CN109939667A - 一种催化剂及合成气直接转化制低碳烯烃的方法 - Google Patents
一种催化剂及合成气直接转化制低碳烯烃的方法 Download PDFInfo
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- CN109939667A CN109939667A CN201810079238.6A CN201810079238A CN109939667A CN 109939667 A CN109939667 A CN 109939667A CN 201810079238 A CN201810079238 A CN 201810079238A CN 109939667 A CN109939667 A CN 109939667A
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
本发明属于合成气直接制备低碳烯烃，具体涉及一种催化剂及合成气直接转化制低碳烯烃的方法，其以合成气为反应原料，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CHA与AEI结构的分子筛或金属修饰的CHA与或AEI分子筛中的一种或二种以上；组分Ⅰ中的活性成份与组分Ⅱ之间的重量比在0.1‑20倍范围之间。反应过程具有很高的产品收率和选择性，其中丙烯与丁烯选择性之和达到40‑75％，低碳烯烃包括乙烯、丙烯和丁烯的选择性之和可以达到50‑90％，同时副产物甲烷选择性低于15％，具有很好的应用前景。
Description
技术领域
本发明属于合成气制备低碳烯烃，具体涉及一种催化剂及合成气直接转化制 低碳烯烃的方法。
背景技术
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，长期以来，低 碳烯烃市场供不应求。目前，低碳烯烃的生产主要采用轻烃(乙烷、石脑油、轻柴 油)裂解的石油化工路线，由于全球石油资源的日渐缺乏和原油价格长期高位运 行，发展低碳烯烃工业仅仅依靠石油轻烃为原料的管式裂解炉工艺会遇到越来越 大的原料难题，低碳烯烃生产工艺和原料必须多元化。选用合成气制取烯烃工艺 可拓宽原材料来源，将以原油、天然气、煤炭和可再生材料为原料生产合成气， 为基于高成本原料如石脑油的蒸汽裂解技术方面提供替代方案。合成气一步法直 接制取低碳烯烃就是一氧化碳和氢在催化剂作用下，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，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。
合成气通过费托合成直接制取低碳烯烃，已成为费托合成催化剂开发的研究 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％。最近，荷兰Utrecht大学de Jong教授团队采用SiC，碳纳米 纤维等惰性载体负载的Fe以及Na、S等助剂修饰的Fe催化剂，取得了很好进 展获得了61％的低碳烯烃选择性，但是转化率升高时，选择性降低。在合成气直 接制烯烃的过程中，由于原料CO与H2是气态，而目标产物中的乙烯沸点低， 一般需要深冷分离，如果能够高选择性的获得含三个碳原子和四个碳原子的烯烃 即丙烯和丁烯C3-C4烯烃产物，则不需要进行深冷分离，大大降低了分离的能耗 与成本，具有重大的应用价值。上述报道中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，产物低碳烯烃选择性低，而其中C3-C4烯烃的选择性更低。
最近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.,Science351(2016)1065-1068)，实现了CO转化率17％时,低碳烯烃80％的选 择性，其中低碳烷烃选择性为14，烯烃与烷烃的比例(烯烷比)达到5.7。当转化 率升高到35％，烯烃的选择性为69％，而烷烃的选择性为20％，烯烷比降为3.5， 丙烯丁烯选择性为40-50％。
发明内容
针对上述问题，本发明提供了一种催化剂及合成气直接转化制低碳烯烃的方 法。
本发明的技术方案为：一种催化剂，所述催化剂包括组分Ⅰ和组分Ⅱ，所述 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CHA或AEI拓扑结构的分子筛；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。
本发明所述CHA与AEI拓扑结构的分子筛，具有八元环孔口，三维孔道， 含有cha笼。
所述CHA或AEI拓扑结构的分子筛的骨架元素组成可以是Si-O、Si-Al-O、 Si-Al-P-O、Al-P-O、Ga-P-O、Ga-Si-Al-O、Zn-Al-P-O、Mg-Al-P-O、Co-Al-P-O中 的一种或二种以上。
所述组分II的分子筛具有中强酸位点，中强酸位点的量是0-0.3mol/kg；优 选为0.003-0.2mol/kg，更优选为0.003-0.06mol/kg；
