CN115245790A - 一种与催化剂一体化的微反应器及其费托合成应用 - Google Patents
一种与催化剂一体化的微反应器及其费托合成应用 Download PDFInfo
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Abstract
本发明公开一种与催化剂一体化的微反应器及其费托合成应用,首先加工制作常规固定床反应器,将钢管截成恒温区长度的短管,经强碱性物质焙烧、在蒸馏水和乙醇中超声清洗、在前驱体溶液中浸渍后焙烧,最后将制备的短钢管填装进常规固定床中构建费托合成的微反应器。本发明避免了机械加工、酸蚀、激光刻蚀或喷砂等繁琐处理工艺,具有制作工艺简单的独特优势;构建的微反应器具有体积较小、结构紧凑,物料、温度和压力等流场分布均匀的特点,通过强化反应和换热过程,容易实现费托合成反应的稳定安全运行;且投资低廉,可在分散的小合成气气源地使用,技术经济性能高。
Description
技术领域
本发明涉及一种与催化剂一体化微反应器及其费托合成应用,更具体地说,涉及一种与催化剂一体化的微反应器的构建方法,并将之应用于费托合成反应。
背景技术
费托合成(Fischer-Tropsch synthesis)作为非常重要的能源替代技术,是以合成气(CO和H2)为原料在催化剂和适当条件下转化为烃类的工艺过程,1923年,由德国化学家Franz Fischer和Hans Tropsch开发,并以其名字命名。费托合成通常采用固定床、浆态床和流化床三类反应器,合成气进入反应器与其中的催化剂固体颗粒接触进行反应。固定床的优点是催化剂和产物容易分离,缺点是催化剂床层可能出现局部飞温,严重时导致催化剂烧结,反应受传热和传质影响很大;浆态床的优点是传热传质性好,催化剂床层压降小,缺点是催化剂与重质烃类分离困难;流化床的优点是产能大、热效率高、催化剂可及时再生,缺点是价格昂贵、催化剂损失量大且易堵塞旋风分离器,因常用于高温费托合成还极易导致积炭和催化剂烧结。显然,这三类反应器均无法同时解决费托合成中传热传质问题和催化剂与反应物/产物分离问题,且规模很大,投资很高,仅适合于大处理量和高产量情形。
为此一些专利公开了体积较小的微反应器以适应合成气量较小且气源分散的情形。如公开发明专利200680010313.9发明了一种采用机械加工成由波面或褶状的蝶形和平片交替堆积的多条钢合金通道的费托合成紧凑型反应器,并在无孔金属的通道基体上涂覆掺入催化材料涂层;公开发明专利202010293615.3在微反应器的金属基底上刻蚀微通道反应区域及微流体输入和输出通道,再通过酸碱处理建立活化金属表面,然后浸入含有有机配体与金属盐的溶液进行催化剂原位制备;公开发明专利201510726326.7、201510726328.6、201510726867.X和201510726870.1及实用新型专利201620580665.9采用酸蚀、激光刻蚀等方法制作平行线型结构和/或网状交叉结构的费托合成反应微通道,分流构件为矩形或菱形,微通道表面则涂覆铁、钴、镍和钌一种或几种的催化剂层,或将这些纳米金属掺入液相介质中;公开发明专利201280014772.X则涉及在微反应器内填装催化剂颗粒进行费托合成反应。
发明内容
上述公开专利的费托合成微反应器及其制作方法均较复杂,为此本发明的目的是提供一种无需繁琐工艺的简单微反应器。
