CN109939722A - 一种有机碱修饰的复合催化剂及一氧化碳加氢制乙烯的方法 - Google Patents
一种有机碱修饰的复合催化剂及一氧化碳加氢制乙烯的方法 Download PDFInfo
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- CN109939722A CN109939722A CN201810079670.5A CN201810079670A CN109939722A CN 109939722 A CN109939722 A CN 109939722A CN 201810079670 A CN201810079670 A CN 201810079670A CN 109939722 A CN109939722 A CN 109939722A
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Abstract
本发明属于合成气直接制备乙烯，具体涉及一种有机碱修饰的复合催化剂及一氧化碳加氢制乙烯的方法，其以一氧化碳和氢气混合气为反应原料，在固定床或移动床上进行转化反应，所述催化剂为复合催化剂，由组分I和组分II以机械混合方式复合在一起，组分I的活性成份为金属氧化物，组分II为有机碱改性的MOR结构的分子筛；组分I中的活性成份与组分II的重量比在0.1‑20范围之间，优选为0.3‑8。反应过程具有很高的产品收率和选择性，C2‑C3烯烃选择性高达78‑87％，其中4个C原子以上的烃类产物选择性低于10％，副产物甲烷选择性极低(<9％)，同时乙烯选择性达到75‑82％，同时具有很好的应用前景。
Description
技术领域
本发明属于一氧化碳加氢制低碳烯烃等高值化学品，具体涉及一种有机碱修饰的复合催化剂及一氧化碳加氢制乙烯的方法。
背景技术
乙烯是非常重要的基本化工原料，是世界上产量最大的化学产品之一，乙烯工业是石油化工产业的核心，在国民经济中占有重要的地位。低碳烯烃是指碳原子数小于或等于4的烯烃。以乙烯、丙烯为代表的低碳烯烃是非常重要的基本有机化工原料，随着我国经济的快速增长，我国乙烯行业发展迅猛，在世界乙烯市场占有重要的地位。长期以来，低碳烯烃市场供不应求。目前，乙烯的生产主要采用石脑油、轻柴油裂解的石油化工路线或者乙烷裂解的技术，由于我国石油长期依赖进口，我国的能源安全存在较大风险，急需开发出不依赖石油的乙烯生产技术。将煤炭、天然气、生物质和其他可再生材料等转化为一氧化碳和氢气的混合气即合成气，合成气中一氧化碳和氢气的比例随原材料不同而不同；再以这些合成气为原料，通过调节一氧化碳和氢气的比例到合适的值之后，使一氧化碳和氢在合适的催化剂作用下，通过费托合成反应直接制得碳原子数小于或等于4的低碳烯烃的过程，这样可以一步生产烯烃，该路线为石脑油裂解技术生产乙烯提供了一条替代方案。该工艺无需像间接法工艺那样从合成气经甲醇或二甲醚，进一步制备烯烃，简化工艺流程，大大减少投资。
通过费托合成直接制取低碳烯烃，一直是合成气直接生产烯烃的研究热点之一。中科院大连化学物理研究所公开的专利CN1083415A中，用MgO等IIA族碱金属氧化物或高硅沸石分子筛(或磷铝沸石)担载的铁-锰催化剂体系，以强碱K或Cs离子作助剂，在合成气制低碳烯烃反应压力为1.0～5.0MPa，反应温度300～400℃下，可获得较高的活性(CO转化率90％)和选择性(低碳烯烃选择性66％)。北京化工大学所申报的专利ZL03109585.2中，采用真空浸渍法制备锰、铜、锌硅、钾等为助剂的Fe/活性炭催化剂用于合成气制低碳烯烃反应，在无原料气循环的条件下，CO转化率96％，低碳烯烃在碳氢化合物中的选择性68％。上述报道的催化剂是采用金属铁或者碳化铁为活性组分，反应遵循金属表面的链增长反应机理，产物低碳烯烃的选择性较低，尤其单种产物如乙烯的选择性低于30％。2016年，上海高等研究院孙予罕研究员及钟良枢研究员报道了一种择优暴露[101]及[020]锰助碳化钴基催化剂，实现了31.8％的CO转化率下，60.8％的低碳烯烃选择性，且甲烷选择性5％。