CN117946716B - 富油煤分级气相催化裂解与气化再生组合制化工原料工艺 - Google Patents
富油煤分级气相催化裂解与气化再生组合制化工原料工艺 Download PDFInfo
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Abstract
本发明提供富油煤分级气相催化裂解与气化再生组合制化工原料工艺,将小于6mm的干燥富油煤粉在下行热解反应器顶端与高温循环半焦实现快速混合升温与快速热解，在下行热解反应器立管下部油气与半焦分离；半焦进入一级提升管气化加热，在提升管顶部高温半焦与合成气气固分离，半焦进入下行热解反应器顶部循环，合成气外排；热解油气直接进入下行催化裂解反应器与高温再生裂解催化剂快速混合升温与催化裂解，在下行催化裂解反应器立管下部油气与待生裂解催化剂分离，裂解油气经分馏塔得到三烯三苯、2‑4环稠环芳烃等基本化工原料，待生裂解催化剂经二级提升管气化再生后循环使用，合成气外排。
Description
技术领域
本发明提供富油煤分级气相催化裂解与气化再生组合制取化工原料工艺，属于煤化工领域。
背景技术
含油率≥7%的低阶煤（褐煤和长焰煤）被称为富油煤，在我国储量丰富，其热解挥发物含有不低于1000亿吨油气，远高于我国石油和天然气现有的600亿吨可采储量，是廉价易得的潜在油气资源。以油气为主要产品的热解提质是业界公认的富油煤清洁高效高值化利用技术路线，但因存在焦油收率较低、含灰较高、装置结焦堵塞和含酚废水难处理、高活性半焦粉自燃和规模化利用困难等瓶颈，目前国内外尚未有能商业化运行的单套规模百万吨级工业装置。
另外，富油煤热解提质所产焦油目前主要用于加氢生产汽柴油，但随着动力电池技术快速迭代以及汽车排放标准更加严格，新能源汽车销量呈指数式快速增长，必将带来汽柴油消费量快速下降。因此，现以车用燃料为目标的煤焦油加工利用技术路线难以满足未来交通能源体系变革的需求，亟需超前研发富油煤直接清洁高效制取大宗化工原料、构建高值化利用产业链的新技术，为富油煤清洁高效利用产业可持续发展提供保障。
发明内容
本发明的目的是为了克服现有煤热解提质技术存在的不足而提出的富油煤分级气相催化裂解与气化再生组合制取化工原料工艺，既解决了低阶煤流化床热解提质的油中带灰、含酚废水、焦油收率低等难题，又合理统筹利用余热，还得到了高附加值的三烯三苯、2-4环稠环芳烃、合成气等化工原料以及燃气，同时解决了半焦粉自燃和规模化利用难题。
本发明的技术方案：
本发明通过将裂解干气活化强化干燥煤粉下行床快速热解和焦油气相催化裂解，破解焦油收率低难题；半焦粉气化再生制合成气，破解半焦粉自燃和规模化利用难题；热解油气直接气相催化裂解制取三烯三苯和2-4环稠环芳烃等大宗高值化工原料，充分利用富油煤中低温快速热解油气的族组成特性，破解焦油高值原料化利用、油中带灰和含酚废水以及系统热能利用效率等难题。
本发明提供富油煤分级气相催化裂解与气化再生组合制取化工原料工艺, 其特征是将小于6mm的干燥富油煤粉加入到下行热解反应器顶端，与550-1000℃循环半焦载体快速混合与升温，并在被循环半焦载体活化的循环裂解干气强化作用下，在500-580℃下快速热解，最大化生成热解油气；在下行热解反应器下部进行热解油气与热解半焦分离，热解半焦返回一级提升管与气化剂在750-1200℃下气化加热，并在一级提升管顶部气固分离，加热合成气经过余热回收后送往耐硫变换和净化工段，750-1200℃的半焦粉作为循环半焦载体流入下行热解反应器顶部与干燥富油煤粉反应；500-580℃的热解油气直接进入下行催化裂解反应器与650-850℃的再生裂解催化剂快速混合与升温，在580-700℃下催化裂解，并在下行催化裂解反应器下部裂解油气与待生裂解催化剂分离，裂解油气经分馏塔得到三烯三苯、2-4环稠环芳烃等基本化工原料以及裂解干气，部分裂解干气返回作为循环裂解干气；待生催化裂解催化剂经二级提升管燃烧再生后，再生催化裂解催化剂返回下行催化裂解反应器顶部与热解油气混合与反应，再生烟气经过余热回收后外排。
循环半焦载体与大中颗粒富油煤的混合比例为2-10：1，热解油气与催化裂解催化剂的剂油比为4-10：1。
催化裂解催化剂为酸性分子筛催化剂、碱性多孔催化剂或酸碱复合催化剂。
待生催化裂解催化剂再生为燃烧再生，或碱性多孔催化剂气化再生。
气化剂为水蒸气与氧气、富氧或空气。
本发明将实施例来详细叙述本发明的特点。
附图说明
附图1为本发明的工艺示意图。附图1的图面设明如下：
