises corn straw, corn cob, wood chip, forestry processing waste material, wooden residue such as bagasse etc.
Embodiment 1
1, preparation catalyzer
Yellow soda ash and Lanthanum trinitrate mechanically mixing is even, make first catalyzer, the mol ratio of yellow soda ash and Lanthanum trinitrate is 16: 1 in first catalyzer;
Yellow soda ash, nickelous nitrate, Lanthanum trinitrate mechanically mixing is even, make second catalyzer, the mol ratio of yellow soda ash, nickelous nitrate and Lanthanum trinitrate is 16: 10: 1 in second catalyzer;
2, raw materials pretreatment
With water ratio is that 25% corn straw places paste roller mill, grinds to be the broken end of 20-40 purpose;
After above-mentioned broken end joined preheater; In preheater, add above-mentioned first catalyzer, stir, in preheater, add tap water again; Stir; Be modulated into water ratio and be 60% semi-fluid slurry, under agitation condition, slurry is preheated to 90 ℃, so that make the slurry and first catalyzer in getting into first reactor drum, can be warming up to the temperature of reaction of water vapor gasification process rapidly; Wherein, the weight proportion at first catalyzer and broken end is 1.5: 100, and the weight proportion at tap water and broken end is 0.54: 1;
3, water vapor gasification process
Open the slurry HPP, the semi-fluid slurry that is heated to 90 ℃ is pumped into first reactor drum after, the heating unit of opening first reactor drum carries out steam heating; Temperature and pressure in first reactor drum raises; Temperature in first reactor drum reaches 240 ℃, begins to calculate the time of water vapor gasification process when absolute pressure reaches 10MPa, and the temperature of control water vapor gasification process process is 240 ℃; Absolute pressure is 10MPa, and the treatment time is 30 minutes;
Generate thick oil and combustion gas on a small quantity after the semi-fluid slurry process water vapor gasification process, thick oil is used to carry out supercritical gasification to be handled, and a small amount of combustion gas is carried out further refining, wherein comprises CO, H in the combustion gas on a small quantity
2, CO
2, CH
4And H
2O, the reaction formula that reacts in the water vapor gasification process process is following:
4, supercritical water gasification is handled
The thick oil that first reactor drum is generated pumps into second reactor drum with HPP, in second reactor drum, adds above-mentioned second catalyzer, stirs; The heating unit of opening second reactor drum carries out steam heating; Temperature and pressure in second reactor drum raises, and the temperature in second reactor drum reaches 600 ℃, begins when absolute pressure reaches 28MPa to calculate the time that supercritical water gasification is handled; Wherein the weight proportion at broken end is 1.5: 100 in second catalyzer and the step 2; The temperature of control supercritical water gasification treating processes is 600 ℃, and absolute pressure is 28MPa, and the treatment time is 20 minutes;
Under these conditions, the gasifying medium water in second reactor drum is in supercritical state, and thick oil is handled the back through supercritical water gasification and generated the coarse biometric combustion gas, comprises H in the coarse biometric combustion gas
2, CO, CO
2, CH
4And H
2O, the reaction formula that reacts in the supercritical water gasification treating processes is following:
5, refined biological combustion gas
After normal pressure is reduced in the combustion gas of generation coarse biometric after a small amount of combustion gas that generates after the water vapor gasification process and the supercritical water gasification processing; Sending into the washing of lowering the temperature in the water wash column handles; Impurity such as the water vapor in the removal combustion gas and the dregs of fat; Wherein control temperature≤45 ℃ of water wash column, the outlet relative pressure is-0.03～-0.02MPa;
Combustion gas after washing handled is sent into and is caught foam in the silk screen mist eliminator and handle, and removes the foam shape impurity greasy dirt that is mingled with in the combustion gas, wherein controls temperature≤30 ℃ of silk screen mist eliminator, and the outlet relative pressure is-0.04～-0.035MPa;
Combustion gas after the silk screen mist eliminator handled is sent into and is carried out processed in the dehydration tower; Combustion gas gets into bucket formula silk screen dehydration layer from the bottom, relative pressure is discharged from the top, removes the moisture that is mingled with in the combustion gas; Promptly make biological flue gas of the present invention; Wherein control dehydration tower outlet relative pressure and be-0.05～-0.06MPa, temperature≤28 ℃, the moisture in the biological flue gas≤0.01%;
Adopt gas chromatograph (GC1690) to measure composition and content in the biological flue gas, wherein GC conditions is: do carrier gas with hydrogen, adopt the TDX-01 chromatographic column to measure;
Adopt the thermal value of volume thermal value calculating biological flue gas among the GB/T 11062-1998;
Calculate the vaporization rate of carbon, calculation formula is following:
The constituent content of biological flue gas and index parameter measurement result see Table 1.