本发明所述中强酸对应NH3-TPD脱附峰的峰顶对应的温度范围为275- 500℃；所述酸强度以NH3-TPD峰来定义，包含弱酸、中强酸、强酸三种酸 性；该NH3-TPD是根据NH3的脱附峰位置，所述脱附峰的位置是指在标准测 试条件下，在样品质量w与载气流速f比值(w/f)＝100g·h/L，10℃/min升 温速度的测试条件下，TCD记录脱附NH3的热导信号，绘制脱附曲线，根据 曲线峰位置顶点将所述无机固体分为三种酸性强度；弱酸是指NH3脱附温度小 于275℃的酸性位；中强酸是NH3脱附温度在275-500℃的酸性位；强酸是NH3脱附温度大于500℃的酸性位。
用丙酮作为探针分子，13C-NMR化学位移位于210-220ppm范围。
组分Ⅰ中的活性成份与组分Ⅱ之间的重量比为0.1-20，优选为0.3-5。
所述组分Ⅰ中还添加有分散剂，金属氧化物分散于分散剂中；所述分散剂为 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。
所述组分Ⅰ中，分散剂的含量在0.05-90wt％，其余为金属氧化物。
所述组分II的分子筛骨架的O元素上可以连接或不连接H；且所述H可以 通过离子交换的方式被Na、Ca、K、Mg、Ge、Zr、Zn、Cr、Ga、Sn、Fe、Co、 Mo、Mn中的一种或两种以上全部或部分取代，取代后总的金属与氧的摩尔比是 0.0002-0.001。
本发明另一方面提供一种合成气直接转化制低碳烯烃的方法，其以合成气为 反应原料，在固定床或移动床上进行转化反应，所采用的催化剂为权利要求1-5 任一所述的催化剂；
所述合成气的压力为0.5-10MPa，优选为1-8MPa；反应温度为300-600℃， 优选为350-450℃；空速为300-12000h-1，优选为1000-9000h-1，更优选为3000- 9000h-1；所述合成气为H2/CO混合气，H2/CO比例为0.2-3.5，优选为0.3-2.5。
本发明所述的催化剂用于合成气一步法直接转化制低碳烯烃，其中丙烯丁烯 选择性达到40-75％，优选为50-75％，同时副产物甲烷选择性低于15％，优选为 <10％。
本发明具有如下优点：
1.本技术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低碳烯烃。
2.产物中丙烯丁烯产物选择性高，可达到40-75％，产物不需深冷便可分离， 大大降低了分离的能耗与成本。
3.催化剂中组分Ⅰ的活性成分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 得更多的低碳烯烃产物。
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 CHA或AEI拓扑结构的分子筛，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.本发明复合催化剂的制备过程简单条件温和；且反应过程具有很高的产 品收率和选择性，C2-C4低碳烯烃的选择性可以达到50-90％，特别C3-C4烯烃 选择性高，同时副产物甲烷选择性低(<15％)，而且催化剂寿命长，>700小时， 具有很好的应用前景。
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。
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售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1ZnO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、组分 II(CHA与AEI拓扑结构的分子筛)的制备：
所述CHA与AEI拓扑结构具有八元环孔口，三维孔道，含有cha笼。
本发明所描述的中强酸可以通过固体核磁的H谱，NH3-TPD，红外，化学滴 定等方式进行测试。但酸性的测试方法不限于上述测试方法。
本发明所述的分子筛可以是商品的酸密度符合本发明要求的具有CHA与 AEI拓扑结构的分子筛，也可以是根据现有文献报道的方法制备的分子筛 (Chemcatchem，2012,4,1428-1435)，本发明以通过水热合成法制备的分子筛为例。
1)具体制备过程为：
按氧化物SiO2:Al2O3:H3PO4:R:H2O＝1.6:16:32:55:150(质量比)称取原料：硅 溶胶30％(质量浓度)；AlOOH；磷酸；TEA(R)；去离子水，室温混合后加入 模板剂0.5倍摩尔量的助剂HF，在30℃下搅拌老化，2h后转移到水热釜中， 200℃下晶化24h。水浴骤冷到室温，反复离心洗涤使得洗涤结束时上清液pH是 7，沉淀物于110℃下烘干17h后，在600℃空气中焙烧3h得到多级孔结构的硅 磷铝无机固体酸。
所述具有CHA与AEI拓扑结构的分子筛的骨架元素组成可以是Si-O、Si- Al-O、Si-Al-P-O、Al-P-O、Ga-P-O、Ga-Si-Al-O、Zn-Al-P-O、Mg-Al-P-O、Co-Al- P-O中的一种或二种以上；
部分骨架的O元素上连接H，对应产物依次定义为分1-7；
表3具有CHA或AEI拓扑结构的分子筛的制备及其性能参数
2)将上述产物分1-8骨架的O元素上连接的H通过离子交换的方式被如下 金属离子部分取代：Na、Ca、K、Mg、Ge、Zr、Zn、Cr、Ga、Sn、Fe、Co、Mo、 Mn，制备过程为：
