CN111171861B - 一种液相加氢工艺及液相加氢反应器 - Google Patents
一种液相加氢工艺及液相加氢反应器 Download PDFInfo
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- CN111171861B CN111171861B CN201811327950.XA CN201811327950A CN111171861B CN 111171861 B CN111171861 B CN 111171861B CN 201811327950 A CN201811327950 A CN 201811327950A CN 111171861 B CN111171861 B CN 111171861B
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Abstract
本发明公开了一种液相加氢工艺及液相加氢反应器。该工艺包括如下内容：溶氢原料油进入加氢反应段与加氢催化剂接触发生加氢反应，得到的反应流出物进入纳/微米氢气注入段，与经陶瓷膜管分散的纳/微米氢气混合，混合物流进入气提段与加氢催化剂接触进行加氢反应，同时氢气将物流中的H2S、NH3反应气体气提出来，经弧形管顶部的气体出口排出，液相反应流出物由反应出口流出。本发明通过设置特殊结构的反应器，实现加氢反应过程的持续高效性、均匀性，在反应过程中将H2S、NH3等抑制反应进行的气体及时移出反应体系，有利于提高加氢反应速率和实现深度加氢。
Description
技术领域
本发明属于石油化工领域，具体为一种液相加氢工艺及液相加氢反应器。
背景技术
现有技术中的液相加氢反应器一般为常规的液相加氢反应器，原料油氢气和先经过静态混合器混合后进入加氢反应器发生加氢反应，在反应过程中加氢脱硫副产物H2S对加氢脱硫反应、加氢脱氮和加氢脱芳反应也有明显的抑制作用。主要有以下两个原因：一是由于H2S分压能够影响加氢脱硫反应的活化能，以甲苯为例，硫化氢分压为0时，反应活化能为16kcal/mol，当H2S分压达到42kpa时，活化能上升到20 kcal/mol；二是H2S在催化剂表面为单层吸附，一旦吸附中心被H2S占据，少量H2S存在就会大大降低加氢脱硫速率，因此采用有效的手段消除H2S的影响是解决深度脱硫的关键问题。
因此，从现有技术中的液相加氢反应过程来看，主要存在以下问题：（1）在反应过程中加氢脱硫副产物H2S对加氢脱硫反应、加氢脱氮和加氢脱芳反应也有明显的抑制作用，在反应过程中不能及时移走，对于实现深度加氢具有不利影响；（2）反应进料中原料油能够溶解的氢气量较少，对于氢油比稍大的加氢反应过程来说，远远不能满足氢耗的需要，就需要通过大量的循环油进行辅助溶解，这样就大幅度降低了反应效率，同时增加了反应系统的体积；（3）反应过程不均匀，主要是由于氢气在原料油中的分散不均匀，使液相加氢反应过程存在反应不均、局部热点的问题，影响催化剂使用寿命。为此，液相加氢反应系统需要进一步改进，即开发适应液相加氢反应的新型反应系统，以提高加氢反应效率、氢气的利用率和加氢反应深度以及催化剂使用寿命。
CN105647577A提出了一种烃类连续液相加氢工艺方法，方法包括：气液混合步骤通过气液混合器进行，液相物流与氢气充分混合为溶解氢气饱和的液相物流；加氢反应步骤用于将流入反应器的溶解氢气饱和的液相物流，按照从反应器底部向反应器顶部流动方向与每级催化剂床层进行液相接触反应，同时通过氢气分配器向液相物流中注入新氢，以实现液相物流的高效加氢反应。同时该方法还公开了一种液相加氢装置，装置包括以气液混合气和一多段反应器，多段反应器连接于气液混合器，每段反应器包括至少两段催化剂床层，相邻的催化剂床层之间设置有一氢气分配器。该方面的目的是在增加氢气在原料油中的溶解分散量，取消循环氢和循环油系统，但是该工艺过程较为复杂，需要多台反应器串联，另外普通的混合器的气液混合能力十分有限，对改进氢气在原料油中的溶解分散量十分有限。