但是乙烯单一选择性却低于20％。中国科学院大连化学物理研究所包信和院士和潘秀莲研究员报道了氧化铝负载的ZnCr2O4氧化物与多级孔SAPO-34分子筛复合双功能催化剂(Jiao et al.,Science 351(2016)1065-1068)，实现了CO转化率17％时,低碳烯烃80％的选择性，但乙烯的选择性低于30％。在他们申请的专利201710129620.9中，使用含有氧空穴与MOR分子筛复合的双功能催化剂用于合成气一步制烯烃反应，将乙烯的选择性提高至75-80％，但副产物中碳原子数超过3的烃类较多，影响了该技术的应用。而本发明进一步通过调变MOR分子筛的酸性特点，使甲烷副产物的选择性进一步降低至9％以下，且C4以上的烃类选择性也进一步降低。
发明内容
本发明技术解决问题：克服现有技术的不足，提供一种碱修饰的催化剂及一氧化碳加氢制乙烯的方法，所发明的催化剂可催化一氧化碳和氢气反应直接生成低碳烯烃，并且C2-C3烯烃的选择性高达78-87％，单种产物乙烯的选择性可高达75-82％，甲烷选择性低于9％，C4及以上烃类选择性低于10％。
本发明的技术方案为：一种催化剂，包括组分I和组分，组分I和组分II以机械混合方式复合在一起，组分I的活性成份为金属氧化物，组分II为MOR拓扑结构的分子筛，II组分中，所述MOR拓扑结构的分子筛经脂肪胺改性处理，所述改性处理是将脂肪胺分散到所述MOR拓扑结构的分子筛的12圆环孔道内的B酸位点。
所述脂肪胺是二甲胺、三甲胺、二乙胺、三乙胺、乙二胺、一丙胺、二丙胺、三丙胺、异丙胺、二异丙胺、1,2-二甲基丙胺、1,2-丙二胺、2-丙烯胺、环丙胺、正丁胺、二正丁胺、异丁胺、仲丁胺、1,4-丁二胺、叔丁胺、二异丁胺己胺、2-乙基己胺、己二胺、三辛胺中的一种或两种以上。
本发明所述机械混合可采用机械搅拌、球磨、摇床混合、机械研磨中的一种或二种以上进行复合。
所述MOR拓扑结构的分子筛经脂肪胺改性处理，可以避免有机碱分子进入8圆环孔道，而是选择性的占据12圆环的B酸位点。
本发明所述所述MOR拓扑结构是一种正交晶系，具有相互平行的椭圆形直通孔道的一维孔道结构，含有8圆环口袋与12圆环一维孔道。
本发明所述脂肪胺改性是指利用脂肪胺分子，占据MOR分子筛12圆环孔道内的B酸位点，可以是完全占据也可以是部分占据。被占据的12圆环孔道中的B酸位点是50-100％。
所述将脂肪胺分散到所述MOR分子筛12圆环孔道内的B酸位点的方法，所有公知的可以实现该目的的方法均可以满足要求，这里以真空脱水吸附法为例，先在真空线上控制温度对分子筛样品进行脱水脱气处理温度350-500℃，压力1Pa-10-5Pa，时间4h-24h，进一步对脱气的分子筛暴露在10Pa-100kPa的脂肪胺的气氛中或惰性气体稀释的有机碱的气氛中，控制吸附温度是室温-300℃，并用无机气体在200-330℃进行吹扫30min-12h后得到脂肪胺改性的分子筛。
所述的金属氧化物为MnOx、MnaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnOx、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CeOx、CoaAl(1-a)Ox、FeaAl(1-a)Ox、GaOx、BiOx、InOx、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)Ox中的一种或二种以上；
所述MnOx、ZnOx、CeOx、GaOx、BiOx、InOx的比表面积是1-100m2/g；优选比表面积是50-100m2/g；
所述MnaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CoaAl(1-a)Ox、FeaAl(1-a)Ox、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)Ox的比表面积是5-150m2/g。优选比表面积是50-150m2/g；
