CN103361087A - 一种热解耦合燃烧循环反应方法及装置 - Google Patents
一种热解耦合燃烧循环反应方法及装置 Download PDFInfo
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- CN103361087A CN103361087A CN2012101359173A CN201210135917A CN103361087A CN 103361087 A CN103361087 A CN 103361087A CN 2012101359173 A CN2012101359173 A CN 2012101359173A CN 201210135917 A CN201210135917 A CN 201210135917A CN 103361087 A CN103361087 A CN 103361087A
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- pyrolysis
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 176
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 108
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 75
- 239000000969 carrier Substances 0.000 claims abstract description 34
- 238000010168 coupling process Methods 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims description 92
- 239000011343 solid material Substances 0.000 claims description 23
- 230000001808 coupling Effects 0.000 claims description 22
- 238000005859 coupling reaction Methods 0.000 claims description 22
- 239000003575 carbonaceous material Substances 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound 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- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 27
- 239000003245 coal Substances 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000004058 oil shale Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 34
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- 238000005516 engineering process Methods 0.000 description 8
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- 238000010517 secondary reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
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- 238000005243 fluidization Methods 0.000 description 3
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Classifications
-
- 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
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
一种热解耦合燃烧循环方法和装置,它将细粒含碳物质(煤炭、生物质、油页岩等)通过快速热解和燃烧转化成油、气、热产品的一体化方法和装置,主要包括流化床燃烧室、热解室和固体循环系统,与现有技术相比,由于采用燃烧和热解结构与功能的一体化集成设计,使燃烧与热解耦合技术的流程得到缩短,装置紧凑,集成度高,占地面积小,热效率高;热解反应热同时由两种方式获得,即由流化床燃烧室内半焦燃烧获得的高温壁面或导热构件和固体热载体同时提供,因而热解能力得以加强,设备生产能力大,油、气产品回收率高。
Description
一种热解耦合燃烧循环反应方法及装置
所属技术领域:
[0001] 本发明涉及含碳固体燃料能源化工领域,具体地,本发明涉及一种热解耦合燃烧循环反应方法及装置,是将细粒含碳物质通过热解和燃烧处理,从而转化成油、气、热产品的方法及装置。这里所指的含碳物质包括煤炭、生物质、油页岩等,也可以是它们的混合物。
背景技术:
[0002] 中国能源资源储量以煤炭为主,石油及天然气资源严重短缺。至2009年底,中国已探明煤炭储量占世界总量的13.9%,而石油与天然气分别只占1.1%及1.3%。石油与天然气的缺乏是我国能源产业存在的主要问题之一,特别是石油短缺已成为限制我国今后经济发展、威胁我国能源安全的严峻问题。迫于这一压力,利用煤、生物质等固态含碳物质制取替代燃(原)料的液化技术备受瞩目。
[0003]目前我国原煤除部分用于炼焦转化加工外,绝大部分用于直接燃烧,导致煤中具有较高经济价值的富氢组分得不到合理利用。煤等含碳物质通过热解处理,可以得到半焦和热解气,对热解气进一步 处理(如冷却、吸收等),可以得到热解油和煤气,半焦则可以通过燃烧方式处理。实践证明,先将含碳物质进行热解处理,继而对半焦进行燃烧处理,可以比较经济地获得油、气、热等产品,且资源利用率高。有关资料表明,煤炭气化、液化法投资远高于热解提油工艺。
[0004] 已开发出多种热解工艺,其中利用块煤的直立炉热解技术已被广泛使用,但细粒煤的热解尚没有商业化的解决办法,急待开发。
[0005]细粒煤等含碳物质热解工艺一般是借助热载体把热量直接传递给含碳物质,受热后的含碳物质发生热解反应。其中,气体热载体热解工艺通常是将燃料燃烧的烟气引入热解室,代表性的有美国的COED工艺,ENCOAL工艺和波兰的双沸腾床工艺等;固体热载体热解工艺则利用高温的半焦、灰渣或其他固体物料与煤在热解室内混合,利用固体热载体的显热将煤热解。与气体热载体热解工艺相比,固体热载体热解避免了煤热解析出的挥发产物被烟气稀释,同时降低了冷却系统的负荷。比较而言,在能获得高温固体热源的情况下,固体热载体热解工艺优势明显。上述固体热载体煤热解工艺起步较早,但至今没有实现商业化应用,其主要原因在于:①无论是以高温半焦还是其它固体物料(如瓷球等)作为热载体,都需要通过额外的燃料燃烧对其供热,导致整个过程热效率较低;②以热解焦循环使用作为热载体,得到的半焦产品是燃烧过的焦渣与新鲜焦渣的混合物,其作为优质燃料的利用价值较低。