CN101993720A提出了一种烃油液相加氢方法，该方法取消了循环氢和循环氢压缩机，氢气在溶剂或者稀释剂的存在下与新鲜原料油和部分循环油混合形成混合物流，混合物流进入反应器与催化剂接触，另一部分或者全部循环油与氢气混合，一路或者分路从反应器催化剂床层之间进入反应器，反应流出物部分脱出H2S作为循环油，另一部分进入分离器，其中氢气在溶剂或者稀释剂中的溶解度大于氢气在新鲜原料油和溶剂或者稀释剂混合物中的溶解度。该方法中一方面将循环油在循环前将H2S脱除，避免H2S与含硫化合物形成表面竞争吸附而抑制加氢脱硫反应；另一方面为了改善原料油中的氢气溶解分散量，加入了大量的溶剂或循环油。该方法中，一方面将循环前在循环前将H2S脱除，但反应过程中生成的H2S并未及时脱除，对加氢脱硫反应仍然有一定的抑制作用；另一方面反应过程中引入了大量的溶剂或循环油来溶解氢气，势必增加了反应系统的体积和复杂性，使生产过程的投资和能耗均较高。
发明内容
针对现有技术的不足，本发明提供一种液相加氢工艺及液相加氢反应器。本发明通过设置特殊结构的反应器，实现液相加氢反应过程的持续高效性、均匀性，在反应过程中将H2S、NH3等抑制反应进行的气体及时移出反应体系，有利于提高加氢反应速率和实现深度加氢反应。
本发明的液相加氢工艺，包括如下内容：溶氢原料油进入加氢反应段与加氢催化剂接触发生加氢反应，得到的反应流出物进入纳/微米氢气注入段，与经陶瓷膜管分散的纳/微米氢气混合，混合物流进入气提段与加氢催化剂接触进行加氢反应，同时氢气将物流中的H2S、NH3等反应气体气提出来，经弧形管顶部的气体出口排出，液相反应流出物由反应出口流出。
本发明工艺中，所述的原料油为能够进行液相加氢的各种油品，一般为馏程在130~550℃范围内任意馏分的烃类原料，可以选自但不限于石脑油、重整生成油、航煤、柴油、蜡油、润滑油、常压渣油、脱沥青油、生物柴油、动物油或植物油等中的一种或多种。所述溶氢原料油一般采用本领域熟知溶氢方式得到，如通过静态混合器将氢气溶解在原料油中。溶氢原料油中氢气与原料油的质量比一般为0.001%～15%，优选0.1%～8%。
所述的工艺中，加氢反应段的加氢反应条件为：反应温度为150～450℃，反应压力为1～18MPaG，液时体积空速为0.5～15h-1。
所述的工艺中，进入纳/微米氢注入段的液相物料的停留时间为0.1～5分钟，优选0.5～2.0分钟，过短的停留时间达不到均匀分散氢气的效果，过长的停留时间会使纳/微米氢气气泡聚并长大为大气泡。纳/微米氢注入段中纳/微米氢的给量与原料油的质量比一般为0.001%～1.5%，优选0.01%～0.15%。
所述的工艺中，气提段的加氢反应条件为：反应温度为150～450℃，反应压力为1～18MPaG，液时体积空速为10～300h-1。
本发明方法中，所述的液相加氢反应采用的催化剂可以根据反应的需要使用适宜的加氢催化剂，实现不同的加氢目的，如加氢精制催化剂、预加氢精制催化剂、加氢改质催化剂、选择性加氢催化剂、加氢处理催化剂、加氢裂化催化剂、补充加氢催化剂等，各种催化剂可以选择商品催化剂，也可以根据现有技术制备。催化反应可以脱除部分或全部烃类原料中的硫、氮、氧、砷、金属、残碳等杂质，或饱和/部分饱和烯烃、芳烃、二烯烃，或发生烃类分子异构化、烷基化、环化、芳构化、裂化、裂解等反应；催化剂活性组分包括但不局限于贵金属、Co、Mo、Ni、W、Mg、Zn、稀土元素等一种或多种组合。