Embodiment 2
1, preparation catalyzer
Salt of wormwood and cerous nitrate mechanically mixing is even, make first catalyzer, the mol ratio of salt of wormwood and cerous nitrate is 10: 1 in first catalyzer;
Salt of wormwood, nickelous nitrate, cerous nitrate mechanically mixing is even, make second catalyzer, the mol ratio of salt of wormwood, nickelous nitrate and cerous nitrate is 10: 8: 1 in second catalyzer;
2, raw materials pretreatment
With water ratio is that 30% corn cob places paste roller mill, grinds to be the broken end of 20-40 purpose;
After above-mentioned broken end joined preheater; In preheater, add above-mentioned first catalyzer, stir, in preheater, add tap water again; Stir; Be modulated into water ratio and be 70% semi-fluid slurry, under agitation condition, slurry is preheated to 120 ℃, so that make the slurry and first catalyzer in getting into first reactor drum, can be warming up to the temperature of reaction of water vapor gasification process rapidly; Wherein, the weight proportion at first catalyzer and broken end is 1: 100, and the weight proportion at tap water and broken end is 0.67: 1;
3, water vapor gasification process
Open the slurry HPP, the semi-fluid slurry that is heated to 120 ℃ is pumped into first reactor drum after, the heating unit of opening first reactor drum carries out steam heating; Temperature and pressure in first reactor drum raises; Temperature in first reactor drum reaches 200 ℃, begins to calculate the time of water vapor gasification process when absolute pressure reaches 12MPa, and the temperature of control water vapor gasification process process is 200 ℃; Absolute pressure is 12MPa, and the treatment time is 15 minutes;
Generate thick oil and combustion gas on a small quantity after the semi-fluid slurry process water vapor gasification process, thick oil is used to carry out supercritical gasification to be handled, and a small amount of combustion gas is carried out further refining, wherein comprises CO, H in the combustion gas on a small quantity
2, CO
2, CH
4And H
2O;
4, supercritical water gasification is handled
The thick oil that first reactor drum is generated pumps into second reactor drum with HPP, in second reactor drum, adds above-mentioned second catalyzer, stirs; The heating unit of opening second reactor drum carries out steam heating; Temperature and pressure in second reactor drum raises, and the temperature in second reactor drum reaches 700 ℃, begins when absolute pressure reaches 25MPa to calculate the time that supercritical water gasification is handled; Wherein the weight proportion at broken end is 1.2: 100 in second catalyzer and the step 2; The temperature of control supercritical water gasification treating processes is 700 ℃, and absolute pressure is 25MPa, and the treatment time is 15 minutes;
Under these conditions, the gasifying medium water in second reactor drum is in supercritical state, and thick oil is handled the back through supercritical water gasification and generated the coarse biometric combustion gas, comprises H in the coarse biometric combustion gas
2, CO, CO
2, CH
4And H
2O;
5, refined biological combustion gas
After normal pressure is reduced in the combustion gas of generation coarse biometric after a small amount of combustion gas that generates after the water vapor gasification process and the supercritical water gasification processing; Sending into the washing of lowering the temperature in the water wash column handles; Wherein control temperature≤45 ℃ of water wash column, the outlet relative pressure is-0.03～-0.02MPa;
Combustion gas after washing handled is sent into and is caught foam in the silk screen mist eliminator and handle, and wherein controls temperature≤30 ℃ of silk screen mist eliminator, and the outlet relative pressure is-0.04～-0.035MPa;
Combustion gas after the silk screen mist eliminator handled is sent into and is carried out processed in the dehydration tower; Combustion gas gets into bucket formula silk screen dehydration layer from the bottom; Relative pressure is discharged from the top, promptly makes biological flue gas of the present invention, wherein control dehydration tower outlet relative pressure and be-0.05～-0.06MPa; Temperature≤28 ℃, the moisture in the biological flue gas≤0.01%;
The constituent content of biological flue gas and index parameter measurement result see Table 1.