为实现此目的,本发明采取的技术方案为:在常规固定床反应器中填装具有微结构的钢管构筑微反应器,该微结构钢管同时作为Fe系催化剂的基体,将其表面腐蚀处理后负载其它组份以制备费托合成催化剂,从而将与催化剂一体化的微反应器应用于费托合成反应。
具体步骤如下:一种与催化剂一体化的微反应器及其费托合成应用,其特征在于包括以下内容:
(1)加工制作直径5 ~100 mm、恒温区长20 ~ 400 mm的常规固定床反应器;
(2)将直径0.5 ~ 5 mm的钢管截成恒温区长度的短管;
(3)将短钢管放入坩埚中,加入淹没短钢管的强碱性物质,确保短钢管相互不接触,移至马弗炉中焙烧,然后于室温冷却;
(4)将焙烧的短钢管放入烧杯中,加入超过短钢管的蒸馏水,超声处理至烧杯底部无沉淀;倒掉蒸馏水,再加入超过短钢管的乙醇,超声清洗后倒掉乙醇,于室温将短钢管晾干;
(5)称取共活性组份的前驱体放入烧杯中,加入蒸馏水并搅拌至充分溶解;
(6)将清洗的短钢管放入盛有前驱体溶液的表面皿中进行浸渍,然后于室温晾干;
(7)将浸渍的短钢管移至烘箱中于90 ℃干燥2.0 h,再移至马弗炉中焙烧,然后于室温冷却;
(8)将制备的短钢管装入(1)的常规固定床中构建费托合成的微反应器。
所述步骤(2)中的钢管材质为不锈钢、碳钢或热镀合金钢,优选为碳钢。
所述步骤(3)中的强碱性物质为NaOH、KOH、Mg(OH)2或Ca(OH)2固体,由于K为费托合成催化剂常见的电子助剂,因而稍加清洗并保留K更有助于提高催化性能,为此优选为KOH固体。
所述步骤(3)中的焙烧温度为300 ~ 700 ℃,焙烧时间为2.0 ~ 6.0 h,优选为500℃、4.0 h。
所述步骤(5)中的共活性组份前驱体为VIII族Co、Ni、Ru和Pd,IVA至VIIA族Ti、V、Cr、Mn和Zr,或镧系稀土La和Ce的硝酸盐、醋酸盐或碳酸盐,优选为Co、Mn和Ce的硝酸盐,再优选为Mn的硝酸盐;溶液浓度为1.0 ~ 3.0 M,优选为2.0 M。
所述步骤(6)中的浸渍时间为1.0 ~ 3.0 h,优选为2.0 h。
所述步骤(7)中的马弗炉焙烧温度为300 ~ 700 ℃、焙烧时间为2.0 ~ 6.0 h,优选为500 ℃、4.0 h。
将制备的短钢管填装进步骤(1)的常规固定床中构建应用于费托合成的与催化剂一体化的微反应器。
将上述与催化剂一体化的微反应器应用于费托合成,以气相色谱仪分析进料和产物组成,并计算CO转化率:X = [(C1-C2)/C1]×100%,其中C1和C2分别为进料和出料中CO的体积分数;CH4、C2-4和C5+产物的选择性:Si = Ci/(C1-C2),其中Ci分别为出料中各产物的体积分数;及各产物的时空收率:Yi = Ci×Mi×V/22.4/W,其中Mi、V和W分别为各产物的摩尔质量、空速和短钢管质量。
本发明的有益效果为:采用在常规固定床中恒温区填装微结构的短钢管构建微反应器,避免了机械加工、酸蚀、激光刻蚀或喷砂等繁琐处理工艺,具有制作工艺简单的独特优势;由于微反应器体积较小、结构紧凑,物料、温度和压力等流场分布均匀,通过强化反应和换热过程,容易实现费托合成反应的稳定安全运行;投资低廉,可在分散的小合成气气源地使用,技术经济性能很高;费托合成的CO转化率不低于85.0 %,CH4的选择性不高于10.0%,C5+的时空收率不低于0.50 kg/(h·kg)。
附图说明
图1为与催化剂一体化的微反应器的结构示意图。
具体实施方案
下面通过具体实施例对本发明做进一步说明,但本发明的保护范围不限于此。如图1所示为与催化剂一体化的微反应器的结构示意图,常规固定床反应器的直径为5 ~ 100mm、恒温区长20 ~ 400 mm,填装进的钢管直径为0.5 ~ 5 mm、长度与固定床的恒温区相等。