本发明方法中，优选采用如下加氢催化剂，该催化剂包括至少一种第VIB 族金属和至少一种第VIII 族金属为加氢活性金属，第VIB族加氢活性金属至少包括Mo，所述的加氢活性金属以硫化物形式存在，以催化剂的重量为基准，加氢活性金属以硫化物计的重量含量为14%~50%，其中第VIII 族金属/（第VIB 族金属+第VIII 族金属）以硫化物计的重量比为0.30~0.55，活性相MoS2的平均片晶长度4~7nm，单个垛层中的平均片晶层数为1~4层，以垛层总个数为基准，层数3~5层的垛层的比例为40%~90%，优选40%~70%。所述的加氢催化剂还包括氧化铝和碳，以催化剂总重量为基准，氧化铝含量为49%~85.6%，碳含量为0.5%~0.9%。加氢催化剂的孔容为0.3~1.3mL/g，比表面积为150~400m2/g。所述的第VIB族金属为Mo和/或W，第VIII族金属为Ni和/或Co。
所述加氢催化剂的制备方法，包括如下内容：（1）配制浸渍溶液，其中溶液含有加氢活性金属、有机助剂、亚甲基双萘磺酸钠和铝盐；（2）大孔氧化铝粉与浸渍溶液混成可塑体，经过混捏、成型、干燥、焙烧后，得到氧化态加氢催化剂；（3）将氧化态催化剂进行硫化处理，得到馏分油加氢处理催化剂。
步骤（1）所述浸渍溶液中含亚甲基双萘磺酸钠2-20克/升，优选为5-15克/升。
步骤（1）所述浸渍溶液中所述的铝盐是氯化铝、硝酸铝、硫酸铝中的一种或多种。
步骤（1）所述浸渍溶液中所述的铝盐以Al3+计与催化剂中加氢活性金属的摩尔比为0.2~6.0，优选为0.3~5.0，加氢活性金属以氧化物计。
步骤（1）所述的有机助剂为有机酸、有机醇或糖类中的一种或多种；有机助剂加入量以C元素重量计，为催化剂重量的0.5wt% ~0.9wt%。
步骤（1）所述的有机酸选自碳数为2~10的二元酸中的至少一种；所述的有机醇选自碳数为3~10的脂肪醇和二元醇中的一种或多种；所述的糖类选自碳数为3~10的单糖、二糖和多糖中的至少一种。
所述的有机酸为柠檬酸、柠檬酸酐、异柠檬酸、苹果酸、酒石酸、草酸、琥珀酸、戊二酸、己二酸、苯甲酸、酞酸、异酞酸、水杨酸、丙二酸中的一种或几种；所述的有机醇为脂肪醇、乙烯乙二醇、丙烯乙二醇、丙三醇、三亚甲醇乙烷、三亚甲醇丙烷、二乙烯乙二醇、二丙烯乙二醇、三亚甲基乙二醇、三乙烯乙二醇、三丁烯乙二醇、四乙烯乙二醇、四丙烯乙二醇、聚乙烯乙二醇、二乙烯甲基乙二醇、二乙烯乙基乙二醇、二乙烯丙基乙二醇、二乙烯丁基乙二醇中的一种或几种。
步骤（2）所述的氧化铝粉与浸渍液的混合过程中可以根据需要加入助挤剂、胶溶剂和水；助挤剂为甲基纤维素、田菁粉、淀粉和聚乙烯醇中的一种或几种，加入量为氧化铝粉总质量的1%~5%；胶溶剂为稀硝酸、稀磷酸和硅酸中的一种或几种，加入量为氧化铝粉总质量的1%~5%。
步骤（2）所述的干燥条件为温度为90~160℃，干燥时间为1~24小时；所述的焙烧温度400~750℃，焙烧时间为2~10小时。
步骤（3）所述的硫化处理采用器内或器外硫化过程，引入硫化剂的量为催化剂理论需硫量的90%~150%，硫化过程采用程序升温，温度升至200~350℃恒温1~16h。
所述的大孔氧化铝粉可以采用常规方法制备，氧化铝粉中可以含有少量的助剂如硅、钛、镁、硼、锆中的一种或多种，助剂含量以元素计为氧化铝粉重量的0.1%~10%。所述氧化铝粉的性质一般要求如下：孔容为0.3~1.5mL/g，比表面积为150~450m2/g。
浸渍液的浓度由所要求的催化剂组成（含量）确定。
本发明的液相加氢反应器，外形为“U形”的管式反应器，包括两侧的直管段、底部连通两侧直管段的水平段，两侧的直管段分别为加氢反应段和气提段，水平段为纳/微米氢注入段；加氢反应段顶部设置液相加氢原料入口，加氢反应段内装填加氢催化剂，纳/微米氢注入段填装若干组陶瓷膜管束，陶瓷膜管束连通外部氢气，气提段内装填加氢催化剂，气提段顶部末端连接弧形管，弧形管的水平切线的高于气提段顶部，弧形管最高点处设置气体出口，弧形管末端设置反应产物出口。