Embodiment 3
1, preparation catalyzer
Lime carbonate and cerous nitrate mechanically mixing is even, make first catalyzer, the mol ratio of lime carbonate and cerous nitrate is 18: 1 in first catalyzer;
Yellow soda ash, nickelous nitrate, cerous nitrate mechanically mixing is even, make second catalyzer, the mol ratio of yellow soda ash, nickelous nitrate and cerous nitrate is 18: 12: 1 in second catalyzer;
2, raw materials pretreatment
With water ratio is that 20% wood chip places paste roller mill, grinds to be the broken end of 20-40 purpose;
After above-mentioned broken end joined preheater; In preheater, add above-mentioned first catalyzer, stir, in preheater, add tap water again; Stir; Be modulated into water ratio and be 60% semi-fluid slurry, under agitation condition, slurry is preheated to 150 ℃, so that make the slurry and first catalyzer in getting into first reactor drum, can be warming up to the temperature of reaction of water vapor gasification process rapidly; Wherein, the weight proportion at first catalyzer and broken end is 1.5: 100, and the weight proportion at tap water and broken end is 0.67: 1;
3, water vapor gasification process
Open the slurry HPP, the semi-fluid slurry that is heated to 150 ℃ is pumped into first reactor drum after, the heating unit of opening first reactor drum carries out steam heating; Temperature and pressure in first reactor drum raises; Temperature in first reactor drum reaches 300 ℃, begins to calculate the time of water vapor gasification process when absolute pressure reaches 6MPa, and the temperature of control water vapor gasification process process is 300 ℃; Absolute pressure is 6MPa, and the treatment time is 40 minutes;
Generate thick oil and combustion gas on a small quantity after the semi-fluid slurry process water vapor gasification process, thick oil is used to carry out supercritical gasification to be handled, and a small amount of combustion gas is carried out further refining, wherein comprises CO, H in the combustion gas on a small quantity
2, CO
2, CH
4And H
2O;
4, supercritical water gasification is handled
The thick oil that first reactor drum is generated pumps into second reactor drum with HPP, in second reactor drum, adds above-mentioned second catalyzer, stirs; The heating unit of opening second reactor drum carries out steam heating; Temperature and pressure in second reactor drum raises, and the temperature in second reactor drum reaches 500 ℃, begins when absolute pressure reaches 32MPa to calculate the time that supercritical water gasification is handled; Wherein the weight proportion at broken end is 1: 100 in second catalyzer and the step 2; The temperature of control supercritical water gasification treating processes is 500 ℃, and absolute pressure is 32MPa, and the treatment time is 20 minutes;
Under these conditions, the gasifying medium water in second reactor drum is in supercritical state, and thick oil is handled the back through supercritical water gasification and generated the coarse biometric combustion gas, comprises H in the coarse biometric combustion gas
2, CO, CO
2, CH
4And H
2O;
5, refined biological combustion gas
After normal pressure is reduced in the combustion gas of generation coarse biometric after a small amount of combustion gas that generates after the water vapor gasification process and the supercritical water gasification processing; Sending into the washing of lowering the temperature in the water wash column handles; Wherein control temperature≤45 ℃ of water wash column, the outlet relative pressure is-0.03～-0.02MPa;
Combustion gas after washing handled is sent into and is caught foam in the silk screen mist eliminator and handle, and wherein controls temperature≤30 ℃ of silk screen mist eliminator, and the outlet relative pressure is-0.04～-0.035MPa;
Combustion gas after the silk screen mist eliminator handled is sent into and is carried out processed in the dehydration tower; Combustion gas gets into bucket formula silk screen dehydration layer from the bottom; Relative pressure is discharged from the top, promptly makes biological flue gas of the present invention, wherein control dehydration tower outlet relative pressure and be-0.05～-0.06MPa; Temperature≤28 ℃, the moisture in the biological flue gas≤0.01%;
The constituent content of biological flue gas and index parameter measurement result see Table 1.
