CN111036282B - Supported catalyst, method for preparing same, and method for preparing alpha-olefin from synthesis gas - Google Patents

Supported catalyst, method for preparing same, and method for preparing alpha-olefin from synthesis gas Download PDF

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CN111036282B
CN111036282B CN201811197915.0A CN201811197915A CN111036282B CN 111036282 B CN111036282 B CN 111036282B CN 201811197915 A CN201811197915 A CN 201811197915A CN 111036282 B CN111036282 B CN 111036282B
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active component
catalyst
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supported catalyst
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CN111036282A (en
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晋超
吴玉
张荣俊
夏国富
侯朝鹏
孙霞
王薇
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425Catalysts; their physical properties
    • C07C1/043Catalysts; their physical properties characterised by the composition
    • C07C1/0435Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron

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Abstract

The present disclosure relates to a supported catalyst, a preparation method thereof and a method for preparing alpha-olefin from synthesis gas, the catalyst comprises a carrier, and an active component and an auxiliary agent loaded on the carrier, wherein the carrier contains a manganese oxide molecular sieve OMS-1, the active component is one or more metal components selected from VIII group metals, and the auxiliary agent is one or more metal components selected from IIB group metals. Compared with the catalyst in the prior art, the supported catalyst has improved catalytic activity and target product selectivity, has the advantages of higher alpha-olefin yield and concentrated product carbon number when being used for preparing alpha-olefin from synthesis gas, and is beneficial to industrial popularization.

Description

负载型催化剂及其制备方法以及由合成气制备α-烯烃的方法Supported catalyst and method for preparing the same, and method for preparing alpha-olefin from synthesis gas

技术领域technical field

本公开涉及一种负载型催化剂及其制备方法以及由合成气制备α-烯烃的方法。The present disclosure relates to a supported catalyst, a preparation method thereof, and a method for preparing alpha-olefins from synthesis gas.

背景技术Background technique

我国能源呈富煤、多天然气、缺油的资源分布局面,通过费托(F-T)合成将煤基或天然气间接转化为洁净、高效液体燃料是合理利用资源的重要方面,是缓解我国石油供需矛盾的主要技术途径。该工艺首先将煤或天然气转化为合成气,再经过F-T合成制成液体燃料。F-T合成技术包括高温F-T合成和低温F-T合成两种,高温F-T合成工艺的操作温度为300-350℃,操作压力为1.5-2.5MPa左右;低温F-T合成工艺的操作温度为210-250℃,操作压力为1.5-2.5MPa左右。高温F-T合成的产品经加工可得到对环境友好的汽油、柴油、溶剂油、烯烃和含氧化合物;低温F-T合成的主产品石蜡可加工成特种蜡或经加氢裂化/异构化生产优质柴油、润滑油基础油,石脑油馏分还是理想的裂解原料。传统的费托合成产物主要有直链烷烃、烯烃、醛醇,以及副产物水和二氧化碳,产物组成复杂,而通过调整工艺条件和催化剂组成则可以实现多产烯烃。直链α-烯烃是一种重要的有机原料和中间体,广泛用于生产共聚单体、润滑油基础油、表面活性剂、聚烯烃树脂、增塑剂、染料、药物制剂等。南非Sasol公司已建成一套从F-T合成产品(富含α-烯烃)中分离1-戊烯、1-己烯的生产装置并成功投产,该工艺最大优点是以煤为原料,把1-戊烯、1-己烯作为副产物回收,工业化生产成本低,获得较高收益。my country's energy resources are distributed in a situation of rich coal, more natural gas, and lack of oil. The indirect conversion of coal-based or natural gas into clean and efficient liquid fuels through Fischer-Tropsch (F-T) synthesis is an important aspect of rational utilization of resources and is an important way to alleviate the contradiction between oil supply and demand in my country. main technical approach. The process first converts coal or natural gas into syngas, which is then synthesized into liquid fuel through F-T. F-T synthesis technology includes two kinds of high-temperature F-T synthesis and low-temperature F-T synthesis. The operating temperature of the high-temperature F-T synthesis process is 300-350 ℃, and the operating pressure is about 1.5-2.5MPa; the operating temperature of the low-temperature F-T synthesis process is 210-250 ℃. The pressure is about 1.5-2.5MPa. The products synthesized by high temperature F-T can be processed to obtain environmentally friendly gasoline, diesel oil, solvent oil, olefins and oxygenates; the main product of low temperature F-T synthesis can be processed into special wax or by hydrocracking/isomerization to produce high-quality diesel , lubricating oil base oil, naphtha fraction is also an ideal cracking raw material. The traditional Fischer-Tropsch synthesis products mainly include linear alkanes, alkenes, aldols, and by-products water and carbon dioxide. The product composition is complex, but by adjusting the process conditions and catalyst composition, more alkenes can be produced. Linear α-olefin is an important organic raw material and intermediate, which is widely used in the production of comonomers, lubricating base oils, surfactants, polyolefin resins, plasticizers, dyes, pharmaceutical preparations, etc. Sasol Company of South Africa has built a set of production equipment for separating 1-pentene and 1-hexene from F-T synthetic products (rich in α-olefins) and successfully put into production. The alkene and 1-hexene are recovered as by-products, the industrial production cost is low, and high returns are obtained.

目前生产α-烯烃的应用最广泛的方法是烯烃齐聚法,但该方法生产成本过高,而且不能生产同样具有市场价值的碳数为奇数的线性α-烯烃。南非Sasol公司从高温F-T费托合成技术从粗产物中抽提线性1-己烯的成本还不到Philips公司采用乙烯三聚法生产的三分之一,同时基于F-T合成产物ASF分布规律,高温F-T合成也可得到奇数碳数的1-戊烯和1-庚烯等高附加值产品。因此,从费托合成产物中分离得到α-烯烃具有重要的商业价值。At present, the most widely used method for producing α-olefin is olefin oligomerization, but the production cost of this method is too high, and the linear α-olefin with odd number of carbons that also has market value cannot be produced. The cost of extracting linear 1-hexene from the crude product by the high temperature F-T Fischer-Tropsch synthesis technology of Sasol Company in South Africa is less than one third of that produced by Philips Company using the ethylene trimerization method. F-T synthesis can also obtain high value-added products such as 1-pentene and 1-heptene with odd carbon numbers. Therefore, the separation of α-olefins from Fischer-Tropsch synthesis products has important commercial value.

目前,工业上一般用铁基催化剂,以浆态床、固定床或流化床工艺生产烯烃。低温F-T合成工艺条件下,产物重质烃含量高,烯烃含量较低,不利于生产α-烯烃。南非Sasol公司采用高温流化床工艺来生产汽油和α-烯烃。这种工艺虽然可以获得低碳数线性α-烯烃,但产物α-烯烃碳数分布过于分散,产率低,不利于分离提纯。At present, iron-based catalysts are generally used in industry to produce olefins in slurry, fixed or fluidized bed processes. Under the low temperature F-T synthesis process conditions, the product has high content of heavy hydrocarbons and low content of olefins, which is not conducive to the production of α-olefins. South African company Sasol uses a high temperature fluidized bed process to produce gasoline and alpha-olefins. Although this process can obtain linear α-olefin with low carbon number, the carbon number distribution of the product α-olefin is too dispersed and the yield is low, which is not conducive to separation and purification.

常见的铁基F-T合成催化剂多为共沉淀法制备:先将活性组分沉淀、过滤洗涤,然后再与载体混合、打浆,最后干燥成型,应用于浆态床反应器或者固定床反应器。沉淀铁F-T合成催化剂机械稳定性差、反应过程中易破碎、积炭严重,体相内活性组分难以还原。由于F-T合成是强放热反应,在固定床中反应时,沉淀铁催化剂在反应器内取热困难,易飞温,使催化剂快速失活。而负载型铁基催化剂的稳定性好、活性组分分布均匀、活性高寿命长。Common iron-based F-T synthesis catalysts are mostly prepared by co-precipitation method: first, the active components are precipitated, filtered and washed, then mixed with the carrier, slurried, and finally dried and formed, which are applied to slurry bed reactors or fixed bed reactors. Precipitated iron F-T synthesis catalysts have poor mechanical stability, are easily broken during the reaction process, have serious carbon deposits, and are difficult to reduce the active components in the bulk phase. Since F-T synthesis is a strong exothermic reaction, when reacting in a fixed bed, it is difficult for the precipitated iron catalyst to take heat in the reactor, and it is easy to fly over temperature, resulting in rapid deactivation of the catalyst. The supported iron-based catalyst has good stability, uniform distribution of active components, high activity and long life.

