CN109628154A - 生物质下行循环床毫秒热解液化-气化耦合多联产工艺 - Google Patents

生物质下行循环床毫秒热解液化-气化耦合多联产工艺 Download PDF

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CN109628154A
CN109628154A CN201811501226.4A CN201811501226A CN109628154A CN 109628154 A CN109628154 A CN 109628154A CN 201811501226 A CN201811501226 A CN 201811501226A CN 109628154 A CN109628154 A CN 109628154A
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gas
biomass
gasification
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田原宇
乔英云
谢克昌
杨朝合
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China University of Petroleum East China
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Abstract

本发明提供生物质下行循环床毫秒热解液化‑气化耦合多联产工艺,生物质粉经热空气提升管干燥和提升并在顶部气固分级分离，空气外排，细颗粒进入半焦返料器，大中颗粒在下行热解反应器顶端与高温循环载体实现快速混合升温与毫秒热解，在反应器立管下部油气、热载体与半焦快速分离；热解油气经分馏塔获得不同馏分油品和干气，热载体和半焦进入气化提升管气化加热；加热后的高温载体经两级气固分离器与合成气分离后，合成气经过空气换热后与干气混合作为燃气用于发电，大中颗粒热载体进入下行热解反应器顶部作为高温循环热载体，细灰进入冷却料仓后外排作为硅钾肥；部分热空气被引到空气提升管底部，部分热空气被引到气化提升管底部。

