CN1900241A - Process for making combustable gas by external high temperature CO2 and biomass reducing reaction - Google Patents
Process for making combustable gas by external high temperature CO2 and biomass reducing reaction Download PDFInfo
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- CN1900241A CN1900241A CN 200610019459 CN200610019459A CN1900241A CN 1900241 A CN1900241 A CN 1900241A CN 200610019459 CN200610019459 CN 200610019459 CN 200610019459 A CN200610019459 A CN 200610019459A CN 1900241 A CN1900241 A CN 1900241A
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Abstract
The reduction reaction process of exogenic high temperature CO2 and biomass for preparing combustible gas includes setting biomass into furnace, and spraying high temperature CO2 and combustion promoting water vapor from external burner so as to gasify ligonocellulose and similar biomass into combustible gas with CO and H2 as main components. The said process can produce combustible gas of high heat value and capable of being used as civil fuel and industrial fuel in high gas producing rate, high carbon converting rate and adjustable gas components.
Description
Technical field
The invention belongs to the external source high temperature CO
2React the technology field of producing inflammable gas with biomass reduction.
Background technology
Under the high temperature, utilizing vaporized chemical to make biomass is that plant material or other carbonaceous solids material transition of timber and so on becomes the thermochemical process of inflammable gas to be called gasification, and just solid or liquid fuel are converted into the thermochemical process of geseous fuel.In gasification installation, free oxygen or carry out chemical reaction in conjunction with the carbon in oxygen and the fuel generates inflammable gas.Utilize the method for gasification that wood material, agricultural crop straw or organic property trade waste are changed into geseous fuel, not only aspect save energy, be significant, and the protection environment, prevent aspect the pollution also significant.
The gasification of biomass is exactly to utilize airborne oxygen or oxygen carrier to be oxidized to the process of inflammable gas as vaporized chemical, with the fixed carbon in the biomass, with adopt the raw material difference, be blown into gas difference (as air, oxygen, water vapor) or service temperature, the equipment difference, the combustible gas component that is produced is also different.
Mostly present biomass pyrogenation gasification technology is with the air to be the gasification mode of vaporized chemical, N in the gas that obtains
2With the tar content height, calorific value is 5000KJ/Nm
3About, the fluidized-bed process operation is complicated, applies to have many difficulties; Directly destructive distillation pyrolysis is though gas heating value can be up to 14000KJ/Nm
3, but gasification efficiency is low.
The most of autothermal that adopts of all biomass gasifying furnaces, only double-fluidized-bed vapourizing furnace will burn and gasification is separated, burning bed adopts the bubbling bed, gasifier bed adopts circulating fluidized bed, conduct heat by thermal barrier between two, wherein how controlling the speed of circulation of thermal barrier and Heating temperature well is still to fail the gordian technique of fine solution at present.The ubiquitous problem of self-heating biomass vapourizing furnace is the balancing that is difficult to set up oxidation and reduction reaction, to keep stable reaction conditions and reaction bed, also just is difficult to adjust by the air capacity that reasonable control enters vapourizing furnace the load of vapourizing furnace.
Summary of the invention
The technical problem to be solved in the present invention provide a kind of with external source high temperature and biomass, particularly the calorific value height is produced in agriculture and forestry organic waste material pyrolysis reduction, tar content is few and H
2: the method for the inflammable gas that the ratio of CO is adjustable.
The present invention solves the problems of the technologies described above with following technical scheme: biomass spray into the high temperature CO by steam combustion-supporting after being placed in the stove
2, utilize carbonic acid gas and water vapor as vaporized chemical, at high temperature, the agriculture and forestry organic waste material gasification is generated with CO, H
2Inflammable gas for main component (＞50%).
Adopt method of the present invention can use the vapourizing furnace of following structure: insulation control of dust interlayer is arranged around the vapourizing furnace, and top connects feeding equipment; The side of vapourizing furnace inner chamber and external source high temperature CO
2Inlet is communicated with, and the cloth screen is arranged at top, and the accumulation of heat packing layer is arranged at the bottom; Also have the cyclonic separator supporting, waste heat recoverer, induced draft fan, strainer, gas storage holder etc. with vapourizing furnace.