CN102408908A公开了一种溶剂相费托合成的生产各种碳数的线性α-烯烃方法。以极性溶剂为反应介质,将传统颗粒状费托合成催化剂悬浮或浸泡在极性溶剂相中进行费托合成反应,由于生成的烃类产物不溶于所述的极性溶剂而自行分相。但使用该方法获得的线性α-烯烃碳数过于分散。CN103525456A公开了一种由煤制烯烃制备合成烃的方法,该方法将煤制烯烃中含有α-烯烃和烷烃的轻油部分在AlCl3催化剂作用下,制备用作高品质润滑油的合成烃基础油产品。US4579986公开了一种制备C10-C20烯烃的方法,在钴基催化剂作用下将CO和H2转化为正构烷烃混合物,分析C20 +以上馏分,通过缓和热裂解将该馏分转化为含C10-C20烯烃的烃类混合物。但该方法中,α-烯烃含量较低。CN102408908A discloses a solvent-phase Fischer-Tropsch synthesis method for producing linear α-olefins with various carbon numbers. Using polar solvent as reaction medium, the traditional granular Fischer-Tropsch synthesis catalyst is suspended or soaked in polar solvent phase to carry out Fischer-Tropsch synthesis reaction, since the generated hydrocarbon product is insoluble in the polar solvent and self-separates. However, the carbon number of linear α-olefins obtained by this method is too dispersed. CN103525456A discloses a method for preparing synthetic hydrocarbons from coal-to-olefins. The method uses the light oil part containing alpha-olefins and alkanes in coal-to-olefins to prepare synthetic hydrocarbon bases for high-quality lubricating oils under the action of AlCl3 catalysts oil products. US4579986 discloses a method for preparing C10 - C20 olefins, converting CO and H2 into a mixture of n-paraffins under the action of a cobalt-based catalyst, analyzing the fraction above C20 + , and converting this fraction into a mixture containing C20+ by mild thermal cracking Hydrocarbon mixtures of C 10 -C 20 olefins. However, in this method, the α-olefin content is relatively low.

因此,开发一种可以使α-烯烃产率高、产物碳数集中的催化剂具有非常现实的意义。Therefore, it is of great practical significance to develop a catalyst that can make the α-olefin yield high and the carbon number of the product concentrated.

发明内容SUMMARY OF THE INVENTION

本公开的目的是提供一种负载型催化剂及其制备方法以及由合成气制备α-烯烃的方法,以克服现有催化剂的α-烯烃产率低、产物碳数过于分散的缺陷。The purpose of the present disclosure is to provide a supported catalyst, a preparation method thereof, and a method for preparing α-olefin from synthesis gas, so as to overcome the defects of low yield of α-olefin and excessive dispersion of carbon number in the product of the existing catalyst.

为了实现上述目的,本公开第一方面:提供一种负载型催化剂,该催化剂包括载体,以及负载在所述载体上的活性组分和助剂,所述载体含有锰氧化物分子筛OMS-1,所述活性组分为选自第VIII族金属的金属组分的一种或多种,所述助剂为选自第IIB族金属的金属组分的一种或多种。In order to achieve the above object, a first aspect of the present disclosure: provide a supported catalyst, the catalyst includes a carrier, and active components and auxiliary agents supported on the carrier, the carrier contains manganese oxide molecular sieve OMS-1, The active component is one or more metal components selected from Group VIII metals, and the auxiliary agent is one or more metal components selected from Group IIB metals.

可选地,以催化剂的干基重量为基准,所述载体的含量为12~94重量%,以金属元素计,所述活性组分的含量为1~70重量%,所述助剂的含量为1~30重量%。Optionally, based on the dry weight of the catalyst, the content of the carrier is 12-94% by weight, in terms of metal elements, the content of the active component is 1-70% by weight, and the content of the auxiliary agent 1 to 30% by weight.

可选地,以催化剂的干基重量为基准,所述载体的含量为30~91重量%,以金属元素计,所述活性组分的含量为2~50重量%,所述助剂的含量为2~25重量%。Optionally, based on the dry weight of the catalyst, the content of the carrier is 30-91% by weight, in terms of metal elements, the content of the active component is 2-50% by weight, and the content of the auxiliary agent is 2 to 25% by weight.

可选地,所述活性组分为Fe组分和/或Co组分;所述助剂为Zn组分和/或Cd组分。Optionally, the active component is Fe component and/or Co component; the auxiliary agent is Zn component and/or Cd component.

可选地,以金属元素计,所述活性组分与助剂的重量比为1:(0.2~5),优选为1:(0.3~3)。Optionally, in terms of metal elements, the weight ratio of the active component to the auxiliary agent is 1:(0.2-5), preferably 1:(0.3-3).

本公开第二方面:提供一种制备本公开第一方面所述的负载型催化剂的方法,该方法包括:将所述活性组分和助剂负载于所述载体上。The second aspect of the present disclosure provides a method for preparing the supported catalyst described in the first aspect of the present disclosure, the method comprising: supporting the active components and auxiliary agents on the carrier.

可选地,将所述活性组分和助剂负载于所述载体上的步骤包括:将含有活性组分前驱物和助剂前驱物的浸渍液与载体接触进行浸渍;Optionally, the step of loading the active component and the auxiliary agent on the carrier includes: contacting the impregnation liquid containing the active component precursor and the auxiliary agent precursor with the carrier for impregnation;

所述浸渍的条件包括:温度为10~80℃,优选为20~60℃;时间为0.1~3h,优选为0.5~1h。The conditions of the impregnation include: the temperature is 10-80° C., preferably 20-60° C.; the time is 0.1-3 h, preferably 0.5-1 h.

可选地,所述活性组分前驱物为所述活性组分的硝酸盐、柠檬酸盐、硫酸盐或氯化物,或者它们中的两种或三种的组合;所述助剂前驱物为所述助剂的硝酸盐、硫酸盐、碳酸盐或氯化物,或者它们中的两种或三种的组合。Optionally, the active component precursor is nitrate, citrate, sulfate or chloride of the active component, or a combination of two or three of them; the auxiliary agent precursor is Nitrates, sulfates, carbonates or chlorides of the adjuvant, or a combination of two or three of them.

可选地,该方法还包括对负载后得到的物料进行干燥和焙烧的步骤;Optionally, the method also includes the steps of drying and roasting the material obtained after the load;

所述干燥的条件包括:温度为80~350℃,优选为100~300℃;时间为1~24小时,优选为2~12小时;The drying conditions include: the temperature is 80-350°C, preferably 100-300°C; the time is 1-24 hours, preferably 2-12 hours;

所述焙烧的条件包括:温度为250℃~900℃,优选300℃~850℃,更优选为350℃~800℃;时间为0.5~12小时,优选为1~8小时,更优选为2~6小时。The roasting conditions include: the temperature is 250°C~900°C, preferably 300°C~850°C, more preferably 350°C~800°C; the time is 0.5~12 hours, preferably 1~8 hours, more preferably 2~8 hours 6 hours.

本公开第三方面:提供一种由合成气制备α-烯烃的方法,该方法包括以下步骤:A third aspect of the present disclosure provides a method for preparing α-olefin from synthesis gas, the method comprising the following steps:

(1)使初始催化剂在含有氢气的还原气氛下进行还原处理,得到还原处理后的催化剂;(1) reducing the initial catalyst in a reducing atmosphere containing hydrogen to obtain the catalyst after the reduction treatment;

(2)将合成气与步骤(1)得到的所述还原处理后的催化剂接触进行反应;(2) contacting the synthesis gas with the catalyst after the reduction treatment obtained in step (1) to react;

其中,所述初始催化剂为本公开第一方面所述的负载型催化剂。Wherein, the initial catalyst is the supported catalyst described in the first aspect of the disclosure.

