CN108424785B - 劣质重油双反应管碱性毫秒催化裂解和气化耦合工艺 - Google Patents

劣质重油双反应管碱性毫秒催化裂解和气化耦合工艺 Download PDF

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CN108424785B
CN108424785B CN201810341347.0A CN201810341347A CN108424785B CN 108424785 B CN108424785 B CN 108424785B CN 201810341347 A CN201810341347 A CN 201810341347A CN 108424785 B CN108424785 B CN 108424785B
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alkaline catalyst
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田原宇
乔英云
张金弘
车远军
唐瑞源
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China University of Petroleum East China
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Abstract

本发明提供劣质重油双反应管碱性毫秒催化裂解和气化耦合工艺，用高效雾化喷嘴将预热的重油喷入下行反应管上部，油雾与从返料器流下高温再生碱性催化剂混合、加热、汽化和裂解；油气和待生碱性催化剂向下高速顺流到下行反应管底部进行气固分离；油气进分馏塔分离，油浆返回重油循环使用，其他作为产品输出；待生碱性催化剂汽提后进入提升管气化反应器下部与氧化剂和水蒸气发生催化气化反应，反应温度750℃‑1000℃后，生成的合成气和再生碱性催化剂向上高速流到提升管气化反应器顶部进行气固分离；高温再生碱性催化剂流入调节返料器一部分作为固体载体进行循环、一部分返回提升管气化反应器下部继续气化，合成气换热后作为产品输出。

Description

劣质重油双反应管碱性毫秒催化裂解和气化耦合工艺
1.技术领域
本发明提供劣质重油双反应管碱性毫秒催化裂解和气化耦合工艺，属于重油加工领域。
2.背景技术
重油轻质化是当今世界各国石油加工的重要课题之一。我国大部分原油中渣油含量高，轻质油含量低，加之近年来一些重质油(稠油)产量不断增长和部分国外重质原油的引进使重油轻质化问题更为突出。重油加工方法常有催化裂化、溶剂脱沥青、减粘、焦化、热裂化、重油加氢等方法，总的说来，不外乎加氢和脱碳两大类，其中重油脱碳加工是当今石油炼制的主要方式，脱出碳的合理利用一直未得到很好解决。在重油固相载体循环裂解工艺中主要有重油催化裂解、灵活焦化、流化焦化、重油流化改质等。重油催化裂化除得到的目的产物 (汽柴油和烯烃化工原料)外，脱除的残碳在再生器中燃烧放热，一部分加热催化剂作为裂解的热源，一部分用取热器取热产生蒸汽外送或发电，反应温度较低约500℃－650℃，对重油原料的残碳和重金属含量要求较高，劣质重油难以满足要求；劣质重油灵活焦化和流化焦化反应温度低，约450℃－600℃，主要是生产焦化汽油、柴油和用作催化原料的焦化蜡油，焦碳燃烧部分循环作为热载体、部分气化产生合成气，但裂解时间过长，轻质油收率较低；劣质重油流化改质(如恩格哈德开发的ART工艺、洛阳石化设计院的HCC工艺等)采用与重油催化裂化工艺相似的循环流化床技术，反应温度约400℃－600℃，裂解时间短，轻质油收率较高，但由于脱除残炭量过大，外取热设计困难而限制了推广应用。
碱性催化剂相对酸性催化剂(如FCC分子筛催化剂、ZSM-5)适应于高温裂解制烯烃、不怕水蒸气高温失活，有利于抑制焦炭生成和焦炭催化气化，重油碱性催化裂解将成为重油预处理和化工型加工研究的一个热点。
另外由于国家环保要求越来越高，石油炼制企业又需要大量的氢气对轻质油品进行加氢精制以生产满足合格的车用燃料，但目前各炼化企业缺乏大量廉价的氢气源。
如何最经济、最清洁、最合理和最大化利用好重油，实现无渣化加工，将已成为我国石油工作者迫待解决的重大课题。
3.发明内容
本发明的目的就是为了克服现有重油加工技术存在的不足而开发出一种劣质重油双反应管碱性毫秒催化裂解和气化耦合工艺，既能高收率生产烯烃和轻质油，又能降低气化反应温度、得到大量廉价的氢气资源，实现重油加工无渣化。
本发明的技术方案：
本发明的目的是通过固体碱性催化剂双反应管循环与利用，高温碱性催化剂裂解重油生产烯烃和轻质油，结焦待生碱性催化剂气化再生生产合成气制取氢气，利用水蒸气气化吸热解决待生碱性催化剂再生热量过剩的难题，高温再生催化剂循环管返料循环催化气化解决了焦炭气化再生速率与重油裂解生焦速率不匹配的难题；低能耗实现重油加工无渣化。其特征是用高效雾化喷嘴将预热到180℃-350℃的劣质重油从下行反应管进料口喷入下行反应管上部，油雾与从双调控返料器流下的700℃-950℃高温再生碱性催化剂毫秒混合、加热、汽化和裂化，裂化反应温度为530℃-850℃，裂化油气和结焦待生碱性催化剂向下高速顺流到下行反应管底部的气固毫秒分离器进行气固分离；裂化油气进入分馏塔激冷和分离，塔底油浆返回与重油混合循环使用，其他汽柴油和液化气以及裂解干气作为中间产品输出；结焦的待生碱性催化剂汽提后通过流量控制器进入提升管气化反应器下部与氧化剂和水蒸气混合发生催化气化再生反应，反应温度为750℃-1000℃，生成的合成气和再生碱性催化剂向上高速流到提升管气化反应器顶部的气固分离器进行气固分离；分离的高温再生碱性催化剂流入双调控返料器，部分高温再生碱性催化剂按照3-12的剂油比流入下行反应管顶部参与循环、裂解重油，其余部分通过循环管返回到提升管气化反应器下部继续参与气化反应；合成气换热后作为产品输出，实现低能耗重油无渣化加工。
氧化剂为氧气、空气和富氧空气中的一种。
固体碱性催化剂为铝酸钙多孔微球、镁铝尖晶石多孔微球、硅酸钙多孔微球、硅酸镁多孔微球、负载碱金属或/和碱土金属的多孔载体中的一种或多种的混合物，粒径范围为10μ m-300μm。
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。
附图的图面设明如下：
1.合成气分离器，2.双调控返料器，3.高效雾化喷嘴，4.下行反应管，5.气固快速分离器， 6.裂解气出口，7.流量调节器，8.蒸汽入口，9.氧化剂入口，10.提升管气化反应器，11.换热器， 12.合成气出口，13.循环管，14.分馏塔
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1，高效雾化喷嘴(3)将预热到180℃-350℃的劣质重油从下行反应管(4)进料口喷入下行反应管(4)上部，油雾与从双调控返料器(2)流下的700℃-950℃高温再生碱性催化剂毫秒混合、加热、汽化和裂化，裂化反应温度为530℃-850℃；裂化油气和结焦待生碱性催化剂向下高速顺流到下行反应管(4)底部的气固快速分离器(5)进行气固分离；裂化油气从裂解气出口(6)进入分馏塔(14)激冷和分离，塔底油浆返回与重油混合循环使用，其他汽柴油和液化气以及裂解干气作为中间产品输出；结焦的待生碱性催化剂汽提后通过流量调节器(7)进入提升管气化反应器(10)下部与水蒸气入口(8)进入的氧气和氧化剂入口(9)进入的水蒸气混合发生气化反应，反应温度为750℃-1000℃，生成的合成气和再生碱性催化剂向上高速流到提升管气化反应器(10)顶部的气固分离器进行气固分离；分离的高温再生碱性催化剂流入双调控返料器(2)，部分高温再生碱性催化剂按照3-12的剂油比流入下行反应管(4)顶部参与循环、裂解重油，其余部分通过循环管(13)返回到提升管气化反应器(10)下部继续参与气化反应；合成气经过换热器(11)换热后从合成气出口(12)作为产品输出，实现低能耗重油无渣化加工。
实施例2，将实施例1中的氧气换为富氧空气，其他相同。
实施例3，将实施例1中的氧气换为空气，其他相同。
本发明所提供的劣质重油双反应管碱性毫秒催化裂解和气化耦合工艺，通过碱性催化剂固体双反应管循环与利用，用下行反应管高温毫秒接触碱性催化裂解残碳20％的重油生产烯烃和轻质油，烯烃收率相对提高10％－30％，轻质油收率提高14个百分点；利用提升管气化反应器进行结焦碱性催化剂气化再生生产合成气制取氢气，利用水蒸气气化吸热解决碱性催化剂再生热量过剩的难题，氢气产率250Nm3，设备结构简单、烧焦强度高，温度低；结焦碱性催化剂与高温水蒸气和氧化剂进行提升管气化再生生产合成气制取氢气，通过高温再生催化剂循环管返料循环催化气化解决了焦炭气化再生速率与重油裂解生焦速率不匹配的难题；氢气成本大大降低(约为70％),气化强度大，设备体积小，钢材耗量低，固定投资大大降低；常压操作简单，开停车方便，连续性好，油种适应性强；石油资源得到充分有效利用，低能耗实现了重油无渣化加工。