取分1-8样品，按照固液质量比为1:30的比例将其与0.5mol/L的待交换的 金属离子硝酸盐溶液混合，在80℃下搅拌6h，洗涤，烘干，连续进行2次，550 度焙烧3h，得到金属离子交换的CHA或AEI。
对应产物依次定义为分9-22。
表4具有CHA或AEI拓扑结构的分子筛的制备及其性能参数
表5其他元素组成的分子筛
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6所示。 表6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300-12000ml/g/h。产物由在线色谱检测分析。
改变温度、压力和空速和合成气中H2/CO的摩尔比，可以改变反应性能。其 中丙烯与丁烯选择性之和达到30-75％，低碳烯烃(乙烯、丙烯、丁烯选择性之 和可以达到50-90％；由于催化剂金属复合物表面加氢活性不高，避免了甲烷的 大量生成，甲烷选择性低。表7列出了催化剂的具体应用及其效果数据。
表7催化剂的具体应用及其效果数据
对比例1催化剂组份Ⅰ为ZnO#4，组份Ⅱ为分1。
对比例4采用的催化剂中分子筛为购自南开大学催化剂厂的商品SAPO-34，其NH3-TPD上中强酸脱附峰对应的温度在390℃,中强酸位点的量是0.6mol/kg。 对比例5采用的催化剂中分子筛为购自南开大学催化剂厂的商品ZSM-5，全微 孔结构，Si/Al＝30。
对比例4和5的反应结果表明，CHA或AEI的拓扑结构及其酸强度对产物选择 性的调变至关重要。
对比例6采用的催化剂是仅有组分I ZnO#1不含有分子筛的样品，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7采用的催化剂是仅有组分II分1分子筛，不含有组分I的样品，催化反 应几乎没有活性。
对比例6,7表面只有组分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。
文献(Jiao et al.,Science 351(2016)1065-1068)对比技术中，所使用的分子SAPO- 34筛酸量较大，根据NH3-TPD测试，中强酸酸量达到0.32mol/kg，因此当转化 率升高到35％，烯烃的选择性为69％，而烷烃的选择性为20％，烯烷比降为3.5， 丙烯丁烯选择性为40-50％。
由上表可以看出分子筛的结构，包括CHA&AEI的拓扑结构及其酸强度和酸量， 以及金属氧化物和分子筛之间的匹配至关重要，直接影响一氧化碳的转化率和丙 烯丁烯的选择性。
Claims (10)
1.一种催化剂，其特征在于：所述催化剂包括组分Ⅰ和组分Ⅱ，所述组分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CHA或AEI拓扑结构的分子筛；
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。
2.按照权利要求所述的催化剂，其特征在于：所述具有CHA或AEI拓扑结构的分子筛的骨架元素组成为Si-O、Si-Al-O、Si-Al-P-O、Al-P-O、Ga-P-O、Ga-Si-Al-O、Zn-Al-P-O、Mg-Al-P-O、Co-Al-P-O中的一种或二种以上。
3.按照权利要求1所述的催化剂，其特征在于：所述分子筛具有中强酸位点，中强酸位点的量是0-0.3mol/kg；优选为0.003-0.2mol/kg，更优选为0.003-0.06mol/kg。
4.按照权利要求1所述的催化剂，其特征在于：组分Ⅰ中的活性成份与组分Ⅱ之间的重量比为0.1-20，优选为0.3-5。
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，金属氧化物分散于分散剂中；所述分散剂为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；所述组分Ⅰ中，分散剂的含量在0.05-90wt％，其余为金属氧化物。
6.按照权利要求1-3所述的催化剂，其特征在于：分子筛骨架的O元素上连接或不连接H。
7.按照权利要求7所述的催化剂，其特征在于：当分子筛骨架的O元素连接H时，所述H通过离子交换的方式被Na、Ca、K、Mg、Ge、Zr、Zn、Cr、Ga、Sn、Fe、Co、Mo、Mn中的一种或两种以上全部或部分取代，取代后总的金属与氧的摩尔比是0.0002-0.001。
8.一种合成气直接转化制低碳烯烃的方法，其特征在于：所述方法以合成气为反应原料，在固定床或移动床上进行转化反应，所采用的催化剂为权利要求1-8任一所述的催化剂。
9.按照权利要求8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；反应温度为300-600℃，优选为350-450℃；空速为300-12000h-1，优选为1000-9000h-1，更优选为3000-9000h-1；所述合成气为H2/CO混合气，H2/CO比例为0.2-3.5，优选为0.3-2.5。
10.按照权利要求8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，C2-4烯烃选择性为50-90％，副产物甲烷选择性<15％。