实施例1
应用于费托合成的与催化剂一体化的微反应器的构建步骤,具体如下所示:
(1)加工制作直径5 mm、恒温区长20 mm的常规固定床反应器;
(2)将直径2 mm的碳钢管截成20 mm的短管;
(3)将短钢管放入坩埚中,加入淹没短钢管的KOH固体,确保短钢管相互不接触,移至马弗炉中于500 ℃焙烧4.0 h,然后于室温冷却;
(4)将焙烧的短钢管放入烧杯中,加入超过短钢管的蒸馏水,超声处理至烧杯底部无沉淀;倒掉蒸馏水,再加入超过短钢管的乙醇,超声清洗后倒掉乙醇,于室温将短钢管晾干;
(5)称取硝酸锰前驱体放入烧杯中,加入蒸馏水配制成2.0 M浓度的溶液,并搅拌至充分溶解;
(6)将清洗的短钢管放入盛有硝酸锰溶液的表面皿中浸渍2.0 h,然后于室温晾干;
(7)将浸渍的短钢管移至烘箱中于90 ℃干燥2.0 h,再移至马弗炉中于500 ℃焙烧4.0 h,然后于室温冷却;
(8)将制备的短钢管填装进步骤(1)的常规固定床中构建费托合成的微反应器。
在进料比H2/CO = 3/2、反应温度250 ℃、反应压力2.0 Mpa和空速4000 h-1条件下进行费托合成催化性能评价,以气相色谱仪分析进料和产物组成,计算得CO转化率为91.2%,CH4选择性为9.3 %,C5+时空收率为0.61 kg/(h·kg)。
实施例2
应用于费托合成的与催化剂一体化的微反应器的构建步骤基本同实施例1,不同之处在于:步骤(1)中常规固定床的直径为20 mm、恒温区长为80 mm,步骤(2)中将直径1 mm的不锈钢管截成80 mm的短管,步骤(5)中的前驱体为1.0 M浓度的硝酸铈溶液,步骤(6)中的浸渍时间为1.0 h。费托合成催化性能评价的CO转化率为90.6 %,CH4选择性为9.6 %,C5+时空收率为0.55 kg/(h·kg)。
实施例3
应用于费托合成的与催化剂一体化的微反应器的构建步骤基本同实施例1,不同之处在于:步骤(1)中固定床的直径为100 mm、恒温区长为400 mm,步骤(2)中将直径3 mm的镀锌合金钢管截成400 mm的短管,步骤(5)中的前驱体为1.0 M浓度的硝酸钴溶液,步骤(6)中的浸渍时间为3.0 h。费托合成催化性能评价的CO转化率为85.2 %,CH4选择性为9.8 %,C5+时空收率为0.50 kg/(h·kg)。
实施例4
应用于费托合成的与催化剂一体化的微反应器的构建步骤基本同实施例1,不同之处在于:步骤(1)中固定床的直径为10 mm、恒温区长为40 mm,步骤(2)中将直径0.5 mm的碳钢管截成40 mm的短管,步骤(5)中的前驱体为3.0 M浓度的硝酸铈溶液,步骤(6)中的浸渍时间为1.0 h。费托合成催化性能评价的CO转化率为95.6 %,CH4选择性为9.5 %,C5+时空收率为0.60 kg/(h·kg)。
实施例5
应用于费托合成的与催化剂一体化的微反应器的构建步骤基本同实施例1,不同之处在于:步骤(1)中固定床的直径为30 mm、恒温区长为120 mm,步骤(2)中将直径4 mm的镀铝合金钢管截成120 mm的短管,步骤(5)中的前驱体为2.0 M浓度的硝酸锰溶液,步骤(6)中的浸渍时间为3.0 h。费托合成催化性能评价的CO转化率为88.4 %,CH4选择性为9.7 %,C5+时空收率为0.54 kg/(h·kg)。
实施例6