所述x的取值范围是0.7～3.7，a的取值范围是0～1；a+b的取值范围是0～1；
本发明所述的a,b,(1-a),(1-a-b),x仅代表金属氧化物中元素化学组成的相对比例，凡是比例相同的金属氧化物视为同一种金属氧化物。
组分I中的活性成份与组分II的重量比为0.1-20倍，优选为0.3-8；多组分协同才能使得反应有效进行，其中一种过多或过少都会不利于反应的进行。
所述组分I中还添加有分散剂，分散剂为Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3、活性炭、石墨烯、碳纳米管中的一种或二种以上，金属氧化物分散于分散剂中，分散剂于I组分中的含量在0.05-90wt％，优选0.05-25wt％，其余为活性金属氧化物。
所述具有MOR拓扑结构的分子筛的骨架元素组成可以是Si-Al-O、Ga-Si-O、Ga-Si-Al-O、Ti-Si-O、Ti-Al-Si-O、Ca-Al-O、Ca-Si-Al-O中的一种或二种以上。
一种合成气直接转化制乙烯的方法，涉及以合成气为反应原料，合成气中还可以含有一定量的二氧化碳，在固定床或移动床上进行转化反应，可以高选择性地生成乙烯，所采用的催化剂为上述的催化剂。
合成气的压力为0.5-10MPa，优选为1-8MPa，更优选为2-8MPa；反应温度为300-600℃，优选为300-450℃；空速为300-10000h-1，优选为500-9000h-1，更优选为500-6000h-1，可以获得更高的时空收率。
所述反应用合成气H2/CO摩尔比为0.2-3.5，优选为0.3-2.5，可以获得更高的时空收率和选择性合成气中还可以含有CO2，其中CO2在合成气中的体积浓度为0.1-50％。
本发明上述催化剂用于合成气一步法直接转化制乙烯或者C2-C3的烯烃，其中C2-C3烯烃的选择性高达78-87％，乙烯选择性达到75-82％，同还时副产物甲烷选择性极低(<9％)，C4及以上烃类选择性低于10％。
本发明具有如下优点：
(1)本发明与传统的甲醇制低碳烯烃技术(简称为MTO)不同，实现了一步直接将合成气转化制乙烯。
(2)本发明产物中乙烯单一产物选择性高，可达到75-82％，且时空收率高(烯烃收率高至1.33mmol/hg)，产物易于分离，具有很好的应用前景。
(3)催化剂中金属氧化物具有较高的比表面积，因此金属氧化物表面上具有更多的活性位点，更有利于催化反应的进行。
(4)催化剂中组分Ⅱ的作用一方面是通过与组分I进行耦合，将组分I产生的活泼气相中间体进一步转化获得低碳烯烃，由于组分II对串联反应平衡拉动的作用可以促进组分I对合成气的活化转化进而提高转化率，另一方面本发明使用的组分II中分子筛特殊的孔道结构，具有独特的择型效应，可以高选择性的获得更多的乙烯产物。
(5)单独分别使用本发明中所述的组分I或组分II完全不能实现本发明的功能，例如单独使用组分I产物中甲烷选择性非常高，且转化率很低，而单独使用组分II几乎不能活化转化合成气，只有组分I与组分II协同催化才能实现高效的合成气转化，并获得优异的选择性。这是由于组分I可以活化合成气生成特定的活泼气相中间体，中间体经由气相扩散到组分II的孔道内，由于本发明选择的MOR结构的分子筛，具有特殊的孔道结构和酸性可以有效的将组分I产生的活泼气相中间体进一步活化转化为烯烃。由于组分II的特殊孔道结构使得产物具有特殊的选择性。
(6)本发明催化剂中组份II使用脂肪胺进行改性，催化合成气转化得到单一组份乙烯的选择性高达75-82％，且甲烷低于9％，并且大大抑制了C4以上的烃类的选择性低于10％。
具体实施方式
下面通过实施例对本发明做进一步阐述，但是本发明的权利要求范围不受这些实施例的限制。同时，实施例只是给出了实现此目的的部分条件，但并不意味着必须满足这些条件才可以达到此目的。
实施例1
一、组分I的制备
