CN101597025A - The biomass supercritical water gasification hydrogen production absorption reactor thermally that solar heat drives - Google Patents
The biomass supercritical water gasification hydrogen production absorption reactor thermally that solar heat drives Download PDFInfo
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- CN101597025A CN101597025A CNA2009100231861A CN200910023186A CN101597025A CN 101597025 A CN101597025 A CN 101597025A CN A2009100231861 A CNA2009100231861 A CN A2009100231861A CN 200910023186 A CN200910023186 A CN 200910023186A CN 101597025 A CN101597025 A CN 101597025A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses the biomass supercritical water gasification hydrogen production absorption reactor thermally that a kind of solar heat drives.This absorption reactor thermally cavity is connected with conical surface solar energy secondary condenser, can effectively improve resorber aperture place heat flow density; Be provided with serpentine tube stream biomass supercritical water reactor in the resorber cavity, the continuous flow in reaction tubes of biomass and supercritical water absorbs focused solar energy direct radiation and cavity inner wall secondary rays, the generating gasification hydrogen production reaction; The serpentine tube flow reactor is divided into preheating section and conversion zone, has realized being rapidly heated of biomass material; This absorption reactor thermally cavity inner wall is built into refractory brick, external application silicate insulating cotton; The absorption reactor thermally angle of inclination can be regulated by the base adjusting screw(rod).This absorption reactor thermally drives one of core in the biomass supercritical water gasification hydrogen production device as solar heat, can carry out the continuous gasification hydrogen manufacturing of various biomass in supercritical water.It is low to have cost, safely and efficiently characteristics.
Description
Technical field
The invention belongs to the clean trans-utilization field of sun power utilization and biomass and organic waste, relate to the biomass supercritical water gasification hydrogen production technology, the biomass supercritical water gasification hydrogen production absorption reactor thermally that particularly a kind of solar heat drives.
Background technology
Along with the exhaustion of fossil energy, reach the pollution of serious environmental day by day that fossil oil brings, it is extremely urgent to develop renewable substitute energy.Hydrogen is considered to the following bridge that connects renewable energy source and chemical fuel as the excellent energy carrier.Therefore, develop the research focus that extensive hydrogen producing technology becomes present energy circle.
The biomass supercritical water hydrogen producing technology is the emerging hydrogen producing technology that begins to grow up the seventies in last century.The characteristics of biomass supercritical water hydrogen producing technology are mild conditions, only need about 600 ℃ temperature, and biomass can obtain higher vaporization rate; Reaction product contains coke, tar hardly, and process is pollution-free; The humidogene material need not be dry, can directly handle, and saved dry required great amount of cost; Biomass material, as agricultural and trade waste, municipal effluent etc. can obtain the synthetic gas of high heating value after treatment, and itself has also obtained purifying treatment.Because it compares traditional biological matter transformation technology and emerging thermo-chemical decomposition of water hydrogen producing technology has above-mentioned plurality of advantages, the countries in the world scholar has carried out extensive and deep research to it.External that early carry out this work is the Modell of MIT, and he is initiative in patent US4113446 to have carried out various organic catalytic gasifications and non-catalyzed gasification experiment in supercritical water environment.The Antal of University of Hawaii provides a kind of biomass supercritical water gasification device in patent WO1996030464, carried out the catalytic gasification of the carbon-contained catalyst of biomass such as glucose, bagasse, mud, and realized being gasified totally of part biological matter.Also have the scholar to utilize the characteristics of supercritical water in addition, carry out a lot of significant work.In patent US20080099377, utilize supercritical water to carry out the pollution-free trans-utilization of hydrocarbon polymers such as heavy oil, pitch as He, Okajima utilizes basic catalyst that papermaking wastewater and waste paper etc. is carried out the supercritical water high-efficiency gasification in patent JP2005270768-A, has realized the separation of carbonic acid gas and the removal of objectionable impurities.At home, the international key lab of the power engineering polyphasic flow of Xi'an Communications University has at first carried out the supercritical water gasification device and the theoretical investigation of biomass, has successively applied for three patents.Wherein, patent ZL02114529.6 provides a kind of small-sized continuous biomass supercritical water reaction apparatus, and adopts CMC and biomass blended method to solve the heterogeneous problem of failing of mixing continuously of high pressure first; The notion that proposed patent ZL200510041633.8 coal and biomass gasify has altogether improved the supercritical water gasification efficient of coal greatly; Apply for a patent CN101058404A and adopt supercritical water fluid bed method, solved the problem of high-concentration raw material gasification, reactor tube walls slagging scorification, the method realization response self-heating of supercritical water partial oxidation is provided.