可选地,步骤(1)中,所述还原处理的条件包括:空速为1000~20000h-1,优选为2000~10000h-1;温度为200~600℃,优选为250~500℃;升温速率为1~30℃/min,优选为5~15℃/min;时间为1~20h,优选为2~10h;Optionally, in step (1), the conditions of the reduction treatment include: the space velocity is 1000-20000h -1 , preferably 2000-10000h -1 ; the temperature is 200-600°C, preferably 250-500°C; The rate is 1~30℃/min, preferably 5~15℃/min; the time is 1~20h, preferably 2~10h;

步骤(2)中,所述反应的条件包括:所述反应在固定床反应器中进行,反应温度为280~320℃,反应压力为0.5~8MPa,所述合成气中H2与CO的摩尔比为(0.4~2.5):1,所述合成气的空速为2000~20000h-1In step (2), the conditions of the reaction include: the reaction is carried out in a fixed-bed reactor, the reaction temperature is 280-320° C., the reaction pressure is 0.5-8 MPa, and the moles of H 2 and CO in the synthesis gas are The ratio is (0.4˜2.5):1, and the space velocity of the syngas is 2000˜20000 h −1 .

通过上述技术方案,与现有技术中的催化剂相比,本公开的负载型催化剂的目标产物选择性得到改善,在用于由合成气制备α-烯烃时具有α-烯烃产率较高且产物碳数集中(碳数集中在C5-C15,而现有技术一般在C5-C30分布)的优点,有利于工业化推广。Through the above technical solutions, compared with the catalysts in the prior art, the supported catalyst of the present disclosure has improved selectivity of the target product, and has higher α-olefin yield and product when used to prepare α-olefin from synthesis gas. The advantages of carbon number concentration (carbon number is concentrated in C 5 -C 15 , while the prior art is generally distributed in C 5 -C 30 ) is beneficial to industrialization.

本公开的其他特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the present disclosure will be described in detail in the detailed description that follows.

附图说明Description of drawings

附图是用来提供对本公开的进一步理解,并且构成说明书的一部分,与下面的具体实施方式一起用于解释本公开,但并不构成对本公开的限制。在附图中:The accompanying drawings are used to provide a further understanding of the present disclosure, and constitute a part of the specification, and together with the following detailed description, are used to explain the present disclosure, but not to limit the present disclosure. In the attached image:

图1是实施例中制备的载体OMS-1的XRD谱图。Fig. 1 is the XRD pattern of the carrier OMS-1 prepared in the Example.

具体实施方式Detailed ways

以下结合附图对本公开的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本公开,并不用于限制本公开。The specific embodiments of the present disclosure will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure, but not to limit the present disclosure.

本公开第一方面:提供一种负载型催化剂,该催化剂包括载体,以及负载在所述载体上的活性组分和助剂,所述载体含有锰氧化物分子筛OMS-1,所述活性组分为选自第VIII族金属的金属组分的一种或多种,所述助剂为选自第IIB族金属的金属组分的一种或多种。A first aspect of the present disclosure: provide a supported catalyst, the catalyst includes a carrier, and active components and auxiliary agents supported on the carrier, the carrier contains manganese oxide molecular sieve OMS-1, the active component is one or more metal components selected from Group VIII metals, and the auxiliary agent is one or more metal components selected from Group IIB metals.

本公开的发明人经过深入研究后发现,当采用特殊的锰氧化物分子筛OMS-1为载体,同时将第VIII族金属组分以及第IIB族金属组分分别作为活性组分和助剂,所得到的催化剂表现出了优异的目标产物选择性。将该催化剂用于由合成气制α-烯烃反应中时,能够获得更高的α-烯烃产率,且产物碳数集中(碳数集中在C5-C15,而现有技术一般在C5-C30分布)。After in-depth research, the inventors of the present disclosure found that when a special manganese oxide molecular sieve OMS-1 is used as a carrier, and the Group VIII metal component and the Group IIB metal component are used as the active component and auxiliary agent, respectively, the The resulting catalyst exhibits excellent selectivity to the target product. When the catalyst is used in the reaction of producing α-olefin from synthesis gas, higher yield of α-olefin can be obtained, and the carbon number of the product is concentrated (the carbon number is concentrated in C 5 -C 15 , while the prior art is generally in C 5 - C30 distribution).

根据本公开,以催化剂的干基重量为基准,所述载体的含量可以为12~94重量%,以金属元素计,所述活性组分的含量可以为1~70重量%,所述助剂的含量可以为1~30重量%。为了进一步提高所述催化剂的目标产物选择性,优选地,以催化剂的干基重量为基准,所述载体的含量为30~91重量%,以金属元素计,所述活性组分的含量为2~50重量%,所述助剂的含量为2~25重量%;进一步优选地,以催化剂的干基重量为基准,所述载体的含量为60~83重量%,以金属元素计,所述活性组分的含量为8~30重量%,所述助剂的含量为3~12重量%。According to the present disclosure, based on the dry weight of the catalyst, the content of the carrier may be 12-94 wt %, based on the metal element, the content of the active component may be 1-70 wt %, the auxiliary agent The content of can be 1 to 30% by weight. In order to further improve the target product selectivity of the catalyst, preferably, based on the dry weight of the catalyst, the content of the carrier is 30 to 91% by weight, and based on the metal element, the content of the active component is 2 ~50wt%, the content of the auxiliary agent is 2~25wt%; further preferably, based on the dry weight of the catalyst, the content of the carrier is 60~83wt%, in terms of metal elements, the The content of the active component is 8-30% by weight, and the content of the auxiliary agent is 3-12% by weight.

根据本公开,所述活性组分与助剂的配比对催化剂的催化效果具有一定的影响。本公开中,以金属元素计,所述活性组分与助剂的重量比可以为1:(0.2~5),优选为1:(0.3~3)。According to the present disclosure, the ratio of the active component and the auxiliary agent has a certain influence on the catalytic effect of the catalyst. In the present disclosure, in terms of metal elements, the weight ratio of the active component to the auxiliary agent may be 1:(0.2-5), preferably 1:(0.3-3).

进一步地,所述活性组分可以为Fe组分和/或Co组分,最优选为Fe组分。所述助剂可以为Zn组分和/或Cd组分,最优选为Zn组分。Further, the active components may be Fe components and/or Co components, most preferably Fe components. The adjuvant may be a Zn component and/or a Cd component, most preferably a Zn component.

本公开第二方面:提供一种制备本公开第一方面所述的负载型催化剂的方法,该方法包括:将所述活性组分和助剂负载于所述载体上。The second aspect of the present disclosure provides a method for preparing the supported catalyst described in the first aspect of the present disclosure, the method comprising: supporting the active components and auxiliary agents on the carrier.

根据本公开,锰氧化物分子筛OMS-1可直接作为所述载体使用,也可以与适宜的助剂(如金属锆等)混合后将所得混合物作为所述载体使用。锰氧化物分子筛OMS-1可以商购得到,也可以采用现有技术中的方法制备得到,其制备步骤例如可以包括:According to the present disclosure, the manganese oxide molecular sieve OMS-1 can be used directly as the carrier, or the resulting mixture can be used as the carrier after being mixed with a suitable auxiliary (such as metal zirconium, etc.). Manganese oxide molecular sieve OMS-1 can be obtained commercially, or can be prepared by methods in the prior art, and the preparation steps can include, for example:

a、将含有还原态锰化合物和镁的无机盐的第一水溶液,与含有氧化态锰化合物的碱性第二水溶液混合,在30~90℃,优选40~70℃进行老化反应10~50h,优选15~40h,得到锰氧化物分子筛前驱体;a. Mix the first aqueous solution containing the reduced manganese compound and the inorganic salt of magnesium with the alkaline second aqueous solution containing the oxidized manganese compound, and perform an aging reaction at 30-90°C, preferably 40-70°C for 10-50 hours, Preferably 15-40h, to obtain manganese oxide molecular sieve precursor;

b、将步骤a得到的所述锰氧化物分子筛前驱体与含有镁的无机盐的第三水溶液混合,在100~200℃,优选120~180℃进行晶化反应12~72h,优选24~60h,收集固体。b. Mix the manganese oxide molecular sieve precursor obtained in step a with the third aqueous solution containing inorganic salt of magnesium, and carry out a crystallization reaction at 100-200°C, preferably 120-180°C for 12-72 h, preferably 24-60 h , collect the solids.