下面通过实施例对本发明做进一步阐述，但是本发明的权利要求范围不受这些实施例的限制。同时，实施例只是给出了实现此目的的部分条件，但并不意味着必须满足这些条件才可以达到此目的。
样品的比表面积可以通过氮气或氩气物理吸附的方法进行测试。
本发明所述的金属氧化物可以通过购买市购的高比表面积的金属氧化物获得，也可以通过下述几种方法获得：
一、催化剂组分Ⅰ的制备
(一)、沉淀法合成具有高比表面的ZnO材料：
(1)分别称取3份、每份0.446g(1.5mmol)Zn(NO3)2·6H2O于3个容器中，再分别称取0.300g(7.5mmol)、0.480g(12mmol)、0.720g(18mmol)NaOH依次加入上述3个容器中，再各量取30ml去离子水加入到3个容器中，70℃搅拌0.5h以上使溶液混合均匀，自然冷却至室温。反应液离心分离收集离心分离后的沉淀物，用去离子水洗涤2次获得ZnO金属氧化物前驱体；
(2)焙烧：上述获得的产物在空气中烘干以后，在气氛中进行焙烧处理，即得到高比表面的ZnO材料。气氛为惰性气体、还原性气体或者氧化性气体；惰性气体为N2、He和Ar中的一种或二种以上；还原性气体为H2、CO的一种或二种，还原气中也可以含有惰性气体；氧化性气体是O2、O3、NO2中的一种或两种以上，氧化气体中也可以含有惰性气体。焙烧温度为300-700℃，时间为0.5h-12h。
焙烧的目的是为了将沉淀后的金属氧化物前驱体在高温下分解为高比表面积的氧化物纳米粒子，并且通过焙烧的高温处理可以将分解生成的氧化物表面吸附物种处理干净。
具体样品及其制备条件如下表1，作为对比例，表中ZnO#4是市售低比表面积的ZnO单晶。
表1 ZnO材料的制备及其参数性能
(二)共沉淀法合成具有高比表面积的MnO材料：
制备过程同上述ZnO#2，不同之处在于将Zn的前驱体换成了Mn的对应的前驱体，可为硝酸锰、氯化锰、醋酸锰中的一种，在此为硝酸锰，对应产物定义为MnO；比表面积是：23m2/g。
(三)共沉淀法合成具有高比表面积的CeO2材料：
制备过程同上述ZnO#2，不同之处在于将Zn的前驱体换成了Ce的对应的前驱体，可为硝酸铈、氯化铈、醋酸铈中的一种，在此为硝酸铈,对应产物定义为CeO2；比表面积是：92m2/g。
(四)共沉淀法合成具有高比表面积的Ga2O3材料：
制备过程同上述ZnO#2，不同之处在于将Zn的前驱体换成了Ga的对应的前驱体，可为硝酸镓、氯化镓、醋酸镓中的一种，在此为硝酸镓，对应产物定义为Ga2O3；比表面积是：55m2/g。
(五)共沉淀法合成具有高比表面积的Bi2O3材料：
制备过程同上述ZnO#2，不同之处在于将Zn的前驱体换成了Bi的对应的前驱体，可为硝酸铋、氯化铋、醋酸铋中的一种，在此为硝酸铋。对应产物定义为Bi2O3；比表面积分别是：87m2/g。
(六)共沉淀法合成具有高比表面积的In2O3材料：
制备过程同上述ZnO#2，不同之处在于将Zn的前驱体换成了In的对应的前驱体，可为硝酸铟、氯化铟、醋酸铟中的一种，在此为硝酸铟，对应产物定义为In2O3；比表面积是：52m2/g
(七)沉淀法合成具有高比表面积的MnaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CoaAl(1-a)Ox、FeaAl(1-a)Ox、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)Ox：
采用硝酸锌、硝酸铝、硝酸铬、硝酸锰、硝酸锆、硝酸铟、硝酸钴、硝酸铁为前驱体，与碳酸铵，在室温下于水中相互混合(其中碳酸铵作为沉淀剂，投料比例为碳酸铵过量或者优选铵离子与金属离子的比例为1:1)；将上述混合液陈化，然后取出洗涤、过滤和干燥，所得的固体在空气气氛下焙烧，获得高比表面的金属氧化物，具体样品及其制备条件如下表2。
表2 高比表面积金属氧化物的制备及其性能参数
(八)、分散剂Cr2O3、Al2O3或ZrO2分散的金属氧化物