Embodiment 4
1, preparation catalyzer
Yellow soda ash and Lanthanum trinitrate mechanically mixing is even, make first catalyzer, the mol ratio of yellow soda ash and Lanthanum trinitrate is 20: 1 in first catalyzer;
Magnesiumcarbonate, nickelous nitrate, Lanthanum trinitrate mechanically mixing is even, make second catalyzer, the mol ratio of magnesiumcarbonate, nickelous nitrate and Lanthanum trinitrate is 20: 20: 1 in second catalyzer;
2, raw materials pretreatment
With water ratio is that 35% bagasse places paste roller mill, grinds to be the broken end of 20-40 purpose;
After above-mentioned broken end joined preheater; In preheater, add above-mentioned first catalyzer, stir, in preheater, add tap water again; Stir; Be modulated into water ratio and be 80% semi-fluid slurry, under agitation condition, slurry is preheated to 100 ℃, so that make the slurry and first catalyzer in getting into first reactor drum, can be warming up to the temperature of reaction of water vapor gasification process rapidly; Wherein, the weight proportion at first catalyzer and broken end is 1.2: 100, and the weight proportion at tap water and broken end is 0.82: 1;
3, water vapor gasification process
Open the slurry HPP, the semi-fluid slurry that is heated to 100 ℃ is pumped into first reactor drum after, the heating unit of opening first reactor drum carries out steam heating; Temperature and pressure in first reactor drum raises; Temperature in first reactor drum reaches 220 ℃, begins to calculate the time of water vapor gasification process when absolute pressure reaches 10MPa, and the temperature of control water vapor gasification process process is 220 ℃; Absolute pressure is 10MPa, and the treatment time is 35 minutes;
Generate thick oil and combustion gas on a small quantity after the semi-fluid slurry process water vapor gasification process, thick oil is used to carry out supercritical gasification to be handled, and a small amount of combustion gas is carried out further refining, wherein comprises CO, H in the combustion gas on a small quantity
2, CO
2, CH
4And H
2O;
4, supercritical water gasification is handled
The thick oil that first reactor drum is generated pumps into second reactor drum with HPP, in second reactor drum, adds above-mentioned second catalyzer, stirs; The heating unit of opening second reactor drum carries out steam heating; Temperature and pressure in second reactor drum raises, and the temperature in second reactor drum reaches 600 ℃, begins when absolute pressure reaches 30MPa to calculate the time that supercritical water gasification is handled; Wherein the weight proportion at broken end is 1.5: 100 in second catalyzer and the step 2; The temperature of control supercritical water gasification treating processes is 600 ℃, and absolute pressure is 30MPa, and the treatment time is 10 minutes;
Under these conditions, the gasifying medium water in second reactor drum is in supercritical state, and thick oil is handled the back through supercritical water gasification and generated the coarse biometric combustion gas, comprises H in the coarse biometric combustion gas
2, CO, CO
2, CH
4And H
2O;
5, refined biological combustion gas
After normal pressure is reduced in the combustion gas of generation coarse biometric after a small amount of combustion gas that generates after the water vapor gasification process and the supercritical water gasification processing; Sending into the washing of lowering the temperature in the water wash column handles; Wherein control temperature≤45 ℃ of water wash column, the outlet relative pressure is-0.03～-0.02MPa;
Combustion gas after washing handled is sent into and is caught foam in the silk screen mist eliminator and handle, and wherein controls temperature≤30 ℃ of silk screen mist eliminator, and the outlet relative pressure is-0.04～-0.035MPa;
Combustion gas after the silk screen mist eliminator handled is sent into and is carried out processed in the dehydration tower; Combustion gas gets into bucket formula silk screen dehydration layer from the bottom; Relative pressure is discharged from the top, promptly makes biological flue gas of the present invention, wherein control dehydration tower outlet relative pressure and be-0.05～-0.06MPa; Temperature≤28 ℃, the moisture in the biological flue gas≤0.01%;
The constituent content of biological flue gas and index parameter measurement result see Table 1.