The advantage that the present invention compared with prior art has
1, can obtain high heating value (10MJ/Nm
3) and high yield gas rate (1.7m
3/ kg).
2, the inflammable gas of Chan Shenging both can be used as domestic fuel, again can be with CO, H
2As industrial raw material.
3, efficiency of carbon conversion height is issued to 88% in the condition of catalyst-free.
4, inflammable gas main component (CO, H
2) can regulate as required.
5, reaction unit is simple, good operation.
Description of drawings
Fig. 1 is an external source high temperature CO of the present invention
2React the flow sheet of producing inflammable gas with biomass reduction.
Embodiment
The vapourizing furnace body is the open circles tubular, is located in the insulation control of dust interlayer 9, and insulation control of dust interlayer pass-out gas port, the loading hopper 1 of charging system and helical screw feeder 2 are positioned at the opening for feed top.The side of vapourizing furnace inner chamber 5 is communicated with external burner 4, and cloth screen 3 is arranged at top, and high-temperature heat accumulation packing layer 6 is arranged at the bottom.
The biomass fines is after loading hopper 1, helical screw feeder 2 are pushed in the stove, and is promptly descending along the cloth screen 3 that tilts, in the way with high temperature CO from external burner 4
2The destructive distillation pyrolytic reaction takes place in gas and the contact of combustion-supporting water vapor, and the pellet after the carbonization then falls by the hole of cloth screen 3, continues and high temperature CO from external burner
2Gas is the reaction of fluidization generation flash gasification, and then with the high-temperature heat accumulation packing layer 6 continuation gasification reactions of gasification air-flow through body of heater inner chamber 5 bottoms, through the reaction of aforementioned three phases, the biomass fines of going into stove is able to abundant gasification to still unreacted carbon granules.The insulation control of dust interlayer 9 in the body of heater outside, by the mass force and the action of gravity of dust-contained airflow, with the ash content dust collection of failing to react in furnace bottom ash bucket 8, simultaneously also to playing insulation effect in the body of heater.The inflammable gas that gasification reaction obtains is then walked around flap 7 and is upwards flowed along insulation control of dust interlayer 9, give vent to anger and enter cyclonic separator 10 and carry out gas solid separation, by waste heat recoverer 11 cooling, entering gas storage holder 14 after by strainer 13 under induced draft fan 12 effects, through inflammable gas outlet 15 outputs.
Embodiment:
1, experiment material
Experimental raw comprises woody and herbaceous plant wood chip, sawdust, bagasse and rice straw, and its concrete technical analysis and results of elemental analyses are as shown in table 1, are vaporized chemical with carbonic acid gas and water vapor, determines under the different temperature, and aerogenesis is formed and corresponding technological conditions.
The full technical analysis of table 1 experimental raw
| Material | Technical analysis | Ultimate analysis | ||||||||
| Moisture (%) | Fugitive constituent (%) | Fixed carbon (%) | Ash (%) | Calorific value (KJ/kg) | H (％) | C (％) | N (％) | S (％) | O (％) | |
| Sawdust wood chip bagasse rice straw | 16 11.7 7 15 | 80.15 84.15 79.6 61.34 | 13.39 15.13 19.7 14.25 | 4.19 0.82 0.7 8.66 | 15533.3 18112.5 14.675 | 5.52 5.62 5.4 0.1 | 46.87 48.69 45.2 36.4 | 0.18 0.64 0.2 0.46 | 0.06 0.21 0.02 0.21 | 40.91 44.02 41.8 32.57 |
2, operating process
(1) vapourizing furnace temperature-rise period: outer thermal source type of heating is taked in test, and temperature-rise period adopts the current chopping method to control automatically, and the intensification chopping speed is since 1.0, and middle intensification chopping speed increases and is spaced apart 0.5, intensification chopping speed growth interval 0.2 after 400 ℃.The difference of preset temp and actual furnace temperature should be less than 50 ℃.General temperature-rise period is (250 ℃--800 ℃) more than 10 hours
(2) feeding manner: continuously feeding; Need before the charging bleed in advance to vapourizing furnace, preventing that flue gas from scurrying outward can't charging.
