CN109609198A - 生物质循环流化床分级热解气化与高温除焦油除尘一体化工艺 - Google Patents

生物质循环流化床分级热解气化与高温除焦油除尘一体化工艺 Download PDF

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CN109609198A
CN109609198A CN201910038001.8A CN201910038001A CN109609198A CN 109609198 A CN109609198 A CN 109609198A CN 201910038001 A CN201910038001 A CN 201910038001A CN 109609198 A CN109609198 A CN 109609198A
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fluidized bed
gas
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semicoke
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CN109609198B (zh
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乔英云
田原宇
宗培杰
李�杰
明雪
姜媛
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China University of Petroleum East China
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Abstract

生物质循环流化床分级热解气化与高温除焦油除尘一体化工艺，生物质进入携带流化床中下部，与来自湍流流化床的高温合成气和热载体混合、加热，发生热解反应，并携带上行；裂解油气在携带流化床中上部发生气相催化裂解，焦油裂解成甲烷、乙烷等；反应后热载体、半焦和燃气经过四级气固分离，一级分离的大颗粒载体和半焦作为燃气裂解催化剂和过滤除尘的滤料，进入移动床过滤器分离出超细灰后返回湍流流化床进行气化反应，超细灰作为硅钾肥产品外送；二级分离的中小颗粒载体和半焦直接循环回湍流流化床，三级分离的细颗粒外排作为硅钾肥产品，四级移动床过滤器将燃气中的少量焦油再次催化裂解成甲烷、乙烷等的同时脱除超细灰，净化燃气作为产品外送。