以分散剂Cr2O3、Al2O3或ZrO2为载体，沉淀沉积法制备Cr2O3、Al2O3或ZrO2分散的金属氧化物。以分散ZnO的制备为例，将商业Cr2O3(比表面积约为5m2/g)、Al2O3(比表面积约为20m2/g)或ZrO2(比表面积约为10m2/g)作为载体预先分散于水中，然后采用硝酸锌为原料，与氢氧化钠沉淀剂在室温下混合沉淀，Zn2+的摩尔浓度为0.067M，Zn2+与沉淀剂的摩尔份数比为1：8；然后在160℃下陈化24小时，获得Cr2O3、Al2O3或ZrO2为载体分散的ZnO(分散剂于组分Ⅰ中的含量依次为0.1wt％、20wt％、85wt％)。得到的样品在空气下500℃焙烧1h，产物依次定义为分散氧化物1-3，其比表面积依次为：148m2/g，115m2/g，127m2/g。
以同样的方法，可以获得SiO2(比表面积约为2m2/g)、Ga2O3(比表面积约为10m2/g)或TiO2(比表面积约为15m2/g)为载体分散的MnO氧化物(分散剂于组分Ⅰ中的含量依次为5wt％、30wt％、60wt％)，产物依次定义为分散氧化物4-6。其比表面积依次为：97m2/g，64m2/g，56m2/g。
以同样的方法，可以获得活性炭(比表面积约为1000m2/g)、石墨烯(比表面积约为500m2/g)或碳纳米管(比表面积约为300m2/g)为载体分散的ZnO氧化物(分散剂于组分Ⅰ中的含量依次为5wt％、30wt％、60wt％)，产物依次定义为分散氧化物7-9。其比表面积依次为：177m2/g，245m2/g，307m2/g。
二、II组分(MOR拓扑结构的分子筛)的制备
所述MOR拓扑结构是一种正交晶系，具有相互平行的椭圆形直通孔道的一维孔道结构，含有8圆环与12圆环平行一维直通孔道，12圆环主孔道侧边存在8圆环口袋连通。
本发明所述的MOR分子筛可以是直接购买的商品分子筛，也可以是自行合成的分子筛。这里使用南开大学催化剂厂生产的MOR分子筛作为MOR1；同时也自行通过水热合成法为例制备了7个具有MOR结构的分子筛；
具体制备过程为：
按照n(SiO2)/n(Al2O3)＝15,n(Na2O)/n(SiO2)＝0.2,n(H2O)/n(SiO2)＝26.
将硫酸铝与氢氧化钠溶液混合，然后加入硅溶胶，搅拌1h得到均一相的初始凝胶，然后将其转移到高压合成釜中，180℃静态晶化24h后骤冷、洗涤、干燥，即得到丝光沸石样品，标记为Na-MOR。
取Na-MOR，将其与1mol/L的氯化铵溶液混合，在90℃下搅拌3h，洗涤，烘干，连续进行4次，450度焙烧6h，得到氢型丝光沸石。
按上述过程制备的具有MOR拓扑结构的分子筛的骨架元素组成可以是Si-Al-O、Ga-Si-O、Ga-Si-Al-O、Ti-Si-O、Ti-Al-Si-O、Ca-Al-O、Ca-Si-Al-O中的一种；
部分骨架的O元素上连接H，对应产物依次定义为MOR1-8；
表3 具有MOR拓扑结构的分子筛的制备及其性能参数
将制备好的分子筛，取适量于真空下进行脱水脱气处理，温度400℃，压力10-4Pa，10h之后降至300℃后，向真空腔体内通入200Pa的有机碱气体，平衡10h后在相同温度下脱附1h。
将MOR1，MOR2，MOR3，MOR4,MOR5,MOR6,MOR7,MOR 8依次使用：二甲胺、三甲胺、二乙胺、三乙胺、乙二胺、一丙胺、二丙胺、三丙胺、异丙胺、二异丙胺、1,2-二甲基丙胺、1,2-丙二胺、2-丙烯胺、环丙胺、正丁胺、二正丁胺、异丁胺、仲丁胺、1,4-丁二胺、叔丁胺、二异丁胺己胺、2-乙基己胺、己二胺、三辛胺处理后，分别得到MOR9，MOR10,MOR11,MOR12,MOR13,MOR14,MOR15,MOR16,MOR17,MOR18,MOR19,MOR20,MOR21,MOR22,MOR23,MOR24,MOR25,MOR26,MOR27,MOR28,MOR29,MOR30,MOR31,MOR32。
三、催化剂的制备
将所需比例的组分Ⅰ和组分Ⅱ加入容器中，利用这些物料和/或容器的高速运动产生的挤压力、撞击力、裁剪力、摩擦力等中的一种或两种以上作用实现分离、破碎、混匀等目的，通过调变温度与载气气氛实现机械能、热能与化学能的转换，进一步调节不同组分间的相互作用。