所述的加氢反应段的高径比为1:1～30:1，优选5:1～15:1。
所述的加氢催化剂可以根据液相加氢过程的实际需要确定装填的加氢催化剂。如加氢脱硫催化剂、加氢脱氮催化剂、加氢脱金属催化剂等等。
所述的陶瓷膜管束为为管壳式结构，管壳内可以包含一根或多根膜管，管内通入氢气，在压差推动下氢气通过管壁上的纳/微米孔道进行渗透扩散，形成纳/微米气泡进入管外的壳体空间，并分散至壳体空间的液相中，形成一种携带了纳/微米气泡氢的液相原料。所述的纳/微米气泡氢的尺寸一般为10nm～1000nm，优选为50nm～500nm。
所述的水平段的长径比15:1~1:15，优选2:1~1:2。
所述的加氢反应段的直径与水平段的直径比1:50~1:1，优选1:10~1:1。
所述的气提段的顶部与加氢反应段的顶部位于同一高度，气提段的管径小于或等于加氢反应段的管径，高径比为1:1～50:1，优选10:1～30:1。
所述的弧形管顶部有气体空间，弧形管最高点处设置气体出口，用于连续或间断排放反应过程中生成的H2S、NH3等反应气体。弧形的圆心角为0°～360°，优选180°～270°。气提段末端位置处设置有出料液位控制，保证加氢反应段和气提段发生反应时为全液相加氢。
本发明的液相加氢反应器与液相加氢反应工艺，具有以下优点：（1）馏分油加氢反应过程中的副产物H2S对加氢脱硫反应、加氢脱氮和加氢脱芳反应也有明显的抑制作用，现有技术中反应过程不能及时移走，这对于对于实现深度加氢具有较大的抑制作用。发明人通过设置特殊结构的“U形”管式加氢反应器，将反应器分为加氢反应段、纳/微米氢注入段、气提段三部分，三部分之间依次连通，形成一体式反应器结构。首先通过加氢反应段与纳/微米氢注入段的连通，一方面实现加氢反应过程的原位补氢，若加氢反应过程中的氢气不足，容易高温结焦，另一方面通过纳/微米氢与反应流出物之间即加氢反应段与纳/微米氢注入段连接位置的导流结构，使来自加氢反应段的物流在水平方向上与纳/微米氢错流接触，增加气液两相的传质推动力，强化纳/微米氢的溶解分散；在纳/微米氢注入段中，将膜管分散器设置为管壳式结构，壳体式的物料有一定的停留时间，目的是将纳/微米氢分散溶解在原料油的过程中，通过一定的时间的物料停留和返混，促使H2S、NH3等反应气体组分的向液相表面扩散与迁移，为后续的气提段的气提提供必要的物理条件；纳/微米氢注入段与气提段的联通，通过水平段与气提段之间的导流变径结构，一方面可以将纳/微米氢注入段的物料快速引入气提段，另一方面可以使反应物料的动能增加，增加H2S、NH3等反应气体扩散时所需的动能，从而实现强化气提的作用，这对于及时将H2S、NH3等反应气体在反应过程中持续的气提出来、消除H2S对加氢脱硫反应速率的影响、提高加氢反应深度具有重要作用。（2）常规液相加氢工艺采用的氢油混合过程及混合器结构，原料油能够溶解分散的氢气量较少，对于氢油比稍大的加氢反应过程来说，远远不能满足氢耗的需要，就需要通过大量的循环油进行辅助溶解，这样就大幅度降低了反应效率，同时增加了反应系统的体积，而本发明通过密集补充纳/微米氢气的方式，则可以保证持续的高加氢反应速率和高反应效率；（3）由于反应过程中H2S、NH3等反应气体的原位脱除对于加氢反应深度具有重要意义，而现有技术的原位气提均是采用反应过程排气的方式进行，不但造成氢气资源的浪费，而且基于操作压力高、物料的流动方式等原因的影响导致气提效果均不理想，而本发明通过“U形”管式加氢反应器的结构，实现强化气提的作用，有利于H2S、NH3等反应气体的气提脱除，提高加氢反应深度。