进一步地,所述氧化态锰化合物和还原态锰化合物是相对而言的;所述氧化态锰化合物一般是指含有相对高价态的锰(如Mn7+、Mn6+等)的化合物,例如可以为高锰酸钾或锰酸钾;所述还原态锰化合物一般是指含有相对低价态的锰(例如Mn2+)的化合物,例如可以为硫酸锰、硝酸锰或氯化锰。所述镁的无机盐可以为氯化镁或硝酸镁。所述氧化态锰化合物、还原态锰化合物和镁的无机盐的重量比可以为1:(1~10):(0.1~5)。所述碱性第二水溶液中的碱可以为常见的无机碱,例如可以为氢氧化钠、氢氧化钾等;所述碱性第二水溶液的碱浓度可以为1~20重量%。更进一步地,该制备步骤还可以包括:步骤a中,分别将所述第一水溶液和碱性第二水溶液加热至30~90℃,优选40~70℃,然后再进行混合。通过上述步骤,可制得XRD谱图符合JCPDS No.38-475的纯相八面体锰氧化物分子筛OMS-1。Further, the oxidized manganese compound and the reduced manganese compound are relative; the oxidized manganese compound generally refers to a compound containing relatively high valence manganese (such as Mn 7+ , Mn 6+ , etc.), such as It can be potassium permanganate or potassium manganate; the reduced manganese compound generally refers to a compound containing relatively low valence manganese (eg Mn 2+ ), such as manganese sulfate, manganese nitrate or manganese chloride. The inorganic salt of magnesium can be magnesium chloride or magnesium nitrate. The weight ratio of the oxidized manganese compound, the reduced manganese compound and the inorganic salt of magnesium may be 1:(1-10):(0.1-5). The alkali in the second alkaline aqueous solution may be a common inorganic base, such as sodium hydroxide, potassium hydroxide, etc.; the alkali concentration of the second alkaline aqueous solution may be 1-20 wt %. Further, the preparation step may further include: in step a, heating the first aqueous solution and the alkaline second aqueous solution to 30-90° C., preferably 40-70° C., and then mixing. Through the above steps, the pure-phase octahedral manganese oxide molecular sieve OMS-1 whose XRD pattern conforms to JCPDS No.38-475 can be obtained.

本公开对所述负载的方法没有特别的限定,可以为本领域常规使用的方法,例如可以采用浸渍法或共沉淀法,优选为浸渍法。所述浸渍可以为一次浸渍,也可以为分步浸渍,分步浸渍可以是将活性组分和助剂依次通过浸渍负载到载体上,也可以是将活性组分和助剂一起溶解形成浸渍液,并将浸渍液分两次或多次浸渍到载体上。The method of loading is not particularly limited in the present disclosure, and can be a method commonly used in the art, for example, a dipping method or a co-precipitation method can be used, and an impregnation method is preferred. The impregnation can be a one-time impregnation, or a step-by-step impregnation, and the step-by-step impregnation can be carried out by sequentially impregnating the active component and the auxiliary agent onto the carrier, or by dissolving the active component and the auxiliary agent together to form an impregnation solution. , and the impregnating liquid is impregnated on the carrier in two or more times.

在本公开的一种可选的实施方式中,将所述活性组分和助剂负载于所述载体上的步骤可以包括:将含有活性组分前驱物和助剂前驱物的浸渍液与载体接触进行浸渍。所述浸渍可以为等体积浸渍法,也可以为饱和浸渍法。所述浸渍的条件可以为常规的,例如,所述浸渍的条件可以包括:温度为10~80℃,优选为20~60℃;时间为0.1~3h,优选为0.5~1h。In an optional embodiment of the present disclosure, the step of loading the active component and the auxiliary agent on the carrier may include: loading the impregnation solution containing the active component precursor and the auxiliary agent precursor with the carrier Contact for impregnation. The impregnation may be an equal volume impregnation method or a saturated impregnation method. The immersion conditions may be conventional, for example, the immersion conditions may include: a temperature of 10-80° C., preferably 20-60° C.; a time of 0.1-3 h, preferably 0.5-1 h.

其中,所述活性组分前驱物是指含有所述活性组分的化合物,例如可以为所述活性组分的硝酸盐、柠檬酸盐、硫酸盐或氯化物,或者它们中的两种或三种的组合;例如,当所述活性组分为Fe组分时,所述活性组分前驱物可以为硝酸铁、柠檬酸铁、氯化铁等。所述助剂前驱物是指含有助剂的化合物,例如可以为所述助剂的硝酸盐、硫酸盐、碳酸盐或氯化物,或者它们中的两种或三种的组合;例如,当所述助剂为Zn组分时,所述助剂前驱物可以为硝酸锌、氯化锌、碳酸锌等。所述浸渍液是指将活性组分前驱物和助剂前驱物溶于溶剂中所得到的溶液。其中,所述溶剂例如可以为水、乙醇、乙醚等,所述溶剂的用量可以为常规的,本公开没有特殊的限制。Wherein, the active component precursor refers to a compound containing the active component, such as nitrate, citrate, sulfate or chloride of the active component, or two or three of them A combination of species; for example, when the active component is an Fe component, the active component precursor can be ferric nitrate, ferric citrate, ferric chloride, and the like. The adjuvant precursor refers to a compound containing an adjuvant, such as nitrate, sulfate, carbonate or chloride of the adjuvant, or a combination of two or three of them; for example, when When the auxiliary agent is a Zn component, the auxiliary agent precursor can be zinc nitrate, zinc chloride, zinc carbonate and the like. The immersion solution refers to a solution obtained by dissolving the active component precursor and the auxiliary agent precursor in a solvent. Wherein, the solvent can be, for example, water, ethanol, diethyl ether, etc., the amount of the solvent can be conventional, and there is no special limitation in the present disclosure.

在上述实施方式中,所述载体、活性组分前驱物、助剂前驱物的用量为使得所制备的催化剂中,以催化剂的干基重量为基准,所述载体的含量为12~94重量%,优选为30~91重量%,以金属元素计,所述活性组分的含量为1~70重量%,优选为2~50重量%,所述助剂的含量为1~30重量%,优选为2~25重量%即可。In the above embodiment, the amount of the carrier, active component precursor, and auxiliary agent precursor is such that in the prepared catalyst, based on the dry weight of the catalyst, the content of the carrier is 12-94% by weight , preferably 30 to 91% by weight, in terms of metal elements, the content of the active component is 1 to 70% by weight, preferably 2 to 50% by weight, and the content of the auxiliary agent is 1 to 30% by weight, preferably What is necessary is just to be 2 to 25 weight%.

根据本公开,该方法还包括对负载后得到的物料进行干燥和焙烧的步骤。该干燥和焙烧的步骤为制备催化剂中的常规步骤,本公开没有特殊的限制。例如,所述干燥的条件可以包括:温度为80~350℃,优选为100~300℃;时间为1~24小时,优选为2~12小时。所述焙烧的条件可以包括:温度为250℃~900℃,优选300℃~850℃,更优选为350℃~800℃;时间为0.5~12小时,优选为1~8小时,更优选为2~6小时。According to the present disclosure, the method further includes the steps of drying and roasting the material obtained after loading. The drying and calcining steps are conventional steps in the preparation of catalysts, and are not particularly limited in the present disclosure. For example, the drying conditions may include: the temperature is 80-350°C, preferably 100-300°C; and the time is 1-24 hours, preferably 2-12 hours. The conditions of the roasting may include: the temperature is 250 ℃~900 ℃, preferably 300 ℃~850 ℃, more preferably 350 ℃~800 ℃; the time is 0.5~12 hours, preferably 1~8 hours, more preferably 2 hours. ~6 hours.