(3) vapor generation: the vapour generator by 0.5MPa produces.After rising to 0.15MPa, charging fully, pressure feeds water vapor.
(4) gas flow: read by the differential pressure type gas meter.
(5) gas sampling: bleed with pump in the air outlet, collect with the gas collection bag simultaneously.
(6) with the online detection of CO on-line detector, the gas that the gas collection bag is collected other component of QF-1904 formula assay determination difficult to understand.
3, data analysis
(1) biogas production characteristics of different material
Lignocellulose-like biomass at first passes through destructive distillation after entering reactor, and the main component in the material after the destructive distillation is a fixed carbon, and its structure may be fine and close, also may be light porous shape, itself and H
2O, H
2, CO
2Reactive behavior differ, relevant with character, pressure and the temperature of reaction of material; The difference of reactive behavior directly has influence on and H
2O, H
2, CO
2Speed of response and reaction conditions, active good material and water vapour can react under lower temperature condition, also can carry out CH simultaneously
4The thermopositive reaction that generates reduces the consumption of oxygen; Carry out gasification reaction at a lower temperature and can avoid taking place the slagging scorification phenomenon.
In the time of 850 ℃, the variation maximum of CO in the gas that the three kinds of materials (bagasse, straw, wood chip) under identical gasification condition generate, straw is up to 35.2%, and bagasse is 22.8%, and wood chip is 16.1%; CO
2Change little; Generate H
2Maximum is straw 13%, and inferior is wood chip 9%, bagasse 4.3%; CH
4Content then be wood chip＞straw＞bagasse.The reason that this difference occurs mainly is because water ratio is straw＞wood chip＞bagasse, H
2Mainly generate the high more H that helps more of moisture with the steam reaction by C and CO etc.
2Generate, and CH
4Generation be subjected to the combined influence of moisture content and temperature, factor more complicated simultaneously.Under 920 ℃ of the same terms, the gaseous constituent of three kinds of materials, similar during to 850 ℃, rice straw CO content is the highest, and H
2Content then is wood chip＞rice straw＞bagasse.As a rule, raw material type has certain influence to the calorific value of gas, and in the low material gasification aerogenesis of fugitive constituent, the amount that the content of CO can the material higher than fugitive constituent generates is higher, directly influences the calorific value of combustion gas; Simultaneously, the material that calorific value own is higher, the resulting combustion gas quality that gasifies is also better.
Three kinds of materials respectively the gas production rate when 850 ℃ and 920 ℃ relatively, the rice straw gas production rate is the highest, secondly is wood chip and bagasse.Though the fugitive constituent of rice straw is not very high, its structure is light porous shape, helps gasification.
By to three kinds of materials more as can be known, no matter woody or herbaceous plant all is to gasify, herbaceous plant except ash content is higher can influence works better, the calorific value of vapourizing furnace on the low side, do not have tangible difference.The calorific value of raw material own is high, and the combustion gas quality of gasification gained just better.It is the N that contains in the gas that gas heating value is had another factor of considerable influence
2Amount, when raw material is comparatively loose, the N that reinforced process is brought into
2More, thus the quality of reduction combustion gas.Although various fuel values have than big difference, the fuel gases calorific value of gasification gained is generally all at 6MJ/m
3More than, illustrate that gasification has adaptability preferably.On the other hand, the result proves from data analysis, and the raw material composition can obviously influence the composition of combustion gas, the raw material low to fugitive constituent, CO in the combustion gas
2Content is higher, and H
2On the low side.