应用于费托合成的与催化剂一体化的微反应器的构建步骤基本同实施例1,不同之处在于:步骤(1)中固定床的直径为70 mm、恒温区长为280 mm,步骤(2)中将直径5 mm的不锈钢管截成280 mm的短管,步骤(5)中的前驱体为3.0 M浓度的硝酸钴溶液,步骤(6)中的浸渍时间为2.0 h。费托合成催化性能评价的CO转化率为86.3 %,CH4选择性为9.9 %,C5+时空收率为0.53 kg/(h·kg)。
综上所述,本发明所提供的微反应器体积较小、结构紧凑,物料、温度和压力等流场分布均匀,通过强化反应和换热过程,容易实现费托合成反应的稳定安全运行;投资低廉,可在合成气量较小的分散气源地使用,技术经济性能很高。
Claims (8)
1.一种与催化剂一体化的微反应器,其特征在于:以常规固定床反应器为基础,内置有紧密排布的钢管,所述钢管经强碱性物质焙烧、在蒸馏水和乙醇中超声清洗、在前驱体溶液中浸渍后焙烧;
所述微反应器的具体处理过程如下:
(1)加工制作直径5 ~100 mm、恒温区长20 ~ 400 mm的常规固定床反应器;
(2)将直径0.5 ~ 5 mm的钢管截成恒温区长度的短管;
(3)将短钢管放入坩埚中,加入淹没短钢管的强碱性物质,确保短钢管相互不接触,移至马弗炉中焙烧,然后于室温冷却;
(4)将焙烧的短钢管放入烧杯中,加入超过短钢管的蒸馏水,超声处理至烧杯底部无沉淀;倒掉蒸馏水,再加入超过短钢管的乙醇,超声清洗后倒掉乙醇,于室温将短钢管晾干;
(5)称取共活性组份的前驱体放入烧杯中,加入蒸馏水并搅拌至充分溶解;
(6)将清洗的短钢管放入盛有前驱体溶液的表面皿中进行浸渍,然后于室温晾干;
(7)将浸渍的短钢管移至烘箱中于90 ℃干燥2.0 h,再移至马弗炉中焙烧,然后于室温冷却;
(8)将制备的短钢管紧密排列,装入(1)的常规固定床中构建费托合成的微反应器。
2.根据权利要求1所述的一种与催化剂一体化的微反应器,其特征在于:所述步骤(2)中的钢管材质为不锈钢、碳钢或热镀合金钢,优选为碳钢。
3.根据权利要求1所述的一种与催化剂一体化的微反应器,其特征在于:所述步骤(3)中的强碱性物质为NaOH、KOH、Mg(OH)2或Ca(OH)2固体,优选为KOH固体。
4.根据权利要求1所述的一种与催化剂一体化的微反应器,其特征在于:所述步骤(3)中的焙烧温度为300 ~ 700 ℃,焙烧时间为2.0 ~ 6.0 h,优选为500 ℃、4.0 h。
5.根据权利要求1所述的一种与催化剂一体化的微反应器,其特征在于:所述步骤(5)中的共活性组份前驱体为VIII族Co、Ni、Ru和Pd,IVA至VIIA族Ti、V、Cr、Mn和Zr,或镧系稀土La和Ce的硝酸盐、醋酸盐或碳酸盐,优选为Co、Mn和Ce的硝酸盐,再优选为Mn的硝酸盐;溶液浓度为1.0 ~ 3.0 M,优选为2.0 M。
6.根据权利要求1所述的一种与催化剂一体化的微反应器,其特征在于:所述步骤(6)中的浸渍时间为1.0 ~ 3.0 h,优选为2.0 h。
7.根据权利要求1所述的一种与催化剂一体化的微反应器,其特征在于:所述步骤(7)中的马弗炉焙烧温度为300 ~ 700 ℃、焙烧时间为2.0 ~ 6.0 h,优选为500 ℃、4.0 h。
8.采用权利要求1-7任一所述的一种与催化剂一体化的微反应器,其特征在于:将之应用于费托合成反应,CO转化率不低于85.0 %,CH4的选择性不高于10.0 %,C5+的时空收率不低于0.50 kg/(h·kg)。
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