本公开第三方面:提供一种由合成气制备α-烯烃的方法,该方法包括以下步骤:A third aspect of the present disclosure provides a method for preparing α-olefin from synthesis gas, the method comprising the following steps:

(1)使初始催化剂在含有氢气的还原气氛下进行还原处理,得到还原处理后的催化剂;(1) reducing the initial catalyst in a reducing atmosphere containing hydrogen to obtain the catalyst after the reduction treatment;

(2)将合成气与步骤(1)得到的所述还原处理后的催化剂接触进行反应;(2) contacting the synthesis gas with the catalyst after the reduction treatment obtained in step (1) to react;

其中,所述初始催化剂为本公开第一方面所述的负载型催化剂。Wherein, the initial catalyst is the supported catalyst described in the first aspect of the disclosure.

根据本公开,步骤(1)中,将本公开所述的负载型催化剂进行还原处理,可将活性组分进行还原活化,以提高催化剂的催化效果。所述还原处理的条件可以包括:空速为1000~20000h-1,优选为2000~10000h-1;温度为100~800℃,优选为200~600℃,更优选为250~500℃;时间为0.5~72h,优选为1~36h,更优选为2~24h。所述还原气氛可以为纯氢气气氛,也可以为氢气和惰性气体(如氮气、氩气、氦气)的混合气氛,氢气分压可以为0.1~4MPa,优选为0.1~2MPa。According to the present disclosure, in step (1), the supported catalyst described in the present disclosure is subjected to reduction treatment, and the active components can be reduced and activated to improve the catalytic effect of the catalyst. The conditions of the reduction treatment may include: the space velocity is 1000-20000h -1 , preferably 2000-10000h -1 ; the temperature is 100-800°C, preferably 200-600°C, more preferably 250-500°C; the time is 0.5-72h, preferably 1-36h, more preferably 2-24h. The reducing atmosphere can be pure hydrogen atmosphere or a mixed atmosphere of hydrogen and inert gas (such as nitrogen, argon, helium), and the partial pressure of hydrogen can be 0.1-4 MPa, preferably 0.1-2 MPa.

根据本公开,所述合成气含有CO和H2,以及可选的N2。将合成气与所述负载型催化剂接触进行反应可以是将现成的合成气与所述负载型催化剂接触进行反应,也可以是按照比例将CO和H2各自通入反应器中与催化剂一起接触进行反应。According to the present disclosure, the syngas contains CO and H2 , and optionally N2 . Contacting the synthesis gas with the supported catalyst for the reaction may be to contact the ready-made synthesis gas with the supported catalyst for the reaction, or to pass CO and H into the reactor in proportion to contact with the catalyst together. reaction.

根据本公开,步骤(2)中,所述反应的条件可以包括:反应温度为280~320℃,反应压力为0.5~8MPa,优选为1~5MPa;所述合成气中H2与CO的摩尔比为(0.4~2.5):1,优选为(0.6~2.5):1,更优选为(0.8~2.2):1;所述合成气的空速为2000~20000h-1。在优选的情况下,所述反应可以在固定床反应器中进行。其中,所述压力均指表压,所述空速均指体积空速。在采用按照合成气的比例将CO和H2各自通入反应器中与催化剂一起接触进行反应的方式时,合成气的空速为CO和H2的合计空速。According to the present disclosure, in step (2), the reaction conditions may include: the reaction temperature is 280-320° C., the reaction pressure is 0.5-8 MPa, preferably 1-5 MPa; the moles of H 2 and CO in the synthesis gas The ratio is (0.4-2.5):1, preferably (0.6-2.5):1, more preferably (0.8-2.2):1; the space velocity of the synthesis gas is 2000-20000 h -1 . In a preferred case, the reaction can be carried out in a fixed bed reactor. Wherein, the pressure refers to gauge pressure, and the space velocity refers to volume air velocity. When CO and H 2 are respectively passed into the reactor according to the ratio of synthesis gas to be contacted with the catalyst to carry out the reaction, the space velocity of the synthesis gas is the total space velocity of CO and H 2 .

以下将通过实施例对本公开进行进一步地详细说明,但并不用于限定本公开。The present disclosure will be further described in detail by the following examples, but it is not intended to limit the present disclosure.

在以下实施例和对比例中:In the following examples and comparative examples:

活性组分和助剂的含量采用X射线荧光光谱分析方法RIPP 132-90(石油化工分析方法(RIPP实验方法),杨翠定、顾侃英、吴文辉编,科学出版社1990年9月第一版,第371-379页)测得。The content of active components and additives was determined by X-ray fluorescence spectroscopic analysis method RIPP 132-90 (Petrochemical Analysis Method (RIPP Experimental Method), edited by Yang Cuiding, Gu Kanying, Wu Wenhui, Science Press, September 1990, first edition, No. 371 -379 pages) measured.

实施例中,载体锰氧化物分子筛OMS-1的制备方法为:取2.014g无水氯化锰与0.636g六水合氯化镁溶于70ml去离子水,50℃水浴中加热搅拌使其充分溶解,得到第一水溶液;取8.2g氢氧化钠溶于70g去离子水中,再向其中加入1.012g高锰酸钾,50℃水浴中加热搅拌使其充分溶解,得到碱性第二水溶液;将上述第一水溶液滴加入碱性第二水溶液中,50℃下水浴中搅拌6h,将所得沉淀抽滤后用80℃的水洗涤3次,得到锰氧化物分子筛前驱体;将42.63g六水氯化镁加入120g去离子水中,得到第三水溶液,向其中加入锰氧化物分子筛前驱体充分搅拌后,转移至250ml的水热釜中,160℃水热晶化36h,收集固体产物,得到载体锰氧化物分子筛OMS-1,其XRD谱图如图1,可见其为符合JCPDS No.38-475的纯相八面体锰氧化物分子筛OMS-1。In the embodiment, the preparation method of the carrier manganese oxide molecular sieve OMS-1 is as follows: dissolving 2.014 g of anhydrous manganese chloride and 0.636 g of magnesium chloride hexahydrate in 70 ml of deionized water, heating and stirring in a water bath at 50 ° C to fully dissolve, to obtain The first aqueous solution; dissolve 8.2 g of sodium hydroxide in 70 g of deionized water, add 1.012 g of potassium permanganate to it, and heat and stir in a 50°C water bath to fully dissolve it to obtain an alkaline second aqueous solution; The aqueous solution was added dropwise to the alkaline second aqueous solution, stirred in a water bath at 50°C for 6 hours, the obtained precipitate was suction filtered and washed with water at 80°C for 3 times to obtain the precursor of manganese oxide molecular sieve; 42.63g of magnesium chloride hexahydrate was added to 120g to remove In ionized water, a third aqueous solution was obtained, into which the manganese oxide molecular sieve precursor was added and stirred thoroughly, then transferred to a 250ml hydrothermal kettle, hydrothermally crystallized at 160°C for 36h, and the solid product was collected to obtain the carrier manganese oxide molecular sieve OMS- 1. Its XRD spectrum is shown in Figure 1, and it can be seen that it is a pure-phase octahedral manganese oxide molecular sieve OMS-1 conforming to JCPDS No.38-475.

实施例1Example 1

将4.04g九水硝酸铁、2.98g六水硝酸锌溶于10mL去离子水中,于50℃水浴中加热搅拌混合均匀,得到浸渍液。取上述浸渍液,与10g载体锰氧化物分子筛OMS-1混合,20℃充分搅拌浸渍1h,然后放置于120℃烘箱中干燥5h,在400℃下焙烧3h,得到本实施例制备的催化剂A1,以金属元素计且以催化剂的干基重量为基准,催化剂A1的组成为10重量%Fe-10重量%Zn/OMS-1。Dissolve 4.04 g of ferric nitrate nonahydrate and 2.98 g of zinc nitrate hexahydrate in 10 mL of deionized water, heat, stir and mix in a 50° C. water bath to obtain an immersion solution. Take the above impregnation solution, mix it with 10 g of carrier manganese oxide molecular sieve OMS-1, fully stir and impregnate it at 20 °C for 1 hour, then place it in an oven at 120 °C to dry for 5 hours, and bake it at 400 °C for 3 hours to obtain the catalyst A1 prepared in this example, The composition of catalyst A1 was 10 wt % Fe-10 wt % Zn/OMS-1 in terms of metal elements and based on the dry weight of the catalyst.