The component concentration of table 1 biological flue gas and index parameter
Can know by table 1 result:
1, H in the biological flue gas of the present invention's preparation
2Volumn concentration is 26-36%, and the CO volumn concentration is 60-70%, CO
2Volumn concentration is 2-5%, CH
4Volumn concentration is 0.3-0.9%, and the thermal value of biological flue gas reaches 46MJ/m
3In addition, the water ratio through material before the adjusting gasification reaction can prepare different H
2The biological flue gas of/CO, wherein H
2With the volume ratio of CO be 0.3-0.6: 1;
2, the vaporization rate of carbon reaches 94-97% in the abandoned biomass of the present invention, explains that the present invention adopts two step gasifying process can make the carbon gasification in the abandoned biomass preferably, and raw material availability is high, thereby helps making full use of biomass resource; In addition, the present invention need not raw material is carried out drying and dehydrating, and technology is simple, energy consumption is low, and solution tar carbon deposit obstruction can be arranged, thereby realizes continuously feeding, helps the large-scale industrialization preparation.
Claims (10)
1. method of utilizing abandoned biomass to prepare biological flue gas comprises as follows step in sequence:
A) abandoned biomass is processed into the semi-fluid slurry;
B) the semi-fluid slurry is carried out the water vapor gasification process and make thick oil;
C) thick oil is carried out the supercritical water gasification processing and make the coarse biometric combustion gas.
2. the method for claim 1 is characterized in that, steps A) comprise as follows step in sequence:
A1) abandoned biomass is carried out fragmentation, make the broken end of biomass;
A2) in the broken end of biomass, add first catalyzer, stir, obtain broken last compound;
A3) in broken last compound, add tap water, stir, be modulated into the semi-fluid slurry.
3. method as claimed in claim 2; It is characterized in that; The weight proportion at first catalyzer steps A 2) and the broken end of biomass is 1.0-1.5: 100, and said first catalyzer comprises carbonate and rare earth nitrate, the mol ratio of carbonate and rare earth nitrate is 10-20: 1.
4. method as claimed in claim 2 is characterized in that, steps A 1) described in the granularity at the broken end of biomass be the 20-40 order, steps A 3) described in the water ratio of semi-fluid slurry be 60-80%.
5. according to claim 1 or claim 2 method; It is characterized in that step B) in the semi-fluid slurry sent into carry out described water vapor gasification process in first reactor drum, the temperature of wherein controlling the water vapor gasification process is 200-300 ℃; Absolute pressure is 6-12MPa, and the treatment time is 15-40 minute.
6. method as claimed in claim 2 is characterized in that step C) comprising: after thick oil is sent into second reactor drum, in second reactor drum, add second catalyzer and carry out said supercritical water gasification processing; Wherein controlling the supercritical water gasification treatment temperature is 500-700 ℃, and absolute pressure is 25-32MPa, and the treatment time is 10-20 minute.
7. method as claimed in claim 6; It is characterized in that; The weight proportion at said second catalyzer and the broken end of biomass is 1.0-1.5: 100; Second catalyzer comprises carbonate, nickelous nitrate and rare earth nitrate, and wherein the mol ratio of carbonate, nickelous nitrate and rare earth nitrate is (10-20): (8-20): 1.
8. like claim 3 or 7 described methods, it is characterized in that said carbonate is selected from alkaline carbonate or alkaline earth metal carbonate, wherein said alkaline carbonate is selected from yellow soda ash or salt of wormwood, and said alkaline earth metal carbonate is selected from magnesiumcarbonate or lime carbonate; Said rare earth nitrate is selected from Lanthanum trinitrate or cerous nitrate.
9. the method for claim 1 is characterized in that, also comprises step C) described in the coarse biometric combustion gas wash processing successively, catch that foam is handled and processed, make biological flue gas.
10. biological flue gas is according to being prepared from like the arbitrary said method of claim 1-9.
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