附图说明
图1是本发明的一种常规固定床液相加氢反应工艺的示意图。
1为原料油，2为氢气，3为氢油混合物，4为液相加氢反应器，5为催化剂床层，6为反应器顶部排放气，7为加氢反应产物。
图2是本发明的液相加氢反应器及液相加氢工艺中“U形”的管式反应器的示意图。
8为溶氢原料油，9为“U形”的管式反应器，10为加氢反应段，11为纳/微米氢注入段，12为陶瓷膜管分散器，13为纳/微米氢注入段注入氢气，14为气提段，15为弧形管，16为气体出口，17为加氢反应产物出口。
图3催化剂A透射电镜图。
具体实施方式
下面结合附图说明和实施例对本发明进行详细说明，但不因此限制本发明。本发明实施例及对比例中的溶氢原料油通过氢油混合设备静态混合器得到。
以附图2说明本发明的液相加氢反应器及液相加氢反应工艺：
溶氢原料油8进入“U形”管式反应器9发生液相加氢反应，“U形”的管式反应器9包含两侧的直管段、底部连通两侧直管段的水平段，两侧的直管段分别为加氢反应段10和气提段14，水平段为纳/微米氢注入段11，纳/微米氢注入段11内设置有陶瓷膜管分散器12，连通外部氢气，将氢气分散为纳/微米氢气气泡；加氢反应段10的顶部设置加氢原料入口，加氢反应段10内装填加氢催化剂，加氢反应原料在加氢反应段10内发生液相加氢反应；完成加氢反应的物料进入纳/微米氢注入段11的壳体，将陶瓷膜管分散器12形成的纳/微米氢气气泡分散至壳体，形成一种携带了纳/微米氢气气泡的加氢反应物料进入气提段14，将其中的H2S、NH3等反应气体在反应过程中持续的气提出来，至弧形管15的最高点设置的气体出口16进行排放，而加氢反应产物经过加氢反应产物出口17流出。
本发明对比例及实施例中采用的原料油为来自某厂常减压装置的常一线，具体性质见表1。对比例1、2及实施例1的加氢反应中采用的保护剂/催化剂为抚顺石油化工研究院的FBN-03B01/FH-40A。实施例2采用的保护剂/催化剂为抚顺石油化工研究院的FBN-03B01/催化剂A。实施例3采用的保护剂/催化剂为抚顺石油化工研究院的FBN-03B01/催化剂B。
其中，催化剂A的制备方法如下：125 g（干基80）大孔氧化铝干胶粉置于滚锅中，加入田菁粉2g，在转动条件下，向滚锅中的氧化铝干胶粉以雾化方式喷入80mL含有22.9g三氧化钼，18.7g碱式碳酸钴，0.3g乙烯乙二醇，2.4g柠檬酸，25g 10%磷酸，0.8g亚甲基双萘磺酸钠，19.9g无水氯化铝的水溶液，溶液喷完后，在滚锅中继续转动30分钟，混捏、成型、110℃干燥4h后，550℃焙烧3h，获得制得氧化态催化剂A。将氧化态催化剂A采用器内硫化过程进行硫化处理，引入硫化剂的量为催化剂理论需硫量的120%、硫化过程采用程序升温，温度升至320℃恒温10h，得成品催化剂A。性质见表2。
催化剂B的制备方法：将125 g（干基80）大孔氧化铝干胶粉置于滚锅中，加入田菁粉2g，在转动条件下，向滚锅中的氧化铝载体以雾化方式喷入80mL含有21.5g三氧化钼，21.1g碱式碳酸钴，0.6g乙烯乙二醇，2.0g柠檬酸，20g 10%硝酸，0.6g亚甲基双萘磺酸钠，52.7g硫酸铝的水溶液，溶液喷完后，在滚锅中继续转动30分钟，混捏、成型、110℃干燥4h后，550℃焙烧3h，制得氧化态催化剂B。将氧化态催化剂B采用器内硫化过程进行硫化处理，引入硫化剂的量为催化剂理论需硫量的120%、硫化过程采用程序升温，温度升至320℃恒温10h，得成品催化剂B，性质见表2。
比表面积和孔容采用低温液氮吸附法测定的。片晶长度及垛层层数比例采用场发射透射电子显微镜测定，方法如下：选取多于350个MoS2片晶统计整理平均层数、平均长度及3~5层晶片比例，统计公式为：