实施例2Example 2

将8.08g九水硝酸铁、2.98g六水硝酸锌溶于10mL去离子水中,于50℃水浴中加热搅拌混合均匀,得到浸渍液。取上述浸渍液,与10g载体锰氧化物分子筛OMS-1混合,20℃充分搅拌浸渍1h,然后放置于120℃烘箱中干燥5h,在400℃下焙烧3h,得到本实施例制备的催化剂A2,以金属元素计且以催化剂的干基重量为基准,催化剂A2的组成为20重量%Fe-10重量%Zn/OMS-1。Dissolve 8.08 g of ferric nitrate nonahydrate and 2.98 g of zinc nitrate hexahydrate in 10 mL of deionized water, heat, stir and mix in a water bath at 50° C. to obtain an immersion solution. Take the above impregnation solution, mix it with 10 g of carrier manganese oxide molecular sieve OMS-1, fully stir and impregnate it at 20 °C for 1 hour, then place it in an oven at 120 °C for 5 hours, and bake it at 400 °C for 3 hours to obtain the catalyst A2 prepared in this example, Catalyst A2 had a composition of 20 wt % Fe-10 wt % Zn/OMS-1 in terms of metal elements and based on the dry weight of the catalyst.

实施例3Example 3

将5.91g六水硝酸钴、1.36g碳酸镉溶于10mL去离子水中,于50℃水浴中加热搅拌混合均匀,得到浸渍液。取上述浸渍液,与10g载体锰氧化物分子筛OMS-1混合,20℃充分搅拌浸渍1h,然后放置于120℃烘箱中干燥5h,在400℃下焙烧3h,得到本实施例制备的催化剂A3,以金属元素计且以催化剂的干基重量为基准,催化剂A3的组成为20重量%Co-10重量%Cd/OMS-1。Dissolve 5.91 g of cobalt nitrate hexahydrate and 1.36 g of cadmium carbonate in 10 mL of deionized water, heat and stir in a water bath at 50° C. to mix uniformly to obtain an immersion solution. Take the above impregnation solution, mix it with 10 g of carrier manganese oxide molecular sieve OMS-1, fully stir and impregnate it at 20 °C for 1 hour, then place it in an oven at 120 °C to dry for 5 hours, and bake it at 400 °C for 3 hours to obtain the catalyst A3 prepared in this example, Catalyst A3 had a composition of 20 wt % Co-10 wt % Cd/OMS-1 on a metal element basis and based on the dry weight of the catalyst.

实施例4Example 4

将4.04g九水硝酸铁、2.12g六水硝酸钴、1.75g六水硝酸锌溶于10mL去离子水中,于50℃水浴中加热搅拌混合均匀,得到浸渍液。取上述浸渍液,与10g载体锰氧化物分子筛OMS-1混合,20℃充分搅拌浸渍1h,然后放置于120℃烘箱中干燥5h,在400℃下焙烧3h,得到本实施例制备的催化剂A4,以金属元素计且以催化剂的干基重量为基准,催化剂A4的组成为10重量%Fe-2重量%Co-5重量%Zn/OMS-1。Dissolve 4.04 g of ferric nitrate nonahydrate, 2.12 g of cobalt nitrate hexahydrate, and 1.75 g of zinc nitrate hexahydrate in 10 mL of deionized water, and heat, stir and mix in a 50° C. water bath to obtain an immersion solution. Take the above impregnation solution, mix it with 10g of carrier manganese oxide molecular sieve OMS-1, fully stir and impregnate it at 20°C for 1 hour, then place it in an oven at 120°C to dry for 5 hours, and bake it at 400°C for 3 hours to obtain the catalyst A4 prepared in this example, Catalyst A4 had a composition of 10 wt % Fe-2 wt % Co-5 wt % Zn/OMS-1 in terms of metal elements and based on the dry weight of the catalyst.

实施例5Example 5

将2.02g九水硝酸铁、5.83g六水硝酸锌溶于10mL去离子水中,于50℃水浴中加热搅拌混合均匀,得到浸渍液。取上述浸渍液,与10g载体锰氧化物分子筛OMS-1混合,20℃充分搅拌浸渍1h,然后放置于120℃烘箱中干燥5h,在400℃下焙烧3h,得到本实施例制备的催化剂A5,以金属元素计且以催化剂的干基重量为基准,催化剂A5的组成为5重量%Fe-25重量%Zn/OMS-1。Dissolve 2.02 g of ferric nitrate nonahydrate and 5.83 g of zinc nitrate hexahydrate in 10 mL of deionized water, heat, stir and mix in a water bath at 50° C. to obtain an immersion solution. Take the above impregnation solution, mix it with 10 g of carrier manganese oxide molecular sieve OMS-1, fully stir and impregnate it at 20 °C for 1 hour, then place it in an oven at 120 °C to dry for 5 hours, and bake it at 400 °C for 3 hours to obtain the catalyst A5 prepared in this example, Catalyst A5 had a composition of 5 wt % Fe-25 wt % Zn/OMS-1 on a metal element basis and based on the dry weight of the catalyst.

实施例6Example 6

将6.17g九水硝酸铁、1.68g六水硝酸锌溶于10mL去离子水中,于50℃水浴中加热搅拌混合均匀,得到浸渍液。取上述浸渍液,与10g载体锰氧化物分子筛OMS-1混合,20℃充分搅拌浸渍1h,然后放置于120℃烘箱中干燥5h,在400℃下焙烧3h,得到本实施例制备的催化剂A6,以金属元素计且以催化剂的干基重量为基准,催化剂A6的组成为16重量%Fe-4重量%Zn/OMS-1。Dissolve 6.17 g of ferric nitrate nonahydrate and 1.68 g of zinc nitrate hexahydrate in 10 mL of deionized water, and heat, stir and mix in a 50° C. water bath to obtain an immersion solution. Take the above impregnation solution, mix it with 10g carrier manganese oxide molecular sieve OMS-1, fully stir and impregnate it at 20°C for 1h, then place it in an oven at 120°C for 5h, and bake it at 400°C for 3h to obtain the catalyst A6 prepared in this example, The composition of catalyst A6 was 16 wt % Fe-4 wt % Zn/OMS-1 on a metal element basis and based on the dry weight of the catalyst.

实施例7Example 7

将2.02g九水硝酸铁、4.67g六水硝酸锌溶于10mL去离子水中,于50℃水浴中加热搅拌混合均匀,得到浸渍液。取上述浸渍液,与10g载体锰氧化物分子筛OMS-1混合,20℃充分搅拌浸渍1h,然后放置于120℃烘箱中干燥5h,在400℃下焙烧3h,得到本实施例制备的催化剂A7,以金属元素计且以催化剂的干基重量为基准,催化剂A7的组成为5重量%Fe-15重量%Zn/OMS-1。Dissolve 2.02 g of ferric nitrate nonahydrate and 4.67 g of zinc nitrate hexahydrate in 10 mL of deionized water, heat, stir and mix in a 50° C. water bath to obtain an immersion solution. Take the above impregnation solution, mix it with 10 g of carrier manganese oxide molecular sieve OMS-1, fully stir and impregnate it at 20 °C for 1 hour, then place it in a 120 °C oven to dry for 5 hours, and bake it at 400 °C for 3 hours to obtain the catalyst A7 prepared in this example, The composition of catalyst A7 was 5 wt % Fe-15 wt % Zn/OMS-1 on a metal element basis and based on the dry weight of the catalyst.