机械混合过程中，可以设置混合温度20-100℃，可以在气氛中或者直接在空气中进行，气氛选自以下任意的气体：
a)氮气和/或惰性气体；
b)氢气与氮气和/或惰性气体的混合气，其中氢气于混合气中的体积为5～50％；
c)CO与氮气和/或惰性气体的混合气，其中CO于混合气中的体积为5～20％；
d)O2与氮气和/或惰性气体的混合气，其中O2于混合气中的体积为5-20％，所述惰性气体为氦气、氩气、氖气中的一种或两种以上。
机械混合可采用机械搅拌、球磨、摇床混合、机械研磨中的一种或二种以上进行复合，具体如下：
机械搅拌：在搅拌槽中，采用搅拌棒将组分Ⅰ和组分Ⅱ进行混合，通过控制搅拌时间(5min-120min)和速率(30-300转/min)，可以调节组分Ⅰ和组分Ⅱ的混合程度。
球磨：利用磨料与催化剂在研磨罐内高速翻滚，对催化剂产生强烈冲击、碾压，达到分散、混合组分Ⅰ和组分Ⅱ的作用。通过控制磨料(材质可以是不锈钢、玛瑙、石英。尺寸范围：5mm-15mm)。与催化剂的比例(质量比范围：20-100:1)。
摇床混合法：将组分Ⅰ和组分Ⅱ预混合，并装入容器中；通过控制摇床的往复振荡或圆周振荡，实现组分Ⅰ和组分Ⅱ的混合；通过调节振荡速度(范围：1-70转/分)和时间(范围：5min-120min)，实现均匀混合。
机械研磨法：将组分Ⅰ和组分Ⅱ预混合，并装入容器中；在一定的压力(范围:5公斤-20公斤)下,通过研具与混合的催化剂进行相对运动(速率范围：30-300转/min)，实现均匀混合的作用。
具体的催化剂制备及其参数特征如表4所示。
表4 催化剂的制备及其参数特征
催化反应实例
以固定床反应为例，但是催化剂也适用于移动床反应器。该装置配备气体质量流量计、在线产物分析色谱(反应器的尾气直接与色谱的定量阀连接，进行周期实时采样分析)。
将上述本发明的催化剂2g，置于固定床反应器中，使用Ar置换反应器中的空气，然后再在H2气氛中升温至300℃，切换合成气(H2/CO摩尔比＝0.2-3.5)，合成气中还可以含有CO2，其中CO2在合成气中的体积浓度为0.1-50％。，合成气的压力为0.5-10MPa，升温至反应温度300-600℃，调节反应原料气的空速至300-10000ml/g/h。产物由在线色谱检测分析。
改变温度、压力和空速，可以改变反应性能。乙烯丙烯在产物中的选择性高达78-87％，原料转化率10-60％；由于分子筛与氧化物有效的协同，避免了甲烷和C4+烃类的大量生成。
表5 催化剂的应用及其效果
对比例2-9的反应结果表明，MOR使用脂肪胺进行后处理对催化性能调控作用明显，相比不使用脂肪胺进行调控的催化剂，调控后的催化剂明显降低了甲烷及C4以上烃类的选择性，同时提高了低碳烯烃和乙烯选择性。
对比例10采用的催化剂的组分I为金属ZnCo，ZnCo摩尔比1：1，其余参数及混合过程等均同催化剂C。
对比例11采用的催化剂的组分I为TiO2，其余参数及混合过程等均同催化剂C。
对比例12采用的催化剂是仅有组分I为ZnO#1不含有MOR分子筛的样品，反应转化率很低，且产物主要以二甲醚，甲烷等副产物为主，几乎没有乙烯生成。
对比例13采用的催化剂是仅有组分II的MOR9分子筛，不含有组分I的作为活性成份的金属氧化物，催化反应几乎没有活性。
对比例12,13表明只有组分I或组分II时反应效果极其差，完全不具备本发明所述的优异反应性能。
提供以上实施例仅仅是为了描述本发明的目的，而并非要限制本发明的范围。本发明的范围由所附权利要求限定。不脱离本发明的精神和原理而做出的各种等同替换和修改，均应涵盖在本发明的范围之内。
Claims (9)
1.一种催化剂，其特征在于：包括组分I和组分II，组分I和组分II以机械混合方式复合在一起，组分I的活性成份为金属氧化物，组分II为MOR拓扑结构的分子筛，II组分中，所述MOR拓扑结构的分子筛经脂肪胺改性处理；
所述改性处理是将脂肪胺分散到所述MOR拓扑结构的分子筛的12圆环孔道内的B酸位点。