[0006] 近年来,随着循环流化床燃烧技术的发展,基于循环流化床的固体热载体煤热解(即热解与燃烧耦合)工艺作为煤炭资源综合利用的最佳方式之一日益受到重视。循环流化床燃烧炉有两个重要特征:一是可以高效地燃烧劣质燃料;二是炉内存在稳定的高温热灰循环流,它携带了大量可在炉外利用的热量。利用这两个特征,可以用循环热灰作为固体热载体将含碳物质热解以产生煤气和焦油,干馏后的半焦用作为燃料送入循环流化床燃烧炉以生产蒸汽、发电或供热,实现热、电、油、气的多联产。类似的技术有济南锅炉厂开发的煤热解的“多联产”工艺、中科院过程工程研究所提出的循环流态化碳氢固体燃料的四联产工艺、中科院工程热物理所开发的煤粉锅炉的炉前煤拔头方法、中科院山西煤炭化学研究所开发的基于循环流化床的煤热解多联产工艺等。上述基于循环流化床燃烧的固体热载体煤热解工艺合理地利用循环流化床锅炉的高温热灰作为煤热解热源,实现热、电、油、气的多联产,克服了传统固体热载体工艺存在的问题,因而比传统工艺更具有竞争力。其优点主要表现在:①循环流化床锅炉提供了大量可在炉外利用的热灰,以此作为稳定的高温热载体来源;②利用循环流化床锅炉燃烧劣质燃料的优势,热解半焦直接返回锅炉燃烧,从而克服了传统固体热载体热解工艺固体产物利用价值低的问题。上述工艺存在的主要不足之处是:流程较长,设备较多;热解反应热仅由高温循环灰提供,因为数量有限,由此限制了热解反应器的生产能力,从而降低了整个系统的生产能力,或者降低了固体含碳物质的热解程度,使油、气产品产率下降;热解过程中产生的热解气不能尽快导出,存在与高温物料接触时间长等问题,因而会导致较多的热解气体发生二次反应,从而降低了油的收率。
[0007] 为了能更多地给热解反应提供热量和减少热解气导出阻力,中国专利ZL201110098415.3公布了一种技术解决方案,S卩,另在热解反应器的外侧建设加热炉(室),通过在固体 物质充填层内设置传热性能好的内置构件(一端与加热炉相连)将加热炉的热量传递给热解反应器,这样,热解反应热就可以由高温循环灰和加热炉共同提供;内构件壁面与含碳物质间构成间隙,提供热解气的排出通道,其不足之处是:需要另建加热炉(室),增加了系统的复杂程度;加热炉(室)通常采用气体燃料加热,从而增加了煤气消耗,降低了系统的效率;由于热解室料层通常较厚(因为热解过程缓慢或为提高热解程度)所以热解气排出路径较长,其次内构件壁面与含碳物质间构成的间隙又常会被细粒物料填充所以热解气导出阻力仍较大,而且热解气是沿高温的内置构件壁面导出的,这都将加剧其二次反应,从而使油产率下降。
[0008] 此外,上述基于循环流化床的煤热解与燃烧耦合的技术(如专利ZL01218480.2和ZL201110098415.3)都采用半焦燃烧炉和热解炉分开独立布置,因而,这些技术方案还存在以下不足:独立布置的燃烧炉和热解炉均对外散热,散热面积较大,因而系统的热损失较大;半焦在燃烧炉燃烧产生的热量仅以高温灰形式传递给热解炉,因而半焦燃烧炉产生的热量只有一小部分被热解过程利用。
发明内容:
[0009] 为了克服现有技术存在的不足,本发明的目的是要提供一种热解耦合燃烧循环反应方法和装置,它具有流程短、设备少、油回收率高、生产能力大、热效率高的优点。
[0010] 为达到上述目的,本发明的技术解决方案是:
[0011 ] 一种热解耦合燃烧循环反应方法,
[0012] a)将固体含碳物质加入热解室,进行热解反应后,产生半焦和含焦油的热解气;含焦油的热解气由热解室的热解气出口排出;半焦和固体热载体从热解室下部排出,经下返料机构送入流化床燃烧室;
[0013] b)向流化床燃烧室通入空气或含有氧气的混合气体;半焦在流化床燃烧室燃烧或气化;来自流化床燃烧室的携带固体颗粒的高温烟气引入气固分离机构,分离出的固体颗粒作为固体热载体经上返料机构送入热解室,与含碳物质混合,直接为热解反应提供热量;由流化床燃烧室排出部分灰渣。
[0014] c)流化床燃烧室燃烧反应产生的热量通过热传导方式间接地为热解反应提供热量。
[0015] 所述的热传导方式为流化床燃烧室和热解室至少有一处共用的壁面或至少在一处流化床燃烧室壁面和热解室壁面紧密接触或至少有一个两端分别与燃烧室与热解室连接的传热性能良好的导热构件。
[0016] 本发明还提供了一种用于实施权利要求1的热解耦合燃烧循环反应装置,该装置为双套筒结构,其中流化床燃烧室为装置的内筒、内筒与外筒之间的环形空间为热解室或者热解室为装置的内筒、内筒与外筒之间的环形空间为流化床燃烧室,所述的装置包括:力口料机构、流化床燃烧室、热解室、气固分离机构、烟气出口、上返料机构、下返料机构、热解气出口、空气入口和排渣口,流化床燃烧室上部设有气固分离机构,气固分离机构的气相出口与烟气出口相连,气固分离 机构的固相出口通过上返料机构与热解室上部相连,热解室上设有加料机构和热解气出口,热解室的下部通过下返料机构与流化床燃烧室相连。