实施例8Example 8

将0.41g九水硝酸铁、9.74g六水硝酸锌溶于10mL去离子水中,于50℃水浴中加热搅拌混合均匀,得到浸渍液。取上述浸渍液,与10g载体锰氧化物分子筛OMS-1混合,20℃充分搅拌浸渍1h,然后放置于120℃烘箱中干燥5h,在400℃下焙烧3h,得到本实施例制备的催化剂A8,以金属元素计且以催化剂的干基重量为基准,催化剂A8的组成为1重量%Fe-30重量%Zn/OMS-1。Dissolve 0.41 g of ferric nitrate nonahydrate and 9.74 g of zinc nitrate hexahydrate in 10 mL of deionized water, heat, stir and mix in a 50° C. water bath to obtain an immersion solution. Take the above impregnation solution, mix it with 10 g of carrier manganese oxide molecular sieve OMS-1, fully stir and impregnate it at 20 °C for 1 hour, then place it in an oven at 120 °C for 5 hours, and bake it at 400 °C for 3 hours to obtain the catalyst A8 prepared in this example, Catalyst A8 had a composition of 1 wt % Fe-30 wt % Zn/OMS-1 on a metal element basis and based on the dry weight of the catalyst.

对比例1Comparative Example 1

将4.04g九水硝酸铁溶于10mL去离子水中,于50℃水浴中加热搅拌混合均匀,得到浸渍液。取上述浸渍液,与10g载体锰氧化物分子筛OMS-1混合,20℃充分搅拌浸渍1h,然后放置于120℃烘箱中干燥5h,在400℃下焙烧3h,得到催化剂D1,以金属元素计且以催化剂的干基重量为基准,催化剂D1的组成为10重量%Fe/OMS-1。Dissolve 4.04 g of ferric nitrate nonahydrate in 10 mL of deionized water, heat and stir in a water bath at 50° C. to mix evenly to obtain an immersion solution. Take the above impregnation solution, mix it with 10 g of carrier manganese oxide molecular sieve OMS-1, fully stir and impregnate it at 20 °C for 1 hour, then place it in an oven at 120 °C for 5 hours, and bake it at 400 °C for 3 hours to obtain catalyst D1, calculated as metal element and The composition of catalyst D1 was 10 wt% Fe/OMS-1 based on the dry weight of the catalyst.

对比例2Comparative Example 2

将2.98g六水硝酸锌溶于10mL去离子水中,于50℃水浴中加热搅拌混合均匀,得到浸渍液。取上述浸渍液,与10g载体锰氧化物分子筛OMS-1混合,20℃充分搅拌浸渍1h,然后放置于120℃烘箱中干燥5h,在400℃下焙烧3h,得到催化剂D2,以金属元素计且以催化剂的干基重量为基准,催化剂D2的组成为10重量%Zn/OMS-1。Dissolve 2.98 g of zinc nitrate hexahydrate in 10 mL of deionized water, heat and stir in a water bath at 50° C. to mix evenly to obtain an immersion solution. Take the above impregnation solution, mix it with 10 g of carrier manganese oxide molecular sieve OMS-1, fully stir and impregnate it at 20 °C for 1 hour, then place it in an oven at 120 °C to dry for 5 hours, and bake it at 400 °C for 3 hours to obtain catalyst D2, calculated as metal element and The composition of catalyst D2 was 10 wt% Zn/OMS-1 based on the dry weight of the catalyst.

测试实施例Test Example

测试实施例1-8和对比例1-2制备的催化剂用于催化由合成气制备α-烯烃时的催化活性。The catalysts prepared in Examples 1-8 and Comparative Examples 1-2 were tested for their catalytic activity when used to catalyze the production of alpha-olefins from syngas.

将初始催化剂装入固定床反应器中,向固定床反应器中通入H2,调整反应器压力为0.1MPa,空速10000h-1,以10℃/min的升温速率升至400℃,恒温4h进行还原处理。The initial catalyst was loaded into the fixed-bed reactor, and H 2 was introduced into the fixed-bed reactor. The pressure of the reactor was adjusted to 0.1 MPa, and the space velocity was 10000 h -1 . 4h for reduction treatment.

还原处理结束后,将反应器温度降至320℃,通入合成气开始反应,空速5000h-1,压力为1.5MPa,合成气组成为H2:CO:N2=56:28:16(体积比),利用在线气相色谱进行尾气组成分析。反应50小时后测得的结果见表1。After the reduction treatment, the temperature of the reactor was lowered to 320° C., and the synthesis gas was introduced to start the reaction. The space velocity was 5000 h −1 , the pressure was 1.5 MPa, and the synthesis gas composition was H 2 :CO:N 2 =56:28:16( volume ratio), the exhaust gas composition was analyzed by on-line gas chromatography. The results measured after 50 hours of reaction are shown in Table 1.

其中:in:

CO的转化率(XCO)、CH4的选择性

Figure BDA0001829268970000131
CO2的选择性
Figure BDA0001829268970000132
α-烯烃的选择性(Sα-烯烯)以及C5以上(C5+)烃类的选择性
Figure BDA0001829268970000133
分别通过以下公式计算得到:CO conversion (X CO ), CH 4 selectivity
Figure BDA0001829268970000131
CO2 selectivity
Figure BDA0001829268970000132
Selectivity to alpha-olefins (S alpha-olefins ) and selectivity to hydrocarbons above C 5 (C 5+ )
Figure BDA0001829268970000133
They are calculated by the following formulas:

Figure BDA0001829268970000134
Figure BDA0001829268970000134

Figure BDA0001829268970000135
Figure BDA0001829268970000135

Figure BDA0001829268970000136
Figure BDA0001829268970000136

Figure BDA0001829268970000137
Figure BDA0001829268970000137

Figure BDA0001829268970000138
Figure BDA0001829268970000138

其中,V1、V2分别表示在标准状况下,某时间段内进入反应系统的原料气的体积和流出反应系统的尾气体积;c1,CO、c2,CO分别表示原料气和尾气中CO的摩尔含量。ncon为参与反应的CO的摩尔数,

Figure BDA0001829268970000141
为生成CO2的摩尔数,
Figure BDA0001829268970000142
为生成的CH4的摩尔数,nα-烯烃为生成α-烯烃的摩尔数,
Figure BDA0001829268970000143
为生成的CH4、C2烃、C3烃和C4烃的摩尔数之和。Among them, V 1 and V 2 respectively represent the volume of feed gas entering the reaction system and the volume of tail gas flowing out of the reaction system in a certain period of time under standard conditions; c 1,CO , c 2,CO represent the raw material gas and tail gas, respectively Molar content of CO. n con is the number of moles of CO involved in the reaction,
Figure BDA0001829268970000141
is the number of moles of CO2 produced,
Figure BDA0001829268970000142
is the moles of CH4 produced, n is the moles of α-olefins produced,
Figure BDA0001829268970000143
is the sum of moles of CH 4 , C 2 hydrocarbons, C 3 hydrocarbons and C 4 hydrocarbons produced.

表1Table 1

Figure BDA0001829268970000144
Figure BDA0001829268970000144

注:油相产物来自于C5 +,油相产物中含有烷烃、α-烯烃、异构烃、含氧化合物等组分。Note: The oil phase product comes from C 5 + , and the oil phase product contains components such as alkanes, α-olefins, isomers, and oxygenates.

由表1可见,本公开的负载型催化剂在用于合成气制备α-烯烃反应中时,一氧化碳转化率较高,α-烯烃的选择性高且产物碳数集中。It can be seen from Table 1 that when the supported catalyst of the present disclosure is used in the reaction of synthesis gas to prepare α-olefin, the conversion rate of carbon monoxide is high, the selectivity of α-olefin is high, and the carbon number of the product is concentrated.

以上结合附图详细描述了本公开的优选实施方式,但是,本公开并不限于上述实施方式中的具体细节,在本公开的技术构思范围内,可以对本公开的技术方案进行多种简单变型,这些简单变型均属于本公开的保护范围。The preferred embodiments of the present disclosure have been described above in detail with reference to the accompanying drawings. However, the present disclosure is not limited to the specific details of the above-mentioned embodiments. Various simple modifications can be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure. These simple modifications all fall within the protection scope of the present disclosure.

另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合,为了避免不必要的重复,本公开对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above-mentioned specific embodiments can be combined in any suitable manner unless they are inconsistent. In order to avoid unnecessary repetition, the present disclosure provides The combination method will not be specified otherwise.