2.根据权利要求1所述的催化剂，其特征在于：所述脂肪胺是二甲胺、三甲胺、二乙胺、三乙胺、乙二胺、一丙胺、二丙胺、三丙胺、异丙胺、二异丙胺、1,2-二甲基丙胺、1,2-丙二胺、2-丙烯胺、环丙胺、正丁胺、二正丁胺、异丁胺、仲丁胺、1,4-丁二胺、叔丁胺、二异丁胺己胺、2-乙基己胺、己二胺、三辛胺中的一种或两种以上。
3.根据权利要求1所述的催化剂，其特征在于：
所述的金属氧化物为MnOx、MnaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnOx、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CeOx、CoaAl(1-a)Ox、FeaAl(1-a)Ox、GaOx、BiOx、InOx、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)Ox中的一种或二种以上；
所述MnOx、ZnOx、CeOx、GaOx、BiOx、InOx的比表面积是1-100m2/g；优选比表面积是50-100m2/g；
所述MnaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CoaAl(1-a)Ox、FeaAl(1-a)Ox、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)Ox的比表面积是5-150m2/g。优选比表面积是50-150m2/g。
所述x的取值范围是0.7～3.7，a的取值范围是0～1；a+b的取值范围是0～1；
4.根据权利要求1所述的催化剂，其特征在于：所述组分I中的活性成份与组分II的重量比为0.1-20，优选为0.3-8。
5.按照权利要求1所述的催化剂，其特征在于：所述组分I中还添加有分散剂，分散剂为Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3、活性炭、石墨烯、碳纳米管中的一种或二种以上，金属氧化物分散于分散剂中，分散剂于I组分中的含量在0.05-90wt％，优选0.05-25wt％，其余为活性金属氧化物。
6.按照权利要求1-5任一项所述的催化剂，其特征在于：所述MOR拓扑结构分子筛的骨架元素组成是Si-Al-O、Ga-Si-O、Ga-Si-Al-O、Ti-Si-O、Ti-Al-Si-O、Ca-Al-O、Ca-Si-Al-O中的一种或二种以上。
7.一种合成气反应高选择性制乙烯的方法，其特征在于：以合成气为反应原料，在固定床或移动床上进行转化反应，得到乙烯为主的低碳烯烃产物，所采用的催化剂为权利要求1-6任一所述的催化剂。
8.根据权利要求7所述的方法，其特征在于：所述合成气的压力为0.5-10MPa，优选为1-8MPa，更优选为2-8MPa；反应温度为300-600℃，优选为300-450℃；空速为300-10000h-1，优选为500-9000h-1，更优选为500-6000h-1。所述合成气为H2/CO混合气，H2/CO摩尔比为0.2-3.5，优选为0.3-2.5；所述合成气中还可以含有CO2，其中CO2在合成气中的体积浓度为0.1-50％。
9.按照权利要求7所述的方法，其特征在于：所述方法以合成气一步法直接转化制C2-4烯烃，乙烯选择性为75-82％，副产物甲烷选择性<9％，4个C原子以上的烃类产物选择性低于10％。
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| AU2019210781A1 (en) | 2020-08-06 |
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| AU2019210781B2 (en) | 2021-08-12 |
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