(2) gas temperature is to the influence of gasification property
The pyrolytic gasification effect of lignocellulose-like biomass depends on thermal decomposition process to a great extent, and gasification is actually the secondary reaction of the gas that produces after the thermolysis.In the pyrolytic process, have the volatiles about 70% to discharge approximately, they have determined the quality of gas and the distribution of gasification product to a great extent.Temperature is the significant parameter that influences the thermolysis effect, temperature raises, gas yield increases, the productive rate of tar and carbon reduces, hydrogen and hydrocarbons content increase in the gas, and carbon dioxide content reduces, and gas heating value improves, therefore improve temperature of reaction, helping with the gasification is the gasification of main purpose.
In whole gasification reaction, the combustionvelocity in the gasification layer is very fast, and dry distillation rate is also fast than the speed of reduction reaction, thus the speed of response of the speed bottle-neck of whole gasification reaction in reducing zone, CO
2Be reduced into the amount of CO, depend primarily on the chemical reaction velocity of reducing zone.C and CO
2Reduction reaction be a thermo-negative reaction, rising gasification reaction temperature helps CO
2Reduction, make and contain the more inflammable gas of CO; The rising of simultaneous temperature with promoting the tar that produces in the gasification that scission reaction at high temperature takes place, generates CnHm, COCH
4H
2Test-results shows that sawdust is high more at the reduction temperature more than 960 ℃, and CO content is low more, and reason is owing to react for a long time more, the content of fixation of C more less, CO
2Excessive institute causes; H
2Content then increase, this is because carbon and water vapor gasify about 900 ℃ of speed of response are twice during at 800 ℃, and the content of alkene and methane reduces.Test-results also shows, the rising of temperature, and the output of object gas increases.The effective transformation efficiency of CO and the ratio in the available gas composition are all relatively stable.The rising of temperature helps obtaining the inflammable gas of higher quality.But the temperature rising can make gas heating value descend, and major cause is because CH
4The decline of content; We have done to influence two experiments that methane generates: one be homogeneous (
), one be non-homogeneous (
); For inhomogeneous reaction, the high more reversed reaction speed of temperature is fast more, is unfavorable for the generation of methane, it is generally acknowledged preferably to be no more than 800 ℃ under normal pressure; Along with the rising of temperature, the methane content of homogeneous reaction than descending of inhomogeneous reaction slowly, but always descend.We can say: methanation reaction is the important reaction of producing higher calorific value gas.Both wished in actual applications that improving temperature guaranteed gaseous mass, the carrying out that also will guarantee methanation reaction is to improve gas heating value.
(3) different gas production influence constantly under the same operating mode
Influence is not very big to gaseous fraction in the variation of furnace temperature on experimental studies have found that, is feasible so test all uses the lower end temperature to represent.From the delta data of sawdust gasification experiment vapourizing furnace upper end variation of temperature and different gaseous fractions constantly thereof as can be seen, the initial stage furnace temperature has obvious downward trend, the back is along with reaction is carried out, keep id reaction and body of heater heat radiation by exothermic heat of reaction, temperature is gone up to some extent, but rangeability is not very big, and the available gas content is very not remarkable simultaneously, so the mean value of available measurement characterizes the entire reaction situation on the industrial production.
(4) gas yield
Factor of created gase be meant behind the material gasification of unit mass the volume of the geseous fuel that produces under standard state.The factor of created gase of four kinds of materials is at 1.3-2.7m
3/ kg.The pyrolytic gasification process is comparatively rapid, because the restriction of gasifying furnace device, one time inlet amount is less, and each gasification test lasted about 8 minutes.
(5) efficiency of carbon conversion
Efficiency of carbon conversion is defined as the percentage ratio that carbon in the fuel is converted into gaseous product.The transformation efficiency of carbon all is an important parameter to the efficient of whole process and the economical operation of process in biomass gasification process.In the experimentation, the efficiency of carbon conversion of every kind of material all reaches more than 90%, and ash is pure, and effect is relatively good, this may be less with the restriction inlet amount that is subjected to device, rapid heating make react completely relevant.In Industrial Plant Design, can further improve efficiency of carbon conversion by the residence time of increase freeboard height, gas and by the flying dust circulation.