[0017] 所述的热解耦合燃烧循环反应装置,在其所述热解室内设置若干个依靠重力作用能引导固体物料逐步下降流动的传热性能好、耐高温的导流构件,至少导流构件的一端或一侧与流化床燃烧室壁面紧密接触。
[0018] 所述的热解耦合燃烧循环反应装置,在其所述热解室内设置的导流构件,所述的导流构件为螺旋式下降的板式结构或呈辐射状的板式结构或断面为U型槽的螺旋式下降结构。
[0019] 所述的热解耦合燃烧循环反应装置,其所述的上返料机构和下返料机构是气动式固体物料阀或螺旋输送机。
[0020] 所述的热解耦合燃烧循环反应装置,其所述的气固分离机构为旋风分离器或惯性分离器或重力沉降器或以上装置的组合。
[0021] 所述的热解耦合燃烧循环反应装置,在其所述的热解室中加入粒径0.2〜2mm之间的颗粒作为固体热载体。
[0022] 本发明与现有技术相比,具有如下有益效果:
[0023] (I)由于本发明采用流化床燃烧室和热解室一体化结构,装置热损失小、热效率闻;
[0024] (2)热解反应热同时由两种方式获得,即由流化床燃烧室内半焦燃烧获得的高温壁面或导热构件和固体热载体共同提供,因而热解能力得以加强,设备生产能力大,油、气产品回收率高;
[0025] (3)本发明中燃烧炉和热解炉实现了结构与功能的一体化集成设计,使燃烧与热解耦合技术的流程得到缩短,装置紧凑,集成度高,占地面积小。
附图说明:
[0026] 图1为本发明含内置导流构件的内筒为燃烧室的双套筒热解装置结构示意图。
[0027] 图2为本发明含内置导流构件的内筒为热解室的双套筒热解装置结构示意图。
[0028] 附图标识
[0029] 1、流化床燃烧室 2、热解室 3、气固分离机构[0030] 4、上返料机构 5、加料机构 6、下返料机构
[0031] 7、导流构件
具体实施方式:
[0032] 本发明的原理是:
[0033] 固体含碳物质在热解室内同时接受来自流化床燃烧室高温壁面或高温导热构件(间接加热)和固体热载体(直接加热)两种形式的热量,发生热解反应,生成半焦和含有焦油的热解气。含焦油的热解气由热解气出口导出,关于回收焦油和煤气净化可按现有成熟技术方式处理。半焦和固体热载体通过下返料机构进入流化床燃烧室,与空气或其它含氧混合气体发生反应,产生热量,使流化床燃烧室壁面成为高温壁面或形成高温的导热构件,并加热固体热载体。燃烧产生的高温烟气携带固体颗粒进入气固分离机构,由此分离出的固体热载体经上返料机构进入热解室上部,与新加入固体含碳物质混合,从而实现了热载体的循环。
[0034] 在热解室内 可以设置若干个依靠重力作用能引导固体物料逐步下降流动的传热性能好、耐高温的导流构件,至少导流构件的一端或一侧与流化床燃烧室壁面紧密接触或与导热构件紧密接触。导流构件可以是螺旋式下降的板式结构,也可以是若干呈辐射状与流化床燃烧室相连的板式结构或断面为U型槽的螺旋式下降结构或上述结构的组合。导流构件的主要作用是:①引导固体物料缓慢向下流动,以减少热解气中粉尘的数量;②借助其良好的导热性能,将流化床燃烧室壁面或高温导热构件的热量传递给更多的被热解的物质为热解气的导出创造良好的条件。当采用螺旋式下降的板式结构的导流构件时,其上表面和流化床燃烧室以及热解室壁面形成固体物料流动通道,适当减小该通道内固体物料的高度(即料层高度适当小于螺距),就可以在料层上表面形成一个空层(即没有固体物料的空间),该空层可成为热解气流动通道,在相应高度上设置若干个热解气出口,就可在较小的阻力下将热解气引出,从而减少其二次反应,提高焦油产率。当采用若干呈辐射状与流化床燃烧室外壁相连的板式结构的导流构件时,由于在热解室外壁的不同高度设有开口向上的热解气出口,热解气导出路径也较常规的热解炉短,从而可减少其发生二次反应,提高焦油产率;当采用断面为U型槽的螺旋式下降结构的导流构件时,可将其一侧与流化床燃烧室壁面紧密接触,固体物料沿U型槽缓慢下降,固体热载体和高温U型槽对其加热,发生热解反应,此时热解气可顺利地由U型槽的另一侧导出,从而减少热解气的二次反应。
