钴基费托催化剂的制备与研究
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摘要
本课题是国家高技术研究发展计划(863计划)项目,“生物质气化集成-费托合成”工艺制取液体燃料的费托合成部分。费托合成是CO和H2在金属催化剂的作用下,生成烃类的反应,是获取清洁燃料油和化工产品的有效途径,对缓解日益严重的石油资源危机有着重大的意义。为获得理想的费托合成反应效果,对费托合成催化剂的改进是主要手段之一,金属负载型费托合成催化剂是近几年人们研究的热点。负载型金属催化剂的载体起到承载、分散金属活性组分的作用,载体的孔道结构、酸性、机械强度等性质,都可能影响到费托合成催化剂的反应活性、产物选择性,因此,选择适宜的载体或对载体的改进,是制备性能优良的费托合成催化剂的关键。
本论文用浸渍法制备了不同载体的钴基费托合成催化剂,并且在小型固定床反应装置上对催化剂进行费托反应性能测试,通过催化剂表征以及费托反应实验结果,来考查载体的性质对催化剂结构和费托反应催化性能的影响。
本论文的具体研究工作和主要结论如下：
(1)在制备钴基催化剂之前,对γ-A1203载体进行水热预处理,以此来改进Co/γ-Al2O3催化剂的费托反应性能。实验结果表明：用10wt%的柠檬酸或正丁胺溶液在高压釜中对γ-A1203进行水热预处理,可提高Co/y-Al2O3催化剂的费托反应活性、C5+烃类的选择性,降低CH4的选择性。
(2)通过对三种不同孔道结构的纯硅分子筛载体(SBA-15、MCM-41、Silicate-1)钴基催化剂费托反应测试实验结果的对比,考查纯硅载体孔道结构对催化剂性能影响。实验结果表明：载体孔道尺寸大,钴基催化剂的反应活性高,CH4选择性高,C5+的选择性低,不利于长链液态烃类产物的生成。
(3)采用过量浸渍法制备Co/Hβ催化剂,考查其FT反应性能,费托反应实验结果表明：Co/Hβ催化剂具有较好的反应活性和稳定性,在2.0MPa、230°C、0.9SLh-lg-1、nH2/nco=2的条件下,其CO转化率可连续46h保持在50%以上。并且适宜的Co担载量和Hp-沸石载体的柠檬酸改性都能提高Co/Hβ催化剂的反应活性和C5+烃类选择性。
(4)按照白松木屑催化裂解的产气组成,配制费托反应合成气,并用配制的合成气对Co/Hβ催化剂进行费托反应测试,实验结果表明：在一定条件下的费托合成反应的CO转化率连续96h稳定在60%以上。
The topic is about Fischer-Tropsch synthesis, which is a part of "Biomass integrated gasification-FT synthesis"technology, supported by the National High Technology Research and Development Program of China(863 Program). Fischer-Tropsch synthesis is a reaction that converts CO and H2 into hydrocarbons over metallic catalysts. It is an available in environment-friendly fuel oil and chemical products synthesis, and may solve the problem of petrol oil resources. To obtain ideal results of FT reaction, the improvement of catalysts for FT synthesis is a key problem, metal supported catalysts have become a hot topic. The support of catalyst is used to support and disperse active compositions, its properties such as pore structure, acidity, mechanical strength, have great influence on catalytic performances.So the selection and improvement of the support are the key stage of catalysts preparation.
In the paper, cobalt catalysts for FT synthesis were prepared by using different supports.Their catalytic performances for FT synthesis were evaluated in a fixed bed reactor.The influence on the catalytic performances of the supports was investigated.
The main work and conclusions of my paper include the following aspects:
(1) To improve the perforrmances of Co/γ-Al2O3 catalyst,γ-AI2O3 was pretreated with 10wt% critic acid or n-butylamine. The experimental results showed that the pretreatment ofγ-Al2O3 support could increase the activity and the selectivity of C5+ hydrocarbons of CO/γ-Al2O3 catalyst.
(2) According to the performances test over Co-based catalysts supported by three kinds of silica molecular sieve(SBA-15, MCM-41, Silicate-1), we got the conclusion that Co-based catalyst supported by the silica molecular sieve with larger poresize, had higher catalytic activity and methane selectivity for FT reaction, but the selectivity of long-chain hydrocarbons was decreased.