Description

生物质下行循环床毫秒热解液化-气化耦合多联产工艺
1.技术领域
本发明提供生物质下行循环床毫秒热解液化-气化耦合多联产工艺，属于生物质能源领域。
2.背景技术
目前我国农林废弃物约8.8亿吨以上，由于缺乏有效利用技术而不得不被焚烧或废弃，不仅浪费资源，也造成雾霾天气、大气污染、土壤矿化、火灾和交通事故等大量社会经济和生态问题，成为公众关注的焦点和难点。现有生物质综合利用途径相当广，很多途径资源利用率和经济效益都很高，如造纸、直燃发电、纤维乙醇和沼气等，但由于规模和消耗量小、使用效率低、污染或特定地域要求，都不能从根本上满足生物质规模化高效高值化清洁的要求。近三十年新兴起的快速热解提炼技术将生物质转化为能量密度大、易于存贮和运输的液体，可生产车用替代燃料、液体燃料和化工原料，是环境友好性、最有希望的石油替代品，不存在产品规模和消费地域限制，能够满足大规模、高效、高值化和清洁无污染的要求，被公认为“本世纪生物能最有工业化发展潜力的技术”，既是目前国际上生物质能研发的重点和热点，又是我国战略新兴产业-新能源领域的前沿探索项目。
国际上代表性工艺主要有荷兰Twente大学的旋转锥式反应工艺、美国Georgia工学院的携带床反应工艺、加拿大Ensyn工程师协会的鼓泡循环流化床工艺、美国国家可再生能源实验室(NREL)涡旋反应工艺、加拿大Laval大学的多层真空热解磨反应工艺等。国内各单位也相继开发了类似技术。但由于工艺缺陷和不足，目前仅有旋转锥工艺、鼓泡循环流化床工艺实现了万吨级工业化生产。在上述工艺中，仅有循环流化床快速热解工艺利用热解产生的部分半焦循环燃烧产生的热量即可满足反应所需热量的需求，能量利用合理、液体收率高、设备简单、易于大型化、也是被国内外研究的最多，被认为是最有可能实现工业化生产的生物质快速热解工艺。但一般循环流化床热解需要流化气、冷却负荷大，流化磨损产生的细粉油中难以脱除。下行循环流化床具有顺重力场并流下行运动、固固或气固接触时间短、反应快、径向分布均匀、返混小、并能灵活地调节固/气或固比等优点，既保持了流化床热解得高液体收率和大规模化生产优点，又无需流化风、热解气停留时间小、颗粒磨损细粉少，降低了冷却负荷和能耗，油中脱灰相对容易，因而下行循环流化床将是生物质快速热解亟待开发和应用的最佳反应器。但由于生物质原料含钾、含水量较高，同时生物质原料以及热解半焦与载体比重差异大，目前国际上典型的快速热解工艺中，普遍存在热质传递与反应调控、油中带灰、油中高含水、液收率低、油气结焦堵塞、半焦载体异重返料、生物油加热自聚、流化气稀释干气和耗能、含钾载体熔融导致床料结焦死床、生物质原料干燥、反应器机械运动部件高温磨损、半焦安全外排和清洁利用等影响生物质快速热解技术工业放大和长周期稳定运行的十一大难题。
本发明人提出的一种固体有机物自混合下行流化床快速热解工艺(ZL200810000615.9)为下行自混合流化床反应器和流化床再生器耦合，形成一个固体热载体循环的反应再生耦合系统，实现了热质传递与反应的调控。尽管通过热载体分级分离，大中颗粒热载体通过下行热解反应器热解、微小颗粒热灰外排，从源头上消除热灰造成的油中带灰难题。但生物质粉干燥后未分级分离,其中的细小颗粒还会从源头上产生油中带灰现象。油气未直接进行分馏，油中高含水问题未能有效解决。另外油气结焦堵塞、半焦载体异重返料、生物油加热自聚和生物质原料干燥难题一直困扰生物质自混合下行流化床快速热解工艺的工业化推广。
3.发明内容
本发明的目的就是为了克服现有生物质热解液化技术存在的不足而提出的一种生物质下行循环床毫秒热解液化-气化耦合多联产工艺，既彻底解决了生物质热解液化的热质传递与反应调控、油中带灰、油中高含水、液收率低、油气结焦堵塞、半焦载体异重返料、生物油加热自聚、流化气稀释干气和耗能、含钾载体熔融导致床料结焦死床、生物质原料干燥、反应器机械运动部件高温磨损、半焦挥发分调控和清洁利用等的十一大工程化共性难题，避免了半焦外排的二次污染和着火的安全隐患，最大化获得液体产品，得到较高热值的燃气用于发电，简化流程，降低投资。
本发明的技术方案：
本发明的目的是通过将生物质粉和热载体均实现分级分离，大中颗粒载体和生物质通过下行热解反应器热解、生物质细粉直接送入气化提升管气化加热，细颗粒载体直接外排做硅钾肥，从源头上消除油中带灰、半焦清洁利用和生物质灰利用以及含钾载体熔融导致床料结焦死床的难题。其特征是将大量当量直径不大于10mm的生物质粉经热空气提升管干燥和提升，并在顶部生物质粉被二级气固分离器分级分离，空气外排，细颗粒生物质通过半焦返料阀进入气化提升管，大中颗粒生物质经旋转进料器在下行热解反应器顶端与通过高温载体返料阀下落的高温循环热载体迅速实现快速混合升温与毫秒热解，在反应器立管下部油气与半焦和热载体在气固分离器作用下快速分离；热解油气经分馏塔获得不同馏分油品和干气，热载体和半焦进入气化提升管气化加热；加热后的高温载体经两级气固分离器与合成气分离后，合成气经过水换热和空气换热后与干气混合作为燃气用于发电，大中颗粒热载体进入下行热解反应器顶部作为高温循环热载体，细灰进入冷却料仓后外排作为硅钾肥；经过加压风机排出的空气经过空气换热器加热后，部分热空气通到热空气提升管底部提升和干燥生物质粉，部分热空气通到气化提升管底部与水蒸气混合作为气化剂与半焦发生气化反应。
气化提升管反应温度为750℃-1000℃。
高温热载体与生物质粉的混合比例为2-8：1。
下行热解反应器出口反应温度为450℃-600℃。
空气换热后温度不大于450℃。
本发明将实施例来详细叙述本发明的特点。
4.附图说明
附图为本发明的工艺示意图。附图的图面设明如下：
1、气化提升管 2、气体分布器 3、进气管 4、惯性气固分离器 5、高温载体返料控制器 6、热载体二级气固分离器 7、细灰冷却料仓 8、下行热解反应器 9、油气气固分离器10、油气分馏塔 11、重油出口 12、轻油出口 13、木醋液出口 14、加压风机 15、热空气提升管 16、合成气一级气固分离器 17、上部料仓 18、旋转进料器 19、合成气二级气固分离器20、空气出口 21、生物质粉入口 22、干气出口 23、半焦返料阀 24、水换热器 25、空气换热器 26、燃气出口。
下面结合附图和实施例来详述本发明的工艺特点。
5.具体实施方式
实施例，
将大量当量直径不大于10mm的生物质粉经生物质粉入口(21)进入热空气提升管(15)干燥和提升，生物质颗粒被合成气一级气固分离器(16)和合成气二级气固分离器(19)分级分离，空气从空气气出口(20)外排，细颗粒生物质通过半焦返料阀(23)进入气化提升管(1)，大中颗粒生物质经旋转进料器(18)在下行热解反应器(8)顶端与通过高温载体返料阀(5)下落的高温循环热载体迅速实现快速混合升温与毫秒热解，在下行热解反应器(8)立管下部油气与半焦和热灰在油气气固分离器(9)作用下快速分离，热载体和半焦通过空气输送的半焦返料阀(23)进入气化提升管(1)与进气管(3)和气体分布器(2)来的空气和水蒸气混合、气化燃烧加热；热解油气经分馏塔(10)获得木醋液(13)、轻油(12)、重油(11)和热解干气(22)；加热后的高温热载体经惯性气固分离器(4)和热载体二级气固分离器(6)与合成气分离后，合成气经过水换热器(24)和空气换热器(25)两级换热后与干气混合作为燃气用于发电，大中颗粒热载体进入下行热解反应器(8)顶部作为高温循环载体，细灰进入冷却料仓(7)后外排作为硅钾肥；经过加压风机(14)排出的空气经过空气换热器(25)加热后，部分热空气被引到热空气提升管(15)底部提升和干燥从生物质粉入口(21)加入的生物质粉，部分热空气被引到气化提升管(1)底部与经过水换热器(24)得到的水蒸气混合作为气化剂与半焦发生气化反应。
气化提升管(1)反应温度为750℃-1000℃。
高温热载体与生物质粉的混合比例为2-8：1。
下行热解反应器(8)出口反应温度为450℃-600℃。
空气换热后温度不大于450℃。
本发明所提供的生物质下行循环床毫秒热解液化-气化耦合多联产工艺，通过将生物质粉和热载体均实现分级分离，大中颗粒载体和生物质通过下行热解反应器热解、生物质细粉和热解半焦直接送入气化提升管气化加热，细热载体直接外排做硅钾肥，从源头上解决了半焦清洁利用、消除油中带灰、流化气稀释干气和耗能和生物质灰利用以及含钾载体熔融导致床料结焦死床的难题。利用气化提升管的高气速、下行管的自由落体以及半焦返料器消除了半焦载体异重返料难题；利用双管(下行反应管和气化提升管)耦合解决了热质传递与反应的调控和反应器机械运动部件高温磨损的难题；利用油汽直接分馏解决了油气结焦堵塞和生物油加热自聚以及油中高含水难题；利用热空气干燥生物质，解决了生物质原料干燥难题，提高了热解升温速率从而提高了液体收率，这些技术措施的集成，从而解决了影响生物质快速热解技术工业放大和长周期稳定运行的十一大工程化共性难题，消除了困扰生物质自混合下行流化床快速热解-气化耦合多联产工艺工业化推广的瓶颈。不同生物质快速热解的液体收率：松木粉68％、杨木粉62％、玉米秸秆39％、棉花秸秆55％，油中含灰小于0.2％，含水小于1％；混合气体热值约2100大卡，硅钾肥收率为10％左右。