[0035] 调节通入流化床燃烧室的空气量,可以调节该燃烧室的温度(影响壁面温度和固体热载体温度)和固体热载体的循环量,从而可调节热解室温度,相应地调节了热解过程。所以,本装置既可以在低温下稳定运行,也可以在较高的温度下稳定运行,这样就可针对不同的原料,以及对产品的不同要求,选择适宜的热解温度。
[0036] 流化床燃烧室既可设计为鼓泡床,也可设计为常规的循环流化床,也可设计为高速流化的输送床,当采用后者时将会增加固体热载体的循环量并减小燃烧室的截面积。
[0037] 上返料机构和下返料机构既可以采用螺旋输送机,也可以采用气动式固体物料阀(如U阀、L阀),当采用后者时可以通过调节其流化风量来调节固体物料输送量,从而可相应的调节固体物料在热解室内的停留时间。
[0038] 固体热载体可以是半焦燃烧后产生的灰渣,也可以采用河沙、氧化铝球等颗粒物质。一般而言,对于灰分含量较低的含碳物质(如生物质)热解时可采用河沙或氧化铝球等作固体热载体,需要定期向热解室或流化床燃烧室中加入这些固体热载体。
[0039] 以下结合附图和实施例对本发明作做进一步详细说明。
[0040] 实施例1
[0041] 热解耦合燃烧循环反应装置为内筒为燃烧室的双套筒结构的一体化装置,如附图1所示,包括:加料机构5、流化床燃烧室1、热解室2、气固分离机构3、烟气出口、上返料机构4、下返料机构6、热解气出口、空气入口和排渣口,其中流化床燃烧室I为装置的内筒,内筒与外筒之间的环形空间为热解室2,流化床燃烧室I上部设置气固分离机构3,其气相出口与烟气出口相连,其固相出口通过上返料机构4与热解室上部相连,热解室上部设有加料机构5和热解气出口,热解室的下部通过下返料机构6与流化床燃烧室I相连。在本例中气固分离机构为旋风分离器,上返料机构和下返料机构为均为气动式固体物料阀。
[0042] 在本实施例中,固体含碳物质在热解室内同时接受来自流化床燃烧室高温壁面(间接加热)和固体热载体(直接加热)两种形式的热量,发生热解反应,生成半焦和含有焦油的热解气。含焦油的热解气 由热解气出口导出。半焦和固体热载体通过固体物料阀进入流化床燃烧室,与空气或其它含氧混合气体发生反应,产生热量,使流化床燃烧室壁面成为高温壁面,并加热固体热载体(灰渣或河沙)。燃烧产生的高温烟气携带固体颗粒进入旋风分离器,由此分离出的固体热载体经固体物料阀进入热解室上部,与新加入固体含碳物质混合,从而实现了热载体的循环。
[0043] 实施例2
[0044] 本实施例是实施例1的改进装置,如图1所示,除在热解室2内设置螺旋式下降的板式结构的导流构件7外,其余部分与实施例1相同。该导流构件的一侧与流化床燃烧室壁面相连,另一侧与热解室壁面相连。
[0045] 本实施例中,由于在热解室内设置了与流化床燃烧室高温壁面相连的导流构件7,会产生如下有益效果:①由流化床燃烧室壁面、导流构件的上表面和热解室壁面构成固体流动通道,由于导流构件具有良好的导热性能,因而这三个壁面都处于高温状态,强化了固体物料在热解室内的间接加热过程;②通过控制加料速度,适当减小上述通道内固体物料的高度(即料层高度适当小于螺距),就可以在料层上表面形成一个空层(即没有固体物料的空间),该空层可成为热解气流动通道,在热解室相应高度上设置若干个热解气出口,可在较小的阻力和较短的路径下将热解气引出,从而减少其二次反应,提高焦油产率;③引导固体物料缓慢向下流动,以减少热解气中粉尘的数量。
[0046] 实施例3
[0047] 热解耦合燃烧循环反应装置为内筒为热解室的双套筒结构的一体化装置,如图2所示,包括:加料机构5、流化床燃烧室1、热解室2、气固分离机构3、烟气出口、上返料机构