1、富油煤加料口 2、下行热解反应器 3、热解油气气固分离器 4、半焦返料器 5、一级提升管 6、气化剂入口 7、半焦气固分离器 8、裂解油气气固分离器 9、待生裂解催化剂返料器 10、加热半焦返料器 11、合成气出口 12、裂解干气活化器 13、分馏塔 14、二级提升管 15、再生催化裂解催化剂气固分离器 16、烟气出口 17、裂解干气出口 18、三烯出口 19、三苯出口 20、2-4环稠环芳烃出口 21、下行催化裂解反应器。
下面结合附图和实施例来详述本发明的工艺特点。
具体实施方式
实施例，将小于6mm的干燥富油煤粉通过富油煤加料口（1）加入到下行热解反应器（2）顶端，与通过加热半焦返料器（10）加入的550-1000℃循环半焦载体快速混合与升温，并在循环裂解干气通过裂解干气活化器（12）被循环半焦载体活化产生的氢和小分子烃自由基强化作用下，在500-580℃下快速热解，最大化生成热解油气；在下行热解反应器（2）下部通过热解油气气固分离器（3）进行热解油气与热解半焦分离，热解半焦通过半焦返料器（4）返回一级提升管（5），与气化剂入口（6）送入的气化剂在750-1200℃下气化加热，并在一级提升管（5）顶部气固分离，加热合成气经过余热回收后送往耐硫变换和净化工段，750-1200℃的半焦粉作为循环半焦载体流入下行热解反应器（2）顶部与干燥富油煤粉反应；500-580℃的热解油气直接进入下行催化裂解反应器（21），与再生催化裂解催化剂气固分离器（15）分离得到的650-850℃再生裂解催化剂快速混合升温，在580-700℃下催化裂解，并在下行催化裂解反应器（21）下部通过裂解油气气固分离器（8）进行裂解油气与待生裂解催化剂分离，裂解油气经分馏塔（13）从三烯出口（18）和三苯出口（19）得到三烯三苯 、从2-4环稠环芳烃出口（20）得到2-4环稠环芳烃等基本化工原料、从裂解干气出口（17）得到裂解干气，部分裂解干气作为循环裂解干气返回裂解干气活化器（12）；从裂解油气气固分离器（8）分离出的待生裂解催化剂经过待生裂解催化剂返料器（9）返回二级提升管（14），在650-850℃下燃烧再生，在二级提升管（14）顶部气固分离，再生烟气经过余热回收后外排，再生催化裂解催化剂返回下行催化裂解反应器（21）顶部与热解油气混合与反应。
本发明所提供的富油煤分级气相催化裂解与气化再生组合制取化工原料工艺，通过将裂解干气活化强化的富油煤快速热解和热解油气直接气相催化裂解制取三烯三苯和2-4环稠环芳烃以及半焦气化再生的过程耦合，焦油相对收率为理论焦油收率的130%以上，油中杂质含量小于0.1%，并将其最大化转化生产三烯三苯、2-4环稠环芳烃和合成气化工原料。以含油13.4%的新疆准东富油煤为原料进行分级气相催化裂解与气化再生组合最大化制取化工原料，焦油相对收率提至140%；以焦油计，乙烯、丙烯和丁烯总收率19.5%、烯烷比为15，粗苯15%、二到四环芳烃馏分50.5%，焦粉全部生成合成气；焦油脱氧率45%、脱硫率60%、脱氮率40%。
Claims (4)
1.富油煤分级气相催化裂解与气化再生组合制化工原料工艺, 其特征是将小于6mm的干燥富油煤粉加入到下行热解反应器顶端，与550-1000℃循环半焦载体快速混合与升温，并在被循环半焦载体活化的循环裂解干气强化作用下，在500-580℃下快速热解，最大化生成热解油气；在下行热解反应器下部进行热解油气与热解半焦分离，热解半焦返回一级提升管在750-1200℃下气化加热，并在一级提升管顶部气固分离，高温加热合成气经过换热器回收余热后送往耐硫变换和净化工段，750-1200℃的半焦粉作为循环半焦载体流入下行热解反应器顶部与干燥富油煤粉反应；500-580℃的热解油气直接进入下行催化裂解反应器与650-850℃的再生裂解催化剂快速混合与升温，在580-700℃下催化裂解，并在下行催化裂解反应器下部裂解油气与待生裂解催化剂分离，裂解油气经分馏塔得到三烯三苯、2-4环稠环芳烃以及裂解干气，部分裂解干气返回作为循环裂解干气；待生催化裂解催化剂经二级提升管燃烧再生后，再生催化裂解催化剂返回下行催化裂解反应器顶部与热解油气混合与反应，再生烟气经过换热器回收余热后外排。
2.根据权利要求1所述的富油煤分级气相催化裂解与气化再生组合制化工原料工艺，其特征在于循环半焦载体与大中颗粒富油煤的混合比例为2-10：1，催化裂解催化剂与热解油气的剂油比为4-10：1。
3.根据权利要求1所述的富油煤分级气相催化裂解与气化再生组合制化工原料工艺，其特征在于催化裂解催化剂为酸性分子筛催化剂、碱性多孔催化剂或酸碱复合催化剂；待生催化裂解催化剂再生为燃烧再生，或碱性多孔催化剂气化再生。
4.根据权利要求1所述的富油煤分级气相催化裂解与气化再生组合制化工原料工艺，其特征在于气化剂为水蒸气与氧气、富氧或空气。
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