Claims (2)
1. external source high temperature CO
2Produce the technology of inflammable gas with biomass reduction reaction, utilize lignocellulose-like biomass pyrolysis reduction system gas, it is characterized in that biomass are placed in the stove after, spray into high temperature CO to the stove endogenous substance by steam combustion supporting
2, utilize carbonic acid gas and water vapor as vaporized chemical, at high temperature, the lignocellulose-like biomass gasification is generated with CO, H
2Inflammable gas for main component.
2. external source high temperature CO
2Produce the processing unit of inflammable gas with biomass reduction reaction, it is characterized in that vapourizing furnace around insulation control of dust interlayer is arranged, top connects loading hopper and helical screw feeder; The cloth screen is arranged at top, and the accumulation of heat packing layer is arranged at the bottom; Also have and supporting cyclonic separator, waste heat recoverer, induced draft fan, strainer, the gas storage holder of vapourizing furnace.
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|---|---|---|---|
| CN2006100194591A CN1900241B (en) | 2006-06-21 | 2006-06-21 | Process for making combustable gas by external high temperature CO2 and biomass reducing reaction |
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| Publication Number | Publication Date |
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| CN1900241A true CN1900241A (en) | 2007-01-24 |
| CN1900241B CN1900241B (en) | 2010-12-08 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2917399A1 (en) * | 2007-06-15 | 2008-12-19 | Bio 3D Applic Soc Par Actions | PROCESS AND SYSTEM FOR TREATING GASEOUS EFFLUENTS FOR INDEPENDENTLY PRODUCING H2 AND CO |
| CN101629715B (en) * | 2008-07-17 | 2011-09-07 | 周德国 | Horizontal type biomass energy furnace |
| CN103361122A (en) * | 2013-07-19 | 2013-10-23 | 黄必录 | Gasifying furnace capable of efficiently self-purifying tar |
| CN103396838A (en) * | 2013-07-19 | 2013-11-20 | 黄必录 | Downdraft gasifier capable of realizing efficient self purification of tar |
| CN108192671A (en) * | 2018-02-11 | 2018-06-22 | 广东国能中林实业有限公司 | A kind of fluidized bed pyrolysis device for preparing high heating value biological fuel gas |
| CN112662436A (en) * | 2019-10-16 | 2021-04-16 | 西安航天源动力工程有限公司 | Anthracite low-methane gasification process and gasifier |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8412278D0 (en) * | 1984-05-14 | 1984-06-20 | English Electric Co Ltd | Gasifier plant |
| US5937652A (en) * | 1992-11-16 | 1999-08-17 | Abdelmalek; Fawzy T. | Process for coal or biomass fuel gasification by carbon dioxide extracted from a boiler flue gas stream |
-
2006
- 2006-06-21 CN CN2006100194591A patent/CN1900241B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2917399A1 (en) * | 2007-06-15 | 2008-12-19 | Bio 3D Applic Soc Par Actions | PROCESS AND SYSTEM FOR TREATING GASEOUS EFFLUENTS FOR INDEPENDENTLY PRODUCING H2 AND CO |
| WO2009004239A3 (en) * | 2007-06-15 | 2009-02-26 | Bio 3D Applic | Method and system for processing gaseous effluents for independently producing h2 and co |
| CN101629715B (en) * | 2008-07-17 | 2011-09-07 | 周德国 | Horizontal type biomass energy furnace |
| CN103361122A (en) * | 2013-07-19 | 2013-10-23 | 黄必录 | Gasifying furnace capable of efficiently self-purifying tar |
| CN103396838A (en) * | 2013-07-19 | 2013-11-20 | 黄必录 | Downdraft gasifier capable of realizing efficient self purification of tar |
| CN108192671A (en) * | 2018-02-11 | 2018-06-22 | 广东国能中林实业有限公司 | A kind of fluidized bed pyrolysis device for preparing high heating value biological fuel gas |
| CN112662436A (en) * | 2019-10-16 | 2021-04-16 | 西安航天源动力工程有限公司 | Anthracite low-methane gasification process and gasifier |
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| Publication number | Publication date |
|---|---|
| CN1900241B (en) | 2010-12-08 |
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