Description

生物质循环流化床分级热解气化与高温除焦油除尘一体化 工艺
1.技术领域
发明提供生物质循环流化床分级热解气化与高温除焦油除尘一体化工艺，属于生物质能源领域。
2.背景技术
我国生物质资源量巨大，又是一种低硫和CO2“零排放”的可再生清洁能源，在世界能源安全和碳减排中都起到至关重要的作用。
作为生物质能规模化高效清洁利用的主要方式之一，气化技术使低能量密度的生物质从固态转化为变成较低分子量高品位的CO、H2、CH4等可燃气体，相对直接燃烧具有燃烧稳定、热效率高、污染低、尤其是PM2.5指数低等优点，可广泛应用于工农业生产的各个领域，如目前的集中供气、供热和发电，工业锅炉和窑炉等，从而实现低品位生物质能的深层次利用，减少矿物燃料消耗量，对于提高农村生活水平、改善生态环境、保障国家能源安全等具有重要意义。
生物质气化技术按气化炉类型可分为固定床气化技术、流化床气化技术及气流床气化技术。固定床气化技术设备结构简单，运行成本低，生物质转化率高达98％以上，但产生较多难处理的焦油以及含酚废水的二次污染，适合用于小规模气化；流化床气化技术能够用于大、中规模气化，操作负荷变化大，焦油含量低，但设备结构相对复杂，操作费用较大，气体热值低；气流床操作温度高、无焦油生成、气体后续处理难度低，但热值低、设备投资大。生物质气化的产品因为规模效应最适合用作燃气，急需开发转化率高、热值高、无焦油，且能有效利用生物质硅和钾资源的生物质气化技术和设备。
本发明人提出的生物质异形循环流化床气化工艺(CN102942965A)和生物质异形循环流化床气化炉(CN103102990A)，通过将先生物质临氢热解，再粗颗粒循环回湍流流化床半焦气化、细颗粒外排作为硅钾肥，既解决了生物质气化热值低、焦油难处理、规模小难题，又合理的利用了生物质的硅和钾资源，得到高含甲烷的燃气，但在原料性质和操作工况变动等工况下，仍难以彻底消除焦油和细灰，难以满足后续发电和供热的要求。而现有传统的消除焦油和粉尘的方法中，旋风分离除尘仅能除去5μm以上的灰尘，超细颗粒和焦油难以消除；水洗可以将焦油和粉尘同时除去，但会造成含酚废水二次污染、浪费能源和资源；填料式过滤可以将焦油和粉尘同时除去，单需要外加滤料，且滤料易堵塞，覆盖在其表面的焦油难以清除，增加了运行成本和投资；热裂解需要消耗部分燃气或半焦产生高温区来促进焦油分解，而催化裂解的催化剂积碳失活、成本高等，急需开发能同时消除焦油和粉尘的低能耗、低成本的气化、脱焦油、除尘一体化工艺。
3.发明内容
本发明的目的就是为了克服现有生物质气化技术存在的不足而提供一种生物质循环流化床分级热解气化与高温除焦油除尘一体化工艺，具有燃气热值高、无需外加滤料和加热实现燃气高温除焦油和粉尘净化一体化，不产生酚水、系统热效率高、能耗低、处理规模大等优势。
本发明的技术方案：
本发明的目的是通过将循环流化床顶部排出的高温燃气与热解半焦和热载体分级分离，大颗粒作为高温移动床催化裂解焦油和过滤除尘的滤料后再返回循环流化床下部的湍流流化床气化，中小颗粒直接循环回湍流流化床进行气化和起稳定燃烧作用，微细颗粒外排作为硅钾肥，净化后的燃气基本不含焦油和灰尘，可直接用于BIGCC发电或工业锅炉、窑炉的燃料，大幅度提高发电效率或燃烧效率，无含酚废水二次污染，无需外加滤料和能源。其特征是小于5mm的生物质颗粒进入循环流化床的携带流化床中下部，少量小于5mm的补充热载体加入到循环流化床的湍流流化床的下部；生物质颗粒与来自湍流流化床的750-950℃的高温合成气和热载体混合、加热、发生高温快速临氢热解反应，并高速携带上行；裂解油气在携带流化床的中上部700-900℃下发生气相临氢载体和半焦协同催化裂解反应，焦油裂解成甲烷、乙烷等低分子气态烃；反应后的热载体、半焦与高温燃气经过四级气固分离，一级气固分离器分离出的大颗粒载体和半焦作为燃气的高温催化裂解催化剂和过滤除尘的滤料，进入移动床高温过滤器，然后过滤后分离出超细灰的大颗粒载体和半焦经返料器返回湍流流化床进行燃烧和气化反应，超细灰作为硅钾肥产品外送；一级净化后的粗燃气进入二级气固分离器，分离出的中小颗粒载体和半焦直接循环回湍流流化床下部进行燃烧和气化反应；二级净化后的粗燃气进入三级气固分离器，分离出的细颗粒外排也作为硅钾肥产品；三级净化后的粗燃气进入四级移动床高温过滤器，将燃气中的少量焦油700-850℃下通过高温载体和半焦协同催化裂解成甲烷、乙烷等低分子烃类的同时脱除超细灰，净化燃气作为产品外送。
所用热载体为粉煤灰、白云石、橄榄石、石灰石、沸石、碱土金属催化剂、铁基催化剂或廉价催化剂中的一种或多种混合物。
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1为本发明的工艺示意图。附图的图面说明如下：
1、生物质颗粒入口 2、热载体入口 3、湍流流化床 4、携带流化床 5、一级气固分离器 6、二级气固分离器 7、三级气固分离器 8、移动床高温过滤器 9、超细灰分离器 10、一级返料器 11、二级返料器 12、净化燃气出口 13、超细硅钾肥产品出口 14、硅钾肥产品出口 15、空气或富氧空气和水蒸气入口 16、循环流化床 17、布风板
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，将小于5mm的生物质颗粒经生物质颗粒入口(1)送入循环流化床(16)中上部的携带流化床(4)的中下部，少量小于5mm的补充热载体从加入热载体入口(2)到循环流化床(16)的湍流流化床(3)的下部；生物质颗粒被来自湍流流化床(3)的750-950℃的高温合成气和高温热载体混合、加热、发生高温快速临氢热解反应，并高速携带上行；裂解油气在携带流化床(4)的中上部700-900℃下发生气相临氢载体和半焦协同催化裂解反应，焦油裂解成甲烷、乙烷等低分子气态烃；反应后的热载体、半焦与高温燃气经过四级气固分离，一级气固分离器(5)分离出的大颗粒载体和半焦，作为燃气的高温催化裂解催化剂和过滤除尘的滤料，进入移动床高温过滤器(8)，然后进入超细灰分离器(9)分离出超细灰后经一级返料器(10)返回湍流流化床(3)进行气化反应，超细灰从超细硅钾肥产品出口(13)排出；一级净化后的粗燃气进入二级气固分离器(6)，分离出的中小颗粒载体和半焦经二级返料器(11)直接循环回湍流流化床(3)下部进行气化和稳定燃烧；二级净化后的粗燃气进入三级气固分离器(7)，分离出的细颗粒从硅钾肥产品出口(14)外排；三级净化后的粗燃气进入四级移动床高温过滤器(8)，将燃气中的少量焦油700-850℃下通过高温载体和半焦协同催化裂解成甲烷、乙烷等低分子烃类的同时脱除超细灰后从净化燃气出口(12)外送。
本发明所提供的生物质循环流化床分级热解气化与高温除焦油除尘一体化工艺，通过燃气与热解半焦和热载体分级分离，大颗粒作为高温移动床过滤除尘的滤料后再返回湍流流化床气化，中小颗粒直接循环回湍流流化床进行气化和起稳定燃烧作用，微细颗粒外排作为硅钾肥；热解半焦流化气化的合成气和热载体为生物质高温快速临氢热解和焦油气相临氢半焦自催化裂解提供热源和临氢气氛，裂解焦油，提高燃气热值；所得高温燃气移动床干法净化预处理后基本不含焦油和灰尘，无含酚废水二次污染，可直接用于BIGCC发电或工业锅炉、窑炉的燃料，大幅度提高发电效率或燃烧效率；同时外排硅钾肥有效解决了因钾离子导致流化床气化易结焦死床的难题，又合理的利用了生物质的硅和钾资源，工艺过程简单，热能利用合理，一举多得。