But, more than to mention the research of various supercritical water gasification hydrogen productions only be the theoretical investigation that stays in the laboratory scope.The development final purpose of hydrogen producing technology becomes the bridge of renewable energy source and chemical energy source.Therefore, utilize renewable energy source must be become by hydrogen production process provides energy potential.Sun power is as the energy the most widely that distributes on the earth, and reserves are huge and do not have a region restriction.Utilize solar hydrogen making, be about to storage of solar energy among chemical energy source,, become the focus of hydrogen preparation field to solve the difficult problem that sun power is discontinuous, disperse, be difficult for storage.At present, the solar hydrogen making technology is divided into solar energy photocatalytic/photochemical transformation hydrogen manufacturing, solar energy bio-transformation hydrogen manufacturing, solar heat chemical conversion hydrogen manufacturing.And direct Driven by Solar Energy thermo-chemical decomposition of water and Wood Adhesives from Biomass hydrogen manufacturing are considered to the most possible in the near future industrialized hydrogen producing technology of realizing.Driven by Solar Energy thermo-chemical decomposition of water and biomass-making hydrogen methods have a variety of, as direct water of decomposition, and two step or multistep processes water of decomposition, methane reforming hydrogen manufacturing or the like, and directly Driven by Solar Energy biomass supercritical water gasification hydrogen production technology is not seen relevant report.
Summary of the invention
The biomass supercritical water gasification hydrogen production absorption reactor thermally that the object of the present invention is to provide a kind of solar heat to drive, the realization of this absorption reactor thermally success the coupling of solar collector and biomass supercritical water reactor.
In order to reach above purpose, the technical solution used in the present invention is:
This absorption reactor thermally comprises solar collector, snakelike biomass supercritical water pipe flow reactor, conical surface solar energy secondary condenser, auxiliary electrical heating, armoured thermocouple, wall thermopair, adjusting screw(rod), pylon.Conical surface solar energy secondary condenser is connected mutually with the solar collector aperture; Solar collector is built-in with snakelike biomass supercritical water pipe flow reactor; Solar collector is supported by pylon, and its angle of inclination is regulated by adjusting screw(rod); The solar collector bottom is provided with the auxiliary electrical heating; Fluid temperature (F.T.) in the snakelike biomass supercritical water pipe flow reactor is monitored by armoured thermocouple, and reactor outside wall temperature and solar collector cavity inner wall temperature are by a plurality of wall thermocouple monitorings.
Described solar collector is square cavity type absorber, and cavity inner wall is built into by refractory brick, the outside lagging material that coats, and its inner wall surface area compares greater than 30 with the aperture area, can do black matrix and handle; The solar collector aperture is connected mutually with conical surface solar energy secondary condenser; The angle of inclination of solar collector is consistent with heliostat spin axis axial angle, and described angle of inclination can be regulated by adjusting screw(rod); Solar collector is supported by pylon, and it has determined it to be more suitable for carrying out industry and amplified based on the characteristics of tower condenser system.
Described snakelike biomass supercritical water pipe flow reactor is divided into preheating section and conversion zone.Adopt snakelike layout, can make reactor energy-flux density distribution everywhere be tending towards even; The distribution design of preheating section and conversion zone has realized being rapidly heated of biomass, can effectively improve the gasification result of biomass supercritical water; Serpentine tube inner fluid temperature is monitored by armoured thermocouple, and the temperature of its monitoring is respectively reactor preheating water temperature in, the hot preheating water of armouring and biomass material mixing temperature, reactor outlet reaction product temperature; Serpentine tube outside wall surface temperature is by a plurality of wall thermocouple monitorings.
Described conical surface solar energy secondary condenser is used for the sun power that heliostat focuses on is carried out secondary condensation, can effectively improve the optically focused ratio, reduces the solar collector thermosteresis.
The heating of described auxiliary electrical is used for keeping the biomass supercritical water hydrogen production reaction under sunlight intermittent phase or situation about weakening.And, hydrogen fuel cell creates conditions for being added to solar-heating biomass supercritical water hydrogen generating system.
Outstanding technical characterstic of the present invention is:
(1) the successful realization solar collector and the coupling of biomass supercritical water reactor.Focusing sunlight directly provides heat for the biomass supercritical water gasification hydrogen production reaction, has avoided the heat transfer loss of middle heat-transfer medium, has improved system efficiency, for the high-efficiency gasification hydrogen production reaction of realizing solar heat driving biomass supercritical water creates conditions.
(2) the biomass supercritical water reactor adopts snakelike deployment tube flow reactor, and heat flow density is evenly distributed.Reaction tubes is divided into preheating section and conversion zone, helps being rapidly heated of biomass material, guaranteed the high-efficiency gasification of biomass.
(3) the solar collector aperture is connected conical surface solar energy secondary condenser, helps improving the optically focused ratio, improves the heat flow density of resorber aperture, reduces the thermosteresis of solar collector.Satisfy hydrogen generating system at the optically focused ratio that guarantees condenser system and require under the prerequisite, the employing of secondary condensation device can reduce the technology of heliostat and make requirement, thereby reduces the optically focused cost.