4、下返料机构6、热解气出口、空气入口和灰渣出口,其中热解室2为装置的内筒,内筒与外筒之间的环形空间为流化床燃烧室1,流化床燃烧室I上部设置气固分离机构3,其入口与流化床燃烧室相连,其气相出口与烟气出口相连,其固相出口通过上返料机构4与热解室上部相连,热解室上设有加料装置5和热解气出口,热解室的下部通过下返料机构6与流化床燃烧室I相连。在本例中气固分离机构为旋风分离器,上返料机构和下返料机构为均为气动式固体物料阀。[0048] 实施例4
[0049] 本实施例是实施例3的改进装置,如图2所示,除在热解室内2设置断面为U型槽的螺旋式下降结构的导流构件7外,其余部分与实施例3相同。
[0050]由于U型槽的外侧与流化床燃烧室壁面紧密接触,固体物料沿U型槽缓慢下降,固体热载体和高温U型槽对物料加热,发生热解反应,此时热解气可顺利地由U型槽上部经其内侧围成的垂直通道导出,从而减少热解气的二次反应。
[0051] 需要指出的是,对于本发明具体的实施方法,如内构件的形状、数量、安装方式,上、下返料机构以及气固分离机构等仍可进行修改和改进,但都不会由此而背离权利要求书中所规定的本发明的范围和基本精神。
[0052] 本发明作为把粉状含碳物质(如煤、油页岩、生物质等)转化成液体、气体化学产品和热能的反应装置,结构简单,投资省,易于操作,液体产品收率高,热解得到的液体产品可做为石油产品的替代品,气体产品可作为燃料或合成气使用,有利于环境保护,符合循环经济的政策,具有广阔 的应用前景。
Claims (8)
1.一种热解耦合燃烧循环反应方法,其特征在于, a)将固体含碳物质加入热解室,进行热解反应后,产生半焦和含焦油的热解气;含焦油的热解气由热解室的热解气出口排出;半焦和固体热载体从热解室下部排出,经下返料机构送入流化床燃烧室; b)向流化床燃烧室通入空气或含有氧气的混合气体;半焦在流化床燃烧室燃烧或气化;来自流化床燃烧室的携带固体颗粒的高温烟气引入气固分离机构,分离出的固体颗粒作为固体热载体经上返料机构送入热解室,与含碳物质混合,直接为热解反应提供热量;由流化床燃烧室排出部分灰渣。 c)流化床燃烧室燃烧反应产生的热量通过热传导方式间接地为热解反应提供热量。
2.根据权利要求1所述的热解耦合燃烧循环反应方法,其特征在于,所述的热传导方式为流化床燃烧室和热解室至少有一处共用的壁面或至少在一处流化床燃烧室壁面和热解室壁面紧密接触或至少有一个两端分别与燃烧室与热解室连接的传热性能良好的导热构件。
3.一种用于实施权利要求1所述方法的热解耦合燃烧循环反应装置,其特征在于,所述的装置为双套筒结构,其中流化床燃烧室为装置的内筒、内筒与外筒之间的环形空间为热解室或者热解室为装置的内筒、内筒与外筒之间的环形空间为流化床燃烧室,所述的装置包括:加料机构、流化床燃烧室、热解室、气固分离机构、烟气出口、上返料机构、下返料机构、热解气出口、空气入口和排渣口,流化床燃烧室上部设有气固分离机构,气固分离机构的气相出口与烟气出口相连,气固分离机构的固相出口通过上返料机构与热解室上部相连,热解室上设有加料机构和热解气出口,热解室的下部通过下返料机构与流化床燃烧室相连。
4.根据权利要求3所述的热解耦合燃烧循环反应装置,其特征在于,在其所述热解室内设置若干个依靠重`力作用能引导固体物料逐步下降流动的传热性能好、耐高温的导流构件,至少导流构件的一端或一侧与流化床燃烧室壁面紧密接触。
5.根据权利要求4所述的热解耦合燃烧循环反应装置,其特征在于,所述的导流构件为螺旋式下降的板式结构或呈辐射状的板式结构或断面为U型槽的螺旋式下降结构。
6.根据权利要求3所述的热解耦合燃烧循环反应装置,其特征在于,其所述的上返料机构和下返料机构是气动式固体物料阀或螺旋输送机。
7.根据权利要求3所述的热解耦合燃烧循环反应装置,其特征在于,其所述的气固分离机构为旋风分离器或惯性分离器或重力沉降器或以上装置的组合。
8.根据权利要求3所述的热解耦合燃烧循环反应装置,其特征在于,在其所述的热解室中加入粒径0.2〜2mm之间的颗粒作为固体热载体。
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