Claims (5)

1.生物质下行循环床毫秒热解液化-气化耦合多联产工艺，其特征是将大量当量直径不大于10mm的生物质粉经热空气提升管干燥和提升，并在顶部生物质粉被二级气固分离器分级分离，空气外排，细颗粒生物质通过半焦返料阀进入气化提升管，大中颗粒生物质经旋转进料器在下行热解反应器顶端与通过高温载体返料阀下落的高温循环热载体迅速实现快速混合升温与毫秒热解，在反应器立管下部油气与半焦和热载体在气固分离器作用下快速分离；热解油气经分馏塔获得不同馏分油品和干气，热载体和半焦进入气化提升管气化加热；加热后的高温载体经两级气固分离器与合成气分离后，合成气经过水换热和空气换热后与干气混合作为燃气用于发电，大中颗粒热载体进入下行热解反应器顶部作为高温循环热载体，细灰进入冷却料仓后外排作为硅钾肥；经过加压风机排出的空气经过空气换热器加热后，部分热空气通到热空气提升管底部提升和干燥生物质粉，部分热空气通到气化提升管底部与水蒸气混合作为气化剂与半焦发生气化反应。
2.根据权利要求1所述的生物质下行循环床毫秒热解液化-气化耦合多联产工艺，其特征在于气化提升管反应温度为750℃-1000℃。
3.根据权利要求1所述的生物质下行循环床毫秒热解液化-气化耦合多联产工艺，其特征在于高温热载体与生物质粉的混合比例为2-8：1。
4.根据权利要求1所述的生物质下行循环床毫秒热解液化-气化耦合多联产工艺，其特征在于下行热解反应器出口反应温度为450℃-600℃。
5.根据权利要求1所述的生物质下行循环床毫秒热解液化-气化耦合多联产工艺，其特征在于空气换热后温度不大于450℃。
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