(4) solar collector adopts cavity type absorber, can effectively reduce the radiation loss of resorber.Its inwall is built into refractory brick, can bear big thermal load.
(5) the solar collector angle of inclination can be regulated by its base screw rod, so that its angle of inclination is adjusted to consistent with the spin axis axial angle of heliostat, has guaranteed spotlight effect.
Description of drawings
Fig. 1 is a solar absorption structure of reactor synoptic diagram of the present invention
Fig. 2 be among Fig. 1 solar absorption reactor A-A to cutaway view Amplified image.
Fig. 3 is the length computation result curve of snakelike biomass supercritical water pipe flow reactor.
Fig. 4 is the distribution curve of certain time point serpentine tube flow reactor outside wall surface temperature.
The present invention is described in further detail below in conjunction with the embodiment of the invention and accompanying drawing.
Embodiment
With reference to Fig. 1, shown in Figure 2, the solar absorption reactor comprises: comprise solar collector 8, snakelike biomass supercritical water pipe flow reactor 4, conical surface solar energy secondary condenser 11, auxiliary electrical heating 14, armoured thermocouple 1,6,13, wall thermopair 3, adjusting screw(rod) 15, pylon 16.
Snakelike biomass supercritical water pipe flow reactor 4 is arranged in solar collector 8 inside, shone by focusing sunlight; Solar collector cavity 19 makes it approach black matrix according to design requirements, after being focused the sunlight irradiation intensification, also can carry out the secondary rays heating to serpentine tube flow reactor 4.Serpentine tube flow reactor 4 is divided into conversion zone 2 and preheating section 9, and preheating section 9 is in order to the heating preheating water, and preheating water and biomass material flow into conversion zone 2 and carry out gasification reaction behind the mixing point thorough mixing.
The preheating water temperature in is by armoured thermocouple 13 monitorings of installing on preheating water inlet tube 12, and the mixing temperature of preheating water and biomass material is by armoured thermocouple 1 monitoring, and conversion zone exports 5 reaction product temperature by armoured thermocouple 6 monitorings; Solar collector 8 inner wall temperatures, serpentine tube flow reactor 4 outside wall temperatures are by a plurality of wall thermopair 3 monitorings; Each temperature value can be gathered by the automatic temp acquisition system of buying.
Auxiliary electrical heating 14 is used for reducing or the intermittent phase in sunlight intensity, for the biomass supercritical water gasification reaction provides auxiliary energy, with guarantee hydrogen production reaction continue carry out; Auxiliary electrical heating 14 is arranged in solar collector cavity 19 bottoms, forms with a plurality of resistance wire coilings.
Need to prove that the cone surface secondary solar energy secondary condenser 11 that the present invention adopts is buying equipment.
Working process:
1, by the preheating water supply system preheating water is delivered in the reaction of serpentine tube stream by the preheating water inlet, and regulates preheating water pressure to preset pressure by booster system.
2, open the solar automatic tracking system of heliostat, focusing sunlight is entered in the solar collector by aperture after assembling through the conical surface solar energy secondary condenser secondary, heating mobile preheating water in reactor.
3, after preheating water fluid temperature (F.T.) and pressure surpass the super critical point of water in the serpentine tube stream reaction tubes, biomass material is delivered to reactor by the feed(raw material)inlet pipe by the biomass material supply system.
4, normal temperature material and high temperature preheating water are behind the mixing point thorough mixing, and heating up rapidly enters conversion zone absorption heat, and the biomass supercritical water gasification hydrogen production reaction takes place.
5, reaction product enters gas-liquid separation device and product analysis, sampling system by the reacting product outlet pipe.
6, provide in the process of energy for whole biomass supercritical water hydrogen production reaction in focusing sunlight,, open the auxiliary electrical heating if the situation of sunlight irradiation strength degradation occurs, to guarantee the supercritical state of water, keep hydrogen production reaction continue carry out.
With reference to shown in Figure 3, X-coordinate is the residence time of supercritical water in reactor, and ordinate zou is the reactor computational length, and the ratio of each bar curve correspondence is the ratio of the mass rate of preheating water and biomass material, calculates according to principle of conservation of energy.Assumed condition is: the reactor outlet temperature is 600 ℃, and the biomass material temperature in is 25 ℃, and reactor pressure is 24MPa; Do not consider reaction heat, biomass slurries rerum natura is taken as the rerum natura of water; Suppose to reclaim reactor outlet fluid section energy by the mode of interchanger, this portion of energy is used to heat preheating water.The reactor outlet fluid is set at 100 ℃ through temperature after the heat exchange, and efficiency of heat exchanger is 0.5, calculates the preheating water temperature in according to energy balance; Reactor inner fluid rerum natura qualitative temperature is that reactor is imported and exported the preheating water medial temperature; Reactor material is 316 stainless steels, and specification is Φ 10 * 2; The sun power incident power is 6Kw, and the reactor assimilated efficiency is 0.6.