此外,本公开的各种不同的实施方式之间也可以进行任意组合,只要其不违背本公开的思想,其同样应当视为本公开所公开的内容。In addition, the various embodiments of the present disclosure can also be arbitrarily combined, as long as they do not violate the spirit of the present disclosure, they should also be regarded as the contents disclosed in the present disclosure.

Claims (16)

1.一种用于由合成气制备碳数集中在C5~C15的α-烯烃的负载型催化剂,其特征在于,该负载型催化剂包括载体,以及负载在所述载体上的活性组分和助剂,所述载体含有锰氧化物分子筛OMS-1,所述活性组分为选自第VIII族金属的金属组分的一种或多种,所述助剂为选自第IIB族金属的金属组分的一种或多种。1. A supported catalyst for preparing α-olefins whose carbon numbers are concentrated in C 5 ~C 15 from synthesis gas, is characterized in that, this supported catalyst comprises a carrier, and an active component that is supported on the carrier and auxiliary agent, the carrier contains manganese oxide molecular sieve OMS-1, the active component is one or more metal components selected from group VIII metals, and the auxiliary agent is selected from group IIB metals one or more of the metal components. 2.根据权利要求1所述的负载型催化剂,其中,以所述负载型催化剂的干基重量为基准,所述载体的含量为12~94重量%,以金属元素计,所述活性组分的含量为1~70重量%,所述助剂的含量为1~30重量%。2. The supported catalyst according to claim 1, wherein, based on the dry weight of the supported catalyst, the content of the carrier is 12 to 94% by weight, in terms of metal elements, the active component The content of the auxiliary agent is 1 to 70% by weight, and the content of the auxiliary agent is 1 to 30% by weight. 3.根据权利要求2所述的负载型催化剂,其中,以所述负载型催化剂的干基重量为基准,所述载体的含量为30~91重量%,以金属元素计,所述活性组分的含量为2~50重量%,所述助剂的含量为2~25重量%。3. The supported catalyst according to claim 2, wherein, based on the dry weight of the supported catalyst, the content of the carrier is 30 to 91% by weight, in terms of metal elements, the active component The content of the auxiliary agent is 2 to 50% by weight, and the content of the auxiliary agent is 2 to 25% by weight. 4.根据权利要求1所述的负载型催化剂,其中,所述活性组分为Fe组分和/或Co组分;所述助剂为Zn组分和/或Cd组分。4 . The supported catalyst according to claim 1 , wherein the active components are Fe components and/or Co components; and the auxiliary agents are Zn components and/or Cd components. 5 . 5.根据权利要求1所述的负载型催化剂,其中,以金属元素计,所述活性组分与助剂的重量比为1:(0.2~5)。5 . The supported catalyst according to claim 1 , wherein, in terms of metal elements, the weight ratio of the active component to the auxiliary agent is 1:(0.2~5). 6 . 6.根据权利要求5所述的负载型催化剂,其中,以金属元素计,所述活性组分与助剂的重量比为1:(0.3~3)。6 . The supported catalyst according to claim 5 , wherein, in terms of metal elements, the weight ratio of the active component to the auxiliary agent is 1:(0.3~3). 7 . 7.一种制备权利要求1~6中任意一项所述的负载型催化剂的方法,其特征在于,该方法包括:将所述活性组分和助剂负载于所述载体上。7. A method for preparing the supported catalyst according to any one of claims 1 to 6, characterized in that, the method comprises: loading the active components and auxiliary agents on the carrier. 8.根据权利要求7所述的方法,其中,将所述活性组分和助剂负载于所述载体上的步骤包括:将含有活性组分前驱物和助剂前驱物的浸渍液与载体接触进行浸渍;8. The method according to claim 7, wherein the step of loading the active component and the auxiliary agent on the carrier comprises: contacting the impregnation solution containing the active component precursor and the auxiliary agent precursor with the carrier to impregnate; 所述浸渍的条件包括:温度为10~80℃,时间为0.1~3h。The conditions of the impregnation include: the temperature is 10-80° C., and the time is 0.1-3 h. 9.根据权利要求8所述的方法,其中,所述浸渍的条件包括:温度为20~60℃,时间为0.5~1h。9 . The method according to claim 8 , wherein the conditions of the impregnation include: a temperature of 20-60° C. and a time of 0.5-1 h. 10 . 10.根据权利要求8所述的方法,其中,所述活性组分前驱物为所述活性组分的硝酸盐、柠檬酸盐、硫酸盐或氯化物,或者它们中的两种或三种的组合;10. The method of claim 8, wherein the active component precursor is nitrate, citrate, sulfate or chloride of the active component, or two or three of them combination; 所述助剂前驱物为所述助剂的硝酸盐、硫酸盐、碳酸盐或氯化物,或者它们中的两种或三种的组合。The adjuvant precursor is nitrate, sulfate, carbonate or chloride of the adjuvant, or a combination of two or three of them. 11.根据权利要求7所述的方法,其中,该方法还包括对负载后得到的物料进行干燥和焙烧的步骤;11. The method according to claim 7, wherein the method further comprises the steps of drying and roasting the material obtained after loading; 所述干燥的条件包括:温度为80~350℃,时间为1~24小时;The drying conditions include: the temperature is 80-350°C, and the time is 1-24 hours; 所述焙烧的条件包括:温度为250℃~900℃,时间为0.5~12小时。The roasting conditions include: the temperature is 250°C to 900°C, and the time is 0.5 to 12 hours. 12.根据权利要求11所述的方法,其中,所述干燥的条件包括:温度为100~300℃,时间为2~12小时;12. The method according to claim 11, wherein the drying conditions comprise: the temperature is 100-300°C, and the time is 2-12 hours; 所述焙烧的条件包括:温度为300℃~850℃,时间为1~8小时。The roasting conditions include: the temperature is 300° C.˜850° C., and the time is 1˜8 hours. 13.根据权利要求12所述的方法,其中,所述焙烧的条件包括:温度为350℃~800℃,时间为2~6小时。13. The method according to claim 12, wherein the roasting conditions comprise: a temperature of 350°C to 800°C and a time of 2 to 6 hours. 14.一种由合成气制备碳数集中在C5~C15的α-烯烃的方法,该方法包括以下步骤:14. A method for preparing α-olefins having carbon numbers concentrated in C 5 to C 15 from synthesis gas, the method comprising the steps of: (1)使初始催化剂在含有氢气的还原气氛下进行还原处理,得到还原处理后的催化剂;(1) The initial catalyst is subjected to reduction treatment in a reducing atmosphere containing hydrogen to obtain a catalyst after reduction treatment; (2)将合成气与步骤(1)得到的所述还原处理后的催化剂接触进行反应;(2) contacting the synthesis gas with the catalyst after the reduction treatment obtained in step (1) for reaction; 其中,所述初始催化剂为权利要求1~6中任意一项所述的负载型催化剂。Wherein, the initial catalyst is the supported catalyst according to any one of claims 1 to 6. 15.根据权利要求14所述的方法,其中,步骤(1)中,所述还原处理的条件包括:空速为1000~20000h-1,温度为100~800℃,时间为0.5~72h;15 . The method according to claim 14 , wherein, in step (1), the conditions for the reduction treatment include: a space velocity of 1000-20000 h −1 , a temperature of 100-800° C., and a time of 0.5-72 h; 15 . 步骤(2)中,所述反应的条件包括:所述反应在固定床反应器中进行,反应温度为280~320℃,反应压力为0.5~8MPa,所述合成气中H2与CO的摩尔比为(0.4~2.5):1,所述合成气的空速为2000~20000h-1In step (2), the conditions of the reaction include: the reaction is carried out in a fixed bed reactor, the reaction temperature is 280-320 °C, the reaction pressure is 0.5-8 MPa, the moles of H 2 and CO in the synthesis gas are The ratio is (0.4~2.5):1, and the space velocity of the syngas is 2000~20000 h −1 . 16.根据权利要求15所述的方法,其中,步骤(1)中,所述还原处理的条件包括:空速为2000~10000h-1,温度为200~600℃,时间为1~36h。16 . The method according to claim 15 , wherein, in step (1), the conditions of the reduction treatment include: a space velocity of 2000-10000 h −1 , a temperature of 200-600° C., and a time of 1-36 h. 17 .
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