其中li代表晶片长度，Ni代表i层的数目，ai代表晶片li的数目，bi代表层数Ni的数目。本发明中wt%表示质量百分数。
表1 原料性质
对比例1
采用附图1所示常规固定床加氢反应器及加氢反应工艺，氢油混合设备采用静态混合器，型号为：SX-2.3-5.0-500；加氢反应进料中氢气的给量为原料油质量的0.244%。加氢反应条件如下：反应温度为260～280℃，反应压力为3.5MPaG，液时体积空速为4.0h-1。
采用表1中的原料油，反应条件及产品性质见表3。
对比例2
采用附图1所示常规固定床加氢反应器及加氢反应工艺，氢油混合设备采用膜管微分散器，将氢气分散为500nm的氢气气泡；加氢反应进料中氢气的给量为原料油质量的0.231%。加氢反应条件如下：反应温度为245～266℃，反应压力为3.5MPaG，液时体积空速为4.0h-1。
采用表1中的原料油。
实施例1
采用附图2所述的液相加氢反应器和液相加氢反应工艺，溶氢原料油中的氢气给量为原料油质量的0.116%；膜管微分散器将氢气分散为50nm的氢气气泡，纳/微米注入氢的氢气给量为原料油质量的0.068%。加氢反应段的反应条件如下：反应温度为240～260℃，反应压力为3.3MPaG，液时体积空速为4.5h-1；气提段的反应条件如下：反应温度为240～260℃，反应压力为3.5MPaG，液时体积空速为86h-1。加氢反应段的直径为200mm，高度为3050mm，高径比为12.2:1；水平段的直径为2000mm，长度为2000mm，长径比为1:1；加氢反应段的直径与水平段的直径比1:10；气提段的直径为80mm，高度为3050米，高径比为38.125:1。采用表1中的原料油，反应条件及产品性质见表3。
实施例2
采用附图2所示的液相加氢反应器和液相加氢反应工艺，溶氢原料油中的氢气给量为原料油质量的0.100%；膜管微分散器将氢气分散为500nm的氢气气泡，纳/微米注入氢的氢气给量为原料油质量的0.08%，氢油混合设备采用膜管微分散器。加氢反应段的反应条件如下：反应温度为240～260℃，反应压力为3.6MPaG，液时体积空速为4.5h-1；气提段的反应条件如下：反应温度为240～260℃，反应压力为3.0MPaG，液时体积空速为57h-1；加氢反应段的直径为500mm，高度为2.5米，高径比为5:1；水平段的直径为1000mm，长度为3米，长径比为3:1；加氢反应段的直径与水平段的直径比1:2；气提段的直径为300mm，高度为2.5米，高径比为8.3:1。
采用表1中的原料油，反应条件及产品性质见表3。
实施例3
采用附图2所述的液相加氢反应器和液相加氢反应工艺，溶氢原料油中的氢气给量为原料油质量的0.103%；膜管微分散器将氢气分散为500nm的氢气气泡，纳/微米注入氢的氢气给量为原料油质量的0.079%。加氢反应段的反应条件如下：反应温度为240～260℃，反应压力为3.0MPaG，液时体积空速为4.5h-1；气提段的反应条件如下：反应温度为240～260℃，反应压力为3.5MPaG，液时体积空速为86h-1。加氢反应段的直径为200mm，高度为2000mm，高径比为10:1；水平段的直径为200mm，长度为500mm，长径比为2.5:1；加氢反应段的直径与水平段的直径比1:2；气提段的直径为100mm，高度为2000mm，高径比为10:1。
采用表1中的原料油，反应条件及产品性质见表3。
表2 催化剂A和B的主要性质
表3反应条件及产品性质