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| CN109704900B (zh) * | 2017-10-26 | 2021-11-30 | 中国石油化工股份有限公司 | 合成气一步法制烯烃的方法 |
| CN109704900A (zh) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | 合成气一步法制烯烃的方法 |
| CN110479364A (zh) * | 2019-09-02 | 2019-11-22 | 太原理工大学 | 一种双功能催化剂及co加氢直接转化制低碳烯烃的方法 |
| CN112705257A (zh) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | 一种用于合成气制低碳烯烃的催化剂及其成型方法和应用 |
| CN112705257B (zh) * | 2019-10-25 | 2023-03-03 | 中国石油化工股份有限公司 | 一种用于合成气制低碳烯烃的催化剂及其成型方法和应用 |
| CN112973659B (zh) * | 2019-12-14 | 2023-08-29 | 中国科学院大连化学物理研究所 | 一种含sapo-17分子筛的双功能催化剂及在合成气制低碳烯烃反应中的应用 |
| CN112973659A (zh) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | 一种含sapo-17分子筛的双功能催化剂及在合成气制低碳烯烃反应中的应用 |
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| CN112973775B (zh) * | 2019-12-14 | 2023-03-21 | 中国科学院大连化学物理研究所 | 一种含mcm-22分子筛的催化剂及其在合成气一步法制液体燃料中的应用 |
| CN111167470A (zh) * | 2020-01-15 | 2020-05-19 | 大连凯信科技研发有限公司 | 合成气制烯烃的催化剂及其制备方法和在烯烃生产中的应用 |
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| CN113926457B (zh) * | 2020-06-29 | 2024-02-02 | 中国石油化工股份有限公司 | 一种用于高温费托合成的催化剂及其制备方法和应用 |
| CN114425385B (zh) * | 2020-10-15 | 2024-02-02 | 中国石油化工股份有限公司 | 费托合成制低碳烯烃的催化剂及其制备方法和应用 |
| CN114425385A (zh) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | 费托合成制低碳烯烃的催化剂及其制备方法和应用 |
| CN115703074A (zh) * | 2021-08-06 | 2023-02-17 | 中国科学院大连化学物理研究所 | 一种含MnGaOx的双功能催化剂及其在一氧化碳高温加氢制低碳烯烃中的应用 |
| CN115703074B (zh) * | 2021-08-06 | 2024-05-17 | 中国科学院大连化学物理研究所 | 一种含MnGaOx的双功能催化剂及其在一氧化碳高温加氢制低碳烯烃中的应用 |
| CN114210259B (zh) * | 2021-11-15 | 2023-10-24 | 广东先导微电子科技有限公司 | 一种三氯化镓制粒包装装置及方法 |
| CN114210259A (zh) * | 2021-11-15 | 2022-03-22 | 广东先导微电子科技有限公司 | 一种三氯化镓制粒包装装置及方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2758849C1 (ru) | 2021-11-02 |
| AU2019211888B2 (en) | 2021-10-14 |
| US20210121859A1 (en) | 2021-04-29 |
| JP2021516146A (ja) | 2021-07-01 |
| US11369951B2 (en) | 2022-06-28 |
| CN109939667B (zh) | 2021-01-05 |
| AU2019211888A1 (en) | 2020-08-06 |
| EP3744423A4 (en) | 2021-11-03 |
| EP3744423A1 (en) | 2020-12-02 |
| WO2019144950A1 (zh) | 2019-08-01 |
| CA3087607A1 (en) | 2019-08-01 |
| CA3087607C (en) | 2022-07-12 |
| JP7007762B2 (ja) | 2022-02-10 |
| ZA202101244B (en) | 2022-09-28 |
| SA520412504B1 (ar) | 2024-02-08 |
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