Claims (3)

1.劣质重油双反应管碱性毫秒催化裂解和气化耦合工艺，其技术特征是用雾化喷嘴将预热到180℃-350℃的劣质重油从下行反应管进料口喷入下行反应管上部，油雾与从双调控返料器流下的700℃-950℃高温再生碱性催化剂毫秒混合、加热、汽化和裂化，裂化反应温度为530℃-850℃；裂化油气和结焦待生碱性催化剂向下高速顺流到下行反应管底部的气固毫秒分离器进行气固分离；裂化油气进入分馏塔激冷和分离，塔底油浆返回与重油混合循环使用，其他汽柴油和液化气以及裂解干气作为中间产品输出；结焦的待生碱性催化剂汽提后通过流量控制器进入提升管气化反应器下部与氧化剂和水蒸气混合发生催化气化再生反应，反应温度为750℃-1000℃，生成的合成气和再生碱性催化剂向上高速流到提升管气化反应器顶部的气固分离器进行气固分离；分离的高温再生碱性催化剂流入双调控返料器，部分高温再生碱性催化剂按照3-12的剂油比流入下行反应管顶部参与循环、裂解重油，其余部分通过循环管返回到提升管气化反应器下部继续参与催化气化反应；合成气换热后作为产品输出。
2.根据权利要求1所述 的劣质重油双反应管碱性毫秒催化裂解和气化耦合工艺，其特征在于氧化剂为氧气、空气和富氧空气中的一种。
3.根据权利要求1所述 的劣质重油双反应管碱性毫秒催化裂解和气化耦合工艺，其特征在于固体碱性催化剂为铝酸钙多孔微球、镁铝尖晶石多孔微球、硅酸钙多孔微球、硅酸镁多孔微球、负载碱金属或/和碱土金属的多孔载体中一种或多种的混合物，粒径范围为5μm-300μm。
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