With reference to shown in Figure 4, among the figure: the distribution sequence of temperature point 1-56 is that conversion zone exports to the preheating section temperature in; The 1-28 measuring point is the conversion zone measuring point, and 30-57 is the preheating section measuring point, and No. 29 measuring points are preheating water and biomass material mixing point, and 57 is preheating section temperature in measuring point, and 1 is conversion zone temperature out measuring point.By accompanying drawing 4 as can be known, 56-30 measuring point wall temperature is the near-linear rule and rises, and temperature value reaches a peak value when rising to No. 30 measuring points; Because high temperature preheating water mixes rapidly at No. 30 measuring point places with the normal temperature biomass material, whole fluid temperature (F.T.) descends rapidly subsequently; Fluid is heated by direct solar radiation and wall secondary rays afterwards, and temperature occurs peak value since No. 30 rapid risings of measuring point up to No. 16 measuring points; After No. 16 measuring points, wall surface temperature tends to balance, but is subjected to the influence of solar irradiation influence of fluctuations and gasification hydrogen production reaction heat, and temperature has fuctuation within a narrow range.Can see that from accompanying drawing 4 curvature of twice temperature uphill process of fluid is very consistent, all present the rule of approximately linear, and climbing speed be very fast.Hence one can see that superperformance that this reactor has the heat absorption efficiency height, is heated evenly, its fast temperature rise rate guaranteed carrying out continually and steadily of biomass gasifying hydrogen making reaction.
Embodiment: as the biomass model compound, in this absorption reactor thermally, carried out the biomass supercritical water gasification hydrogen production experiment with 0.2mol/L glucose.The experiment place: Xi'an, 108 ° 55 of east longitude ', 34 ° 15 of north latitude ', the direct irradiation intensity average out to of the sun on same day 720w/m
2Serpentine tube flow reactor pipe range 30m, preheating section is 0.6 with conversion zone length ratio; Preheating water and biomass material slurries mass rate are respectively 3.6kg/h and 1.2kg/h; The reactor fluid pressure is 24MPa; Solar collector cavity aperture diameter is 250mm; The solar collector angle of inclination is 19.4 °.Under these conditions, this reactor has been realized lasting highly effective hydrogen yield, and the glucose vaporization rate surpasses 110%, and the carbon gasification rate is the highest to surpass 77%, and hydrogen volumetric concentration in gaseous product surpasses 51%.
Annotate: biomass quality * 100% of vaporization rate=gaseous product quality/participation reaction
Biomass carbon quality * 100% of the carbon quality of carbon gasification rate=gasification product/participation reaction
Claims (3)
1, a kind of biomass supercritical water gasification hydrogen production absorption reactor thermally of solar heat driving, comprise solar collector (8), snakelike biomass supercritical water pipe flow reactor (4), conical surface solar energy secondary condenser (11), electrical auxiliary heater (14), armoured thermocouple (1,6,13), wall thermopair (3), adjusting screw(rod) (15), pylon (16), it is characterized in that conical surface solar energy secondary condenser (11) is connected with solar collector (8) aperture (10); Solar collector (8) is built-in with snakelike biomass supercritical water pipe flow reactor (4); Solar collector (8) is supported by pylon (16), and its angle of inclination is regulated by adjusting screw(rod) (15); Solar collector (8) bottom is provided with electrical auxiliary heater (14); Fluid temperature (F.T.) in the snakelike biomass supercritical water pipe flow reactor (4) is monitored by armoured thermocouple (1,6,13), armoured thermocouple (1,6,13) is connected with snakelike biomass supercritical water pipe flow reactor (4) respectively, and snakelike biomass supercritical water pipe flow reactor (4) outside wall temperature and solar collector (8) cavity inner wall temperature are monitored by a plurality of wall thermopairs (3).
2, the biomass supercritical water gasification hydrogen production absorption reactor thermally of solar heat driving according to claim 1, it is characterized in that, solar collector (8) is square cavity type absorber, cavity inner wall is built into by refractory brick (20), the outside lagging material (21) that coats, its inner wall surface area and aperture (10) area ratio is greater than 30; The angle of inclination of solar collector (1) and heliostat spin axis axial angle are consistent.
3, the biomass supercritical water gasification hydrogen production absorption reactor thermally of solar heat driving according to claim 1, it is characterized in that, snakelike biomass supercritical water pipe flow reactor (4) is divided into preheating section (9) and conversion zone (2), adopt snakelike layout, the normal temperature biomass material mixes with the high temperature fluid in preheating section (9) exit and the back that is rapidly heated flows into rapid generating gasification hydrogen production reaction in the conversion zone (2).
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