由本实施例及对比例的加氢反应效果可以看出，采用本发明的液相加氢反应器及液相加氢工艺，与现有技术相比，采用原位补氢的方式可以避免原料油高温结焦、聚合，而纳/微米氢多点密集补充及与原料油错流接触可以强化氢气的溶解分散程度，使加氢反应达到相同的技术效果时可采用更为缓和的条件，如温度和压力可以更低、空速可以更高、氢气消耗也更低，可以降低操作成本和能耗，提高催化剂使用寿命。以航煤加氢过程为例，通过本发明方法中的纳/微米氢分散时物料在膜管分散器内的停留和返混，实现H2S、NH3等反应气体组分的表面扩散与迁移，为气提段发挥气提功能提供必要的物理条件，这对于后续实现和强化原位气提功能具有重要作用，有利于H2S、NH3等反应气体的气提脱除，从而提高加氢反应深度。
Claims (11)
1.一种液相加氢工艺，其特征在于包括如下内容：溶氢原料油进入加氢反应段与第一加氢催化剂接触发生加氢反应，得到的反应流出物进入纳/微米氢气注入段，与经陶瓷膜管分散的纳/微米氢气混合，混合物流进入气提段与第二加氢催化剂接触进行加氢反应，同时氢气将物流中的H2S、NH3反应气体气提出来，经气体出口排出，液相反应流出物由反应出口流出，
其中，第一、第二加氢催化剂包括至少一种第VIB族金属和至少一种第VIII族金属为加氢活性金属，第VIB族加氢活性金属至少包括Mo，所述的加氢活性金属以硫化物形式存在，以催化剂的重量为基准，加氢活性金属以硫化物计的重量含量为14%~50%，活性相MoS2的平均片晶长度4~7nm，单个垛层中的平均片晶层数为1~4层，以垛层总个数为基准，层数3~5层的垛层的比例为40%~90%；第一、第二加氢催化剂还包括氧化铝和碳，以催化剂总重量为基准，氧化铝含量为49%~85.6%，碳含量为0.5%~0.9%，
加氢反应段的加氢反应条件为：反应温度为150～450℃，反应压力为1～18MPaG，液时体积空速为0.5～15h-1
气提段的加氢反应条件为：反应温度为150～450℃，反应压力为1～18MPaG，液时体积空速为10～300h-1。
2.根据权利要求1所述的液相加氢工艺，其特征在于：所述的溶氢原料油中氢气与原料油的质量比为0.001%～15%。
3.根据权利要求1所述的液相加氢工艺，其特征在于：纳/微米气泡氢的尺寸为10nm～1000nm。
4.根据权利要求1所述的液相加氢工艺，其特征在于：进入纳/微米氢注入段的液相物料的停留时间为0.1～5分钟。
5.根据权利要求1所述的液相加氢工艺，其特征在于：纳/微米氢注入段中纳/微米氢的给量与原料油的质量比为0.001%～1.5%。
6.一种液相加氢反应器，其特征在于：外形为“U形”的管式反应器，包括两侧的直管段、底部连通两侧直管段的水平段，两侧的直管段分别为加氢反应段和气提段，水平段为纳/微米氢注入段；加氢反应段顶部设置液相加氢原料入口，加氢反应段内装填加氢催化剂，纳/微米氢注入段填装若干组陶瓷膜管束，陶瓷膜管束连通外部氢气，气提段内装填加氢催化剂，气提段顶部末端连接弧形管，弧形管的水平切线高于气提段顶部，弧形管最高点处设置气体出口，弧形管末端设置反应产物出口，所述的加氢反应段的高径比为1:1～30:1。
7.根据权利要求6所述的液相加氢反应器，其特征在于：所述的陶瓷膜管束为管壳式结构，管壳内包含一根或多根膜管，膜管壁上为纳/微米孔道。
8.根据权利要求6所述的液相加氢反应器，其特征在于：所述的水平段的长径比15:1~1:15。
9.根据权利要求6所述的液相加氢反应器，其特征在于：所述的加氢反应段的直径与水平段的直径比1:50~1:1。
10.根据权利要求6所述的液相加氢反应器，其特征在于：所述的气提段的顶部与加氢反应段的顶部位于同一高度，气提段的管径小于或等于加氢反应段的管径，气提段的高径比为1:1～50:1。
11.根据权利要求6所述的液相加氢反应器，其特征在于：所述的弧形管顶部有气体空间，弧形管最高点处设置气体出口，弧形的圆心角为180°～270°。
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