Claims (2)

1.生物质循环流化床分级热解气化与高温除焦油除尘一体化工艺，其特征是小于5mm的生物质颗粒进入循环流化床的携带流化床中下部，少量小于5mm的补充热载体加入到循环流化床的湍流流化床的下部；生物质颗粒与来自湍流流化床的750-950℃的高温合成气和热载体混合、加热、发生高温快速临氢热解反应，并高速携带上行；裂解油气在携带流化床的中上部700-900℃下发生气相临氢载体和半焦协同催化裂解反应，焦油裂解成甲烷、乙烷等低分子气态烃；反应后的热载体、半焦与高温燃气经过四级气固分离，一级气固分离器分离出的大颗粒载体和半焦作为燃气的高温催化裂解催化剂和过滤除尘的滤料，进入移动床高温过滤器，然后过滤后分离出超细灰的大颗粒载体和半焦经返料器返回湍流流化床进行燃烧和气化反应，超细灰作为硅钾肥产品外送；一级净化后的粗燃气进入二级气固分离器，分离出的中小颗粒载体和半焦直接循环回湍流流化床下部进行燃烧和气化反应；二级净化后的粗燃气进入三级气固分离器，分离出的细颗粒外排也作为硅钾肥产品；三级净化后的粗燃气进入四级移动床高温过滤器，将燃气中的少量焦油700-850℃下通过高温载体和半焦协同催化裂解成甲烷、乙烷等低分子烃类的同时脱除超细灰，净化燃气作为产品外送。
2.根据权利要求1所述的生物质循环流化床分级热解气化与高温除焦油除尘一体化工艺，其特征在于所用热载体为粉煤灰、白云石、橄榄石、石灰石、沸石、碱土金属催化剂、铁基催化剂或廉价催化剂中的一种或多种混合物。
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