(3) The performances of Co/HβFT catalyst was tested. The results showed that the catalyst had great catalytic activity and stability for FT reaction, the catalyst could be improved by suitable Co loading and treating (3 support with O.lmol/L critic acid.
(4) According to the composition of products of biomass gasification, we compounded syngas for FT synthesis. The performances of Co/Hβcatalyst was investigated by using the syngas. The results showed that under particular reaction conditions, its CO conversion stayed above 60% for 96h.
本论文用浸渍法制备了不同载体的钴基费托合成催化剂,并且在小型固定床反应装置上对催化剂进行费托反应性能测试,通过催化剂表征以及费托反应实验结果,来考查载体的性质对催化剂结构和费托反应催化性能的影响。
本论文的具体研究工作和主要结论如下：
(1)在制备钴基催化剂之前,对γ-A1203载体进行水热预处理,以此来改进Co/γ-Al2O3催化剂的费托反应性能。实验结果表明：用10wt%的柠檬酸或正丁胺溶液在高压釜中对γ-A1203进行水热预处理,可提高Co/y-Al2O3催化剂的费托反应活性、C5+烃类的选择性,降低CH4的选择性。
(2)通过对三种不同孔道结构的纯硅分子筛载体(SBA-15、MCM-41、Silicate-1)钴基催化剂费托反应测试实验结果的对比,考查纯硅载体孔道结构对催化剂性能影响。实验结果表明：载体孔道尺寸大,钴基催化剂的反应活性高,CH4选择性高,C5+的选择性低,不利于长链液态烃类产物的生成。
(3)采用过量浸渍法制备Co/Hβ催化剂,考查其FT反应性能,费托反应实验结果表明：Co/Hβ催化剂具有较好的反应活性和稳定性,在2.0MPa、230°C、0.9SLh-lg-1、nH2/nco=2的条件下,其CO转化率可连续46h保持在50%以上。并且适宜的Co担载量和Hp-沸石载体的柠檬酸改性都能提高Co/Hβ催化剂的反应活性和C5+烃类选择性。
(4)按照白松木屑催化裂解的产气组成,配制费托反应合成气,并用配制的合成气对Co/Hβ催化剂进行费托反应测试,实验结果表明：在一定条件下的费托合成反应的CO转化率连续96h稳定在60%以上。
The topic is about Fischer-Tropsch synthesis, which is a part of "Biomass integrated gasification-FT synthesis"technology, supported by the National High Technology Research and Development Program of China(863 Program). Fischer-Tropsch synthesis is a reaction that converts CO and H2 into hydrocarbons over metallic catalysts. It is an available in environment-friendly fuel oil and chemical products synthesis, and may solve the problem of petrol oil resources. To obtain ideal results of FT reaction, the improvement of catalysts for FT synthesis is a key problem, metal supported catalysts have become a hot topic. The support of catalyst is used to support and disperse active compositions, its properties such as pore structure, acidity, mechanical strength, have great influence on catalytic performances.So the selection and improvement of the support are the key stage of catalysts preparation.
In the paper, cobalt catalysts for FT synthesis were prepared by using different supports.Their catalytic performances for FT synthesis were evaluated in a fixed bed reactor.The influence on the catalytic performances of the supports was investigated.
The main work and conclusions of my paper include the following aspects:
(1) To improve the perforrmances of Co/γ-Al2O3 catalyst,γ-AI2O3 was pretreated with 10wt% critic acid or n-butylamine. The experimental results showed that the pretreatment ofγ-Al2O3 support could increase the activity and the selectivity of C5+ hydrocarbons of CO/γ-Al2O3 catalyst.
(2) According to the performances test over Co-based catalysts supported by three kinds of silica molecular sieve(SBA-15, MCM-41, Silicate-1), we got the conclusion that Co-based catalyst supported by the silica molecular sieve with larger poresize, had higher catalytic activity and methane selectivity for FT reaction, but the selectivity of long-chain hydrocarbons was decreased.
(3) The performances of Co/HβFT catalyst was tested. The results showed that the catalyst had great catalytic activity and stability for FT reaction, the catalyst could be improved by suitable Co loading and treating (3 support with O.lmol/L critic acid.
(4) According to the composition of products of biomass gasification, we compounded syngas for FT synthesis. The performances of Co/Hβcatalyst was investigated by using the syngas. The results showed that under particular reaction conditions, its CO conversion stayed above 60% for 96h.
引文
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